Effective Interaction Parameter Research Articles

Connecting Dynamics and Thermodynamics in Polymer–Resin Cured Systems

This work connects the calorimetric responses of different rubber–resin blends with varying resin contents with their alpha relaxation dynamics. We used differential scanning calorimetry and broadband dielectric spectroscopy to characterize the calorimetric and dielectric responses of styrene–butadiene, polybutadiene, and polyisoprene with different resin contents. To model the results, we used the Gordon–Taylor equation combined with an extension of the Adam–Gibbs approach. Thus, we propose a simple and effective model that allows us to estimate the blend dynamics from the temperature dependence of the relaxation times of the pure components and the calorimetric measurement of the glass transition temperature of only one blend composition. By estimating an effective interaction parameter from calorimetry, we achieved accurate alpha relaxation dynamics predictions for different resin concentrations. Our highly predictive approach provides a realistic description of the expected dynamics. This study offers valuable insights into the dynamic properties of polymer compounds, paving the way for the fast and effective development of advanced and more sustainable materials.

Prethermalization in coupled one-dimensional quantum gases

We consider the problem of the development of steady states in one-dimensional Bose gas tubes that are weakly coupled to one another through a density-density interaction. We analyze this development through a Boltzmann collision integral approach. We argue that when the leading order of the collision integral, where single particle-hole excitations are created in individual gases, is dominant, the state of the gas evolves first to a non-thermal fixed point, i.e. a prethermalization plateau. This order is dominant when a pair of tubes are inequivalent with, say, different temperatures or different effective interaction parameters, \gammaγ. When both tubes are in the strongly interacting regime we additionally characterize this non-thermal prethermalization plateau by constructing the quasi-conserved quantities that control the existence of this plateau as well as the associated generalized Gibbs ensemble.

Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing.

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor Tv and of the substrate Ts on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting Tv/Ts combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.

Site Occupancy Preference and Magnetic Properties in Nd2(Fe,Co)14B

Partial replacement of Fe by Co is an effective method to increase Curie temperature (TC), which improves the thermal stability of magnetic properties in Nd2Fe14B-based permanent magnets. The correlation between Fe substitution and magnetic properties has been studied in Nd2(Fe,Co)14B via a first-principles calculation. The calculated Fe substitution energies indicate that the Co atoms avoid the 8j2 site, which agrees with the experiments. The Co atoms are ferromagnetically coupled with Fe sublattice and show magnetic moments of about 1.2 to 1.7 μB at different crystallographic sites, less than that of Fe (2.1–2.7 μB), resulting in the decrease in total magnetization at ground state (0 K) with increasing Co content. The effective exchange interaction parameter, derived from the energy difference between varied magnetic structures, increases from 7.8 meV to 17.0 meV with increasing Co content from x = 0 to x = 14 in Nd2Fe14−xCoxB. This change in the effective exchange interaction parameter is responsible for the enhancement of TC in Nd2(Fe,Co)14B. The total magnetization at 300 K, derived from mean-field theory, shows a peak maximum value at x = 1 in Nd2Fe14−xCoxB. The phenomenon results from the interplay between the reduction of the magnetic moment in the Fe(Co) sublattice and the enhancement of TC with increasing Co content.

Effect of cosolvents on the phase separation of polyelectrolyte complexes.

Evidence is shown that cosolvent mixtures control the coacervation of mixtures of oppositely charged polyelectrolytes. Binary and ternary solvent mixtures lead to non-monotonic solubility as a function of the average dielectric constants of the solvent mixtures. These data are rationalized by considering both electrostatic-driven phase separation and solvophobic-driven phase separation using group contribution effects on solubility parameters. These estimates are introduced into an effective Flory-Huggins interaction parameter within the framework of Voorn-Overbeek theory with variable dielectric constants and temperature dependences. Despite its simplicity, the model recovers salient experimental observations not only on their coacervate stabilities, but also on their lower critical solution temperature behaviors. These observations highlight the importance of weak van der Waals interactions in determining the phase behaviors of polyelectrolyte complexes relative to electrostatic correlations.

