Properties of calcium copper titanate and barium titanate filled epoxy composites for electronic applications: effect of filler loading and hybrid fillers

Inorganic ceramics such as calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO) and barium titanate (BaTiO₃) were used as fillers to produce epoxy thin film composites for capacitor application. The effects of filler types and loading range on the dielectric, tensile, morphology, and thermal properties of the epoxy thin film composites were determined. Results showed that epoxy thin film composites with 20 vol% filler loading of CCTO and BaTiO₃ showed good dielectric properties, thermal stability, and thermal conductivity. However, the tensile properties of the CCTO/epoxy thin film composite was reduced as the filler loading increased. On the other hand, the tensile properties of BaTiO₃/epoxy thin film composite improved as the filler loading increased. Hybrid fillers CCTO and BaTiO₃ filled epoxy composites were fabricated and the effect of hybrid fillers on the dielectric properties and morphology of the epoxy thin film composites were investigated. Results indicated that positive hybrid effect in dielectric constant and dielectric loss showed by the hybrid composites.     

Study on thermal and mechanical properties of nano-calcium carbonate/epoxy composites

A study on evaluating the effect of nano-CaCO₃ particles on thermal and mechanical properties of epoxy resin cast was performed by TGA and mechanical tests. A silane coupling agent KH550 as an interfacial modifier was introduced into nanocomposites through preparing KH550/nano-CaCO₃ master batch. It is revealed that epoxy resin cast filled with nano-CaCO₃ particles represents higher thermal stability and mechanical strength. The improvement of thermal and mechanical properties is attributed to the surface modification of nano-particles, which can enhance the interfacial properties between nano-CaCO₃ fillers and epoxy resin. The mechanical properties of nano-CaCO₃/epoxy/carbon fibres composites based on the modified epoxy matrix are also enhanced.     

硅烷偶联剂改性的木粉/P34HB复合包装材料的制备

目的研究硅烷偶联剂KH550含量对木粉/P34HB复合包装材料性能的影响。采用KH550改性木粉,提高与聚(3-羟基丁酸酯-4-羟基丁酸酯)(P34HB)的结合强度,改善复合材料的力学性能和界面相容性。方法以KH550为改性剂,木粉和P34HB为原料,利用共混热压工艺制备改性木粉/P34HB复合材料;通过对复合材料的形貌进行观察,以及傅里叶变换红外光谱(FTIR)、热重分析(TGA)和力学性能分析,研究KH550质量分数不同时对复合材料界面相容性、力学性能和热性能的影响。结果添加KH550后,复合材料的的界面相容性得到改善;FTIR分析表明,KH550已经成功接枝到木粉中;适量的KH550提高了复合材料的热稳定性;复合材料的储能模量增加;复合材料的力学性能也有所提高。此外还得到了最佳的KH550添加量,即质量分数为0.5%。结论 KH550不仅使得木粉与P34HB的相容性得到改善,同时也增强了复合包装材料的力学性能和热性能。     

Effects of Kaolinite additions on sintering behavior and dielectric properties of CaCu3Ti4O12 ceramics

Commercial Kaolinite was employed as sintering aid to reduce the sintering temperature of CaCu₃Ti₄O₁₂ (CCTO) ceramics. The effects of Kaolinite content and sintering temperature on the densification, microstructure and dielectric properties of CCTO ceramics have been investigated. The density characterization results show that the addition of Kaolinite significantly enhanced the relative density of CCTO ceramics to about 92 %. X-ray diffraction results show CCTO ceramics with a low amount of Kaolinite exhibited perovskite-like structure, but 1.0 wt% Kaolinite additions resulted in the formation of a secondary phase, CaO–TiO₂–Al₂O₃–SiO₂ glass phase was formed and improved the dielectric constant of ceramics, which was supported by scanning electron microscopy–energy dispersive X-ray results. CCTO ceramic with 1.0 wt% Kaolinite addition possessed well temperature and frequency stability of dielectric constant. It was found that Kaolinite lowered the dielectric loss of the samples.     

