Rigid amorphous fraction and melting behavior of poly(ethylene terephthalate)

The multiple melting behavior of poly(ethylene terephthalate) (PET) is generally attributed to the fusion of original crystals recrystallized during the heating at conventional scanning rate. In the present study, the triple and double melting behavior that is observed after isothermal crystallization at T _c lower and higher than 215 °C, respectively, is put in relation with the presence and absence of rigid amorphous fraction around the original primary crystal lamellae. The complex melting behavior is explained by assuming that two different morphologies of primary crystals develop during crystallization at temperatures lower than 215 °C, in a proportion that is a function of the crystallization temperature: chain cluster aggregations with a high percentage of rigid amorphous fraction on the boundaries and small crystals with a high percentage of adjacent reentry folding and reduced constraints at the amorphous/crystal interphase. These distinct morphologies differently transform upon heating at low scanning rate, originating two endotherms. On the contrary, after crystallization at T _c ?>?215 °C, all the primary crystalline structure, which probably are characterized by the same morphology made of tightly chain folded lamellae and absence of rigid amorphous fraction, undergo the same reorganization route, originating a single endotherm.     

The triple melting behavior of poly(ethylene terephthalate): Molecular weight effects

The melting behavior of isothermally crystallized PET has been studied using linear heating in a differential scanning calorimeter (DSC). Variables such as crystallization temperature, crystallization time, heating rate, and average molecular weight are the main focus of the study. On the basis of several experimental techniques, a correlation of the melting behavior of PET with the amount of secondary crystallization was found to exist. It was observed that the triple melting of PET is a function of programmable DSC variables such as crystallization temperature, crystallization time, and heating rate. However, in testing the hypothesis that there was a correlation between melting endotherms and secondary crystallization inside spherulites, it was found necessary to use a DSC-independent variable in order to enhance the observed effects. Therefore, on the basis of a crystallization model that involves secondary branching along the edges of parent lamellar structures, it was speculated that an increase in the average molecular weight could affect the triple melting of PET due to an increase of rejected portions of the macromolecules. It was found that the second melting endotherm increased, apparently, at the expense of the third one as the average molecular weight was increased. The second melting endotherm was also found to correlate proportionally with the amount of secondary crystallization inside spherulites. The results support a model of crystallization which basically consists of parent crystals and at least one population of secondary, probably metastable, crystals. This latter structural component must involve excluded portions of the macromolecules that did not crystallize during the isothermal crystallization period of the parent crystals. An increase of molecular weight gives rise to a higher entanglement density which in turn increases the fraction of initially rejected chain sections and therefore the amount of secondary crystallization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1757–1774, 1997     

Effects of thermal history on the rigid amorphous phase in poly(phenylene sulfide)

The rigid amorphous phase of semicrystalline poly(phenylene sulfide) (PPS) has been studied as a function of thermal history using scanning calorimetry, dielectric relaxation, density, and small-angle x-ray scattering (SAXS). Based on the new heat of fusion of perfect crystalline PPS, which is 26.7±0.8 cal/gram, the weight fraction of rigid amorphous phase is shown to be nearly twice as large as previously reported [1]. The mass fraction of the rigid amorphous phase ranges from 0.24 to 0.42 and is dependent upon thermal treatment. We have taken the approach of assuming a three-phase model for the morphology of semicrystalline PPS consisting of crystalline lamellae, mobile amorphous, and rigid amorphous components. Using this three-phase model, we determine that the average density of the rigid amorphous fraction is 1.325 g/cc, which is slightly larger than the density of the mobile amorphous phase fraction and was insensitive to thermal history. From the SAXS long period, the layer thicknesses of the mobile amorphous phase, rigid amorphous phase, and crystal lamellae were estimated. Only the lamellar thickness shows a systematic variation with thermal history, increasing with melt or cold crystallization temperature, or with decreasing cooling rate.     

