Ostwald ripening in an immiscible hydrogenated polybutadiene and high-density polyethylene blend

The long-time regime coarsening in a phase-segregated blend of hydrogenated polybutadiene (HPB) with high-density polyethylene (HDPE) was studied. The blend consisted of 10 wt% of HPB in a HDPE matrix. The morphology of the system was studied by etching the HPB particles from the HDPE matrix and observing the etched specimens in a scanning electron microscope. The average volume of the HPB particles was found to increase with storage time in the melt, and to follow a temporal exponent of 1 in agreement with the predictions of the Ostwald ripening theory. This indicated that the particles coarsen by the evaporation-condensation mechanism on which the Ostwald ripening theory is based. The rate constant from the Ostwald ripening theory was calculated and compared to the rate constant determined from the experimental data. The theoretical rate constant, K, calculated from Ostwald ripening theory, was 3.6 × 10^?18 cm³/s compared to an experimentally determined rate constant of 4.8 × 10^?18 cm³/s. The agreement between the theoretical and experimental rate constants was quite good. The significance attached to the good agreement between the theoretical and experimental rate constants might be mollified to some extent by the uncertainty involved in the parameters used to calculate the theoretical rate constant; viz. the interfacial tension, mutual-diffusion coefficient, and equilibrium concentration of the HPB in the matrix phase that are not known to high accuracy. In reality, because other theories were used to determine the interfacial tension, mutual-diffusion coefficient, and equilibrium phase compositions, this study was a test of several theories simultaneously. However, the agreement of the experimental temporal exponent and rate constant with the predictions of Ostwald ripening theory strongly indicates that the HPB/HDPE system coarsens by the evaporation-condensation mechanism upon which the Ostwald ripening theory is based. © 1994 John Wiley & Sons, Inc.     

Crystallization of isotactic polypropylene and high-density polyethylene under negative pressure resulting from uncompensated volume change

The melting behavior of spherulites in thin sections of isotactic polypropylene bulk samples and high-density polyethylene thin films crystallized isothermally at various temperatures has been studied by polarized light microscopy. The regions around cavities and multiple boundary points between spherulites have higher melting temperatures than the other parts of spherulites crystallized in Regime III. The increase in melting temperature is explained as a result of crystallization under negative pressure arising locally in pockets of occluded melt due to density change during spherulitic crystallization. The negative pressure lowers locally the equilibrium melting temperature and therefore decreases the undercooling, which results in an increase in lamellar thickness. Sectioning of bulk samples releases frozen negative pressure and reveals the increase in melting temperature of those parts of spherulites that were crystallized at lower undercooling. © 1993 John Wiley & Sons, Inc.     

Effects of different ultrahigh molecular weight polyethylene contents on the formation and evolution of hierarchical crystal structure of high-density polyethylene/ultrahigh molecular weight polyethylene blend fibers

In this paper, the blend fibers of ultrahigh molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE) were prepared by solution blending and gel spinning process. The uniformity of the blend fibers has been confirmed by rheological data and thermodynamic unimodal curve. They were further characterized by single fiber strength test, scanning electron microscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, and so forth, to explore the structural evolution mechanism with the change of UHMWPE content. The results showed that when the molar content of UHMWPE was only 2.9 mol%, entanglement appeared in the structure of shish-kebab, and when the proportion reached 20 mol%, an interlocking structure could be observed. With the increase of UHMWPE content, kebab began to be networked, and when the content reached 33 mol%, kebab's orientation reached its peak. After that, the interlocking network structure gradually improved. When the content reached 50 mol%, the shish's orientation reached saturation, and the shish-kebab network became perfect. In addition, with the increase of UHMWPE content, stress-induced recrystallization occurred on the wafer, some kebab would be converted into shish crystals, and when the content exceeded 50 mol%, the microfibers began to merge, and the wafer became denser, but still had entanglements. Our work has proposed a quantitative explanation for the evolution of hierarchical crystal structure of HDPE/UHMWPE blend fibers.     

