Time resolved study of oriented crystallisation of poly(lactic acid) during rapid tensile deformation

Poly(l-lactic acid) with 4% d-lactic acid comonomer has been drawn in the amorphous state at 80, 90, 100, 110 and 120 °C at an extension rate of 4 s⁻¹ while simultaneously recording WAXS and SAXS patterns at intervals of 0.12 s. At 80, 90 and 100 °C, crystallisation is very rapid (1-4 s⁻¹) and follows a first order transformation process to give highly oriented crystals. SAXS patterns were barely detectable at these temperatures despite fractional crystallinity of ∼0.2. At 110 and 120 °C, crystallisation was very slow (∼0.01 s⁻¹) and gave rise to crystals with a lower degree of orientation. After eventual crystallisation at 120 °C, a two-point SAXS pattern develops with narrow lateral spread, suggesting ‘shish kebab’ morphology. When the 80 °C drawn sample was annealed at 120 °C, a strong four point SAXS pattern develops. The change in drawing and crystallisation behaviour at higher draw temperature is attributed to the onset of chain retraction relaxation processes. The WAXS fibre pattern after annealing shows sampling on intermediate layer lines that is consistent with the α crystal form with a 10₃ helix. However, prior to annealing, sampling indicates a different, less defined helical configuration.     

In situ WAXD study of structure changes during uniaxial deformation of ethylene-based semicrystalline ethylene-propylene copolymer

In situ strain-induced structure changes during uniaxial deformation of an ethylene-propylene copolymer, containing 78 wt% (or 85 mol%) of ethylene moiety, were studied by synchrotron wide-angle X-ray diffraction (WAXD). The chosen sample could crystallize into orthorhombic, pseudo hexagonal or a mixed form, depending on the annealing conditions. Crystallization at high temperatures (e.g. 50 °C) favored the formation of orthorhombic form, while crystallization at low temperatures (e.g. 20 °C) favored the formation of pseudo hexagonal form. Under deformation, the transition from orthorhombic to pseudo hexagonal form was observed at relatively low strains (e.g. 0.12). At higher strains, WAXD data indicated the occurrence of direction-dependent crystal destruction at strains <0.25 and subsequent re-crystallization with extended-chain conformation at high strains (>1.0) all of the pseudo hexagonal form. The drastic changes in the crystalline structures (orthorhombic to pseudo hexagonal) and phase transitions (crystal destruction and re-crystallization) at modest strains can be attributed to the high mobility of the amorphous ethylene-propylene segments at room temperature.     

Observations of structure development during crystallisation of oriented poly(ethylene terephthalate)

Two types of SAXS and WAXS experiments have been made using synchrotron radiation to observe the transformation from smectic to crystalline phases in oriented poly(ethylene terephthalate) (PET). In step-anneal experiments, PET was drawn slowly at 30 °C and then observed after annealing at 5 °C steps up to 100 °C. In the other experiments, time-resolved observations were made while drawing at 90 °C at rates up to 10 s⁻¹. Up to 70 °C the WAXS data in the step-anneal experiments showed the smectic meridional reflection reducing in lateral width, indicating an increase in lateral long range order with annealing. Between 70 and 100 °C, there was a reduction in the intensity of the smectic reflection which correlated with an increase in the intensity of crystalline reflections. The SAXS from the step-anneal experiments showed an intense equatorial streak which has a correlation peak around 20 nm and which diminishes with annealing above 70 °C. It is concluded that this feature is a characteristic of the presence of the mesophase in oriented PET and is due to elongated domains of smectic mesophase with a length >75 nm and with an interdomain spacing of around 20 nm. Between 70 and 100 °C the SAXS data showed additional diffuse diffraction which correlated quantitatively with the crystalline phase and evolved from a cross-like appearance to a well resolved four-point pattern. The time-resolved drawing experiments were limited by the time resolution of the SAXS detector. They showed the same development of four-point diffuse SAXS patterns as was observed in the step-anneal experiments and a very weak equatorial streak. Differences in phase transformation kinetics between the two types of experiment are attributed to the different chain relaxation processes available under different conditions.     

