Synthesis of long-chain branched isotactic-rich polystyrene via cationic polymerization

Cationic polymerization of styrene was conducted with 1-chloro-1-phenylethane (SCl)/AlCl₃/phenyl methyl ether (PME) initiating system in hexane/CH₂Cl₂ (60/40, v/v) at ?80 °C. The kinetics for cationic polymerization of styrene was investigated by in-situ ATR-FTIR spectroscopy. The isotactic-rich polystyrene (iPS) with m dyad of 81%, mm triad of 63% and mmmm pentad of 50% could be synthesized. Small amounts of crystalline regions in iPS formed after flow-induced crystallization and the crystallinity increased with increasing the molecular weight of iPS. Furthermore, the long-chain branched isotactic-rich polystyrene (biPS) with around 12 times higher molecular weight than that of corresponding iPS could be synthesized via cationic polymerization of styrene by introducing a small amount of isoprene (Ip) as a comonomer and branching sites as well. The possible mechanism for long-chain branching formation via intermolecular alkylation reaction by using Ip structural units along polymer chain as branching sites was proposed. The nucleation rate of biPS could be greatly enhanced with increasing the content of branching sites, leading to an obvious increase in crystallinity. The multi-melting temperatures from 140 °C to 237 °C were observed in DSC curves of these PS products. The tensile strength of commercial atactic polystyrene could be improved remarkably from 41.4 MPa to 55.7 MPa by adding 16.7% of biPS.     

Simultaneous SAXS/WAXS experiments on shear induced iPP crystallization near nominal melting temperature

Simultaneous small- and wide-angle synchrotron radiation X-ray scattering was performed to monitor the evolution of crystalline structure within the iPP melt during and after applying pulse shear. The iPP melt was subjected to a strong pulse shear of 240 s^?1 for 6 s at temperatures between 150 and 170 °C below and above the nominal melting temperature T_m. It was found that the imposed shear affected the melt only at lowest temperature. Structures generated during flow above 150 °C were too dilute to be detected. To extract the hidden structure, the melt was cooled to crystallization temperature of 150 °C either immediately after shearing or after annealing at shear temperature for up to 30 min. This treatment manifested with an anisotropic structure in a few minutes after quenching, undetectable when both shear and annealing temperatures presented the same value. The data obtained revealed also close correlations between annealing time, shear temperature and incubation time.     

Products Formed During Thermo-oxidative Degradation of Phytosterols

Oxidative degradation of cholesterol has been extensively researched, however, not all products formed have been established. When a phytosterols standard was heated at 60, 120 and 180 °C for different period of time the following groups of components were detected: oxidized phytosterols, fragmented phytosterol molecules, volatile compounds and oligomers. Taking into account all the components formed, we were able to balance the amounts of disappearing sterols with components formed. We established that the amount and type of products formed during thermo-oxidative degradation is affected by temperature and time. The amount of intact phytosterols decreased when temperature and time increase. The amount of oxidized phytosterols was at the highest level when a temperature of 120 °C was applied, whereas the lowest amounts were observed when a temperature of 60 °C was used. At a temperature of 180 °C the amount of oxidized sterols was lower than at 120 °C and it decreased when the heating time was increased. This indicates that oxidized sterols were the main precursors involved in the formation of other components during thermo-oxidative degradation. The amount and type of volatile compounds formed increased when time and temperature increased. We observed diversified groups of volatile compounds formed and most of them are defined as off-flavor compounds for rancid oils.     