Renormalized one-loop theory of correlations in disperse polymer blends.

Polymer blends are critical in many commercial products and industrial processes and their phase behavior is therefore of paramount importance. In most circumstances, such blends are formulated with samples of high dispersity, which have generally only been studied at the mean-field level. Here, we extend the renormalized one-loop theory of concentration fluctuations to account for blends of disperse polymers. Analyzing the short and long length-scale fluctuations in a consistent manner, various measures of polymer molecular weight and dispersity arise naturally in the free energy. Thermodynamic analysis in terms of moments of the molecular weight distribution(s) provides exact results for the inverse susceptibility and demonstrates that the theory is not formally renormalizable. However, physically motivated approximations allow for an "effective" renormalization, yielding (1) an effective interaction parameter, χe, which depends directly on the sample dispersities (i.e., Mw/Mn) and leaves the form of the mean-field spinodal unchanged, and (2) an apparent interaction parameter χa that depends on higher-order dispersity indices, for instance Mz/Mw, and characterizes the true limits of blend stability accounting for long-range off-critical fluctuations. We demonstrate the importance of dispersity on several example systems, including both "toy" models that may be realized in computer simulation and more realistic industrially relevant blends. We find that the effects of long-range fluctuations are particularly prominent in blends where the component dispersities are mismatched, especially when there is a small quantity of the high-dispersity species. This can be understood as a consequence of the shift in the critical concentration(s) from the monodisperse value(s).

Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Nuclear Equation of State and many-body phase-space correlations in the Constrained Molecular Dynamics

Many-body correlations characterizing the Constrained Molecular Dynamics (CoMD) are analyzed in the case of finite and zero-range effective microscopic interactions. The study begins by analyzing the case of infinite nuclear matter at zero temperature. A comparison with the predictions in the mean-field (MF) limit corresponding to different effective masses, highlights non-negligible differences regarding the produced Equation of State (EoS). A procedure is illustrated to determine the necessary corrections of the effective interaction parameters in the CoMD model so to reproduce the chosen EoS. The specific model calculations, the general feature of the discussed correlations gives a wider meaning to the resulting differences, which are in fact strongly related both to the Pauli principle constraint and to the localization effects related to wave-packets dynamics. Moving on to finite systems, preliminary results are shown in relation to the reaction mechanisms in the N64i+48Ca system described by the CoMD model. Therefore, the topic covered illustrates the effects produced by the correlations of the CoMD dynamics on the EoS and on some observables commonly studied in heavy ion collisions.

Dissipative particle dynamics simulation for peptoid nanosheet with non-empirical parameter set

Peptoids are biomimetic materials in which the substituent groups are located on the nitrogen atom of the peptide bond, facilitating the formation of nanosheet structures as reported by Mannige et al. [Nature, 526, 415 (2015)]. Dissipative particle dynamics (DPD) simulations were performed to investigate the aggregation stability of peptoids with different unit lengths. The crucial effective interaction parameters were determined by fragment MO (FMO) calculations, which allowed to evaluate different molecular interactions (electrostatic and dispersion) in a balanced way. The experimental observation of the unit length dependence was finally reproduced by this FMO-DPD method.

Thermodynamics of Highly Interacting Blend PCHMA/dPS by TOF-SANS.

We investigate the thermodynamics of a highly interacting blend of poly(cyclohexyl methacrylate)/deuterated poly(styrene) (PCHMA/dPS) with small-angle neutron scattering (SANS). This system is experimentally challenging due to the proximity of the blend phase boundary (>200 °C) and degradation temperatures. To achieve the large wavenumber q-range and flux required for kinetic experiments, we employ a SANS diffractometer in time-of-flight (TOF) mode at a reactor source and ancillary microscopy, calorimetry, and thermal gravimetric analysis. Isothermal SANS data are well described by random-phase approximation (RPA), yielding the second derivative of the free energy of mixing (G″), the effective interaction (χ̅) parameter, and extrapolated spinodal temperatures. Instead of the Cahn-Hilliard-Cook (CHC) framework, temperature (T)-jump experiments within the one-phase region are found to be well described by the RPA at all temperatures away from the glass transition temperature, providing effectively near-equilibrium results. We employ CHC theory to estimate the blend mobility and G″(T) conditions where such an approximation holds. TOF-SANS is then used to precisely resolve G″(T) and χ̅(T) during T-jumps in intervals of a few seconds and overall timescales of a few minutes. PCHMA/dPS emerges as a highly interacting partially miscible blend, with a steep dependence of G″(T) [mol/cm3] = -0.00228 + 1.1821/T [K], which we benchmark against previously reported highly interacting lower critical solution temperature (LCST) polymer blends.

