Effect of nucleating agents upon the kinetics of poly(ethylene terephthalate) crystallization

Experiments have been conducted to examine the effect of the following agents: TiO₂, CaO, MgO, BaSO₄, SiO₂, and Al₂O₃ as modifiers on the poly(ethylene terephthalate) crystallization kinetics. Modifier concentration in the polymer varied from 0.5% to 3%. Crystallization rate measurements at a temperature of 237°C were performed by dilatometric method and measurements of spherulitic growth rate, by microscopic method. It has been stated that the addition of a modifier affects the crystallization rate, dimension, and homogeneity of spherulitic sizes. The spherulitic growth rate, with the exception of that modified by CaO, does not depend on the kind and the concentration of a modifier. Heterogeneous nucleating agents exert an effect, then, mainly on the heterogeneous nucleation process. In the presence of the agents, the nucleation in the poly(ethylene terephthalate) is of athermal character. The kind of a modifier applied exerts also an effect on the final crystallization degree.     

Effect of nucleating agents on the temperature-dependent melt crystallization kinetics of poly(1-butene)

The effect of additives (mostly nucleating agents) on the crystallization rate of isotactic poly(1-butene) has been investigated by differential scanning calorimetry. Isothermal crystallization half-times and crystallization temperatures have been measured for polymer-additive blends. The crystallization temperature and the cooling rate at which the ultimate fraction transformed becomes less than 1 is calculated as a function of nucleation density, and this is used to characterize the effect of the additives on crystallization rate. The relationship between the isothermal crystallization half-time and the crystallization temperature is also calculated theoretically and is compared with experimental results.     

Effective nucleating chemical agents for the crystallization of poly(trimethylene terephthalate)

This study focused on the crystallization promotion of poly(trimethylene terephthalate) (PTT), with an aim at engineering thermoplastics applications. The effects of organic sodium (Na) salts, including Na stearate, Na benzoate, disodium‐p‐phenolsulfonate (2Na‐p‐PS), disodium‐p‐hydroxybenzoate (2Na‐p‐HB), and the sodium ionomer of poly(ethylene‐co‐methacrylic acid) (Na‐EMAA), were investigated as nucleating chemical agents with differential scanning calorimetry and capillary viscometry. For comparison, the effect of fine talc powder was also examined. The chemical agents were generally more effective than fine talc powder. Na stearate and Na benzoate caused large‐scale decomposition of PTT. 2Na‐p‐PS was quite thermally stable and caused little decomposition. 2Na‐p‐HB was the most efficacious of the nucleating chemical agents and caused mild decomposition. Na‐EMAA was the most thermally stable and induced an increase in melt viscosity. A remarkable improvement in the crystallization rate of PTT was successfully attained at a minimum polymer decomposition cost by the introduction of a suitable amount of 2Na‐p‐PS, 2Na‐p‐HB, or Na‐EMAA or by the concurrent proper incorporation of both of the latter two agents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 590–601, 2004     

Crystallization kinetics of pure and fiber-reinforced poly(phenylene sulfide)

Isothermal DSC investigations on pure as well as glass, carbon, and aramid fibre-reinforced poly(phenylene sulfide) (PPS) were carried out in order to obtain informations on the crystallization kinetics, that is, the Avrami exponent, constant, half-time of crystallization, and (final) degree of crystallinity. PPS is a typical representative of semicrystalline polymers with a maximum degree of crystallinity of about 60%. The Avrami exponent reaches values from n = 2.1–2.7 depending on fibre type but independent of crystallization temperature. The system aramid fibre/PPS has a much shorter half-time of crystallization than the other three systems that could be attributed to the high nucleation effect of the aramid fibre surface to PPS. As a consequence of the high nuclei density a transcrystalline zone is built up around the aramid fibre. The relatively low value of the Avrami constant was discussed and a computer simulation attempt was made to understand the measured value quantitatively. © 1994 John Wiley & Sons, Inc.     

