Modeling of the dynamic mechanical properties of semicrystalline thermoplastic matrix composites

The modeling of the viscoelastic properties of semicrystalline polymeric matrix composites is discussed. Different mathematical models are applied to describe the development of the storage modulus, measured by dynamic mechanical analysis, as a function of the crystalline content during isothermal crystallization experiments. Best results are obtained with an empirical power law model developed in this work. The application of the Halpin-Tsai equation and of a theoretical model, based on a combination of parallel-series arrangements of viscoelastic elements representing the crystalline and amorphous phases, is also discussed. The main objective of this research is the comparison between experimental results obtained by differential scanning calorimetry and dynamic mechanical analysis during crystallization processes.     

Characterisation of thermoplastic matrix composites using variable frequency microwave

Abstract

In most industrial microwave processing operations, the frequency of the microwave energy launched into the waveguide or cavity containing the sample is fixed. This brings with it inherent heating uniformity problems. This paper describes a new technique for microwave processing, known as variable frequency microwave (VFM) processing, which alleviates the problems brought about by fixed frequency microwave processing. In VFM processing, microwave energy over a range of frequencies is transmitted into the cavity in a short time, e.g. 20 μs. It is therefore necessary to determine the best frequency range for processing a material. The best range frequency for microwave processing of five different thermoplastic matrix composites using the VFM facilities has been determined. The optimum frequency band for microwave processing of these five materials was in the range 8–12 GHz. This data enables bonding of the materials using microwave energy under the most favourable conditions.     

Dielectric properties of low molecular weight poly(ethylene glycol)s

This paper reports the measured values of dielectric permittivity ε′ and dielectric loss ε″ of ethylene glycol, diethylene glycol and poly(ethylene glycol)s of average molecular weight 200, 300, 400 and 600 g mol⁻¹ in the pure liquid state. The measurements have been carried out in the frequency range 200 MHz to 20 GHz at four different temperatures of 25, 35, 45 and 55 °C. The complex plane plots (ε″ versus ε′) of these molecules are Cole–Cole arcs. The static dielectric constant ε₀, high‐frequency limiting dielectric constant ε_∞, average relaxation time τ₀ and distribution parameter α have been determined from these plots. The value of the Kirkwood correlation factor g and the dielectric rate free energy of activation ΔF have also been evaluated. The dependence of relaxation time on molecular size and viscosity has been discussed. A comparison has also been made with the dielectric behaviour of these molecules in dilute solutions of non‐polar solvents, which were carried out earlier in this laboratory. The influences of intermolecular hydrogen bonding and molecular chain coiling on the dielectric relaxation of these molecules have been recognized. © 2000 Society of Chemical Industry     

Morphology and mechanical properties of thermoplastic composites containing a thermotropic liquid crystalline polymer

Blends of two thermotropic liquid crystalline polymers (TLCPs), with brittle and ductile matrix materials were both injection molded and spun into fibers, in order to investigate the mechanism of in-situ mechanical reinforcement. In the injection molded samples, the TLCP was only moderately elongated into fibrils, and the mechanical properties were below predictions of the rule of mixtures. Fibers spun out of the blends contained numerous fine fibrils with nearly infinite aspect ratio, and as expected, the modulus increased linearly with the TLCP volume fraction, obeying the Tsai-Halpin equation for transversely isotropic composites. Wide angle X-ray diffraction measurements, as well as determination of the fiber-moduli, revealed that during spinning not only a macroscopic elongation of the fibrils was achieved, but also a considerable molecular orientation within the TLCP domains.     

Effect of molecular weight on the mechanical properties of polytetrafluoroethylene (PTFE)

Molecular weight has a considerable influence on the mechanical properties and density of polytetrafluoroethylene. Empirical equations have been found relating tensile properties and density to the number-average molecular weight.     