Time resolved WAXS study of the role of mesophase in oriented crystallisation of poly(ethylene terephthalate-co-isophthalate) copolymers

Poly(ethylene terephthalate-co-isophthalate) copolymers containing up to 18 mol% isophalate have been drawn at 90 °C at a deformation rate of ∼15 s⁻¹ while recording two dimensional wide angle X-ray scattering patterns. All polymers, including homopolymer controls, show the development of an oriented smectic mesophase during the last stages of deformation. After the end of deformation, the mesophase decays and is replaced by oriented triclinic crystals which increase according to first order transformation kinetics. The characteristic meridional spacing of the smectic mesophase reduces systematically with increasing isophthalate comonomer and indicates that the comonomer participates in the smectic structure. Unlike isotropic crystallisation from the melt, the crystallinity and crystallisation rate show little variation with comonomer content. This is attributed to the fact that both monomers participate in the intermediate smectic mesophase.     

Growth mechanisms of WC in WC-5.75 wt% Co

The grain growth mechanisms of WC in WC-5.75 wt% Co are studied in this work. The two well known growth modes of WC in cemented carbides (coalescence process and solution/reprecipitation process) are both observed and show temperature dependence. At low temperatures (1100 and 1200 °C), the growth of WC grains is mainly through coalescence. At intermediate temperatures (1300 °C), coarsening of most WC grains takes place via isotropic growth, accompanied by the shape relaxation leading to the faceting of round grains. At high temperatures (1400 °C), layer-by-layer structures, resulting from anisotropic growth, are observed. Both isotropic growth at 1300 °C and anisotropic growth at 1400 °C are assisted by the solution/reprecipitation process. This is the first time that layer-by-layer structures are observed for WC crystals in WC-Co. The formation mechanism of layer-by-layer structures has been discussed based on the 2D nucleation and growth mechanism and the diffusion rates of W and C atoms within the Co binder at different temperatures.     

Observations on a low-angle X-ray diffraction peak for AR-HP mesophase pitch

Using wide angle x-ray diffraction on AR-HP mesophase pitch, a diffraction peak was detected at approximately 7° (2Θ). The low-angle peak was reproducible using different diffractometers and different sample-to-detector distances, and was observed for all pitch samples irrespective of the flow history, but not for carbon fibers derived from the same precursor fibers. The interplanar 002 peak at ∼25° was observed at the equatorial position, whereas, the peak at 7° was in the meridional position, i.e., the peaks are nominally 90° apart in an azimuthal scan. This signifies that the low angle peak was due to diffraction from planes that are orthogonal to (002) planes. The 7° peak is equivalent to a d-spacing of 1.25 nm, which corresponds to the nominal lateral dimension of the mesogen molecules that constitute the mesophase pitch. A typical MALDI analysis showed predominance of molecular weights of ∼500 au. Edges of such a constituent of mesophase pitch molecules, which lead to a lateral ordered spacing of approximately 1.1 nm, can lead to a diffraction peak at approximately 7°.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 2. Crystallisation behaviour

The crystallisation behaviour of copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T), 13 wt% crystallisable tetra-amide segments of uniform length units (two-and-a-half repeating unit of nylon-6,T) and dodecanediol (C12) was studied. The crystallisation rate of the T6T6T units was found to be very high despite the high T_g/T_m ratio. The supercooling (T_m−T_c) as measured by DSC is 18 °C at a cooling rate of 20 °C/min. WAXD has elucidated that the tetra-amide units remain organised in the melt.     

Amorphous phase and crystalline morphology in blend of two polymorphic polyesters: Poly(hexamethylene terephthalate) and poly(heptamethylene terephthalate)

Crystalline/crystalline blends of two polymorphic aryl-polyesters, poly(hexamethylene terephthalate) (PHT) and poly(heptamethylene terephthalate) (PHepT), were prepared and the crystallization kinetics, polymorphism behavior, spherulite morphology, and miscibility in this blend system were probed using polarized-light optical microscopy (POM), differential scanning calorimetry (DSC), temperature-resolved wide-angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS). The PHT/PHepT blends of all compositions were proven to be miscible in the melt state or quenched amorphous glassy phase. Miscibility in PHT/PHepT blend leads to the retardation in the crystallization rate of PHT; however, that of PHepT increases, being attributed to the nucleation effects of PHT crystals which are produced before the growth of PHepT crystals. In the miscible blend of polymorphic PHT with polymorphic PHepT, the polymorphism states of both PHT and PHepT in the blend are influenced by the other component. The fraction of the thermodynamically stable β-crystal of PHT in the blend increases with increasing PHepT content when melt-crystallized at 100 °C. In addition, when blended with PHT, the crystal stability of PHepT is altered and leads to that the originally polymorphic PHepT exhibits only the β-crystal when melt-crystallized at all T_c's. Apart from the noted polymorphism behavior, miscibility in the blend also shows great influence on the spherulite morphology of PHT crystallized at 100 °C, in which the dendritic morphology corresponding to the β-crystal of PHT changes to the ring-banded in the blend with higher than 50 wt% PHepT. In blends of PHT/PHepT one-step crystallized at 60 °C, PHepT is located in both PHT interlamellar and interfibrillar region analyzed using SAXS, which further manifests the miscibility between PHT and PHepT.     

