Thermal and mechanical properties of particulate fillers filled epoxy composites for electronic packaging application

Epoxy composites containing particulate fillers‐fused silica, glass powder, and mineral silica were investigated to be used as substrate materials in electronic packaging application. The content of fillers were varied between 0 and 40 vol%. The effects of the fillers on the thermal properties—thermal stability, thermal expansion and dynamic mechanical properties of the epoxy composites were studied, and it was found that fused silica, glass powder, and mineral silica increase the thermal stability and dynamic thermal mechanical properties and reduce the coefficient of thermal expansion (CTE). The lowest CTE value was observed at a fused silica content of 40 vol% for the epoxy composites, which was traced to the effect of its nature of low intrinsic CTE value of the fillers. The mechanical properties of the epoxy composites were determined in both flexural and single‐edge notch (SEN‐T) fracture toughness properties. Highest flexural strength, stiffness, and toughness values were observed at fillers content of 40 vol% for all the filled epoxy composites. Scanning electron microscopy (SEM) micrograph showed poor filler–matrix interaction in glass powder filled epoxy composites at 40 vol%. Copyright © 2007 John Wiley & Sons, Ltd.     

Rice Husk‐derived Hierarchical Micro/Mesoporous Carbon–Silica Nanocomposite as Superior Filler for Green Electronic Packaging Material

In this study, a carbon‐controllable hierarchical micro/mesoporous carbon–silica material derived from agricultural waste rice husk was easily synthesized and utilized as filler in an epoxy matrix for electronic packaging applications. Scanning electron microscopy, thermogravimetric analysis, and N₂ adsorption/desorption isotherms were used to characterize the morphology, thermal stability, carbon content, and porous structural properties, respectively, of the as‐obtained carbon–silica material, namely rice husk char (RHC ). As a filler material, the uniformly dispersed RHC filler in the epoxy/RHC composite was easily prepared through hydrogen bonding of the silanol group of silica with the epoxy matrix. For electronic packaging applications, the thermal conductivity and thermomechanical properties (storage modulus and coefficient of thermal expansion) of the epoxy/RHC composites improved with increasing carbon content. Moreover, loading of the 40% RHC filler substantially enhanced the storage modulus of the epoxy/RHC composite (5735 MPa ) compared to the epoxy with 40% commercial silica filler (3681 MPa ). Considerable commercial potential is expected for the carbon–silica composite because of the simple synthesis process and outstanding performance of the prepared packaging material.     

Epoxy nanocomposites with high thermal conductivity and low loss factor: Realize 3D thermal conductivity network at low content through core-shell structure and micro-nano technology

Dielectric polymers with high thermal conductivity are very promising in the fields of aerospace and electronic device packaging. However, composites with excellent dielectric properties usually have low thermal conductivity. It is usually to fill the polymer with thermal conductivity particles to improve the thermal conductivity, but the high content of filler often reduces the mechanical properties of the polymer. In this paper, the traditional insulating polymer epoxy resin was used as the matrix, by covering the surface of silicon carbide with graphene to form a core-shell structure and co-filled with nano diamonds to achieve the preparation of high-performance epoxy resin at low content. The results showed that at the filling content of 30 wt%, the thermal conductivity of epoxy nanocomposites showed a dramatic thermal conductivity enhancement of 1263%, the energy storage modulus increased by 1.1 GPa, and the dielectric loss remained unchanged at 50 Hz. The advantages of the composite are the structural design and surface modification of the filler, which not only take advantage of its inherent advantages, but also improve the interface area with the epoxy matrix. The composite materials with excellent properties are expected to provide theoretical guidance for the application of high thermal conductivity dielectric materials.     

Thermal behavior and flammability of epoxy/glass fiber composites containing clay and decabromodiphenyl oxide

