Synthesis and characterization of carbon nanotube-reinforced epoxy: Correlation between viscosity and elastic modulus

We report the synthesis and characterization of nanocomposite thin films consisting of single-walled carbon nanotubes with different functionalization schemes dispersed in an epoxy matrix. The thermal, rheological, and mechanical properties of nanocomposite thin films were experimentally characterized to establish a relationship between processing and performance. The results from the rheological analysis confirmed that the nanotube type and functionalization strongly affect the resin viscosity during cure. A correlation between the rheological behaviour and the measured elastic properties was established. Nanotubes produced by plasma and functionalized with carboxyl group had the lowest influence on viscosity and led to the highest improvement in elastic properties. The measured increase in elastic modulus was consistent with predictions based on Mori–Tanaka micromechanics.     

Enhanced Mechanical Properties of Epoxy Nanocomposites by Mixing Noncovalently Functionalized Boron Nitride Nanoflakes

The influence of surface modifications on the mechanical properties of epoxy‐hexagonal boron nitride nanoflake (BNNF) nanocomposites is investigated. Homogeneous distributions of boron nitride nanoflakes in a polymer matrix, preserving intrinsic material properties of boron nitride nanoflakes, is the key to successful composite applications. Here, a method is suggested to obtain noncovalently functionalized BNNFs with 1‐pyrenebutyric acid (PBA) molecules and to synthesize epoxy–BNNF nanocomposites with enhanced mechanical properties. The incorporation of noncovalently functionalized BNNFs into epoxy resin yields an elastic modulus of 3.34 GPa, and 71.9 MPa ultimate tensile strength at 0.3 wt%. The toughening enhancement is as high as 107% compared to the value of neat epoxy. The creep strain and the creep compliance of the noncovalently functionalized BNNF nanocomposite is significantly less than the neat epoxy and the nonfunctionalized BNNF nanocomposite. Noncovalent functionalization of BNNFs is effective to increase mechanical properties by strong affinity between the fillers and the matrix.     

Conditions of applying Oliver–Pharr method to the nanoindentation of particles in composites

The indentation test is a popular experimental method to measure a material’s mechanical properties such as elastic modulus and hardness, and the Oliver–Pharr method is commonly used in commercial indentation instruments to obtain these two quantities. To apply the Oliver–Pharr method correctly in all of these cases, it is essential to know the limitations of this method. The present study focuses on the applicability of the Oliver–Pharr method to measure the mechanical properties of particles in composites. The finite element method is used to undertake virtual indentation tests on a particle embedded in a matrix. In our numerical studies, the indentation “pile-up” phenomenon is generally observed in our numerical case studies, which indicates that the contact area used for predicting the elastic modulus should be measured directly, not be estimated from the indentation curve. The Oliver–Pharr method based on the real contact area is applied to estimate the elastic modulus of the particles by using the indentation curve from the numerical simulation, with the estimated elastic modulus being compared with the input value. Applying the real contact area value (not the one predicted from the indentation curve) we show that the Oliver–Pharr method can still be applied to measure the elastic modulus of the particle with sufficient accuracy if the indentation depth is smaller than the particle-dominated depth, a value defined in this work. The influences of the matrix and particle properties on the particle-dominated depth are studied using a dimensional analysis and parametric study. Our results provide guidelines to allow the practical application of the Oliver–Pharr method to measure the elastic modulus of particles in composites. This could be particularly important where particles are formed in situ in a matrix (as opposed to being preformed and subsequently incorporated in a matrix), or when the modulus of individual performed particles is required such as for subsequent modelling, but the modulus of individual material particles (or its material) cannot readily be determined.     

Mechanical properties of thin glassy polymer films filled with spherical polymer-grafted nanoparticles

It is commonly accepted that the addition of spherical nanoparticles (NPs) cannot simultaneously improve the elastic modulus, the yield stress, and the ductility of an amorphous glassy polymer matrix. In contrast to this conventional wisdom, we show that ductility can be substantially increased, while maintaining gains in the elastic modulus and yield stress, in glassy nanocomposite films composed of spherical silica NPs grafted with polystyrene (PS) chains in a PS matrix. The key to these improvements are (i) uniform NP spatial dispersion and (ii) strong interfacial binding between NPs and the matrix, by making the grafted chains sufficiently long relative to the matrix. Strikingly, the optimal conditions for the mechanical reinforcement of the same nanocomposite material in the melt state is completely different, requiring the presence of spatially extended NP clusters. Evidently, NP spatial dispersions that optimize material properties are crucially sensitive to the state (melt versus glass) of the polymeric material.     

