Characterization of the interphase in carbon fiber/polymer composites using a nanoscale dynamic mechanical imaging technique

The interphase of fiber reinforced polymer composites is a narrow region around the fiber, and the mechanical performance of a composite strongly depends on the properties of the interphase. The interphase of carbon fiber reinforced polymer composites (CFRPs) is difficult to quantitatively characterize because of its nanometer dimension. To solve this problem, we present a nanomechanical imaging technique for mapping the dynamic mechanical property around the interphase region in CFRPs, and for providing nanoscale information of the interfacial dimension. The experimental results show that this method can determine the width and topography of the interphase with nanoscale lateral resolution, based on the storage modulus profile on the cross section of the composite. The average interphase thicknesses of a T300 carbon fiber/epoxy resin composite and a T700 carbon fiber/bismaleimide resin composite are 118 nm and 163 nm, respectively, and the size of interphase is uneven in width and “river-like”, which is consistent with the surface topography of the carbon fibers. Furthermore, the effect of water-aging on the interphase of the T300/epoxy composite was analyzed using the in situ imaging technique. An increase in the interphase width and interface debonding were revealed, implying a degradation in the interphase region.     

Electrodeposition of a polymer interphase in carbon-fiber composites

The performance of an electrodeposited interphase of poly(butadiene-co-maleic anhydride) (BMA) in carbon-fiber composites is investigated. Carbon fibers are electrocoated with BMA from an aqueous solution and the coated fibers are fabricated into composite bars for evaluation of mechanical properties. These composites show superior impact strength, but lower interlaminar shear strength, compared to composites made from commercially treated fibers. It is suggested that unsaturation in the butadiene segments of the interphase polymer leads to the formation of a crosslinked layer during electrodeposition and subsequent drying. Inadequate penetration of this interphase by bulky epoxy molecules leads to a weak interphase/matrix interface which is the locus of failure, generating the observed mechanical properties. These conclusions are supported by examination of the fracture surfaces by Scanning Electron Microscopy. Further evidence of lack of matrix penetration into the interphase comes from electron microprobe line scans for bromine performed on cross-sections of single-filament composites, the bromine being introduced into the matrix via a brominated epoxy resin. Appropriate control of the chemical structure and physical characteristics of the interphase polymer is thus indicated, for acieving simultaneous improvements in impact and interlaminar shear strengths.     

Relationship between interfacial phenomena and viscoelastic behavior of laminated materials

A literature review shows that the main arguments used to describe viscoelastic behavior of polymer composites are the existence of an interphase and/or physico-chemical matrix-reinforcement interactions. The purpose of this investigation was to study the influence of both of these parameters on the viscoelastic behavior of a sandwich structure. Using a theoretical approach of the mechanical coupling between phases in laminate composites, the interphase influence is shown to be negligible. In order to understand the influence of an interphase on viscoelastic features of laminates, some metal/polymer/metal laminates were processed under various conditions to obtain different degrees of metal/polymer adhesion. Dynamic mechanical spectroscopy tests reveal that both the amplitude of the main loss factor peak and the low temperature apparent modulus increase with the adhesion. Finite elements calculations show that discontinuities of displacements at the metal/polymer interface explain the loss peak changes. The continuity of displacements is ensured only from a threshold value of the peel energy.     

TEM study of carbon fibre reinforced aluminium matrix composites: influence of brittle phases and interface on mechanical properties

The microstructure of A357 aluminium alloy (7 wt% Si+0.6 wt% Mg) reinforced by 1D-M40J carbon fibres is characterised using different techniques of transmission electron microscopy (diffraction, HRTEM, EDX, EELS). The microstructure of the high modulus PAN based fibre and of the pyrolytic carbon coating (Cp) is fully characterised. Silicon and Mg₂Si grains which determine matrix-reinforcement adhesion are investigated. On the basis of the microstructural features, the mechanical properties of the composites are discussed. The mechanical behaviour of composites prepared with and without Cp interphases corresponds to a brittle matrix reinforced by brittle fibres. In the case of the composite without Cp interphase, the most influent parameter is the high resistance to sliding at the interface between silicon and fibres which leads to a strong fibre-matrix “bonding” and thus, to a weak and brittle material. The interfacial resistance to decohesion and to sliding is lower in the composite with Cp interphase resulting in higher strength and limited pull out. This lower interfacial resistance is due to the successive microporous and layered microstructures of the pyrolytic carbon coating.     

