The pressure and temperature effects on brittle-to-ductile transition in PS and PMMA

Tensile experiments in polystyrene (PS) and poly(methyl methacrylate) (PMMA) conducted at constant strain rate over a wide range of pressure and temperature have shown that a brittle-to-ductile transition is induced in these amorphous polymers by the superposition of hydrostatic pressure as well as by the raise of the experimental temperature. A detailed stress–strain analysis permits explanation of the mechanism for the brittle-to-ductile transition in terms of interaction between two competing processes of plastic yielding—crazing and shear banding phenomena. The crazing and shear banding processes respond quite differently to changes of pressure or temperature, causing shifting of the brittle-to-ductile transition point to where the craze initiation stress and shear band initiation stress again become equal. The evidence that the brittle-to-ductile transition pressure becomes lower with increasing temperature refutes a previously suggested concept that the transition relates primarily to mechanical relaxation phenomena.     

Free volume behavior in spincast thin film of polystyrene by energy variable positron annihilation lifetime spectroscopy

Free volume behavior in polystyrene thin films with thickness ranging from 22 to 1200 nm on silicon substrates was studied by energy variable positron annihilation lifetime spectroscopy (EVPALS). The films were prepared by spincasting from toluene solutions of 0.5-5.0 wt% polystyrene with M_w = 1?090?000 g/mol. Distinct deviations from bulk polystyrene in thermal expansion of the free volume holes and the glass transition temperature associated with free volume behavior were observed for the thinnest film with 22 nm thickness, indicating its exclusively high chain mobility. Comparison of the polystyrene concentration in the precursor solution around the overlap concentration suggests that the high chain mobility is due to less entangled chains caused by rapid removal of the solvent from the diluted solution in order to prepare very thin film.     

Structure of oriented polystyrene monofilaments and its relationship to brittle-to-ductile transition

Oriented atactic polystyrene monofilaments show brittle-to-ductile transition in the vicinity of a degree of birefringence Δn = ?2 × 10^?3 (at a temperature of 20°C and at the stretching rate of 100%/min) independently of the various spinning conditions. The amorphous orientation of a cylindrically symmetric system was investigated by wide-angle x-ray scattering experiments. The orientation of polystyrene monofilaments in real space is denoted by P₂(cos α) within the precision of measurement. The coefficient D₂(r) of the second term in an expansion of cylindrical distribution function in spherical harmonics has two main peaks, near r = 1.6 Å and r = 4 ～ 5 Å. The negative peak near r = 1.6 Å indicates orientation of phenyl groups in a plane perpendicular to the fiber axis. The positive peak near r = 5 Å (brittle region) or near r = 4 Å (ductile region) indicates the piling up of phenyl groups for the direction of the fiber axis. It is most probable that the amorphous state of atactic polystyrene consists of an appropriate cohesion of planar zigzag chains of syndiotactic polystyrene. The lower spacing (r = 4 Å) of the positive second peak in ductile region suggests that there are interchain phenyl groups near r = 5 ～ 6 Å in a plane perpendicular to the fiber axis and that the molecular chains are extended parallel to the direction of the fiber axis. This parallel packing of chain segments along the fiber axis suppresses the formation and growth of cracks of polystyrene monofilaments resulting in ductile fracture.     

Self-organized pattern formation on silicon,stainless steel and zinc coated steel substrates

In this research, a self-organized pattern formation employing polystyrene/aluminum bilayer coatings on three different substrates was studied. Two new substrate materials, stainless steel and zinc coated steel for self-organization application were introduced. Influence of polystyrene molar mass on pattern formation was studied with five different polystyrene samples having molar masses between 27 and 247 × 10³ g/mol. Polystyrene/toluene solutions were applied onto the substrates using the spin coating technique and aluminum layer was created by chemical vapor deposition (CVD). Self-organized pattern formation was induced thermally, by heating the layered substrate/polystyrene/aluminum structures above the glass transition temperature of polystyrene. Sub-micron–micron sized wrinkles or island-like surface patterns were achieved on all substrates. The molar mass of polystyrene was found to have effect on the dimensions of the formed structures. It was also observed that the characteristic surface structure of substrates influences self-organization and thereby directs the structure formation.     