The three-phase structure and mechanical properties of poly(ethylene terephthalate)

The relation between the mechanical properties and the microstructure of PET has been investigated, combining results from WAXS, SAXS, FTIR, DSC, and uniaxial compression tests. The rigid amorphous fraction in the PET was explicitly taken into consideration in interpreting structure–property relations. WAXS results prove that glass crystallized PET with a high volume fraction of rigid amorphous material and small crystal size, on uniaxial compression shows a considerable loss in crystalline fraction. FTIR results in combination with these WAXS results suggest that during this loss in crystallinity, short-range conformational order is retained, while long-range structural order is lost. At the same time, material with small crystals and a high amount of rigid amorphous material was found to show unexpectedly low yield stress. It is concluded that in the interpretation of these phenomena it is necessary to take the three-phase structure of PET, including the rigid amorphous fraction into account. This is expected to hold for other semicrystalline polymers, where a rigid amorphous fraction is prominent, such as PHB, PBT, PEN, PEEK, etc. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2092–2106, 2004     

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.     

Linear Relations of Activation Energy in Non-isothermal Kinetics

Temperature-modulated DSC (TMDSC) measurements at reasonably high frequencies allow for the determination of base-line heat capacity. In this particular case vitrification and devitrification of the rigid amorphous fraction (RAF) can be directly observed. 0.01 Hz seems to be a reasonably high frequency for bisphenol-A polycarbonate (PC). The RAF of PC is established during isothermal crystallization. Devitrification of the RAF seems to be related to the lowest endotherm. For PC the melting of small crystals between the lamellae is expected to yield the lowest endotherm. This revised version was published online in July 2006 with corrections to the Cover Date.     

TMDSC and Atomic Force Microscopy Studies of Morphology and Recrystallization in Polyesters Including Oriented Films

The thermal and crystal morphological properties of poly[ethylene teraphthalate] (PET) and poly(ethylene-2,6-naphthalenedicarboxylate) (PEN) biaxially oriented films were compared to amorphous and other isotropic semi-crystalline samples. Crystal melting as a function of temperature was characterized by temperature modulated DSC (TMDSC) and found to begin just above the glass transition for both oriented films. About 75°C above the glass transitions, substantial exothermic recrystallization begins and continues through the final melting region in oriented films. The maximum in the non-reversing TMDSC signal for the oriented films signifies the maximum recrystallization exothermic activity with peaks at 248°C and 258°C for PET and PEN, respectively. The final melting endotherm detected was 260°C and 270°C for PET and PEN, and is shown by the TMDSC data and by independent rapid heating rate melting point determinations to be due to the melting of species recrystallized during the heating scan. The results are compared with TMDSC data for initially amorphous and melt crystallized samples. The volume fraction of rigid species (F_rigid=total crystal fraction plus rigid amorphous or non-crystalline species) were measured by TMDSC glass transition data, and contrasted with the area fraction of rigid species at the oriented film surface characterized with very high resolution atomic force microscopy (AFM) phase data. The data suggest that the 11 nm wide hard domains in PET, and 21 nm wide domains in PEN film detected by AFM consist of both crystal and high stiffness interphase species.This revised version was published online in November 2005 with corrections to the Cover Date.     

Rigid amorphous fraction in poly(ethylene terephthalate) determined by dilatometry

Volumetric thermal analysis of semicrystalline poly(ethylene terephthalate), PET, with different content of crystalline phase was carried out using mercury-in-glass dilatometry. The effect of crystals on the thermal properties of amorphous phase (glass transition temperature, T _g, thermal expansion coefficients, α) were determined. At cold-crystallization (106°C, up to 4 h), crystalline content of 2.4–25.3 vol.% was achieved. Increasing content of crystalline phase broadens the glass transition region and increases T _g. The change of thermal expansion coefficient during glass transition is lower than that predicted by the two-phase model, which indicates the presence of a third fraction — rigid amorphous fraction (RAF), whose content steadily increases during crystallization. However, its relative portion (specific RAF) is significantly reduced. Further significant decrease in specific RAF appears after annealing at a higher temperature.     

The microstructure and macrostructure of sulfonated poly(ethylene terethphalate) fibers

The effects of fiber-forming processes on the microstructure and macrostructure and overall orientation in sulfonated poly(ethylene terephthalate) (SPET) fibers are reported. The processing parameters examined include drawing, crimping, relaxing, and annealing. Drawing and annealing cause changes in both the crystalline structure and molecular packing in the noncrystalline regions, while crimping and relaxing appear to affect only the noncrystalline regions. A bimodal melting endotherm was observed for the SPET fibers. Experimental data suggest the low-temperature endotherm of the SPET fibers originates from melting of the crystalline structure formed on drawing, and that the high-temperature endotherm results from melting the heat-induced crystals formed during fiber processing and/or thermal analysis. Compared to the PET fibers, the SPET chains in the undrawn fibers appear to have higher mobility, are easier to crystallize, and form smaller crystals upon drawing as well as DTA heating. At the crimped stage, the SPET fibers have higher overall molecular packing but lower overall orientation than the PET fibers. The differences in physical and thermal properties between the analogous SPET and PET fibers are related to their different responses to processing variations because of molecular weight and sidegroup effects. © 1993 John Wiley & Sons, Inc.     

