nozzle and production method of the same

专利摘要:
NOZZLE AND PRODUCTION METHODS OF THE SAMEThe present invention relates to a nozzle and a method of producing it. The method includes (a) providing a microstructured mold pattern defining at least a portion of a mold and comprising a plurality of nozzle orifices and flat control cavity replicas; (b) molding a first material into a microstructured nozzle forming pattern using the microstructured mold pattern, with the microstructured nozzle forming pattern comprising a plurality of nozzle orifice forming characteristics and control cavity forming characteristics ; (C) forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the nozzle preform comprising a plurality of nozzle preform holes and flat sacrifice control cavities; and (d) forming a nozzle from the nozzle preform, said nozzle formation comprising removing sufficient of the second material to remove the flat sacrifice control cavities, so as to transform a top surface of the nozzle preform. nozzle on a flat top surface of the nozzle, and to turn each of the nozzle preform holes into a nozzle through hole.
公开号:BR112013019670A2
申请号:R112013019670-0
申请日:2012-02-02
公开日:2020-08-04
发明作者:Barry S. Carpenter；Ryan C. Shirk；Robert J. DeVoe；James C. Novack
申请人:3M Innovative Properties Company；
IPC主号:

专利说明:

1 I 77
"NOZZLE AND METHODS OF PRODUCTION OF THE SAME" Field of the Invention This invention relates generally to nozzles, including nozzles suitable for use in a fuel injector for an internal combustion engine.
The invention 5 additionally applies to fuel injectors that incorporate such nozzles.
This invention also relates to methods of making such nozzles.
The present invention is also applicable to methods of manufacturing injectors incorporating such nozzles.
Background Fuel injection is increasingly becoming the preferred method for mixing fuel and air in internal combustion engines.
Fuel injection can, in general, be used to increase the engine's fuel efficiency and reduce hazardous emissions.
Fuel injectors generally include a lime with a plurality of nozzle through holes for atomizing the fuel under pressure for combustion.
Increasingly stringent environmental standards call for more efficient fuel injectors.
Summary of the Invention In one aspect of the present invention, a method for producing a nozzle is provided.
The method comprises: (a) providing a microstructured mold pattern defining at least a portion of a mold and comprising a plurality of nozzle orifices and flat control cavity replicas; (b) molding a first material into a microstructured nozzle forming pattern using the microstructured mold pattern, with the microstructured nozzle forming pattern comprising a plurality of nozzle orifice forming characteristics and control cavity forming characteristics flat; (c) forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the nozzle preform comprising a plurality of nozzle preform holes and flat sacrifice control cavities; and (d) forming a nozzle from the nozzle preform, forming a nozzle comprising removing sufficient of the second material to remove the flat sacrifice control cavities so as to transform a top surface of the nozzle preform. on a flat top surface of the nozzle, and to turn each of the nozzle preform holes into a nozzle through hole.
In one embodiment of this method, the microstructured mold pattern can be provided by (a) transforming a third material into a microstructured mold forming pattern that comprises a plurality of nozzle orifice forming feature replicas and forming feature replicas flat control cavities; and (b) forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with the replicas of nozzle orifice characteristics being substantially negative replicas of the replicas of the nozzles.
2 I 77 nozzle orifices, and the replicas of flat control cavity-forming characteristics being substantially negative replicas of the replicas of flat control cavities.
In another aspect of the present invention, another method for producing a nozzle is provided.
The method comprises: (a) providing a microstructured mold pattern defining at least a portion of a mold and comprising a plurality of nozzle orifice replicas; (b) molding a first material into a microstructured nozzle pattern using the microstructured mold pattern, with the microstructured nozzle pattern comprising a plurality of nozzle orifice characteristics; (c) forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the nozzle reform comprising a plurality of nozzle preform holes, 1 second material comprising a plurality of different second materials, and the nozzle preform being formed by sequentially depositing each of the second materials as a layer on the microstructured nozzle forming pattern so that the resulting nozzle preform comprises the accumulation of multiple layers , with each layer being a second different material; and (d) forming a nozzle from the nozzle preform, forming a nozzle comprising removing sufficient second material to open an outlet opening in each of the nozzle preform holes and forming each one. the nozzle preform holes in a nozzle through hole.
In one embodiment of this method, the microstructured pattern can be provided by: (a) forming a third material in a microstructured molding pattern that comprises a plurality of replicas of nozzle orifice characteristics; and (b) forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with replicas of nozzle orifice characteristics being substantially negative replicas of replicas of nozzle orifices.
In a further aspect of the present invention, a microstructured pattern is provided to form a nozzle preform comprising a plurality of nozzle preform holes, flat sacrifice control cavities and a flat outer periphery.
The microstructured pattern comprises a plurality of nozzle orifice forming characteristics that are substantially negative replicas of the nozzle preform orifices, and a plurality of flat control cavity forming characteristics that are substantially negative replicas of the flat control cavities of sacrifice.
In another aspect of the present invention, a nozzle preform is provided to form a nozzle comprising a plurality of nozzle through holes, each nozzle through holes comprising an inlet opening and at least one outlet opening. connected to the inlet opening by a hollow cavity defined by an inner surface.
The nozzle preform comprises a plurality of pre-opening holes
3 I 77 nozzle shape corresponding to the nozzle through holes; and a plurality of flat sacrifice control cavities, wherein each of said nozzle preform holes is connected to at least one of said flat sacrifice control cavities.
In another aspect of the present invention, a nozzle is provided which comprises a microstructured pattern which comprises a plurality of nozzle through holes, each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the opening opening. entry through a hollow cavity defined by an inner surface, in which the microstructured pattern has an outer periphery, and the nozzle comprises an accumulation of multiple layers, with each layer being a different material, and with or (a) none of the multiple layers forming in the form of a thin electrically conductive initial particle layer, (b) multiple layers being at least three layers, or (c) both (a) and (b). In a further aspect of the present invention, a nozzle is provided which comprises a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the outlet opening. entrance of a hollow cavity defined by an interior surface, and the microstructured pattern having an external periphery; and at least one fluid channel feature connecting at least one nozzle through hole to (a) at least one other nozzle through hole, (b) a portion of the outer periphery of said microstructured pattern, or (c) both (a) and (b). In another aspect of the present invention, a nozzle is provided which comprises a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening. a hollow cavity defined by an inner surface, and the microstructured pattern having an outer periphery; and at least one fluid feather shape control feature for controlling the shape of a feather formed by a fluid that flows through and exits the outlet openings of said nozzle through holes.
In another aspect of the present invention, a nozzle is provided which comprises a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening. a hollow cavity defined by an inner surface, and the microstructured pattern having an outer periphery; and at least one nozzle through hole having an interior surface comprising at least one fluid flow that affects the characteristic to cause cavitation, turbulence, or otherwise obstruct the flow of a fluid through the nozzle, so as to positively affect an
4 I 77 plume of drops formed by the fluid passing through the nozzle through hole and leaving the corresponding opening through the nozzle through hole.
Brief Description of the Drawings The invention can be understood and appreciated more fully by taking into consideration the following detailed description of the various modalities of the invention, together with the accompanying drawings in which: Figures 1A to 1M are schematic representations of buildings in intermediate stages or stages in a process for the manufacture of a nozzle; Figure 2 is a schematic three-dimensional view of a microstructure; Figure 3 is a schematic three-dimensional view of another microstructure; Figure 4 is a schematic three-dimensional view of another microstructure; Figure 5 is a schematic three-dimensional view of another microstructure; Figure 6 is a schematic of a microstructure base; Figures 7 and 8 are schematic and top views of a microstructure, respectively; Figure 9A is a schematic three-dimensional view of a nozzle orifice feature or microstructure used to form a nozzle orifice; Fig. 98 is a schematic three-dimensional view of the microstructure of Fig. 9A with a flat control cavity forming feature; Figure 10O is a schematic of the base (orifice entrance) of the microstructure (nozzle orifice) shown in figure 9; Figure 11 is a schematic top view of the microstructure (nozzle orifice) shown in Figure 9; Figure 12 is a schematic three-dimensional view of a nozzle orifice (microstructure); Figure 13 is a diagram of the orifice (base) of the nozzle orifice (microstructure) shown in Figure 12; Figure 14 is a schematic top view of the nozzle orifice (microstructure) shown in Figure 12; Figures 15A and B are schematic top views of two different sets of holes (microstructures); Figure 16 is a schematic three-dimensional view of a plurality of nozzle holes (microstructures); Figure 17 is a schematic side view of a microstructure; Figure 18 is a schematic side view of an exposure system; Figures 19 and 20 are two scanning electron micrographs (SEM) of a group of microstructures;
) I 5 I 77
Figure 21 is a SEM of a group of polycarbonate microstructures; Figures 22 and 23 are optical micrographs of the respective entry holes and entry hole of a group of holes; Figure 24 is a schematic side view of a nozzle; 5 Figure 25 is a SEM of one of the holes shown in figures 22 and 23; Figure 26A is a schematic side view of a nozzle orifice forming feature or microstructure, with a curved side and a flat control cavity forming feature configured to form a circular shaped outlet orifice; Figure 268 is a schematic perspective view of the microstructure of Figure 26A; Figure 26C is a schematic top view of the microstructure of Figure 26A; Figure 260 is a schematic side view of the microstructure of Figure 26A with its characteristic of forming a flat control cavity having been removed; Figure 26E is a schematic perspective view of the microstructure of Figure 260; Figure 26F is a top perspective view of the microstructure of Figure 260; Figure 27 is a schematic side view of a nozzle orifice microstructure, with a curved side and a flat control cavity forming feature configured to form a circular shaped outlet port, where the curved side includes flow of annular fluid or output shape control characteristics; Figure 28 is a schematic side view of a nozzle orifice microstructure, with a curved side and a flat control cavity forming feature configured to form a circular shaped outlet port, where the curved side includes flow of discrete source fluid or output format control features; Figure 29 is a schematic side view of a nozzle orifice microstructure, with a curved side and a flat control cavity forming feature configured to form a circular shaped outlet hole, where the curved side includes flow of convergent / divergent multiple fluid or output shape control characteristics; Figure 30 is a schematic side view of a nozzle orifice microstructure, with a curved side and a flat control cavity forming feature configured to form a circular shaped outlet port, where the curved side includes flow convergent / divergent single fluid or output shape control feature; Figure 31A is a schematic perspective view of a nozzle orifice forming microstructure with a curved side and a flat control cavity forming feature configured to form a star shaped outlet orifice;
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Figure 318 is a schematic perspective view of the microstructure of Figure 31A with its flat control cavity characteristic removed; Figure 32A is a schematic perspective view of a nozzle orifice forming microstructure with a curvilinear side and a flat control cavity forming feature configured to form a cross shaped outlet port; Figure 328 is a schematic perspective view of the microstructure of Figure 32A with its flat control cavity characteristic removed; Figure 33 is a schematic perspective view of a nozzle orifice forming microstructure with a curved side and a flat control cavity forming feature configured to form a cross-shaped outlet orifice; Figure 34 is a perspective view [schematic of a nozzle orifice forming microstructure with a curvilinear side and a flat control cavity forming feature configured to form a cross shaped outlet orifice; Figure 35 is a schematic perspective view of a nozzle orifice forming microstructure with a curvilinear side and a flat control cavity forming feature configured to form a cross-shaped exit orifice; Figure 36 is a schematic perspective view of a nozzle orifice forming microstructure with a curvilinear side and a flat control cavity forming feature configured to form a cross shaped outlet orifice; Figure 37 is a schematic perspective view of a nozzle orifice forming microstructure with a straight side and a flat control cavity forming feature configured to form a cross-shaped exit orifice; Figure 38A is a schematic side view of an embodiment of a nozzle orifice microstructure with a curved side and a flat control cavity-forming feature configured to form a rectangular slit-shaped exit orifice; Figure 388 is a schematic perspective view of the microstructure of Figure 38A; Figure 38C is a schematic top view of the microstructure of Figure 38A; Figure 380 is a schematic perspective view of the microstructure of Figure 38A with its characteristic of flat control cavity removed; Figure 39A is a schematic perspective view of a microstructured pattern of mold formation comprising a single group located in the center of the replica of nozzle orifice forming microstructures, replicates of flat control cavity forming characteristics and replication of formation of additional fluid inflow channels;
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Figure 398 is a schematic top view of the microstructured molding pattern of Figure 39A; Figure 39C is a schematic side view of the microstructured molding pattern of Figure 39A; Figure 40A is a schematic perspective view of the bottom of a microstructured nozzle formed using a microstructured mold forming pattern of Figure 39A, with the microstructured nozzle comprising a plurality of nozzle passage holes and inflow channels. additional fluids; Figure 408 is a schematic bottom view of the microstructured nozzle of Figure 40A; Figure 40C is a schematic cross-sectional view of the microstructured nozzle of Figure 408 taken along line 1oC-40C; Figure 41 is a schematic perspective view of the bottom of a microstructured nozzle formed using a microstructured molding pattern in accordance with the present invention, with the microstructured nozzle comprising a plurality of nozzle through holes and channels inflow of additional and alternative fluids; Figure 42A is a schematic perspective view of a microstructured mold forming pattern comprising two groups of replica nozzle orifice forming microstructures with corresponding replicates of flat control cavity forming features, and a nozzle separation feature with an additional set of replicas of flat control cavity-forming characteristics; Figure 428 is a schematic side view of the microstructured molding pattern of Figure 42A; Figure 43A is a schematic perspective view of the top of a microstructured mold pattern made using the microstructured mold forming pattern of Figure 42A; Figure 438 is a schematic top view of the microstructured pattern of the microstructured mold of Figure 43A; Figure 43C is a schematic cross-sectional view of the microstructured mold pattern of Figure 438 taken along line 43C-43C; Figure 430 is a schematic cross-sectional view of the microstructured mold pattern of Figure 438 taken along line 430-430; Figure 44A is a schematic perspective view of a microstructured nozzle forming pattern made using the microstructured mold pattern of Figure 43A; Figure 448 is a schematic cross-sectional view of the microstructured nozzle-forming pattern of Figure 44A taken along line 448-448;
8 I 77 Figure 45 is a schematic cross-sectional view of a linear arrangement of the microstructured nozzle forming pattern of Figure 44A taken along line 448-448, with a linear arrangement of nozzle preforms formed therein; Figure 46 is a schematic bottom view of a linear arrangement of connected nozzles 5, which are formed from the arrangement of a nozzle preform of Figure 45 and are easily separable from each other; Figure 47 is a schematic cross-sectional side view of a miçroe_stn pattern: nozzle forming tip and a multi-component nozzle preform deposited thereon; ~ Fifura 48 is a photograph of a cross section of the fuel injector convinc1ona1. 1 In the specification, the same reference number used in multiple figures refers to the same or similar elements that have the same or similar properties and functionality. Detailed Description The nozzles shown include one or more through-holes designed to optimize the spray direction and fluid dynamics at the orifice inlet, orifice wall and orifice outlet. The presented nozzles can be advantageously incorporated into the fuel injection systems to optimize fuel efficiency. The presented nozzles can be manufactured using multiphotons, such as biphotonic processes. In particular, multiphotonic processes can be used to manufacture various microstructures. These microstructures can include at least one or more orifice characteristics, which can, in turn, be used as molds to manufacture orifices for use in nozzles or other applications. It should be understood that the term "mouthpiece" can have many different meanings in the art. In specific references, the term mouthpiece has a broad definition. For example, the US patent publication. No. 2009/0308953 A1 (Palestrant et al.) features an "atomizing nozzle" that includes a number of elements, including an occlusive chamber 50. This differs from the understanding and definition of the nozzle presented in the annex. For example, the nozzle of the present description would generally correspond to the orifice insert 24 of Palestrant et al. In general, the nozzle of this description can be understood as the final tapered portion of an atomizing spray system from which the spray is finally emitted, see, for example, the Merriam Webster dictionary definition for nozzle ("a short tube with a bottleneck or contraction used (as in a hose) to accelerate or direct a flow of fluid "). Additionally, the understanding can be obtained by reference to the US patent in
5,716,009 (Ogihara et al.) Issued to Nippondenso Co., Ltd. (Kariya, Japan). In this reference, again, the fluid injection nozzle is broadly defined as a valve element
9 I 77 composed of multiple parts 1O ("fuel injection valve 1O acting as a fluid injection nozzle ..." - see col. 4, lines 26-27 by Ogihara et al.). This definition and understanding of the term "nozzle" for use in the present invention would be related to the first and second orifice plates 130 and 132 and potentially to the sleeve 138 (see figures 14 and 15 of 5 Ogihara et al.), For example, which are located immediately adjacent to the fuel sprinkler.
A similar understanding of the term "mouthpiece" to that described herein is used in US Patent No. 5,127,156 (Yokoyama et al.) Granted to Hitachi, Ltd. (lbaraki, Japan). There, the nozzle 1O is defined separately from elements of the attached and integrated structure, such as "tourbillon" 12 (see Figure 1 (11). The understanding defined above must be understood when the term "nozzle" is mentioned throughout the remainder of the description and claims "J In some cases, a microstructure shown may be u" (three-dimensional rectilinear body such as a polyhedron, such as a tetrahedron or hexahedron, a prism or a pyramid or a portion or combination of such bodies, such as a trunk.
For example, figure 2 is a schematic three-dimensional view of a microstructure 220 that is arranged on a substrate 21 O and includes a planar or flat base 230, a planar or flat top 240 and a side 250 that connects the top to the base.
Side 250 includes a plurality of planar or flat facets, such as facets 260, 265 and 270. Microstructure 220 can be used as a template for making holes for use in, for example, a nozzle.
In some cases, a microstructure shown may be a three-dimensional curvilinear body or a portion of such a body, such as a segment of a sphere, a sphere, an ellipse, a spheroid, a paraboloid, a cone or a truncated cone or a cylinder.
For example, Figure 3 is a schematic three-dimensional view of a microstructure 320 that is arranged on a substrate 31 O and includes a planar or flat base 330, a planar or flat top 340 and a curved side 350 that connects the top to the base .
In the exemplary microstructure 320, the top 340 and the base 330 have the same shape, but different sizes.
Microstructure 320 tapers more narrowly from base 330 to top 340. As a result, top 340 has a smaller area than base 330. Microstructure 320 can be used as a template to make holes for use in, for example, example, a mouthpiece.
In some cases, some of the characteristics of a presented microstructure change from the bottom to the top.
For example, in some cases, a microstructure shown may be a tapered microstructure.
For example, Figure 4 is a schematic three-dimensional view of a microstructure 420 that can be manufactured using a multiphotonic process.
Microstructure 420 can be used as a template to manufacture holes for use in, for example, a nozzle.
Microstructure 420 is arranged on a substrate 410 and includes a base 430, a top 440 and a side 450 connecting the top to the base.
Microstructure 420 has a height or thickness h1 which is the distance between the base 430 and the top 440 along the z axis. THE
10 I 77 microstructure 420 is tapered.
In particular, the cross-sectional area of the microstructure along the thickness of the microstructure decreases from the base 430 to the top 440. For example, the microstructure 420 includes a cross section 460 at height h2 in the xy plane and a cross section 470 in the height h3> h 2 in the xy plane.
The cross-sectional area 5 470 is smaller than the cross-sectional area 460, and the cross-sectional area 460 is smaller than the area of the base 430. The base 430 has a first shape and the top 440 has a second shape which is different from the first format.
In some cases, the first shape is an elliptical shape and the second shape is a circular shape.
For example, figure 5 is a schematic three-dimensional view of a microswitch 520 that includes an elliptical base 530, a circular top 540 and a side 550 that connects the fool to the base.
The elliptical base 530 has a main axis 560 along the y direction having a length "a" and a minor axis 570 along the direction x having a length "b" other than "a". The circular top 540 has a radius r.
Microstructure 520 is tapered.
In particular, the area of the circular top 540 is smaller than the area of the elliptical base 530. As another example, the first shape can be a racetrack or oval and the second shape can, for example, be a circle.
For example, figure 6 is a schematic of a base 630 which can be the base of a presented microstructure.
Base 630 includes two circles 642 and 644 and a medium portion 650. Base 630 has a perimeter 660 that includes curved portions or arcs 632 and 634 and linear portions 636 and 638. Circles 642 and 644 have a radius ra and rb, respectively, where ra and rb can be the same or different.
The curved portions 632 and 634 are portions of the respective circles 642 and 644. In some cases, a microstructure shown has a cross section along the thickness or height direction of the microstructure that rotates from the base of the microstructure to the top of the microstructure.
For example, figure 7 is a schematic three-dimensional view of a microstructure 720 that includes a base 730 arranged in the xy plane, a top 740 arranged in the xy plane, and a side 780 that connects the top to the base.
Microstructure 720 has a height h4. Microstructure 720 has a cross section xy that rotates clockwise from the top 740 to the base 730. In particular, the top 740 has an axis of symmetry 742 along the x direction, a cross section xy 750 of the microstructure at a height h5 <h4 has an axis of symmetry 752 that rotates clockwise with respect to axis of symmetry 742, a cross section xy 755 of the microstructure at a height h5 <hs has an axis of symmetry 757 that rotates clockwise with respect to axis of symmetry 752, a cross section xy 760 of the microstructure at height h7 <h 6 has a axis of symmetry 762 that rotates clockwise with respect to axis of symmetry 757, and base 730 has a axis of symmetry 732 along the y-axis that rotates clockwise in relation to the axis of symmetry 762. Equivalently, microstructure 720 has a cross-section xy that rotates counterclockwise from base 730 to top 740. Figure 8
11 I 77 is a schematic top view of microstructure 720 illustrating the top 740 and its axis of symmetry 742, the cross section 750 and its axis of symmetry 752, the cross section 755 and its axis of symmetry 757, the cross section 760 and its axis of symmetry 762, and base 730 and its axis of symmetry 732. Seen from the top, the axes of symmetry of the cross sections rotate 5 clockwise from the top to the base.
Such rotation results in a twist in the microstructure along its height or thickness.
In some cases, each cross section can be an ellipse with a corresponding main axis acting as a symmetry axis.
In such cases, the main axis rotates from the base to the top.
In some cases, such as when the microstructure is tapered and twisted, the cross sections rotate and become smaller from the base to the top. For example, an elliptical base 730 has a main axis 732 along the y direction and has a length " ~ "and a minor axis 734 along the x direction having a length" b "other than" a ". As the main axis rotates from the base to the top, the a / b ratio is reduced, for example, decreasing "a" results in a smaller ellipse that can eventually become a circle at the top (a = b) . In general, a presented microstructure can include a taper and / or a twist or spiral along the thickness of the microstructure from the base to the top.
Microstructure 720 can be used as a mold to manufacture one or more orifices in a nozzle with the orifices having substantially the same profile as the microstructure 720. For example, fabrication results in an orifice 720 having an orifice inlet 730, an outlet orifice 740 and a wall 752 extending from the orifice inlet to the orifice outlet.
The orifice tapers and spirals or twists from the orifice inlet to the orifice outlet.
A spiraling or twisting nozzle orifice can be advantageously used in a fuel injector to change the speed of the fuel flow, reduce the droplet size and optimize the mixture of the fuel with the air.
The microstructure can be understood as having a "diameter" at different heights of the microstructure (for example h6, hs, etc.). The diameter can be understood as the maximum distance between the edges of the microstructure at a common height.
In the situation where there is an elliptical base, as in the orifice entrance 730, the diameter will be the distance between the edges of the microstructure along the main axis 732. At the opposite end of the structure, corresponding to the exit orifice 740, the diameter will be similar to maximum distance between the edges of the microstructure at a common height (here, h 4). Thus, the distance between the edges of the microstructure along axis 742 corresponds to the diameter of the exit orifice.
In some embodiments, the orifice inlet may have a diameter of less than 300 microns, or less than 200 microns, or less than or equal to 160 microns, or less than 140 microns.
In some embodiments, the outlet port may have a diameter of less than 300 microns, or less than 200 microns, or less than 100 microns, or less than or equal to 40 microns, or less than 25 microns.
In some cases, a cross section of the nozzle orifice 720 has an increased rate of rotation from the orifice inlet to the orifice outlet.
In some cases, a nozzle orifice cross section 720 has a decreased rate of rotation from the orifice inlet to the orifice outlet.
In some cases, a cross section has a constant rate of rotation from the orifice inlet to the orifice outlet.
In general, a base or a lateral cross section of a presented microstructure, or an entry orifice or a lateral cross-section of a presented nozzle orifice, can have any cross-section that may be desirable in an application.
In some cases, the base or the entry hole may have a perimeter that includes the outer arcs of the juxtaposed circles, where the outer arcs are connected by curved fillets.
For example, Figure. 9A is a schematic three-dimensional view of an orifice feature or microstructure 920 that includes a base 930 used to form the entry hole, an upper part 940, which can define the exit hole, and a side 950 that connects the base to the top and is used to define the orifice walls.
Figure 98 is a schematic three-dimensional view of the orifice or microstructure forming feature 920 with a replica of the flat control cavity forming feature 920A that is used to form a flat control cavity or planarization cone.
Figure 10 is a schematic of the base 930 having a perimeter 1090 that includes the outer arcs of four juxtaposed circles, where the outer arcs are connected by curved threads.
In particular, perimeter 1090 includes an outer arc 1010 of a circle 1020, an outer arc 1O12 of a circle 1022, an outer arc 1O11 of a circle 1024, and an outer arc 1016 of a circle 1026, where outer arcs 1010 and 1012 are connected by curve like 1030 thread or straight line 1030A (shown in dashed line), outer arcs 1012 and 1014 are connected by curve like 1032 thread or straight line 1032A (shown in dashed line), outer arcs 1014 and 1016 are connected by curve like fillet 1034 or straight line 1034A (shown in dashed line) and outer arcs 1016 and 1010 are connected by curve like fillet 1036 or straight line 1036a (shown in dashed line). Circles 1010, 1012, 1014 and 1016 form a square arrangement of equal circles that touch where each circle has a radius r1, r2, r3 and r4 that are the same or different.
The base 930 includes a 1040 symmetry axis. The lateral cross sections of microstructure 920 rotate and the radius r1 decreases from the base 930 to the top 940 resulting in a microstructure that spirals and tapers more narrowly from the base 930 to the top 940. Equally, a nozzle orifice 920 includes an orifice inlet 930, an orifice outlet 940 and a wall 950 extending from the orifice inlet to the orifice outlet.
The orifice 920 has a lateral cross section that rotates and is smaller from the orifice inlet to the orifice outlet.
Figure 11 is a schematic top view of the nozzle orifice (or microstructure) 920 illustrating orifice entrance 930 which has axis of symmetry 1040 and orifice exit 940 which has axis of symmetry 942. Seen from the top, the axes of symmetry of sections transverse holes 920 rotate counterclockwise from the hole inlet to the 5 hole outlet.
Such rotation results in a twist in the hole along its height or thickness.
As another example, figure 12 is a schematic three-dimensional view of a nozzle orifice (or microstructure) 1220 that has a height k1 and includes an orifice entrance 1230, an orifice exit 1240, and a wall 1250 extending from from the orifice inlet to the orifice outlet.
Figure 13 is a schematic of the orifice entrance 1O 1230 having a perimeter 1235 which includes the outer arcs of two circles juxtaposed or touching, where the outer arcs are connected by curved threads.
In particular, perimeter 1090 includes an outer arc 1270 of a circle 1280 and an outer arc 1272 of a circle 1282, where each circle has a radius r2 and outer arcs 1270 and 1272 are connected by curved threads 1290 and 1292. The entrance orifice 1230 includes an axis of symmetry 1232. The lateral cross sections of the nozzle orifice 1220 rotate and the radius r2 decreases from orifice 1230 to orifice 1240 resulting in a microstructure that spirals and tapers narrower from orifice entry 1230 to orifice outlet 1240. In particular, the top 1240 has an axis of symmetry 1242 along the x direction, a cross section xy 1264 of the orifice at a height k2 <k 1 has a axis of symmetry 1265 that rotates clockwise with respect to axis of symmetry 1242, a cross section xy 1262 of the hole at a height k3 <k2 has a axis of symmetry 1263 that rotates clockwise with respect to axis of symmetry 1265, a tra section nsversal xy 1260 of the orifice at a height k4 <k3 has an axis of symmetry 1261 that rotates clockwise with respect to axis of symmetry 1263, and orifice entry 1230 has an axis of symmetry 1232 along axis y that rotates in clockwise in relation to the axis of symmetry 1261. Then, hole 1220 has a cross section xy that rotates clockwise from hole exit 1240 to hole entrance 1230. Equally, hole 1220 has a cross section xy that rotates counterclockwise from the hole inlet to the hole outlet.
