Analysis of the isothermal mechanical response of a shape memory polymer rheological model

In this paper, we derive the isothermal mechanical response of a 4‐element rheological model for shape memory polymers (SMP) in the context of (i) constant stress, (ii) constant strain, (iii) constant stress rate, (iv) constant strain rate, (v) periodic strain. The effect of shape memory strain (modeled by a friction element) and the temperature dependence of the material properties on the SMP response are examined for a polyurethane shape memory polymer of the polyester polypole series. In particular, it is possible to identify a threshold frequency during periodic loading, near which the damping capacity of the SMP is strongly affected by an increasing shape memory strain. On the other hand, when the applied frequency is much greater than the threshold value, an increasing shape memory strain ceases to have any effect on the damping. It is also shown that at a given frequency (significantly greater than the threshold value), the damping capacity as a function of temperature attains a maximum. While this maximum value is frequency‐dependent (being inversely proportional), the temperature at which the maximum is attained is frequency‐independent, and is analytically shown to be the glass transition temperature.     

Influence of rheological properties on the sagging of polypropylene and abs sheet for thermoforming applications

The isothermal sagging resistance of different grades of conventional and a high melt strength (HMS) PP has been correlated with the rheological characteristics of the polymers, such as dynamic shear properties, melt strength, and zero shear viscosity. A thermoforming grade of acrylonitrile‐butadiene‐styrene (ABS) was used as a reference material. At 190°C, ABS had the highest viscosity and elastic modulus in the frequency range measured, showing that this polymer is highly elastic. HMS PP had a greater shear thinning behavior than conventional PP because of its broader molecular weight distribution. The tan δ of the polymers showed that conventional PP had a higher tendency to flow than HMS PP and ABS when heated above 172°C. This was confirmed with sagging experiments performed in an air circulating oven, where the rate of sagging decreased as the melt strength and the zero shear viscosity of the polymer increased.     

Effects of high hydrostatic pressure on the mechanical behavior of a crystalline polymer–polyoxymethylene

The true stress-true strain behavior of polyoxymethylene, n(-CH₂O), as an example of a bulk semi-crystalline polymer, has been investigated for constant hydrostatic environmental pressures from 1 atmosphere to 8 kilobars with the principal objectives of elucidating the factors controlling flow and fracture. Experiments were conducted in uniaxial tension at room temperature and constant strain rate. The tensile observations were supplemented by measurements of bulk compressibility and stress relaxation behavior at pressure. In contrast with metals and inorganic compounds, the modulus, yield stress and fracture stress of POM increase strongly with pressure by a factor of approximately three at 8 kilobars. The modulus increase is shown from the stress relaxation measurements to be associated with a pressure-induced increase in the β-transition temperature which points to the potential usefulness of the concept of pressure-temperature super-position of mechanical behavior. The characteristics of the pressure dependence of the yield stress demonstrate that yield criteria based on continum mechanics considerations, including the Mohr or Coulomb-Navier criterion, are not valid for general deformation (non-plane strain) conditions in this polymer. The concept of a critical volume change determining the initiation of yielding is suggested to be applicable to semi-crystalline polymers. Comparison with analogous changes in yield stress with temperature points to an increasing contribution to the control of yielding by the initially disordered regions with increasing pressure or decreasing temperature. The fracture behavior observed at pressure eliminates the concepts of a critical stress as a fracture criterion for POM and of a simple reduction in normal stress at points of stress concentration as the principal effect of the applied pressure on fracture.     

Network model for the viscoelastic behavior of polymer nanocomposites

A theoretical network model reproducing some significant features of the viscoelastic behavior of unentangled polymer melts reinforced with well dispersed non-agglomerated nanoparticles is presented. Nanocomposites with low filler volume fraction (∼10%) and strong polymer-filler interactions are considered. The model is calibrated based on results obtained from discrete simulations of the equilibrium molecular structure of the material. This analysis provides the statistics of the network of chains connecting fillers, of dangling strands having one end adsorbed onto fillers, and that of the population of loops surrounding each nanoparticle. The network kinetics depends on the attachment-detachment dynamics of grafted chains of various types and is modeled by using a set of convection equations for the probability distribution functions. The overall viscoelastic response depends strongly on the lifetime of the polymer-filler junctions. The largest reinforcement is observed at low strain rates and low frequency oscillations. A solid like behavior is predicted for systems in which the polymer molecules interact strongly with the nanoparticles, effect which is associated with the behavior of the network of bridging segments.     

