The combination of materials to form a new material system with enhanced material properties is a well documented historical fact. For example, the ancient Jewish workers during their tenure under the Pharaohs used chopped straws in bricks as a means of enhancing their structural integrity. The Japanese Samurai warriors were known to use laminated metals in the forging of their swords to obtain desirable material properties. Even certain artisans from the Mediterranean and Far East used a form of composite technology in molding art works which were fabricated by layering cut paper in various sizes for producing desired shapes and contours.

Introduction To Composite Materials

We review the present state of polymer nanocomposites research in which the fillers are single-wall or multiwall carbon nanotubes. By way of background we provide a brief synopsis about carbon nanotube materials and their suspensions. We summarize and critique various nanotube/polymer composite fabrication methods including solution mixing, melt mixing, and in situ polymerization with a particular emphasis on evaluating the dispersion state of the nanotubes. We discuss mechanical, electrical, rheological, thermal, and flammability properties separately and how these physical properties depend on the size, aspect ratio, loading, dispersion state, and alignment of nanotubes within polymer nanocomposites. Finally, we summarize the current challenges to and opportunities for efficiently translating the extraordinary properties of carbon nanotubes to polymer matrices in hopes of facilitating progress in this emerging area.

Polymer Nanocomposites Containing Carbon Nanotubes

There have been a number of review papers on layered silicate and carbon nanotube reinforced polymer nanocomposites, in which the fillers have high aspect ratios. Particulate–polymer nanocomposites containing fillers with small aspect ratios are also an important class of polymer composites. However, they have been apparently overlooked. Thus, in this paper, detailed discussions on the effects of particle size, particle/matrix interface adhesion and particle loading on the stiffness, strength and toughness of such particulate–polymer composites are reviewed. To develop high performance particulate composites, it is necessary to have some basic understanding of the stiffening, strengthening and toughening mechanisms of these composites. A critical evaluation of published experimental results in comparison with theoretical models is given.

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Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites

The role of structural hierarchy in determining bulk material properties is examined. Dense hierarchical materials are discussed, including composites and polycrystals, polymers, and biological materials. Hierarchical cellular materials are considered, including cellular solids and the prediction of strength and stiffness in hierarchical cellular materials.

