CN103074532A - Method for preparing solid solution toughened wolfram-base composite material through laser rapid forming - Google Patents
Method for preparing solid solution toughened wolfram-base composite material through laser rapid forming Download PDFInfo
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Abstract
The invention belongs to the technical field of laser rapid forming, and particularly relates to preparation of a solid solution toughened wolfram-base composite material. A preparation method of the solid solution toughened wolfram-base composite material is as follows: original mixed powder comprises W (wolfram) powder and TiC powder, wherein the TiC powder is 1-1.5wt percent of the total content; and the mixed powder is ball-milled in a high-energy mechanical ball mill for 30-45 h, and then the TiC/W composite material is formed by using a selective laser melting process. The parameters of the adopted laser process are as follows: the powder-bed depth is 50-60 Mum, the laser spot diameter is 200-210 Mum, the laser power is 120-140 W, the laser scanning rate is 100-300 mm/s, and the laser scanning interval is 120-140 Mum. According to the invention, the solid solution toughened wolfram-base composite material is successfully prepared through the method that combines high-energy mechanical ball milling and the selective laser melting process, and the fragility of W material is effectively improved.
Description
Technical field
The invention belongs to the Laser Rapid Prototyping Technique field, particularly to the preparation of the toughness reinforcing tungsten-based composite material of a kind of solid solution.
Background technology
W and alloy thereof because their superior performances, such as high-melting-point, high elastic coefficient, high thermal-shock resistance and low thermal expansivity and good hot strength, make them become desirable high-temperature structural material.Yet, their more distinctive fragility, namely low temperature brittleness, recovery and recrystallization fragility and irradiation fragility have greatly limited W and alloy thereof as the application of structured material.Studies show that, the fragility of W and alloy thereof mainly is owing to locating the generation of crackle in the grain boundary and expanding to cause, and the toughness of W and alloy thereof and grain-size and distribute closely related, grain-size is less, distribute more even, its toughness better (its ductile-brittle transition temperature reduces), this is that the attenuation of grain boundary is poorer because grain-size is less.Especially, by in the pure tungsten matrix, adding nano level ceramic particle, can improve well the fragility of W.Because at high temperature, nano particle hindered the grain boundary movement, suppressed growing up of recovery and recrystallization and crystal grain, improved toughness and the creep-resistant property of W based composites.Specifically, under higher energy, nano-ceramic particle can be solidly soluted in the middle of the W matrix, forms gap/displacement solid solution phase; And gap/displacement solid solution phase can cause the W lattice that local distortion occurs, and then the stress field of generation centered by gap/displacement position, when the crystal cracking tip interacts with this stress, can cause the effects such as crackle deflects, branch, stop the continuation expansion of crackle, improved the toughness of W based composites.
Generally speaking, most of W metallic substance adopts the powder metallurgy process preparation, because its high-melting-point characteristic, so must under higher temperature, carry out sintering processing to it, and carry out subsequently heat treatment.Yet W and alloy thereof are in hot procedure, and crystal grain will be exposed in the hot environment for a long time, cause the grain growth of W and alloy thereof; Because the attenuation on the grain boundary will obviously reduce the high-temperature behavior of W and alloy thereof.So in order to improve the toughness of W and alloy thereof, reduce growing up of W crystal grain in the course of processing, be necessary to adopt a kind of preparation method of Quick-forming.
Summary of the invention
The objective of the invention is: provide the preparation method of the toughness reinforcing tungsten-based composite material of a kind of solid solution, to improve the fragility problem of W material.
The present invention is achieved by the following technical solutions: at first adopt high-energy mechanical ball milling technique to prepare the TiC/W nano composite powder, utilize subsequently precinct laser fusion (Selective Laser Melting, SLM) technique that composite powder is carried out the Quick-forming preparation.Set rational laser technical parameters (laser power, sweep velocity, sweep span, shop powder thickness), utilize higher laser energy that nano TiC is solidly soluted in the middle of the W.Wherein the Ti atom enters in the middle of the W lattice in the mode of displacement, forms Ti
xW
1-x(x=0.1 ~ 0.86) solid solution phase; And the C atom enters in the middle of the W lattice in the mode in gap, finally forms W
2The C ceramic phase.In addition, because the fusing/solidification rate of laser fast forming technique is fast, W crystal grain has little time to grow up, and has finally prepared the toughness reinforcing W based composites of solid solution of small-size grains, has improved the fragility of W material.
