CN105397344A - Preparation method of in-situ growth graphene/carbon nano tube reinforced Ti-based brazing filler metal - Google Patents
Preparation method of in-situ growth graphene/carbon nano tube reinforced Ti-based brazing filler metal Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 91
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 91
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 238000005219 brazing Methods 0.000 title description 5
- 239000000945 filler Substances 0.000 title description 4
- 239000000843 powder Substances 0.000 claims abstract description 106
- 229910000679 solder Inorganic materials 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000003756 stirring Methods 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 40
- 238000000151 deposition Methods 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910010380 TiNi Inorganic materials 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910017693 AgCuTi Inorganic materials 0.000 claims description 3
- 229910008424 SnCuTi Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- AHOUBRCZNHFOSL-YOEHRIQHSA-N (+)-Casbol Chemical compound C1=CC(F)=CC=C1[C@H]1[C@H](COC=2C=C3OCOC3=CC=2)CNCC1 AHOUBRCZNHFOSL-YOEHRIQHSA-N 0.000 claims 1
- 239000002071 nanotube Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
原位生长石墨烯/碳纳米管增强Ti基钎料的方法，本发明涉及Ti基钎料的制备方法。本发明要解决现有石墨烯与碳纳米管在Ti基钎料中难以均匀分散以及传统Ti基钎料热膨胀系数较高及高温力学性能差的问题。本发明的方法：一、以乙醇为溶剂将TiH2粉与Ni(NO3)2·6H2O混合，磁力搅拌并加热至无水乙醇挥发得到Ni(NO3)2/TiH2复合粉末；二、采用等离子体增强化学气相沉积法制备石墨烯/碳纳米管增强TiH2粉末；三、将制备的石墨烯/碳纳米管增强TiH2粉末与金属粉末混合，充分研磨后得到石墨烯/碳纳米管增强Ti基钎料。本发明用于原位生长石墨烯/碳纳米管增强Ti基钎料的方法。The invention discloses a method for in-situ growth of graphene/carbon nanotubes to reinforce Ti-based solder, and the invention relates to a preparation method of Ti-based solder. The invention aims to solve the problems that the existing graphene and carbon nanotubes are difficult to uniformly disperse in the Ti-based solder, and the traditional Ti-based solder has a high thermal expansion coefficient and poor high-temperature mechanical properties. The method of the present invention: 1. Mix TiH 2 powder and Ni(NO 3 ) 2 ·6H 2 O with ethanol as a solvent, stir magnetically and heat until absolute ethanol volatilizes to obtain Ni(NO 3 ) 2 /TiH 2 composite powder; 2. Prepare graphene/carbon nanotube-reinforced TiH 2 powder by plasma-enhanced chemical vapor deposition; 3. Mix the prepared graphene/carbon nanotube-reinforced TiH 2 powder with metal powder, and obtain graphene/carbon nanotube after sufficient grinding Nanotube reinforced Ti-based solder. The invention is used for the method for in-situ growth of graphene/carbon nanotubes to reinforce Ti-based solder.
Description
技术领域technical field
本发明涉及Ti基钎料的制备方法。The invention relates to a preparation method of Ti-based solder.
背景技术Background technique
一直以来，陶瓷和金属的连接问题都是焊接技术领域研究的重点，在众多的连接方法中，钎焊因工艺简单且接头力学性能好，成为当前连接陶瓷与金属的主要方法。当前，在许多情况下，陶瓷与金属连接构件需要在高温环境下使用，而已有研究表明，陶瓷与金属连接构件的高温使用性，关键取决于钎料的高温力学性能，但由于陶瓷和金属的热膨胀系数差异较大，在接头产生的较大残余应力会大幅降低构件的高温力学性能；此外，钎料与母材的界面反应问题也会严重影响接头的高温力学性能。传统的钎料很难解决上述问题，因此合理的采用增强体来改善钎料的高温力学性能十分必要。For a long time, the connection between ceramics and metals has been the focus of research in the field of welding technology. Among the many connection methods, brazing has become the main method for connecting ceramics and metals due to its simple process and good mechanical properties of the joints. At present, in many cases, ceramic-metal connecting components need to be used in high-temperature environments, and existing studies have shown that the high-temperature usability of ceramic-metal connecting components depends critically on the high-temperature mechanical properties of the solder, but due to the high-temperature mechanical properties of the ceramic and metal Due to the large difference in thermal expansion coefficient, the large residual stress generated in the joint will greatly reduce the high-temperature mechanical properties of the component; in addition, the interface reaction between the solder and the base metal will also seriously affect the high-temperature mechanical properties of the joint. It is difficult for traditional solder to solve the above problems, so it is necessary to use reinforcements reasonably to improve the high-temperature mechanical properties of solder.
