高导热金刚石／铝和金刚石／铜复合散热材料的研究进展

人造金刚石由于其自身高的热导率、低的热膨胀系数和相对低的价格已成为制造新型散热材料的研究热点。本文主要介绍了近年来在金刚石／铝和金刚石／铜复合散热材料的致密度、合成方法、热导率、界面等方面的一些研究进展。添加活碳元素（硼、铬等）和在高压下使金刚石直接成键可能是提高金刚石／金属散热材料热导率的两种有效途径。     

镀钨金刚石/铜复合材料的制备及导热性能（英文）

使用热扩散法在金刚石表面镀钨,并采用不同工艺参数制备镀钨金刚石/铜复合材料,观察不同样品的微观形貌,并使用激光闪射法测量样品的热导率,探索制备高热导率金刚石/铜复合材料的最佳工艺参数。研究结果表明,在金刚石表面镀钨可以改善界面结合,当镀覆时间为60 min时,镀层完整、均匀、平整,样品的热导率达到486 W/(m·K)。镀层的完整性和均匀性比镀层厚度更为重要。进一步对镀钨金刚石进行退火处理后,镀层与金刚石之间的冶金结合增强,制备得到的复合材料的热导率提高到559 W/(m·K)。     

Cr镀层对金刚石/铝硼硅玻璃复合材料中金刚石氧化反应的抑制研究

为研究在镀铬金刚石/铝硼硅玻璃复合材料中Cr镀层对金刚石氧化反应的抑制作用,将不同镀层厚度的镀铬金刚石和铝硼硅玻璃在相同工艺下烧制成试样,检测试样的体积膨胀率和抗折强度,观察其断面形貌;同时分析烧结后金刚石单颗粒抗压强度和金刚石-结合剂界面的成分。结果表明：Cr镀层具有消耗和隔绝氧元素的双重保护作用,能有效抑制金刚石的氧化。同时,镀层厚度对金刚石氧化反应影响显著：镀层太薄,不能在高温烧结过程中持续保护金刚石;镀层太厚,会由于应力匹配问题产生裂纹或成片剥落,使金刚石暴露在有氧环境中,反而失去保护作用。对于粒度号为140/170的金刚石,最佳镀层厚度为1.58μm。     

金刚石–SiC/Al复合材料的构型设计与导热性能

以SiC和镀钨金刚石增强体为原料制备预制体,通过气压浸渗技术在800 ℃,5 MPa条件下制备金刚石–SiC/Al复合材料。利用扫描电镜、红外热成像仪、激光导热仪等对复合材料性能进行分析,研究SiC和金刚石的含量与粒径比对复合材料构型的影响,从而优化复合材料导热性能。结果表明:在相同的SiC粒径下,金刚石体积分数的增加将使复合材料的导热性能明显提升。当金刚石体积分数为30%时,含F100 SiC的复合材料导热性能最佳,其热导率为344 W/(m?K)。当金刚石体积分数相同,粒径比从0.07增大到0.65时,复合材料导热性能依次提升;且在金刚石体积分数为15%时,复合材料的热导率增幅最大,从174 W/(m?K)增大到274 W/(m?K),增长了57%。通过改善金刚石–SiC/Al复合材料中增强体的含量和粒径比可以调控复合材料构型,充分发挥复合材料的导热潜力。      

金刚石/铜复合材料在电子封装材料领域的研究进展

金刚石/铜复合材料作为新型电子封装材料受到了广泛的关注。综述了金刚石/铜复合材料作为电子封装材料的国内外研究现状,介绍了金刚石/铜复合材料的制备工艺,并从材料科学的原理综述了该复合材料主要性能指标（热导率）的影响因素,同时对金刚石/铜复合材料的界面问题进行了分析,最后对金刚石/铜复合材料的未来应用进行了展望。     