A kind of laser fast forming prepares the method for the toughness reinforcing tungsten-based composite material of solid solution, it is characterized in that carrying out according to the following steps:
(1) mixed powder by purity is more than 99.8%, average particle size particle size is 50 ~ 70 nm TiC powder and purity be more than 99.9%, average particle size particle size is the W powder constituent of 4.5 ~ 5.5 μ m, wherein the TiC powdery components accounts for 1 ~ 1.5wt.% of total content;
(2) adopt single tank planetary high-energy ball mill to carry out ball milling, argon gas is protected, and adds diameter and be the Stainless Steel Ball of Ф 6 ~ Ф 10 mm as ball-milling medium, and the mass ratio of abrading-ball and powder is 8:1 ~ 10:1, drum's speed of rotation is 250 ~ 300 rpm, and Ball-milling Time is 30 ~ 45h;
(3) set up test specimen model to be processed, and utilize delamination software to carry out hierarchy slicing in the model short transverse;
(4) in the laser forming process, a formation cylinder substrate is horizontally fixed on the platform, argon gas is filled with in the tightness system and protects, and power spreading device is layered on powder on the formation cylinder substrate, and spreading powder thickness is 50 ~ 60 μ m; Subsequently, laser beam successively scans powder bed surface according to the design good model; Laser technical parameters is as follows: laser spot diameter 200 ~ 210 μ m, laser power 120 ~ 140 W, laser scanning speed 100 ~ 300 mm/s, laser scanning spacing 120 ~ 140 μ m.
Used SLM technique in the technical scheme of the present invention, SLM is as a kind of novel Rapid Prototyping technique, can utilize high energy laser beam to melt selectively/solidify the bulky powder thin layer, successively produce fast the 3 d part with complicated shape, and do not need subsequent disposal.SLM is based on fully fusing/coagulation mechanism, and the microstructure of material and over-all properties are significantly improved; Simultaneously, laser technical parameters can greatly affect the mass formation of shaping sample:
(1) laser power
How much endergonic the size of laser power directly determines in the powder unit time, and laser power is excessively low, and the ability of powder absorption is on the low side, causes in the molten bath amount of liquid phase on the low side, is unfavorable for liquid spreading, causes shaping test specimen density low; Otherwise laser power is excessive, easily causes " nodularization effect ", because the higher meeting of energy that powder receives makes the molten bath overheated, the thermal stresses that produces in the solidified structure is larger, causes part deformation and cracking simultaneously.
(2) laser scanning speed
Scanning speed and laser power density complement each other, if the suitable laser scanning speed that reduces, then the liquid phase lifetime prolongs relatively, and this is to liquid phase flow and sprawl very favourablely, is beneficial to simultaneously the wettability of improving solid liquid phase, improves the density of shaping sample.
(3) laser scanning spacing
The laser scanning spacing has significant impact to the surface topography of laser forming sample; When sweep span reduced within the specific limits, the surface smoothness of shaping test specimen can well be improved.
(4) spread powder thickness
Generally speaking, square relation of being inversely proportional to of shaping density and powder thickness, the density that namely is shaped reduces and increases with powder layer thickness; But simultaneously, when pawnshop powder thickness is too small, cause that easily the shaping sample shrinks, and spread the powder roller equipment and make easily that sintered layer is subjected to displacement in predetermined position, and then cause the test specimen density to descend.
Adopt the SLM complete processing to prepare the toughness reinforcing W based composites of solid solution, because it makes starting powder melt/solidify at short notice, W crystal grain has little time to grow up; In addition, higher energy can make nano-ceramic particle be solidly soluted in the middle of the W matrix, the final toughness reinforcing W based composites of preparation solid solution that is shaped.
Advantage of the present invention is: the method that the present invention adopts high-energy mechanical ball milling and SLM fast shaping technology to combine prepares the toughness reinforcing W based composites of solid solution, the interaction of powder particle and laser is different from other traditional powder metallurgical technique processes, because its fusing/behavior of solidifying is different from other technique.Principal character is the following aspects:
(1) the liquid phase molten bath lifetime in the forming process is shorter, and rate of cooling is about 10
5~ 10
6K/s.The fusing of this quick forming method/solidify is a kind of height nonequilibrium process, has higher condensate depression and rate of cooling, and setting time is extremely short, and crystal grain does not have the sufficient time to grow up.