近年来，新型碳纳米材料研究十分火热，它们往往具有优异的热学性能、电学性能及机械性能等特性，在航空航天、光电器件、电化学电容器等领域有着十分广阔的应用前景。石墨烯和碳纳米管具有极高的强度、韧度、优异的热稳定性，此外，它们具有极低的线膨胀系数，分别为-8.0×10-6K-1、-5.86×10-9K-1，是用来降低传统钎料线膨胀系数的理想增强体。然而当前，采用传统方法制备的石墨烯/碳纳米管增强复合材料方法比较复杂，且石墨烯和碳纳米管在复合钎料中的分散性较差并容易团聚，导致了它们物理化学性能的下降，从而严重影响钎料的高温力学性能。In recent years, research on new carbon nanomaterials has been very hot. They often have excellent thermal, electrical, and mechanical properties, and have broad application prospects in aerospace, optoelectronic devices, and electrochemical capacitors. Graphene and carbon nanotubes have extremely high strength, toughness, and excellent thermal stability. In addition, they have extremely low linear expansion coefficients, which are -8.0×10 -6 K -1 , -5.86×10 -9 respectively K -1 is an ideal reinforcement used to reduce the linear expansion coefficient of traditional solder. However, at present, the method of graphene/carbon nanotube reinforced composite materials prepared by traditional methods is relatively complicated, and the dispersion of graphene and carbon nanotubes in the composite solder is poor and easy to agglomerate, resulting in the decline of their physical and chemical properties. , thus seriously affecting the high temperature mechanical properties of the solder.
发明内容Contents of the invention
本发明要解决现有石墨烯与碳纳米管在Ti基钎料中难以均匀分散以及传统Ti基钎料热膨胀系数较高及高温力学性能差的问题，而提供原位生长石墨烯/碳纳米管增强Ti基钎料的方法。The present invention solves the problems that the existing graphene and carbon nanotubes are difficult to uniformly disperse in the Ti-based solder, and the traditional Ti-based solder has a high thermal expansion coefficient and poor high-temperature mechanical properties, and provides in-situ growth of graphene/carbon nanotubes A method for strengthening Ti-based solder.
原位生长石墨烯/碳纳米管增强Ti基钎料的方法，具体是按照以下步骤进行的：In-situ growth graphene/carbon nanotubes strengthen the method for Ti-based solder, specifically carry out according to the following steps:
一、将Ni(NO3)2·6H2O和TiH2粉末置于无水乙醇中混合，然后在温度为80℃～100℃的条件下，磁力搅拌至无水乙醇全部挥发，再经研磨，得到Ni(NO3)2·TiH2复合粉末；1. Mix Ni(NO 3 ) 2 ·6H 2 O and TiH 2 powders in absolute ethanol, then stir magnetically at a temperature of 80°C to 100°C until the absolute ethanol is completely volatilized, and then grind , to obtain Ni(NO 3 ) 2 ·TiH 2 composite powder;
所述的Ni(NO3)2·6H2O与TiH2粉末的质量比为1:(1～10)；The mass ratio of Ni(NO 3 ) 2 ·6H 2 O to TiH 2 powder is 1:(1～10);
二、将Ni(NO3)2·TiH2复合粉末置于等离子体增强化学气相沉积真空装置中，抽真空至5Pa以下，以气体流量为10sccm～40sccm通入氢气，调节等离子体增强化学气相沉积真空装置中压强为100Pa～400Pa，并在压强为100Pa～400Pa和氢气气氛下，以20℃/min的升温速率将温度升温至500℃～560℃；2. Place the Ni(NO 3 ) 2 ·TiH 2 composite powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to below 5Pa, and feed hydrogen gas with a gas flow rate of 10sccm-40sccm to adjust the plasma-enhanced chemical vapor deposition The pressure in the vacuum device is 100Pa-400Pa, and under the pressure of 100Pa-400Pa and hydrogen atmosphere, the temperature is raised to 500-560℃ at a heating rate of 20℃/min;
三、以气体流量为10sccm～80sccm通入甲烷气体，调节氢气的气体流量为5sccm～20sccm，调节等离子体增强化学气相沉积真空装置中压强为200Pa～800Pa，然后在射频功率为100W～300W、压强为200Pa～800Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为15min～45min；3. Introduce methane gas with a gas flow rate of 10sccm to 80sccm, adjust the gas flow rate of hydrogen to 5sccm to 20sccm, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa to 800Pa, and then set the radio frequency power to 100W to 300W, pressure Deposition is carried out under the conditions of 200Pa～800Pa and temperature 500℃～560℃, and the deposition time is 15min～45min;