热处理对金刚石/2024Al复合材料微观组织和热物理性能的影响

采用挤压铸造法制备粒径为5μm、体积分数为50%的金刚石/2024Al 复合材料。退火处理后对其金相组织界面反应、界面结合情况以及金刚石颗粒的内部缺陷进行观察与分析,并对其热物理性能进行测试与研究。结果表明,金刚石/2024Al 复合材料的组织致密,无明显的气孔、夹杂等缺陷;颗粒为不规则多边形,有棱角,分布比较均匀。透射电镜观察表明,部分金刚石颗粒内部有位错和层错存在,而2024Al 基体中的位错密度较大,金刚石/2024Al界面处有较多的界面反应物生成,可能为Al2Cu。复合材料在20~100°C温度区间内的平均热膨胀系数为8.5×10-6°C-1,退火处理的复合材料其热膨胀系数有一定程度的降低;随着温度的升高,复合材料的平均热膨胀系数也呈现增加的趋势。复合材料的热导率约为100 W/（m·K）,退火处理能够提高复合材料的热导率。     

粉末冶金法制备金刚石/铜复合材料热导率研究

为研制更高热导率的产品,采用粉末冶金法将金刚石与高纯度铜粉热压在一起,制备新型金刚石/铜复合材料。通过正交分析法,研究了金刚石/铜复合材料热导率的影响因素。结果表明:用粉末冶金法制备的金刚石/铜复合材料,其热导率最高为245.89 W/（m·K）。对金刚石/铜复合材料热导率影响最大的因素是金刚石与铜粉的体积比,并且随着体积比的增大,金刚石/铜复合材料热导率逐渐下降。金刚石/铜复合材料的致密度以及界面结合程度是影响金刚石/铜复合材料热导率大小的重要因素,致密度高、界面结合好的复合材料热导率高,反之则低。      

放电等离子烧结法制备Cu/金刚石复合材料的性能与显微组织

由于具备较高的热导率,铜/金刚石复合材料已成为应用于电子封装领域的新一代热管理材料。采用放电等离子烧结工艺（SPS）成功制备含不同金刚石体积分数的Cu/金刚石复合材料,研究复合材料的相对密度、微观结构均匀性和热导率（TC）随金刚石体积分数（50%、60%和70%）和烧结温度的变化规律。结果表明：随着金刚石体积分数的降低,复合材料的相对密度、微观结构均匀性和热导率均升高;随着烧结温度的提高,复合材料的相对密度和热导率不断提高。复合材料的热导率受到金刚石体积分数、微观结构均匀性和复合材料相对密度的综合影响。     

Pressure infiltrated Cu/diamond composites for LED applications

Diamond reinforced copper (Cu/diamond) composites were prepared by a pressure infiltration technique.The composites show a super high conductivity of 713 W m-1 K-1 in combination with an extremely low coefficient of thermal expansion (CTE) of 7.72 × 10-6 K-1 (25-100 ℃),which are achieved by modifying the copper matrix with adding 0.3 wt.% of boron to get a good thermal contact between the matrix and the diamond particles.By adopting a series of postmachining techniques the composites were made into near-net-shape parts,and an electroless silver coating was also successfully plated on the composites.Finally,their potential applications in the thermal management of light emitting diodes (LED) were illustrated via prototype examples.     

金刚石/铜复合材料与氧化铝陶瓷的Ag-Cu-Ti活性钎焊(英文)

金刚石/铜复合材料具有低膨胀系数和高热导率等优异性能,使其成为一种理想的电子封装材料。采用97%(72Ag-28Cu)-3%Ti活性钎料对金刚石/铜复合材料和氧化铝陶瓷进行钎焊。发现活性钎料在氧化铝陶瓷和金刚石薄膜表面均具有良好的润湿性,在两者表面的平衡润湿角均小于5°。讨论了主要钎焊条件(如钎焊温度和保温时间等)对接头性能的影响。发现钎焊过程中Ti元素聚集在金刚石颗粒的表面形成TiC化合物,且TiC化合物的形貌与钎焊接头的剪切强度具有紧密联系。推测合适的TiC化合物层厚度可改善钎焊接头的剪切强度,而颗粒状的TiC化合物及过厚的TiC化合物层却会损害钎焊接头的性能。获得的最大剪切强度为117MPa。     

高导热金刚石/铝复合材料的真空热压制备

以纯铝粉末和金刚石为基体材料,采用真空热压固相烧结方式制备出热导率为677 W/(m·K)的高导热金刚石/铝复合材料.利用激光导热仪、热膨胀仪对金刚石/铝复合材料性能进行表征,并通过对制备温度、保温时间及金刚石基本颗粒尺寸的调控来优化制备工艺.研究发现:随制备温度升高,金刚石/铝复合材料的密度及致密度均有所提高,其热导...     

