专利摘要:
The present invention relates to a process for manufacturing a titanium aluminide turbomachine blade, comprising steps of: - (E1) forming a titanium aluminide ingot; - (E2) spinning the ingot through an orifice of a die having a main branch and at least one side branch, so as to obtain a bar-shaped spun ingot having a cross-section having a main branch and at least one lateral branch substantially perpendicular to the main branch; - (E3) transverse cutting of the ingot spun so as to obtain sections of spun ingot; - (E4) forging each piece of ingot spun so as to obtain a turbomachine blade.
公开号:FR3036640A1
申请号:FR1554696
申请日:2015-05-26
公开日:2016-12-02
发明作者:Gilbert Leconte;Jean-Michel Franchet;Pierre Sallot
申请人:Safran SA;SNECMA SAS;
IPC主号:
专利说明:

[0001] FIELD OF THE INVENTION The present invention relates to the field of manufacturing processes for turbomachine blades. The present invention applies particularly advantageously to the manufacture of turbomachine rotor blades, but can also be applied to the manufacture of stator vanes.
[0002] STATE OF THE ART Conventionally, as illustrated in FIG. 1a, a mobile turbine blade 4 comprises a blade 30 extending along the main axis of the blade, between the proximal and distal ends (ie inside and outside) of dawn. At its proximal end, the blade 30 comprises a foot 10 by which it is fixed to the turbomachine, and in particular to a disk of the rotor of the turbomachine in the case of a turbine engine rotor blade. At its distal end, or free end, the blade 30 may comprise a transverse element, called the heel 20. When several moving blades 30 are fixed on a rotor disc, their heels 20 are arranged edge to edge so as to form a crown circumferential which has, in particular, the function of delimiting externally the flow vein of the gas passing through the turbomachine and thus to limit gas leakage there. In operation, the rotation of the mobile turbine blade 4 generates a centrifugal force oriented in the direction of the main axis of the moving blade 4, hereinafter called the loading axis Ac. In particular, the foot 10, which provides the mechanical connection between the blade 30 and the rotor disc, is the seat of significant mechanical stresses oriented along the axis of loading of the blade. The turbomachine blades 4 are conventionally made of nickel base alloy by traditional foundry. Furthermore, titanium aluminide-based titanium aluminide alloys, hereafter referred to as titanium aluminides or TiAl, are known alloys consisting of titanium aluminide in which a minority fraction of the aluminum and titanium atoms can be used. be replaced by other atoms, such as zirconium, iron, molybdenum, silicon, or niobium.
[0003] 3036640 2 TiAl alloys have comparable mechanical properties up to 750 ° C comparable to traditional nickel foundry base alloys. The TiAl alloys have, at least partially, a lamellar grain structure which increases their mechanical strength. In addition, the TiAl has a low density, of the order of 4, 5 significantly lower than that of the nickel base alloys, which is of the order of 8. Therefore, it has been envisaged to manufacture the blades turbomachine TiAl replacing nickel base alloys, with the aim of reducing the mass of turbomachine blades. TiAl alloys, however, have several major disadvantages that complicate their use for the manufacture of turbomachine blades. In particular, they exhibit low temperature brittleness resulting in low elongation at break, and reduced crack resistance. Moreover, the shaping of the TiAl alloy, to manufacture a mobile turbine engine blade, is very delicate, because the industrial forgeability window, namely the compromise between temperature and shaping speed, is very narrow. Pourability is also problematic because the rapid rate of solidification of these alloys exposes the final part to risks of shrinkage and large porosities. As illustrated in FIG. 1b, it has been proposed to manufacture TiAl blades by casting, an ingot being formed by liquid metal casting (VIM) in a step El 1, then shaped by casting in a step E12, followed by a step E13 of hot isostatic pressing (HFI) to give them good properties, before being machined in the mass during a step E14. The shaping of the TiAl alloy by casting is extremely difficult because of the poor flowability of the TiAl alloy which does not allow the casting of thin enough thicknesses to produce finished rib pieces, that is to say having the shape of the final piece. It is therefore necessary to machine the entire periphery of the casting to obtain the final piece. As illustrated in FIG. 1b, it has also been proposed to manufacture blades TiAl by forging, an ingot being formed by liquid metal casting (VIM) in a step El 1 or by atomization of powder in a step E12 in a sheath 7, followed by a HIP step E13 and a stripping step E15, and then shaped by conventional forging in a step E17. The shaping of the TiAl alloy by conventional forging E17 into hot matrices is also very difficult. Indeed, on the TiAl alloy, no window of industrial forgeability could be determined, all the tests led to the cracking of the forged part. In addition, the conventional forging method E17 does not allow for direct forging of the final piece. Indeed, significant extra thickness remaining after the forging step, it is necessary to perform a final machining step E 18 to obtain the final piece. Although the E16 isothermal forging makes it possible to approach the finished ribs significantly more, an important E18 machining step is still necessary. In addition, isothermal forging E16 is not very productive and expensive, mainly because of the short life of the dies. In addition, in all the processes of the state of the art to implement the TiAl alloys, it is necessary to use a hot isostatic pressing (HIP) step E13 to give them good properties. This step is expensive, does not give a particular shape to the material and involves high temperatures that tend to make the grain grow. There is therefore an important need for a turbomachine moving blade manufacturing process by shaping the TiAl alloy, which does not have these disadvantages.