Figure 14 is a schematic top view of the orifice of the nozzle 1220 illustrating the exit of the orifice 1242 and its axis of symmetry 1242 along the x axis, the cross section 1264 and its axis of symmetry 1265, the cross section 1262 and its axis of symmetry 1263, cross section 1260 and its axis of symmetry 1261 and orifice entry 1230 and its axis of symmetry 1232 along the y axis.
Viewed from the top, the axes of symmetry of the lateral cross sections of the orifice rotate clockwise from the orifice outlet to the orifice inlet.
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Similarly, a microstructure 1220 includes a base 1230, a top 1240 and a side 1250 that connects the base to the top.
The microstructure 1220 has a cross section that rotates and is smaller from the base to the top.
As shown in figures 2 to 14, the microstructures shown in the present invention that serve as nozzles can be monolithic structures.
In other words, microstructures 220, 320, 420 etc. that form the true nozzles are created from, and essentially form, a single and common piece of material.
This can be understood as being different from the nozzles that are formed through a combination of numerous different parts, where such parts are potentially made of different materials.
Accordingly, as shown in the figures mentioned above, the mouths shown in the present invention can be monolithic structures.
In general, a plurality of microstructures or orifices presented can have any arrangement that may be desirable in an application.
For example, in some cases, the holes shown may be arranged regularly or irregularly.
For example, figure 15A is a schematic top view of a two-dimensional square set 1500 of holes or microstructures 151 O, and figure 158 is a schematic top view of a two-dimensional hexagonal set 1520 of holes or microstructures 1530, where the holes or microstructures 1510 and 1530 can be any nozzle orifice or microstructure shown in the present invention.
In some cases, a plurality of microstructures or holes shown may be arranged on a non-planar surface.
For example, figure 16 is a schematic three-dimensional view of a plurality of nozzle holes or microstructures 1610 arranged or placed on a spherical surface 1620. In some cases, a microstructure or hole shown may have one or more fillets for ease of fabrication and / or to reduce local stress.
For example, figure 17 is a schematic side view of a microstructure 1720 that is arranged on a substrate 171 O and includes a base 1730, a top 17 40 and a side 1750 connecting the base to the top.
Microstructure 1720 includes fillets 1760 and 1761 uniformly joining side 1750 and top 17 40, and fillets 1770 and 1771 uniformly joining side 1750 and top surface 1705 of substrate 171 O.
The through holes or nozzle holes and the microstructured patterns or microstructures described herein can be manufactured using the various methods described herein, including that described with reference to Figures 1A-1M.
The method provides flexibility and control in the production of a variety of microstructures and individual holes in a single set, however it can be used to obtain low desirable medium surface roughness levels, while maintaining manufacturing speeds or "process time" industrially acceptable.
15 I 77
Figure 1A is a schematic side view of a layer 115 of a first material disposed on a substrate 110. The first material is capable of being subjected to a multiphotonic reaction simultaneously absorbing multiple photons.
For example, in some cases, the first material is capable of undergoing a reaction of two photons simultaneously absorbing 5 two photons.
The first material can be any material or material system that is capable of being subjected to multiphotons, as a reaction of two photons, such as those described in pending application US serial number 11/313482, "Process For Making Microlens Arrays And Masteroforms" ( Registration summary No. 60893US002), deposited on December 21, 2005; US Patent Application Publication 2009/0175050, "Process For Making Light Guides With Extraction Structures And Light Guides Produced Thereby" (Attorney Dossier No. 62162US007), filed May 17, 2007; and PCT publication WO 2009 / 0487f5, "Highly Functional Multiphoton Curable Reactive Species" (Lawyer file no. 63221W0003), filed on September 9, 2008; all of which are incorporated by reference.
In some cases, the first material may be a photoreactive composition that includes at least one reactive species that is capable of undergoing a chemical reaction initiated by an acid or radical, and at least one multiphoton photoinitiator system.
Reactive species suitable for use in photoreactive compositions include both curable and non-curable species.
Exemplary curable species include those added with polymerizable monomers and oligomers and added with crosslinkable polymers (such as polymerizable species with free radicals or ethylenically unsaturated crosslinkable including, for example, acrylates, methacrylates and certain vinyl compounds such as styrenes), as well as monomers and oligomers cationically polymerizable and cationically crosslinkable polymers (whose species are most commonly initiated by acid and which include, for example, epoxies, vinyl ethers, cyanate esters, etc.), and the like, and mixtures thereof.
Exemplary non-curable species include reactive polymers whose solubility can be increased by the reaction induced by acid or radical.
Such reactive polymers include, for example, aqueous insoluble polymers that have ester groups that can be converted by photogenerated acid to aqueous soluble acid groups (e.g., poly (4-tert-butoxycarbonyloxystyrene). Non-curable species also include chemically amplified photoresists. .
The multi-photon photoinitiator system allows polymerization to be confined or limited to the focal region of a focused beam of light used to expose the first material.
Such a system of preference is a system with two or three components that includes at least one multiphotonic photosensitizer, at least one photoinitiator (or electron receiver) and, optionally, at least one electron donor.
Layer 115 of the first material can be coated on substrate 11O using any coating method that may be desirable in an application.
For example, the
16 I 77 first material can be coated on substrate 11 O by soaking coating.
Other exemplary coating methods include sheet coating, notch coating, reverse coating, etching coating, spray coating, bar coating, rotation coating and dip coating. 5 Substrate 110 can be chosen from a wide variety of films, sheets and other surfaces (including silicon wafers and glass plates), depending on the particular application and the exposure method to be used.
In some cases, substrate 11O is sufficiently flat so that layer 115 of the first material is of uniform thickness.
In some cases, layer 115 may be exposed in bulk form.
In such cases, substrate 11 O can be excluded from the manufacturing process.
In some cases, such as when the process includes one or more electroplating steps, the substrate 11 O can be electrically conductive or semiconductive.
Then, the first material is selectively exposed to incident light having sufficient intensity to cause simultaneous absorption of multiple photons by the first material in the exposed region.
Exposure can be performed by any method that is capable of providing sufficient light.
Exemplary exposure methods are described in US patent application publication 2009/0099537, "Process For Making Microneedles, Microneedle Arrays, Masters, And Replication Tools" (Registration Summary No. 61795US005), filed on March 23, 2007, which is incorporated herein by reference.
Figure 18 is a schematic side view of an example display system 1800 for exposing layer 115 of the first material.
The display system includes an 1820 light source emitting 1830 light and an 1810 platform that is capable of moving in one, two or three dimensions.
The substrate 11 The coated with the layer of the first material 115 is placed on the platform.
The 1840 optical system focuses the light emitted 1830 on a focal region 1850 within the first material.
In some cases, the 1840 optical system is designed so that the simultaneous absorption of multiple photons by the first material occurs only in the focal region or very close to it 1850. The regions of layer 115 that are subjected to the reaction of multiple photons become more or less soluble in at least one solvent compared to regions of layer 115 that do not undergo the reaction of multiple photons.
The focal region 1850 can scan a three-dimensional pattern within the first material using the 181 O mobile platform and / or 1830 light and / or one or more components, such as one or more mirrors, in the 1840 optical system. illustrated in figures 1A and 18, layer 115 is arranged on an 11 O planar substrate.
In general, substrate 11 O can be of any shape that may be desirable in an application.
For example, in some cases, substrate 110 may be spherical in shape.
The 1820 light source can be any light source that is capable of producing sufficient light intensity to perform multiphotonic absorption.
Light sources
17 I 77 examples include lasers, such as femtosecond lasers, operating in a range from about 300 nm to about 1500 nm, or from about 400 nm to about 1100 nm, or from about 600 nm to about 900 nm, or from about 750 to about 850 nm.
1840 optical systems may include, for example, refractive optical elements 5 (for example, sets of lenses or micro lenses), reflective optical elements (for example, retro-reflectors or focus mirrors), diffractive optical elements (for example, reticles, masks phase and holograms), polarizing optical elements (for example, linear and retarding polarizers), dispersive optical elements (for example, prisms and reticles), diffusers, Pockel cells, waveguide and the like.
Such optical elements are useful for focusing, releasing beam, formatting beam / squeegee, formatting the pulse and timing the pulse.
L After the selective exposure of layer 115 of the first material by the 1800 exposure system, the exposed layer is placed in a solvent to dissolve regions of greater solubility in the solvent.
Exemplifying solvents that can be used to develop the first exposed material include aqueous solvents such as, for example, water (for example, having a pH in the range 1 to 12) and miscible blends of water with organic solvents (for example, methane! , ethane !, propanol, acetone, acetonitrile, dimethyl formamide, n-methyl pyrrolidone, and the like, and mixtures thereof); and organic solvents and organic solvents.
Exemplary useful organic solvents include alcohols (for example, methane !, ethane! And propanol), ketones (for example, acetone, cyclopentanone and methyl ethyl ketone), aromatics (for example, toluene), halocarbons (for example, methylene chloride and chloroform), nitriles (for example, acetonitrile), esters (for example, ethyl acetate and propylene glycol methyl ether acetate), ethers (for example, diethyl ether and tetrahydrofuran), amides (for example, n-methyl pyrrolidone) , and the like, and mixtures thereof.
Figure 1B is a schematic side view of a first microstructured pattern 121 formed on the first material using the multiphotonic process.
The first microstructured pattern includes a first group 122 of microstructures or characteristics 120 and a second group 124 of microstructures or characteristics 125, where microstructures 120 and 125 can be any microstructure including any microstructures shown in the present invention.
In some cases, microstructures 120 and 125 have different structures.
In some cases, microstructures 120 and 125 have the same structure.
In the first exemplifying microstructured pattern 121, microstructures 120 and 125 have heights t1. Each microstructure 120 and 125 includes a nozzle orifice forming feature replica 120b and 125b, and (differentiated by dashed lines) flat control cavity forming feature replica 120a and 125a, which are used to form the control cavities planarization planes or cones.
When planarization cones are used, it may be preferable that they have a tapered angle of about 45 degrees.
18 I 77
Figures 19 and 20 are scanning electron microscopy of a group or replica arrangement of nozzle orifice formation characteristics or microstructures 120 manufactured in accordance with the processes described herein.
The microstructures in Figures 19 and 20 are similar to the characteristic of nozzle orifice formation or microstructures 5 1220 shown in Figure 12. In figure 19, the microstructures are visualized along the minor axes of the microstructure bases and in figure 20, the microstructures are visualized along the major axes of the microstructure bases.
The plurality of microstructures or microstructured pattern in figure 19 (and figure 20) is arranged in a set of concentric circles that includes a more outer circle 191 O.
The microstructures are arranged so that no diameter of the outermost circle includes at least one microstructure distinct from each circle in the set of concentric circles.
For example, a diameter 1920 of the outermost circle 191 O includes microstructures 1901 to 1905, but not microstructures 1930 and 1931. Each circle in the set of concentric circles in figure 19 includes distinctly spaced microstructures.
Similarly, in some cases, a nozzle includes a plurality of holes that are arranged in a set of concentric circles that include a more outer circle.
The nozzle orifices or discrete nozzle orifices are arranged so that no diameter of the outermost circle includes at least one distinct nozzle orifice from each circle in the set of concentric circles.
In some cases, each circle in the set of concentric circles comprises equally spaced separate nozzle holes.
Then, as schematically illustrated in Figure 1C, the top or exposed surface 126 of the first microstructured pattern 121 is metallized or made electrically conductive by coating the top surface with a thin layer of electrically conductive starting particle 127. The layer of conductive starting particle 127 can include any electrically conductive material that is desirable in the application.
Exemplary conductive materials include silver, chrome, gold and titanium.
In some cases, the initial particle layer 127 has a thickness that is less than about 50 nm, or less than about 40 nm, or less than about 30 nm, or less than about 20 nm.
Then, as schematically illustrated in Figure 1D, the initial particle layer 127 is used to galvanize the first microstructured pattern 121 with a second material resulting in a layer 130 of the second material.
In some cases, the electroplating of the first microstructured pattern 121 is maintained until the minimum thickness t 2 of layer 130 is greater than k The second materials suitable for electroplating include silver, passivated silver, gold, radio, aluminum, aluminum with optimized reflectivity, copper , indium, nickel, chromium, tin, and alloys of these substances.
19 I 77
In some cases, layer 130 of the second material has an uneven or rough top surface 132. In such cases, layer 130 of the second material is polished or ground resulting in a layer 135 of second material having a thickness t3> t1 as illustrated schematically in figure 1E.
The grinding or polishing can be carried out 5 using any grinding method that may be desirable in an application.
Exemplary grinding methods include surface grinding and mechanical grinding.
In some cases, the layer of the second material 130 can be directly deposited on the first microstructured pattern 121 without first coating the pattern 121 with the initial particle layer 127. In such cases, the layer 130 can be coated on the pattern r using the use of any method of ion bombardment and deposition of chemical vapors. including, for example,
Then, substrate 11O and the first material are removed resulting in a first mold 140 of the second material schematically shown in figure 1F.
For ease of viewing and without loss of generality, the initial particle layer 127 is not shown in figure 1 F.
In some cases, substrate 11O and the first material provided with a pattern can be separated from layer 135 manually.
In some cases, the separation can be carried out before the layer 130 is crushed. The first mold 140 includes a second microstructured pattern 141 which is exactly, essentially, or at least substantially the negative replica or image (for example, reverse or mirror) of first microstructured pattern 121. In particular, the first mold 140 of the second material includes a first group 146 of microstructures 145 and a second group 147 of microstructures 148, where microstructures 145 are exactly, essentially, or at least substantially negative replicas or images of microstructures 120 and microstructures 148 are exactly, essentially, or at least substantially negative replicas or images of microstructures 125. Then, the second microstructured pattern is replicated in a third material 150, which is the same or different than the first material and different from the second material, by eliminating the third material between the first mold 140 of the second material and a substrate 155 that has a flat top surface 157, as illustrated schematically in Figure 1G.
The replication process can be carried out using any suitable replication method.
For example, in some cases, replication can be performed using an injection molding process.
In such cases, the first mold 140 and substrate 155 can form at least part of two halves of a molding matrix, and a third melt 150 can be introduced between substrate 155 and first mold 140 and solidified after the third melt. fill the second microstructured pattern.
The third material 150 can be any material that is capable of replicating a pattern.
Third exemplifying materials include polycarbonate and other
20 I 77 thermoplastics such as polystyrene, acrylic, styrene acrylonitrile, polymethyl! methacrylate (PMMA), cycloolefin polymer, polyethylene terephthalate, 2,6-naphthalate polyethylene and fluoropolymers.
After the replication process, the first mold 140 of the second material and the substrate 155 are removed, resulting in a second mold 160 of the third material which 5 has a substrate portion 162 and a third microstructured pattern 161 which is exactly, essentially or, at least substantially the negative replica or image (e.g., reverse or mirror) of the second microstructure pattern 141 and exactly, essentially, or at least substantially a positive replica or image of the first microstructure pattern 121. Third microstructure pattern 161 includes a first group 16f of microstructures 165 and a second group 169 of microstructures 159, where microstructures 165 are exactly, essentially, or at least substantially negative replicas or images of microstructures 145 and microstructures 159 are exactly, essentially, or at least substantially negative replicates or microstructure images 148. In some cases, microstructures 16 5 are exactly, essentially, or at least substantially positive replicates or images of microstructures 120 and microstructures 159 are exactly, essentially, or at least substantially positive replicates or images of microstructures 125. Figure 21 is a scanning electron micrograph of a group of polycarbonate microstructures 165 manufactured according to the processes presented in the present invention.
Then, as schematically illustrated in Figure 11, the top surface 154 of the third microstructured pattern 161 is metallized or made electrically conductive by coating the top surface with a thin layer of electrically conductive starting particle 167 similar to the starting particle layer 127. Then, as schematically illustrated in Figure 1J, the initial particle layer 167 is used to galvanize the third microstructured pattern 161 with a fourth material different from the third material resulting in a nozzle preform or layer 170 of the fourth material that has a top surface 172. In some cases, the electroplating of the second microstructured pattern 161 is maintained until the minimum thickness t5 of layer 130 is greater than t4, the height of the microstructures in the second mold 160. In some cases, the height t4 is substantially equal to height t 1. Rooms suitable for electroplating include silver, passivated silver, gold, rhodium, aluminum, aluminum with optimized reflectivity, copper, indium, nickel, chromium, tin, and alloys of these substances.
In other embodiments, the fourth material may be a ceramic that is deposited in the third microstructured pattern 161. Such a ceramic material may be formed, for example, by the sol-gel process as described in US patent No. 5,453,104 of common ownership and assignment, or by photo-curing a pre-ceramic or ceramic-filled polymer composition as described in US patents No. 6,572,693,
21 I 77
6,387,981, 6,899,948, 7,393,882, 7,297,374 and 7,582,685 of common ownership and attribution, each of which is incorporated herein by reference, in its entirety. Such ceramic materials may comprise, for example, silica, zirconia, alumina, titanium oxide, or oxides of yttrium, strontium, barium, hafnium, niobium, tantalum, tungsten, bismuth, 5 molybdenum, tin, zinc, lanthanide elements (ie elements having atomic numbers in the range 57 to 71, inclusive), cerium and combinations thereof. Then, as schematically illustrated in Figure 1K, the top surface 172 of the nozzle preform 170 is grounded or otherwise removed until the flat sacrifice control cavities 171 of the microstructures 165 and control cavities close to sacrifice 173 of microstructures 159 be completely or at least substantially removed. Thus, it may be desirable that the third material is softer than the fourth material. For example, in some cases, the third material is a polymeric material (for example, polycarbonate) and the fourth material is a metallic material (for example, a nickel or iron alloy). The sacrifice flat control cavities 171 and 173 are considered to be substantially removed when the tops 184 and 186 of all nozzle orifice microstructures 180 and 181 in the third microstructure pattern 161 are sufficiently exposed to ensure that the required fluid flow is obtained consistently, within acceptable tolerances, through each of the corresponding nozzles 192 and 193. This process results in the removal of a layer 175 of the fourth material, planarization of the third microstructured pattern 161 in order to remove the flat sacrifice control cavities (shown in dashed lines), and the exposure of the tops 185 of the microstructures for forming the orifices. nozzle 180 and 181 (i.e., the desired orifice outlet openings of the nozzle through holes) in the third microstructured pattern 161. Layer 175 of the fourth material has a top surface 177 which is substantially uniform with the tops 184 of the microstructures 180 and the tops 186 of the microstructures
181. Microstructures 180 and 181 have a relatively uniform height t6. The top surface 172 of the nozzle preform 170 is preferably removed using a planarization process in an effort to obtain more uniform outlet holes 183 and 197 from the nozzle through holes 195 and 198. As shown in Figures 1K and 1L, uniform openings of orifice outlets 183 and 197 are obtained by planarizing the top surface 172 so that the top and bottom surfaces of layer 190 are parallel. It may be important to control the uniformity and size of the nozzle through-hole outlets, for example, to control the rate of fluid flow through the nozzle. The flat sacrifice control cavities 171 and 173 are designed (that is, sized and configured) to be removed in such a way that the corresponding nozzle through holes (ie, the orifice outlets) can be opened in one direction.
22 I 77 desired shape (for example, to obtain a required fluid flow rate and / or a desired fluid flow pattern through the nozzle). Although the present invention allows smaller nozzle through holes to be formed, it also provides a greater through hole density per unit area of the nozzle surface, in an effort to provide sufficient open area (i.e., the open area). combined through the mouth passage outlets) to obtain the required fluid flow rate through the nozzle. Referring to Figure 1K, the flat control cavity forming characteristics 184 also help to ensure that any air trapped in the material (for example, a polymeric melting or otherwise liquid material) used to make the microstructure pattern of formation of nozzle 161 ', especially the rr trapped in the filling material of the nozzle orifice forming characteristics 159 and 165, will install in the flat control cavity forming characteristics 184, instead of in the nozzle orifice forming characteristics 159 and 165 The structural integrity of the nozzle orifice forming characteristics 159 and 165 can be impaired if pockets or air bubbles are captured in them. The structural integrity of the nozzle orifice forming characteristics 159 and 165 is important to ensure the desired formation of the corresponding nozzle through-holes. This advantage of the flat control cavity-forming characteristics of the invention is particularly applicable when the microstructured nozzle-forming pattern is formed by molding (i.e., injection molding) a moldable polymeric material. Description of the planarization The planarization of the top surface, and the bottom surface, of the nozzle can be carried out using conventional techniques. For example, in one technique, a modified version of an Ultrapol edge polisher, built by ultra-Tec Manufacturing, lnc, can be used. There are many other equivalent systems available on the market. This system allows the workpiece to be brought into contact with the horizontally rotating printing roll. The system provides adjustment mechanisms to control the pitch and roll angles of the component being ground in relation to the printing roll.
For the purpose of that description, the tilt, rotation & yaw axis graph refer to the photo machine above. The 12 o'clock position of the substrate is on the x-axis, the 3 o'clock position of the substrate is on the y-axis.
23 I 77
A sample of substrate from the nozzle is mounted nickel side down on a fixture so that it is mounted on the machine and kept in contact with the polishing film on the rotating cylinder.
Planarization begins with approximate alignment with respect to the outer perimeter 5 of the substrate, by slowly lowering the workpiece until it is in contact with the grinding media.
The contact point is then observed and the tilt and rotation are adjusted accordingly.
For example; if the point of contact occurs within 12 hours, the injector substrate is "nose down", and the tilt is adjusted to decrease the contact angle (lowering the tail of the workpiece.
Another example; if after the initial contact, the contact point is at the 3 o'clock position, then it is necessary to adjust the speed.
Rotation & tilt are adjusted until most of the upper plane the substrate is in contact with the grinding media The grinding of the foot and posterior continues until one or more of the flat sacrifice control cavities or flattening cones are exposed on the newly surface ground.
The diameters of the holes at opposite edges of the nozzle assembly are measured and tilt and rotation adjustments are made accordingly.
Additional crushing with small rotation & tilt adjustments can be done until all the planarizing cone diameters of the nozzle through holes are the same.
When the planarization has opened a hole in the planarization cones; the diameter of the planarization cone holes can be used to determine the distance down to the top of the nozzle through holes; Distance down to the top of a nozzle or tip through hole equal to the height of the planarization cone minus the radius divided by Tan (half the cone angle). For example; If half the cone angle is 21 °, the height of the cone is 50 1-Jm and the diameter of the measured orifice is equal to 30 1-Jm (radius = 15), then the distance to the nozzle tip = 50- 15 / Tan 21 = 11 1-Jm.
Using a transparent or translucent injection molded plastic preform and suitable fixation devices; another metric is to measure clear open area of the nozzle.
Mounting the nozzle preform in a fixture with an open opening directly behind the nozzle tips, this allows the nozzle to be backlit under a high magnification microscope for measuring the area (see the photo in Figure 23). Then, as illustrated schematically in Figure 1D, the second mold 160 is removed, resulting in a layer 190 of the fourth material that includes a plurality of holes 106 that correspond to a plurality of microstructures 159 and 165, in the third microstructured pattern 161. In in particular, layer 190 of the fourth material includes a first group or set 192 of nozzle through holes 195 and a second group or set 193 of nozzle through holes 198. In some cases, holes 195 are substantially negative replicas of microstructures 125b and orifices 198 are substantially negative replicas of microstructures 120b.
Holes 195 include
24 I 77 orifice or inlets 182 and orifice outlets or outlets 183 and orifices 198 include orifice inlets or inlets 196 and orifice outlets or outlets 197. Figures 22 and 23 are optical micrographs of the respective orifice inlets 182 and outlets of orifice 183 of a group 192 of orifices 195 produced according to the 5 processes presented in the present invention.
Figure 25 is a scanning electron micrograph of one of the holes 195, viewed from the side of the orifice entrance.
The orifice has a 251 O orifice inlet and an 2520 orifice outlet that is smaller than the orifice inlet.
The micrograph clearly illustrates a taper and a twist in the hole.
In some cases, as illustrated schematically in Figure 1M, two assemblies 192 and 193 are separated along a direction 199, resulting in a first nozzle 102 and a separate one and, in some substantially identical cfsos, second nozzle 103. i 'nozzles 102 and 103 can be used, for example, in a spray device and / or a fuel injector.
Figure 24 is a schematic side view of a nozzle 2400 that includes a hollow interior 241 0 and a wall 2405 separating the hollow interior from the exterior 2430 of the nozzle.
The nozzle additionally includes at least one hole, such as a hole 2420, which connects the hollow interior 241 O to the outside 2430 of the nozzle.
The orifices distribute gas or liquid from the hollow inside to the outside.
Hole 2420 can be any hole shown in the present invention.
Orifice 2420 includes an orifice entry 2440 on an inner surface 2406 of wall 2405 and an orifice outlet 2445 on an outer surface 2407 of wall 2405. Orifice inlet 2440 is also hollow inside 241 O of the nozzle and outlet of orifice 2445 is outside 2430 of the nozzle.
In some cases, orifice inlet 2440 has a first shape and orifice inlet 2445 has a second shape that is different from the first shape.
For example, in some cases, the first shape is an elliptical shape and the second shape is a circular shape.
As another example, in some cases, the first shape can be a racetrack or oval shape and the second shape can be a circular shape.
As another example, in some cases, the second shape can be a circle or an ellipse and the perimeter of the first shape can include outer arcs of a plurality of overlapping circles, where the outer arcs are connected to each other by curved fillets.
In some cases, the first shape may be substantially the same as the second shape, but they may have different magnitudes or sizes.
For example, the first shape can be a circle with a radius of 1 and the second shape can also be a circle, but with a radius of 2 other than a 1. In some cases, orifice 2420 has a lateral cross section that rotates from orifice entrance 2440 to orifice outlet 2445 where the lateral cross section refers to a cross section that is substantially perpendicular to the general flow direction of,
25 I 77 for example, a liquid or gas inside the orifice.
In some cases, a cross section has an increased rate of rotation from the hole inlet to the hole outlet.
In some cases, a cross section has a decreased rate of rotation from the hole inlet to the hole outlet.
In some cases, a cross section has a constant rate of rotation from the hole inlet to the hole outlet.
Some of the advantages of the microstructures, holes, layers, constructions and methods of this invention are further illustrated by the following example and modalities.
The specific materials, amounts and dimensions mentioned in the example, as well as other conditions and details, should not be interpreted as unduly limiting this invention.
Unless otherwise specified, all chemical procedures were performed under a dry nitrogen atom with dry solvents and deoxygenated reagents.
Unless otherwise specified, all solvents and reagents have been or may be obtained from Aldrich Chemical Co., Milwaukee, WI, USA.
Rhodamine hexafluoroantimonate 8 was prepared by metathesis of rhodamine chloride 8 with sodium hexafluoroantimonate.
For use in the present invention, SR368 refers to tris- (2-hydroxyethia) isocyanurate triacrylate (obtained from Sartomer Co.
Inc., Exton, PA, USA); SR9008 refers to a tri-functional acrylate ester (obtained from Sartomer); SR1 012 refers to diaryliodonium hexafluoroantimonate (obtained from Sartomer); SU-8 R2150 refers to an epoxy negative photoresist (obtained from MicroChem Corp., Newton, MA, USA); THF refers to tetrahydrofuran; LEXAN HPS1 R refers to a thermoplastic polycarbonate (obtained from Sabic Innovative Plastics, Pittsfield, MA, USA; and lnco S-Rounds refers to nickel (obtained from Vale Inco America's, Inc., Saddle 8rook, NJ, Example 1: A circular silicon wafer (substrate 110 in Figure 1A), 10.2 in diameter, was obtained from Wafer World, Inc., West Paim 8each, Florida, USA.