四、停止通入氢气，以气体流量为15sccm～45sccm通入氩气，调节甲烷气体流量为5sccm～50sccm，调节等离子体增强化学气相沉积真空装置中压强为500Pa～1000Pa，然后在射频功率为100W～300W、压强为500Pa～1000Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为15min～45min，沉积结束后，停止通入甲烷气体，在氩气气氛下冷却，得到石墨烯/碳纳米管增强TiH2复合粉末；4. Stop feeding hydrogen, feed argon with a gas flow rate of 15 sccm to 45 sccm, adjust the methane gas flow rate to 5 sccm to 50 sccm, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 500Pa to 1000Pa, and then set the radio frequency power to 100W ～300W, the pressure is 500Pa～1000Pa and the temperature is 500℃～560℃, and the deposition time is 15min～45min. After the deposition is completed, stop feeding methane gas and cool it under the argon atmosphere to obtain graphene/ Carbon nanotube reinforced TiH 2 composite powder;
五、将石墨烯/碳纳米管增强TiH2复合粉末、TiH2粉末及金属粉末混合并研磨，得到原位生长石墨烯/碳纳米管增强Ti基钎料，即完成原位生长石墨烯/碳纳米管增强Ti基钎料的方法；5. Mix and grind graphene/carbon nanotube-reinforced TiH 2 composite powder, TiH 2 powder and metal powder to obtain in-situ growth graphene/carbon nanotube-reinforced Ti-based solder, that is, complete in-situ growth of graphene/carbon Nanotube reinforced method for Ti-based solder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiZrCuNi钎料时，所述的金属粉末为Zr金属粉末、Cu金属粉末和Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiZrCuNi solder, the metal powder is Zr metal powder, Cu metal powder and Ni mineral powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiZrCu钎料时，所述的金属粉末为Zr金属粉末和Cu金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiZrCu solder, the metal powder is Zr metal powder and Cu metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强AgCuTi钎料时，所述的金属粉末为Cu金属粉末和Ag金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti base solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced AgCuTi solder, the metal powder is Cu metal powder and Ag metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiCuNi钎料时，所述的金属粉末为Cu金属粉末和Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiCuNi solder, the metal powder is Cu metal powder and Ni metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiNi钎料时，所述的金属粉末为Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiNi solder, the metal powder is Ni metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiNiNb钎料时，所述的金属粉末为Ni金属粉末和Nb金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiNiNb solder, the metal powder is Ni metal powder and Nb metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiCuCo钎料时，所述的金属粉末为Cu金属粉末和Co金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiCuCo solder, the metal powder is Cu metal powder and Co metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强SnCuTi钎料时，所述的金属粉末为Sn金属粉末和Cu金属粉末。When the in-situ-grown graphene/carbon nanotube-reinforced Ti-based solder obtained in step five is in-situ-grown graphene/carbon nanotube-reinforced SnCuTi solder, the metal powders are Sn metal powder and Cu metal powder.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明原位生长石墨烯/碳纳米管增强Ti基钎料的方法，通过等离子体增强化学气相沉积方法，在低温的条件下，于TiH2上制备了均匀分散的石墨烯和碳纳米管，石墨烯和碳纳米管均具有优异的高温强度以及极低的线膨胀系数，可以发挥双重强化作用，进而可降低Ti基钎料的线膨胀系数，有效提高钎料的高温力学性能。同时，所制备的石墨烯/碳纳米管具有三维混合结构，可以进一步强化复合钎料的性能。The method for in-situ growing graphene/carbon nanotubes of the present invention to strengthen the Ti-based brazing filler metal, through the plasma-enhanced chemical vapor deposition method, under low temperature conditions, prepared evenly dispersed graphene and carbon nanotubes on TiH2, Both graphene and carbon nanotubes have excellent high-temperature strength and extremely low linear expansion coefficient, which can play a dual strengthening role, thereby reducing the linear expansion coefficient of Ti-based solder and effectively improving the high-temperature mechanical properties of the solder. At the same time, the prepared graphene/carbon nanotubes have a three-dimensional hybrid structure, which can further enhance the performance of the composite solder.
