(Stress at Break)/(Shore A) Balance in Propylene/Ethylene Elastomers

Propylene/ethylene elastomers with ethylene content in the range 10–20 wt % are known to exhibit elastomeric properties when ethylene is randomly distributed along the polypropylene chains: this condition favors the formation of small crystallites during solidification from the melt and mechanical straining. These small crystals act as physical crosslinks for the rest of the amorphous chains and promote elastomeric behavior. Based upon these concepts a mathematical relationship between stress-at-break and Shore A hardness, was developed in the form of an S-shaped curve and validated with a series of polymers containing different amounts of ethylene. These polymers were produced with both Ziegler-Natta (at 100°C) and metallocene catalysis. It was seen that the catalysis type has a marginal influence on elastomer performances. There is a slightly better balance between Shore A and stress-at-break at low ethylene contents for the metallocene elastomers whereas the Ziegler-Natta catalysis results in elastomers with better thermal properties. Addition of PP homopolymer worsens the balance between Shore A and stress-at-break; the same happens following the addition of inorganic filler. In contrast, the addition of a low-molecular-weight paraffinic hydrocarbon promotes softer elastomers with the same stress-at-break/Shore A balances of the parent elastomers.     

Small-angle X-Ray scattering from polyurethane elastomers

Small-angle X-ray scattering is shown to be an effective technique, complementary to mechanical and thermal methods, for the study of structural ordering in polyurethane elastomers. Wide variations in intensity were found for different sample compositions and are interpreted in terms of the degree of hard segment aggregation. The results support previous conclusions regarding the organization in these samples based on analysis by scanning thermal methods. The polyether polyurethanes studied showed a higher degree of organization than the equivalent polyesters, and longer urethane segments enhance the extent of domain structure. Studies of the temperature dependence of scattering strengthen the previous assignment of a transition at about 150°C to the disordering of domain structure.     

Fluorescence Chemosensor for Determination of Carbon Dioxide and Its Application for Biodegradation Analysis of Polymers

A novel fluorescence sensor has been developed and applied for the determination of carbon dioxide released from the biodegradation of polymer materials and for the evaluation of the biodegradability of polymers. The proposed analytical method is based on the extraordinarily quenching effect of carbonate on fluorescence signal of N,N-diphenylthiourea system. Under the optimized experimental conditions, the fluorescence quenching system performed satisfactorily in a linear detection concentration ranging from 2.00 × 10^?4 to 9.00 × 10^?3 mol L^?1 of carbonate. The detection limit is 8.33 × 10^?5 mol L^?1 for carbonate. This proposed fluorescence system for the selective sensing of carbonate has been successfully applied to determine the biodegradability of polybutylene succinate and related polymers under controlled composting environment with devices assembled in our laboratory. The results exhibited that the biodegradation rate and final biodegradation percentage of biodegradable thermoplastic poly(ester urethane) elastomers, which embodies the block copolymer of poly(butylene succinate) with poly(diethylene glycol succinate), were correlated to the amount of poly(diethylene glycol succinate). In addition, the maximum biodegradation percentage of the testing polymers has reached 45.01%. This research demonstrates the development of chemosensors for rapid, selective, and sensitive detection of carbon dioxide is important and significant for both environmental and biological science.     

Phase transitions and soft elasticity of smectic elastomers

Smectic-C elastomers can be prepared by cross-linking, e.g., liquid crystal polymers, in the smectic-A phase followed by a cooling through the smectic-A to smectic-C phase transition. This transition from D(infinityh) to C(2h) symmetry spontaneously breaks rotational symmetry in the smectic plane as does the transition from a smectic-A to a biaxial smectic phase with D(2h) symmetry. We study these transitions and the emergent elasticity of the smectic-C and biaxial phases in three related models and show that these phases exhibit soft elasticity analogous to that of nematic elastomers.     

Mechanisms of reversible thermal deformation of oriented polymers

Reversible thermal deformation coefficients (TDCs) of oriented samples of a flexible-chain polymer (polyethylene) and of a number of rigid-chain polymers were measured in the longitudinal and transverse directions near room temperature. The same samples were used to measure the TDCs of crystallites by x-ray diffraction. The magnitudes of the TDCs of macroscopic oriented samples and of constituting crystallites and the characteristics of the thermal deformation of flexible-chain and rigid-chain polymers are compared. A conclusion is made that the mechanisms that determine thermal deformation in the longitudinal and transverse directions for the flexible-chain and rigid-chain polymers are different.     

