A modulated dsc study on the in situ polymerization of cyclic butylene terephthalate oligomers

The polymerization of a cyclic butylene terephthalate (CBT) oligomer was studied as a function of temperature (T=200 and 260°C, respectively) by modulated DSC (MDSC). The first heating was followed by cooling after various holding times (5, 15 and 30 min) prior to the second heating which ended always at T=260°C. This allowed us to study the crystallization and melting behavior of the resulting polybutylene terephthalate (PBT), as well. In contrary to the usual belief, the CBT polymerization is exothermic and the related process is superimposed to that of the CBT melting. The melting behavior of the PBT was affected by the polymerization mode (performed below or above the melting temperature of the PBT product) of the CBT. Annealing above the melting temperature of PBT yielded a product featuring double melting. This was attributed to the presence of crystallites with different degrees of perfection. The crystals perfection which occurred via recrystallization/remelting was manifested by a pronounced exothermic peak in the non-reversing trace.     

Reversible Melting of Thermally Fractionated Polyethylene

Different grades of linear low density polyethylenes (LLDPEs) have been quenched cooled step-wise and crystallised isothermally at (a series of increasing) temperatures in a DSC (thermal fractionated samples). These samples have been investigated by temperature modulated DSC (MDSC). The heat flow curves of the thermal fractionated materials were compared with those obtained from samples crystallised at a relatively slow cooling rate of 2 K min^-1(standard samples). The melting enthalpy obtained from the total heat flow of the thermal fractionated samples was 0-10 J g^-1higher than those of standard samples. The melting enthalpy obtained from the reversing heat flows was 13-31 J g^-1lower in the thermal fractionated samples than in the standard samples. The ratio of the reversing melting enthalpy to the total melting enthalpy increased with decreasing density of the PE. The melting temperature of the endotherms formed by the step-wise cooling was 9 K higher than the crystallisation temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Multiple Melting Endotherms of Syndiotactic Polystyrene in β Crystalline Form

Multiple melting behaviors have been studied extensively. Syndiotactic polyStyrene(SPS), in 6 crystalline form exhibited such phenomena. It was suggested that arecrystallization process occurred since it has been clarified that no other modificationswere observed during the DSC heating scanl. In this study, a series of SPS samples in 0form were prepared by cooling from the melt at various cooling ratesl and the factors thatinfluence the multiple melting behavior of SPS in 0 form were exam…     

Comparison of reversible melting behaviour of poly(3-hydroxybutyrate) using quasi-isothermal and other modulated temperature differential scanning calorimetry techniques

Melting behaviour of poly(3-hydroxybutyrate) (PHB) has been investigated by conventional DSC and each of several methods of modulated temperature differential scanning calorimetry (mT-DSC) such as heat-cool, iso-scan, step-scan and quasi-isothermal (QI). Thermal properties were investigated after fast and slow cooling crystallisation treatments. Multiple melting peak behaviour was observed for all methods except conventional melting with an average heating rate. Comparison of the mT-DSC data revealed that PHB underwent reversing melting including several reversible events and some non-reversible contributions under the modulation conditions. The main melting of PHB was irreversible, as were crystallisation and annealing, where the crystals can approach equilibrium. The various fusion enthalpy values were measured and they confirmed significant melt-recrystallisation of PHB with different melting conditions. Only the QI method revealed a true reversible contribution.     

剪切应力场中聚丙烯熔体在近熔点处冷却结晶的晶体结构研究

通过自主设计的动态保压注塑成型装置研究剪切应力场下聚丙烯(PP)熔体在近熔点处冷却结晶的晶体结构.用扫描电子显微镜(SEM)、示差扫描量热法(DSC)和广角X射线衍射(WAXD)分析了PP试样在近熔点处冷却后从表层到剪切层的结晶结构的变化.SEM研究表明,与传统注塑成型样品(SL)和剪切力场中高熔体温度下冷却得到的试样(DH)相比,近熔点附近冷却得到的PP试样(DL)从表层到剪切层的结晶结构和形态有明显变化.DL从表层到剪切层均生成了尺寸较大的取向结晶结构,无明显的串晶产生.DSC研究表明,与SL和DH相比,DL剪切层无脊纤维晶熔融峰且晶片熔融温度较高,证明其样品内部晶片尺寸较大.WAXD进一步研究显示,DL内部主要晶面(110,040和130)的结晶尺寸与SL和DH相比并没有发生明显改变.     

