Mechanism of polymorph selection during crystallization of random butene-1/ethylene copolymer

Starting from an initial sample of butene-1/ethylene copolymer with stable form I’, we examined the nucleation of different crystalline polymorphs (here metastable form II and stable form I’) at different isothermal crystallization temperatures after being melted at different melt temperature (T _melt). When T _melt was just above the melting temperature (T _m) of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When T _melt was a few degrees above the T _m, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.     

Mechanistic insights into the shear effects on isotactic polypropylene crystallization containing <Emphasis Type="Italic">β</Emphasis>-nucleating agent

The crystalline structures and crystallization behaviors of iPP containing β nucleation agent TMB-5 (iPP/TMB-5) were investigated by synchrotron radiation wide angel X-ray diffraction (SR-WAXD), differential scanning calorimeter (DSC) and polarized light microscope (PLM). It was found that α-crystallization lagged behind β-crystallization at normal temperatures, but the discrepancy reduced with increasing temperature. TMB-5 could not induce β-iPP when the nucleation agent is wrapped up with α-crystal that crystallized at high temperatures. The polymorphic composition of iPP/TMB-5 was susceptible to the introductory moment of shear. New crystallization process of β-nucleated iPP was proposed to understand the experimental phenomena which could not be explained by those reported in the literature. It was supposed that polymer crystallization initiated from mesophase, and the formations of iPP crystals involved the organization of helical conformation ordering within mesophase. It was proposed that the iPP melt contained mesophases with stereocomplex-type ordering of right-handed and left-handed helical chains which could be disturbed by shear or TMB-5, leading to different polymorphic structures.     

Concentration,temperature, and isotopy effects on the heat capacity of aqueous urea

Relations for the apparent molar heat capacity ?_c of urea in an aqueous solution depending on the molality m and temperature were obtained. A transition to the relations ?_c(m,T) for D₂O-(ND₂)₂CO and T₂O-(NT₂)₂CO systems was effected by temperature scaling. At low temperatures, the isotherms of the molar heat capacity C _p(m) of the protium and deuterium systems have minima shifted to more dilute solutions at elevated temperatures. At m = 1, C _p of a solution does not depend on temperature in both systems. The dependences C _p(T) also have minima at constant concentrations. The temperature of the minimum heat capacity is most effectively lowered by small additions of urea. For m = 0.25, T _min is 7.5 K lower than T _min of pure water, and its heat capacity is 0.08 J/(mol K) higher. A transition from m = 1.5 to m = 2 lowers the temperature of the minimum heat capacity by 3.6 K; thus, the heat capacity of solutions differs by 0.02 J/(mol K) only.     

The structural organization of liquid low-molecular-weight epoxy oligomers

The possibility of the existence and the behavior of molecular aggregates in low-molecular-weight epoxy resins were studied. The globular morphology of all liquid resins was determined using transmission electron microscopy. The lamellar morphology of crystallized ED24 was established by additionally using atomic-force microscopy. The thermal behavior of oligomeric epoxides was studied over the temperature range ?100–100°C. The T _g and T _ll transitions were recorded for liquid resins by differential scanning calorimetry. For solid ED24, the T _m peak of resin melting situated between T _g and T _ll was observed. The existence of the T _ll transition was substantiated by positron annihilation measurements. The morphological picture was thermally unstable and became completely degenerate at T _ll. The morphology and thermophysical parameters of the resins changed substantially after their vibrational treatment. The morphology of oligomers was shown to be “hereditarily” (genetically) related to that of the corresponding network polymers.     

Non-Isothermal Crystallization Behavior of β-Nucleated Isotactic Polypropylene/Multi-Walled Carbon Nanotube Composites with Different Melt Structures

In this study, the melt structure status of isotactic polypropylene/multi-walled carbon nanotubes composites (iPP/MWCNTs) nucleated with β-NA was tuned by changing the fusion temperature T _f . The non-isothermal crystallization behavior and subsequent melting behavior of the sample were studied in detail. The results showed that under different cooling rates (2, 5, 10, 20 and 40 deg/min), the crystallization temperature increased gradually with the decrease of T _f , meanwhile, when T _f was in the temperature range of 166–174°C where ordered structures survived in the melt (named Region II), the crystallization activation energy was significantly lower compared with the case T _f > 174°C or T _f < 166°C. On the subsequent melting curves, the occurrence of the melt structure can be observed at all the cooling rates studied; the location of the Region II was constant, which did not show dependency on the cooling rates; low cooling rate and relative low T _f within 166–174°C encouraged the formation of more β-phase triggered by melt structure.     

