熔盐法合成高导热磷化硼及其热管理性能研究

随着电力电子器件封装密度提高, 开发导热性能优异的热界面材料受到了广泛关注。绝大多数传统导热填料的热导率较低, 因此合成新型高导热填料是提高热界面材料导热性能的重要途径。本研究通过简单的熔盐法合成了高导热的磷化硼(BP)颗粒, 与氮化硼(h-BN)混合并通过搅拌和浇注的方法填充到环氧树脂(EP)基体中制备得到树脂基复合材料(BP-BN/EP)。实验结果表明：采用三盐法(NaCl : KCl : LiCl)合成的BP产率最高达到74%, 相对于单盐法(41%)和双盐法(39%)分别提高了33%和35%。对于BP-BN/EP复合材料, 复合材料的微结构显示BP和BN颗粒均匀分布在环氧树脂基体。当混合填料体积分数为30%时, 该复合材料的热导率达到1.81 W•m^-1•K^-1, 是纯树脂热导率(0.21 W•m^-1•K^-1)的8.6倍, 这与BP颗粒作为桥梁连接相邻BN颗粒形成导热网络有关。除此以外, 相较于不含BP的复合材料(SBN-BN/EP), BP-BN/EP复合材料展现出更加优异的热导率、热稳定性和较好的热力学性能。因此, 熔盐法合成的BP在热管理领域具有较大的应用前景。     

The dispersion of SWCNTs treated by dispersing agents in glass fiber reinforced polymer composites

It is an obstacle issue for carbon nanotubes (CNTs) particularly for single-wall carbon nanotubes (SWCNTs) with nano-level dispersion in fiber reinforced polymer matrix composites. In this paper, the dispersing agents such as Volan and BYK-9076 were employed to treat SWCNTs to improve their dispersion in the glass fiber/epoxy (GF/EP) composites. The dispersing results of SWCNTs in composites were observed by scanning electron microscopy (SEM). Then the glass transition temperature (T_g) of these kinds of composites with treated and untreated SWCNTs were obtained by dynamic mechanical thermal analysis (DMTA). Moreover, the flexural tests were performed on these composites. Based on the experiment results, the dispersion of SWCNTs was improved and the flexural property of SWCNTs/GF/EP composite was enhanced too.     

Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials

Carbon materials, such as graphite oxides, carbon nanotubes and graphenes, have exceptional thermal conductivity, which render them excellent candidates as fillers in advanced thermal interface materials for high density electronics. In this paper, these carbon materials were functionalized with 4,4′-diaminodiphenyl sulphone (DDS), to enhance the bonding between the carbon materials and the resin matrix. Their visibly different properties were investigated. It seems that DDS-functionalization can obviously improve the interfacial heat transfer between the carbon materials and the epoxy matrix. The thermal conductivity enhancement of D-Graphene composites (0.493 W/m K) was about 30% higher than that of D-MWNTs composites (0.387 W/m K) at 0.5 vol.% loading. The different effects among EGO, D-EGO, MWNTs, D-MWNTs and D-Graphene in polymer composites were also discussed. It was demonstrated that DDS-functionalized carbon materials had an obvious effect on the thermal performances of composite materials and were more effective in thermal conductivity enhancement.     

Effect of interface debonding on the thermal conductivity of microencapsulated-paraffin filled epoxy matrix composites

Microcapsules containing phase change materials (microPCMs) can be filled in polymeric matrix forming smart temperature-controlling composites. The aim of this study was to investigate the effect of interface debonding on the thermal conductivity of microPCMs containing paraffin/epoxy composites. The shell thickness and average size of microPCMs were controlled by regulating the core/shell ratios and emulsion stirring rates. Test results indicated that the thermal conductivity (K_e) of all composites decreased after a thermal shock treatment. SEM and thermography measurements were applied to observe the interface behaviors of composites after a violent thermal treatment process. It was proved that the interface debonding was generated because of the mismatch of expansion coefficient between shell and epoxy. A modeling analysis of the relative thermal conductivity (K_r) indicated that the effective approach to decrease the debonding is to enhance the molecule tangling degree between shell and matrix.     