Dynamic mechanical properties of some epoxy matrix composites

Dynamic mechanical properties of some epoxy matrix composites have been studied, comparing experimental data with theoretical models. The matrix in all composite samples was Shell Epon 828, a diglycidyl ether of bisphenol A, cured with meta-phenylenediamine. Fibrous composite samples were made with glass and graphite fibers. Particulate composite samples were made with glass microspheres, atomized aluminum, powdered silica, alumina, asbestos, mica, carbon black, and graphite. The dynamic elastic modulus and damping of these samples were measured at temperatures between 85° and 345°K by a free-free flexural resonance technique. The dynamic modulus of parallel fiber composites follows the linear rule of mixtures for low fiber volume fractions; deviations from linearity at higher volume fractions appear to be due to defects caused by the sample fabrication technique. Dynamic moduli of the particulate composites conform, within experimental error, to the static modulus theory of Wu up to filler volume fractions of 0.35 to 0.40. Deviations from Wu's theory at higher volume fractions may be due to agglomeration of filler particles. The damping of particulate composites with quasi-spherical filler particles appears to follow the rule of mixtures. In particulate composites with needle- and flake-type fillers, and in fibrous composites, the fillers are more highly stressed; with more of the strain energy in the low-damping fillers, overall damping is reduced. Damping greater than that attributable to the matrix and filler may be due to slippage at the interface between them. In addition to supporting Wu's theory of the elastic modulus of a particulate composite, this study demonstrates the utility of the nondestructive free-free flexural resonance techniques for obtaining a large body of reliable data in a short time from relatively few small samples. This greatly facilitates the experimental testing of theoretical models and the evaluation of fillers, matrix materials, and fabrication techniques.     

Fundamental aspects of wood as a component of thermoplastic composites

In order to utilize wood‐based particles and fibers effectively as fillers or reinforcements in thermoplastic composites, a fundamental understanding of the structural and chemical characteristics of wood is required. Wood is the secondary xylem of trees, shrubs, and woody lianas (vines). Although the physiological function of wood is similar among different groupings of trees, significant differences are found in the basic anatomical structure of the broadest groupings of gymnosperms (coniferous trees or “softwoods”) and angiosperms (broad‐leaved trees or “hardwoods”). In addition, there are anatomical differences in wood structure among the various species of trees. These structural differences may have effects on the use of these materials in composites. Wood cell walls comprise three major organic constituents, namely, cellulose hemicelluloses, and lignin. In addition to these structural polymers, numerous other organic materials (“extractives”) may be present within the wood. The chemical composition of wood varies between species. The basic characteristics of anatomy and structure combine to impart variations in permeability, bulk chemistry, and surface chemistry. Characterization of particle size and shape, as well as surface tension characteristics as indicators of wettability, becomes important as we try to understand how these biopolymeric materials will behave when introduced into synthetic polymer systems.     

Surfactant properties of low molecular weight phospholipids

Surface tensions, critical micelle concentrations (CMCs), contact angles on hydrophobic polyethylene, and foaming characteristics of phosphatidic acids, phosphatidylcholines, phosphatidylethanolamines, and phosphatidylglycerols were measured to determine their suitability as substitutes for traditional surfactants. These phospholipids have fatty acid chains of 5 to 12 carbon atoms, a range over which they are soluble at room temperature. Their surface tensions decrease with increasing concentrations until their CMCs are reached, above which their plateau surface tensions are as low as 21 mN/m, indicating excellent surface activities. In general, plateau surface tensions decrease with increasing chain length within each phospholipid type. The classical relationship for In CMC vs. chain length is followed with slopes typical of anionic surfactants for phosphatidic acids and phosphatidylglycerols and resembling zwitterionic surfactants for phosphatidylcholines and phosphatidylethanolamines, consistent with the charge on the hydrophilic group. The wetting capabilities of aqueous solutions on polyethylene are good and foam heights and stabilities are high, the latter two properties being comparable to traditional anionic (sodium dodecylsulfate) and nonionic (octylphenol polyethoxylate) surfactants. Some anomalies are observed regarding the effect of chain length on wetting and foaming, probably due to the depletion effect. Many phospholipids slowly degrade in aqueous solution. We conclude that short-chain phospholipids exhibit excellent surfactant properties and may be useful in many applications.     