Prospect of nanoscale interphase evaluation to predict composite properties

For meeting the requirements of lightweight and improved mechanical properties, composites could be tailor-made for specific applications if the adhesion strength which plays a key role for improved properties can be predicted. The relationship between wettability and adhesion strength has been discussed. The microstructure of interphases and adhesion strength can be significantly altered by different surface modifications of the reinforcing fibers, since the specific properties of the interphase result from nucleation, thermal and/or intrinsic stresses, sizing used, interdiffusion, and roughness. The experimental results could not confirm a simple and direct correlation between wettability and adhesion strength for different model systems. The main objective of the work was to identify the interphases for different fiber/polymer matrix systems. By using phase imaging and nanoindentation tests based on atomic force microscopy (AFM), a comparative study of the local mechanical property variation in the interphase of glass fiber reinforced epoxy resin (EP) and glass fiber reinforced polypropylene matrix (PP) composites was conducted. As model sizings for PP composites, γ-aminopropyltriethoxysilane (APS) and either polyurethane (PU) or polypropylene (PP) film former on glass fibers were investigated. The EP-matrix was combined with either unsized glass fibers or glass fibers treated with APS/PU sizing. It was found that phase imaging AFM was a highly useful tool for probing the interphase with much detailed information. Nanoindentation with sufficiently small indentation force was found to be sufficient for measuring actual interphase properties within a 100-nm region close to the fiber surface. Subsequently, it also indicated a different gradient in the modulus across the interphase region due to different sizings. The possibilities of controlling bond strength between fiber surface and polymer matrix are discussed in terms of elastic moduli of the interphases compared with surface stiffness of sized glass fibers, micromechanical results, and the mechanical properties of real composites.     

Characterizing elastic properties of carbon nanotube‐based composites by using an equivalent fiber

Effective elastic properties for carbon nanotube (CNT)‐reinforced composites are obtained through a variety of micromechanics techniques. An embedded CNT in a polymer matrix and its surrounding interphase is replaced with an equivalent fiber for predicting the mechanical properties of the CNT/polymer composite. Formulas to extract the effective material constants from solutions for the representative volume element under three loading cases are derived based on the elasticity theory. The effects of an interphase layer between the nanotubes and the polymer matrix as result of effective interphase layer are also investigated. Furthermore, this research is aimed at characterizing the elastic properties of CNTs‐reinforced composites using Eshelby–Mori–Tanaka approach based on an equivalent fiber. The variations of mechanical properties with tube radius, interphase thickness, and degree of aggregation are investigated. It is shown that the presence of aggregates has stronger impact than the interphase thickness on the effective modulus of the composite. This is because aggregates have significantly lower modulus than individual CNTs. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Composites having ionomer bonds with silanes at the interface

—Silane coupling agents have been developed for bonding virtually all thermoset and thermoplastic polymers to glass and metal surfaces. Bonding to the polymer is generally through interdiffusion of oligomeric siloxanes at the interface with possible crosslinking to interpenetrating polymer networks in the interphase region. Such structures provide very stable, water-resistant bonds across the interfaces for composites prepared under low shear. Under high shear, such as in injection molding, the bonds that are initially formed are torn by mechanical and thermal stress. A new mechanism of bonding across the interface has been discovered in which acid-functional silanes on the substrate bond to acid groups in the polymer in the presence of metal ions through ionomer bonds. Ionomers are fluid under conditions of high temperature and high shear, but reform at room temperature to tough water-resistant structures.     