Low-temperature heat conduction characteristics of diamond/Cu composite by pressure infiltration method

In this paper,diamond/CuCr and diamond/CuB composites were prepared using the pressure infiltration method.The physical property measurement system(PPMS)was adopted to evaluate the thermal conductivity of diamond/Cu and MoCu composites within the range of100–350 K,and a scanning electron microscope(SEM)was utilized to analyze the microstructure and fracture appearance of the materials.The research indicates that the thermal conductivity of diamond/Cu composite within the range of100–350 K is 2.5–3.0 times that of the existing MoCu material,and the low-temperature thermal conductivity of diamond/Cu composite presents an exponential relationship with the temperature.If B element was added to a Cu matrix and a low-temperature binder was used for prefabricated elements,favorable interfacial adhesion,relatively high interfacial thermal conductivity,and favorable low-temperature heat conduction characteristics would be apparent.     

Effect of processing parameters on the microstructure and thermal conductivity of diamond/Ag composites fabricated by spark plasma sintering

Diamond/metal composites with 50 vol.% diamond have been produced by spark plasma sintering (SPS) using pure Ag as a matrix and diamond particles as reinforcement. Three kinds of powder mixing processes were used to prepare the mixture of diamond/Ag powders: dry mixing without milling medium, wet mixing and magnetic blending. Subsequently, they were all consolidated by SPS at various processing parameters to produce bulk diamond/Ag composites. Then samples were heat treated in order to obtain a higher thermal conductivity. The effect of processing parameters on the morphologies of the mixed powders, the microstructure and the thermal conductivity of the composites were investigated by comparing the experimental data. It reveals that particles were easy to agglomerate and the distribution of mixed powders was inhomogeneous by dry mixing method, and wet mixing method is too complex. The most favorable mixing process is magnetic blending by which the powders can be homogenously mixed and the composites prepared by optimized SPS processing parameters can obtain the highest relative density and the best thermal conductivity among the composites prepared by different processes. The magnetic blending diamond/Ag composites even have a 23% increase in thermal conductivity compared with pure silver sintered by SPS.     

直接转化法合成大尺寸纯相多晶金刚石

在不同热力学条件下,以不同碳源为初始材料,采用直接转化法合成不同晶粒尺寸、不同颜色的纯相多晶金刚石块体（φ6 mm×6 mm）,并用X射线衍射、Raman光谱及扫描电镜等方法检测验证。采用维氏压痕法测得纳米结构的黄色透明样品硬度为130~270 GPa（加载3 N）。对黄色透明样品进行砂轮对磨实验,其磨耗比达1.658×106,约为现在市场上主流钴基石油用金刚石复合片的25倍。差热分析表明:黄色透明样品的热稳定性与克拉级单晶金刚石基本持平;以纳米结构多晶金刚石与金刚石大单晶对磨,测定其磨耗比为2.5,表现出比金刚石大单晶更优越的耐磨性。      

高温高压烧结金刚石-铜复合材料的研究

采用高温高压烧结工艺制备了金刚石体积分数为80%的金刚石-铜复合材料。研究了金刚石颗粒大小、烧结温度、烧结时间等因素对复合材料成分、界面状态和热导率的影响。结果表明:金刚石颗粒直径为80μm时,在高温高压条件下可获得热导率高达639 W.m-1.K-1的金刚石-铜复合材料。当金刚石体积分数一定时,存在一临界粒径,随金刚石颗粒直径增大复合材料热导率先增大后减小。恰当的烧结温度和时间有助于获得黏结良好的界面和高热导率。     

Effect of carbide formers on microstructure and thermal conductivity of diamond-Cu composites for heat sink materials

Diamond-copper composites were prepared by powder metallurgy, in which the diamond particles were pre-coated by magnetic sputtering with copper alloy containing a small amount of carbide forming elements (including B, Cr, Ti, and Si). The influence of the carbide forming element additives on the microstructure and thermal conductivity of diamond composites was investigated. It is found that the composites fabricated with Cu-0.5B coated diamond particles has a relatively higher density and its thermal conductivity approaches 300 W/(m·K). Addition of 0.5%B improves the interfacial bonding and decreases thermal boundary resistance between diamond and Cu, while addition of 1%Cr makes the interfacial layer break away from diamond surface. The actual interfacial thermal conductivity of the composites with Cu-0.5B alloy coated on diamond is much higher than that of the Cu-1Cr layer, which suggests that the intrinsic thermal conductivity of the interfacial layer is an important factor for improving the thermal conductivity of the diamond composites.     