[0004] SUMMARY OF THE INVENTION The invention proposes a method for manufacturing a turbomachine blade by shaping an TiAl alloy. For this purpose, the invention proposes a process for manufacturing a titanium aluminide turbomachine blade, comprising steps of: forming a titanium aluminide ingot; - spinning the ingot through an orifice of a die having a main slot and at least one side slot, so as to obtain a bar-shaped spun ingot having a cross section having a main branch and at least one lateral branch substantially perpendicular to the main branch; transverse cutting of the ingot spun to obtain sections of spun ingot; forging each spun ingot section so as to obtain a turbomachine blade. By "substantially perpendicular", it may be considered a lateral branch slightly inclined relative to the main branch, this inclination may be a few degrees to about ten degrees or thirty degrees.
[0005] Spinning makes it possible to refine the structure of the TiAl alloys, in order to reduce the flow stress of the alloy, namely the stress necessary to cause a plastic deformation of the alloy. It is then possible to use, after spinning, conventional forging means making it possible to obtain parts near the ribs, that is to say close to the final shape and the final dimensions of the blade, which makes it possible to obtain was impossible in state-of-the-art processes. The invention thus makes it possible to limit the subsequent machining steps, which consequently saves time and reduces the amount of material lost. The proposed method makes it possible to eliminate the hot isostatic compression step. At the same time, spinning enables the spun ingot to have a cross-sectional shape with a main branch and at least one lateral branch substantially perpendicular to the main branch, thereby forming the blade root by forging in the first lateral branch, and the heel, if it exists, in the second lateral branch. Thus, the shape of the spun ingot approaches that of the final piece, which reduces the deformation required during the final stage of conventional forging.
[0006] Finally, the forging of the side branch of the spun ingot causes an orientation of the lamellae of the alloy, by the action of the deformation work, in the direction perpendicular to the loading axis of the blade. The orientation of the lamellae of the alloy in the direction perpendicular to the axis of loading of the blade makes it possible to increase the resistance of the blade to the mechanical stresses to which it will be subjected during operation.
[0007] The invention is advantageously supplemented by the following characteristics, taken individually or in any of their technically possible combinations. The orifice of the die has a single lateral slot, so as to obtain a rod-shaped bar-shaped ingot having a main branch and a single lateral branch, the blade of the blade being forged in the main branch while the foot of dawn 25 will be forged in the side branch. Alternatively, the orifice of the die has a first side slot that extends from one end of the main slot perpendicular to it, and a second side slot that extends from the other end the main slot substantially perpendicularly thereto, so as to obtain a rod-shaped bar-shaped ingot having a section having a main branch, a first side branch extending substantially perpendicular to the main branch from a end thereof, and a second lateral branch extending substantially perpendicular to the main branch from the other end thereof. The blade is then forged in the main branch, with the root of the blade being forged in the first side branch, and the heel in the second side branch. Forging is done in the open, which is less restrictive than isothermal forging.