Effect of a Boron Nitride Interphase That Debonds between the Interphase and the Matrix in SiC/SiC Composites

Typically, the debonding and sliding interface enabling fiber pullout for SiC-fiber-reinforced SiC-matrix composites with BN-based interphases occurs between the fiber and the interphase. Recently, composites have been fabricated where interface debonding and sliding occur between the BN interphase and the matrix. This results in two major improvements in mechanical properties. First, significantly higher failure strains were attained due to the lower interfacial shear strength with no loss in ultimate strength properties of the composites. Second, significantly longer stress-rupture times at higher stresses were observed in air at 815°3C. In addition, no loss in mechanical properties was observed for composites that did not possess a thin carbon layer between the fiber and the interphase when subjected to burner-rig exposure. Two primary factors were hypothesized for the occurrence of debonding and sliding between the BN interphase and the SiC matrix: a weaker interface at the BN/matrix interface than the fiber/BN interface and a residual tensile/shear stress-state at the BN/matrix interface of melt-infiltrated composites. Also, the occurrence of outside debonding was believed to occur during composite fabrication, i.e., on cooldown after molten silicon infiltration.     

Investigation of composite interphase using dynamic mechanical analysis: Artifacts and reality

The fiber-matrix interface is an important factor determining the overall mechanical properties of composites. This interface is no longer regarded as a sharp boundary, but is now considered to be an „interphase,”︁ i.e., a region surrounding the fiber where properties differ from those of the bulk matrix. Although the concept of the interphase is rapidly gaining acceptance, its in situ detection and characterization remains a largely unsolved problem. Dynamic mechanical analysis (DMA) is a technique known for its sensitivity in the detection of inhomogeneity in polymer morphology. Recent publications have claimed that the interphase in unidirectional fiber-reinforced composites is detectable using DMA. We have been evaluating a Du Pont 982 DMA on its uses in characterization of composites and their individual components. We have found that using heating rates higher than 2°C/min produces an artificial peak in the DMA loss spectrum of glass-fiberreinforced epoxy composites at temperatures above the matrix glass-transition temperature (T_g). This peak was not present in the data from the unreinforced matrix nor in data from carbon-fiber-reinforced samples. This artifact could be interpreted as evidence of an interphase. However, our investigations revealed that it is in fact due to a complex interaction of the instrument, the thermal conductivity of the sample, the heating rate, and the sample modulus above T_g. Despite this artifact, the high sensitivity of the Du Pont 982 DMA enables detection of inhomogeneities in the composite matrix that are attributable to an interphase.     

Interfacial contributions in lignocellulosic fiber‐reinforced polyurethane composites

Whereas lignocellulosic fibers have received considerable attention as a reinforcing agent in thermoplastic composites, their applicability to reactive polymer systems remains of considerable interest. The hydroxyl‐rich nature of natural lignocellulosic fibers suggests that they are particularly useful in thermosetting systems such as polyurethanes. To further this concept, urethane composites were prepared using both unused thermomechanical pulp and recycled newsprint fibers. In formulating the materials, the fibers were considered as a pseudo‐reactant, contributing to the network formation. A di‐functional and tri‐functional poly(propylene oxide)‐based polyol were investigated as the synthetic components with a polyol‐miscible isocyanate resin serving as a crosslinking agent. The mechanical properties of the composites were found to depend most strongly on the type of fiber, and specifically the accessibility of hydroxy functionality on the fiber. Dynamic mechanical analysis, swelling behavior, and scanning electron micrographs of failure surfaces all provided evidence of a substantial interphase in the composites that directly impacted performance properties. The functionality of the synthetic polyol further distinguished the behavior of the composite materials. Tri‐functional polyols generally increased strength and stiffness, regardless of fiber type. The data suggest that synthetic polyol functionality and relative accessibility of the internal polymer structure of the fiber wall are dominant factors in determining the extent of interphase development. Considerable opportunity exists to engineer the properties of this material system given the wide range of natural fibers and synthetic polyols available for formulation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 546–555, 2001     

Influence of precursor concentration on the densification efficiency and properties of SiC/SiC composites

The SiC/SiC composites were manufactured by polymer precursor impregnation pyrolysis process with near stoichiometric SiC fiber 2D preform as the reinforcing phase, the mixed solution of polycarbosilane (PCS), and xylene as impregnant. The effects of PCS concentration on the densification process, microstructure, and mechanical behavior of SiC/SiC composites were investigated using mechanical property testing, scanning electron microscopy, and other characterization techniques. Results showed the porosity and flexural strength of SiC/SiC composites increased first and then decreased with the increase of PCS concentration. When the concentration of PCS was 55% and 60%, the flexural strength of SiC/SiC composites reached 565.77 and 573.02 MPa, respectively. The mechanical behavior of SiC/SiC composites presented typical pseudoplastic characteristics such as fiber pulling-out, fiber bridging, and interface layer peeling, which would meet the dual requirements of optimizing the matrix and interface structure.     

