WO2021114940A1 - 一种原位纳米TiB晶须增强钛基复合材料的制备方法 - Google Patents

一种原位纳米TiB晶须增强钛基复合材料的制备方法 Download PDF

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WO2021114940A1
WO2021114940A1 PCT/CN2020/124993 CN2020124993W WO2021114940A1 WO 2021114940 A1 WO2021114940 A1 WO 2021114940A1 CN 2020124993 W CN2020124993 W CN 2020124993W WO 2021114940 A1 WO2021114940 A1 WO 2021114940A1
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powder
tib
titanium
based composite
composite material
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刘允中
周志光
詹强坤
王凯冬
刘小辉
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华南理工大学
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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    • B33Y70/00—Materials specially adapted for additive manufacturing
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    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
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    • C22C49/11—Titanium
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/22—Driving means
    • B22F12/226—Driving means for rotary motion
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    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/60—Planarisation devices; Compression devices
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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    • B22F2998/10—Processes characterised by the sequence of their steps
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention belongs to the technical field of titanium-based composite materials and additive manufacturing, and specifically relates to a method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material.
  • Titanium-based composite materials have higher specific strength and better wear resistance and high temperature performance than titanium alloys. In aerospace, weaponry and other fields, it is one of the best candidate materials for improving mechanical properties, reducing weight, and improving efficiency. .
  • the in-situ autogenous method is to generate a reinforcing phase in the matrix through a chemical reaction, and a composite material with good interface bonding, clean and pollution-free can be obtained.
  • Discontinuously reinforced titanium-based composites have the characteristics of isotropy and low cost, which have become the main research direction at present. In particular, TiB whiskers and TiC particles are considered to be the best reinforcement phases in titanium-based composites.
  • discontinuous reinforced titanium-based composite materials have been mainly prepared by melting and casting methods and powder metallurgy methods.
  • the fusion casting method has the phenomenon of coarse grains, many defects, coarse reinforcement phases and mainly agglomerated on the grain boundaries. It usually requires further thermal processing to improve its mechanical properties, and then machining to make parts with a certain shape. Titanium alloy machining has problems such as high cutting temperature, strong chemical activity, and serious sticking phenomenon. Compared with the matrix titanium alloy, the machining of titanium-based composite materials is more difficult. Therefore, the preparation of titanium-based composites by the melting and casting method has the problems of high energy consumption, low material utilization, and serious cutting tool wear. Powder metallurgy is the earliest application and the most used preparation method for titanium-based composite materials.
  • the room temperature and high temperature properties of the prepared materials are significantly improved compared to the base materials.
  • Huang Junjun and others used this method to successfully prepare (TiB+TiC)/TC4 titanium-based composites with different reinforcement phase contents, of which 3 vol.% (TiB+TiC)/TC4 titanium-based composites have better strengthening effects and yield
  • the strength is 1066MPa
  • the tensile strength is 1129MPa
  • the elongation is 2.4%.
  • In situ (TiBw + TiCp)/Ti 6 Al 4 V composites with a network reinforcement distribution Materials Science and Engineering A 527 (2010) 6723–6727.
  • the powder metallurgy method requires high equipment, complex procedures, and high cost, and it is difficult to prepare large-scale parts, complex-shaped parts and mass production.
  • the lightweight design of components has important application value. On the one hand, it can be achieved by using higher specific strength materials. For titanium products, the specific strength of the material can be effectively improved by designing titanium-based composite materials; on the other hand, it can be achieved based on structural optimization design, such as integrated complex structures. , Special-shaped topology optimization structure, hollow sandwich/thin-wall reinforced structure, hollow lattice structure, and the above structure optimization through traditional casting forge welding and machining methods will not only increase the cost of parts preparation, but also difficult to meet its requirements. As a kind of additive manufacturing, SLM technology has the characteristics of short part development cycle, high material utilization rate, and the ability to form complex parts with arbitrary shapes. It has significant advantages in integrated forming and net forming.
  • the purpose of the present invention is to provide a method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material.
  • the method not only effectively overcomes the shortcomings of the above-mentioned traditional preparation technology, but also prepares titanium-based composite material structural parts with complex shapes.
  • the composite powder prepared by this method undergoes SLM forming and stress relief annealing, and the grains of the products obtained are significantly refined, and the strength, hardness, and wear resistance are significantly improved compared to the TC4 titanium alloy material.
  • the preparation method of in-situ nano-TiB whisker-reinforced titanium-based composite material provided by the present invention is a process for preparing in-situ nano-TiB whisker-reinforced titanium-based composite material by SLM forming.
  • the present invention adopts the following technical scheme: adopting a combination of short-time low-energy ball milling, laser selective melting and forming, and stress relief annealing. And by controlling the above three processes in the process to prepare the required materials.
  • the method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material provided by the present invention includes the following steps:
  • step (1) The composite powder described in step (1) is used for SLM forming.
  • the powder spreading device places the composite powder on the forming substrate, and melts the composite powder in the slicing area by a laser beam, and waits for it to condense.