Heating rate effects on the crystallization behavior of isotactic polypropylene from mesophase – A de-polarized light transmission study

It was ever reported in a communication of this journal that the large crystal grains having “bamboo leaf-like (BL)” morphology were produced by a rapid heating of isotactic polypropylene (iPP) from the mesophase. In order to optimize the condition to generate the BL crystals, heating rate effects on the crystallization behavior from the mesophase of iPP have been studied by utilizing a de-polarized light transmission (DPLT) method. The DPLT sensitively detected not only the cold crystallization from the mesophase around 100–120 °C but also the crystal grain growth in a narrow temperature region just below the melting temperature. With increasing the heating rate, both the temperature regions of the cold crystallization and the crystal grain growth shifted toward the higher temperatures. When the heating rate is slow (<20 °C/min), the crystal grain growth was not conspicuous. With increasing the heating rate, the rate of the crystal grain growth increased and showed a maximum when the heating rate is approximately 60–80 °C/min. However, excessively fast heating (>100 °C/min) also suppressed the crystal grain growth.     

Crystallization morphology of a thermotropic liquid crystalline polymide

Crystallization morphology of an aromatic thermotropic liquid crystalline polyimide was studied by means of polarized light microscopy. The polyimide was synthesized from 1, 2, 4, 5-benzenetetracarboxylic dianhydride (PMDA) and 1, 3-bis[4'(4′ aminophenoxy) cumyl] benzene (BACB), which exhibited three exothermic peaks at onset temperatures of 292, 279, and 250°C in the DSC cooling curve. The results of polarized light microscopy revealed that the polyimide quenched from 350°C in air exhibited fine structure, frozen liquid crystalline texture. The liquid crystalline texture disappeared when the sample was heated to 298°C. However, the polymer melt still exhibited, to some degrees, birefringence until the temperature reached 340°C, where the polyimide was in the truly isotropic state. Isothermal crystallization experiments were carried out at both the isotropic temperature range and the non-isotropic temperature range. Two types of negative spherulites with lamellar structure and positive needle-like crystals formed from the isotropic melt have been observed. Interestingly, with a further decrease of the crystallization temperature to the liquid crystalline state temperature, the whole field was covered by the liquid crystalline texture. However, if the sample was kept at 286°C for a long time, and then reheated to 305°C to melt the liquid crystalline phase, negative spherulites with loose structures formed from the liquid crystalline state could be observed. Surprisingly, if the sample was kept at 305°C for a period of time, further crystallization could be observed using the spherulites formed at 286°C as nuclei. Composite spherulites were developed if the low-high temperature crystallization process was repeated.     

Carbon-rich SiCN ceramics derived from phenyl-containing poly(silylcarbodiimides)

Novel phenyl-containing polysilylcarbodiimides were synthesized and their thermolysis and crystallization behavior up to 2000 °C was investigated. The Si/C ratio of the preceramic polymer was varied in a defined way by starting from dichlorosilanes with different organic substituents, namely R and R′ with R = phenyl and R′ = H, phenyl, methyl or vinyl. Several techniques were employed to study the structural features of the polymers and their thermolysis products. The temperature of crystallization depends on the carbon content of the precursors. Thus, in the sample with the highest carbon content the separation of β-SiC from the amorphous SiCN matrix is observed at T > 1500 °C, resulting in the highest temperature of thermal stability against crystallization ever reported for a SiCN ceramic derived from polysilylcarbodiimides. Moreover, no crystallization of β-Si₃N₄ was observed.     

Effect of microstructural evolution on the mechanical properties of lepidolite based glass-ceramics

In this paper, effect of microstructural evolution on mechanical property of lepidolite based glass-ceramics of MgO–Al₂O₃–SiO₂–Li₂O–R₂O–F(R=Na, K) system during the crystallization process has been studied. The results show that two distinct regions of strength dependence on grain size are found. The critical values of the flake diameter and aspect ratio of lepidolite are 1.8 and 4.6μm, respectively. The crystallization temperature (T_C) of critical point locates at 1060 °C. When T_C⩽1060 °C, the bending strength increases with heat-treatment temperature ascribing to the randomly oriented and interlocked lepidolite crystallites, which cause crack divert or blunt to limit the further development of the flaw size and increase the surface energy of fracture. While T_C> 1060 °C, the increased boundary shear stress arising from the mismatch of thermal coefficient between the lepidolite crystallite and the residual glass phase results in the decrease of strength.     