Epoxy/glass fiber hybrid composites with organo-montmorillonite (OMMT) and decabromodiphenyl oxide (DBDPO) flame retardants were prepared by vacuum-assisted resin infusion technique. The effects of OMMT and DBDPO on the flammability properties of epoxy/glass fiber hybrid composites were evaluated through UL-94 vertical flammability test and limiting oxygen index (LOI). Thermal decomposition was studied by means of thermogravimetric analyzer (TG). Field emission scanning electron microscopy (FESEM) was used to study the char morphology of the epoxy hybrid composites after being subjected to UL-94 vertical flammability test. Epoxy/glass fiber/OMMT hybrid composites with DBDPO loading of 40 wt% showed V-1 rating, whereas an increase to 50 wt% loading showed V-0 rating. The LOI values increased from 22.7 to 39.9 % as the loading of DBDPO increased. The obtained TG results showed that the thermal stability of epoxy hybrid composites decreased as the DBDPO loading increased. DBDPO decomposed at a lower temperature to form bromine radicals, which reacted with the combustible gases to form hydrogen bromide to inhibit the flame spread in the gas phase. The condensed phase activity was shown in FESEM, in which a layer of compact and continuous char was formed in epoxy/glass fiber/OMMT/DBDPO hybrid composites.     

Non-linear material characterization and numerical modeling of cross-ply basalt/epoxy laminate under low velocity impact

The low velocity impact behavior of basalt/epoxy composites, seen as an eco-friendly replacement of glass-epoxy composites, has not been studied systematically so far. Here, the elastic elasto-plastic properties, strengths, intralaminar and interlaminar fracture energies were determined. The intralaminar energies were determined using compact tension and compression tests. The elasto-plastic properties needed in the plastic potential were determined using off-axis test. These properties are used in Finite Element (FE) code with an elasto-plastic damage model developed earlier to simulate the impact response of cross-ply laminates basalt/epoxy laminates. Low velocity impact (LVI) experiments at 10 J, 20 J and 30 J are performed on these composites. The FE simulation is successful in capturing force, energy, deflection histories and damage zones showing a close match to the experiments. A comparison of impact force history and damage area (ultrasonic C-scan) of basalt-epoxy laminates with glass epoxy laminates having same volume fraction shows nearly similar peak forces but the major axis of the ellipsoidal damage zone was bigger in glass/epoxy laminates.     

Thermal and electrical behaviors of acid functionalized MWCNT/ABC-type triblock copolymer grafted-MWCNT nanocomposites

In this work, ABC-type triblock copolymer grafted onto the surface of the MWCNT/acid functionalized MWCNT (MWCNT-COOH) composites were prepared and the properties of nanocomposites were characterized extensively using differential scanning calorimetry (DSC), scanning electronic microscopy (SEM), thermogravimetric analysis (TGA), ac electrical conductivity and dielectrical measurements.

DSC study showed that the glass transition temperatures of the nanocomposites are a some higher than that of the matrix polymer. The increase in oxidized MWCNT in the nanocomposite improved the thermal stability of the composite, according to initial decomposition temperatures. The ac electrical conductivity has increased moderately with increasing frequency, but has increased slowly with increase in the oxidized MWCNT content in the nanocomposites. The electrical conductivity increases slowly with increasing temperature to about the glass transition temperature, then it increases faster. The dielectric constants for the matrix polymer and all the composites decreases slightly with increasing frequency from 0.1 kHz to 2.0 kHz. The dielectric constant increases slightly with increasing temperature up to about the glass transition temperature region and then the increase in temperature is accelerated the increase in the dielectric constant.     

The thermal and dielectric properties of high performance cyanate ester resins/microcapsules composites

Novel high performance bisphenol A dicyanate ester (BADCy) resins/poly(urea-formaldehyde) microcapsules filled with epoxy resins (MCEs) composites have been prepared. The effects of different contents of MCEs on the thermal and dielectric properties of cured BADCy were investigated using dynamic mechanical analyzer (DMA), thermalgravimetric analyzer (TGA) and broadband dielectric analyzer. The dielectric properties of BADCy/MCEs treated in hot water and hot air were also discussed. The morphologies of BADCy/MCEs composites were characterized by scanning electron microscopy (SEM). Results indicate that the appropriate content of MCEs can improve or maintain the thermal stability, the low dielectric constant and dielectric loss of cured BADCy mainly owing to higher conversion of cyanate ester (-OCN) groups. After aged in hot water and hot air, respectively, BADCy/MCEs composites with small content of MCEs can retain the low dielectric constant and dielectric loss.     

