Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

The prediction of glass transition temperature from chemical structure has a great significance to select and design new high-properties materials. However, for the estimation and correlation methods, the deficiency of parameters for newer groups will lead to invalidity of Tg prediction or greater deviation from experiment. In the present work, we predicted Tg for a polyimide (PI) ensemble with rigid moieties, and analyzed structural factor that regards to the rotation barrier of the bridging…     

Thin Film of Mesoporous MCM-41 Grown on Indium-Tin-Oxide Glass Substrate

ThemesoporousM4lSmaterialshaveattractedconsiderableattentionsincetheywerefirstdiscoveredin19921'2.Thesematerials,amongwhichistheMCM-41molecularsievewithahexagonalarrayofmesopores(diameter15-100A),haveenormouspotentialinapplicationssuchascatalysis',host-guestchemistry"'andseparation'.UniformthinfilmsbasedonMCM-417-ichavealsobeenpreparedattheinterfacesofsolution/solidandair/solution.However,thepreviously-reportedfilmsweregrowninvariablyfromanacidicsolutioncontainingsurfactantmoleculesasthest…     

Investigation of Viscoelastic Properties of Amorphous Selenium near Glass Transition Using Depth‐Sensing Indentation

Abstract

New procedures involving depth‐sensing indentation are used to measure the submicron scale elastic modulus, hardness, viscosity, and activation energy and volume for creep of amorphous selenium below glass transition. The accurate measurement of Young's modulus in a highly viscoelastic situation using depth‐sensing indentation remains a challenge, and a creep correction procedure is employed here to measure the modulus. The measured Young's modulus exhibits a strong decreasing trend from ～10 GPa to 4.4 GPa as temperature increases from ～302 K to 309 K, in reasonably good agreement with bulk behavior. Two new procedures are also proposed here to measure the viscosity. The measured shear viscosity decreases from ～1×10¹² Pa‐s to ～2×10¹⁰ Pa‐s when the temperature increases over the same range, and the variation with temperature is found to obey an Arrehnius rate equation. The activation energy for the viscous creep process is found to be ～463 kJ/mol. Both the viscosity and the activation energy are lower than the bulk values, and this is thought to be due to the much higher stress levels of over 200 MPa involved in the nanoindentation experiments here. The apparent activation volume exhibits a rising trend from 1.04×10^?31 to 2.35×10^?30 m³ over the same temperature range.     

Glass fiber reinforced composites of phenolic–urea–epoxy resin blends

The present work aims to modify conventional epoxy resin by blending with four different phenolic–urea oligomers. These oligomers are similar to phenolic–urea resin matrix and simultaneously function as amino curing agent for epoxy matrix. In this context, phenolic–urea oligomers were prepared respectively by polycondensation reaction of four phenols namely phenol, m-cresol, resorcinol and 1,5-dihydroxy naphthalene, respectively with formaldehyde and urea in presence of acid catalyst. The resulting oligomers were characterized by elemental analysis, spectral studies (IR & NMR), number average molecular weight $(\overline{M}n)$ estimated by non-aqueous conductometric titration and thermal stability by thermogravimetric analysis (TGA). Each of these oligomers was used in resin matrix as a blending component for the modification of commercial epoxy resin for fabricating glass fiber reinforced laminates. Finally these laminates were evaluated for their synergetic thermal stability, mechanical properties and chemical resistance to different reagents.     

Influence of Isosorbide on Glass‐Transition Temperature and Crystallinity of Poly(butylene terephthalate)

Copolyesters of isosorbide and 1,4‐butane diol were prepared by Ti(OBu)₄‐catalyzed transesterifications with dimethyl terephthalate in bulk at temperatures up to 250°C. The content of isosorbide was considerably lower than expected from the feed ratio and the molar masses were low, so that no DSC measurements were conducted. Copolycondensations of isosorbide and 1,4‐butane diol with terephthaloyl chloride were either performed in dichloromethane at 40°C or in toluene at 100°C. The second method gave the higher molar masses. However, both series of polycondensations had the content of isosorbide roughly paralleled the feed ratios in common. The DSC measurements revealed that even 6 mol% of isosorbide is sufficient to raise the glass‐transition temperature (T_g) by 10–12°C (up to 55°C). With 50 mol% of isosorbide, the T_g reaches 100°C. Yet, incorporation of isosorbide also reduces the melting temperature T_m and the degree of crystallinity, and a mol percentage above 30% prevents crystallization completely. In summary, incorporation of isosorbide allows for fine‐tuning of T_g and T_m of poly(butylene terephthalate) over a wide range.     