The Si tablet was cleaned by dipping it for approximately ten minutes in a 3: 1 mixture by volume of concentrated sulfuric acid and 30% by weight of aqueous hydrogen peroxide.
The tablet was then rinsed with deionized water and then with isopropanol, after which it was subjected to drying under an air flow.
The tablet was then dipped in a two percent weight solution of 3- (trimethoxysilyl) propyl methacrylate in test 190 ethanol which was made acidic (pH between 4 and 5) with acetic acid.
The tablet was then rinsed with absolute ethanol and then heated in an oven at 130oC for ten minutes.
Poly (methyl methacrylate), having an average numerical molecular weight of approximately 120,000, SR9008 and SR368 were combined in a weight ratio of 30:35:35 resulting in a monomer mixture that was dissolved in sufficient 1,2-dichloroethane to provide a solution that was 54 percent, by weight, of the monomer mixture.
To this solution, aliquots of concentrated photosensitizer
26 I 77 rhodamine hexafluoroantimonate Well THF and SR1012 and THF enough to result in a coating solution that was 0.5 weight percent rhodamine hexafluoroantimonate and 1.0 weight percent SR1012 with based on the total weight of the solids.
This coating solution was filtered through a 1 micron syringe filter and applied 5 per rotation to the silicon wafer.
The coated tablet was placed in a forced air oven at 60 ° C for 18 hours to provide a silicon wafer coated with a coating (layer 115 of the first material in figure 1A) substantially solvent free (hereafter in this document, "dry") having a thickness of approximately 300 µm.
Polymerization of two photons of the dry coating was carried out using a Ti: sapphire laser diode (obtained from Spectralhysics, Mountain View, CA, USA), which was operated at 800 nm, with a pulse width of 80 fs, a pulse repetition rate of 80 MHz and an average power of about 1 W.
The coated tablet was placed in a three-axis, computer-controlled stage (obtained from Aerotech, Inc., Pittsburgh, PA, USA). The laser beam was attenuated by neutral density filters and was focused on the dry coating using a galvoscanner with a telescope to control the x, y and z axes (available from Nutfield Technology, Inc., Windham, NH, USA). A Nikon CFI Plan Achromat 50X oil N.A. 0.90 lens with a working distance of 0.400 mm and a focal length of 4.0 mm was applied directly to the surface of the dry coating.
The average energy was measured at the objective lens output using a wavelength-calibrated photodiode (obtained from Ophir Optronics, Ltd., Wilmington, MA, USA) and was determined to be approximately 8 mW.
After the exposure scan was completed, the exposed dry coating was developed in a MicroChem SU-8 developer, rinsed and dried, resulting in a first microstructured pattern 121 (figure 1b). The surface of the first microstructured pattern was made conductive by ion bombardment of a thin layer (about 100 angstrons) of silver (Ag) on the surface of the pattern.
The metallized front surface was then galvanized with S-Rounds (nickel) until it was approximately 2 mm thick.
The galvanized nickel pellet was then separated from the first pattern and crushed and machined resulting in a first mold 140 having a second microstructured pattern 141 (figure 1F). The first mold was then placed in an injection die mold which was placed in a single spindle plastic injection molding system to inject thermoplastic polycarbonate (LEXAN HPS1 R) into the mold cavity resulting in a second mold 160 having a third microstructured pattern 161 (figure 1H). The front surface of the second mold was then metallized by ionic bombardment of the surface with about 100 silver angstrons.
The second metallized mold was
27 I 77 then galvanized with lnco S-Rounds (nickel) to fully cover the third microstructured pattern resulting in a layer of nickel 170 (figure 1J). After rinsing the combined construction of the nickel layer and the second mold with deionized water, the front surface 172 (Figure 1J) of the nickel layer was ground flat to remove the nickel material from the tops 171 of the third microstructured pattern.
After the crushing was complete (all the tops of the microstructure were exposed), the galvanized nickel layer was separated from the polycarbonate mold 160 resulting in a nickel disk, approximately 8 mm in diameter and 160 µm thick, having 37 holes. passage arranged in a circular hexagonal gasket arrangement.
The separation between the neighboring holes was about 200 µm.
Each hole had a hole entry in the shape of a modified racetrack with fillets along the linear portions of the racetrack.
The racetrack had a larger diameter of about 80 tJm and a smaller diameter of about 50 tJm.
Each orifice had an orifice outlet in the shape of a smaller racetrack with a larger diameter of about 50 tJm and a smaller diameter of about 35 tJm.
Seen from the side of the orifice outlet, the larger diameters of the orifice cross section rotated clockwise from the orifice outlet to the orifice inlet by about 30 degrees for every 50 tJm of depth below the orifice outlet.
For use in the present invention, terms such as "vertical", "horizontal", "above", "below", "left", "right", "upper", "lower", "clockwise" and "anti-clockwise" - time ", and other similar terms, refer to relative positions, as shown in the figures.
In general, a physical modality may have a different orientation, in which case the terms refer to relative positions modified to the actual orientation of the device.
For example, even if the image in figure 1B is flipped compared to the orientation in the figure, surface 126 is still considered to be the top surface.
Multiphoton description Definitions As used in this patent application: "curing" means carrying out polymerization and / or carrying out cross-linking; "electronic excitation state" means an electronic state of a molecule that is greater in energy than the electronic fundamental state of the molecule, which is accessible through absorption of electromagnetic radiation, and which has a life span greater than 10-13 seconds ; "exposure system" means an optical system plus a light source; "master" means an article originally manufactured that can be used to make a tool for replication;
28 I 77 '
"multiphotonic absorption" means the simultaneous absorption of two or more photons to achieve a state of reactive electronic excitation, which is energetically inaccessible by absorbing a single photon of the same energy; "numerical aperture" means the ratio between the diameter of a lens and its focal length (or number 1 / f); "Optical system" means a system for controlling light, the system, including at least one element chosen from refractive optical elements, such as lenses, reflective optical elements, such as mirrors, and diffractive optical elements, such as lattices.
The optical elements must also include diffusers, waveguides and other elements known in the optical arts; "Photochemically effective quaftities" (of the components of the photoinitiator system) means an amount sufficient to allow the reactive species to undergo at least partial reaction under the selected exposure conditions (as evidenced, for example, by a change in density, 15 viscosity, color, pH, refractive index, or other physical or chemical properties); "Photosensitizer" means a molecule that reduces the energy needed to activate a photoinitiator by absorbing light with less energy than that required by the photoinitiator for activation and interacting with the photoinitiator to produce a photonic initiator from it; 20 "Simultaneous" means two events that occur within the period of 1 - 14 seconds or less; "sufficient light" means light of sufficient intensity and adequate wavelength to affect multiphotonic absorption; and Multiphotonic reaction 25 The molecular absorption of two photons was predicted by Goppert-Mayer in 1931. With the invention of the pulsed ruby laser in 1960, experimental observation of absorption of two photons became a reality.
Subsequently, the excitation of two photons has found application in biology and optical data storage, as well as in other fields.
There are two main differences between photoprocesses induced by two photons and 30 processes induced by a single photon.
While the absorption of a single photon is linear with the intensity of the incident radiation, the absorption of two photons is quadratic.
Higher order absorptions are related to a greater power of incident intensity.
As a result, it is possible to perform multiphotonic processes with three-dimensional spatial resolution.
In addition, because multiphotonic processes involve the simultaneous absorption of two or more photons, the absorption chromophore is excited with a series of photons whose total energy is equal to the energy of an electronic state of excitation of the multiphotonic photosensitizer that is used, despite of each photon to have individually
29 I 77 insufficient energy to excite the chromophore.
Because the excitation light is not attenuated by the absorption of a single photon within a matrix or a curable material, it is possible to selectively excite molecules to a greater depth within a material than would be possible through excitation by a single photon through the use of a beam, which is focused to that depth in the material.
These two phenomena also apply, for example, to an excitation in tissues or other biological materials.
The main advantages have been achieved through the application of multiphotonic absorption to the areas of photopolymerization and microfabrication.
For example, in multiftonic lithography or stereolithography, the linear multiphotonic absorption scale with intensity provided the ability to write features that are smaller than the light diffraction limit used, such as the ability to write features in three dimensions (which tam is also of interest for holography). Multiphotonic initiated reactions that cause a change in the solubility of a reactive material are useful in multiphotonic microfabrication (also known as two-photon fabrication). These reactions may involve polymerization, cross-linking, depolymerization, or change in solubility due to reactions involving the transformation of functional groups, for example, from polar to non-polar, or non-polar to polar.
The reactions are initiated by the absorption of at least two photons by a multiphotonic photoinitiation system capable of undergoing the simultaneous absorption of two or more photons to form free radicals and / or acids capable of initiating reactions of free or cationic radicals.
Exposure of reactive multiphotonic compositions to sufficient light to form an image can be accomplished by focusing a beam from a suitable laser system (see page 22-23, in this document) on the multiphotonic reactive composition.
The reaction occurs close to the focal point of the focused laser beam to cause a change in the solubility of the exposed composition.
The smallest region in which the reaction occurs is a three-dimensional imaging element, or voxel.
A voxel is the smallest feature that can be manufactured by multiphotonic lithography, and can be a size that is less than the diffraction limit used.
The voxel can be as small as 100 nm or smaller, at x, y and z, and as large as 10 microns or larger at z and 4 microns or larger, at x and Y, depending on the numerical aperture of the lens used to focus the laser beam.
In the x, y, and z directions, the axes are perpendicular to the beam path (x, y), or in parallel with the beam path (z). Preferably, the voxel has at least one dimension that is less than 2 microns, preferably less than 1 micron, more preferably less than 0.5 microns, Reactive species Reactive species suitable for use in photoreactive compositions include both species , curable and non-curable.
Curable species are generally preferred and include, for example, polymerizable monomers and oligomers of
30 I 77 addition and crosslinkable addition polymers (such as polymerizable species with free radicals or ethylenically unsaturated crosslinkable including, for example, acrylates, methacrylates and certain vinyl compounds such as styrenes), as well as cationically polymerizable monomers and oligomers and cationically crosslinkable polymers (cationically crosslinkable polymers) 5 species are most commonly initiated by acid and which include, for example, epoxies, vinyl ethers, cyanate esters, etc.), and the like, and mixtures thereof.
Suitable ethylenically unsaturated species are described, for example, by Palazzotto et al. in US Patent No. 5,545,676 in column 1, line 65, up to column 2, line 26, and include mono-, di- and poly-acrylates and methacrylates (for example, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylate isopropyl, n-hexyl, stearyl acrylate, allyl acrylate, glycerol diacrylate acrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol dihydrate -propanediol, trimethylolpropane triacrylate, 1,2,4-trimethylolpropane butanotriol, 1,4-hexanediol diacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexacrylate [1] -p-ethoxyphenyldimethylmethane, bis [1 (3-acryloxy-2-hydroxy)] -p- propoxyphenyldimethylmethane, trimethacrylate trishhydroxyethyl-isocyanurate, bis - acrylates and bis-methacrylates of polyethylene glycols of about 200-500, as monomer mixtures acrylic copolymerisables such as those of US Patent No. 4,652,274, and acrylate oligomers such as those of US Patent No. 4,642,126); Unsaturated amides (for example, methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, diethylene tri-acrylamide and beta-methacrylaminoethyl methacrylate); vinyl compounds (for example, as styrene, diaryl phthalate, divinyl succinate, divinyl adipate); and divinyl phthalate and the like; and mixtures of these.
Suitable reactive polymers include polymers with pendent (meth) acrylate groups, for example, containing from 1 to about 50 (meth) acrylate groups per polymer chain.
Examples of such polymers include aromatic acid (meth) acrylate ester resins such as Sarbox ™ resins available from Sartomer (for example, Sarbox ™ 400, 401, 402, 404, and 405). Other useful reactive polymers curable by free radical chemistry include polymers that have a hydrocarbyl backbone and pendant peptide groups with polymerizable free radical functionality attached thereto, such as those described in US Patent No. 5,235,015 (Ali et al.). Mixtures of two or more monomers, oligomers and / or reactive polymers can be used if desired.
Preferred ethylenically unsaturated species include acrylates, aromatic acid (meth) acrylate ester resins, and polymers that have a hydrocarbyl backbone and pendant peptide groups with radically free polymerizable functionality attached thereto.
31 I 77
Suitable cationically reactive species are described, for example, by Oxman et al. in US Patent Nos. 5,998,495 and 6,025,406 and include epoxy resins.
Such materials, widely called epoxides, include epoxides and monomeric epoxy compounds of the polymeric type and can be aliphatic, alicyclic, aromatic, or heterocyclic.
These materials 5 generally have at least 1 polymerizable epoxy group per molecule, preferably at least (at least about 1.5, and most preferably at least about 2). Polymeric epoxides include linear polymers that have epoxy-terminated groups (for example, a polyoxyalkylene glycol diglycidyl ether), polymers with oxirane skeletal units (for example, polyepoxide polybutadiene), polymers with pendant epoxy groups (for example , a glycidyl methacrylate polymer or copolymer). Epoxides can be pure compounds or they can be mixtures of compounds containing one, two or more epoxy groups per molecule.
These epoxy-containing materials can vary greatly in the nature of the main chain or backbone and substituent groups.
For example, the backbone can be of any type and its substituting groups can be any group that does not substantially interfere with cationic curing at room temperature.
Illustrative examples of permitted substituent groups include halogens, ester groups, ethers, sulfonate groups, siloxane groups, carbosilane groups, nitro groups, phosphate groups, and the like.
The molecular weight of epoxy-containing materials can vary from about 58 to about 100,000 or more.
Other epoxy-containing materials that are useful include glycidyl ether monomers of the following formula
R '(OCH2 -CH -CH2) n
"" 'o / where R' is alkyl or aryl and n is an integer from 1 to 8. Examples are glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of a hydrochlorine such as epichlorohydrin (for example, o diglycidyl ether of 2,2-bis- (2,3-epoxypropoxyphenol-) propane). Additional examples of such epoxides are described in US Patent No. 3,018,262, and in Lee and Neville's Handbook of Epoxy Resins, McGraw-Hill Book Co., New York, USA (1967). Numerous commercially available monomers or epoxy resins can be used.
Epoxides that are readily available include, but are not limited to, octadecylene oxide; epichlorohydrin; styrene oxide; vinylcyclohexene oxide; glycidol; glycidyl methacrylate; Bisphenol A diglycidyl ethers (for example, those available as "EPON 815C", "EPON 813", "EPON 828", "EPON 1004F", and "EPON 1001 F" from Hexion Specialty Chemicals, Inc., Columbus, OH, USA); and diglycidyl ether of bisphenol F (for example, those available as "ARALDITE GY281" from Ciba Specialty Chemicals Holding Company,
32 I 77
Basel, Switzerland, and "EPON 862" with Hexion Specialty Chemicals, Inc.). Other aromatic epoxy resins include SU-8 resins available from MicroChem Corp., Newton, MA, USA.
Other exemplary epoxy monomers include cyclohexene vinyl dioxide (available from SPI Supplies, West Chester, PA, USA); 4-vinyl-1-cilcohexene 5 diepoxide (available from Aldrich Chemical Co., Milwaukee, WI, USA); 3,4-epoxycyclohexylmethyl-3,4-carboxylate epoxycyclohexene (for example, one available as "CYRACURE UVR-611 O" from Dow Chemical Co., Midland, Ml, USA); 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexane carboxylate; 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methadioxane; bis (3,4-epoxycyclohexylmethyl) adipate (for example, one available as "CYRACURE UVR-6128" from 9ow Chemical Co.); bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; 3,4-epoxy-6-methylcyclrhexane carboxylate; and dipentene dioxide.
Still other exemplary epoxy resins include epoxidated polybutadiene (for example, one available as "POL Y BD 605E" available from Sartomer Co., Inc., Exton, PA, USA); epoxy silanes (for example, 3,4-epoxycyclohexylethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, commercially available from Aldrich Chemical Co., Milwaukee, Wl, USA); flame retardant epoxy monomers (for example, one available as "DER-542", a type of brominated bisphenol epoxy monomer available from Dow Chemical Co., Midland, Ml, USA); 1,4-butane diol diglicidyl ether (for example, one available as "ARALDITE RD-2" from Ciba Specialty Chemicals); hydrogenated bisphenol A-based epoxy monomers (eg, one available as "EPONEX 1510" from Hexion Specialty Chemicals, Inc.); novolak phenol-formaldehyde polyglycidyl ether (for example, one available as "DEN-431" and "DEN-438" from Dow Chemical Co.); and epoxidized vegetable oils such as epoxidized linseed and soybean oils available as "VIKOLOX" and "VIKOFLEX" from Atofina Chemicals (Philadelphia, PA, USA). Suitable additional epoxy resins include commercially available alkyl glycidyl ethers from Hexion Specialty Chemicals, Inc. (Columbus, OH) as "HELOXY". Exemplary monomers include "HELOXY MODFIER 7" (at C8 -C 10 glycidyl alkyl ether), "HELOXY MODIFIER 8" (at C1rC 14 glycidyl alkyl ether), "HELOXY MODIFIER 61" (butyl glycidyl ether), "HELOXY MODIFIER 62 "(cresyl glycidyl ether)," HELOXY MODIFIER 65 "(p-tert-butylphenyl glycidyl ether)," HELOXY MODIFIER 67 "(1,4-butanediol diglycidyl ether)," HELOXY 68 "(alkyl glycidyl ether neopentyl glycol), "HELOXY MODIFIER 107" (cyclohexane dimethanol diglycidyl ether), "HELOXY MODIFIER 44" (ethylic trimethylol ether), "HELOXY MODIFIER 48" (trimethylol propane triglycidyl ether), "HELOXY MODIFIER 84" polyglycidyl ether of an aliphatic polyol), and "HELOXY MODIFIER 32" (polyglycol diepoxide). Other useful epoxy resins include copolymers of glycidol acrylic acid esters (such as glycidyl acrylate and glycidyl methacrylate) with one or more
33 I 77 copolymerizable vinyl compounds.
Examples of such copolymers are 1: 1 styrene glycidyl methacrylate and 1: 1 methyl methacrylate - glycidyl acrylate.
Other useful epoxy resins are well known and include epoxides such as epichlorohydrins, alkylene oxides (for example propylene oxide), styrene oxide, alkenyl oxide (for example, butadiene oxide), and glycidyl esters (for example, ethyl glycidate). Useful epoxy-functional polymers include epoxy-functional silicones, such as those described in US Patent No. 4,279,717 (Eckberg et al.), Which are commercially available from The General Electric Company.
These are polydimethylsiloxanes in which 1 to 20 mol% of silicon atoms have been replaced by epoxy alkyl groups (preferably, cyclohexylethyl epoxy, as described in US Patent No. 5,753,346 (Leir et al.). Blends of various materials containing epoxy can also be used.
Such blends can comprise two or more average molecular weight distributions of the epoxy containing compounds (such as low molecular weight (less than 200), intermediate molecular weight (about 200 to 1000), and high molecular weight (above about 1000). Alternatively or additionally, the epoxy resin may contain a blend of materials containing epoxy having different chemical natures (such as aliphatic and aromatic) or functionalities (such as polar and non-polar) .Cationically reactive polymers (such as vinyl ethers and the like) can be additionally incorporated, if desired.
Preferred epoxies include aromatic glycidyl epoxies (for example, EPON resins available from Hexion Specialty Chemicals, Inc. and SU-8 resins available from MicroChem Corp., Newton, MA, USA), and the like, and mixtures thereof.
Most preferred are SU-8 resins and mixtures thereof.
Suitable cationically-reactive species include vinyl monomers, ether oligomers and reactive polymers (eg, methyl vinyl ether, ethyl vinyl ether, tert-butyl ether, isobutyl vinyl ether, triethylene glycol divinyl ether (RAPI-CURE DVE-3, available with International Specialty Products, Wayne, NJ), trivinyl trimethylolpropane ether, and VECTOMER divinyl ether resins with Morflex, Inc., Greensboro, NC (eg VECTOMER 1312, VECTOMER 4010, VECTOMER 4051, and VECTOMER 4060 and equivalents available from other manufacturers), and mixtures thereof.
Blends (in any proportion) of one or more vinyl ether resins and / or one or more epoxy resins can also be used.
Polyhydroxy-functional materials (such as those described, for example, in U.S. Patent No. 5,856,373 (Kaisaki et al.) Can also be used in combination with functional epoxy and / or vinyl ether materials.
Non-curable species include, for example, reactive polymers whose solubility can be increased by the reaction induced by acid or radical.
Such reactive polymers include, for example, aqueous insoluble polymers that have ester groups that can be converted by photogenerated acid to aqueous soluble acid groups (for example, poly (4-tert-
34 I 77 butoxycarbonyloxystyrene). Non-curable specifications also include the chemically amplified photoresists described by R. D.
Allen et al. in "High Performance Acrylic Polymers for Chemically Amplified Photoresist Applications," J.
Vac.
Know.
Technol.
B, -ª · 3357 (1991). The chemically amplified photoresist concept is now widely used for integrated circuit manufacturing, especially with sub-0.5 micron (or even sub-0.2 micron) characteristics. In such photoresist systems, catalytic species (typically hydrogen ions) can be generated by irradiation, which induces a cascade of chemical reactions.
This cascade occurs when hydrogen ions initiate reactions that generate more hydrogen ions or other acidic species, thereby increasing the reaction speed.
Example!. of typical acid-catalyzed chemically amplified photoresist systems include fesprotection (for example, t-butoxycarbonyloxystyrene as described in US patent No. 4,491,628, tetrahydropyran (THP) materials based on methacrylate, THP- phenolic materials such as those described in US patent no. 3,779,778, materials based on t-butyl methacrylate such as those described in R.
D Allen et al. in Proc.
SPIE 2438, 474 (1995), and the like); depolymerization (for example, materials based on polyphthalaldehyde); and reorganization (for example, materials based on pinacol reorganizations). If desired, mixtures of different types of reactive species can be used in the photoreactive compositions.
For example, mixtures of reactive species by free radicals and cationically reactive species are also useful.
Photoinitiator system The photoinitiator system is a multi-photon photoinitiator system, while the use of such a system allows the reaction to be confined or limited to the focal region of a focused beam of light.
Such a system is preferably a system with two or three components comprising at least one multiphotonic photosensitizer, at least one photoinitiator (or electron receiver) and, optionally, at least one electron donor.
Such multi-component systems can provide improved sensitivity, allowing photoreaction to be performed in a short period of time, thus decreasing the probability of problems due to the movement of the sample and / or one or more components of the exposure system.
Preferably, the multiphoton photoinitiator system comprises photochemically effective amounts of (a) at least one multiphoton photosensitizer which is capable of absorbing at least two photons simultaneously, and which optionally, but preferably, has an absorption of two photons in cross section greater than fluorescein; (b) optionally, at least one electron donor compound different from the multiphotonic photosensitizer and capable of donating an electron to a state of electronic excitation of the photosensitizer; and (c) at least one photoinitiator that is capable of being photosensitized by accepting an electron from an electronic state of excitation of the photosensitizer, resulting in the formation of at least one free radical and / or acid.
35 I 77
Alternatively, the multi-photon photoinitiator system can be a one-component system comprising at least one photoinitiator.
Photoinitiators useful as an acyl component multiphoton photoinitiator systems include phosphine oxides (for example, those sold by Ciba under the trade name lrgacure ™ 819, such as 2,4,6 5 trimethyl benzoyl ethoxyphenyl phosphine oxide sold by BASF Corporation under the trade name Lucirin ™ TPO-L) and stilbene derivatives with covalently bonded sulfonium salt portions (for example, those described by W.
Zhou et al. in Science 296, 1106 (2002). Other conventional ultraviolet (UV) photoinitiators, such as benzyl ketal, can also be used, although their multiphotonic photoinitiation sensitivities will generally be relatively low.
Multiphoton photosensitizers, electron donors, phototinitiators (or electron receptors) useful in two- or three-component multi-photon initiator systems are described below. (1) Multiphoton photosensitizers Multiphoton photosensitizers suitable for use in Multiphoton photoinitiator systems of photoreactive compositions are those that are capable of absorbing at least two photons simultaneously when exposed to sufficient light.
Preferably, photosensitizers have an absorption of two photons of cross-section greater than that of fluorescein (i.e., greater than 3 ', 6'-dihydroxy spiro [isobenzofuran-1 (3H), 9' - [9H] xanten] 3 -one). In general, the preferred cross section can be greater than about 50 x 1 o-50 cm 4 sec / photon, as measured by the method described by C.
Xu and W. W.
Webb in J.
Opt.
Soe.
Am.
B, ~. 481 (1996) (which is referred to by Marder and Perry et al. In the international publication WO 98/21521 on page 85, lines 18-22). More preferably, the two-photon absorption cross-section of the photosensitizer is greater than about 1.5 times greater than fluorescein (or greater than about 75 x 1 - 50 cm 4 sec / photon, as measured by the method above); even more preferably, greater than about twice than fluorescein (or greater than about 100 x 1 - 50 cm 4 sec / photon); most preferably, greater than about three times that of fluorescein (or, alternatively, greater than about 150 x 10-50 cm 4 sec / photon); and ideally, greater than about four times that of fluorescein (or, alternatively, greater than about 200 x 1 - 50 cm 4 sec / photon). Preferably, the photosensitizer is soluble in reactive species (if the reactive species is a liquid), or is compatible with the reactive species and with any binders (as described below) that are included in the composition.
More preferably, the photosensitizer is also capable of sensitizing 2-methyl-4,6-bis (trichloromethyl) -s-triazine under continuous irradiation over a wavelength range that overlaps the
36 I 77 single photon absorption spectrum of the photosensitizer (single photon absorption conditions), using the test procedure described in US Patent No. 3,729,313. Preferably, a photosensitizer can also be selected based, in part, on stability considerations during storage. 5 Consequently, selection of a particular photosensitizer may depend to some extent on the specific reactive species used (as well as on the choices of the electron donor compound and / or photoinitiator). Particularly preferred multiphoton photosensitizers include those that have large cross sections of multiphotonic absorption, such as Rhodamine B (i.e., N- [9 - (2-carboxylphenyl) -6 - (diethylamino) -3H-xanthen-3-ylidene] -N-chloride and (ylethanaminium or hexafluoroantimonate) the four classes of photosensitizers described, for example, by Marder and Perry et al. in International Patent Publication WO 98/21521 and WO 99/53242. The four classes can be described as follows: (a) molecules in which two donors are connected to a TI (pi) electron-TI conjugated bridge; (b) molecules in which two donors are connected to a TI (pi) electron-TI conjugated bridge that is replaced with one or more electron receptor groups; (c) molecules in which two receptors are connected to a TI (pi) electron-TI conjugated bridge; and (d) molecules in which two receptors are connected to a TI (pi) electron-TI conjugated bridge that is replaced with one or more electron donor groups (where "bridge" means a molecular fragment that connects two or more chemical groups, "donor" means an atom or group of atoms with a low ionization potential that can be linked TI (pi) to a conjugated electron-TI bridge, and "receptor" means an atom or group of atoms with a high electron affinity that can TI (pi) attached to a conjugated electron-TI bridge). The four classes of photosensitizers described above can be prepared by reaction of aldehydes with ilides under standard Wittig conditions or by means of the McMurray reaction, as detailed in the international patent publication WO 98/21521. Other compounds are described by Reinhardt et al. (for example, in US patents 6,100,405, 5,859,251, and 5,770,737) as having large multiphotonic absorption cross sections, although these cross sections were determined by a method other than that described above.
Preferred photosensitizers include the following compounds (and mixtures thereof):
37 I 77 + Et 2 X- where X ::::; Cl-, PF6-, SbF6-, AsF 6-, BF 4-, CF 3S0 3- y o o y ó o
N 5 (2) Electron donor compounds The electron donor compounds useful in the multiphoton photoinitiator system of photoreactive compositions are those compounds (different from the photosensitizer itself) that are capable of donating an electron to an electronically excited state of the photosensitizer. Such compounds can be used, optionally, to increase the multiphoton photosensitivity of the photoinitiator system, thereby reducing the exposure necessary to effect the photoreaction of the photoreactive composition. Electron donor compounds preferably have an oxidation potential, which is greater than zero and less than or equal to that of p-dimethoxy benzene. Preferably, the oxidation potential is between about 0.3 and 1 volt versus a standard saturated calomel electrode ("S. C. E."). The electron donor compound is preferably soluble also in reactive species and is selected based, in part, on stability considerations during storage (as described above). Suitable donors are generally able to increase the cure speed or image density of a photoreactive composition when exposed to light of the desired wavelength.
38 I 77 When working with cationically-reactive species, those skilled in the art will recognize that the electron donor compound, if significantly basic, can adversely affect the cationic reaction. (See, for example, the discussion in US Patent No. 6,025,406 (Oxman et al.) In column 7, line 62, up to column 8, line 49.) 5 In general, electron donor compounds suitable for use with certain photosensitizers and photoinitiators can be selected by comparing oxidation and reduction potentials of the three components (as described, for example, in US Patent No. 4,859,572 (Farid et al.). These potentials can be measured experimentally (for example , by the methods described by RJ Cox, Photographic Sensitivity, Chapter 15, Acaremic Press (1973) or can be obtained from references such as NL Weinburg, E4 ·· Technique of Electroorganic Synthesis Part !! Techniques of Chemistrv, Vol. V (1975 ), and CK Mann and KK Barnes, Electrochemical Reactions in Nonaqueous Systems (1970). The potentials reflect the relative energy relationships and can be used to guide the selection of the electron donor compound. Suitable ones include, for example, those described by D. F. Eaton in Advances in Photochemistrv, edited by 8. Voman et al., Volume 13, pages 427-488, John Wiley and Sons, New York (1986); by Oxman et al. in US patent 6,025,406 in column 7, lines 42-61; and by Palazzotto et al. in the US patent in
