Experimental evidence for reduced chain segment mobility in poly(amide)-6/clay nanocomposites

Poly(amide)-6/clay nanocomposites are investigated by means of modulated temperature differential scanning calorimetry. The importance of polymer–filler interaction is explored by comparing nanocomposites based on untreated and organically modified clay. During quasi-isothermal crystallization experiments, an excess contribution is observed in the recorded heat capacity signal due to reversible melting and crystallization. The magnitude of this excess contribution depends on the nanocomposite investigated. We suggest that it is directly related to the segmental mobility of the polymer chains in the interphase region. As such, the magnitude of this excess contribution can be used to quantify the efficiency of the polymer–clay interaction. Depending on the clay type used, differences in interfacial interaction can be achieved, which is of great importance with respect to the improvement of material properties. Based on thermal analysis results, a simple interphase model is proposed that is able to account for both the thermal and mechanical properties of poly(amide)-6/clay nanocomposites.     

The Role of Interfacial Interactions in the Toughening of Precipitated Calcium Carbonate–Polypropylene Nanocomposites

This paper investigates the effect of the interphase properties and the interfacial interactions between matrix and filler on mechanical properties of precipitated calcium carbonate (PCC)–polypropylene nanocomposites. PCC particles were coated with stearic acid (SA). The weight ratio of SA on the particles (w _SA) ranged from 0 to 0.135 g SA/g PCC. The introduction of PCC particles resulted in an increase in stiffness and yield stress compared with the pristine polymeric matrix and, at the same time, it increased the impact resistance. The maximum improvement in the impact behaviour was achieved for the composites with w _SA =0.045 corresponding to the theoretical monolayer ratio. A decrease in interfacial interactions between monolayer coated PCCs and the matrix with respect to the uncoated particles was observed by using a semi-empirical equation developed by Pukànszky. The low degree of interfacial interactions between particulate filler and matrix allows a matrix–particle debonding phenomenon, as shown by scanning electron microscopy analysis. Extensive plastic deformations were evident as well, promoting an improvement in toughness. The thickness of the interphase between particles and matrix was evaluated by using the Shen–Li model which is based on the hypothesis of a non-homogeneous interphase. It results that the thickness increased in the order uncoated < monolayer coated < 3% SA coated ? 13.5% SA coated particles. The thinner and stronger interphase found for the composite with uncoated particles can be explained with the high interaction between matrix and filler and the consequent low mobility of the polymeric chains.     

Interfacial region in blends of linear polymers formed in situ

Blends of linear polyurethane and poly(methyl methacrylate) were obtained by the simultaneous curing of the mixture of two monomers. It was shown that the blends obtained in situ are two-phase systems in which two phases enriched in one of the blend components are separated by an intermediate region, the interphase. From the DSC data the compositions of two phases were estimated. It was observed that introduction of a filler leads to the appearance of an additional temperature transition lying between glass transition temperatures of the two phases. The fraction of the interphase was calculated from the calorimetric data. The introduction of a filler increases this fraction. This may be considered as some improving of compatibility of the two components in the presence of a filler.     

Thickness dependence of elastic modulus of polycarbonate interphase

The oligomer of bis-phenol A (oligo-PC) with M _w = 1300 and bis-phenol A polycar-bonate (PC) with M _w = 20 000 were deposited onto E-glass surface using SiCl₄ as the grafting and cross-linking agent. Thickness of the deposited layers was varied from 30 to 10⁶ nm and the layers were investigated as prepared and after thermal annealing at 245°C for 10 min in the air. Vibrational piezoelectric resonator technique and the speed of Rayleigh wave measurement were used to determine elastic moduli of the ultra thin layers deposited on flat E-glass substrate as a function of their thickness. In all cases, increase of the Young modulus of the interphase, E _i, with decreasing layer thickness, t _i, was observed. At a given thickness, the E _i of PC layer was significantly lower than that for the oligo-PC layer. Thermal annealing of the deposited PC layer resulted in a significant increase of its E _i compared to the as received layer. No significant change was observed for oligo-PC interphases. Increase of the shear strength of the interface, τ _a, with reducing interphase thickness, t _i, was observed. The observed increase of E _i with the decreasing t _i was ascribed to the reduction of the molecular mobility of chains near solid surface compared to their mobility in the bulk. Most probably, the observed increase of E _i after thermal annealing of PC was caused by rearrangement of both segment density distribution in individual PC coils near the solid surface and cooperative rearrangements of multiple PC chains. Since the oligomers attached to the surface attained presumably more regular extended conformations with lower conformation entropy compared to the PC random coils, the effect of thermal annealing was negligible. In agreement with theoretical predictions, increase of E _i at the same extent of interfacial interactions resulted in the observed increase of the τ _a measured using the single embedded fiber test.     

