技术领域Technical field
本发明属于金属基复合材料制备技术领域，具体涉及一种高导热金刚石/银铜基复合材料及其制备方法。The invention belongs to the technical field of metal matrix composite material preparation, and specifically relates to a high thermal conductivity diamond/silver copper matrix composite material and a preparation method thereof.
背景技术Background technique
随着电子设备朝着高性能、小型化和高度集成化方向快速发展，电子元器件的功率密度越来越大，单位面积的发热量迅速攀升，散热问题已成为制约电子信息产业发展的技术瓶颈之一。With the rapid development of electronic equipment in the direction of high performance, miniaturization and high integration, the power density of electronic components is getting larger and larger, and the heat generation per unit area is rising rapidly. The heat dissipation problem has become a technical bottleneck restricting the development of the electronic information industry. one.
为提高电子元器件的工作稳定性和安全可靠性，高性能热管理材料应运而生，它能够将电子元器件产生的多余热量及时排除，使温度始终保持在正常工作允许的范围内。热管理材料通常需具备较高的热导率，与半导体器件相匹配的热膨胀系数以及轻量化和高强度等特点。In order to improve the working stability, safety and reliability of electronic components, high-performance thermal management materials have emerged. They can remove excess heat generated by electronic components in a timely manner and keep the temperature within the allowable range of normal operation. Thermal management materials usually need to have high thermal conductivity, thermal expansion coefficient matching that of semiconductor devices, lightweight and high strength.
金刚石颗粒室温热导率1500-2200W/(m·K)，铜室温热导率400W/(m·K)，理论上金刚石/铜复合材料的最高热导率大于1000W/(m·K)。然而，由于材料特性及制备工艺问题，金刚石/铜复合材料实际热导率仅有700-900W/(m·K)左右。首先，金刚石的高温不稳定性。由于纯铜熔点高(1083℃)，金刚石/铜复合材料制备温度高达1150-1300℃，高温环境会造成金刚石热损伤，降低金刚石的本征热导率，进而影响复合材料的热导率。其次，金刚石颗粒与铜亲和性差，二者界面热阻较高，必须通过金刚石表面改性方法在金刚石表面形成一层较薄的碳化物层来改善。然而，较高的制备温度容易导致碳化物层厚度过大，降低复合材料热导率。另外，纯铜的流动性较差。由于液态铜表面张力较大，高温下铜流动性较差，容易粘模，不能很好地填充到金刚石孔隙中，制成的复合材料致密度较低。复合材料中间的孔隙会增大复合材料的热阻，降低复合材料的热导。除了以上问题，现有的金刚石/铜复合材料制备方法还存在时间长、工艺过程复杂，高温环境对设备要求高，制造成本高等弊端。The room temperature thermal conductivity of diamond particles is 1500-2200W/(m·K), the room temperature thermal conductivity of copper is 400W/(m·K), and the theoretical maximum thermal conductivity of diamond/copper composite materials is greater than 1000W/(m·K) ). However, due to material characteristics and preparation process issues, the actual thermal conductivity of diamond/copper composite materials is only about 700-900W/(m·K). First, diamond is unstable at high temperatures. Due to the high melting point of pure copper (1083°C), the preparation temperature of diamond/copper composite materials is as high as 1150-1300°C. The high temperature environment will cause thermal damage to diamond and reduce the intrinsic thermal conductivity of diamond, thereby affecting the thermal conductivity of the composite material. Secondly, diamond particles have poor affinity with copper, and the thermal resistance of their interface is high, which must be improved by forming a thin carbide layer on the diamond surface through diamond surface modification. However, higher preparation temperatures can easily lead to excessive thickness of the carbide layer and reduce the thermal conductivity of the composite material. In addition, pure copper has poor fluidity. Due to the large surface tension of liquid copper, copper fluidity is poor at high temperatures, and it is easy to stick to the mold. It cannot fill the diamond pores well, and the composite material produced has a low density. The pores in the middle of the composite material will increase the thermal resistance of the composite material and reduce the thermal conductivity of the composite material. In addition to the above problems, the existing diamond/copper composite material preparation methods also have disadvantages such as long time, complicated process, high equipment requirements in high temperature environment, and high manufacturing cost.
以上问题限制了金刚石/铜复合材料热导率的提升，也很难大幅降低金刚石/铜的制备成本。因此，亟需寻找一种制备温度低、基体流动性好的金刚石增强金属基复合材料，并且能够简便制备，降低生产成本，提高生产率。The above problems limit the improvement of the thermal conductivity of diamond/copper composite materials, and it is also difficult to significantly reduce the preparation cost of diamond/copper. Therefore, there is an urgent need to find a diamond-reinforced metal matrix composite material with low preparation temperature and good matrix fluidity, which can be easily prepared, reduce production costs, and improve productivity.
发明内容Contents of the invention
针对上述现有技术的不足，本发明提供了一种高导热金刚石/银铜基复合材料及其制备方法，是一种低成本、高效率的高导热金刚石/银铜基复合材料的制备方法。In view of the above deficiencies in the prior art, the present invention provides a high thermal conductivity diamond/silver copper-based composite material and a preparation method thereof, which is a low-cost, high-efficiency preparation method of a high thermal conductivity diamond/silver copper-based composite material.
为解决上述技术问题，本发明采用以下技术方案：In order to solve the above technical problems, the present invention adopts the following technical solutions:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：对金刚石颗粒进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Pre-process the diamond particles with pickling, alkali washing, absolute ethanol cleaning, and drying;
S2：将上步骤预处理后的金刚石颗粒填装在成形模具中，然后用振实机振实，形成金刚石坯料；S2: Fill the diamond particles pretreated in the previous step into the forming mold, and then vibrate them with a vibrator to form a diamond blank;
S3：将上步骤得到的金刚石坯料连同成形模具一起放置于分体式双温区压力浸渗装置的真空气压浸渗炉下腔室中，将银铜基体合金放置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚；然后对感应加热炉上腔室、真空气压浸渗炉下腔室抽真空，当真空度降至10-10-2Pa后，加热，待感应加热炉上腔室、真空气压浸渗炉下腔室分别达到设定的温度恒温后，将熔化的银铜基体合金熔液浇注到成型模具中；停止感应加热炉上腔室加热和抽真空，再从真空气压浸渗炉下腔室通入高纯惰性气体，增加炉内压力至常压后停止通气；S3: Place the diamond blank obtained in the previous step together with the forming mold in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place the silver-copper matrix alloy in the split dual-temperature zone pressure impregnation device. The molten metal crucible in the upper chamber of the induction heating furnace of the device; then evacuate the upper chamber of the induction heating furnace and the lower chamber of the vacuum and air pressure impregnation furnace. When the vacuum degree drops to 10-10-2 Pa, heat it and wait for induction After the upper chamber of the heating furnace and the lower chamber of the vacuum air pressure impregnation furnace reach the set temperature respectively, the molten silver-copper matrix alloy melt is poured into the forming mold; the heating and vacuuming of the upper chamber of the induction heating furnace are stopped. Then introduce high-purity inert gas from the lower chamber of the vacuum pressure impregnation furnace, increase the pressure in the furnace to normal pressure and then stop ventilation;
所述的银铜基体合金为银铜铬合金或银铜锆合金，银铜基体合金成分按质量百分比计为Ag：60-70％、Cr或Zr：0.5-1.2％、Cu：余量；The silver-copper matrix alloy is a silver-copper-chromium alloy or a silver-copper-zirconium alloy. The components of the silver-copper matrix alloy are Ag: 60-70%, Cr or Zr: 0.5-1.2%, and Cu: balance in terms of mass percentage;
所述的感应加热炉上腔室设定温度为950-1050℃，真空气压浸渗炉下腔室设定温度为860-950℃；The set temperature of the upper chamber of the induction heating furnace is 950-1050°C, and the set temperature of the lower chamber of the vacuum air pressure impregnation furnace is 860-950°C;
S4：快速拆装感应加热炉上腔室，旋入真空气压浸渗炉下腔室的炉盖；对真空气压浸渗炉下腔室通入高压高纯惰性气体至5-20MPa后，银铜基体合金熔液在气体压力作用下浸渗到金刚石颗粒孔隙中，与此同时银铜基体合金熔液中的铬或锆元素与金刚石颗粒反应，在金刚石颗粒表面生成厚度为100-200nm的碳化铬或碳化锆，恒温恒压5-20min后再关闭加热电源随炉冷却到200℃以下，获得金刚石/银铜基复合材料；S4: Quickly disassemble and assemble the upper chamber of the induction heating furnace, and screw in the furnace cover of the lower chamber of the vacuum and air pressure impregnation furnace; after passing high-pressure, high-purity inert gas into the lower chamber of the vacuum and air pressure impregnation furnace to 5-20MPa, the silver copper The matrix alloy melt infiltrates into the pores of the diamond particles under the action of gas pressure. At the same time, the chromium or zirconium element in the silver-copper matrix alloy melt reacts with the diamond particles to generate chromium carbide with a thickness of 100-200nm on the surface of the diamond particles. Or zirconium carbide, keep the temperature and pressure constant for 5-20 minutes, then turn off the heating power and cool the furnace to below 200°C to obtain the diamond/silver copper-based composite material;
步骤S3所述的分体式双温区压力浸渗装置，包括可快拆快装的感应加热炉上腔室、真空气压浸渗炉下腔室、真空系统、充气系统和电气控制系统；其中的真空气压浸渗炉下腔室与真空系统、充气系统连接，电气控制系统控制整个分体式双温区压力浸渗装置；The split dual-temperature zone pressure impregnation device described in step S3 includes an upper chamber of an induction heating furnace that can be quickly disassembled and assembled, a lower chamber of a vacuum air pressure impregnation furnace, a vacuum system, an air filling system and an electrical control system; wherein The lower chamber of the vacuum air pressure impregnation furnace is connected to the vacuum system and the inflation system, and the electrical control system controls the entire split dual-temperature zone pressure impregnation device;
所述的感应加热炉上腔室为中频感应炉，从外至内依次是中频感应炉炉壳、感应线圈和熔金属坩埚；所述的感应加热炉上腔室通过电缆与中频电源连接，其中电缆为快拆快接结构；The upper chamber of the induction heating furnace is an intermediate frequency induction furnace, and from the outside to the inside are the intermediate frequency induction furnace shell, induction coil and molten metal crucible; the upper chamber of the induction heating furnace is connected to the intermediate frequency power supply through a cable, wherein The cable has a quick-detach and quick-connect structure;
所述的真空气压浸渗炉下腔室，从外至内依次是钟罩式保温筒、石墨发热体、浸渗复合模具；所述的真空气压浸渗炉下腔室的底部设置充气接口和真空接口；The lower chamber of the vacuum pneumatic impregnation furnace contains, from the outside to the inside, a bell-type insulation cylinder, a graphite heating element, and an impregnation composite mold; the bottom of the lower chamber of the vacuum pneumatic impregnation furnace is provided with an inflatable interface and Vacuum interface;
在感应加热炉上腔室的底部与真空气压浸渗炉下腔室的钟罩式保温筒顶部均设置有金属液体流通小孔，感应加热炉上腔室和真空气压浸渗炉下腔室通过旋入式卡槽配合连接；The bottom of the upper chamber of the induction heating furnace and the top of the bell-type insulation cylinder of the lower chamber of the vacuum and air pressure impregnation furnace are both provided with small holes for metal liquid circulation. The upper chamber of the induction heating furnace and the lower chamber of the vacuum and air pressure impregnation furnace pass through Screw-in card slot matching connection;
所述的感应加热炉上腔室1台与真空气压浸渗炉下腔室2-5台组合，进行步进生产。One upper chamber of the induction heating furnace is combined with 2-5 lower chambers of the vacuum pneumatic impregnation furnace for step production.