  • To complete the formation of a layer lower the working cylinder to the height of the preset powder layer thickness, lay the next layer of powder, and continue to melt the composite powder in the slicing area through the laser beam. After the next layer of composite powder is solidified, repeat the above steps , Until the three-dimensional block sample is formed;
  • step (3) The three-dimensional bulk sample and the substrate of step (2) are subjected to stress relief annealing treatment in a vacuum sintering furnace, and then the sample member is cut from the substrate by wire cutting to obtain the in-situ nano-TiB whiskers Reinforced titanium-based composite materials.
  • the morphology of the micron TC4 titanium alloy powder is spherical, the particle size of the micron TC4 titanium alloy powder is 15-53 ⁇ m, and the oxygen content of the micron TC4 titanium alloy powder is less than 1000 ppm.
  • Spherical TC4 titanium alloy powder has good fluidity, which is beneficial to optimize the powder spreading effect.
  • the oxygen content of TC4 titanium alloy powder needs to be controlled. If it is too high, it is not conducive to material formation and mechanical properties. Irregular nano TiB 2 powder is conducive to more uniform ceramic particles. Ground embedded TC4 titanium alloy powder surface.
  • step (1) the morphology of the nano TiB 2 powder is irregular, and the average particle size of the nano TiB 2 powder is 100 nm.
  • the mass fraction of the nano-TiB 2 powder is 0.59wt%-1.76wt%.
  • the TiB in the in-situ nano-TiB whisker-reinforced titanium-based composite material The volume fraction of the reinforcing phase is 1-3%.
  • the ball milling medium used in the ball milling process in step (1) is stainless steel balls, and the ball-to-material ratio is 4:1-10:1.
  • the ball milling treatment is short-time low-energy ball milling, the rotation speed of the ball milling treatment is 120-180 rpm, and the time of the ball milling treatment is 1-3 h.
  • the ball milling speed is too low or the time is too short, the original agglomerated nano TiB2 powder is not easy to disperse, and the dispersion and fitting effects are not good; if the ball milling speed is too high or the time is too long, it will cause serious damage to the sphericity of the TC4 titanium alloy powder , Is not conducive to SLM forming.
  • the process parameters of the SLM forming in step (2) the laser power is 60-160W, the scanning speed is 200-1000mm/s, the scanning distance is 50-90 ⁇ m, the powder layer thickness is 30-50 ⁇ m, and the substrate is preheated The temperature is 160-200°C.
  • the powder If the energy density is too low, the powder will not be fully melted, large-scale irregular pores are prone to appear, and the interlayer welding effect is not good; if the energy density is too high, the melt splash will be serious, the surface will be uneven, and the phenomenon of scraping will easily occur. As a result, the SLM forming process is interrupted. At the same time, because the temperature of the molten pool is far above the boiling point of the metal element, a large number of spherical keyholes appear, reducing the density of the material.
  • the temperature of the stress relief annealing treatment in step (3) is 500-650° C.
  • the time of the stress relief annealing treatment is 2-6 hours.
  • the directly cut shaped sample is prone to cracks, so that its mechanical properties are extremely low.
  • the invention designs short-time low-energy ball milling technology and combines SLM technology to prepare in-situ nano-TiB whisker-reinforced titanium-based composite materials.
  • the composite powder prepared by short-term low-energy ball milling can meet the powder characteristics of SLM forming, and solve the uneven distribution, unreliable combination, serious damage of sphericity, and introduction of mechanical powder mixing, high-energy ball milling, and electrostatic self-assembly methods. Impurities and other issues.
  • the titanium-based composite material prepared by SLM technology has high density, fine grains, and uniform reinforcement phase distribution. At the same time, it has obvious advantages in forming complex-shaped titanium-based composite material structures.
  • the present invention has the following advantages and beneficial effects:
  • the preparation method provided by the present invention adopts a short-time low-energy ball milling process to prepare composite powder with nano TiB 2 particles evenly embedded on the surface of TC4 titanium alloy powder. Compared with micron TiB 2 particles, nano TiB 2 particles are evenly embedded in TC4 titanium.
  • the ball milling energy required on the surface of the alloy powder is much lower, so that the sphericity of the TC4 titanium alloy powder can be maximized, so that it can still maintain good powder fluidity;
  • element B Due to the extremely fast cooling rate and extremely high temperature gradient during the SLM forming process, the matrix structure is easy to form fine columnar crystals, and the reinforcing phase is too late to grow up to the nanometer scale; and in the preparation method provided by the present invention, element B The introduction of is conducive to the formation of a larger component supercooled zone in the melt, which not only significantly increases the nucleation rate, further refines the grains, but also suppresses the formation of columnar crystals to a certain extent and reduces the anisotropy of the material;
  • the performance of titanium-based composite materials prepared with pure titanium as the matrix is not outstanding, and the application is limited.
  • the present invention uses high-strength TC4 titanium alloy as the matrix, and succeeds in adjusting the TiB content and optimizing the laser process parameters.
  • the preparation of high-performance titanium-based composite materials to further improve the specific strength has good application prospects in the aerospace field.
  • Figure 1 is a diagram of the morphology of the composite powder prepared in Example 2;
  • Figure 2 is a scanning electron micrograph of the titanium-based composite material prepared in Example 2;
  • Figure 3 is a transmission electron micrograph of the SLM formed TC4 titanium alloy material and the titanium-based composite material prepared in Example 2;
  • Example 4 is a graph showing the compression performance of SLM formed TC4 titanium alloy material and the titanium-based composite material prepared in Example 2;
  • Example 5 is a graph showing the tensile properties of the SLM formed TC4 titanium alloy material and the titanium-based composite material prepared in Example 2.
