技术领域Technical field
本发明涉及金刚石/铜复合材料技术领域，特别涉及一种金刚石/铜复合材料制备方法。The invention relates to the technical field of diamond/copper composite materials, and in particular to a preparation method of diamond/copper composite materials.
背景技术Background technique
随着微电子技术的不断发展，半导体的封装集成度越来越高。器件在小型化的同时功率越来越大，对电子封装材料的导热性能要求也不断提升。目前在集成常用的电子封装材料热导率远远不能满足集成电路和芯片技术的发展需求，因此，更高导热的电子封装材料的研发变得迫在眉睫。新一代电子封装材料不仅要有高的导热性能，而且还必须具备与半导体材料相匹配的热膨胀性能。With the continuous development of microelectronics technology, the packaging integration of semiconductors is getting higher and higher. As devices become smaller and more powerful, the thermal conductivity requirements for electronic packaging materials are also increasing. The thermal conductivity of electronic packaging materials currently commonly used in integration is far from meeting the development needs of integrated circuits and chip technology. Therefore, the development of electronic packaging materials with higher thermal conductivity has become urgent. The new generation of electronic packaging materials must not only have high thermal conductivity, but also must have thermal expansion properties that match those of semiconductor materials.
应用于电子封装领域的传统导热材料主要包括W/Cu、Mo/Cu、Invar合金、Kovar合金、Al2O3、AlN和氮化硅等，这些材料由于导热率低或热膨胀系数高等原因已不能满足应用要求，对其正常工作效率和使用寿命构成巨大威胁，尤其是以高功率的绝缘栅双极型晶体管(IGBT)、车载高功率LED灯、微波、电磁、光电等器件为典型应用的高科技技术领域和以有源相控阵雷达、高能固体激光器等为典型应用的国防技术领域的迫切应用需求。Traditional thermal conductive materials used in the field of electronic packaging mainly include W/Cu, Mo/Cu, Invar alloy, Kovar alloy, Al2 O3 , AlN and silicon nitride. These materials can no longer be used due to low thermal conductivity or high thermal expansion coefficient. To meet application requirements, it poses a huge threat to its normal working efficiency and service life, especially for high-power devices with typical applications such as high-power insulated gate bipolar transistors (IGBT), automotive high-power LED lights, microwaves, electromagnetics, and optoelectronics. Urgent application needs in the fields of science and technology and national defense technology with active phased array radars and high-energy solid lasers as typical applications.
金刚石/铜复合材料凭借其超高的热导率和可调节的热膨胀系数被称为第四代电子封装材料，理论热导率高达1000 W/(m • K)，具有广阔的应用前景。然而，铜与金刚石之间存在界面结合和润湿性差的问题，导致复合材料致密度偏低、界面热阻高，严重阻碍了其性能提升与热管理应用。现在普遍采用金刚石表面镀覆碳化钛、碳化钼、碳化锆和碳化铬等，提高与铜的润湿性和结合力，从而提高界面热导率。Diamond/copper composite materials are called the fourth generation electronic packaging materials due to their ultra-high thermal conductivity and adjustable thermal expansion coefficient. The theoretical thermal conductivity is as high as 1000 W/(m • K), and they have broad application prospects. However, there are problems with interface bonding and poor wettability between copper and diamond, resulting in low density and high interface thermal resistance of the composite material, which seriously hinders its performance improvement and thermal management applications. Nowadays, diamond surface coating with titanium carbide, molybdenum carbide, zirconium carbide, chromium carbide, etc. is commonly used to improve the wettability and bonding force with copper, thereby increasing the interface thermal conductivity.
现有技术中，如图4所示，采用盐浴镀覆和化学镀覆制备的双镀层金刚石粉末表面粗糙，球形度不高，流动性差，松装密度低，且存在卫星粉的现象，导致在3D打印或者真空热压烧结的过程中，送粉或者铺粉的流量不好控制，容易出现堵粉现象，且成形件密度低，烧结过程中成形件收缩不均匀，获得的金刚石/铜复合材料制品精度和热导率低（热导率一般为550 W/(m • K)左右）的问题。In the existing technology, as shown in Figure 4, the double-coated diamond powder prepared by salt bath plating and chemical plating has a rough surface, low sphericity, poor fluidity, low bulk density, and the phenomenon of satellite powder, resulting in In the process of 3D printing or vacuum hot pressing sintering, the flow of powder feeding or spreading is difficult to control, and powder blocking is easy to occur. Moreover, the density of the formed parts is low, and the formed parts shrink unevenly during the sintering process. The obtained diamond/copper composite The problem of material product accuracy and low thermal conductivity (thermal conductivity is generally around 550 W/(m • K)).