Effects of γ-irradiation on the morphology and slow crack growth in high-density polyethylene

The effects of γ-irradiation were measured in a HDPE and in the resin after it was recrystallized. The fracture mode of the initial material transformed from crazing to complete brittle failure at a critical dose. The failure mode of the recrystallized material transformed from crazing to shear deformation, which produced an extremely long failure time, and finally, at a higher dose, its fracture became brittle. The relationship between morphology and slow crack growth is presented where crosslinking was the major factor. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1211–1218, 1998     

Influence of gamma irradiation on high density polyethylene/ethylene‐vinyl acetate/clay nanocomposites

The study of high density polyethylene (HDPE)/ethylene‐vinyl acetate (EVA)/and organically‐modified montmorillonite (OMT) nanocomposites prepared by melt intercalation followed by exposure to gamma‐rays have been carried out. The morphology and properties of the nanocomposites were studied using X‐ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and cone calorimetry. The purpose of the study focuses on the influence of gamma irradiation on the morphology, thermal stability and flammability properties of the nanocomposites. XRD studies and TEM images verified that the ordered intercalated nanomorphology of the nanocomposites was not disturbed by gamma irradiation. TGA data showed that the nano‐dispersion of clay throughout the polymer inhibited the irradiation degradation of HDPE/EVA blend, which led to the nanocomposites exhibiting superior irradiation‐resistant properties than that of the pure blend. Cone calorimetry results indicated that the improvement in heat release rate (HRR) for irradiated HDPE/EVA blend was suppressed efficiently when clay was present. Increasing clay loading from 2 to 10% was beneficial by improving the flammability properties of the nanocomposites, but promoted a rapid increase in the sub‐peak HRR at high irradiation dose level. Copyright © 2004 John Wiley & Sons, Ltd.     

The effects of annealing on fatigue crack propagation in polyethylene

Fatigue crack propagation tests on annealed and quenched medium-density polyethylene showed the annealed specimens to have much lower resistance to crack initiation and subsequent propagation. Although the same fracture mechanism, in which the brittle crack gradually becomes more ductile, prevailed in both cases, the voided and fibrillated crack tip root craze in the annealed material was much weaker that the nonfibrillated quenched root craze. Microstructural analyses indicate that the annealed material had separate crystallite populations, whereas the quenched material had a more homogeneous morphology. The highest melting fraction of the annealed material was composed of lamellae that were about 270 Å thick, and the quenched lamellae were estimated to be 160 Å thick. The reduced fatigue crack propagation resistance of the annealed material was suggested to be a result of a lower concentration of tie molecules and its reduced damping capability, compared to the quenched material. © 1995 John Wiley & Sons, Inc.     

Shear Viscosity of Dilute Polymer Solutions Compared and Contrasted with Mechanical Properties of Nylon Plus Plasticizer

Abstract

Both the shear viscosity η(c) of dilute polymer solutions and Young's modulus Y(c) of nylon plus plasticizer with concentration c are assumed to be expressible as a power series in concentration. Scaling arguments are then presented which reveal an intimate relation between the coefficients of O(c) and O(c²) terms in both η(c) and Y(c) The coefficient of the O(²) term is predicted always to be positive, while that of the O(c) term can in principle have either sign. Comparison with experiment is made for η(C) and Y(c) Some further experiments are proposed for both Y(c) and η(c)     

Crystal and phase morphology of dynamic-packing-injection-molded high-density polyethylene/ethylene vinyl acetate blends

The effect of shear stress, provided by so-called dynamic-packing injection molding, on crystal morphology and phase behavior was investigated for high-density polyethylene (HDPE) in blends with ethylene vinyl acetate (EVA) of various viscosities and vinyl acetate (VA) contents, with the aid of differential scanning calorimetry, two-dimensional small-angle X-ray scattering (2D SAXS), and scanning electron microscopy (SEM). A shish-kebab pattern was found in the oriented zones of dynamic samples, and the ratio of shish to kebab increased as a function of the EVA content in the blends up to 20 wt %, regardless of the VA content. This showed that molecules of HDPE could easily be stretched to form a shish structure in the presence of EVA. Moreover, a large increase in the long spacing, characterized by 2D SAXS measurements, was achieved because of the presence of EVA. The SEM results showed an obvious decrease in the domain size of the EVA phase under the effect of shear stress. All these results suggested shear-induced mixing between HDPE and EVA, in that ethylene segments of EVA molecules could be forged in the shish structure during shear and the other fractions of EVA were located in the amorphous regions between the adjacent lamellae of HDPE. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1831–1840, 2004     

Photocrosslinking of ultra high strength polyethylene fibers

Ultra high strength polyethylene (HSPE) fibers have been successfully photocrosslinked using benzophenone as photoinitiator. The introduction of photoinitiator without disturbing the fiber structure is a difficult problem which was solved by vapor absorption at elevated temperature while keeping the fiber under constant strain. The crosslinked fiber showed no decrease in mechanical properties at room temperature as is the case when fibers are crosslinked by other reported methods such as radiation and chemical crosslinking. The crosslinked fiber showed enhanced high temperature resistance as well as much lower creep rate on prolonged stressing. Photocrosslinking of HSPE fiber is superior to other crosslinking methods reported in the literature.     