5,545,676 in column 4, line 14 through column 5, line 18. These electron donor compounds include amines (including triethanolamine, hydrazine, 1,4-diazabicyclo [2.2.2] octane, triphenylamine (and their triphenylphosphine triphenylsine and analogues) ), aminoaldehydes and aminosilanes), amides (including phosphoramides), ethers (including thioethers), ureas (including thioureas), sulfinic acids and their salts, ferrocyanide ascorbic acid salts and their salts, dithiocarbamic acid and its salts, xanthate salts, salts of ethylene diamino tetra-acetic acid, cheap (alkyl) n (aryl) salts (n + m = 4) (preferred tetraalkyl ammonium salts), various organo-metallic compounds as SnR4 compounds (where each R is independently chosen between alkyl, arylalkyl (particularly, benzyl), aryl, and alkaryl groups) (for example, as compounds such as nC 3 HySn (CH 3 h, (alyl) Sn (CH 3 h, and (benzii) Sn (nC 3 Hy)) 3), ferrocene, and the like, and mixtures thereof. The electron donor compound can be unsubstituted or may be substituted with one or more non-interfering substituents. Particularly preferred electron donor compounds contain an electron donor atom (such as nitrogen, oxygen, phosphorus or sulfur atom), and a hydrogen atom that can be abstracted attached to an alpha carbon or silicon atom to the electron donor atom . Preferred electron donor amine compounds include alkyl-, aryl-, alkaryl- and aralkyl-amines (e.g., methylamine, ethylamine, propylamine, butylamine, triethanolamine, amylamine, hexylamine, 2,4-dimethylaniline, 2,3-dimethylaniline , o-, me p-toluidine, benzylamine, aminopyridine, N, N '-dimethylethylenediamine, N, N'-
39 I 77 diethylethylenediamine N, N'-dibenzylethylenediamine, N, N-diethyl-1,3-propanediamine, N, N 'diethyl-2-butene-1,4-diamine, N, N'-dimethyl-1, 6- hexanediamine, piperazine, 4.4 trimethylenedipiperidine, 4,4'-ethylenedipiperidine, pN, N-dimethyl-and aminophenethanol (pN-dimethylaminobenzonitrile); aminoaldehydes (for example, pN, N-dimethylaminobenzaldehyde, 5 pN, N-diethylaminobenzaldehyde, 9-carboxaldehyde julolidine and 4-morpholinobenzaldehyde); aminosilanes and (for example, trimethylsilylmorpholine, trimethylsilylpiperidine, bis (dimethylamino) diphenylsilane, tris (dimethylamino) methylsilane, N, N-diethylaminotrimethylsilane, tris (dimethylamino) phenyl silane, tris (methylsilyl) amine, trisine) ) amine, N, N-bis (dimethylsilyl) aniline, N-phenyl-N-dimethylsilylaniline, and N, N-dimethyl-10 N-dimethylsilylamine); and mixtures of these.
Tertiary aromatic alkylamines, particularly those having at least one electron receptor group in the aromatic ring, have been found to provide good stability during storage, especially.
Good stability during storage has also been achieved using amines that are solid at room temperature.
Good photosensitivity has been achieved using amines that contain one or more julolidinyl moieties.
Preferred electron donor amide compounds include N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-phenylacetamide, hexamethylphosphoramide, hexaethylphosphoramide, hexapropylphosphorphine phosphate phosphinephine phosphate oxide, trypphine phosphine phosphate oxide.
Preferred alkylarylborate salts include Ar3B- (n-C4Hg) N + (C2Hs) 4 Ar3B- (n-C4Hg) N + (CH3) 4 Ar3B- (n-C4Hg) N + (n-C4H9) 4 Ar3B- (n-C4H 9) Li + Ar3B- (n-C4Hg) N + (CeHd4 Ar3B - (C4Hg) N + (CH3h (CH2) 2C02 (CH2) 2CH3 Ar3B - (C4Hg) N + (CH3h (CH2) 20CO (CH2) 2CH3 Ar3B-- (sec-C4Hg) N + (CH3) 3 (C H2) 2C02 (CH2) 2CH3 Ar3B - (sec-C4Hg) N + (CeH13) 4 Ar3B - (C4Hg) N + (CsH11) 4 Ar3B - (C4Hg) N + (CH3) 4 (p-CH30-CeH4hB- (n-C4H9) N + (n-C4H9) 4 Ar3B - (C4Hg) N + (CH3) 3 (CH2) 20H ArB- (n-C4Hg) 3N + (CH3) 4 ArB- (C2HshN + (CH3) 4 Ar2B- (n-C4Hg) 2N + (CH3) 4 Ar3B- (C4Hg) N + (C4H9) 4
40 I 77
J r4E3- ~ + ((; 4ri9) 4
J rE3- ((;; ri3h ~ + ((; ri3) 4 (n - (; 4ri9) 4E3- ~ + ((; ri3) 4 I r3E3- ((;; 4rig) P + ((; 4ri9) 4 5 (where 1 r is phenyl, naphthyl, substituted phenyl (preferably fluorine-substituted) substituted naphthyl, and similar groups having a greater number of fused aromatic rings), as well as tetramethylammonium butyltriphenylborate n-tetrabutylammonium and n-hexyl-tris ( 3 - fluorophenyl) cheap, and mixtures thereof.
Suitable electron donor ether compounds include 4,4 '-dimoxybiphenyl, 1,2,4-trimethoxybenzene, 1,2,4,5-tetramethylbenzene, and the like, and their mixtures.
Suitable electron donor urea compounds include ~. ~ · Dimethylurea, ~. ~ -dimethylurea, ~. ~ '-diphenylurea, tetramethylthiourea, tetraethylthiourea, tetra-n-butylthiourea, ~. ~ -di-n-butiltiourea, ~. ~ '-di-n-butiltiourea, ~. ~ -difeniltiourea, ~. ~ '-diphenyl- ~. ~ '-dietiltiourea, and the like, and mixtures thereof.
Preferred electron donor compounds for reactions induced by free radicals include amines containing one or more portions of julolidinyl, alkylalarylborate salts, and aromatic sulfinic acid salts. However, for such reactions, the electron donor compound can also be omitted, if desired (for example, to improve stability during storage of the photoreactive composition or to modify resolution, contrast and reciprocity). Preferred electron donor compounds for acid-induced reactions include 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoate acetate, 3-dimethylaminobenzoic acid, 4-dimethylaminobenzoine, 4-dimethylaminobenzaldehyde, 4-dimethylaminobenzonitrile, 4-dimethylaminophenyl alcohol, 4-dimethylamine , 2,4-trimethoxybenzene. (3) Photoinitiators (or electron receptors) Suitable photoinitiators (ie, electron receptor compounds) for the reactive species of photoreactive compositions are those that are capable of being photosensitized by accepting an electron from an electronic state of excitation of the multiphotonic photosensitizer, resulting in the formation of at least one free radical and / or acid.
Such photoinitiators include iodonium salts (for example, diaryliodonium salts), sulfonium salts (for example, triarylsulfonium salts optionally substituted with alkyl or alkoxy groups, and optionally having 2.2 'oxy groups linking adjacent aryl moieties), and the like, and mixtures thereof.
The photoinitiator is preferably soluble in reactive species and is preferably stable in storage (that is, they do not spontaneously promote reaction of reactive species when dissolved in them in the presence of the photosensitizer and the electron donor compound). (; consequently, the selection of a particular photoinitiator may depend to some extent on the particular reactive species, the photosensitizer and the compound
41 I 77 electron donor chosen, as described above. If the reactive species is capable of undergoing an acid-initiated chemical reaction, then the photoinitiator is an onium salt (for example, an iodonium or sulfonium salt). Suitable iodonium salts include those described by Palazzotto et al. US Patent No. 5,545,676 in column 2, lines 28 to 46. Suitable iodonium salts are also described in US Patent Nos. 3,729,313, 3,741,769, 3,808,006, 4,250,053 and
4,394,403. The iodonium salt can be a simple salt (for example, containing an anion such as cr, 8 (, r or C 4 Hs so3-) or a complex metal salt (for example, containing SbF6-. PF 6- , BF 4-, tetrakis (perfluorophenyl) borate, SbF 5 OH- or AsF 6} Mixtures of iodonium salts can be used if desired. Examples of useful aromatic iodonium photoinitiators include the diphenyliodonium tetrafluoroborate complex salt; di (4-heptyphenyl) iodonium di (4-methylphenyl) iodonium di (3-nitrophenyl) iodonium (di (4-chlorophenyl) hexafluorophosphate; di (4-methylphenyl iodium; phenyl-4-methylphenyl tetrafluoroborate; di (4-chlorophenyl); ) iodonium; di (4-trifluoromethylphenyl) iodonium; diphenyliodonium hexafluorophosphate; di (4-methylphenyl) iodonium; diphenyliodonium hexafluorophosphate; di (4-trifluorophosphate); 3,5-dimethylpyrazolyl-4-pheni liodonium; diphenyliodonium hexafluoroantimonate; 2,2'-diphenyliodonium tetrafluoroborate; di (2,4-dichlorophenyl) iodonium hexafluorophosphate; di (4-bromophenyl) iodonium hexafluorophosphate; di (4-methoxyphenyl) iodonium hexafluorophosphate; di (3-carboxyphenyl) iodonium hexafluorophosphate; di (3-methoxycarbonylphenyl) iodonium hexafluorophosphate; di (3-methoxysulfonylphenyl) iodonium hexafluorophosphate; di (4-acetamidophenyl) iodonium hexafluorophosphate; di (2-benzothienyl) iodonium hexafluorophosphate; and diphenyliodonium hexafluoroantimonate; and the like; and mixtures of these. Complex iodonium aromatic salts can be prepared by metathesis of corresponding simple aromatic iodonium salts (such as, for example, diphenyliodonium bisulfate), in accordance with the teachings of Beringer et al., J. Am. Chem. Soe. -ª1_, 342 (1959). Preferred salts include diphenyliodonium iodonium salts (such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate and diphenyliodonium tetrafluoroborate), diaryliodonium hexafluoroantimonate (e.g. SarCat ™ SR 1012 available from Sartomer Company), and mixtures of the same. Useful sulfonium salts include those described in US Patent No. 4,250,053 (Smith) in column 1, row 66, up to column 4, row 2, which can be represented by the formulas: ~ Y: 3 R2 "') ~' OR R2 in that R1, R2, and R3 are each independently selected from aromatic groups having from about 4 to about 20 carbon atoms (for example, phenyl
42 I 77 substituted or unsubstituted, naphthyl, thienyl, and furanyl, where the substitution can be with groups such as alkoxy, alkylthio, arylithium, halogen, and so on), and alkyl groups having from 1 to about 20 atoms of carbon.
As used herein, the term "alkyl" includes substituted alkyl (for example, substituted with groups such as halogen, hydroxy, alkoxy, or 5 aryl). At least one of R1, R2, and R3 is aromatic, and preferably each is independently aromatic.
Z is selected from the group consisting of a covalent bond, oxygen, sulfur, -S (= O) -, -C (= O) -, - (O =) S (= O) -, and -N (R) - , where R is aryl (from about 6 to about 20 carbons, like phenyl), acyl (from about 2 to about 20 carbons, like acetyl, benzoyl, and so on), a carbon-carbon bond, or - (R4-) C (-Rs) -, where R4 and Rs are independently selected from the group consisting of hydrogen, alkyl groups having from 1 to about 4 carbon atoms, and alkenyl groups having from about 2 to about 4 carb atoms no. x- is an anion, as described below.
Suitable anions, x-, for the sulfonium salts (and for any of the other types of photoinitiators) include a variety of anion types such as, for example, imide, metho, boron-centered, phosphorus-centered, antimony centered, arsenic-centered, and aluminum-centered.
Illustrative, but not limiting, examples of suitable imide and methoic anions include (C2FsS0 2) 2N-, (C4FgS02) 2N-, (CsF17S02) 3G, (CF3S02) 3G, (CF3S02) 2N-, (C4FgS02hG, (CF3S02h (C4FgS02) G, (CF3S02) (C4FgS02) N-, ((CF3) 2NC2F4S02hN-, (CF3) 2NC2F4S02G (S02 CF3) 2, (3,5-bis (CF3) C5H3) S02N-S02CF3, C6HsS02C- (S02CF3) 2, C5HsS02N-S02CF3, and the like.
Preferred anions of this type include those represented by the formula (RtS02) 3c-, where Rt is a perfluoroalkyl radical having from 1 to about 4 carbon atoms.
Illustrative, but not limiting, examples of suitable boron-centered anions include F48-, (3,5-bis (CF3) C6H3) 48-, (C6Fs) 48-, (p-CF3C5H4) 48-, (m-CF3C5 H4) 48-, (p- FC5H4) 48-, (C6Fsh (CH3) 8-, (C6Fsh (n-C4Hg) 8-, (p-CH3C6H4h (C6Fs) B-, (C6FshFB-, (C6Hsh (C6Fs) B- , (CH 3h (p-CF3C5H4) 28-, (C5Fsh (n-C1 8H370) B-, and the like.
Preferred boron-centered anions generally contain 3 or more halogen groups substituted with aromatic hydrocarbon radicals associated with boron, with fluorine being the preferred halogen.
Illustrative, but not limiting, examples of preferred anions include (3,5-bis (CF3) C5H3) 48-, (C6Fs) 48-, (C6Fsh (n-C4Hg) 8-, (C6FshFB-, and (C6Fsh (CH3) B-. Suitable anions containing other metal or metalloid centers include, for example, (3,5-bis (CF3) C6H3) 4Ar, (C6Fs) ~ r, (C6FshF4P-, (C6Fs) FsP-, F6P-, (C6Fs) FsSb-, F6Sb-, (HO) FsSb-, and F6As- The lists mentioned above are not intended to be exhaustive, other boron-centered non-nucleophilic salts being useful, as well as other useful anions containing other metals or metalloids, will be readily apparent (from the general formulas above) to those skilled in the art.
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Preferably, the anion, x-, is selected from tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and hydroxypentafluoroantimonate (for example, for use with cationically reactive species such as epoxy resins). Examples of suitable sulfonium salt photoinitiators include: 5 tetrafluoroborate tetrafluoroborate trifenilsulfônio hexafluorophosphate metildifenilsulfônio of dimetilfenilsulfônio hexafluorophosphate trifenilsulfônio trifenilsulfônio hexafluoroantimonate difenilnaftilasulfônio hexafluoroarsenato tritolisulfônio hexafluorofosfatoi anisildifenilsulfônio hexafluoro ntimonato 4-butoxifenildifenilsulfônio tetrafluoroborate 4-clorofenildifenilsulfônio tri hexafluorophosphate (4-phenoxyfenil) sulfonium hexafluorophosphate di (4 ethoxyphenyl) metilsulfônio hexafluoroarsenato acetonilfenildifenilsulfônio tetrafluoroborate 4-4-tiometoxifenildifenilsulfônio hexafluorophosphate di (metoxisulfonilfenil) metilsulfônio hexafluoroantimonate di (nitrophenyl) fenilsulfônio hexafluoroantimonate di (carbomethoxyphenyl) hexafluorophosphate 4-metilsulfônio acetamidofenildifenilsulfônio tetrafluoroborate dimetilnaftilsulfônio hexafluorophosphate trifluorometildifenilsulfônio tetrafluoroborate p- (phenylthiophenyl) difenilsulfônio hexafluoroantimonate 10-methylphenoxathinate hexafluorophosphate 5-methyltyanthrene hexafluorophosphate 10-phenyl-9,9-dimethylthioxyanthene hexafluorophosphate 10-phenyl-9-oxotioxanthenium tetrafluoroborate 5-methyl-1-oxetanthiophenyl-5-oxetanthiotranthioxy Preferred sulfonium include triaryl-substituted salts such as triaryl sulfonium hexafluoroantimonate (eg SarCat ™ SR1 01 O available from Sartomer Company), triaryl sulfonium hexafluorophosphate (eg SarCat ™ SR 1011 available from Sartomer Company), and triaryl sulfonium hexafluorophosphate (for example , SarCat ™ Kl85 available from Sartomer Company).
Preferred photoinitiators include iodonium salts (more preferably, aryliodonium salts), sulfonium salts, and mixtures thereof.
Most preferred are aryliodonium salts and mixtures thereof.
Preparation of photoreactive composition 5 Reactive species, multiphoton photosensitizers, electron donor compounds, and photoinitiators can be prepared by the methods described above or by other methods known in the art and many are commercially available.
These four components can be combined under "light safety" conditions using any order and manner of combination (optionally, with mixing or stirring), although it is sometimes preferable (from the point of view of service life and thermal stability to add the last photoinitiator (f after any heating step that is optionally used to facilitate the dissolution of other components.) A solvent can be used, if desired, as long as the solvent is chosen so as not to react appreciably with the components of the Suitable solvents include, for example, acetone, dichloromethane, and acetonitrile.
Reactive species themselves can sometimes also serve as a solvent for the other components.
The three components of the photoinitiator system are present in photochemically effective amounts (as defined above). In general, the composition can contain at least about 5% (preferably at least about 10%; more preferably, at least about 20%) to about 99.79% (preferably, up to about 95 %, more preferably, up to about 80%) by weight of one or more reactive species; at least about 0.01% (preferably at least about 0.1%; more preferably at least about 0.2%) to about 10% (preferably up to about 5%; with more preferably, up to about 2%) by weight of one or more photosensitizers; optionally up to about 10% (preferably up to about 5%) by weight of one or more electron donor compounds (preferably at least about 0.1%; more preferably, about 0.11%) % to about 5%); and from about 0.1% to about 10% by weight of one or more electron receptor compounds (preferably from about 0.1% to about 5%) based on the total weight of solids (or (ie the total weight of components other than the solvent). A wide variety of adjuvants can be included in the photoreactive compositions, depending on the desired end use.
Suitable adjuvants include solvents, diluents, resins, binders, plasticizers, pigments, dyes, reinforcing or enlarging fillers, inorganic or organic (in preferred amounts of about 10% to 90% by weight based on the total weight of the composition), thixotropic agents, indicators, inhibitors, stabilizers, ultraviolet ray absorbers, and the like.
The amounts and types of such adjuvants and their manner of addition to the compositions will be familiar to those skilled in the art.
45 I 77 It is within the scope of this invention to include non-reactive polymeric binders in the compositions in order, for example, to control viscosity and provide film forming properties. Such polymeric binders can generally be chosen to be compatible with reactive species. For example, polymeric binders that are 5 soluble in the same solvent that is used for reactive species, and that are free of functional groups that can negatively affect the reaction course of reactive species, can be used. Binders can be of an appropriate molecular weight to achieve the desired film forming and solution rheology properties (for example, molecular weights between about 5,000 and 1,000,000 Daltons; preferably between about 10,000 and 500,000 Daltons; more preferably , between about 15,000 and
250,000 Daltons). Suitable polymeric binders include, for example, polystyrene, poly (methyl methacrylate), poly (styrene) -co- (acrylonitrile), cellulose acetate butyrate, and the like. Prior to exposure, the resulting photoreactive compositions can be coated onto a substrate, if desired, by any of a variety of coating methods known to those skilled in the art (including, for example, slide coating and rotation coating). The substrate can be chosen from a wide variety of films, sheets and other surfaces (including silicon wafers and glass plates), depending on the particular application and the exposure method to be used. Preferred substrates are generally sufficiently flat to allow the preparation of a layer of photoreactive composition that is uniform in thickness. For applications where the coating is less desirable, photoreactive compositions can, alternatively, be exposed in bulk. Exposure system and its uses In carrying out the process of the invention, a photoreactive composition can be exposed to light in conditions such that multiphotonic absorption occurs, thus causing a region of differential solubility characteristics (for example, greater or lesser solubility in a given solvent ), compared to the photoreactive composition before exposure. Such exposure can be achieved by any known means, capable of achieving sufficient light intensity. One type of exemplary manufacturing system that can be used includes a light source, an optical system that comprises a final optical element (optionally including mirror mirrors and a telescope to control beam divergence) and a mobile phase. Phase 16 is mobile in one, two, or, more typically, three dimensions. A substrate mounted on the phase has a photoreactive composition layer on it. A beam of light from the light source passes through the optical system and exits through the final optical element, which concentrates the light at a point P within the layer, thereby controlling the three-dimensional spatial distribution of the light intensity within the composition and making at least
46 I 77 a portion of the photoreactive composition in the vicinity of point P becomes more or less soluble in at least one solvent than it was immediately before exposure to the light beam.
The exposed portion of the photoreactive composition in the vicinity of point P causing a change in solubility is a three-dimensional imaging element, or voxel. 5 By shifting the phase, or directing the light beam (for example, moving a laser beam using mirror mirrors and a telescope) in combination with the movement of one or more elements of the optical system, the focal point P can be digitized or translated into a three-dimensional pattern that corresponds to a desired shape.
The resulting reacted or partially reacted portion of the photoreactive composition then creates a three-dimensional structure with the desired shape.
For examplej in a single pass the surface profile (which corresponds to a pixel thickness of one pixel in volume or voxel) of one or more orifice forming characteristics of a microbocal mold pattern can be exposed or imaged, which after development it may be in the form of one or more nozzle orifice forming features used to make a pattern of one or more set of micro nozzles.
The exposure or imaging of the surface profile of the microbocal mold pattern can be done by scanning at least the perimeter of a flat slice of a desired three-dimensional structure and then scanning a plurality of preferably parallel and flat slices to complete the structure .
The cut thickness can be controlled to achieve a resolution high enough for the shape of each nozzle orifice feature.
For example, smaller slice thicknesses may be desirable in regions of higher structure taper to assist in achieving high structure fidelity, but greater cut thicknesses may be used in areas of lower structure taper to assist in maintaining manufacturing times Useful.
In this way, highly detailed features with dimensions smaller than the slice thickness (preferably less than about half the slice thickness; more preferably, less than about a quarter of the slice thickness) can be obtained without sacrificing the speed of manufacture (the yield or the number of sets or patterns of microbocal molds manufactured per unit time). The light source can be any light source that produces sufficient light intensity to perform multiphotonic absorption.
Suitable sources include, for example, titanium near infrared femtosecond oscillators (for example, those available from Coherent, Santa Clara, California, as "MIRA OPTIMA 900-F") pumped by an argon ion laser (for example, those available from Coherent as "IN NOVA"). This laser, operating at 76 MHz, has a pulse width of less than 200 femtoseconds, is adjustable between 700 and 980 nm, and has an average power of up to 1.4 Watts.
Another useful laser is available from Spectra-Physics, Mountain View, California, under the trade name "MAl
47 I 77
TAl ", tunable to wavelengths in the 750-850 nm range, and having a repetition frequency of 80 megahertz, and a pulse width of about 100 femtoseconds (1x10-13 sec), with an average power level of up to 1 Watt.
However, any light source (for example, a laser), which provides sufficient intensity to effect multiphotonic absorption at an appropriate wavelength so that the multiphoton absorber used in the photoreactive composition can be used.
Such wavelengths can generally be in the range of about 300 to about 1500 nm; preferably, from about 400 to about 1100 nm; more preferably, from about 600 to about 900 nm; more preferably, from about 750 to about 850 nm, included.
Typically, the fluency of light (for example, the piT intensity of a pulsed laser) is greater than about 2 W / cm. The upper limit for fluency of light is generally dictated by the ablation threshold of the photoreactive composition.
For example, Q-switched Nd: YAG lasers (for example, those available from Spectra-Physics as "QUANTA-RAY PRO"), dye lasers for visible wavelengths (for example, those available from Spectra-Physics as "SIRAH" pumped by a Q-switched Nd: YAG laser from Spectra-Physics under the trade name "Quanta-Ray PRO"), and lasers pumped by Q-switched diode (for example, those available from Spectra-Physics as " FCBAR ") can also be used.
Preferred light sources are pulsed near-infrared lasers, having a pulse length of less than about 10-8 seconds (more preferably, less than about 10-9 seconds; most preferably, less than about 10-11 second). Other pulse lengths can be used, as long as the criteria above peak intensity and ablation threshold are met.
Pulsed radiation can, for example, have a pulse frequency of about one kilohertz to about 50 megahertz, or even higher.
Continuous wave lasers can also be used.
Optical systems may include, for example, refractive optical elements (for example, sets of lenses or micro lenses), reflective optical elements (for example, retro-reflectors or focus mirrors), diffractive optical elements (for example, reticles, phase masks and holograms), polarizing optical elements (for example, linear and retarding polarizers), dispersive optical elements (for example, prisms and reticles), diffusers, Pockel cells, waveguide and the like.
Such optical elements are useful for focusing, releasing beam, formatting beam / mode, formatting the pulse and timing the pulse.
Generally, combinations of optical elements can be used, and other appropriate combinations will be recognized by those skilled in the art.
The final optical element can include, for example, one or more refractive, reflective and / or diffractive optical elements.
In one embodiment, an object, such as those used in microscopy, can be conveniently obtained from commercial sources, such as, for example, Carl Zeiss, North America, Thornwood, New York, and used as the final optical element .
For example, the
48 I 77 manufacturing system may include a confocal scanning microscope (for example, those available from Bio-Rad Laboratories, Hercules, California, as "MRC600") equipped with an objective 0.75 (NA) numerical aperture (such as, for example, those available from Carl Zeiss, North America as "20X FLUAR"). 5 It may often be desirable to use lenses with a relatively large numerical aperture to provide highly stabbed light.
However, any combination of optical elements that provides a desired intensity profile (and their spatial positioning) can be used.
Exposure times will generally depend on the type of exposure system used to extend the reaction of reactive species in the photoreactive composition (and its monitoring variables, such as numerical aperture, geometry of the spatial distribution of light intensity, peak light intensity during and laser pulse (higher intensity and shorter pulse duration correspond approximately to a peak light intensity), as well as the nature of the photoreactive composition.
Generally, the highest peak light intensity in the focusing regions allows for shorter exposure times, if everything else is the same. Linear imaging or "write" speeds in general can be from about 5 to 100,000 microns I second, using a laser pulse duration of about 1 to 1 1 to 15 seconds (for example, about 10 to 11 to 10 -14 seconds) and about 10 2 to 10 9 pulses per second (for example, about 10 3 to 10 8 pulses per second). In order to facilitate the solvent development of the exposed photoreactive composition and obtain a pattern structure of manufactured microbocal mold, a threshold dose of light (i.e., the threshold dose) can be used.
This threshold dose is typically process specific, and may depend on variables such as, for example, wavelength, pulse frequency, light intensity, specific photoreactive composition, specific structure of the microbocal mold pattern being manufactured, or the process used for solvent development.
Thus, each set of process parameters can typically be characterized by a threshold dose.
Higher doses of light than the threshold can be used, and can be beneficial, but higher doses (once above the threshold dose) can typically be used with a slower recording speed and / or light intensity taller.
Increasing the light dose tends to increase the volume and aspect ratio of voxels generated by the process.
Thus, in order to obtain the low aspect ratio voxels, it is generally preferable to use a light dose that is less than about 10 times the threshold dose, preferably less than about 4 times the threshold dose and, more preferably less than about 3 times the threshold dose.
In order to obtain the low aspect ratio voxels, the radial intensity profile of the light beam is preferably Gaussian.
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Through multiphotonic absorption, the light beam induces a reaction in the photoreactive composition that produces a region of material volume with different solubility characteristics than the unexposed photoreactive composition.
The resulting pattern of differential solubility can then be achieved by a conventional development process, for example, by removing exposed or unexposed regions.
The exposed photoreactive composition can be developed, for example, by placing the exposed photoreactive composition in solvent to dissolve the regions of greatest solubility in solvents, by washing with solvent, by evaporation, by erosion by oxygen plasma, by other known methods, and by combinations thereof.
Solvents that can be used to develop the exposed photoreactive composition include aqueous solvents such as, for example, water (for example, having a pH in the range 1 to 12) and miscible water blends with organic solvents (for example, methane !, ethane !, propanol, acetone, acetonitrile, dimethyl formamide, n-methyl pyrrolidone, and the like, and mixtures thereof); and organic solvents.
Exemplary useful organic solvents include alcohols (for example, methane !, ethane! And propanol), ketones (for example, acetone, cyclopentanone and methyl ethyl ketone), aromatics (for example, toluene), halocarbons (for example, methylene chloride and chloroform), nitriles (for example, acetonitrile), esters (for example, ethyl acetate and propylene glycol methyl ether acetate), ethers (for example, diethyl ether and tetrahydrofuran), amides (for example, n-methyl pyrrolidone) , and the like, and mixtures thereof.
An optional baking after exposure to light under conditions of multiphotonic absorption, but before the development of the solvent, can be useful for some photoreactive compositions such as, for example, reactive species of epoxy type. Typical baking conditions include temperatures in the range of about 40 ° C to about 200 ° C, sometimes in the range of about 0.5 minutes to about 20 minutes.
Optionally, after exposing only the surface profile of a pattern or microbocal mold arrangement, preferably followed by solvent development, a nonimagewise exposure using actinic radiation can be performed to perform the reaction of the remaining unreacted photoreactive composition.
Such nonimagewise exposure can preferably be performed using a one-photon process.
Three-dimensional microbocal complexes and microbocal arrangements can be prepared in this way.
Modalities Microstructure modalities Referring to Figures 26A-26F, a modality of a nozzle orifice forming feature or microstructure includes a circular base 806, together with a curved side 804 and flat control cavity forming feature 800
50 I 77 configured to form an exit hole in a circular shape, as indicated by the shape of its 802 microstructure top. With reference to figure 27, another embodiment of a nozzle orifice characteristic or microstructure includes a base circular 814, together with a 5 curved side 812 and flat control cavity forming feature 808 configured to form a circular orifice outlet, as indicated by the shape of its microstructure top 810. The curved side 812 includes a first set of annular fluid flow interruption characteristics in the form of multiple circumferential grooves 816, which are spaced apart, parallel to each other and start halfway between base 814 and top 810. A second set where such features 818 are arranged adjacent to each other and formed near the base 814. The nozzle-forming feature or microstructure of Figure 28 includes a circular base 828, along with a curved side 824 and a flat control cavity forming feature 820 configured to form a circular hole outlet, as indicated by the shape of its microstructure top 822. The curved side 824 includes a variety of discrete source or point 825, 826, and 827 fluid flow interruption characteristics. A fluid flow interruption characteristic is a characteristic that causes, when transmitted to the inner surface of the nozzle through passage, the fluid flowing is interrupted through the nozzle passage holes.
Such features may include, for example, features that cause or induce any or a combination of (a) cavities, (b), turbulence, (c), pressure waves in the fluid that seeps through the nozzle's through holes. and that result in changes in the fluid flowing past the nozzle outlet port.
The nozzle orifice microstructure of Figure 29 includes a circular base 836, together with a curved side 834 and a flat control cavity-forming feature 830 configured to form a circular orifice outlet as indicated by the shape from its microstructure top 832. The curved side 834 is configured to include double or multiple convergent / divergent fluid flow characteristics that cause fluid flowing through the corresponding nozzle through hole to converge and diverge several times before to exit through the hole exit.
The nozzle orifice forming feature of Figure 30, similarly includes a circular base 844, along with a curved side 842 and a flat control cavity forming feature 838 configured to form an orifice outlet. circular, as indicated by the shape of its microstructure top 840. The curved side 842 is structured similarly to the modality of figure 29, but with a unique divergent convergent fluid flow characteristic, which causes the fluid flowing through the nozzle through through-holes converge and diverge once, before exiting through the orifice outlet.
51 I 77 Referring to Figures 31 A and 318, an alternative to the nozzle orifice microstructure includes a circular base 852, along with a curvilinear side 850 and flat control cavity forming features 846 configured to form a star-shaped exit orifice, as indicated by the star shape of its 848 microstructure top. Figure 318 shows the microstructure of Figure 31A with its flat control cavity forming features 846 removed to show the shape of expected star for the corresponding orifice outlet. The star-shaped top 848, and therefore the corresponding outlet port, is defined by a plurality of rectangular shaped grooves or branches 848b extending outwardly from a core 848a like the spokes of a wheel. Five rectangular shaped slots 8488 are illustrated, but other branch shapes and a different number of branches may be desirable. The 850 side includes a curved section 850a and a linear section 850b for each of the 848b branches. The nozzle orifice microstructure of Figures 32A and 328 includes a circular base 860, with a curvilinear side 858 and flat control cavity forming characteristics 854 configured to form a cross-shaped or shaped outlet hole of X, as indicated by the shape of its top microstructure
