奥地利专利AT515007A1 Material with multi-phase structure

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专利摘要:
The material having a multiphase structure comprising at least a first solid phase and at least one second solid phase is characterized in that the first phase and the second phase are each a metal, a metal alloy, a ceramic material or combinations thereof in the form of a composite material, the phases of the microstructure are macroscopically distinguishable from one another, the multi-phase microstructure is formed as an interstitial structure or as a three-dimensional interpenetration microstructure, the interstitial microstructure having the first phase as a matrix phase continuously occurring in three spatial dimensions and the second phase as a discontinuous randomly distributed intercalation phase; Phase is made by sintering.
公开号:AT515007A1
申请号:T829/2013
申请日:2013-10-28
公开日:2015-05-15
发明作者:
申请人:Neubauer Erich；
IPC主号:

专利说明:

The invention relates to a material having a multiphase structure comprising at least a first solid phase and at least one second solid phase, the individual phases being characterized in that they are present in a macrostructure and are distinguishable from one another with the naked eye.
The invention further relates to a method of making this material and to the use of the material. For jewelery, luxury items, and other items, components having a macrostructure (e.g., watch cases, rings, tags, etc.) made by multiple forming metal foil stacks are used. These components are characterized by a visually striking and attractive, two- or mehrfärbigesausausaus. The pattern is formed by arranging two or more different metals in a periodic or irregular manner, requiring a plurality of process steps. In addition, the process is limited to the use of ductile metals, i. on materials that can be reforested especially at room temperature without the use of temperature.
The individual process steps of the above-mentioned method can basically be described as follows. First, (1 >) metal foils of two or more metals are alternately stacked and then bonded together to form a multilayer semi-finished product via a pressure and temperature (2) diffusion process. From the multi-layer semifinished product, for example, one (3) rod is then cut out and this {4) is twisted, deformed or machined. Depending on the degree of deformation, in some cases intermediate (5) annealing is required between the forming steps to allow the semifinished product to be re-deformed. Deformation is usually associated with a hardening of the material. After annealing, semi-finishing is then transferred to the desired final contour (e.g., a ring) via (6) other mechanical machining processes (hammering, forging, wales, etc.) and then transferred to the (7) final product by over-cutting processes or grinding processes.
This technique described has several disadvantages: a) it is limited to metals that are very ductile and allow a high degree of deformation. The requirement for ductility often leads to the disadvantage that the achievable surface hardness is limited. For example, combinations of very ductile metals, such as silver and gold, can be deformed with other metals, such as copper, but the hardness of these materials is limited; b) it is limited to metals that are available in suitable starting form (e.g., films); c) many process steps must be done by hand, which limits automation or large-scale manufacturing; d) ceramic materials or mixtures of metals and ceramics can not be produced with this technology.
The invention therefore aims to provide a material with multi-phase structure and a
Specify a manufacturing method with which the above-mentioned disadvantages can be avoided. In particular, the invention should enable an expanded diversity of materials and a significant reduction of the process steps.
To achieve this object, the invention according to a first aspect provides a material having a multiphase structure comprising at least a first solid phase and at least one second solid phase, the first phase and the second phase each being a metal, a metal alloy, a ceramic material or combinations thereof in the form a composite material, wherein the phases of the microstructure are macroscopically distinguishable from one another, the polyphase microstructure being in the form of interstitials or three-dimensional intermeshing microstructures, the interstitial microstructure comprising the first phase as matrix phase continuously occurring in three spatial dimensions and the second phase as discontinuous randomly distributed intercalation phase, and the first phase being powders produced in the course of the manufacturing process by sintering.
In the context of the present invention, when reference is made to a multi-phase structure, it is to be understood as a structure of two or more phases.
The at least two phases are macroscopic, i. as far as visible to the naked eye, sharply demarcated from one another. Only in the microscopic range can the
Interfacial region between two phases may be present at most reaction products and intermediate phases from reactions at the interfaces between the phases.
Further, reaction products may be comprised of reactions of the phases with oxygen, carbon and / or nitrogen. Based on the total volume of the workpiece, however, the described reaction products and intermediate phases are preferably present only in an amount of less than 10% by volume.
The multiphase structure according to the invention is formed either as an interstitial structure or as a penetration structure. An intercalation structure is present when at least one phase (intercalation phase) is intermittently intercalated into at least one other, continuous phase {matrix phase). According to the invention, the matrix phase continuously occurs in three spatial dimensions, and the particles of the intercalation phase are arranged distributed in three spatial dimensions in the matrix phase. In this case, the intercalated phase may well be in higher concentration than the matrix phase.
Depending on the manufacturing process, a preferred orientation of the individual phases in one or two spatial directions may occur.