CF/EP composite laminates with carbon black and copper chloride for improved electrical conductivity and interlaminar fracture toughness

An experimental study was conducted to improve the electrical conductivity of continuous carbon fibre/epoxy (CF/EP) composite laminate, with simultaneous improvement in mechanical performance, by incorporating nano-scale carbon black (CB) particles and copper chloride (CC) electrolyte into the epoxy matrix. CF/EP laminates of 65 vol.% of carbon fibres were manufactured using a vacuum-assisted resin infusion (VARI) technique. The effects of CB and the synergy of CB/CC on electrical resistivity, tensile strength and elastic modulus and fracture toughness (K_IC) of the epoxy matrix were experimentally characterised, as well as the transverse tensile modulus and strength, Mode I and Mode II interlaminar fracture toughness of the CF/EP laminates. The results showed that the addition of up to 3.0 wt.% CB in the epoxy matrix, with the assistance of CC, noticeably improved the electrical conductivity of the epoxy and the CF/EP laminates, with mechanical performance also enhanced to a certain extent.     

Enhancement of ablative and interfacial bonding properties of EPDM composites by incorporating epoxy phenolic resin

Effects of epoxy phenolic resin (EPR) on ablative and interfacial bonding properties of EPDM composites were evaluated. Ablative properties of EPDM composites were enhanced by two folds with incorporating 10 phr EPR. This significant enhancement was attributed to positive effect of EPR on thermal stability and thermal insulating properties of EPDM composites as well as formation of compact char layer onto composites. Furthermore, interfacial shear strength of EPDM composites with carbon fiber/epoxy (CF/EP) composites was increased by 55.6% with incorporating 10 phr EPR, due to interfacial chemical reaction of epoxide groups of EPR molecule from EPDM composites with amine group of hardener from CF/EP composites.     

Thermally conducting aluminum nitride polymer-matrix composites

Thermally conducting, but electrically insulating, polymer-matrix composites that exhibit low values of the dielectric constant and the coefficient of thermal expansion (CTE) are needed for electronic packaging. For developing such composites, this work used aluminum nitride whiskers (and/or particles) and/or silicon carbide whiskers as fillers(s) and polyvinylidene fluoride (PVDF) or epoxy as matrix. The highest thermal conductivity of 11.5 W/(m K) was attained by using PVDF, AlN whiskers and AlN particles (7 μm), such that the total filler volume fraction was 60% and the AlN whisker–particle ratio was 1:25.7. When AlN particles were used as the sole filler, the thermal conductivity was highest for the largest AlN particle size (115 μm), but the porosity increased with increasing AlN particle size. The thermal conductivity of AlN particle epoxy-matrix composite was increased by up to 97% by silane surface treatment of the particles prior to composite fabrication. The increase in thermal conductivity is due to decrease in the filler–matrix thermal contact resistance through the improvement of the interface between matrix and particles. At 60 vol.% silane-treated AlN particles only, the thermal conductivity of epoxy-matrix composite reached 11.0 W/(m K). The dielectric constant was quite high (up to 10 at 2 MHz) for the PVDF composites. The change of the filler from AlN to SiC greatly increased the dielectric constant. Combined use of whiskers and particles in an appropriate ratio gave composites with higher thermal conductivity and low CTE than the use of whiskers alone or particles alone. However, AlN addition caused the tensile strength, modulus and ductility to decrease from the values of the neat polymer, and caused degradation after water immersion.     

The effect of interfacial state on the thermal conductivity of functionalized Al2O3 filled glass fibers reinforced polymer composites

Rapidly increasing packaging density of electronic devices puts forward higher requirements for thermal conductivity of glass fibers reinforced polymer (GFRP) composites, which are commonly used as substrates in printed circuit board. Interface between fillers and polymer matrix has long been playing an important role in affecting thermal conductivity. In this paper, the effect of interfacial state on the thermal conductivity of functionalized Al₂O₃ filled GFRP composites was evaluated. The results indicated that amino groups-Al₂O₃ was demonstrated to be effective filler to fabricate thermally conductive GFPR composite (1.07 W/m K), compared with epoxy group and graphene oxide functionalized Al₂O₃. It was determined that the strong adhesion at the interface and homogeneous dispersion of filler particles were the key factors. Moreover, the effect of interfacial state on dielectric and thermomechanical properties of GFRP composites was also discussed. This research provides an efficient way to develop high-performance GFRP composites with high thermal conductivity for integrated circuit packaging applications.     