880. Figure 328 shows the microstructure of Figure 32A with its flat control cavity forming characteristics 854 removed to show the expected shape for the corresponding orifice outlet. The top 856, and therefore the corresponding outlet port, is defined by four rectangular shaped slots 856b or branches 856a that extend outwardly from a core like the spokes of a wheel. Side 858 includes a curved section 858a and a linear section 858b for each of branches 856b. Similarly, the nozzle orifice microstructure of Figure 33 includes a circular base 868, together with a curvilinear side 866 and flat control cavity-forming features 862 configured to form a cross-shaped exit orifice. or X-shaped, as indicated by the shape of its top microstructure 864. The top 864, and therefore the corresponding outlet hole, is defined by four rectangular slots or branches extending outwardly from a nucleus like the spokes of a wheel. The 866 side includes a curved section 866a and a linear section 866b for each of the branches. The nozzle orifice microstructure of Figure 34 includes a circular base 876, together with a curvilinear side 874 and flat control cavity-forming features 870 configured to form a cross-shaped or cross-shaped exit orifice. X, as indicated by the shape of its top microstructure 872. The top 872, and therefore the corresponding outlet hole, is defined by four rectangular slots or branches extending outwardly from a
52 I 77 core like the spokes of a wheel.
Side 87 4 includes a curved section 87 4a and a linear section 87 4b for each of the branches.
Base 876 is connected to side 87 4 by a circumferential curved thread 87 4c.
The nozzle orifice microstructure of Figure 35 includes a circular base 884, together with a curvilinear side 882 and flat control cavity-forming features 5 configured to form a cross-shaped or shaped outlet port. of X, as indicated by the shape of its top microstructure 880. The top 880, and therefore the corresponding outlet, is defined by four rectangular grooves or branches extending outwardly from a core such as the spokes of a wheel.
Side 882 includes a curved section 882a and a linear section .882b for each of the branches.
The buttonhole forming microstructure of Figure 36 includes a base 892, together with a curved side 890 and flat control cavity forming features 886 configured to form a cross-shaped or X-shaped outlet hole , as indicated by the shape of its top microstructure 888. The top 888, and therefore the corresponding outlet hole, is defined by four rectangular shaped grooves or branches extending outwardly from a core like the spokes of a wheel.
Side 890 includes a curved section 890a and a linear section 890b for each of the branches.
In contrast, the nozzle orifice microstructure of Figure 37 includes a circular base 898, but together with a rectilinear side 897 and flat control cavity formation features 894 configured to form a cross-shaped exit orifice. or X-shaped, as indicated by the shape of its top microstructure 896. The top 896, and therefore the corresponding outlet hole, is defined by four rectangular grooves or branches extending outwardly from a nucleus like the spokes of a wheel. side 897 includes a first linear section 897a and a second linear section 897b for each of the branches.
Referring to Figures 38A-38D, a different embodiment of a nozzle orifice microstructure includes a semi-circular base 1106, together with a curved side 1104 and flat control cavity forming features 1100 configured to form a single exit hole in the form of a rectangular slot, as indicated by the shape of its microstructure top 1102. the top 1102, and therefore the corresponding exit hole, is defined by a single rectangular slot. the side 1104 includes a single curved section 11 04A and linear section 11 04b.
It may be desirable to combine any two or more of the characteristics described above in a given nozzle orifice microstructure.
It is believed that the curvilinear side structures (that is, each set of a curved and linear section) of the microstructures of Figures 31 to 36 and 38, as well as the structure
53 I 77 rectilinear side of the microstructure of Figure 37, will produce nozzle passage holes with corresponding internal surfaces that cause different portions of the fluid flowing through it to move closer and reaching its exit orifice in two or more vectors different strengths, as a result of the fluid flowing along two or more different pathways along the inner surface that defines the nozzle through hole. It is also believed that such different force vectors will result in cutting off the fluid leaving the outlet port, which in turn will cause small droplets of the liquid to eventually form outside the port outlet. It is further theorized that the increase in shear forces exerted on the fluid leaving the outlet port can produce even smaller droplets. For the nozzle passages with grooves or branches extending out of the core like the rays of a ro a (for example, like the microstructures in Figures 31 to 37), it is also believed that such cutting forces will cause the fluid to flow out of each groove or branch to separate into several individual streams, equal to the number of branches, as the fluid exits the outlet port. It is further believed that each of these currents will eventually turn into droplets that are smaller than the droplets formed from a circular or rectangular hole with the same total opening area as the branched outlet hole. These smaller droplets can be about, or approximately as many times smaller as the number of branches that form the exit orifice, compared to the droplets formed from a single circular or rectangular exit orifice, with the same total opening area about to leave. Referring to Figures 39A to 39C, an embodiment of a microstructured mold forming pattern 1116 includes a single replica group or set with centrally located microstructures or nozzle orifice forming features 1108, replicas of cavity forming features control planes 1112, and replicas of additional fluid inflow channel forming characteristics
1114. The microstructured pattern 1116 is formed on a substrate 111 O, using a material 1135 capable of undergoing a multiphotonic reaction when simultaneously absorbing several photons, according to the previous teachings. Referring to Figures 40A to 40C, a microstructured nozzle 1118 formed using the microstructured mold forming pattern 1116 of Figures 39, includes a group of nozzle through holes 1122 located in the center of pattern 1116 and a set of additional separate channels fluid inlet 1120. Each through hole 1122 includes an inner surface 1126 connecting an inlet hole 1128 to an outlet hole 1124. As can be seen, the inlet holes 1128 of the through holes in the nozzle 1122 are tightly together in the nozzle plate 1118 center, while orifice 1124 outlets are separate. This is possible because orifice inlets 1128 are considerably larger in area than orifice outlets 1124. Each of the channels 1120 is connected to a single through-hole 1122a located on the outer periphery of the through-hole cluster. The remaining through-holes 1122b are not so connected to any channel 1120. The channels 1120 5 can be used to supply additional fluid through the nozzle 1118 from a fluid source separate from that which supplies the other through holes 1122b. Because the through-hole outlets present can be very small in size (for example, in diameter), the through-hole inlets of the nozzles of the invention can be arranged very close together or grouped together, for example, as shown in Figures 40 and 41. Such a grouping of through-hole inlets can at least reduce, and even eliminate all, the majority, or + at least a substantial amount of any negative back pressure exerted against the surface on the inlet side of the nozzle by the fluid that it passes through the nozzle, because such a grouping near the orifice entrances can eliminate or at least significantly reduce the surface area between the inlet openings of the through holes. With orifice inlets being larger than orifice outlets, reducing back pressure is also facilitated by using through-holes that have interior walls that taper down or do not include a curved arch from the inlet to the orifice about to leave. The microstructured nozzle 1130 of Figure 41 includes an alternative pattern of nozzle through-holes 1134 and alternative alternative fluid inflow channels 1132. As can be seen, there are two groups or sets of nozzle through-holes
1132. One group of through holes 1134a is in a circular pattern and located adjacent to the outer circumferential periphery of the 1130 nozzle plate. The other group of through holes 1134b is located centrally in the nozzle 1130. Each of the additional inflow channels of fluids 1132 is connected only to one of the through holes 1134a forming the outer ring of the through holes of the nozzle. Referring to Figures 42A and 42B, another embodiment of a microstructured mold forming pattern 1136 includes two groups or sets of replicates of microstructures or nozzle orifice formation characteristics 1138, with respective replicas of cavity forming characteristics. flat control elements being optional, and a replica of ring-shaped nozzle separation characteristics 1140 with an additional or alternative set of at least 3 and preferably 4 replicates of flat control cavity-forming characteristics 1142 arranged on the ring replica of separation 1140. A replica group of nozzle orifice forming microstructures 1138a is in a circular pattern located near the 1140 separation ring, and the other group of replica of nozzle orifice forming 1138b is centrally located in the microstructured pattern of formation of
55 I 77 mold 1136. The microstructured pattern 1136 is formed on a substrate 111 O, according to the previous teachings. When replicas of flat control cavity forming characteristics 1142 are formed in the replica of separation ring 1140, replicas of nozzle orifice forming microstructures 1138 need not require their own control cavity forming characteristic replica. flat. Alternatively, instead of using features 1142 or using a flat control cavity forming feature replica for each 1138 microstructure, the number of replica nozzle orifice forming microscopes 1138 that has a replica of cavity forming features of Flat control can be limited to at least 3 and 4 and preferably 4. For ease of fabrication, the 1140 p1 separation ring replica includes two or more replicas of the 1144 nozzle connection characteristics, which are used when it is desirable to manufacture a batch. of nozzles at the same time, instead of one at a time. This 1144 feature will be discussed in more detail below. The microstructured mold forming pattern 1136 can be used to form a microstructured mold pattern or the first mold 1146 (shown in dashed line). Referring to Figures 43A to 430, the microstructured mold pattern or the first mold 1146, made using the microstructured mold forming pattern 1136 of Figure 42, is a negative image of the pattern 1136, with the first mold 1146 having a corresponding nozzle orifice replica outer ring 1148a, a nozzle orifice replica center group 1148b, and an annular separation channel 1150, which includes a corresponding number of replicas of flat control cavities 1152 and nozzles connecting grooves 1154. Referring to Referring to Figures 44A and 44B, a microstructured nozzle formation pattern 1156 is made using the microstructured mold pattern 1146 of Figure 43. The pattern 1156 includes two groups or sets of microstructures or features 1158 forming nozzle holes, with respective characteristics flat control cavity forming options being optional, and a ring-shaped nozzle separation characteristics 1160 with an additional or alter set native of at least 3 and preferably 4 characteristics of formation of flat control cavities 1162 arranged on the separation ring 1160. A group of nozzle orifice formation microstructures 1158a is in a circular pattern and located adjacent to the separation ring 1160 , and the other group of nozzle orifice forming microstructures 1158b is centrally located in the microstructured mold pattern
1146. The microstructure mold pattern 1146 is a unitary structure formed, for example, by injection molding using the microstructure mold pattern 1146 according to the previous teachings. When the flat control cavity forming characteristics 1162 are formed on the separating ring 1160, the nozzle orifice forming microstructures 1158 need not require two own replicates of the flat control cavity forming characteristic. Alternatively, instead of using features 1162 or using
56 I 77 a flat control cavity forming feature for each microstructure 1158, the number of nozzle orifice forming microstructures 1158 that has a flat control cavity forming feature can be limited to at least 3 and preferably 4 For ease of fabrication, the separating ring 1160 can include two or more 5 connection characteristics of the 1164 nozzles, which are used when it is desirable to manufacture a lot of nozzles at the same time, instead of one nozzle at a time. For example, the linear array of any desired length of connected nozzles 1166 of Figure 46 can be made by first aligning a linear array of the microstructured nozzle forming pattern 1156 in its respective connection characteristics 1164, as shown in Figure 45. Thus, a flat arrangement of any desired area of conical nozzles 1166 (not shown) can also be made by forming the required number of additional connection characteristics 1164 on each separation ring 1160 to form at least one connection or sprue feature. 1170 between adjacent nozzles 1166. The number and location of connection characteristics 1164 will depend on the desired packaging pattern used to position the individual 1156 nozzle-forming microstructure pattern (eg hexagonal, cubic, etc.) A corresponding set of pre - nozzle shape 1165 is then formed, for example, by depositing a suitable material in each adjacent patterns 1156. Next, the set of preforms 1165 has its exposed surface planarized down to the level 1167 necessary to discover the exit of the desired size hole for each of the nozzle through holes 1168a and 1168b, which are formed by corresponding orifice forming characteristics 1158a and 1158b of the 1156 standard. Because of the connection characteristics 1164, the resulting arrangement of nozzles 1166 is connected by springs or connection characteristics 1170, which can be easily separated (for example, broken, cut, etc.) to separate the individual nozzles
1166. Thus, the entire resulting set of nozzles 1166 can be removed from pattern set 1156 in one piece, and individual nozzles 1166 removed as desired. Figure 47 is a schematic cross-sectional side view of a microstructured nozzle formation pattern and a multi-component nozzle preform deposited thereon; With reference to figure 47, when making a nozzle preform (for example, see Figure 1J), one or more initial layers 1127 and 1186, of one or more materials can be deposited or otherwise applied in a microstructured pattern nozzle formation 1194, having nozzle orifice formation characteristics 1182 and flat control cavity formation characteristics 1184, so as to form the inlet side surface of the resulting nozzle preform (i.e. nozzle), including the inner surface of the nozzle preform holes (i.e. nozzle through holes). One or more of other layers 1188, 1190 and 1192 of one or more others
57 I 77 materials can be deposited to complete the formation of the nozzle preform. The corresponding nozzle can then be made as described above, removing the characteristics 1184 and corresponding applied materials along the dashed line. Likewise, in addition or alternatively, by making a mold pattern or microstructured the first mold (for example, see Figure 1D), the initial stages of 1127 and 1186 can be deposited or otherwise applied to form the surface on the inlet side of the first mold. The other layers 1188, 1190 and 1192 can be deposited or otherwise applied to it or in a different way, in order to form the volume or the remainder of the first mold. As an example only, layer 1127 can be an initial particle layer to impart conductivity, which is electrical to the surface of the 1194 microstructured pattern. The next layer 1186 can be a structure and / or performance providing layer. Layer 1188 can be a volume layer that forms a large part or all of the rest of the nozzle and / or first mold. One or both of the layers 1190 and 1192 can then be optional or applied to provide the desired structural characteristics and / or performance for the rest of the nozzle and / or first mold. In this way, for example, the first mold and / or nozzle may have a surface on the inlet side formed by a material with better performance and / or more expensive (for example, high corrosion temperature and / or wear-resistant metal, which is electrodeposited), with the volume or remainder of the first mold and / or nozzle to be formed using a material of lower and / or cheaper performance. Thus, cheaper materials can be used to make most of the first mold and / or nozzle without substantially sacrificing performance. The present process for making fuel injector nozzles can also be more efficient (for example, involving fewer steps) and be less expensive than existing conventional nozzle manufacturing processes that use molding close to the final shape, with the machining of orifices. passage. Referring to figure 48, the nozzles of the present invention can be used in a conventional fuel injector 1172, which includes a control valve 1180 that seals against a seal 1174 and a nozzle plate 1178 typically welded along its periphery 1176 with seal 1174, with nozzle 1178 having a group of through holes 1178. Additional modalities Method
1. A method for making a nozzle, the method comprising: (a) providing a microstructured mold pattern defining at least a portion of a mold cavity and comprising a plurality of nozzle orifice replicas and control cavity replicas flat. Each replica orifice
58 I 77 nozzle may or may not be connected to (for example, be in fluid communication with) at least one flat control cavity replica. (b) molding a first material into a microstructured nozzle forming pattern using the microstructured mold pattern, with the nozzle forming microstructure pattern comprising a plurality of nozzle orifice characteristics and cavity forming characteristics. flat control.
Each nozzle orifice forming feature may or may not be connected to (for example, being in fluid communication with) at least one flat control cavity forming feature.
The nozzle orifice forming characteristics are substantially negative replicas (i.e., negative replicas of all, most, or at least a subsfential portion) of the nozzle orifice replica, and the flat control cavity forming characteristics are replicas. substantially negative (i.e., negative replicates of all, most, or at least a substantial portion) of the replicates of flat control cavities. (c) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a second material in a nozzle preform using the nozzle microstructured forming pattern, with the preform of nozzle comprising a plurality of nozzle preform holes and flat sacrifice control cavities.
Each nozzle preform orifice comprises an inlet opening and may or may not be connected to (for example, being in fluid communication with) at least one flat sacrifice control cavity.
The nozzle preform holes are substantially negative replicas (i.e., negative replicates of all, most, or at least a substantial portion) of the nozzle orifice forming characteristics and the flat sacrifice control cavities are substantially replicates negative (i.e., negative replicates of all, most, or at least a substantial portion) of the characteristics of formation of flat control cavities.
That is, the nozzle preform holes are substantially positive replicas (i.e., positive replicates of all, most, or at least a substantial portion) of the nozzle orifice replica and the flat sacrifice control cavities are replicas substantially positive (i.e., positive replicates of all, most, or at least a substantial portion) of the replicates of flat control cavities. (d) forming at least one nozzle from the nozzle preform, the nozzle formation comprises removing sufficient of the second material to remove the flat sacrifice control cavities (for example, by electrical discharge machining, mechanical grinding, etc. .) in order to form a top surface of the nozzle preform on a flat top surface (that is, planarize the top surface) of the nozzle, and so as to form each of the nozzle preform holes in a finished nozzle through hole comprising an inlet hole and an outlet hole connected to (for example, being in fluid communication)
59 I 77 with the entry hole through a hollow cavity defined by an inner surface. The nozzle can also have a flat bottom surface, and the flat top surface and the flat bottom surface can be parallel to each other or at an acute angle to each other.
2. The method according to modality 1, in which the second material comprises a plurality of different second materials, and the nozzle preform is formed by separate deposition of each of the second materials as a layer over all, a most or at least a substantial portion of the microstructured nozzle formation pattern so that the resulting nozzle preform, and therefore the nozzle, comprises an accumulation or otherwise comprises multiple (i.e., 2 , 3, 4, 5 or more) layers, with each layer being a different second material.
3. The method according to mode ~ 2, in which the plurality of different second materials is at least three different second materials, the first of the second materials being deposited as a layer on the microstructured nozzle forming pattern forming an electrically layer conductive.
4. The method according to modality 2 or 3, in which none of the multiple layers is in the form of an initial electrically conductive fine particle layer.
5. The method according to any of modalities 2 to 4, in which at least one of the multiple layers is a combustion catalyst (for example, palladium, platinum, gold, ruthenium, rhodium, and iridium) which is the first layer deposited on the microstructured nozzle formation pattern and is in a form that is sufficiently soluble in the fuel (for example, gasoline, alcohol, diesel fuel, etc.), undergoing combustion (ie, being burned), in order to be delivered with the fuel inside the combustion chamber of the internal combustion engine, a corrosion inhibitor, a combustion by-product deposit inhibitor, a ceramic, a metal alloy, or any other material in the form of a layer that facilitates the fuel flow rate (for example, where the surface of the layer in contact with the fuel passing through the nozzle has low friction at the interface between the fuel and the internal surface of the nozzle), to feed the air mixture, and / ora desired heat transfer between the fuel injector comprising the nozzle and the outer part of the nozzle exposed to the combustion chamber of an internal combustion engine. The second materials deposited as layers on the microstructured nozzle formation pattern can also be chosen so that the first deposited layer is made of a second material that is compatible with the fuel that passes through the nozzle, the last layer is made of a second material that is suitable to be exposed to the environment inside a combustion chamber of an internal combustion engine, and at least one other layer deposited between the first and last layers is made of a second material that may not be suitable as the first layer, last
60 I 77 layer, or both the first and the last layer, but it has other desirable properties (for example, it is relatively inexpensive, it has desirable thermal, vibration and / or acoustic characteristics, etc.). When a combustion catalyst is used as one of the layers, it is the first layer deposited and can also function as a seed layer. 5 It may be desirable to deposit the combustion catalyst material so that the resulting layer is relatively porous (i.e., has a relatively low density), in order to significantly increase the surface area of the interface between the deposited combustion catalyst material and the fuel that passes through the nozzle.
6. The method according to any of modalities 1 to 5, in which the first material is different from the second material.
7. The method according to any of the features 1 to 6, wherein each replica of the nozzle orifice microstructured mold pattern has an interior surface comprising at least one or more features affecting the flow of fluid (for example, interrupting the fluid flow) ). The characteristics affecting the fluid flow of each nozzle orifice replica are configured (for example, size, shape and design) in order to be transferable as a negative replica of the outer surface of a corresponding nozzle orifice characteristic, of the microstructured nozzle formation pattern, and then as a positive replica for the interior surface of a corresponding nozzle preform hole of the nozzle preform (i.e., the interior surface of the corresponding through hole of the finished nozzle ). The characteristics affecting fluid flow are structural features on the inner surface of the nozzle orifice replica which, when transferred to the inner surface of the nozzle through holes, are intended to induce or otherwise cause, for example: cavitations, turbulence , or otherwise prevent or interrupt the flow of a fluid (for example, a liquid fuel) through the nozzle in order to positively affect the current, spray, ligament, plume of droplets or individual droplets formed by the fluid exiting the nozzle . These characteristics affecting the fluid flow can be, for example, in the form of protrusions, continuous annular ribs, discontinuous spaced ribs (for example, formed concentrically around the inner surface of the nozzle through hole or along the longitudinal axis of the nozzle through hole), streaks (for example, perpendicular or parallel to the flow of fluid through the nozzle through hole), as well as other structural obstructions that are compatible with the method of the invention. It is believed that these characteristics affecting fluid flow may help to cause the atomization of fluid (for example, liquid fuel) leaving the nozzle. The degree of atomization of liquid fuel and its plume configuration within a combustion chamber is believed to affect both fuel consumption and exhaust emissions from an internal combustion engine.
61 I 77
8. The method according to any of modalities 1 to 7, in which the microstructured mold pattern comprises at least one or more fluids (that is, a gas or liquid), recess or channel characteristics connecting at least one nozzle orifice replica with (a) at least one other orifice orifice replica, (b) a portion of the mold in addition to the outer periphery of the microstructured mold pattern, or (c) both (a) and {b). The fluid channel characteristics of the microstructured mold pattern are configured (for example, size, shape and design) so as to be transferable as a corresponding negative replica or ridge characteristic to the top surface of the nozzle forming microstructure pattern , and then as a positive replica or channel feature to the inteer surface of the nozzle preform (i.e., the finished nozzle). These channel characteristics can be designed for use, for example, as additional ports, such as (a), for the introduction of additional fluid (for example, fuels, gas or liquid, air, oil, fuel additives, catalysts, etc.) for the flow of fuel from a desired number of nozzle orifices from an alternative source separate from the main fuel injector source, (b) to connect two or more nozzle orifices in fluid communication, for example, to adjust the fluid flow rates and / or pressures in the connected nozzle orifices in relation to the unconnected nozzle orifices, (c) to be used with converging and / or diverging nozzles, (d) for the production of flow flows colliding fuel to effect a better atomization of the fuel, (e), in order to decrease fuel pressures, (f), to extract the air coming from the combustion chamber (that is, the engine cylinder) and for circulation in d direction to the flow of fuel flowing through the nozzle through hole to better atomize the fuel, or (g) any combination of (a) to (f), and for any other desired reason.
9. The method according to any of modalities 1 to 8, in which each of at least three replica nozzle holes of the microstructured mold pattern is connected (for example, is in fluid communication with), at least one flat control cavity replica. It may be desirable that all nozzle orifice replicas are thus connected to a flat control cavity replica. 1O. The method according to modality 9, wherein the microstructured mold pattern defines a nozzle orifice replica pattern or pattern, the arrangement having a periphery and at least three nozzle orifice replicas and flat control cavity replicas connected are separated at the periphery of the arrangement.
11. The method according to modality 9 or 10, in which each replica of nozzle orifices and their connected flat control cavity replica is configured (that is, the size, shape and design) so that, after removal of the corresponding flat control sacrifice cavity to form the upper flat surface of the nozzle, the holes
62 I 77 nozzle passages are configured to form at least one shape or output control feature (for example, a fuel flow or plume) of the fluid flow.
Such characteristics can be used to control the shape of a fluid that exits the nozzle through-holes.
For example, these characteristics can be used 5 to control (for example, interrupt) the flow of fuel flowing out of the nozzle passage holes in an effort to form a fuel plume with fuel droplets of a size, shape and distribution desired.
Such fluid outlet shape control features may include (a) an outlet opening of the nozzle through hole that has a star shape, cross shape or X shape, for example, as shown in figures 31 to 37, (b) an inside surface of the nozzle through hole which is fluted to provide rotation for the quel fluid flows through the nozzle through holes in a direction around the longitudinal axis of the corresponding nozzle through hole, before exiting through the corresponding outlet opening of the nozzle through hole, for example, as shown in Figure 14 and indicated by Figure 9A, (c) at least one or a plurality of nozzle through holes each having at least at least one, two or more curved interior surfaces (for example, quarter-turn interior surfaces) and at least one, two or more groove-shaped outlet openings, where the surface (s) ) inter The curved value (s) of each nozzle through hole is configured to cause fluid to exit through the outlet opening (s) at an angle (for example, an acute angle), from the longitudinal axis through the nozzle through hole, for example, as shown in Figures 31 to 36 and 38, or (d) any combination of (a) to (c). In addition to the related teachings found elsewhere in this document, it has also been found that by controlling the direction of the liquid that sail from the orifices of the mouth (for example, by adjusting the relative orientation of the curved inner surface or quarter-circle orifices through the nozzle), the resulting fluid outlet (e.g., a stream and / or fluid plume droplets) can be directed as desired.
It may be desirable to control the direction of a fuel fluid outlet, for example, to direct the current and / or fuel plume in one or more desired locations inside an internal combustion engine, oven, etc. combustion chamber, or to avoid fuel collision, for example, on the engine piston, valve and / or combustion chamber wall of an internal combustion engine. Such a fuel collision can cause any combination of: (a) cooling of the fuel, valve, piston and / or combustion chamber during the combustion process, (b) removal of oil or other lubricant from the valve and / or piston (which can cause harmful wear), (c) "loss by wind friction" harmful, and / or (d) the fuel being misdirected away from the periphery of the spark plug in the combustion chamber.
Such a characteristic can
63 I 77 also have the ability to generate a non-symmetric fuel flow and / or plume, which may have some advantages by controlling the size, distribution, location or other aspects of the fuel flow and / or plume within the combustion chamber.
12. The method according to any of modalities 1 to 11, in which at least 5 of the replicas of flat control cavities are not connected (for example, are not in fluid communication with) a replica of standard nozzle holes microstructured mold. It may be desirable that none of the replicas of flat control cavities be connected to any of the replicas of nozzle orifices.
13. The method according to any of modalities 1 to 12, wherein the nozzle has a peripheral edge, and the microstructured pattern of nozzle formation comprises a nozzle separation characteristics that form or at least deflate the peripheral edge of the nozzle . The nozzle separation characteristics can be in the form of a separation ring for each nozzle.
14. The method according to modality 13, in which at least three, and preferably 4, replicates of flat control cavities are formed in the nozzle separation characteristic. Replicas of flat control cavities may be, but need not be, the only such characteristics of forming part of the microstructured mold pattern.
