Mechanism of necking as revealed by ultrasonic cavitation of polyethylene single crystals

Ultrasonic cavitation of polyethylene single crystals and single-crystal aggregates in the form of cakes results in lamella fragmentation and necking involving the transformation of lamellar crystals into fibrillar crystals between 20 to 400 Å in diameter. The smaller fibrils (～20–30 Å) have a very smooth appearance, whereas the larger ones (～100–400 Å) contain a beady structure about 100 Å periodically spaced along the fibrils. The smoother microfibrils are suggested to contain extended chains that are formed by unfolding of molecules directly from the chain-folded lamellae as well as from the folded-chain crystals contained within the beady fibrils. The presence of the chain-folded crystals within the larger beady fibrils is shown in numerous instances to be due to incorporation of mosaic crystalline blocks originally present, but weakly connected to one another, in the lamellar single crystals. The necking process is deduced by observation to involve primarily a mechanical shearing of mosaic crystalline blocks along the c-axis plus a rotation into the fibril direction. Observation of extreme resistance of lamellae in the overgrowth regions to cavitation damage suggests the presence of tie molecules and/or interpenetrating cilia between these lamellae. The suggestion finds strong support from additional studies carried out on lamellae that have been tied together at the folds by cross-linking with γ rays.     

Temperature dependence of morphology of supermolecular structures growing in the thin layer melt of fractions of poly(ethylene oxide)

Poly(ethylene oxide) fractions with molecular weights in the range from 1.55 × 10³ to 1.5 × 10⁵ were studied. The optical microscopic observations of the morphology of supermolecular structures grown isothermally from the melt were used to determine the dependance of structural-morphological changes on temperature. Two morphological transitions were established: (1) a high temperature transition at 49 [Ptilde] 3° C from hedritic structures to positive spherulitoids and (2) a low temperature transition at 38 [Ptilde] 2° C from positive spherulitoids to negative spherulites. It is supposed that the transition from hedrites to positive spherulitoids proceeds through a transition from b-axis-oriented lamellae with tilted chains to [401] lamellae with chains perpendicular to the lamellar surface.     

Piezoelectric relaxations in polymers: Spherical dispersion model

For the interpretation of piezoelectric relaxation in oriented polymers, a spherical dispersion model is proposed in which piezoelectric spheres are dispersed in a nonpiezoelectric medium. The influence of the dielectric and elastic relaxations in the medium and the sphere on the piezoelectric stress constant and strain-constant is analyzed in detail. The origins of piezoelectric relaxations in oriented poly-γ-methyl-L-glutamate are assigned to the elastic relaxation (at about ?70°) and the dielectric relaxation (at about 0°C) in the piezoelectric phase, and the elastic relaxation (at about 100°C) in the non-piezoelectric phase, respectively.     

Processing and characterization of α-elastin electrospun membranes

Elastin isolated from fresh bovine ligaments was dissolved in a mixture of 1,1,1,3,3,3-Hexafluoro-2-propanol and water were electrospun into fiber membranes under different processing conditions. Fiber mats of randomly and aligned fibers were obtained with fixed and rotating ground collectors and fibrils were composed by thin ribbons whose width depends on electrospinning conditions; fibrils with 721 nm up to 2.12 μm width were achieved. After cross-linking with glutaraldehyde, α-elastin can uptake as much as 1700 % of PBS solution and a slight increase on fiber thickness was observed. The glass transition temperature of electrospun fiber mats was found to occur at ～80 °C. Moreover, α-Elastin showed to be a perfect elastomeric material, and no mechanical hysteresis was found in cycle mechanical measurements. The elastic modulus obtained for random and aligned fibers mats in a PBS solution was 330±10 kPa and 732±165 kPa, respectively. Finally, the electrospinning and cross-linking process does not inhibit MC-3T3-E1 cell adhesion. Cell culture results showed good cell adhesion and proliferation in the cross-linked elastin fiber mats.     