Effective Interaction between Homo- and Heteropolymer Block of Poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) Diblock Copolymers.

We investigated the segregation behavior of a molten diblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate-r-styrene) (PBA-b-P(MMA-r-S)), wherein styrene (S) is incorporated as a comonomer in the second block to modulate the effective interaction between homopolymer and a random copolymer block. The temperature dependence of the effective interaction parameter χeff between n-butyl acrylate (BA) and the average monomer of the MMA-r-S random block was evaluated from small-angle X-ray scattering (SAXS) analysis using the random phase approximation (RPA) approach. The calculated χeff, as a function of the styrene fraction in the random copolymer block, shows a good agreement with the mean-field binary interaction model. This consistency indicates that the effective interaction between component BA and the average monomer of the random copolymer block is smaller than the interactions between pure components (χBA,MMA,χBA,S). The present study suggests that the introduction of a random copolymer block to a block copolymer can effectively reduce the degree of incompatibility of the block copolymer system without altering the constituent species, which may serve as a viable methodology in designing novel thermoplastic elastomers based on triblock or multiblock copolymers.

Crosslink-Induced Conformation Change of Intrinsically Disordered Proteins Have a Nontrivial Effect on Phase Separation Dynamics and Thermodynamics.

Biomolecule condensates formed via liquid-liquid phase separation (LLPS) play crucial roles within various cellular processes. Despite numerous theoretical and experimental discoveries, the general principle by which the protein conformation affects the propensity for LLPS remains poorly understood. Here, we systematically address this issue using a general coarse-grained model of intrinsically disordered proteins (IDPs) with different degrees of intrachain crosslinks. We find that an increased conformation collapse due to higher intrachain crosslink ratio f enhances the thermodynamic stability of protein phase separation and found the critical temperature Tc has a good scaling law with the proteins' average radius of gyration Rg. Such correlation is robust regardless of interaction types and sequence patterns. Strikingly, the growth dynamics of the LLPS process, contrary to the thermodynamic observation, is generally more favored at proteins with extended conformation. Faster condensate growing speed is again observed for higher-f collapsed IDPs, resulting altogether in a nonmonotonic dynamics as a function of f. A phenomenological understanding of the phase behavior is provided by a mean-field model with an effective Flory interaction parameter χ, which is found to have a good scaling law with conformation expansion. Our study shed lights on the general mechanism for understanding and modulation of phase separation with different conformation profiles and may provide new evidence in reconciling the contradictions in thermodynamic- and dynamic-controlled experimental LLPS observations.

THE HALAL PURCHASING STRATEGIES ON MANUFACTURING PERFORMANCE

Abstract 
 Purpose – The purpose of this study is to introduce a new framework to optimize the design of halal purchasing strategies towards the manufacturing industries performance.
 
 Design/methodology/approach – The study utilizes large group of executives and managers in the purchasing and supply chain department from manufacturing firm in Malaysia.
 Findings – The finding shows that the purchasing strategies (effective negotiation, collaborative relationship and interaction, effective cost management, supply base management, and strategic sourcing management) and halal policy (responsibility, scope, assurance, and method of assurance) determine the manufacturing purchasing performance. More empirical research is needed to further refine the Halal Purchasing Strategies for different product–market combinations. Second, conduct qualitative research to various industries.
 
 Research limitations/implications – This research shows that halal purchasing strategies is different from conventional purchasing method, which requires a halal policy and specific design parameters for effective negotiation, collaborative relationship and interaction, effective cost management, supply base management, and strategic sourcing management.
 