15. The method according to any of modalities 1 to 14, wherein providing a microstructured mold pattern comprises: (a) forming a third material in a microstructured mold forming pattern comprising a plurality of replication of forming characteristics nozzle orifices and replicates of flat control cavity-forming characteristics. Each nozzle orifice forming feature replica may or may not be connected to (for example, being in fluid communication with) at least one flat control cavity forming feature replica. (b) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with replicas of forming characteristics of nozzle orifices being substantially negative replicas (i.e., a negative replica of the whole, the majority, or at least a substantial portion) of the nozzle orifice replicas, and the replicas of flat control cavity forming characteristics being replicas substantially negative (i.e., a negative replica of the whole, the majority, or at least a substantial portion) of the replicate flat control cavities. Each of the above described characteristics affecting fluid flow, fluid channel or recess characteristics, and fuel plume shape control characteristics can each be formed initially as a corresponding characteristic in any microstructured mold forming pattern being used for making the nozzle, or if a microstructured mold forming pattern is not used (i.e., the microstructured mold pattern is formed without such a step), then these characteristics can initially be formed in the microstructured mold pattern.
16. The method according to modality 15, in which the fourth material 5 comprises a plurality of different material rooms, and the pattern of microstructured mold is formed by separate deposition of each of the four materials as a layer over the whole, a most or at least a substantial portion of the microstructured molding pattern so that the resulting microstructured mold pattern comprises an accumulation or otherwise comprises several layers, with each layer being a fourth different material.
17. The method according to modality 15 or 16, in which the first material is different from the fourth material, the second material is different from the first and third materials, and the third material is different from the fourth material.
18. The method according to modality 17, in which the first material is the same or different from the third material, and the second material is the same or different from the fourth material.
19. The method according to any of modalities 15 to 18, in which the third material is capable of undergoing a multi-photon curing reaction while simultaneously absorbing several photons, and the microstructured pattern of mold formation is formed on the third material using a multiphotonic process that causes a multiphoton curing reaction in the third absorbent material while simultaneously absorbing multiple photons at desired / specified locations in the third material, which causes the microstructured mold formation pattern to be constructed.
20. A method for making a nozzle, the method comprising: (a) providing a first material, such as one that is capable of undergoing a multiphotonic reaction while simultaneously absorbing several photons; (a) forming a first material in a first microstructured pattern using (1) a multiphotonic process that causes a multiphotonic reaction in the first material while simultaneously absorbing multiple photons at desired / specified locations within the first material and / or (2) a process of sintering, with the first microstructured pattern comprising a plurality of replicas of nozzle orifice characteristics for forming nozzle through holes and replicas of flat control cavity formation characteristics. Each nozzle orifice forming feature replica may or may not be connected to (for example, being in fluid communication with) at least one flat control cavity forming feature replica. (b) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a second material in a second pattern
65 I 77 microstructured using the first microstructured pattern, with the second microstructured pattern defining at least a portion of a mold cavity and comprising a substantially negative replica (i.e., a negative replica of all, most, or at least one substantial portion) of the first microstructured pattern; That is, the second microstructured pattern comprises a plurality of replicas of nozzle holes and replicates of flat control cavities.
Each nozzle orifice replica may or may not be connected to (for example, be in fluid communication with) at least one flat control cavity replica. (c) molding a third material into a third microstructured pattern using the second microstructured pattern of the mold, with the third microstructured pattern comprising a plurality of nozzle hole forming characteristics and flat control cavity forming characteristics.
Each nozzle orifice forming feature may or may not be connected to (for example, being in fluid communication with) at least one flat control cavity forming feature.
The third microstructured pattern comprises a substantially negative replica (i.e., a negative replica of all, most, or at least a substantial portion) of the second microstructured pattern.
In other words, the third microstructured pattern comprises a substantially positive replica (i.e., a positive replica of all, the majority, or at least a substantial portion) of the first microstructured pattern, including the plurality of replicas of orifice characteristics. nozzle and replicates of characteristics of formation of flat control cavities; (d) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a fourth material in a fourth microstructured pattern using the third microstructured pattern, with the fourth microstructured pattern comprising a plurality of nozzle preform orifices and flat sacrifice control cavities, and each nozzle preform orifice comprising an inlet opening and may or may not be connected to (e.g., be in fluid communication with) the least one flat sacrifice control cavity.
The fourth microstructured pattern comprises a substantially negative replica (i.e., a negative replica of the whole, the majority, or at least a substantial portion) of the third microstructured pattern, including the plurality of nozzle orifice forming characteristics and forming characteristics of flat control cavities.
That is, the fourth microstructured pattern comprises a substantially positive replica (that is, a positive replica of the whole, the majority, or at least a substantial portion) of the second microstructured pattern; and (e) forming a nozzle from the fourth microstructured pattern, the formation of the nozzle comprising the removal (for example, by electrical discharge machining, mechanical grinding, etc.) sufficient of the fourth material to remove the cavities from
66 I 77 control sacrifice planes, in order to transform a top surface of the microstructured standard room into a flat top surface (that is, planarize the top surface) of the nozzle, and form each of the preform holes of nozzle in a finished nozzle through hole comprising an inlet opening and at least one connected outlet opening (for example, being in fluid communication with) the inlet opening through a cavity defined by an inner surface. The nozzle can also have a flat bottom surface, and the flat top surface and the flat bottom surface can be parallel to each other or at an acute angle to each other.
21. The method according to modality 20, in which the second material is different from the first material, the third material is different from the second material, and the fourth material is different from the first and third material
22. The method according to the · 21 modality, in which the third material is the same or different from the first material, and the fourth material is the same or different from the second material.
23. A method for making a nozzle, the method comprising: (a) providing a microstructured mold pattern defining at least a portion of a mold cavity and comprising a plurality of nozzle orifice replicas; (b) molding a first material into a microstructured nozzle pattern using the microstructured mold pattern, with the microstructured nozzle pattern comprising a plurality of nozzle orifice characteristics; (c) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the pre nozzle shape comprising a plurality of nozzle preform holes, the second material comprising a plurality of different second materials, and the nozzle preform is formed by separate deposition of each of the second materials, as a separate layer or other portion on the whole, most, or at least a substantial portion of the microstructured nozzle formation pattern so that the resulting nozzle preform, and therefore the nozzle, comprises an accumulation of, or other mode comprises multiple layers or portions, with each portion or layer being a second different material; and (d) forming a nozzle from the nozzle preform, forming the nozzle comprising removing (for example, by electrical discharge machining, mechanical grinding, etc.) sufficient of the second material to open an outlet opening at each one of the nozzle preform holes and thus form each of the nozzle preform holes in a finished nozzle through hole comprising an inlet opening and
67 I 77 at least one exit opening connected to (for example, being in fluid communication with) the entrance opening of a hollow cavity defined by an interior surface.
24. The method according to modality 23, in which the plurality of different second materials is at least three different second materials, the first of the 5 second materials being deposited as a layer on the microstructured nozzle forming pattern forms an electrically layer conductive.
25. The method according to modality 23 or 24, in which none of the multiple layers is in the form of an initial electrically conductive fine particle layer.
26. The method according to any of the modalities 23 to 25, in which at least one of the multiple layers is a corrosion inhibitor, a combustion by-product deposit inhibitor, ceramic, or metal alloy.
7. The method according to any of embodiments 23 to 26, wherein the provision of a microstructured mold pattern comprises: (a) forming a third material in a microstructured mold forming pattern comprising a plurality of replicas of characteristics forming nozzle holes; (b) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with replicas of forming characteristics of nozzle orifices being substantially negative replicas (i.e., a negative replica of the whole, the majority, or at least a substantial portion) of the nozzle orifice replicas.
28. The method according to modality 27, in which the fourth material comprises a plurality of different material rooms, and the pattern of microstructured mold is formed by separate deposition of each of the four materials as a layer over the whole, the largest part or at least a substantial portion of the microstructured molding pattern so that the resulting microstructured mold pattern comprises an accumulation or otherwise comprises several layers, with each layer being a fourth different material.
29. The method according to modality 27 or 28, in which the first material is different from the fourth material, the second material is different from the first and third materials, and the third material is different from the fourth material.
30. The method according to modality 29, in which the first material is the same or different from the third material, and the second material is the same or different from the fourth material.
31. A method for making a mouthpiece, the method comprising:
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(a) providing a first material, such as, for example, one that is capable of undergoing a multiphotonic reaction when simultaneously absorbing several photons; (a) forming a first material in a first microstructured pattern using (1) a multiphotonic process that causes a multiphotonic reaction in the first material by simultaneously absorbing multiple photons at desired / specified locations within the first material and / or (2) a process sintering, with the first microstructured pattern comprising a plurality of replicas of nozzle orifice characteristics for forming nozzle through-holes; (b) sintering, metal injection molding (MIM), electro-deposition, or otherwise the deposition or the formation of a second material in a second microstructured pattern using the first microstructured pattern, with the second microstructured pattern defined by at least a portion of a mold cavity and comprising a substantially negative replica (i.e., a negative replica of all, most, or at least a substantial portion) of the first microstructured pattern; That is, the second microstructured pattern comprises a plurality of nozzle orifice replicas. (c) molding a third material into a third microstructured pattern using the second microstructured pattern of the mold, with the third microstructured pattern comprising a plurality of nozzle orifice characteristics.
The third microstructured pattern comprises a substantially negative replica (i.e., a negative replica of all, most, or at least a substantial portion) of the second microstructured pattern.
In other words, the third microstructured pattern comprises a substantially positive replica (i.e., a positive replica of all, the majority, or at least a substantial portion) of the first microstructured pattern, including the plurality of replicas of orifice characteristics. nozzle; (d) sintering, metal injection molding (MIM), electro-deposition, or otherwise depositing or forming a fourth material in a fourth microstructured pattern using the third microstructured pattern, with the fourth microstructured pattern comprising a plurality of nozzle preform holes to a fourth material comprising a plurality of different material quarters, and the standard microstructured fourth is formed by separate deposition of each of the material quarters as a layer over the whole, most or at least a substantial portion of the microstructured fourth pattern so that the resulting nozzle preform, and therefore the nozzle, comprises an accumulation or otherwise comprises multiple layers, with each layer being a different fourth material; and (e) forming a nozzle from the fourth microstructured pattern, the formation of the nozzle comprising the removal (for example, by electrical discharge machining, mechanical grinding, etc.) sufficient of the fourth material to open an outlet opening in each of the nozzle preform holes and thus form each of the nozzle preform holes in a finished nozzle through hole comprising an inlet opening and at least one outlet opening connected to (for example, being in communication fluid with) the inlet opening of a hollow cavity defined by an inner surface.
32. The method according to modality 20 or 31, in which the first material comprises poly (methyl methacrylate).
33. The method of modality 20 or 31, in which the first material is capable of undergoing a biphotonic reaction.
34. The method of modality 20 or 31, in which the first microstructured pattern comprises a plurality of distinct microstructures.
35. The method of modality 34, in which the plurality of different microstructures comprises a distinct microstructure which is a three-dimensional rectilinear body.
36. The method of modality 34, wherein the plurality of distinct microstructures comprises a distinct microstructure which is a portion of a three-dimensional rectilinear body.
37. The method of modality 34, in which the plurality of distinct microstructures comprises a distinct microstructure which is a three-dimensional curvilinear body.
38. The method of modality 34, wherein the plurality of distinct microstructures comprises a distinct microstructure which is a portion of a three-dimensional curvilinear body.
39. The method of modality 34, wherein the plurality of distinct microstructures comprises a portion of a polyhedron.
40. The method of modality 34, wherein the plurality of distinct microstructures comprises a portion of a cone.
41. The method of modality 34, in which the plurality of different microstructures comprises a different tapered microstructure.
42. The method of modality 34, in which the plurality of distinct microstructures comprises a distinct spiral microstructure.
43. The method of modality 20 or 31, in which the first microstructured pattern is formed in the first material using a biphotonic process.
44. The method of modality 20 or 31, wherein the step of forming the first microstructured pattern in the first material comprises exposing at least a portion of the first material to cause simultaneous absorption of multiple photons.
45. Method 44, wherein the step of forming the first microstructured pattern in the first material comprises removing the exposed portions of the first material.
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46. Method 44, wherein the step of forming the first microstructured pattern in the first material comprises removing the unexposed portions of the first material.
47. The method of modality 20 or 31, in which the replication of the first microstructured pattern 5 in the second material comprises the electroplating of the first microstructured pattern.
48. The method of modality 20 or 31, in which the second material comprises an electroplating material.
49. Method 20 or 31, wherein the mold comprises a metal.
50. The 20 or 31 modalid method, where the mold comprises a Ni.
51. The 20 or 31 modality method, wherein the second microstructure pattern is at least substantially a negative replica of the first microstructure pattern.
52. The method of modality 20 or 31, wherein the third microstructured pattern is at least substantially a negative replica of the second microstructured pattern and at least substantially a positive replica of the first microstructured pattern.
53. The method of modality 20 or 31, wherein the step of molding a third material into a third microstructured pattern using the second microstructured pattern of the mold comprises injection molding.
54. Method 20 or 31, wherein the third material comprises a polymer.
55. Method 20 or 31, wherein the third material comprises polycarbonate.
56. Method 20 or 31, wherein the second mold comprises a polymer.
57. The method of modality 20 or 31, wherein the third microstructured pattern is at least substantially a negative replica of the second microstructured pattern.
58. The method of modality 20 or 31, in which the step of forming a fourth material in a fourth microstructured pattern using the third microstructured pattern comprises electroplating the third microstructured pattern with the fourth material.
59. The method of modality 20 or 31, wherein the step of forming a fourth material in a fourth microstructured pattern using the third microstructured pattern comprises coating the third microstructured pattern with the fourth material.
60. The 20 or 31 modality method, in which the step of removing enough of the fourth material is carried out by a method of mechanical grinding or by electrical discharge machining.
61. The method of modality 20 or 31, in which the fourth material comprises an electroplating material.
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62. The method of modality 20 or 31, wherein the nozzle comprises a metal, a ceramic, or a combination of a metal and a ceramic.
63. The method of modality 20 or 31, in which the mouthpiece comprises a ceramic selected from the group comprising silica, zirconia, alumina, titanium oxide, 5 or yttrium, strontium, barium, hafnium, niobium, tantalum, tungsten, oxides, bismuth, molybdenum, tin, zinc, and lanthanide elements that have atomic numbers in the range 57 to 71, cerium and combinations thereof. Microstructured standard modalities
64. Microstructured pattern for forming a nozzle preform comprising a plurality of nozzle preform holes, flat sacrifice control cavities and an upper flat periphery, the microstructured pattern comprising: a plurality of nozzle forming features nozzle orifices which are substantially negative replicas of the nozzle preform orifices, and a plurality of flat control cavity forming characteristics which are substantially negative replicas of the flat sacrifice control cavities.
65. The microstructured standard according to modality 64, in which each nozzle orifice forming feature may or may not be connected to at least one flat control cavity forming feature.
66. The microstructured pattern according to mode 64 or 65, further comprising an annular peripheral wall to define the outer planar periphery of the nozzle preform.
67. The microstructured pattern according to modality 66, in which the peripheral wall is connected to at least one planar control characteristic. Nozzle Preform Modes
68. A nozzle preform for forming a nozzle comprising a plurality of nozzle through holes, each nozzle through hole comprising an inlet opening and at least one outlet opening connected to (e.g. being in fluid communication with) the entrance opening of a cavity defined by an interior surface, the nozzle preform comprising: a plurality of nozzle preform holes corresponding to the nozzle passage holes; and a plurality of flat sacrifice control cavities, wherein each of said nozzle preform holes may or may not be connected to at least one of said flat sacrifice control cavities.
69. The nozzle preform according to modality 68, in which each nozzle preform orifice is in fluid communication with at least one flat sacrifice control cavity.
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70. The nozzle preform according to mode 68 or 69, wherein the nozzle preform and, therefore, the nozzle comprises an accumulation of multiple layers, with each layer being a different material.
71. The nozzle preform according to modality 70, in which the multiple 5 layers are deposited layers of different materials, in the form of a monolithic structure.
72. The nozzle preform according to mode 70 or 71, wherein the multiple layers are at least three layers, with a first layer of multiple layers being an electrically conductive layer.
73. The nozzle preform according to any of the modalities 70 to 72, wherein none of the multiple layers is in the form of a layer of fine electrically conductive starting particle.
74. The nozzle preform according to any of the modalities 70 to 73, wherein the material forming at least one of the multiple layers is a corrosion inhibitor, a combustion by-product deposit inhibitor, ceramic, or alloy of metal. Nozzle modes
75. A nozzle comprising a microstructured pattern comprising a plurality of nozzle through holes, each nozzle through hole comprising an inlet opening and at least one connected outlet opening (for example, being in fluid communication with) the inlet opening through a hollow cavity defined by an inner surface, in which the microstructured pattern has an outer periphery, and the nozzle comprises an accumulation of multiple layers, with each layer being a different material, and with or (a) none of the multiple layers being in the form of a thin electrically conductive initial particle layer, (b) the multiple layers being at least three layers, or (c) both (a) and (b).
76. The nozzle according to modality 75, in which the multiple layers are deposited layers of different materials, in the form of a monolithic structure.
77. The nozzle preform according to mode 75 or 76, wherein the multiple layers are at least three layers, with a first layer of multiple layers being an electrically conductive layer.
78. The nozzle according to any of the modalities 75 to 77, wherein the material forming at least one of the multiple layers is a corrosion inhibitor, a combustion by-product deposit inhibitor, ceramic, or metal alloy. The nozzle according to any of the modalities 75 to 78 further comprising a flat bottom surface and a flat top surface, wherein the flat bottom surface and the flat top surface are either parallel to each other or at an acute angle each other.
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80. The nozzle according to any of the modalities 75 to 79, wherein each of the multiple layers is an electro-deposited layer of metallic material, inorganic non-metallic material, or a combination thereof.
81. The nozzle according to any of the modalities 75 to 79, wherein each of the multiple layers is a layer of sintered metal, inorganic non-metallic material, or a combination thereof.
82. The nozzle according to any of the modalities 75 to 81, wherein none of the multiple layers in the form of a thin layer of electrically conductive starting particle. . 83. The nozzle preform according to any of the modalities 75 to 82, in which the multiple layers are at least three layers.
84. The nozzle according to any of the modalities 75 to 83, additionally comprising at least one or more fluids (i.e., a gas or liquid), channel or recess characteristics connecting at least one nozzle through hole for (a ) at least one other nozzle through hole, (b) a portion of the outer periphery of the microstructured pattern, or (c) both (a) and (b).
85. The nozzle according to any of the modalities 75 to 84, further comprising at least one fluid feather shape control feature to control the shape of a feather formed by a fluid flowing through and exiting the outlet openings of said nozzle passage holes.
86. The nozzle according to modality 85, in which the fluid feather shape control feature is operatively adapted to break a stream of fluid flowing out of said nozzle through holes to control the size and distribution of drops of fluid forming the plume.
87. The nozzle according to modality 86, in which the fuel feather shape control feature comprises (a) at least one of the outlet openings having a cross shape or X shape, (b) the inner surface of at least one of the nozzle passage holes being fluted, so as to give rotation to a fluid flowing through the nozzle through holes in a direction around the longitudinal axis of the nozzle holes, before exiting through the opening of the nozzle. corresponding outlet of the nozzle through hole, (c) at least one or a plurality of nozzle through holes that have at least one, two or more interior curved surfaces (e.g., quarter-turn interior surfaces) and at least one, two or more openings in the form of an exit slit, in which the curved inner surface (s) of the nozzle orifices are configured to cause the fluid to escape through the ( s) outlet opening (s) with an angle ( for example, an acute angle), from the longitudinal axis of the nozzle holes, or (d) any combination of (a) to (c).
88. The nozzle according to any of the modalities 75 to 87, further comprising at least one through-hole of the nozzle having an interior surface, which comprises at least one or more characteristics affecting the flow of fluid to induce or otherwise cause cavitations, turbulence, or otherwise obstruct the flow of a fluid 5 (for example, a liquid fuel) through the nozzle so as to positively affect a plume of droplets formed by the fluid passing through the nozzle's through hole and exiting the outlet opening of the corresponding nozzle through hole.
89. The nozzle according to mode 88, wherein the characteristic affecting the flow of fluid comprises at least one or any combination of protrusions, 10O continuous annular ribs, separate discontinuous ribs and striations.
90. A nozzle comprising: a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle outlet opening comprising an inlet opening and at least one connected outlet opening (for example, in fluid communication) com) the entrance opening of a cavity defined by an interior surface, and the microstructured pattern having an external periphery; and at least one or more fluids (i.e., a gas or liquid), channel or recess features connecting at least one nozzle through hole to (a) at least one other nozzle through hole, (b) a portion the outer periphery of the microstructured pattern, or (c) both (a) and (b).
91. A nozzle comprising: a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle outlet opening comprising an inlet opening and at least one connected outlet opening (for example, in fluid communication) com) the entrance opening of a cavity defined by an interior surface, and the microstructured pattern having an external periphery; and at least one fluid feather shape control feature for controlling the shape of a feather formed by a fluid that flows through and exits the outlet openings of said nozzle through holes.
92. The nozzle according to mode 91, wherein the fluid feather shape control feature is operatively adapted to break a stream of fluid flowing out of said nozzle through holes to control the size and distribution of drops of fluid forming the plume.
93. The nozzle according to mode 92, in which the fuel feather shape control feature comprises (a) at least one of the outlet openings having a cross shape or X shape, (b) the inner surface of at least one of the nozzle passage holes being fluted, so as to give a rotation to a fluid
75 I 77 flowing through the nozzle through holes in a direction around the longitudinal axis of the nozzle holes, before exiting through the corresponding outlet opening of the nozzle through hole, (c) at least one or a plurality of through-holes of the nozzle having at least one, two or more interior curved surfaces (for example, 5 quarter-turn interior surfaces) and at least one, two or more opening slit-shaped openings, in which the curved inner surface (s) of the nozzle orifices are configured to cause fluid to exit through the outlet opening (s) at an angle (for example, an acute angle) ), from the longitudinal axis of the nozzle holes, or (d) any combination of (a) to (c).
94. A bocjl that understands: a pattern! microstructured comprising a plurality of nozzle through holes, with each nozzle outlet opening comprising an inlet opening and at least one outlet outlet connected (for example, in fluid communication with) the inlet opening of a cavity defined by an inner surface, and the microstructured pattern having an outer periphery; and at least one through-port of the nozzle having an interior surface, comprising at least one or more features affecting the flow of fluid to induce or otherwise cause cavitation, turbulence, or otherwise obstruct the flow of a fluid (e.g. a liquid fuel) through the nozzle so as to positively affect a plume of droplets formed by the fluid passing through the nozzle through hole and exits the corresponding nozzle through outlet opening.
95. The nozzle according to modality 94, in which the characteristic affecting the fluid flow comprises at least one or any combination of protrusions, continuous annular ribs, separate discontinuous ribs and striations.
96. The nozzle according to any of the modes 75 to 95, wherein the inlet and outlet opening of each through-hole of the nozzle have different shapes.
97. The nozzle according to any of the 75 to 95 modes, in which the inlet and outlet opening of each through-hole nozzle have different shapes, the shapes being selected from the group of shapes consisting of an elliptical shape, a circular shape, a race track shape.
98. The nozzle according to any of the modes 75 to 95, wherein only one of the inlet and outlet opening of at least one nozzle through hole is shaped with a perimeter comprising outer arcs of circles juxtaposed, with the outer arches being connected by the curve like a fillet.
99. The nozzle according to any of the 75 to 98 modes, where each inlet opening has a diameter of less than 300 microns, 200 microns, or less than or equal to 160 microns.
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100. The nozzle according to any of the 75 to 99 modalities, in which each outlet opening has a diameter less than 300 microns, less than 100 microns, or less than or equal to 40 microns.
101. The nozzle according to any of the 75 to 100 modes, where the 5 nozzle is a fuel injector nozzle
102. The nozzle according to any of the modalities 75 to 101, wherein the nozzle comprises a metallic material, an inorganic non-metallic material (for example, a ceramic), or a combination thereof.
103. The nozzle according to mode 102, in which the nozzle comprises a ceramic selected from the group which comprises silica, zirconia, alumina, titanium oxide, or oxides of yttrium, strontium! barium, hafnium, niobium, tantalum, tungsten, bismuth, m11ibdenum, tin, zinc, and lanthanide elements that have atomic numbers in the range 57 to 71, cerium and combinations thereof.
104. The nozzle according to any of the modalities 75 to 103, wherein the inner surface of at least one through-hole of the nozzle has a cross section that rotates from its inlet opening to its outlet opening.
105. The nozzle according to mode 104, in which the cross section has at least one of an increase in the rotation speed, a decrease in the rotation speed, a constant rotation speed, or a combination thereof.
106. The nozzle according to any of the modalities 75 to 105, wherein at least one nozzle through hole is a plurality of nozzle through holes arranged in a set of concentric circles, comprising an outer circle, in which the nozzle through holes are arranged in such a way that no diameter of the outermost circle comprises at least one nozzle through hole of each circle in the set of concentric circles.
107. The nozzle according to mode 106, in which each circle in the set of concentric circles comprises distinctly spaced nozzle passage holes Thickness of the veneer layer; Preferred initial particle layer thickness :::; 50 J.Jm or :::; 100 IJm with a maximum thickness of :::; 200 IJm. Galvanizing thickness range of (some) protective materials: Hard chrome 8 j.Jm (0.0003 ") to 50 j.Jm (0.002"). Nickel without external current source 2.5! Jm (0.0001 ") to 127! Jm (0.005"). Zinc 5 j.Jm (0.0002 ") to 15 j.Jm (0.0006") PTFE / level / phosphorus
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Ion bombardment and ion plating could be other coating methods.
It may be desirable for the thickness of a fuel injector nozzle to be at least about 100 µm, preferably greater than about 200 µm; and less than 5 about 3 mm, preferably less than about 1 mm, more preferably less than about 500 µm.
All patents, patent applications and other publications cited above are hereby incorporated by reference in this document, as if reproduced in their entirety.
While specific examples of the invention are described in detail above to facilitate explanation of various aspects of the invention, it should be understood that the intention is not to limit the invention to the characteristics of the examples.
Instead, the intention is to cover all modifications, modalities and alternatives that fit the spirit and scope of the invention, as defined by the appended claims.