Materials with structural hierarchy

Graphene-polymer nanocomposites for structural and functional applications

Preface. 1 Introduction. 1.1 Definition. 1.2 Characteristics. 1.3 Classification. 1.4 Particulate Composites. 1.5 Fiber-Reinforced Composites. 1.6 Applications of Fiber Composites. Exercise Problems. References. 2 Fibers, Matrices, and Fabrication of Composites. 2.1 Advanced Fibers. 2.1.1 Glass Fibers. 2.1.2 Carbon and Graphite Fibers. 2.1.3 Aramid Fibers. 2.1.4 Boron Fibers. 2.1.5 Other Fibers. 2.2 Matrix Materials. 2.2.1 Polymers. 2.2.2 Metals. 2.3 Fabrication of Composites. 2.3.1 Fabrication of Thermosetting Resin Matrix Composites. 2.3.2 Fabrication of Thermoplastic-Resin Matrix Composites (Short-Fiber Composites). 2.3.3 Fabrication of Metal Matrix Composites. 2.3.4 Fabrication of Ceramic Matrix Composites. Suggested Reading. 3 Behavior of Unidirectional Composites. 3.1 Introduction. 3.1.1 Nomenclature. 3.1.2 Volume and Weight Fractions. 3.2 Longitudinal Behavior of Unidirectional Composites. 3.2.1 Initial Stiffness. 3.2.2 Load Sharing. 3.2.3 Behavior beyond Initial Deformation. 3.2.4 Failure Mechanism and Strength. 3.2.5 Factors Influencing Longitudinal Strength and Stiffness. 3.3 Transverse Stiffness and Strength. 3.3.1 Constant-Stress Model. 3.3.2 Elasticity Methods of Stiffness Prediction. 3.3.3 Halpin-Tsai Equations for Transverse Modulus. 3.3.4 Transverse Strength. 3.4 Prediction of Shear Modulus. 3.5 Prediction of Poisson's Ratio. 3.6 Failure Modes. 3.6.1 Failure under Longitudinal Tensile Loads. 3.6.2 Failure under Longitudinal Compressive Loads. 3.6.3 Failure under Transverse Tensile Loads. 3.6.4 Failure under Transverse Compressive Loads. 3.6.5 Failure under In-Plane Shear Loads. 3.7 Expansion Coefficients and Transport Properties. 3.7.1 Thermal Expansion Coefficients. 3.7.2 Moisture Expansion Coefficients. 3.7.3 Transport Properties. 3.7.4 Mass Diffusion. 3.8 Typical Unidirectional Fiber Composite Properties. Exercise Problems. References. 4 Short-Fiber Composites. 4.1 Introduction. 4.2 Theories of Stress Transfer. 4.2.1 Approximate Analysis of Stress Transfer. 4.2.2 Stress Distributions from Finite-Element Analysis. 4.2.3 Average Fiber Stress. 4.3 Modulus and Strength of Short-Fiber Composites. 4.3.1 Prediction of Modulus. 4.3.2 Prediction of Strength. 4.3.3 Effect of Matrix Ductility. 4.4 Ribbon-Reinforced Composites. Exercise Problems. References. 5 Analysis of an Orthotropic Lamina. 5.1 Introduction. 5.1.1 Orthotropic Materials. 5.2 Stress-Strain Relations and Engineering Constants. 5.2.1 Stress-Strain Relations for Specially Orthotropic Lamina. 5.2.2 Stress-Strain Relations for Generally Orthotropic Lamina. 5.2.3 Transformation of Engineering Constants. 5.3 Hooke's Law and Stiffness and Compliance Matrices. 5.3.1 General Anisotropic Material. 5.3.2 Specially Orthotropic Material. 5.3.3 Transversely Isotropic Material. 5.3.4 Isotropic Material. 5.3.5 Specially Orthotropic Material under Plane Stress. 5.3.6 Compliance Tensor and Compliance Matrix. 5.3.7 Relations between Engineering Constants and Elements of Stiffness and Compliance Matrices. 5.3.8 Restrictions on Elastic Constants. 5.3.9 Transformation of Stiffness and Compliance Matrices. 5.3.10 Invariant Forms of Stiffness and Compliance Matrices. 5.4 Strengths of an Orthotropic Lamina. 5.4.1 Maximum-Stress Theory. 5.4.2 Maximum-Strain Theory. 5.4.3 Maximum-Work Theory. 5.4.4 Importance of Sign of Shear Stress on Strength of Composites. Exercise Problems. References. 6 Analysis of Laminated Composites. 6.1 Introduction. 6.2 Laminate Strains. 6.3 Variation of Stresses in a Laminate. 6.4 Resultant Forces and Moments: Synthesis of Stiffness Matrix. 6.5 Laminate Description System. 6.6 Construction and Properties of Special Laminates. 6.6.1 Symmetric Laminates. 6.6.2 Unidirectional, Cross-Ply, and Angle-Ply Laminates. 6.6.3 Quasi-isotropic Laminates. 6.7 Determination of Laminae Stresses and Strains. 6.8 Analysis of Laminates after Initial Failure. 6.9 Hygrothermal Stresses in Laminates. 6.9.1 Concepts of Thermal Stresses. 6.9.2 Hygrothermal Stress Calculations. 6.10 Laminate Analysis Through Computers. Exercise Problems. References. 7 Analysis of Laminated Plates and Beams. 7.1 Introduction. 7.2 Governing Equations for Plates. 7.2.1 Equilibrium Equations. 7.2.2 Equilibrium Equations in Terms of Displacements. 7.3 Application of Plate Theory. 7.3.1 Bending. 7.3.2 Buckling. 7.3.3 Free Vibrations. 7.4 Deformations Due to Transverse Shear. 7.4.1 First-Order Shear Deformation Theory. 7.4.2 Higher-Order Shear Deformation Theory. 7.5 Analysis of Laminated Beams. 7.5.1 Governing Equations for Laminated Beams. 7.5.2 Application of Beam Theory. Exercise Problems. References. 8 Advanced Topics in Fiber Composites. 8.1 Interlaminar Stresses and Free-Edge Effects. 8.1.1 Concepts of Interlaminar Stresses. 8.1.2 Determination of Interlaminar Stresses. 8.1.3 Effect of Stacking Sequence on Interlaminar Stresses. 8.1.4 Approximate Solutions for Interlaminar Stresses. 8.1.5 Summary. 8.2 Fracture Mechanics of Fiber Composites. 8.2.1 Introduction. 8.2.2 Fracture Mechanics Concepts and Measures of Fracture Toughness. 8.2.3 Fracture Toughness of Composite Laminates. 8.2.4 Whitney-Nuismer Failure Criteria for Notched Composites. 8.3 Joints for Composite Structures. 8.3.1 Adhesively Bonded Joints. 8.3.2 Mechanically Fastened Joints. 8.3.3 Bonded-Fastened Joints. Exercise Problems. References. 9 Performance of Fiber Composites: Fatigue, Impact, and Environmental Effects. 9.1 Fatigue. 9.1.1 Introduction. 9.1.2 Fatigue Damage. 9.1.3 Factors Influencing Fatigue Behavior of Composites. 9.1.4 Empirical Relations for Fatigue Damage and Fatigue Life. 9.1.5 Fatigue of High-Modulus Fiber-Reinforced Composites. 9.1.6 Fatigue of Short-Fiber Composites. 9.2 Impact. 9.2.1 Introduction and Fracture Process. 9.2.2 Energy-Absorbing Mechanisms and Failure Models. 9.2.3 Effect of Materials and Testing Variables on Impact Properties. 9.2.4 Hybrid Composites and Their Impact Strength. 9.2.5 Damage Due to Low-Velocity Impact. 9.3 Environmental-Interaction Effects. 9.3.1 Fiber Strength. 9.3.2 Matrix Effects. Exercise Problems. References. 10 Experimental Characterization of Composites. 10.1 Introduction. 10.2 Measurement of Physical Properties. 10.2.1 Density. 10.2.2 Constituent Weight and Volume Fractions. 10.2.3 Void Volume Fraction. 10.2.4 Thermal Expansion Coefficients. 10.2.5 Moisture Absorption and Diffusivity. 10.2.6 Moisture Expansion Coefficients. 10.3 Measurement of Mechanical Properties. 10.3.1 Properties in Tension. 10.3.2 Properties in Compression. 10.3.3 In-Place Shear Properties. 10.3.4 Flexural Properties. 10.3.5 Measures of In-Plane Fracture Toughness. 10.3.6 Interlaminar Shear Strength and Fracture Toughness. 10.3.7 Impact Properties. 10.4 Damage Identification Using Nondestructive Evaluation Techniques. 10.4.1 Ultrasonics. 10.4.2 Acoustic Emission. 10.4.3 x-Radiography. 10.4.4 Thermography. 10.4.5 Laser Shearography. 10.5 General Remarks on Characterization. Exercise Problems. References. 11 Emerging Composite Materials. 11.1 Nanocomposites. 11.2 Carbon-Carbon Composites. 11.3 Biocomposites. 11.3.1 Biofibers. 11.3.2 Wood-Plastic Composites (WPCs). 11.3.3 Biopolymers. 11.4 Composites in "Smart" Structures. Suggested Reading. Appendix 1: Matrices and Tensors. Appendix 2: Equations of Theory of Elasticity. Appendix 3: Laminate Orientation Code. Appendix 4: Properties of Fiber Composites. Appendix 5: Computer Programs for Laminate Analysis. Index.

