Thermal studies on melting and crystallization of polyamide fibres

Effect of heating rate on melting and crystallization of polyamide fibres has been examined using differential scanning calorimetric (DSC) technique. Peak temperature for melting (T m) and crystallization (T k) get suppressed with the increase in the heating rate which has been explained on the basis of chain orientation. Heat of melting (DeltaH m) and crystallization (DeltaH k) have been measured.DeltaH m vs. T m shows a nonlinear dependence which has been explained on the basis of entropy change. Quantitative difference inDeltaH m andDeltaH k values has been explained on the basis of orientation and degradation of the polymer.

Orientational melting and reorientational motion in a cubane molecular crystal: A molecular simulation study

Detailed molecular simulations are carried out to investigate the effect of temperature on orientational order in cubane molecular crystal. We report a transition from an orientationally ordered to an orientationally disordered plastic crystalline phase in the temperature range 425-450 K. This is similar to the experimentally reported transition at 395 K. The nature of this transition is first order and is associated with a 4.8% increase in unit Cell volume that is comparable to the experimentally reported unit cell volume change of 5.4% (Phys. Rev. Lett. 1997, 78, 4938). An orientational order parameter, eta(T), has been defined in terms of average angle of libration of a molecular 3-fold axis and the orientational melting has been characterized by using eta(T). The orientational melting is associated with an anomaly in specific heat at constant pressure (C-p) and compressibility (kappa). The enthalpy of transition and entropy of transition associated with this orientational melting are 20.8 J mol(-1) and 0.046 J mol(-1) K-1, respectively. The structure of crystalline as well as plastic crystalline phases is characterized by using various radial distribution functions and orientational distribution functions. The coefficient of thermal expansion of the plastic crystalline phase is more than twice that of the crystalline phase.

Melting and superheating of nanowires-a nanotube approach

We have investigated the size-dependent melting of nanotubes based on a thermodynamic approach and shown that the melting temperature of nanotubes depends on the outer radius and on the inner radius through the thickness of the nanotubes. Size-dependent melting of nanowires and thin films has been derived from that of nanotubes. We validate the size-dependent melting of nanotubes, nanowires and thin films by comparing the results with available molecular dynamic simulations and experimental results. It has also been inferred that superheating occurs when the melting starts from the inner surface and proceeds towards the outer surface, while melting point depression occurs when the melting starts from the outer surface and proceeds towards the inner surface.

Electron-beam melting and centrifugal splat-quenching technique for rapid solidification of titanium alloys

An electron-beam melting and centrifugal splat-quenching technique for the production of microflakes of Ti-6A1-4V (wt%) alloy quenched at an average cooling rate of about 105 K sec–1 is described. The effect of substrate angle on the shape, size, microstructure and average cooling rate of the flakes of major sieve fractions is discussed. Morphologies of particles of minor sieve fractions are dealt with briefly.