综上本发明原位生长石墨烯/碳纳米管增强Ti基钎料的方法具有以下优点：In sum, the method for in-situ growth graphene/carbon nanotubes of the present invention to strengthen Ti-based solder has the following advantages:
1、本发明采用等离子体增强化学气相沉积方法，较传统的化学气相沉积方法能够大幅降低工作温度。1. The present invention adopts the plasma-enhanced chemical vapor deposition method, which can greatly reduce the working temperature compared with the traditional chemical vapor deposition method.
2、本发明中石墨烯和碳纳米管均具有优异的高温强度以及极低的线膨胀系数，可以发挥双重强化作用，进而可降低Ti基钎料的线膨胀系数，有效提高钎料的高温力学性能。2. Both graphene and carbon nanotubes in the present invention have excellent high-temperature strength and extremely low linear expansion coefficient, which can play a dual strengthening role, thereby reducing the linear expansion coefficient of Ti-based solder, and effectively improving the high-temperature mechanical properties of the solder. performance.
3、本发明在TiH2上同时原位制备碳纳米管和石墨烯，均匀分散的石墨烯/碳纳米管具有三维混合结构，可以强化复合钎料的性能。3. The present invention simultaneously prepares carbon nanotubes and graphene in situ on TiH 2 , and the uniformly dispersed graphene/carbon nanotubes have a three-dimensional mixed structure, which can strengthen the performance of the composite solder.
本发明采用的方法简单、高效，适合工业生产。The method adopted by the invention is simple, efficient and suitable for industrial production.
本发明用于原位生长石墨烯/碳纳米管增强Ti基钎料的方法。The invention is used for the method for in-situ growth of graphene/carbon nanotubes to reinforce Ti-based solder.
具体实施方式detailed description
本发明技术方案不局限于以下所列举的具体实施方式，还包括各具体实施方式之间的任意组合。The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
具体实施方式一：本实施方式所述的原位生长石墨烯/碳纳米管增强Ti基钎料的方法，具体是按照以下步骤进行的：Specific embodiment one: the in-situ growth graphene/carbon nanotube described in the present embodiment strengthens the method for Ti-based solder, specifically carries out according to the following steps:
一、将Ni(NO3)2·6H2O和TiH2粉末置于无水乙醇中混合，然后在温度为80℃～100℃的条件下，磁力搅拌至无水乙醇全部挥发，再经研磨，得到Ni(NO3)2·TiH2复合粉末；1. Mix Ni(NO 3 ) 2 ·6H 2 O and TiH 2 powders in absolute ethanol, then stir magnetically at a temperature of 80°C to 100°C until the absolute ethanol is completely volatilized, and then grind , to obtain Ni(NO 3 ) 2 ·TiH 2 composite powder;
所述的Ni(NO3)2·6H2O与TiH2粉末的质量比为1:(1～10)；The mass ratio of Ni(NO 3 ) 2 ·6H 2 O to TiH 2 powder is 1:(1～10);
二、将Ni(NO3)2·TiH2复合粉末置于等离子体增强化学气相沉积真空装置中，抽真空至5Pa以下，以气体流量为10sccm～40sccm通入氢气，调节等离子体增强化学气相沉积真空装置中压强为100Pa～400Pa，并在压强为100Pa～400Pa和氢气气氛下，以20℃/min的升温速率将温度升温至500℃～560℃；2. Place the Ni(NO 3 ) 2 ·TiH 2 composite powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate to below 5Pa, and feed hydrogen gas with a gas flow rate of 10sccm-40sccm to adjust the plasma-enhanced chemical vapor deposition The pressure in the vacuum device is 100Pa-400Pa, and under the pressure of 100Pa-400Pa and hydrogen atmosphere, the temperature is raised to 500-560℃ at a heating rate of 20℃/min;
三、以气体流量为10sccm～80sccm通入甲烷气体，调节氢气的气体流量为5sccm～20sccm，调节等离子体增强化学气相沉积真空装置中压强为200Pa～800Pa，然后在射频功率为100W～300W、压强为200Pa～800Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为15min～45min；3. Introduce methane gas with a gas flow rate of 10sccm-80sccm, adjust the gas flow rate of hydrogen to 5sccm-20sccm, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 200Pa-800Pa, and then set the radio frequency power to 100W-300W, pressure Deposition is carried out under the conditions of 200Pa～800Pa and temperature 500℃～560℃, and the deposition time is 15min～45min;