Wave formation by heating in thin metal film on an elastomer

Wave formation by heating rather than the usual cooling in a thin metal film on an elastomer is presented. A simple model is used to relate the wavelength of the waves thus formed to the heating temperature. An indirect method of estimating Young's modulus at elevated temperatures emerges from the analysis. The waves formed by heating can be made to appear or not to appear by the selection of the temperature to which the sample is heated. A relationship is given for the critical temperature that determines the appearance or nonappearance of the waves. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1122–1128, 2001     

Tensile deformation of electrospun nylon‐6,6 nanofibers

Nylon‐6,6 nanofibers were electrospun at an elongation rate of the order of 1000 s^?1 and a cross‐sectional area reduction of the order of 0.33 × 10⁵. The influence of these process peculiarities on the intrinsic structure and mechanical properties of the electrospun nanofibers is studied in the present work. Individual electrospun nanofibers with an average diameter of 550 nm were collected at take‐up velocities of 5 and 20 m/s and subsequently tested to assess their overall stress–strain characteristics; the testing included an evaluation of Young's modulus and the nanofibers' mechanical strength. The results for the as‐spun nanofibers were compared to the stress–strain characteristics of the melt‐extruded microfibers, which underwent postprocessing. For the nanofibers that were collected at 5 m/s the average elongation‐at‐break was 66%, the mechanical strength was 110 MPa, and Young's modulus was 453 MPa, for take‐up velocity of 20 m/s—61%, 150 and 950 MPa, respectively. The nanofibers displayed α‐crystalline phase (with triclinic cell structure). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1482–1489, 2006     

The influence of short-chain branching on the creep behavior of oriented polyethylene,and its effect on the efficiency of crosslinking by electron irradiation

Studies have been made of the creep behavior of oriented (15:1) polyethylenes containing 0.4 and 1.3 butyl branches per 1000 C atoms. Increasing the branch concentration reduces significantly the creep strain and the equilibrium strain rate. The data have been fitted to an established model comprising two thermally activated processes in parallel, relating to the amorphous network at low stress, and the crystal phase at high stress. Analysis based on this model indicates the similarity between branching, entanglements, and crosslinks on the creep response. The creep behavior of electron-beam-irradiated materials shows that increasing the branch concentration makes the polyethylene more susceptible to mainchain scission, indicated by increased creep flow rates at higher stress, consistent with previous rubber elasticity studies. Irradiation in an acetylene atmosphere with low (< 1 Mrad) doses is shown to reduce the creep rates at all accessible stresses, and this attributed to an increase in crosslinking compared with scission. © 1994 John Wiley & Sons, Inc.     

Hardness and Young's modulus of transcrystalline polypropylene by Vickers and Knoop microindentation

A study of the anisotropic microhardness and Young's modulus of transcrystalline isotactic polypropylene grown from the surface of high modulus carbon fibers is described. Static microindentation experiments were performed with Knoop and Vickers tips. The Young's moduli of the transcrystalline region were estimated from Knoop microindentation data by using a method recently developed in our laboratory. Data for the different lamellar directions were generated using the Knoop tip, which is sensitive to material anisotropy. We found that the hardness and Young's modulus of the transcrystalline layer are higher by up to 30% when the longer diagonal of the probing Knoop tip is perpendicular to the transcrystalline growth direction, compared to when the diagonal is parallel to that direction. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 523–530, 1999     

Mesoscopic model for mechanical characterization of biological protein materials

Mechanical characterization of protein molecules has played a role on gaining insight into the biological functions of proteins, because some proteins perform the mechanical function. Here, we present the mesoscopic model of biological protein materials composed of protein crystals prescribed by Go potential for characterization of elastic behavior of protein materials. Specifically, we consider the representative volume element (RVE) containing the protein crystals represented by C(alpha) atoms, prescribed by Go potential, with application of constant normal strain to RVE. The stress-strain relationship computed from virial stress theory provides the nonlinear elastic behavior of protein materials and their mechanical properties such as Young's modulus, quantitatively and/or qualitatively comparable with mechanical properties of biological protein materials obtained from experiments and/or atomistic simulations. Further, we discuss the role of native topology on the mechanical properties of protein crystals. It is shown that parallel strands (hydrogen bonds in parallel) enhance the mechanical resilience of protein materials.     