Antarctic ice shelf melting and its impact on the global sea ice-ocean system

Earth s ice shelves are mainly located in Antarctica. They cover about 44% of the Antarctic coastline and are a salient feature of the continent. Antarctic ice shelf melting (AISM) removes heat from and inputs freshwater into the adjacent Southern Ocean. Although playing an important role in the global climate, AISM is one of the most important components currently absent in the IPCC climate model. In this study, AISM is introduced into a global sea ice-ocean climate model ORCA2-LIM, following the approach of Beckmann and Goosse (2003; BG03) for the thermodynamic interaction between the ice shelf and ocean. This forms the model ORCA2-LIM-ISP (ISP: ice shelf parameterization), in which not only all the major Antarctic ice shelves but also a number of minor ice shelves are included. Using these two models, ORCA2-LIM and ORCA2-LIM-ISP, the impact of addition of AISM and increasing AISM have been investigated. Using the ORCA2-LIM model, numerical experiments are performed to investigate the sensitivity of the polar sea ice cover and the Antarctic Circumpolar Current (ACC) transport through Drake Passage (DP) to the variations of three sea ice parameters, namely the thickness of newly formed ice in leads (h0), the compressive strength of ice (P*), and the turning angle in the oceanic boundary layer beneath sea ice (θ). It is found that the magnitudes of h0 and P* have little impact on the seasonal sea ice extent, but lead to large changes in the seasonal sea ice volume. The variation in turning angle has little impact on the sea ice extent and volume in the Arctic but tends to reduce them in the Antarctica when ignored. The magnitude of P* has the least impact on the DP transport, while the other two parameters have much larger influences. Numerical results from ORCA2-LIM and ORCA2-LIM-ISP are analyzed to investigate how the inclusion of AISM affects the representation of the Southern Ocean hydrography. Comparisons with data from the World Ocean Circulation Experiment (WOCE) show that the addition of AISM significantly improves the simulated hydrography. It not only warms and freshens the originally too cold and too saline bottom water (AABW), but also warms and enriches the salinity of the originally too cold and too fresh warm deep water (WDW). Addition of AISM also improves the simulated stratification. The close agreement between the simulation with AISM and the observations suggests that the applied parameterization is an adequate way to include the effect of AISM in a global sea ice-ocean climate model. We also investigate the models capability to represent the sea ice-ocean system in the North Atlantic Ocean and the Arctic regions. Our study shows both models (with and without AISM) can successfully reproduce the main features of the sea ice-ocean system. However, both tend to overestimate the ice flux through the Nares Strait, produce a lower temperature and salinity in the Hudson Bay, Baffin Bay and Davis Strait, and miss the deep convection in the Labrador Sea. These deficiencies are mainly attributed to the artificial enlargement of the Nares Strait in the model. In this study, the impact of increasing AISM on the global sea ice-ocean system is thoroughly investigated. This provides a first idea regarding changes induced by increasing AISM. It is shown that the impact of increasing AISM is global and most significant in the Southern Ocean. There, increasing AISM tends to freshen the surface water, to warm the intermediate and deep waters, and to freshen and warm the bottom water. In addition, increasing AISM also leads to changes in the mixed layer depths (MLD) in the deep convection sites in the Southern Ocean, deepening in the Antarctic continental shelf while shoaling in the ACC region. Furthermore, increasing AISM influences the current system in the Southern Ocean. It tends to weaken the ACC, and strengthen the Antarctic coastal current (ACoC) as well as the Weddell Gyre and the Ross Gyre. In addition to the ocean system, increasing AISM also has a notable impact on the Antarctic sea ice cover. Due to the cooling of seawater, sea ice concentration and thickness generally become higher. In austral winter, noticeable increases in sea ice concentration mainly take place near the ice edge. In regards with sea ice thickness, large increases are mainly found along the coast of the Weddell Sea, the Bellingshausen and Amundsen Seas, and the Ross Sea. The overall thickening of sea ice leads to a larger volume of sea ice in Antarctica. In the North Atlantic, increasing AISM leads to remarkable changes in temperature, salinity and density. The water generally becomes warmer, more saline and denser. The most significant warming occurs in the subsurface layer. In contrast, the maximum salinity increase is found at the surface. In addition, the MLD becomes larger along the Greenland-Scotland-Iceland ridge. Global teleconnections due to AISM are studied. The AISM signal is transported with the surface current: the additional freshwater from AISM tends to enhance the northward spreading of the surface water. As a result, more warm and saline water is transported from the tropical region to the North Atlantic Ocean, resulting in warming and salt enrichment there. It would take about 30 40 years to establish a systematic noticeable change in temperature, salinity and MLD in the North Atlantic Ocean according to this study. The changes in hydrography due to increasing AISM are compared with observations. Consistency suggests that increasing AISM is highly likely a major contributor to the recent observed changes in the Southern Ocean. In addition, the AISM might contribute to the salinity contrast between the North Atlantic and North Pacific, which is important for the global thermohaline circulation.

Investigations on the melting and bending modulus of polymer grafted bilayers using dissipative particle dynamics

Understanding the influence of polymer grafted bilayers on the physicomechanical properties of lipid membranes is important while developing liposomal based drug delivery systems. The melting characteristics and bending moduli of polymer grafted bilayers are investigated using dissipative particle dynamics simulations as a function of the amount of grafted polymer and lipid tail length. Simulations are carried out using a modified Andersen barostat, whereby the membrane is maintained in a tensionless state. For lipids made up of four to six tail beads, the transition from the low temperature L-beta phase to the L-alpha phase is lowered only above a grafting fraction of G(f)=0.12 for polymers made up of 20 beads. Below G(f)=0.12 small changes are observed only for the HT4 bilayer. The bending modulus of the bilayers is obtained as a function of G(f) from a Fourier analysis of the height fluctuations. Using the theory developed by Marsh Biochim. Biophys. Acta 1615, 33 (2003)] for polymer grafted membranes, the contributions to the bending modulus due to changes arising from the grafted polymer and bilayer thinning are partitioned. The contributions to the changes in kappa from bilayer thinning were found to lie within 11% for the lipids with four to six tail beads, increasing to 15% for the lipids containing nine tail beads. The changes in the area stretch modulus were also assessed and were found to have a small influence on the overall contribution from membrane thinning. The increase in the area per head group of the lipids was found to be consistent with the scalings predicted by self-consistent mean field results. (C) 2010 American Institute of Physics.

Role of surface tension driven convection in pulsed - laser melting and solidification

Surface melting by a stationary, pulsed laser has been modelled by the finite element method. The role of the surface tension driven convection is investigated in detail. Numerical results are presented for a triangular laser pulse of durations 10, 50 and 200 ms. Though the magnitude of the velocity is high due to the surface tension forces, the present results indicate that a finite time is required for convection to affect the temperature distribution within the melt pool. The effect of convection is very significant for pulse durations longer than 10 ms.

The melting and solidification of nanoscale Bi particles embedded in a glassy and crystalline matrix

We report the formation of an amorphous phase in nanosized Pi particles embedded in an Al-based glassy alloy matrix. High-resolution electron microscopy (HREM) has been used to show that the particles contain crystalline and amorphous portions. A depression of the melting point by more than 100 K of the crystalline portion of the Pi particles was found by differential scanning calorimetric studies and by in-situ electron microscopy using a heating stage. The same techniques established the absence of an amorphous phase in the particles when the matrix is crystallized. It is shown that the formation of the amorphous phase and the depression of the melting point cannot be explained by the pressure developed by the volume change during solidification in this constrained system.

