Time resolved WAXS/SAXS observations of crystallisation in oriented melts of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (UHMWPE) has been drawn in the melt state at 140, 145 and 150 °C at extension rates ∼1 s⁻¹ while simultaneously recording two dimensional SAXS and WAXS with a time resolution of 0.1 s. The first observable crystallisation is mainly in the orthorhombic form at a level of about ∼1 wt%. At higher draw ratios additional crystallisation is in the hexagonal form up to ∼10 wt%. The crystallisation is accompanied by strong SAXS equatorial scatter with maxima at ∼25 nm period; in some cases meridional maxima are also visible at ∼120 nm. Substantial crystallisation occurs on subsequent cooling to 130 °C, accompanied by strong meridional maxima of narrow lateral width. The observed crystal forms are consistent with a temperature-strain phase diagram, favouring hexagonal at higher strains. There are indications that the thermodynamic orthorhombic to hexagonal transition T_tr is above 150 °C so that all the observable hexagonal structures are metastable. The initial orthorhombic crystals are associated with the high molecular weight tail and provide the strain hardening to enable the formation of subsequent hexagonal crystals. The equatorial SAXS lobes are interpreted in terms of lateral density fluctuations that are associated with an arrangement of columns of oriented chains comprising both orthorhombic and hexagonal structures. The columns are embryonic shish structures that on cooling nucleate kebab overgrowths.     

Effect of salt additive on the formation of microporous poly(vinylidene fluoride) membranes by phase inversion from LiClO4/Water/DMF/PVDF system

The effect of a salt additive, lithium perchlorate, on the morphology and crystal structure of PVDF membranes prepared by wet phase inversion process was studied. The gelation phase boundaries of the quaternary system, LiClO4/water/DMF/PVDF, were determined at 25 °C. It was found that the gelation lines shifted up progressively with increasing salt contents in this system. For a salt-free casting dope, the formed membrane exhibited a typical asymmetric structure characterized by the skin, parallel columnar macrovoids, and cellular pores. WAXD analysis indicated that PVDF crystallized into ‘α’ (type II) structure in this membrane. By contrast, when PVDF was precipitated from high salt-content dopes (e.g. ≥5 wt%), the macrovoids bent and extended towards the bottom region while the original cellular pores evolved into very large voids. The PVDF crystallites became ‘β’ form (type I) in these membranes. Thermal analysis (DSC) of all membranes showed dual melting peaks at low heating rates (≤5 °C/min), suggesting that the crystallites formed in the immersion-precipitation process were imperfect and they underwent re-crystallization during the heating process. Using low voltage SEM at high magnifications (e.g. 100 KX at 0.55 KV) on uncoated samples, the fine structures (10-20 nm) of the PVDF crystallites were observed. And at very high magnifications (225 KX at 0.59 KV), it was observed that the skin region of the membrane prepared from high salt-content dopes actually contained many nano-pores (e.g. 20 nm). This contributes to the high permeation rate and low solute rejection as revealed from the water-flux measurements.     

Radiation effects and re-crystallization mechanism of syndiotactic polystyrene with β′-crystalline form

