Crystallization of Lightly Sulfonated Poly(ethylene terephthalate) Ionomer. I. Isothermal Crystallization from the Melt

Thermal properties and overall rates of isothermal crystallization from the melt of a commercial ionic copolyester (K‐X/SPET) based on poly(ethylene terephthalate) (PET) were analyzed in detail over a composition range from pure PET to a copolymer containing 10.1 mol% of potassium‐neutralized sulfonated PET. For measurements, differential scanning calorimetry (DSC) was used. Copolyesters with the ionic group content of 4.4 mol% or more were unable to crystallize. The isothermal melt crystallization of the copolyesters was analyzed using both the Avrami and the modified Lauritzen‐Hoffman equations. It was found that both the overall rate constant, as well as the Avrami parameter for the primary crystallization stage, varied with the sulfonated unit percentage—but surface free energy and work of folding were practically independent of them. The observed changes in the thermal properties and the kinetic parameters of crystallization were attributed to the comonomer effects and the intermolecular aggregation of the ionic groups.     

Crystallization Behavior of PEO in Nano‐Structured PEO‐b‐PS/PPO Blends

Blends of poly (ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer and poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) homopolymer were obtained by solution blending, and the morphologies of PEO dispersed nanoparticles in PPO/PS matrix were observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The isothermal crystallization kinetics was studied using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nonisothermal crystallization kinetics was studied using DSC. The results showed that PEO segments were easier to crystallize in the blend than in the copolymer probably due to the interfaces of PPO acting as nucleation sites to promote the crystallization of PEO. The crystallization of PEO blocks destroyed the pre‐existing microdomain structure even though the glass transition temperature of the matrix was much higher than the crystallization temperature.     

Isothermal Crystallization Kinetics and Melting Behavior of Poly(ethylene terephthalate)/Attapulgite Nanocomposites Studied by Step-scan DSC

The crystallization kinetics of poly(ethylene terephthalate)/attapulgite (AT) nanocomposites and their melting behaviors after isothermal crystallization from the melt were investigated by DSC and analyzed using the Avrami method. The isothermal crystallization kinetics showed that the addition of AT increased both the crystallization rate and the isothermal Avrami exponent of PET. Step-scan differential scanning calorimetry was used to study the influence of AT on the crystallization and subsequent melting behavior in conjunction with conventional DSC. The results revealed that PET and PET/AT nanocomposites experience multiple melting and secondary crystallization processes during heating. The melting behaviors of PET and PET/AT nanocomposites varied in accordance with the crystallization temperature and shifted to higher temperature with the increase of AT content and isothermal crystallization temperature. The main effect of AT nanoparticles on the crystallization of PET was to improve the perfection of PET crystals and weaken its recrystallization behavior.     

Crystallization Behavior of Modified Polyester with Varied Macromolecular Architecture

Several modified polyesters with varied macromolecular architecture, such as branched poly(ethylene terephthalate) (PET) based on glycerol (GL) from 0.004 to 0.05 mol ratio as a branching agent, blocked and branched poly(butylene terephthalate)‐polyether containing poly(tetramethylene oxide) (PTMO) as soft segment and GL as a branching unit, as well as segmented poly(ethylene terephthalate)‐polyether,were prepared. Their crystallization behavior was studied by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). It was found that a small extent of branching may enhance the crystallization of poly(ethylene terephthalate), while high degrees of branching (0.035–0.05) could block the development of crystallization. On the other hand, for even a small extent of incorporation of GL in the more flexible poly(butylene terephthalate)‐polyether chains, no enhanced crystallization was observed; blocking of crystallization from a branching defect may play the main role. The introduction of PTMO in poly(ethylene terephthalate) chains to a small degree facilitated the nucleation and speeded crystallization, but decreased the melting points of the polymers. A small number of nuclei and the greater induction time were found for branched PETs. The spherulities developed in branched PETs were larger and more perfect than those in PET due to less truncation of spherulites resulting from fewer nuclei, whereas the size of spherulities in poly(ethylene terephthalate)‐polyether became smaller with the increase of PTMO.     

The Nucleation Effect of Grafted Carbon Black on Crystallization of Poly(Ethylene Terephthalate)/Grafted Carbon Black Composite

Poly(ethylene terephthalate)/grafted carbon black (PET/GCB) and poly(ethylene terephthalate)/carbon black (PET/CB) composites were prepared by melt blending. The nucleating effect of CB and GCB were investigated using differential scanning calorimetry (DSC) analysis. The morphologies of the spherulites in PET, PET/CB and PET/GCB composites were observed by means of scanning electron microscopy (SEM). All results showed that GCB had higher nucleating activity than CB in PET and PET/GCB composite had higher rate of nucleation and crystallization. The melting behaviors of neat PET, PET/CB and PET/GCB composites after non‐isothermal crystallization were investigated as well. It was evident that the melting behavior of PET is greatly influenced by addition of CB and GCB.     