[0008] The forging is carried out with a tooling temperature of between 6000 and 950 ° C., which is less restrictive than isothermal forging. For the alloy TiAl 48-2-2 (Ti-48Al-2Cr-2Nb (atomic%)), when the ingot is obtained by atomization of the powders, the manufacturing process also comprises a step of sheathing the ingot before spinning. and a stripping step between the spinning step and the forging step. The ingot being formed by pouring liquid metal. In the case where the ingot is made by casting, the structure obtained is a relatively heterogeneous solidification structure and with a very large casting size. In this case, the spinning will homogenize and refine the coarse seed grain structure until a small grain size of about 50 μm is obtained. The ingot being formed by atomization of powder. The combined use of a fine powder as well as spinning makes it possible to obtain bars having a chemically homogeneous microstructure and having a small grain size. In the case where the ingot is produced by atomization of powders, the spinning step makes it possible to combine in a single step the compaction of the powder, its sintering, its shaping and above all to preserve a fine microstructure, which the It can be increased if necessary The method may further include a machining step after the forging step that allows to finalize the piece. The invention also provides a turbomachine blade obtained by a method as described. The turbomachine blade obtained by a process as described is characterized by the grain of the alloy which constitutes it. Indeed, the grain of the alloy constituting a turbomachine blade obtained by a process as described is of a size of the order of 50-100M, substantially lower than the grain of the alloy of a turbomachine blade obtained by another method. In addition, a turbomachine blade obtained by a method as described is distinguished from a turbomachine blade obtained by another method in that the lamellar grains of the alloy are oriented in the direction perpendicular to the axis loading dawn. The invention also proposes a turbomachine rotor comprising at least one turbomachine blade obtained by a method as described above.
[0009] The invention also proposes a turbomachine comprising at least one turbomachine blade obtained by a method as described above. DESCRIPTION OF THE FIGURES Other objectives, features and advantages will become apparent from the detailed description which follows with reference to the drawings given by way of non-limiting illustration, among which: FIG. 1a, discussed above, represents a moving blade of a turbomachine. FIG. 1b, discussed above, presents the various processes for shaping the TiAl alloy of the prior art. FIG. 2a illustrates the flow stress of a 48-2-2 alloy ingot, as a function of the deformation exerted, for a ligot before spinning (dotted line) and for a spun ingot (solid line). - Figure 2b is a section of a ligot 48-2-2 alloy before spinning. Figure 2c is a sectional view of a 48-2-2 alloy tie after spinning. - Figure 3 illustrates the different steps of the method according to the invention, according to several possibilities. FIGS. 4a to 4f illustrate the first embodiment of the method according to the invention and in particular FIG. 4a shows an ingot before spinning; - Figure 4b shows the die seen from the front; - Figure 4c shows an ingot after spinning; - Figure 4d shows an ingot cut into sections; FIG. 4e schematically illustrates the forging step; Figure 4f shows the ingot section after the forging step. FIGS. 5a to 5e illustrate the second embodiment of the method according to the invention. In particular, FIG. 5a shows an ingot before spinning; Figure 5b shows the die viewed from the front; - Figure 5c shows an ingot after spinning; - Figure 5d shows an ingot cut into sections; - Figure 5e schematically illustrates the forging step; Figure 5f shows the ingot section after the forging step. FIGS. 6a to 6d illustrate the spinning step, FIGS. 6a and 6b illustrating non-sheathed spinning and FIGS. 6c and 6d illustrating a sheath spinning. DETAILED DESCRIPTION OF THE INVENTION As illustrated in FIG. 3, the method of manufacturing a turbomachine blade comprises stages of forming a titanium aluminide ingot 1; - E2 spinning ingot 1; E3 transverse cutting of the spun ingot 2 so as to obtain sections 3 of spun ingot; - E4 forging the sections 3 of ingot spun so as to obtain a turbomachine blade 4.