The double melting behavior of syndiotactic polystyrene (sPS) with β′-form crystallites was systematically investigated by several analytical techniques, including differential scanning calorimetry (DSC), polarized light microscopy (PLM), transmission electron microscopy (TEM), as well as wide-angle and small-angle X-ray scattering (WAXD, SAXS). For preventing the possible chain re-organization during intermediate melting, a high-energy electron beam (e-beam) radiation was carried out on the melt-crystallized samples to chemically cross-link the amorphous chains between lamellar crystals. The WAXD intensity profiles of the irradiated sPS samples revealed that no crystal transformation took place, and the crystallinity fraction remained unchanged for a received dose up to 2.4 MGy. As the received dose was increased, however, the high melting temperature peak was gradually diminished and finally disappeared after 1.8 MGy e-beam radiation, suggesting that the double melting phenomenon was mainly attributed to the melting/re-crystallization/re-melting behavior. The re-crystallization mechanism of sPS samples was studied using DSC and PLM to reveal the effects of heating rate and annealing temperature on the Avrami exponent and re-crystallization rate constant. In addition, the lamellar morphologies of the re-crystallized samples were also investigated by means of SAXS and TEM. With increasing heating rate or annealing temperature, the derived Avrami exponent was slightly decreased from 1.4 to 1.1; in comparison, the re-crystallization rate showed a shallow maximum at a rate of 10 °C/min, but it became evidently reduced at high annealing temperatures. Based on the morphological observations, we proposed that the re-crystallization of β^′-form sPS crystals involved with the presence of broad lamellar thickness distribution as well as abundant irregular loose folding chains on the lamellar surfaces, which became tightened and crystallized into the un-melted lamellae when the neighboring thinner lamellae trapped in-between were melted. Thus, the high melting temperature is dependent on the average thickness of lamellae consisting of the un-melted lamellae developed initially and thickened ones associated with re-crystallization.     

Fracture behaviour of polypropylene films at different temperatures: fractography and deformation mechanisms studied by SEM

The fracture surfaces and the deformation micro-mechanisms of one polypropylene homopolymer and three ethylene-propylene block copolymers (EPBC) have been studied by scanning electron microscopy. The results are compared to the essential work of fracture parameters obtained in a previous study with deeply double-edge-notched-tension samples of films fractured between −40 and 70 °C. The homopolymer shows shear-yielding at T≥−20 °C, but at lower T, crazing prevails. The EPBC display shear-yielding for T>0 °C, while a combination of cavitation and shear-yielding occurs at lower T, which is responsible for stress-whitening. The variations of the specific essential fracture work and specific plastic work with T and with ethylene content have been successfully explained in terms of the prevalent deformation mechanisms.     

Structure and morphology development during deformation of propylene based ethylene-propylene copolymer and its blends with isotactic polypropylene

The structure and morphology development during the deformation of metallocene based ethylene-propylene copolymers with dominant propylene moiety (C3 M-EP) and its isotactic polypropylene (M-iPP) blends were investigated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) using synchrotron radiation, high temperature tensile testing and differential scanning calorimetry (DSC). X-ray results showed that the structure and morphology in the blends of M-iPP/C3 M-EP are dictated by the M-iPP component. During stretching at room temperatures, both pure M-iPP and polymer blends exhibited the same transition from the α-form crystal to the mesophase. However, the α-form was found to be unchanged during the deformation of C3 M-EP copolymer, which indicated that the effect of local stress on the crystal domain in pure copolymer was too small to induce the phase transition. Although the DSC results showed that the blends in their isotropic state were immiscible with each other, the mechanical properties of the blends at high temperature (70 °C) indicated that they follow the conventional rule of mixing.     

Transient crystallization during drawing from ultra-high molecular weight polyethylene melts having different entanglement characteristics

The relationship between entanglement characteristics and transient crystallization during drawing from ultra-high molecular weight polyethylene (UHMW-PE) melts is discussed, based on a combination of in situ X-ray measurement and stress profile analysis. Films having different entanglement characteristics were prepared by solution blending of higher and lower MW samples having a viscosity average MW of 1.07 × 10⁷ (higher) and 1.73 × 10⁶ (lower), followed by compression molding at 180 °C. Stress profiles recorded at 155 °C above the melting temperature of 135 °C exhibited a plateau stress region, whose stress level was lower for the film prepared with more of the lower MW component. With drawing, an amorphous scattering gradually concentrated on the equator. Beyond the beginning point of the plateau stress region, such amorphous scattering abruptly disappeared and crystallization into a transient hexagonal phase occurred simultaneously. As soon as this hexagonal phase appeared, it rapidly transformed into an orthorhombic phase for the film exhibiting higher plateau stress. In contrast, the film exhibiting lower plateau stress exhibited a gentle transformation and a resurgence of the hexagonal phase in the later stage of drawing. These results demonstrate that “entanglement phase separation” proceeds during melt-drawing of UHMW-PE.     