Effect of coupling agents on the dielectric properties of CaCu3Ti4O12/PVDF composites

Phase-pure calcium copper titanate (CaCu₃Ti₄O₁₂, CCTO) ceramic particles were synthesized via a sol–gel route. The CCTO was treated by bis[3-(triethoxysilyl)propyl]tetrasulfide (Si69) to give CCTO@Si69. The dielectric composites based on CCTO (or CCTO@Si69) and polyvinylidene fluoride (PVDF) were molded with desirable dielectric properties by mechanical mixing process and hot-pressing. The structures of CCTO and CCTO@Si69 were investigated by scanning electron microscopy (SEM) energy spectrum, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The stretching vibration of SO at 1096 cm⁻¹ in FTIR is an indication that chemical bond was formed between Si69 and CCTO. The influence of Si69 on the preparation and the dielectric properties of CCTO/PVDF dielectric composites were discussed. When the content of Si69 was 0.1 mL (relative to 1 g of CCTO), the dielectric constant (ε) (at a frequency of 1 kHz) of CCTO@Si69/PVDF composites reached the maximum value of 84, this value is 5.25 times that of an equal amount of CCTO of CCTO/PVDF composites (ε ≈ 16). The CCTO/PVDF and CCTO@Si69/PVDF composites had very stable dielectric properties over a wide range of temperatures (20–160 °C). These composites can be applied as high-energy–density capacitors in electronic and electrical engineering fields.     

Influence of adsorbed moisture on the properties of cyanate ester/BaTiO3 composites

The effect of moisture adsorbed on BaTiO₃ on the properties of cyanate ester (CE)/BaTiO₃ dielectric composites is examined using undried and dried BaTiO₃ particles. The influence of moisture on the dielectric constant, thermal stability, dynamic mechanical properties, flexural behavior and micro morphology of the composites is investigated. Dielectric constant (ε) and dielectric loss (tan δ) of composites with the dried BaTiO₃ are both higher than composites manufactured with undried filler at the same frequency. The dielectric properties of the dried system are stable over a broader temperature range than the undried composites. Adsorbed moisture causes the initial decomposition temperature and the maximum degradation temperature of the composite to decrease by 27 °C and 15 °C, respectively. By removing the moisture from BaTiO₃, the CE/BaTiO₃ composite exhibits a lower modulus (E′), higher strength, higher flexural elongation and a dramatically increased glass transition temperature (T_g).     

复配偶联剂对SiO_2/聚四氟乙烯复合材料性能的影响

制备了不同组分配比的氨丙基三乙氧基硅烷(KH550)-苯基三甲氧基硅烷(Z6124)复配偶联剂(KH550-Z6124)改性SiO2/聚四氟乙烯(PTFE)复合材料,系统地研究了KH550-Z6124组分配比对复合材料介电性能、吸水率和导热性能的影响。采用Lichtenecker模型计算了SiO2/PTFE复合材料的介电常数和介电损耗理论值,并与实验值进行对比。结果表明:当KH550、Z6124的含量(以SiO2的质量为基准)分别为0.3wt%和1.7wt%时,KH550-Z6124改性SiO2/PTFE复合材料的介电损耗由Z6124改性SiO2/PTFE复合材料的1.7×10-3降低至1.0×10-3,吸水率由0.082 6wt%降低至0.020 3wt%,导热率提高66%;SEM形貌分析发现KH550-Z6124改性SiO2颗粒在PTFE基体中均匀分散,界面连接更紧密;KH550-Z6124改性SiO2/PTFE复合材料的介电常数和介电损耗实验值更接近其理论值。     

碳纳米管的偶联剂修饰及其在环氧树脂复合材料中的应用

为了在环氧树脂( EP) 复合材料中改善碳纳米管(CNTs) 的分散性和获得优良的界面特性, 利用Fenton 试剂对CNTs 进行了羟基化处理, 然后分别利用硅烷偶联剂KH550、KH560、KH570 和钛酸酯偶联剂NDZ201对羟基化CNTs 进行表面修饰, 通过SEM、TGA、DSC 和阻抗分析仪研究偶联剂修饰对CNTs/ EP 复合材料性能的影响。实验结果表明: Fenton 试剂和4 种偶联剂修饰都能显著改善CNTs 在复合材料中的分散性, 提高EP的玻璃化温度(T_g) 和热稳定性, 其中偶联剂修饰比Fenton 试剂处理更有效; 然而这些改性却大幅度降低了复合材料的导电性能、介电常数以及介电损耗。4 种偶联剂中, KH560 对应的复合材料的T_g最高, 热稳定性和导电性能最好, 同时具有较高的介电常数和较低的介电损耗。      

