Fractionated crystallization and fractionated melting of confined PEO microdomains in PB-b-PEO and PE-b-PEO diblock copolymers

The confined crystallization of poly(ethylene oxide) (PEO) in predominantly spherical microdomains formed by several diblock copolymers was studied and compared. Two polybutadiene-b-poly(ethylene oxide) diblock copolymers were prepared by sequential anionic polymerization (with approximately 90 and 80 wt % polybutadiene (PB)). These were compared to equivalent samples after catalytic hydrogenation that produced double crystalline polyethylene-b-poly(ethylene oxide) diblock copolymers. Both systems are segregated into microdomains as indicated by small-angle X-ray scattering (SAXS) experiments performed in the melt and at lower temperatures. However, the PB-b-PEO systems exhibited a higher degree of order in the melt. A predominantly spherical morphology of PEO in a PB or a PE matrix was observed by both SAXS and transmission electron microscopy, although a possibly mixed morphology (spheres and cylinders) was formed when the PEO composition was close to the cylinder-sphere domain transitional composition as indicated by SAXS. Differential scanning calorimetry experiments showed that a fractionated crystallization process for the PEO occurred in all samples, indicating that the PE cannot nucleate PEO in these diblock copolymers. A novel result was the observation of a subsequent fractionated melting that reflected the crystallization process. Sequential isothermal crystallization experiments allowed us to thermally separate at least three different crystallization and melting peaks for the PEO microdomains. The lowest melting point fraction was the most important in terms of quantity and corresponded to the crystallization of isolated PEO spheres (or cylinders) that were either superficially or homogeneously nucleated. This was confirmed by Avrami index values of approximately 1. The isothermal crystallization results indicate that the PE matrix restricts the crystallization of the covalently bonded PEO to a higher degree compared to PB.

Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

Melt structure and its transformation by sequential crystallization of the two blocks within poly(L-lactide)-block-poly(epsilon-caprolactone) double crystalline diblock copolymers

Sequential crystallization of poly(L-lactide) (PLLA) followed by poly(epsilon-caprolactone) (PCL) in double crystalline PLLA-b-PCL diblock copolymers is studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Three samples with different compositions are studied. The sample with the shortest PLLA block (32 wt.-% PLLA) crystallizes from a homogeneous melt, the other two (with 44 and 60% PLLA) from microphase separated structures. The microphase structure of the melt is changed as PLLA crystallizes at 122 degrees C (a temperature at which the PCL block is molten) forming spherulites regardless of composition, even with 32% PLLA. SAXS indicates that a lamellar structure with a different periodicity than that obtained in the melt forms (for melt segregated samples). Where PCL is the majority block, PCL crystallization at 42 degrees C following PLLA crystallization leads to rearrangement of the lamellar structure, as observed by SAXS, possibly due to local melting at the interphases between domains. POM results showed that PCL crystallizes within previously formed PLLA spherulites. WAXS data indicate that the PLLA unit cell is modified by crystallization of PCL, at least for the two majority PCL samples. The PCL minority sample did not crystallize at 42 degrees C (well below the PCL homopolymer crystallization temperature), pointing to the influence of pre-crystallization of PLLA on PCL crystallization, although it did crystallize at lower temperature. Crystallization kinetics were examined by DSC and WAXS, with good agreement in general. The crystallization rate of PLLA decreased with increase in PCL content in the copolymers. The crystallization rate of PCL decreased with increasing PLLA content. The Avrami exponents were in general depressed for both components in the block copolymers compared to the parent homopolymers. Polarized optical micrographs during isothermal crystalli zation of (a) homo-PLLA, (b) homo-PCL, (c) and (d) block copolymer after 30 min at 122 degrees C and after 15 min at 42 degrees C.

Thermal Fractionation and isothermal crystallization of polyethylene nanocomposites prepared by in situ polymerization