发明内容Contents of the invention
基于此，本发明的目的是提供一种金刚石/铜复合材料制备方法，用于解决现有技术中铜包覆金刚石粉末球形度不高，流动性差，松装密度低，导致在3D打印或者真空热压烧结的过程中，送粉或者铺粉的流量不好控制，容易出现堵粉现象，导致最终的产品出现空隙或缺陷，以及成形件密度低，烧结过程中成形件收缩不均匀，获得的金刚石/铜复合材料制品精度和热导率低的问题。Based on this, the purpose of the present invention is to provide a diamond/copper composite material preparation method to solve the problem in the existing technology that copper-coated diamond powder has low sphericity, poor fluidity, and low bulk density, resulting in problems in 3D printing or vacuum printing. During the hot pressing sintering process, the flow of powder feeding or powder spreading is difficult to control, and powder blocking is easy to occur, resulting in gaps or defects in the final product, low density of the formed parts, uneven shrinkage of the formed parts during the sintering process, and the obtained The problem of low precision and thermal conductivity of diamond/copper composite products.
本发明提供一种金刚石/铜复合材料制备方法，包括：The invention provides a method for preparing diamond/copper composite materials, which includes:
获取若干金刚石颗粒，在金刚石颗粒表面盐浴镀覆碳化物，所述碳化物包括碳化钼、碳化钛、碳化钨、以及碳化锆；Obtain several diamond particles, and coat the surface of the diamond particles with carbides in a salt bath. The carbides include molybdenum carbide, titanium carbide, tungsten carbide, and zirconium carbide;
在镀有碳化物的金刚石颗粒表面进行化学镀覆铜处理，制备得到双镀层金刚石粉末；Perform electroless copper plating on the surface of carbide-plated diamond particles to prepare double-coated diamond powder;
将所述双镀层金刚石粉末与固体分散剂进行均匀混合以得到混合粉末，所述固体分散剂包括微纳米鳞片石墨粉；The double-coated diamond powder and a solid dispersant are uniformly mixed to obtain a mixed powder, and the solid dispersant includes micro-nano flake graphite powder;
将所述混合粉末在还原性气氛中进行高温热处理以使铜熔融并浸润金刚石，并在表面张力的作用下收缩成球，而后随炉冷却凝固；The mixed powder is subjected to high-temperature heat treatment in a reducing atmosphere to melt the copper and infiltrate the diamond, shrink into balls under the action of surface tension, and then cool and solidify in the furnace;
去除微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末，通过所述铜包覆金刚石球形粉末，采用3D打印或真空热压烧结技术制备得到高导热金刚石/铜复合材料。Micro-nano flake graphite powder is removed to obtain copper-coated diamond spherical powder. Through the copper-coated diamond spherical powder, a high thermal conductivity diamond/copper composite material is prepared using 3D printing or vacuum hot pressing sintering technology.
