Zirconium tungstate/cyanate ester nanocomposites with tailored thermal expansivity

The dimensional stability of polymer matrix composites can be enhanced by reducing the mismatch in the coefficient of thermal expansion (CTE) between the high CTE polymer matrix and low CTE fiber reinforcements, which leads to development of residual stresses and matrix microcracking. A potential strategy to diminish these residual stresses involves development of polymer nanocomposites with well dispersed nanoparticles that reduce the extent of mismatch in CTE. In this work, we explore the potential for development of bulk polymer nanocomposites with tailored thermal expansivity through incorporation of zirconium tungstate nanoparticles that are characterized by a negative CTE in a unique low viscosity bisphenol E cyanate ester (BECy) thermosetting polymer matrix. Incorporation of up to 10 vol.% whisker-like nanoparticles, synthesized by a hydrothermal method, results in a 20% reduction in the CTE of the polymer matrix. However, the nanoparticles exert a dramatic catalytic effect on the cure reaction of BECy resin and subsequently decrease the onset temperature of the glass transition for the cured polymer network, at high filler loadings.     

Matrix solidification and the resulting residual thermal stresses in composites

The disparate thermal expansion properties of the fibres and matrices in high-performance composites lead to an inevitable build up of residual thermal stresses during fabrication. We first discuss the thermal expansion behaviour of thermoplastic and thermoset polymers that may be used as high-performance composite matrices. The three classes of polymers considered are epoxies, amorphous thermoplastics, and semicrystalline thermoplastics. The relevant thermal expansion data for prediction of the magnitude of the residual stresses in composites is the zero (atmospheric)-pressure thermal expansion data; these data are plotted for a range of thermoplastics and a typical epoxy. Using the technique of photoelasticity, we have measured the magnitude of the residual stresses in unidirectional graphite composites with an amorphous thermoplastic matrix (polysulfone) and with an epoxy matrix (BP907). The temperature dependence of the residual stress build up and the resulting magnitude of the residual stresses correlate well with the thermal and physical properties of the matrix resin.     

Effect of annealing on the thermal expansion and residual stresses of bidirectional thermoplastic composite laminates

Thermal expansion measurements have been conducted on various [(±30)_N]_S laminates fabricated by combining different types of matrix and fibers. The main objective was to link the coefficient of thermal expansion (CTE) of these laminates to the thermophysical characteristics of the matrix. The results show how these laminates can be used to analyze the influence of annealing and glass transition temperatures on the CTE and the release of residual stresses. It is shown that to ensure a reproductive expansion during thermal cycling, the composite must be annealed at a temperature high enough over T_g of the matrix (below the melt temperature) in order to completely release the residual stresses induced during the molding phase and uniformize the crystalline structure of the matrix. Once this is done, the response of the material under thermal cycling gives reproducible coefficient of thermal expansion (CTE) with almost no distortion after each cycle.     

Thermische Ausdehnung,innere Spannungen und Porenverteilung in AlSiCp Metallmatrix‐ verbundwerkstoffen

Thermal expansion, internal stresses and porosity distribution in AlSiCp MMC AlSi7Mg/SiC/70p (AlSiC) is used for heat sinks because of its good thermal conductivity combined with a low coefficient of thermal expansion (CTE). These properties are important for power electronic devices where heat sinks have to provide efficient heat transfer to a cooling device. A low CTE is essential for a good surface bonding of the heat sink material to the isolating ceramics. Otherwise mismatch in thermal expansion would lead to damage of the bonding degrading the thermal contact within the electronic package. Therefore AlSiC replaces increasingly copper heat sinks. The CTE mismatch between isolation and a conventional metallic heat sink is transferred into the metal matrix composite (MMC). The stability of the external and internal interface bonding is essential for the heat sink function of AlSiC. In situ thermal cycling (RT – 400 °C) measurements of an AlSi7Mg/SiC/70p MMC are reported yielding the pore volume fraction and internal stresses between the matrix and the reinforcements in function of temperature. The changes in pore volume fractions are determined by synchrotron tomography and residual stresses by synchrotron diffraction at ESRF‐ID15A. The measurements show a relationship between thermal expansion, residual stresses and pore formation in the MMC. The results obtained from the in situ measurements reveal a thermo elastic range with inversion of the dominant tensile stresses in the matrix into compressive up to 200 °C followed by plastic matrix deformation reducing the volume of pores during heating. A reverse process takes place during cooling from 500 °C starting with elastic matrix strains converting into tensile stresses increasing the pore volume fraction again. Below 200 °C, the CTE behaves again according to thermo elastic calculations. Damage like in low cycle fatigue could be observed after multiple extreme cooling‐heating cycles between –100 °C and +400 °C, which increase the volume fraction and the size of the voids.     