The phase behaviors of adsorbed polymethylene chains

The phase behaviors of a single adsorbed polymethylene chain are investigated by using molecular dynamics simulations. In the free space, it is confirmed in our calculation that the isolated polymer chain exhibits a disordered coil state at high temperatures, and collapses into a condensed state at low temperatures, i.e., the coil-to-globule transition, and finite chain length effects are considered since the critical region may depend on the chain length. When the chain is adsorbed on an attractive surface, however, the equilibrium properties may not only depend on chain length but also depend on the adsorption energy. For short chain of N = 40 monomers, a coil-to-globule transition is found for weak adsorption energy of w = 2.5 kcal/mol, but the critical temperature is lower than the free chain, and for strong adsorptions of w = 3.5 and 4.5 kcal/mol, the structures at low temperatures are adsorbed hairpin like, so we may call the transition process coil-to-hairpin transition. For long chains of N = 80 monomers and N = 120 monomers, the critical regions are the same for the free chains both at T = 265 K, and for the adsorption energies of w = 2.5, 3.5, and 4.5 kcal/mol, the curves of the heat capacities are smooth when T > 200 K, and while T < 200 K, the values of the heat capacities decrease as the temperatures decreasing, so the transition may be from loose globular structures to compact globular structures, and for more stronger adsorption energy of w = 6.5 and 8.5 kcal/mol, the critical regions are obvious and they are coil-to-crystal like transitions.     

Parametric numerical simulation of impact response of carbon nanotube/polymer nanocomposites

A numerical model has been developed using the explicit FE code LS-DYNA in order to study the effect of geometrical and material parameters on the low-velocity impact response of carbon nanotube (CNT)/polymer nanocomposites. The model is based on a Representative Volume Element (RVE). The RVE is prismatic with a rectangular cross-section while the impactor is spherical. The simulations show that the presence of CNT significantly enhances the impact stiffness and the energy absorption capacity of the material. The enhancement increases with the CNT's volume fraction and it is larger at larger impact velocities. The effect of CNT's aspect ratio is found to be minor. The orthotropic behaviour of CNT assigns the RVE a higher energy absorption capacity than the isotropic behaviour at small impact velocities. The prediction of impact damage at large impact velocities indicates that the CNT makes the polymer more susceptible to fracture.     

Atomistic origin of brittle-to-ductile transition behavior of polycrystalline 3C–SiC in diamond cutting

The machinability of hard brittle polycrystalline ceramic has a strong correlation with internal microstructures and their accommodated deformation behavior. In the present work, we investigate the mechanisms governing the brittle-to-ductile transition behavior of polycrystalline 3C–SiC in diamond cutting by means of molecular dynamics simulations. Simulation results reveal the co-existence of dislocation slip and amorphization-dominated ductile deformation and cracking along grain boundaries-mediated brittle fracture, as well as the correlation of individual deformation modes with machining force variation and machined surface morphology. In addition, inter-granular fracture, grain boundary sliding and grain pull-up are also operating brittle deformation modes of polycrystalline 3C–SiC. The strong competition between above heterogeneous deformation modes determines the brittle-to-ductile transition behavior in grooving of polycrystalline 3C–SiC. Simulation results also demonstrate that grain size has a strong impact on the brittle-to-ductile transition and material deformation behavior of polycrystalline 3C–SiC under diamond cutting.     

Toughening of polypropylene with calcium carbonate particles

Polypropylene-CaCO₃ composites were prepared on a twin screw extruder with a particle content of 0-32 vol%. The influence of particle size (0.07-1.9 μm) and surface treatment of the particles (with and without stearic acid) on the toughening properties were studied. The matrix molecular weight of the polypropylene was also varied (MFI 0.3-24 dg/min). The experiments included tensile tests, notched Izod impact tests, differential scanning calorimetry (DSC), scanning electron microscopy and rheology experiments. The modulus of the composites increased, while the yield stress was lowered with filler content. This lowering of yield stress was connected to the debonding of the particles from the polypropylene matrix. From DSC experiments it was shown that the particle content had no influence on the melting temperature or crystallinity of the PP phase, also particle size showed no effect on the thermal properties. The impact resistance showed large improvement with particle content. The brittle-to-ductile transition was lowered from 90 to 40 °C with the addition of CaCO₃ particles. Notched Izod fracture energy was increased from 2 up to 40-50 kJ/m². The stearic acid coating on the particle surface showed a large positive effect on the impact strength. This was mainly due to the improved dispersion of the CaCO₃ particles. Aggregates of particles clearly had a detrimental effect on the impact behaviour of the composites. The smaller particle sizes (<0.7 μm) showed coarse morphologies and this lowered the toughening efficiency. The molecular weight of the polypropylene matrix had a profound effect on the toughening properties. A higher molecular mass shifted the brittle-to-ductile transition towards lower temperatures. At the higher filler loads (>20 vol%), however, still problems seem to occur with dispersion, lowering the toughening efficiency. Of all particle types used in this study the stearic acid treated particles of 0.7 μm were found to give the best combination of properties. From the study of the micro-toughening mechanism it was shown that at low strain the particles remain attached to the matrix polymer. At higher strain the particles debond and this leads to a change in stress state at the particle size level. This prevents crazing of the matrix polymer and allows extensive plastic deformation, resulting in large quantities of fracture energy.     

