CN114393209B - Titanium-based composite powder with core-shell structure and preparation method and application thereof - Google Patents
Titanium-based composite powder with core-shell structure and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 215
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000010936 titanium Substances 0.000 title claims abstract description 177
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 177
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000000919 ceramic Substances 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 23
- 238000005516 engineering process Methods 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 23
- 239000012300 argon atmosphere Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 230000003014 reinforcing effect Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims 1
- 229910033181 TiB2 Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 description 11
- 230000002787 reinforcement Effects 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010288 cold spraying Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
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- Y02P10/00—Technologies related to metal processing
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Abstract
Description
技术领域Technical field
本发明涉及用于钛基复合材料技术领域，特别涉及一种核壳结构的钛基复合粉末及其制备方法和应用。The invention relates to the technical field of titanium-based composite materials, and in particular to a titanium-based composite powder with a core-shell structure and its preparation method and application.
背景技术Background technique
钛基复合材料具有高比强度、耐高温等优异性能，是应用于航空航天技术领域的重要材料，如采用钛基复合材料制备飞行器的零部件。增材制造技术是将粉末原料一体化成型的制造技术，是目前制备钛基复合材料零部件的主要技术手段。Titanium-based composite materials have excellent properties such as high specific strength and high temperature resistance. They are important materials used in the field of aerospace technology. For example, titanium-based composite materials are used to prepare aircraft parts. Additive manufacturing technology is a manufacturing technology that integrates powder raw materials into molding. It is currently the main technical means for preparing titanium-based composite parts.
现有相关技术中，利用增材制造技术制备钛基复合材料的方法主要有如下三种：(1)先将钛金属粉末和细小的增强体粉末混合均匀，使陶瓷粉末分布在钛金属粉末颗粒的表面，然后利用增材制造技术制作钛基复合材料，但分布在钛金属表面的陶瓷与钛金属的结合强度弱，送粉过程中陶瓷容易脱落，进而影响制得的钛基复合材料的微观结构和性能。此外，在增材制造的过程中，陶瓷粉末和钛金属粉末会发生原位自生反应，该反应为放热反应，造成局部热应力增大，进而增加钛基复合材料的开裂风险。(2)先利用热压烧结或熔铸法将钛金属和陶瓷加工成钛基复合材料棒，然后利用气雾化制粉技术或旋转电极制粉技术将上述钛基复合材料棒加工成钛基复合粉末，再利用增材制造技术将钛基复合粉末制成钛基复合材料。该方法制得的钛基复合粉末质量高，性能好，并且，由于制作钛基复合粉末的过程中发生了原位自生反应，使后续增材制造钛基复合材料的过程中不会发生原位自生反应，也就避免了由该反应引起的热应力问题。但该方法制备工艺复杂，周期长，成本高。(3)利用两套送粉系统分别将钛金属粉末和陶瓷粉末送入熔池，直接利用增材制造技术制备钛基复合材料。但该方法容易造成两种粉末混合不均匀，反应不充分，从而使制得的钛基复合材料内部产生缺陷，微观结构差，性能差。In the existing related technology, there are three main methods for preparing titanium-based composite materials using additive manufacturing technology: (1) First, mix titanium metal powder and fine reinforcement powder evenly, so that the ceramic powder is distributed among the titanium metal powder particles. The surface of the titanium-based composite material is then made using additive manufacturing technology. However, the bonding strength between the ceramics distributed on the surface of the titanium metal and the titanium metal is weak, and the ceramics are easy to fall off during the powder feeding process, thus affecting the microscopic properties of the titanium-based composite material. Structure and performance. In addition, during the additive manufacturing process, ceramic powder and titanium metal powder will undergo an in-situ autogenic reaction. This reaction is an exothermic reaction, causing an increase in local thermal stress, thereby increasing the risk of cracking of the titanium-based composite material. (2) First use hot-pressing sintering or melting and casting methods to process titanium metal and ceramics into titanium-based composite rods, and then use gas atomization powdering technology or rotating electrode powdering technology to process the above-mentioned titanium-based composite rods into titanium-based composite rods. powder, and then use additive manufacturing technology to make titanium-based composite powder into titanium-based composite materials. The titanium-based composite powder produced by this method has high quality and good performance. Moreover, due to the in-situ autogenous reaction that occurs during the production of titanium-based composite powder, in-situ reactions will not occur during the subsequent additive manufacturing of titanium-based composite materials. Self-generated reaction avoids the thermal stress problem caused by this reaction. However, the preparation process of this method is complex, the cycle is long, and the cost is high. (3) Use two sets of powder feeding systems to feed titanium metal powder and ceramic powder into the molten pool respectively, and directly use additive manufacturing technology to prepare titanium-based composite materials. However, this method can easily cause uneven mixing of the two powders and insufficient reaction, resulting in internal defects, poor microstructure, and poor performance of the titanium-based composite material produced.
发明内容Contents of the invention
本发明实施例提供了一种核壳结构的钛基复合粉末及其制备方法和应用，能够提供一种核壳结构的钛基复合粉末及其制备方法，该钛基复合粉末应用于增材制造技术制备钛基复合材料。The embodiment of the present invention provides a core-shell structure titanium-based composite powder and its preparation method and application. It can provide a core-shell structure titanium-based composite powder and its preparation method. The titanium-based composite powder is used in additive manufacturing. Technology to prepare titanium matrix composites.