Analysis and Performance of Fiber Composites

A theoretical analysis using finite element methods has been applied to oriented short-fiber composites and spherical particle composites in order to predict the influence of a finite layer at the interface on mechanical properties. In this study the interfacial layer has been modeled by assuming that a layer surrounds the interface and that this layer has a modulus of elasticity different than both the fiber and the matrix. The stress distribution near the interface has been determined as a function of the elastic constants of the interface layer and the interface layer volume fraction. This analysis has also been performed for two volume fractions of fibers and two fiber length to diameter ratios. From this stress distribution, the composite modulus and toughness have been determined as a function of interface modulus. It is theoretically shown that the toughness, measured by amount of strain energy absorbed, can be maximized by controlling the interface modulus. Furthermore, recent experimental results appear to verify the theory.

A theoretical study of the effect of an interfacial layer on the properties of composites

The mechanical properties of glass bead (30 micron diameter glass spheres) filled epoxy and polyester resins have been studied as a function of volume fraction of filler and the strength of the interfacial bond. The bonding between glass and resin was varied by chemically surface treating the glass using a silicone mold release to prevent chemical bonding at one extreme and a silane coupling agent to maximize bonding at the other extreme. Theoretical predictions of the elastic modulus and tensile strength have been made utilizing a finite element method. Excellent agreement is obtained with the experimental results. Izod impact energies have been measured for these composites as a function of filler content and interface treatment.

Mechanical properties of particulate composites

Diffusion of water in a glassy epoxy resin has been studied by the sorption method. Film thickness scaling is used as a diagnostic tool for non-Fickian sorption processes. A sorptiondesorption cycle effectively increases the preexisting free volume in the resin and renders the subsequent sorption process different from the original. The effect is understood by considering the time scale for diffusion and that for molecular relaxation of the glassy polymer network. A non-Fickian sorption process is observed for an insufficiently cured resin and is caused by the resin undergoing further postcuring in the sorption process. It is shown that oxidation of the resin during sorption also gives rise to non-Fickian processes previously described in the literature as diffusion anomalies for epoxies. It is further shown that the difference between sorption and resorption curves is not caused by irreversible damage to the resin but due to reversible changes in network conformations.

Moisture diffusion in epoxy resins Part I. Non-Fickian sorption processes

Plates of bisphenol-A polycarbonate and poly(methyl methacrylate) have been quenched in ice water from temperatures slightly above their glass transition temperatures. Residual stresses are thus created, Measurement of these residual stresses has been accomplished by the “layer removal” method and the stress distributions through the thickness are presented. Compressive stresses, approximately 3000 psi, exist at the surface while tensile stresses-of at least 1000 psi exist in the interior. It is shown that these residual stresses can influence the notched Izod impact strengths for polycarbonates. The mechanism is thought to be suppression of craze initiation in advance of the notch due to the presence of residual compressive stresses for specimens notched prior to quenching. In the case of poly(methyl methacrylate), it is shown that compressive residual stresses at the surface can cause plastic yielding to occur in bending experiments resulting in permanent deformation and greater energy absorption.

L. J. Broutman

Papers

Analysis and Performance of Fiber Composites

A theoretical study of the effect of an interfacial layer on the properties of composites

Mechanical properties of particulate composites

Moisture diffusion in epoxy resins Part I. Non-Fickian sorption processes

Residual stresses in polymers and their effect on mechanical behavior