Glass Transition Temperature Of Polystyrene Research Articles

New Double-Infiltration Methodology to Prepare PCL-PS Core-Shell Nanocylinders Inside Anodic Aluminum Oxide Templates.

Melt nanomolding of core-shell nanocylinders of different sizes, employing anodic aluminum oxide (AAO) templates, is reported here for the first time. The core-shell nanostructures are achieved by a new melt double-infiltration technique. During the first infiltration step, polystyrene (PS) nanotubes are produced by an adequate choice of AAO nanopore diameter size. In the second step, PCL is infiltrated inside the PS nanotubes, as its melting point (and infiltration temperature) is lower than the glass transition temperature of PS. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) measurements verified the complete double-infiltration of the polymers. Differential scanning calorimetry (DSC) experiments show that the infiltrated PCL undergoes a confined fractionated crystallization with two crystallization steps located at temperatures that depend on which surface is in contact with the PCL nanocylinders (i.e., alumina or PS). The melt double-infiltration methodology represents a novel approach to study the effect of the surrounding surface on polymer crystallization under confinement.

Close-Packed Spherical Morphology in an ABA Triblock Copolymer Aligned with Large-Amplitude Oscillatory Shear

A microphase-separated poly(styrene-b-(lauryl-co-stearyl acrylate)-b-styrene) (SAS) triblock copolymer exhibiting a disordered spherical microstructure with randomly oriented grains was aligned through the application of large-amplitude oscillatory shear (LAOS) at a temperature below the order–disorder transition temperature of the triblock copolymer, yet above the glass transition temperature of the polystyrene spherical domains. The thermoplastic elastomeric behavior of the SAS triblock copolymer provided a convenient means to observe the aligned morphology. Following application of LAOS, the specimen was quenched to room temperature (below the glass transition temperature of polystyrene), and small-angle X-ray scattering data were obtained in the three principal shear directions: shear gradient, velocity, and vorticity directions. The analysis revealed that the SAS triblock copolymer formed coexisting face-centered cubic and hexagonally close-packed spherical microstructures. The presence of a close-pa...

Crystallization behaviour of poly(ethylene oxide) under confinement in the electrospun nanofibers of polystyrene/poly(ethylene oxide) blends.

We have studied the confined crystallization behaviour of poly(ethylene oxide) (PEO) in the electrospun nanofibers of the phase-separated blends of polystyrene (PS) and PEO, where PS was present as the major component. The size and shape of PEO domains in the nanofibers were considerably different from those in the cast films, presumably because of the nano-dimensions of the nanofibers and the extensional forces experienced by the polymer solution during electrospinning. The phase-separated morphology in turn influenced the crystallization behaviour of PEO in the blend nanofibers. At a PEO weight fraction of ≥0.3, crystallization occurred through a heterogeneous nucleation mechanism similar to that in cast blend films. However, as the PEO weight fraction in the blend nanofibers was reduced from 0.3 to 0.2, an abrupt transformation of the nucleation mechanism from the heterogeneous to predominantly homogenous type was observed. The change in the nucleation mechanism implied a drastic reduction of the spatial continuity of PEO domains in the nanofibers, which was not encountered in the cast film. The melting temperature and crystallinity of the PEO crystallites developed in the nanofibers were also significantly lower than those in the corresponding cast films. The phenomena observed were reconciled by the morphological observation, which revealed that the phase separation under the radial constraint of the nanofibers led to the formation of small-sized fibrillar PEO domains with limited spatial connectivity. The thermal treatment of the PS/PEO blend nanofibers above the glass transition temperature of PS induced an even stronger confinement effect on PEO crystallization.

Plasticization of amorphous polystyrene by volatile organic compounds

The plasticizing effect of 4 model volatile compounds (n-hexane, toluene, p-xylene, and ethylbenzene), able to be sorbed on polystyrene (PS) was studied. A large weight fraction range was investigated (up to 0.35) using differential scanning calorimetry. Mathematical modeling, using Fox, Kelly-Bueche, Chow and Gordon-Taylor models, was performed to model the behavior of the glass transition temperature of PS after VOC sorption. A strong plasticization of PS was evidenced by a significant reduction in the glass transition temperature of the binary mixtures (T gm). Among the four studied molecules, the linear one, n-hexane, displayed a better plasticizing efficiency than the aromatic ones, which lay in the same range. Indeed, a 15 % (w w−1) n-hexane content in PS decreased the T gm by 84 K. The Gordon-Taylor model was the best model to fit the experimental data for all the volatile organic compounds tested.