  • This embodiment relates to a method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material, wherein the volume fraction of TiB is 1%, and includes the following steps:
  • Step 1 Mix TC4 titanium alloy powder with a particle size of 15 ⁇ 53 ⁇ m and TiB 2 particles with a particle size of 100nm in a glove box, and place them in a ball mill tank, and fill the ball mill tank with argon as a protective gas.
  • the mass fraction of TiB 2 is 0.59%.
  • Step 2 Place the ball mill jar containing the mixed powder on a planetary ball mill for short-time low-energy ball milling to prepare composite powder for SLM.
  • the ball milling medium is stainless steel balls, the ball-to-material ratio is 5:1, the ball milling speed is 130rpm, and the ball milling time is 2h.
  • Step 3 Use the above-mentioned composite powder for SLM forming, and the model of SLM forming equipment is EOS M290.
  • the specific SLM forming process is as follows:
  • the powder spreading device evenly spreads a layer of 40 ⁇ m composite powder on the formed substrate; the laser beam melts the composite powder in the slicing area according to the CAD model, where the spot diameter is 100 ⁇ m, the laser power is 150w, and the scanning rate is 1000mm/ s, the scanning distance is 60 ⁇ m, and the current layer is formed after it is condensed;
  • Step 4 Perform stress relief annealing on the sample and substrate after the above-mentioned forming in a vacuum sintering furnace, and then cut the sample from the substrate by wire cutting, using a stress relief annealing temperature of 500°C and a duration of 3 hours to obtain The in-situ nano-TiB whisker reinforced titanium matrix composite material (1vol.% TiB whisker reinforced titanium matrix composite material).
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material and the TC4 titanium alloy material prepared by SLM forming the same matrix powder in this example were subjected to a micro Vickers hardness test.
  • the hardness of the 1vol.%TiB whisker-reinforced titanium-based composite material was 421Hv
  • the hardness of TC4 titanium alloy material is 390Hv.
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material in this embodiment is compressed at room temperature, and the strain rate is set to 5 ⁇ 10 -4 s -1 .
  • the yield strength of the 1vol.% TiB whisker reinforced titanium matrix composite is 1418MPa, and the compressive strength is 1583MPa.
  • This embodiment relates to a method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material, wherein the volume fraction of TiB is 2%, and includes the following steps:
  • Step 1 Mix TC4 titanium alloy powder with a particle size of 15-53 ⁇ m and TiB 2 particles with a particle size of 100nm in a glove box, and place them in a ball mill tank, and fill the ball mill tank with argon as a protective gas, where the mass fraction of TiB 2 is 1.18%.
  • Step 2 Place the ball mill jar containing the mixed powder on a planetary ball mill for short-time low-energy ball milling to prepare composite powder for SLM.
  • the ball milling medium is stainless steel balls, the ball-to-material ratio is 5:1, the ball milling speed is 140rpm, and the ball milling time is 2h.
  • Step 3 Use the above-mentioned composite powder for SLM forming, and the model of SLM forming equipment is EOS M290.
  • the specific SLM forming process is as follows:
  • the powder spreading device evenly spreads a layer of 40 ⁇ m composite powder on the formed substrate; the laser beam melts the composite powder in the slicing area according to the CAD model, where the spot diameter is 100 ⁇ m, the laser power is 120w, and the scanning rate is 600mm/ s, the scanning distance is 60 ⁇ m, and the current layer is formed after it is condensed;
  • Step 4 Perform stress relief annealing on the formed sample and the substrate in a vacuum sintering furnace, and then cut the sample from the substrate by wire cutting.
  • the stress relief annealing temperature is 550°C and the duration is 3 hours.
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material in this example was subjected to a micro Vickers hardness test, and the hardness of the 2vol.% TiB whisker-reinforced titanium-based composite material was 445Hv.
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material and the TC4 titanium alloy material prepared by SLM forming the same matrix powder in this example were subjected to room temperature compression and tensile experiments, and the strain rate was set to 5 ⁇ 10 -4 s -1 , where , Apply an extensometer in the room temperature tensile experiment to accurately measure the elongation.
  • the yield strength of the 2vol.%TiB whisker-reinforced titanium matrix composite is 1530MPa and the compressive strength is 1692MPa; the yield strength of the TC4 titanium alloy material is 1216MPa, and the compressive strength is 1466MPa.
  • the yield strength of the 2vol.%TiB whisker-reinforced titanium matrix composite is 1378 MPa, the tensile strength is 1434 MPa, and the elongation is 3.7%; the yield strength of the TC4 titanium alloy material is 1076 MPa, and the tensile strength is 1140MPa, the elongation rate is 7.6%, please refer to Figure 4 and Figure 5.
  • the 2vol.%TiB whisker-reinforced titanium-based composite material has a 26% increase in compressive yield strength, a 15% increase in compressive strength, a 28% increase in tensile yield strength, and a 26% increase in tensile strength. The strengthening effect is remarkable.
