Effect of fiber surface treatments on the fiber–matrix interaction in banana fiber reinforced polyester composites

Cellulosic fibers have been used as cost-cutting fillers in plastic industry. Among the various factors, the final performance of the composite materials depends to a large extent on the adhesion between the polymer matrix and the reinforcement and therefore on the quality of the interface. To achieve optimum performance of the end product, sufficient interaction between the matrix resin and the cellulosic material is desired. This is often achieved by surface modification of the resin or the filler. Banana fiber, the cellulosic fibers obtained from the pseudo-stem of banana plant (Musa sepientum) is a bast fiber with relatively good mechanical properties. The fiber surface was modified chemically to bring about improved interfacial interaction between the fiber and the polyester matrix. Various silanes and alkali were used to modify the fiber surface. Modified surfaces were characterized by SEM and FTIR. The polarity parameters of the chemically modified fibers were investigated using the solvatochromic technique. The results were further confirmed by electrokinetic measurements. Chemical modification was found to have a profound effect on the fiber–matrix interactions. The improved fiber–matrix interaction is evident from the enhanced tensile and flexural properties. The lower impact properties of the treated composites compared to the untreated composites further point to the improved fiber–matrix adhesion. In order to know more about the fiber–matrix adhesion, fractured surfaces of the failed composites where further investigated by SEM. Of the various chemical treatments, simple alkali treatment with NaOH of 1% concentration was found to be the most effective. The fiber–matrix interactions were found to be dependent on the polarity of the modified fiber surface.     

The influence of particle distribution and interphase on the thermal expansion coefficient of particulate composites by the use of a new model

In this work, the thermal expansion coefficient (CTE) of a composite containing spherical particles surrounded by an inhomogeneous interphase embedded in an isotropic matrix is evaluated by means of a new model. The thermomechanical properties of the interphase are formulated as continuous radial functions. It is assumed that this third phase developed between the polymeric matrix and the filler particles contains both areas of absorption interaction in polymer surface layers onto filler particles as well as areas of mechanical imperfections. It can be said that the concept of boundary interphase is a useful tool to describe quantitatively the adhesion efficiency between matrix and particles and that there is an effect of this phase on the thermomechanical properties of the composite. The thickness and volume fraction of this phase were determined from heat capacity measurements for various filler contents. On the other hand, it is assumed that the particle arrangement (distribution) which can be considered as an influence of neighboring inclusions and their interaction should affect the thermomechanical constants of the composite. The theoretical predictions were compared with experimental results as well as with theoretical values from expressions obtained from other workers and they were found to be in satisfactory agreement.     

Interphase formation and fiber matrix adhesion in carbon fiber reinforced epoxy resin: influence of carbon fiber surface chemistry

The chemistry and morphology of the carbon fiber surface are important parameters which govern the properties of the interfacial region and the adhesion between carbon fibers and polymeric matrix in carbon fiber reinforced polymers. In the presented paper the surface chemistry of the fibers is varied while the surface morphology is left unchanged. We analyze chemical functionality and morphology of carbon fiber surfaces showing different degrees of activation, together with the adhesion of these fibers to an epoxy matrix and the width of the interfacial region between fiber and matrix. An increase of the oxygen and nitrogen concentration of the fiber surface, in particular in form of carboxyl functional groups, results in a significant increase of interfacial shear strength. Also the width of the interphase, as determined by scanning force microscopy in nanomechanical mode, depends on the activation degree of the carbon fibers. However, no direct correlation between interphase width, surface chemistry and fiber matrix adhesion is found, suggesting no direct influence of interphase width on adhesion properties.     