生物基没食子酸环氧树脂/纳米氧化锌抗菌涂层的制备与性能EI北大核心CSCD

以没食子酸为主要原料制备生物基没食子酸环氧树脂(GAER),将硅烷偶联剂KH550表面改性的纳米ZnO与GAER进行复合,以丁二酸酐为固化剂,制备KH550-nano-ZnO/GAER生物基复合涂层。对纳米ZnO改性前后微观结构的变化进行表征;采用示差扫描量热仪对丁二酸酐/GAER体系的固化过程进行研究,测试KH550-nano-ZnO的加入对GAER固化膜力学性能、热性能、动态力学性能以及抗菌性能的影响。结果表明:适量KH550-nano-ZnO的加入,可以增加GAER固化体系的玻璃化温度,提高涂层表面的抗冲击性,KH550-nano-ZnO含量的增加使得涂层的硬度增加,附着力下降,热稳定性增加。复合涂层的起始热失重温度(T5%)比纯GAER高12.6~15.4℃。当KH550-nano-ZnO含量为2%(质量分数)时,玻璃化转变温度与纯GAER树脂相比增加了30.7℃。KH550-nano-ZnO/GAER固化涂膜对大肠杆菌和金黄色葡萄球菌的抗菌率均达到99.99%。     

CaCu3Ti4O12 ceramics from different methods: microstructure and dielectric

CaCu₃Ti₄O₁₂ (CCTO) ceramics were synthesized by methods of sol–gel, traditional solid-state reaction, and thermal decomposition of organic solution. The results exhibit that the microstructures and electric characteristics are affected by the methods of synthesis. The X-ray diffraction patterns show that all samples have a perovskite-like CCTO phase. Moreover, CCTO ceramic from traditional solid-state reaction have the phases of TiO₂ and CuO. The scanning electron microscopy images show that CCTO ceramics from different methods have different grain sizes, grain boundaries, and densities. Dielectric properties of the CCTO ceramics were characterized in a broad frequency range (10–10⁷ Hz) at room temperature. The CCTO ceramics from thermal decomposition of organic solution have the dielectric constant of more than 5 × 10⁴ at 10 Hz. The nonlinear relationship between the current density and the electric field strength can be observed in all the three samples.     

Electric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>(BIT)–CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> (CCTO) composite substrates for high dielectric constant devices

A study of the effect of the presence of BIT (Bi₄Ti₃O₁₂) in the dielectric and optical properties of the CaCu₃Ti₄O₁₂ (CCTO) is presented. The samples were prepared by the solid state procedure. Mechanical alloying followed by the solid state procedure has been used successfully to produce powders of CaCu₃Ti₄O₁₂ (CCTO) and BIT (Bi₄Ti₃O₁₂) to be used in the composites. We also look at the effect of the grain size of the BIT and CCTO in the final properties of the composite. The samples were studied using X-Ray diffraction, scanning electron microscopy (SEM), Raman and infrared spectroscopy. We also did a study of the dielectric function K and dielectric loss of the samples. The role played by the grain size of CCTO and BIT in the dielectric constant and structural properties of the substrates are discussed. For frequencies below 10 MHz the K value presented by the CCTO100 sample is always higher than the K value presented by the BIT100 sample. At 100 Hz the value of K 1900 for the CCTO100 sample and 288 for the BIT100 sample. However for the composite sample one has an unexpected result. The dielectric constant is higher for all the frequencies under study. At 100 Hz the value of the K is around 10.000 for the BIT10 sample. Which is more than one order bigger compared to the CCTO100 value for the same frequency. Therefore, these measurements confirm the potential use of such materials for small high dielectric planar devices. These composites are also attractive for capacitor applications and certainly for microelectronics, microwave devices (cell mobile phones for example), where the miniaturization of the devices is crucial.     

Tailoring of thermal and dielectric properties of LDPE-matrix composites by the volume fraction,density, and surface modification of hollow glass microsphere filler