Microstructure and thermal conductivity of copper matrix composites reinforced with mixtures of diamond and SiC particles

The thermal conductivity of diamond hybrid SiC/Cu,diamond/Cu and SiC/Cu composite were calculated by using the extended differential effective medium (DEM) theoretical model in this paper.The effects of the particle volume fraction,the particle size and the volume ratio of the diamond particles to the total particles on the thermal conductivity of the composite were studied.The DEM theoretical calculation results show that,for the diamond hybrid SiC/Cu composite,when the particle volume fraction is above 46% and the volume ratio of the diamond particles to the SiC particles is above 13:12,the thermal conductivity of the composite can reach 500 W·m-1·K-1.The thermal conduc-tivity of the composite has little change when the particle size is above 200μm.The experimental results show that Ti can improve the wettability of the SiC and Cu.The thermal conductivity of the diamond hybrid SiCTi/Cu is almost two times better than that of the diamond hybrid SiC/Cu.It is feasible to predict the thermal conductivity of the composite by DEM theoretical model.     

Effect of powder mixing process on the microstructure and thermal conductivity of Al/diamond composites fabricated by spark plasma sintering

Two powder mixing processes, mechanical mixing (MM) and mechanical alloying (MA), were used to prepare mixed Al/diamond powders, which were subsequently consolidated using spark plasma sintering (SPS) to produce bulk Al/diamond composites. The effects of the powder mixing process on the morphologies of the mixed powders, the microstructure and the thermal conductivity of the composites were investigated. The results show that the powder mixing process can significantly affect the microstructure and the thermal conductivity of the composites. Agglomerations of the particles occurred in mixed powders using MM for 30 min, which led to high pore content and weak interfacial bonding in the composites and resulted in low relative density and low thermal conductivity for the composites. Mixed powders of homogeneous distribution of diamond particles could be obtained using MA for 10 min and MM for 2 h. The composite prepared through MA indicated a high relative density but low thermal conductivity due to its defects, such as damaged particles, Fe impurity, and local interfacial debonding, which were mainly introduced in the MA process. In contrast, the composite made by MM for 2 h demonstrated high relative density and an excellent thermal conductivity of 325 W·m-1·K-1, owing to its having few defects and strong interfacial bonding.     

磷对铜基金刚石工具胎体性能的影响

以铜、银、锡、锌、磷等为原料,采用热压快速烧结工艺制备铜基金刚石工具。研究磷对铜基结合剂抗弯强度、洛氏硬度和冲击韧性的影响;采用X衍射、扫描电镜分析结合剂的组织结构及其对金刚石的包镶能力。结果表明:磷能促进铜基结合剂的烧结,降低烧结温度,样品在400~460℃即可达到完全烧结;当烧结温度为420℃、磷含量(质量分数)为6%时,结合剂洛氏硬度达到90.4HRB,抗弯强度达到966.04MPa,综合性能最佳;加入金刚石粒度为30/35,浓度为100%时,其抗弯强度达到425.70MPa。     

Effect of particle size on the microstructure and thermal conductivity of Al/diamond composites prepared by spark plasma sintering

Spark plasma sintering (SPS) was used to fabricate Al/diamond composites. The influence of diamond particle size on the microstructure and thermal conductivity (TC) of composites was investigated by combining experimental results with model prediction. The results show that both composites with 40 μm particles and 70 μm particles exhibit high density and good TC, and the composite with 70 μm particles indicates an excellent TC of 325 W·m⁻¹·K⁻¹. Their TCs lay between the theoretical estimated bounds. In contrast, the composite with 100 μm particles demonstrates low density as well as poor TC due to its high porosity and weak interfacial bonding. Its TC is even considerably less than the lower bound of the predicted value. Using larger diamond particles can further enhance thermal conductive performance only based on the premise that highly dense composites of strong interfacial bonding can be obtained.