Nonisothermal Crystallization Behaviors of Flame-Retardant Copolyester/Montmorillonite Nanocomposites

In order to obtain poly(ethylene terephthalate) (PET) engineering plastics with good flame retardancy, heat resistance, and mechanical properties, a novel phosphorus-containing copolyester (PET-co-DDP)/organo-montmorillonite (OMMT 1%) nanocomposite (PET-co-DDP/OMMT) was prepared by in situ intercalating polymerization. Nonisothermal crystallization kinetics and nanoscale morphology of this composite have been investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). Based on the results of the nonisothermal crystallization kinetics, the flame-retardant copolyester PET-co-DDP has a lower crystallization rate than pure PET, while PET-co-DDP/OMMT nanocomposite has a higher crystallization rate than pure PET. Based on the Augis and Bennett method, the activation energies for nonisothermal crystallization of pure PET, PET-co-DDP, and PET-co-DDP/OMMT nanocomposite were evaluated as 101, 138, and 76 kJ mol^?1, respectively. All the evidence shows that PET-co-DDP strongly influences the crystallization behavior because of its irregular chain structure, while the addition of nanoscale OMMT to this copolymer can significantly enhance the crystallization rate owing to its remarkable nucleating effect. An understanding of the above crystalline behaviors will be beneficial in preparing PET engineering plastics with good overall comprehensive performance.     

TIME-RESOLVED SAXS/WAXS STUDY OF PHASE BEHAVIOR AND CRYSTALLIZATION IN POLYMER BLENDS

Real-time SAXS and WAXS patterns have been simultaneously obtained during isothermal melt-crystallization of blends of low-molecular-weight poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA). The analysis of results shows that the originally homogeneous, single-phase polymer blend separates into two phases. The PMMA molecules diffuse from the blend and form completely segregated regions while PEO starts to crystallize. The first and dominating effect at the beginning of crystallization is the formation of unstable lamellae of nonintegrally folded chains (NIF). The real-time crystallinity and density of the PEO crystalline phase in absolute units were obtained from the time-resolved SAXS/WAXS results. The structure development proceeds in two steps. A very fast evolution of PEO crystals from the melt starts to crystallize in disordered NIF lamellae with thick amorphous interlayers and with a lower density of crystalline phase. The steep growth of crystallinity and crystalline density mean quick thickening of crystalline part of lamellae and improvement of their crystalline structure. In the second step, the structure of the crystalline phase gradually improves and crystallinity grows very slowly. The recrystallization of NIF lamellae into extended chain lamellae (EC) and lamellae with once folded chains (1F) proceeds during both stages of crystallization.     

The Melting Behavior of Poly(Ethylene Terephthalate)/SiO2 Nanocomposites

The melting and recrystallization behavior of poly(ethylene terephthalate) (PET)/SiO₂ nanocomposites after isothermal crystallization from the melt was studied by step-scan differential scanning calorimetry (SDSC). The influences of SiO₂ contents, crystallization temperature, and crystallization time on the melting process were examined. Two melting endotherms (in the SDSC C_P.A curves, reversible part) and one recrystallization exotherm (in the SDSC C_P.IsoK curves, irreversible part) of PET/SiO₂ nanocomposites after isothermal crystallization were observed during the melting process. All are ascribed to the melting–recrystallization mechanism. The low-temperature endotherm is attributed to the melting of initial crystals formed during the isothermal treatment and the high temperature endotherm to the melting of recrystallization materials. The reason why more recrystallization happened with the increase of SiO₂ content is given and the process of recrystallization was described in detail. The effects of crystal perfection and recrystallization were minimized by increasing crystallization temperature and time.     

Effect of Dispersion of Carbon Black on Electrical and Thermal Properties of Poly(Ethylene Terephthalate)/Carbon Black Composites

A type of grafted carbon black (GCB), prepared with a low molecular weight antioxidant compound by in-situ reaction, was dispersed in poly(ethylene terephthalate) (PET) by a melt-blending process. Dispersion of fillers, volume resistivity, and thermal properties were investigated using scanning electron microscopy, a high-resistance meter, differential scanning calorimetry, and thermogravimetric analysis, respectively. The results show that, compared with carbon black (CB) particles, GCB particles dispersed better in the PET matrix, whereas the conductivity percolation threshold of PET/GCB was higher than that of PET/CB. The addition of GCB or CB elevated the cold crystallization temperature of PET, reflecting the effectiveness of carbon fillers as nucleating agents. But carbon fillers decreased the crystallization enthalpy of PET during both heating and cooling process. Both CB and GCB elevated the starting temperature of thermal degradation of PET and increased the amount of residues for the composites over that of neat PET.     

Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

BLENDS OF THERMOTROPIC LIQUID CRYSTALLINE POLYESTER AND POLY(ETHYLENE TEREPHTHALATE)

Two kinds of blends of thermotropic liquid crystalline polymers (LCPs) and poly(ethylene terephthalate) (PET) were prepared by solution and melt blending, respectively. Crystallization behavior of the blends was observed by differential scanning calorimetry (DSC). The LCP in both blends considerably decreased the cold crystallization temperature of PET and increased the crystallization rate in the low-temperature region, but did not show any significant effect on crystallization in the high-temperature region. Phase behavior of samples prepared by melt blending was investigated with the scanning electronic microscope (SEM). It was found that LCP/PET blends display a biphasic structure with an aromatic unit-rich phase as a dispersed domain, and a highly oriented fibrous structure was formed on the fracture surface of the blends. During the melt blending process, PET reacted with LCP through transesterification, as indicated by both DSC and SEM measurements.     

Single-molecule single crystals of poly(ethylene oxide)

Single-molecule single crystals were prepared from two fractions of poly(ethylene oxide) (PEO) with narrow molar mass distribution and an equimolar mixture of the two fractions. It was proven that the molar mass distribution of the single-molecule single crystals from the mixed sample corresponds to an addition of those of the pure fractions. Well-shaped crystals were obtained after isothermal crystallization or on annealing. A variety of morphologies typical for multimolecule single crystals of PEO were found and are described on the basis of the various known modes of twinning. The results are in agreement with the known unit cell of PEO.     

Structure and crystallization of molecular complexes between poly(ethylene oxide) and hydroxybenzenes

The phase diagrams of the binary systems poly(ethylene oxide) (PEO)-resorcinol and poly(ethylene oxide)-p-nitrophenol show the presence of molecular complexes with well-defined stoichiometries. The crystal structure of these two molecular complexes has been determined from wide-angle x-ray diffraction patterns of stretched films and spherulites. The morphology of the two complexes crystallized from the melt is investigated by differential scanning calorimetry and small-angle x-ray scattering. The crystallization of the PEO-resorcinol complex from the melt gives integral-folded crystals with either extended chains (EC) or n-folded chains (n-FC). As observed for PEO oligomers, the fraction of EC crystals of the PEO-resorcinol complex increases with the crystallization temperature to give finally only EC crystals but in a larger range of crystallization temperatures than for pure PEO. On the other hand, the PEO-p-nitrophenol complex crystallizes over all the studied crystallization range as stable nonintegral-folded (NIF) crystals. Two proposals related to the crystal structure of these complexes and their mode of growth are invoked to explain these two greatly different morphologies at the lamellar level.     

CRYSTALLIZATION IN PARTIALLY MOLTEN ORIENTED BLENDS OF POLYCONDENSATES AS REVEALED BY X-RAY STUDIES*

Oriented fibers or films of binary polymer blends from polycondensates were investigated by two-dimensional (2D) wide-angle X-ray scattering (WAXS) during the finishing process of microfibrillar reinforced composite (MFC) preparation, that is, heating to a temperature between the melting temperatures of the two components, isothermal annealing, and subsequent cooling. It is shown that the crystallization behavior in such MFC from polycondensates depends not only on the blend composition, but also on thermal treatment conditions. Poly(ethylene terephthalate)/polyamide 12 (PET/PA12), poly(butylene terephthalate)/poly(ether ester) (PBT/PEE), and PET/PA6 (polyamide 6) composites were prepared in various compositions from the components. Materials were investigated using rotating anode and synchrotron X-ray source facilities. The effect of the annealing time on the expected isotropization of the lower melting component was studied in the PET/PA6 blend. It was found that PA6 isotropization took place after 2 h; shorter (up to 30 min) and longer (up to 8 h) melt annealing results in oriented crystallization due to different reasons. In PET/PA12 composites, the effect of PA12 transcrystallization with reorientation was confirmed for various blend compositions. The relative strength of the effect decreases with progressing bulk crystallization. Earlier presumed coexistence of isotropic and highly oriented crystallites of the same kind with drawn PBT/PEE blend was confirmed by WAXS from a synchrotron source.