Penetration structures are given when all the phases represented in the material occur continuously. This is generally the case when the phases in the form of sponge-like network structures penetrate three-dimensionally.
Within the scope of the invention, it is important that the phases of the microstructure are macroscopic, that is, visible to the naked eye, distinguishable from one another. This means that the microstructure is limited to the structures visible to the naked eye. In the case of an interstitial structure, this means, for example, that the second phase has discontinuous regions which in the projection have an area of at least 0.2 mm 2, preferably at least 1 mm 2. Towards the top, the discontinuous regions of the second phase are limited to a diameter of, for example, 10 mm.
The phases of the material may each be composed of atoms of a single chemical element so that there is one phase. But the phases can also exist as alloy or composite material {mixed phase). When a composite material is used for the first phase and / or the second phase, it preferably consists of a matrix of a first material into which fillers having a particle size of < 100pm are included. This substructure can not be resolved with the naked eye without the aid of optical aids.
The invention allows the use of a variety of different materials. The first phase is preferably formed of a metal, a metal alloy, a metal composite, a ceramic material, a metal-ceramic composite or a ceramic composite.
The second phase is preferably of a metal, a metal alloy, a metallic composite, a ceramic material, a metal-ceramic
Composite material, a ceramic composite material,
Plastic or a plastic composite formed.
It is essential that the material of the first phase and the material of the second phase do not alloy during the manufacturing process but form distinct sharply demarcated phases. In each case, only similar particles agglomerate with one another to form the individual phases. The microstructure of the material preferably arises from a random arrangement or mixture of the powder, powder granulate or particulate starting components "in situ". in its manufacture.
The large number of usable materials is made possible by the fact that the first phase is produced by sintering according to the invention. Thus, a powder or powder granular component is used which is sintered in a compression operation under temperature and pressure. Process parameters are preferably used for the densification process, which on the one hand prevent, for the respective combination of materials, from leading to significant diffusion / reaction between the individual components, which would lead to an extinction of the desired multiphase structure. At the same time, the process must take long enough or the temperatures must be so high that, in the case of the use of powder granules, they sinter into a dense body and come to a positive connection of the individual components, ideally with a very well controlled, small diffusion zone.
In summary, the present invention offers the following advantages: a) Extension of the material combinations to ceramic ceramics; Metal ceramics, metals / alloys metals / alloys, including their combinations, and their composites. This extends the achievable property combinations that result from the macrostructure composites. b) By using powders for the production of one or more components of the material according to the invention, there are few restrictions with regard to the availability of suitable starting materials or materials. c) There is no limitation of the composition to metals with high ductility at room temperature or with good forming behavior at elevated temperature, or the manufacturing technology used does not require intermediate annealing in order to obtain further Allow forming steps. The material according to the invention is produced by means of a compression process, in contrast to the repeated repetition of forming steps in the prior art. d) The technologies used to manufacture are automatable and scalable. e) The composites produced can be made, using appropriate combinations of the starting powder and processing technique, to be made with a random (non-deterministic) macrostructure. f) The composites produced make it possible to produce phases of very high hardness and wear resistance when the individual phases are composed of a substructure, i. a matrix incorporating hard-shell particles in the microscale.
According to a preferred embodiment, it is provided that the first phase is made of a material having a lower sintering or molding temperature than the second phase. This ensures that during production, ie during the compacting or sintering process, first the first, powdered or powdered granular Component is formed into a continuous phase. The sintering temperature is understood to mean that temperature at which the powdery starting components merge into a solid via diffusion processes. Depending on the material, this temperature is about 0.5-0.95% of the melting point (measured in Kelvin) of the starting component. The forming temperature or molding temperature is the temperature at which the material begins to flow under application of pressure and temperature or plastic deformation occurs.
The second phase can also be formed by sintering. Alternatively, the second phase may be prepared by incorporating particles in the first phase in their initial powdered state. The incorporation is accomplished, for example, by preparing a mixture of the powder or powder granules of the first component with the particles of the second component. Thereafter, the mixture is subjected to a densification process, whereby the first phase is sintered and the particles of the second component are respectively enclosed in the sintered first phase. In this case, the particles of the second component may be subjected to a forming process.
It is preferably provided that the particles have a length to diameter ratio of 1: 1 to 3: 1. The particles are for example spheres, ellipsoids,
Flakes, platelets, chips, sheets, pieces of sheet metal, wires, fragments or the like. Formed.
A preferred embodiment further provides that the particles have an average volume equivalent spherical diameter of 0.3-10 mm, preferably Q, 5-3 mm.
The particles of the second phase may be either in the same orientation or randomly oriented.