第一方面，一种核壳结构的钛基复合粉末的制备方法，包括：In the first aspect, a method for preparing core-shell structure titanium-based composite powder includes:
步骤一：将钛金属粉末和陶瓷粉末混合均匀，得到混合物，其中，所述陶瓷粉末的粒径小于所述钛金属粉末的粒径；Step 1: Mix titanium metal powder and ceramic powder evenly to obtain a mixture, wherein the particle size of the ceramic powder is smaller than the particle size of the titanium metal powder;
步骤二：将所述混合物进行加热处理，使混合物的温度升高至预设温度，所述预设温度为使钛金属粉末和陶瓷发生原位自生反应的温度；Step 2: Heat the mixture to raise the temperature of the mixture to a preset temperature. The preset temperature is the temperature at which an in-situ autogenic reaction occurs between the titanium metal powder and the ceramic;
步骤三：在所述预设温度下对所述混合物进行保温处理后，得到具有核壳结构的所述钛基复合粉末。Step 3: After the mixture is heat-insulated at the preset temperature, the titanium-based composite powder with a core-shell structure is obtained.
优选地，在步骤一中，所述钛金属粉末为纯钛粉末、TC4钛合金粉末或TA15钛合金粉末，所述陶瓷粉末为石墨粉末、TiB2粉末或B4C粉末。Preferably, in step one, the titanium metal powder is pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder, and the ceramic powder is graphite powder, TiB 2 powder or B 4 C powder.
优选地，在步骤一中，所述钛金属粉末的粒径为50～200μm，所述陶瓷粉末的粒径为0.5～8μm。Preferably, in step one, the particle size of the titanium metal powder is 50-200 μm, and the particle size of the ceramic powder is 0.5-8 μm.
优选地，在步骤一中，包括：Preferably, step one includes:
将所述钛金属粉末和所述陶瓷粉末在氩气气氛中进行球磨处理3～6h，所述球磨处理的转速为150～250r/min，球料比为(2～6):1。The titanium metal powder and the ceramic powder are ball milled in an argon atmosphere for 3 to 6 hours, the rotation speed of the ball milling is 150 to 250 r/min, and the ball to material ratio is (2 to 6):1.
优选地，所述球磨处理的球磨罐和磨球均采用硬质合金制成。Preferably, the ball mill jar and grinding balls for the ball milling process are made of cemented carbide.
优选地，在步骤一中，在所述球磨处理后，将得到的混合物在氩气气氛中进行静置处理，所述静置处理的时间大于5h。Preferably, in step one, after the ball milling treatment, the obtained mixture is left to stand in an argon atmosphere, and the stand treatment time is greater than 5 h.
优选地，在步骤二中，所述加热处理在真空环境下进行，所述真空环境的真空度为1×10-3～1×10-2Pa，所述预设温度为700～1100℃。Preferably, in step 2, the heating treatment is performed in a vacuum environment, the vacuum degree of the vacuum environment is 1×10 -3 to 1×10 -2 Pa, and the preset temperature is 700 to 1100°C.
优选地，在步骤三中，所述保温处理在真空环境下进行，所述真空环境的真空度为1×10-3～1×10-2Pa，所述保温处理的处理时间为0.5～2h。Preferably, in step three, the heat preservation treatment is performed in a vacuum environment, the vacuum degree of the vacuum environment is 1×10 -3 ~ 1 × 10 -2 Pa, and the treatment time of the heat preservation treatment is 0.5 ~ 2h. .
第二方面，本发明提供一种核壳结构的钛基复合粉末，采用上述第一方面中任一所述的制备方法制备得到。In a second aspect, the present invention provides a titanium-based composite powder with a core-shell structure, which is prepared by the preparation method described in any one of the above-mentioned first aspects.
优选地，所述钛基复合材料中增强相的体积分数为1～10vol.％。Preferably, the volume fraction of the reinforcing phase in the titanium-based composite material is 1 to 10 vol.%.
第三方面，本发明提供一种核壳结构的钛基复合粉末的应用，所述钛基复合粉末为上述第二方面所述的钛基复合粉末，所述钛基复合粉末应用于采用增材制造技术制备钛基复合材料。In a third aspect, the present invention provides an application of a titanium-based composite powder with a core-shell structure. The titanium-based composite powder is the titanium-based composite powder described in the second aspect. The titanium-based composite powder is used in additive manufacturing applications. Manufacturing technology to prepare titanium matrix composites.
本发明与现有技术相比至少具有如下有益效果：Compared with the prior art, the present invention at least has the following beneficial effects:
在本发明中，先将钛金属粉末和陶瓷粉末混合均匀，使细小的陶瓷粉末均匀地包裹在钛金属粉末的颗粒表面，得到具有陶瓷包裹钛金属结构的混合物。将混合物进行加热处理，使温度达预设温度，在该预设温度下，陶瓷和钛金属发生原位自生反应，钛金属颗粒表面的钛元素开始与包裹在其表面的陶瓷反应生成增强相。在该预设温度下对混合物进行保温处理，为陶瓷和钛金属发生的原位自生反应提供充足的反应时间，让该反应进行的更加充分，使包裹在钛金属颗粒表面的陶瓷完全反应形成增强相，增强相包裹在钛金属颗粒表面形成核壳结构，从而得到具有核壳结构的钛基复合粉末。In the present invention, titanium metal powder and ceramic powder are first mixed evenly so that fine ceramic powder is evenly wrapped on the particle surface of the titanium metal powder to obtain a mixture with a ceramic-wrapped titanium metal structure. The mixture is heated until the temperature reaches a preset temperature. At the preset temperature, an in-situ autogenic reaction occurs between the ceramic and the titanium metal. The titanium element on the surface of the titanium metal particle begins to react with the ceramic wrapped on its surface to form a reinforcing phase. The mixture is insulated at this preset temperature to provide sufficient reaction time for the in-situ autogenic reaction of ceramics and titanium metal, allowing the reaction to proceed more fully and allowing the ceramic wrapped on the surface of the titanium metal particles to completely react to form an enhanced phase, the reinforcing phase is wrapped on the surface of titanium metal particles to form a core-shell structure, thereby obtaining a titanium-based composite powder with a core-shell structure.