 Originality/value – The halal purchasing strategies can be an important instrument to design and manage halal purchasing in extending halal integrity from source to point of consumer purchase. It could be implemented as a practice mediating the impact on manufacturing performance in order to remain competitive in the challenging and competitive business environment.

Multiterminal open quantum dot circuit operating in the fractional quantum Hall regime

We study theoretically a large quantum dot in the fractional quantum Hall regime that is strongly coupled to $\mathcal{M}$ leads via single-mode quantum point contacts. In the case $\mathcal{M}=2$, when the system is mapped onto the two-channel charge Kondo problem, we predict a universal expression for the conductance in the vicinity of a strong-coupling fixed point. The power of the leading temperature correction to the maximal conductance is determined by the fractional filling factor $\ensuremath{\nu}=1/m$. For $\mathcal{M}>2$, we examine the case in which $\mathcal{M}\ensuremath{-}1$ quantum point contacts are fully open, reproducing a single-channel circuit coupled to a dissipative Ohmic environment. The system is treated as a Luttinger liquid with an impurity, whose effective interaction parameter is defined as $K=\ensuremath{\nu}(\mathcal{M}\ensuremath{-}1)/\mathcal{M}$. Conductance scaling in the weak and strong tunnel regimes is used to discuss the low-temperature transport behavior of multichannel single- and double-charge Kondo devices.

Electrostatic Interaction on Liquid–Liquid Phase Separation at Low Salt Fraction Revealed by Scattering Techniques

Past studies on salt-doped polymer blends indicate that the electrostatic effect is complicated due to the combined effects of translational entropy of dissociated ions, ion solvation, ion–ion correlation, and ion clustering, especially at high salt concentrations. It still remains a challenge to unveil the electrostatic interaction of dissociated ions on phase separation explicitly in experiments. To address this challenge, the key principle of this study is to have the salt at extremely low concentrations, while its effect on phase separation is significant enough to be detected by scattering techniques. This experimental design enables the solvation of dissociated ions as the dominating factor, carefully avoiding complications from other effects. We characterize concentration fluctuations at full length scales by small-angle laser light scattering, X-ray scattering, and neutron scattering. The measured cloud points, spinodal temperatures, correlation lengths, and effective interaction parameters exhibit significant increase with the salt fraction, indicating that the electrostatic interaction promotes phase separation. We further reveal the electrostatic interaction of cations and anions, respectively. The asymmetric deflection of the phase diagram is quantitatively explained by the composition-dependent solvation of dissociated ions. This fundamental research provides experimental support for the progress of recent theoretical work and is helpful to guide the structural control in polymer electrolytes.

Accounting for the ultraviolet divergence in field-theoretic simulations of block copolymer melts.

This study examines the ultraviolet (UV) divergence in field-theoretic simulations (FTSs) of block copolymer melts, which causes an unphysical dependence on the grid resolution, Δ, used to represent the fields. Our FTSs use the discrete Gaussian-chain model and a partial saddle-point approximation to enforce incompressibility. Previous work has demonstrated that the UV divergence can be accounted for by defining an effective interaction parameter, χ=z∞χb+c2χb 2+c3χb 3+⋯, in terms of the bare interaction parameter, χb, used in the FTSs, where the coefficients of the expansion are determined by a Morse calibration. However, the need to use different grid resolutions for different ordered phases generally restricts the calibration to the linear approximation, χ ≈ z∞χb, and prevents the calculation of order-order transitions. Here, we resolve these two issues by showing how the nonlinear calibration can be translated between different grids and how the UV divergence can be removed from free energy calculations. By doing so, we confirm previous observations from particle-based simulations. In particular, we show that the free energy closely matches self-consistent field theory (SCFT) predictions, even in the region where fluctuations disorder the periodic morphologies, and similarly, the periods of the ordered phases match SCFT predictions, provided the SCFT is evaluated with the nonlinear χ.