本发明中：In the present invention:
步骤S1所述的金刚石颗粒的粒径为45μm-450μm，在其它条件相同时，随金刚石颗粒粒径增加，银铜基体合金与金刚石颗粒之间界面热阻减小，金刚石/银铜基复合材料热导率增加，但复合材料的抗弯强度也随之降低，综合热导率和抗弯强度两个性能指标，金刚石颗粒的粒径优选为45μm-450μm。The particle size of the diamond particles described in step S1 is 45 μm-450 μm. When other conditions are the same, as the diamond particle size increases, the interface thermal resistance between the silver-copper matrix alloy and the diamond particles decreases, and the diamond/silver-copper matrix composite material Thermal conductivity increases, but the flexural strength of the composite material also decreases. Combining the two performance indicators of thermal conductivity and flexural strength, the particle size of the diamond particles is preferably 45 μm-450 μm.
步骤S3所述的银铜基体合金为银铜铬合金或银铜锆合金，银铜基体合金成分按质量百分比计为Ag：60-70％、Cr或Zr：0.5-1.2％、Cu：余量，该合金熔点为779-820℃。有研究表明，980℃以上金刚石颗粒表皮会出现较明显的似月球表面的凹坑，并且出现部分表层脱落，使金刚石的本征热导有所下降，本发明选用共晶成分附近的Ag-30～40wt.％Cu合金作为基体，熔点低、流动性好，制备温度860-950℃即可(比熔点高80-130℃)，较低的制备温度可有效避免金刚石的热损伤问题，保证金刚石的高导热性能，最终获得高导热复合材料。另外，由于金刚石与银铜基体合金润湿性较差，二者界面结合弱，界面热阻较高，严重影响了复合材料热导率。因此，在银铜基体合金中添加了质量分数为0.5-1.2％的铬或锆元素，高温高压浸渗过程中铬或锆会与金刚石颗粒表面发生界面反应生成碳化铬或碳化锆反应层，从而明显改善金刚石与银铜基体合金的界面结合，降低界面热阻，有利于获得具有较高热导率的复合材料。铬或锆元素含量过低时，生成的碳化铬或碳化锆反应层较薄，达不到改善界面结合效果；铬或锆元素含量过高时，生成的碳化铬或碳化锆反应层较厚，使得界面热阻增加，同时银铜基体合金的热导率也会随铬或锆元素含量的增加而降低，因此优选质量分数为0.5-1.2％的铬或锆。The silver-copper matrix alloy described in step S3 is a silver-copper-chromium alloy or a silver-copper-zirconium alloy. The components of the silver-copper matrix alloy are Ag: 60-70%, Cr or Zr: 0.5-1.2%, and Cu: balance in terms of mass percentage. , the melting point of this alloy is 779-820℃. Studies have shown that the surface of diamond particles above 980°C will have obvious pits like the moon surface, and part of the surface layer will fall off, which will reduce the intrinsic thermal conductivity of diamond. The present invention selects Ag-30 near the eutectic component. ~40wt.% Cu alloy is used as the matrix, with low melting point and good fluidity. The preparation temperature is 860-950°C (80-130°C higher than the melting point). The lower preparation temperature can effectively avoid the problem of thermal damage of diamond and ensure diamond High thermal conductivity, and finally obtain high thermal conductivity composite materials. In addition, due to the poor wettability of diamond and the silver-copper matrix alloy, the interface between the two is weak and the interface thermal resistance is high, which seriously affects the thermal conductivity of the composite material. Therefore, a chromium or zirconium element with a mass fraction of 0.5-1.2% is added to the silver-copper matrix alloy. During the high-temperature and high-pressure impregnation process, the chromium or zirconium will react with the surface of the diamond particles at the interface to form a chromium carbide or zirconium carbide reaction layer, thus Significantly improve the interface bonding between diamond and silver-copper matrix alloy, reduce the interface thermal resistance, and be conducive to obtaining composite materials with higher thermal conductivity. When the chromium or zirconium element content is too low, the generated chromium carbide or zirconium carbide reaction layer is thin and cannot improve the interface bonding effect; when the chromium or zirconium element content is too high, the generated chromium carbide or zirconium carbide reaction layer is thicker. The interface thermal resistance increases, and the thermal conductivity of the silver-copper matrix alloy also decreases with the increase in chromium or zirconium element content. Therefore, the mass fraction of chromium or zirconium is preferably 0.5-1.2%.
在步骤S3中，所述的感应加热炉上腔室设定温度为950-1050℃，真空气压浸渗炉下腔室设定温度为860-950℃，银铜基体合金的熔点为779-820℃，感应加热炉上腔室温度设定为950-1050℃是为了确保银铜基体合金充分熔化并具有较好的流动性，有利于银铜基体合金熔液自上而下流入真空气压浸渗炉下腔室与成形模具进行浸渗复合，真空气压浸渗炉下腔室温度860-950℃为浸渗温度，是为了避免破坏金刚石颗粒原本的热导性能。In step S3, the set temperature of the upper chamber of the induction heating furnace is 950-1050°C, the set temperature of the lower chamber of the vacuum air pressure impregnation furnace is 860-950°C, and the melting point of the silver-copper matrix alloy is 779-820°C. ℃, the temperature of the upper chamber of the induction heating furnace is set to 950-1050 ℃ to ensure that the silver-copper matrix alloy is fully melted and has good fluidity, which is conducive to the flow of the silver-copper matrix alloy melt from top to bottom into the vacuum and pneumatic impregnation. The chamber under the furnace and the forming mold are impregnated and compounded. The temperature of the chamber under the vacuum and air pressure impregnation furnace is 860-950°C as the impregnation temperature to avoid damaging the original thermal conductivity of the diamond particles.
在步骤S3中，所述的感应加热炉上腔室的加热采用感应加热，升温速率为200-300℃/min，感应加热的目的是使银铜基体合金迅速升温熔化，从而避免合金氧化，并提高生产效率；所述真空气压浸渗炉下腔室的加热采用石墨发热体加热，升温速率为10-20℃/min，石墨发热体加热可精确控制真空气压浸渗炉下腔室浸渗温度，并控制金刚石与银铜基体合金中铬或锆的扩散反应速率，从而达到精确控制金刚石表面碳化铬或碳化锆层厚度的效果。In step S3, the upper chamber of the induction heating furnace is heated by induction heating with a heating rate of 200-300°C/min. The purpose of induction heating is to quickly heat up and melt the silver-copper matrix alloy, thereby avoiding oxidation of the alloy, and Improve production efficiency; the lower chamber of the vacuum pneumatic impregnation furnace is heated by a graphite heating element with a heating rate of 10-20°C/min. The graphite heating element heating can accurately control the impregnation temperature of the lower chamber of the vacuum pneumatic impregnation furnace. , and control the diffusion reaction rate of chromium or zirconium in diamond and silver-copper matrix alloy, thereby achieving the effect of accurately controlling the thickness of chromium carbide or zirconium carbide layer on the diamond surface.
步骤S3所述的感应加热炉上腔室设置有提升杆，提升杆从感应加热炉上腔室顶部穿过熔金属坩埚底部与流通小孔对应；所述的电缆，做成快拆快接结构是为了在银铜基体合金熔液浇注后能够快速撤除感应加热炉上腔室，避免撤除过程中真空气压浸渗炉下腔室温度的大幅波动和空气进入。The upper chamber of the induction heating furnace described in step S3 is provided with a lifting rod. The lifting rod passes from the top of the upper chamber of the induction heating furnace through the bottom of the molten metal crucible and corresponds to the circulation hole; the cable is made into a quick-release and quick-connect structure. The purpose is to quickly remove the upper chamber of the induction heating furnace after the silver-copper matrix alloy melt is poured, and to avoid large temperature fluctuations and air intrusion in the lower chamber of the vacuum air pressure impregnation furnace during the removal process.