On the mechanism of fibril rotation at the early stages of amorphous-crystalline polymer reorientation

The microdeformation behavior of polyamide-6 (PA6) oriented films is studied by X-ray diffraction at the early stages of reorientation at an angle of 45° to the direction of primary orientation. In the elastic strain range (up to 22%), the shear of crystallites and the rotation of fibrils take place simultaneously. The rotation is provided by the mutual slip of neighboring lamellas inside the fibrils.     

Structural Analysis of Aluminum Oxyhydroxide Aerogel by Small Angle X-Ray Scattering

The work presents studies on the microstructure and mesostructure of nanostructured aluminum oxyhydroxide formed as a high porous monolithic material through the surface oxidation of aluminum liquidmetal solution in mercury in a temperature- and humidity-controlled air atmosphere. The methods of X-ray diffraction analysis, thermal analysis, the low temperature adsorption of nitrogen vapors, transmission electron microscopy, small-angle and very small-angle neutron scattering, and small-angle X-ray scattering are used for comprehensive investigation of the samples synthesized at 25°С as well as that annealed at temperatures up to 1150°C. It is found that the structure of the monolithic samples can be described within the framework of a three-level model involving primary heterogeneities (typical length scale of rc ≈ 9–19 Å), forming fibrils (cross-sectional radius R ≈ 36–43 Å and length L ≈ 3200–3300 Å) or lamellae (thickness T ≈ 110 Å and width W ≈ 3050 Å) which, in turn, are integrated into large-scale aggregates (typical size R _c ≈ 1.25–1.4 μm) with an insignificant surface roughness. It is shown that a high specific surface (~200 m²/g) typical for the initial sample is maintained upon its thermal annealing up to 900°С, and it decreases to 100 m²/g after heat treatment at 1150°С due to fibrillary agglomeration.     

CRITICAL STRAINS DETERMINING THE YIELD BEHAVIOR OF s-PP*

Video-controlled tensile deformation experiments giving true stressstrain curves were carried out on samples of s-PP. Dividing the total tensile deformation into elastic and plastic parts shows three critical strains (A, B, C) for which the differential compliance and the recovery properties change. It was found that all critical strains remain constant on varying the crystallite thickness or the testing temperature. Point A marks the end of the linearelastic range. The yield point, as given by the maximum on the engineering stress-strain curve for a necking sample, essentially corresponds to the second critical point, although the yield point is shifted relative to B to higher strains and varies with temperature. It is associated with the collective onset of inter- and intralamellar slip processes. At the third critical strain (C), the lamellae become destroyed, and fibrils are formed. The texture changes accompanying the drawing determined by a simultaneous measurement of wide-angle X-ray scattering (WAXS) patterns indicate a common activity of intra- and interlamellar slip processes setting in at A and a dominance of intralamellar block slips at moderate deformations above B. The Young's modulus and the yield stress show a large decrease with temperature, whereas there are only minor changes in the crystallinity. We understand it as resulting from a change of coupling, both between the crystalline lamellae and of the blocks within the lamellae.

     

Investigation of decomposition processes in alloy Cu-Ge-Ti

The process of the decomposition of alloy Cu-6 at.% Ge-2.8 at.% Ti in the 400–700°C temperature range was investigated by transmission electron microscopic methods and by a study of the kinetics of the change of electrical resistance. After quenching in water decomposition at 500–600° occurs in two stages. In the first stage the coherent phase precipitates as lamellae with habit plane 100. The second stage is associated with the occurrence of semicoherent lamellae of the same phase. The effect of hardening conditions of the character of decomposition is investigated.     