上述金刚石/铜复合材料制备方法，通过在金刚石颗粒表面依次进行镀覆碳化物及铜而得到双镀层金刚石粉末，然后将其与微纳米鳞片石墨粉进行均匀混合得到混合粉末，再将混合粉末在还原性气氛中进行高温热处理以使铜熔融并浸润金刚石，并在表面张力的作用下收缩成球，而后随炉冷却凝固；去除固体分散剂以得到铜包覆金刚石球形粉末，该铜包覆金刚石球形粉末的表面光滑，球形度高，流动性好，松装密度高，在送粉或者铺粉的过程中不易出现堵粉现象，从而保证了最终产品的高热导率和产品质量，且成形件密度高，烧结过程中成形件收缩均匀，获得的金刚石/铜复合材料制品精度和热导率高。通过该铜包覆金刚石球形粉末制备得到高导热金刚石/铜复合材料，解决了现有技术中由于金刚石粉末和铜粉的球形度不高，流动性差，松装密度低，导致3D打印或者真空热压烧结的过程中，送粉或者铺粉的流量不好控制，容易出现堵粉的现象，导致最终的产品出现空隙或缺陷的技术问题，以及成形件密度低，烧结过程中成形件收缩不均匀，获得的金刚石/铜复合材料制品精度和热导率低的问题。The above-mentioned diamond/copper composite material preparation method is to sequentially plate carbide and copper on the surface of diamond particles to obtain double-coated diamond powder, and then uniformly mix it with micro-nano flake graphite powder to obtain mixed powder, and then mix the mixed powder in High-temperature heat treatment is performed in a reducing atmosphere to melt the copper and infiltrate the diamond, shrink it into balls under the action of surface tension, and then solidify with cooling in the furnace; remove the solid dispersant to obtain copper-coated diamond spherical powder, which is copper-coated diamond Spherical powder has a smooth surface, high sphericity, good fluidity, and high bulk density. It is not easy to cause powder blocking during the powder feeding or spreading process, thus ensuring the high thermal conductivity and product quality of the final product, and forming parts The density is high, the formed parts shrink evenly during the sintering process, and the diamond/copper composite products obtained have high precision and thermal conductivity. The high thermal conductivity diamond/copper composite material is prepared by the copper-coated diamond spherical powder, which solves the problem of 3D printing or vacuum thermal problems in the existing technology due to the low sphericity, poor fluidity and low bulk density of diamond powder and copper powder. During the pressure sintering process, the flow rate of powder feeding or powder spreading is difficult to control, and powder blocking is easy to occur, resulting in technical problems such as gaps or defects in the final product, as well as low density of the formed parts and uneven shrinkage of the formed parts during the sintering process. , the problem of low accuracy and thermal conductivity of the diamond/copper composite products obtained.
另外，根据本发明上述的金刚石/铜复合材料制备方法，还可以具有如下附加的技术特征：In addition, according to the above-mentioned diamond/copper composite material preparation method of the present invention, it can also have the following additional technical features:
进一步地，在获取若干金刚石颗粒，在金刚石颗粒表面盐浴镀覆碳化物的步骤中：Further, in the step of obtaining several diamond particles and coating carbide in a salt bath on the surface of the diamond particles:
选取的金刚石颗粒的尺寸为50um-300um，碳化物的镀覆厚度为200nm-1um。The size of the selected diamond particles is 50um-300um, and the carbide plating thickness is 200nm-1um.
进一步地，在将所述双镀层金刚石粉末与固体分散剂进行均匀混合以得到混合粉末的步骤中：Further, in the step of uniformly mixing the double-coated diamond powder and the solid dispersant to obtain mixed powder:
所述双镀层金刚石粉末与微纳米鳞片石墨粉的混合方式为机械搅拌混合，混合质量比为5：1-5，其中，所述微纳米鳞片石墨粉的尺寸为200nm-1um。The mixing method of the double-coated diamond powder and the micro-nano flake graphite powder is mechanical stirring and mixing, and the mixing mass ratio is 5:1-5, where the size of the micro-nano flake graphite powder is 200nm-1um.
进一步地，将所述混合粉末在还原性气氛中进行高温热处理以使铜熔融并浸润金刚石的步骤中：Further, in the step of subjecting the mixed powder to high-temperature heat treatment in a reducing atmosphere to melt the copper and infiltrate the diamond:
所述高温热处理为在高于铜熔点50℃-100℃的温度热处理，并保温5min-10min，还原性气氛中的气体为氢气、氢氩混合气或一氧化碳中的一种。The high-temperature heat treatment is heat treatment at a temperature of 50°C to 100°C higher than the melting point of copper, and the temperature is maintained for 5min to 10min. The gas in the reducing atmosphere is one of hydrogen, a hydrogen-argon mixture, or carbon monoxide.
进一步地，在去除微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末的步骤中：Further, in the step of removing micro-nano flake graphite powder to obtain copper-coated diamond spherical powder:
用乙醇浸泡上述得到的混合粉末，通过超声清洗除去微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末。The mixed powder obtained above is soaked in ethanol, and the micro-nano flake graphite powder is removed by ultrasonic cleaning to obtain copper-coated diamond spherical powder.