步骤S3所述的真空气压浸渗炉下腔室设置有炉盖，真空气压浸渗炉下腔室与炉盖通过旋入式卡槽配合连接；所述的真空气压浸渗炉下腔室的浸渗复合模具，包括石墨坩埚和成形模具；所述的石墨发热体和石墨坩埚表面均有一薄层化学气相沉积所得的碳化硅材料，以提高石墨发热体和石墨坩埚抗氧化性能。The lower chamber of the vacuum pneumatic impregnation furnace described in step S3 is provided with a furnace cover, and the lower chamber of the vacuum pneumatic impregnation furnace and the furnace cover are connected through a screw-in slot; the lower chamber of the vacuum pneumatic impregnation furnace is The impregnated composite mold includes a graphite crucible and a forming mold; the surface of the graphite heating element and the graphite crucible has a thin layer of silicon carbide material obtained by chemical vapor deposition to improve the oxidation resistance of the graphite heating element and the graphite crucible.
步骤S3所述的真空气压浸渗炉下腔室中的钟罩式保温筒的内外层为金属薄板，金属薄板采用铆接或焊接工艺连接，在两层薄板之间填充有保温材料。The inner and outer layers of the bell-type insulation cylinder in the lower chamber of the vacuum pneumatic impregnation furnace described in step S3 are metal sheets. The metal sheets are connected by riveting or welding technology, and insulation materials are filled between the two layers of sheets.
步骤S3所述的感应加热炉上腔室和真空气压浸渗炉下腔室均为双层水循环金属壳体；所述的感应加热炉上腔室和真空气压浸渗炉下腔室通过旋入式卡槽配合连接，旋入式卡槽配合连接可满足感应加热炉上腔快拆快装要求；同时，满足抽真空和充气时感应加热炉上腔室和真空气压浸渗炉下腔室连接处密封要求。The upper chamber of the induction heating furnace and the lower chamber of the vacuum and air pressure impregnation furnace described in step S3 are both double-layer water circulation metal shells; the upper chamber of the induction heating furnace and the lower chamber of the vacuum and air pressure impregnation furnace are screwed in The screw-in card slot matching connection can meet the requirements of quick disassembly and quick installation of the upper chamber of the induction heating furnace; at the same time, it can meet the connection between the upper chamber of the induction heating furnace and the lower chamber of the vacuum air pressure impregnation furnace during vacuuming and inflation. sealing requirements.
步骤S3所述的将熔化的银铜基体合金熔液浇注到成型模具中，是恒温结束后，提起感应加热炉上腔室的熔金属坩埚中的提升杆，银铜基体合金熔液自流通小孔流入真空气压浸渗炉下腔室的成形模具中。The molten silver-copper matrix alloy melt is poured into the forming mold as described in step S3. After the constant temperature is completed, the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace is lifted. The silver-copper matrix alloy melt has a small flow rate. The holes flow into the forming mold in the lower chamber of the vacuum pneumatic impregnation furnace.
步骤S3所述的感应加热炉上腔室1台与真空气压浸渗炉下腔室2-5台组合，进行步进生产，具体为：在感应加热炉上腔室与第1台真空气压浸渗炉下腔室组合工作时，第2-5台真空气压浸渗炉内放置好装有金刚石坯料的成形模具，并按步进生产流程先后开启加热电源，在惰性气体保护下加热；感应加热炉上腔室熔化银铜基体合金并浇注到第1台真空气压浸渗炉下腔室的成形模具后，将感应加热炉上腔室与第1台真空气压浸渗炉下腔室快速分离，第1台真空气压浸渗炉进而进行步骤S4操作；打开第2台真空气压浸渗炉下腔室炉盖，旋入感应加热炉上腔室，快速接好感应加热炉上腔室电缆；再打开感应加热炉炉盖，放入银铜基体合金，开启电源升温熔化银铜基体合金；接下来第2台真空气压浸渗炉下腔室打开真空系统，开始抽真空，待感应加热炉上腔室、真空气压浸渗炉下腔室达到程序设定温度后，按照“提起提升杆-银铜基体合金熔液浇注-关闭真空系统-充气至常压-感应加热炉上腔室与真空气压浸渗炉下腔室分离-真空气压浸渗炉下腔室进行步骤S4操作”进行，之后感应加热炉上腔室参照以上步骤依次与第3、第4、第5台真空气压浸渗炉下腔室陆续组合，进行步进生产。One upper chamber of the induction heating furnace described in step S3 is combined with 2-5 lower chambers of the vacuum pneumatic impregnation furnace to perform step-by-step production. Specifically, the upper chamber of the induction heating furnace is combined with the first vacuum pneumatic impregnation furnace. When the combination of the lower chamber of the infiltration furnace is working, the forming molds containing diamond blanks are placed in the 2nd to 5th vacuum and air pressure impregnation furnaces, and the heating power is turned on successively according to the step-by-step production process, and heating is performed under the protection of inert gas; induction heating After the silver-copper matrix alloy is melted in the upper chamber of the furnace and poured into the forming mold of the lower chamber of the first vacuum pneumatic impregnation furnace, the upper chamber of the induction heating furnace is quickly separated from the lower chamber of the first vacuum pneumatic impregnation furnace. The first vacuum air pressure impregnation furnace proceeds to step S4; open the lower chamber lid of the second vacuum air pressure impregnation furnace, screw into the upper chamber of the induction heating furnace, and quickly connect the cable to the upper chamber of the induction heating furnace; then Open the lid of the induction heating furnace, put in the silver-copper matrix alloy, turn on the power to heat up and melt the silver-copper matrix alloy; then open the vacuum system in the lower chamber of the second vacuum pneumatic impregnation furnace and start vacuuming, and wait until the upper chamber of the induction heating furnace After the chamber and the lower chamber of the vacuum air pressure impregnation furnace reach the programmed temperature, follow the steps of "Lift the lifting rod - pour the silver-copper matrix alloy melt - close the vacuum system - inflate to normal pressure - connect the upper chamber of the induction heating furnace with the vacuum air pressure impregnation Separation of the lower chamber of the infiltration furnace - the lower chamber of the vacuum and air pressure impregnation furnace is operated in step S4, and then the upper chamber of the induction heating furnace is sequentially connected to the lower chamber of the 3rd, 4th and 5th vacuum and air pressure impregnation furnace according to the above steps. The rooms are assembled one after another for step-by-step production.
所述的步骤S4，具体为：打开感应加热炉上腔室和真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室炉盖，密封真空气压浸渗炉下腔室；对真空气压浸渗炉下腔室充入高压高纯惰性气体至5-20MPa后，恒温恒压保持5-20min，完成银铜基体合金与金刚石之间的复合；停止真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；恒温恒压保持5-20min的目的一是使银铜基体合金熔液浸渗到金刚石颗粒孔隙中，另一目的是使银铜基体合金熔液中的铬或锆元素与金刚石颗粒发生反应，在金刚石颗粒表面形成100-200nm厚的碳化铬或碳化锆。由于碳化锆或碳化铬的热导率为20-120W/(m·K)，热导率较低，因此在制备金刚石增强金属基复合材料时，在碳化铬或碳化锆覆盖完整基础上，碳化铬或碳化锆层的厚度愈薄，金刚石增强金属基复合材料的热导率愈高。Described step S4 is specifically: open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the vacuum pneumatic impregnation furnace, quickly remove the upper chamber of the induction heating furnace, and screw it into the lower chamber of the vacuum pneumatic impregnation furnace. The chamber furnace cover seals the lower chamber of the vacuum pneumatic impregnation furnace; after filling the lower chamber of the vacuum pneumatic impregnation furnace with high-pressure, high-purity inert gas to 5-20MPa, maintain it at constant temperature and pressure for 5-20 minutes to complete the silver-copper matrix alloy. Composite with diamond; stop heating the lower chamber of the vacuum air pressure impregnation furnace, and cool it with the furnace. When it cools to below 200°C, take out the diamond/silver copper-based composite material; the purpose of maintaining constant temperature and pressure for 5-20 minutes is to make the The silver-copper matrix alloy melt is infiltrated into the pores of the diamond particles. Another purpose is to react the chromium or zirconium elements in the silver-copper matrix alloy melt with the diamond particles to form 100-200nm thick chromium carbide or zirconium carbide on the surface of the diamond particles. Zirconium carbide. Since the thermal conductivity of zirconium carbide or chromium carbide is 20-120W/(m·K) and the thermal conductivity is low, when preparing diamond-reinforced metal matrix composite materials, on the basis of complete coverage of chromium carbide or zirconium carbide, carbonization The thinner the thickness of the chromium or zirconium carbide layer, the higher the thermal conductivity of the diamond-reinforced metal matrix composite.
步骤S4中所述的金刚石/银铜基复合材料中金刚石颗粒增强相体积分数为40-80％。The volume fraction of the diamond particle reinforcement phase in the diamond/silver-copper matrix composite material described in step S4 is 40-80%.
本发明还涉及一种高导热金刚石/银铜基复合材料，采用上述一种高导热金刚石/银铜基复合材料的制备方法得到，所述的金刚石/银铜基复合材料中金刚石颗粒增强相体积分数为40-80％，金刚石颗粒表面碳化铬或碳化锆层厚度为100-200nm，复合材料致密度达99.1-99.5％，热导率为720-1152W/(m·K)。The invention also relates to a high thermal conductivity diamond/silver copper-based composite material, which is obtained by adopting the above-mentioned preparation method of a high thermal conductivity diamond/silver copper-based composite material. The diamond particles in the diamond/silver copper-based composite material enhance the phase volume. The fraction is 40-80%, the thickness of the chromium carbide or zirconium carbide layer on the surface of the diamond particles is 100-200nm, the density of the composite material reaches 99.1-99.5%, and the thermal conductivity is 720-1152W/(m·K).