Large deformation mechanical behavior of flexible nanofiber filled polymer nanocomposites

In the present work, the large deformation behavior of high aspect ratio flexible nanofiber reinforced polymer composites is investigated. Simple or successive tensile tests are performed at room temperature, i.e. in the rubbery state. By studying two different types of fibers, namely cellulose nanofibrils and carbon nanotubes, with two processing routes, the role of entanglements and of interactions existing between fibers—within the nanofiber network that can be formed in the material—on the composite properties is highlighted. For cellulosic nanofillers, strong hydrogen bonds between fibers lead to a spectacular reinforcement effect combined with a decrease of the composite ultimate strain and an irreversible damage of composite properties after first deformation (rigid network). When such strong interactions between fillers are limited (soft entangled network or simple contacts between non-entangled fibers) the resulted reinforcement is less important and no decrease of the deformation at break is observed. For carbon nanotube fillers, the evolution of the filler network during tensile test is finally highlighted by in situ electrical measurements.     

Polymer-Impregnated mortars I. Effect of polymer state on mechanical behavior

Mortar specimens were impregnated with methyl methacrylate, n-butyl acrylate, styrene, and crosslinking agents in various combinations. After polymerization of the monomers in situ, studies of mechanical properties such as Young's modulus and compressive strength were made. In one experiment, various ccpolymers of methyl methacrylate and n-butyl acrylate were prepared and tested as a function of temperature. Excellent reinforcement was obtained with any combination of monomers as long as the resulting polymer was at a temperature below its glass transition temperature. This suggests that the modulus of the reinforcing polymer is crucial, glassy behavior being required. The addition of crosslinking agents such as TMPTMA increased the high temperature strength, however.     

A coarse-grained model for the mechanical behavior of multi-layer graphene

Graphene is the strongest and highest weight-to-surface ratio material known, rendering it an excellent building block for nanocomposites. Multi-layer graphene (MLG) assemblies have intriguing mechanical properties distinct from the monolayer that remain poorly understood due to spatiotemporal limitations of experimental observations and atomistic modeling. To address this issue, here we establish a coarse-grained molecular dynamics (CG-MD) model of graphene using a strain energy conservation approach. The model is able to quantitatively reproduce graphene’s mechanical response in the elastic and fracture regimes. The hexagonal symmetry of graphene’s honeycomb lattice is conserved, and therefore the anisotropy in the non-linear large-deformation regime between the zigzag and armchair directions is preserved. The superlubricity effect, namely the strong orientational dependence of the shear rigidity between graphene layers, is also captured. We demonstrate the applicability of the model by reproducing recent experimental nanoindentation results in silico. Our model overcomes the limitations of current CG-MD approaches, in accurately predicting the fracture properties, the interlayer shear response, and the intrinsic anisotropy of MLG. Additionally, our fast, transferable force-field can be straightforwardly combined with existing coarse-grained models of polymers and proteins to predict the meso-scale behavior of hybrid carbon nanomaterials.     

A predictive model for the mechanical behavior of particulate composites

A method for predicting the stress-strain and volumetric behavior of particulate composites from constituent properties has been developed for large values of strain. This approach allows a simple model for systems in which damage occurs without resorting to complicated constitutive equations. An energy balance derived from the first law of thermodynamics and the equations of linear elasticity calculates critical strain values at which filler particles will dewet when subjected to uniaxial tension and superimposed pressure. Calculations of critical strains over the entire strain history using reevaluated material properties accounting for the damage yield highly nonlinear stress-strain and volumetric curves. Experimentally observed dependences on particle size, filler concentration, matrix and filler properties, and superimposed pressure are correctly predicted. The method has no adjustable parameters, and allows several idealized models of the dewetting process to be examined. Comparisons of model predictions to experimental data show good agreement.     

Size-dependent mechanical behavior of nanoscale polymer particles through coarse-grained molecular dynamics simulation

Anisotropic conductive adhesives (ACAs) are promising materials used for producing ultra-thin liquid-crystal displays. Because the mechanical response of polymer particles can have a significant impact in the performance of ACAs, understanding of this apparent size effect is of fundamental importance in the electronics industry. The objective of this research is to use a coarse-grained molecular dynamics model to verify and gain physical insight into the observed size dependence effect in polymer particles. In agreement with experimental studies, the results of this study clearly indicate that there is a strong size effect in spherical polymer particles with diameters approaching the nanometer length scale. The results of the simulations also clearly indicate that the source for the increases in modulus is the increase in relative surface energy for decreasing particle sizes. Finally, the actual contact conditions at the surface of the polymer nanoparticles are shown to be similar to those predicted using Hertz and perfectly plastic contact theory. As ACA thicknesses are reduced in response to reductions in polymer particle size, it is expected that the overall compressive stiffness of the ACA will increase, thus influencing the manufacturing process.     