Mechanical properties characterisation of welded joint of austenitic stainless steel using instrumented indentation technique

The instrumented indentation test is a promising nondestructive technique for evaluating mechanical properties of metallic materials. In this study, the localised mechanical properties of welded joint of 304 austenitic stainless steel were characterised with the instrumented indentation test. The single V-groove welded joint was produced using the electric arc welding. A series of instrumented indentation tests were carried out at different regions, including base material, weld zone and heat-affected zone (HAZ). A soft zone regarding strength properties was found in the coarse-grain HAZ. The results show that the HAZ has the lowest yield strength and tensile strength (263.6 MPa, 652.5 MPa) compared with the base material (307.4 MPa, 807.9 MPa) and the weld zone (285.6 MPa, 702.1 MPa). In addition, characterisations of microstructure, microhardness and conventional tensile tests have been performed for comparison. The results reveal that the localised mechanical properties of welded joint of austenitic stainless steel can be represented effectively with the instrumented indentation technique.     

Effect of straight and wavy carbon nanotube on the reinforcement modulus in nonlinear elastic matrix nanocomposites

Elastomers, particularly rubbers, are viscoelastic polymers with low Young’s modulus. In this research, carbon nanotubes were used in the rubber and a rubber–carbon nanotube composite was modeled by ABAQUS™ software. Due to hyperelastic behavior of the rubber, strain function energy was used for the modeling. A sample of rubber was tested and uniaxial, biaxial, as well as planar test data obtained in these tests were used to get an energy function. Polynomial and reduced polynomial form are two common methods to achieve strain energy function. In this paper, elasticity modulus and Poisson ratio were measured for a representative volume element (RVE) of composite. Rubber was also considered as an elastic material and its composite properties in this state compared by hyperelastic rubber matrix assumption. ABAQUS was used to create a three dimensional finite element model of a single long wavy nanotube with diameter of D which perfectly bonded to matrix material. Nanotube waviness was modeled by sinusoidal carbon nanotube shape. Results showed that mechanical properties of the rubber will extremely change by adding carbon nanotube. Furthermore, several volume fractions of carbon nanotube in rubber were modeled and it was shown that stiffness of nanocomposite increases by more volume fraction of carbon nanotubes.     

Characterisation of interphase nanoscale property variations in glass fibre reinforced polypropylene and epoxy resin composites

The local microstructure can be altered significantly by various fibre surface modifications, causing property differences between the interphase region and the bulk matrix. By using tapping mode phase imaging and nanoindentation tests based on the atomic force microscope (AFM), a comparative study of the sized fibre surface topography and modulus as well as the local mechanical property variation in the interphase of E-glass fibre reinforced epoxy resin and E-glass fibre reinforced modified polypropylene (PPm) matrix composites was conducted. The phase imaging AFM was found a highly useful tool for probing the interphase with much detailed information. Nanoindentation experiments indicated the chemical interaction during processing caused by a gradient profile in the modulus across the interphase region of γ-aminopropyltriethoxy silane (γ-APS) and polyurethane (PU)-sized glass fibre reinforced epoxy composite. The interphase with γ-APS/PU sizing is much softer than the PPm matrix, while the interphase with the γ-APS/PP sizing is apparently harder than the matrix, in which the modulus was constant and independent of distance away from the fibre surface. The interphase thickness varied between less than 100 and ≈300 nm depending on the type of sizing and matrix materials. Based on a careful analysis of ‘boundary effect’, nanoindentation with sufficient small indentation force was found to enable measuring of actual interphase properties within 100 nm region close to the fibre surface. Special emphasis is placed on the effects of interphase modulus on mechanical properties and fracture behaviour. The interphase with higher modulus and transcrystalline microstructure provided simultaneous increase in the tensile strength and the impact toughness of the composites.     

