Transitions from solid to liquid in isotactic polystyrene studied by thermal analysis and X-ray scattering

A three-phase model, comprising mobile amorphous fraction (MAF), rigid amorphous fraction (RAF) and crystalline fraction (C), has been applied to interpret the thermal transitions and structure of cold-crystallized isotactic polystyrene (iPS) from below the glass transition temperature, T_g, to above the melting point. Quenched amorphous iPS films were isothermally crystallized at different temperatures for 12 h. The fraction of crystalline phase, ?_c, was measured by differential scanning calorimetry (DSC), wide angle X-ray scattering and Fourier Transform infrared spectroscopy. The fraction of the mobile amorphous phase, ?_MAF, was obtained from the heat capacity increment at the glass transition temperature. In the three-phase model, the fraction of the rigid amorphous phase, ?_RAF, was found from 1−?_MAF−?_c. Specific heat capacity measurements by standard DSC confirm that the experimental baseline heat capacity conforms to a three-phase model for temperatures ranging from below T_g, up to the relaxation of RAF. The relaxation of RAF appears as a sigmoidal change in heat capacity accompanied by excess enthalpy, in which solid-like RAF is converted to an identical amount of liquid-like MAF.At temperatures above the relaxation of RAF, either one or two major crystal melting endotherms are observed in standard DSC, dependent upon crystallization temperature. However, using quasi-isothermal temperature modulated DSC, we always observed two reversing melting endotherms. The effects of annealing on iPS structure during the quasi-isothermal measurement were assessed using small angle X-ray scattering (SAXS). Combining the DSC and SAXS results, a model for the melting of iPS lamellae at low heating rates is presented.     

A comparison of crystallization behavior for melt and cold crystallized poly (l-Lactide) using rapid scanning rate calorimetry

A unique rapid scanning rate differential scanning calorimeter is used to examine the differences in melt and cold crystallized poly (l-Lactide) (PLLA), a biodegradable semi-crystalline polymer. After isothermal melt and cold crystallization at various temperatures, both melt and cold crystallized PLLA are characterized by similar melting temperatures (T_m) and exhibit multiple melting behavior on heating at 500 °C/min. However, cold crystallization results in a higher degree of crystallinity (w_c) compared to melt crystallization. While the overall amorphous fraction is higher for melt crystallization, the mobile amorphous fraction (w_a) is found to be higher for cold crystallization. The rigid amorphous fraction (w_raf) in PLLA is determined to be higher for melt crystallization than for cold crystallization at almost all temperatures. The higher values of w_raf also appear to result in higher values of the glass transition temperature (T_g) for melt crystallized samples due to a reduction in mobility of amorphous phase. These dramatic differences depending on whether the material is brought to the crystallization temperature from the melt or the glassy state, could have profound implications for processing and optimizing the properties of PLLA.     

Constraints in semicrystalline polymers: Using quasi-isothermal analysis to investigate the mechanisms of formation and loss of the rigid amorphous fraction

The nanoscale phase behavior of a semicrystalline polymer is important for mechanical, thermal, optical and other macroscopic properties and can be analyzed well by thermal methods. Using quasi-isothermal (QI) heat capacity measurements, we investigate the formation behavior of the crystalline, mobile amorphous, and rigid amorphous fractions in poly(trimethylene terephthalate), PTT. The crystal and rigid amorphous phases comprise the total solid fraction in PTT at temperatures above T_g, the glass transition temperature of the mobile amorphous fraction. PTT was quasi-isothermally cooled step-wise from the melt which causes its crystalline fraction to be fixed below 451 K. Between the high temperature fulfillment of the T_g step and 451 K, the temperature dependent rigid amorphous fraction (RAF) is completely determined. For PTT, most of the RAF vitrifies between 451 K and T_g step by step during QI cooling after the crystals have formed. The constraints imposed by the crystal surfaces reduce the mobility of the highly entangled polymer chains. We suggest the vitrification of RAF proceeds outward away from the lamellar surfaces in a step by step manner during QI cooling. Upon reheating, devitrification of RAF occurs at a temperature above its previous vitrification temperature, due to the effects of densification brought by physical aging during the long period of quasi-isothermal treatment. Finally, we consider recent concepts related to jamming, which have been suggested to apply to filled polymer systems, and may also be applicable in describing constraints exerted by crystal lamellae upon the RAF.     