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.     

Thermal memory of poly(3‐hydroxybutyrate) using temperature‐modulated differential scanning calorimetry

The influence of thermal history on morphology, melting, and crystallization behavior of bacterial poly(3‐hydroxybutyrate) (PHB) has been investigated using temperature‐modulated DSC (TMDSC), wide‐angle X‐ray diffraction (WAXRD) and polarized optical microscopy (POM). Various thermal histories were imparted by crystallization with continuous and different modulated cooling programs that involved isoscan and cool–heat segments. The subsequent melting behavior revealed that PHB experienced secondary crystallization during heating and the extent of secondary crystallization varied with the cooling treatment. PHB crystallized under slow, continuous, and moderate cooling rates were found to exhibit double melting behavior due to melting of TMDSC scan‐induced secondary crystals. PHB underwent considerable secondary crystallization/annealing that took place under modulated cooling conditions. The overall melting behavior was interpreted in terms of recrystallization and/or annealing of crystals. Interestingly, the PHB analyzed by temperature modulation programs showed a broad exotherm before the melting peak in the nonreversing heat capacity curve and a multiple melting reversing curve, verifying that the melting–recrystallization and remelting process was operative. WAXRD and POM studies supported the correlations from DSC and TMDSC results. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 70–78, 2006     

Effect of the crosslinking density and the method of sample preparation on the observed microstructure of macroporous and conventional poly(N,N-dimethylacrylamide) hydrogels

SEM micrographs of macroporous and conventional poly(N,N-dimethylacrylamide) hydrogels were obtained for specimens synthesized in different conditions and prepared for microscopy by different methods (freeze drying of different solvents and critical point drying). The crosslinking density of both types of samples was determined through T _g measurements. Open structures (honeycomb-like, fibrillar networks) were more frequently observed in specimens prepared by freeze drying of benzene, which was attributed to its large pressure and temperature at the triple point. In spite of the different structure in the millimeter scale, there is no significant difference in the mesh size of fibrillar networks observed for macroporous and conventional samples, and in both cases it decreases with increasing crosslinking density. Other effects of the crosslinking density are that only incomplete honeycomb-like structures were formed in low-crosslinking samples and that collapsed structures were developed by phase separation throughout polymerization in highly crosslinked samples. Fibrillar networks of 1-μm mesh size were observed for the uncrosslinked polymer.     

Thermal analysis of the double-melting behavior of poly(L-lactic acid)

The melting and crystallization behavior of poly(L -lactic acid) (PLLA; weight-average molecular weight = 3 × 10⁵) was studied with differential scanning calorimetry (DSC). DSC curves for PLLA samples were obtained at various cooling rates (CRs) from the melt (210 °C). The peak crystallization temperature and the exothermic heat of crystallization determined from the DSC curve decreased almost linearly with increasing log(CR). DSC melting curves for the melt-crystallized samples were obtained at various heating rates (HRs). The double-melting behavior was confirmed by the double endothermic peaks, a high-temperature peak (H) and a low-temperature peak (L), that appeared in the DSC curves at slow HRs for the samples prepared with a slow CR. Peak L increased with increasing HR, whereas peak H decreased. The peak melting temperatures of L and H [T_m(L) and T_m(H)] decreased linearly with log(HR). The appearance region of the double-melting peaks (L and H) was illustrated in a CR–HR map. Peak L decreased with increasing CR, whereas peak H increased. T_m(L) and T_m(H) decreased almost linearly with log(CR). The characteristics of the crystallization and double-melting behavior were explained by the slow rates of crystallization and recrystallization, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 25–32, 2004     