In principle, virtually any combination of materials is conceivable within the scope of the invention. Preferably, both the first phase and the second phase is a metal. Particularly preferred is a construction in which the first and second phases are each a noble metal or a noble metal alloy such as an element or an alloy of the platinum group. Alternatively, ceramic particles may form the second phase, which are randomly distributed in a sintered metal phase.
Preferably, the first phase is made of a material having a thermal conductivity of > 150 W / mK such as Ag, Cu or Al, and the second phase of a material having a thermal expansion of < 8 ppm / K, such as W, Mo, T1B2, Zr {Wo4) 2.
A further preferred embodiment provides that the first and / or the second phase is a composite material which has a continuous matrix in which at least one particulate filler is introduced.
The volume fraction of the first phase is preferably 10-95%, preferably 30-70%, preferably 40-60%. The volume fraction of the second phase, in particular produced by sintering, is 10-95%, preferably 30-70%, preferably 40-60%.
If the second phase is not formed by sintering but by particles, a preferred embodiment provides that the volume fraction of the second phase produced by incorporation of particles into the first phase is 10-60%, preferably 20-50%, preferably 30-40% , In this case, the embedded particles with a size of preferably at least 300 μm are present.
According to a second aspect, the invention relates to a method of producing the above-described material from at least one powdered or powdered powdery component and at least a second component, comprising the following steps: mixing the at least one first component with the at least one second component, compacting the components in one Press mold using pressure and temperature, whereby the first component is sintered to a first phase of a multi-phase structure.
It should be noted that features described above in relation to the material according to the invention are analogous in the
Under the method according to the invention can be realized.
Preferably, the procedure is such that the second component is used in powder form or as powder granules and is sintered in the compacting step to form a second phase of the multiphase structure.
Preferably, the powder of the first phase and, if necessary, the second phase has a particle size of < 300μιη, preferably < 150μτα, preferably < ΙΟΟμτη, preferably < 50μιη on.
One advantageous procedure envisages that the compression step as hot pressing, hot isostatic pressing, direct hot pressing, spark plasma sintering,
Pressing and sintering or extrusion and their modified forms is formed.
The densification step preferably comprises applying pressure at a rate of > 0.001 MPa / s, preferably> 0.1MPa / s and more preferably > 10 MPa / s. Preferably, the pressure application rate is at most 106 MPa / s. Further, the compacting step may involve heat input at a heating rate of > 10 K / min, preferably > 100 K / min, more preferably > 1000 K / min.
The compacting step preferably comprises, after the application of pressure and heat input, a holding step in which the temperature and pressure are maintained over a period of < 6 hours, preferably < 1 hour, more preferably 1-60 seconds are held.
The pressure during the holding step is preferred > 1 MPa, preferably > 10 MPa, more preferably > 100 MPa.
The compression step can take place in protective gas, vacuum or air.
According to another embodiment of the invention, the manufacturing process is carried out as follows.
Step 1:
Step 1 covers the preparation of the starting components. The following starting components can be used:
The first component is in particular a powder of sinterable metallic or ceramic particles.
These powders may have particle sizes of less than 300 μm, preferably less than 100 μm, particularly preferably less than 45 μm.
The first component can also consist of powder granules. These are formed by converting sinterable metallic or ceramic powder into granules having a size of 0.5-10 mm, preferably 1-5 mm, with water or by addition of solvent (for example via spray drying, freeze drying or the like) or with granulation aids (eg binder components, polymers, waxes) become.
The second component, like the first component, may consist of another powder of a sinterable metallic or ceramic particle. These powders may have particle sizes of less than 300pm, preferably less than 100pm, more preferably less than 45μιη. Likewise, the second component may be prepared from powder granules (such as the first component).
Another embodiment includes the possibility that the second component may be formed of particles having a one-dimensional or two-dimensional direction, e.g. Wire pieces or wires with a diameter of 0.3 mm to 5 mm, preferably 0.5 mm to 2 mm or fibers with a diameter of 0.3 mm to 5 mm, preferably 0.5 mm to 2 mm, or flakes, platelets, chips, sheets or sheet metal pieces. These have characteristic dimensions with a length which is greater than the thickness, wherein the thickness of the particles is in a range of 0.1 mm to 5 mm, preferably 0.5 mm to 1 mm. The particles must be characterized by having ductile properties at room temperature and / or when applying pressure and temperature.
The second component may also be formed by particles having a regular (e.g., spheres) or irregular shape (e.g., bits, chips, ...). These fillers may have a mean diameter of 0.3mm to 10mm, preferably between 1mm to 5mm. The particles of this type may be, for example, easily deformable bulk materials with the potential for deformation under the influence of pressure and temperature.