The effect of phase transformation on the thermal expansion property in Al/ZrW2O8 composites

This article studied the effect of phase transformation on the thermal expansion property in Al/ZrW₂O₈ composites. The Al/ZrW₂O₈ composites of low-thermal expansion were fabricated by a squeeze casting method. The coefficient of thermal expansion (CTE) of as-made composites was discovered sharply increased at around 130 °C. The X-ray diffraction (XRD) spectra showed the existence of high-pressure γ-phase in the as-made composites. This high-pressure γ-phase was considered to be induced by the compressive residual stress originated from the thermal mismatch between Al matrix and ZrW₂O₈ particles. The in situ high-temperature XRD and the differential scanning calorimetry technique were used to study this thermally expanded abruption phenomenon. It was found that the phase transformation from high-pressure γ-phase to the low-pressure phases (α/β phase) in the composites should be responsible for fluctuation in the CTE of composites. Furthermore, using a proper heat treatment to eliminate the high-pressure phase in the composite, the Al/ZrW₂O₈ composites of low and uniform CTE (from 20 to 200 °C) could be achieved. And when temperature increased again, the thermal mismatch stresses between the metal matrix and ceramic particles in the composite were not large enough to re-induce the α-γ transformation.     

Numerical aspects of finite element simulations of residual stresses in metal matrix composites

When a metal matrix composite (MMC) is cooled down from the fabrication or annealing temperature to room temperature, residual stresses are induced in the composite due to the mismatch of the thermal expansion coefficients of the matrix and reinforcement. A thermomechanical model describing these processes is presented considering that the reinforcement component has a thermo‐elastic behaviour and that the matrix material exhibits a thermo‐elastoviscoplastic behaviour. The model is implemented with a semi‐implicit forward gradient finite element method algorithm and the resulting code is used to perform numerical simulations and calculate thermally induced residual stress fields in MMCs. Several tests are performed on a continuously reinforced MMC and a short cylindrical particle MMC in order to optimize the algorithm and define its governing parameters. Good agreement was obtained with results from other authors. Copyright © 2001 John Wiley & Sons, Ltd.     

The influence of residual stresses implicated via cure volume shrinkage on CF/VEUH—composites

This paper presents a thermal finite element analysis (FEA) of a unidirectional carbon fibre reinforced vinylester urethane hybrid matrix system. The evolution of the thermal residual stresses due to the mismatch in the coefficient of thermal expansion (CTE) of the single components in the cooling phase have been investigated. Additionally, the cure volume shrinkage was implemented into the FE-model. The model allows the transition of the homogeneous unidirectional composite material properties on a microscopic spot, where the properties of the fibres and the matrix can be considered separately. It could be shown, that the cure volume shrinkage (CVS) has a dramatic effect on the fibre/matrix interface region due to radial compression stresses along the fibre. Further, this may lead to microcracking or fibre/matrix debonding before any kind of load is applied to the material.     