在本发明中，由于增强相是直接在钛金属颗粒表面反应生成，所以，增强相和钛金属颗粒的界面结合强度高，不易脱落。此外，由于本发明提供的核壳结构的钛基复合粉末已经在制备时发生原位自生反应，所以，利用该核壳结构的钛基复合粉末采用增材制造技术制备钛基复合材料时，不会发生原位自生反应，从而避免了增材制造钛基复合材料的过程中出现局部热应力增大的问题，进而使制得的钛基复合材料的性能好、不易开裂。In the present invention, since the reinforcing phase is directly reacted on the surface of the titanium metal particles, the interface between the reinforcing phase and the titanium metal particles has a high bonding strength and is not easy to fall off. In addition, since the titanium-based composite powder with core-shell structure provided by the present invention has already undergone in-situ autogenic reaction during preparation, when using the titanium-based composite powder with core-shell structure to prepare titanium-based composite materials using additive manufacturing technology, it is not necessary to In-situ autogenous reactions will occur, thereby avoiding the problem of local thermal stress increase during the additive manufacturing of titanium-based composite materials, thereby making the titanium-based composite materials produced have good performance and are not easy to crack.
在本发明中，只需将钛金属粉末和陶瓷粉末混合均匀后进行加热保温处理即可得到核壳结构的钛基复合粉末，该方法的制备工艺简单，周期短，成本低。此外，制得的核壳结构的钛基复合粉末球形度高，流动性好，可通过调整钛金属粉末和陶瓷粉末的种类、粒径和质量比，来调整粉末的种类、大小和增强相的含量，本发明提供的钛基复合粉末适合用于增材制造技术。In the present invention, titanium metal powder and ceramic powder can be obtained by simply mixing titanium metal powder and ceramic powder evenly and then performing heating and heat preservation treatment to obtain titanium-based composite powder with a core-shell structure. This method has a simple preparation process, a short cycle, and low cost. In addition, the core-shell structure titanium-based composite powder produced has high sphericity and good fluidity. The type, size and reinforcement phase of the powder can be adjusted by adjusting the type, particle size and mass ratio of titanium metal powder and ceramic powder. content, the titanium-based composite powder provided by the present invention is suitable for use in additive manufacturing technology.
附图说明Description of the drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are: For some embodiments of the present invention, those of ordinary skill in the art can also obtain other drawings based on these drawings without exerting creative efforts.
图1是本发明实施例2提供的一种核壳结构的钛基复合粉末颗粒的剖面电镜图；Figure 1 is a cross-sectional electron microscope view of a titanium-based composite powder particle with a core-shell structure provided in Embodiment 2 of the present invention;
图2是本发明实施例2提供的一种核壳结构的钛基复合粉末颗粒的剖面电镜图的局部放大图；Figure 2 is a partially enlarged view of a cross-sectional electron microscope image of a core-shell structure titanium-based composite powder particle provided in Embodiment 2 of the present invention;
图3是本发明实施例2提供的一种核壳结构的钛基复合粉末颗粒的表面面电镜图；Figure 3 is a surface electron microscope image of a titanium-based composite powder particle with a core-shell structure provided in Embodiment 2 of the present invention;
图4是本发明实施例2提供的一种核壳结构的钛基复合粉末颗粒的表面面电镜图的局部放大图。Figure 4 is a partially enlarged view of a surface electron microscope image of a titanium-based composite powder particle with a core-shell structure provided in Embodiment 2 of the present invention.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments These are some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without any creative work are protected by the present invention. scope.
本发明实施例提供了一种核壳结构的钛基复合粉末的制备方法，包括：Embodiments of the present invention provide a method for preparing core-shell structure titanium-based composite powder, which includes:
步骤一：将钛金属粉末和陶瓷粉末混合均匀，得到混合物，其中，所述陶瓷粉末的粒径小于所述钛金属粉末的粒径；Step 1: Mix titanium metal powder and ceramic powder evenly to obtain a mixture, wherein the particle size of the ceramic powder is smaller than the particle size of the titanium metal powder;
步骤二：将所述混合物进行加热处理，使混合物的温度升高至预设温度，所述预设温度为使钛金属粉末和陶瓷发生原位自生反应的温度；Step 2: Heat the mixture to raise the temperature of the mixture to a preset temperature. The preset temperature is the temperature at which an in-situ autogenic reaction occurs between the titanium metal powder and the ceramic;
步骤三：在所述预设温度下对所述混合物进行保温处理后，得到具有核壳结构的所述钛基复合粉末。Step 3: After the mixture is heat-insulated at the preset temperature, the titanium-based composite powder with a core-shell structure is obtained.
