Phase behavior of polymer blends

The present report deals with some results on phase behavior, miscibility and phase separation for several polymer blends casting from solutions. These blends are grouped as the amorphous polymer blends, blends containing a crystalline polymer or two crystalline polymers. The blends of PMMA/PVAc were miscible and underwent phase separation at elevated temperature, exhibited LCST behavior. The benzoylated PPO has both UCST and LCST nature. For the systems composed of crystalline polymer poly(ethylene oxide) and amorphous polyurethane, of two crystalline polymers poly(epsilon-caprolactone) and poly[3,3,-bis-(chloromethyl) oxetane], appear a single T-g, indicating these blends are miscible. The interaction parameter B's were determined to be -14 J cm(-3), -15 J cm(-3) respectively. Phase separation of phenolphthalein poly(ether ether sulfone)/PEO blends were discussed in terms of thermal properties, such as their melting and crystallization behavior.

Isothermal and nonisothermal crystallization of poly(aryl ether ketone ketone) with all-para phenylene linkage

Isothermal and nonisothermal crystallization behavior for PEKK(T) was studied using differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and electron diffraction (ED). In the isothermal crystallization process, the Avrami parameters obtained were n = 2.33-2.69, which shows crystal growth of two-dimensional extensions consistent with our observations by TEM. The lamellar thickness increases with the crystallization temperature of PEKK(T) crystallized isothermally from the melt. However, for the nonisothermal crystallization of PEKK(T), the results from the modified Avrami analysis show two different crystallization processes. Avrami exponents n(1) = 3.61-5.30, obtained from the primary crystallization process, are much bigger than are the secondary n(2) = 2.26-3.04 and confirmed by the observation of the spherulite morphology. PEKK(T) crystallized isothermally from the melt possesses the same crystal structure (Form I) as that from nonisothermal melt crystallization. The results from TEM observation show that the spherulite radius decreases with an increasing cooling rate. (C) 2001 John Wiley & Sons, Inc.

Effect of nucleating agent on the isothermal crystallization kinetics of PHBV

The crystallization behavior of PHBV, poly(beta -hydroxybutyrate-co-beta -hydrxyvalerate), with nucleating agents under isothermal conditions was investigated. A differential scanning calorimeter was used to monitor the crystallization process from the melt. During isothermal crystallization, the dependence of relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of BN and Tale causes a considerable increase in the overall crystallization rate of PHBV but does not influence the Avrami exponent n, mechanism of nucleation and spherulite growth mode of PHBV. A little of nucleating agent will increase the crystallization rate and decrease the fold surface free energy sigma (e), remarkably. The effect of BN is more significant than that of Talc.

Nonisothermal crystallization kinetics: poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymer and poly(ethylene oxide) homopolymer

The nonisothermal crystallization behavior of polyethylene oxide (PEO) in poly(ethylene terephthalate)poly(ethylene oxide) (PETPEO) segmented copolymer and PEO homopolymer has been studied by means of differential scanning calorimetry, as well as transmission electron microscope. The kinetics of PEO in copolymer and PEO homopolymer under nonisothermal crystallization condition has been analyzed by Ozawa equation. The results show that Ozawa equation only describes the crystallization behavior of PEO-6000 homopolymer successfully, but fails to describe the whole crystallization process of PEO in copolymer because the secondary crystallization in the later stage could not be neglected. Due to the constraint of PET segments imposed on the PEO segments, a distinct two stage of crystallization of PEO in copolymer has been investigated by using Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. In the case of PEO-6000 homopolymer, good linear relation for the whole crystallization process is obtained owing to the secondary crystallization does not occur under our experimental condition. (C) 2001 Elsevier Science Ltd. All rights reserved.

Influence of the size of ultrafine CaCO3 powder on PP crystallization

The effects of CaCO3 on the crystallization behavior of polypropylene (PP) were studied by means of DSC and WAXD. The average sizes of the CaCO3 powders used were 0.1 mum (UC) and 0.5 mum (GC), respectively. The PP/CaCO3 composites at compositions of 1 phr and 10 phr were investigated. The results showed that the addition of CaCO3 reduced the supercooling, the rate of nucleation and the overall rate of crystallization (except for the 10 phr UC/PP sample). The crystallinity of PP was increased and the size distribution of the crystallites of alpha -PP; was: broadened. On the other hand,the crystallization rate of 10 phr UC/PP is 1.5 times higher than that of neat PP. It has an overall rate of crystallization 2 times as much as that of the neat PP and has the maximum crystallinity. The sizes of crystallites and the unit cell parameters of alpha -PP were varied by the addition of CaCO3. beta -PP was formed by addition of Ge and was not detected by addition of UC. The differences of crystallization behaviors of PP might be attributed to the combined effects of the content and size of CaCO3 filled.