[0010] Ingot formation 1 Step E1 consists of forming an ingot 1 of titanium aluminide. The process can be applied to any type of titanium aluminides. In particular, the process can be applied to Ti-48Al-2Cr-2Nb alloy (atomic%)), subsequently denoted TiAl 48-2-2. It constitutes an acceptable compromise in terms of mechanical properties. In particular, the process can be applied to beta-type alloys represented by the formula Ti-Al (a) Nb (b) Mo (c) 13 (d) in which 'a', 'b', 'c' and d are expressed as an atomic percentage, ranging from about 44 to about 48, b being from about 2 to about 6, and varying from about 0 to about 2 and varying from about 0 , 01 and about 1.0. These alloys have excellent strength and hardness. The process can also be applied to alloys of the type represented by the formula Ti-Al-Cr-Nb-Si-Fe-Mo-Zr, such as, for example, an alloy containing 44 to 49% aluminum atoms, 0.5 at 3% of zirconium, 0.5 to 2% of iron, 0.5 to 2% of molybdenum, 0% to 30% of silicon, 0 to 3% of niobium, the balance of 100% titanium and inevitable impurities. The ingot is typically made by liquid metal casting (a process commonly known as VIM for Vacuun Induction Melting '). During the casting of the liquid metal, the various constituents for forming the alloy are fused by heating, and the bath of molten metal material is poured into a vacuum chamber. The ingot 1 is typically cylindrical in shape of circular section. For this purpose, the enclosure is of hollow cylindrical shape. In the case where the ingot is made by casting in a vacuum chamber, the structure obtained is a relatively heterogeneous solidification structure and with a very large casting size (of the order of 300-500 pm). In this case, the spinning will homogenize and refine the coarse structure of starting grain, until small grain size of the order of 50 pm. Beta-type alloys tend to segregate chemically during their preparation. Spinning acts on grain size but has no impact on the chemical homogeneity of the alloy. This is why for the latter, it may be interesting to start from powders to form a half-product, before forging, more homogeneous chemically. For this purpose, the casting of liquid metal is followed by a powder atomization. This method comprises atomizing a net of material obtained from the bath of molten metal material. The droplets of material solidify in an atomization chamber by convective exchange with the ambient gas, typically argon, and give powder. This is collected at the exit of the atomizing gas and placed in a sheath 7, which can be machined in a material different from that of the powder such as stainless steel. The sheath 7 is typically hollow cylindrical. The use of powder metallurgy makes it possible to remedy the difficulties of homogenization of segregating alloys. All the operations of handling the powder, filling the sheath and its saddlery must be performed in a neutral atmosphere or under vacuum so as to limit the contamination of the latter by oxygen. The combined use of a fine powder as well as spinning makes it possible to obtain bars having a chemically homogeneous microstructure and having a small grain size. In the case where the ingot is produced by atomization of powders, the spinning stage makes it possible to group in a single step the compaction of the powder, its sintering, its shaping and especially to preserve a fine microstructure, which the it will be able to enlarge if necessary 3036640 9 Ingot ingot 1 In step E2, the ingot is shaped by spinning. The spinning allows the ingot to be shaped by compression. The spin-shaped ingot is referred to as the spun ingot 2. Step E2 is to pass the ingot (possibly ductile by heating to the so-called spinning temperature) through an orifice 52 of a spinneret 53 as shown in FIG. Figures 6a and 6b. As illustrated in FIG. 6a, the ingot 1, generally placed in a container 51, is pushed into the die 53 by means of a press 54, typically a hydraulic press, a pump or an extruder screw, so to bring it out through the orifice 52 by exerting a thrust. From a certain force exerted by the press 54, there is plastic flow of the ingot through the orifice 52 of the die 53, as illustrated in FIG. 6b. The spun ingot 2 is therefore of a shape with a cross section corresponding to the shape of the orifice 52. The spinning makes it possible to homogenize and refine the structure of the alloy very strongly and consequently to reduce the flow stress. that is, the stress required to cause plastic deformation of the alloy. As can be seen in Figure 2b, which is a sectional view of a 48-2-2 alloy ingot before spinning, and Figure 2e, which is a sectional view of a 48-2-2 alloy tie after spinning. , spinning makes it possible to refine the structure of the alloy, that is to say to reduce the size of grains of the alloy. The results of the inventors, illustrated in FIG. 2a, show that the spinning step 20 makes it possible to reduce the flow stress of the 48-2-2 alloy by 30 to 40%. The inventors have obtained similar results with other TiAl alloys and in particular with a Ti-45Al-2.4Si alloy. At the same time, the spinning enables the spun ingot to be shaped whose cross-section is defined by the shape of the orifice 52 of the die 53. The shape of the orifice 52 of the die 53 is chosen so as to the shape of the spun ingot approaches that of the final piece, which reduces the deformation required during the final stage of conventional forging. It is then possible to obtain by conventional forging a piece close to the shape of the final part, and thus to limit the final machining step. For this purpose, the ingot 1 is spun in a die whose orifice 52 has a main slot 55 and at least one lateral slot 56. The lateral slot 56 extends perpendicularly to the main slot 55, from the one end thereof, and on both sides thereof, as illustrated in Figures 4b and 5b. A spun ingot 2 is thus obtained in the form of a cross-section bar having a main branch 30 and at least one side branch 26 perpendicular to the main branch 25, as illustrated in FIGS. 4c and 5c. Here, the side branch is substantially perpendicular to the main slot. However, it may be considered a lateral branch slightly inclined with respect to the main branch, this inclination being of a few degrees to about ten degrees or even thirty degrees. In a first embodiment illustrated in FIGS. 4a to 4f, the orifice 52 of the die 53 has a main slot 55 and a single lateral slot 56 that extends from one end of the main slot 55 perpendicular thereto, as illustrated in FIG. 4b. In other words, the orifice 52 of the die 53 is T-shaped. The ingot is spun so as to obtain a T-shaped bar shaped bar-shaped ingot 2 having a main branch 25 and a side branch 26. perpendicular to the main branch 25, as shown in Figure 4c. The blade 30 will be forged in the main branch 25 while the root 10 of the blade will be forged in the side branch 26.