(2) linear energy density of the input of the laser in the course of processing is very high, is about 600 ~ 1300 J/m.The high density energy that laser irradiation provides makes the ceramic particle fusing, and is solidly soluted in the middle of the W matrix, has formed Ti
xW
1-x(x=0.1 ~ 0.86) solid solution phase and W
2The C ceramic phase, thus the expansion of crackle suppressed, improved the fragility of W based composites.
Description of drawings
Fig. 1 is the XRD figure spectrum of SLM shaping sample among the embodiment 1;
Fig. 2 is the SEM picture in SLM shaping sample cross section among the embodiment 1;
Fig. 3 is the energy spectrogram in SLM shaping sample cross section among the embodiment 1;
Fig. 4 is the XRD figure spectrum of SLM shaping sample among the embodiment 2;
Fig. 5 is the SEM picture in SLM shaping sample cross section among the embodiment 2;
Fig. 6 is the energy spectrogram in SLM shaping sample cross section among the embodiment 2;
Fig. 7 is the XRD figure spectrum of SLM shaping sample among the embodiment 3;
Fig. 8 is the SEM picture in SLM shaping sample cross section among the embodiment 3;
Fig. 9 is the energy spectrogram in SLM shaping sample cross section among the embodiment 3.
Embodiment
Below in conjunction with example the present invention is further elaborated.
Embodiment 1:
Step 1: mixed powder by purity is more than 99.8%, average particle size particle size is 50 ~ 70 nm TiC powder and purity be more than 99.9%, average particle size particle size is the W powder constituent of 4.5 ~ 5.5 μ m, wherein the TiC powdery components accounts for the 1wt.% of total content, and is placed in addition ball milling of the German Fristsch Pulverisette of company 6 single tank planetary high-energy ball mills; Adopt argon gas to protect, Stainless Steel Ball is as ball-milling medium, adds diameter and be the Stainless Steel Ball of Ф 6 ~ Ф 10 mm as ball-milling medium, and the mass ratio of abrading-ball and powder is 8:1, and rotational speed of ball-mill is 250 rpm, and the setting Ball-milling Time is 30 h; After ball milling finished, the ball grinder temperature can be very high, can opening after it cools off fully; In the vacuum operating case, open ball grinder, powdered sample is packed in the sample bag.
Step 2: the SLM shaping system of use mainly comprises: superpower Nd:YAG(λ=1.064 μ m) computer system, automatic power spreading device and the protective atmosphere device of laser apparatus, the control that be used for to be shaped.The computer aided design (CAD) of model test specimen to be processed (CAD) model, and utilize delamination software to carry out hierarchy slicing in the model short transverse.In the laser forming process, a formation cylinder substrate is horizontally fixed on the platform, argon gas is filled with in the tightness system and protects, and power spreading device is layered on powder on the formation cylinder substrate, and spreading powder thickness is the thin layer of 60 μ m; Subsequently, laser beam successively scans the powder bed surface according to the cad model that designs.Laser technical parameters is as follows: spot diameter 210 μ m, laser power 120 W, scanning speed 100 mm/s, sweep span 140 μ m.
Figure 1 shows that the XRD figure spectrum of SLM shaping sample among the embodiment 1, can be found out by the XRD figure of Fig. 1, have Ti in the W based composites of embodiment 1 preparation
xW
1-x(x=0.1 ~ 0.86) and W
2Two kinds of phases of C, show: the nano TiC in the ball-milled powder melts fully, and is solidly soluted in the middle of the W crystal grain, has formed solid solution alloy Ti
xW
1-x(x=0.1 ~ 0.86) and W
2The C ceramic phase.Figure 2 shows that the SEM picture of SLM shaping sample cross among the embodiment 1, as seen from the figure, the columnar crystal structure that the crystal grain performance is special, this is because W is face-centered cubic lattice, it is three＜100〉face directions that its preferential crystallographic is learned orientation, and the final direction of growth of selecting will be and v usually
sOne＜100〉planar orientation of (interface setting rate) angle minimum.What Figure 3 shows that SLM shaping sample cross among the embodiment 1 can spectrogram, as can be seen from the figure, contains three kinds of elements of W, Ti and C in the sample, has Ti and C element in the middle of W crystal grain has been described, has proved that further TiC melts fully, and has been solidly soluted in the middle of the W crystal grain.Table one is hardness and the fracture toughness property thereof of SLM shaping sample among the embodiment 1, and as shown in Table 1, the hardness of the W based composites of embodiment 1 preparation reaches 28.3 GPa, fracture toughness property is 11.52 MPa m
1/2, show that the toughness reinforcing W based composites of solid solution of laser fusion Quick-forming preparation has higher toughness.