However, they may also be non-deformable or difficultly deformable materials, which are essentially inert in a matrix: in particular ceramic fillers or else carbon-based fillers, in particular diamond, which can not be easily deformed even when using very high temperatures and pressures.
Step 2:
Weighing the at least one first component and the at least one second component and mixing them in the desired ratio.
Step 3:
In the third step, the shaping takes place. To do this, the mixture is filled into a suitable mold and compacted at room temperature by the application of pressure to produce a stable, handleable " green part ".
A particular embodiment in this context involves the ply-by-layer filling of a mold whereby layers of different concentrations of the individual phases are combined. Here, for example, a gradient material, a sandwich or multilayer material can be produced. It is also possible to selectively introduce the multiphase material locally or to press it directly onto a carrier body.
If disintegration of the body occurs despite the application of high pressing forces, an additional plastic binder may be added to the starting material, which on the one hand enables the shaping process and on the other hand stabilizes the component.
Alternatively, the mixture may also be filled directly into the die and then subjected to the compression process at temperature and pressure.
Step 4:
After the green compact has been present, if this contains a high proportion of plastic binder, it can be freed from the binder in an optional debinding step. Subsequently, the green compact-provided with a release agent-is placed in a suitable mold and compacted into a compact component using pressure and temperature.
The additional molding step described herein may also be dispensed with, depending on the densification process, and the densification of the starting material may be carried out directly in the mold.
Likewise, it is also possible here to place the multiphase material from layers of different composition of the individual phases, as a gradient material, in a sandwich version or else as an insert in a specific area. At the same time, it can also be pressed directly onto a base body. For the compaction process, process parameters are used which on the one hand prevent a significant diffusion / reaction between the individual components from occurring for the respective material combination, which would lead to an extinction of the desired multi-phase structure. At the same time, the process must take long enough or the temperatures must be so high that, in the case of the use of powder granules, they sinter into a dense body and form-fit the individual components, ideally with a very well-controlled, low diffusion zone.
Particularly advantageous for achieving very high densities have been pressure-assisted hot-pressing processes, in particular processes characterized by a very rapid compaction process (conventional hot pressing, spark plasma sintering, direct heated hot pressing, inductive hot pressing, capacitor discharge sintering, etc.). With these methods, it is possible to compact sinterable materials into a compact material in just a few minutes. Other methods that can be used are high pressure, high temperature processes, as well as processes that include in air in a press, pulsed (forging) or compressing by the second (e.g., powder forging). In the case of the processes taking place in air, in particular, a rapid quenching process can also take place in the course of production and, if appropriate, the reactions with the atmosphere can also be utilized. For example, a rapid densification process makes it possible to maintain very fine-grained microstructures of the sintered phases, which has an advantageous effect on the material properties of the final product.
Step 5:
After the preparation of the material according to the invention, an additional heat treatment may optionally be applied, in particular when very rapid compression methods are used. This can be used for the controlled formation of a diffusion zone or to relax tension in the material.
Step 6:
After the material according to the invention has been produced, a forming process can optionally take place, which makes it possible, for example, to convert semifinished products into other geometries as well as to produce some preferred orientation thereof. Prerequisite for this
Forming steps is the appropriate ductility of the materials. Possible processes are forming processes, such as Roll, Pull, Hammer, Roll, Extrude, Severe Plastic Deformation.
Step Ix
For finishing the materials, processes such as turning, milling, grinding, wire eroding, die sinking, laser machining or the like may be used to influence the geometry of the semifinished product or to perform a surface finish.
Step 8:
Depending on the composition of the multiphase structure, additional surface treatment methods may optionally be employed. These may have the task of changing the color of the component or of the material properties, e.g. to affect the hardness or wear resistance.
The methods of surface treatment may include the following methods; a) Thermodiffiffusion treatment: In this case, the component is provided with powdery or paste-like sizes. A heat treatment causes the component to react with the powdery or pasty mass.
The heat treatment can lead to the formation of reactions that lead to a different visual appearance or change the functional properties of the component (s). b) Heat Treatment in Gases: Gases, e.g., oxygen and / or nitrogen, are used to generate reaction products on the surface of the device, e.g. Nitrides or oxides. The heat treatment may also take place in air. c) Chemical treatment: a chemical treatment using current / voltage can be used, for example, to anodize surfaces. The choice of the electrolyte and the voltage / current characteristic can influence the layer thicknesses of nitrides / oxides etc. produced. d) treatment with a plasma as well as the combinations of a plasma with gases for selective surface modification. e) surface treatment by mechanical processes by means of brushes, ball beads, sandblasting, electropolishing, trovalizing or the like. f) etching of the surface g) coating with a transparent wear resistant layer, e.g. with diamond, DLC or lacquer / plastic layers.