[0011] In a second embodiment illustrated in FIGS. 5a to 5f, the orifice 52 of the die 53 has a main slot 55, a first lateral slot 56 which extends from one end of the main slot 55 perpendicularly thereto, and a second side slot 57 extending from the other end of the main slot 55 perpendicularly thereto, as shown in Figure 5b. In other words, the orifice 52 of the die 53 has an H-shaped section. The ingot is spun to obtain a bar-shaped spun bar 2 having an H-shaped section, having a main branch 25, a first lateral branch 26, extending perpendicularly to the main branch 25 from one end thereof, and a second side branch 27 extending perpendicular to the main branch 25 from the other end thereof; as shown in Figure 5c. As in the first embodiment, the blade 30 will be forged in the main branch 25 while the root 10 of the blade will be forged in the first side branch 26. In addition, the heel 20 of the blade will be forged in the second side branch 26.
[0012] For the TiAl 48-2-2 alloy, spinning is a relatively delicate step. Casing-free spinning tests of casting ingots often show deep cracks in some areas of the bar. In this case, the ingot 1 is advantageously coated with a sheath 7, for example of stainless steel, during a cladding step El ', in order to reduce the parietal cooling of the ingot during spinning and thus avoid deformation at a temperature too low locally that can cause cracks. The ingot 1 coated with its sheath 7 is brought to the spinning temperature before passing through the die 53 through a spinning pot 51. In this case, after spinning, it is necessary to provide a stripping step E6 of the spun ingot. 2 which consists in eliminating the sheath, for example by turning, before forging. It may also be advantageous to remove the cladding material by chemical removal. On the other hand, for the beta-type alloys, which are less loaded with Al but are more loaded with Nb and Mo, giving them better forgeability than the 48-2-2, the spinning can be done without sheath.
[0013] Thermal post-treatment Depending on the desired mechanical properties for the functionality of the final part, a conventional heat treatment may be necessary to regenerate a controlled microstructure. Indeed, the structures after forging will be fine or very fine.
[0014] Certain properties such as creep, will not be optimal after forging. Cutting of the ingot spun in section In step E3, the ingot is cut into a section. For this purpose, the ingot is cut along transverse planes by conventional metal cutting techniques such as water jet cutting, laser cutting, or wire cutting. Forging As explained above, the spinning allows, prior to the forging, to refine the TiAl alloy structure, in order to reduce the flow stress of the alloy, namely the stress necessary to cause a plastic deformation of the alloy. alloy. It is then possible to use, after spinning, conventional forging means to obtain a piece close to the final shape of the blade, which was not possible in the prior art. Conventional forging refers to open-air and hot-die forging as opposed to isothermal forging.