Shape oscillations and path transition of bubbles rising in a model bubble column

We investigate experimentally the occurrence of shape oscillations accompanied by path transition of periodically produced air bubbles rising in water. Within the period of bubble formation, the induced velocity is measured to examine bubble-liquid and bubble-bubble interactions. The flow is produced in a small-scale bubble column with square-shaped cross section. A capillary aerator produces bubbles of size 3.4 mm at a frequency of 5 Hz. Measuring techniques employed are high-speed imaging to capture bubble shape oscillations and path geometry, and laser-Doppler anemometry (LDA) to measure the velocity in the liquid near the rising bubbles. The experimentally obtained bubble shape data are expanded in Legendre polynomials. The results show the occurrence of oscillations by the periodicity of the expansion coefficients in space. Significant shape oscillations accompanied by path transition are observed as the second-mode oscillation frequency converges to the frequency of the initial shape oscillations. The mean velocity field in the water obtained by LDA agrees well with potential theory. An analysis of the decay of the induced flow shows that there is no interaction between the flow fields of two succeeding 3.4 mm bubbles in the rectilinear path when the bubble production frequency is lower than 7.4 Hz.     

Effects of environment on the mechanical properties of plastics under high pressure

Polystyrene (PS), high-impact polystyrene (HIPS), and polyethylene (PE) have been investigated studying the pressure dependence of stress-elongation behavior in tension over the range from atmospheric pressure to four kilobars at room temperature. The effect of strain rate was also observed for PS specimens. Tensile deformation of PS and HIPS has shown that the pressure-transmitting fluid (silicon oil) acts as a stress crazing and cracking agent. Non-sealed specimens of PS showed a brittle-to-ductile transition at 2.95 kbar while specimens sealed from the environment showed the same transition at only 0.35 kbar. Scales HIPS and PE specimens exhibited ductile behavior at all pressures. The extent of plastic deformation for PE was affected when specimens where exposed to the silicon oil environment. Surprisingly, HIPS exposed to the oil exhibited two transitions as the applied hydrostatic pressure was raised: a ductile-to-brittle followed by a brittle-to-ductile transition. Analysis of the stress-elongation curves for sealed PS and HIPS specimens indicated that the pressure dependency of craze-initiation stress differs from that of shear band initiation stress. The brittle-to-ductile transition occurred when the initiation stresses of both processes became equal. The principal stress for craze initiation showed almost no pressure dependency, suggesting that crazes initiate when the principal stress level of the tensile specimen reaches a critical value irrespective of the applied hydrostatic pressure.     

Co-continuous polycarbonate/ABS blends

Co-continuous PC/ABS (50/50) blends were studied with a variable polybutadiene (PB) content (0-40%) in ABS. Polycarbonate (PC), styrene-acrylonitrile (SAN) and PB were blended in two steps using a twin screw extruder. Rectangular bars were injection moulded and notched Izod impact tested at different temperatures and in single edge notch tensile tests at 1 m/s and different temperatures. Co-continuous PC/ABS gave a brittle-to-ductile transition temperature lower than expected based on notched Izod results for dispersed ABS in PC. The brittle-to-ductile transition temperature, in the co-continuous PC/ABS blends, decreased with increasing rubber content in SAN. The fracture energies showed an optimum at 15% PB in SAN while at the same time a delamination was seen on the ductile fracture surface, due to failure of the PC/SAN interface. Delamination disappeared when the rubber content in SAN or the temperature was increased. Specimens containing a welding were injection moulded to study the influence of rubber and AN content in the SAN on the interface. Weldline strength of the blends was very poor compared to PC, but improved with increasing rubber content in SAN.     