Analysis of Molecular and Morphological Effects on Slow Crack Growth in Modern PE Pipe Grades by Cyclic Fracture Mechanics Tests

Summary: Three different polyethylene (PE) pipe grades as well as three different lots of one of the grades were investigated by cyclic tests with cracked round bar (CRB) specimens, concerning resistance to slow crack growth. To enhance the test sensibility and proof its applicability for a quick quality assurance method various molecular and morphological characterizations on compression molded plates were carried out, with special attention on the influence of molecular and morphological differences, as well as lot to lot variations on the resistance to slow crack growth. The cyclic CRB tests allowed a ranking of the different pipe grades and lots with short testing times per material and testing machine, as a function of failure time as well as of crack initiation time with further reduction of testing time of about 50%. Moreover the ranking corresponded to the expectations based on the molecular and morphological properties of the materials, where only minor changes in the molecular mass distribution and the co-monomer concentration in case of lot to lot variations were proofed reliably.     

Extracting uncrosslinked material from low modulus sylgard 184 and the effect on mechanical properties

Commercial silicone elastomers are commonly used in soft materials research due to their easily tunable mechanical properties. However, conventional polydimethylsiloxane (PDMS) elastomers with moduli below ∼100 kPa contain uncrosslinked free molecules, which play a significant role in their behavior. To utilize these materials, it is important to quantify what role these free molecules play in the mechanical response before and after their removal. We present a simple and inexpensive extraction method that enables the removal of free molecules from a lightly crosslinked sheet of Sylgard 184, a commercially available PDMS elastomer. The materials can contain a majority of free molecules yet maintain a thin and flat geometry without fractures after extraction. Subsequently, we compare the modulus, maximum stretchability, and hysteresis behavior with mixing ratios ranging from 60:1 to 30:1, before and after extraction. We show that the modulus, maximum stretchability, and dissipation increase upon extraction. Moreover, our approach offers a route to prepare crosslinked silicone elastomers with a modulus as low as ∼20 kPa without free molecules from a commercially available kit. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 343–351     

The mechanism of fatigue failure in a polyethylene copolymer

The fatigue behavior of an ethylene-hexene copolymer was investigated. The effects of R, frequency, relative times under the maximum and minimum stress, and waveform were measured. The phenomenological aspects were related to the microscopic aspects of the failure process. The maximum stress produces damage by disentangling the molecules in the fibrils of the craze and the minimum stress produces damage by bending the fibrils. The net damage, which is a product of these two damage processes, has been represented by a simple equation which accounts for the phenomenological observations.     

Mechanical Properties of a Single Electrospun Fiber and Its Structures

Summary: A method to measure the Young's modulus of a single electrospun polyacrylonitrile (PAN) fiber is reported. The Young's modulus can be calculated from the force‐displacement curves obtained by the bending of a single fiber attached to an atomic force microscopy (AFM) cantilever. It is suggested that the high modulus of electrospun fibers is caused by the orientation of molecular chains, which is confirmed by wide‐angle X‐ray diffraction (WAXD) measurements. The communication will provide a basic understanding of the relationship between mechanical properties and structures of electrospun fibers.

A PAN fiber was attached to a contact mode cantilever to facilitate the measurement of force‐displacement curves and Young's modulus.     

Investigating the morphology and mechanical properties of blastomeres with atomic force microscopy

Atomic force microscopy (AFM) was used to directly investigate the morphology and mechanical properties of blastomeres during the embryo development. With AFM imaging, the surface topography of blastomeres from two‐cell, four‐cell, and eight‐cell stages was visualized, and the AFM images clearly revealed the blastomere's morphological changes during the different embryo developmental stages. The section measurements of the AFM topography images of the blastomeres showed that the axis of the embryos nearly kept constant during the two‐cell, four‐cell, and eight‐cell stages. With AFM indenting, the mechanical properties of living blastomeres from several embryos were measured quantitatively under physiological conditions. The results of mechanical properties measurements indicated that the Young's modulus of the two blastomeres from two‐cell embryo was different from each other, and the four blastomeres from the four‐cell embryo also had variable Young's modulus. Besides, the blastomeres from two‐cell embryos were significantly harder than blastomeres from four‐cell embryos. These results can improve our understanding of the embryo development from the view of cell mechanics. Copyright © 2013 John Wiley & Sons, Ltd.