[0015] Forging consists in applying a large force to the spun ingot 2 in order to force it to conform to the shape of the final part, namely the turbomachine blade. The forging is carried out by applying a large force to the spun ingot 2 by means of a striking device 41, such as a matrix moved hydraulically at a controlled speed, and a support 42, such as an anvil or a fixed matrix, as shown in Figures 4e and 5e. The spun ingot 2 having a cross-sectional shape having a main branch 25 and at least one side branch 26 perpendicular to the main branch 25, the blade 10 of the blade is forged in the main branch 25, and the foot 10 of the blade is formed by forging in the lateral branch 26. If the cross section of the spun ingot has two lateral branches 25 and 27, the root 10 of the blade will be formed by forging in one of the lateral branches 25, and the heel 20 in the other side branch 26. Thus, the shape of the spun ingot 2 approaches that of the final part 4, which reduces the deformation required during the forging step. The blades 4 obtained by forging are more resistant to mechanical stresses because the deformation of metals generates a large number of metallurgical phenomena, both microscopically and macroscopically. In particular, the spinning causes, by the shape of the spun ingot, an orientation of the lamellar grains of the alloy, by the action of the deformation work, in the direction perpendicular to the loading axis of the blade. The orientation of the lamellar grains of the alloy in the direction perpendicular to the axis of loading of the blade makes it possible to increase the resistance of the blade to the mechanical stresses to which it will be subjected during operation. Forging does not need to be isothermal (isothermal forging requires that the tooling be brought to the heating temperatures of the metal to be forged ie more than 1000 °) and can be done in the open air in hot matrices with a tooling temperature typically between 600 ° and 950 ° C.
权利要求:
Claims (12)
[0001]
REVENDICATIONS1. A process for producing a titanium aluminide turbomachine blade (4) comprising a step of: - (El) forming a titanium aluminide ingot (1); the manufacturing method being characterized in that it further comprises steps of: - (E2) spinning the ingot (1) through an orifice (52) of a die (53), the orifice (52) having a main slot (55) and at least one side slot (56) extending from one of the ends of the main slot (55) substantially perpendicular thereto, so as to obtain a spun ingot (2 ) having the shape of a cross-sectional bar having a main branch (25) and at least one side branch (26) substantially perpendicular to the main branch (26); - (E3) transverse cutting of the ingot spun (2) so as to obtain sections (3) of spun ingot; - (E4) forging each section (3) of spun ingot so as to obtain a turbomachine blade (4).
[0002]
A method of manufacturing a turbomachine blade (4), according to claim 1, wherein the orifice (52) of the die (53) has a single lateral slot (56) extending from the one of the ends of the main slot (55) perpendicular thereto, so as to obtain a section bar-shaped spun ingot (2) having a main branch (25) and a single side branch (26) which extends from one of the ends of the main branch (25) perpendicularly thereto.
[0003]
3. A method of manufacturing a turbomachine blade (4), according to claim 1, wherein the orifice (52) of the die (53) has a first lateral slot (56) which extends from the one end of the main slot (55) substantially perpendicular thereto, and a second side slot (57) extending from the other end of the main slot (55) substantially perpendicular thereto, to obtain a rod-shaped bar-shaped ingot (2) having a section having a main branch (25), a first side branch (26) extending substantially perpendicular to the main branch (25) from one end thereof, and a second side branch (27) extending substantially perpendicular to the main branch (25) from the other end thereof.
[0004]
4. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, the forging being carried out in the open air. 10
[0005]
5. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, the forging being made in hot matrices with a temperature between 600 ° and 950 ° C.
[0006]
6. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, further comprising a sheathing step (El ') of the ingot (1) prior to spinning (E2) and a step of stripping (E6) between the spinning step (E2) and the forging step (E4).
[0007]
7. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, the ingot (2) being formed by pouring liquid metal.
[0008]
8. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, the ingot (2) being formed by atomization of powder. 25
[0009]
9. A method of manufacturing a turbomachine blade (4) according to one of the preceding claims, further comprising a machining step after the forging step.
[0010]
10. Turbomachine blade (4) obtained by a method according to one of the preceding claims.
[0011]
11. Turbomachine rotor comprising at least one turbomachine blade (4) obtained by a method according to one of claims 1 to 9.
[0012]
12. Turbomachine comprising at least one turbomachine blade (4) obtained by a method according to one of claims 1 to 9.
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CN107666977A|2018-02-06|
JP6873922B2|2021-05-19|
US10758957B2|2020-09-01|
US20180304329A1|2018-10-25|
RU2706933C2|2019-11-21|
FR3036640B1|2017-05-12|
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RU2017145407A3|2019-10-22|
CN107666977B|2020-05-22|
JP2018528864A|2018-10-04|
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EP3302874B1|2021-10-13|
WO2016189254A1|2016-12-01|
CA2986788A1|2016-12-01|
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优先权:
申请号 | 申请日 | 专利标题
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