Hollow glass microsphere (HGM) filled low-density polyethylene (LDPE) composites were prepared, and the effects of density, content, and surface modification of HGM on the thermal and dielectric properties of the composites were investigated. It is found that the thermal conductivity of the composites decreases with increasing HGM content or decreasing HGM density. At the same HGM content and density, the composites filled with suitable amount of silane coupling agent (KH570) modified HGM exhibit higher thermal conductivity than unmodified-HGM filled composites. The dielectric constant at 1 MHz of the composites also decreases with increasing HGM content or decreasing HGM density, but their dielectric loss increases with increasing HGM content or increasing HGM density. By modifying the surface of HGM with suitable amount of KH570, the dielectric constant and loss at 1 MHz of the composites can be decreased at the same time. The results of microwave dielectric properties of the composites indicate that the dielectric constant decreases with increasing HGM content or decreasing HGM density, the quality factor (Q × f) decreases with increasing HGM content or increasing HGM density, but both dielectric constant and quality factor are slightly affected by the surface modification of HGM. Due to lower intrinsic thermal conductivity and dielectric constant but higher dielectric loss of HGM than LDPE, the thermal conductivity and dielectric properties of the composites can be controlled with adding HGM and varying its volume fraction. The surface modification of HGM improves the interface contact between HGM and LDPE in the composites, which is confirmed by the SEM observation, and thus the heat conduction and dielectric properties at low frequency are improved. Based on calculated thermal conductivity and dielectric constant of HGM, the experimental trends of thermal conductivity and dielectric constant at 1 MHz of the composites are analyzed by using different models, including typical models for particles-filled composites and special models developed for hollow microsphere filled composites. The results from suitable models show close correlation with the experimental values.     

Inorganic whiskers reinforced bismaleimide composites

The whisker-reinforced polymer composites have good friction and wear properties and widely used in many fields. Potassium titanate (K₂Ti₆O₁₃) whiskers have good properties, lower prices and show good foreground in whisker-reinforced polymer matrix composites. The surface properties of the whisker are vital for the performance of the reinforced composites. In this paper, the friction and wear properties of potassium titanate whiskers reinforced bismaleimide copmposites and the surfaces of whiskers treated by coupling agents were studied. Two coupling agents, a silane compound (KH550) and a titanate (NDZ311) were selected to treat the surface of K₂Ti₆O₁₃ whiskers, respectively. Three whisker-reinforced BMI composites, K₂Ti₆O₁₃/BMI, K₂Ti₆O₁₃ (KH550)/BMI and K₂Ti₆O₁₃ (NDZ311)/BMI, were prepared and their tribological behaviors were investigated. Results show that the wear-resistance of the matrix improved by the incorporation of whiskers into the matrix, while the improvement efficiency is depended on the nature of the surface of whiskers and whisker content. The composite containing KH550 treated whiskers has the best wear-resistance, and that containing untreated whiskers has the poorest wear-resistance among the three composites. Experiment results were explained from the point of the interfacial adhesion between the matrix and whiskers as well as the surface morphologies of worn surface and wear particles of the matrix and composites.     

偶联剂对玻璃纤维增强淀粉/聚乳酸复合材料性能的影响

分别以马来酸酐、KH550、KH560和KH570为偶联剂对玻璃纤维进行预处理,再与淀粉、聚乳酸(PLA)复合,通过熔融挤出法制备玻璃纤维增强淀粉/PLA复合材料。研究了偶联剂种类对玻璃纤维增强复合材料熔融指数、力学性能、热性能和熔融流变性能的影响。实验发现马来酸酐、KH550、KH570、KH560处理玻璃纤维增强淀粉/PLA复合材料的熔融指数和力学性能都依次增大,表明KH560处理玻璃纤维增强淀粉/PLA复合材料的界面黏结作用最强。对热性能进行表征发现,马来酸酐、KH550、KH570、KH560处理玻璃纤维增强淀粉/PLA复合材料玻璃化转变温度、重结晶温度、结晶度和热稳定性均依次提高。受玻璃纤维与淀粉/PLA基体界面黏结效果的影响,马来酸酐、KH550、KH570、KH560处理玻璃纤维增强淀粉/PLA体系的储能模量和复数黏度依次增大。     

Improved dielectric properties of CaCu3Ti4O12 thin films on oxide bottom electrode of La0.5Sr0.5CoO3

We report on the effect of La_0.5Sr_0.5CoO₃ (LSCO) bottom electrode to the dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown on Ir/Ti/SiO₂/Si substrates. Compared with the films grown directly on Ir/Ti/SiO₂/Si substrates, the dielectric constant has been increased greatly about 100%, and the dielectric loss decreased to lower than 0.2 in the frequency range of 1-100 kHz. The origin has been discussed in details based on the analysis of the X-ray diffraction and impedance spectra measurements. Results of the impedance spectra suggest that the absence of undesired interfacial layer between Ir/CCTO thin films might be one of the major reasons of the improvement of the dielectric properties when the LSCO was introduced as the bottom electrode.     