The steps 1 to 8 described are summarized again in the following overview.
Step 1: Preparation of the Auseangskornponenten
Step 2: Weigh in and mix the components
Step 3: Forming by pressure assist process (making a "greenware") alternatively directly to step 4
Step 4: Compressing the components by exposure to pressure and / or temperature (e.g., by hot pressing, spark plasma sintering, etc)
Step 5: Optional: Heat Treatment
Step 6: Optional: Forming process (eg: rolling, extruding, hammering, etc.)
Step 7: Finishing the multiphase structure
Step 8: Optional: Surface finish such as: curing, coating or etching
The invention allows the manufacture of articles whose multiphase structure gives a unique and individual macrostructure which can be used, for example, as an authentication feature or security element. Since the macrostructure obtained according to the invention is not reproducible, it can not be copied.
The material according to the invention or that can be produced according to the invention is particularly suitable for the production of jewelery articles, luxury articles and technical functional materials.
Of particular use, in particular in the jewelry and luxury goods sector, is the non-determined macrostructure. This imparts the products uniqueness due to an aesthetic appearance, especially when it is precious metals or platinum group elements and their alloys, and at the same time constitutes a security element. The surface of an article having the macrostructure simultaneously has a copy-protection function because it is difficult to obtain the non-determined macrostructure without a considerable expense to reproduce.
Thus, luxury items, such as Watches, jewelery and rings, or even articles with labels, such as Pockets, as well as consumer-grade premium products (e.g., cell phone cases) having a non-deterministic macrostructure. High-quality products can be protected by this without the need for additional labeling.
Likewise, the macrostructure can be used with the possibility of unique identification in order to produce high quality investment objects such as coins, medals as well as ingots. It is particularly advantageous if materials with ductility are used, since these can also be subsequently embossed. Also, combination with other materials is possible, such as producing bi-metal coins consisting of a metal rim in which an insert of the macrostructure composite is embedded in the center, or vice versa.
Security features based on numbers, image codes or holograms, such as those used in the field of software, are only applicable in the jewelry and LuKUs area because they change the appearance. In the document field, for example, holograms and plastic security features with relief structure are used, or pigments with special properties.
The present invention provides a solution by using the nondeterminant macrostructure characterized by bi- or multicolor. At the same time, these materials are visually attractive and therefore can be used for luxury articles and jewelery, especially when constructed from noble metals or platinum group elements and their alloys. Here, the bi- or multicolor macrostructure not only satisfies the aesthetic appearance requirement, but at the same time makes it possible to use this hard-copy macro pattern as a security element. By means of a
Image recognition software may consist of the optical differences, e.g. in color or reflectance, emissivity or the like, a unique code is generated. For this purpose, a semifinished product consisting of two or more phases which differ in their visual appearance, for example in color or reflectance, by processes of transformation or mechanical processing, e.g. by milling,
Turning or the like, converted into a component, which is subsequently used in the Schuck, luxury and premium product range, such as e.g. Watch cases, rings, mobile phone casesetc. For the use of the surface of the material according to the invention as an authentication feature, it can be assumed that the manufacturer of a product consisting of the material or containing it creates an image of the macrostructure on the surface, wherein the image section covers the entire product or only a defined area thereof. This image is uniquely assigned to the product as an authentication feature. If possible copies appear on the market, the characteristic pattern can be determined via the image recognition and compared with the manufacturer's database.
In addition, the macrostructure of the product can be converted into a binary pattern by means of image recognition and a numerical code can be generated by means of an algorithm. This number code can be used as a second security feature.
The invention will be explained in more detail below with reference to several embodiments.
Example 1:
As the first component, dendritic copper powder having a grain size < 45pm used. This powder is subjected to a granulation process by adding a granulating binder dissolved in alcohol (2% by weight) to give granules of 3-5 mm in size, with the resulting fines having a particle size of less than 1 mm being removed through a sieve The granules are also mixed in a volume ratio of Cu: Ag of 60:40% and then at 150 MPa in a ring steel mold having an outside diameter 65%. The body is then debind in an oven at a temperature of 450 ° C. so that the wax components are removed 750 ° C heated mold inserted and by applying 10 0 MPa compressive pressure compressed in air in 30 seconds and then expelled from the mold. To affect the microstructure (hardness), the material can be quenched directly in water or oil. After compression, the ring blank is rotated and then finely polished. The relative density is 99.9% of the theoretical calculated density. The blank is shown in FIG.