  • Figure 1 is the morphology of the composite powder prepared in Example 2. From the composite powder morphology of Figure 1, it can be seen that the nano-TiB 2 particles are evenly embedded on the surface of the TC4 titanium alloy powder, and the TC4 titanium alloy powder can maintain good Sphericity.
  • Figure 2 is a scanning electron micrograph of the titanium-based composite material prepared in Example 2. It can be seen from the scanning electron micrograph of Figure 2 that TiB aggregates into whisker clusters near the columnar primary ⁇ crystal grains, and TiB crystals inside the initial columnar ⁇ crystal grains The whiskers are uniformly distributed, and the radial dimension of a single TiB whisker reaches the nanometer level.
  • Figure 3 is a transmission electron micrograph of the SLM formed TC4 titanium alloy material and the titanium-based composite material prepared in Example 2.
  • Part (a) of Figure 3 is a transmission electron microscope image of the SLM formed TC4 titanium alloy material
  • part (b) of Figure 3 This is the transmission electron microscope image of the titanium-based composite material prepared in Example 2. It can be seen from the transmission electron microscope image of Figure 3 that compared to the SLM formed TC4 titanium alloy material, the in-situ nano-TiB whisker-reinforced titanium-based composite material has significant grains Refinement.
  • This embodiment relates to a method for preparing an in-situ nano-TiB whisker-reinforced titanium-based composite material, wherein the volume fraction of TiB is 3%, and includes the following steps:
  • Step 1 Mix TC4 titanium alloy powder with a particle size of 15 ⁇ 53 ⁇ m and TiB 2 particles with a particle size of 100nm in a glove box, and place them in a ball mill tank, and fill the ball mill tank with argon as a protective gas.
  • the mass fraction of TiB 2 is 1.76%.
  • Step 2 Place the ball mill jar containing the mixed powder on a planetary ball mill for short-time low-energy ball milling to prepare composite powder for SLM.
  • the ball milling medium is stainless steel balls, the ball-to-material ratio is 5:1, the ball milling speed is 150rpm, and the ball milling time is 2h.
  • Step 3 Use the above-mentioned composite powder for SLM forming, and the model of SLM forming equipment is EOS M290.
  • the specific SLM forming process is as follows:
  • the powder spreading device evenly spreads a layer of 40 ⁇ m composite powder on the formed substrate; the laser beam melts the composite powder in the slicing area according to the CAD model, where the spot diameter is 100 ⁇ m, the laser power is 70w, and the scanning rate is 200mm/ s, the scanning distance is 60 ⁇ m, and the current layer is formed after it is condensed;