Polycarbazoles and polytriphenylamines showing aggregation-induced emission (AIE) and intramolecular charge transfer (ICT) behavior for the optical detection of nitroaromatic compounds

Acceptor-substituted polycarbazoles (PCzTPAN) and polytriphenylamines (PTPATPAN) bearing electron-deficient 2,3,3-triphenylacrylonitrile (TPAN) side groups have been successfully synthesized. Both of them are aggregation-induced emission (AIE)-active and show intramolecular charge transfer (ICT) behavior. PCzTPAN and PTPATPAN aggregates in 90% water/THF were used for the detection of 1,3,5-trinitrobenzene (TNB) as prototypical nitroaromatic compound. They show amplified PL quenching upon addition of TNB with a maximum quenching constant of 5.5 × 105 M−1. As additional application example, the detection of the glass transition temperature of polystyrene (PS) was accomplished for PTPATPAN blended into PS at doping concentrations of 0.1–1.0 wt%.

Polymericaly modified clays to preparation of polystyrene nanocomposite by nitroxide mediated radical polymerization and solution blending methods

Polymericaly modified clays that contain an oligomeric poly(styrene‐co‐chloromethyl styrene) ammonium salt have been prepared and used to preparation of polystyrene (PS) nanocomposites. First, PS and poly(styrene‐co‐chloromethyl styrene) [P(St‐co‐CMSt)] were synthesized by nitroxide mediated living free radical polymerization (NMRP) by TEMPO iniferter .Then the copolymer was coupled with N, N‐dimethyl hexadecyl amine to prepare polymeric modifier by anion exchange of chlorine group of chloromethyl styrene (CMSt) by quaternary amine. The synthesized polymeric modifier was mixed with nanoparticle of silica to change the property of clay surface from hydrophilic to hydrophobic via cation exchange of Na+ with alkylammonium ions. For synthesizing of nanocomposites, we used polymericaly modified montmorillonite and PS that was synthesized by NMRP technique. Intercalated nanocomposites and in some cases, exfoliated or mixed intercalated/exfoliated nanocomposites of all of these polymers have been produced by solution blending method. The prepared materials were characterized by X‐ray diffraction, Transmission electron microscopy, Fourier‐transform infrared, 1H nuclear magnetic resonance, and gel permeation chromatography techniques. Effect of layered silicates on thermal properties and glass transition temperature of PS was investigated using TGA and DSC techniques. POLYM. COMPOS., 38:1127–1134, 2017. © 2015 Society of Plastics Engineers

Effect of hybrid nanoparticles on glass transition temperature of polymer nanocomposites

Changes in the glass transition temperatures of composites based on polystyrene and nanosized macromolecular nanostructures (molecular silicasols, dendrimers) are reported. Silicasols are nanosized particles consisting of a silica core and an ethyl phenyl shell; dendrimers are formed using a carbosilane core with ethyl phenyl end groups. It has been observed that the glass transition temperatures of the composites (Tgc) may be either above or below the glass transition temperature of polystyrene, depending on the size of the filler particles. A theoretical model based on the relation between the glass transition temperature and the configurational entropy of the composite, which satisfactorily describes the experimental dependence, was developed. It is found that the effect of the size of the hybrid nanoparticles on Tgc was determined using two factors. First, the presence of an organic layer on the surface of nanoparticles increases the number of degrees of freedom and the entropy of the system, thereby reducing Tgc. Second, the particles present in the polymer reduce the number of configuration states of macromolecules, which reduces the disorientation entropy. This effect leads to an increase Tgc. The competition between these two main factors determines the sign of the glass transition temperature deviation. The size of the particles and their organic surface layer play the key roles in the thermodynamic properties of the composites. POLYM. COMPOS., 37:1978–1990, 2016. © 2015 Society of Plastics Engineers

Lithium Dendrite Growth in Glassy and Rubbery Nanostructured Block Copolymer Electrolytes

Enabling the use of lithium metal anodes is a critical step required to dramatically increase the energy density of rechargeable batteries. However, dendrite growth in lithium metal batteries, and a lack of fundamental understanding of the factors governing this growth, is a limiting factor preventing their adoption. Herein we present the effect of battery cycling temperature, ranging from 90 to 120°C, on dendrite growth through a polystyrene-block-poly(ethylene oxide)-based electrolyte. This temperature range encompasses the glass transition temperature of polystyrene (107°C). A slight increase in the cycling temperature of symmetric lithium-polymer-lithium cells from 90 to 105°C results in a factor of five decrease in the amount of charge that can be passed before short circuit. Synchrotron hard X-ray microtomography experiments reveal a shift in dendrite location from primarily within the lithium electrode at 90°C, to primarily within the electrolyte at 105°C. Rheological measurements show a large change in mechanical properties over this temperature window. Time-temperature superposition was used to interpret the rheological data. Dendrite growth characteristics and cell lifetimes correlate with the temperature-dependent shift factors used for time-temperature superposition. Our work represents a step toward understanding the factors that govern lithium dendrite growth in viscoelastic electrolytes.

Dissipative particle dynamics with an effective pair potential from integral equation theory of molecular liquids.

We present a method of DPD simulation based on a coarse-grained effective pair potential obtained from the DRISM-KH molecular theory of solvation. The theory is first used to calculate the radial distribution functions of all-atom solute monomers in all-atom solvent and then to invert them into an effective pair potential between coarse-grained beads such that their fluid without solvent accounts for molecular specificities and solvation effects in the all-atom system. Bonded interactions are sampled in relatively short MD of the all-atom system and modeled with best multi-Gaussian fit. Replacing the heuristically defined conservative force potential in DPD, the coarse-grained effective pair potential is free from the artificial restrictions on potential range and shape and on equal volume of solute and solvent blobs inherent in standard DPD. The procedure is flexible in specifying coarse-grained mapping and enormously increases computational efficiency by eliminating solvent. The method is validated on polystyrene chains of various length in toluene at finite concentrations for room and polystyrene glass transition temperature. It yields the chain elastic properties and diffusion coefficient in good agreement with experiment and all-atom MD simulations. DPD with coarse-grained effective pair potential is capable of predicting both structural and dynamic properties of polymer solutions and soft matter with high accuracy and computational efficiency.

Design of Soft Materials from Liquid Triblock Co-Oligomers and Metal Nanoparticles

Thermally processable soft material networks with adjustable mechanical properties made from very low molar mass α,ω-dithiol functionalized ABA triblock co-oligomers (α,ω-dithiol oligo(isoprene-b-styrene-b-isoprene) (TISIT)) using AgNP as thermally reversible cross-linking points are highlighted in the present work. Liquid TISIT oligomers were synthesized by sequential anionic polymerization and subsequently cross-linked with AgNP. Low molar masses (4200–4800 g mol–1) were engaged, assuring disordered microstructures and therefore, low viscosities at elevated temperatures. Smooth films with homogeneous nanoparticle distributions of the resulting quasi-segmented soft material networks (TISIT@AgNP) were made by heat pressing. The interplay of styrene and AgNP as the structure-supplying portions in TISIT@AgNP samples facilitates access to materials with tensile strengths up to 5.58 MPa, toughness up to 13.3 MN mm–2, and tensile moduli up to 80.1 MPa at room temperature and strongly decreased elasticity and viscosity at elevated temperatures, even below the glass transition temperature of polystyrene.

Síntese e caracterização de nanocompósitos de poliestireno/hidroxissal lamelar

Polystyrene/layered hydroxide salt (LHS) modified with sodium dodecyl sulfate was synthesized by in situ polymerization. The materials synthesized were characterized by gravimetry, X-ray diffraction (XRD), thermogravimetry analyses (TGA), differential scanning calorimetry (DSC) and the flammability test (FT). XRD demonstrated that synthesized nanocomposites in all compositions studied showed poor global dispersion of LHS in polystyrene. TGA showed a slight decrease in thermal stability. DSC curves showed that the glass transition temperature of polystyrene and nanocomposites were similar. The FT showed that the nanocomposite with low load of LHS exhibited good results.

Solvent-assisted and thermal wrinklings of argon plasma treated polystyrene coatings on silicon substrate

We report results of preparation of wrinkled polystyrene (PS) surfaces on silicon substrate employing two different methods, solvent-assisted wrinkling (SAW) and thermal wrinkling (TW). In both methods an argon (Ar) plasma treatment of PS/silicon bi-layer by reactive ion etching (RIE) was used for creation of cross-linked PS layer acting as a capping layer. In SAW method the layered system was exposed after the plasma treatment to solvent vapor and in TW method the layered system was heated above the glass-transition temperature of PS employed. Wave-like patterns were achieved with the both initiation methods and using the two polystyrenes having different molar masses. The plasma treatment time was found to have influence on the wrinkle formation by affecting the thickness of the cross-linked part of PS layer, and influencing slightly the dimensions of the wrinkles. The molar mass of PS was found to have effect on overall size-scale of the forming patterns. Moreover, employing TW as a wrinkling method yielded somewhat higher wrinkles.

Self-organized pattern formation on silicon, stainless steel and zinc coated steel substrates

In this research, a self-organized pattern formation employing polystyrene/aluminum bilayer coatings on three different substrates was studied. Two new substrate materials, stainless steel and zinc coated steel for self-organization application were introduced. Influence of polystyrene molar mass on pattern formation was studied with five different polystyrene samples having molar masses between 27 and 247×103g/mol. Polystyrene/toluene solutions were applied onto the substrates using the spin coating technique and aluminum layer was created by chemical vapor deposition (CVD). Self-organized pattern formation was induced thermally, by heating the layered substrate/polystyrene/aluminum structures above the glass transition temperature of polystyrene. Sub-micron–micron sized wrinkles or island-like surface patterns were achieved on all substrates. The molar mass of polystyrene was found to have effect on the dimensions of the formed structures. It was also observed that the characteristic surface structure of substrates influences self-organization and thereby directs the structure formation.

Rupture of molecules upon fracture of adhesive joint between two polymer samples

The surfaces formed after fracture of the joint of two polystyrene (PS) samples have been studied by attenuated total reflection Fourier-transform infrared spectroscopy. The adhesive joint between samples was created by pressing them one against another and holding at a pressure of 0.8 MPa and a temperature of 80°C, which is ∼23°C lower than the glass transition temperature of PS. It has been found that, after the joint fracture, the concentration of molecule ends formed after the rupture of carbon-carbon bonds in the back-bone of the PS molecule increases.

In situ X-ray crystallographic study of the structural evolution of colloidal crystals upon heating.

The structural evolution of colloidal crystals made of polystyrene hard spheres has been studied in situ upon incremental heating of a crystal in a temperature range below and above the glass transition temperature of polystyrene. Thin films of colloidal crystals having different particle sizes were studied in transmission geometry using a high-resolution small-angle X-ray scattering setup at the P10 Coherence Beamline of the PETRA III synchrotron facility. The transformation of colloidal crystals to a melted state has been observed in a narrow temperature interval of less than 10 K.

Preparation of polystyrene–clay nanocomposite by solution intercalation technique

Polymer–clay nanocomposites of commercial polystyrene (PS) and clay laponite were prepared via solution intercalation technique. Laponite was modified suitably with the well known cationic surfactant cetyltrimethyl ammonium bromide by ion-exchange reaction to render laponite miscible with hydrophobic PS. X-ray diffraction analysis in combination with scanning electron microscopy gives an idea of structural and morphological information of PS–laponite nanocomposite for different varying organo-laponite contents. Intercalation of PS chain occurs into the interlayer spacings of laponite for low organo-laponite concentration in the PS–O-laponite mixture. However, aggregation and agglomeration occur at higher clay concentration. The molecular bond vibrational profile of laponite as well as PS–laponite nanocomposite have been explored by Fourier transform infrared spectroscopy. Thermogravimetric analysis along with differential scanning calorimetry results reveal the enhancement of both thermal stability and glass transition temperature of PS due to the incorporation of clay platelets.

In situ thermal reduction of graphene oxide in a styrene-ethylene/butylene-styrene triblock copolymer via melt blending

We report an in situ thermal reduction of graphene oxide (GO) in a styrene–ethylene/butylene–styrene (SEBS) triblock copolymer matrix during a melt-blending process. A relatively high degree of reduction was achieved by melt-blending premixed GO/SEBS nanocomposites in a Haake mixer for 25 min at 225 °C. Infrared spectral results revealed the successful thermal reduction of, and the strong adsorption of SEBS on, the graphene sheets. The glass transition temperature of polystyrene (PS) segments in SEBS was enhanced by the incorporation of thermally reduced graphene oxide (TRGO). The resultant TRGO/SEBS nanocomposites were used as a masterbatch to improve the mechanical properties of PS. Both the elongation at break and the flexural strength of PS/SEBS blends were enhanced with the addition of the TRGO. Our demonstration of the in situ thermal reduction of GO via melt blending is a simple, efficient strategy for preparing nanocomposites with well-dispersed TRGO in the polymer matrix, which could be an important route for large-scale fabrication of high-performance graphene/polymer nanocomposites. © 2013 Society of Chemical Industry

Modulus, Confinement, and Temperature Effects on Surface Capillary Wave Dynamics in Bilayer Polymer Films Near the Glass Transition

We report relaxation times (τ) for surface capillary waves on 27-127 nm polystyrene (PS) top layers in bilayer films using x-ray photon correlation spectroscopy. At ∼10 °C above the PS glass transition temperature (T(g)), τ tracks with underlayer modulus, being significantly smaller on softer substrates at low in-plane scattering wave vector. Relative to capillary wave theory, we also report stiffening behavior upon nanoconfinement of the PS layers. At PS T(g)+40 °C, both effects become negligible. We demonstrate how neighboring polymer domains impact dynamics over substantial length scales.

Viscoelastic properties of solutions of polystyrene melts and carbon dioxide: Analysis of a transient shear rheology approach

In this work, the viscoelastic, thermal, and diffusion properties of solutions of polystyrene melts and carbon dioxide (CO2) were analyzed using plate–plate rheometry in the transient mode. The objective of this study was to evaluate a transient shear rheology approach for high viscosity polymer melts, to verify superposition principles for polystyrene/CO2 solutions, and to measure the glass transition temperature as a function of pressure and CO2 concentration. Two different procedures of saturating polystyrene with carbon dioxide were applied, i.e., loading with the blowing agent below the glass transition temperature of polystyrene and at the measurement temperature. Stress-growth experiments in shear were performed in order to measure the transient viscosity of polystyrene/CO2 solutions in the linear regime. A shift of the transient viscosity data to a mastercurve was applied in order to determine the shift factor of the viscosity and the average relaxation time. Our data indicate that the steady-state viscosity and the average relaxation time are proportional to the temperature–pressure–concentration shift factor aT,p,c within experimental scatter, and consequently a time–temperature–pressure–concentration superposition principle holds for polystyrene/CO2 solutions. Whereas the viscosity of polystyrene strongly depends on the applied temperature and pressure, the elastic equilibrium compliance depicts only a weak dependence on temperature and pressure.

Superior Reinforcement Effect of TEMPO-Oxidized Cellulose Nanofibrils in Polystyrene Matrix: Optical, Thermal, and Mechanical Studies

Polystyrene (PS) composites reinforced with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with various weight ratios were fabricated by casting and vacuum-drying mixtures of PS/N,N-dimethylformamide (DMF) solution and TOCN/DMF dispersion. TOCNs of 3 to 4 nm width were dispersed homogeneously at the individual nanofibril level in the PS matrix, such that the TOCN/PS nanocomposite films exhibited high optical transparencies and their tensile strengths, elastic moduli, and thermal dimensional stabilities increased with increasing TOCN content. Dynamic mechanical analysis showed that the storage modulus of the TOCN/PS films increased significantly with TOCN content above the glass-transition temperature of PS by the formation of an interfibrillar network structure of TOCNs in the PS matrix, based on percolation theory. The outstanding and effective polymer reinforcement by TOCNs results from their high aspect ratio, high crystallinity, and nanodispersibility in the PS matrix.