Example 2:
A similar procedure is chosen as in example 1. Instead of copper, titanium powder having a grain size < 45pm used. The powder granule mixture is filled into a 38ram diameter graphite die and densified by direct heated hot pressing at 50 MPa at 830 ° C with a holding time of 3 minutes. The achieved relative density is 99.8% of the theoretically calculated density. The blank is shown in FIG. 1, wherein a heat treatment has already been carried out here as a test. The blank will be transferred by milling into a watchcase and polished. Subsequent heat treatment at 600 ° C in air causes only the titanium areas to change color. The watchcase is photographed and made into a binary image which uniquely identifies the watch case due to the particular macrostructure. This is characterized by the fact that the unidirectional application of the pressing force results in different macrostructures in the pressing direction and transversely thereto.
Example 3:
Silver powder with a grain size < 45pm is mixed with particles of boron carbide (B4C) in an attritor, with the proportion of B4C particles being at 5% by volume and the particles having a particle size below 10μm. The composite powder of Ag and B4C is mixed with brass chips (in a ratio of 50:50 vol%) having a size of about 4-6mmin in length and about 0.5-lm in width and depth, respectively the mixture is filled into a die (diameter 30 mm) and compacted at 150 MPa. The resulting green compact is placed in a permanently heated die at 680 ° C and compacted at 120 MPa for 60 seconds. Thereafter, the blank becomes one
Ring processed further. When measuring the hardness of the residuals of the individual phases it could be shown that the addition of B4C in the silver matrix increases the hardness by 22% compared to the pure silver matrix.
Example 4
Silver powder granules as in Example 1 and gold chips about 3-5 mm in length and about 0.5-2 mm thick / wide are mixed (in the ratio 55:45 vol%) and the mixture is poured into a graphite mold having a dimension of ca. 27mm x 40mm filled. The mixture is compacted in a direct hot press at 50 MPa and a temperature of 820 ° C over a period of 5 minutes. In this case, vacuum is used. The resulting blank with a dimension of 40x40x8mm has a relative density of 99.7%. Due to the lower pressing force, the differences in macrostructure in the pressing direction and across are not so pronounced. Thereafter, the block is milled and subsequently heat treated and transferred in a rolling process through a plurality of forming steps in which the rolling direction is changed into a plate having a thickness of 2 mm. The density of the plate increases by this process to> 99.9%. At the same time, there is an increased alignment of the gold regions in the x-y direction. From the semi-finished product various jewelery items are worked out: a cross-shaped pendant, inserts soldered into cufflink holders, rings and key holders.
Example 5:
Aluminum powder with a grain size < 63pm is made by adding a binder in a granule with a
Granule particle size of 3-5mm transferred. Subsequently, the granules are mixed with titanium shavings using a ratio of aluminum powder to titanium shavings of 70: 30% by volume. The mixture is filled into a graphite mold (diameter 30 mm) which is provided with release agent. The compaction takes place in an induction heated hot press at a temperature of 630 ° C and a pressure of 35 MPa. For the production, a high heating rate of 200 K / min is used and the holding time is 5 minutes. In the final product there are indications of TiAl phases, in particular at the transition zone between the Ti phase and the Al phase. The TiAl phases are present in volume at about 5% by volume. After preparation, the material is ground and polished and subsequently surface-modified by glass bead blasting. If it is found that the phases have a different hardness and therefore a different surface structure, the phases hardly differ in color.
Only after performing a heat treatment at 550 ° C change the phases, in particular the titanium phase, the color. From the part of a trailer is made.
Example 6:
A titanium alloy powder (Ti ^ Al ^ V) having a grain size < 63pm is transferred to granules with a granule particle size of 3-6mm. This is mixed with spheres of glassy carbon having a diameter of 1.5 mm so that the proportion of the titanium alloy matrix is 65 vol%. The powder is hot pressed in a graphite mold with a diameter of 76mm with a height of 8mm. Then rings and pendants are milled out. The rings are subjected to additional heat treatment under nitrogen at 800 ° C for one hour. This results in a change in the color of the titanium component, which is accompanied by an improvement in surface hardness of more than 25% and also increases the wear resistance.
Example 7;
ZrOa powder with 8 mol% Y 2 O 3 stabilization as the first component and ZrOa with 8 mol% Y 2 O 3 stabilization and an addition of 3% by weight C0O 3 as second components are mixed in each case by means of attritor and then by addition of binder (2% by weight). ) are transferred into two granular materials with a grain size of about 3-5mm. These are mixed and subsequently, at 300 MPa in a steel mold, a 30mm diameter green compact is produced. After a debinding process at 450 ° C for 1 hour, the green compact is placed in a graphite mold and compacted by inductive hot press at 50 MPa and a temperature of 1350 ° C in less than 15 minutes. After processing by grinding and polishing, a two-color ceramic is present. Due to a reducing environment during hot pressing by the graphite mold, the component is subsequently oxidized again in air at 1,000 ° C at a slow heating rate. There is a change of colors. After re-grinding and polishing, the part is enclosed with a metal frame and serves as a pendant.