Glass transition behavior and dynamic fragility in polylactides containing mobile and rigid amorphous fractions

The segmental dynamics of polylactide chains covering the T_g − 30 °C to T_g + 30 °C range was studied in absence and presence of a crystalline phase by dynamic mechanical analysis (DMA) using the framework provided by the WLF theory and the Angell's dynamic fragility concept. An appropriate selection of stereoisomers combined with a thermal conditioning strategy to promote crystallization (above T_g) or relaxation of chains (below T_g) was revealed as an efficient method to tune the ratio of the rigid and mobile amorphous phases in polylactides. A single bulklike mobile amorphous phase was taken for poly(d,l-lactide) (PDLLA). In turn three phases, comprising a mobile amorphous fraction (MAF, X_MA), a rigid amorphous fraction (RAF, X_RA) and a crystalline fraction (X_c) were determined in poly(l-lactide) (PLLA) by modulated differential scanning calorimetry (MDSC) according to a three-phase model. The analysis of results confirms that crystallinity and RAF not only elevate the T_g and the breadth of the glass transition region but also yields an increase in dynamic fragility parameter (m) which entails the existence of a smaller length-scale of cooperativity of polylactide chains in confined environments. Consequently it is proposed that crystallinity is acting in polymeric systems as a topological constraint that, preventing longer range dynamics, provides a faster segmental dynamics by the temperature dependence of relaxation times according to the strong-fragile scheme.     

The three-phase structure of isotactic poly(1-butene)

A detailed analysis of the three-phase structure of isotactic poly(butene) was conducted by conventional and temperature-modulated calorimetry. The development of the crystalline, mobile amorphous, and rigid amorphous fractions was analyzed as a function of thermal history, upon isothermal and non-isothermal crystallization. It was found that, under the chosen experimental conditions, the amount of rigid amorphous phase (w_RA) in PB-1 ranges from w_RA = 0.14 to 0.23, with higher values formed when the polymer is crystallized at low temperatures or at high cooling rates from the melt. Comparison of total and frequency-dependent reversing heat capacity curves suggested that the rigid amorphous phase of isotactic poly(1-butene) vitrifies after completion of the crystallization process and that its full mobilization takes place at around 50 °C. The exact temperature of complete devitrification is slightly affected by the thermal history of the material. An effort to link the mechanical properties of PB-1 to the three-phase structure was attempted, and a correlation of Young's modulus with the solid fraction at the temperature of analysis, composed of crystalline and rigid amorphous phases, was proposed.     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

Nanostructure of atmospheric and high-pressure crystallized poly(ethylene-2,6-naphthalate). Part II: structure-microhardness correlations

The microhardness of poly(ethylene naphthalene-2,6-dicarboxylate) (PEN), with a detailed characterized nanostructure has been investigated. PEN samples were crystallized from the glassy state at atmospheric pressure and from the melt at high pressure and were characterized using small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). Results show that the degree of crystallinity derived from WAXS, for both atmospheric and high-pressure crystallized PEN, is smaller than that obtained by density and calorimetry. For high-pressure crystallized samples, both, crystallinity and microhardness values are larger than those found for the material crystallized under atmospheric pressure. In the latter case, the hardness values depend on the volume fraction of lamellar stacks within spherulites X_L that depends on the crystallization temperature T_c. For T_c<200 °C, X_L is found to be less than 50%. Thus, for T_c<200 °C a linear relationship between H and T_c is observed provided a sufficiently long crystallization time is used. Results are discussed in terms of the rigid amorphous fraction that appears as a consequence of the molecular mobility restrictions due to the crystal stacks.     

The rigid amorphous fraction of cold-crystallized polyamide 6

The rigid amorphous fraction (RAF) of polyamide 6 ordered/crystallized on heating initially fully amorphous glassy samples has been analyzed. Variation of the maximum annealing temperature allowed generation of partially ordered samples with different amount, perfection and morphology of mesophase or crystals. In samples with low fraction of mesophase between 0 and 20 %, the RAF increases with increasing mesophase fraction to reach a maximum value of 50 %. Further increase of the fraction and perfection of the ordered phase achieved by annealing at high temperature leads to a decrease of the RAF. The ratio between mobile and rigid amorphous fractions increases with increasing crystallinity, suggesting increasing decoupling of crystals and amorphous phase in samples of high crystallinity, and confirming results obtained earlier on poly(ethylene terephthalate) and isotactic polypropylene. The study contains a comparison of the RAF estimated from calorimetric analysis of the heat-capacity increment and dynamic-mechanical analysis of the area of the loss-factor peak on devitrification the mobile amorphous fraction, and a discussion of the effect of the phase composition of cold-ordered/crystallized PA 6 on the stiffness.     