Polymorphic crystalline forms of 8OCB

For most alkoxycyanobiphenyls (3OCB, 5OCB, 6OCB, 7OCB and 9OCB) it has been observed that slow or delayed cooling gave rise to a lower melting crystalline polymorphic form which then slowly converted into the higher melting stable crystalline structure. Although under slow evaporation from a solvent, polymorphic crystalline structures were observed also for 8OCB, a polymorphism on cooling like that in other nOCBs has not previously been reported. We have now observed that 8OCB also shows polymorphism, which brings it into line with the other homologues. On keeping the material between 35 and 38 °C after it was cooled from above the melting point of the stable crystal form (55 °C), regular platelets grow usually from one point and fill the whole sample. The texture is stable for weeks at room temperature. Upon heating it shows a melting point at 50 °C, i.e. 5 degrees below the stable crystalline melting point. It is interesting that all platelets are non-symmetric and have the same handedness.     

Multiple melting in nylon 66

Either of the two endothermic melting peaks found by differential thermal analysis of nylon 66 may be converted to the other by appropriate choice of annealing conditions. The two peaks are considered due to the melting of two morphological species, forms I and II. Form I is relatively fixed in melting temperature, while the form II melting temperature varies with annealing conditions and can be either above or below form I. The two forms can be distinguished by whether or not the conversion I → II takes place; if the sample is in form II no change in the thermogram is observed under suitable conversion conditions. The conversion of form I to form II also takes place during cold drawing. It has been previously shown that form I results from rapid cooling from the melt, and form II results from slow cooling. Form I appears to be kinetically favored, while form II is thermodynamically preferred. The variability in the form II melting point is attributed to variable crystal size and/or perfection.     

Analysis of the complex thermal behavior of poly(L‐lactic acid) film. II. Samples crystallized from the melt

The complex thermal behavior of poly(l ‐lactic acid) films crystallized from the melt, either isothermally or nonisothermally, was studied by differential scanning calorimetry (DSC), wide angle X‐ray diffraction, and small angle X‐ray scattering. The variation of the thermal behavior with crystallization temperature, time, and cooling rate was documented and analyzed. After nonisothermal crystallization at low cooling rates that develop high crystallinity, an obvious double melting peak appears at modest heating rates (e.g., 10 °C/min). At higher heating rates, these samples exhibit only single melting. However, an unusual form of double melting occurs under the majority of the conditions studied under either isothermal or nonisothermal conditions. In this case, double melting is marked by the appearance of a recrystallization exotherm just prior to the final melting that obscures the observation of the melting of the crystals formed during the initial crystallization process. The occurrence of double melting in melt‐crystallized samples was concluded to be the result of a melt‐recrystallization process occurring during the subsequent DSC heating scan; it is a function of crystalline perfection, not the initial crystallinity, nor whether or not the crystallization reached completion at the crystallization temperature. Many other very interesting observations are also discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3378–3391, 2006     

Polymorphic crystalline forms of 8OCB

For most alkoxycyanobiphenyls (3OCB, 5OCB, 6OCB, 7OCB and 9OCB) it has been observed that slow or delayed cooling gave rise to a lower melting crystalline polymorphic form which then slowly converted into the higher melting stable crystalline structure. Although under slow evaporation from a solvent, polymorphic crystalline structures were observed also for 8OCB, a polymorphism on cooling like that in other nOCBs has not previously been reported. We have now observed that 8OCB also shows polymorphism, which brings it into line with the other homologues. On keeping the material between 35 and 38 °C after it was cooled from above the melting point of the stable crystal form (55 °C), regular platelets grow usually from one point and fill the whole sample. The texture is stable for weeks at room temperature. Upon heating it shows a melting point at 50 °C, i.e. 5 degrees below the stable crystalline melting point. It is interesting that all platelets are non-symmetric and have the same handedness.     

Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites

The role of organically modified silicate (OMS), Lucentite STN on the formation of β‐crystalline phase of poly(vinylidene fluoride) (PVDF) is investigated in the present study. The OMS was solution blended with PVDF and cast on glass slide to form PVDF‐OMS nanocomposites. Solution cast samples were subjected to various thermal treatments including annealing (AC‐AN), melt‐quenching followed by annealing (MQ‐AN), and melt‐slow cooling (MSC). Fourier‐transform infrared spectroscopy (FT‐IR), wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the crystalline structure of thermally treated samples. As a special effort, the combination of in situ thermal FT‐IR, WAXD, and DSC studies was utilized to clearly assess the thermal properties. FT‐IR and WAXD results of MQ‐AN samples revealed the presence of β‐phase of PVDF. Ion‐dipole interaction between the exfoliated clay nanolayers and PVDF was considered as a main factor for the formation of β‐phase. Melt‐crystallization temperature and subsequent melting point were enhanced by the addition of OMS. Solid β‐ to γ‐crystal phase transition was observed from in situ FT‐IR and WAXD curves when the representative MQ‐AN sample was subjected to thermal scanning. Upon heating, β‐phase was found to disappear through transformation to the thermodynamically stable γ‐phase rather than melting directly. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2173–2187, 2008     

Thermal characterization of polyethylene glycols applied in the pharmaceutical technology using differential scanning calorimetry and hot stage microscopy

In the present study, the effect of the molecular weight and thermal treatments on commercial polyethylene glycols (PEG) samples used in the pharmaceutical processing technology, has been analyzed using DSC and HSM. The molecular weight of these polymers range from 1500 to 200000. Thermal investigations on the melting behavior of original PEG samples (as received from the manufacturer) showed only one single melting DSC endotherm effect before 373 K. This fact was associated to the presence of only one type of polymeric chain. Using standard conditions, PEG samples were solidified from the melt at 373 K, either by flash cooling (using liquid nitrogen and an ice bath) and by slow cooling, soaked and by slow cooling at room temperature. They were further studied by DSC. It was found that after cooling, PEG with molecular weight 1500 and 15000 showed DSC thermograms with a single endothermic peak. However, thermograms for PEG 4000 and 6000 produced a splitted melting endotherm. This fact was attributed to the presence of two types of chains, that are the folded and extended chains.Ageing time influences also the shape of the DSC endothermal effects. It was concluded that the endotherms obtained after heating these PEG indicate that the thermal history determine the structure (extended or folded chain type forms) and the degree of crystallinity, as evidenced by changes in heat of fusion values, melting points and structures after crystallization. The relationships between melting enthalpies and melting points, as deduced from DSC diagrams, with molecular weight of the polymers are also presented.     

Effects of carbon nanotubes on crystallization and melting behavior of poly(L‐lactide) via DSC and TMDSC studies

In this work, multiwalled carbon nanotubes (MWNTs) were surface‐modified and grafted with poly(L ‐lactide) to obtain poly(L ‐lactide)‐grafted MWNTs (i.e. MWNTs‐g‐PLLA). Films of the PLLA/MWNTs‐g‐PLLA nanocomposites were then prepared by a solution casting method to investigate the effects of the MWNTs‐g‐PLLA on nonisothermal and isothermal melt‐crystallizations of the PLLA matrix using DSC and TMDSC. DSC data found that MWNTs significantly enhanced the nonisothermal melt‐crystallization from the melt and the cold‐crystallization rates of PLLA on the subsequent heating. Temperature‐modulated differential scanning calorimetry (TMDSC) analysis on the quenched PLLA nanocomposites found that, in addition to an exothermic cold‐crystallization peak in the range of 80–120 °C, an exothermic peak in the range of 150–165 °C, attributed to recrystallization, appeared before the main melting peak in the total and nonreversing heat flow curves. The presence of the recrystallization peak signified the ongoing process of crystal perfection and, if any, the formation of secondary crystals during the heating scan. Double melting endotherms appeared for the isothermally melt‐crystallized PLLA samples at 110 °C. TMDSC analysis found that the double lamellar thickness model, other than the melting‐recrystallization model, was responsible for the double melting peaks in PLLA nanocomposites. Polarized optical microscopy images found that the nucleation rate of PLLA was enhanced by MWNTs. TMDSC analysis found that the incorporation of MWNTs caused PLLA to decrease the heat‐capacity increase (namely, ΔC_p) and the C_p at glass transition temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1870–1881, 2007     