The chemical and dielectric properties of epoxy/(Ba0.8Sr0.2)(Ti0.9Zr0.1)O3 composites for embedded capacitor application

The characteristics of epoxy/(Ba_0.8Sr_0.2)(Ti_0.9Zr_0.1)O₃ (BSTZ) composites are investigated for the further application in embedded capacitor device. The effects of BSTZ ceramic powder filler ratio on the chemical, physical and dielectric properties of epoxy/BSTZ composites are studied. Differential scanning calorimeter (DSC) thermal analysis is conducted to determine the optimum values of hardener agent, curing temperature, reaction heat, and glass transition temperature (T_g). The hardener reaction process starts at about 115 °C and completes at about 200 °C, for that it is appropriate to process of epoxy/BSTZ composites in the range of temperature. The highest glass transition temperature (T_g) of 155 °C is obtained at one equivalent weight ratio (hardener/epoxy). Only the BSTZ phase can be detected in the XRD patterns of epoxy/BSTZ composites. The more BSTZ ceramic powder is mixed with epoxy, the higher crystalline intensity of tetragonal BSTZ phase are revealed in the XRD patterns. The dielectric constant measured at 1 MHz increases from 5.8 to 23.6 as the content of BSTZ ceramic powder in the epoxy/BSTZ composites increases from 10 to 70 wt%. The loss tangents of the epoxy/BSTZ composites slightly increase with the increase of measurement frequency.     

Glass fiber reinforced bismaleimide/epoxy BaTiO3 nano composites for high voltage applications

BaTiO₃/bismaleimide/epoxy/glass fiber reinforced composites were prepared using E-glass fiber (E-GF) and silane coated E-glass fiber (SC-EGF) separately as reinforcement. BaTiO₃ nanoparticles were prepared by hydrothermal method. Results show that the addition of BaTiO₃ nanoparticles has significant effects on the mechanical and dielectric properties of the composite. Both E-GF and SC-EGF reinforced BaTiO₃/bismaleimide/epoxy composites with 2 wt percentages of BaTiO₃ nanoparticles showed improved tensile strength, flexural strength and dielectric constant and those with 3% showed high dielectric strength indicating this composition is more adaptable for high voltage insulating applications. Dielectric constants and dielectric loss of the fabricated nanocomposites have been obtained at higher frequencies (in GHz) by using Vector Network Analyser at room temperature and was found to be highest for the BMI-Epoxy nanocomposite with 1% weight nanofiller.     

Preparation and properties characterization of gallic acid epoxy resin/succinic anhydride bionanocomposites modified by green reduced graphene oxide

Graphene oxide was reduced into reducing-graphene oxide (r-GO) successfully using gallic acid (GA) as a green reducing agent. Biobased gallic acid epoxy resin (GAER) was synthesized from renewable GA, and the biobased GAER/r-GO nanocomposites and glass fiber-reinforced composites were prepared with succinic anhydride as a curing agent. The dynamic mechanical, thermal, and mechanical properties of the composites with varying r-GO contents were characterized. When the content of r-GO was 0.5 wt%, the glass transition temperature was 10.4°C higher than the pure resin system. The thermal and mechanical properties were increased with increasing r-GO content; when the r-GO content was 1.0 wt%, the initial degradation temperature was enhanced by approximately 6.8°C, the tensile and impact strengths were 34.5% and 49.1% higher, respectively, than the pure cured GAER. The impact strength of GAER was higher than that of the bisphenol A epoxy resin/SUA curing system, but the tensile strength was lower than it.     

带甲基侧基的环氧树脂增容剂对炭黑在丁苯橡胶中分散度的影响

用自制的带甲基侧基的环氧树脂(TMBP)作为界面增容剂, 从拉伸性能、键合胶含量、动态性能、扫描电镜和流变性能等方面, 研究了TMBP对炭黑在丁苯橡胶中分散度的影响, 并与市售通用双酚A型环氧树脂(E-51)和橡胶工业常用软化剂邻苯二甲酸二辛酯(DOP)进行了比较. 结果表明, 带甲基侧基的环氧树脂TMBP在提高炭黑分散性方面的效果远比E-51好， 其作用模式具有典型的增容特性.     