Conformation transition and crystalline phase variation of long chain branched isotactic polypropylenes (LCB-iPP)

The changes of conformation and crystalline structure of long chain branched isotactic polypropylene (LCB-iPP) under different crystallization temperatures and the effects of their special molecular architecture on the crystallization behavior were investigated by a combination of Fourier transform infrared spectroscopy (FT-IR), wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). In these polymers, long chain branching was introduced via in situ polymerization of polypropylene and an asymmetric diene monomer using the metallocene catalyst technology. Through the characterization of the specific IR band variation, it was proved that the conformational orders of helical sequences of LCB-iPP show great changes in different crystallization temperature ranges. In lower crystallization temperature range (100-130 °C), the intensities of all regular helical conformation bands of LCB-iPP increase with the increasing crystallization temperature and the regular helical conformation bands with more monomer units increase faster than that with less monomer units. In higher crystallization temperature range (130-150 °C), the intensities of all regular helical conformation bands of LCB-iPP decrease with the increasing crystallization temperature and the regular helical conformation bands with more monomer units decrease faster than that with less monomer units. The results of WAXD and DSC showed that LCB-iPP crystallizes from the melt as a mixture of α and γ forms. The content of the γ form increases with the increasing crystallization temperature, reaches a maximum value at 130 °C, and then decreases with a further increase of the temperature. At the same time, the crystallization of γ form is favored by the presence of the LCB structure of iPP. Moreover, the transitional temperatures of different helical conformations and crystallization structures of LCB-iPP show obvious correlations.     

Direct melt-crystallization of isotactic poly-1-butene with form I′ using high-pressure CO2

In this work, we found a new method to obtain isotactic poly-1-butene (iPB-1) with form I′ through direct melt-crystallization using high-pressure CO₂. The non-isothermal melt-crystallization behaviors of iPB-1 under atmospheric N₂ and 0.5-10 MPa CO₂ at cooling rates ranging from 0.25 to 5 °C/min were carefully studied using high-pressure differential scanning calorimeter (DSC) and analyzed using the modified Avrami method. Wide-angle X-ray diffraction (WAXD) measurements showed that the crystal structure of non-isothermally melt-crystallized iPB-1 changed from form II under atmospheric N₂ and 0.5-8 MPa CO₂ to form I′ under 10 MPa CO₂. In-situ high-pressure Fourier transform infrared (FTIR) was also used to investigate the non-isothermal melt-crystallization at CO₂ pressure up to 18 MPa at the cooling rate of 1 °C/min. Likewise, it was found that form II crystallized under atmospheric N₂ and 0.5-8 MPa CO₂, and form I′ melt-crystallized directly at CO₂ pressures higher than 10 MPa, which was confirmed by the followed DSC and WAXD characterizations on the iPB-1 films after FTIR measurements. The crystal morphology of the melt-crystallized iPB-1 films, characterized by using polarized optical microscopy (POM), showed that the Maltese cross pattern of iPB-1 spherulite became more diffuse with increasing CO₂ pressure, and the spherulite size decreased abruptly at the CO₂ pressure of 10 MPa.     

Polycarbonate/liquid crystalline polymer blend: Crystallization of polycarbonate

The enhanced crystallization of polycarbonate in the blend of liquid crystalline polymer/polycarbonate/(ethylene-methyl acrylate-glycidyl methacrylate) copolymer (LCP/PC/E-MA-GMA) was studied by wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The LCP/PC/E-MA-GMA 5/95/5 blends annealed at 200 °C, for 2, 4, 6, and 10 h, present an obvious crystalline structure corresponding to PC crystallization. The PC crystal obtained shows two melting temperature, T_m1 of about 214 °C and T_m2 of about 231 °C, with a total heat of fusion of 29 J/g (annealing time = 10 h). The preliminary results indicate that amorphous PC can be induced to crystallization by the synergistic action of LCP dispersed phase and reactive compatibilizer.     