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明所述的一种高导热金刚石/银铜基复合材料，采用银铜基体合金做复合材料基体，制备温度可低至950℃及以下，金刚石发生高温热损伤的可能性大大降低；同时，较低的制备温度可促使银铜基体合金中铬或锆元素与金刚石的反应速率明显降低，从而能够精确控制碳化铬或碳化锆反应层厚度，确保获得低界面热阻、高热导率的金刚石/银铜基复合材料；另外，银铜基体合金的流动性优于纯铜；熔体流动性与熔体表面张力和黏度有关，纯铜中加入银后可以降低熔体表面张力，减小黏度，提高熔体的流动性。如1085℃时液态纯Cu的表面张力为1330mN/m，而液态Ag-40％Cu合金的表面张力为940mN/m，表面张力随Ag含量的增加而降低。银铜基体合金较好的流动性有利于其自上而下流入金刚石颗粒间隙中进行浸渗复合，从而确保了复合材料较好的致密性。1. A high thermal conductivity diamond/silver-copper matrix composite material according to the present invention uses a silver-copper matrix alloy as the composite material matrix. The preparation temperature can be as low as 950°C and below, and the possibility of high-temperature thermal damage to diamond is greatly reduced; At the same time, the lower preparation temperature can significantly reduce the reaction rate between chromium or zirconium elements in the silver-copper matrix alloy and diamond, thus enabling precise control of the thickness of the chromium carbide or zirconium carbide reaction layer to ensure low interface thermal resistance and high thermal conductivity. Diamond/silver-copper matrix composite material; In addition, the fluidity of silver-copper matrix alloy is better than that of pure copper; the melt fluidity is related to the melt surface tension and viscosity. Adding silver to pure copper can reduce the melt surface tension and reduce the Viscosity, improve the fluidity of the melt. For example, the surface tension of liquid pure Cu at 1085°C is 1330mN/m, while the surface tension of liquid Ag-40% Cu alloy is 940mN/m. The surface tension decreases with the increase of Ag content. The better fluidity of the silver-copper matrix alloy facilitates its top-down flow into the gaps between diamond particles for impregnation and compounding, thereby ensuring better compactness of the composite material.
2、本发明所述的一种高导热金刚石/银铜基复合材料的制备方法，采用分体式双温区压力浸渗装置的感应加热炉上腔室与真空气压浸渗炉下腔室通过旋入式卡槽配合连接，满足抽真空和充气时上下腔连接处密封要求；同时，满足感应加热炉上腔室快拆快装要求。当感应加热炉上腔室完成银铜基体合金的熔炼、浇注任务后即被快速撤除，然后迅速旋入真空气压浸渗炉下腔室的炉盖，密封真空气压浸渗炉下腔室，在真空气压浸渗炉下腔室内完成气压浸渗任务。与现有的压力浸渗装置相比，本装置的真空气压浸渗部分的装置尺寸明显减小，设备制造、维护和运营成本显著降低。2. The preparation method of a high thermal conductivity diamond/silver-copper matrix composite material according to the present invention adopts the upper chamber of the induction heating furnace of the split dual-temperature zone pressure impregnation device and the lower chamber of the vacuum air pressure impregnation furnace through rotating The in-type card slot cooperates with the connection to meet the sealing requirements of the upper and lower chamber connections during vacuuming and inflation; at the same time, it meets the requirements for quick disassembly and quick assembly of the upper chamber of the induction heating furnace. When the upper chamber of the induction heating furnace completes the smelting and pouring tasks of the silver-copper matrix alloy, it is quickly removed, and then quickly screwed into the furnace cover of the lower chamber of the vacuum pneumatic impregnation furnace to seal the lower chamber of the vacuum pneumatic impregnation furnace. The air pressure impregnation task is completed in the lower chamber of the vacuum air pressure impregnation furnace. Compared with the existing pressure impregnation device, the device size of the vacuum pneumatic impregnation part of the device is significantly reduced, and the equipment manufacturing, maintenance and operating costs are significantly reduced.
3、本发明所述的一种高导热金刚石/银铜基复合材料的制备方法，采用的分体式双温区压力浸渗装置的感应加热炉上腔室0.5小时即可熔化银铜基体合金，且可以快拆快装；而真空气压浸渗炉下腔室预热、浸渗和冷却模具通常需要数小时，因此1台感应加热炉上腔室能够与2-5台真空气压浸渗炉下腔室组合，进行步进生产，设备效能和产能高，满足实际生产线不间断浸渗产品要求，且材料制造成本明显降低。3. The preparation method of a high thermal conductivity diamond/silver-copper matrix composite material according to the present invention uses the upper chamber of the induction heating furnace of the split-type dual-temperature zone pressure impregnation device to melt the silver-copper matrix alloy in 0.5 hours. And it can be quickly disassembled and assembled; while it usually takes several hours to preheat, impregnate and cool the mold in the lower chamber of a vacuum pneumatic impregnation furnace, so the upper chamber of one induction heating furnace can be used with the lower chamber of 2-5 vacuum pneumatic impregnation furnaces. The combination of chambers enables step-by-step production, with high equipment efficiency and production capacity, meeting the requirements of uninterrupted impregnation of products in actual production lines, and significantly reducing material manufacturing costs.
附图说明Description of the drawings
图1为本发明实施例所述的制备高导热金属基复合材料的分体式双温区压力浸渗装置的结构示意图；Figure 1 is a schematic structural diagram of a split dual-temperature zone pressure impregnation device for preparing high thermal conductivity metal matrix composite materials according to the embodiment of the present invention;
图2为本发明实施例所述的制备高导热金属基复合材料的分体式双温区压力浸渗装置的撤除感应加热炉上腔室后的结构示意图；Figure 2 is a schematic structural diagram of the split dual-temperature zone pressure impregnation device for preparing high thermal conductivity metal matrix composite materials according to the embodiment of the present invention after removing the upper chamber of the induction heating furnace;
图3为本发明实施例1所述的一种高导热金刚石/银铜基复合材料的制备方法得到的金刚石/银铜基复合材料实物图；Figure 3 is a physical diagram of a diamond/silver-copper-based composite material obtained by a method for preparing a highly thermally conductive diamond/silver-copper-based composite material according to Embodiment 1 of the present invention;
图4为本发明实施例1所述的一种高导热金刚石/银铜基复合材料的制备方法得到的金刚石/银铜基复合材料的100倍光学照片的图。Figure 4 is a 100x optical photograph of a diamond/silver copper-based composite material obtained by a method for preparing a highly thermally conductive diamond/silver-copper-based composite material according to Embodiment 1 of the present invention.
其中，附图中标记为：Among them, marked in the attached figure are:
1、感应加热炉上腔室；2、真空气压浸渗炉下腔室；3、中频感应炉炉壳；4、熔金属坩埚；5、感应线圈；6、充气接口；7、真空接口；8、石墨发热体；9、成形模具；10、钟罩式保温筒；11、流通小孔；12、炉盖；13、石墨坩埚；14、提升杆。1. Upper chamber of induction heating furnace; 2. Lower chamber of vacuum pneumatic impregnation furnace; 3. Medium frequency induction furnace shell; 4. Molten metal crucible; 5. Induction coil; 6. Inflatable interface; 7. Vacuum interface; 8 , Graphite heating element; 9. Forming mold; 10. Bell-type insulation cylinder; 11. Circulation hole; 12. Furnace cover; 13. Graphite crucible; 14. Lifting rod.
具体实施方式Detailed ways
以下通过实施例进一步详细描述本发明，但这些实施例不应认为是对本发明的限制。The present invention is described in further detail below through examples, but these examples should not be considered as limiting the present invention.
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，所描述的实施例仅仅是本发明的一部分实施例，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作出创造性劳动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。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.