Early stages of nucleation and growth in melt crystallized polyethylene

Time-resolved synchrotron small angle X-ray scattering (SAXS) was used to investigate the early stages of crystallization in melt crystallized polyethylene. Classic Gibbs nucleation or density fluctuation theory can be used to describe the primary nucleation mechanism. At 110 °C, no signal of crystallization can be detected by SAXS for 30 min. When it is lower than 110 °C, the low q scattering intensity (0.008 < q < 0.03 Å^?1) begins to upturn, and the primary nucleation process starts. The measured fractal dimension of the critical nuclei is in the vicinity of 3 which is close to the prediction of classic Gibbs nucleation theory. The growth rate of density ?uctuations R(q) at different scattering vector q for different temperatures was obtained by analyzing the increase of scattering intensities. The results show that the growth rate of density ?uctuation gets much bigger with the decrease of the isothermal crystallization temperature, but there is no signal of spinodal decomposition mechanism, in which there should be a linear relationship between R(q)/q² and q².     

Preparation and crystallization of forsterite fibrous gels

Transparent forsterite fibrous gels were prepared from the hydrolysis of alkoxide precursor sols with acetic acid and water, and the crystallization process of gel fibers was studied after heat treatments up to 1500 °C. Appropriate amount of acetic acid not only promoted the formation of spinnable linear-type polymeric species, but also enhanced the chemical homogeneity and reduced the crystallization temperature of the resultant gels. On heating, fibrous gels started to crystallize into forsterite at 550 °C as investigated by infrared spectrum, X-ray diffraction and thermal analysis. Single phase forsterite fiber thus could be obtained up to 1500 °C when the amount of hydrolysis water was limited. However, fibrous gel derived from the high-water-content sol displayed a few secondary phases of the magnesia (MgO) and protoenstatite (MgSiO₃) following heating at 1000 and 1400 °C, respectively; similarly, xerogels derived from without or with insufficient amount of acetic acid also revealed the segregation of second phases on heating. The synthesized forsterite fibers displayed nanocrystalline structure up to 1100 °C. On heating to 1300 °C, fired fibers exhibited grain growth into around 0.3–0.5 μm in size, with the room temperature dielectric constants of around 6.8–7.2 (at 1 MHz).     

Crystallization and morphology of reactor-made blends of isotactic polypropylene and ethylene-propylene rubber

The crystallization and morphology of reactor-made blends of isotactic polypropylene (PP) with a large content of ethylene-propylene rubber (EPR) (i.e., > 50%) were investigated. In the blends, PP was found to form spherulites during the crystallization process, with the growth rate constant under isothermal conditions. For crystallization temperatures in the range of 118–152°C, the birefringence of the spherulites varied from negative to positive by decreasing crystallization temperature, while homopolypropylene (homo-PP), the same as used in the blends as a matrix, showed negative spherulites in the whole temperature range investigated (118–152°C). Both the spherulite growth rate and the overall crystallization rate were slower for the blends than for homo-PP. The density of the crystallization nuclei was lower in the blends than in the homo-PP. It was concluded that a large amount of EPR content in the reactor-made blends of PP retards and hinders the crystallization of the matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1007–1014, 1997     

Thermal properties and crystallization behaviors of medium-chain-length poly(3-hydroxyalkanoate)s