陶瓷基复合材料疲劳损伤模拟与界面优化设计

本文从界面损伤模拟出发研究了陶瓷基复合材料(CMCs)的抗疲劳设计方法.以CMCs微观结构演变为切入点,在微观尺度建立复合材料各组分损伤机制的物理模型,然后集成到细观尺度的有限元分析之中,从而建立CMCs疲劳损伤的数值模拟方法,并对界面相组成、结构等因素影响疲劳性能的作用机制进行探究,以实现界面的抗疲劳设计.通过多尺度...     

Interfacial Mechanical Characterization of Nicalon SiC Fiber/Alumina-Based Composites

Interfacial mechanical properties of both Nicalon SiC/aluminum borate and Nicalon SiC/aluminum phosphate with various fiber coatings and heat treatments were evaluated using a commercially-available indenter to induce fiber sliding during load cycling experiments. Varying degrees of sliding due to different coating materials were found. The interfacial characteristics including the shear, the residual axial fiber, and debond stresses were estimated by matching the experimental stress-displacement curves with curves predicted from an existing model. The elastic modulus and hardness of the interphase/interface in ceramic matrix composites were also evaluated. These results provided important insights into the ultimate mechanical performance of fiber-reinforced ceramic-matrix composites.     

Interfacial Mechanical Characterization of Nicalon SiC Fiber/Alumina-Based Composites

Interfacial mechanical properties of both Nicalon SiC/aluminum borate and Nicalon SiC/aluminum phosphate with various fiber coatings and heat treatments were evaluated using a commercially-available indenter to induce fiber sliding during load cycling experiments. Varying degrees of sliding due to different coating materials were found. The interfacial characteristics including the shear, the residual axial fiber, and debond stresses were estimated by matching the experimental stress-displacement curves with curves predicted from an existing model. The elastic modulus and hardness of the interphase/interface in ceramic matrix composites were also evaluated. These results provided important insights into the ultimate mechanical performance of fiber-reinforced ceramic-matrix composites.     

Investigation of the nanoscale mechanical properties of carbon fiber/epoxy resin interphase. I. analysis of fiber‐stiffening effect during the nanoindentation process based on numerical simulation

The interphase in fiber reinforced polymer composites is a narrow region around the fiber with the thickness in nanoscale, and its properties have a significant effect on the composite mechanical properties. Nanoindentation method was widely accepted for the measurement of the interphase properites. Different from the homogenous material, the modulus diffence between fiber and matrix is very obvious, it is difficult to get the intrinsic properties of the interphase just depending on the experimental data due to the fiber‐stiffening effect. A numerical method is developed to simulate the nanoindentation process, to understand the fiber‐stiffening effect during the nanoindentation process in the carbon fiber/epoxy composites. The predicted results reveal that the fiber impacts the indentation response in the vicinity region of the fiber. When the indent contacts the fiber, there will be a mutation in the load–displacement curve, and the fiber‐stiffening effect is obvious, which is less affected by the thickness and modulus of the interphase and the resin matrix modulus. If the interphase thickness is smaller than the distance of indent contacting the fiber, it is nearly impossible to get the intrinsic modulus of the interphase due to the effect of fiber. On the other hand, if the interphase thickness is larger than that, in the near region about 100 nm away the indent contacting the fiber, the indentation response can reflect the difference of the interphase modulus. The gradient of the curve, that is, the indentation force varying with the distance from the fiber surface, decreases with the increase in the interphase modulus. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of Oxidation on Crack Deflection in SiC/Al2O3 Laminated Ceramic Composites

Laminated composites consisting of SiC and a thin porous alumina interphase were exposed to air at 500°C to produce a persistent, nearly uniform oxidation product layer. Crack deflection at the interface was then studied using a four-point bend testing procedure and interfacial fracture resistances were found to decrease with increasing oxidation times. Electron microscopy observations of the fractured interface show a complex multi-phase microstructure. These results show that oxidation can produce a sufficiently weak interface in a SiC-porous alumina interphase composite, in contrast to most other SiC composites where interface oxidation produces a strongly bonded interface which inhibits crack deflection.     