Interphase Modelling of Human Osteoblasts Spread on Pure Titanium Surface Covered with TiO2 Nanotubes

The purpose of the present work was to define some parameters of compatibility between the titanium nanotubes surface and the human cells layer. The nanotube–matrix interphase provided the necessary information concerning the possibility of compatibility between a titanium prosthesis and human tissue. An important point of view was the biomechanical response of the interphase created by the surfaces involved (interface modelling). The viscoelastic hybrid interphase model developed for the determination of the interphasial stress and strain fields as well as for the prediction of the stiffness variation within the area of the interphase material has been applied in the special case of a substrate containing human osteoblasts and the pure titanium surface covered with titanium nanotubes. The results showed that in order to achieve a strong fixation of the metal to the tissue while at the same time to develop a good environment for the development of the osteoblast cells, extreme values corresponding to both, perfect adhesion or zero adhesion, should be excluded. It was found that the optimum condition is achieved for nanotube–matrix adhesion factor 'k' of intermediate value.     

Effect of surface-grafted molecular brushes on the adhesion performance of bonded polymers and composite interfaces

This paper reviews the theoretical principles of the macromolecular design of polymer interface/interphase systems for obtaining maximum adhesion and fracture performance of composite materials and adhesively bonded assemblies. Subsequently, a relatively simple and industry-feasible technology for surface grafting molecular brushes is discussed in detail and supported by a range of experimental examples. It is shown, in agreement with contemporary theory, that the use of chemically attached graft chemicals of controlled spatial geometry and chemical functionality enables a significant increase in the strength and fracture energy of the interphase, to the point of cohesive fracture of the substrate, or that of an adjacent medium such as adhesive, elastomer or matrix material. This occurs even after prolonged exposure of investigated systems to adverse environments such as hot water.     

The influence of structure of the interface and interphase on paint adhesion

It has been demonstrated earlier that significant adhesion enhancement to chemically inert polyolefins can be attained through surface grafted connector molecules reactive with oxidized substrate surface. The effectiveness of adhesion improvement through such tethered interfaces was shown to depend on the mode of interaction with the adjacent medium: interpenetration or chemical reaction, as well as surface density and length of grafted molecules. We have frequently observed that some systems, such as in painted products, fail through the delamination of the coating from the substrate surface at the stress levels well below the anticipated load-bearing capacity of the tethered interface. Two interim hypotheses have been formulated to explain the observed phenomenon: (i) The chain scission in surface oxidized polyolefins takes place not only in the uppermost polymer surface, but may propagate into the sub-surface region, thus creating a weak boundary layer which fails cohesively through its bulk, (ii) In order to increase the load-bearing capacity of the interphase, the sub-surface region of the substrate needs to be reinforced by short-chain molecules penetrating into and subsequently providing effective crosslinks between individual fragments of excessively oxidized and hence, weaker sub-surface part of the interphase. In this paper we verify the above hypotheses. The oxidized sub-surface layer reinforced by polyethyleneimine becomes an integral part of the effective interphase in addition to the tethered interface and the interpenetrated network of connector molecules and the paint.     

Stress field calculation around a particle in elastic–plastic polymer matrix under multiaxial loading as basis for the determination of adhesion strength

The stress distribution around a single particle coated with an elastic interphase embedded within an elastic–plastic polymer matrix under multiaxial load was considered. The specimen has a curved (necked) geometry, which causes multiaxial local stresses in the neighbourhood of the particle. The motivation for the calculations is to determine the maximum radial stress (debonding strength) at the particle surface as a function of applied load. The effect of the particle size on failure initiation is considered. Assuming that the normal stress at the interface is responsible for debonding, the adhesion strength can be determined from the critical load at debonding initiation. Because of the matrix yielding, the relation between the applied load and the maximum radial stress at the particle/interphase interface is a non-linear one. Using this relation, the determination of interfacial strength will be possible by a tensile test.     

