Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

Dynamics of Glass Forming Liquids with Randomly Pinned Particles

It is frequently assumed that in the limit of vanishing cooling rate, the glass transition phenomenon becomes a thermodynamic transition at a temperature T-K. However, with any finite cooling rate, the system falls out of equilibrium at temperatures near T-g(> T-K), implying that the very existence of the putative thermodynamic phase transition at T-K can be questioned. Recent studies of systems with randomly pinned particles have hinted that the thermodynamic glass transition may be observed for liquids with randomly pinned particles. This expectation is based on the results of approximate calculations that suggest that the thermodynamic glass transition temperature increases with increasing concentration of pinned particles and it may be possible to equilibrate the system at temperatures near the increased transition temperature. We test the validity of this prediction through extensive molecular dynamics simulations of two model glass-forming liquids in the presence of random pinning. We find that extrapolated thermodynamic transition temperature T-K does not show any sign of increasing with increasing pinning concentration. The main effect of pinning is found to be a rapid decrease in the kinetic fragility of the system with increasing pin concentration. Implications of these observations for current theories of the glass transition are discussed.

Length scales in glass-forming liquids and related systems: a review

The central problem in the study of glass-forming liquids and other glassy systems is the understanding of the complex structural relaxation and rapid growth of relaxation times seen on approaching the glass transition. A central conceptual question is whether one can identify one or more growing length scale(s) associated with this behavior. Given the diversity of molecular glass-formers and a vast body of experimental, computational and theoretical work addressing glassy behavior, a number of ideas and observations pertaining to growing length scales have been presented over the past few decades, but there is as yet no consensus view on this question. In this review, we will summarize the salient results and the state of our understanding of length scales associated with dynamical slow down. After a review of slow dynamics and the glass transition, pertinent theories of the glass transition will be summarized and a survey of ideas relating to length scales in glassy systems will be presented. A number of studies have focused on the emergence of preferred packing arrangements and discussed their role in glassy dynamics. More recently, a central object of attention has been the study of spatially correlated, heterogeneous dynamics and the associated length scale, studied in computer simulations and theoretical analysis such as inhomogeneous mode coupling theory. A number of static length scales have been proposed and studied recently, such as the mosaic length scale discussed in the random first-order transition theory and the related point-to-set correlation length. We will discuss these, elaborating on key results, along with a critical appraisal of the state of the art. Finally we will discuss length scales in driven soft matter, granular fluids and amorphous solids, and give a brief description of length scales in aging systems. Possible relations of these length scales with those in glass-forming liquids will be discussed.

Two-Phase Metallic Thermal Interface Materials Processed Through Liquid Phase Sintering Followed by Accumulative Roll Bonding

Thermal interface materials (TIMs) form a mechanical and thermal link between a heat source and a heat sink. Thus, they should have high thermal conductivity and high compliance to efficiently transfer heat and accommodate any differential strain between the heat source and the sink, respectively. This paper reports on the processing and the characterization of potential metallic TIM composite solders comprising of Cu, a high conductivity phase, uniformly embedded in In matrix, a highly compliant phase. We propose the fabrication of such a material by a two-step fabrication technique comprising of liquid phase sintering (LPS) followed by accumulative roll bonding (ARB). To demonstrate the efficacy of the employed two-step processing technique, an In-40 vol. % Cu composite solder was produced first using LPS with short sintering periods (30 or 60 s at 160 degrees C) followed by ARB up to five passes, each pass imposing a strain of 50%. Mechanical response and electrical and thermal conductivities of the fabricated samples were evaluated. It was observed that processing through ARB homogenizes the distribution of Cu in an In matrix, disintegrates the agglomerates of Cu powders, and also significantly increases thermal and electrical conductivities, almost attaining theoretically predicted values, without significantly increasing the flow stress. Furthermore, the processing technique also allows the insertion of desired foreign species, such as reduced graphene oxide, in In-Cu for further enhancing a target property, such as electrical conductivity.

DIFFUSE X-RAY EMISSION FROM STAR-FORMING GALAXIES

We study the diffuse X-ray luminosity (L-X) of star-forming galaxies using two-dimensional axisymmetric hydrodynamical simulations and analytical considerations of supernovae-(SNe-) driven galactic outflows. We find that the mass loading of the outflows, a crucial parameter for determining the X-ray luminosity, is constrained by the availability of gas in the central star-forming region, and a competition between cooling and expansion. We show that the allowed range of the mass loading factor can explain the observed scaling of L-X with star formation rate (SFR) as L-X alpha SFR2 for SFR greater than or similar to 1 M-circle dot yr(-1), and a flatter relation at low SFRs. We also show that the emission from the hot circumgalactic medium (CGM) in the halo of massive galaxies can explain the large scatter in the L-X-SFR relation for low SFRs (less than or similar to few M-circle dot yr(-1)). Our results suggest that galaxies with small SFRs and large diffuse X-ray luminosities are excellent candidates for the detection of the elusive CGM.

Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid

We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.

Short-Time Beta Relaxation in Glass-Forming Liquids Is Cooperative in Nature

Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. Using molecular dynamics simulations for three model glass-forming liquids, we show that the short-time beta relaxation is cooperative in nature. Using finite-size scaling analysis, we extract a growing length scale associated with beta relaxation from the observed dependence of the beta relaxation time on the system size. We find, in qualitative agreement with the prediction of the inhomogeneous mode coupling theory, that the temperature dependence of this length scale is the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time alpha-relaxation regime.