在本发明中，先将钛金属粉末和陶瓷粉末混合均匀，使细小的陶瓷粉末均匀地包裹在钛金属粉末的颗粒表面，得到具有陶瓷包裹钛金属结构的混合物。将混合物进行加热处理，使温度达预设温度，在该预设温度下，陶瓷和钛金属发生原位自生反应，钛金属颗粒表面的钛元素开始与包裹在其表面的陶瓷反应生成增强相。在该预设温度下对混合物进行保温处理，为陶瓷和钛金属发生的原位自生反应提供充足的反应时间，让该反应进行的更加充分，使包裹在钛金属颗粒表面的陶瓷完全反应形成增强相，增强相包裹在钛金属颗粒表面形成核壳结构，从而得到具有核壳结构的钛基复合粉末。In the present invention, titanium metal powder and ceramic powder are first mixed evenly so that fine ceramic powder is evenly wrapped on the particle surface of the titanium metal powder to obtain a mixture with a ceramic-wrapped titanium metal structure. The mixture is heated until the temperature reaches a preset temperature. At the preset temperature, an in-situ autogenic reaction occurs between the ceramic and the titanium metal. The titanium element on the surface of the titanium metal particle begins to react with the ceramic wrapped on its surface to form a reinforcing phase. The mixture is insulated at this preset temperature to provide sufficient reaction time for the in-situ autogenic reaction of ceramics and titanium metal, allowing the reaction to proceed more fully and allowing the ceramic wrapped on the surface of the titanium metal particles to completely react to form an enhanced phase, the reinforcing phase is wrapped on the surface of titanium metal particles to form a core-shell structure, thereby obtaining a titanium-based composite powder with a core-shell structure.
在本发明中，由于增强相是直接在钛金属颗粒表面反应生成，所以，增强相和钛金属颗粒的界面结合强度高，不易脱落。此外，由于本发明提供的核壳结构的钛基复合粉末已经在制备时发生原位自生反应，所以，利用该核壳结构的钛基复合粉末采用增材制造技术制备钛基复合材料时，不会发生原位自生反应，从而避免了增材制造钛基复合材料的过程中出现局部热应力增大的问题，进而使制得的钛基复合材料的性能好、不易开裂。In the present invention, since the reinforcing phase is directly reacted on the surface of the titanium metal particles, the interface between the reinforcing phase and the titanium metal particles has a high bonding strength and is not easy to fall off. In addition, since the titanium-based composite powder with core-shell structure provided by the present invention has already undergone in-situ autogenic reaction during preparation, when using the titanium-based composite powder with core-shell structure to prepare titanium-based composite materials using additive manufacturing technology, it is not necessary to In-situ autogenous reactions will occur, thereby avoiding the problem of local thermal stress increase during the additive manufacturing of titanium-based composite materials, thereby making the titanium-based composite materials produced have good performance and are not easy to crack.
在本发明中，只需将钛金属粉末和陶瓷粉末混合均匀后进行加热保温处理即可得到核壳结构的钛基复合粉末，该方法的制备工艺简单，周期短，成本低。此外，制得的核壳结构的钛基复合粉末球形度高，流动性好，可通过调整钛金属粉末和陶瓷粉末的种类、粒径和质量比，来调整粉末的种类、大小和增强相的含量，本发明提供的钛基复合粉末适合用于增材制造技术。In the present invention, titanium metal powder and ceramic powder can be obtained by simply mixing titanium metal powder and ceramic powder evenly and then performing heating and heat preservation treatment to obtain titanium-based composite powder with a core-shell structure. This method has a simple preparation process, a short cycle, and low cost. In addition, the core-shell structure titanium-based composite powder produced has high sphericity and good fluidity. The type, size and reinforcement phase of the powder can be adjusted by adjusting the type, particle size and mass ratio of titanium metal powder and ceramic powder. content, the titanium-based composite powder provided by the present invention is suitable for use in additive manufacturing technology.
根据一些优选的实施方式，在步骤一中，所述钛金属粉末为纯钛粉末、TC4钛合金粉末或TA15钛合金粉末，所述陶瓷粉末为石墨粉末、TiB2粉末或B4C粉末。According to some preferred embodiments, in step one, the titanium metal powder is pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder, and the ceramic powder is graphite powder, TiB 2 powder or B 4 C powder.
在本发明中，选取纯钛粉末、TC4钛合金粉末或TA15钛合金粉末来制备核壳结构的钛基复合粉末，其中，TA15钛合金具有优异的耐高温的性能；同时也可以根据使用需求选择钛合金粉末的类型。In the present invention, pure titanium powder, TC4 titanium alloy powder or TA15 titanium alloy powder are selected to prepare titanium-based composite powder with a core-shell structure. Among them, TA15 titanium alloy has excellent high temperature resistance; it can also be selected according to the use requirements. Types of titanium alloy powder.
在本发明中，TiB2陶瓷粉末与钛金属粉末混合后能够在预设温度下发生原位自生反应形成稳定的TiB增强相。石墨粉末与钛金属粉末混合后能够在预设温度下发生原位自生反应形成稳定的TiC增强相。B4C陶瓷粉末与钛金属粉末混合后能够在预设温度下发生原位自生反应形成稳定的TiC和TiB增强相。In the present invention, after TiB 2 ceramic powder and titanium metal powder are mixed, an in-situ autogenic reaction can occur at a preset temperature to form a stable TiB reinforcement phase. After graphite powder and titanium metal powder are mixed, an in-situ autogenic reaction can occur at a preset temperature to form a stable TiC reinforcement phase. After B 4 C ceramic powder and titanium metal powder are mixed, an in-situ autogenic reaction can occur at a preset temperature to form stable TiC and TiB reinforcement phases.
需要说明的是，钛金属粉末不限于上述钛合金粉末，任何含钛的合金都适用于本发明提供的制备方法。It should be noted that the titanium metal powder is not limited to the above-mentioned titanium alloy powder, and any titanium-containing alloy is suitable for the preparation method provided by the present invention.