实施例1：Example 1:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：对金刚石颗粒进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Pre-process the diamond particles with pickling, alkali washing, absolute ethanol cleaning, and drying;
S2：将所述预处理后的金刚石颗粒填装在成形模具中，然后用振实机振实，形成金刚石坯料；S2: Fill the pretreated diamond particles into the forming mold, and then vibrate them with a vibrator to form a diamond blank;
S3：将所述金刚石坯料连同成形模具一起放置于分体式双温区压力浸渗装置的真空气压浸渗炉下腔室，银铜基体合金放置于分体式双温区压力浸渗装置的感应加热炉上腔室的石墨坩埚中；然后对上下腔抽真空、加热，待上下腔分别达到设定的温度恒温后，将熔化的银铜基体合金熔液浇注到成型模具中；停止感应加热炉上腔室加热和抽真空，再通入高纯惰性气体，增加炉内压力至常压后停止通气；S3: Place the diamond blank together with the forming mold in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place the silver-copper matrix alloy in the induction heating of the split dual-temperature zone pressure impregnation device. into the graphite crucible in the upper chamber of the furnace; then evacuate and heat the upper and lower chambers. After the upper and lower chambers respectively reach the set temperature constant, pour the molten silver-copper matrix alloy melt into the forming mold; stop the induction heating furnace The chamber is heated and evacuated, then high-purity inert gas is introduced, the pressure in the furnace is increased to normal pressure and then ventilation is stopped;
S4：快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室的炉盖；对真空气压浸渗炉下腔室通入高压高纯惰性气体，银铜基体合金熔液在气体压力作用下浸渗到金刚石颗粒孔隙中，与此同时银铜基体合金熔液中的铬或锆元素与金刚石颗粒反应，在金刚石颗粒表面生成100-200nm的碳化铬或碳化锆层，恒温恒压5-20min后再关闭加热电源随炉冷却，获得金刚石/银铜基复合材料；S4: Quickly remove the upper chamber of the induction heating furnace, screw in the furnace cover of the lower chamber of the vacuum and air pressure impregnation furnace; pass high-pressure, high-purity inert gas into the lower chamber of the vacuum and air pressure impregnation furnace, and the silver-copper matrix alloy melt will be in the gas Under pressure, it penetrates into the pores of diamond particles. At the same time, the chromium or zirconium element in the silver-copper matrix alloy melt reacts with the diamond particles to form a 100-200nm chromium carbide or zirconium carbide layer on the surface of the diamond particles. Under constant temperature and constant pressure After 5-20 minutes, turn off the heating power and let the furnace cool down to obtain the diamond/silver copper-based composite material;
实施例1-5中，分体式双温区压力浸渗装置示意图如图1-2所示，包括可快拆快装的感应加热炉上腔室1、真空气压浸渗炉下腔室2、真空系统、充气系统和电气控制系统；In Embodiment 1-5, the schematic diagram of the split dual-temperature zone pressure impregnation device is shown in Figure 1-2, including an upper chamber 1 of the induction heating furnace that can be quickly disassembled and assembled, a lower chamber 2 of the vacuum air pressure impregnation furnace, Vacuum system, inflation system and electrical control system;
所述感应加热炉上腔室1为中频感应炉，从外至内依次是中频感应炉炉壳3、熔金属坩埚4和感应线圈5；所述的感应加热炉上腔室1通过电缆与中频电源连接，其中电缆为快拆快接结构；所述真空气压浸渗炉下腔室2包括充气接口6、真空接口7、石墨发热体8、浸渗复合模具和钟罩式保温筒10等；The upper chamber 1 of the induction heating furnace is an intermediate frequency induction furnace. From the outside to the inside, there are the intermediate frequency induction furnace shell 3, the molten metal crucible 4 and the induction coil 5; the upper chamber 1 of the induction heating furnace is connected to the intermediate frequency through cables. Power connection, in which the cable is a quick-release and quick-connect structure; the lower chamber 2 of the vacuum and air pressure impregnation furnace includes an inflatable interface 6, a vacuum interface 7, a graphite heating element 8, an impregnation composite mold and a bell-type insulation cylinder 10, etc.;
在感应加热炉上腔室1底部与真空气压浸渗炉下腔室2的钟罩式保温筒顶部均设置有金属液体流通小孔11，感应加热炉上腔室1和真空气压浸渗炉下腔室2通过旋入式卡槽配合连接；旋入式卡槽配合连接可满足感应加热炉上腔室1快拆快装要求；同时，满足抽真空和充气时感应加热炉上腔室1和真空气压浸渗炉下腔室2连接处密封要求；电缆做快拆快接结构是为了金属基体熔化浇注后能够快速拆挪感应加热炉上腔室1，避免拆挪过程中真空气压浸渗炉下腔室2温度的大幅波动和氧气进入；Metal liquid circulation holes 11 are provided at the bottom of the upper chamber 1 of the induction heating furnace and the lower chamber 2 of the vacuum pneumatic impregnation furnace. Chamber 2 is connected through a screw-in slot; the screw-in slot fit and connection can meet the requirements for quick disassembly and quick installation of the upper chamber 1 of the induction heating furnace; at the same time, it can meet the requirements of the upper chamber 1 and the upper chamber of the induction heating furnace during vacuuming and inflation. Sealing requirements for the connection of the lower chamber 2 of the vacuum pneumatic impregnation furnace; the cable has a quick-release quick-connect structure so that the upper chamber 1 of the induction heating furnace can be quickly dismantled after the metal matrix is melted and poured, so as to avoid the vacuum pneumatic impregnation furnace during the disassembly process. Large fluctuations in temperature of lower chamber 2 and entry of oxygen;
感应加热炉上腔室1内设置提升杆14，提升杆14从感应加热炉上腔室1顶部穿过熔金属坩埚4底部与流通小孔11对应；A lifting rod 14 is provided in the upper chamber 1 of the induction heating furnace. The lifting rod 14 passes from the top of the upper chamber 1 of the induction heating furnace through the bottom of the molten metal crucible 4 and corresponds to the circulation hole 11;
真空气压浸渗炉下腔室2设置炉盖12，真空气压浸渗炉下腔室2与炉盖12通过旋入式卡槽配合连接，该连接可在充气和抽真空时保证真空气压浸渗炉下腔室2和真空气压浸渗炉炉盖12连接部位的密封性；真空气压浸渗炉下腔室2的浸渗复合模具包括石墨坩埚13和成形模具9，钟罩式保温筒10内外层为金属薄板，金属薄板采用铆接或焊接工艺连接，在两层薄板之间填充有保温材料，感应加热炉上腔室1和真空气压浸渗炉下腔室2均为双层水循环金属壳体；The lower chamber 2 of the vacuum air pressure impregnation furnace is provided with a furnace cover 12. The lower chamber 2 of the vacuum air pressure impregnation furnace and the furnace cover 12 are connected through a screw-in slot. This connection can ensure vacuum air pressure impregnation during inflation and vacuuming. The sealing of the connection between the lower chamber 2 of the furnace and the lid 12 of the vacuum pneumatic impregnation furnace; the impregnation composite mold of the lower chamber 2 of the vacuum pneumatic impregnation furnace includes a graphite crucible 13 and a forming mold 9, and the inside and outside of the bell jar type insulation cylinder 10 The upper chamber 1 of the induction heating furnace and the lower chamber 2 of the vacuum air pressure impregnation furnace are both double-layer water circulation metal shells. ;
S3的具体操作为：首先将预处理后的金刚石颗粒放入成形模具9中，再一起放入分体式双温区压力浸渗装置的真空气压浸渗炉下腔室的石墨坩埚13内，将银铜基体合金置于分体式双温区压力浸渗装置的感应加热炉上腔室1的熔金属坩埚4中；其次通过真空系统从真空接口7对感应加热炉上腔室1和真空气压浸渗炉下腔室2同时抽真空，当上下腔室内真空度降至10-10-2Pa后，启动加热装置使上下腔室达到各自设定的温度进行恒温；恒温结束后，提起感应加热炉上腔室熔金属坩埚中的提升杆14，银铜基体合金熔液自流通小孔11流入真空气压浸渗炉下腔室2的成形模具13中；随后停止感应加热炉上腔室加热，再停止抽真空，从真空气压浸渗炉下腔室充气接口6充入高纯惰性气体，待上下腔室至常压后停止充气；The specific operation of S3 is: first put the pretreated diamond particles into the forming mold 9, and then put them together into the graphite crucible 13 in the lower chamber of the vacuum pressure impregnation furnace of the split dual-temperature zone pressure impregnation device. The silver-copper matrix alloy is placed in the molten metal crucible 4 of the upper chamber 1 of the induction heating furnace of the split dual-temperature zone pressure impregnation device; secondly, the upper chamber 1 of the induction heating furnace and the vacuum pressure impregnation are connected from the vacuum interface 7 through the vacuum system The lower chamber 2 of the seepage furnace is evacuated at the same time. When the vacuum degree in the upper and lower chambers drops to 10-10-2 Pa, the heating device is started to make the upper and lower chambers reach their respective set temperatures for constant temperature; after the constant temperature is completed, lift the induction heating furnace Lifting rod 14 in the molten metal crucible in the upper chamber, the silver-copper matrix alloy melt flows into the forming mold 13 of the lower chamber 2 of the vacuum air pressure impregnation furnace through the circulation hole 11; then the heating of the upper chamber of the induction heating furnace is stopped, and then Stop vacuuming, fill in high-purity inert gas from the gas filling interface 6 of the lower chamber of the vacuum air pressure impregnation furnace, and stop filling after the upper and lower chambers reach normal pressure;
S4的具体操作为：快速撤除感应加热炉上腔室1，旋入真空气压浸渗炉下腔室的炉盖12；从充气接口6向真空气压浸渗炉下腔室通入高压高纯惰性气体至5-20MPa，基体银铜液在气体压力作用下浸渗到金刚石颗粒孔隙中，与此同时银铜基体中的铬或锆元素与金刚石颗粒反应，在金刚石颗粒表面生成100-200nm的碳化铬或碳化锆，恒温恒压5-20min后再关闭加热电源随炉冷却，获得金刚石/银铜基复合材料。The specific operations of S4 are: quickly remove the upper chamber 1 of the induction heating furnace, screw in the furnace cover 12 of the lower chamber of the vacuum air pressure impregnation furnace; pass high-pressure, high-purity inert gas from the gas filling interface 6 to the lower chamber of the vacuum air pressure impregnation furnace. When the gas reaches 5-20MPa, the matrix silver-copper liquid infiltrates into the pores of the diamond particles under the action of gas pressure. At the same time, the chromium or zirconium element in the silver-copper matrix reacts with the diamond particles to generate 100-200nm carbonization on the surface of the diamond particles. Chromium or zirconium carbide, maintain constant temperature and pressure for 5-20 minutes, then turn off the heating power and cool down in the furnace to obtain a diamond/silver copper-based composite material.