Numerical characterisation of fullerene based polymer nanocomposites considering interface effects

In this investigation, the effective mechanical properties of fullerene nanocomposites considering interface effects were characterised. Load transfer in nanocomposite materials is achieved through the fullerene/matrix interface. Thus, to determine nanocomposite mechanical properties, the interface behaviour must be determined. A single fullerene and the surrounding polymer matrix are modelled. Two cases of perfect bonding and an elastic interface are considered. Two models are suggested for elastic interface. The first elastic interface model consists of a thin layer of an elastic material surrounding the fullerene. In the second elastic interface model, a series of spring elements are used as the fullerene/matrix interface. The results of numerical models indicate the importance of adequate interface bonding for a more effective strengthening of polymer matrix by fullerene. Also, Young’s modulus prediction for fullerene in epoxy matrix is compared to experimental data investigated by Rafiee et al. (2011), and good agreement is observed.     

Challenges and Progress in High‐Throughput Screening of Polymer Mechanical Properties by Indentation

Depth‐sensing or instrumented indentation is an experimental characterization approach well‐suited for high‐throughput investigation of mechanical properties of polymeric materials. This is due to both the precision of force and displacement, and to the small material volumes required for quantitative analysis. Recently, considerable progress in the throughput (number of distinct material samples analyzed per unit time) of indentation experiments has been achieved, particularly for studies of elastic properties. Future challenges include improving the agreement between various macroscopic properties (elastic modulus, creep compliance, loss tangent, onset of nonlinear elasticity, energy dissipation, etc.) and their counterpart properties obtained by indentation. Sample preparation constitutes a major factor for both the accuracy of the results and the speed and efficiency of experimental throughput. It is important to appreciate how this processing step may influence the mechanical properties, in particular the onset of nonlinear elastic or plastic deformation, and how the processing may affect the agreement between the indentation results and their macroscopic analogues.     

Inherent sensing and interfacial evaluation of carbon nanofiber and nanotube/epoxy composites using electrical resistance measurement and micromechanical technique

Inherent sensing of load, micro-damage and stress transferring effects were evaluated for carbon nanotube (CNT) and carbon nanofiber (CNF)/epoxy composites (with various added contents) by an electro-micromechanical technique, using the four-point probe method. Carbon black (CB)/epoxy composites, with conventional nanosize material added, were used for the comparison with CNT and CNF composites. Subsequent fracture of the carbon fiber in the dual matrix composites (DMC) was detected by acoustic emission (AE) and by the change in electrical resistance, ΔR due to electrical contacts of neighboring CNMs. Stress/strain sensing of the nanocomposites was detected by an electro-pullout test under uniform cyclic loading/subsequent unloading. CNT/epoxy composites showed the best sensitivity to fiber fracture, matrix deformation and stress/strain sensing, whereas CB/epoxy composite exhibited poorer sensitivity. From the apparent modulus (as a result of matrix modulus and interfacial adhesion), the stress transferring effects reinforced by CNT was highest among three CNMs. The thermodynamic work of adhesion, W_a as found by dynamic contact angle measurements of the CNT/epoxy composite as a function of added CNT content was correlated and found to be consistent with the apparent mechanical modulus. Uniform dispersion and interfacial adhesion appear to be key factors for improving both sensing and mechanical performance of nanocomposite. Thermally treated-CNF composites exhibited a slightly higher apparent modulus, whereas higher testing temperatures appeared to lower the apparent modulus.     

Thermo-mechanical properties of randomly oriented carbon/epoxy nanocomposites

The thermo-mechanical properties of epoxy-based nanocomposites based on low weight fractions (from 0.01 to 0.5 wt%) of randomly oriented single- and multi-walled carbon nanotubes were examined. Preparation methods for the nanocomposites, using two types of epoxy resins, were developed and good dispersion was generally achieved. The mechanical properties examined were the tensile Young's modulus by Dynamic Mechanical Thermal Analysis and the toughness under tensile impact using notched specimens. Moderate Young's modulus improvements of nanocomposites were observed with respect to the pure matrix material. A particularly significant enhancement of the tensile impact toughness was obtained for specific nanocomposites, using only minute nanotube weight fractions. No significant change in the glass transition temperature of SWCNT/epoxy nanocomposites was observed, compared to that of the epoxy matrix. The elastic modulus of the SWNT-based nanocomposites was found to be slightly higher than the value predicted by the Krenchel model for short-fiber composites with random orientation.     