Nanocomposites of high-density polyethylene (HDPE) and carbon nanotubes (CNT) of different geometries (single wall, double wall, and multiwall; SWNT, DWNT, and MWNT) were prepared by in situ polymerization of ethylene on CNT whose surface had been previously treated with a metallocene catalytic system. In this work, we have studied the effects of applying the successive self-nucleation and annealing thermal fractionation technique (SSA) to the nanocomposites and have also determined the influence of composition and type of CNT on the isothermal crystallization behavior of the HDPE. SSA results indicate that all types of CNT induce the formation of a population of thicker lamellar crystals that melt at higher temperatures as compared to the crystals formed in neat HDPE prepared under the same catalytic and polymerization conditions and subjected to the same SSA treatment. Furthermore, the peculiar morphology induced by the CNT on the HDPE matrix allows the resolution of thermal fractionation to be much better. The isothermal crystallization results indicated that the strong nucleation effect caused by CNT reduced the supercooling needed for crystallization. The interaction between the HDPE chains and the surface of the CNT is probably very strong as judged by the results obtained, even though it is only physical in nature. When the total crystallinity achieved during isothermal crystallization is considered as a function of CNT content, it was found that a competition between nucleation and topological confinement could account for the results. At low CNT content the crystallinity increases (because of the nucleating effect of CNT on HDPE), however, at higher CNT content there is a dramatic reduction in crystallinity reflecting the increased confinement experienced by the HDPE chains at the interfaces which are extremely large in these nanocomposites. Another consequence of these strong interactions is the remarkable decrease in Avrami index as CNT content increases. When the Avrami index reduces to I or lower, nucleation dominates the overall kinetics as a consequence of confinement effects. Wide-angle X-ray experiments were performed at a high-energy synchrotron source and demonstrated that no change in the orthorhombic unit cell of HDPE occurred during crystallization with or without CNT.

Crystallization and stereocomplexation behavior of poly(D- and L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) block copolymers

The thermal properties, crystallization, and morphology of amphiphilic poly(D-lactide)-b-poly(N,N-dimethylamino- 2-ethyl methacrylate) (PDLA-b-PDMAEMA) and poly (L-lactide)-b-poly(N,N-dimethylamino-2-ethyl methacrylate) (PLLA-b-PDMAEMA) copolymers were studied and compared to those of the corresponding poly(lactide) homopolymers. Additionally, stereocomplexation of these copolymers was studied. The crystallization kinetics of the PLA blocks was retarded by the presence of the PDMAEMA block. The studied copolymers were found to be miscible in the melt and the glassy state. The Avrami theory was able to predict the entire crystallization range of the PLA isothermal overall crystallization. The melting points of PLDA/PLLA and PLA/PLA-b-PDMAEMA stereocomplexes were higher than those formed by copolymer mixtures. This indicates that the PDMAEMA block is influencing the stability of the stereocomplex structures. For the low molecular weight samples, the stereocomplexes particles exhibited a conventional disk-shape structure and, for high molecular weight samples, the particles displayed unusual star-like shape morphology.

Grain size effect on the warm deformation behaviour of a Ti-IF steel

The effect of grain size on the warm deformation behaviour of a titanium stabilized interstitial free (IF) steel was investigated using hot torsion. The initial work hardening regime is followed by the development of a broad stress peak after which work softening occurs. The hypothetical saturation stress (Estrin–Mecking model) and the stress at final strain were relatively insensitive to grain size. However, the strain to the peak stress was strongly dependent on the grain size at low values of the Zener–Hollomon parameter. A simple phenomenological approach, using a combined Estrin–Mecking model and an Avrami type equation, was used to model the flow curves. The hypothetical saturation stress, the stress at final strain and the strain to peak stress were modelled using three different hyperbolic sine laws. A comparison with independent data from the literature shows that the apparent activation energy of deformation determined in this work (Q=372 kJ/mol) can be used to rationalize the steady-state stress in compression data found in the literature.

Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.

Nonisothermal Crystallization Behavior of Poly(m-xylene adipamide)/Montmorillonite Nanocomposites

This article reports the nonisothermal crystallization behavior of MXD6 and its clay nanocomposite system (MXD6/MMT) using differential scanning calorimetry (DSC). The DSC experimental data were analyzed by theoretical modeling of the crystallization kinetics using the Avrami, Ozawa, Jeziorny, and the combined Avrami―Ozawa semiempirical models. It has been determined that these models adequately described the crystallization behavior of the MXD6 nanocomposite at cooling rates below 20 °C/min, but there was a deviation from linear dependence at higher cooling rates. This was attributed to changes of both the free energy and the cooling crystallization function K(T) over the entire crystallization process, as well as possible relaxation effects leading to structural rearrangements. In addition, the activation energy determined using the differential isoconversional method of Friedman was also found to vary, indicating changes in both the free energy and crystallization mechanism. Despite the lack of a reliable theoretical model, the heterogeneous nucleating activity of the MMT nanoparticles was demonstrated and quantified using Dobreva's method (Φ = 0.71), and the crystallization rate for the nanocomposite system was found to be greater than pure MXD6 by up to 79% at 40 °C/min.