Creation of microcracks in porcelain during firing

Quartz porcelain samples were tested by acoustic emission (AE) and sonic resonant methods (sensitive to nucleation and motion of structural defects) during a cooling stage of the firing process from temperature of 1250 °C. As a consequence of the mismatch of thermal expansion coefficients of the glass and the mullite phases, and the quartz particles, microcracking begun at the temperature of the glass transition (∼800 °C) and continued in several stages until the temperature reached 300 °C. A non-monotonous behaviour of the Young's modulus and temporary vanishing of the AE signals on cooling between 573 and 500 °C confirm the significance of the β → α transition, which lies mainly upon the reversal of thermal stresses acting on the glass matrix and the quartz particles. Consequently, above this temperature, radial cracks nucleating at the quartz particles appear, whereas below this temperature, circumferential cracks around the particles are produced.     

Effect of processing method on physical properties of Nb2O5

Samples of Nb₂O₅ were prepared by laser floating zone (LFZ) technique and by solid-state reaction in order to study some of their physical properties as a function of synthesis conditions. Single crystals fibres were obtained by LFZ, while a structural orthorhombic to monoclinic phase transition was observed in samples sintered at temperature higher than 800 °C. Transmission optical spectroscopy and photoconductivity measurements allowed identifying a ∼3.2 eV bandgap energy for the H-Nb₂O₅ monoclinic crystalline phase. Band gap shrinkage of ∼100 meV was observed from 14 K to RT. For the orthorhombic phase (T-Nb₂O₅), the photoconductivity measurements evidence a higher energy bandgap. The sintered samples have shown a broad recombination luminescence band at the orange/red spectral region while no luminescence was detected from the LFZ grown fibres. A dielectric constant of ∼40 was found for the 800 °C and 1200 °C sintered pellets while that of 1000 °C reached four times that value.     

The effect of SiC addition on the crystallization kinetics of atmospheric plasma–sprayed basalt-based coatings

The crystallisation kinetics of the conversion of a glass coating layer made from a mixture of natural basalt volcanic rock and SiC into glass-ceramic have been investigated. The process depends on the crystallisation temperature, time and amount of the SiC added. Coating powders were prepared from pure basalt and from basalt containing 10–50 wt% SiC. The powders were coated by an atmospheric plasma spray technique on the pre-coated AISI 1040 steel substrate with Ni–Al. The coating layer was vitrified by sudden cooling. The amorphous structure of the coatings was verified by X-ray diffraction (XRD) analysis. To obtain glass-ceramic, coatings were subjected to crystallisation heat treatment in an argon atmosphere. Crystallisation heat treatment temperatures of 800 °C, 900 °C and 1000 °C were chosen by using DTA. After the heat treatment process, augite, ferrian-diopsite, diopside, albite, andesine, and moissonite phases formed in the coating layer and were verified by XRD analysis. The crystallisation activation energies were determined to be between 323.4 kJ/mol and 253.2 kJ/mol, depending on SiC addition. The crystallisation activation energies decreased with increasing amounts of SiC addition. The Avrami parameters of the crystallisation process varied between 1.60 and 3.33, which indicates that internal crystallisation dominated for all of the compositions.     