根据一些优选的实施方式，在步骤一中，所述钛金属粉末的粒径为50～200μm(例如，可以是50μm、100μm、150μm或200μm)，所述陶瓷粉末的粒径为0.5～8μm(例如，可以是0.5μm、1μm、2μm、3μm、4μm、5μm、6μm、7μm或8μm)。According to some preferred embodiments, in step one, the particle size of the titanium metal powder is 50-200 μm (for example, it can be 50 μm, 100 μm, 150 μm or 200 μm), and the particle size of the ceramic powder is 0.5-8 μm ( For example, it may be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm).
在本发明中，陶瓷粉末的粒径为0.5～8μm，钛金属粉末的粒径为50～200μm，如此，两种粉末混合均匀后，细小的陶瓷粉末能够包裹在钛金属粉末颗粒的表面。In the present invention, the particle size of the ceramic powder is 0.5-8 μm, and the particle size of the titanium metal powder is 50-200 μm. In this way, after the two powders are evenly mixed, the fine ceramic powder can be wrapped on the surface of the titanium metal powder particles.
根据一些优选的实施方式，在步骤一中，包括：According to some preferred embodiments, step one includes:
将所述钛金属粉末和所述陶瓷粉末在氩气气氛中进行球磨处理3～6h(例如，可以是3h、4h、5h或6h)，所述球磨处理的转速为150～250r/min(例如，可以是150r/min、200r/min或250r/min)，球料比为(2～6):1(例如，可以是2:1、3:1、4:1、5:1或6:1)。The titanium metal powder and the ceramic powder are ball milled in an argon atmosphere for 3 to 6 hours (for example, it can be 3h, 4h, 5h or 6h), and the rotation speed of the ball milling treatment is 150 to 250 r/min (for example, it can be 3h, 4h, 5h or 6h). , can be 150r/min, 200r/min or 250r/min), the ball-to-material ratio is (2~6):1 (for example, it can be 2:1, 3:1, 4:1, 5:1 or 6: 1).
在本发明中，利用球磨处理能够将钛金属粉末和陶瓷粉末充分混合均匀，且氩气气氛能够保护钛金属粉末和陶瓷粉末在球磨过程中不被氧化。球磨的过程中，在磨球的作用下，陶瓷粉末粘附包裹在钛金属粉末颗粒的表面。In the present invention, the titanium metal powder and the ceramic powder can be fully mixed evenly by ball milling, and the argon atmosphere can protect the titanium metal powder and the ceramic powder from being oxidized during the ball milling process. During the ball milling process, under the action of the grinding ball, the ceramic powder adheres and wraps on the surface of the titanium metal powder particles.
需要说明的是，在本发明的方案中，转速为150-250r/min的低能球磨处理就能够满足本发明中对均匀度的需求。根据一些优选的实施方式，所述球磨处理的球磨罐和磨球均采用硬质合金制成。It should be noted that in the solution of the present invention, low-energy ball milling with a rotation speed of 150-250 r/min can meet the requirements for uniformity in the present invention. According to some preferred embodiments, the ball mill jar and grinding balls for ball milling are made of cemented carbide.
在本发明中，硬质合金具有硬度高、耐磨、强度韧性好、耐热、耐腐蚀等一系列优良性能，特别是它的高硬度和耐磨性，适合用于制作球磨罐和磨球。采用硬质合金制成的球磨罐和磨球进行球磨处理，能够使陶瓷粉末更均匀地粘附包裹在钛金属粉末颗粒的表面。In the present invention, the cemented carbide has a series of excellent properties such as high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance, etc., especially its high hardness and wear resistance, and is suitable for making ball milling tanks and grinding balls. . Using ball milling tanks and grinding balls made of cemented carbide for ball milling can make the ceramic powder adhere and wrap more uniformly on the surface of the titanium metal powder particles.
根据一些优选的实施方式，在步骤一中，在所述球磨处理后，将得到的混合物在氩气气氛中进行静置处理，所述静置处理的时间大于5h。According to some preferred embodiments, in step 1, after the ball milling treatment, the obtained mixture is subjected to a standing treatment in an argon atmosphere, and the standing treatment time is greater than 5 hours.
在本发明中，由于球磨处理后混合物粉末的温度较高，将混合物在氩气气氛中进行静置处理使混合物粉末的热量降至室温(15～35℃)，能够避免高温的混合物粉末与氧气反应发生氧化进而污染混合物粉末。In the present invention, since the temperature of the mixture powder after ball milling is relatively high, the mixture is allowed to stand in an argon atmosphere to reduce the heat of the mixture powder to room temperature (15-35°C), which can avoid high-temperature mixture powder and oxygen. The reaction causes oxidation which contaminates the mixture powder.
根据一些优选的实施方式，在步骤二中，所述加热处理在真空环境下进行，所述真空环境的真空度为1×10-3～1×10-2Pa，所述预设温度为700～1100℃(例如，可以是700℃、800℃、900℃、1000℃或1100℃)。According to some preferred embodiments, in step 2, the heating treatment is performed in a vacuum environment, the vacuum degree of the vacuum environment is 1×10 -3 ~ 1×10 -2 Pa, and the preset temperature is 700 ~1100°C (for example, it can be 700°C, 800°C, 900°C, 1000°C or 1100°C).