实施例2：Example 2:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：称取5kg粒径为200μm的金刚石单晶颗粒，进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Weigh 5kg of diamond single crystal particles with a particle size of 200 μm, perform acid washing, alkali washing, absolute ethanol cleaning pretreatment, and drying;
S2：将预处理后的金刚石颗粒填装在成形模具中，用振实机振实，形成金刚石坯料；S2: Fill the pretreated diamond particles into the forming mold and vibrate them with a vibrator to form a diamond blank;
S3：将装有金刚石颗粒的成形模具放入分体式双温区压力浸渗装置的真空气压浸渗炉下腔室的石墨坩埚内，将10kg 70Ag-29.2Cu-0.8Cr合金置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚内；首先通过真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至10Pa后，启动加热装置使感应加热炉上腔室温度为950℃，真空气压浸渗炉下腔室温度为890℃，待感应加热炉上腔室70Ag-29.2Cu-0.8Cr合金在熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室70Ag-29.2Cu-0.8Cr合金熔液自流通小孔流入真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；S3: Place the forming mold filled with diamond particles into the graphite crucible in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place 10kg of 70Ag-29.2Cu-0.8Cr alloy in the split dual-temperature zone pressure impregnation device. In the molten metal crucible in the upper chamber of the induction heating furnace of the temperature zone pressure impregnation device; first, the upper chamber of the induction heating furnace and the lower chamber of the vacuum air pressure impregnation furnace are simultaneously Evacuate, when the vacuum degree in the cavity drops to 10Pa, start the heating device to make the temperature of the upper chamber of the induction heating furnace 950°C, and the temperature of the lower chamber of the vacuum pressure impregnation furnace to 890°C. When the upper chamber of the induction heating furnace is 70Ag- After the 29.2Cu-0.8Cr alloy is melted, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace, so that the 70Ag-29.2Cu-0.8Cr alloy melt in the upper chamber of the induction heating furnace flows into the vacuum pressure immersion through the circulation hole. into the forming mold of the lower chamber of the impregnation furnace; then stop heating the upper chamber of the induction heating furnace, then stop vacuuming, fill the lower chamber of the vacuum air pressure impregnation furnace with high-purity inert gas, and stop after the upper and lower chambers reach normal pressure. inflate;
S4：打开感应加热炉上腔室和真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室炉盖，密封真空气压浸渗炉下腔室；对真空气压浸渗炉下腔室充入高压高纯惰性气体至5MPa后，恒温恒压保持15min，完成银铜基体合金与金刚石之间的复合；停止真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；S4: Open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the vacuum and pneumatic impregnation furnace, quickly remove the upper chamber of the induction heating furnace, screw in the lid of the lower chamber of the vacuum and pneumatic impregnation furnace, and seal the vacuum. The lower chamber of the air pressure impregnation furnace; after filling the lower chamber of the vacuum air pressure impregnation furnace with high-pressure, high-purity inert gas to 5MPa, maintain it at constant temperature and pressure for 15 minutes to complete the composite between the silver-copper matrix alloy and diamond; stop the vacuum air pressure impregnation The lower chamber of the infiltration furnace is heated and cooled with the furnace. When cooled to below 200°C, the diamond/silver copper-based composite material is taken out;
图3为本实施例制备的高导热金刚石/银铜基复合材料实物图，该高导热金刚石/银铜基复合材料的尺寸为20×20×3mm，尺寸精度为±0.1mm，表面粗糙度Ra为0.8μm，从图中可以看出该复合材料表面平整，完整，没有明显缺陷，说明本实施例工艺参数合理，银铜基体合金实现了优异的浸渗效果；Figure 3 is a physical picture of the highly thermally conductive diamond/silver copper-based composite material prepared in this embodiment. The size of the highly thermally conductive diamond/silver copper-based composite material is 20×20×3mm, the dimensional accuracy is ±0.1mm, and the surface roughness Ra It is 0.8μm. It can be seen from the figure that the surface of the composite material is smooth and complete with no obvious defects, indicating that the process parameters of this embodiment are reasonable and the silver-copper matrix alloy achieves excellent impregnation effect;
图4为本实施例制备的高导热金刚石/银铜基复合材料100倍光学照片；从图中可以看出，金刚石颗粒均匀的分布在银铜基体合金中，界面结合良好，组织致密；Figure 4 is a 100x optical photo of the high thermal conductivity diamond/silver copper matrix composite material prepared in this example; it can be seen from the picture that the diamond particles are evenly distributed in the silver copper matrix alloy, with good interface bonding and dense structure;
经测，本实施例获得的高导热金刚石/银铜基复合材料中金刚石体积分数为65％，金刚石颗粒表面碳化铬层厚度为150nm，复合材料致密度达99.2％，热导率为816W/(m·K)。After testing, the diamond volume fraction in the highly thermally conductive diamond/silver copper-based composite material obtained in this embodiment is 65%, the thickness of the chromium carbide layer on the surface of the diamond particles is 150nm, the density of the composite material reaches 99.2%, and the thermal conductivity is 816W/( m·K).
实施例3：Example 3:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：称取2.5kg粒径为45μm和3.5kg粒径为450μm的金刚石单晶颗粒，进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Weigh 2.5kg of diamond single crystal particles with a particle size of 45μm and 3.5kg of diamond single crystal particles with a particle size of 450μm, perform pickling, alkali washing, absolute ethanol cleaning pretreatment, and drying;
S2：将预处理后的金刚石颗粒填装在成形模具中，用振实机振实，形成金刚石坯料；S2: Fill the pretreated diamond particles into the forming mold and vibrate them with a vibrator to form a diamond blank;
S3：将装有金刚石颗粒的成形模具放入分体式双温区压力浸渗装置的真空气压浸渗炉下腔室的石墨坩埚中，将8.9kg 70Ag-29.3Cu-0.5Zr合金置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚内；首先通过真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至10-1Pa后，启动加热装置使感应加热炉上腔室温度为980℃，真空气压浸渗炉下腔室温度为860℃，待感应加热炉上腔室中70Ag-29.3Cu-0.5Zr合金熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室70Ag-29.3Cu-0.5Zr合金熔液自上而下流入真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；S3: Place the forming mold containing diamond particles into the graphite crucible in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place 8.9kg of 70Ag-29.3Cu-0.5Zr alloy in the split type In the molten metal crucible in the upper chamber of the induction heating furnace of the dual-temperature zone pressure impregnation device; first, the upper chamber of the induction heating furnace and the lower chamber of the vacuum pneumatic impregnation furnace are pumped through the vacuum pump on one side of the lower chamber of the vacuum pneumatic impregnation furnace. At the same time, vacuum is drawn. When the vacuum degree in the cavity drops to 10-1 Pa, start the heating device to make the temperature of the upper chamber of the induction heating furnace 980°C, and the temperature of the lower chamber of the vacuum pressure impregnation furnace 860°C. After the induction heating furnace is After the 70Ag-29.3Cu-0.5Zr alloy in the chamber is melted, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace so that the 70Ag-29.3Cu-0.5Zr alloy melt in the upper chamber of the induction heating furnace flows from top to bottom. It flows into the forming mold in the lower chamber of the vacuum air pressure impregnation furnace; then stops heating the upper chamber of the induction heating furnace, then stops vacuuming, and fills the high purity inert gas from the lower chamber of the vacuum air pressure impregnation furnace until the upper and lower chambers reach Stop inflating after normal pressure;
S4：打开感应加热炉上腔室和真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室炉盖，密封真空气压浸渗炉下腔室；对真空气压浸渗炉下腔室充入高压高纯惰性气体至20MPa后，恒温恒压保持5min，完成银铜基体合金与金刚石之间的复合；停止真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；S4: Open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the vacuum and pneumatic impregnation furnace, quickly remove the upper chamber of the induction heating furnace, screw in the lid of the lower chamber of the vacuum and pneumatic impregnation furnace, and seal the vacuum. The lower chamber of the air pressure impregnation furnace; after filling the lower chamber of the vacuum air pressure impregnation furnace with high-pressure, high-purity inert gas to 20MPa, keep it at constant temperature and pressure for 5 minutes to complete the composite between the silver-copper matrix alloy and diamond; stop the vacuum air pressure impregnation The lower chamber of the infiltration furnace is heated and cooled with the furnace. When cooled to below 200°C, the diamond/silver copper-based composite material is taken out;
经测，本实施例获得的高导热金刚石/银铜基复合材料中金刚石体积分数为80％，金刚石颗粒表面碳化锆层厚度为100nm，复合材料致密度达99.5％，热导率为1152W/(m·K)。After testing, the diamond volume fraction in the highly thermally conductive diamond/silver copper-based composite material obtained in this embodiment is 80%, the thickness of the zirconium carbide layer on the surface of the diamond particles is 100nm, the density of the composite material reaches 99.5%, and the thermal conductivity is 1152W/( m·K).
