Comparative study of the kinetics of non-isothermal melt solidification of random copolymers of butene-1 with either ethylene or propylene

The kinetics of non-isothermal melt solidification of random butene-1/propylene copolymers has been compared with that of random butene-1/ethylene copolymers. Analysis of the distance between neighbored chain segments in the crystal phase revealed inclusion of propylene chain defects into crystals, while ethylene co-units are excluded from crystallization. As a consequence of different acceptance of propylene and ethylene chain defects to participate in crystallization, the kinetics of the transition of the melt into ordered phase is significantly slower in random butene-1/ethylene copolymers. For samples of similar co-unit concentration, the decrease of the crystallization temperature and of the critical cooling rate to suppress ordering/crystallization is higher in random butene-1/ethylene copolymers than in butene-1/propylene copolymers. Due to the required rejection of ethylene co-units at the crystal growth front, ultimately, the maximum crystallinity is lower in butene-1/ethylene copolymers than in butene-1/propylene copolymers of similar amount of co-units.     

Effect of Linear and Ring-like Co-units on the Temperature Dependence of Nucleation and Growth in II-I Phase Transition of Butene-1 Copolymers

The phase transition from tetragonal form II to hexagonal form I was studied for the butene-1/ethylene and butene-1/1,5-hexadiene random copolymers, which have comparable molecular weight but distinct linear ethylene and ringlike methylene-1,3-cyclopentane (MCP) structural co-units, respectively. It is known that this solid phase transition follows the nucleation-growth mechanism, so the stepwise annealing protocol was utilized to investigate the influences of co-units on the optimal nucleation and growth temperatures. Compared with optimal nucleation and growth temperatures of ?10 and 35 °C, respectively, in polybutene-1 homopolymer, two butene-1/ethylene copolymers with 1.5 mol% and 4.3 mol% co-units have the slightly lower optimal nucleation temperature of ?15 °C but much higher optimal growth temperature of 50 °C. Clearly, the effect of ethylene co-unit is more significant on varying optimal temperature for growth than for nucleation. Furthermore, when the incorporated co-unit is ringlike MCP, the optimal nucleation temperature is ?15 °C for 2.15 mol% co-units, the same with above BE copolymers, but ?13 °C for a very low concentration of 0.65 mol%. Interestingly, the optimal growth temperature of butene-1/1,5-hexadiene copolymers with 0.65 mol%?2.15 mol% MCP counits increases to 55 °C, which is also independent on co-unit concentration. These obtained values of optimal temperatures provide crucial parameters for rapid II-I phase transition.     

Effect of co-unit type in random propylene copolymers on the kinetics of mesophase formation and crystallization

Fast scanning chip calorimetry has been employed to study the effect of the type and concentration of co-units on the rate of mesophase formation and crystallization in random isotactic copolymers of propylene and 1-alkenes, including ethylene, 1-butene, 1-hexene, and 1-octene. The dependence of the rate of ordering on temperature of the propylene homopolymer shows two distinct maxima around 300 and 340–350 K which are related to mesophase formation and crystallization, respectively. Addition of 1-alkene co-units leads to a decrease of the maximum rate of both crystallization and mesophase formation. At comparable temperature and molar percentage of co-units in the propylene chain, ethylene, and 1-butene co-units cause less reduction of the maximum rate of ordering than 1-hexene or 1-octene co-units. The experimental observations are discussed in the context of possible incorporation of these chain defects into the ordered structures.     

Crystallization kinetics and morphology of binary phenolic/poly(ϵ-caprolactone) blends

For the first time, quantitative analyses of the crystallization kinetics, surface free energy of chain folding, and morphology in phenolic/poly(ϵ-caprolactone) (PCL) binary blends have been studied. The spherulite growth rate and the overall crystallization rate depend on the crystallization temperature and PCL content in the blend. In addition, the crystallization and melting temperatures of the PCL phase decrease with an increase in the phenolic content. An Avrami analysis shows that the addition of phenolic to PCL results in a decrease in the overall crystallization rate of the PCL phase. The presence of an amorphous phenolic phase results in a reduction in the rate of the spherulite growth of PCL. The surface free energy of folding increases with increasing phenolic content, and the crystal thickness of a phenolic/PCL blend, according to small-angle X-ray scattering (SAXS), is greater than that of pure PCL because of the increase in the surface free energy of chain folding and the decrease in the degree of supercooling. The observed domain size of the crystalline/amorphous phase (5.9 nm) from SAXS is also consistent with that from solid-state NMR (3–20 nm). All these results indicate that the crystallization ability of PCL decreases with increasing phenolic content in the blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 117–128, 2004     

Structure and properties for binary blends of isotactic-polypropylene with ethylene-α-olefin copolymer. 1. Crystallization and morphology