Study on the algorithm of computational ghost imaging based on discrete fourier transform measurement matrix

We have developed a model and realized an algorithm for the calculation of the coefficient of coherent (direct) transmission of light through a layer of liquid crystal (LC) droplets in a polymer matrix. The model is based on the Hulst anomalous diffraction approximation for describing the scattering by an individual particle and the Foldy-Twersky approximation for a coherent field. It allows one to investigate polymer dispersed LC (PDLC) materials with homogeneous and inhomogeneous interphase surface anchoring on the droplet surface. In order to calculate the configuration of the field of the local director in the droplet, the relaxation method of solving the problem of minimization of the free energy volume density has been used. We have verified the model by comparison with experiment under the inverse regime of the ionic modification of the LC-polymer interphase boundary. The model makes it possible to solve problems of optimization of the optical response of PDLC films in relation to their thickness and optical characteristics of the polymer matrix, sizes, polydispersity, concentration, and anisometry parameters of droplets. Based on this model, we have proposed a technique for estimating the size of LC droplets from the data on the dependence of the transmission coefficient on the applied voltage.     

Structural model for the reinforcement of polymethyl methacrylate/carbon nanotube nanocomposites at an ultralow nanofiller content

The structural basis of the anomalously high reinforcement of polymer/carbon nanotube nanocomposites at an ultralow nanofiller content is studied. This effect is shown to be caused by the absence of interaction between carbon nanotubes and the related sharp increase in the interphase adhesion. From the standpoint of a nanofiller structure, the effect disappears when three critical points related to the structure of carbon nanotubes in a polymer matrix are reached. These points are a percolation threshold, an aggregative nanofiller stability threshold, and the beginning of formation of closed circular carbon nanotube structures.     

Effect of surface elasticity on scattering of elastic P-waves from a nanofiber including an inhomogeneous interphase

Scattering of elastic P-waves from a nanofiber in a matrix is studied analytically throughout this paper. An inhomogeneous interphase region is considered between the nanofiber and the matrix. Dividing the interphase into homogeneous sublayers, surface elasticity effects are studied in the layers adjacent to matrix and nanofiber. Wave function expansion method is used to solve the corresponding equations in all three phases including fiber, interphase, and matrix. Dynamic stress concentration factors around the nanofiber are calculated and utilizing a parametric study, effects of different parameters, such as nanoscale interface, interphase thickness, and interphase rigidity are investigated. The results indicate that considering the effects of surface elasticity in wave scattering problems from inhomogeneous interphases show a major impact on the results. The dimensionless equations presented in this paper provide the possibility of further numerical studies.     

Investigating interphase development in woodpolymer composites by inverse gas chromatography

The influence of secondary interactions on the development of interfacial structure in composites of wood and amorphous thermoplastic polymers is not well understood. This study used inverse gas chromatography to investigate the effect of different polymers on the surface energy of partially or fully coated white pine wood meal. In this way, the development of the interphase was monitored as a function of polymer depth on the wood surface. The polymers were selected to provide a range of functional groups and included polystyrene, poly(methyl methacrylate), poly(vinyl chloride), polymethacrylic acid, and polymethacrylonitrile. The overall variation of the dispersive component of the surface energy and the ratio of acceptor to donor coefficients appeared to group themselves into two categories based upon the polarity of the polymer's functional groups. In addition, the high loadings required for stabilization of the less polar polymers suggested that a relatively large volume of the matrix phase is affected by the wood filler.     

Application of nano-indentation, nano-scratch and single fibre tests in investigation of interphases in composite materials