实施例4：Example 4:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：称取4kg粒径为100μm的金刚石单晶颗粒，进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Weigh 4kg of diamond single crystal particles with a particle size of 100 μm, perform acid washing, alkali washing, absolute ethanol cleaning pretreatment, and drying;
S2：将预处理后的金刚石颗粒和2kg粒径为100μm的纯铜粉混合填装在成形模具中，用振实机振实，形成金刚石坯料；S2: Mix and fill the pretreated diamond particles and 2kg of pure copper powder with a particle size of 100μm in the forming mold, and vibrate with a vibrator to form a diamond blank;
S3：将装有金刚石颗粒的成形模具放入分体式双温区压力浸渗装置的真空气压浸渗炉下腔室的石墨坩埚中，将8kg 60Ag-38.8Cu-1.2Cr合金置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚内；首先通过真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至5×10-1Pa后，启动加热装置使感应加热炉上腔室温度为1050℃，真空气压浸渗炉下腔室温度为950℃，待感应加热炉上腔室的60Ag-38.8Cu-1.2Cr合金熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室的60Ag-38.8Cu-1.2Cr合金熔液自流通小孔流入真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；S3: Place the forming mold containing diamond particles into the graphite crucible in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place 8kg of 60Ag-38.8Cu-1.2Cr alloy in the split dual-temperature zone pressure impregnation device. In the molten metal crucible in the upper chamber of the induction heating furnace of the temperature zone pressure impregnation device; first, the upper chamber of the induction heating furnace and the lower chamber of the vacuum air pressure impregnation furnace are simultaneously Evacuate. When the vacuum degree in the cavity drops to 5×10-1 Pa, start the heating device to make the temperature of the upper chamber of the induction heating furnace 1050°C and the temperature of the lower chamber of the vacuum pressure impregnation furnace 950°C. Wait for the induction heating furnace to After the 60Ag-38.8Cu-1.2Cr alloy in the upper chamber is melted, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace to allow the 60Ag-38.8Cu-1.2Cr alloy melt in the upper chamber of the induction heating furnace to flow freely. The small hole flows into the forming mold in the lower chamber of the vacuum air pressure impregnation furnace; then the heating of the upper chamber of the induction heating furnace is stopped, and then the vacuum is stopped, and high-purity inert gas is filled from the lower chamber of the vacuum air pressure impregnation furnace. Stop inflating when the chamber reaches normal pressure;
S4：打开感应加热炉上腔室和真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室炉盖，密封真空气压浸渗炉下腔室；对真空气压浸渗炉下腔室充入高压高纯惰性气体至10MPa后，恒温恒压保持20min，完成银铜基体合金与金刚石之间的复合；停止真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；S4: Open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the vacuum and pneumatic impregnation furnace, quickly remove the upper chamber of the induction heating furnace, screw in the lid of the lower chamber of the vacuum and pneumatic impregnation furnace, and seal the vacuum. The lower chamber of the air pressure impregnation furnace; after filling the lower chamber of the vacuum air pressure impregnation furnace with high-pressure, high-purity inert gas to 10MPa, maintain it at constant temperature and pressure for 20 minutes to complete the composite between the silver-copper matrix alloy and diamond; stop the vacuum air pressure impregnation The lower chamber of the infiltration furnace is heated and cooled with the furnace. When cooled to below 200°C, the diamond/silver copper-based composite material is taken out;
经测，本实施例获得的高导热金刚石/银铜基复合材料中金刚石体积分数为40％，金刚石颗粒表面碳化铬层厚度为200nm，复合材料致密度达99.3％，热导率为720W/(m·K)。After testing, the diamond volume fraction in the highly thermally conductive diamond/silver copper-based composite material obtained in this embodiment is 40%, the thickness of the chromium carbide layer on the surface of the diamond particles is 200nm, the density of the composite material reaches 99.3%, and the thermal conductivity is 720W/( m·K).
实施例5：Example 5:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：称取3.2kg粒径为200μm的金刚石单晶颗粒，进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Weigh 3.2kg of diamond single crystal particles with a particle size of 200 μm, perform pickling, alkali washing, absolute ethanol cleaning pretreatment, and drying;
S2：将预处理后的金刚石颗粒和1.8kg粒径为100μm的纯铜粉混合填装在成形模具中，用振实机振实，形成金刚石坯料；S2: Mix and fill the pretreated diamond particles and 1.8kg of pure copper powder with a particle size of 100 μm in the forming mold, and vibrate with a vibrator to form a diamond blank;
S3：将装有金刚石颗粒的成形模具放入分体式双温区压力浸渗装置的真空气压浸渗炉下腔室的石墨模具中，将7kg 65Ag-34Cu-1Zr合金置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚内；首先通过真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至2×10-1Pa后，启动加热装置使感应加热炉上腔室温度为990℃，真空气压浸渗炉下腔室温度为910℃，待感应加热炉上腔室65Ag-34Cu-1Zr合金熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室65Ag-34Cu-1Zr合金熔液自流通小孔流入真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；S3: Place the forming mold containing diamond particles into the graphite mold in the lower chamber of the vacuum air pressure impregnation furnace of the split dual-temperature zone pressure impregnation device, and place 7kg of 65Ag-34Cu-1Zr alloy in the split dual-temperature zone In the molten metal crucible in the upper chamber of the induction heating furnace of the pressure impregnation device; first, the upper chamber of the induction heating furnace and the lower chamber of the vacuum and air pressure impregnation furnace are evacuated simultaneously through the vacuum pump on the side of the lower chamber of the vacuum and air pressure impregnation furnace. , when the vacuum degree in the cavity drops to 2×10-1 Pa, start the heating device to make the temperature of the upper chamber of the induction heating furnace 990°C, and the temperature of the lower chamber of the vacuum pressure impregnation furnace to 910°C. After the 65Ag-34Cu-1Zr alloy is melted in the chamber, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace, so that the 65Ag-34Cu-1Zr alloy melt in the upper chamber of the induction heating furnace flows into the vacuum air pressure impregnation furnace through the circulation hole. into the forming mold of the lower chamber; then stop heating the upper chamber of the induction heating furnace, then stop vacuuming, fill the lower chamber of the vacuum pressure impregnation furnace with high-purity inert gas, and stop inflating after the upper and lower chambers reach normal pressure;
S4：打开感应加热炉上腔室和真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入真空气压浸渗炉下腔室炉盖，密封真空气压浸渗炉下腔室；对真空气压浸渗炉下腔室充入高压高纯惰性气体至15MPa后，恒温恒压保持20min，完成银铜基体与金刚石之间的复合；停止真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；S4: Open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the vacuum and pneumatic impregnation furnace, quickly remove the upper chamber of the induction heating furnace, screw in the lid of the lower chamber of the vacuum and pneumatic impregnation furnace, and seal the vacuum. The lower chamber of the air pressure impregnation furnace; after filling the lower chamber of the vacuum air pressure impregnation furnace with high-pressure, high-purity inert gas to 15MPa, keep it at constant temperature and pressure for 20 minutes to complete the composite between the silver-copper matrix and diamond; stop the vacuum air pressure impregnation The chamber under the furnace is heated and cooled with the furnace. When cooled to below 200°C, the diamond/silver copper-based composite material is taken out;
经测，本实施例获得的金刚石/银铜基复合材料中金刚石体积分数为55％，金刚石颗粒表面碳化锆层厚度为175nm，复合材料致密度达99.1％，热导率为790W/(m·K)。After testing, the diamond volume fraction in the diamond/silver-copper-based composite material obtained in this example is 55%, the thickness of the zirconium carbide layer on the surface of the diamond particles is 175nm, the density of the composite material reaches 99.1%, and the thermal conductivity is 790W/(m· K).
实施例6：Example 6:
一种高导热金刚石/银铜基复合材料的制备方法，包括以下步骤：A method for preparing high thermal conductivity diamond/silver copper matrix composite material, including the following steps:
S1：称取1.5kg粒径为50μm和1.6kg粒径为350μm金刚石单晶颗粒混合均匀，进行酸洗、碱洗、无水乙醇清洗预处理，并烘干；S1: Weigh 1.5kg of diamond single crystal particles with a particle size of 50μm and 1.6kg of diamond single crystal particles with a particle size of 350μm, mix them evenly, carry out pickling, alkali washing, absolute ethanol cleaning pretreatment, and drying;
S2：将预处理后的金刚石颗粒平均填装在2个成形模具中，用振实机振实，形成金刚石坯料；S2: Fill the pretreated diamond particles evenly into two forming dies and vibrate them with a vibrator to form a diamond blank;
S3：将2个装有金刚石颗粒的成形模具对应放入1#、2#分体式双温区压力浸渗装置的真空气压浸渗炉下腔室，将7kg 65.2Ag-34.2Cu-0.6Cr合金置于分体式双温区压力浸渗装置的感应加热炉上腔室的熔金属坩埚内；首先将2#真空气压浸渗炉下腔室盖好炉盖，通入惰性气体，启加加热电源，控制温度为900℃，1#真空气压浸渗炉下腔室则与感应加热炉上腔室通过卡槽旋入式连接；通过1#真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和1#真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至4×10-1Pa后，启动加热装置使感应加热炉上腔室温度为970℃，1#真空气压浸渗炉下腔室温度为900℃，待感应加热炉上腔室65.2Ag-34.2Cu-0.6Cr合金熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室的65.2Ag-34.2Cu-0.6Cr合金熔液自流通小孔流入1#真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从1#真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；S3: Put the two forming molds containing diamond particles into the lower chamber of the vacuum air pressure impregnation furnace of the 1# and 2# split dual-temperature zone pressure impregnation devices, and place 7kg of 65.2Ag-34.2Cu-0.6Cr alloy Place it in the molten metal crucible in the upper chamber of the induction heating furnace of the split dual-temperature zone pressure impregnation device; first, cover the lower chamber of the 2# vacuum air pressure impregnation furnace with the lid, introduce inert gas, and turn on the heating power , the control temperature is 900°C, and the lower chamber of the 1# vacuum air pressure impregnation furnace is connected to the upper chamber of the induction heating furnace through a slot screw-in connection; the induction is controlled by the vacuum pump on the side of the lower chamber of the 1# vacuum air pressure impregnation furnace. The upper chamber of the heating furnace and the lower chamber of the 1# vacuum air pressure impregnation furnace are evacuated at the same time. When the vacuum degree in the chamber drops to 4×10-1 Pa, the heating device is started to make the temperature of the upper chamber of the induction heating furnace 970°C. The temperature of the lower chamber of the 1# vacuum air pressure impregnation furnace is 900°C. After the 65.2Ag-34.2Cu-0.6Cr alloy in the upper chamber of the induction heating furnace is melted, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace. The 65.2Ag-34.2Cu-0.6Cr alloy melt in the upper chamber of the induction heating furnace flows into the forming mold in the lower chamber of the 1# vacuum air pressure impregnation furnace through the circulation hole; then stops heating the upper chamber of the induction heating furnace, and then stops Evacuate, fill the lower chamber of the 1# vacuum air pressure impregnation furnace with high-purity inert gas, and stop filling after the upper and lower chambers reach normal pressure;