Electronic structure of poly(p-phenylene sulfide)

The electronic structure of poly(p-phenylene sulfide) (PPS) was studied through steady state photocurrent spectra and temperature dependence of dark conductivity for undoped film, by changes in the in situ optical absorption and ESR spectra under photoirradiation, and optical absorption spectra for doped film. The charge carriers in the undoped state are electronic since the photoconductivity is large and the kink point in the temperature dependence of dark conductivity is higher than the glass transition temperature. A sharp peak near the absorption edge in the photocurrent spectrum of undoped PPS is caused by the diffusion of photocarriers in a sheet with high surface recombination under conditions of low applied field. The in situ optical absorption and ESR spectra of SO₃-doped PPS were similar to those of di-p-tolyl sulfide (a monomer unit of PPS) and the formation of sulfur-centered radical cations was suggested rather than bipolaron states. The stable conduction of SO₃-doped PPS after exposure to atmosphere was analyzed by the classical Lorentz model and the existence of nearly free carriers within subchains was suggested. Their conductivity and mobility were estimated to be 2 S/cm and 3.6 cm²/Vs, respectively. Inter-chain conduction appears to be very low.     

聚苯硫醚热氧化处理研究

研究了聚苯硫醚在空气环境下经过热处理的合成化学改性.采用高温凝胶渗透色谱、光电子能谱、热失重、红外光谱和高压毛细管流变技术对聚苯硫醚进行表征.结果表明:低相对分子质量的聚苯硫醚和高相对分子质量的聚苯硫醚经过热处理,相对分子质量都会大幅提高;聚苯硫醚经过热处理过程会同时发生氧化反应、氧化交联反应、热交联反应和链增长反应.     

Isothermal cold crystallization kinetics of polylactide/nucleating agents

The isothermal cold crystallization kinetics of polylactide (PLA)/nucleating agents (CaCO₃, TiO₂, and BaSO₄, content from 0.5–2.0 wt %) was investigated by differential scanning calorimetry in the temperature range of 120–124°C. With blending nucleating agents, the crystallinity of PLA had a maximum crystallinity of 14.9%. Crystallization rate decreased with increasing crystallization temperature in the researched content range. The crystallization rate followed the Avrami equation with the exponent n around 4.5. From Lauritzen–Hoffman equation, the nucleation parameter K_g was estimated. And from the value of K_g, regime II crystallization behavior can be concluded. Then the lateral and fold surface free energy were calculated from K_g. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 310–317, 2007     

Surface modification and bonding of poly(p-phenylene sulfide)

It is demonstrated that both chemical oxidation, e.g. by using acetic acid/hydrogen peroxide or chromosulfuric acid, and plasma treatment of poly(p-phenylene sulfide) (PPS) surfaces introduce polar groups. The changes of the surface chemistry are detected by FTIR spectroscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The increased polarity is partially responsible for better adhesion as verified by lap shear measurements using acrylic adhesive. Another important contribution to the improved adhesion originates from increased surface roughness after surface modification as measured by atomic force microscopy. This effect is very pronounced for PPS surfaces treated with chromosulfuric acid.     

Crystallization morphologies and non-isothermal crystallization kinetics of isotactic polypropylene modified by α/β compounded nucleating agents

采用偏光显微镜(POM)及示差扫描量热(DSC)法考察了3种α/β复合成核剂NA40/NABW、NA40/HHPA-Ba、NA40/PA-03对成核等规聚丙烯(iPP)的结晶形态及非等温结晶动力学的影响。对成核iPP结晶形态的研究结果表明：α/β复合成核剂的加入能够减小iPP的球晶尺寸。影响α/β复合成核剂成核iPP结晶形态的主要因素是ΔT_Cp（ΔT_Cp为成核iPP结晶峰值温度与iPP结晶峰值温度的差值）,即复合体系中ΔT_Cp较大的成核剂在iPP结晶过程中起主导作用,最终的结晶形态与单独添加这一成核剂时iPP的结晶形态相类似;当两种成核剂的ΔT_Cp接近相同时,两者竞争成核,成核iPP的结晶形态表现为两种成核剂共同作用的结果。因此,通过改变α/β复合成核剂的复合比例即改变两种成核剂的添加浓度,进而改变其ΔT_Cp,可以得到结晶形态完全不同的iPP。采用Caze法对非等温动力学进行了研究,结果表明：添加α/β复合成核剂能够提高iPP的结晶温度,缩短半结晶时间。复合成核剂成核iPP的结晶行为也同样受成核剂ΔT_Cp的影响,复合成核iPP的Avrami指数接近于复合体系中ΔT_Cp较大的成核剂单独添加时iPP的Avrami指数。     