SiC晶须增强铝基复合材料热膨胀行为与内应力关系的研究

本文作者研究了600℃水淬和600℃退火处理的碳化硅晶须增强铝基复合材料的热膨胀行为,阐述两者热膨胀行为与内应力的内在关系。结果表明:淬火后复合材料基体的位错密度、内应力、及材料的有效屈服强度较高;而退火后复合材料基体的位错密度、内应力、及材料的有效屈服强度较低。当材料在600℃淬火后,升温过程中材料的热膨胀系数曲线在80℃和245℃各出现一个峰值,且后者明显高于前者;而600℃退火后材料的热膨胀系数曲线只在80℃出现一个波峰,且其峰值低于淬火材料相应的峰值。分析表明:材料热膨胀系数曲线出现的第一个峰是基体内拉应力释放的结果;而淬火后材料热膨胀系数曲线出现的第二个峰是基体压应力释放速率的标志。     

A theoretical approach for the thermal expansion behavior of the particulate reinforced aluminum matrix composite Part I A thermal expansion model for composites with mono-dispersed spherical particles

Microstructural observation revealed that the increase in the volume fraction of SiC particles lowers the coefficient of thermal expansion (CTE) of the composite, and the CTE of the metal matrix composites is proportional to the size of the Si phase. To analyze the thermal expansion behavior of aluminum matrix composites, a new model for the CTE of the mono-dispersed binary composite on the basis of Ashelby's cutting and welding approach was proposed. In the theoretical model, it was considered that during cooling relaxation of residual stresses could create an elasto-plastic deformation zone around a SiC or Al₂O₃ particle in the matrix. The size of reinforced particles and other metallurgical factors of the matrix alloy and composite were also considered. In this model, the interacting effect between the reinforced hard particle and the soft matrix is considered by introducing the influence of the elasto-plastic deformation zone around a particle, which is distinguished from the previous models. It was revealed that the CTE of the composite are influenced by the particle volume fraction, the elastic modulus and Poisson's ratio as well as the elasto-plastic deformation zone size and the particle size.     

Internal stresses and voids in SiC particle reinforced aluminum composites for heat sink applications

Metal-matrix composites (MMC) are being developed for power electronic IGBT modules, where the heat generated by the high power densities has to be dissipated from the chips into a heat sink. As a means of increasing long term stability a base plate material is needed with a good thermal conductivity (TC) combined with a low coefficient of thermal expansion (CTE) matching the ceramic insulator. SiC particle reinforced aluminum (AlSiC) offers the high TC of a metal with the low CTE of a ceramic. Internal stresses are generated at the matrix-particle interfaces due to the CTE mismatch between the constituents of the MMC during changing temperatures. Neutron and synchrotron diffraction was performed to evaluate the micro stresses during thermal cycling. The changes in void volume fraction, caused by plastic matrix deformation, are visualized by synchrotron tomography. The silicon content in the matrix connecting the particles to a network of hybrid reinforcement contributes essentially to the long term stability by an interpenetrating composite architecture.     

Thermal residual stresses in metal matrix composites: A review

Recently, metal matrix composites (MMCs) have generated a considerable interest in the materials field because of their attractive physical and mechanical properties. However, during the fabrication of MMCs, thermal residual stresses are reportedly developed in the matrix as a result of the mismatch of the thermal expansion coefficients between the reinforcement and the matrix. It is well established that these residual stresses have a significant effect on the composite properties. For example, due to the presence of thermal residual stresses, it is almost never possible to achieve the maximum elastic response of the composites. In addition, yield stress and fracture toughness of the composites are significantly affected by thermal residual stresses. In this paper, a critical review of the published literature on thermal residual stresses in MMCs and their effect on composite properties are presented. Also, experimental and numerical techniques that are currently available to measure and estimate thermal residual stresses are reviewed and discussed.     