     

对苯二甲酸乙二醇酯-ε-己内酯共聚酯中硬链段结晶特性研究

利用广角X射线衍射和傅里叶变换红外光谱研究了对苯二甲酸乙二醇酯-ε-己内酯(TCL)共聚酯中对苯二甲酸乙二醇酯(ET)硬链段的晶区结构和结晶特性。结果表明,在ET硬段含量较高的TCL共聚酯中,ET链段的结晶特性与纯的聚对苯二甲酸乙二醇酯(PET)基本相同。ET硬段晶区的尺寸和结晶度均随链段序列长度的减小而减小。     

Confined crystallization in phase-separated poly(ethylene terephthalate)/poly(ethylene naphthalene 2,6-dicarboxilate) blends

The isothermal cold crystallization of poly(ethylene terephthalate)(PET) in cryogenic mechanical alloyed blends of PET and Poly(ethylene naphthalene 2,6-dicarboxilate)(PEN) 1:1 by weight has been investigated by simultaneous small and wide angle X-ray scattering (SAXS and WAXS) and dielectric spectroscopy (DS). For transesterification levels higher than 23% the blends tend to transform into a one-phase system and the crystallization of PET is strongly inhibited due to the significant reduction of the PET segment length. For lower levels of transesterification the blends are phase separated and the overall crystallization behaviour can be explained considering the confined nature of the PET domains in these blends. The formation of a rigid amorphous phase in the intra-lamellar stack amorphous regions is reduced in the blends due to a lower probability of stack formation in the confined PET-rich domains. The more effective filling of the space by the lamellar crystals in the blends provokes a stronger restriction to the amorphous phase mobility of PET in the blends than in pure PET.     

About impedance spectra and dynamics of charge carriers in neat poly(ethylene oxide) structures

Impedance spectra of linear and cross-linked poly(ethylene oxide) (PEO) are analyzed in a wide range of temperature. Dielectric responses differ at low and high temperature due to tendency of PEO to crystallization below melting temperature. Extent of crystallization depends on cross-linking density. The network in PEO with high cross-linking density is rigid and morphology transition shifts to very low temperature. Debye-like relaxation appears at low temperature similar as in ionic liquids. Onset of polarization relaxation shifts to higher temperature with increasing mesh size that is coupling of electric and structural relaxation appears. This is also nicely reflected by scaled conductivity. It demonstrates that the structure in cross-linked systems is a superposition of chemical and physical networks. They relax separately at low temperature and frequency under condition of sufficient rigidity.     

Latent-Crimp Behavior of PET/PTT Elastomultiester and a Concise Interpretation

The latent-crimp behavior of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) elastomultiester was investigated by comparing the crimp state before and after annealing at different temperatures. Both the work of crimp extension and the work of crimp retraction in a multicycle tensile-recovery action are introduced to characterize the crimp transition. The variations of the work with the number of cycles and the ultimate work ratio were analyzed by a nonlinear fitting method to find some relation with the annealing temperature, and the morphological changes of the crimp were observed. The governing mechanism for crimp development was also studied by contrasting the shrinkage behaviors of PET/PTT, with PET and PTT single-component filaments. Two criteria were applied to determine the optimum temperature for PET/PTT to fully develop its crimp, and the results were only slightly different. Finally, isothermal shrinkage kinetic measurements were also performed to find a proper annealing duration for PET/PTT at an optimum temperature.     

Isothermal Crystallization and Subsequent Melting Behavior of Poly(ethylene terephthalate)/Silica Nanocomposites

The crystallization process of poly(ethylene terephthalate)/silica nanocomposites were investigated by differential scanning calorimetry (DSC) and then analyzed using the Avrami method. The results indicated that the crystallization of pure poly(ethylene terephthalate) (PET) was fitted for thermal nucleation and three‐dimensional spherical growth throughout the whole process, whereas the crystallization of PET/silica nanocomposites exhibits two stages. The first stage corresponds to athermal nucleation and three‐dimensional spherical growth, and the second stage corresponds to recrystallization caused by the earlier spherulites impingement. The crystallization rate increases remarkably and the activation energies decrease considerably when silica nanoparticles are added. The subsequent melting behavior of the crystallized samples shows that the melting point (T _m) of nanocomposites is higher than that of pure PET, which might be caused by two factors: (1) The higher melting point might be due to some hindrance to the PET chains caused by the nanoparticles at the beginning of the melting process; (2) it might also be the case that more perfect crystals can be formed due to the higher crystallization temperatures and lower activation energies of PET/silica nanocomposites.     

Interfacial morphology and friction properties of thin PEO and PEO/PAA blend films

The scanning force microscope (SFM) was used to investigate morphology of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blend. The effect of solvent and dewetting in surface structure of PEO film was reported. The results manifested that the crystallization of PEO could be suppressed completely in ultrathin region via using chloroform as a solvent, and the branched-like crystallization was recovered after dewetting. Also, the effect of thickness, the ratio of PEO/PAA and dewetting in surface morphology of PEO-PAA blend films were investigated. These results showed that the crystallization was highly dependent on the ratio of PEO/PAA and the thickness of blend film. Furthermore, we assembled the PEO/PAA layer-by-layer film by spin-casting method for the first time, which exhibited highly efficiency. As a complementary tool, we also used lateral force microscopy (LFM) to explore surface information of these films. The result was indicative of interfacial constraints in ultrathin region, and also was supported by the results showing the spin-casting PEO/PAA blends rather than heterogeneous mixture.