Characterization of commercial polybutylenes. part II. Crystallinity and tensile properties

A series of previously characterized polybutylenes were compression molded using various cooling conditions. Crystallinity decreased as cooling rate increased. The samples exhibited three types of tensile behavior. The crystallinity of samples containing around 5% ethylene was about 40%. These behaved as elastomers, exhibiting typical entropic elasticity. For the remaining samples, crystallinities between 55% and 70% were observed, depending on grade, and more particularly on cooling conditions. For these, lower crystallinity levels favor sample necking and stress-induced orientation, producing high elongation at break and high tensile strength values, while the higher crystallinity samples show high moduli and elasticity values coupled with uniform deformation. In the former case, significant crystalline deformation—causing alignment of the c axes of the crystallites towards the stretching direction, and thereby reinforcing the sample—is responsible for the high elongations and tensile strength encountered. In the higher-crystallinity case much of the deformation is taken up by interlamellar void generation, with little or no c-axis alignment, this elastic mechanism having been termed “hard elasticity.”     

Activation Energy for the Glass Transition of a Confined Elastomer in HDPE/PP Blends

Blends of two highly crystalline polymers containing an elastomer were prepared to study the glass transition of the confined elastomer. The polymers chosen were high density poly ethylene (HDPE), polypropylene (PP), and two elastomers of a different nature: natural number (NR) and EPDM. The dynamic mechanical analyzer (DMA) technique was used to analyze the storage modulus of blends with elastomer content from 0% to 30% by weight, with the remainder made up of equal amounts of HDPE and PP, and blends with 10% of the elastomer, but varied ratios of polyolefins. We used the differentiation modification of the Arrhenius method in the kinetic analysis assuming an n‐order relaxation mechanism, which allowed detecting the percolation threshold of NR. Results indicate that both temperature and activation energy for glass transition (T _g ) are dependent on the types of polymers in the blend and blend composition. The T _g and E values of the unblended elastomers are higher than those in blends; this behavior is associated with the elastomer confinement and blend morphology.     

DYNAMICS IN POLY(OXYMETHYLENE) AND POLY(OXYMETHYLENE-CO-OXYETHYLENE) AS STUDIED VIA A COMBINED CREEP RATE SPECTROSCOPY/DIFFERENTIAL SCANNING CALORIMETRY APPROACH

The peculiarities and kinetics of segmental dynamics in a few semi-crystalline poly(oxymethylene) (POM) samples and in poly(oxymethylene-co-oxyethylene) with 1.5% ethylene oxide units were studied over the temperature range from 110 to 430K. Differential scanning calorimetry (DSC) and laser-interferometric creep rate spectroscopy (CRS) were used. The latter was operated under uniaxial tension or compression. A number of dynamic anomalies were observed. These included a suppressed glass transition (T _g) with its transformation into segmental relaxations below and above T _g, and a pronounced dynamic heterogeneity, with the dispersion of activation energies of segmental motion ranging from 60 to 500 kJ mol^?1. Formation of anomalous long folds in POM and the copolymer structure is assumed from DSC data, indicating a predominant contribution of “straightened out” tie chains to the structure of disordered regions in these isotropic polymers. Discrete high-resolution CRS analysis showed that numerous peaks (separate types of segmental motion) constituted dynamics in the interlamellar layers of the polymers under study. Considerable influence of comonomer or small additives, or preliminary treatments (quenching, small pre-straining) on discrete CR spectra was observed and are discussed in the text. All the anomalies observed could be treated in terms of the concept of the common segmental nature of α and β relaxations in flexible-chain polymers; as the breakdown of intermolecular motional cooperativity due to nanoscale confinement effect, and as a different constraining influence of crystallites on dynamics in the intercrystalline layers.     

Size effects on the structure and phase transition behavior of baddeleyite TiO2

High-pressure structural transitions in nanocrystalline systems are of significant interest as models of first-order phase transitions. We demonstrate size-induced lattice expansion and significant atomic rearrangements in the crystal structure of nanocrystalline high-pressure baddeleyite-TiO₂. The α-PbO₂ structured TiO₂ recovered after dozens of pressure cycles in the α-PbO₂-baddeleyite pressure field displayed elongate 25-35 nm crystallites, compared to starting 34-nm anatase crystallites, suggesting crystallite coherency across anatase, baddeleyite, and α-PbO₂ structures and ‘single structural domain’ behavior of the nanocrystalline system.     