Achieving full effective microwave absorption in X band by double-layered design of glass fiber epoxy composites containing MWCNTs and Fe3O4 NPs

The glass fiber epoxy composites containing MWCNTs and Fe₃O₄ NPs were manufactured by composites liquid molding process. The microwave absorbing properties of single-layered and double-layered glass fiber/MWCNTs/epoxy and glass fiber/Fe₃O₄ NPs/epoxy composites were evaluated. The reflection loss(RL) were calculated by the measured complex permittivity and permeability using waveguide method by vector network analyzer. Based on the mechanism analysis and deficiency of single-layer absorber, the double-layered composites were fabricated by using matching layer and absorbing layer to enhance the microwave absorption performance, which can be modulated by tailoring the electromagnetic parameters and thicknesses of each layer. The optimized microwave absorbing properties of double-layered composites with minimum RL of −45.7 dB and full X-band effective absorption can be achieved when the total thickness of the matching layer and absorbing layer is 1.8 mm, which can be attributed to synergistic effect of improved impedance matching characteristic and superior microwave attenuation characteristic of the absorbing layer. The combined utilization of dielectric loss and magnetic loss absorbent and their double-layered structure design shows great design flexibility and diversity and can be a promising candidate for designing high performance microwave absorbing materials.     

Enhanced Thermal Stability in SiO2/Carbon Filler Derived from Rice Husk via Microwave Treatment for Electronic Packaging Application

Here we report the effect of microwave treatment on a silica–carbon (SiO₂ /C) filler derived from rice husk and the function of the microwave‐treated filler in an epoxy matrix for electronic packaging applications. Thermogravimetric analysis revealed improved thermal stability of the SiO₂ /C filler upon microwave treatment. X‐ray diffraction analysis indicated partial SiC formation after the microwave treatment. For packaging applications, compared to that of the pure epoxy polymer, the thermal conductivity of the epoxy–SiO₂ /C composite was improved by 178% at 40 wt % content of the microwave‐treated SiO₂ /C filler. Furthermore, an improvement of 149% in storage modulus and 17.6°C in glass transition temperature of the epoxy–SiO₂ /C composites was realized. The improvement in thermal stability of SiO₂ /C filler could be achieved via a simple microwave treatment, which in turn enhanced the thermal stability, thermal conduction, and thermomechanical strength of the electronic packaging materials.     

偶联剂对玻璃纤维/环氧树脂基复合材料介电性能的影响

偶联剂对玻璃纤维／环氧树脂基复合材料介电性能的影响陈平刘胜平张明艳（哈尔滨理工大学电工材料系哈尔滨１５００４０）关键词环氧树脂基复合材料，介电性能，偶联剂，浸润性玻璃纤维／环氧树脂基复合材料（ＧＦＲＰ）具有优异的电气和力学性能．然而孔隙的存在强烈地...     

Effects of novel polyhedral oligomeric silsesquioxane containing hydroxyl group and epoxy group on the dicyclopentadiene bisphenol dicyanate ester composites

Two types of novel Polyhedral Oligomeric Silsesquioxanes respectively containing hydroxyl group and epoxy group (P-POSS and E-POSS) were achieved and evaluated. The structure had been characterized by IR spectra and NMR spectra. Dicyclopentadiene bisphenol dicyanate ester (DCPDCE) composites were then prepared using P-POSS and E-POSS respectively. Their effect on the curing kinetics, dielectric, mechanical, flame-retardant and thermal properties and water absorption of the resulting composites were investigated. The results suggested that the addition of modified POSS could facilitate the curing reaction of DCPDCE. Besides, the DCPDCE composites containing modified POSS exhibited excellent flame-retardant property over pure DCPDCE resin. Adding only a little amount as small as 1.5 wt% P-POSS or 2.5 wt% E-POSS could change the UL-94V of DCPDCE resin from V-2 to V-0. The composite with P-POSS exhibited better flame-retardant and thermal properties than the composite with E-POSS. However, composite filled with E-POSS presented better dielectric property and lower water absorption.     

高性能环氧树脂/碳纳米管复合物的热分析研究

用差示扫描量热仪(DSC)、热失重分析仪(TGA)和动态力学热分析仪(DMTA)研究了多壁碳纳米管(MWNTs)/高性能4,4′-二氨基二苯甲烷四缩水甘油环氧树脂(TGDDM)/4,4′-二氨基二苯基砜(DDS)复合物的热性能.Kissinger和Flynn-Wall-Ozawa的非等温固化动力学研究发现,随着MWNTs含量的增加,复合物固化反应的活化能先减小后增大.TGA研究表明,MWNTs的添加对环氧树脂热稳定性影响很小.碳纳米管填充到TGDDM/DDS体系后,复合物的储存模量随着MWNTs含量的增加而增大,而玻璃化温度却随之减小.     