Uncertainty evaluation of peak energy of giant dipole resonance propagated from uncertainty of parameters of effective interaction

We evaluate uncertainty of giant dipole resonance (GDR) peak energy propagated from the uncertainty of effective interaction parameter. The Monte Carlo calculation of microscopic random phase approximation using randomized parameter sets is performed. Under the condition that correlations between the parameters are considered, the calculated GDR peak energy has an uncertainty of ∼1 MeV irrespective of nuclear mass and is strongly correlated with the parameters, in the present calculations. Our result serves as a guide for a new parametrization of effective interaction.

Variation of magnetism by defects and impurities in two-dimensional magnetic materials based on spin spiral method: A case of δ-(Ga, Mn)As

There is still no effective solution of first-principles calculations to the critical question of how defects and impurities affect magnetism, especially when multi-nearest-neighbor magnetic interactions are involved. In this paper, we use the Heisenberg model and the generalized Bloch condition to evaluate the magnetic interactions of magnetic atoms in various environments. By calculating the dispersion relationship E(q) between the energy E and the wave vector q of the spin spiral in δ-(Ga, Mn)As, the effective multi-nearest neighbor interaction parameters Jxi of Mnx are fitted (x means different types of Mn atoms close to or far away from defects or impurities). The Exi(q) of each kind of Mn sublattice is constructed then with Jxi, and the Curie temperature of each sublattice is obtained by mean field approximation (MFA) and random phase approximation (RPA), respectively. Defect is detrimental to the FM properties at both low and high temperature, while Ga impurity improves FM properties at low temperature by increasing the magnetic stiffness of δ-(Ga, Mn)As.

Comparison of Cyclic and Linear Poly(lactide)s Using Small-Angle Neutron Scattering.

Small-angle neutron scattering (SANS) experiments were conducted on cyclic and linear polymers of racemic and l-lactides (PLA) with the goal of comparing chain configurations, scaling, and effective polymer-solvent interactions of the two topologies in acetone-d 6 and THF-d 8. There are limited reports of SANS results on cyclic polymers due to the lack of substantial development in the field until recently. Now that pure, well-defined cyclic polymers are accessible, unanswered questions about their rheology and physical conformations can be better investigated. Previously reported SANS experiments have used cyclic and linear polystyrene samples; therefore, our work allowed for direct comparison using a contrasting (structurally and sterically) polymer. We compared SANS results of cyclic and linear PLA samples with various microstructures and molecular weights at two different temperatures, allowing for comparison with a wide range of variables. The results followed the trends of previous experiments, but much greater differences in the effective polymer-solvent interaction parameters between cyclic and linear forms of PLA were observed, implying that the small form factor and hydrogen bonding in PLA allowed for much more compact conformations in the cyclic form only. Also, the polymer microstructure was found to influence polymer-solvent interaction parameters substantially. These results illustrate how the difference in polymer-solvent interactions between cyclic and linear polymers can vary greatly depending on the polymer in question and the potential of neutron scattering as a tool for identification and characterization of the cyclic topology.

Ab initio calculation of the Hubbard U and Hund exchange J in local moment magnets: The case of Mn-based full Heusler compounds

Mn-based full Heusler compounds possess well-defined local atomic Mn moments, and thus the correlation effects between localized d electrons are expected to play an important role in determining the electronic and magnetic properties of these materials. Employing ab-initio calculations in conjunction with the constrained random-phase approximation (cRPA) method, we calculate the strength of the effective on-site Coulomb interaction parameters (Hubbard U and Hund exchange J) in the case of X2MnZ full Heusler compounds with X being one of Ni, Pd or Cu, and Z being one of In, Sn, Sb or Te. We show that the Z element (or sp element) in Heusler compounds significantly reduces the strength of the Hubbard U parameter for Mn 3d electrons compared to the elementary bulk Mn. On the contrary, the effect of the sp-atom on the strength of the U parameter of Ni, Cu or Pd valence d electrons is not so substantial with respect to the elementary bulk values. The U values for all transition metal atoms decrease with increasing sp electron number in the In-Sn-Sb-Te sequence. Our cRPA calculations reveal that despite their well-defined local magnetic moments, the Mn-based full Heusler alloys fall into the category of the weakly correlated materials.