在本发明中，在真空环境下，将温度升高至预设温度，既能使陶瓷和钛金属发生反应，又不会使钛金属粉末熔化，而且，生成的增强相尺寸小，分布均匀。若加热处理的温度不能达到700℃，则无法使陶瓷和钛金属充分反应，会残留陶瓷；若加热处理的温度高于1100℃，则会导致钛金属粉末严重软化并相互粘黏成块，制得的钛基复合材料粉末质量差，粉末率低。In the present invention, by raising the temperature to a preset temperature in a vacuum environment, ceramics and titanium metal can react without melting the titanium metal powder. Moreover, the generated reinforcement phase is small in size and evenly distributed. If the temperature of the heat treatment cannot reach 700°C, the ceramic and titanium metal will not be able to fully react, and the ceramic will remain; if the temperature of the heat treatment is higher than 1100°C, the titanium metal powder will be severely softened and stick to each other into lumps. The obtained titanium-based composite material powder has poor quality and low powder rate.
根据一些优选的实施方式，在步骤三中，所述保温处理在真空环境下进行，所述真空环境的真空度为1×10-3～1×10-2Pa，所述保温处理的处理时间为0.5～2h(例如，可以是0.5h、1h、1.5h或2h)。According to some preferred embodiments, in step three, the heat preservation treatment is performed in a vacuum environment, the vacuum degree of the vacuum environment is 1×10 -3 ~ 1×10 -2 Pa, and the processing time of the heat preservation treatment is It is 0.5~2h (for example, it can be 0.5h, 1h, 1.5h or 2h).
在本发明中，在真空环境下对混合物进行保温处理，使陶瓷能够完全反应，陶瓷全部生成增强相。In the present invention, the mixture is heat-insulated in a vacuum environment so that the ceramics can react completely and all the ceramics generate reinforcing phases.
本发明实施例还提供一种核壳结构的钛基复合粉末，采用上述任一所述的制备方法制备得到。Embodiments of the present invention also provide a titanium-based composite powder with a core-shell structure, which is prepared by any one of the above preparation methods.
经实验证实，如图1-4所示，本发明实施例提供的钛基复合粉末具有核壳结构，在电镜图中，可以观察到纳米级的TiB增强相晶须均匀地包裹在钛金属颗粒的外部，其中，TiB增强相晶须的横向尺寸为纳米级，长径比较大，钛基复合粉末的球形度高。It has been experimentally confirmed that, as shown in Figures 1-4, the titanium-based composite powder provided by the embodiment of the present invention has a core-shell structure. In the electron microscope image, it can be observed that nanoscale TiB reinforcement phase whiskers are evenly wrapped around the titanium metal particles. On the outside, the lateral size of the TiB reinforced phase whiskers is nanoscale, the aspect ratio is large, and the titanium-based composite powder has a high sphericity.
根据一些优选的实施方式，所述钛基复合材料中增强相的体积分数为1～10vol.％。According to some preferred embodiments, the volume fraction of the reinforcing phase in the titanium-based composite material is 1 to 10 vol.%.
在本发明中，若采用石墨粉末和钛金属粉末制备钛基复合粉末，则能够得到增强相的体积分数为1～5vol.％(例如，可以为1vol.％、2vol.％、3vol.％、4vol.％或5vol.％)的TiC增强钛基复合粉末，其中，钛金属粉末的质量分数为99～99.8wt.％(例如，可以为99wt.％、99.1wt.％、99.2wt.％、99.3wt.％、99.4wt.％、99.5wt.％、99.6wt.％、99.7wt.％或99.8wt.％)，石墨粉末的质量分数为0.2～1wt.％(例如，可以为0.2wt.％、0.3wt.％、0.4wt.％、0.5wt.％、0.6wt.％、0.7wt.％、0.8wt.％、0.9wt.％或1wt.％)；In the present invention, if graphite powder and titanium metal powder are used to prepare titanium-based composite powder, the volume fraction of the reinforcing phase can be obtained from 1 to 5 vol.% (for example, it can be 1 vol. %, 2 vol. %, 3 vol. %, 4vol.% or 5vol.%) TiC-reinforced titanium-based composite powder, wherein the mass fraction of titanium metal powder is 99-99.8wt.% (for example, it can be 99wt.%, 99.1wt.%, 99.2wt.%, 99.3wt.%, 99.4wt.%, 99.5wt.%, 99.6wt.%, 99.7wt.% or 99.8wt.%), the mass fraction of graphite powder is 0.2~1wt.% (for example, it can be 0.2wt. %, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.% or 1wt.%);
若采用TiB2粉末和钛金属粉末制备钛基复合粉末，则能够得到增强相的体积分数为1～10vol.％(例如，可以为1vol.％、2vol.％、3vol.％、4vol.％、5vol.％、6vol.％、7vol.％、8vol.％、9vol.％或10vol.％)的TiB增强钛基复合粉末，其中，钛金属粉末的质量分数为94～99.5wt.％(例如，可以为94wt.％、95wt.％、96wt.％、97wt.％、98wt.％、99wt.％或99.5wt.％)，TiB2粉末的质量分数为0.5～7wt.％(例如，可以为0.5wt.％、1wt.％、2wt.％、3wt.％、4wt.％、5wt.％、或6wt.％)；If TiB 2 powder and titanium metal powder are used to prepare titanium-based composite powder, the volume fraction of the reinforcing phase can be obtained from 1 to 10 vol.% (for example, it can be 1vol.%, 2vol.%, 3vol.%, 4vol.%, 5vol.%, 6vol.%, 7vol.%, 8vol.%, 9vol.% or 10vol.%) TiB reinforced titanium-based composite powder, wherein the mass fraction of titanium metal powder is 94 to 99.5wt.% (for example, It can be 94wt.%, 95wt.%, 96wt.%, 97wt.%, 98wt.%, 99wt.% or 99.5wt.%), and the mass fraction of TiB 2 powder is 0.5~7wt.% (for example, it can be 0.5 wt.%, 1wt.%, 2wt.%, 3wt.%, 4wt.%, 5wt.%, or 6wt.%);