  • Step 4 Perform stress relief annealing on the sample and substrate after the above forming in a vacuum sintering furnace, and then cut the sample from the substrate by wire cutting, using a stress relief annealing temperature of 550°C and a duration of 3 hours to obtain The in-situ nano-TiB whisker-reinforced titanium-based composite material (3vol.% TiB whisker-reinforced titanium-based composite material).
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material in this example was subjected to a micro Vickers hardness test, and the hardness of the 3vol.% TiB whisker-reinforced titanium-based composite material was 467Hv.
  • the in-situ nano-TiB whisker-reinforced titanium-based composite material in this example was compressed at room temperature, and the strain rate was set to 5 ⁇ 10 -4 s -1 , and the yield strength of the 3vol.% TiB whisker-reinforced titanium-based composite material was 1605 MPa, and the resistance The compressive strength is 1760MPa.

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Abstract

一种原位纳米TiB晶须增强钛基复合材料的制备方法，包括以下步骤：S1、选用纳米TiB2颗粒和微米TC4钛合金粉末，在手套箱中按比例称量上述两种粉末置于球磨罐中；S2、将混合粉末置于行星式球磨机上进行短时低能球磨以制备纳米TiB2颗粒均匀镶嵌于TC4钛合金粉末表面的复合粉末；S3、将复合粉末用于激光选区熔化成形制备原位TiB晶须增强钛基复合材料；S4、将SLM成形试样连同基板在真空烧结炉内进行去应力退火，再用线切割将试样从基板上切割下来。该方法制备的钛基复合材料晶粒细化明显，强度、硬度、耐磨性显著提高，在航空航天等领域具有良好的应用前景。

Description

一种原位纳米TiB晶须增强钛基复合材料的制备方法 技术领域
本发明属于钛基复合材料及增材制造技术领域，具体地，涉及一种原位纳米TiB晶须增强钛基复合材料的制备方法。
 背景技术
钛基复合材料具有比钛合金更高的比强度及更优异的耐磨性、高温性能, 在航空航天、武器装备等领域，是提高力学性能、降低重量、提高效能的最佳候选材料之一。其中，原位自生法是通过化学反应在基体内生成增强相，可以得到界面结合良好、干净无污染的复合材料。非连续增强钛基复合材料具有各向同性、成本较低等特点，成为目前主要研究方向，尤其是TiB晶须和TiC颗粒被认为是钛基复合材料中最佳的增强相。近年来，主要采用熔铸法和粉末冶金法制备非连续增强钛基复合材料。然而，熔铸法存在晶粒粗大、缺陷较多、增强相粗化且主要团聚在晶界上的现象，通常需进一步热加工以提高其力学性能，再经机加工制成具有一定形状的零件。钛合金机加工时存在切削温度高、化学活性强、粘刀现象严重等问题，而钛基复合材料相比其基体钛合金机加工难度更高。因此，熔铸法制备钛基复合材料存在能耗高、材料利用率低、切削刀具损耗严重的问题。粉末冶金法是钛基复合材料最早应用也是采用最多的制备方法，制备的材料室温及高温性能相比基体材料均有明显的提高。如：黄陆军等人采用此法成功制备不同增强相含量的(TiB+TiC)/TC4钛基复合材料，其中3 vol. % (TiB+TiC)/TC4钛基复合材料强化效果较好，屈服强度为1066MPa，抗拉强度为1129MPa，延伸率为2.4%。（In situ (TiBw + TiCp)/Ti 6Al 4V composites with a network reinforcement distribution，Materials Science and Engineering A 527 (2010) 6723–6727）。但粉末冶金法对设备要求高，工序复杂，成本较高，难以制备大型零件、复杂形状零件及大批量生产。