Effect of molecular weight and crystallinity on poly(lactic acid) mechanical properties

Several samples of poly(lactic acid) with different molecular weights and tacticity have been prepared, and some PLLA injection moulded specimens have been annealed to promote their crystallization. From the characterization data, poly(L -lactide) showed more interesting mechanical properties than poly(D, L -lactide), and its behavior significantly improves with crystallization. In fact, annealed specimens possess higher values of tensional and flexural modulus of elasticity, Izod impact strength, and heat resistance. The plateau region of flexural strength as a function of molecular weights appears around M_v = 35,000 for PDLLA and amorphous PLLA and at higher molecular weight, around M_v = 55,000, for crystalline PLLA. The study of temperature effect shows that at 56°C only crystalline PLLA still exhibits useful mechanical properties. © 1996 John Wiley & Sons, Inc.     

Preparation and characterization of thermoplastic olefin/nanosilica composites using a silane-grafted polypropylene matrix

This work reports the morphology and physical properties of silane-grafted polypropylene (PP-g-VTEOS) reinforced with silica nanoparticles and toughened with an elastomeric ethylene-octene copolymer (POE). Vinyltriethoxysilane (VTEOS) was grafted to polypropylene (PP) to form (PP-g-VTEOS), using a peroxide-initiated melt compounding technique. TEM observations of composites containing up to 7 wt% of the nanosilica revealed good dispersion of the silica nanoparticles, which partitioned selectively within the PP-g-VTEOS matrix. Rheological characterization in the linear viscoelasticity region showed significant increases in the low-frequency complex viscosity, storage and loss moduli, which stem from the polymer/filler and filler/filler interactions. The effects of surface treatment of the nanosilica on the morphology, thermal and mechanical properties of the composites were also investigated. The mechanical properties of the composites were greatly enhanced in terms of tensile and flexural strength, while impact strength was preserved when the silane-treated nanosilica was used.     

Construction of thermoplastic cellulose esters matrix composites with enhanced flame retardancy and mechanical properties by embedding hydrophobic magnesium hydroxide

Biomass-based composites with renewability and biodegradability have attracted extensive researches, but their applications are hindered by poor mechanical properties and flame retardancy. Cellulose ester matrix composites (CEMC), a kind of biomass-based composites, were prepared with inorganic crystals as flame retardant and reinforcement. Cellulose acetate oleate (CAO) prepared by mechanical activation-assisted solid-phase reaction was used as thermoplastic matrix. Hydrophobic oleate-magnesium hydroxide (O-MH), which was surface-modified with oleic acid, was embedded into CAO to prepare O-MH/CAO composites by hot pressing. The introduction of oleoyl contributed to favorable thermoplasticity of cellulose ester, resulting in enhanced thermal stability and mechanical properties of CEMC. The uniform dispersion of O-MH in the CAO matrix via metal–organic coordination increased the mechanical properties and flame retardancy of O-MH/CAO composites, ascribing to the toughening effect and combustion inhibition effect induced by O-MH. This study provides a feasible technology for fabricating the CEMC with outstanding thermal stability and mechanical properties.     

Profile extrusion and mechanical properties of crosslinked wood–thermoplastic composites

Challenges for wood‐thermoplastic composites to be utilized in structural applications are to lower product weight and to improve the long‐term load performance. Silane crosslinking of the composites is one way to reduce the creep during long‐term loading and to improve the mechanical properties. In this study, silane crosslinked wood‐polyethylene composites were produced by reactive extrusion and subsequently manufactured into rectangular profiles. The silane crosslinked composites were stored in a sauna at 90 °C to increase the degree of crosslinking. The toughness of the silane crosslinked composites was significantly higher than for the non‐crosslinked composites. Improved adhesion between the wood and polyethylene phases is most likely the reason for the improved toughness of the crosslinked composites. There was no significant difference in flexural modulus between the crosslinked and non‐crosslinked composites. In addition, impact testing showed that the impact strength of the crosslinked composites was considerable higher (at least double) than the non‐crosslinked. The effect of temperature on the impact strength of the composites indicated slightly higher impact strength at −30 °C than at 0° and at 25 °C, and then an incrase in impact strength at 60 °C. Crosslinking also reduced the creep response during short‐term loading. Moreover, scanning electron microscopy on the fracture surface of the crosslinked composites revealed good adhesion between the polyethylene and wood phases. POLYM. COMPOS. 27:184–194, 2006. © 2006 Society of Plastics Engineers     