Analytical solutions for heat transfer during cyclic melting and freezing of a phase change material used in electronic or electrical packaging

In this paper we develop an analytical heat transfer model, which is capable of analyzing cyclic melting and solidification processes of a phase change material used in the context of electronics cooling systems. The model is essentially based on conduction heat transfer, with treatments for convection and radiation embedded inside. The whole solution domain is first divided into two main sub-domains, namely, the melting sub-domain and the solidification sub-domain. Each sub-domain is then analyzed for a number of temporal regimes. Accordingly, analytical solutions for temperature distribution within each subdomain are formulated either using a semi-infinity consideration, or employing a method of quasi-steady state, depending on the applicability. The solution modules are subsequently united, leading to a closed-form solution for the entire problem. The analytical solutions are then compared with experimental and numerical solutions for a benchmark problem quoted in the literature, and excellent agreements can be observed.

Melting and mechanical properties of polymer grafted lipid bilayer membranes

The influence of polymer grafting on the phase behavior and elastic properties of two tail lipid bilayers have been investigated using dissipative particle dynamics simulations. For the range of polymer lengths studied, the L(c) to L(alpha) transition temperature is not significantly affected for grafting fractions, G(f) between 0.16 and 0.25. A decrease in the transition temperature is observed at a relatively high grafting fraction, G(f) = 0.36. At low temperatures, a small increase in the area per head group, a(h), at high G(f) leads to an increase in the chain tilt, inducing order in the bilayer and the solvent. The onset of the phase transition occurs with the nucleation of small patches of thinned membrane which grow and form continuous domains as the temperature increases. This region is the co-existence region between the L(beta)(thick) and the L(alpha)(thin) phases. The simulation results for the membrane area expansion as a function of the grafting density conform extremely well to the scalings predicted by self-consistent mean field theories. We find that the bending modulus shows a small decrease for short polymers (number of beads, N(p) = 10) and low G(f), where the influence of polymer is reduced when compared to the effect of the increased a(h). For longer polymers (N(p) > 15), the bending modulus increases monotonically with increase in grafted polymer. Using the results from mean field theory, we partition the contributions to the bending modulus from the membrane and the polymer and show that the dominant contribution to the increased bending modulus arises from the grafted polymer. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3631940]

Melting and solidification behavior of Pb-Sn embedded alloy nano-particles

Nano-sized bimetallic dispersoids consisting of (Pb) and beta-(Sn) phases of eutectic composition (Pb26.1Sn73.9) embedded in aluminum and Al-Cu-Fe quasicrystalline matrices have been prepared by rapid solidification processing. The two phases, face centered cubic (Pb) and body center tetragonal, beta-(Sn) solid solution co-exist in all the embedded nanoparticles at room temperature. The phases bear crystallographic orientation relationship with the matrix. In situ TEM study has been carried out for the alloy particles to study the melting and the solidification behavior. The detailed microscopic observations indicate formation of a single-phase metastable fcc (Pb) in the nano-particles prior to the melting during heating. Solidification of these particles begins with nucleation of fcc (Pb), which phase separates into fcc (Pb) and beta-(Sn) lamellae in the solid state. In situ X-ray diffraction study is carried out to obtain lattice parameter of metastable fcc (Pb) and thereby an estimate of amount of Sn dissolved in the metastable (Pb) prior to the melting. The results are discussed in terms of a metastable phase diagram between fcc Pb and fcc Sn and invoking the size effect on the metastable phase diagram. The size factor is found to play a critical role in deciding the pathway of phase transformation as well as the extension of solid solubility of Sn in fcc (Pb) in the nano-particles.

Melting and Crystallization of Nd60Al10Fe20Co10 Bulk Metallic Glass under High Pressure

Crystallization, melting and structural evolution upon crystallization in Nd60Al10Fe20Co10 bulk metallic glass (BMG) are in situ investigated by x-ray diffraction with synchrotron radiation under high pressure. It is found that the crystallization is pressure promoted, while themelting is inhibited. The crystallization and melting process are also changed under high pressure. The features of the crystallization and melting under high pressure are discussed.

The effect of Co-60 gamma-rays on the crystal structure, melting and crystallization behavior of poly(butylene succinate)

The results obtained for poly(butylene succinate) (PBS) after Co-60 gamma-ray irradiation, studied by wide-angle X-ray diffraction (WAXD), differential scanning calorimeter (DSC) and polarizing optical microscopy (POM), revealed that the degree of crystallinity, melting temperature and enthalpy decreased with increasing irradiation dose, but that the crystal structure of PBS did not vary when compared to non-irradiated PBS. By using Scherrer equation, small changes occurred in the crystal sizes of L-020, L-110 and L-111. The spherulitic morphology of PBS was strongly dependent on irradiation dose and changed significantly at higher irradiation dosages. The crystallization kinetics of PBS indicated that the Avrami exponent (n) for irradiated PBS was reduced to 2.3, when compared to non-irradiated PBS (3.3).