Analysis of structure transition and compatibility of PTT/PC blend without transesterification

Poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends were prepared by solvent mixing to avoid transesterification during high temperature blending. The influences of compositions on the thermal behavior, crystallization morphology and structure of the blends were studied. FTIR results indicated that there was no COO linking to two phenyl groups on each side chain and DSC results supported no transesterification reaction. DSC curves showed that T _c and T _mc increased to maximum range when PC contents were between 7 wt%-15 wt%, however, T _m decreased constantly with the increase of PC contents. It was observed from POM that PTT spherulitic morphology and crystallization kinetics were obviously influenced by the change of PC contents. Structural evolutions during cooling were investigated by SAXS which showed L _c of PTT remained a constant with different PC contents and also fixed during crystallization, nevertheless, it revealed a maximum value of L _nc for sample PTT₉₃. It was concluded that PC chains could be permeated into not only amorphous crystallite structure but also amorphous lamellae structure and 7 wt% PC content was supposed to be the “proper” penetration amount into PTT lamellae structure which led to a maximum capacity of amorphous lamellar layer. Fringedmicelle crystal model was adopted to illustrate semi-crystalline physical structures of the blend in two kinds of component aggregation states.     

Analysis and characterization of the transition from the Arrhenius to non-Arrhenius structural relaxation in fragile glass-forming liquids

We have studied the transition from an Arrhenius-like to a non-Arrhenius-like structural relaxation behavior in fragile glass-forming liquids. This transition is denoted by the temperature T_A that usually occurs above the melting point T_m and the dynamic crossover temperature T_B. Recent studies reveal that T_A is a characteristic temperature related with the dynamical properties of the system. However, its unambiguous determination is not easy. In this work, a method to obtain the temperature T_A from the experimental data of α-relaxation time is presented. The obtained T_A is compared with the cooperativity onset temperature T_x extracted from the bond strength–coordination number fluctuation model. The result reveals that T_A is close to T_x for fragile liquids. From the result of the present analyses combined with the linear relation T_x \(\propto\) T₀, where T₀ is the Vogel temperature, the Arrhenius crossover phenomenon in fragile liquids is linked to the low-temperature structural relaxation dynamics.     

Method for calculating the sizes of nucleation centers upon homogeneous crystallization from a supercooled liquid

An alternative approach to calculating critical sizes l_k of nucleation centers and work A_k of their formation upon crystallization from a supercooled melt by analyzing the variation in the Gibbs energy during the phase transformation is considered. Unlike the classical variant, it is proposed that the transformation entropy be associated not with melting temperature T_L but with temperature T < T_L at which the nucleation of crystals occurs. New equations for l_k and A_k are derived. Based on the results from calculating these quantities for a series of compounds, it is shown that this approach is unbiased and it is possible to eliminate known conflicts in analyzing these parameters in the classical interpretation.     

Apparent Molar Volumes of Aqueous Solutions of Magnesium Tetraborate from 283.15 to 363.15 K and 0.1 MPa

Densities for aqueous solutions of magnesium tetraborate MgB₄O₇(aq) at the molalities of (0.00556–0.03341) mol·kg^?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V _? ) of MgB₄O₇(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB₄O₇(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a₀?+?a₁?×?T?+?a₂?×?T ²?+?a₃/T?+?a₄?×?ln(T)?+?a₅?×?T ³ (where T is temperature in Kelvin, a _i are model parameters) for MgB₄O₇ were obtained for the first time.     

Biodegradable poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-butylene dimerized fatty acid)s: Synthesis,crystallization, mechanical properties,and rheology

Poly(butylene succinate-co-butylene dimerized fatty acid) (P(BS-co-BDFA)) copolyesters were synthesized from succinic acid (SA) and dimerized fatty acid (DFA) with 1,4-butanediol (BDO) through a two-step process of esterification and polycondensation. The polyester compositions and physical properties of copolyesters were investigated by GPC, ¹H NMR and ¹³C NMR, DSC, WAXD, DMA, TGA, tensile and rheology test. The melting temperature (T_m), and crystallization temperature (T_c) decreased gradually as the content of DFA monomer increased. P(BS-co-BDFA) copolyesters showed the same crystal structure as the PBS homopolyester. Besides, TGA results indicated that P(BS-co-BDFA)s were of higher thermal stabilities. Moreover, it was found that the synthesized P(BS-co-BDFA)s showed the maximum elongation at break (591%) as the DFA contents were 10 mol%. Rheology analysis indicated that the viscoelastic behavior of the polyesters greatly depended on the molecular weight of polyesters.     