纤维增强复合材料考虑损伤的温度胀缩细观力学模型

采用细观力学方法,建立了纤维增强复合材料（FRC）包含基体微裂纹和纤维/基体脱粘的热胀/冷缩理论模型。模型考虑了基体、界面中不同分布取向的微裂纹在升温和降温过程中张开、闭合情况的差异,及其对复合材料平均热胀/冷缩系数（CTE/CTC）的影响,同时还考虑了细观应力分布不均匀的因素。建立了细观有限元模型对理论模型进行验证。研究发现：复合材料损伤后CTE和CTC不一致,且取决于损伤模式：基体微裂纹损伤使得复合材料的横向CTE高于无损材料,而横向CTC低于无损材料,但对纵向CTE/CTC影响不大;纤维界面脱粘能较明显地减小复合材料的纵向CTC,但对横向CTC的影响可忽略。     

化学镀铜层厚度对铜包覆钨酸锆/铝基复合材料热稳定性能的影响

采用化学镀铜的方法在陶瓷颗粒表面沉积不同厚度的铜颗粒,对陶瓷颗粒进行表面修饰,在陶瓷颗粒与金属基体间形成过渡层以缓解制备过程中材料内部产生的内应力。研究了添加不同镀层厚度颗粒的复合材料的热膨胀系数和相变性能,结果表明铜镀层可以在一定程度上缓解内应力,减少ZrW2O8向高压相的转变,提高复合材料的热稳定性。     

Elevated temperature X-ray measurement of residual stresses in a fibre reinforced Al alloy

Thermal residual stresses have been measured using X-ray diffraction in an Al-2% Mg matrix with 10, 20 or 26 vol % Al₂O₃ short fibres. Stress measurements were made at room temperature as well asin situ at elevated temperatures up to 250?C. The thermal stresses arise due to the difference in coefficient of thermal expansion (CTE) between the matrix and the reinforcement. The largest CTE is found in the matrix, resulting in tensile residual stresses after a temperature drop, e.g. after processing or annealing. A high fraction of reinforcement implies higher matrix stresses than a low fibre content. The stresses decrease with increasing temperature for all fibre volume fractions. Measurements are compared with calculations using a modified Eshelby model for equivalent inclusions. Parameters taken into account in the model are coefficient of thermal expansion, Young's modulus, and volume fraction and geometric shape of the reinforcing phase. A good correlation between calculations and experimental results has been found, bearing in mind that no plasticity is taken into account in the Eshelby model. The plastic behaviour of the composites has been described using a model based on a rigid spherical cavity in an elastic-plastic matrix.     

Predicting crack initiation in composite material systems due to a thermal expansion mismatch

Residual stresses due to curing and thermal stresses due to differences between the thermal expansion coefficients of the matrix and fiber may have a major effect on the micro-stresses within a composite material system and must be added to the stresses induced by the external mechanical loads. Such microstresses are often sufficient to produce micro-cracking even in the absence of external loads, example during the cooling process. In this investigation, a micro-mechnics approach is used in which the fibers of a composite material system are modeled as cylindrical inclusions that are embedded into a matrix plate. The model is then used to predict, analytically, the residual stresses due to a thermal expansion mismatch, e.g. during a cooling process. Additionally, some critical effects due to a load transverse to the direction of the fibers are examined. The analysis provides a better understanding of how residual stresses are developed and how they may be controlled in material systems where small strains are present. Moreover, the results are used to identify locations of possible crack failure and to derive a fracture criterion for crack initiation at the local level. Comparison with experimental evidence for matrix cracking in intermetallic composites caused by thermal expansion mismatch shows a good agreement. This revised version was published online in July 2006 with corrections to the Cover Date.     

Residual stresses in structures reinforced with adhesively bonded straps designed to retard fatigue crack growth

The residual stresses induced when adhesively bonding patches to a 7085 alloy SENT (side edge notched tension) specimen in order to produce fatigue crack growth retardation have been investigated. Knowledge of the induced residual stresses is important as they affect the beneficial bridging effect of the strap. The strap materials studied were: Titanium, GLARE (fibre metal laminate), GFRP (glass fibre reinforced polymer) and CFRP (carbon fibre reinforced polymer). The residual stresses were measured using neutron diffraction and are compared with those predicated by FE (finite element) simulation. The measured and modelled residual stresses were in reasonable correlation. Tensile residual stresses were found close to the strap, whereas small compressive residual stresses were found on the un-bonded side. The residual stresses were induced due to the mismatch in the coefficient of thermal expansion (ΔCTE) between the SENT and the strap. The magnitude of the stresses induced by the bonded crack retarders depend both on the ΔCTE and the stiffness ratio between the reinforced structure and the strap. For the straps studied, the magnitude of the peak residual stresses found were in the following descending order: CFRP, titanium, GFRP and GLARE.     