若采用B4C粉末和钛金属粉末制备钛基复合粉末，则能够得到增强相的体积分数为1～5vol.％(例如，可以为1vol.％、2vol.％、3vol.％、4vol.％或5vol.％)的TiB+TiC增强钛基复合粉末，其中，钛金属粉末的质量分数为99～99.8wt.％(例如，可以为99wt.％、99.1wt.％、99.2wt.％、99.3wt.％、99.4wt.％、99.5wt.％、99.6wt.％、99.7wt.％或99.8wt.％)，B4C粉末的质量分数为0.2～1wt.％(例如，可以为0.2wt.％、0.3wt.％、0.4wt.％、0.5wt.％、0.6wt.％、0.7wt.％、0.8wt.％、0.9wt.％或1wt.％)。If B 4 C powder and titanium metal powder are used to prepare titanium-based composite powder, the volume fraction of the reinforcing phase can be obtained from 1 to 5 vol.% (for example, it can be 1 vol. %, 2 vol. %, 3 vol. %, 4 vol. %) Or 5 vol.%) TiB+TiC reinforced titanium-based composite powder, wherein the mass fraction of titanium metal powder is 99 to 99.8wt.% (for example, it can be 99wt.%, 99.1wt.%, 99.2wt.%, 99.3 wt.%, 99.4wt.%, 99.5wt.%, 99.6wt.%, 99.7wt.% or 99.8wt.%), the mass fraction of B 4 C powder is 0.2 to 1wt.% (for example, it can be 0.2wt .%, 0.3wt.%, 0.4wt.%, 0.5wt.%, 0.6wt.%, 0.7wt.%, 0.8wt.%, 0.9wt.% or 1wt.%).
本发明实施例还提供一种核壳结构的钛基复合粉末的应用，所述钛基复合粉末为上述的钛基复合粉末，所述钛基复合粉末应用于采用增材制造技术制造钛基复合材料。Embodiments of the present invention also provide an application of a titanium-based composite powder with a core-shell structure. The titanium-based composite powder is the above-mentioned titanium-based composite powder. The titanium-based composite powder is used in manufacturing titanium-based composites using additive manufacturing technology. Material.
需要说明的是，增材制造技术包括但不限于激光增材、电子束增材、电弧增材以及冷热喷涂等。It should be noted that additive manufacturing technologies include but are not limited to laser additive, electron beam additive, arc additive, and hot and cold spraying.
在本发明中，核壳结构的钛基复合粉末能够应用于增材制造钛基复合材料，使制得的钛基复合材料具备致密的微观结构和良好的力学性能。In the present invention, the titanium-based composite powder with a core-shell structure can be used in additive manufacturing of titanium-based composite materials, so that the produced titanium-based composite materials have a dense microstructure and good mechanical properties.
为了更加清楚地说明本发明的技术方案及优点，下面通过几个实施例对一种核壳结构的钛基复合粉末及其制备方法进行详细说明。In order to more clearly illustrate the technical solutions and advantages of the present invention, a titanium-based composite powder with a core-shell structure and a preparation method thereof will be described in detail below through several examples.
实施例1Example 1
将100μm的TA15钛合金粉末和4μm的TiB2粉末在氩气气氛中进行球磨处理5h，其中，TA15钛合金粉末的质量分数为95wt.％，TiB2粉末的质量分数为4wt.％，球磨处理的转速为200r/min，球料比为4:1，在氩气气氛中静置6h后，得到混合物；100 μm TA15 titanium alloy powder and 4 μm TiB 2 powder were ball milled in an argon atmosphere for 5 h. The mass fraction of TA15 titanium alloy powder was 95 wt.% and the mass fraction of TiB 2 powder was 4 wt.%. Ball milling treatment The rotation speed is 200r/min, the ball-to-material ratio is 4:1, and after standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至900℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 900°C;
继续在真空度为1×10-3的环境下保温1h，得到具有核壳结构的增强相体积分数为6.8vol.％的TiB增强钛基复合粉末。Continue to maintain the temperature in an environment with a vacuum degree of 1×10 -3 for 1 hour, and obtain a TiB-reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 6.8 vol.%.
实施例2Example 2
将50μm的TC4钛合金粉末和0.5μm的TiB2粉末在氩气气氛中进行球磨处理3h，其中，TC4钛合金粉末的质量分数为93wt.％，TiB2粉末的质量分数为6wt.％，球磨处理的转速为150r/min，球料比为2:1，在氩气气氛中静置5h后，得到混合物；50 μm TC4 titanium alloy powder and 0.5 μm TiB 2 powder were ball milled in an argon atmosphere for 3 hours. The mass fraction of TC4 titanium alloy powder was 93 wt.% and the mass fraction of TiB 2 powder was 6 wt.%. Ball milling The processing speed is 150r/min, the ball-to-material ratio is 2:1, and after standing for 5 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至1000℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 1000°C;
继续在真空度为1×10-3的环境下保温1.5h，得到具有核壳结构的增强相体积分数为10vol.％的TiB增强钛基复合粉末。Continue to maintain the temperature in an environment with a vacuum degree of 1×10 -3 for 1.5 hours, and obtain a TiB-reinforced titanium-based composite powder with a core-shell structure and a reinforcement phase volume fraction of 10 vol.%.