在航空航天和国防领域中，构件的轻量化设计具有重要的应用价值。一方面可以通过采用更高比强度的材料来实现，就钛产品而言，通过设计钛基复合材料可有效提高材料的比强度；另一方面可以基于结构优化设计来实现，如一体化复杂结构、异形拓扑优化结构、中空夹层/薄壁加筋结构、镂空点阵结构，而通过传统铸锻焊及机加工方式来实现以上结构优化，不仅会加重零件制备成本，还难以满足其要求。SLM技术作为增材制造的一种，具有零件开发周期短、材料利用率高、可成形任意形状复杂零件等特点，在一体化成形及净成形方面具有显著优势。同时，得益于SLM成形过程中非常快的冷却速度（约为10 3-10 6k/s），不仅基体晶粒明显细化，增强相也显著细化，可达纳米级，可进一步提高钛基复合材料力学性能。目前，SLM成形钛基复合材料的研究报道较少，且主要选择强度较低的纯钛作为基体材料，其强化效果虽然显著，但与SLM成形TC4的性能相比并无优势，进而限制了其应用。如：Hooyar Attar等人采用SLM成功制备了8.35vol.%TiB/Ti复合材料，该材料硬度、抗压强度达到402Hv、1421MPa（Selective laser melting of in situ titanium–titanium boride composites: Processing, microstructure and mechanical properties，Acta Materialia 76 (2014) 13-22）。Beibei He等人采用SLM成功制备了5vol.%TiC/Ti复合材料，其抗拉强度仅为914 MPa（The formation mechanism of TiC reinforcement and improved tensile strength in additive manufactured Ti matrix nanocomposite，Vacuum 143 (2017) 23-27）。作为对比，本工作也制备了SLM成形TC4钛合金材料，其硬度、抗压强度、抗拉强度分别为390Hv、1461 MPa、1140 MPa。因此，采用强度更高的钛合金作为基体是SLM成形钛基复合材料的重点发展方向之一。
技术解决方案
本发明目的在于提供一种原位纳米TiB晶须增强钛基复合材料的制备方法。该方法不仅有效克服上述传统制备技术的不足之处，还能制备复杂形状的钛基复合材料结构件。此方法制备的复合粉末经SLM成形及去应力退火所得制品晶粒显著细化，强度、硬度、耐磨性相对于TC4钛合金材料显著提高。
本发明提供的原位纳米TiB晶须增强钛基复合材料的制备方法是一种SLM成形制备原位纳米TiB晶须增强钛基复合材料的工艺。
本发明为实现其技术目的采用如下技术方案：采用短时低能球磨、激光选区熔化成形、去应力退火相结合的方法。并通过控制以上三个过程中的工艺来制备所需材料。
本发明提供的一种原位纳米TiB晶须增强钛基复合材料的制备方法，包括如下步骤：
（1）选用纳米TiB 2颗粒和微米TC4钛合金粉末为原材料，根据公式vol.% TiB= 1.7×wt.% TiB 2，在手套箱中按比例称量上述两种粉末置于球磨罐，向球磨罐中充入氩气作为保护气体；然后在氩气气氛下进行球磨处理，使纳米TiB 2颗粒均匀镶嵌于TC4钛合金粉末表面，并保持良好的粉末球形度，得到复合粉末；
（2）将步骤（1）所述复合粉末用于SLM成形，在SLM过程中，铺粉装置将复合粉末铺放在成形基板上，通过激光束熔化切片区内的复合粉末，待其冷凝后完成一层成形，将工作缸下降预设铺粉层厚的高度，铺设下一层粉末，继续通过激光束熔化切片区域内的复合粉末，待所述下一层复合粉末凝固后，重复以上步骤，直至三维块体试样成形完毕；
（3）将步骤（2）所述三维块体试样连同基板在真空烧结炉内进行去应力退火处理，然后采用线切割将样品构件从基板上切割下来，得到所述原位纳米TiB晶须增强钛基复合材料。
进一步地，步骤（1）所述微米TC4钛合金粉末的形貌呈球形，所述微米TC4钛合金粉末的粒径为15-53μm，所述微米TC4钛合金粉末的含氧量<1000ppm。
球形TC4钛合金粉末流动性好，有利于优化铺粉效果，TC4钛合金粉末含氧量需要控制，过高则不利于材料成形及其力学性能，不规则纳米TiB 2粉末有利于陶瓷颗粒更均匀地嵌入TC4钛合金粉末表面。
进一步地，步骤（1）所述纳米TiB 2粉末的形貌呈不规则状，所述纳米TiB 2粉末的平均粒径为100nm。
进一步地，在步骤（1）所述复合粉末中，纳米TiB 2粉末的质量分数为0.59wt%-1.76wt%，相对应的，在所述原位纳米TiB晶须增强钛基复合材料中TiB增强相的体积分数为1-3%。
在所述原位纳米TiB晶须增强钛基复合材料中，若TiB体积分数低于1%，则增强效果不明显，若TiB体积分数高于3%，SLM成形过程中容易产生裂纹。
进一步地，步骤（1）所述球磨处理采用的球磨介质为不锈钢球，球料比为4:1-10:1。所述球磨处理处理为短时低能球磨，球磨处理的转速为120-180rpm，球磨处理的时间为1-3h。
如果球磨转速过低或时间过短，原始团聚的纳米TiB2粉末不易打散，分散和嵌合效果均不佳；如果球磨转速过高或时间过长，则会导致TC4钛合金粉末球形度破坏严重，不利于SLM成形。
进一步地，步骤（2）所述SLM成形的工艺参数： 激光功率为60-160W，扫描速度为200-1000mm/s，扫描间距为50-90μm，铺粉层厚为30-50μm，基板预热温度为160-200℃。
若能量密度过低，粉末熔化不充分，易出现较大尺度的不规则孔隙，层间焊合效果不佳；若能量密度过高，熔体飞溅严重，表面不平整，易出现刮刀现象，从而导致SLM成形过程中断，同时由于熔池温度远超金属元素沸点，出现大量球形匙孔，降低材料致密度。
进一步地，步骤（3）所述去应力退火处理的温度为500-650℃，去应力退火处理的时间为2-6h。
若在线切割前未进行去应力退火，直接切割下来的成形样易出现裂纹，从而使其力学性能极低。
本发明设计了短时低能球磨技术，并结合SLM技术制备原位纳米TiB晶须增强钛基复合材料。其中，短时低能球磨制备的复合粉末可满足SLM成形对粉末的特性要求，解决了机械混粉、高能球磨、静电自组装法易出现的分布不均匀、结合不牢靠、球形度破坏严重、引入杂质等问题。SLM技术制备的钛基复合材料致密度高，晶粒细小，增强相分布均匀，同时，在成形复杂形状钛基复合材料结构件方面具有明显的优势。
 有益效果
与现有技术相比，本发明具有如下优点和有益效果：
（1）本发明提供的制备方法，采用短时低能球磨工艺制备纳米TiB 2颗粒均匀镶嵌于TC4钛合金粉末表面的复合粉末，相较于微米TiB 2颗粒，纳米TiB 2颗粒均匀镶嵌于TC4钛合金粉末表面所需要的球磨能量低得多，从而能最大化保持TC4钛合金粉末球形度，使其仍能保持较好的粉末流动性；