Morphology and isothermal growth rates of spherulites for the binary blends consisting of an isotactic polypropylene (i-PP) and an ethylene-1-hexene rubber (EHR) were examined as a function of the crystallization temperature ranging from 388 K to 418 K. In this study, two types of EHR's were employed: “ethylene rich” EHR and “1-hexene rich” EHR. The blends of i-PP with the EHR of 51 mol % 1-hexene are miscible in the molten state, whereas the blends with the EHR of 33 mol % 1-hexene are immiscible in the molten state. It is found that the isothermal spherulite growth rate of the miscible i-PP/EHR blends decreases with increasing the EHR fraction, whereas the spherulite growth rate of the immiscible i-PP/EHR blends is independent of the blend composition and is the same as that of the i-PP. Optical microscope observation of the miscible blends crystallized isothermally shows that there are no rubber domains either in the intraspherulitic or in the interspherulitic contact regions. On the other hand, the immiscible i-PP/EHR blends show a phase-separated morphology. Furthermore, the number of tangential lamellae of the miscible i-PP/EHR blends is found to be increased by blending of the EHR, leading to the spherulite with negative birefringence. The sign of birefringence of spherulites is unaffected by the regime transition as well as by the fold surface free energy. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 953–961, 1997     

The crystallization characteristics of ethylene block copolymers

Block copolymers of ethylene and butadiene with short ethylene sequences and degrees of polymerization up to 250 have been studied calorimetrically to determine their structure in the melt and also on crystallization. Crystallization rate characteristics and the thermodynamic parameters of the melting of block copolymers were studied. Block copolymers with ethylene sequences with degrees of polymerization below 20–30 were amorphous. Those with ethylene sequences of 35–45 units crystallized with extended chain crystals; above 45 units the polyethylene blocks crystallized with chain folding. There was a corresponding reduction in the melting point of the crystals and in the surface free energy of the crystals. The extent of crystallinity that developed within the copolymers was dependent on crystallization temperature and independent of time. This behavior was unlike that exhibited by polyethylene samples of similar molecular weight and was considered due to the effect of phase separation of the two blocks in the melt and nucleation control of the crystallization of the isolated domains. Analogous behavior was observed with polyethylene for polymer blends with polystyrene.     

Evolution of concentric spherulites in crystalline-crystalline poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-b-poly(ethylene glycol) copolymers

Crystalline-crystalline poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly (ethylene glycol) (PEG) block copolymers (PHEGs) were synthesized by telechelic hydroxylated PHBV2000 and PEG with different number-average molecular weights. The synthesized PHEGs were analyzed using gel permeation chromatography and proton nuclear magnetic resonance. The cooling curves of the differential scanning calorimetry showed that the range of the melt-crystallization temperature of the PEG and PHBV blocks in the PHEGs partially overlapped. The spherulite of each PEG block and each PHBV block in the PHEGs crystallizes individually, but nucleated in the same site to form a concentric spherulite. The observations of the hot-stage polarized microscope (HSPM) showed that the first spherulite growth acted as a template for the later spherulite growth in the PHBV-b-PEG concentric spherulite. The spherulite growth rate of individual spherulite from the PEG block and PHBV block in PHEGs depends on the crystallization environment. The evolution of concentric spherulites in PHEGs at different crystallization conditions was studied in this study.     

Study of crystallization kinetics of trans-1,4-polyisoprene

The concentrations and the growth rates of high- and low-melting type spherulites of trans-1,4-polyisoprene were measured in the temperature range 39–49°C. It was shown that above about 40°C., the crystallization rate of trans-1,4-polyisoprene is determined primarily by the radial growth rate of high-melting form (HMF) spherulites, whereas the predominance of the low-melting form (LMF) crystals below 40°C. can be attributed to the high rate of formation of LMF primary nuclei at lower crystallization temperatures. Temperature-independent rate parameters were calculated from optical and dilatometric measurements and were found to be in good agreement. Both the change in nucleation habit and spherulite growth rate with temperature can be explained on the basis of a lower end surface free energy of LMF crystals of trans-1,4-polyisoprene compared to that of the HMF crystals.     