Structure formation in poly(ethylene terephthalate) upon annealing as revealed by microindentation hardness and X-ray scattering

The micromechanical properties (microindentation hardness, H, elastic modulus, E) of poly(ethylene terephthalate) (PET), isothermally crystallized at various temperatures (T_a) from the glassy state are determined to establish correlations with thermal properties and nanostructure. Analysis of melting temperature and crystal thickness derived from the interface distribution function analysis of SAXS data reveals that for T_a<190 °C the occurrence of two lamellar stack populations prevails whereas for samples annealed at T_a>190 °C a population of lamellar stacks with a unimodal thickness distribution emerges. The H and E-values exhibit a tendency to increase with the degree of crystallinity. The results support a correlation E/H∼20 in accordance with other previously reported data. The changes of microhardness with annealing temperature are discussed in terms of the crystallinity and crystalline lamellar thickness variation. Unusually high hardness values obtained for PET samples crystallized at T_a=190 °C are discussed in terms of the role of the rigid amorphous phase which offers for the hardness of amorphous layers constrained between lamellar stacks a value of H_a∼150 MPa. On the other hand, for T_a=240 °C the decreasing H-tendency could be connected with the chemical degradation of the material at high temperature.     

The suppression of strain induced crystallization in PET through sub micron TiO2 particle incorporation

The effects of TiO₂ particles on the crystallization and uniaxial stress-strain behavior of poly(ethyleneterephthalate) (PET) films from amorphous precursors were investigated. The addition of small fraction of sub micron sized TiO₂ particles were found to suppress the mechanical relaxation processes associated with high temperature side of the β relaxation while enhancing the low temperature relaxation. When crystallized from unoriented precursors, TiO₂ particles act as a nucleation agent and enhance the thermally induced crystallization of the PET chains. However, when stretched from the amorphous precursors in rubbery temperature range (T_g<T_p<T_cc), the TiO₂ concentration levels as low as 0.35 wt% was found to reduce the overall stress and retard strain hardening and accompanying stress induced crystallization. As a result, under the same stretching conditions, the films containing TiO₂ were found to possess lower crystallinity and orientation levels. This was attributed to suppression of stress induced crystallization as these particles act to disrupt the formation of crystalline lattice by their physical presence. This may be as a result of the reduction of chain entanglements in the presence of these sub micron sized TiO₂ particles in the structure of the polymers that retard the formation of physical network whose nodes are made up of entanglements and small crystalline domains. The development of this long range ‘connected’ network is primarily responsible for the rapid upturn in the stresses at the onset of strain hardening observed in stress strain curves.This method represent a unique way to apply ‘anti-nucleating agent’ effect to control the development of stress induced crystallization that will help control the film and fiber forming processes.     

Dynamic mechanical and dielectric relaxation characteristics of poly(trimethylene terephthalate)

The dynamic mechanical and dielectric relaxation properties of a commercial poly(trimethylene terephthalate) [PTT] have been investigated for both quenched and isothermally melt-crystallized specimen films. The relaxation characteristics of PTT were consistent with those of other low-crystallinity semiflexible polymers, e.g. PET and PEEK. While the sub-glass relaxation was largely unperturbed by the presence of the crystalline phase, both calorimetric and broadband dielectric measurements across the glass transition indicated the existence of a sizeable rigid amorphous phase (RAP) fraction in melt-crystallized PTT owing to the constraining influence of the crystal surfaces over the crystal-amorphous interphase region. A strong increase in measured dielectric relaxation intensity (Δ?) with temperature above T_g indicated the progressive mobilization of the RAP material, as well as an overall loss of correlation amongst the responding dipoles.     

Chain confinement in electrospun nanocomposites: using thermal analysis to investigate polymer-filler interactions

We investigate the interaction of the polymer matrix and filler in electrospun nanofibers using advanced thermal analysis methods. In particular, we study the ability of silicon dioxide nanoparticles to affect the phase structure of poly(ethylene terephthalate), PET. SiO₂ nanoparticles (either unmodified or modified with silane) ranging from 0 to 2.0 wt% in PET were electrospun from hexafluoro-2-propanol solutions. The morphologies of both the electrospun (ES) nanofibers and the SiO₂ powders were observed by scanning and transmission electron microscopy, while the amorphous or crystalline nature of the fibers was determined by real-time wide-angle X-ray scattering. The fractions of the crystal, mobile amorphous, and rigid amorphous phases of the non-woven, nanofibrous composite mats were quantified by using heat capacity measurements. The amount of the immobilized polymer layer, the rigid amorphous fraction, was obtained from the specific reversing heat capacity for both as-spun amorphous fibers and isothermally crystallized fibers. Existence of the rigid amorphous phase in the absence of crystallinity was verified in nanocomposite fibers, and two origins for confinement of the rigid amorphous fraction are proposed. Thermal analysis of electrospun fibers, including quasi-isothermal methods, provides new insights to quantitatively characterize the polymer matrix phase structure and thermal transitions, such as devitrification of the rigid amorphous fraction.     