碳纤维-氧化石墨烯/环氧树脂复合材料的制备及表征

采用改进的Hummers法制备了五种具有不同氧化程度的氧化石墨烯（GO）。借助元素分析、X射线光电子能谱及FTIR红外光谱测试对所制备GO的组成及结构衍变进行了表征。利用光学显微镜对不同GO在固化剂异佛尔酮二胺（IPDA）中的分散状态进行观察,并将分散效果最佳的GO试样用于改性碳纤维/环氧树脂（CF/EP）复合材料。结果表明,随着氧化剂用量及反应时间的增加,GO的氧化程度也随之增加。在氧化程度较低时,GO表面官能团主要以羰基、羧基和酚羟基为主。随着氧化程度的不断提高,GO表面官能团主要为醚、环氧和醇羟基结构。GO在IPDA中的分散状态与其氧化程度密切相关,氧化程度最低和最高的GO均出现明显的聚集现象。另外,GO表面在分散过程中可被IPDA化学改性。在EP基体中加入分散效果最佳的GO（0.2wt%）后,与CF/EP复合材料相比,CF-GO/EP复合材料的弯曲强度、层间剪切强度和Ⅱ型层间断裂韧性分别提高了14%、17%和14%。     

Influence of electroless nickel-plating on fracture toughness of pitch-based carbon fibre reinforced composites

Nickel-Pitch-based carbon fibres (Ni-PFs) were prepared by electroless nickel-plating to enhance fracture toughness of Ni-PFs reinforced epoxy matrix composites (Ni-PFs/epoxy). The surface properties of Ni-PFs were determined by scanning electron microscopy (SEM), X-ray photoelectron spectrometry (XPS), and X-ray diffraction (XRD). The fracture toughness of the Ni-PFs/epoxy was assessed by critical stress intensity factor (K_IC) and critical strain energy release rate (G_IC). The fracture toughness of Ni-PFs/epoxy was enhanced compared to those of PFs/epoxy. These results were attributed to the increase of the degree of adhesion at interfaces between Ni-PFs and matrix resins in the composites.     

表儿茶素修饰BN对BN@表儿茶素/环氧树脂复合材料性能的影响

用表儿茶素(EC)作为非共价改性剂,对BN进行表面处理,研究了不同质量分数EC修饰的BN对BN@EC/环氧树脂(EP)复合材料性能的影响。采用FTIR、 XRD、 SEM、 TG等对BN、 BN@EC和BN@EC/EP复合材料的结构和性能进行表征,研究证明EC对BN改性成功,且改性过程中没有对BN的晶型结构产生影响;经EC改性后的BN在树脂基体中的分散性得到改善;SEM测试结果表明,与未改性的BN粒子相比,经EC改性后的BN粒子的团聚程度降低, BN@EC在基体中的分散性更好;经改性的BN@EC在水中的稳定性得到提高;当EC质量分数为10wt%时, BN@EC/EP复合材料的导热性能最好,热导率达1.27 W·m^-1·K^-1,与BN/EP的热导率(0.62 W·m^-1·K^-1)相比提高了106%。最后,分析了EC的加入对复合材料热稳定性能和硬度的影响,结果表明, EC的加入会略微提高复合材料的热稳定性。     

氧化石墨烯有序排列对碳纤维增强环氧树脂复合材料低温性能影响

为了提高碳纤维增强环氧树脂复合材料在低温(77 K)循环条件下的微裂纹抗性,文中采用共沉淀法制备了具有良好顺磁性的四氧化三铁/氧化石墨烯(Fe_3O_4/GO),采用红外光谱、X射线衍射、扫描电镜、透射电镜等手段研究了Fe_3O_4/GO在环氧树脂基体中的有序排列对环氧树脂及碳纤维增强环氧树脂复合材料低温性能的影响。结果表明,Fe_3O_4/GO的有序排列可有效提高环氧树脂基体的低温力学性能及降低环氧树脂基体的热膨胀系数,并可明显改善碳纤维增强环氧树脂(CF/EP)复合材料的低温微裂纹抗性;相对于纯环氧树脂,改性环氧树脂的热膨胀系数和低温环境下的微裂纹密度分别降低了36.5%和37.5%。     

Effect of the incorporation of interfacial elements on the thermophysical properties of Cu/VGCNFs composites