进一步地，去除微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末，通过所述铜包覆金刚石球形粉末，采用3D打印或真空热压烧结技术制备得到高导热金刚石/铜复合材料的步骤包括：Further, the micro-nano flake graphite powder is removed to obtain copper-coated diamond spherical powder. The steps of preparing a high thermal conductivity diamond/copper composite material using 3D printing or vacuum hot-pressing sintering technology through the copper-coated diamond spherical powder include:
其中，当采用真空热压烧结技术将所述铜包覆金刚石球形粉末制备得到高导热金刚石/铜复合材料时：将铜包覆金刚石球形粉末直接装入石墨模具中以制备得到高导热金刚石/铜复合材料，压力为40MPa-80MPa，温度为800℃-950℃，真空度为10-2Pa -10-3Pa，保温10 min-50min。Among them, when the copper-coated diamond spherical powder is prepared using vacuum hot-pressing sintering technology to prepare a high thermal conductivity diamond/copper composite material: the copper-coated diamond spherical powder is directly loaded into a graphite mold to prepare a high thermal conductivity diamond/copper composite material. Composite material, the pressure is 40MPa-80MPa, the temperature is 800℃-950℃, the vacuum degree is 10-2 Pa -10-3 Pa, and the heat preservation is 10 min-50min.
进一步地，制备得到的双镀层金刚石粉末，其含铜体积分数为30%-60%。Further, the prepared double-coated diamond powder has a copper volume fraction of 30%-60%.
附图说明Description of the drawings
图1为本发明实施例中所使用的金刚石原料的扫描电子显微镜照片；Figure 1 is a scanning electron microscope photograph of the diamond raw material used in the embodiment of the present invention;
图2为本发明通过盐浴镀得到的镀覆碳化钼金刚石的扫描电子显微镜照片；Figure 2 is a scanning electron microscope photograph of coated molybdenum carbide diamond obtained by salt bath plating in the present invention;
图3为本发明通过铜包覆金刚石粉体和微纳米鳞片石墨混合热处理得到的铜包覆金刚石球形粉末的扫描电子显微镜照片；Figure 3 is a scanning electron microscope photo of the copper-coated diamond spherical powder obtained by the mixed heat treatment of copper-coated diamond powder and micro-nano flake graphite according to the present invention;
图4为现有技术制备得到的铜包覆金刚石粉末的扫描电子显微镜照片。Figure 4 is a scanning electron microscope photograph of copper-coated diamond powder prepared by the prior art.
如下具体实施方式将结合上述附图进一步说明本发明。The following specific embodiments will further illustrate the present invention in conjunction with the above-mentioned drawings.
具体实施方式Detailed ways
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的若干实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容更加透彻全面。In order to facilitate understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. Several embodiments of the invention are shown in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及／或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the invention belongs. The terminology used herein in the description of the invention is for the purpose of describing specific embodiments only and is not intended to limit the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
为了解决现有技术中由于铜包覆金刚石粉末球形度不高，流动性差，松装密度低，导致在3D打印或者真空热压烧结的过程中，送粉或者铺粉的流量不好控制，容易出现堵粉现象，导致最终的产品出现空隙或缺陷，以及成形件密度低，烧结过程中成形件收缩不均匀，获得的金刚石/铜复合材料制品精度和热导率低的问题。本申请提出一种金刚石/铜复合材料制备方法，用于制备高导热金刚石/铜复合材料，通过将盐浴镀覆和化学镀覆制备的铜包覆金刚石粉末与微纳米鳞片石墨粉末混合，在还原性气氛热处理，铜熔体浸润金刚石表面，同时与微纳米石墨粉末不浸润，并收缩成球，最后冷却凝固成球，得到铜包覆金刚石球形粉末，然后采用3D打印或真空热压烧结的方式制备得到高导热金刚石/铜复合材料。In order to solve the problem in the existing technology, due to the low sphericity, poor fluidity and low bulk density of copper-coated diamond powder, during the process of 3D printing or vacuum hot pressing sintering, the flow rate of powder feeding or spreading is difficult to control, and it is easy to Powder blocking occurs, resulting in voids or defects in the final product, low density of the formed parts, uneven shrinkage of the formed parts during the sintering process, and low accuracy and thermal conductivity of the diamond/copper composite products obtained. This application proposes a method for preparing diamond/copper composite materials, which is used to prepare high thermal conductivity diamond/copper composite materials. The copper-coated diamond powder prepared by salt bath plating and chemical plating is mixed with micro-nano flake graphite powder. During heat treatment in a reducing atmosphere, the copper melt infiltrates the diamond surface while not infiltrating the micro-nano graphite powder and shrinks into a ball. Finally, it is cooled and solidified into a ball to obtain copper-coated diamond spherical powder, which is then sintered by 3D printing or vacuum hot pressing. High thermal conductivity diamond/copper composite materials were prepared by this method.
