Effect of the nature of a polymer matrix on the enthalpy of adhesion interactions in composites filled with nickel nanoparticles

Interfacial interactions in composites filled with nickel nanoparticles are studied experimentally. The concentration dependences of the enthalpy of mixing of rubbery and glassy homo- and copolymers of different polarities with nickel nanoparticles coated with a carbon shell are measured via isothermal calorimetry. On the basis of these data, the values of adhesion and the structural contributions to the enthalpy of mixing are calculated. A decrease in the kinetic flexibility of macromolecular chains with an increase in the glasstransition temperature of the polymer causes a gain in the positive structural contribution to the enthalpy of mixing of the composite. The contribution of adhesion interaction is negative and predominantly determined by electrostatic forces of the induction type. The maximum enthalpy of adhesion is proportional to the squared dipole moment of a polymer unit and independent of the relaxation state of the polymer matrix.     

Influence of surface properties on the interfacial adhesion in carbon fiber/epoxy composites

A polyacrylonitrile‐based carbon fiber was electrochemically oxidized in an aqueous ammonium bicarbonate solution with current density of up to 2.76 A/m² at room temperature. X‐ray photoelectron spectroscopy revealed that the oxygen content increased with increasing current density before approaching saturation. The increase can be divided into two regions, the rapid increase region (0–1.78 A/m²) and a plateau region (1.78–2.76 A/m²). The surface chemistry analysis showed that the interlaminar shear strength (ILSS) value of the carbon fiber/epoxy composite could be improved by 24.7%. The carbon structure was examined using Raman spectroscopy in terms of order/disorder in the graphite structure and the results indicated that the relative percentage of graphite carbon in the form of sp² hybridization increased above a current density of 1.39 A/m². The increasing non‐polar graphite carbon on the carbon fiber surface decreased the surface energy. As a result, both the surface free energy () and its polar component () decreased when current density increased above 1.78 A/m². The ILSS value had no direct relationship with the nature and surface density of the oxygen‐containing functional groups nor with the carbon structure. It is the surface free energy (), especially the polar component (), which played a critical role in affecting the interfacial adhesion of carbon fiber/epoxy composites. The ILSS value changed with increasing current density and could be divided into three distinct regions, as chemical interaction region (I), anchor force region (II) and matrix damage region (III). Copyright © 2013 John Wiley & Sons, Ltd.     

Measurement of interfacial adhesion between glassy polymers using the JKR method

The surface and interfacial energies of polymers are measured using the JKR-type experiments. A novel method has been developed to prepare samples of glassy polymers for adhesion measurements. A thin layer of a polymer is coated on the surface of an O₂-plasma modified cross-linked poly(dimethylsiloxane) [PDMS] spherical cap resulting in the formation of a composite. Using the JKR theory, the surface energies of polystyrene [PS] and poly(methyl methacrylate) [PMMA] are determined from the measurements of the contact radius as a function of applied load. The results of the JKR-type experiments are compared to adhesion measurements done using the surface forces apparatus (SFA). Adhesion hysteresis was observed for PS-PS contact as well as PMMA-PMMA contact. However, no hysteresis was observed for PDMS-PDMS, PDMS-PS, and PDMS-PMMA contacts. The exact origin of the hysteresis is not clear at present. The current evidence suggests that hysteresis is due to rearrangement of the interface during contact.     

Estimation of flocculation structure in filled polymer composites by dynamic rheological measurements

 The frequency and concentration dependences of the storage modulus (G ^′) for carbon black and short-carbon-fiber-filled polymer composites were investigated by means of dynamic rheological measurements. It was found that G ^′ at low frequencies and amplitudes could be used as a sensitive experimental parameter for detecting the flocculation structure of the ultra-fine-particle-filled polymer composites. Correlation of electrical resistivity of the composites to the relative storage modulus, G ^′ _r(=G ^′ _c/ G ^′ _p), revealed that the three-dimensional interparticle networks start to construct through the matrix when G ^′ _r increases to 7 regardless of the composite systems. Quantitative calculations in order to determine the flocculation structure were carried out by means of the modified Kerner equation. A plot of the calculated value, defined as the floc index A, dependence of electrical resistivity for various systems was found to be a universal curve. Accordingly, we suggest that A might universally correspond to the flocculation structure of the filler, which is independent of the nature of the filler, the molecular weight, the chemical composition of the polymer and the temperature at which the measurement is made. This method is particularly effective for estimating the flocculation structure of ultra-fine-particle-filled polymer composites no matter whether the filler is conductive or not. Received: 26 May 1999/Accepted in revised form: 28 September 1999     