Three novel experimental techniques were employed in this work in order to investigate the influence of the interphase region in polymer–glass composites on the bulk material properties: (i) the microdroplet test is a single fibre test designed to characterize the fibre–matrix bond (interface region) and to determine the interfacial shear stress in composite material; (ii) the nano-indentation test, a novel nano-hardness technique with ability to produce an indent as low as a few nanometres was employed in order to measure nano-hardness of the fibre–matrix interphase region; and (iii) the nano-scratch test, used in conjunction with the nano-indentation test for measurement of the interphase region width. The microdroplet test (MDT) has been used to characterize the interfacial bond in fibrous composite materials. The specimen consists of a fibre with a drop of cured resin pulled while the drop is being supported by a platinum disc with a hole. A properly tested specimen fails at the droplet’s tip–fibre interface, revealing the ultimate interfacial shear strength. In this study, finite element analysis (FEA) of the MDT has been focused toward simulation of the fibre–matrix interphase region. The influence of several functional variations of the material properties across the interphase layer on the stress distribution at the droplet’s tip was analysed. The results showed that the variation of the interphase properties significantly affects the stress distribution at the fibre–droplet interface, and, therefore, the stress redistribution to composite material. These results led to further experimental investigation of the interphase region, in order to obtain the material properties essential for the interfacial stress analysis. The interphase region in dry and water aged polymer–glass composite materials was investigated by means of the nano-indentation and the nano-scratch techniques. The nano-indentation test involved indentation as small as 30 nm in depth, produced along a 14 μm path between the fibre and the matrix. The distinct properties of the interphase region were revealed by 2–3 indents in dry materials and up to 15 indents in water aged, degraded materials. These results indicated interdiffusion in water aged interphase regions. The nano-scratch test involves moving a sample while being in contact with a diamond tip. The nano-scratch test, used in conjunction with the nano-indentation test, accurately measured the width of the interphase region. The results showed that the harder interphase region dissolved into the softer interphase region (both regions being harder/stronger than the matrix) expanding its width after aging in water.     

Roughness and fibre reinforcement effect onto wettability of composite surfaces

Wettability of glass/epoxy and carbon/epoxy composites materials has been determined via sessile drop technique. Good-Van Oss approach has been used to evaluate surface free energy parameters of smooth and rough surfaces. Results obtained point out the influence of fibre reinforcement on surface free energy of composite materials. In addition, the interest of surface treatment to increase surface roughness has been discussed in terms of wettability. To sum up, results obtained clearly demonstrate the necessity of considering properties of a given composite surface not only as a polymer but a fibre/polymer couple. The drawn conclusions are of great interest as it may have numerous consequences in applications such as adhesion.     

Biomass-derived oxygenate reforming on Pt(111): A demonstration of surface science using d-glucose and its model surrogate glycolaldehyde

Molecules derived from cellulosic biomass, such as glucose, represent an important renewable feedstock for the production of hydrogen and hydrocarbon-based fuels and chemicals. Development of efficient catalysts for their reformation into useful products is needed; however, this requires a detailed understanding of their adsorption and reaction on catalytically active transition metal surfaces. In this paper we demonstrate that the standard surface science techniques routinely used to characterize the reaction of small molecules on metals are also amenable for use in studying the adsorption and reaction of complex biomass-derivatives on single crystal metal surfaces. In particular, Temperature Programmed Desorption (TPD) and High Resolution Electron Energy Loss Spectroscopy (HREELS) combined with Density Functional Theory (DFT) calculations were used to elucidate the adsorption configuration of d-glucose and glycolaldehye on Pt(111). Both molecules were found to adsorb in an η₁ aldehyde configuration partially validating the use of simple, functionally-equivalent model compounds for surface studies of cellulosic oxygenates.     

Surface Interactions at the Phase Interface in the Boron Oxide–Polypropylene System

The interphase interaction of highly dispersed boron oxide (99.3% of B ¹¹) in a polypropylene matrix has been investigated by IR spectroscopy. In the region of absorption of hydroxyl groups, maxima at 3500 and 3340 cm^–1 had been detected, which were assigned to the surface OH groups which interact with the polymer matrix and which respectively are bound with the trigonally and tetrahedrally coordinated boron atoms.     

Plasma‐Substrate Interaction during Plasma Deposition on Polymers

The initial stage of film growth during plasma deposition on polymers determines many film properties such as morphology and structure, interphase formation and adhesion. Therefore, the plasma‐substrate interaction is investigated regarding the energy density during film growth, which is defined by the energy flux per depositing atom. The flux of film‐forming species and the flux of energetic particles were determined for metal sputtering (silver films) and plasma polymer deposition (amino‐functional hydrocarbon films). It is shown that enhanced energy densities can be obtained during the initial film growth due to reduced deposition rates and mixing with the polymer substrate (interphase formation). Thus, good adhesion on polymers such as polyethylene terephthalate (PET) has been achieved. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Calculation of ionic crystal-metal interaction characteristics

The adhesion properties of composites based on simple metals and ionic crystals with an NaCl lattice are investigated using the electron density functional method. Corrections due to the nonuniformity of the electron density and the discrete nature of the crystal structure are taken into account. The interphase energy, the adhesion energy and the adhesion interaction forces are calculated as a function of the distance between the surfaces of the contacting materials.     