Effect of melt history on the crystallization kinetics of poly(phenylene sulfide)

Differential scanning calorimetry (DSC) was used to study the effects of melt history on the isothermal crystallization kinetics of poly(phenylene sulfide) (PPS). Crystallization of the polymer was shown to be permanently altered by both the time and the temperature spent in the melt. Suggested explanations are nonequilibrium melting, chain scission, chain extension, and crosslinking. Molecular weight was also shown to affect the rates of these processes, PPS of lower molecular weight being more susceptible to the observed changes.     

Kinetic analysis of the crystallization of poly(p-phenylene sulphide)

Growth rates of spherulites were measured in poly(p-phenylene sulphide) crystallized from the melt and the quenched glass over the temperature range 100°C–280°C, possibly the most extensive overall range yet reported for any polymer and, as such, most propitious for study of régime III crystallization. For a medium M.wt. polymer, a régime II → III transition was obtained at 208°C using values of transport parameters common to many polymers ($\text{U1 = 1400}\text{cal mol}{}^{\mathrm{?1}}$, T_∞ ? T_g = 30°C) together with experimentally determined values of T⁰_m(315°C) and T_g(92°C). Under these conditions, the régime III/II slope ratio was found to be 2.07 (i.e. only 3.5% higher than predicted by régime theory), and reasonable estimates of surface free energies and of the work of chain folding were obtained. Other choices of the transport terms, including WLF and zero values, did not allow successful kinetic analyses. Although a régime I → II transition is predicted to occur at the high-temperature end of our growth-rate data, we found no experimental evidence for it. For a low M.wt. polymer, our analysis showed that régime III kinetics is obeyed at low temperatures, while at higher ones there is a continuous departure from that behaviour without, however, full attainment of régime II kinetics.     

Heterogeneous nucleating agents for polypropylene crystallization

A model nucleating agent for polypropylene crystallization is described. A series of compounds consisting mainly of organocarboxylic acid salts is evaluated as heterogeneous nucleating agent for polypropylene crystallization by measuring their effect upon the polymer supercooling. Sodium benzoate and basic aluminium dibenzoate were among the best nucleating agents found. The nucleating abilities of the various compounds are discussed in terms of their structural features.     

Poly(p-phenylene sulfide)/liquid crystalline polymer blends. II. Crystallization kinetics

The crystallization kinetics of blends made of poly(p-phenylene sulfide) (PPS) with a liquid crystalline polymer (LCP) was studied. The blends were found to be immiscible by dynamic mechanical thermal analysis (DMTA). Results of non-isothermal and isothermal crystallization experiments made by differential scanning calorimetry (DSC) showed that both components had their crystallization temperatures increased; also the LCP melting temperature was found to increase in the blends. It was concluded that the addition of LCP to the PPS increased the PPS overall crystallization rate due to heterogeneous nucleation. The fold interfacial free energy, σ_e of the PPS in the blends was observed not to vary with composition. © 1996 John Wiley & Sons, Inc.     

Thermodynamic properties and crystallization behavior of poly(p-phenylene succinate)

The equilibrium thermodynamic properties and crystallization behavior of poly(p-phenylene succinate) (PPSc) were examined using differential scanning calorimetry (DSC) and a wide-angle X-ray diffractometer. When PPSc quenched into liquid nitrogen, the PPSc still showed 60 J/g of the heat of fusion, indicating that PPSc crystallizes too fast to be quenched to a glassy state. The equilibrium heat of fusion (ΔH°) of PPSc and its equilibrium entropy of fusion (ΔS°) were estimated to be 28 and 48 J/mol K, respectively. The effect of the molecular weight and undercooling on PPSc crystallization was analyzed by the Avrami expression. The crystallization rate of PPSc was highest at about 276°C, regardless of molecular weight when the sample was isothermally crystallized. This temperature was higher than that of poly(ethylene terephthalate) (PET) by 100°C. The crystallization rate was highest when the number average molecular weight of PPSc was about 20,000 g/mol. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 801–806, 1999     