四、停止通入氢气，以气体流量为15sccm～45sccm通入氩气，调节甲烷气体流量为5sccm～50sccm，调节等离子体增强化学气相沉积真空装置中压强为500Pa～1000Pa，然后在射频功率为100W～300W、压强为500Pa～1000Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为15min～45min，沉积结束后，停止通入甲烷气体，在氩气气氛下冷却，得到石墨烯/碳纳米管增强TiH2复合粉末；4. Stop feeding hydrogen, feed argon with a gas flow rate of 15 sccm to 45 sccm, adjust the methane gas flow rate to 5 sccm to 50 sccm, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to 500Pa to 1000Pa, and then set the radio frequency power to 100W ～300W, the pressure is 500Pa～1000Pa and the temperature is 500℃～560℃, and the deposition time is 15min～45min. After the deposition is completed, stop feeding methane gas and cool it under the argon atmosphere to obtain graphene/ Carbon nanotube reinforced TiH 2 composite powder;
五、将石墨烯/碳纳米管增强TiH2复合粉末、TiH2粉末及金属粉末混合并研磨，得到原位生长石墨烯/碳纳米管增强Ti基钎料，即完成原位生长石墨烯/碳纳米管增强Ti基钎料的方法；5. Mix and grind graphene/carbon nanotube-reinforced TiH 2 composite powder, TiH 2 powder and metal powder to obtain in-situ growth graphene/carbon nanotube-reinforced Ti-based solder, that is, complete in-situ growth of graphene/carbon Nanotube reinforced method for Ti-based solder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiZrCuNi钎料时，所述的金属粉末为Zr金属粉末、Cu金属粉末和Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiZrCuNi solder, the metal powder is Zr metal powder, Cu metal powder and Ni mineral powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiZrCu钎料时，所述的金属粉末为Zr金属粉末和Cu金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiZrCu solder, the metal powder is Zr metal powder and Cu metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强AgCuTi钎料时，所述的金属粉末为Cu金属粉末和Ag金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti base solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced AgCuTi solder, the metal powder is Cu metal powder and Ag metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiCuNi钎料时，所述的金属粉末为Cu金属粉末和Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiCuNi solder, the metal powder is Cu metal powder and Ni metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiNi钎料时，所述的金属粉末为Ni金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiNi solder, the metal powder is Ni metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiNiNb钎料时，所述的金属粉末为Ni金属粉末和Nb金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiNiNb solder, the metal powder is Ni metal powder and Nb metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强TiCuCo钎料时，所述的金属粉末为Cu金属粉末和Co金属粉末；When the in-situ growth graphene/carbon nanotube reinforced Ti-based solder obtained in step 5 is the in-situ growth graphene/carbon nanotube reinforced TiCuCo solder, the metal powder is Cu metal powder and Co metal powder;
步骤五中得到的原位生长石墨烯/碳纳米管增强Ti基钎料为原位生长石墨烯/碳纳米管增强SnCuTi钎料时，所述的金属粉末为Sn金属粉末和Cu金属粉末。When the in-situ-grown graphene/carbon nanotube-reinforced Ti-based solder obtained in step five is in-situ-grown graphene/carbon nanotube-reinforced SnCuTi solder, the metal powders are Sn metal powder and Cu metal powder.
本实施方式的有益效果是：The beneficial effects of this embodiment are:
1、本实施方式采用等离子体增强化学气相沉积方法，较传统的化学气相沉积方法能够大幅降低工作温度。1. This embodiment adopts the plasma-enhanced chemical vapor deposition method, which can greatly reduce the working temperature compared with the traditional chemical vapor deposition method.