Vapour grown carbon nanofibres exhibit high mechanical properties and thermal conductivities. Therefore they are potential reinforcements in composites materials for high strength and high thermal conductivity applications. A problem not yet solved is the promotion of an improved copper/carbon interface. Several strategies have been envisaged for the incorporation of alloying elements (Ni, Co, B and Ti) at the interface. These techniques are based on duplex electroless plating coatings (combination of Cu and Ni or Cu and Co), electroless plating of alloys (Cu-B) and addition of metal nanoparticles (Ti) to Cu matrix deposited by electroless plating. The effect of the incorporation of these metallic elements on the microstructure and thermophysical properties is discussed. B and Ti lead to higher interaction at the Cu/C interface over Ni and Co. This allows the reduction of the coefficient of thermal expansion but regarding the thermal conductivity it was not possible to obtain a value higher than that of copper.     

BN表面沉积纳米Sn对BN/环氧树脂复合材料导热绝缘性能的影响

采用液相还原法,制备了BN表面沉积纳米Sn粒子(BN-Sn NPs)杂化材料,用于环氧树脂(EP)的导热绝缘填料。BN-Sn NPs表面纳米Sn的粒径和熔点分别为10~30 nm 和166.5~195.3℃。BN表面沉积纳米Sn后,粉体Zeta电位及压片的导热系数增加,EP滴在压片表面的接触角降低。在BN-Sn NPs/EP复合材料固化过程中,BN-Sn NPs表面纳米Sn熔融烧结,有利于填料相互桥联在一起,降低接触热阻,并改善界面性能,从而提高BN-Sn NPs/EP复合材料的导热系数。当填料体积含量为30vol%时,BN-Sn NPs/EP复合材料的导热系数达1.61 W(m·K)?1,比未改性BN/EP复合材料的导热系数(1.08 W(m·K)?1)提高了近50%。Monte Carlo法模拟表明,BN和BN-Sn NPs在EP基体中的接触热阻(R_c)分别为6.1×106 K·W?1和3.7×106 K·W?1。与未改性BN/EP复合材料相比,BN-Sn NPs/EP复合材料的介质损耗增加,介电强度及体积电阻率降低,但仍具有良好电绝缘性能。      

气泡和气隙影响六方氮化硼/环氧树脂复合材料导热性能的有限元模拟

气泡和气隙严重影响环氧树脂基复合材料的导热性能,研究气泡和气隙对复合材料热导率的影响有助于提高导热模型的准确性,可为进一步优化环氧树脂基复合材料的导热性能提供指导方向。采用有限元方法建立一种含气泡、气隙的六方氮化硼(h-BN) /环氧树脂复合材料单胞模型,分析气泡、气隙的尺寸和数量对复合材料导热性能的影响。通过与其他模型、实验数据的对比对模型的有效性进行了验证。结果表明,随着气泡尺寸和数量的增加,h-BN/环氧树脂复合材料热导率逐渐下降,且热导率随气泡尺寸的变化曲线存在转折点,直径大于单胞厚度的气泡对复合材料热导率的影响较大。随着气隙直径和厚度的增加,h-BN/环氧树脂复合材料热导率先缓慢后快速减小、最后呈直线趋势下降;随着气隙数量的增加,h-BN/环氧树脂复合材料热导率逐渐下降,且相较于基材中的气隙,位于填料与基材界面处的气隙对热导率的减弱更显著。      

石墨烯纳米片/(酚酞聚芳醚酮-环氧树脂)双逾渗导热复合材料的制备和性能

为在较低的导热填料含量下提高环氧树脂(EP)的热导率,通过溶液法制备了石墨烯纳米片/(酚酞聚芳醚酮-EP) (GNP/(PEK-C-EP))复合材料。基于接触角测量计算并预测了GNP的选择性分布,并通过SEM和激光闪光法研究了GNP和PEK-C含量对GNP/(PEK-C-EP)复合材料的微观结构和热导率的影响。结果表明,当PEK-C的含量为20wt%时,GNP选择性分布在PEK-C中,形成了双逾渗结构的GNP/(PEK-C-EP)复合材料,从而构建了连续导热通道。当GNP含量为1wt%时,GNP/EP复合材料导热率最高达0.375 W(m·K)?1。当GNP含量为0.5wt%时,GNP/(PEK-C-EP)复合材料导热率最高达0.371 W(m·K)?1,较GNP含量为0.5wt%的GNP/EP复合材料热导率高48%,与GNP含量为1wt%的GNP/EP复合材料的热导率基本相同。表明GNP/(PEK-C-EP)复合材料的填料量减少了50%,利用双逾渗效应可以有效减少导热填料用量。此外,比较了纯EP和GNP/(PEK-C-EP)复合材料的玻璃化转变温度、热稳定性和热膨胀系数,结果表明,GNP/(PEK-C-EP)复合材料的热性能优于纯EP。      