Synthesis and characterization of poly(epoxy‐imide) crosslinked networks

Poly(epoxy imide)s were prepared by a reaction between a hydroxyl‐group‐containing soluble copolyimide and commercial epoxy resins at 220 °C for 2 h. Poly(epoxy imide) thin films exhibited higher thermal stability and lower dielectric constants than a commercial flip‐chip package material (U300). The thermal stabilities of the poly(epoxy imide)s were 1.4–2.0 times higher than that of U300. The thermal stability increased with increasing crosslink density and with decreasing bulky CF₃ groups (which were easily decomposable). The dielectric constants of the poly(epoxy imide)s were 1.1–1.3 times lower than that of U300, and this is highly desirable for the microelectronic packaging industry. The dielectric constant dramatically decreased when bulky CF₃ groups were added and when the functionalities of epoxy resins decreased. The residual stresses, slopes in the cooling curves, and glass‐transition temperatures of the poly(epoxy imide)s were measured with a thin‐film stress analyzer. Low residual stresses and slopes in the cooling curves were achieved with a higher crosslink density. However, in the presence of bulky CF₃ groups, the copolyimide backbone structure did not affect the residual stress values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4293–4302, 2004     

Morphology and interphase formation in epoxy/PMMA/glass fiber composites: effect of the molecular weight of the PMMA

In this work ternary composites based on an epoxy thermoset modified with a thermoplastic polymer and reinforced with glass fibers were prepared. The aim of this study is to analyze the influence of the molecular weight of the thermoplastic polymer on the final morphologies. To obtain tailor made interphases four poly(methylmethacrylate), PMMA, which differ in their molecular weight (34,000, 65,000, 76,000 and 360,000 g/mol) were chosen to modify the epoxy resin. The amount of PMMA in the composites was fixed to 5 wt.%. Neat polymer matrices (epoxy-PMMA without fibers) were also prepared for comparison. To study all systems dynamic mechanical analysis (DMA), atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used. Although all the systems showed the typical phase separation in the epoxy/PMMA blend, DMA experiments revealed a new phase with more restricted mobility when the glass fibers are present. The amount of this phase increases as molecular weight of PMMA does. The morphologies as well as the fracture surface in the immediate surroundings of the fibers were found to be different from those observed further away from the surface of the fiber, suggesting therefore that, in this case, different fracture mechanism operates. These observations allow us to conclude that an interphase with specific properties is formed. This interphase is based on a polymer or a polymer blend (epoxy-PMMA) enriched in the component with lower mobility.     

Improved mechanical properties of epoxy‐based composites with hyperbranched polymer grafting glass‐fiber

A glass‐fiber, grafted by hyperbranched polymer with hydroxyl group (GF‐HBPH), reinforced epoxy‐based composite was evaluated for mechanical properties and compared with the neat epoxy and silanized glass‐fiber, GF‐APS. The epoxy/GF‐HBPH composites were studied by attenuated total internal reflectance infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, thermal gravimetric analysis, mechanical properties analysis, and field emission‐scanning electron microscopy. The results showed that the incorporation of GF‐HBPH could simultaneously enhance the mechanical properties of the epoxy composites. Field emission‐scanning electron microscopy images of the fracture surfaces of the test specimens were used to support the results and conclusions. Copyright © 2016 John Wiley & Sons, Ltd.     

In situ thermoset molecular composites

The polymerization of rigid rod polymer precursors in a reactive matrix precursor, which is later cured in the mold, constitutes the in situ process. A poly-azomethine (PAM) was used as the rigid rod molecule. The resin used was an epoxy. We discuss the prediction of mechanical properties using micromechanics equations for chopped fiber composites. The chemistry used to synthesize the rigid rod polymer PAM in the epoxy precursor is reviewed. Approaches to better control the cure of these epoxy systems through cure kinetics and cure rheology studies completes the thermoset in situ molecular composite process. There was a 71% increase in tensile modulus in comparison to that of the neat epoxy resin. Molecular modeling simulations and continuum mechanics are used to help understand these findings. PAM/epoxy systems were used as a matrix material in the fabrication of unidirectional glass fiber/(PAM/epoxy) structural composites. © 1994 John Wiley & Sons, Inc.