S4：打开感应加热炉上腔室和1#真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入1#真空气压浸渗炉下腔室炉盖，密封1#真空气压浸渗炉下腔室；对1#真空气压浸渗炉下腔室充入高压高纯惰性气体至10MPa后，恒温恒压保持10min，完成银铜基体与金刚石之间的复合；停止1#真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料；1#真空气压浸渗炉下腔室随炉冷却过程中，打开2#真空气压浸渗炉下腔室炉盖，迅速旋入感应加热上腔室，快速接好感应加热炉上腔室电缆；再打开感应加热炉炉盖，放入7kg65.2Ag-34.2Cu-0.6Cr合金，通过2#真空气压浸渗炉下腔室一侧的真空泵对感应加热炉上腔室和2#真空气压浸渗炉下腔室同时抽真空，当腔内真空度降至4×10-1Pa后，启动加热装置使感应加热炉上腔室温度为970℃，2#真空气压浸渗炉下腔室温度保持在900℃，待感应加热炉上腔室65.2Ag-34.2Cu-0.6Cr合金熔化后，提起感应加热炉上腔室熔金属坩埚中的提升杆，使感应加热炉上腔室的65.2Ag-34.2Cu-0.6Cr合金熔液自流通小孔流入2#真空气压浸渗炉下腔室的成形模具中；随后停止感应加热炉上腔室加热，再停止抽真空，从2#真空气压浸渗炉下腔室充入高纯惰性气体，待上下腔室至常压后停止充气；打开感应加热炉上腔室和2#真空气压浸渗炉下腔室两侧旋入式卡槽，快速撤除感应加热炉上腔室，旋入2#真空气压浸渗炉下腔室炉盖，密封2#真空气压浸渗炉下腔室；对2#真空气压浸渗炉下腔室充入高压高纯惰性气体至10MPa后，恒温恒压保持10min，完成银铜基体与金刚石之间的复合；停止2#真空气压浸渗炉下腔室加热，随炉冷却，待冷却到200℃以下时取出金刚石/银铜基复合材料。S4: Open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the 1# vacuum and air pressure impregnation furnace, quickly remove the upper chamber of the induction heating furnace, and screw in the lower chamber of the 1# vacuum and air pressure impregnation furnace. Cover and seal the lower chamber of the 1# vacuum air pressure impregnation furnace; after filling the lower chamber of the 1# vacuum air pressure impregnation furnace with high-pressure and high-purity inert gas to 10MPa, maintain it at constant temperature and pressure for 10 minutes to complete the connection between the silver-copper matrix and the diamond. Composite; stop heating the lower chamber of the 1# vacuum pneumatic impregnation furnace, and cool it with the furnace. When it cools to below 200°C, take out the diamond/silver copper-based composite material; the lower chamber of the 1# vacuum pneumatic impregnation furnace will follow the cooling process of the furnace. , open the lid of the lower chamber of the 2# vacuum air pressure impregnation furnace, quickly screw into the upper chamber of the induction heating furnace, and quickly connect the cable of the upper chamber of the induction heating furnace; then open the lid of the induction heating furnace and put in 7kg65.2Ag- 34.2Cu-0.6Cr alloy, through the vacuum pump on the side of the lower chamber of the 2# vacuum air pressure impregnation furnace, the upper chamber of the induction heating furnace and the lower chamber of the 2# vacuum air pressure impregnation furnace are evacuated at the same time. When the vacuum in the chamber drops After reaching 4×10-1 Pa, start the heating device so that the temperature of the upper chamber of the induction heating furnace is 970°C, and the temperature of the lower chamber of the 2# vacuum air pressure impregnation furnace is maintained at 900°C. When the temperature of the upper chamber of the induction heating furnace is 65.2Ag- After the 34.2Cu-0.6Cr alloy is melted, lift the lifting rod in the molten metal crucible in the upper chamber of the induction heating furnace, so that the 65.2Ag-34.2Cu-0.6Cr alloy melt in the upper chamber of the induction heating furnace flows into 2# from the circulation hole. into the forming mold in the lower chamber of the vacuum pneumatic impregnation furnace; then stop heating the upper chamber of the induction heating furnace, then stop vacuuming, and fill the lower chamber of the 2# vacuum pneumatic impregnation furnace with high-purity inert gas. Stop inflating after reaching normal pressure; open the screw-in slots on both sides of the upper chamber of the induction heating furnace and the lower chamber of the 2# vacuum air pressure impregnation furnace, quickly remove the upper chamber of the induction heating furnace, and screw in the 2# vacuum air pressure impregnation furnace. The furnace cover of the lower chamber of the furnace seals the lower chamber of the 2# vacuum and air pressure impregnation furnace; after filling the lower chamber of the 2# vacuum and air pressure impregnation furnace with high-pressure and high-purity inert gas to 10MPa, keep it at constant temperature and pressure for 10 minutes to complete the silver copper Composite between the matrix and diamond; stop heating the lower chamber of the 2# vacuum air pressure impregnation furnace and cool it with the furnace. When it cools to below 200°C, take out the diamond/silver copper matrix composite material.
对比例1：Comparative example 1:
一种高导热金刚石/银铜基复合材料的制备方法，制备过程同实施例2，不同的是S3和S4步骤中将70Ag-29.2Cu-0.8Cr合金换成了70Ag-30Cu合金；A method for preparing a high thermal conductivity diamond/silver copper-based composite material. The preparation process is the same as Example 2, except that in steps S3 and S4, the 70Ag-29.2Cu-0.8Cr alloy is replaced by a 70Ag-30Cu alloy;
经测，本对比例获得的金刚石/银铜复合材料中金刚石颗粒的体积分数为55％，金刚石颗粒表面无碳化铬层，复合材料热导率仅为436W/(m·K)；与实施例2相比，对比例1的银铜基体合金中未添加铬元素，在同等制备条件下热导率降低了46.6％；After testing, the volume fraction of diamond particles in the diamond/silver-copper composite material obtained in this comparative example is 55%, there is no chromium carbide layer on the surface of the diamond particles, and the thermal conductivity of the composite material is only 436W/(m·K); compared with the Example 2. Compared with 2, no chromium element was added to the silver-copper matrix alloy of Comparative Example 1, and the thermal conductivity was reduced by 46.6% under the same preparation conditions;
因此，实施例2中银铜合金基体的铬元素对于降低金刚石颗粒与银铜基体合金的界面热阻，获得高导热金刚石/银铜基复合材料起着关键作用。Therefore, the chromium element in the silver-copper alloy matrix in Example 2 plays a key role in reducing the interface thermal resistance between the diamond particles and the silver-copper matrix alloy and obtaining a high thermal conductivity diamond/silver-copper matrix composite material.
对比例2：Comparative example 2:
一种高导热金刚石/银铜基复合材料的制备方法，制备过程同实施例3，不同的是S3和S4步骤中将70Ag-29.3Cu-0.5Zr合金换成Cu-1.2Zr合金，且步骤S3中启动加热装置使感应加热炉上腔室温度为1250℃，真空气压浸渗炉下腔室温度为1150℃；A method for preparing a highly thermally conductive diamond/silver copper-based composite material. The preparation process is the same as in Example 3. The difference is that in steps S3 and S4, the 70Ag-29.3Cu-0.5Zr alloy is replaced by a Cu-1.2Zr alloy, and step S3 Start the heating device in the middle so that the temperature of the upper chamber of the induction heating furnace is 1250°C and the temperature of the lower chamber of the vacuum air pressure impregnation furnace is 1150°C;
经测，本实施例获得的金刚石/铜基复合材料中金刚石体积分数为80％，金刚石颗粒表面碳化锆层厚度为460nm，复合材料致密度为98.5％，热导率为785W/(m·K)；和实施例3相比，对比例2的基体合金由低熔点的银铜锆合金换成高熔点的铜锆合金，导致感应加热炉上腔室温度由980℃增加至1250℃，真空气压浸渗炉下腔室温度由860℃增加至1150℃，较高的制备温度使得金刚石表面碳化锆厚度增加了78.3％，复合材料致密度下降了1％，最终导致复合材料的热导率降低了31.9％；After testing, the diamond volume fraction in the diamond/copper-based composite material obtained in this example is 80%, the thickness of the zirconium carbide layer on the surface of the diamond particles is 460nm, the density of the composite material is 98.5%, and the thermal conductivity is 785W/(m·K ); Compared with Example 3, the base alloy of Comparative Example 2 was changed from a low-melting-point silver-copper-zirconium alloy to a high-melting-point copper-zirconium alloy, causing the upper chamber temperature of the induction heating furnace to increase from 980°C to 1250°C, and the vacuum air pressure The chamber temperature under the impregnation furnace increased from 860°C to 1150°C. The higher preparation temperature increased the thickness of zirconium carbide on the diamond surface by 78.3%, and the density of the composite material decreased by 1%, which ultimately led to a reduction in the thermal conductivity of the composite material. 31.9%;
因此，实施例3中银铜合金基体中的质量百分比计为60-70％的银对于降低制备温度、降低金刚石颗粒表面碳化物层厚度及最终获得高导热金刚石增强银铜基复合材料起着关键作用。Therefore, the mass percentage of 60-70% silver in the silver-copper alloy matrix in Example 3 plays a key role in reducing the preparation temperature, reducing the thickness of the carbide layer on the surface of the diamond particles, and ultimately obtaining a high thermal conductivity diamond-reinforced silver-copper matrix composite material. .
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制。任何熟悉本领域的技术人员，在不脱离本发明的精神实质和技术方案的情况下，都可利用上述揭示的方法和技术内容对本发明技术方案做出许多可能的变动和修饰，或修改为等同变化的等效实施例。因此，凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所做的任何简单修改、等同替换、等效变化及修饰，均仍属于本发明技术方案保护的范围内。The above descriptions are only preferred embodiments of the present invention and do not limit the present invention in any form. Any person familiar with the art can make many possible changes and modifications to the technical solution of the present invention using the methods and technical content disclosed above, or modify it to be equivalent, without departing from the spirit and technical solution of the present invention. Varied equivalent embodiments. Therefore, any simple modifications, equivalent substitutions, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of protection of the technical solution of the present invention.
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| CN202310776190.5ACN116786794A (en) | 2023-06-28 | 2023-06-28 | A high thermal conductivity diamond/silver copper matrix composite material and its preparation method |
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