Nonisothermal crystallization behavior of the poly(ethylene glycol) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Effect of the poly(L-lactide) block length

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L-lactide)poly(ethylene glycol) (PLLA-PEG) diblock copolymers were investigated with wideangle X-ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L-lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000-PEG5000 at a larger degree of supercooling was different from that of PLLA2500-PEG5000, PLLA5000-PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively.

Miscibility and crystallization behavior of PBT/epoxy blends

The miscibility and the isothermal crystallization kinetics for PBT/Epoxy blends have been studied by using differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The Avrami exponents n were obtained for PBT/Epoxy blends. An addition of small amount of epoxy resin (3%) leads to an increase in the number of effective nuclei, thus resulting in an increase in crystallization rate and a stronger trend of instantaneous three-dimensional growth. For isothermal crystallization, crystallization parameter analysis showed that epoxy particles could act as effective nucleating agents, accelerating the crystallization of PBT component in the PBT/Epoxy blends. The Lauritzen-Hoffman equation for DSC isothermal crystallization data revealed that PBT/Epoxy 97/3 had lower nucleation constant K, than 100/0, 93/7, and 90/10 PBT/Epoxy blends. Analysis of the crystallization data of PBT/Epoxy blends showed that crystallization occurs in regime II. The fold surface free energy, sigma(e) = 101.7-58.0 x 10(-3) J/m(2), and work of chain folding, q = 5.79-3.30 kcal/mol, were determined. The equilibrium melting point depressions of PBT/Epoxy blends were observed and the Flory-Huggins interaction parameters were obtained.

The thermal cycling behavior of Lanthanum-Cerium Oxide thermal barrier coating prepared by EB-PVD

Bulk material and coatings of Lanthanum-Cerium Oxide (La2Ce2O7) with a fluorite structure were studied as a candidate material for thermal barrier coating (TBC). It has been showed that such material has the properties of low thermal conductivity about four times lower than YSZ, the difference in the thermal expansion coefficient between La2Ce2O7 and bond coat is smaller than that of YSZ in TBC systems, high phase stability between room temperature and 1673 K, about 300 K higher than that of the YSZ. The coating prepared by electron beam physical vapor deposition (EB-PVD) showed that it has good thermal cycling behavior, implying that Such material can be a promising thermal barrier coating material. The deviation of coating composition from ingot can be overcome by the addition of excess La2O3 during ingot preparation and/or by adjusting the process parameters.

Study on the phase behavior of BaEu2Mn2O7 through heat treatment of a single crystal

A new orthorhombic phase of BaEu2Mn2O7 with the space group of Ccmm (no.63) was identified for single crystals after heat treatment and its Crystal Structure was determined by single crystal X-ray diffractometry. The volume Of the unit cell has twice the fundamental tetragonal cell and corner-shared MnO6 octahedra are slightly distorted and Mn-O-Mn angle between the neighboring octahedra tilts with an angle by around 3 degrees from b-axis. It is concluded from the results of the heat treatment of single crystals at various temperatures that this orthorhombic phase changes into a tetragonal One With superstructure (P4(2)/mnm) at 402 K and changes once more into the fundamental tetragonal phase (I4/mmm) above 552 K. The tetragonal phase with superstructure which has been expected to be an unstable one is stable between the two temperatures.

Isothermal crystallization behavior of the poly(L-lactide) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Influence of the PEG block as a diluted solvent

Isothermal crystallization kinetics and morphology of the poly(L-lactide) block in poly(L-lactide)poly(ethylene glycol) diblock copolymers were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The results were compared with that of the PLLA homopolymer. The introduction of the PEG block accelerated the crystallization rate of the PLLA block and promoted to form ring-banded spherulites. The analysis of isothermal crystallization kinetics has shown that the PLLA homopolymer accorded with the Avrami equation. But the PLLA block of the diblock copolymers deviated from the Avrami equation, which resulted from increasing of the crystallization rate and occurring of the second crystallization process. The equilibrium melting temperature (T,,) of the PLLA block fell with its molecular weight decreasing. The conditions to obtain more regular ring-banded spherulites were below: the sample was the PLLA block of LA(5) EG(5); the crystallization temperature was about from 95 degrees C to 100 degrees C, which almost corresponded to regime II.