Example 8:
Granulated brass powder with a granule size of 4-5 mm is mixed with stainless steel 316L powder granules with a granule size of 3-6 mm in the ratio 60:40 vol.%. The granulate mixture is cold pressed in a 39mm x 26mm steel tool at 80 MPa and then provided with a release agent. The green part is hot pressed at 700 ° C and 100 MPa for 2 minutes in a steel mold and then ejected. The component is then cleaned in a blasting process. Due to the low temperature selected, the second component is not sintered and therefore can be removed by blasting. This results in a porous body with a macrostructure, which, due to its visual appearance, can be used for a jewelery article, such as e.g. a key fob or a brooch can be used. Likewise, 3-dimensional porosity can be highlighted by optical staining. Further fields of application of the body with macroporosity are filter elements in the technical plant sector.
Example 9:
Fig. 2 shows a two-phase structure of silver and brass in a ratio of 50:50 vol .-%.
Example 10:
Fig. 3 shows a two-phase structure of gold and silver in a ratio of 50:50 vol .-%.
Example 11
Fig. 4 shows a detail of the macrostructure of a two-phase microstructure serving as an authentication feature for the article made therefrom. As shown in Fig. 4, the cutout can be converted to a black-and-white image to be better processed in this way, e.g. to be transformed into a binary code.
Example 12
Powder granules as in Example 1 are used and filled together with a powder granulate having a composition of Cu: Ag of 40:60 vol.% In a mold in the form of layers. The layers of Cu: Ag are 40:60 vol.% Outdoor and the center is a 60:40 vol.% Layer. The resulting sandwich structure consists of a 60:40 Cu: Ag core that is 4mm thick and surrounded by two layers of Cu: Ag of 40:60 vol%, which are about 1.5 mm thick.
Examples 13-18
Fig. 6 shows a polyphase material consisting of two layers with different concentrations of the individual phases.
Fig. 7 shows a polyphase material consisting of three layers (sandwich arrangement) with different concentrations.
Fig. 8 shows a polyphase material consisting of a gradient structure.
Fig. 9 shows a polyphase material which is pressed directly onto a carrier material.
Fig. 10 shows a combination of a multi-phase material with a carrier body.
Fig. 11 shows a multiphase material introduced locally into a carrier body.

权利要求:
Claims (31)
[1]
Claims 1. A multiphase material comprising at least one first solid phase and at least one second solid phase, wherein the first phase and the second phase are each a metal, a metal alloy, a ceramic material or combinations thereof in the form of a composite, the phases of the microstructure being macroscopically distinguishable from one another wherein the multi-phase microstructure is formed as an interstitial structure or as a three-dimensional interpenetration microstructure, wherein the interstitial microstructure comprises the first phase as the matrix phase continuously occurring in three spatial dimensions and the second phase as the discontinuous randomly distributed intercalation phase, wherein the first phase is produced by sintering.
[2]
A material according to claim 1, characterized in that the first phase is made of a material having a lower sintering or deformation temperature than the second phase.
[3]
3. Material according to claim 1 or 2, characterized in that the second phase is plastic or a plastic composite material.
[4]
4. Material according to claim 1, 2 or 3, characterized in that the second phase is prepared by sintering or by incorporating particles in the first phase in its powdery initial state.
[5]
5. Material according to claim 4, characterized in that the particles have a length to diameter ratio of 1: 1-5: 1.
[6]
6. Material according to claim 4 or 5, characterized in that the particles are formed as spheres, ellipsoids, flakes, platelets, chips, sheets, pieces of sheet metal, wires, fragments or the like.
[7]
7. Material according to claim 4, 5 or 6, characterized in that the particles have a mean volume equivalent spherical diameter of 0.3-10mm, preferably 0.5-3mm.
[8]
Material according to any one of Claims 1 to 7, characterized in that the first and second phases are each a noble metal (Ag, Au) or a noble metal alloy or a platinum group metal (Ru, Rh, Pd, Os, Ir, Pt) or an alloy of the platinum group is.
[9]
A material according to any one of claims 1 to 8, characterized in that the first phase is made of a material with a thermal conductivity of > 150 W / mK such as Ag, Cu or Al, and the second phase of a material having a thermal expansion of < 8 ppm / K, such as, W, Mo, T1B2, Zr (Wo4) 2.
[10]
10. Material according to one of claims 1 to 9, characterized in that the first and / or the second phase is a composite material having a continuous matrix, in which at least one particulate or fibrous filler is introduced and the size of the fillers below 50 pm, preferably below 10 pm lies.