Medium-chain-length poly(3-hydroxyalkanoate)s (mcl-P(3HA)s) with different side-chain length ranging from C3–C9 were synthesized from 2-alkenoic acids of C6–C12 by using a metabolically engineered strain of Escherichia coli. The effect of side-chain length of mcl-P(3HA)s on thermal properties and crystallization behaviors was investigated by DSC and X-ray analyses. All mcl-P(3HA)s formed a chain-packed crystalline structure in the solvent-cast films. Melting temperatures of solvent-cast film of mcl-P(3HA)s first decreased from 59 °C to 45 °C with the change of side-chain from C3 to C4 and thereafter increased to 69 °C with an extension of side-chain to C9. The X-ray diffraction patterns indicate the formation of a layered structure aligned the main-chains in planes involving side-by-side packing of side-chains with a periodic distance of 1.6–2.8 nm for the mcl-P(3HA)s with over C4 side-chain. The interlayer distance increased proportionally to the length of side-chain for the mcl-P(3HA)s with over C4 side-chain, while the corresponding value of mcl-P(3HA) with C3 side-chain was apparently deviated from the extrapolated line plotted the distance against side-chain length. These results indicate that the changeover in crystallization manner occurs between P(3HA)s with under C3 side-chain and with over C4 side-chain. For the mcl-P(3HA)s with side-chain carbon number over C7, two distinct phase transitions were happened during heating process from a melt-quenched amorphous state. At lower temperature region, the mcl-P(3HA) molecules formed a smectic liquid-crystalline structure owing to the side-chain interactions, and the structure was disrupted at temperatures between 20 and 50 °C. After the disruption of smectic aggregates, the crystallization of mcl-P(3HA) chains immediately occurred with participation of both main- and side-chains.     

Crystallization kinetics for SiO2 formed during SiC fiber oxidation in steam

The crystallization kinetics for SiO₂ formed by oxidation of Hi-Nicalon^™-S SiC fiber between 800 and 1600°C in Si(OH)₄(g) saturated steam were determined. Glass SiO₂ scale always formed first. Glass scale eventually crystallized to cristobalite, and during further oxidation the scale formed directly as cristobalite. Growth stress relaxed by viscous flow in SiO₂ that formed as glass. Cristobalite formed by crystallization of this glass was relatively undeformed. In SiO₂ that formed directly as cristobalite, growth stress relaxed by intense plastic deformation accompanied by dynamic recrystallization. There were therefore two layers in cristobalite scale: a heavily deformed inner layer and an undeformed outer layer. These layers were distinguished by TEM. SiO₂ crystallization times were determined from the thicknesses of undeformed cristobalite and the SiC oxidation kinetics for glass scale formation. SiO₂ crystallization kinetics were determined from the crystallization time distributions at different SiC oxidation temperatures in steam. For all temperatures the crystallization time growth exponent (n) was 1. There was a large decrease in crystallization rate between 1000 and 1100°C. Between 800 and 1000°C the activation energy (Q) for crystallization was 65 kJ/mol, between 1100 and 1500°C it was 110 kJ/mol, and at 1600°C it was ~500 kJ/mol. Analysis methods and results are discussed.     

Phase evolution of YAG powders obtained by gel combustion combined with field-assisted rapid synthesis technique

Yttrium aluminum garnet (YAG) nanopowders were synthesized by a novel method combining gel combustion and field-assisted rapid synthesis technique. It is noted that hexagonal YAlO₃ (YAH) is formed first at 800–830 °C by crystallization from the amorphous, and completely transforms to YAG at about 925 °C. The grain size of YAG powders calcined at 925 °C for 3 min is about 60 nm. Moreover, the phase evolution due to different heat treatment methods was also investigated. The results indicate that the crystallization pathways are related to the atmosphere and heating rate. In air, YAG is directly crystallized from amorphous precursors without any intermediate phases. In an anoxic atmosphere, phase formation follows an amorphous-YAH-YAG route at a rapid heating rate, while the amorphous-YAH+YAG-YAG route is observed in the case of slow heating.     

Crystallization behavior and sintering of cordierite synthesized by an aqueous sol–gel route

The purpose of the research was to investigate crystallization behavior and sintering of cordierite synthesized by a low-price aqueous sol–gel route starting from silicic acid and magnesium and aluminum salts. Viscous sintering of the gel occurred in the temperature range of 800–850 °C, followed by μ-cordierite crystallization at about 900 °C, which proves the homogeneity of the gel. Decreasing of μ-cordierite crystallinity in a wide temperature range prior to commencing of α-cordierite crystallization at about 1200 °C indicates reconstructive type of μ- → α-cordierite transformation. The transformation was fully completed at 1350 °C. The value of the Avrami parameter indicates that μ-cordierite crystallization was controlled by surface or interface nucleation, which implies that viscous sintering occurred in the primary gel particles, which leads to shrinkage, and thereafter nucleation occurred on the surface or interface of the particles. The overall activation energy of μ-cordierite crystallization was 382.0 kJ/mol. The sinterability of the powder obtained by calcination at 1300 °C, where well-crystallized α-cordierite was formed, was better than that of the powder obtained by calcination at 850 °C, where the most intensive shrinkage occurred before the onset of crystallization of μ-cordierite.     

Synchronous and separate homo-crystallization of enantiomeric poly(l-lactic acid)/poly(d-lactic acid) blends

High-molecular-weight poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) are blended at different ratios and their crystallization behavior was investigated. Solely homo-crystallites mixtures of PLLA and PDLA were synchronously and separately formed during isothermal crystallization in the temperature (T_c) range of 90–130 °C, irrespective of blending ratio, whereas in addition to homo-crystallites, stereocomplex crystallites were formed in the equimolar blends at T_c above 150 and 160 °C. Interestingly, in isothermal crystallization at T_c = 130 °C, the spherulite morphology of blends became disordered, the periodical extinction (periodical twisting of lamellae) in spherulites disappeared, and the radial growth rate of spherulite (G) of the blends was reduced by the synchronous and separate crystallization of PLLA and PDLA and the coexistence of PLLA and PDLA homo-crystallites. However, the interplane distance (d), the crystallinity (X_c), the transition crystallization temperature (T_c) from α′-form to α-form, the alternately stacked structure of the crystalline and amorphous layers, and the nucleation mechanism were not altered by the synchronous and separate crystallization of PLLA and PDLA and the coexistence of PLLA and PDLA homo-crystallites. The unchanged d, X_c, transition T_c, long period of stacked lamellae, and nucleation mechanism strongly suggest that the chiral selection of PLLA or PDLA segments on the growth sites of PLLA or PDLA homo-crystallites to some extent was performed during solvent evaporation and this effect remained even after melting.     

Crystallization temperature effect on the solid-state rheology of a high-density polyethylene under compression

The plane-strain compression test provides quantitative data on the polymer rheology in homonogeneous large deformation at constant strain-rate, and on the friction shear stress between the film and the dies. Thin HDPE films with a homogeneous morphology were formed by quenching or isothermal crystallization. The structure was modified by varying the crystallization temperature over a wide range: 118°C ? T_c ? 130°C. A mechanical model with a pressure-dependent rheology and two friction laws was tested. The rheological parameters are different in tension and in compression. The occurrence of brittle fracture under compression depends on the crystallization temperature, but the rheological parameters are almost independent of the crystallization conditions.     

Lead-free high-temperature dielectrics with wide temperature stability range induced from BiFeO3-BaTiO3-based system

Lead-free BNSTNZ ((Bi,Na,Ba,Sr)(Ti,Nb,Zr)O₃)-modi?ed BF35BT (0.65BiFeO₃-0.35BaTiO₃) dielectrics were investigated by conventional solid-state reaction method. Dielectric permittivity of BFBT-BNSTNZ ceramics was suppressed through addition of BNSTNZ content, while dielectric temperature stability range was expanded from 105 °C to 412 °C as BNSTNZ content increases from 0.025 to 0.1, due to the ferroelectric-relaxor phase transition. In particular, x = 0.10 exhibits the widest stability temperature range from 88 °C to 500 °C having small variation of (Δε_m/ε_{m 150 °C} ≤ 15%) with high dielectric permittivity (> 1000) and low dielectric loss (tan? ≤ 0.1) in temperature range from 50 °C to 250 °C. Moreover, high room temperature energy storage density (W_store) of 0.75 and 0.57 J/cm³ with energy storage efficiency (?) of 57% and 78% for x = 0.03 and x = 0.10, respectively, was achieved. These results indicate that BFBT-BNSTNZ can be a promising system for high-temperature dielectric and energy storage applications.     

Modification of rheological properties of a thermotropic liquid crystalline polymer by melt-state reactive processing

Thermotropic main-chain liquid crystalline polymers typically have very low melt viscosity with strong temperature dependence compared to other common thermoplastics. While this is beneficial in some processing applications, such as injection molding, it presents challenges for others, such as coextrusion. In this study, the rheological properties of a thermotropic main-chain liquid crystalline polymer (Vectra A950) were enhanced by melt-state reactive processing with triphenyl phosphite (TPP), which can react with up to three polymer chain-ends through their chain-end functionalities. The influence of processing time and TPP content on the shear viscosity and other important material properties were investigated. Optimal conditions, which increased the shear viscosity by nearly a factor of 20 over the neat polymer, were found to be 4 wt% TPP and 30 min of reaction time at 290 °C. Further results from differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscopy confirmed that coupling with TPP did not affect the microstructure, melting/crystallization behavior or liquid crystallinity. The stability of TPP-modified samples was also studied at 80 °C in air and following melt reprocessing at 290–300 °C under N₂ or air. Samples were stable (as measured by shear viscosity) for more than one month at 80 °C in air or when reprocessed in N₂ at 290 °C for up to 10 min. However, when reprocessed at 300 °C in air, the viscosity enhancement was partially reversed due to scission of P–O bonds that were formed during the initial reaction between the polymer chain-ends and TPP.     

Low temperature graphitization of interphase polyacrylonitrile (PAN)

Ordered polyacrylonitrile (PAN) interphase structures were formed in solution-cast PAN/carbon nanotube (CNT) composite films by enhancing polymer crystallization conditions and processing parameters for five types of CNTs. All film samples were heat-treated using similar stabilization and carbonization (up to 1100 °C) processes. Both the precursor and carbonized materials were characterized by electron microscopy and X-ray spectroscopy. Highly ordered graphitic structure was formed predominantly in the carbonized materials at 1100 °C (i.e., ∼1500 °C lower than the temperature used in a commercial graphitization process). The ordering of the graphite structure formed at 1100 °C was further improved by heat treatment up to 2100 °C. Multiple characterization results indicate that the early onset of PAN conversion to graphite is directly related to the polymer interphase formation as well as the CNT type. Based on the stabilization and carbonization parameters used in this study, PAN/single-wall carbon nanotube (SWNT) samples showed more prevalent graphite formation at 1100 °C. This work demonstrates the influence of CNT type regarding interfacial confinement toward this low-temperature polymer-to-graphite conversion process.     

Mechanical properties and microstructure evolution of 3D Cf/SiBCN composites at elevated temperatures

3D C_f/SiBCN composites were fabricated by an efficient polymer impregnation and pyrolysis (PIP) method using liquid poly(methylvinyl)borosilazanes as precursor. Mechanical properties and microstructure evolution of the prepared 3D C_f/SiBCN composites at elevated temperatures in the range of 1500‐1700°C were investigated. As temperature increased from room temperature (371 ± 31 MPa, 31 ± 2 GPa) to 1500°C (316 ± 29 MPa, 27 ± 3 GPa), strength and elastic modulus of the composite decreased slightly, which degraded seriously as temperature further increased to 1600°C (92 ± 15 MPa, 12 ± 2 GPa) and 1700°C (84 ± 12 MPa, 11 ± 2GPa). To clarify the conversion of failure mechanisms, interfacial shear strength (IFSS) and microstructure evolution of the 3D C_f/SiBCN composites at different temperatures were investigated in detail. It reveals that the declines of the strength and changes of the IFSS of the composites are strongly related to the defects and SiC nano‐crystals formed in the composites at elevated temperatures.