Evolution of Morphology and Structure During Crystallization and Melting in Syndiotactic Polypropylene

Polypropylene( PP) has developed into one of the most useful plastic materials.Ithas many attractive properties,among them,a relatively low price.It also possesses awide range of possibilities for chemical modification[1 ,2 ] .The structure and morphologyof PP have a directimpacton the final properties. Therefore,there is growing interestinunderstanding the structure and morphology of stereoregular PP[1～ 6] .　For isotactic PP(i PP) ,extensive structural and morphological studies have be…     

Thermal analysis of the multiple melting behavior of poly(butylene succinate‐co‐adipate)

The melting behavior of poly(butylene succinate‐co‐adipate) (PBSA) isothermally crystallized from the melt was investigated by differential scanning calorimetry. Triple, double, or single melting endotherms were observed in subsequent heating scan for the samples isothermally crystallized at different temperatures. These endothermic peaks were labeled as I, II, and III for low‐, middle‐, and high‐temperature melting endotherms, respectively. The independence of endotherm III to the crystallization temperature, the existence of an exothermic crystallization peak just below the endotherm III, and the heating rate dependence of endotherm III indicated that endotherm III was due to the remelting of recrystallized lamellar during a heating scan. The influence of crystallization time on the melting behavior of PBSA showed that endotherms II and III developed prior to endotherm I; endotherm III developed rather simultaneously with endotherm II. Further investigation showed that the peak temperature of endotherm I increased linearly with the logarithm of the crystallization time. It suggested that endotherm II was attributed to the melting of the primary lamellae, while endotherm I was due to the melting of secondary lamellae. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3077–3082, 2005     

The multiple melting endotherms from poly(butylene terephthalate)

The melting behavior of poly(butylene terephthalate) (PBT) has been investigated, and a simulation has been performed to determine whether the multiple melting endotherms observed during the thermal analysis of PBT can be explained by the simultaneous melting and recrystallization of an initial distribution of crystal melting temperatures that contains only one maximum and two inflection points. Specimens that were cooled at constant rates from the melt showed between one and three melting endotherms upon heating in a differential scanning calorimeter (DSC). The position and breadth of the crystallization exotherms upon cooling from the melt and small-angle x-ray scattering showed that as the cooling rate is increased, the distribution of melting temperatures broadens and shifts to lower temperatures. By combining temperature-dependent recrystallization with an initial distribution of melting temperatures, simulated DSC curves were produced that agreed well with experimental DSC curves. In instances of triple peaked curves, the high temperature peak was due to crystals formed during the scanning process, and the middle and low temperature peaks were due to crystals originally present in the material. Satisfactory agreement between the experimental and simulated curves was found without considering additional crystallization from the amorphous regions during the scanning process.     

含间位取代苯基聚醚酮酮的结晶与晶体结构研究

通过差示扫描法（ＤＳＣ）及广角Ｘ 射线衍射（ＷＡＸＤ）技术研究了含间位取代苯基聚醚酮酮（ＰＥＫｍＫ）的结晶行为与晶体结构．Ｘ 射线结果表明，从熔融态及玻璃态结晶时，ＰＥＫｍＫ只有一种晶型，其晶胞参数为：ａ＝０７６７２ｎｍ，ｂ＝０６１４９ｎｍ，ｃ＝１５９９ｎｍ．ＤＳＣ结果表明，ＰＥＫｍＫ热分析曲线都出现了熔融双峰，低熔融峰（ＤＯＷｎ）热焓占总热焓４～７％，它源于初始结晶形成的同一晶型不同厚度片晶．低熔融峰在２５０℃以上结晶转化成高熔融峰（Ｉ），ＰＥＫｍＫ平衡熔点为２９５℃     

DSC analysis of isothermally melt-crystallized bacterial poly(3-hydroxybutyrate-<Emphasis Type="Italic">co</Emphasis>-3-hydroxyhexanoate) films

The multiple melting behavior of isothermally melt-crystallized poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) from its melt was investigated using differential scanning calorimetry (DSC). PHBHHx exhibits a fourfold endothermic melting phenomenon, which were expressed as A, I, II, and III from low to high temperature, and attributed to the melting of secondary lamellae formed at room temperature, the melting of secondary lamellae at crystallization temperature, the melting of primary lamellae, and the melting of the recrystallized lamellae of different stabilities, respectively. Secondary crystallization is much slower than the primary crystallization and needs a relatively long period of time to occur. Furthermore, secondary crystallization at room temperature is heterogeneous, which depends on the presence of the primary lamellae and the secondary lamellae formation.     