权利要求:
Claims (23)
[1]
1. Method for making a nozzle, said method FEATURED by the fact that it comprises: (a) providing a microstructured mold pattern defining at least a portion of a mold and comprising a plurality of nozzle orifice replicas and cavity replicas flat control; (b) molding a first material into a microstructured nozzle forming pattern using the microstructured mold pattern, with the microstructured nozzle forming pattern comprising a plurality of nozzle orifice forming characteristics molded from replicas of nozzle orifices and characteristics of flat control cavity formation molded from replicates of flat control cavities; (c) forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the nozzle preform comprising a plurality of nozzle preform holes formed from orifice forming characteristics of nozzles and flat sacrifice control cavities formed from characteristics of flat control cavity formation; and (d) forming a nozzle from the nozzle preform, said nozzle formation comprising removing sufficient of the second material to remove the flat sacrifice control cavities, so as to transform a top surface of the nozzle preform. nozzle on a flat top surface of the nozzle, and to transform each of the nozzle preform holes into a nozzle through hole, removing the flat sacrifice control cavities allows the nozzle through the holes to be open as desired.
[2]
2. Method according to claim 1, CHARACTERIZED by the fact that the second material comprises a plurality of different second materials, and the nozzle preform is formed by depositing each of the second materials as a layer on the pattern nozzle forming microstructure so that the resulting nozzle preform comprises an accumulation of multiple layers, with each layer being a different second material.
[3]
3. Method according to claim 1 or 2, CHARACTERIZED by the fact that the microstructured mold pattern comprises at least one fluid channel feature connecting at least one nozzle orifice replica to (a) at least one other replica nozzle orifice, (b), a portion of the mold beyond the outer periphery of the microstructured mold pattern, or (c) both (a) and (b).
[4]
4. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that there are at least three replicates of flat control cavities.
[5]
5. Method, according to claim 4, CHARACTERIZED by the fact that each nozzle orifice replica and its connected replica of planar control cavity are configured in such a way that after removal of the corresponding flat sacrifice control cavity, for To form the flat nozzle top surface, the nozzle through holes are configured to form at least one fuel feather shape control feature.
[6]
6. Method according to any one of claims 1 to 5, CHARACTERIZED by the fact that said supply of a microstructured mold pattern comprises: (a) forming a third material in a microstructured mold forming pattern comprising a plurality nozzle orifice characteristics replicas and flat control cavity formation characteristics replicas; and (b) forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with replicas of nozzle orifice characteristics being substantially negative replicas of replicas of nozzle orifices, and replicas of characteristics of flat control cavity formation being substantially negative replicas of flat control cavity replicas.
[7]
7. Method for making a nozzle, said method CHARACTERIZED by the fact that it comprises: (a) forming a first material in a first microstructured pattern that comprises a plurality of replicas of formation characteristics of nozzle orifices and replicas of formation characteristics flat control cavity; (b) forming a second material in a second microstructured pattern using the first microstructured pattern, with the second microstructured pattern defining at least a portion of a mold and substantially comprising a negative replica of the first microstructured pattern; (c) molding a third material into a third microstructured pattern using the second microstructured pattern of the mold, with the third microstructured pattern substantially comprising a negative replica of the second microstructured pattern; (d) forming a fourth material in a fourth microstructured pattern using the third microstructured pattern, with the fourth microstructured pattern comprising a plurality of nozzle preform holes and flat sacrifice control cavities that substantially form a negative replica of the third pattern microstructured; and (e) forming a nozzle from the fourth microstructured pattern, said nozzle formation comprising sufficient removal of the fourth material to remove the flat sacrifice control cavities, so as to form a top surface of the fourth microstructured pattern in one flat top surface of the nozzle, and form each of the nozzle preform holes into a nozzle through hole.
[8]
8. Method for making a nozzle, said method CHARACTERIZED by the fact that it comprises: (a) providing a microstructured mold pattern defining at least a portion of a mold and comprising a plurality of nozzle orifice replicas; (b) molding a first material into a microstructured nozzle pattern using the microstructured mold pattern, with the microstructured nozzle pattern comprising a plurality of nozzle orifice characteristics; (c) forming a second material in a nozzle preform using the microstructured nozzle forming pattern, with the nozzle preform comprising a plurality of nozzle preform holes, the second material comprising a plurality of different second materials, and the nozzle preform being formed by depositing each of the different second materials as a separate portion on the microstructured nozzle forming pattern so that the resulting nozzle preform comprises multiple portions, with each portion a second material being different; and (d) forming a nozzle from the nozzle preform, said nozzle formation comprising sufficient removal of the second material to open an outlet opening in each of the nozzle preform holes and the formation of each one of the nozzle preform holes in a nozzle through hole.
[9]
9. Method according to claim 8, CHARACTERIZED by the fact that said supply of a microstructured mold pattern comprises: (a) forming a third material in a microstructured mold forming pattern comprising a plurality of replicas of characteristics forming nozzle holes; and (b) forming a fourth material for the microstructured mold pattern using the microstructured mold forming pattern, with replicas of nozzle orifice characteristics being substantially negative replicas of replicas of nozzle orifices.
[10]
10. Method for making a nozzle, said method CHARACTERIZED by the fact that it comprises: (a) forming a first material in a first microstructured pattern comprising a plurality of replicas of nozzle orifice characteristics; (b) forming a second material in a second microstructured pattern using the first microstructured pattern, with the second microstructured pattern defining at least a portion of a mold and substantially comprising a negative replica of the first microstructured pattern;
(c) molding a third material into a third microstructured pattern using the second microstructured pattern of the mold, with the third microstructured pattern substantially comprising a negative replica of the second microstructured pattern; (d) forming a fourth material in a fourth microstructured pattern using the third microstructured pattern, with the fourth microstructured pattern comprising a plurality of nozzle preform holes, the fourth material comprising a plurality of different material quarters, and the fourth pattern microstructured is formed by depositing each of the material quarters as a layer in the standard microstructured room so that the resulting nozzle preform comprises an accumulation of multiple layers, with each layer being a different fourth material; and (e) forming a nozzle from the fourth microstructured pattern, said nozzle formation comprising sufficient removal of the fourth material to open an outlet opening in each of the nozzle preform holes and the formation of each one. holes in the nozzle preform in a nozzle through hole.
[11]
11. Method according to claim 7 or 10, CHARACTERIZED by the fact that the first microstructured pattern comprises a plurality of separate microstructures, and the plurality of distinct microstructures comprises a distinct microstructure which is a three-dimensional curvilinear body.
[12]
12. Microstructured pattern for the formation of a nozzle preform, CHARACTERIZED by the fact that it comprises a plurality of nozzle preform holes, flat sacrifice control cavities and an outer flat periphery, said microstructured pattern comprising: a plurality of nozzle orifice forming characteristics which are substantially negative replicas of the nozzle preform orifices, and a plurality of flat control cavity forming characteristics which are substantially negative replicas of the flat sacrifice control cavities.
[13]
13. Nozzle preform to form a nozzle, CHARACTERIZED in that it comprises a plurality of nozzle through holes, each nozzle through holes comprising an inlet opening and at least one outlet opening connected to the opening inlet of a hollow cavity defined by an inner surface, said nozzle preform comprising: a plurality of nozzle preform holes corresponding to the nozzle through holes; and a plurality of flat sacrifice control cavities, each of said nozzle preform holes being connected to at least one of said flat sacrifice control cavities.
[14]
14. Nozzle comprising a microstructured pattern, CHARACTERIZED by the fact that it comprises a plurality of nozzle through holes, each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening by a hollow cavity defined by an inner surface, wherein said microstructured pattern has an outer periphery, and said nozzle comprises an accumulation of multiple layers, with each layer being a different material, and with or (a) none of said multiple layers being in the form of a thin electrically conductive initial particle layer, (b) said multiple layers being at least three layers, or (c) both (a) and (b).
[15]
15. Nozzle according to claim 14, CHARACTERIZED by the fact that it additionally comprises at least one fluid channel feature connecting at least one nozzle through hole to (a) at least one other nozzle through hole, ( b) a portion of the outer periphery of said microstructured pattern, or (c) both (a) and (b).
[16]
16. Nozzle according to claim 14 or 15, CHARACTERIZED by the fact that it additionally comprises at least one fluid feather shape control feature to control the shape of a feather formed by a fluid that flows through and leaves the outlet openings of said nozzle through holes, wherein said fluid plume shape control feature is operatively adapted to break a stream of fluid flowing out of said nozzle through holes to control size and distribution drops of fluid forming the plume.
[17]
17. Nozzle, FEATURED by the fact that it comprises: a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening of a hollow cavity defined by an inner surface, and said microstructured pattern having an outer periphery; and at least one fluid channel feature connecting at least one nozzle through hole to (a) at least one other nozzle through hole, (b) a portion of the outer periphery of said microstructured pattern, or (c) both (a) and (b).
[18]
18. Nozzle, CHARACTERIZED by the fact that it comprises: a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening of a hollow cavity defined by an inner surface, and said microstructured pattern having an outer periphery; and at least one fluid feather shape control feature for controlling the shape of a feather formed by a fluid that flows through and exits the outlet openings of said nozzle through holes.
[19]
19. Nozzle according to claim 18, CHARACTERIZED by the fact that said fluid feather shape control feature is operatively adapted to break a fluid stream flowing out of said nozzle passage holes to control the size and distribution of drops of fluid forming the plume.
[20]
20. Nozzle, CHARACTERIZED by the fact that it comprises: a microstructured pattern comprising a plurality of nozzle through holes, with each nozzle through hole comprising an inlet opening and at least one outlet opening connected to the inlet opening of a hollow cavity defined by an inner surface, and said microstructured pattern having an outer periphery; and at least one nozzle through hole having an interior surface comprising at least one fluid flow that affects the characteristic to cause cavitation, turbulence, or otherwise obstruct the flow of a fluid through said nozzle, so as to affect positively a plume of drops formed by the fluid passing through said nozzle through hole and leaving the corresponding outlet opening of said nozzle through hole.
[21]
21. Nozzle according to any one of claims 14 to 20, CHARACTERIZED by the fact that each inlet opening has a diameter less than 300 microns.
[22]
22. Nozzle according to any of claims 14 to 21, CHARACTERIZED by the fact that each outlet opening has a diameter less than 300 microns, less than 100 microns, or less than or equal to 40 microns.
[23]
23. Nozzle according to any one of claims 14 to 22, CHARACTERIZED by the fact that the nozzle is a fuel injector nozzle.