Crystallization and melting of a branched polyethylene with precisely controlled chemical structure

The heat capacity of a linear polyethylene with dimethyl branches, at every 21st backbone atom was analyzed by differential scanning calorimetry (DSC) and quasi-isothermal temperature-modulated DSC. This novel copolyethylene (PE2M) is relatively difficult to crystallize from the melt. On subsequent heating, a first, sharp melting peak is followed by a sharp cold-crystallization and crystal perfection and a smaller endotherm, before reaching the main melting at 315–320 K, close to the melting temperatures of eicosane and tetracontane. The low-temperature melting is sensitive to the cooling rate and disappears below 1.0 K min⁻¹. The cold crystallization can be avoided by heating with rates faster than 80 K min⁻¹. The PE2M exhibits some reversing and reversible melting, which is typical for chain-folded polymers. The glass transition of semicrystalline PE2M is broadened and reaches its upper limit at about 260 K (midpoint at about 0.355 K). Above this temperature, the crystals seem to have a heat capacity similar to that of the liquid. A hypothesis is that the melting transition can be explained by changes in crystal perfection without major alteration of the crystal structure and the lamellar morphology. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3461–3474, 2006     

Temperature modulated dynamic mechanical analysis

Temperature modulated dynamic mechanical analysis (TMDMA) was performed in the same way as temperature modulated DSC (TMDSC) measurements. Temperature modulation with amplitude 0.5 K and period 20 min was realised by a series of linear heating and cooling cycles (saw-tooth modulation). As in TMDSC TMDMA allows for the investigation of reversible and non-reversible phenomena in the melting and crystallisation region of polymers. The advantage of TMDMA compared to TMDSC is the high sensitivity for small and slow changes in crystallinity, e.g. during re-crystallisation. The combination of TMDMA and TMDSC yields new information about local processes at the surface of polymer crystallites. It is shown that during and after isothermal crystallisation the surface of the individual crystallites is in equilibrium with the surrounding melt.     

冷冻升华制备的超高分子量聚乙烯寡链、多链晶体的凝聚态

在10^-3～10^-5g/mL浓度范围内,用冷冻升华法制备了超高分子量聚乙烯(UHPE)单链、寡链、多链的折叠链晶聚集体.长达几万纳米的UHPE分子链可以以不同的片晶参与结晶,或自身形成数个晶粒,即形成单链多晶.DSC研究结果表明,随着溶液浓度的降低,冷冻升华样品的熔点和结晶度均降低.由熔点估算了晶粒的体积和晶粒中包含的链数,它们亦随溶液浓度降低而降低.冷冻升华得到的小晶粒中链的缠结少,晶体具有较高的完善性.用WAXD测试晶粒的(110)和(200)面的法向尺寸,由此计算晶粒的平均体积,与熔点计算得到的数值一致.     

Scanning force microscopy experiments probing micromechanical properties on polymer surfaces using harmonically modulated friction techniques II. Investigations of heterogeneous systems

Applying a high-frequency lateral vibration between tip and sample in a scanning force microscope (SFM), a harmonically modulated lateral (friction) force image can be obtained using lock-in techniques. Harmonically modulated lateral force microscopy (HM-LFM) offers several advantages compared with standard lateral force microscopy (LFM). After a brief investigation of the scan velocity dependence of LFM and HM-LFM, two samples were investigated. First, the surface of a poly(acrylonitrile-co-styrene)/polybutadiene blend (ABS) was used to demonstrate the ability of the new technique to decrease the stick effects of the SFM tip. Second, an interface between two chemically very similar polymers was prepared by melting polypropylene (PP) and poly(propene-block-ethene) (PP-block-PE) films on each other. After cutting, the surface roughness of this sample was very high. It is shown that only HM-LFM clearly resolves the local micromechanical properties without artefacts.