2、本实施方式中石墨烯和碳纳米管均具有优异的高温强度以及极低的线膨胀系数，可以发挥双重强化作用，进而可降低Ti基钎料的线膨胀系数，有效提高钎料的高温力学性能。2. In this embodiment, both graphene and carbon nanotubes have excellent high-temperature strength and extremely low linear expansion coefficient, which can play a dual strengthening role, thereby reducing the linear expansion coefficient of Ti-based solder and effectively improving the high temperature of the solder. mechanical properties.
3、本实施方式在TiH2上同时原位制备碳纳米管和石墨烯，均匀分散的石墨烯/碳纳米管具有三维混合结构，可以强化复合钎料的性能。3. In this embodiment, carbon nanotubes and graphene are simultaneously prepared in situ on TiH 2 , and the uniformly dispersed graphene/carbon nanotubes have a three-dimensional mixed structure, which can strengthen the performance of the composite solder.
本实施方式采用的方法简单、高效，适合工业生产。The method adopted in this embodiment is simple and efficient, and is suitable for industrial production.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤二中以气体流量为20sccm通入氢气，调节等离子体增强化学气相沉积真空装置中压强为300Pa，并在压强为300Pa和氢气气氛下，以20℃/min的升温速率将温度升温至520℃。其它与具体实施方式一相同。Specific embodiment two: the difference between this embodiment and specific embodiment one is that in step two, the gas flow rate is 20sccm to pass into hydrogen gas, and the pressure in the plasma enhanced chemical vapor deposition vacuum device is adjusted to be 300Pa, and when the pressure is 300Pa and hydrogen gas Under the atmosphere, the temperature was raised to 520° C. at a heating rate of 20° C./min. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二之一不同的是：步骤二中以气体流量为25sccm通入氢气，调节等离子体增强化学气相沉积真空装置中压强为200Pa，并在压强为200Pa和氢气气氛下，以20℃/min的升温速率将温度升温至550℃。其它与具体实施方式一或二相同。Specific embodiment three: the difference between this embodiment and specific embodiment one or two is that in step 2, the gas flow rate is 25 sccm to feed hydrogen, and the pressure in the plasma-enhanced chemical vapor deposition vacuum device is adjusted to be 200 Pa, and at the pressure The temperature was raised to 550° C. at a rate of 20° C./min under a hydrogen atmosphere of 200 Pa. Others are the same as in the first or second embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤三中以气体流量为20sccm通入甲烷气体，调节氢气的气体流量为10sccm。其它与具体实施方式一至三相同。Embodiment 4: This embodiment differs from Embodiment 1 to Embodiment 3 in that: in step 3, methane gas is introduced with a gas flow rate of 20 sccm, and the gas flow rate of hydrogen gas is adjusted to be 10 sccm. Others are the same as the specific embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：步骤三中调节等离子体增强化学气相沉积真空装置中压强为300Pa，然后在射频功率为200W、压强为300Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为20min。其它与具体实施方式一至四相同。Specific embodiment five: the difference between this embodiment and one of specific embodiments one to four is: in step 3, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to be 300Pa, and then when the radio frequency power is 200W, the pressure is 300Pa and the temperature is The deposition is carried out under the condition of 500° C. to 560° C., and the deposition time is 20 minutes. Others are the same as the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：步骤三中以气体流量为50sccm通入甲烷气体，调节氢气的气体流量为10sccm。其它与具体实施方式一至五相同。Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that: in step 3, methane gas is introduced with a gas flow rate of 50 sccm, and the gas flow rate of hydrogen gas is adjusted to be 10 sccm. Others are the same as those in Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：步骤三中调节等离子体增强化学气相沉积真空装置中压强为300Pa，然后在射频功率为175W、压强为300Pa和温度为550℃的条件下进行沉积，沉积时间为30min。其它与具体实施方式一至六相同。