Dielectric behavior of CCTO/epoxy and Al-CCTO/epoxy composites

A composite of epoxy embedded with a giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) was fabricated. Various theoretical models were employed to rationalize the dielectric behavior of these biphasic composites. Amongst different models that were employed to predict the dielectric properties of the composites, the effective dielectric constants (ε_eff), obtained via Yamada model were in close agreement with the experimental values. A metallic inclusion in CCTO/epoxy composite was found to be effective way to enhance its dielectric constant. A three phase percolative composite (Al-CCTO/epoxy) was fabricated and percolation theory was employed to describe its dielectric behavior.     

Preparation of high k expanded graphite/CaCuTi4O12/cyanate ester composites with low dielectric loss through controlling the interfacial action between conductors and ceramics

New composites with high dielectric constant and low dielectric loss, based on expanded graphite (EG), CaCuTi₄O₁₂ (sCCTO) and cyanate ester (CE) resin, were developed by controlling the interaction between EG and sCCTO. Difference from EG, surface modified EG (mEG) has an additional strong chemical interaction with sCCTO, this not only improves the dispersion of fillers, but also enhances the filler-matrix interfacial adhesion, leading to different micro-structures and dielectric properties. Specifically, the percolation thresholds of mEG/sCCTO/CE and EG/sCCTO/CE composites are 3.45 vol% and 2.86 vol%, respectively. When the loading of conductors approaches the percolation threshold, mEG/sCCTO/CE composite has much higher dielectric constant and lower dielectric loss than EG/sCCTO/CE composite. The nature behind these attractive data was revealed by building an equivalent circuit.     

碱式硫酸镁晶须/橡胶复合材料的制备

将超声分散后的硅烷偶联剂3-氨丙基三乙氧基硅烷改性碱式硫酸镁晶须（KH550-MgOS_W）分散液加入天然胶乳（NR）中,对其进行补强,制得绿色环保高性能的KH550-MgOS_W/NR复合材料。系统研究了KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能。结果表明,用KH550改性后的MgOS_W与橡胶基体具有很好的相容性。KH550-MgOS_W/NR复合材料的力学性能、阻燃性能及热稳定性能均比纯胶有所提高。当KH550-MgOS_W与NR质量比为4%时,KH550-MgOS_W/NR复合材料的各项性能均达到最佳,300%定伸应力、拉伸强度、撕裂强度、断裂伸长率、交联密度比纯胶胶膜分别提高了25.0%、36.8%、37.3%、11.4%、44.2%,垂直燃烧等级由FV-1提高到了FV-0级,比纯胶的起始热降解温度（T₀）、最大热降解温度（T_p）和终止热降解温度（T_f）分别提高了6.2℃、5.2℃和4.1℃。     

Dielectric properties of Poly(vinylidene fluoride)/CaCu3Ti4O12 composites

The possibility of obtaining relatively high dielectric constant polymer–ceramic composite by incorporating the giant dielectric constant material, CaCu₃Ti₄O₁₂ (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X-ray diffraction, Thermal analysis, scanning electron microscope, and impedance analyzer. The effective dielectric constant (ε_eff) of the composite increased with increase in the volume fraction of CCTO at all the frequencies (100 Hz–1 MHz) under study. The dielectric loss did not show any variation up to 40% loading of CCTO, but showed an increasing trend beyond 40%. The room temperature dielectric constant as high as 95 at 100 Hz has been realized for the composite with 55 vol.% of CCTO, which has increased to about 190 at 150 °C. Theoretical models like Maxwell’s, Clausius–Mossotti, Effective medium theory, logarithmic law and Yamada were employed to rationalize the dielectric behaviour of the composite and discussed.     

Development and electrical characterization of carbon soot filled polyester graded composites

In this paper a novel method to develop carbon soot filled polyester graded composites has been reported. Dielectric measurements were conducted on these graded composites in the temperature range from 30 to 150 °C and in the frequency range 1–10 kHz to study and analyse the effect of temperature and frequency variation on dielectric constant (ε′) and dielectric dissipation factor (tan δ). It was observed that an increase of carbon soot content increased the dielectric constant gradually, which established the formation of a graded structure. Dielectric data were analysed using existing theoretical models. It was observed that Maxwell–Garnett model fits best for the dielectric data obtained experimentally for these graded composites. Compensation law confirmed the semi conducting behaviour of the composites. Cole–Cole plot for graded composites showed dielectric relaxation probably due to dipolar groups of polyester and interfacial polarization that occurred in the composites.