Investigation of the rigid amorphous fraction in Nylon-6

A three-phase model, comprising crystalline, mobile amorphous, and rigid amorphous fractions (χ _c, χ _MA, χ _RA, respectively) has been applied in the study of semicrystalline Nylon-6. The samples studied were Nylon-6 alpha phase prepared by subsequent annealing of a parent sample slowly cooled from the melt. The treated samples were annealed at 110°C, then briefly heated to 136°C, then re-annealed at 110°C. Temperature-modulated differential scanning calorimetry (TMDSC) measurements allow the devitrification of the rigid amorphous fraction to be examined. We observe a lower endotherm, termed the ‘annealing’ peak in the non-reversing heat flow after annealing at 110°C. By brief heating above this lower endotherm and immediately quenching in LN₂-cooled glass beads, the glass transition temperature and χ _RA decrease substantially, χ _MA increases, and the annealing peak disappears. The annealing peak corresponds to the point at which partial de-vitrification of the rigid amorphous fraction (RAF) occurs. Re-annealing at 110°C causes the glass transition and χ _RA to increase, and χ _MA to decrease. None of these treatments affected the measured degree of crystallinity, but it cannot be excluded that crystal reorganization or recrystallization may also occur at the annealing peak, contributing to the de-vitrification of the rigid amorphous fraction. Using a combined approach of thermal analysis with wide and small angle X-ray scattering, we analyze the location of the rigid amorphous and mobile amorphous fractions within the context of the Heterogeneous and Homogeneous Stack Models. Results show the homogeneous stack model is the correct one for Nylon-6. The cooperativity length (ξ_A) increases with a decrease of rigid amorphous fraction, or, increase of the mobile amorphous fraction. Devitrification of some of the RAF leads to the broadening of the glass transition region and shift of T _g.     

The double melting behavior of a liquid crystalline polyimide derived from PMDA and 1,3‐bis[4‐(4′‐aminophenoxyl) cumyl] benzene

The double melting behavior of a thermotropic liquid crystalline polyimide was studied by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), transmission electron microscopy (TEM), wide‐angle X‐ray diffraction (WAXD), and small‐angle X‐ray scattering (SAXS). This liquid crystalline polyimide exhibited a normal melting peak around 278 °C and transformed into a smectic A phase. The smectic A phase changed to nematic phase upon heating to 298 °C, then became isotropic melt around 345 °C. The samples annealed or isothermally crystallized at lower temperature showed double melting endotherms during heating scan. The annealing‐induced melting endotherm was highly dependent on annealing conditions, whereas the normal melting endotherm was almost not influenced by annealing when the annealing temperature was low. Various possibilities for the lower melting endotherm are discussed. The equilibrium melting points of both melting peaks were extrapolated to be 283.2 °C. Combined analytical results showed that the double melting peaks were from the melting of the two types of crystallites generated from two crystallization processes: a slow and a fast one. Fast crystallization may start from the well‐aligned liquid crystal domains, whereas the slow one may be from the fringed or amorphous regions. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3018–3031, 2000     

FTIR spectroscopic analysis of poly(ethylene terephthalate) on crystallization

The vibrational spectrum of partially crystalline poly(ethylene terephthalate), PET, appears to be unduly complex in that the absorption bands are split into amorphous and crystalline modes and are sensitive to chain configuration and orientation. Assignment of the bands has accordingly proved to be difficult and lead to differences in interpretation. Two-dimensional infrared spectroscopy is a recent novel analytical technique in vibrational spectroscopy which can be used to interpret differences in the spectra with time or temperature accompanying changes in structure and morphology and has been used to analyze the development of crystallinity within a polymer in which amorphous regions are transformed into crystalline regions and involving changes in molecular configuration.Two-dimensional IR correlation spectroscopy has been successfully applied to these problems in the attempt to measure the fractional extent of crystallinity in PET as a function of time and crystallization temperature as well as changes to molecular configuration.     