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同族专利:

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公开号 | 公开日

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WO2012106512A3|2012-11-08|

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JP2017122455A|2017-07-13|

---

KR20140003581A|2014-01-09|

---

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---

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---

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---

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---

WO2012106512A2|2012-08-09|

---

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---

CA2826443A1|2012-08-09|

---

JP2014504699A|2014-02-24|

---

CN103459824B|2017-06-27|

---

CN103459824A|2013-12-18|

---

US10054094B2|2018-08-21|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3018262A|1957-05-01|1962-01-23|Shell Oil Co|Curing polyepoxides with certain metal salts of inorganic acids|

---

US3808006A|1971-12-06|1974-04-30|Minnesota Mining & Mfg|Photosensitive material containing a diaryliodium compound, a sensitizer and a color former|

---

US3729313A|1971-12-06|1973-04-24|Minnesota Mining & Mfg|Novel photosensitive systems comprising diaryliodonium compounds and their use|

---

US3779778A|1972-02-09|1973-12-18|Minnesota Mining & Mfg|Photosolubilizable compositions and elements|

---

US3741769A|1972-10-24|1973-06-26|Minnesota Mining & Mfg|Novel photosensitive polymerizable systems and their use|

---

AU497960B2|1974-04-11|1979-01-25|Minnesota Mining And Manufacturing Company|Photopolymerizable compositions|

---

US4250053A|1979-05-21|1981-02-10|Minnesota Mining And Manufacturing Company|Sensitized aromatic iodonium or aromatic sulfonium salt photoinitiator systems|

---

US4279717A|1979-08-03|1981-07-21|General Electric Company|Ultraviolet curable epoxy silicone coating compositions|

---

US4491628A|1982-08-23|1985-01-01|International Business Machines Corporation|Positive- and negative-working resist compositions with acid generating photoinitiator and polymer with acid labile groups pendant from polymer backbone|

---

JPS649184B2|1982-12-29|1989-02-16|Mitsubishi Rayon Co|

---

US4642126A|1985-02-11|1987-02-10|Norton Company|Coated abrasives with rapidly curable adhesives and controllable curvature|

---

CA1254238A|1985-04-30|1989-05-16|Alvin P. Gerk|Process for durable sol-gel produced alumina-basedceramics, abrasive grain and abrasive products|

---

US4652274A|1985-08-07|1987-03-24|Minnesota Mining And Manufacturing Company|Coated abrasive product having radiation curable binder|

---

CA1323949C|1987-04-02|1993-11-02|Michael C. Palazzotto|Ternary photoinitiator system for addition polymerization|

---

US4859572A|1988-05-02|1989-08-22|Eastman Kodak Company|Dye sensitized photographic imaging system|

---

JPH0710471B2|1989-09-25|1995-02-08|株式会社日立製作所|Concentric coupling method for precision parts composed of multiple members, and method for assembling fuel injection nozzle using the same|

---

JPH0395073U|1990-01-18|1991-09-27|

---

JP2519568Y2|1990-08-31|1996-12-04|いすゞ自動車株式会社|Fuel injection nozzle|

---

US5235015A|1991-02-21|1993-08-10|Minnesota Mining And Manufacturing Company|High speed aqueous solvent developable photopolymer compositions|

---

TW268969B|1992-10-02|1996-01-21|Minnesota Mining & Mfg|

---

DE4404021A1|1994-02-09|1995-08-10|Bosch Gmbh Robert|Nozzle plate, in particular for injection valves and methods for producing a nozzle plate|

---

JPH07289953A|1994-03-03|1995-11-07|Nippondenso Co Ltd|Fluid injecting nozzle|

---

DE4409848A1|1994-03-22|1995-10-19|Siemens Ag|Device for metering and atomizing fluids|

---

US5856373A|1994-10-31|1999-01-05|Minnesota Mining And Manufacturing Company|Dental visible light curable epoxy system with enhanced depth of cure|

---

WO1996030643A1|1995-03-29|1996-10-03|Robert Bosch Gmbh|Perforated disc, especially for injection valves|

---

US5924634A|1995-03-29|1999-07-20|Robert Bosch Gmbh|Orifice plate, in particular for injection valves, and method for manufacturing an orifice plate|

---

CN1149907A|1995-03-29|1997-05-14|罗伯特·博施有限公司|Process for producing perforated disk|

---

DE19527846A1|1995-07-29|1997-01-30|Bosch Gmbh Robert|Valve, in particular fuel injector|

---

WO1998021521A1|1996-11-12|1998-05-22|California Institute Of Technology|Two-photon or higher-order absorbing optical materials and methods of use|

---

US6608228B1|1997-11-07|2003-08-19|California Institute Of Technology|Two-photon or higher-order absorbing optical materials for generation of reactive species|

---

US6025406A|1997-04-11|2000-02-15|3M Innovative Properties Company|Ternary photoinitiator system for curing of epoxy resins|

---

US5998495A|1997-04-11|1999-12-07|3M Innovative Properties Company|Ternary photoinitiator system for curing of epoxy/polyol resin compositions|

---

US5859251A|1997-09-18|1999-01-12|The United States Of America As Represented By The Secretary Of The Air Force|Symmetrical dyes with large two-photon absorption cross-sections|

---

US5770737A|1997-09-18|1998-06-23|The United States Of America As Represented By The Secretary Of The Air Force|Asymmetrical dyes with large two-photon absorption cross-sections|

---

US5933700A|1998-09-21|1999-08-03|Tilton; Charles L|Method for manufacturing pressure swirl atomizers|

---

US6100405A|1999-06-15|2000-08-08|The United States Of America As Represented By The Secretary Of The Air Force|Benzothiazole-containing two-photon chromophores exhibiting strong frequency upconversion|

---

JP2001030306A|1999-07-27|2001-02-06|Nippon Sheet Glass Co Ltd|Resin erect lens array and its manufacture|

---

AU3505400A|1999-10-28|2001-05-08|3M Innovative Properties Company|Dental materials with nano-sized silica particles|

---

US6572693B1|1999-10-28|2003-06-03|3M Innovative Properties Company|Aesthetic dental materials|

---

US6387981B1|1999-10-28|2002-05-14|3M Innovative Properties Company|Radiopaque dental materials with nano-sized particles|

---

JP2002115627A|2000-10-05|2002-04-19|Optonix Seimitsu:Kk|Orifice plate and its manufacturing method|

---

US7393882B2|2002-01-31|2008-07-01|3M Innovative Properties Company|Dental pastes, dental articles, and methods|

---

US6824378B2|2002-05-31|2004-11-30|3M Innovative Properties Company|Microreplication tool with gas release features|

---

JP3759918B2|2002-10-16|2006-03-29|三菱電機株式会社|Fuel injection valve|

---

JP2004316598A|2003-04-18|2004-11-11|Denso Corp|Fuel injection nozzle for internal combustion engine|

---

JP3941109B2|2003-04-30|2007-07-04|株式会社デンソー|Fuel injection valve|

---

DE102004005727A1|2004-02-05|2005-09-01|Robert Bosch Gmbh|fuel injection system|

---

JP4345522B2|2004-03-03|2009-10-14|株式会社デンソー|X-ray material processing method|

---

JP2006002720A|2004-06-21|2006-01-05|Mitsubishi Electric Corp|Fuel injection device and method for manufacturing the same|

---

JP4324881B2|2004-10-26|2009-09-02|株式会社デンソー|Fuel injection valve|

---

CN101094898B|2004-12-29|2013-07-17|3M创新有限公司|Multi-photon polymerizable pre-ceramic polymeric compositions|

---

US7297374B1|2004-12-29|2007-11-20|3M Innovative Properties Company|Single- and multi-photon polymerizable pre-ceramic polymeric compositions|

---

US7237730B2|2005-03-17|2007-07-03|Pratt & Whitney Canada Corp.|Modular fuel nozzle and method of making|

---

DE102005017420A1|2005-04-15|2006-10-19|Robert Bosch Gmbh|Fuel injector|

---

US7583444B1|2005-12-21|2009-09-01|3M Innovative Properties Company|Process for making microlens arrays and masterforms|

---

JP2007182767A|2006-01-05|2007-07-19|Hitachi Ltd|Fuel injection valve|

---

WO2007112309A2|2006-03-24|2007-10-04|3M Innovative Properties Company|Process for making microneedles, microneedle arrays, masters, and replication tools|

---

EP2018263B1|2006-05-18|2017-03-01|3M Innovative Properties Company|Process for making light guides with extraction structures|

---

JP2008064038A|2006-09-07|2008-03-21|Denso Corp|Fuel injection device|

---

EP2207820A4|2007-10-11|2011-10-26|3M Innovative Properties Co|Highly functional multiphoton curable reactive species|

---

JP2009098237A|2007-10-15|2009-05-07|Toyota Central R&D Labs Inc|Nonreflective structure, optical element, metallic mold and their manufacturing method|

---

US20090308953A1|2008-06-16|2009-12-17|Amfog Nozzle Technology, Inc.|Atomizing nozzle|JP6129197B2|2011-11-02|2017-05-17|スリーエム イノベイティブ プロパティズ カンパニー|Nozzle manufacturing method|

---

US9516735B2|2012-07-13|2016-12-06|Perkinelmer Health Sciences, Inc.|Torches and methods of using them|

---

US10993309B2|2012-07-13|2021-04-27|Perkinelmer Health Sciences, Inc.|Torches and methods of using them|

---

CN104736836B|2012-08-01|2019-01-11|3M创新有限公司|Fuel injector with improved fuel draining coefficient|

---

KR101337713B1|2012-12-20|2013-12-06|주식회사 현대케피코|Vehicular gdi injector with valve seat body for fuel atomization|

---

CN104995396A|2012-12-21|2015-10-21|3M创新有限公司|Method for making a nozzle including injection molding|

---

JP6186130B2|2013-02-04|2017-08-23|日立オートモティブシステムズ株式会社|Fuel injection valve and fuel injection valve manufacturing method|

---

EP2808533B1|2013-05-29|2019-08-14|Delphi Technologies IP Limited|Fuel injector|

---

WO2015034780A1|2013-09-06|2015-03-12|3M Innovative Properties Company|Injection molded nozzle preform with undercut micro features|

---

US10830198B2|2015-08-27|2020-11-10|Westpoint Power Inc.|Deposit mitigation for gaseous fuel injectors|

---

SE539875C2|2015-09-14|2017-12-27|Scania Cv Ab|A fuel injector|

---

DE102016000761A1|2016-01-27|2017-07-27|Roman TANIEL|Emulsifying system and emulsifying method|

---

DE102016103202A1|2016-02-24|2017-08-24|Klingelnberg Ag|A method of providing a fluid delivery device and use of such|

---

US10697756B2|2016-09-15|2020-06-30|Delavan Inc.|3D scanning systems|

---

CN110100047A|2016-12-23|2019-08-06|3M创新有限公司|The method of electric casting micro structure product|

---

JP2020504262A|2016-12-23|2020-02-06|スリーエム イノベイティブ プロパティズ カンパニー|Fabrication of nozzle structures on structured surfaces|

---

WO2018116179A1|2016-12-23|2018-06-28|3M Innovative Properties Company|Nozzle structures with thin welding rings and fuel injectors using the same|

---

WO2019126457A1|2017-12-21|2019-06-27|3M Innovative Properties Company|Fluid injector nozzle with swirl chamber|

---

WO2019133585A1|2017-12-26|2019-07-04|3M Innovative Properties Company|Fuel injector nozzle structure with choked through-hole outlet opening|

---

CN108149281B|2018-01-12|2021-11-05|河南理工大学|Machining method of metal nozzle|

---

WO2019215642A1|2018-05-09|2019-11-14|3M Innovative Properties Company|Fuel injector nozzle plate and valve guide|

---

US11015559B2|2018-07-27|2021-05-25|Ford Global Technologies, Llc|Multi-hole fuel injector with twisted nozzle holes|

---

CN110801954A|2018-08-05|2020-02-18|大连理工大学|Nozzle with partially twisted 8-shaped spray holes|

---

CN110801948A|2018-08-05|2020-02-18|大连理工大学|Nozzle with torsional 8-shaped spray hole|

---

WO2020056270A1|2018-09-13|2020-03-19|3M Innovative Properties Company|Nozzle with counterbored through-hole|

---

CN109898104A|2019-02-20|2019-06-18|合肥永淇智材科技有限公司|A kind of FMM electroforming motherboard production method of conical mouths|

---

WO2020263400A1|2019-06-27|2020-12-30|The Regents Of The University Of California|Additive-free manufacturing of geometrically complex components for electrical energy storage systems|

---

CN110424032A|2019-09-10|2019-11-08|江苏师范大学|A kind of jet stream electric deposition device and its method for principal axis of pressing machine reparation|

法律状态:
2020-08-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2020-11-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-02-23| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

---

2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201161438848P| true| 2011-02-02|2011-02-02|

---

US61/438,848|2011-02-02|

---

PCT/US2012/023624|WO2012106512A2|2011-02-02|2012-02-02|Nozzle and method of making same|

---