Numerical characterization of CNT-based polymer composites considering interface effects

Carbon nanotubes (CNTs) possess exceptional mechanical properties and are therefore suitable candidates for use as reinforcements in composite materials. Load transfer in nanocomposite materials is achieved through the CNT/matrix interface. Thus, to determine nanocomposite mechanical properties, the interface behavior must be determined. In this investigation, finite element method is used to investigate the effects of interface strength on effective CNT-based composite mechanical properties. Nanocomposite mechanical properties are evaluated using a 3D nanoscale representative volume element (RVE). A single nanotube and the surrounding polymer matrix are modeled. Two cases of perfect bonding and an elastic interface are considered. For the perfect bonding interface, the no slip conditions are applied. To better investigate the elastic interface behavior, two models are proposed for this type of interface. The first elastic interface model consists of a thin layer of an elastic material surrounding the CNT. In the second elastic interface model, a series of spring elements are used as the nanotube/matrix interface. The results of numerical models indicate the importance of adequate interface bonding for a more effective strengthening of polymer matrix by CNT’s.     

Mechanical properties of magnetite (Fe3O4), hematite (α-Fe2O3) and goethite (α-FeO·OH) by instrumented indentation and molecular dynamics analysis

Hardness and elastic properties of pure (crystal) and complex (product of corrosion) iron oxides, magnetite (Fe₃O₄), hematite (α-Fe₂O₃) and goethite (α-FeO·OH), were determined by means of molecular dynamics analysis (MDA) and instrumented indentation. To determine local mechanical properties by indentation, multicyclic loading is performed by using incremental mode. Moreover to study the influence of visco-elastoplastic behaviour of the material, various load-dwell-times were applied at each loading/unloading cycle. To support the indentation results, molecular dynamics analysis based on shell model potential is performed for pure oxides to determine Young's modulus, bulk modulus, Poisson's ratio and shear modulus. The comparison between experimental and theoretical values both with the literature data allows the evaluation of the mechanical properties of the pure oxides. Subsequently, this allows the validation of the mechanical properties of complex oxides which can only be deduced from indentation experiments.     

Nanoindentation in polymer nanocomposites

This article reviews recent literature on polymer nanocomposites using advanced indentation techniques to evaluate the surface mechanical properties down to the nanoscale level. Special emphasis is placed on nanocomposites incorporating carbon-based (nanotubes, graphene, nanodiamond) or inorganic (nanoclays, spherical nanoparticles) nanofillers. The current literature on instrumented indentation provides apparently conflicting information on the synergistic effect of polymer nanocomposites on mechanical properties. An effort has been done to gather information from different sources to offer a clear picture of the state-of-the-art in the field. Nanoindentation is a most valuable tool for the evaluation of the modulus, hardness and creep enhancements upon incorporation of the filler. It is shown that thermoset, glassy and semicrystalline matrices can exhibit distinct reinforcing mechanisms. The improvement of mechanical properties is found to mainly depend on the nature of the filler and the dispersion and interaction with the matrix. Other factors such as shape, dimensions and degree of orientation of the nanofiller, as well as matrix morphology are discussed. A comparison between nanoindentation results and macroscopic properties is offered. Finally, indentation size effects are also critically examined. Challenges and future perspectives in the application of depth-sensing instrumentation to characterize mechanical properties of polymer nanocomposite materials are suggested.     

Reinforcing epoxy resin with nitrogen doped carbon nanotube: A potential lightweight structure material

The outstanding mechanical properties of nanocarbon materials, especially carbon nanotube (CNT), make them one of the most promising reinforcing nanofillers for the high-performance lightweight structural material. However, the complicated but not eco-friendly surface functionalization processes (e.g. HNO₃ oxidation) are generally necessary to help disperse nanocarbon materials into epoxy or build chemical bonds between them. Herein, nitrogen doped carbon nanotube (NCNT) was used to replace CNT to reinforce the epoxy resin, and the mechanical properties of the NCNT/epoxy nanocomposite showed significant superiorities over the CNT/epoxy nanocomposites. The fabrication process was simple and environmentally friendly, and avoided complicated, polluting and energy intensive surface functionalization processes. Moreover, the NCNT/epoxy suspension exhibited a relative low viscosity, which was favorable for the subsequent application. The reinforcing mechanism of NCNT was also proposed. The present work gives out an easy solution to the preparation of a high-performance nanocomposite as a potential lightweight structure material.     