Study on Properties and Structure of Near Melt Point Extruded High‐Density Polyethylene

The effect of extrusion temperature on the mechanical properties of high‐density polyethylene (HDPE) was examined using solid‐state extrusion (SSE) and melt‐state extrusion (MSE) techniques. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) investigations were employed to provide evidence for explaining the relationship between mechanical properties and morphology of extrusion moldings. Extruded from a convergence‐divergence die, compared with samples obtained by MSE, the yield strength of samples obtained by SSE was enhanced in both longitudinal and transverse directions with a ductile failure. The yield strength decreased sharply with increasing extrusion temperature. The maximum longitudinal yield strength of samples extruded at 112°C was 181 MPa with an 87% elongation at break; the corresponding values were 28 MPa and 800% for samples extruded at 140°C (MSE); in the transverse direction the yield strength was 27 MPa with a 101% elongation at break for samples extruded at 140°C, while the maximum yield strength was 51 MPa with a 45% of elongation at break for samples extruded at 116°C. Compared with sheets extruded at 140°C, DSC data shows a 5.3°C increase in melting point, a 9.5°C decrease in melt point width, and a 7.1% decrease in crystallinity for sheets extruded at 112°C. SEM indicates that spherulites predominate in MSE samples, while a preferred orientation of the lamellae along the extrusion direction were mainly produced by SSE.     

Temperature Effect on the Elasticity of Acrylamide-n-Isopropylacrylamide Copolymers

Acrylamide (AAm) – N-isopropylacrylamide (NIPA) copolymers were prepared via free radical crosslinking copolymerization with various weight percentages (wt%) of AAm and NIPA. The temperature dependence of the compressive elastic modulus, G, and toughness, U_T, of the PAAm- NIPA copolymers due to a volume phase transition was found using a compressive testing technique. It was observed that the compressive elastic modulus increased comprehensively when the temperature was increased between 30°C and 60°C. The PAAm- NIPA copolymers presented higher values of the compressive elastic modulus than pure NIPA above the lower critical solution temperature (LCST) (NIPA exhibits a volume phase transition from hydrophilic to hydrophobic in water at 31°C) and their compressive elastic modulus and toughness had a strong temperature dependence.     

ON MORPHOLOGY AND MULTIPLE MELTING IN POLYPROPYLENE

A series of polypropylenes, including two modern high crystallinity materials (HCPP) were subjected to a stepwise crystallization procedure as a guide to their properties. The results were complicated by the development of double melting endotherms at the highest crystallization temperature. Both HCPP, when grown at the temperature of 145°C, give a double melting peak, but the proportions of the two peaks varied according to the density of nucleation. By partially melting a specimen between the two peaks, it was possible to assign the higher peak to radial dominant lamellae and the lower peak to mostly tangential subsidiary lamellae filling the space in between. Uniformly cross-hatched lamellae at the center of spherulites melt along with the lower melting population in the outer regions of the spherulites. Even if differences in crystallization temperature are eliminated, the properties of nucleated as opposed to nonnucleated PP may therefore be influenced by differences between the center and periphery of spherulites, with “central” properties much more in evidence in nucleated material. The development of these double endotherms is related to morphological constraint, rather than molecular fractionation. Their form is strongly influenced by cross-hatching, but the phenomenon is still found at 160°C where cross-hatching does not form.     

Observation of the nuclear rainbow scattering for12C+12C atE Lab =300 MeV

The elastic and inelastic scattering of¹²C on¹²C has been measured in the angular range between 2.8° and 70.4° in the c.m. system atE _Lab =300 MeV. Optical model calculations have been performed with Woods-Saxon and folded potentials, the ground state and the first 2⁺-state were coupled in the calculations. The large cross sections of the elastic scattering at large angles is related to the nuclear rainbow scattering, which is centered at about 56°. This requires a potential depth of 100 MeV at a distance of 3 fm, the fit to the data is sensitive down to this region. The calculations with the folded potential show a better agreement with the data than those with the Woods-Saxon shape. The total reaction cross section of 1,420 mb, obtained from the optical model analysis, corresponds to the geometrical value; no transparency is observed.     