如图1-3所示，通过本申请提供的金刚石/铜复合材料制备方法制造得到的铜包覆金刚石球形粉末的球形度高，颗粒尺寸分布可控，分布窄，流动性好，松装密度高，氧含量可低于100ppm以下，将其通过3D打印或真空热压烧结技术得到高导热金刚石/铜复合材料，使得制备得到的金刚石/铜复合材料具有高制品精度及高热导率，同时，该工艺方法简单，生产效率高，可以制备复杂形状的器件，是一种可规模化生产高导热金刚石/铜复合材料的制备方法。As shown in Figures 1-3, the copper-coated diamond spherical powder produced by the diamond/copper composite material preparation method provided by this application has high sphericity, controllable particle size distribution, narrow distribution, good fluidity, and bulk density. High, the oxygen content can be lower than 100ppm. High thermal conductivity diamond/copper composite materials can be obtained through 3D printing or vacuum hot pressing sintering technology, so that the prepared diamond/copper composite materials have high product precision and high thermal conductivity. At the same time, The process is simple, has high production efficiency, can prepare devices with complex shapes, and is a preparation method that can produce high thermal conductivity diamond/copper composite materials on a large scale.
本申请提供的金刚石/铜复合材料制备方法，包括步骤S11-步骤S15：The diamond/copper composite material preparation method provided by this application includes steps S11 to S15:
S11、获取若干金刚石颗粒，在金刚石颗粒表面盐浴镀覆碳化物。S11. Obtain a number of diamond particles and coat carbides on the surface of the diamond particles in a salt bath.
作为一个具体示例，所述碳化物包括碳化钼、碳化钛、碳化钨、以及碳化锆；具体地，在金刚石颗粒表面盐浴镀覆碳化物，增强金刚石与铜基体的润湿性和结合性，降低界面热阻，增强复合材料热导率。进一步地，在本实施例中，选取的金刚石颗粒尺寸为50um-300um，碳化物的镀覆厚度为200nm-1um。As a specific example, the carbide includes molybdenum carbide, titanium carbide, tungsten carbide, and zirconium carbide; specifically, carbide is plated in a salt bath on the surface of the diamond particles to enhance the wettability and bonding of the diamond and the copper matrix, Reduce interface thermal resistance and enhance thermal conductivity of composite materials. Further, in this embodiment, the selected diamond particle size is 50um-300um, and the carbide plating thickness is 200nm-1um.
S12、在镀有碳化物的金刚石颗粒表面进行化学镀覆铜处理，制备得到双镀层金刚石粉末。S12. Perform electroless copper plating on the surface of carbide-plated diamond particles to prepare double-coated diamond powder.
在本实施例中，制备得到的双镀层金刚石粉末，其含铜体积分数为30%-60%。In this embodiment, the prepared double-coated diamond powder contains a copper volume fraction of 30%-60%.
S13、将所述双镀层金刚石粉末与微纳米鳞片石墨粉进行均匀混合以得到混合粉末。S13. Evenly mix the double-coated diamond powder and micro-nano flake graphite powder to obtain mixed powder.
在本实施例中，所述双镀层金刚石粉末与微纳米鳞片石墨粉的混合方式为机械搅拌混合，混合质量比为5：1-5，其中，所述微纳米鳞片石墨粉的尺寸为200nm-1um。In this embodiment, the mixing method of the double-coated diamond powder and micro-nano flake graphite powder is mechanical stirring and mixing, and the mixing mass ratio is 5:1-5, wherein the size of the micro-nano flake graphite powder is 200nm- 1um.
S14、将所述混合粉末在还原性气氛中进行高温热处理以使铜熔融并浸润金刚石，并在表面张力的作用下收缩成球，而后随炉冷却凝固。S14. The mixed powder is subjected to high-temperature heat treatment in a reducing atmosphere to melt the copper and infiltrate the diamond, shrink into balls under the action of surface tension, and then solidify with cooling in the furnace.