Small-angle x-ray scattering from poly(tetramethyl-p-silphenylene) siloxane (TMPS) fractions

Small-angle x-ray scattering studies were made on bulk-crystallized samples and annealed oriented films of TMPS. The temperature dependence of the small-angle scattering was determined over a range of annealing conditions. The effect of sample molecular weight on the small-angle peaks was also studied. The peak intensity, measured at room temperature after annealing, was strongly dependent on the annealing conditions. The position of the peak gradually moved to smaller angles (larger d spacings) as the annealing temperature was raised. Surface free energies were deduced from the melting point dependence of the crystallite size. This surface energy was found to increase with molecular weight in accord with values deduced for spherulite growth rate-temperature dependence.     

An x-ray diffraction study of nonlinear polyethylene. II. Small-angle scattering observations near the melting point

A method is presented for obtaining from the zeroth-order peak in small-angle x-ray scattering (SAXS) patterns the weight average of the thickness C of crystalline lamellae in polymers close to the melting point. The method fails if a first-order peak can be discerned to be superimposed on the zeroth-order peak. The method was applied, together with the one described in Part I of this series for obtaining the number average of C, to three polyethylene samples of different side-group content which were heated to temperatures close to the melting point. While heating always causes an increasing number of lamellae to melt, a linear sample also shows pronounced thickening of the remaining lamellae. This effect, however, decreases with increasing side-group content, and is virtually absent in a vinyl acetate copolymer containing 53 side groups per 1000 C atoms. A qualitative explanation for the role of the side groups in limiting the crystal thickening processes is put forward. By comparing results obtained after isothermal annealing and during isothermal crystallization from the melt it is concluded that at temperatures close to the melting point the polymers approach a final state which no longer depends on the thermal history of the sample.     

Equilibrium Crystallization Temperature of Syndiotactic Polystyrene <Emphasis Type="Italic">γ</Emphasis> Form

The crystallization behavior of syndiotactic polystyrene (sPS) γ form undergoing annealing at various temperatures was investigated using the thermodynamic phase diagram based on Strobl's crystallization theory.On the basis of the differential scanning calorimetric results,it was observed that γ form melt-recrystallization occurred at a higher temperature with the increasing lamellar thickness,which resulted from the pre-annealing at the elevating temperature after acetone induced crystallization.Further temperature dependent small-angle X-ray scattering (SAXS) measurement revealed the evolution of the γ form lamellae upon heating until phase transition,involving three different regimes:lamellae stable region (25-90 ℃),melt-recrystallization region (90-185 ℃) and pre-phase transition region (185-195 ℃).As a result,recrystallization line,equilibrium recrystallization line and melting line were developed for the sPS γform crystallization process.Since the melt of γform involved a γto-α/β form phase transition,the melting line was also denoted as the phase transition line in this special case.Therefore,the equilibrium crystallization temperature and melting (phase transition)temperatures were determined at around 390 and 220 ℃ on the basis of the thermodynamic phase diagram of the sPS γform.     