An in-situ X-ray scattering study during uniaxial stretching of ionic liquid/ultra-high molecular weight polyethylene blends

An ionic liquid (IL) 1-docosanyl-3-methylimidazolium bromide was incorporated into ultra-high molecular weight polyethylene (UHMWPE) and formed IL/UHMWPE blends by solution mixing. The structure evolution of these blends during uniaxial stretching was followed by in-situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. During deformation at room temperature, deformation-induced phase transformation from orthorhombic to monoclinic phase was observed in both IL/UHMWPE blends and neat UHMWPE. The elongation-to-break ratios of IL/UHMWPE blends were found to increase by 2-3 times compared with that of pure UHMWPE, while the tensile strength remained about the same. In contrast, during deformation at high temperature (120 °C), no phase transformation was observed. However, the blend samples showed much better toughness, higher crystal orientation and higher tilting extent of lamellar structure at high strains.     

Synthesis and NTC properties of YCr1−xMnxO3 ceramics sintered under nitrogen atmosphere

YCr_1−xMn_xO₃ (0 ≤ x ≤ 0.8) negative temperature coefficient (NTC) compositions were synthesized by classical solid state reaction at 1200 °C, and sintered under nitrogen atmosphere at 1500 °C and 1600 °C. XRD patterns analysis has revealed that for x ≤ 0.6, the structure consists of a solid solution of an orthorhombic perovskite YCrO₃ phase with Mn substitute for Cr. For x ≥ 0.8, a second phase with a structure similar to the hexagonal YMnO₃ phase appears. SEM images and calculated open porosity have shown that the substitution of Mn for Cr results in a decrease in porosity. Whatever the sintering temperature, the electrical characterizations (between 25 and 900 °C) have shown that the increase in the manganese content involves the decrease in both resistivity and material constant B (parameter which characterizes the thermal sensitivity of material) when x ≤ 0.6. The magnitude order of the resistivity at 25 °C is of 10⁴-10⁸ Ω cm and activation energies vary from 0.28 to 0.99 eV at low and high temperatures, respectively.     

The synthesis and characterization of a super-activated carbon containing substitutional boron (BCx) and its applications in hydrogen storage

A new family of porous boron-substituted carbon (BC_x) materials with controlled structure is investigated. The chemistry involves a B-precursor polymer, i.e., poly(borachlorophenyldiacetylene), containing inorganic additives (templates). At pyrolysis <400 °C, the B-precursor engages in easy inter-chain reactions to form dark solid with high yield (>85%). Above 600 °C, the amorphous carbon-like BC_x materials containing up to 12% B have been prepared, which show an extended fused hexagonal ring structure with B-puckered curvature. This out of planar B moiety maintains its electron deficiency, due to limited π-electron delocalization, and exhibits super-activated properties to enhance H₂ binding energy (20-10 kJ/mol) and adsorption capacity. After removing the inorganic additives by water-washing, the resulting porous BC_x shows a surface area 500-800 m²/g. Evidently, the pore size distribution is directly related to melting temperature and distribution of the inorganic salts. As the temperature increases to >1400 °C, the distorted ring structure gradually flatten out to form a multi-layer (crystalline) BC_x structure. The resulting planar graphitic layer only can accommodate a reduced B content (<3% at 1800 °C) and low surface area. The B moieties also lose their acidity due to the extensive π-electron delocalization.     

Eutectic melting behavior of polyamide 10,T-co-6,T and 12,T-co-6,T copolyterephthalamides

Semi-aromatic polyterephthalamides 10,T and 12,T were synthesized with 0-60 wt-% PA-6,T comonomer by a melt polycondensation process. Molecular weights of the copolymers ranged from 12,000 to 27,000 g/mol and all produced tough melt-pressed films. The substituted aromatic carbon of the ¹³C NMR spectra revealed that comonomer sequences are statistical; e.g., 50:50 wt-% PA-12,T-co-6,T copolymer had 12,T-12,T:12,T-6,T:6,T-6,T sequence ratios of approximately 1:2:1. Copolymers of both PA-10,T and 12,T exhibited a eutectic melting point at 30 wt-% PA-6,T, with melting points decreasing linearly from 315 and 292 °C to minima of 280 and 272 °C, respectively. Melting enthalpies showed similar minima at ca. 35 wt-% PA-6,T. WAXD and DMA were used to further characterize the eutectic behavior, and a comprehensive analysis of PA-6,T copolymer melting behavior is given.     