SLM prepares hardness and the fracture toughness property of sample among table one embodiment 1
Embodiment 2:
Step 1: mixed powder by purity is more than 99.8%, average particle size particle size is 50 ~ 70 nm TiC powder and purity be more than 99.9%, average particle size particle size is the W powder constituent of 4.5 ~ 5.5 μ m, wherein the TiC powdery components accounts for the 1.3wt.% of total content, and is placed in addition ball milling of the German Fristsch Pulverisette of company 6 single tank planetary high-energy ball mills; Adopt argon gas to protect, Stainless Steel Ball is as ball-milling medium, adds diameter and be the Stainless Steel Ball of Ф 6 ~ Ф 10 mm as ball-milling medium, and the mass ratio of abrading-ball and powder is 8:1, and rotational speed of ball-mill is 300 rpm, and the setting Ball-milling Time is 35 h; After ball milling finished, the ball grinder temperature can be very high, can opening after it cools off fully; In the vacuum operating case, open ball grinder, powdered sample is packed in the sample bag.
Step 2: the SLM shaping system of use mainly comprises: superpower Nd:YAG(λ=1.064 μ m) computer system, automatic power spreading device and the protective atmosphere device of laser apparatus, the control that be used for to be shaped.The computer aided design (CAD) of model test specimen to be processed (CAD) model, and utilize delamination software to carry out in the hierarchy slicing laser forming process in the model short transverse, a formation cylinder substrate is horizontally fixed on the platform, argon gas is filled with in the tightness system and protects, power spreading device is layered on powder on the formation cylinder substrate, and spreading powder thickness is the thin layer of 50 μ m; Subsequently, laser beam successively scans the powder bed surface according to the cad model that designs.Laser technical parameters is as follows: spot diameter 200 μ m, laser power 130 W, scanning speed 200 mm/s, sweep span 130 μ m.
Figure 4 shows that the XRD figure spectrum of SLM shaping sample among the embodiment 2, can be found out by the XRD figure of Fig. 4, there is Ti in the W based composites of embodiment 2 preparations
xW
1-x(x=0.1 ~ 0.86) and W
2Two kinds of phases of C, show: the nano TiC in the ball-milled powder melts fully, and is solidly soluted in the middle of the W crystal grain, has formed solid solution alloy Ti
xW
1-x(x=0.1 ~ 0.86) and W
2The C ceramic phase.Figure 5 shows that the SEM picture of SLM shaping sample cross among the embodiment 2, as seen from the figure, the special columnar crystal structure of crystal grain performance in the material, this is because W is face-centered cubic lattice, it is three＜100〉face directions that its preferential crystallographic is learned orientation, and the final direction of growth of selecting will be and v usually
sOne＜100〉planar orientation of (interface setting rate) angle minimum.What Figure 6 shows that SLM shaping sample cross among the embodiment 2 can spectrogram, as can be seen from the figure, contains three kinds of elements of W, Ti and C in the sample, has Ti and C element in the middle of W crystal grain has been described, has proved that further TiC melts fully, and has been solidly soluted in the middle of the W crystal grain.Table two is hardness and the fracture toughness property thereof of SLM shaping sample among the embodiment 2, and as shown in Table 2, the hardness of the W based composites of embodiment 2 preparations reaches 28.6 GPa, fracture toughness property is 11.76 MPa m
1/2, show that the toughness reinforcing W based composites of solid solution of laser fusion Quick-forming preparation has higher toughness.
SLM prepares hardness and the fracture toughness property of sample among table two embodiment 2
Embodiment 3:
Step 1: mixed powder by purity is more than 99.8%, average particle size particle size is 50 ~ 70 nm TiC powder and purity be more than 99.9%, average particle size particle size is the W powder constituent of 4.5 ~ 5.5 μ m, wherein the TiC powdery components accounts for 1.5 wt.% of total content, and is placed in addition ball milling of the German Fristsch Pulverisette of company 6 single tank planetary high-energy ball mills; Adopt argon gas to protect, Stainless Steel Ball is as ball-milling medium, adds diameter and be the Stainless Steel Ball of Ф 6 ~ Ф 10 mm as ball-milling medium, and the mass ratio of abrading-ball and powder is 10:1, and rotational speed of ball-mill is 300 rpm, and the setting Ball-milling Time is 45 h; After ball milling finished, the ball grinder temperature can be very high, can opening after it cools off fully; In the vacuum operating case, open ball grinder, powdered sample is packed in the sample bag.