Determination of Silver by Stripping Voltammetry at Composite Pyrocarbon–Glass Ceramic Electrodes

Characteristic features of the process of Ag(I) discharge and ionization at a composite pyrocarbon–glass ceramic electrode were studied by stripping voltammetry. The optimal measurement conditions were selected, and n× 10^–6g/L Ag(I) was determined in drinking water (n= 4, RSD = 4%).     

Synthesis and Nonlinear Optical Property of a Polyphosphazene with High Glass Transition Temperature

A new polyphosphazene containing binaphtholyl and indole azo chromophores as side chains with high glass transition temperature(Tg) was synthesized by a post-functional method.The polymer was well characterized.Its Tg was tested to be 168 ℃,and the poled film of P2 reveals a resonant d33 value of 20 pm/V by second harmonic generation(SHG) measurements.     

Mode-Coupling Theory for Glass Transition of Active-Passive Binary Mixture?

Collective behaviours of active particle systems have gained great research attentions in recent years. Here we present a mode-coupling theory (MCT) framework to study the glass transition of a mixture system of active and passive Brownian particles. The starting point is an effective Smoluchowski equation, which governs the dynamics of the probability distribution function in the position phase space. With the assumption of the existence of a nonequilibrium steady state, we are able to obtain dynamic equations for the intermediate scattering functions (ISFs), wherein an irreducible memory function is introduced which in turn can be written as functions of the ISFs based on standard mode-coupling approximations. The effect of particle activity is included through an effective diffusion coefficient which can be obtained via short time simulations. By calculating the long-time limit of the ISF, the Debye-Waller (DW) factor, one can determine the critical packing fraction η_c of glass transition. We find that for active-passive (AP) mixtures with the same particle sizes, η_c increases as the partial fraction of active particle x_A increases, which is in agreement with previous simulation works. For system with different active/passive particle sizes, we find an interesting reentrance behaviour of glass transition, i.e., η_c shows a non-monotonic dependence on x_A. In addition, such a reentrance behaviour would disappear if the particle activity is large enough. Our results thus provide a useful theoretical scheme to study glass transition behaviour of active-passive mixture systems in a promising way.     

Nanostructure Pt Electrode Obtained via Self-assembly of Nanoparticles on Conductive Oxide-coated Glass Substrate

Self-assembly of platinum nanoparticles were applied to fabrication of counter electrode for dye-sensitized solar cells on conductive oxide-coated glass substrate. The present Pt electrode exhibits high exchange current density of 220 mA/cm^2, which is comparable to those prepared by electrodeposition, magnetron sputtering or thermal decomposition of platinum chloride. After analysis by transmission electron microscopy (TEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), it was found that the catalyst was structurally characterized as nanosized platinum metal clusters and was continuously arranged on electrode surface. The present nanostructure electrode had high electrocatalytic activity for the reduction of iodine in organic solution.     

New Photoluminescence Phenomena of Ge／SiO2 Glass Synthesized by Sol-gel Method

New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV) and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photoluminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS).     

Evolution of Er^3＋ Distribution in the Oxyfluoride Glass Ceramics with Heating

The distribution characteristics of Er3+ ions doped in the oxyfluoride glass ceramics containing LaF3 nanocrystals heat-treated at 650 ℃ for different durations were investigated. The results of the integral absorption cross-section analysis demonstrated that the partition fraction of Er3+ in LaF3 nanocrystals increases with prolonging of heating time. The anomalous phenomena of Er3+ emissions in the up-and the down-conversion fluorescence spectra are well explained based on the calculated results.     

Preparation of Silicon Oxycarbide Glass Fibers by Sol-Gel Method—Effect of Starting Sol Composition on Tensile Strength of Fibers

Silicon oxycarbide (Si—O—C) glass fibers were prepared by heat-treating the gel fibers drawn from the solution containing tetra-ethyl-ortho-silicate (TEOS), tri-ethoxysilane (HTES) and methyl-tri-ethoxysilane (MTES) in the course of sol-gel reaction.The replacement of TEOS by HTES in the solution, with the molar ratio of MTES to total alkoxysilanes being kept constant at 1/3, resulted in remarkable improvement of tensile strength of the glass fibers prepared at 1300°C. The decrease in the content of free carbon was observed in such fibers, even by an amount as small as a few wt%, and was considered to be related to the suppression of devitrification of the fibers to form -SiC and to the enhancement of mechanical strength.     