Recrystallization of 304SS during and after high strain rate deformation

During the hot working of austenitic stainless steels the shape of the flow curve is strongly influenced by the strain rate. Low strain rate deformation results in flow curves typical of dynamic recrystallization (DRX) but as the strain rate increases the shape changes to a ‘flat-top’ curve. This has traditionally been thought to indicate no DRX is taking place and that dynamic recovery (DRV) is the only operating softening mechanism. Examining the work-hardening behaviour and corresponding deformation microstructures showed this is not the case for austenitic stainless steel, as clear evidence of dynamic recrystallization process can be seen. The post-deformation recrystallization kinetics can be modelled using a standard Avrami equation with an Avrami exponent, n, of 1.15. With an increasing value of the Zener-Hollomon parameter it was found that the kinetics of recrystallization become less strain rate sensitive until at the highest values (highest strain rates/lowest temperatures) the recrystallization kinetics become strain rate insensitive.

Crystalline Structures and α → β and γ polymorphs transformation induced by nanoclay in PVDF-based nanocomposite

Poly(vinylidene fluoride) (PVDF) nanocomposites were prepared by melt-mixing. The dispersion of clay platelets and rheology of nanocomposites were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and rheometric mechanical spectrometer (RMS). The transformation of α to β and γ phase in PVDF was induced by the addition of nanoclay and subsequently the isothermal crystallization kinetics of neat PVDF and its nanocomposite have been investigated. The interaction between clay nanofillers and PVDF macromolecular chains induced the change of conformation from trans-gauche to all-trans crystal structure in PVDF segment. The isothermal crystallization of PVDF/clay nanocomposites was carried out by Differential Scanning Calorimetry (DSC) technique. The influence of clay platelets on nucleation crystallization rate and Avrami exponent were studied. PVDF/clay nanocomposite showed higher crystallization rate indicating that nanoclay has acted as an effective nucleation agent. This nucleation effect of nanoclay increased the Avrami exponent and decreased the degree of crystallinity. © 2014 World Scientific Publishing Company.

Identify kinetic features of fibers growing, branching, and bundling in microstructure engineering of crystalline fiber network

Fibers growing, branching, and bundling are essential for the development of crystalline fiber networks of molecular gels. In this work, for two typical crystalline fiber networks, i.e. the network of spherulitic domains and the interconnected fibers network, related kinetic information is obtained using dynamic rheological measurements and analysis in terms of the Avrami theory. In combination with microstructure characterizations, we establish the correlation of the Avrami derived kinetic parameter not only with the nucleation nature and growth dimensionality of fibers and branches, but also with the fiber bundles induced by fiber-fiber interactions. Our study highlights the advantage of simple dynamic rheological measurements over other spectroscopic methods used in previous studies for providing more kinetic information on fiber-fiber interactions, enabling the Avrami analyses to extract distinct kinetic features not only for fibers growing and branching, but also for bundling in the creation of strong interconnected fibers networks. This work may be helpful for the implementation of precise kinetic control of crystalline fiber network formations for achieving desirable microstructures and rheological properties for advanced applications of gel materials. This journal is © the Partner Organisations 2014.

Decomposition properties of PVA/graphene composites during melting-crystallization

Abstract The thermal decomposition of PVA and PVA composites during the melting-crystallization process is still unclear due to indistinct changes in chemical compositions. Using graphene as a model, the decomposition properties of PVA and PVA-graphene composites were systematically analyzed under multiple melting-crystallization cycles. And a series of isothermal decomposition experiments around the melting-crystallization temperature were carried out to simulate the corresponding decomposition kinetics. Based on multiple cycle melting-crystallization, the weight loss of PVA and PVA/graphene composites was successfully quantified. Further morphology investigation and chemical structure analysis indicated that the decomposition was non-uniformly distributed, rendering the possibility of crystallization for PVA and PVA/graphene composites after multiple heating-cooling cycles. In addition, isothermal decomposition analysis based on reduced time plot approach and model-free iso-conversional method indicated that Avrami-Eroffev model could well match the decomposition process of the neat PVA and PG-0.3 composite, while the Avrami-Eroffev and first order models could precisely forecast the decomposition of PG-0.9 composite. Both analyses during multiple cycle melting-crystallization and isothermal decomposition demonstrated that graphene served as decomposition accelerator in the whole thermal decomposition process, and particularly the decomposition of neat PVA and PVA/graphene composites was highly related to the band area ratios of C-H and O-H vibrations in Fourier transform infrared (FTIR) spectrum.