Physico-chemical characterization of the fibre/matrix interaction in polyethylene fibre/epoxy matrix composites

The interphase in polyethylene fibre/epoxy matrix composites is studied with FT-IR microspectroscopy using a set-up to investigate the matrix as close to the fibre as a few μm or less. It is shown that moisture present on the fibre surface is able to influence the polymerization reaction of the epoxy/anhydride matrix in an irreversible manner. This effect is enhanced for composites from the more hydrophilic polyvinylalcohol fibre. The fibre/matrix interaction in these thermoplastic fibre composites is also studied with DSC through the characterization of the fibre melting. A decreased 'DSC interaction parameter' is found if the composition of the interphase is changed by moisture. For a composite with an epoxy/amine matrix, on the other hand, the DSC interaction parameter is unaffected by moisture from the fibre surface.     

Probing bacterial interactions: integrated approaches combining atomic force microscopy, electron microscopy and biophysical techniques

Recent developments in the application of Atomic Force Microscopy (AFM) and other biophysical techniques for the study of bacterial interactions and adhesion are discussed in the light of established biological and microscopic approaches. Whereas molecular-biological techniques combined with electron microscopy allow the identification and localization of surface constituents mediating bacterial interactions, with AFM it has become possible to actually measure the forces involved in bacterial interactions. Combined with the flexibility of AFM in probing various types of physical interactions, such as electrostatic interactions, specific ligand-receptor interactions and the elastic forces of deformation and extension of bacterial surface polymers and cell wall, this provides prospects for the elucidation of the biophysical mechanism of bacterial interaction. However, because of the biochemical and a biophysical complexity of the bacterial cell wall, integrated approaches combining AFM with electron microscopy and biophysical techniques are needed to elucidate the mechanism by which a bacterium interacts with a host or material surface. The literature on electron microscopy of the bacterial cell wall is reviewed, with particular emphasis on the staining of specific classes of cell-wall constituents. The application of AFM in the analysis of bacterial surfaces is discussed, including AFM operating modes, sample preparation methods and results obtained on various strains. For various bacterial strains, the integration of EM and AFM data is discussed. Various biophysical aspects of the analysis of bacterial surface structure and interactions are discussed, including the theory of colloidal interactions and Bell's theory of cell-to-cell adhesion. An overview is given of biophysical techniques used in the analysis of the properties of bacterial surfaces and bacterial surface constituents and their integration with AFM. Finally, we discuss recent progress in the understanding of the role of bacterial interactions in medicine within the framework of the techniques and concepts discussed in the paper.     

脉冲高能量密度等离子体材料表面改性及其应用

脉冲高能量密度等离子体（pulsed high energy density plasma, PHEDP）是一项新的材料表面改性技术.它集高电子温度、高能量密度、高定向速度于一身,在制备薄膜时具有沉积薄膜的温度低、沉积效率高、能量利用率高的优点,并兼具表面溅射、离子注入、冲击波和强淬火效应等综合效应;它可以制备纳米晶或非晶硬质薄膜,提高基底材料的表面硬度和耐磨、耐蚀性能;能够实现非金属材料表面金属化,所制备薄膜与基底之间存在很宽的混合过渡区,因此膜/基结合良好.文章主要介绍了作者近年来在该领域的部分研究成果,简要介绍了脉冲高能量密度等离子体的原理、特点及应用.分析了脉冲等离子体与材料相互作用的基本物理现象.