Enthalpy relaxation of polymers: comparing the predictive power of two configurational entropy models extending the AGV approach

The Tool-Narayanaswamy-Moynihan (TNM) phenomenological model is widely accepted in order to describe the structural relaxation of glasses. However several quantitative discrepancies can be found in the literature that cannot be entirely ascribed to the experimental errors. In this work we compare the predictive power of two recently proposed configurational entropy approaches extending the TNM formalism. Both of them change the treatment of non linearity by adding a free parameter. We use Differential Scanning Calorimetry (DSC) experiments in order to test the models in two different polymers. One of them is a commercial PMMA sample, the other is a side chain liquid crystal azo-benzene polymer properly synthesized for optical nanorecording purposes. Different results were found for the two systems. In the PMMA sample only one of the new models was able to improve the agreement between DSC experiments and theory with respect to the TNM model, whereas in the second polymer both the approaches were able to describe the experiments better than TNM model.Received: 25 February 2004, Published online: 21 October 2004PACS: 64.70.Pf Glass transitions - 61.43.Fs Glasses - 61.41. + e Polymers, elastomers, and plastics     

Exploring the melting of a semirigid-chain polymer with temperature-resolved small-angle <Emphasis Type="Italic">X</Emphasis>-ray scattering

The thermal behavior of semirigid semicrystalline polymers differs significantly from that of flexible-chain polymers. The origin of the differences is believed to lie in the higher energy expenditure associated with the formation of adjacent re-entry folds at the crystalline surface in the case of semirigid chains. The effect of constraints imposed by the interlamellar amorphous regions on the neighboring crystals was studied with temperature-resolved synchrotron radiation small-angle X-ray scattering (SAXS). The analysis of SAXS patterns with a generalized paracrystalline lamellar stack model indicates that melting of a semirigid-chain polymer is not a random process but that the crystals grown in the smallest amorphous gaps melt first. This suggests that the hitherto largely neglected geometrical confinement effects may play an important role in determining the thermodynamic stability of semirigid-chain polymer crystals.Received: 5 March 2004, Published online: 4 May 2004PACS: 61.41. + e Polymers, elastomers, and plastics - 64.70.Dv Solid-liquid transitions - 81.10.Aj Theory and models of crystal growth; physics of crystal growth, crystal morphology and orientation     

Deformation of cholesteric elastomers by uniaxial stress along the helix axis

The deformation of cholesteric elastomers by mechanical stress applied parallel to the helix axis is studied by calculation of the free-energy density. The Frank-elasticity contribution is taken into account. A chiral solvent, present at cross-linking time, is in general considered to be replaced after cross-linking by a solvent with different chirality. Two special cases considered are zero and unchanged solvent chirality, the first known as that of imprinted cholesteric elastomers, the latter equivalent to intrinsic cholesteric elastomers with chemically attached chiral groups. Depending on material parameters and imposed strain, the director can show a tilt towards the helix axis up to the maximum tilt, corresponding to a nematic state. In case of intrinsic elastomers with low conformation anisotropy, direct transitions from untilted to nematic states can be induced by straining. The helix structure of the director field is coarsened with an average wave number different to that of the information inscribed in the network at cross-linking time, if this lowers the average free-energy density. Switching between different states can be achieved with electric fields of reasonable values applied parallel to the helix axis. Spectra of the reflection of polarized light are calculated.     

X-ray investigations concerning the physical structure of crosslinking in urethane elastomers. III. Common structure principles for extensions with aliphatic diamines and diols

Physical crosslinking of urethane elastomers is essentially based on statistical systems of hydrogen bonds within the hard segment domains. Two dimensional models of these systems, given in previous papers, are now replaced by three-dimensional models in the case of butane diol and pentane diol extenders, respectively. A suggestion is made for the transverse crosslinking mechanism with diamine extenders. Taking into account the conditions for three-dimensional hydrogen bonded systems a correlation between the cross-linking structure and heat-distortion temperature of diamine and diol extended elastomers is obtained.     

Weiterer Beitrag zum Kristallisationsprozeß von Selen

In continuation to previous work by the authors, use was made of X-rays and polarised light to determine the nature of the crystallites formed from thin films of amorphous selenium when heated. It is concluded that two distinct types of crystallites are formed on a mica base viz. smooth crystallites with or without spiral cracks and also rosette-shaped crystallites. The formation of two types are probably due to the distribution of K-ions that are part of the lattice of the mica and are situated on its surface.     

FTIR研究热处理对RIM PUU的形态及力学性能的影响

将PUU(聚氨酯脲)样品薄膜放入FTIR恒温池内进行原位扫描。FTIR红外谱图的结果表明,在一定温度下,随着热处理时间的延长,氢键化的脲键的吸收逐渐增加,达到一定时间后,吸收变化甚微。在热处理过程中,有序氢键化脲键基团吸收的变化率(反映微相分离动力学)随着温度的提高而增加。PUU材料在热处理之前,羰基振动区内游离的氨酯键、无序氢键化的氨酯键、有序氢键化氨酯键、无序的氢键化脲键和有序的氢键化脲键等多种羰基并存,热处理后仅存游离的氨酯键、氢键化的氨酯键及有序的脲键3种吸收谱带。在100℃下,热处理时间(超过8h)越长,力学性能越差。而在相同的热处理时间(8h)内,热处理温度在100℃,PUU弹性体具有较好的综合力学性能。     