Preparation of highly crystalline nanofibers on Fe and Fe-Ni catalysts with a variety of graphene plane alignments

The present study confirmed that highly crystalline nanofibers with controlled structure may be prepared over Fe and Fe-Ni alloy catalysts. The degree of graphitization of various carbon nanofibers (CNFs) was analyzed by using C(0 0 2) peaks from the XRD profiles. The C(0 0 2) peaks of CNFs over Fe catalyst shifted to higher angle and became narrower as the preparation temperature increased from 560 to 620 °C. Tubular CNFs prepared at temperature higher than 630 °C showed lower 2θ angles compared to those of platelet fibers. CNFs prepared over Fe-Ni catalysts tended to resemble those prepared over Fe catalysts. The degree of graphitization of platelet CNFs resembled natural graphite, while d_0 0 2 of the tubular CNFs showed values below the 3.39 Å reported as a theoretical minimum for a cylindrical alignment. Lc_0 0 2 of platelet and tubular CNFs increased by heat treatment at 2000 and 2800 °C though d_0 0 2 changed little. A transverse section of platelet and tubular CNFs had a hexagonal shape, not a round shape. The hexagonal column allows AB stacking of hexagonal planes that can give perfect hexagonal alignment.     

Continuous synthesis of metal nanoparticles in supercritical methanol

Metal nanoparticles were synthesized continuously in supercritical methanol (scMeOH) without using reducing agents at a pressure of 30 MPa and at various reaction temperatures ranging 150-400 °C. Wide angle X-ray diffraction (WAXD) analysis revealed that metallic nickel (Ni) nanoparticles were synthesized at a reaction temperature of 400 °C while mixtures of nickel hydroxide (α-Ni(OH)₂) and metallic Ni were produced at lower reaction temperatures of 250-350 °C. In contrast, metallic silver (Ag) nanoparticles were produced at reaction temperatures above 150 °C while metallic cupper (Cu) nanoparticles were produced at reaction temperatures above 300 °C. Mixtures of copper oxide (CuO and Cu₂O) and metallic Cu were produced at lower reaction temperatures of 250 °C. Scanning electron microscopy (SEM) showed that the particles size and morphology changed drastically as the reaction temperature increased. The average diameters of Ni, Cu and Ag particles synthesized at 400 °C were 119 ± 19 nm, 240 ± 44 nm, and 148 ± 32 nm, respectively. The scMeOH acted both as a reaction medium and a reducing agent. A possible reduction mechanism in scMeOH is also presented.     

Thermal analysis, X-ray and electron diffraction studies on crystalline phase transitions in solvent-treated poly(hexamethylene terephthalate)

The crystal polymorphism, transformation, and morphologies in chloroform solvent-cast poly(hexamethylene terephthalate) (PHT) were examined by using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and temperature in situ transmission electron microscopy (TEM). Solvent-induced crystallization of PHT at room temperature yielded an initial crystal of γ-form, as confirmed by WAXD. Upon DSC scanning, the original γ-form in PHT exhibited three endothermic peaks, whose origins and association were carefully analyzed. The first peak, much smaller than the other two, is in the temperature range of ca. 100-120 °C. It was found that the solvent-induced γ-form was transformed to β-form at 125 °C via a solid-to-solid transformation mechanism. In addition, WAXD showed that γ- and β-forms co-existed in the temperature range of 100-125 °C. These mixed crystal forms were further identified using TEM, and the selected-area electron diffraction (ED) patterns revealed that both γ- and β-form crystals co-existed and were packed within the same spherulite. Solid-solid transformation from the solvent-induced γ-form to β-form in PHT upon heat scanning was presented with evidence and discussed.     