Evaluation on the thermal and mechanical properties of HNT-toughened epoxy/carbon fibre composites

Halloysite nanotubes (HNT) were effectively incorporated into epoxy resin and used for infusion of carbon fibre textiles, resulting in epoxy/halloysite nanotube/carbon fibre (EP/HNT/CF) multi-scale composites. The distribution of nanotubes in the composites was examined by SEM. The thermomechanical properties of the composites were characterized by dynamic mechanical analyser (DMA). A 25% enhancement was recorded for the storage modulus of EP/HNT/CF composite in the glassy state. Moreover, the T_g of the laminates increased with the addition of HNT, and the values were even higher than the T_g of their matrix. Additionally, the Izod impact strength of the composites has been improved. These results indicate a synergistic effect between HNT and carbon fibres.     

湿热老化对玻璃纤维/环氧树脂复合材料性能的影响

为研究玻璃纤维(GF)/环氧树脂复合材料湿热老化机制, 首先, 利用称重法、动态热机械分析仪(DMA)、SEM和矢量网络介电分析仪研究了湿热老化对GF/环氧树脂608(EP608)复合材料性能的影响;然后, 分析了复合材料的吸湿率、力学性能、介电性能与老化时间的关系, 并对其老化机制进行了探讨。结果表明:随老化时间延长, GF/EP608复合材料的力学性能和介电性能均有不同程度的下降;湿热老化对GF/EP608复合材料吸湿率的影响符合Fickian扩散定律;树脂基体的塑化、水解和基体-纤维界面的破坏是造成GF/EP608复合材料力学性能和介电性能下降的主要因素。所得结论可为GF增强环氧树脂基复合材料的应用提供科学依据。      

BN&AlN&SiC/环氧树脂复合材料线膨胀系数对LED寿命的影响

在全球大规模推广使用LED照明的今天,使用寿命是制约LED发展的瓶颈,其中,封装材料的线膨胀系数对大功率LED的使用寿命具有重要的影响。由于大功率LED粘接层材料比其相邻材料的线膨胀系数大,在循环工作时各层之间的膨胀收缩不一致,导致层与层之间产生翘曲裂纹现象,从而影响LED的使用寿命。文中采用向环氧树脂(EP)中分别加入氮化硼(BN)、氮化铝(AlN)、碳化硅(SiC)微粉颗粒制备出3种——BN/EP、AlN/EP、SiC/EP复合材料,并对其进行对比分析。研究结果表明,BN/EP复合材料性能最佳,线膨胀系数可降至3.86×10-5 K-1。且当BN质量分数为55%时,导热系数达到1.598 W/(m·K),粘接强度为53.83 MPa。与纯环氧树脂相比,可使1 W LED芯片结温降低约29.6℃,寿命提高约2.2×104 h。     

BN表面改性对BN/环氧树脂复合材料导热性能的影响

采用十八烷基三甲基溴化铵（OTAB）阳离子表面活性剂对BN微米片进行有机化改性,研究了BN表面改性对BN/环氧树脂复合材料导热性能的影响。当OTAB浓度为0.6 g · L^-1时,BN表面的OTAB吸附量接近饱和。BN表面改性提高了环氧树脂对BN的浸润性,降低了BN的导热系数。SEM观察及黏度测试结果表明：BN表面改性改善了BN/环氧树脂复合材料的界面性能及体系相容性。由于界面热阻的降低,改性BN/环氧树脂复合材料的导热系数高于未改性BN/环氧树脂复合材料,当BN填充量为30%（填料与树脂基体的质量比）时,改性BN/环氧树脂复合材料的导热系数为1.03 W （m · K）^-1,是未改性BN/环氧树脂导热系数（0.48 W （m · K）^-1）的2.15倍。