聚环氧乙烷的双层片晶

聚环氧乙烷(M_n=7000)的双层片晶形态用透射电镜和差示扫描量热计进行了研究。在结晶温区54—56℃,现察到双层片晶,高于这个温区,同时看到双层片晶及单层片晶,低于这个温区,只看到单层片晶。双层片晶的熔点稍高于单层片晶。根据非整数次折迭链晶向整数次折迭链晶的转变,讨论了双层片晶和单层片晶的生长过程。在双层片晶界面上的H键降低了表面自由能,这是形成双层片晶的主要原因。     

High-melting bisphenol-A polycarbonate from annealing of vapor-induced crystals

Polycarbonate is known to crystallize thermally, but only slowly and to a limited (25%) extent. The melting points reported exhibit a wide variation. We have found that the melting temperature of polycarbonate may be drastically increased by employing a sequence of vapor-induced crystallization and annealing treatments. The crystals formed by the treatment with organic vapor act as a nucleation or precursor state for further crystallization into larger, more perfect lamellae. An initial peak melting temperature of 195°C has been annealed up to 239°C, and then to 295°C by a double-heat treatment. This sample is 60% crystalline, based on heat-of-fusion calculations. An equilibrium melting point of 335°C has been obtained for PC from an extrapolation of reciprocal lamellar thickness.     

Effect of crystallization time on the properties of melt-crystallized linear polyethylene

Linear polyethylene was crystallized isothermally from the melt. Specimens were removed at different crystallization times and quenched to room temperature. The density, static mechanical properties, and small-angle x-ray scattering (SAXS) behavior of these specimens were measured at room temperature. The density and Young's modulus increased with crystallization time, whereas the upper yield point decreased with crystallization time. SAXS data showed that a zero-angle peak gradually disappeared as crystallization time increased. Concurrently, the breadth of the SAXS peaks, the Bragg angle, and the integrated intensity decreased. Changes in the ratio of second- and first-order peak intensities were also noted. On the basis of the SAXS and density data, it was concluded that a competition exists between the thickening of existing crystals and the creation of new crystallites between the older ones. At relatively low crystallization times, numerous new crystals can form during quenching to room temperature, whereas quenching after prolonged crystallization primarily results in the additional thickening of existing crystals. No change in the density of the amorphous material is found. A model is given whereby the upper yield stress is coupled to these morphological changes through a stress concentration effect caused by a decreased population of chains connecting adjacent crystallites. The tie-chain population change occurs by their elimination as crystallites disappear.     

Morphological investigations on the nanostructured poly(vinylidene fluoride)/polyamide 11 blends by high-shear processing

Nanostructured poly(vinylidene fluoride) (PVDF)/polyamide 11 (PA 11) blends of various compositions were prepared using a high-shear extruder. The lamellar morphology of the nanoblends consisting of two crystalline constituents was investigated by transmission electron microscopy (TEM) and temperature-variable small-angle X-ray scattering (SAXS). The average lamellar long period and the thickness of the amorphous part for the high-shear-processed blends were larger than those for the low-shear-processed sample, indicating the molecular incorporations between PVDF and PA 11 upon high-shear processing. A novel scattering peak, corresponding to the long period of 25.2 nm, is observed when the SAXS measurements were carried out at a temperature between the melting points of PVDF and PA 11. The structural change with time at high temperature was investigated in situ by SAXS. It was found that the intensity of the new peak increased with time at high temperature and the peak position slowly shifted in the low-angle direction, indicating a gradual increase of the long period for PA 11 crystals upon annealing. The novel scattering peak originates from the enlarged PA 11 lamellar long period in the nanodomain because the peak cannot be observed for the same blends prepared by low-shear-processing. It is considered that the melt PVDF chains are gradually diffused into the galleries of PA 11 lamellae in the PA11 nanodomain, which enlarged the long period of PA 11 because of the more favorable interaction at high temperature. The chain diffusion can only occur from the interface between the PVDF and PA 11 phases, and therefore, almost no change was observed for the long period of bulk PA 11 crystals in the nanoblend.     