Nonisothermal crystallization kinetics of PEO in ethylene terephthalate-ethylene oxide segmented copolymers

The nonisothermal crystallization behavior of Ethylene Terephthalate-Ethylene Oxide (ET-EO) segmented copolymers has been studied with the use of differential scanning calorimetry (DSC). The kinetics of PEO in ET-EO segmented copolymer under nonisothermal crystallization conditions has been analyzed with the Ozawa equation. The results show that there is no agreement with Ozawa's theoretical predictions in the whole crystallization process owing to the constraint of ET segments imposed on the EO segments. A distinct two-crystallization process has been investigated by using the Avrami equation modified by Jeziorny to deal with the nonisothermal crystallization data. The value of the Avrami exponent n is independent of the length of soft segments. However, the crystallization rate is sensitive to the length of soft segments. The longer the soft segments, the faster the crystallization will be.

Non-isothermal crystallization kinetics of the poly(3-alkylthiophenes)

According to the data obtained from Differential Scanning Calorimetry (DSC),the method of Jeziorny, BOPOXOBCKHH and a new approach proposed by our laboratry are applied to study the nonisothermal crystallization behavior of poly( 3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT),and Kissinger method is used to get the value of the crystallization activation energy. The effect of the different alkyl substitution on crystallization is also investigated. In comparison to the methods of Jeziorny and BOPOXOBCKHH in which it can be found that the deviation from the line occurs in the later stage of crystallization, the new approach appears applicable due to the better linear relation. The values of the crystallization activation energy of P3DDT and P3ODT are estimated as 184.78kJ/mol and 246.93kJ/mol, respectivley, which implies that it is easiser to crystallize P3DDT than P3ODT.

Crystallization behevior of poly(3-dodecylthiophene)

The crystallization behavior of poly (3-dodecylthiophene) (P3DDT) is studied bq differential scanning calorimetry (DSC) under different cooling rates. When the methods of Jeziorny., Ozawa and a new one proposed by our laboratory are applied to describe its nonisothermal crystallization behavior, the new one is confirmed to be the best and convenient. By determining kinetic parameters, the analysis of the nonisothermal crystallization behavior is performed. According to Kissinger method, the crystallization activation energy of P3DDT is also evaluated.

Isothermal and non-isothermal crystallization kinetics of syndiotactic polypropelene

Isothermal and non-isothermal crystallization kinetics of a syndiotactic polypropylene(sPP) sample synthesized by new metallocene catalyst at different annealing temperatures and different cooling rates have been investigated by using differential scanning calorimetry(DSC) and density analysis. The equilibrium melting temperature( T-m(0)) is 158 degrees C by Hoffman-Weeks method. The equilibrium heat of fusion(Delta H-m(0)) is 88J/g in terms of the density analysis and DSC methods. The lateral and end surface free energies derived from the Lauritzen-Hoffman spherulitic growth rate equation are sigma = 5.2erg/cm(2) and sigma(e) = 69erg/cm(2), respectively. The work of chain folding is determined to be q = 33.75kJ/mol. Modified Avrami equation and Ozawa equation can be used to describe the non-isothermal crystallization behavior. And a new and convenient approach by combining the Avrami equation and Ozawa equation in a same crystallinity is used to describe the non-isothermal behavior as well. The crystallization activation energies are evaluated to be 73.7kJ/mol and 73.1kJ/mol for isothermal crystallization and non-isothermal crystallization, respectively. The Avrami exponent n is 1.5 similar to 1.6 for isothermal crystallization procedure, while the Avrami exponent n,is 2.5 similar to 3.5 for non-isothermal crystallization procedure. This indicated the difference of nucleation and growth between the two procedures.

Miscibility and crystallization of PHB PMA blends

The miscibility, crystallization behavior and morphological structure of PHB/PMA blends have been studied by the differential scanning calorimeter (DSC) and polarized optical microscopy (POM). The chemical repeat units of the two components of the blend are isomers. The results indicate that PHB and PMA are miscible in the melt. The addition of PMA into PHB results in a depression in the spherulite growth rate of PHB. With increasing PMA content in the blends, the texture of PHB spherulite becomes more open.