Nonisothermal crystallization kinetics of poly(lactide)—effect of plasticizers and nucleating agent

Poly(lactide), a bio‐based aliphatic polyester, is a subject to large research effort. One point of optimization is the acceleration of its crystallization kinetics to promote crystallinity under nonisothermal polymer processing conditions by means of compounding with nucleating agents and plasticizers. The nonisothermal crystallization kinetics of neat and formulated poly(L,D ‐lactide) (PDLLA) from the melt with talc and polyethylene glycol (PEG) or acetyl tributyl citrate (ATBC) were studied with the help of the Avrami–Jeziorny and Liu–Mo analysis. Talc showed to be a moderately efficient nucleating agent, as it causes only small increase of crystallization kinetics and shows no effect on the crystallization activation energy. A synergistic effect with plasticizers was observed, expanding the crystallization window significantly. PEG was found to be a more efficient plasticizer than ATBC but causes large decrease in the molecular weight average of PDLLA upon thermal treatment. The talc/ATBC system is efficient starting with an ATBC concentration of 9 wt%. The acceleration observed was a crystallization half‐time decrease of 30% compared to neat PLA and reaching maximum crystallization enthalpies even at cooling rate of 25°C min^?1. The ATBC/talc system can be recommended as an efficient system for acceleration of nonisothermal crystallization kinetics of PDLLA. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

加入不同种类成核剂抗冲击共聚PP的非等温结晶动力学

采用差示扫描量热仪研究了加入羧酸盐类成核剂和有机磷酸盐类成核剂的抗冲击共聚聚丙烯2500H的熔融、结晶和非等温结晶行为。结果表明:加入质量分数为0.02%的成核剂后,2500H的结晶度和所有结晶特征温度均提高,其中,结晶度提高0.3%~3.0%,结晶温度提高4.4~11.0℃,结晶起始温度提高4.4~12.2℃,结晶终止温度提高6.3~11.6℃。与加入有机磷酸盐类成核剂的2500H相比,加入羧酸盐类成核剂的2500H具有更低的结晶过冷度,成核能力相对较高;但加入有机磷酸盐类成核剂的2500H表现出更快的结晶速率,而加入羧酸盐类成核剂的2500H虽然在高温条件下能促使2500H较快形成晶核,但并不利于结晶速率的提高。     

Isothermal crystallization kinetics of poly(phenylene sulfide)/TLCP composites

The isothermal crystallization kinetics, the morphology, and the melting behavior of melt‐processed composites of poly(phenylene sulfide) (PPS) with a thermotropic liquid crystalline copolyester, Vectra A950, (TLCP) were studied by differential scanning calorimetry (DSC) and optical microscopy. The crystallization behavior of PPS in PPS/TLCP composites is observed to be highly sensitive to T_c and immiscible TLCP content in the composites. The spherulite growth rate, the overall crystallization rate, and the activation energy of PPS in PPS/TLCP composites are markedly depressed by the presence of TLCP. The analysis of the Avrami kinetic parameters (n and k) indicates that blending of TLCP with PPS causes heterogeneous growth process and nucleation mechanisms. At low T_cs, the PPS crystallization rate is faster than that neat PPS with ≤30 wt% TLCP loading whereas at high T_cs it remains almost unchanged. The analysis of the melting behavior of these composites indicates that the stability of PPS crystals and their reorganization is influenced both by the T_cs and the composite compositions. The sizes and the number of spherulites change a great extent with composite composition with a drop of spherulite rapid growth rate, at constant T_c, with increasing content of TLCP in composites. The analysis based on the Lauritzen‐Hoffmann secondary nucleation theory, using present DSC data, indicates that present data predominantly follow a linear growth trend over a present range of T_cs and PPS crystallization in composites still occurs according to regime II kinetics, whereby multiple surface nuclei form on the substrate with multiple nucleation acts commencing before initially formed growth layer is completed. The fold surface free energy of PPS chains in composites is found higher than that of neat PPS, leading to an average higher work of chain folding and is ascribed to a general development of the PPS chain mobility in the composite melt. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers