Order-disorder Transition Temperature Research Articles

Sustainable thermoplastic elastomers with a transient network

Vegetable oils and their fatty acids are convenient sources for polymers due to their wide availability, ease of functionalization, and lack of toxicity; however, the long alkyl chains of the fatty acids have a large impact on the resulting polymer properties. Polymers with bulky constituents, such as the long alkyl side-chains of fatty acid-derived polymers, typically exhibit poor mechanical performance due to lack of entanglements. In this study, hydrogen bonding moieties were incorporated into the fatty acid-based midblock of a thermoplastic elastomeric triblock copolymer as a means to improve its mechanical behavior. Poly(styrene-b-(lauryl acrylate-co-acrylamide)-b-styrene), containing lauryl acrylate (a derivative of lauric acid) and the hydrogen bonding comonomer acrylamide in the midblock, was synthesized via reversible addition-fragmentation chain transfer polymerization. The chemical and physical properties of triblock copolymers of varying composition were explored. Quantitative FTIR analysis confirmed the formation of a transient network, which exhibited a reduction in crosslink density with increasing temperature, beneficial for high temperature melt processing. The triblock copolymers exhibited spherical morphologies lacking long-range order at room temperature, which were unaffected by the presence of acrylamide. Moreover, the order-disorder transition temperature reduced with increasing acrylamide content, due to a reduction in the Flory-Huggins interaction parameter. Importantly, incorporation of acrylamide into the midblock greatly improved both the tensile strength and strain at break. Incorporation of a transient network into the midblock is therefore an effective method of improving the mechanical properties of triblock copolymer-based thermoplastic elastomers containing bulky constituents.

Order-disorder transition in p-oligophenyls.

Poly(para-phenylene) has been recognized as one important family of conducting polymers upon doping with donors or acceptors. This system possesses a chain-like structure with infinite benzene rings linked with a single C-C bond. Oligophenyls as models of poly(para-phenylene) with short chains in the para position were found to exhibit superconductivity at transition temperatures ranging from 3 K to 123 K upon doping. Structural studies have revealed that there exist order-disorder transitions in many p-oligophenyls with almost doubled lattice constants in the b and c directions at low temperatures. Such a transition is of relevance to the understanding of the emergence of novel quantum functionality where unconventional polaronic interactions are relevant for the new emerging theory of superconductivity in this system. However, the accurate temperatures for the order-disorder transitions amongst these p-oligophenyls are still needed to be determined. The chain length effects on the order-disorder transitions in this system remain unknown. Here we report the systematic investigation of the evolution of the vibrational properties of the crystalline p-oligophenyls over a wide temperature range. The order-disorder transition is identified by three indicators, the lowest energy peak together with the intensity ratios between the 1280 cm-1 and 1220 cm-1 modes and between the two modes at around 1600 cm-1. A phase diagram of the order-disorder transition temperature and the melting curve for p-oligophenyls are thus established. The former is found to increase with the chain length and saturates at around 350 K for poly(para-phenylene).

Ordering of carbon in highly supersaturated α-Fe

Metropolis Monte Carlo is used to investigate the Zener ordering as the carbon content of body centered cubic iron is increased. Thanks to a fast simulation algorithm, the equilibrium state for a wide range of temperature and carbon content are investigated. These results are compared to a thermodynamical mean-field model that accounts for long range elastic interaction and configurational entropy. At carbon levels of above 2 at.%, it is found that the mean-field model overestimates the order–disorder transition temperature. This is due to local repulsive C–C interactions not accounted for in the mean-field model. Forbidding some strongly repulsive configurations leads to a better agreement between the mean-field model and Metropolis Monte Carlo simulations. At high concentration carbon atoms in solid solution exhibits local configurations typical of the Fe16C2 carbide.

Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies.

We report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS-PB) diblock copolymer comprising 20 vol % PB below the order-disorder transition temperature (TODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time-temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < TODT. Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time-temperature superposed, and the shift factors were fit using the Williams-Landel-Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125-140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, TODT - T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominant relaxation mode in the supercooled disordered liquid transitions from ergodic dynamics governed by chain exchange to a nonergodic regime dominated by local rearrangement of micellar particles at T ≈ Terg, where Terg denotes the ergodicity temperature.

Evolution of Microstructure in Block Copolymer Thin Films during Zone Annealing

The effect of zone annealing on a microstructure from horizontal and vertical cylinders in the microphase-separated films of polystyrene–polybutadiene–polystyrene triblock copolymer and polystyrene–poly(4-vinylpyridine) diblock copolymer is studied. It is shown that processing of the films of different thicknesses at various maximum thermal front temperatures which do not exceed the temperature of orderdisorder transition does not lead to a noticeable increase in their degree of ordering. On the contrary, once the transition temperature is approached, the interfacial area between domains formed by different types of blocks is increased and the order in their arrangement disappears, with the thermal stability of the structure falling with an increase in film thickness. Thus, the substantial microstructure ordering during the cold zone annealing of the polystyrene–poly(methyl methacrylate) diblock copolymer described in the literature has not yet been reproduced for other systems. The maximum rate of gradient zone motion at which this effect is to be expected is estimated.

Rheological characterisation of xanthan gum in brine solutions at high temperature

Xanthan gum solutions are used in the oil industry for flooding, drilling and completion operations. The stabilization of the structure of xanthan gum solutions in presence of salts increases the value of both the order-disorder transition temperature and the gel strength. This effect is very important in order to design drilling and completion fluids since not only density and viscosity of the fluid can be improved by increasing the concentration of salts but also the range of temperature where the solution shows viscoelastic behaviour can be extended.This paper presents results from a study on the rheological behaviour of xanthan gum solutions in different saturated brines. Chloride and formate potassium brines not only increase the viscosity of the solution but also extend the shear thinning behaviour to temperatures near 200 °C, maintaining a simple relaxation mechanism over the whole range of temperature where the ordered conformation dominates the rheological behaviour.

Unusual irradiation-induced disordering in Cu3Au near the critical temperature: An in situ study using electron diffraction

Abstract

L10 ordered phase formation at solid state reactions in Cu/Au and Fe/Pd thin films

To understand the mechanism of mass transfer during solid state reactions and order-disorder transitions the formation processes of CuAuI and L10-FePd ordered structures at solid state reactions in Cu/Au и Fe/Pd bilayer thin films have been carried out using the method of in situ electron diffraction (ED). The value of the long-range order (LRO) parameter has been estimated for the L10 type ordered structures being formed; the order-disorder transition temperatures have been determined. The formation mechanism of the L10 type ordered structures formed at the initial stages of the solid state reaction in the Cu/Au and Fe/Pd thin films has been suggested. In the case of Cu/Au it has been shown that the interdiffusion of copper and gold at the initial stage of the solid state reaction results in the reduced size of the grains of the initial materials, as a result, nanocrystalites of the Cu-Au solid solution are formed, and further, grains of the CuAuI ordered solid solution appear and their growth begins.

Predicting the phase behavior of ABAC tetrablock terpolymers: Sensitivity to Flory–Huggins interaction parameters

Self-consistent field theory (SCFT) is a powerful tool for discovering new nanostructures in self-assembling block polymers. However, the reliability of the resulting predictions depend strongly on the Flory-Huggins interaction parameters χij used to quantify the excess free energy of mixing of different blocks i and j arising from segment-segment interactions. The problem is especially significant for multiblock polymers, owing to the multitude of χij parameters and the sensitivity of the resulting phase behavior when the χij do not differ substantially for different block pairs. To illuminate this issue, we examine how the SCFT-predicted phase behavior of a poly(styrene)-b-poly(isoprene)-b-poly(styrene)'-b-poly(ethylene oxide) (SIS'O) tetrablock terpolymer changes depending on the method used to estimate the trio of χij parameters for this chemistry. SIS'O is an ideal model system for our purposes, as it exhibits a large number of poly(ethylene oxide) sphere-forming phases, emerging from the segregation of the poly(ethylene oxide) block due to the relatively high values of χSO and χIO, accompanied by subtle matrix segregation effects arising due to the smaller χIS between poly(isoprene) and poly(styrene). We first use χIS, χIO, and χSO available in the literature that were estimated using mean-field theory order–disorder transitions of the relevant diblock polymers. As this method is expected to lead to significant errors in χij that propagate into the SCFT predictions, we also consider two fluctuation-corrected approaches to extract χij from diblock polymer data, namely (i) fitting the order-disorder transition temperature to that predicted by molecular dynamics simulations and (ii) renormalized one-loop theory predictions for the structure factor of the disordered state. While even the fluctuation-corrected χ parameters do not lead to SCFT phase behavior that exactly matches experiments, the SCFT calculations using the molecular dynamics-fitted χ parameters correctly predict stable Frank–Kasper A15 and σ phases. The results presented here highlight the challenges in predictively modeling the phase behavior of multiblock polymers using SCFT, a critical task for the discovery of new multiblock polymer materials.

Ordered Nanostructures of Carbon Nanotube–Polymer Composites from Lyotropic Liquid Crystal Templating

AbstractA series of polymer nanocomposites containing single‐walled carbon nanotubes (SWNTs) are prepared from polymerizable quaternary ammonium surfactants using photo‐polymerization and investigated by means of polarized optical microscopy, small‐angle X‐ray scattering, and rheological measurements. The surfactant monomers with various alkyl chains of nonpolar tails form lyotropic liquid crystalline (LLC) mesophases in aqueous medium with hexagonal packing of cylindrical micelles. The physical adsorption of nonpolar tails of surfactants on the surface of SWNTs results in de‐bundled nanotubes. The LLC phase diagram is investigated as functions of alkyl chain length, concentration, temperature, and SWNTs. As such, addition of SWNTs does not change the hexagonal mesophases but enhances the order–disorder transition temperatures and alters the rheological behaviors. After photo‐polymerization, the microstructures of hexagonal packing are changed while addition of SWNTs does not disrupt the resulting microstructures. The polymerized composites are consistent with both lamellar and gyroid nanostructures and a possible model is proposed to interpret the observed phenomenon. Under the shear flow, the defect‐free monodomain structures are obtained in the LLC phase and subsequently locked in the solid film after polymerization.

Second nearest-neighbor modified embedded-atom method interatomic potentials for the Pd-M (M = Al, Co, Cu, Fe, Mo, Ni, Ti) binary systems

Palladium (Pd) has attracted attention as one of the major components of noble metal catalysts due to its excellent reactivity to a wide range of catalytic reactions. It is important to predict and control the atomic arrangement in catalysts because their properties are known to be affected by it. Therefore, to enable atomistic simulations for investigating the atomic scale structural evolution, we have developed interatomic potentials for Pd-M (M = Al, Co, Cu, Fe, Mo, Ni, Ti) binary systems based on the second nearest-neighbor modified embedded-atom method formalism. These potentials reproduce various fundamental properties of the alloys (the structural, elastic and thermodynamic properties of compound and solution phases, and order-disorder transition temperature) in reasonable agreements with experimental data, first-principles calculations and CALPHAD assessments. Herein, we propose that these potentials can be applied to the design of robust bimetallic catalysts by predicting the shape and atomic arrangement of Pd bimetallic nanoparticles.

Directed Self-Assembly of High χ Poly(styrene-b-(lactic acid-alt-glycolic acid)) Block Copolymers on Chemical Patterns via Thermal Annealing.

We demonstrated the synthesis and directed self-assembly (DSA) of poly(styrene-b-(lactic acid-alt-glycolic acid)) (PS-b-PLGA). Lamellae-forming PS-b-PLGAs with a range of molecular weights were synthesized by ring-opening polymerization (ROP) of LGA (d,l-3-methyl-1,4-dioxane-2,5-dione) from hydroxy-terminated polystyrene (PS-OH) with stannous octoate as the catalyst and characterized by 1H NMR spectroscopy, GPC, DSC, TGA, SAXS, and rheometry. The order-disorder transition temperatures (TODT) of four PS-b-PLGA block copolymers were determined by temperature sweep measurements and verified by variable-temperature SAXS, which were used to determine the temperature dependence of χ. The χ value of PS-b-PLGA is twice as large as that of poly(styrene-b-racemic lactide) (PS-b-PDLLA) at 150 °C, while the surface energies (γ) of PS and PLGA are nearly equal. Thin films of PS-b-PLGA were successfully directed to assemble on stripe chemical patterns with a range of pattern periods (LS) upon thermal annealing. SEM analysis of the assembled films revealed that long-range ordered perpendicularly oriented lamellae were registered on chemical patterns with 2× density multiplication. These results qualify PS-b-PLGA as an attractive candidate for next-generation lithography with sub-10 nm resolution.

Kinetics of pattern formation in symmetric diblock copolymer melts.

In equilibrium, copolymers self-assemble into spatially modulated phases with long-range order. When the system is quenched far below the order-disorder transition temperature, however, such an idealized, defect-free structure is difficult to obtain in experiments and simulations, instead a fingerprint-like structure forms. The relaxation toward long-range order is very protracted because it involves numerous thermally activated processes, and the rugged free-energy landscape has been likened to that of glass-forming systems. Using large-scale particle-based simulations of high-aspect-ratio, quasi-two-dimensional systems with periodic boundary condition, we study the kinetics of structure formation in symmetric, lamella-forming diblock copolymers after a quench from the disordered state. We characterize the ordering process by the correlation length of the lamellar structure and its Euler characteristic and observe that the growth of the correlation length and the rate of change of the Euler characteristic significantly slow down in the range of incompatibilities, 15 ≤ χN ≤ 20, studied. The increase of the time scale of ordering is, however, gradual. The density fields of snapshots of the particle-based simulations are used as starting values for self-consistent field theory (SCFT) calculations. The latter converge to the local, metastable minimum of the free-energy basin. This combination of particle-based simulations and SCFT calculations allows us to relate an instantaneous configuration of the particle-based model to a corresponding metastable free-energy minimum of SCFT-the inherent morphology-and we typically observe that a change of a free-energy basin is associated with a change of the Euler characteristic of the particle-based morphology, i.e., changes of free-energy basins are correlated to changes of the domain topology. Subsequently, we employ the string method in conjunction with SCFT to study the minimum free-energy paths (MFEPs) of changes of the domain topology. Since the time scales of relaxing toward the inherent morphology within a free-energy basin and jumps between free-energy basins are not well separated, the MFEP may overestimate the barriers encountered in the course of ordering.

Effect of Systematic Hydrogenation on the Phase Behavior and Nanostructural Dimensions of Block Copolymers.

Unsaturated polydienes are frequently hydrogenated to yield polyolefins that are more chemically stable. Here, the effects of partial hydrogenation on the phase behavior and nanostructure of polyisoprene-containing block copolymers are investigated. To ensure access to the order-disorder transition temperature (TODT) over a wide temperature range, we examine copolymers with at least one random block. Dynamic rheological and scattering measurements indicate that TODT increases linearly with increasing hydrogenation. Small-angle scattering reveals that the temperature-dependence of the Flory-Huggins parameter changes and the microdomain period increases, while the interfacial thickness decreases. The influence of hydrogenation becomes less pronounced in more constrained multiblock copolymers.

Origins of low-symmetry phases in asymmetric diblock copolymer melts

Cooling disordered compositionally asymmetric diblock copolymers leads to the formation of nearly spherical particles, each containing hundreds of molecules, which crystallize upon cooling below the order-disorder transition temperature (TODT). Self-consistent field theory (SCFT) reveals that dispersity in the block degrees of polymerization stabilizes various Frank-Kasper phases, including the C14 and C15 Laves phases, which have been accessed experimentally in low-molar-mass poly(isoprene)-b-poly(lactide) (PI-PLA) diblock copolymers using thermal processing strategies. Heating and cooling a specimen containing 15% PLA above and below the TODT from the body-centered cubic (BCC) or C14 states regenerates the same crystalline order established at lower temperatures. This memory effect is also demonstrated with a specimen containing 20% PLA, which recrystallizes to either C15 or hexagonally ordered cylinders (HEXC) upon heating and cooling. The process-path-dependent formation of crystalline order shapes the number of particles per unit volume, n/V, which is retained in the highly structured disordered liquid as revealed by small-angle X-ray scattering (SAXS) experiments. We hypothesize that symmetry breaking during crystallization is governed by the particle number density imprinted in the liquid during ordering at lower temperature, and this metastable liquid is kinetically constrained from equilibrating due to prohibitively large free energy barriers for micelle fusion and fission. Ordering at fixed n/V is enabled by facile chain exchange, which redistributes mass as required to meet the multiple particle sizes and packing associated with specific low-symmetry Frank-Kasper phases. This discovery exposes universal concepts related to order and disorder in self-assembled soft materials.

How Strong Is the Hydrogen Bond in Hybrid Perovskites?

Hybrid organic–inorganic perovskites represent a special class of metal–organic framework where a molecular cation is encased in an anionic cage. The molecule–cage interaction influences phase stability, phase transformations, and the molecular dynamics. We examine the hydrogen bonding in four AmBX3 formate perovskites: [Am]Zn(HCOO)3, with Am+ = hydrazinium (NH2NH3+), guanidinium (C(NH2)3+), dimethylammonium (CH3)2NH2+, and azetidinium (CH2)3NH2+. We develop a scheme to quantify the strength of hydrogen bonding in these systems from first-principles, which separates the electrostatic interactions between the amine (Am+) and the BX3– cage. The hydrogen-bonding strengths of formate perovskites range from 0.36 to 1.40 eV/cation (8–32 kcalmol–1). Complementary solid-state nuclear magnetic resonance spectroscopy confirms that strong hydrogen bonding hinders cation mobility. Application of the procedure to hybrid lead halide perovskites (X = Cl, Br, I, Am+ = CH3NH3+, CH(NH2)2+) shows that these compounds have significantly weaker hydrogen-bonding energies of 0.09 to 0.27 eV/cation (2–6 kcalmol–1), correlating with lower order–disorder transition temperatures.

Molecular Tailoring of Poly(styrene-b-methyl methacrylate) Block Copolymer Toward Perpendicularly Oriented Nanodomains with Sub-10 nm Features.

We demonstrate a novel approach for fabricating vertically orientated, sub-10 nm, block copolymer (BCP) nanodomains on a substrate via molecular tailoring of poly(styrene-b-methyl methacrylate) (PS-b-PMMA) BCP, one of the most widely used BCPs for nanopatterning. The idea is to incorporate a short middle block of self-attracting poly(methacrylic acid) (PMAA) between the PS and PMMA blocks, where the PMAA middle block promotes phase separation between PS and PMMA, while maintaining the domain orientation perpendicular to the substrate. The designed PS-b-PMAA-b-PMMA triblock copolymers, which were synthesized via well-controlled anionic polymerization, exhibited order-disorder transition temperatures higher than that of pristine PS-b-PMMA BCPs, indicating the promotion of phase separation by the middle PMAA block. For PS-b-PMAA-b-PMMA BCPs with total molecular weights of 21 and 18 kg/mol, the domain spacing corresponds to 19.3 and 16.7 nm, respectively, allowing us to fabricate sub-10 nm nanodomain structures. More importantly, it was demonstrated that the PMAA middle block, which has a higher surface energy than PS and PMMA, does not significantly alter lateral concentration fluctuations, which are responsible for phase-separation in the lateral direction. This enabled the vertical orientation of microdomains with sub-10 nm feature size on a PS-r-PMMA neutral surface without an additional neutral top layer. We anticipate that this approach provides an important platform for next-generation lithography and nanopatterning applications that require sub-10 nm features over large areas with simple process and reduced cost.

Physical Behavior of Triblock Copolymer Thermoplastic Elastomers Containing Sustainable Rosin-Derived Polymethacrylate End Blocks

A rosin-derived polymethacrylate, poly(dehydroabietic ethyl methacrylate) (PDAEMA), was evaluated as a sustainable end block in triblock copolymer-based thermoplastic elastomers. Triblock copolymers containing glassy PDAEMA end blocks and a rubbery poly(n-butyl acrylate) (PnBA) midblock were synthesized through atom transfer radical polymerization. The volume fraction of PDAEMA in the triblock copolymer was varied at constant midblock molecular weight. At lower PDAEMA content, the triblock copolymers exhibited microphase separated morphologies lacking long-range order, which transitioned to a well-defined cylindrical morphology as the PDAEMA content was increased. Observed thermal properties were consistent with the presence of distinct PDAEMA and PnBA domains. The order–disorder transition temperature increased with increasing PDAEMA content in the block copolymer, and the Flory–Huggins interaction parameter of PDAEMA/PnBA was strongly temperature-dependent yet small in value. The triblock copolymers exh...

Magnetic Properties of L10 FeNi Phase Developed Through Annealing of an Amorphous Alloy

Chemically ordered L10 FeNi phase observed in Fe-based meteorite has the potential to replace high-cost rare-earth-based permanent magnets in the future. However, artificial production of this phase is extremely difficult due to negligible atomic diffusion around order–disorder transition temperature (~320 °C). Here, we report a method for producing high-quality L10 FeNi phase and its magnetic properties. We show that a highly disordered metastable state, that is, amorphous can be utilized to produce a highly ordered state, which is not possible with the conventional processing techniques. Amorphous Fe42Ni41.3Si x B12− x P4Cu0.7 ( $x=0$ to 8 at.%) alloy ribbons were studied. Crystallization of amorphous ribbons at 400 °C results in adequate atomic diffusion at low temperatures to precipitate L10 FeNi grains. Structural characterization revealed a high degree of chemical ordering ( $S \ge 0.8$ ), but the volume fraction of precipitated L10 grains is low. The crystallized ribbons of FeSiBPCu are composed of two magnetic phases (hard magnetic L10 FeNi grains embedded in a soft magnetic matrix). Alloys with higher concentration of Si are shown to produce high coercivity ( $H_{c}\sim 700$ –750 Oe). The soft magnetic matrix strongly influences the H c . The actual switching field (≥3.7 kOe) of L10 FeNi has been found to be much higher than that of H c . In this paper, the L10 FeNi phase is shown to form at temperatures higher than the reported order–disorder temperature. Our results of temperature-dependent magnetization and thermal analyses suggest that the L10 FeNi phase can survive at temperatures ≤550 °C. The magnetization reversal mechanism was understood by angular dependence of $H_{c}$ , and it is shown to be a domain-wall pinning type. Due to structural and magnetic similarities between L10 FeNi and L10 FePt, ribbon samples with low-volume fraction of L10 FePt grains in a soft magnetic matrix were prepared with a similar technique. Magnetization behavior of L10 FeNi is shown to be similar to that of L10 FePt.

Second nearest-neighbor modified embedded-atom method interatomic potentials for the Pt-M (M = Al, Co, Cu, Mo, Ni, Ti, V) binary systems

Interatomic potentials for Pt-M (M = Al, Co, Cu, Mo, Ni, Ti, V) binary systems have been developed on the basis of the second nearest-neighbor modified embedded-atom method (2NN MEAM) formalism. The parameters of pure Mo have also been newly developed to solve a problem in the previous 2NN MEAM potential in which the sigma and α-Mn structures become more stable than the bcc structure. The potentials reproduce various materials properties of alloys (structural, thermodynamic and order-disorder transition temperature) in reasonable agreements with relevant experimental data and other calculations. The applicability of the developed potentials to atomistic investigations for the shape and atomic configuration of Pt bimetallic nanoparticles is demonstrated.