Crystallization of micelles and matrix in dilute diblock copolymer/homopolymer solutions

The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEG. However, the "soft" micelles formed in the solution (meaning that the glass transition temperatures (T-g) of the micelle is lower than the T-m of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a "hard" PMMA core (meaning that the T-g of the core is higher than the T-m of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. (C) 1998 John Wiley & Sons, Inc.

Isothermal and nonisothermal crystallization kinetics of nylon-11

Analysis of the isothermal, and nonisothermal crystallization kinetics of Nylon-11 is carried out using differential scanning calorimetry. The Avrami equation and that modified by Jeziorny can describe the primary stage of isothermal and nonisothermal crystallization of Nylon-11. In the isothermal crystallization process, the mechanism of spherulitic nucleation and growth are discussed; the lateral and folding surface free energies determined from the Lauritzen-Hoffman equation are sigma = 10.68 erg/cm(2) and sigma(e) = 110.62 erg/cm(2); and the work of chain folding q = 7.61 Kcal/mol. In the nonisothermal crystallization process, Ozawa analysis failed to describe the crystallization behavior of Nylon-ii. Combining the Avrami and Ozawa equations, we obtain a new and convenient method to analyze the nonisothermal crystallization kinetics of Nylon-11; in the meantime, the activation energies are determined to be -394.56 and 328.37 KJ/mol in isothermal and nonisothermal crystallization process from the Arrhonius form and the Kissinger method. (C) 1998 John Wiley & Sons, Inc.

Epitaxial crystallization of sPP on the (100) lattice plane of HDPE crystals

Crystallization behavior of syndiotactic polypropylene(sPP) on the (100) lattice plane of high-density polyethylene(HDPE) crystals was studied by means of transmission electron microscopy and electron diffraction. The results indicate that sPP crystals can grow epitaxially on the (100) PE lattice plane with their chain directions +/-37 degrees apart from the chain direction of the HDPE substrate. The contact planes are (100) lattice planes for both polymers. This kind of epitaxy is explained in terms of parallel alignment of HDPE chains along the rows formed by the {CH3, CH2,CH3} groups in the (100) lattice plane of the sPP crystals. This implies that in the epitaxial crystallization of sPP with fiber oriented HDPE substrate, not only the (110) but also the (100) HDPE lattice planes can act as the oriented nucleation sites. Furthermore, according to the poor matching between HDPE chains in the (100) lattice plane and the {CH3, CH2, CH3} group rows in the (100) lattice plane of the sPP crystals, it is concluded that the geometric matching is not the only controlling factor for the occurrence of polymer epitaxy.

Crystallization kinetics and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends

The crystallization behavior and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends have been studied with DSC, POM, SAXS and WAXD methods. The results indicate that the overall crystallization rate and spherulite growth rate are slower in the blends than that in the pure PHB. The addition of PVAc has no effect on the crystal structure of PHB, but affects its crystalline morphology. During crystallization of PHB, PVAc chains were being rejected into the region between the lamellae of crystalline PHB. (C) 1997 Elsevier Science Ltd.

Critical crystallization temperature for the occurrence of epitaxy between high-density polyethylene and isotactic polypropylene

The crystallization behavior of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) at elevated temperatures (e.g., from 125 to 128 degrees C), was studied using transmission electron microscopy and electron diffraction. The results show that epitaxial crystallization of HDPE on the highly oriented iPP substrates occurs only in a thin layer which is in direct contact with the iPP substrate, when the HDPE is crystallized from the melt on the oriented iPP substrates at 125 degrees C. The critical layer thickness of the epitaxially crystallized HDPE is not more than 30 nm when the HDPE is isothermally crystallized on the oriented iPP substrates at 125 degrees C. When the crystallization temperature is above 125 degrees C, the HDPE crystallizes in the form of crystalline aggregates and a few individual crystalline lamellae. But both the crystalline aggregates and the individual crystalline lamellae have no epitaxial orientation relationship with the iPP substrate. This means that there exists a critical crystallization temperature for the occurrence of epitaxial crystallization of HDPE on the melt-drawn oriented iPP substrates (i.e., 125 degrees C). (C) 1997 John Wiley & Sons, Inc.