Spatially inhomogeneous crystallinity in heterogeneous ethylene‐α‐olefin copolymers

The crystallinity development in heterogeneous ethylene‐1‐butene copolymers is compared with that in ethylene copolymers, with more bulky 1‐heptene as a comonomer. The thermal transitions of the 1‐heptene based copolymers persistently occur at higher temperatures than of the corresponding 1‐butene copolymers. The earlier crystallization onset is reflected in thicker primary crystals, which in turn are associated with the presence of longer ethylene sequences because of the inaccessibility of 1‐heptene to sterically shielded catalytic sites. In addition, the 1‐heptene based copolymers are characterized by a higher degree of primary crystallinity, whereas the 1‐butene copolymers exhibit more prominent secondary crystallization. The 1‐butene based copolymers thus have a less heterogeneous chemical composition distribution. At high comonomer contents, the highly heterogeneous nature of the 1‐heptene copolymers is emphasized by a more pronounced presence of low crystalline spherulite inclusions accomplished by the liquid–liquid phase separation of dissimilar polymeric chains before crystallization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3000–3018, 2005     

Structure formation of random isotactic copolymers of propylene and 1-hexene or 1-octene at rapid cooling

The effect of variation the cooling rate in a wide range between 10^?2 and 10³ K s^?1 on solidification the relaxed melt of random isotactic copolymers of propylene with low amount of 1-hexene or 1-octene has been studied. Emphasis has been placed on the structure formation at rapid cooling and an evaluation of the conditions required to permit crystallization, mesophase formation, or suppression of any ordering. The presence of low amount of either 1-hexene or 1-octene co-units in the propylene chain decreases drastically the critical cooling rate required for suppression of crystallization from about 150–200 K s^?1 in the homopolymer to about only 10 K s^?1 in the copolymers; increasing the cooling rate beyond these limits allowed mesophase formation or even generation of fully amorphous samples. The study of the kinetics of formation of specific structures is completed by a complementary analysis of the X-ray structure, morphology and superstructure of the ordered phase. The hindrance of non-isothermal crystallization and mesophase formation of random copolymers of propylene with 1-hexene or 1-octene is compared with that in propylene–1-butene copolymers; addition of only 2–3 mol% 1-hexene or 1-octene into the propylene chain leads to even larger hindrance of the ordering process than the addition of more than 10 mol% 1-butene.     

Crystallization of tethered polyethylene in confined geometries

Ordered poly(ethylene)‐poly(vinylcyclohexane) (PE‐PVCH) block copolymers are employed to study the crystallization of tethered PE in confined geometries. The high T_g of the PVCH component of these materials forces PE chains to crystallize in well‐defined geometries dictated by the mesophase structure of the block copolymer. Effects of chain tethering on crystallization are examined through comparison of singly‐tethered PE chains in PE‐PVCH (EV) diblocks and doubly‐tethered PE in PVCH‐PE‐PVCH (VEV) triblocks. Crystallinity is independent of the block copolymer mesophase structure in both the EV and VEV systems, although crystallinity in VEV depends on the molecular weight of the PE block of the copolymer. Melting temperature data indicate that spatial confinement reduces crystallite size in EV and VEV, and that the double tethering of PE chains in VEV reduces crystallite size further through topological constraints. Crystal nucleation and growth depend strongly on the type of microstructure in both EV and VEV block copolymers. Differences in the overall rate of crystallization are correlated with the dimensional continuity of the PE microdomains. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37:2053–2068, 1999     

Heterogeneous nucleation of crystallization of high polymers from the melt. III. Nucleation kinetics and interfacial energies

In the melt crystallization of isotactic polypropylene, poly(ethylene oxide) and poly(butene-1) in contact with substrates, the existence of a fixed number of nucleating sites on the substrate surfaces has been established. When these sites become active successively (the transient in the number of nuclei is long) during crystallization, pseudohomogeneous nucleation on the substrate occurs. Nucleation rates for poly(butene-1) and poly(ethylene oxide) on substrates and in bulk have been measured. These data can be used for comparing the nucleating ability of substrates. Estimates of the variation of bulk nucleation rates from one volume element to another as well as for repeated crystallization within a given volume element have been included. Finally, the temperature coefficients of heterogeneous nucleation rates have been combined with the temperature coefficient of spherulitic growth rate of poly(butene-1), to yield values of the interfacial energy parameters appearing in the theory of heterogeneous nucleation. The quantitative characterization of the nucleating ability of substrates by this method is an improvement over the mere use of nucleation densities or nucleation rates.     

Self‐decelerated crystallization in blends of polyhydroxyether of bisphenol A and poly(ethylene oxide) upon isothermal crystallization

The growth of spherulites of poly(ethylene oxide) in blends with poly(hydroxyether of bisphenol A) was investigated. In a very narrow range of crystallization temperatures, the spherulite growth deviates from the usual constant growth rate regime in a systematic manner in which the growth rate decreases with time. This is explained by local and overall changes in the composition with the proceeding crystallization that are due to the competition between the crystallization and diffusional chain displacement rates, respectively. These kinetic phenomena and processes can quantitatively be described by a suitable analysis of the experimental findings. Deceleration is predominantly caused by a slowing of the chain motion by the glass‐transition temperature being approached (i.e., vitrification) and, to a lesser extent, by dilution. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1250–1257, 2000     