Step 2: the SLM shaping system of use mainly comprises: superpower Nd:YAG(λ=1.064 μ m) computer system, automatic power spreading device and the protective atmosphere device of laser apparatus, the control that be used for to be shaped.The computer aided design (CAD) of model test specimen to be processed (CAD) model, and utilize delamination software to carry out hierarchy slicing in the model short transverse.In the laser forming process, a formation cylinder substrate is horizontally fixed on the platform, laser beam scans the powder bed surface according to the cad model that designs; Argon gas is filled with in the tightness system and protects, and power spreading device is layered on powder on the formation cylinder substrate, and spreading powder thickness is the thin layer of 50 μ m; Subsequently, laser beam successively scans the powder bed surface according to the cad model that designs.Laser technical parameters is as follows: spot diameter 200 μ m, laser power 140 W, scanning speed 300 mm/s, sweep span 120 μ m.
Figure 7 shows that the XRD figure spectrum of SLM shaping sample among the embodiment 3, can be found out by the XRD figure of Fig. 7, there is Ti in the W based composites of embodiment 3 preparations
xW
1-x(x=0.1 ~ 0.86) and W
2Two kinds of phases of C, show: the nano TiC in the ball-milled powder melts fully, and is solidly soluted in the middle of the W crystal grain, has formed solid solution alloy Ti
xW
1-x(x=0.1 ~ 0.86) and W
2The C ceramic phase.Figure 8 shows that the SEM picture of SLM shaping sample cross among the embodiment 3, as seen from the figure, the special columnar crystal structure of crystal grain performance in the material, this is because W is face-centered cubic lattice, it is three＜100〉face directions that its preferential crystallographic is learned orientation, and the final direction of growth of selecting will be and v usually
sOne＜100〉planar orientation of (interface setting rate) angle minimum.What Figure 9 shows that SLM shaping sample cross among the embodiment 3 can spectrogram, as can be seen from the figure, contains three kinds of elements of W, Ti and C in the sample, has Ti and C element in the middle of W crystal grain has been described, has proved that further TiC melts fully, and has been solidly soluted in the middle of the W crystal grain.Table three is hardness and the fracture toughness property thereof of SLM shaping sample among the embodiment 3, and as shown in Table 3, the hardness of the W based composites of embodiment 3 preparations reaches 28.8 GPa, fracture toughness property is 11.63 MPa m
1/2, show that the toughness reinforcing W based composites of solid solution of laser fusion Quick-forming preparation has higher toughness.
SLM prepares hardness and the fracture toughness property of sample among table three embodiment 3
Claims (5)
1. a laser fast forming prepares the method for the toughness reinforcing tungsten-based composite material of solid solution, it is characterized in that carrying out according to the following steps:
(1) mixed powder by purity is more than 99.8%, average particle size particle size is 50 ~ 70 nm TiC powder and purity be more than 99.9%, average particle size particle size is the W powder constituent of 4.5 ~ 5.5 μ m, wherein the TiC powdery components accounts for 1 ~ 1.5wt.% of total content;
(2) adopt single tank planetary high-energy ball mill to carry out ball milling, argon gas is protected, and adds diameter and be the Stainless Steel Ball of Ф 6 ~ Ф 10 mm as ball-milling medium, and the mass ratio of abrading-ball and powder is 8:1 ~ 10:1, drum's speed of rotation is 250 ~ 300 rpm, and Ball-milling Time is 30 ~ 45h;
(3) set up test specimen model to be processed, and utilize delamination software to carry out hierarchy slicing in the model short transverse;
(4) in the laser forming process, a formation cylinder substrate is horizontally fixed on the platform, argon gas is filled with in the tightness system and protects, and power spreading device is layered on powder on the formation cylinder substrate, and spreading powder thickness is 50 ~ 60 μ m; Subsequently, laser beam successively scans powder bed surface according to the design good model; Laser technical parameters is as follows: laser spot diameter 200 ~ 210 μ m, laser power 120～140 W, laser scanning speed 100～300 mm/s, laser scanning spacing 120 ~ 140 μ m.
2. the method for the toughness reinforcing tungsten-based composite material of laser fast forming solid solution according to claim 1 is characterized in that in the composite granule, and the TiC powdery components accounts for 1 ~ 1.5wt.% of total content.
3. the method for the toughness reinforcing tungsten-based composite material of laser fast forming solid solution according to claim 1, it is characterized in that: adopting diameter in the mechanical ball milling is that the Stainless Steel Ball of Ф 6 ~ Ф 10 mm is as ball-milling medium, the mass ratio of abrading-ball and powder is 8:1, rotational speed of ball-mill is 250 rpm, and Ball-milling Time is 30 h; Spreading powder thickness is 60 μ m, laser spot diameter 210 μ m, laser power 120 W, laser scanning speed 100 mm/s, laser scanning spacing 140 μ m.
4. the method for the toughness reinforcing tungsten-based composite material of laser fast forming solid solution according to claim 1, it is characterized in that: adopting diameter in the mechanical ball milling is that the Stainless Steel Ball of Ф 6 ~ Ф 10 mm is as ball-milling medium, the mass ratio of abrading-ball and powder is 8:1, rotational speed of ball-mill is 300 rpm, and Ball-milling Time is 35 h; Spreading powder thickness is 50 μ m, laser spot diameter 200 μ m, laser power 130 W, laser scanning speed 200 mm/s, laser scanning spacing 130 μ m.
5. the method for the toughness reinforcing tungsten-based composite material of laser fast forming solid solution according to claim 1, it is characterized in that: adopting diameter in the mechanical ball milling is that the Stainless Steel Ball of Ф 6 ~ Ф 10 mm is as ball-milling medium, the mass ratio of abrading-ball and powder is 10:1, rotational speed of ball-mill is 300 rpm, and Ball-milling Time is 45 h; Spreading powder thickness is 50 μ m, laser spot diameter 200 μ m, laser power 140 W, laser scanning speed 300 mm/s, laser scanning spacing 120 μ m.
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| CN103949639B (en) * | 2014-05-19 | 2016-08-17 | 北京航空航天大学 | The method that a kind of selective laser smelting technology prepares Nb-Si based ultra-high temperature alloy |
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| CN106312048A (en) * | 2016-09-18 | 2017-01-11 | 广东工业大学 | Metal ceramic particle and preparation method and application thereof |
| CN106392081B (en) * | 2016-09-18 | 2019-02-22 | 广东工业大学 | A kind of surface layer is rich in the hard alloy and preparation method thereof of ceramic phase |
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| CN107541633A (en) * | 2017-08-15 | 2018-01-05 | 清华大学 | Tungsten alloy and preparation method thereof |
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| CN111511486A (en) * | 2017-10-05 | 2020-08-07 | 普兰西股份有限公司 | Additive manufactured component and method of manufacturing the same |
| US11565322B2 (en) * | 2017-10-05 | 2023-01-31 | Plansee Se | Additively manufactured component and production method therefor |
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| CN108893634A (en) * | 2018-06-08 | 2018-11-27 | 南京航空航天大学 | The former WC ceramic matric composite and its method of precinct laser fusion preparation |
| CN108907214A (en) * | 2018-08-16 | 2018-11-30 | 北京科技大学 | A kind of manufacturing process of tungsten base components |
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| WO2020102834A1 (en) | 2018-11-19 | 2020-05-28 | Plansee Se | Additively-manufactured refractory metal component, additive manufacturing process, and powder |
| WO2020102832A1 (en) | 2018-11-19 | 2020-05-28 | Plansee Se | Additively-manufactured refractory metal component, additive manufacturing process, and powder |
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| CN110842199A (en) * | 2019-11-22 | 2020-02-28 | 中南大学 | Method for preparing pure tungsten component with complex structure by selective laser melting |
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| CN114559051A (en) * | 2022-01-25 | 2022-05-31 | 中北大学 | Laser forming method of TiC/WC/17-4PH high-temperature wear-resistant steel |
| CN114559051B (en) * | 2022-01-25 | 2023-05-26 | 中北大学 | Laser forming method of TiC/WC/17-4PH high-temperature wear-resistant steel |
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