 （2）由于SLM成形过程中极快的冷却速率和极高温度梯度，基体组织易形成细小的柱状晶，增强相来不及长大，可达纳米尺度；而本发明提供的制备方法中，B元素的引入有利于熔体中形成较大成分过冷区，不仅显著提高形核率，进一步地细化晶粒，还能一定程度上抑制柱状晶的形成，降低材料的各向异性；
（3）对于SLM成形钛基复合材料，以纯钛为基体制备的钛基复合材料性能并不突出，应用有限，本发明以高强度TC4钛合金作为基体，通过调控TiB含量和优化激光工艺参数成功制备高性能钛基复合材料，进一步提高比强度，在航空航天领域有良好的应用前景。
 附图说明
图1是实施例2制备的复合粉末形貌图；
图2是实施例2制备的钛基复合材料扫描电镜照片；
图3是SLM成形TC4钛合金材料与实施例2制备的钛基复合材料的透射电镜照片；
图4是SLM成形TC4钛合金材料与实施例2制备的钛基复合材料的压缩性能图；
图5是SLM成形TC4钛合金材料与实施例2制备的钛基复合材料的拉伸性能图。
 本发明的实施方式
以下结合实例对本发明的具体实施作进一步说明，但本发明的实施和保护不限于此。需指出的是，以下若有未特别详细说明之过程，均是本领域技术人员可参照现有技术实现或理解的。所用试剂或仪器未注明生产厂商者，视为可以通过市售购买得到的常规产品。
实施例1
本实施例涉及一种原位纳米TiB晶须增强钛基复合材料的制备方法，其中TiB的体积分数为1%，包括以下步骤：
步骤一: 在手套箱中将粒度为15～53μm的TC4钛合金粉末和100nm的TiB 2颗粒混合置于球磨罐中，向球磨罐中充入氩气作为保护气体，其中TiB 2的质量分数为0.59%。
步骤二：将装有混合粉末的球磨罐置于行星式球磨机上进行短时低能球磨以制备SLM用复合粉末。球磨介质为不锈钢球，球料比为5:1，球磨转速为130rpm，球磨时间为2h。
步骤三：将上述复合粉末用于SLM成形，SLM成形设备型号为EOS M290。具体的SLM成形过程如下：
（1）将复合粉末置于真空干燥箱中进行干燥处理，干燥温度为100℃，干燥时间为3h；
（2）将干燥后的复合粉末置于SLM成形设备的送粉缸内，接着充入氩气，保证成形***中含氧量低于1200ppm；加热成形基板直至预热温度160℃；
（3）铺粉装置在成形基板上均匀地铺一层40μm的复合粉末；激光束根据CAD模形熔化切片区内的复合粉末，其中，光斑直径为100μm，激光功率为150w，扫描速率为1000mm/s, 扫描间距为60μm，待其冷凝后完成当前层成形；
（4）成形缸活塞下降预设铺粉层厚（40μm）的高度，铺设下一层粉末，继续通过激光束熔化切片区域内的复合粉末，待所述下一层复合粉末凝固后，重复以上步骤，直至成形完毕；
步骤四：将上述成形完毕后的试样连同基板在真空烧结炉内进行去应力退火，再采用线切割将样品从基板上切割下来，采用的去应力退火温度为500℃，时长为3h，得到所述原位纳米TiB晶须增强钛基复合材料（1vol.% TiB晶须增强钛基复合材料）。
对本实施例中原位纳米TiB晶须增强钛基复合材料和采用相同基体粉末SLM成形制备的TC4钛合金材料进行显微维氏硬度测试，1vol.%TiB晶须增强钛基复合材料的硬度为421Hv，TC4钛合金材料的硬度为390Hv。
对本实施例中原位纳米TiB晶须增强钛基复合材料进行室温压缩，设定应变速率为5×10 -4 s -1。1vol.% TiB晶须增强钛基复合材料的屈服强度为1418MPa, 抗压强度为1583MPa。
实施例2
本实施例涉及一种原位纳米TiB晶须增强钛基复合材料的制备方法，其中TiB的体积分数为2%，包括以下步骤：
步骤一: 在手套箱中将粒度为15-53μm的TC4钛合金粉末和100nm的TiB 2颗粒混合置于球磨罐中，向球磨罐中充入氩气作为保护气体，其中TiB 2的质量分数为1.18%。
步骤二：将装有混合粉末的球磨罐置于行星式球磨机上进行短时低能球磨以制备SLM用复合粉末。球磨介质为不锈钢球，球料比为5:1，球磨转速为140rpm，球磨时间为2h，。
步骤三：将上述复合粉末用于SLM成形，SLM成形设备型号为EOS M290。具体的SLM成形过程如下：
（1）将复合粉末置于真空干燥箱中进行干燥处理，干燥温度为100℃，干燥时间为3h；
（2）将干燥后的复合粉末置于SLM成形设备的送粉缸内，接着充入氩气，保证成形***中含氧量低于1200ppm；加热成形基板直至预热温度180℃；
（3）铺粉装置在成形基板上均匀地铺一层40μm的复合粉末；激光束根据CAD模形熔化切片区内的复合粉末，其中，光斑直径为100μm，激光功率为120w，扫描速率为600mm/s, 扫描间距为60μm，待其冷凝后完成当前层成形；
（4）成形缸活塞下降预设铺粉层厚（40μm）的高度，铺设下一层粉末，继续通过激光束熔化切片区域内的复合粉末，待所述下一层复合粉末凝固后，重复以上步骤，直至成形完毕；
步骤四：将上述成形后的试样连同基板在真空烧结炉内进行去应力退火，再采用线切割将样品从基板上切割下来，采用的去应力退火温度为550℃，时长为3h，得到所述原位纳米TiB晶须增强钛基复合材料（2vol.% TiB晶须增强钛基复合材料）
对本实施例中原位纳米TiB晶须增强钛基复合材料进行显微维氏硬度测试，2vol.%TiB晶须增强钛基复合材料的硬度为445Hv。
对本实施例中原位纳米TiB晶须增强钛基复合材料和采用相同基体粉末SLM成形制备的TC4钛合金材料进行室温压缩及拉伸实验，设定应变速率为5×10 -4 s -1，其中，在室温拉伸实验中施加引伸计对延伸率进行准确测量。压缩实验中，2vol.%TiB晶须增强钛基复合材料的屈服强度为1530MPa，抗压强度为1692MPa；TC4钛合金材料的屈服强度为1216MPa, 抗压强度为1466MPa。拉伸实验中，2vol.%TiB晶须增强钛基复合材料的屈服强度为1378 MPa, 抗拉强度为1434MPa, 延伸率为3.7%；TC4钛合金材料的屈服强度为1076 MPa,抗拉强度为1140MPa，延伸率为7.6%，可参照图4和图5所示。经计算，2vol.%TiB晶须增强钛基复合材料相较于TC4钛合金材料压缩屈服强度提升26%，抗压强度提升15%，拉伸屈服强度提升28%，抗拉强度提升26%，强化效果显著。