Study of the thermal behaviour of alipharomatic polyesters around the glass–rubber transition region by thermomechanical analysis: the mobile and rigid amorphous fraction

The objective of this work was the study using thermomechanical analysis (TMA) of a peculiar behaviour, which was observed some years ago, around the glass–rubber transition region in some thermoplastic alipharomatic polyesters. For this purpose a series of nine alipharomatic polyesters was prepared by the two‐stage melt polycondensation method in a glass batch reactor and subjected to TMA in both penetration and expansion mode. Differential scanning calorimetry (DSC) was additionally used and the results are discussed focusing mainly on the first derivative curve of TMA thermograms in the penetration mode. From this curve, which shows two distinct peaks, the first peak could be attributed to the glass transition temperature (T_g) of the mobile amorphous fraction, since the value coincides with that obtained from DSC and is due to the abrupt shrinkage of the amorphous part of the sample. The second peak (up to 40 °C higher than T_g) is due most probably to the softening of the rigid amorphous fraction and the passage of the polymeric sample from the glass region to the cold crystallization region. When the sample is more crystalline than amorphous then the first peak is smaller or is completely absent. Copyright © 2006 Society of Chemical Industry     

Unique orientation of lamellae in film processed poly (phenylene sulfide)

The morphology of poly(phenylene sulfide), PPS, obtained as processed film has been studied using wide angle X-ray scattering (WAXS), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). A unique morphology has been identified in the original film. The spherulites are very small in size and possess a cylindrical symmetry with their lamellae oriented on the edge. In these processed PPS films, the a-axis of the lattice is preferentially aligned perpendicular to the film plane, while the b and c axes are predominantly in the film plane. In the PPS isothermally crystallized from the melted, original film, there is no such preferential orientation. Thermal analysis of the original and melt crystal-lized PPS shows that while the degree of crystallinity is about the same, the nature of the amorphous phase in the two materials is different. In the original film, we did not observe a heat capacity increment at a glass transition temperature by DSC, indicating that all of the amorphous phase belongs to the category of rigid amorphous phase. In the melt crystallized PPS, a distinct glass transition was seen, though only a portion of the amorphous phase becomes mobile at T_g. The differences in orientation and mobility of the amorphous phase in the original film compared to melt crystallized PPS are explained by the different thermal processing procedures used for the two materials.     

Glass transition and the rigid amorphous phase in semicrystalline blends of bacterial polyhydroxybutyrate PHB with low molecular mass atactic R, S-PHB-diol

The glass transition and the crystallinity of blends of isotactic bacterial PHB and low molecular mass atactic R, S-PHB-diols was investigated by means of differential scanning calorimetry (DSC), temperature-modulated DSC and dielectric spectroscopy. It was found that (i) T_g of crystallized blends is much lower than T_g of quenched blends, (ii) the semi-crystalline blends can only be described with a three-phase model. From the experimental results the amount of the oligomer component in the mobile amorphous as well as in the rigid amorphous phase was determined. It could be shown that the low molecular mass atactic R, S-PHB-diol is enriched in the mobile amorphous phase of the semi-crystalline blends, but 5-15% oligomer remains, however, in the rigid amorphous phase.     

A combined differential scanning calorimetry-dynamic mechanical thermal analysis approach for the estimation of constrained phases in thermoplastic polymer nanocomposites

Poly(butylene terephthalate) (PBT) nanocomposites reinforced with different weight fractions of montmorillonite (MMT), and nanoprecipitated calcium carbonate (NPCC) were prepared by a two-step melt compounding method. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses were employed to explore the effect of nanofiller inclusion on the crystalline structure of PBT nanocomposites. The mobile amorphous fraction (MAF) and the rigid amorphous fraction (RAF) were first measured using the specific heat capacity (C_p ) and melting enthalpy data. However, the contributors to total RAF, including interfacial RAF (RAF_int ) and crystalline RAF (RAF_c ), could not be discerned using only DSC. A novel and simple method was hence developed by employing a combined DSC-dynamic mechanical thermal analysis (DMTA) approach (CDDA) to disentangle the RAF components and determine the fractions of constrained volume constituents. To validate the results, the MAF calculated by CDDA were compared to those of DSC. The values obtained using CDDA were relatively higher, owing to the more significant sensitivity of this approach to polymer chain mobility.     