Influence of colloidal structure of polymer mixes on adhesion strength of polyolefin compositions

Mixtures of low-density polyethylene and ethylene-vinyl acetate (EVA) copolymer are studied. It is shown that the adhesion value is defined by the polymer that forms a dispersion medium in the adhesive compositions and the type of fracture depends on the competing influence of the physical and mechanical parameters and the reduced acidity parameter of the polymer, which forms a continuous phase.     

Effect of rubbing-induced polymer chain alignment on adhesion and friction of glassy polystyrene surfaces

The friction and adhesion properties of polystyrene surfaces are studied below the glass transition temperature by means of atomic force microscopy in argon. Even at a temperature far below the glass transition, the repeated sliding of a polystyrene bead tip on the non-cross-linked polystyrene surface causes significant reduction of friction and adhesion forces. There is no measurable wear of the polystyrene surface due to repeated sliding. These decreases are associated with the alignment of the outermost polymer segments induced by repeated rubbing. There are only little changes in friction and adhesion on the cross-linked polystyrene surface in which the covalent cross-linking prevents chain realignment.     

Evolution of the structure and phase state in nonequilibrium heterogeneous polymer systems

Structural and phase transformations in the course of the multistage physical aging of semi-inter-penetrating polymer networks based on crosslinked polyurethane and linear polystyrene are studied. Dynamic mechanical and thermophysical studies make it possible to assume that, as a result of the physical aging, a heterogeneous polymer system experiences structural rearrangements and the fraction of the inter-facial region increases.     

Time dependence of piezoresistance for the conductor‐filled polymer composites

The piezoresistance and its time dependence of conductor‐filled polymer composites have been investigated. To reveal the origin of the time dependence of piezoresistance, the creep of the polymer matrix is also studied. Based on the interparticle separation change under the applied stress, a model has been developed to predict the piezoresistance and its time dependence. By analyzing this model, the influences of applied stress, filler particle diameter, filler volume fraction, matrix compressive modulus, potential barrier height, and the matrix creep behavior on the piezoresistance and its time dependence are interpreted quantitatively. These predicted results are compared with the experimental data obtained on the polymer composites filled with conductor fillers, and good agreements were obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2739–2749, 2000     

Combined SPM investigation on the interfacial structure of a phthalocyanine/conjugated polymer composite film

The morphology of the composite film of organic semiconductors determines the properties and performances of devices to a large extent. In this work, we present a combined AFM and STM study on the interfacial structures of CuPcOC8 and CuPcOC8/PmPV composite films on graphite surface. For CuPcOC8 thin films, the face-on epitaxial growth of CuPcOC8 could persist within 3 to 5 monolayers and the formation of π-π stacked columns will occur with edge-on configuration when the film thickness further increases. For the CuPcOC8/PmPV composite film with 1:1 weight ratio, STM results reveal a preferential adsorption of PmPV on graphite surface, while AFM results indicate the phase segregation in the upper layer. STM also reveals in the molecular scale good compatibility of CuPcOC8 with PmPV.     

Influence of substrate stiffness on cell-substrate interfacial adhesion and spreading: a mechano-chemical coupling model

Highly ordered three dimensionally macroporous carbon spheres (3DMPCS) were successfully prepared against removable colloidal silica crystal bead templates by carbonization of glucose. The unique structural characteristics of the well-developed three dimensionally interconnected macropores were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and nitrogen adsorption. The 3DMPCS have uniform large pore structures with size about 250 nm. Pt nanoparticles were supported on the macroporous carbon spheres by two aqueous impregnation methods, and it was found that the 3DMPCS supported Pt exhibited high electrocatalytic activity for methanol oxidation.     