在本申请中，在还原性气氛中对混合粉末进行高温热处理，使得金刚石表面包裹的铜熔化，且与微纳米鳞片石墨粉不浸润，并在表面张力的作用下收缩成球，而后随炉冷却凝固。利用铜与微纳米鳞片石墨粉之间固液不浸润的特点，使铜熔融并浸润金刚石，并在表面张力的作用下收缩成球，而后随炉冷却凝固，得到铜包覆金刚石球形粉末。具体的，高温热处理为在高于铜熔点50-100℃的温度热处理，并保温5-10min，还原性气氛中的气体为氢气、氢氩混合气或一氧化碳。In this application, the mixed powder is subjected to high-temperature heat treatment in a reducing atmosphere, so that the copper wrapped on the diamond surface is melted and does not wet with the micro-nano flake graphite powder, and shrinks into balls under the action of surface tension, and then is cooled in the furnace. solidification. Taking advantage of the non-wetting characteristics of solid and liquid between copper and micro-nano flake graphite powder, the copper melts and infiltrates the diamond, shrinks into balls under the action of surface tension, and then cools and solidifies in the furnace to obtain copper-coated diamond spherical powder. Specifically, the high-temperature heat treatment is heat treatment at a temperature 50-100°C higher than the melting point of copper, and the temperature is maintained for 5-10 minutes. The gas in the reducing atmosphere is hydrogen, a hydrogen-argon mixture, or carbon monoxide.
S15、去除微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末，通过所述铜包覆金刚石球形粉末，采用3D打印或真空热压烧结技术制备得到高导热金刚石/铜复合材料。S15. Remove the micro-nano flake graphite powder to obtain copper-coated diamond spherical powder. Use the copper-coated diamond spherical powder to prepare a high thermal conductivity diamond/copper composite material using 3D printing or vacuum hot pressing sintering technology.
具体的，用乙醇浸泡上述得到的混合粉末，通过超声清洗除去微纳米鳞片石墨粉以得到铜包覆金刚石球形粉末。在本申请中，利用铜包覆金刚石球形粉末球形度高、表面光滑、流动性好、松装密度高的特点，在3D打印或真空热压烧结时，送粉或铺粉的过程中不易出现堵粉现象，保证了最终产品的高热导率和产品质量。Specifically, the mixed powder obtained above is soaked in ethanol, and the micro-nano flake graphite powder is removed by ultrasonic cleaning to obtain copper-coated diamond spherical powder. In this application, the characteristics of copper-coated diamond spherical powder are used to have high sphericity, smooth surface, good fluidity, and high bulk density. When 3D printing or vacuum hot pressing sintering, it is not easy to occur during powder feeding or spreading. The powder blocking phenomenon ensures the high thermal conductivity and product quality of the final product.
作为一个具体示例，当采用真空热压烧结技术将所述铜包覆金刚石球形粉末制备得到高导热金刚石/铜复合材料时：将铜包覆金刚石球形粉末直接装入石墨模具中以制备得到高导热金刚石/铜复合材料，压力为40MPa-80MPa，温度为800℃-950℃，真空度为10-2Pa-10-3Pa，保温10min-50min。As a specific example, when using vacuum hot-pressing sintering technology to prepare the copper-coated diamond spherical powder to obtain a high thermal conductivity diamond/copper composite material: the copper-coated diamond spherical powder is directly loaded into a graphite mold to prepare a high thermal conductivity Diamond/copper composite material, pressure is 40MPa-80MPa, temperature is 800℃-950℃, vacuum degree is 10-2 Pa-10-3 Pa, heat preservation 10min-50min.