Preparation of physical gel consisting of syndiotactic polystyrene and poly(ethylene glycol)

Syndiotactic polystyrene (s-PS) was blended with poly(ethylene glycol) (PEG) in 1,2-dichloroethane (DCE) solvent. The mixture became a homogeneous solution at 155 °C depending on the composition ratio of PEG to DCE. When the solution was cooled at the rate of 5 °C/min to room temperature, a thermoreversible gelation was occurred. Wide angle X-ray diffraction (WAXD) measurements revealed that the polymer chain of s-PS in the obtained gel was crystallized with a helical conformation, while that in the non-gelated sample was done with an all-trans planar zigzag conformation.After drying gelated samples at 70 °C for 24 h, a novel polymer blend type of the physical gel consisting of s-PS and PEG was obtained. Dynamic mechanical analysis (DMA) revealed that the physical gel had a high modulus and a long elastic plateau in the temperature range of −80-270 °C.     

The role of interlamellar chain entanglement in deformation-induced structure changes during uniaxial stretching of isotactic polypropylene

In-situ small-angle X-ray scattering (SAXS), and wide-angle X-ray diffraction (WAXD) were carried out to investigate the deformation-induced structure changes of isotactic polypropylene (iPP) films during uniaxial stretching at varying temperatures (room temperature, 60 °C and 160 °C). From the WAXD data, mass fractions of amorphous, mesomorphic and crystal phases were estimated. Results indicate that at room temperature, the dominant structure change is the transformation of folded-chain crystal lamellae (monoclinic α-form) to oriented mesomorphic phase; while at high temperatures (>60 °C); the dominant change is the transformation of amorphous phase to oriented folded-chain crystal lamellae. This behavior may be explained by the relative strength between the interlamellar entangled network of amorphous chains, which probably directly influence the tie chain distribution, and the surrounding crystal lamellae. It appears that during stretching at low temperatures, the interlamellar entanglement network is strong and can cause lamellar fragmentation, resulting in the formation of oriented mesomorphic phase. In contrast, during stretching at high temperatures, the chain disentanglement process dominates, resulting in the relaxation of restrained tie chains and the formation of more folded-chain lamellae.     

The effect of powder sintering on the palladium-catalyzed formation of carbon nanofibers from ethylene-oxygen mixtures

Carbon nanofiber growth on palladium particles from ethylene-oxygen mixtures was investigated with respect to thermal history. Electron microscopy, combined with focused ion beam cross-sectioning show particles sinter quickly, but can be stabilized by the addition of a short carbon deposition step at a temperature below the general reaction temperature. This step generates a thin layer of carbon on the catalyst which reduces sintering once the temperature is raised to the optimal reaction temperature. For example, high temperature (e.g. 500 °C) catalyst pre-treatment leads to catalyst particle sintering, and subsequent fiber growth produces large diameter fibers. In contrast, small diameter fibers form on catalyst particles pretreated at low temperature (ca. 350 °C), even if the fibers are grown at a temperature at which deposition rates are faster (e.g. 550 °C). These results led to the development of unique multiple temperature fiber growth protocols that produce smaller diameter fibers while improving the deposition rate.     

Nanoscale fibrillar crystals of PET from dilute quiescent solution

The crystallization behavior of poly(ethylene terephthalate) (PET, IV∼2 dL/g) from solution in biphenyl-diphenyl ether mixed solvent is examined. Reversible gelation of the polymer solution is observed during cooling of the solutions. Light scattering and DSC analysis are used to follow the heating and cooling processes, thus determining the crystallization temperature and the melting point, which are found to be nearly independent of the polymer concentration (0.25-5%). High degree of crystallization (>50%) is observed in the PET crystallized from the solution at 170 °C. Morphological characteristics of the crystals obtained after solvent removal are determined by WAXD, FTIR, SEM and TEM examination. The crystallization of PET into unique high aspect ratio fibrillar morphology during cooling of the solutions explains their gelation even at low PET concentration. Thin films made from the thus obtained PET could be drawn five times at 250 °C, resulting in only moderate values of modulus and strength.