Modelling the structural and physicomechanical properties of substituted poly(p-phenylene)s using molecular mechanical and molecular orbital methods

Conducting polymers are important technological materials that are finding increasing use in batteries and display devices. The conformation and packing of these polymers in the amorphous glassy state are poorly understood, despite the fact that they dictate their most important physical and mechanical properties. The processing of currently known conducting polymers is difficult and there is a strong incentive to increase their processability through functionalization. Developing an ability to predict the structure and structure-property relations of conducting polymers in the bulk will help with the design of new structures that combine processability with favourable electronic properties and facilitate their use in future high-technology applications. In this work, we concentrate on substituted poly(p-phenylene)s. Detailed atomistic molecular models have been developed with the help of molecular mechanics and semi-empirical quantum mechanical calculations using Cerius and MOPAC V6.0 program packages and structural, volumetric, and mechanical properties, e.g. geometrical values, densities, have been calculated by simulations on these models. The results from both methods have been compared with simulated and experimental data and conclusions have been drawn on the methodology and the approximations used. This study was used to compare with results obtained on unsubstituted poly(p-phenylene)s carried out earlier and to continue to develop our methodology for calculating structure, physical and mechanical properties that will be generally applicable to conductive polymers.     

Improvement of the thermal properties of poly(3‐hydroxybutyrate) (PHB) by low molecular weight polypropylene glycol (LMWPPG) addition

In this work, blends of poly(3‐hydroxybutyrate) (PHB) with 5, 10, 15, and 20 wt % low molecular weight poly(propylene glycol) (LMWPPG) have been prepared and characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) with attenuated total reflectance (ATR) accessory and simultaneous thermal analysis (TG/DTA). FTIR and thermal analyses suggested that the presence of LMWPPG led to a maximum crystallinity for the blend PHB/PPG (90/10) blend. The presence of LMWPPG also caused a significant increase of the PHB processability window, i.e., the difference of the melting and degradation temperature, of PHB from 105 to 134°C, which is extremely important for the industrial uses of PHB. This PHB stabilization effect is discussed in terms of an intermolecular interaction of the PHB carbonyl with LMWPPG methyl groups which probably hinders the classical radon β‐scission PHB intramolecular decomposition mechanism. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure and mechanical properties of the compositions of polyisocyanurate polymers with low molecular weight rubbers

The structure and properties of the compositions of polyisocyanurates modified with low molecular weight rubber networks have been investigated by means of dynamical mechanical analysis (DMA), electron microscopy, and stress-relaxation experiments. The network compositions consist of two different polymeric networks. The first component (macrodi-isocyanate based on low molecular weight polybutadiene or copolymers of tetrahydrofuran and propylene oxide) has bulky cross-linked points connected by short flexible chains. The second component (diphenylmethanediisocyanate) also has bulky cross-linked points of the same structure, but the linear fragments between them in this case are very small and rigid. These compositions result in the formation of the heterophase system. As a result, transparent samples were prepared, which differ from the mechanical properties of both the glassy and rubbery polymers. These materials have a modulus of elasticity (from 10³ to 10 MPa) that is usual for the transition zone between the glassy and rubbery states; nevertheless, these materials show elastic (and not viscoelastic) properties. For the materials investigated, the modulus is decreased not more than 10 times in the wide temperature interval from 200 to 500 K. A new state of the polymer, which differs from both the glassy and rubbery states, has been identified in the present case. © 1995 John Wiley & Sons, Inc.     