为了便于理解本发明，下面将给出了本发明的若干实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容更加透彻全面。In order to facilitate understanding of the present invention, several embodiments of the present invention will be given below. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
实施例一Embodiment 1
本实施例中的金刚石/铜复合材料制备方法，方法包括以下步骤：The diamond/copper composite material preparation method in this embodiment includes the following steps:
采用平均尺寸为100um左右的MBD8型金刚石粉末作为原料，在本实施例中，优选尺寸为100um的MBD8型金刚石粉末，首先采用乙醇和丙酮对金刚石颗粒进行除油处理，随后分别采用15%NaOH溶液和30%HNO3溶液煮沸对其进行活化和粗化处理，再用去离子水清洗并干燥。将预处理过的金刚石颗粒与钼粉按照摩尔比10:1装入球磨罐中，加入2wt%酒精，以200rpm球磨混合2h，料球比为1:1；将混合后粉末装入氧化铝坩埚中，在其表面平铺混合盐（NaCl:KCl摩尔比1:1），混合粉末与混合盐质量比为1:2。随后将坩埚放入真空管式炉中，在1050℃进行反应烧结15min，升温和降温速率为5℃/min，降至300℃待自然冷却后取出，用去离子水超声清洗以溶解去除氯盐后干燥。配置化学镀液：Cu2SO4·5H2O(15g/L),Na2EDTA·2H2O(30g/L)和甲醛HCHO(37% 15ml/L)，用NaOH（10mol/L）溶液调制镀液ph为12-13，将镀覆碳化钼层的金刚石颗粒在镀液中45℃下反应12h，然后洗涤干燥得到表面镀铜层的双镀层金刚石粉末。MBD8 diamond powder with an average size of about 100um is used as raw material. In this embodiment, MBD8 diamond powder with a preferred size of 100um is used. First, ethanol and acetone are used to degrease the diamond particles, and then 15% NaOH solution is used respectively. Boil with 30% HNO3 solution to activate and roughen it, then wash and dry with deionized water. Put the pretreated diamond particles and molybdenum powder into a ball mill tank according to the molar ratio of 10:1, add 2wt% alcohol, and mix by ball milling at 200 rpm for 2 hours. The material-to-ball ratio is 1:1; put the mixed powder into an alumina crucible. , spread mixed salt (NaCl:KCl molar ratio 1:1) on its surface, and the mass ratio of mixed powder to mixed salt is 1:2. Then put the crucible into a vacuum tube furnace and carry out reaction sintering at 1050°C for 15 minutes. The heating and cooling rate is 5°C/min. After cooling down to 300°C, take it out and take it out after natural cooling. Use deionized water for ultrasonic cleaning to dissolve and remove the chlorine salt. dry. Configure chemical plating solution: Cu2 SO4 ·5H2 O (15g/L), Na2 EDTA ·2H2 O (30g/L) and formaldehyde HCHO (37% 15ml/L), use NaOH (10mol/L) solution The pH of the plating solution is adjusted to 12-13, and the diamond particles coated with the molybdenum carbide layer are reacted in the plating solution at 45°C for 12 hours, and then washed and dried to obtain double-coated diamond powder with a copper layer on the surface.
随后将上述双镀层金刚石粉末与尺寸为400nm左右的鳞片石墨粉混合，在本实施例中，优选400nm的鳞片石墨粉，按质量比为5:3配比，采用机械搅拌方法进行均匀混合。Then, the above-mentioned double-coated diamond powder is mixed with flake graphite powder with a size of about 400 nm. In this embodiment, 400 nm flake graphite powder is preferred. The mass ratio is 5:3, and the mechanical stirring method is used for uniform mixing.
将混合好的双镀层金刚石粉末/鳞片石墨的混合粉末放入氧化铝坩埚中，坩埚放进退火炉的加热区，抽真空到6×10-3Pa，然后通入0.02MPa的氢气，加热到550℃，保温30min。随后将退火炉加热区快速加热到1150℃以使温度高于铜熔点，保温5min后，随炉冷却以凝固成球。Put the mixed double-coated diamond powder/flake graphite mixed powder into an alumina crucible, put the crucible into the heating area of the annealing furnace, evacuate to 6×10-3 Pa, then pass in 0.02MPa hydrogen, and heat to 550 ℃, keep warm for 30 minutes. Then the heating zone of the annealing furnace is quickly heated to 1150°C to make the temperature higher than the melting point of copper. After being kept for 5 minutes, it is cooled with the furnace to solidify into balls.