Application of instrumented falling dart impact to the mechanical characterization of thermoplastic foams

The applicability of instrumented falling weight impact techniques in characterizing mechanically thermoplastic foams at relatively high strain rates is presented in this paper. In order to try simulating impact loading of foams against sharp elements, an instrumented dart having a hemispherical headstock was employed in the tests. Failure strength and toughness values were obtained from high-energy impact experiments, and the elastic modulus could be measured from both flexed plate and indentation low-energy impact tests. The results indicate a dependence of the failure strength, toughness, and the elastic modulus on the foam density, the foaming process, and the chemical composition. This influence was found to be similar to that of pure nonfoamed materials and also to that observed from low-rate compression tests. The results also indicate that the indentation low-energy impact tests were more accurate in obtaining right values of the elastic modulus than the flexed plate low-energy impact tests usually used to characterize rigid plastics. The foam indentation observed with this test configuration contributes to obtaining erroneous values of the elastic modulus if only a simple flexural analysis of plates is applied.     

Modeling carbon nanotube reinforced composite materials with the cylindrical method of cells

Micromechanics modeling, utilizing a cylindrical method of cells (CMOC) model, is employed to obtain the effective mechanical properties of an elastic transversely isotropic, isothermal material system consisting of a hollow carbon nanotube (CNT) embedded in an isotropic polymeric material matrix. It is shown that weak interfacial bonding between the CNT and polymeric matrix, which is characteristic of this type of material system, can be modeled with the CMOC. Numerical solutions of the effective independent material constants are obtained, based upon appropriate values of the properties of the carbon nanotube and epoxy matrix. The numerical results are presented graphically and compared with corresponding classical closed‐form solutions. Copyright © 2015 John Wiley & Sons, Ltd.     

压痕硬度测试法的主要研究内容及其应用

详细分析了压痕硬度测试方法自发展以来所研究的主要内容,即建立不同硬度之间的关系、硬度与弹性性能的关系、硬度与强度的关系、硬度与蠕变性能的关系、材料显微组织对硬度的影响以及硬度在薄膜力学测试中的应用等。其中,研究重点主要集中在建立硬度与力学性能参量之间的数学关系方面,即通过压痕硬度测试中获取的有关数据来得到相关的力学参量。同时提出了压痕硬度测试法的研究现状及存在的主要问题。     

Characterization of epoxy functionalized graphite nanoparticles and the physical properties of epoxy matrix nanocomposites

This work presents a novel approach to the functionalization of graphite nanoparticles. The technique provides a mechanism for covalent bonding between the filler and matrix, with minimal disruption to the sp² hybridization of the pristine graphene sheet. Functionalization proceeded by covalently bonding an epoxy monomer to the surface of expanded graphite, via a coupling agent, such that the epoxy concentration was measured as approximately 4 wt.%. The impact of dispersing this material into an epoxy resin was evaluated with respect to the mechanical properties and electrical conductivity of the graphite–epoxy nanocomposite. At a loading as low as 0.5 wt.%, the electrical conductivity was increased by five orders of magnitude relative to the base resin. The material yield strength was increased by 30% and Young’s modulus by 50%. These results were realized without compromise to the resin toughness.     

Mechanical and thermal behavior of non-crimp glass fiber reinforced layered clay/epoxy nanocomposites

Mechanical and thermal properties of non-crimp glass fiber reinforced clay/epoxy nanocomposites were investigated. Clay/epoxy nanocomposite systems were prepared to use as the matrix material for composite laminates. X-ray diffraction results obtained from natural and modified clays indicated that intergallery spacing of the layered clay increases with surface treatment. Tensile tests indicated that clay loading has minor effect on the tensile properties. Flexural properties of laminates were improved by clay addition due to the improved interface between glass fibers and epoxy. Differential scanning calorimetry (DSC) results showed that the modified clay particles affected the glass transition temperatures (T_g) of the nanocomposites. Incorporation of surface treated clay particles increased the dynamic mechanical properties of nanocomposite laminates. It was found that the flame resistance of composites was improved significantly by clay addition into the epoxy matrix.