Relationship between melting behavior and morphological changes of semicrystalline polymers

The present study on the case of poly(hexamethylene succinate) is to provide a basis for a better understanding of the subtle relationship between melting behavior and morphological changes of semicrystalline polymers. The melting behavior and morphological changes of poly(hexamethylene succinate) during both isothermal secondary crystallization and annealing processes were investigated by DSC and SAXS. DSC results showed that, with increasing crystallization time or annealing time, the melting endotherm continuously shifted to higher temperature, which suggested that some minor structural or morphological changes must occur. However, almost no changes at all on the crystal thickness were observed from SAXS measurements. The observed evidence confirmed that the increase in the melting temperature is not attributed to crystal thickening but crystal perfection. More exactly, the rearrangement and smoothing of tie molecules at the folding surface result in the reduction of the fold surface free energy, which dominantly contributes to the increase in the melting peak temperature. The origin of the new endothermic peak observed after annealing at elevated temperature was also discussed. TMDSC results indicated that the annealing peak resulted from the enthalpy relaxation and devitrification transition of rigid amorphous fraction formed by the driving force of thermodynamic nonequilibrium, rather than usually regarded as the melting of thin lamellae or imperfect crystals formed by annealing secondary crystallization.     

Study on Melting and Recrystallization of Poly(butylene succinate) Lamellar Crystals via Step Heating Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) has been widely applied to study crystallization and melting of materials.However,for polymeric lamellar crystals,the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms,which may result from changes of metastability via recrystallization process.Sometimes,the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm.In this work,we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly(butylene succinate) (PBS) crystals.With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior.The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature.For instance,PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon.High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior.Furthermore,the melting endotherms were fitted via the melting kinetics equations.The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range,which is attributed to the different degrees of stabilization.Finally,the mechanism of melting-recrystallization is briefly discussed.We propose that apparent meltrecrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.     

Nucleation of crystallization in molten isotactic polybutene-1

Droplet experiments have been performed on polybutene-1. It was found that this polymer can be cooled to room temperature without homogeneous nucleation of crystallization. It was also found that when the polymer was heterogeneously nucleated, form I (as well as form II) could be crystallized directly from the melt. The melting point of droplets crystallized in form I near room temperature decreased with increasing crystallization temperature, while the melting point of the droplets crystallized in form I at the highest temperatures increased with increasing crystallization temperature. There was a broad minimum at about 60°C. in the melting point versus crystallization temperature curve.     

Study on melting and recrystallization of poly(butylene succinate) lamellar crystals <Emphasis Type="Italic">via</Emphasis> step heating differential scanning calorimetry

Differential scanning calorimetry (DSC) has been widely applied to study crystallization and melting of materials. However, for polymeric lamellar crystals, the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms, which may result from changes of metastability via recrystallization process. Sometimes, the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm. In this work, we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly(butylene succinate) (PBS) crystals. With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior. The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature. For instance, PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon. High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior. Furthermore, the melting endotherms were fitted via the melting kinetics equations. The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range, which is attributed to the different degrees of stabilization. Finally, the mechanism of melting-recrystallization is briefly discussed. We propose that apparent melt-recrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.     

Crystal structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate)

The structure and thermal behavior of cold-crystallized poly(trimethylene terephthalate) (PTT) are revealed in detail by DSC, AFM, TEM, and WAXD as well as in situ FTIR and SAXS techniques. There is no effect of crystallization temperature and initial state on the crystal modification, yet the morphology is strongly affected by these two factors. First, the small rod-like lamellae for PTT are obtained during the cold crystallization instead of the spherulites formed in the melt crystallization. Second, the edge-on lamellar orientation in thin films is identified during the cold crystallization. The thickness and the lateral width of rod-like lamellae get larger and larger with increasing crystallization temperature. Thin lamellar crystals assemble randomly when the cold-crystallization temperature is lower, while lamellar stacks composed of thicker lamellae are observed when the PTT was annealed at elevated temperature. Moreover, for the cold-crystallized PTT, the final melting temperature does not vary with the crystallization temperature. This phenomenon is explained by the structural improvement during the heating process. For the cold-crystallized PTT sample at lower temperature, three transitions occur when it is heated again: the relaxation of the rigid amorphous phase, the reorganization of molecules in the intermediate phase, and then the melt–recrystallization behavior. Those transitions finally lead to thicker lamellae besides a higher crystallinity before the final fusion. Therefore, the final melting peak of these lamellae is at the same temperature.     