用乙醇浸泡上述得到的混合粉末，通过超声清洗得到铜包覆金刚石球形粉末。图3为得到的铜包覆金刚石球形粉末外观的扫描电子显微镜照片，由图可得，通过本申请中的制备方法制备得到的铜包覆金刚石球形粉末，其表面光滑，且球形度高，从而使得铜包覆金刚石球形粉末的流动性好，便于控制送粉或者铺粉的流量，避免出现堵粉现象，在本实施例中，球形颗粒尺寸在120um-180um，氧含量为83ppm。最后将得到的铜包覆金刚石球形粉末装入石墨模具，采用真空热压烧结的方式，压力为70MPa，温度为850℃，保温20min。冷却后得到金刚石/铜复合材料，使用激光导热仪测量得到该金刚石/铜复合材料的热导率为723 W/(m • K)。The mixed powder obtained above is soaked in ethanol and cleaned by ultrasonic to obtain copper-coated diamond spherical powder. Figure 3 is a scanning electron microscope photo of the appearance of the obtained copper-coated diamond spherical powder. From the figure, it can be seen that the copper-coated diamond spherical powder prepared by the preparation method in this application has a smooth surface and high sphericity, thus This makes the copper-coated diamond spherical powder have good fluidity, making it easy to control the flow rate of powder feeding or spreading, and avoid powder blocking. In this embodiment, the size of the spherical particles is 120um-180um, and the oxygen content is 83ppm. Finally, the obtained copper-coated diamond spherical powder was put into a graphite mold and sintered by vacuum hot pressing with a pressure of 70MPa, a temperature of 850°C, and heat preservation for 20 minutes. After cooling, a diamond/copper composite material was obtained. The thermal conductivity of the diamond/copper composite material was measured using a laser thermal conductivity meter to be 723 W/(m • K).
综上，本发明上述实施例当中的金刚石/铜复合材料制备方法，通过在金刚石颗粒表面依次进行镀覆碳化物及铜而得到双镀层金刚石粉末，然后将其与微纳米鳞片石墨粉进行均匀混合得到混合粉末，再将混合粉末在还原性气氛中进行高温热处理以使铜熔融并浸润金刚石，并在表面张力的作用下收缩成球，而后随炉冷却凝固，去除固体分散剂以得到铜包覆金刚石球形粉末。该铜包覆金刚石球形粉末的表面光滑，球形度高，流动性好，松装密度大，在送粉或者铺粉的过程中不易出现堵粉现象，从而保证了最终产品的高热导率和产品质量，且成形件密度高，烧结过程中成形件收缩均匀，获得的金刚石/铜复合材料制品精度和热导率高。通过该铜包覆金刚石球形粉末制备得到高导热金刚石/铜复合材料，解决了现有技术中由于铜包覆金刚石粉末表面粗糙，球形度不高，流动性差，松装密度低，导致3D打印或者真空热压烧结的过程中，送粉或者铺粉的流量不好控制，容易出现堵粉的现象，导致最终的产品出现空隙或缺陷，以及成形件密度低，烧结过程中成形件收缩不均匀，获得的金刚石/铜复合材料制品精度和热导率低的问题。In summary, the diamond/copper composite material preparation method in the above embodiments of the present invention is to sequentially plate carbide and copper on the surface of diamond particles to obtain double-coated diamond powder, and then uniformly mix it with micro-nano flake graphite powder. The mixed powder is obtained, and then the mixed powder is subjected to high-temperature heat treatment in a reducing atmosphere to melt the copper and infiltrate the diamond, shrink into balls under the action of surface tension, and then cool and solidify with the furnace, and remove the solid dispersant to obtain copper coating. Diamond spherical powder. The copper-coated diamond spherical powder has a smooth surface, high sphericity, good fluidity, and high bulk density. It is not prone to powder clogging during the powder feeding or spreading process, thus ensuring the high thermal conductivity and product quality of the final product. The quality of the formed parts is high, the formed parts shrink evenly during the sintering process, and the diamond/copper composite products obtained have high precision and thermal conductivity. The high thermal conductivity diamond/copper composite material is prepared by the copper-coated diamond spherical powder, which solves the problem in the existing technology that the copper-coated diamond powder has a rough surface, low sphericity, poor fluidity, and low bulk density, resulting in 3D printing or During the vacuum hot pressing sintering process, the flow of powder feeding or spreading is difficult to control, and powder blocking is easy to occur, resulting in gaps or defects in the final product, low density of the formed parts, and uneven shrinkage of the formed parts during the sintering process. The obtained diamond/copper composite products have problems with low accuracy and thermal conductivity.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。In the description of this specification, reference to the terms "one embodiment," "some embodiments," "an example," "specific examples," or "some examples" or the like means that specific features are described in connection with the embodiment or example. , structures, materials or features are included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the patent scope of the present invention. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.
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