Influence of temperature on hydrogen electrosorption into palladium-noble metal alloys. Part 1: Palladium-gold alloys

Hydrogen electrosorption into Pd-rich (>70 at.% Pd in the bulk) Pd-Au alloys obtained by electrodeposition was studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. The influence of temperature (in the range between 283 and 313 K) on the amount of absorbed hydrogen, the potential of the α-β phase transition, absorption-desorption hysteresis and the potential of absorbed hydrogen oxidation was examined. It was found that for the temperature range studied the potentials of the α → β and β → α phase transitions are shifted negatively with increasing temperature and positively with decreasing Pd content in the alloy bulk. Thermodynamic parameters (Gibbs free energy, enthalpy and entropy) of the β-phase formation and decomposition were determined from the temperature dependence of the potential of the α-β phase transition. The absolute values of enthalpy and entropy of the β-phase formation and decomposition increase with the decrease in Pd bulk concentration in Pd-Au alloys. The maximum hydrogen absorption capacity of Pd-Au alloys slightly decreases with increasing temperature. The potential of absorbed hydrogen oxidation peak is shifted negatively with increasing temperature and decreasing Pd bulk content.     

The rotational and translational dynamics of molecular hydrogen physisorbed in activated carbon: A direct probe of microporosity and hydrogen storage performance

We have measured Incoherent Inelastic Neutron Scattering (IINS) spectra of H₂ physisorbed in high purity chemically activated carbon (AC) at different surface coverage and at temperatures near the triple point of bulk hydrogen. Our experimental results and DFT calculations show that at low surface coverage, due to the very low corrugation of the adsorption potential, and in the absence of H₂-H₂ lateral interactions, the adsorbed molecules are practically free to translate in the 2D plane parallel to the surface. Model calculations show that a complete mixing between the sub-states of the J = 1 manifold occurs on the free surface. The J = 0-to-1 rotational transition should split if the H₂ molecule is adsorbed in a slit type pore. Rotational splitting of up to 13 meV is found in the narrowest pores of around 6 Å investigated. The calculated isosteric heat of adsorption for molecules adsorbed on the free surface, at different sites and molecule orientations, range between −39 and −42 meV/H₂ at 77 K. In the optimum size slit pores, these numbers double up. Micropore volume of 0.34-0.45 ml/g carbon, and an upper limit of 4 wt% hydrogen storage is anticipated for the investigated material.     

Rheological behavior of thermoset/thermoplastic blends during isothermal curing: Experiments and modeling

The evolution of the viscoelastic properties of a molten thermoplastic/thermoset system during the course of the isothermal polymerization of the thermoset precursors has been investigated and modeled. Such systems are initially homogenous and phase separate upon polymerization of the monomers. In the present study, atactic polystyrene (85 and 60 wt%) is blended to a stoichiometric mixture diglycidyl ether of bisphenol A with 4,4′-methylenebis(2,6-diethylaniline). During the polymerization, polystyrene becomes the thermoplastic-rich matrix and an epoxy-rich dispersed phase appears. Both phases experience changes in their composition and viscoelastic properties. A rheokinetic model is proposed to take into account four contributions to the viscoelastic behavior: progressive deplastification of the polystyrene matrix involving a modification of the glass transition and thus of free volume, dilution of the network of entanglements of the matrix by the non yet converted low molar weight molecules, emulsion behavior after the separation of the epoxy-rich phase and finally interparticular interactions being assimilated to a mechanical percolation. Provided that the glass transition temperature of the matrix and the dynamic moduli of the neat components are known, the changes in the viscoelastic behavior of the system with time can be predicted with no ad hoc parameter and model calculations are in good agreement with the experimental data.     

Granular temperature: Comparison of Magnetic Resonance measurements with Discrete Element Model simulations

The Discrete Element Model (DEM) is a very promising modelling strategy for two-phase granular systems. However, owing to a lack of experimental measurements, validation of numerical simulations of two-phase granular systems is still an important issue. In this study, a small two-dimensional gas-fluidized bed was simulated using a Discrete Element Model. The dimensions of the simulated bed were 44 × 10 × 120 mm and the fluidized particles had a diameter d_p = 1.2 mm and density ρ_p = 1000 kg m^− 3. The influence of different drag-force correlations was investigated. Preliminary numerical experiments were also performed to study the effects of (i) the coefficient of restitution and (ii) the modelled transverse thickness of the two-dimensional bed. Experimental measurements were made using Magnetic Resonance (MR), with the comparisons between DEM simulations and experimental measurements performed on the basis of the time-averaged velocity and granular temperature profiles of the particles. It was found that the DEM simulations of the time-averaged vertical velocity of the particles agreed well with the MR measurements. The drag-force correlation proposed by [R. Beetstra, M.A. van der Hoef and J.A.M. Kuipers, Drag force of intermediate Reynolds number flow past mono- and bidispersed arrays of spheres. AIChE Journal, 53, 489-501 (2007).] showed the best agreement with the experimental data. Fair agreement was found if the granular temperature calculated by the DEM simulations was compared with MR measurements. At lower fluidization velocities and closer to the distributor the DEM simulations under-predicted both the velocity and the granular temperature measurements using MR.     