Effect of heat treatment on the mechanical and microstructural characterization of Mg-AZ91E/TiC composites

Mg-AZ91E/TiC_p composite was fabricated using a spontaneous infiltration technique at 950 °C under an argon atmosphere. The composites produced have 37 vol.% of metal matrix and 63 vol.% of TiC-like reinforcement. The obtained composites were subsequently solution heat-treated at 413 °C during 24 h, cold water quenched, and subsequently artificially aged at 168 and 216 °C during 16 h in an argon atmosphere. Effect of heat treatment on the microstructure and mechanical properties was evaluated. Microstructural characterization was analyzed using different techniques such as X-ray diffraction (XRD) and scanning electron microscopy (SEM). Interface between matrix and reinforcement was examined using transmission electron microscopy (TEM), and mechanical properties were evaluated by measuring the elastic modulus and hardness. Mg, TiC, Al, and Mg₁₇Al₁₂ phases through XRD were detected. Meanwhile, using TEM analysis in heat-treated composites MgAl₂O₄, MgO, and Al₂O₃ were identified. The as-fabricated composite have elastic modulus and hardness of 162 GPa and 316 Hv, respectively. After solution heat treatment and aging at 168 °C during 12 h, the composites reaches values of 178 GPa and 362 Hv for the elastic modulus and hardness, respectively. Time of aging was correlated with measures of elastic modulus and hardness.     

Crystallization of polycarbonate from the glassy state. part I. Thin films cast from solution

The morphology of glassy amorphous thin polycarbonate film cast from solution is affected by thermal treatments. Annealing above 80° C and below T_g results in an increase in the size of the ordered regions, nodules, up to several hundred Angströms. The crystallization process from the glass, taking place at 145° C, is divided into three major steps. At first the nodules merge into patches which aggregate to form lamellar planar structures. In some cases the planar structures are well-formed single crystals. Following this, spherulitic arms develop from the planar structures as centers. These arms at first consist of aggregates of large nodules which recrystallize to form lamellae; the final morphology is spherulitic in nature. The effect of film thickness and of several substrates on the morphology has been observed. Applying stress at room temperature to the crystalline film results in a breaking up of the lamellae into small blocks.     

Porous monoliths consisting of aluminum oxyhydroxide nanofibrils: 3D structure,chemical composition,and phase transformations in the temperature range 25–1700 °C

We present a study on the chemical and structural transformations in highly porous monolitic materials consisting of the nanofibrils of aluminum oxyhydroxides (NOA, Al₂O₃·nH₂O) in the temperature range 20–1700 °C. A remarkable property of the NOA material is the preservation of the monolithic state during annealing over the entire temperature range, although the density of the monolith increases from ~0.02 up to ~3 g/cm³, the total porosity decreases from 99.3 to 25% and remains open up to 4 h annealing at the temperature ~1300 °C. The physical parameters of NOA monoliths such as density, porosity, specific area were studied and a simple physical model describing these parameters as the function of the average size of NOA fibrils—the basic element of 3D structure—was proposed. The observed thermally induced changes in composition and structure of NOA were successfully described and two mechanisms of mass transport in NOA materials were revealed. (i) At moderate temperatures (T?≤?800 °C), the mass transport occurs along a surface of amorphous single fibril, which results in a weak decrease of the length-to-diameter aspect ratio from the initial value ~24 till ~20; the corresponding NOA porosity change is also small: from initial ~99.5 to 98.5%. (ii) At high temperatures (T >?800 °C), the mass transport occurs in the volume of fibrils, that results in changes of fibrils shape to elliptical and strong decrease of the aspect ratio down to ≤?2; the porosity of NOA decreases to 25%. These two regimes are characterized by activation energies of 28 and 61 kJ/mol respectively, and the transition temperature corresponds to the beginning of γ-phase crystallization at 870 °C.

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Graphical abstract

     

Solid-state synthesis of molybdenum–vanadium mixed oxide of tubular morphology

The thermally stimulated processes in the disperse carbon–V₂O₅: MoO₃ mixed oxide composite at 400°C were studied by electron microscopy, Raman spectroscopy, and EPR. The mixed oxide phase recrystallized to form tubulene-like structures in the form of rolled lamellae.     