Specific embodiment seven: the difference between this embodiment and one of the specific embodiments one to six is: in step 3, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to be 300Pa, and then when the radio frequency power is 175W, the pressure is 300Pa and the temperature is The deposition is carried out under the condition of 550° C., and the deposition time is 30 minutes. Others are the same as those in Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：步骤四中以气体流量为30sccm通入氩气，调节甲烷气体流量为45sccm。其它与具体实施方式一至七相同。Embodiment 8: This embodiment differs from Embodiment 1 to Embodiment 7 in that: in step 4, argon gas is introduced at a gas flow rate of 30 sccm, and the methane gas flow rate is adjusted to 45 sccm. Others are the same as those in Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：步骤四中调节等离子体增强化学气相沉积真空装置中压强为1000Pa，然后在射频功率为100W～300W、压强为1000Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为20min。其它与具体实施方式一至八相同。Embodiment 9: The difference between this embodiment and one of Embodiments 1 to 8 is that in step 4, the pressure in the plasma-enhanced chemical vapor deposition vacuum device is adjusted to 1000Pa, and then the RF power is 100W-300W, the pressure is 1000Pa and The deposition is carried out at a temperature of 500° C. to 560° C., and the deposition time is 20 minutes. Others are the same as those in Embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：步骤四中以气体流量为40sccm通入氩气，调节甲烷气体流量为50sccm，调节等离子体增强化学气相沉积真空装置中压强为750Pa，然后在射频功率为100W～300W、压强为750Pa和温度为500℃～560℃的条件下进行沉积，沉积时间为25min。其它与具体实施方式一至九相同。Specific embodiment ten: The difference between this embodiment and one of specific embodiments one to nine is that in step 4, the gas flow rate is 40 sccm to feed argon gas, the methane gas flow rate is adjusted to 50 sccm, and the plasma enhanced chemical vapor deposition vacuum device is adjusted. The pressure is 750Pa, and then deposition is carried out under the conditions of radio frequency power of 100W-300W, pressure of 750Pa and temperature of 500°C-560°C, and the deposition time is 25min. Others are the same as the specific embodiments 1 to 9.
采用以下实施例验证本发明的有益效果：Adopt the following examples to verify the beneficial effects of the present invention:
实施例一：Embodiment one:
本实施例所述的原位生长石墨烯/碳纳米管增强Ti基钎料的方法，具体是按照以下步骤进行的：The in-situ growth graphene/carbon nanotube described in the present embodiment strengthens the method for Ti-based solder, specifically carries out according to the following steps:
一、将Ni(NO3)2·6H2O和TiH2粉末置于无水乙醇中混合，然后在温度为100℃的条件下，磁力搅拌至无水乙醇全部挥发，再经研磨，得到Ni(NO3)2·TiH2复合粉末；1. Mix Ni(NO 3 ) 2 ·6H 2 O and TiH 2 powders in absolute ethanol, then stir magnetically at a temperature of 100°C until the absolute ethanol is completely volatilized, and then grind to obtain Ni (NO 3 ) 2 ·TiH 2 composite powder;
所述的Ni(NO3)2·6H2O与TiH2粉末的质量比为1:5；The mass ratio of Ni(NO 3 ) 2 ·6H 2 O to TiH 2 powder is 1:5;
二、将Ni(NO3)2·TiH2复合粉末置于等离子体增强化学气相沉积真空装置中，抽真空至5Pa以下，以气体流量为25sccm通入氢气，调节等离子体增强化学气相沉积真空装置中压强为200Pa，并在压强为200Pa和氢气气氛下，以20℃/min的升温速率将温度升温至550℃；2. Put the Ni(NO 3 ) 2 ·TiH 2 composite powder in the plasma-enhanced chemical vapor deposition vacuum device, evacuate the vacuum to below 5Pa, feed hydrogen gas with a gas flow rate of 25 sccm, and adjust the plasma-enhanced chemical vapor deposition vacuum device The medium pressure is 200Pa, and under the pressure of 200Pa and hydrogen atmosphere, the temperature is raised to 550°C at a heating rate of 20°C/min;
三、以气体流量为50sccm通入甲烷气体，调节氢气的气体流量为10sccm，调节等离子体增强化学气相沉积真空装置中压强为300Pa，然后在射频功率为175W、压强为300Pa和温度为550℃的条件下进行沉积，沉积时间为30min；Three, be that 50sccm is passed into methane gas with gas flow rate, the gas flow rate of regulating hydrogen is 10sccm, regulates that the pressure in plasma-enhanced chemical vapor deposition vacuum device is 300Pa, and then in the radio frequency power is 175W, pressure is 300Pa and temperature is 550 ℃ Deposit under the conditions, the deposition time is 30min;