T1 THEOREM FOR BESOV SPACES ON NONHOMOGENEOUS SPACES

Suppose μ is a Radon measure on Rd, which may be non doubling. The only condition assumed on μ is a growth condition, namely, there is a constant Co ＞ 0 such that for all x ∈ supp(μ) and r ＞ 0,μ(B(x,r)) ≤ Corn, where 0 ＜ n ≤ d. We prove T1 theorem for non doubling measures with weak kernel conditions. Our approach yields new results for kernels satisfying weakened regularity conditions, while recovering previously known Tolsa's results. We also prove T1 theorem for Besov spaces on nonhomogeneous spaces with weak kernel conditions given in [7].     

The Effect of ZrO2 Interphase on Interfacial Frictional Stresses in SiC/ZrO2/SiCf Composites

Two types of SiC fiber tows (Hi-Nicalon? and Hi-Nicalon S?) were coated with stabilized ZrO₂ and composited using preceramic polymer impregnation pyrolysis to form SiC/SiC_f minicomposites. Properties of the fiber/matrix interface in composites were investigated using the indentation method in which a pyramidal indenter was used to push on an individual fiber and cause sliding at the interface. The interfacial frictional stresses were determined from the force–displacement relation. The composites reinforced by the ZrO₂-coated fibers have smaller interfacial frictional stresses than composites reinforced by the initial fibers and show fibers sliding relatively more easily with respect to the SiC matrix.     

Finite element prediction of debonding onset in short fiber reinforced polymers incorporating a hybrid interphase region

A robust finite element procedure for investigating damage evolution in short fiber reinforced polymeric composites under external loads is developed. This procedure is based on an axisymmetric unit cell composed of a fiber, surrounding interphase and bulk matrix. The hybrid interphase concept involves a degraded material phase, the extent of which is material and property dependent. One of the most significant features of the model relies on establishment of variable adhesion conditions between the primary material phases. The unit cell is discretized into linearly elastic elements for the fiber and the matrix and interface elements which allow debonding in the fiber–matrix interface. The interface elements fail according to critical stress and critical energy release rate criteria. The tension and shear aspects of failure are uncoupled, although the resulting nonlinear problem is solved implicitly utilizing quasi-static incremental loading conditions. Final failure resulting from saturation and breakage is modeled by the vanishing interface element technique. Details of the propagation of interface cracks and the initiation of debonds are also observed and discussed for various shapes of fiber end. Numerical results reveal an intense effect of the fiber-end geometry on the initial fiber–matrix de-cohesion. The present finite element procedures can generate meaningful results in the analysis of fiber-reinforced composites.     

Effect of Geometry,Loading and Elastic Moduli on Critical Parameters in a Nanoindentation Test in Polymeric Matrix Composites with a Nonhomogeneous Interphase

Fiber nanoindentation models are developed for polymeric matrix composites with nonhomogeneous interphases. Using design of experiments, the effects of geometry, loading and material parameters on the critical parameters of the indentation test such as the load–displacement curve, the maximum interfacial shear and normal stresses are studied. The sensitivity analysis shows that the initial load–displacement curve is dependent only on the indenter type, and not on parameters such as fiber volume fraction, interphase type, thickness of interphase, and boundary conditions. The interfacial tensile radial stresses are not sensitive to indenter type, or to type and thickness of interphase, while the interfacial compressive radial stresses are sensitive mainly to boundary conditions and thickness of interphase; however, the influence of these factors on the interfacial radial stresses can be large. In contrast, the interfacial shear stress is sensitive to all factors, but the influence of the factors is relatively small.     

A Fiber-Bundle Pull-out Test for Surface-Modified Glass Fibers in GF/Polyester Composite

The development of high-performance polymer composites is tightly bound with the functional surface modification of reinforcements. A new method, based on the principle of the fiber-bundle pull-out test, is proposed to analyze the interfacial properties between the long fibers in the form of a bundle and the polymer matrix. Specimen geometry and a test fixture were designed using finite element analysis. The method was verified for unsized and sized glass fibers embedded in polyester resin to demonstrate its applicability for a wide range of adhesion between fibers and the polymer matrix. The pull-out test can be used for a relative comparison of different surface modifications if the bundle geometry is unknown. The results of high reproducibility and sensitivity for interfacial properties make the method attractive.     

Probing the properties of particle-matrix interphase in reactive rubber-grafted polybenzoxazine resins by atomic force microscopy

Atomic force microscopy (AFM) is employed to study the amine-terminated poly (butadiene-co-acrylonitrile) (ATBN) rubber-modified polybenzoxazine resin. Topographic mapping of the fracture surface is performed in conjunction with lateral force microscopy (LFM) and force–distance curve measurements (F–d). Matrix T _g reduction is attributed to the dissolved rubber and the increased mechanical damping (tan δ) is derived from the phase-separated rubber. Saturation of the rubber in the matrix is defined at 6 wt% above which the matrix T _g is not influenced upon rubber loading. The solubility limit of the reactive rubber in the matrix phase is determined from the fractured surface using LFM. The torsional force analyzed in the matrix phase increases upon the addition of rubber and levels off at 6 wt%. The results provide a direct correlation between bulk properties acquired by DMA and fractured surface probed by AFM. The presence of interphase between the separated rubbery domain and the continuous matrix phase is confirmed and its thickness is quantified from F–d curves. Moreover, it is found that interphase properties exhibit a strong rubber-concentration dependence.