Compaction of thick carbon/phenolic fabric composites with autoclave method

Carbon/phenolic composites are used in the nozzle parts of solid rocket motors due to their heat-resisting, ablative, and high strength characteristics, which are required to endure the high temperature and pressure of combustion gas passing through the nozzle. But the thick axi-symmetric structure of the composite nozzle induces high thermal residual stresses due to the large difference of coefficient of thermal expansion (CTE) between the in-plane and the out-of-plane. In this work, in order to reduce the through-thickness CTE and the void content, a compression in the thickness direction was applied to the composite prepreg by a compressive jig during manufacturing of composite to supplement the low autoclave pressure. The through-thickness CTE of the fabric composite was calculated by a compaction model and compared with the measured one by thermo-mechanical analysis. The through-thickness CTE changed drastically with respect to the compaction amount, and the void content of the carbon/phenolic fabric composite laminate showed different characteristics from the ordinary fabric laminates with respect to the autoclave pressure and the jig pressure.     

Effect of curing stresses on the behaviour of fibre reinforced plastic composites under biaxial loading

Residual stresses are induced in fibre reinforced plastic (FRP) composites during fabrication and environmental exposure. The curing residual stresses induced during fabrication are mainly due to the thermal expansion mismatch of the constituents. The residual stresses can be either microresidual or macroresidual stresses. Macroresidual stresses in 0° plies and 90° plies of [90/0]_s symmetric cross-ply laminates are calculated starting with ply elastic and thermal properties for different material systems. The calculated curing stresses in Kevlar49/Epoxy unidirectional tape plies in the transverse direction are more than the transverse strength of the corresponding ply. First ply failure (FPF) envelopes are plotted using classical lamination theory and Tsai-Wu quadratic failure theory with and without considering the curing residual stresses. There is a significant effect of residual stresses on the FPF envelopes.     

铜基封装材料的研究进展

具有高导热性的铜基封装材料可以满足大功率器件即时快速大量散热的要求,是一种重要的封装材料.综述了Cu/Mo、Cu/W传统铜基封装材料和Cu/C纤维、Cu/Invar(Mo、Kovar)/Cu层状材料、Cu/ZrW2O8(Ti-Ni)负热膨胀材料及Cu/SiC、Cu/Si轻质材料等新型铜基封装材料的性能特点、制备工艺与问题.指出轻质Cu/Si复合材料将是铜基封装材料中一个新的具有前景的研究方向.     

Effect of filler geometry on coefficient of thermal expansion in carbon nanofiber reinforced epoxy composites

This study involves the investigation of the geometry effect of nano-fillers on thermally induced dimensional stability of epoxy composites by experimentally evaluating the linear coefficient of thermal expansion (CTE). Carbon nanofibers (CNF) were chosen as the filler in epoxy matrix to investigate the effect of an aspect ratio on the CTE of the nanocomposites at three different volume fractions of 0.5, 1, and 2% of the nano-filler. The composites were fabricated using a mechanical mixing method. The CTE values were evaluated by measuring thermal strains of the composites and also compared with a micromechanics model. It was observed that the composites with short CNF (average L/d = 10) show better thermal stability than one of the composites with long CNF (average L/d = 70), and the thermal stability of the composites was proportional to the volume fraction of the filler in each composite. In addition, the CTE of mutliwalled carbon nanotubes (MWNT) reinforced epoxy composites was evaluated and compared with the CTE of the CNF reinforced composites. Interestingly, the MWNT reinforced composites show the greatest thermal stability with an 11.5% reduction in the CTE over the pure epoxy. The experimental data was compared with micromechanics model.