Time-resolved SAXS studies of morphological changes in cold crystallized poly(ethylene terephthalate) during annealing and heating

Structural changes occurring during crystallization of quenched amorphous poly(ethylene terephthalate) (PET) and subsequent cooling/heating cycles have been studied by real-time small-angle x-ray scattering (SAXS), using synchrotron radiation. Initial crystallization is found to occur by insertion of new lamellae between the existing ones, while rapid continuous melting/recrystallization happens when the cold-crystallized PET samples are heated above the previous highest annealing temperature. Such melting/recrystalization results in irreversible increases in the lamellar long period, the crystal thickness and the density difference between the crystalline and amorphous regions; in contrast, at temperatures below the prior highest crystallization temperature, the structural changes are dominated by reversible effects such as thermal expansion. However, throughout the entire temperature range up to the melting point around 250 °C, the crystal core thickness remains quite small, less than ca. 50 Å, and the linear crystallinity of lamellar stacks remains nearly constant around 0.3. Such a low crystallinity indicates the presence of thick order-disorder interfacial layers on the lamellar surface, whose thickness increases with temperature.Dedicated to Prof. E. W. Fischer on the occasion of his 65th birthday.     

Crystallization and melting of isotactic polypropylene in response to temperature modulation

Isotactic polypropylene (iPP) was crystallized using temperature modulation in a differential scanning calorimeter (DSC) to thicken the crystals formed on cooling from the melt. A cool-heat modulation method was adopted for the preparation of the samples under a series of conditions. The effect of modulation parameters, such as temperature amplitude and period was monitored with the heating rate that followed. Thickening of the lamellae as a result of the crystallization treatment enabled by the cool-heat method lead to an increase in the peak melting temperature and the final traces of melting. For instance, iPP melting peak shifted by up to 3.5°C with temperature amplitude of 1.0°C while the crystallinity was increased from 0.45 (linearly cooled) to 0.53. Multiple melting endotherms were also observed in some cases, but this was sensitive to the temperature changes experienced on cooling. Even with a slower underlying cooling rate and small temperature amplitudes, some recrystallization and reorganization occurred during the subsequent heating scan. The crystallinity was increased significantly and this was attributed to the crystal perfection that occurred at the crystal growth surface. In addition, temperature modulated differential scanning calorimetry (TMDSC) has been used to study the melting of iPP for various crystallization treatments. The reversing and non-reversing contribution under the experimental time scale was modified by the relative crystal stability formed during crystallization. Much of the melting of iPP was found to be irreversible.This revised version was published online in November 2005 with corrections to the Cover Date.     

热历史对尼龙1212熔融行为的影响

利用DSC方法研究了不同热历史条件对尼龙1212熔融行为的影响.不同的热历史条件下,在DSC曲线上,观察到尼龙1212产生2个或3个熔融峰,依据聚合物结晶理论,对各峰的来源进行了分析.在160℃下不同温度退火120 min的尼龙1212样品DSC曲线上,低温结晶熔融峰主要由低温结晶形成的一些微晶体或者片晶熔融产生,其晶体完善程度较差,熔融峰值较低,峰面积较小;主熔融峰是由样品在淬火过程中形成的晶体和升温过程中低温结晶形成的晶体的熔融重结晶形成较为完善的晶体熔融所产生,熔融峰值较高,峰面积较大.在不同的升温速率条件下,熔融峰温度有所移动,表明不同升温速率条件下产生的熔融峰的结晶晶型是相同的.在不同结晶时间下结晶,延长结晶时间对较高完善程度晶体的生长有利.在不同温度下依次退火处理的样品,熔融产生两个附加峰,这两个附加峰的峰温都比它们相应的退火温度高,而峰高和峰面积随退火温度降低而减小.根据等温结晶结果,由Hoffman方法确定了尼龙1212的平衡熔融温度为202.8℃.