Differential thermal analysis of polyethylene under high pressure

The design of a differential thermal analysis apparatus for use at elevated pressure is described. Experiments on melting and crystallization of folded-chain crystals of polyethylene and poly(ethylene–butene-1) copolymer, and melting of extended-chain polyethylene crystals have been conducted at pressures up to 4200 bars. The precision in transition temperature measurement was ±1°C. The Clausius-Clapeyron equation predicts the melting point increase with pressure at atmospheric pressure to be 32.0°C/kb. The melting point depression due to copolymerization remained constant over the complete pressure range analyzed on the poly(ethylene–butene-1) used in this study. Crystallization of polyethylene is retarded at elevated pressures, and a 50% larger degree of supercooling is necessary at 5000 bars to give a crystallization rate equal to that observed at atmospheric pressure. The difference in melting point between folded-chain and extended-chain polyethylene increases from 8.4°C at 1 bar to 25.6°C at 3000 bars.     

尼龙6/蒙脱土纳米复合材料的等温结晶动力学研究

用ＤＳＣ法研究了熔体插层制备的尼龙６／蒙脱土纳米复合材料的等温结晶行为．结果表明,加入少量的蒙脱土可明显提高尼龙６的结晶速率,降低球晶径向生长的单位面积表面自由能．从Ａｖｒａｍｉ方程和Ｈｏｆｍａｎ理论出发,得出蒙脱土纳米粒子的存在可明显改变尼龙６的结晶行为     

聚乳酸-聚乙二醇嵌段共聚物晶行为研究

用1H NMR, SEC, XRD和DSC对聚乳酸(PLLA)-聚乙二醇(PEG)二嵌段共聚物进行了表征. 由于共聚物中两种组分比例的不同, 表现出某组分单独结晶或两种组分共同结晶. 用DSC和POM方法, 对两组分含量相当的共聚物进行了熔体结晶行为研究, 并采用Avrami方程进行了结晶动力学计算. 用Lauritzen-Hoffmann理论对PLLA-PEG结晶机理进行了分析. 在70~94 ℃范围内, 得到成核参数Kg(POM)=5.23×105 K2. 共聚物的Kg和链折叠自由能σe都比均聚物的文献报道值高, 表明PEG链段的存在影响了PLLA的结晶, 使得其成核较均聚物困难.     

Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer

The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l-lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d-lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth (G) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d-lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d-lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications.     

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.     

The effect of the addition of polypropylene grafted SiO2 nanoparticle on the crystallization behavior of isotactic polypropylene

The crystallization behavior of isotactic polypropylene (iPP)/silica particle (SiO₂, 26 nm) nanocomposite has been investigated. In addition to the non surface-modified SiO₂, iPP grafted SiO₂ was synthesized and adopted to this study with an aim to understand the role of grafted polymer chain on the crystallization process. The crystallization rate of non surface-modified iPP/SiO₂ composite stays constant up to 1 vol%. It suggests the very weak nucleation ability of nano-sized silica particle. While large acceleration effect was observed for iPP-grafted SiO₂/iPP composite. The spherulite density increased with increasing SiO₂ contents, and more interestingly, the spherulite growth rate also increased. This finding leads to the conclusion that the grafted iPP chain has a plasticizing effect that reduces the chain entanglements at the interface. Further increase in SiO₂ contents, the crystallization rate, the spherulite density, and the spherulite growth rate showed the steep decreases at higher SiO₂ content range regardless of the surface modifications of SiO₂. It was attributed to the confinement of matrix chain since the inter-particle distance of adjacent SiO₂ approaches to the end-to-end distance of matrix chain, which a large molecular motion is restricted. Moreover, the average size of SiO₂ aggregation in iPP matrix was successfully evaluated by analyzing the contents dependence of the growth rate, assuming that the inter-particle distance with zero growth rate coincided with end-to-end distance of matrix iPP chain.     

Spherulite growth rates of in situ prepared poly(propylene terephthalate)/SiO2 nanocomposites

The spherulite growth rates of in situ prepared PPT/SiO₂ nanocomposites containing 2–5 wt% nano-silica were studied. Measurements of the spherulite growth rates were carried out by applying non-isothermal experiments using polarized light microscopy (PLM). Comparison with results from isothermal PLM tests showed good agreement. Isothermal crystallizations after self-nucleation were also performed using differential scanning calorimetry (DSC) and the inverse crystallization half-times were estimated. The Lauritzen–Hoffman analysis was applied by using data from both isothermal and non-isothermal PLM experiments and the DSC results. Regimes II–III transition were observed at critical breakpoint close to 195 °C. The regimes I–II transition was not so clear, because of the semi-rigid macromolecular chains of the polymers. Results using DSC data were in satisfactory agreement to those using PLM spherulite growth data.