First-order phase transformation and structural studies in Se<Subscript>85</Subscript>In<Subscript>15−x</Subscript>Zn<Subscript>x</Subscript> chalcogenide glasses

Present research work describes the crystallization kinetics and structural studies in Se₈₅In_15?xZn_x chalcogenide glasses. Bulk alloys of Se₈₅In_15?xZn_x were synthesized by melt-quenching procedure. High resolution X-ray diffraction (HRXRD) was used to confirm the amorphous nature of synthesized samples. Non-isothermal differential scanning calorimetry (DSC) measurements were performed at 5, 10, 15, 20 and 25 K min^?1 heating rates to study kinetics of crystallization in Se₈₅In_15?xZn_x. Various crystallization parameters such as glass transition (T _g), onset crystalline (T _c), peak crystallization (T _p) and melting temperature (T _m) were calculated from DSC curves. The activation energies of structural relaxation (ΔE _t) and crystallization (ΔE _c) were determined by using Kissinger, Moynihan and Ozawa approaches. ΔE _t is found to be the lowest for Se₈₅In₆Zn₉ sample which shows this sample has the highest probability of escape to a state of lower configurational energy and has greater stability. Thermal stability of various compositions was studied and found to vary with Zn content. Further, HRXRD and field emission scanning electron microscope were used for the study of first phase transformation in Se₈₅In_15?xZn_x samples.     

Glass-forming ability and thermal stability of Se<Subscript>100−x</Subscript>(Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript>)<Subscript>x</Subscript> glassy alloys

Glassy Se_100?x(Ge₂Sb₂Te₅)_x (x?=?5, 10, 15 and 20) bulk alloys were prepared by melt-quenched technique and studied by using differential scanning calorimetry at different heating rates under non-isothermal condition. The detailed thermal analysis shows that the glass transition temperature (T_g) depends on heating rates and x content. In particular, it is found that the glass-forming ability, thermal stability (T_c???T_g) and crystallization activation energy (E_c) increase with increased x content in amorphous Se, whereas glass transition activation energy (E_g) and fragility index (F) decrease with increased x contents. Variation in these parameters can be explained on the basis of network-forming ability of Se and bonding arrangement among the constituent atoms of alloys.     

Vapor pressure and heat capacities of perfluoro-<Emphasis Type="Italic">N</Emphasis>-(4-methylcyclohexyl)piperidine

Heat capacities of perfluoro-N-(4-methylcyclohexyl)piperidine (PMCP) have been measured by low-temperature adiabatic calorimetry. The purity of the compound, its triple-point temperature, and its enthalpy and entropy of fusion have been determined. The saturated vapor pressure was determined by comparative ebulliometry as a function of temperature in the 6.2–101.6 kPa pressure range and 374.2–460.9 K temperature range. The calorimetric enthalpy of vaporization at T = 298.15 K has been measured. The following thermodynamic properties were calculated for PMCP: normal boiling temperature, enthalpy of vaporization Δ_vap H _m ⁰ (T) as a function of temperature, and critical parameters. The enthalpies of vaporization at 298.15 K obtained experimentally and by calculation methods match within their error limits, which validates their adequacy and the adequacy of the Δ_vap H _m ⁰ = f(T) equation as an extrapolation.     

Effect of Ag addition on crystallization kinetics and thermal stability of As–Se chalcogenide glasses

Chalcogenide glasses of (As₅₀Se₅₀)_100?xAg_x (0 ≤ x ≤ 25) were prepared using the melt quenching technique under non-isothermal conditions. Differential scanning calorimetry curves measured at different heating rates (5 ≤ β ≤ 40 K min^?1) are used to characterize the as-quenched samples. The thermal stability was monitored through the calculation of the temperature difference T _c ? T _g, stability parameter S and crystallization rate factor K _p. The glass-forming ability (GFA) was investigated on the basis of Hurby parameter H _r which is a strong indicator of GFA. In addition, the activation energy of glass transition E _t, activation energy of crystallization E _c and Avrami exponent n of the studied compositions were determined. The mechanism of crystallization was found to be a combination of two- and three-dimensional crystal growth.     

The effect of organoclay and graphene on the crystallization of PP in ABS/PP blends

In the present research, the isothermal and non-isothermal crystallization of polypropylene (PP) phase in PP-rich poly(acrylonitrile–butadiene–styrene)/polypropylene (ABS/PP) blends was studied. The effect of nanofillers’ incorporation and specialty of organically modified montmorillonite (OMMT) and graphene, into the prepared blends on the isothermal and non-isothermal crystallization of PP phase, were investigated. Moreover, kinetic study of their isothermal crystallization process was carried out, by applying the Avrami equation. The addition of ABS to the PP matrix increased the crystallization rate of PP at 130 °C. The incorporation of OMMT in pure PP accelerated slightly the crystallization process, whereas in ABS/PP blends, it seemed to retard crystallization, due to interactions between ABS phase and organoclay. The incorporation of graphene in pure PP accelerated impressively its isothermal crystallization, while the addition of ABS in graphene/PP nanocomposite slowed down the crystallization rate of PP. The effect of ABS and nanofillers, separately or in combination, on the crystallization of PP phase was reflected on the kinetic parameters of the Avrami equation. Regarding the non-isothermal crystallization, ABS/PP blends presented higher crystallization temperature (T _c) compared to pure PP. The organoclay reinforcement did not have any obvious effect on this temperature, whereas graphene caused significant increase, acting as nucleating agent. The presence of ABS to PP increased the concentration of the β-crystalline phase, reaching its maximum value at 30 mass% ABS content. The organoclay decreased the β-PP in ABS/PP blends, whereas graphene eliminated it.     

Formation of Nd<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript> Nanocrystals under Conditions of Glycine-Nitrate Synthesis

Nd_1–xBi_xFeO₃ nanocrystals with crystallite size 30?60 nm have been prepared under conditions of glycine–nitrate burning. Single-phase Nd_1–xBi_xFeO₃ nanocrystals are formed over the entire studied concentrations range if the glycine–nitrate synthesis is performed in excess of the oxidizer. Under these conditions, a continuous range of the Nd_1–xBi_xFeO₃ solid solutions (0 ≤ х ≤ 0.75) crystallized in the rhombic system (space group Pbnm) are formed without crystallization of the burning intermediates. The Nd_1–xBi_xFeO₃ solid solutions (х = 0.775, 0.8) crystallize in the rhombic system (space group Pbаm).     

Heat capacity and thermodynamic functions of ferrocenemethanol

The heat capacity (C _{p, m}) of ferrocenemethanol (FM) C₅H₅FeC₅H₄CH₂OH have been measured by the low-temperature adiabatic calorimetry method in the range 6–371 K. The triple point temperature, the enthalpy of fusion, and the purity of the substance under consideration have been determined. The ideal gas thermodynamic functions of FM—absolute entropy S _m(g) ⁰ and change in the enthalpy Δ ₀ ^T H _m at 298.15 K—have been derived from the heat capacity data and the known values of the saturation vapor pressure and enthalpy of sublimation. The ideal gas thermodynamic functions C _{p, m} ⁰ and S _m(g) ⁰ and the enthalpy of formation of FM have been calculated by the empirical difference method at T = 298.15 K. The experimental and calculated values of the thermodynamic functions are consistent within error limits, which proves their reliability.     

Isothermal crystallization of polypropylene/surface modified silica nanocomposites

In the present work, 3-methacryloxypropyltrimethoxy-silane silanized silica(SiO_2-WD70) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide immobilized silica(SiO_2-WD70-DOPO) nanoparticles were prepared. Silica, SiO_2-WD70 and SiO_2-WD70-DOPO were incorporated into polypropylene(PP) by melt compounding. Differential scanning calorimetry(DSC), X-ray diffraction(XRD) and polarized optical microscopy(POM) were employed to investigate the isothermal crystallization behavior of PP and PP/silica composites. The kinetic constant(kn), and half crystallization time(t1/2) were calculated by Avrami equation,while the surface free energy of folding was calculated by Lauritzen-Hoffman theory. The increased kn, decreased t1/2 and the surface free energy(σe) in the order of PP, PP/SiO_2, PP/SiO_2-WD70 and PP/SiO_2-WD70-DOPO nanocomposites were attributed to the surface modification of silica. XRD indicated that SiO_2-WD70-DOPO addition had no effect on PP crystal structure but accelerated the crystallization rate. POM determined that SiO_2-WD70-DOPO addition promoted the nucleation of PP by inducing a higher nucleation density during isothermal conditions. The surface modified nanoparticle SiO_2-WD70-DOPO might find possible application as a new type of inorganic nano-sized nucleation agent for PP.     

Structure and dynamics of a free aquaporin (AQP1) by a coarse-grained Monte Carlo simulation

Structure and dynamics of a free aquaporin (AQP1) are studied by a coarse-grained Monte Carlo simulation as a function of temperature using a phenomenological potential with the input of a knowledge-based residue–residue interaction. Response of the radius of gyration (R _g) of the protein to the temperature (T) is found to be nonlinear: Decay of R _g at T ≤ T _c is followed by a continuous increase at T ≥ T _c before reaching its saturation. In thermo-responsive regime, the protein exhibits segmental globularization with the persistence of three regions along its sequence involving residues ¹M–²⁵V and ²⁵⁰V–²⁶⁹K toward the beginning and end segments with a narrow intermediate region around ¹⁵⁵A–¹⁶³D. A detail analysis of the structure factor S(q) shows a global random coil conformation at high temperatures with an effective dimension D _e ~ 1.74 and a globular structure (D _e ~ 3) at low temperatures. In thermo-responsive regime, the variation of S(q) with the wave vector q reveals a systematic redistribution of self-organizing residues (in globular and fibrous sections) that depends on the length scale and the temperature.