Broad-line NMR investigation of the amorphous component of poly(trans-1,4-butadiene) and poly(4-methyl pentene-1) crystals wetted by carbon disulfide

Broad-line (proton) NMR measurements were made at temperatures from -15 to -96°C on crystals of poly(4-methyl pentene-1) wetted with a nonprotonated solvent, CS₂. The mobile fraction, A_n, is found to depend on the crystal morphology and subsequent annealing treatments of dried crystals. A_n varies with temperature in the -30 to -70°C region; changes in the slope of the A_n vs temperature plot in this region with annealing treatment are interpreted in terms of changes in the amorphous portions of the lamellae. Previous NMR results for poly(trans-1, 4-butadiene) have been reanalyzed and the new A_n values obtained are given; annealing dry PTBD crystals at 80°C is shown to bring about a significant decrease in A_n.     

In-situ strain localization analysis in low density transformation-twinning induced plasticity steel using digital image correlation

The effect of deformation temperature on the strain localization has been evaluated by an adapted digital image correlation (DIC) technique during tensile deformation. The progress of strain localization was traced by the corresponding strain maps. The electron backscatter diffraction analysis and tint etching technique were utilized to determine the impact of martensitic transformation and deformation twinning on the strain localization in both elastic and plastic regimes. In elastic regime the narrow strain bands which are aligned perpendicular to the tension direction were observed in temperature range of 25 to 180 °C due to the stress-assisted epsilon martensite. The strain bands were disappeared by increasing the temperature to 300 °C and reappeared at 400 °C due to the stress-assisted deformation twinning. In plastic regime strain localization continued at 25 °C and 180 °C due to the strain-induced alfa-martensite and deformation twinning, respectively. The intensity of plastic strain localization was increased by increasing the strain due to the enhancement of martensite and twin volume fraction. The plastic strain showed more homogeneity at 300 °C due to the lack of both strain-induced martensite and deformation twinning.     

Investigation of the Melt‐Crystallization of Polypropylene by a Temperature Slope Method

Abstract

To investigate the in‐situ ordering process of isotactic polypropylene (iPP) from a melt state, a stationary growth front was prepared by the temperature slope crystallization (TSC) method. During the melt‐crystallization, iPP was crystallized into the α‐phase or β‐phase depending on the crystallizing conditions. The mechanism of the melt‐crystallization at the growth front was precisely observed by wide‐angle and small‐angle x‐ray scattering (WAXS and SAXS) using a strong synchrotron beam. In the TSC apparatus, the sample was crystallized in between a heater, controlled to 220°C, and a cooler, cooled by water to 25°C. We define the z‐axis parallel to the temperature gradient. A‐lamellae and B‐lamellae are also defined as those whose lamellar normal are perpendicular and parallel to the z‐axis, respectively. In a sample‐stop (SS) stage before the TSC, the original α‐phase lamellae became thicker, approaching to the melt‐solid boundary by annealing. The annealing process showed that the α‐phase B‐lamellae remained and the SAXS reflection was stronger on the meridian near the melt‐solid boundary in the SS stage. In the beginning of the TSC, the α‐phase B‐lamellae developed as a primary crystallization. During secondary crystallization under high supercooling, the SAXS cross pattern appeared showing that the α‐phase developed both A‐ and B‐lamellae. As the growth direction of A‐lamellae is parallel to the z‐axis, A‐lamellae grow faster than B‐lamellae. By the self‐epitaxial mechanism on the side surface of the A‐lamellae, the B‐lamellae grow on the base of the A‐lamellae. Following appearance of a spontaneous β‐nucleus, the β‐phase lamellae grew preferentially, excluding the α‐phase, and occupied the whole area of the sample. In this case also, A‐lamellae are advantageous to grow because of the growth direction parallel to the z‐axis. As a result, the SAXS β‐phase reflection appeared on the equator.