Curing behavior and mechanical behavior of fully and semi-interpenetrating polymer networks based on polyurethane and acrylics

Polyurethane (PU) was made by reacting stoichiometric equivalent of trimethylol propane (TMP) and desmodur L. Fully interpenetrating polymer networks (fully IPN's) of various compositions based on PU and poly(ethylene glycol) diacrylate (PEGDA) were prepared by blending various ratios of PU/PEGDA, and cured by benzoyl peroxide (BPO). Semi-interpenetrating polymer networks based on PU and poly(ethylene glycol) monomethyl ether of acrylate (PEGMEA) were prepared in a similar way. Shift of exothermic peaks during IPN formation were examined with dynamic DSC. Viscosity increases were investigated with a Brookfield RVT type viscometer. Dynamic mechanical properties were probed via a rheometric dynamic spectroscopy (RDS).Expermintal results revealed a good compatibility of both IPN systems, as evidenced from the single damping peak of the RDS curves for each composition. Shifts of exothermic peaks to higher temperatures during the formation of fully IPN were observed, especially for the composition of PU/PEGDA = 50/50, which showed an exothermic peak at the highest temperature. Experimental results also revealed delayed viscosity increases and decreased gel fractions for all fully IPN's. On the contrary, the semi-IPN did not exhibibt similar phenomena. All these findings supported an effect of network interlock during fully IPN formation. The existence of a network not only provided a sterically hindered environment, but also restrained the chain mobility of the growing network, and vice versa, thus retarding the curing rates of both networks. Network interlock also broadened the width of the half damping peak, T_1/2, and subsequently led to improved mechanical properties such as the impact resistance and Young's modulus of fully IPN material.     

Application of a mathematical model to the study of the glass transition temperature in polymer electrolyte precursor systems

To the purpose of studying the effect of composition on the glass transition temperature (Tg) of a series of polymer electrolytes based on blends of polyethylene oxide (PEO), poly(octafluoropentoxytrifluoroethoxy)phosphazene (PPz) and poly(epichlorhydrine), a mathematical model was applied to results obtained through DSC determination using seven ternary blends selected by an experimental design. The parameters of the model were chosen by means of stepwise linear regression method. The final model proved to be appropriate (R² = 0.997; s = 0.99 K) to predict the Tg values. From a structural point of view it was found that the lowest Tg values were obtained for the blends containing the smallest PECH portion. Received: 18 November 1996/Revised: 2 December 1996/Accepted: 3 December 1996     

A qualitative model for the mechanical behavior of pretreated asbestos-epoxy composites

The aim of the present work was to investigate the effect of fiber pretreatment, fiber content, coating concentration, and also pretreatment procedure on the tensile properties of asbestos-epoxy composites. These composites comprise materials of considerable industrial importance. Asbestos exhibits unique properties. Occasionally it is difficult to disperse asbestos properly because the individual fibrils are very small and tend to agglomerate, but there is no evidence that asbestos is not easily wetted out by all systems. However, the higher potential aspect ratio of asbestos fibers compared with glass is not always realized in practice because the fibers break in length to fine diameters. Accordingly, the very considerable new surface created makes successful wetting difficult or impossible. For this reason, asbestos was precoated with a well adhered film of poly(hexamethylene adipamide), a polymer especially compatible with the epoxy phase. The pretreatment procedure followed was based on the principles of the interfacial polymerization involving the serial application to the asbestos of two immiscible solutions of hexamethylenediamine and adipoyl chloride. Accordingly, epoxy-nylon-chrysotile composites were made while varying pretreated fiber volume fraction, concentration of the polyamide coating, and reactants application order. Results obtained from tensile measurements proved quite interesting: Relative modulus of elasticity and relative ultimate strength exhibited a similar behavior when correlated with the ratio of polyamide to asbestos concentration. The corresponding curves pass through distinct maxima at which severe improvement of the material performance is effected. A thorough interpretation of these results is also included.     