[11]
11. Material according to one of claims 1 to 10, characterized in that the volume fraction of the first phase is 10-95%, preferably 30-70%, preferably 40-60%.
[12]
12. Material according to one of claims 1 to 11, characterized in that the volume fraction of the second phase, in particular produced by sintering 10-95%, preferably 30-70%, preferably 40-60%.
[13]
13. Material according to one of claims 4 to 12, characterized in that the volume fraction of the second phase produced by the incorporation of particles into the first phase is 10-60%, preferably 20-50%, preferably 30-40%.
[14]
Material according to any one of claims 1 to 13, characterized in that the material contains less than 10% by volume of reaction products and intermediate phases of reactions at the interfaces between the phases and of reactions of the phases with oxygen, carbon and / or nitrogen.
[15]
15. A method for producing a material according to any one of claims 1 to 14 from at least one first, powder or powder granular component and at least one second component, comprising the following steps; Mixing the at least one first component with the at least one second component, compressing the components in a mold using pressure and temperature, thereby sintering the first component into a first phase of a multiphase structure.
[16]
A method according to claim 15, characterized in that the second component is used in powder form or as powder granules and is sintered in the compacting step to a second phase of the multiphase structure. Process according to claim 15 or 16, characterized in that the powder of the first phase and optionally the second phase has a particle size of < 300pm, preferably < 150pm, preferably < 100 μm, preferably < 50pm.
[17]
18. The method according to claim 15, 16 or 17, characterized in that the second component is used in the form of particles.
[18]
Process according to any one of Claims 15 to 18, characterized in that the compacting step is in the form of hot pressing, hot isostatic pressing, direct hot pressing, spark plasma sintering, pressing and sintering or extruding.
[19]
A method according to any one of claims 15 to 19, characterized in that the compacting step comprises applying pressure at a rate of> 90 °. 0.001 MPa / s, more preferably> 0.1 MPa / s, more preferably > 10 MPa / s, wherein the printing rate is preferably at most 106 MPa / s.
[20]
A method according to any one of claims 15 to 20, characterized in that the compacting step involves heat input at a heating rate of > 10 K / min, preferably > 100 K / min, more preferably > 1000 K / min includes.
[21]
A method according to any one of claims 15 to 21, characterized in that the compacting step after the application of pressure and the heat input comprises a holding step in which the temperature and the pressure are maintained for a period of time of < 6 hours, preferably < 1 hour, more preferably 30-60 seconds, wherein the pressure during the holding step is preferably > 1 MPa, preferably > 10 MPa, more preferably > 100 MPa is.
[22]
23. The method according to any one of claims 15 to 22, characterized in that the compression step takes place in a technical gas, in inert gas, in vacuum or in air.
[23]
24. Use of the microstructure of a material according to one of claims 1 to 14 or of a material produced according to the method according to any one of claims 15 to 23 as an authentication feature.
[24]
An article made of or containing a material according to any one of claims 1 to 14 or prepared by the method of any one of claims 15 to 23.
[25]
The article of claim 25, wherein the article is a jewel, in particular a bracelet, collar, pendant, finger ring, foot jewelry, earring, pin, brooch, button, tie pin, cufflink, belt buckle or watch.
[26]
The article of claim 25, wherein the article is a heat sink, a heat sink, or a heat spreader, for example, an electronic component.
[27]
The article of claim 25, wherein the article is a luxury article, in particular a housing for a mobile phone, handles for cutlery, letter opener, fountain pen, pen or case.
[28]
An article according to claim 25, wherein the article is a plant object, in particular a coin, medal, bar or an art object.
[29]
An article according to any of claims 25 to 29, comprising a portion formed by a body and a portion made of the material.
[30]
An article according to any one of claims 25 to 30, comprising a portion formed by the material having a first structure and a portion made of the material having a second structure, wherein the first and second structures have the first and / or second phase material or volume ratio at least a first to at least a second phase are different from each other.
[31]
32, article according to any one of claims 25 to 30, characterized in that the material is present in a volume ratio of the at least one first to at least one second phase having at least one spatial extent of the article having a gradient.

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同族专利:

公开号 | 公开日

WO2015061817A3|2015-07-02|

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WO2015061817A2|2015-05-07|

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

ATA829/2013A|AT515007B1|2013-10-28|2013-10-28|Material with multi-phase structure|ATA829/2013A| AT515007B1|2013-10-28|2013-10-28|Material with multi-phase structure|

PCT/AT2014/000197| WO2015061817A2|2013-10-28|2014-10-28|Material having a multiphase structure|

EP14812120.5A| EP3063103A2|2013-10-28|2014-10-28|Material having a multiphase structure|

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