Nonisothermal crystallization behavior of glass-bead-filled polypropylene

The effects of the glass-bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass-bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half-time for crystallization decreased with an increase in the glass-bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass-bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass-bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass-bead blends based on the Kissinger method was evaluated.

Crystallization behavior of carbon nanotubes-filled polyamide 1010

The nanocomposites of polyamide1010 (PA1010) filled with carbon nanotubes (CNTs) were prepared by melt mixing techniques. The isothermal melt-crystallization kinetics and nonisothermal crystallization behavior of CNTs/PA1010 nanocomposites were investigated by differential scanning calorimetry. The peak temperature, melting point, half-time of crystallization, enthalpy of crystallization, etc. were measured. Two stages of crystallization are observed, including primary crystallization and secondary crystallization. The isothermal crystallization was also described according to Avrami's approach. It has been shown that the addition of CNTs causes a remarkable increase in the overall crystallization rate of PA1010 and affects the mechanism of nucleation and growth of PA1010 crystals. The analysis of kinetic data according to nucleation theories shows that the increment in crystallization rate of CNTs/PA1010 composites results from the decrease in lateral surface free energy.

Thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure of poly(propylene carbonate)/ethyl cellulose blends

Maleic anhydride end capped poly(propylene carbonate) (PPC-MA) was blended with ethyl cellulose (EC) by casting from dichloromethane solutions. The thermotropic liquid crystallinity, thermal decomposition behavior, and aggregated structure were investigated by differential scanning calorimetry (DSC), thermogravimetry (TGA), and wide angle X-ray diffraction (WAXD). DSC exhibits thermotropic liquid crystallinity in the rich EC composition range. TGA shows that thermal decomposition temperatures were elevated upon interfusing EC into PPC-MA. WAXD corroborates that EC and PPC-MA/EC blend films cast from dilute dichloromethane solution possessed cholesteric liquid crystalline structure in the rich EC composition range, and that dilution of PPC-MA with EC increased the dimension of noncrystalline region, leading to a more ordered packed structure.

Phase transition behavior and structure of the thermotropic liquid crystal 6-{[(4 '-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyne

The phase transition behaviors and corresponding structures of 6-{[(4'-([(undecyl)carbonyl]oxy)biphenyl-4yl)carbonyl]oxyl-l-hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X-ray diffraction (WAXD). In comparison with the published homologues, 5- [(4'-heptoxy-biphenyl-4-yl)carbonyl]oxyl-1-pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5-{ [(4'-heptoxybiphenyl-4-yl)oxy]carbonyl)- I-pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5-{[(4'-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5 degrees C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69 angstrom.

Nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) dibloick copolymer

The nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) ( PLLA-PEG) diblock copolymer was studied by means of real-time WAXD, DSC and POM, and Ozawa equation was used to analyze the kinetics of PLLA-PEG under nonisothermal crystallization conditions. During the crystallization of the high-T-m block (PLLA), the low-T-m block (PEG) acts as a noncrystalline diluent, and the crystallization behavior of PLLA obeys the Ozawa theory. When the PEG block begins to crystallize, the PLLA phase is always partially solidified and the presence of the spherulitic microstructure of PLLA profoundly restricts its crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. Furthermore, the study of the crystalline morphology of PLLA-PEG at different cooling rates indicates that when the cooling rate is from low to high, the crystalline morphology undergoes a transformation from the ring-banded spherulites to the typical Maltese cross spherulites, which experiences the mixed crystalline morphologies of ring-banded and typical Maltese cross spherulites, and the spherulitic size becomes smaller.