Characterization,spectroscopic investigation of defects by positron annihilation,and possible application of synthesized PbO nanoparticles

Nanocrystalline samples of highly pure lead oxide were prepared by the sol-gel route of synthesis.X-ray diffraction and transmission electron microscopic techniques confirmed the nanocrystallinity of the samples,and the average sizes of the crystallites were found within 20 nm to 35 nm.The nanocrystallites exhibited specific anomalous properties,among which a prominent one is the increased lattice parameters and unit cell volumes.The optical band gaps also increased when the nanocrystallites became smaller in size.The latter aspect is attributable to the onset of quantum confinement effects,as seen in a few other metal oxide nanoparticles.Positron annihilation was employed to study the vacancy type defects,which were abundant in the samples and played crucial roles in modulating their properties.The defect concentrations were significantly larger in the samples of smaller crystallite sizes.The results suggested the feasibility of tailoring the properties of lead oxide nanocrystallites for technological applications,such as using lead oxide nanoparticles in batteries for better performance in discharge rate and resistance.It also provided the physical insight into the structural build-up process when crystallites were formed with a finite number of atoms,whose distributions were governed by the site stabilization energy.     

Relaxation processes and structural transitions in stretched films of polyvinylidene fluoride and its copolymer with hexafluoropropylene

Relaxation processes and structural transitions in nonstretched and uniaxially stretched films of poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) and its homopolymer polyvinylidene fluoride (PVDF) for comparison were investigated with the aim of understanding the electromechanical properties of this lower-modulus ferroelectric copolymer. The mechanical and the dielectric response at the glass transition (?? _a relaxation) exhibit similar temperature dependence of the relaxation time, whereas mechanical and dielectric processes above the glass transition are not related. They represent a continuous softening process within the amorphous phase and the dielectric ?? _c relaxation, respectively. The latter is attributed to conformational changes of VDF segments in lamellae of spherulites constituting the nonpolar crystalline ?? phase. Furthermore, there is a contribution from melting of secondary crystallites formed in the amorphous phase during annealing or storage. Mechanically, this transition appears in nonstretched and stretched films as an accelerated decrease of the elastic modulus that terminates the rubber plateau. Dielectrically, this transition becomes visible as a frequency-independent loss peak only in stretched films, because stretching removes the ?? _c relaxation, which superimposes the transition in nonstretched films. Melting of secondary crystallites is shown to appear in the homopolymer, too, though less pronounced because of more complete primary crystallisation. Stretching increases the modulus above the glass transition only slightly, and it does not significantly influence the softening process. On the other hand, stretching causes a spontaneous polarisation and introduces order within the amorphous phase, rendering it more polar. Melting of secondary crystallites provides an additional contribution to the polarisation. These findings may explain the relatively high electromechanical activity of P(VDF-HFP) but also its relatively low thermal stability. Moreover, they may be important for correct procedure and analysis of temperature-dependent dielectric measurements on partially crystalline polymers, in particular on those with less favourable sterical conditions for primary crystallisation.     

On the behaviour of supercooled liquids and polymers in nano-confinement

ABSTRACT

Size effects play an important role in structural phase transitions, melting transitions, in martensitic materials, glass transitions, etc. Very often the question arises, whether a measured size effect originates from the geometrical confinement itself, or if it appears due to the interaction with the limiting surface. Using dynamic mechanical analysis (DMA) technique we have studied various microphase segregated polymers, molecular glass forming liquids and supercooled water confined in nanoporous silica as well as in biological tissues. Here we show on some selected examples that DMA measurements can be used to study relaxation processes in detail and to disentangle in favourable cases pure pore size effects from effects that are induced by the confining surface.     

Theory of radiative and nonradiative transitions for semiconductor nanocrystals

Existing calculations on the radiative and nonradiative transitions in semiconductor crystallites are reviewed with particular emphasis on indirect band-gap materials like silicon for which the quantum confinement effects are more spectacular. It is shown that the crystallite gaps and radiative recombination rates can be predicted with fair accuracy. Effects related to atomic relaxation in the excited state (Stokes shift) are calculated and it is shown that small enough crystallites lead to self-trapped excitons which provide another source of luminescence, much less dependent on size effects. Nonradiative processes are then examined: intrinsic, due to Auger recombination, and extrinsic, due to dangling bond surface states. Both are found to play an essential role in the interpretation of experimental data. Finally, dielectric screening is studied, justifying the use of a reduced internal dielectric constant and providing an estimate of the Coulomb shift due to charging effects.