Effects of heat treatment on mechanical and dielectric properties of 3D Si3N4f/BN/Si3N4 composites by CVI

In this study, three-dimensional silicon nitride fiber-reinforced silicon nitride matrix (3D Si₃N_4f/BN/Si₃N₄) composites with a boron nitride (BN) interphase were fabricated through chemical vapor infiltration. Through comparing the changes of microstructure, thermal residual stress, interface bonding state, and interface microstructure evolution of composites before and after heat treatment, the evolution of mechanical and dielectric properties of Si₃N_4f/BN/Si₃N₄ composites was analyzed. Flexural strength and fracture toughness of composites acquired the maximum values of 96 ± 5 MPa and 3.8 ± 0.1 MPa·m^1/2, respectively, after heat treatment at 800 °C; however, these values were maintained at 83 ± 6 MPa and 3.1 ± 0.2 MPa·m^1/2 after heat treatment at 1200 °C, respectively. The relatively low mechanical properties are mainly attributed to the strong interface bonding caused by interfacial diffusion of oxygen and subsequent interfacial reaction and generation of turbostratic BN interphase with relatively high fracture energy. Moreover, the Si₃N_4f/BN/Si₃N₄ composites also displayed moderate dielectric constant and dielectric loss fluctuating irregularly around 5.0 and 0.04 before and after heat treatment, respectively. They were mainly determined based on the intrinsic properties of materials system and complex microstructure of composites.     

微纳多层功能复合材料的制备新技术

介绍了微纳多层共挤出技术是通过简单地对高分子熔体进行分割-变流-合并过程来增加层数的技术。说明通过微纳多层共挤出技术制得的微纳交替多层复合材料在结构上不同于传统加工方法制得的复合材料,其力学性能、阻隔性能、导电性能、光学性能具有独特的优点。指出微纳多层共挤出技术还可用于开发新型的中间相材料;这种交替多层结构形态为界面张力、粘接、结晶、扩散等理论研究提供了一个很好的模型。     

Measuring interdiffusion at an interface between two elastomers with tapping-mode and contact-resonance atomic force microscopy imaging

Despite the common use of tapping-mode atomic force microscopy to image composites or polymer blends, very few studies have focused on the measurement of the interdiffusion at an interface between two polymers in contact. In this study, we show how to assess the interphase between two polymers with two methods. First, stable and robust tapping conditions are established, and the problem of the phase contrast is discussed. Second, a contact-resonance method is presented: the tip in contact with the sample is electrostatically excited at its resonance frequency by a self-controlled oscillator. The gain and frequency images allow us to measure the interdiffusion width. Both methods (using high and weak mechanical solicitation) give the same assessment of the interdiffusion width. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) reinforced by poly(lactic acid) fibers

Biodegradable composites of poly(butylene succinate‐co‐butylene adipate) (PBSA) reinforced by poly(lactic acid) (PLA) fibers were developed by hot compression and characterized by Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), dynamic mechanical analyzer, and tensile testing. The results show that PBSA and PLA are immiscible, but their interface can be improved by processing conditions. In particular, their interface and the resulting mechanical properties strongly depend on processing temperature. When the temperature is below 120 °C, the bound between PBSA and PLA fiber is weak, which results in lower tensile modulus and strength. When the processing temperature is higher (greater than 160 °C), the relaxation of polymer chain destroyed the molecular orientation microstructure of the PLA fiber, which results in weakening mechanical properties of the fiber then weakening reinforcement function. Both tensile modulus and strength of the composites increased significantly, in particular for the materials reinforced by long fiber. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43530.