Flow behavior of stampable sheet with a rib part

The effect of die design on the flow characteristics of compression molded three-layer long glass fiber reinforced polypropylene composite, known as “stampable sheet,” was investigated. The flow behavior of each layer was observed by optical and soft X-ray photographs. The fiber flow length into the rib part was measured by an image processing system. The results showed that during compression resin exudation occurred and that this depended on the die's rib width. Thus, the larger the rib width, the lower the amount of resin exuded. Resin exudation was found to occur earlier in a die with zero fillet radius. The fiber flow length into the rib part was enhanced by using a die with a large fillet radius. The results were confirmed by a short-shot molding process. In this process, the stamping operation was stopped short of making a complete part. A finite element method was used to study the flow process. The results agree with the experimental results confirmed by short-shot molding.     

Application of a constitutive equation to polymer melts

Yamamoto's integral constitutive equation in which the memory function is dependent on the second invariant of the rate of deformation tensor at past times has been found to be successful in predicting many of the nonlinear viscoelastic functions from the linear viscoelastic data for melts of linear polyethylenes, polypropylenes, and polystryene but not for those of branched polyethylenes with high level of long-chain branching. A specific functional form for the rate-dependent relaxation spectrum is used and is based on the physical meaning resulting from the molecular entanglement theory of Graessley on steady shearing flow. No arbitrary constant is involved in such an interconversion scheme. The data examined are dynamic storage modulus and loss modulus, steady flow viscosity, first normal stress difference, and parallel superimposed small oscillations on steady shear flow. The theory predicts that in such parallel superimposed experiments, storage modulus G′(ω,\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm \dot \gamma } $\end{document}) divided by the square of frequency shows a maximum under finite shear and that G′(ω,\documentclass{article}\pagestyle{empty}\begin{document}$ {\rm \dot \gamma } $\end{document}) would itself become negative at a frequency whose value is about one third the superimposed rate of shear. The experiments are in line with such predictions. Possible reasons for the failure of the theory for branched polyethylenes are considered, and a possible approach is suggested so that the interconversion scheme may be successful for such resins.     

Erosive wear behavior and dynamic mechanical analysis of textile material reinforced polymer composites

The present analysis intends to look into the needlepunched nonwoven textile material reinforced polymer composites. The solid particle erosion wear behavior of needlepunched nonwoven fabric mat reinforced epoxy composites were assessed using silica sand particles with the size of 250, 350, and 450 μm. Taguchi analysis was also carried out on the basis of design of experiments (DoE) approach to establish the interdependence of operating parameters. Mechanical and physical properties of composites were also evaluated experimentally, and the storage modulus (E′), loss modulus (E″) and damping factor (tan δ) characteristics were analyzed with the help of dynamic mechanical analyzer (DMA) in the temperature range of 20–200°C. Surface morphology of the eroded surfaces of composites were also analyze by scanning electron microscopic (SEM) to discuss the feasible erosion mechanism on composite surfaces. The result reveals that fiber content and impact velocity has an invulnerable impact on the erosion rate of needlepunched nonwoven fabric mat‐epoxy composites. The mechanical and physical properties are meliorating with incorporation of fabric mat weight percentage in composites, and the measured damping factor (tan δ) peaks of T _g for needlepunched nonwoven fabric mat epoxy composites ranged from 100 to 110°C. POLYM. COMPOS., 38:2201–2211, 2017. © 2015 Society of Plastics Engineers     

The mechanical behavior of polymer coatings: Solvent removal in polyamic acid films

The development of the mechanical properties and stresses during the formation of polyamic acid (PAA) coatings has been studied using methods such as a “propagating wave technique.” The shrinkage stress due to solvent removal in PAA coatings under a one dimensional constraint was determined to be 8 MPa. A coupling between the residual stress and solvent removal process has been observed.     

Extrusion of highly filled flexible polymer sheet

Highly-filled polymer systems include color masterbatches, feedstocks for powder injection molding, and rigid sheets with high levels of flame retardants, but they have not been explored for flexible sheet. This work investigated the (a) selecting a polymer matrix with enough melt strength and flexibility to form a stable sheet with high filler loading, (b) the maximum achievable filler loading for the sheet, and (c) optimizing the process of extruding a highly-filled flexible polymer system. Extrusion grade low-density polyethylene (LDPE) provided sufficient flexibility and permitted a maximum filler loading of 36 vol% (~78 wt%). Good dispersion of the nanoparticle filler, however, required two passes through multiple screw extruders and a small reduction in the viscosity of the LDPE. Sheet with thickness of 415 μm, surface roughness of <1 μm, and sufficient flexibility was extruded continuously at a rate of 10 m/min., but it required a more traditional coat hanger manifold to prevent filler hang up in the sheet die. The filler particles were distributed uniformly through the core and skin of the sheet, giving the sheet good mechanical properties.