Influence of an interfacial agent on the structure of polypropylene-polyamide fibres

In this paper the structure and properties of fibres prepared from the polypropylene/polyamide (PP/PA6) blend have been studied as a function of the interfacial-agent (IFA) content. For this purpose the grafted polypropylene-maleic anhydride copolymer was used. Fibres containing 20% of PA6 and 80% of PP possess the phase matrix-fibril structure. The size and distribution of fibres in the dispersed PA6 phase in the PP matrix depend on the interfacial-agent amount. Due to the indirect nucleating effect the PA6 phase has been found to act, in the presence of the interfacial agent, on the PP crystallization during fibre formation. As a result, undrawn fibres have the more pre-oriented and crystalline PP matrix with the morphological rod-like structure. The pre-orientation of the dispersed fibrilar PA6 phase is minimum. Mechanical properties of the drawn blended fibres are favourably influenced provided that the interfacial-agent concentration is higher than 1%. The growing rate of the mutual interaction between the components was mostly reflected in the increased values of Young's modulus.     

Temperature stability of the interfacial structure between a sulfonated crystalline alkyl side-chain polymer and a soft adhesive

The fracture toughness of interfaces between a sulfonated alkyl side-chain graft copolymer and a soft acrylic random copolymer containing acrylic acid monomers was investigated with a probe test method. Interfaces between a thin (100 nm) layer of the block copolymer and a thick (100 microm) layer of the acrylic copolymer were prepared at room temperature and subsequently annealed for 7 h at different temperatures. After the annealing step, the interface was quenched to room temperature and tested, a strategy that provides the advantage of keeping constant the mechanical properties of the materials on both sides of the interface so that any major difference in adhesive behavior can only be attributed to a change in the interfacial structure. For annealing temperatures below the crystalline to liquid crystalline transition temperature (86 degrees C), the adhesion energy remained very low and failure occurred by interfacial crack propagation. However when the interface was annealed above that temperature, a much higher adhesion energy was observed at room temperature because of the formation of a fibrillar structure upon debonding. The results indicate that the crystalline order at low temperature is very stable presumably because of the strong interactions between the sulfone groups in the side chains. However, when these interactions weaken and the side chains become liquid crystalline, the surface reconstruction mechanism cannot be prevented and strong interactions formed between the polar parts of the copolymer and the acrylic acid. These strong interactions remain during the cooling step, and a mechanism of surface reconstruction is proposed.     

Effects of different compatibilizing agents on the interfacial adhesion properties of polypropylene/magnesium oxysulfate whisker composites

The effects of maleic anhydride-grafted polypropylene(PP-g-MAH) and maleic anhydride-grafted polyolefin elastomer(POE-g-MAH) on interfacial adhesion properties of the polypropylene/magnesium oxysulfate whiskers(PP/MOSw) composites were investigated via mechanical, thermal, ATR-FTIR and rheological tests. Although significant increases in yield strength and Young's modulus were observed in PP-g-MAH treated composites, a sharp decline in these properties was observed in POE-g-MAH treated composites. ATR-FTIR results indicated that esterification occurred between the hydroxyl groups of MOSw and the carbonyls of anhydrides of both compatibilizers but POE-g-MAH was still incompatible with the PP matrix, as verified by the presence of shoulder peaks in DTG curves and numerous voids in SEM micrographs. On the other hand, PP-g-MAH was highly compatible with the PP matrix, as evidenced by the peaks in DTG curves and vague interfaces with wrapped melts on the surface of MOSw. Rheological behaviors also confirmed that introducing PP-g-MAH resulted in a transition from liquid-like to solid-like, which was attributed to the stronger interfacial adhesion between MOSw and the PP matrix. POE-g-MAH treated composites, in contrast to PP-g-MAH, maintained liquidlike rheological behaviors as typical molten polymers. There is likely a MOSw network formed in the PP/15PP-gMAH/15 MOSw composite as suggested by the significant deviation of G′ versus G″ plots and the two crossover frequencies observed in plots of tan? versus frequency.     