Two-step micro cellular foaming of amorphous polymers in supercritical CO2

Microcellular foaming of amorphous rigid polymers, polymethylmethacrylate (PMMA) and polystyrene (PS) was studied in supercritical CO₂ (ScCO₂) in the presence of several types of additives, such as triblock (styrene-co-butadiene-co-methylmethacrylate, SBM and methylmethacrylate-co-butylacrylate-co-methylmethacrylate, MAM) terpolymers. This work is focused in the two-step foaming process, in which the sample is previously saturated under ScCO₂ being expanded in a second step out of the CO₂ vessel (e.g. in a hot oil bath) where foaming is initiated by the change of temperature near or above the glass transition temperature of the glass/polymer glassy system. Samples were saturated under high pressures of CO₂ (300 bar), at room temperature, for 16 h, followed by a quenching at a high depressurization rate (150 bar/min). In the last step, foaming was carried out at different temperatures (from 80 °C to 140 °C) and different foaming times (from 10 s to 120 s). It was found that cellular structures were controlled selecting either the additive type or the foaming conditions. Cell sizes are ranging from 0.3 μm to 300 μm, and densities from 0.50 g/cm³ to 1 g/cm³ depending on the polymers considered.     

Electrosorbed carbon monoxide monolayers on Pt(1 1 1)

We review structures of high-density CO monolayers on Pt(1 1 1) surfaces in CO-saturated electrolytes or in gaseous CO at near atmospheric pressure, using surface X-ray scattering (SXS) and scanning tunneling microscopy (STM). In electrolytes, we confirmed the well-known (2 × 2)-3CO and (√19 × √19)-13CO structures and were able to study the transition between them. For gas-phase studies, we were able to stabilize extremely well-ordered CO monolayers by emersion transfer from an electrochemical cell. We found that the hexagonal close-packed (2 × 2)-3CO structure is the equilibrium phase at room temperature in ∼1 atm CO gas pressure. This commensurate (C) phase transforms continuously to an incommensurate (IC) phase at elevated temperature (a second-order phase transition). We also confirm that the (√19 × √19)-13CO structure is stable at lower CO partial pressure. This C phase transforms discontinuously to an IC phase (a first-order phase transition). A tentative phase diagram and a brief review of structure details of the (2 × 2)-3CO and (√19 × √19)-13CO phases will be presented.     

Crosslinking vs. filler effect of carboxylate-substituted zirconium oxo clusters on the thermal stability of polystyrene

Inorganic-organic hybrid materials were prepared by step-wise free radical polymerization of styrene in the presence of zirconium oxo clusters of the general compositions Zr₆O₄(OH)₄(carboxylate)₁₂ (carboxylate = 5-norbornene-2-carboxylate or isobutyrate/methacrylate) and Zr₁₂O₈(OH)₈(carboxylate)₂₄ (carboxylate = acetate/propionate, vinylacetate, or acetate/methacrylate). Clusters with non-polymerizable ligands resulted in cluster/polystyrene blends which were soluble in toluene, whereas clusters with polymerizable ligands gave cluster-crosslinked, swellable polymers for which solvent uptake correlated with the functionality of the corresponding cluster. The onset temperatures of thermal decomposition and the glass transition temperatures of all cluster-containing polymers were higher than that of neat polystyrene, independent of whether the clusters were crosslinking or blended into the polymer.     

Evaluation of the elastic constants of nanoparticles from atomistic simulations

We present an approach to estimate the elastic constants of molecules and nanoparticles, based on the analysis of thermal fluctuations from Monte Carlo (MC) or molecular-dynamics (MD) atomistic simulations. The method and the force-field used for these calculations have been tested by the calculation of Young's modulus of a graphite sample along the basal plane; the calculated value was found to be 1.07 TPa, in very good agreement with the experimentally determined one of 1.02 TPa.The results on a carbon-based nanotube indicate that for the longitudinal direction of the particle, the value of the elastic constant is on the order of 400 GPa. The elastic constant of the considered nanotube in the radial direction is significantly lower, the predicted values being in the range 4-7 GPa.The method was also applied to the elastic constants of a type of siloxane-based nanostructure, whose longitudinal elastic constant (30 GPa) is an order of magnitude lower than the corresponding value for the carbon-based nanotube.