Vitrification and crystallization of low-temperature amorphous condensates of water and methane—water mixture

Low-temperature condensates of water and water-methane mixture are studied in the temperature range of 65–200 K. Amorphous samples are obtained by molecular beam deposition under vacuum conditions on the substrate cooled with liquid nitrogen. The vitrification and crystallization temperatures are determined from the changes in the dielectric properties of the condensates upon heating. The kinetics of crystallization of amorphous water layers is studied by differential thermal analysis. The temperature conditions for the growth of thick methane crystalline hydrate layers during the low-temperature condensation of molecular water-gas mixture beams are found.     

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     

Cooperativity length evolution during crystallization of poly(lactic acid)

Effects of stereoregularity and crystallization mode on the amorphous phase dynamics are investigated for poly(lactic acid) PLA. An isothermal crystallization from the melt and a cold crystallization are imposed. For each PLA, the cold crystallization leads to the appearance of a less perfect crystalline phase and to an important rigid amorphous fraction RAF content (35%), although only 10% of RAF is generated after crystallization from the melt. Temperature Modulated Differential Scanning Calorimetry is used to determine the Cooperative Rearranging Regions (CRR) size at the glass transition temperature in the mobile amorphous phase MAP. It is shown that the CRR size in the MAP is not modified by the appearance and the spherulite growth. For the intra-spherulite MAP, a confining effect is evidenced, causing an amorphous phase thickness decrease during crystallization, and inducing a drastic CRR size reduction.     

How did we find the rigid amorphous phase?

The first experimental evidence of the existence of the rigid amorphous phase was reported by Menczel and Wunderlich [1]: when trying to clarify the glass transition characteristics of the first main chain liquid crystalline polymers [poly(ethylene terephthalate-co-p-oxybenzoate) with 60 and 80 mol% ethylene terephthalate units] [2], the absence of the hysteresis peak at the lower temperature glass transition became evident when the sample of this copolymer was heated much faster than it had previously been cooled. Since this glass transition involved the ethylene terephthalate-rich segments of the copolymer, we searched for the source of the absence of the hysteresis peak in PET. There, the gradual disappearance of the hysteresis peak with increasing crystallinity was confirmed [1]. At the same time it was noted that the higher crystallinity samples showed a much smaller ΔC _p than could be expected on the basis of the crystallinity calculated from the heat of fusion (provided that the crystallinity concept works). Later it was confirmed that the hysteresis peak is also missing at the glass transition of nematic glasses of polymers. When checking other semicrystalline polymers, the sum of the amorphous content calculated from the ΔC _p at the glass transition, and the crystallinity calculated from the heat of fusion was far from 100% for a number of semicrystalline polymers. For most of these polymers, the sum of the amorphous content and the crystalline fraction was 0.7, meaning that ca. 30% rigid amorphous fraction was present in these samples after a cooling at 0.5 K min⁻¹ rate. Thus, the presence of the rigid amorphous phase was confirmed in five semicrystalline polymers: PET, Nylon 6, PVF, Nylon 66 and polycaprolactone [1]. Somewhat later poly(butylene terephthalate) and bisphenol-A polycarbonate [3] were added to this list.     

Melting and crystallization of poly(butylene terephthalate) by temperature‐modulated and superfast calorimetry

Quantitative temperature‐modulated differential scanning calorimetry (TMDSC) and superfast thin‐film chip calorimetry (SFCC) are applied to poly(butylene terephthalate)s (PBT) of different thermal histories. The data are compared with those of earlier measured heat capacities of semicrystalline PBT by adiabatic calorimetry and standard DSC. The solid and liquid heat capacities, which were linked to the vibrational and conformational molecular motion, serve as references for the quantitative analyses. Using TMDSC, the thermodynamic and kinetic responses are separated between glass and melting temperature. The changes in crystallinity are evaluated, along with the mobile–amorphous and rigid–amorphous fractions with glass transitions centered at 314 and 375 K. The SFCC showed a surprising bimodal change in crystallization rates with temperature, which stretches down to 300 K. The earlier reported thermal activity at about 248 K was followed by SFCC and TMDSC and could be shown to be an irreversible endotherm and is not caused by a glass transition and rigid–amorphous fraction, as assumed earlier. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1364–1377, 2006