实施例3Example 3
将200μm的纯钛粉末和5μm的TiB2粉末在氩气气氛中进行球磨处理6h，其中，纯钛粉末的质量分数为99.5wt.％，TiB2粉末的质量分数为0.6wt.％，球磨处理的转速为250r/min，球料比为6:1，在氩气气氛中静置6h后，得到混合物；200 μm pure titanium powder and 5 μm TiB 2 powder were ball milled in an argon atmosphere for 6 hours. The mass fraction of pure titanium powder was 99.5 wt.% and the mass fraction of TiB 2 powder was 0.6 wt.%. Ball milling treatment The rotation speed is 250r/min, the ball-to-material ratio is 6:1, and after standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-2的环境下进行加热处理，使混合物的温度升高至800℃；The mixture is heated in an environment with a vacuum degree of 1×10 -2 to increase the temperature of the mixture to 800°C;
继续在真空度为1×10-2的环境下保温0.5h，得到具有核壳结构的增强相体积分数为1vol.％的TiB增强钛基复合粉末。Continue to maintain the temperature in an environment with a vacuum degree of 1×10 -2 for 0.5 h, and obtain a TiB-reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 1 vol.%.
实施例4Example 4
将100μm的TA15钛合金粉末和3μm的石墨粉末在氩气气氛中进行球磨处理5h，其中，TA15钛合金粉末的质量分数为99wt.％，石墨粉末的质量分数为1wt.％，球磨处理的转速为200r/min，球料比为4:1，在氩气气氛中静置6h后，得到混合物；100 μm TA15 titanium alloy powder and 3 μm graphite powder were ball milled in an argon atmosphere for 5 hours. The mass fraction of TA15 titanium alloy powder was 99 wt.% and the mass fraction of graphite powder was 1 wt.%. The rotation speed of the ball milling treatment was is 200r/min, the ball-to-material ratio is 4:1, and after standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至900℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 900°C;
继续在真空度为1×10-3的环境下保温1h，得到具有核壳结构的增强相体积分数为5vol.％的TiC增强钛基复合粉末。Continue to maintain the temperature in an environment with a vacuum degree of 1×10 -3 for 1 hour, and obtain a TiC-reinforced titanium-based composite powder with a core-shell structure and a reinforcement phase volume fraction of 5 vol.%.
实施例5Example 5
将100μm的TA15钛合金粉末和4μm的石墨粉末在氩气气氛中进行球磨处理5h，其中，TA15钛合金粉末的质量分数为99.8wt.％，石墨粉末的质量分数为0.2wt.％，球磨处理的转速为200r/min，球料比为4:1，在氩气气氛中静置6h后，得到混合物；100 μm TA15 titanium alloy powder and 4 μm graphite powder were ball milled in an argon atmosphere for 5 hours. The mass fraction of TA15 titanium alloy powder was 99.8 wt.% and the mass fraction of graphite powder was 0.2 wt.%. Ball milling treatment The rotation speed is 200r/min, the ball-to-material ratio is 4:1, and after standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至800℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 800°C;
继续在真空度为1×10-3的环境下保温1h，得到具有核壳结构的增强相体积分数为1vol.％的TiC增强钛基复合粉末。Continue to maintain the temperature for 1 hour in an environment with a vacuum degree of 1×10 -3 to obtain a TiC-reinforced titanium-based composite powder with a core-shell structure and a reinforcement phase volume fraction of 1 vol.%.
实施例6Example 6
将100μm的TA15钛合金粉末和4μm的B4C粉末在氩气气氛中进行球磨处理5h，其中，TA15钛合金粉末的质量分数为99wt.％，B4C粉末的质量分数为1wt.％，球磨处理的转速为200r/min，球料比为4:1，在氩气气氛中静置6h后，得到混合物；100 μm TA15 titanium alloy powder and 4 μm B 4 C powder were ball milled in an argon atmosphere for 5 hours, where the mass fraction of TA15 titanium alloy powder was 99 wt.% and the mass fraction of B 4 C powder was 1 wt.%. The rotation speed of the ball milling process is 200r/min, and the ball-to-material ratio is 4:1. After standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至1000℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 1000°C;
继续在真空度为1×10-3的环境下保温1h，得到具有核壳结构的增强相体积分数为5vol.％的TiB+TiC增强钛基复合粉末。Continue to maintain the temperature in an environment with a vacuum degree of 1×10 -3 for 1 hour, and obtain a TiB+TiC reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 5 vol.%.
实施例7Example 7
将100μm的TA15钛合金粉末和4μm的B4C粉末在氩气气氛中进行球磨处理5h，其中，TA15钛合金粉末的质量分数为99.8wt.％，B4C粉末的质量分数为0.2wt.％，球磨处理的转速为200r/min，球料比为4:1，在氩气气氛中静置6h后，得到混合物；100 μm TA15 titanium alloy powder and 4 μm B 4 C powder were ball milled in an argon atmosphere for 5 hours. The mass fraction of TA15 titanium alloy powder was 99.8wt.% and the mass fraction of B 4 C powder was 0.2wt. %, the rotation speed of the ball milling process is 200r/min, the ball-to-material ratio is 4:1, and after standing for 6 hours in an argon atmosphere, the mixture is obtained;
将混合物在真空度为1×10-3的环境下进行加热处理，使混合物的温度升高至900℃；The mixture is heated in an environment with a vacuum degree of 1×10 -3 to increase the temperature of the mixture to 900°C;
继续在真空度为1×10-3的环境下保温1h，得到具有核壳结构的增强相体积分数为1vol.％的TiB+TiC增强钛基复合粉末。Continue to maintain the temperature for 1 hour in an environment with a vacuum degree of 1×10 -3 to obtain a TiB+TiC reinforced titanium-based composite powder with a core-shell structure and a reinforced phase volume fraction of 1 vol.%.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be used Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent substitutions are made to some of the technical features; however, these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
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