图1是实施例2制备的复合粉末形貌图；由图1的复合粉末形貌图可以看出，纳米TiB 2颗粒均匀地镶嵌于TC4钛合金粉末表面，且TC4钛合金粉末能保持良好的球形度。
图2是实施例2制备的钛基复合材料扫描电镜照片；由图2的扫描电镜图可以看出，在柱状初生β晶粒附近TiB聚集成晶须簇，在初始柱状β晶粒内部TiB晶须分布均匀，单个TiB晶须的径向尺度达到纳米级。
图3是SLM成形TC4钛合金材料与实施例2制备的钛基复合材料的透射电镜照片，图3的（a）部分是SLM成形TC4钛合金材料的透射电镜图，图3的（b）部分是实施例2制备的钛基复合材料的透射电镜图；由图3的透射电镜图可以看出，相对于SLM成形 TC4钛合金材料，原位纳米TiB晶须增强钛基复合材料的晶粒显著细化。
实施例3
本实施例涉及一种原位纳米TiB晶须增强钛基复合材料的制备方法，其中TiB的体积分数为3%，包括以下步骤：
步骤一: 在手套箱中将粒度为15～53μm的TC4钛合金粉末和100nm的TiB 2颗粒混合置于球磨罐中，向球磨罐中充入氩气作为保护气体，其中TiB 2的质量分数为1.76%。
步骤二：将装有混合粉末的球磨罐置于行星式球磨机上进行短时低能球磨以制备SLM用复合粉末。球磨介质为不锈钢球，球料比为5:1，球磨转速为150rpm，球磨时间为2h。
步骤三：将上述复合粉末用于SLM成形，SLM成形设备型号为EOS M290。具体的SLM成形过程如下：
（1）将复合粉末置于真空干燥箱中进行干燥处理，干燥温度为100℃，干燥时间为3h；
（2）将干燥后的复合粉末置于SLM成形设备的送粉缸内，接着充入氩气，保证成形***中含氧量低于1200ppm；加热成形基板直至预热温度200℃；
（3）铺粉装置在成形基板上均匀地铺一层40μm的复合粉末；激光束根据CAD模形熔化切片区内的复合粉末，其中，光斑直径为100μm，激光功率为70w，扫描速率为200mm/s, 扫描间距为60μm，待其冷凝后完成当前层成形；
（4）成形缸活塞下降预设铺粉层厚（40μm）的高度，铺设下一层粉末，继续通过激光束熔化切片区域内的复合粉末，待所述下一层复合粉末凝固后，重复以上步骤，直至成形完毕；
步骤四：将上述成形完毕后的试样连同基板在真空烧结炉内进行去应力退火，再采用线切割将样品从基板上切割下来，采用的去应力退火温度为550℃，时长为3h，得到所述原位纳米TiB晶须增强钛基复合材料（3vol.% TiB晶须增强钛基复合材料）。
对本实施例中原位纳米TiB晶须增强钛基复合材料进行显微维氏硬度测试，3vol.%TiB晶须增强钛基复合材料的硬度为467Hv。
对本实施例中原位纳米TiB晶须增强钛基复合材料进行室温压缩，设定应变速率为5×10 -4 s -1，3vol.%TiB晶须增强钛基复合材料的屈服强度为1605MPa,抗压强度为1760MPa。
以上实施例仅为本发明较优的实施方式，仅用于解释本发明，而非限制本发明，本领域技术人员在未脱离本发明精神实质下所作的改变、替换、修饰等均应属于本发明的保护范围。

Claims (7)

  1. 一种原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，包括如下步骤：
    （1）将纳米TiB 2颗粒和微米TC4钛合金粉末加入球磨罐中，在氩气气氛下进行球磨处理，得到复合粉末；
    （2）将步骤（1）所述复合粉末用于SLM成形，在SLM过程中，铺粉装置将复合粉末铺放在成形基板上，通过激光束熔化切片区内的复合粉末，待其冷凝后完成一层成形，将工作缸下降预设铺粉层厚的高度，铺设下一层粉末，继续通过激光束熔化切片区域内的复合粉末，待所述下一层复合粉末凝固后，重复以上步骤，直至三维块体试样成形完毕；
    （3）将步骤（2）所述三维块体试样连同基板在真空烧结炉内进行去应力退火处理，然后采用线切割将样品构件从基板上切割下来，得到所述原位纳米TiB晶须增强钛基复合材料。
  2. 根据权利要求1所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，步骤（1）所述微米TC4钛合金粉末的形貌呈球形，所述微米TC4钛合金粉末的粒径为15-53μm，所述微米TC4钛合金粉末的含氧量<1000ppm。
  3. 根据权利要求1所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，步骤（1）所述纳米TiB 2颗粒的形貌呈不规则状，所述纳米TiB 2颗粒的平均粒径为100nm。
  4. 根据权利要求1所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，在步骤（1）所述复合粉末中，纳米TiB 2粉末的质量分数为0.59wt%-1.76wt%。
  5. 根据权利要求1所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，步骤（1）所述球磨处理采用的球磨介质为不锈钢球，球料比为4:1-10:1；所述球磨处理处理为短时低能球磨，球磨处理的转速为120-180rpm，球磨处理的时间为1-3h。
  6. 根据权利要求1所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，步骤（2）所述SLM成形的工艺参数：激光功率为60-160W，扫描速度为200-1000mm/s，扫描间距为50-90μm，铺粉层厚为30-50μm，基板预热温度为160-200℃。
  7. 根据权利要求1~6任一项所述的原位纳米TiB晶须增强钛基复合材料的制备方法，其特征在于，步骤（3）所述去应力退火处理的温度为500-650℃，去应力退火处理的时间为2-6h。
     
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