Different thermal analysis technique application in determination of fold surface-free energy

In this work, the crystallization rates and spherulitic growth rate of miscible blends of poly(vinylidene fluoride) (PVDF) and acrylic rubber (ACM) were determined using differential scanning calorimetry (DSC), real-time FTIR, and optical microscopy. FTIR results suggest that blending does not induce the creation of polymorphic crystalline forms of PVDF. SAXS data demonstrate the formation of interlamellar structure after blending. The fold surface-free energy (σ e) was analyzed and compared using different thermal analysis techniques. The isothermal crystallization curves obtained using real-time FTIR and DSC explored in two different methods: t 1/2 or Avrami equation. While the Avrami equation is more widespread and precise, both analytical methods gave similar free energy of folding values. However, it was found that the direct optical method of measuring spherulitic growth rate yields σ e values 30-50 % lower than those obtained from the overall crystallization rate data. Conversely, the σ e values were found to increase with increasing amorphous ACM phase content regardless of the analytical methods.

Constitutive analysis of hot deformation behavior of a Ti6Al4V alloy using physical based model

The effect of deformation parameters on the flow behavior of a Ti6Al4V alloy has been studied to understand the deformation mechanisms during hot compression. Cylindrical samples with partially equiaxed grains were deformed in the α+β phase region at different thermo-mechanical conditions. To develop components with tailored properties, the physically based Estrin and Mecking (EM) model for the work hardening/dynamic recovery combined with the Avrami equation for dynamic recrystallization was used to predict the flow stress at varying process conditions. The EM model revealed good predictability up to the peak strain, however, at strain rates below 0.01s^-1, a higher B value was observed due to the reduced density of dislocation tangles. In contrast, the flow softening model revealed higher value of constants a and b at high strain rates due to the reduction in the volume fraction of dynamic recrystallization and larger peak strain. The predicted flow stress using the combined EM+Avrami model revealed good agreement with the measured flow stress resulted in very low average absolute relative error value. The microstructural analysis of the samples suggests the formation of coarse equiaxed grains together with the increased β phase fraction at low strain rate leads to a higher flow softening.

A sincronização de osciladores de Rössler acoplados

Neste trabalho utiliza-se como sistema dinâmico o circuito eletrônico que integra o sistema de equações acopladas de Rossler modificado. Este sistema possui uma nãolinearidade dada por uma função linear por partes e apresenta comportamento caótico para certos valores dos seus parâmetros. Isto e evidenciado pela rota de dobramento de período obtida variando-se um dos parâmetros do sistema. A caracterização experimental da dinâmica do sistema Rossler modificado e realizada através do diagrama de bifurcações. Apresenta-se uma fundamentação teórica de sistemas dinâmicos introduzindo conceitos importantes tais como atratores estranhos, variedades invariantes e tamb em uma análise da estabilidade de comportamentos assintóticos como pontos fixos e ciclos limites. Para uma caracterização métrica do caos, apresenta-se a definção dos expoentes de Lyapunov. São introduzidos também os expoentes de Lyapunov condicionais e transversais, que estão relacionados com a teoria de sincronizção de sistemas caóticos. A partir de uma montagem mestre-escravo, onde dois osciladores de Rossler estão acoplados unidirecionalmente, introduz-se a de nição de sincronização idêntica, sincronização de fase e variedade de sincronização. Demonstra-se a possibilidade de sincronização em uma rede de osciladores caóticos de Rossler, acoplados simetricamente via acoplamento de primeiros vizinhos. A rede composta por seis osciladores mostrou ser adequada pelo fato de apresentar uma rica estrutura espacial e, ao mesmo tempo, ser experimentalmente implementável. Além da sincronização global (osciladores identicamente sincronizados), obtém-se a sincronização parcial, onde parte dos osciladores sincronizam entre si e a outra parte não o faz. Esse tipo de sincronização abre a possibilidade da formação de padrões de sincronização e, portanto, exibe uma rica estrutura de comportamentos dinâmicos. A sincronização parcial e investigada em detalhes e apresentam-se vários resultados. A principal ferramenta utilizada na análise experimental e numérica e a inspeção visual do gráfico yi yj , fazendo todas as combinações entre elementos diferentes (i e j) da rede. Na análise numérica obtém-se como resultado complementar o máximo expoente de Lyapunov transversal, que descreve a estabilidade da variedade de sincronização global.