Surface modification of carbon fiber for improving the interfacial adhesion between carbon fiber and polymer matrix

In this study, the reinforcing mechanism of amine functionalized on carbon fibers (CFs) has been precisely discussed, and the differences between aliphatic and aromatic compounds have been illustrated. Polyacrylonitrile‐based CFs were functionalized with ethylenediamine, 4,4‐diaminodiphenyl sulphone, and p‐aminobenzoic acid (PAB), and CF‐reinforced epoxy composites were prepared. The structural and surface characteristics of the functionalized CFs were investigated using X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT‐IR), and scanning electron microscopy (SEM). Mechanical properties in terms of tensile and flexural strengths and moduli were studied. The FT‐IR results confirm the success in bonding amines on the CF surface. After treatment of CFs, the oxygen and nitrogen contents as well as the N/C ratio showed an increase. XPS results provided evidence of the chemical reaction during functionalization, rather than being physically coated on the CF surface. Chemical modification of CF with diamines led to considerable enhancement in compatibility of CF filaments and epoxy resin, and remarkable improvements were seen in both tensile and flexural properties of the reinforced composites. SEM micrographs also confirmed the improvement of interface adhesion between the modified CFs and epoxy matrix. Finally, it can be concluded that PAB is a promising candidate to functionalize CF in order to improve interfacial properties of CF/epoxy composites. Copyright © 2015 John Wiley & Sons, Ltd.     

Features of the structure formation of polymer composites modified by a liquid lubricant

Structure formation processes in polytetrafluoroethylene under the action of liquid lubricant components and zeolite particles are considered. Based on the results of single crystal X-ray diffraction, electron and atomic force microscopic, chromato mass spectroscopic studies, the formation mechanisms of polymer composites, which were obtained by liquid phase filling with motor oils, are proposed.     

Influence of solvent quality on polymer solutions: a Monte Carlo study of bulk and interfacial properties

The effect of solvent quality on dilute and semidilute regimes of polymers in solution is studied by means of Monte Carlo simulations. The equation of state, adsorption near a hard wall, wall-polymer surface tension, and effective depletion potential are all calculated as a function of concentration and solvent quality. We find important differences between polymers in good and theta solvents. In the dilute regime, the physical properties for polymers in a theta solvent closely resemble those of ideal polymers. In the semidilute regime, however, significant differences are found.     

The effect of temperature on the enthalpy of mixing of polyelectrolyte solutions

The effect of temperature on the enthalpies of mixing of sodium dextran sulphate and sodium alginate with sodium chloride has been determined and the results compared with the predictions based on the line charge theory. Better agreement between experimental and calculated values is obtained at the higher reaction temperature, as previously found for the enthalpies of dilution. Measurement of the additional enthalpy changes occurring when different alkali metal chlorides are mixed with the sodium salt of the polyanion gives the sequence Li⁺ > Na⁺ > K⁺ in order of decreasing overall endothermic enthalpies of reaction. The same sequence is observed with polysulphates and polycarboxylates at different temperatures.     

Enhanced interfacial adhesion,mechanical, and thermal properties of natural flour-filled biodegradable polymer bio-composites

This study examined the interfacial adhesion, mechanical, and thermal properties of compatibilizing agent-treated and non-treated biocomposites as a function of the type of compatibilizing agent. The tensile strength, interfacial adhesion, and heat deflection temperature (HDT) of maleic anhydride-grafted poly(butylene succinate) (PBS-MA) and maleic anhydride-grafted poly(lactic acid) (PLA-MA)-treated biocomposites are greater than those of untreated maleic anhydride-grafted poly(styrene-b-ethylene-co-butylene-b-styrene) triblock copolymer (SEBS-MA) and maleic anhydride-grafted polypropylene (MAPP)-treated biocomposites. The storage modulus (E′) values and the tan δ_max temperatures (T _g) of PBS-MA and PLA-MA-treated biocomposites were slightly higher than that of the untreated biocomposites.     

Powder and fiber filled interpenetrating network of metal polymer composites (INMPC) of polypropylene

The mechanical properties of conductive powder and fiber-filled interpenetrating network of polymer metal composites (INMPC) of polypropylene with metal alloys based on Sn, Zn, Mo, Al, Cu, Ag, and Sb are reported. New nomenclature, terminologies, and definitions are presented. New models are also discussed.