四、停止通入氢气，以气体流量为25sccm通入氩气，调节甲烷气体流量为50sccm，调节等离子体增强化学气相沉积真空装置中压强为1000Pa，然后在射频功率为175W、压强为1000Pa和温度为550℃的条件下进行沉积，沉积时间为30min，沉积结束后，停止通入甲烷气体，在氩气气氛下冷却，得到石墨烯/碳纳米管增强TiH2复合粉末；Four, stop feeding hydrogen, feed argon gas with gas flow rate of 25 sccm, adjust the methane gas flow rate to 50 sccm, adjust the pressure in the plasma-enhanced chemical vapor deposition vacuum device to be 1000Pa, and then use the radio frequency power of 175W, pressure of 1000Pa and temperature The deposition is carried out under the condition of 550° C., and the deposition time is 30 minutes. After the deposition is completed, the feeding of methane gas is stopped, and cooling is carried out under an argon atmosphere to obtain graphene/carbon nanotube-reinforced TiH 2 composite powder;
五、将石墨烯/碳纳米管增强TiH2复合粉末、TiH2粉末及金属粉末混合并研磨，得到原位生长石墨烯/碳纳米管增强TiNi钎料，即完成原位生长石墨烯/碳纳米管增强Ti基钎料的方法；5. Mix and grind graphene/carbon nanotube-reinforced TiH 2 composite powder, TiH 2 powder and metal powder to obtain in-situ growth graphene/carbon nanotube-reinforced TiNi solder, that is, complete in-situ growth graphene/carbon nanotube A method for reinforcing Ti-based brazing filler metals;
所述的石墨烯/碳纳米管增强TiH2复合粉末与TiH2粉末的质量比为1:1；所述的石墨烯/碳纳米管增强TiH2复合粉末与金属粉末的质量比为2:3；Described graphene/carbon nanotube strengthens TiH The mass ratio of composite powder and TiH powder is 1 :1; Described graphene/carbon nanotube strengthens TiH The mass ratio of composite powder and metal powder is 2 :3 ;
步骤五中所述的金属粉末为Ni金属粉末。The metal powder described in step five is Ni metal powder.
本实施例采用等离子体增强化学气相沉积方法，在低温的条件下，于TiH2上制备了均匀分散的石墨烯和碳纳米管，石墨烯和碳纳米管均具有优异的高温强度以及极低的线膨胀系数，可以发挥双重强化作用，进而可降低Ti基钎料的线膨胀系数，有效提高钎料的高温力学性能。同时，所制备的石墨烯/碳纳米管具有三维混合结构，可以进一步强化复合钎料的性能。This embodiment adopts the plasma-enhanced chemical vapor deposition method, under the condition of low temperature, on TiH Prepared the graphene and the carbon nanotube of uniform dispersion, the graphene and the carbon nanotube all have excellent high-temperature strength and extremely low The linear expansion coefficient can play a dual strengthening role, thereby reducing the linear expansion coefficient of the Ti-based solder and effectively improving the high-temperature mechanical properties of the solder. At the same time, the prepared graphene/carbon nanotubes have a three-dimensional hybrid structure, which can further enhance the performance of the composite solder.
本实施例制备的原位生长石墨烯/碳纳米管增强TiNi钎料钎焊SiO2-BN陶瓷与金属Nb，获得高质量的钎焊接头，接头在室温的抗剪强度为89MPa，在600℃及800℃下的高温抗剪强度分别达到82MPa和61MPa。实施例制备的原位生长石墨烯/碳纳米管增强TiNi钎料的热膨胀系数为7.3×10-6K-1。The in-situ grown graphene/carbon nanotubes prepared in this example reinforced TiNi brazing filler metal to braze SiO 2 -BN ceramics and metal Nb to obtain high-quality brazed joints. The shear strength of the joints at room temperature was 89MPa, and the And the high temperature shear strength at 800 ℃ reaches 82MPa and 61MPa respectively. The coefficient of thermal expansion of the in-situ grown graphene/carbon nanotube reinforced TiNi solder prepared in the example is 7.3×10 -6 K -1 .
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| CN110252030A (en) * | 2019-05-30 | 2019-09-20 | 辽宁兰晶科技有限公司 | A kind of preparation method and application of quantum graphene automobile filter filter material |
| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | Preparation method of in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube-supported copper nanoparticles |
| CN112427759A (en) * | 2020-10-27 | 2021-03-02 | 哈尔滨工业大学 | ZrC-SiC ceramic and TC4 titanium alloy brazing method |
| CN113070543A (en) * | 2021-05-20 | 2021-07-06 | 哈尔滨工业大学 | Method for brazing carbon material and nickel-based alloy by adopting Ag-Cr composite brazing filler metal |
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