Micro-phase separation and crystallization behavior of amorphous oriented PLLA/PVAc blends during heat treatment under strain

Amorphous oriented poly(l-lactide) (PLLA)/poly(vinyl acetate) (PVAc) 50/50 films were prepared by uniaxial drawing of melt-mixed blends at 65 °C. The morphology development and crystal organization of the blends during heat treatment under strain were investigated using small angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). Equatorial scattering maxima in the SAXS patterns for samples annealed at 75 °C were observed before the appearance of crystal reflections. Further annealing of the samples at higher temperature induced two further discrete meridian scattering maxima. The observations indicated that homogenous oriented PLLA/PVAc film undergoes micro-phase separation first, followed by crystallization of PLLA in the PLLA-rich phase. The micro-phase separated PVAc nanodomains are aligned parallel to the stretching direction, whereas the crystallized PLLA lamellae are oriented perpendicular to the stretching direction (crystal c-axis along the stretching direction). Micro-phase separation was not observed when films were annealed at 120 °C, at which temperature the high crystallization rate of PLLA overwhelmed the micro-phase separation process.     

Correlation of compaction pressure, green density, pore size distribution and sintering temperature of a nano-crystalline 2Y-TZP-Al2O3 composite

Highly sinter-active nano crystalline composite powder of 2 mol% yttria doped tetragonal zirconia polycrystal (2Y-TZP) with 2 wt% alumina was synthesized by co-precipitation method. Crystallization temperature of the amorphous precursor powder, measured from simultaneous thermogravimetric (TG) and differential thermal analysis (DTA) techniques was found to be ∼470 °C. The powder was calcined at different temperatures in the range of 700-1000 °C. XRD patterns of the calcined powders revealed the presence of a single tetragonal phase. Particle size of the calcined powder measured by different techniques (X-ray line broadening, BET surface area and laser scattering technique) indicated an increase in the average particle size with calcination temperature. The study of compaction behaviour revealed the presence of soft agglomerates in the calcined powder. Pore size distribution of the green compacts obtained from a mercury porosimeter was found to be monomodal above a critical pressure. The onset temperature of sintering was found to increase with calcination temperature. Powders calcined at 800 °C and 900 °C had shown better sinterability at 1200 °C owing to the presence of finer pores with a narrow size distribution in the green compacts. Sintering behaviour of the powder calcined at 700 °C was found to be marginally poorer in comparison to the other samples, whereas the powder calcined at 800 °C had demonstrated best densification behaviour, especially when compacted at 300 MPa.     

Densification and characterization of SiO2B2O3CaOMgO glass/Al2O3 composites for LTCC application

A glass/ceramic composite using lead-free low melting glass (SiO₂B₂O₃CaOMgO glass) with Al₂O₃ fillers was investigated. X-ray diffraction analysis revealed that the anorthite and cordierite phase appeared in the sintered composites. The dilatometric analysis showed that the onset of shrinkage took place at ∼624 °C for all the samples and the onset temperature was independent on the content of glass. The low melting glass significantly promoted densification of the composites and lowered the sintering temperature to ∼875 °C. The addition of 50 wt% glass sintered at 875 °C showed ε_r of 7.3, tan δ of 1.15×10⁻³, TEC of 5.41 ppm/°C, thermal conductivity of 3.56 W/m °C, and flexural strength of 184 MPa. The results showed that the SiO₂B₂O₃CaOMgO glass/Al₂O₃ composites were strong potential candidates for low temperature cofired ceramic substrate applications.     

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.     

Effect of sintering temperature on ferroelectric properties of 0.94(K0.5Na0.5)NbO3–0.06LNbO3 system

Lead free 0.94(K_0.5Na_0.5NbO₃)–0.06(LiNbO₃) (KNN–LN) system was synthesized by conventional solid state reaction route (CSSRR). The KNN–LN system was calcined at 850 °C for 6 h for the formation of single perovskite phase whereas the sintering was done at 1050 °C, 1080 °C and 1100 °C for 4 h, respectively. The KNN–LN samples sintered at 1080 °C show better properties: room temperature (RT) dielectric constant (?_r) ∼936, dielectric loss (tan δ) ∼0.016 at 1 MHz, a relatively high bulk density (ρ) ∼4.385 g/cm³, which is 97.5% of the theoretical density (TD ∼ 4.51), remnant polarization (P_r) ∼6.4 μC/cm² and coercive field (E_c) ∼9.6 kV/cm have been observed.     