Chain confinement in electrospun nanofibers of PET with carbon nanotubes

Composite nanofibers of poly(ethylene terephthalate), PET, with multiwalled carbon nanotubes (PET/MWCNT) were prepared by the electrospinning method. Confinement, chain conformation, and crystallization of PET electrospun (ES) fibers were analyzed as a function of the weight fraction of MWCNTs. For the first time, we have characterized the rigid amorphous fraction (RAF) in polymer electrospun fibers, with and without MWCNTs. The addition of MWCNTs causes polymer chains in the ES fibers to become more extended, impeding cold crystallization of the fibers, resulting in more confinement of PET chains and an increase in the RAF. The fraction of rigid amorphous chains greatly increased with a small amount of MWCNT loading: with addition of 2% MWCNTs, RAF increased to 0.64, compared to 0.23 in homopolymer PET ES fibers. Spatial constraints also inhibit the folding of polymer chains, resulting in a decrease in crystallinity of PET. For fully amorphous PET/MWCNT composites, MWCNTs do not affect the chain conformation of PET in the ES fibers. For cold crystallized PET/MWCNT composite nanofibers, more trans conformers were formed with the addition of MWCNTs. The increase of RAF (chain confinement) is associated with an increase of the concentration of the trans conformers in the amorphous region as the MWCNT concentration increases in the semicrystalline nanofibers.     

Isothermal crystallization and chain mobility of poly(L-lactide)

Isothermal melt crystallization of poly(L-lactide) (PLLA) has been studied in the temperature range of 90 to 135°C. A maximum in crystallization kinetic was observed around 105°C. A transition from regime II to regime III is present around 115°C. The crystal morphology is a function of the degree of undercooling. At crystallization temperatures (T_c) below 105°C, further crystallization occurs upon heating; this behavior is not detected for T_c above 110°C. The analysis of the heat capacity increment at glass transition temperature (T_g) and of dielectric properties of PLLA indicates the presence of a fraction of the amorphous phase which does not relax at the T_g, and the amount of this so-called rigid amorphous phase is a function of T_c. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 911–919, 1997     

Thermal and structural properties of blends of isotactic with atactic polystyrene

Blends of isotactic polystyrene (iPS) with non-crystallizable atactic polystyrene (aPS) were studied by differential scanning calorimetry and small angle X-ray scattering. The iPS/aPS blends, prepared by solution casting, were found to be miscible in the melt over the entire composition range. Both quenched amorphous and semicrystalline blends exhibit a single, composition-dependent glass transition temperature, depressed from that of either of the homopolymer components. Addition of aPS causes a decrease in crystallinity and in the rigid amorphous fraction, and suppression of the reorganization/recrystallization of iPS during thermal scanning: only one melting peak is observed for blends with larger aPS content. Formation and devitrification of the rigid amorphous fraction of iPS are also affected by aPS addition. The annealing peak, which is due to the relaxation of rigid amorphous fraction in parallel with melting of a tiny amount of crystals, is retarded with an increase of the composition of aPS, resulting in the slow devitrification of RAF in parallel with the melting of large amount of crystals. X-ray scattering shows that the long period in the iPS/aPS blends is greater than in the iPS homopolymer, and long period increases slightly as aPS content increases. Comparison of the volume fraction of phase 1 with the volume fraction crystallinity from DSC suggests that more and more amorphous phase is rejected outside the lamellar stacks as aPS content increases. The effect of aPS addition is to reduce the confinement of the amorphous phase chains. The cooperativity length, ξ_A, which is calculated from thermal analysis of the T_g region, increases with aPS addition. The interlamellar and extra-lamellar amorphous chains both contribute to the glass transition relaxation process.     

Thermal properties relevant to the processing of PET fibers

The thermal properties of poly(ethylene terephthalate) (PET) conventional fibers and microfibers are measured and compared to bulk samples. It is shown that the glass transition temperature (T_g) of the fibers can be monitored with modulated differential scanning calorimetry (MDSC). The T_g region is about 30°C wide and shifted to approximately 110°C for conventional as well as for micro‐PET fibers. The T_g of these fibers is compared to the T_g of cold‐crystallized bulk samples. Upon crystallization, a shift and even a split up of T_g is observed. The second T_g is much broader and is situated around 90°C. This T_g is related to the appearance of a rigid amorphous phase. In comparison, the mobility of the amorphous phase in fibers is even more restricted. The whole multiple melting profile observed on the fibers is the result of a continuous melting and recrystallization process, in contrast to bulk PET. The heat‐set temperature is shown to trigger the start of melting and recrystallization. It is seen in the MDSC as an exotherm in the nonreversing signal and an excess contribution in the heat‐capacity signal. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3840–3849, 2003