Physicochemical properties of acylated low molecular weight chitosans

Hydrophobically modified chitosans are developing progressively in drug delivery system due to their ability to encapsulate drugs with the amphiphilic architecture. In this study, low molecular weight chitosans were acylated with hexanoyl (LCh-C6), octanoyl (LCh-C8) and decanoyl (LCh-C10) groups to study their physicochemical properties for the potential as drug carriers. Both fourier transform-infrared (FT-IR) and ¹H NMR (Nuclear Magnetic Resonance) analyses confirmed the successful acylation of alkyl chains onto chitosan backbone. LCh-C6, LCh-C8 and LCh-C10 showed the similar value of critical aggregation concentration around 40?µg?L^?1. The average particle size of LCh-C6, LCh-C8 and LCh-C10 obtained by dynamic light scattering measurement was compared to by mean of transmission electron microscopy. Acylated low molecular weight chitosans (LChA) showed higher encapsulation efficiency and drug loading toward hydrophobic salicylic acid as compared to hydrophilic caffeine, as well as exhibited higher increment in particle size due to possible inner volume expansion. Both long alkyl chains and high degree of substitution contributed to better drug encapsulation of LChA.     

Optically transparent self-reinforced poly(ethylene terephthalate) composites: molecular orientation and mechanical properties

Self-reinforced composites have been fabricated by compaction of oriented polyethylene terephthalate (PET) fibers under pressure at temperatures near, but below, their melting point. The originally white fiber bundles, which were about 40% crystalline, show increased crystallinity (55%) but optical translucency after processing. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were used to study the crystallization and orientation of the fibers, revealing that the degree of crystallinity was somewhat insensitive to compaction conditions while the melting point increased substantially with increasing compaction temperature. Crystalline orientation, gauged using the Hermans orientation parameter from WAXD data, indicated that no significant loss in orientation of the crystalline fraction occurs due to compaction. Mechanical characterization revealed a stepwise decrease in flexural modulus (9.4-8.1 GPa) and concomitant increase in transverse modulus and strength on increasing the compaction temperature from 255 to 259 °C. This transition in behavior was accompanied by a loss of optical transparency and a change in the distribution of amorphous fraction from fine intrafibrillar domains to coarse interfibrillar domains as seen with electron microscopy. We argue then that the mechanical properties of PET compactions are influenced more by orientation of the amorphous phase than that of the crystalline phase. The impact properties of compacted materials, characterized using an unnotched Charpy test method, showed remarkable impact resistance after compaction, with impact toughness decreasing as compaction temperature was increased.     

Improvement of mechanical properties of graphene oxide/poly(allylamine) composites by chemical crosslinking

Graphite oxide was prepared by oxidation of graphite using the Hummers method, and its ultrasonication in water yielded dispersed graphene oxide (GO) sheets. These sheets were then crosslinked with a water soluble polymer, namely poly (allylamine) hydrochloride (PAH), by carbodiimide coupling. Free standing composite films were obtained by filtration. These crosslinked composites showed better mechanical properties than unmodified GO films and those of composites that were made by simple mixing of GO and PAH. The filtration process was optimized to produce strong GO films which were subsequently crosslinked with PAH in-situ to produce very strong composites with tensile strengths up to146 MPa.     

Biodegradability,mechanical, and thermal properties of thermoplastic starch/cuttlebone composites

This work focused on improvements to the properties of thermoplastic starch (TPS) by using cuttlebone (CB) as the bio‐filler. The effect of CB on the properties of TPS was compared to that of commercial calcium carbonate (CC). The good adhesion achieved between the TPS matrix and the cuttlebone powder produced improvements in the tensile strength of their composites, whereas the tensile strength of TPS/CC composite was lower due to the presence of filler agglomerates. The biodegradation of the TPS and the composites were analyzed by the soil burial test. This showed that cuttlebone decreased the biodegradation rate. The thermal degradation temperatures of TPS, a TPS/CC composite and a TPS/CB composite showed very similar behavior. POLYM. COMPOS., 36:1401–1406, 2015. © 2014 Society of Plastics Engineers