Polypropylene-graphite nanocomposites made by solid-state shear pulverization: Effects of significantly exfoliated, unmodified graphite content on physical, mechanical and electrical properties

Nanocomposites made from polypropylene and as-received graphite were prepared by solid-state shear pulverization (SSSP) as a function of graphite loading (0.3-8.4 wt%). X-ray diffraction indicates that SSSP employing harsh pulverization conditions yields substantial graphite exfoliation at 0.3-2.7 wt% graphite content with less exfoliation being achieved at higher graphite content. With increasing graphite content, thermal degradation temperature and non-isothermal onset crystallization temperature increase substantially (by as much as 35 and 23 °C relative to neat polypropylene) while isothermal crystallization half-time decreases dramatically. In contrast, Young’s modulus and tensile yield strength exhibit maxima (∼100% and ∼60% increases, respectively, relative to neat polypropylene) at 2.7 wt% graphite content, with all nanocomposites retaining high elongation at break values except at the highest filler loading. Electrical conductivity measurements indicate percolation of graphite at 2.7 wt% and higher graphite content, consistent with rheology measurements showing the presence of a solid-like response of melt-state shear storage modulus as a function of frequency. Significant tunability of graphite exfoliation and property enhancements is demonstrated as a function of SSSP processing.     

Transitions of domain ordering and domain size in a spherical-forming polystyrene-block-poly(ethylene oxide) copolymer and its composites with colloidal cadmium sulfide quantum dots

With specific annealing schemes applied to a neat polystyrene-block-poly(ethylene oxide) (SE) and its composites with cadmium sulfide quantum dots (CdS QD), we have observed microdomain structures and phase transitions in the system using temperature-resolved small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). Both TEM images and SAXS results show clearly that incorporation of surfactant-tethered CdS QD preferentially into PEO blocks leads to increases in thermal stabilities of both bcc-packed lattice (referred as long-range order) and microdomains themselves in the sphere-forming SE/CdS composites. The bcc-packed lattice in the SE/CdS composites sustains better than that in the neat SE, during a temperature elevation to ∼160 °C, at which the bcc-packed SE/CdS spheres start to transform into micelles with a short-range liquid-like order. Quantitative model analysis shows that the PEO/CdS micelles can retain their size in the SE/CdS composites up to 200 °C, whereas the PEO micelles shrink after the softening of the PS matrix around 100 °C, and disassociate largely into the PS matrix of the neat SE at 160 °C.     

Microstructural development of a vitrified hindered phenol compound during thermal annealing

Structural changes in vitrified 3,9-bis{1,1-dimethyl-2[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5,5]-undecane (AO-80) during the annealing process were studied by DSC, WAXD and FT-IR. The initial AO-80 is highly crystalline, whereas AO-80 obtained by cooling from its melting state is an amorphous material. Annealing treatments below the melting point of AO-80 resulted in structural development. In addition, the modification of the crystal formed by annealing treatment depended on the annealing conditions. The IR spectra of various crystal modifications were different. Analysis of the microstructures of the crystals that formed indicated that the crystal formed by annealing at 100 °C is a smectic crystal, whereas the crystal formed by annealing at 80 °C is a nematic crystal. The AO-80 crystal formed within the chlorinated polyethylene (CPE) matrix during annealing at 100 °C is also a nematic crystal. Though the CPE matrix decreased regularity of AO-80 crystals, it raised the growth rate of AO-80 crystals.     

Liquid-liquid phase separation and crystallization behavior of poly(ethylene terephthalate)/poly(ether imide) blend

The liquid-liquid (L-L) phase separation and crystallization behavior of poly(ethylene terephthalate) (PET)/poly(ether imide) (PEI) blend were investigated with optical microscopy, light scattering, and small angle X-ray scattering (SAXS). The thermal analysis showed that the concentration fluctuation between separated phases was controllable by changing the time spent for demixing before crystallization. The L-L phase-separated specimens at 130 °C for various time periods were subjected to a temperature-jump of 180 °C for the isothermal crystallization and then effects of L-L phase separation on crystallization were investigated. The crystal growth rate decreased with increasing L-L phase-separated time (t_s). The slow crystallization for a long t_s implied that the growth path of crystals was highly distorted by the rearrangement of the spinodal domains associated with coarsening. The characteristic morphological parameters at the lamellar level were determined by the correlation function analysis on the SAXS data. The blend had a larger amorphous layer thickness than the pure PET, indicating that PEI molecules in the PET-rich phase were incorporated into the interlamellar regions during crystallization.