Contribution of Temperature Modulated DSC® to the Study of the Molecular Mobility in Glass Forming Pharmaceutical Systems

The temperature modulated differential scanning calorimetry (MDSC^®) technique has been used to characterise the low frequency molecular mobility of indomethacin and maltitol just above their respective calorimetric glass transition temperatureT _g. Analysis has been made using the concept of complex specific heat. Spectroscopic information are thus obtained through the temperature dependence of the isochronal real and imaginary parts C′ and C″. This gives access to the fragility index m and the stretched exponent β. The comparison with dielectric spectroscopy has been performed to check the coherence of spectroscopic information. Measurements on maltitol enable to demonstrate the useful complementarity of the technique when the low frequencies dielectric relaxations are occulted by the presence of conductors default.     

Metal–Organic Framework Crystal–Glass Composite Membranes with Preferential Permeation of Ethane

Metal–organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal–glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C₂H₆ permeance of 41 569 gas permeation units (GPU) and a C₂H₆/C₂H₄ selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C₂H₆ and promotes C₂H₆ transport in the membrane, and thus the GCG membrane exhibits ultrahigh C₂H₆ permeance and good C₂H₆/C₂H₄ selectivity.     

SILAR Deposition of CdS Thin Films on Glass Substrates Modified with 3‐Mercaptopropyltrimethoxysilane

Glass substrates modified with 3‐mercaptopropyltrimethoxysilane (MPS) were used to deposit CdS thin films in the process of successive ionic layer adsorption and reaction (SILAR). The films were characterized by X‐ray diffraction, optical absorption, and atomic force microscopy (AFM). AFM showed that the modified substrates were in favor of the growth of the films by comparison with the unmodified ones. The depositing rate of the films was faster on modified substrates than on unmodified ones.     

Glass transition and crystallization kinetics analysis of Sb–Se–Ge chalcogenide glasses

Differential thermal analysis (DTA) has been employed to investigate the effect of Ge addition on the glass transition behavior and crystallization kinetics of Sb₁₀Se_90?xGe_x (x = 0, 19, 21, 23, 25, 27) alloys. The three characteristic temperatures viz. glass transition (T _g), crystallization (T _c), and melting (T _m) have been determined and found to vary with the heating rates and Ge content. Thermal stability and glass forming tendency have been evaluated in terms of ΔT (= T _c ? T _g) and reduced glass transition temperature. The activation energies for glass transition and crystallization have been used to analyze the nucleation and growth process. The activation energy analysis also determines the suitability of alloys to be used in switching applications. Results have been interpreted in terms of bond energies and structural transformations in the investigated alloys.     

A Mesoscopic Self-assembled Ring of a Femtomole Fluorescein Sessile Droplet on Glass Slide Support

Since the solvent evaporation of a droplet on a hydrophobically pretreated glass slide, femtomole amount of fluorescent materials is carried by the evaporation and results in outward capillary flow to the perimeter of the droplet spot where the solute deposits, and forms afluorescent ring like deposit (RLD) with submicrometer-scale structures.     

Synthesis of Sulfur/Selenium-containing Polyester with Recyclability and Controllable Hydrophilicity and Glass Transition Temperature

We present a ring-opening polymerization of bridged cyclic lactone utilizing alcohol as the initiator and organic base as the catalyst.Bridged γ-butyrolactone monomers(PhSGBL and PhSeGBL) were synthesized efficiently from commercially available 3-cyclohexene-1-carboxylic acid. Due to the ring strain of the bridged structure, ring-opening polymerization of this type of γ-butyrolactone derivative was successfully carried out under mild conditions, e.g., using ethylene glycol as the initiator and a...     

Density,Viscosity, and Glass Transition of an Ethylenediamine–Ethylene Glycol Binary System

Densities ρ and viscosities η were measured for the binary mixtures of ethylenediamine (EDA) and ethylene glycol (EG) in the temperature range 288.15–323.15 K for ρ and at 273.15–323.15 K for η, both of which are broader temperature ranges than those reported previously. The value of ρ monotonously decreases against the mole fraction of EDA, x _EDA, and increasing temperature. The concentration dependence of η exhibits a maximum in the intermediate concentration range at all temperatures measured. The glass transition temperature, T _g, for samples with x _EDA < 0.7 was measured using differential scanning calorimetry. The measured T _g values show a peak in the intermediate concentration range, which is a behavior similar to that of η; however, the peak concentrations for η and T _g did not precisely align because of a deviation in the maximum hydrogen-bond density. The partial molar volumes for EDA and EG and the thermal expansivities, α, were obtained from ρ. Results in the present study are discussed in terms of the extensively increasing hydrogen-bond density for polyamine–polyhydric alcohol systems.     

Low Temperature Synthesis,Structure and Bioactivity of 2CaO⋅3SiO2 Glass

Glasses of composition 2CaO3SiO₂ were prepared by means of the sol-gel route starting from tetramethyl orthosilicate and calcium nitrate tetrahydrate and the melt-quenching technique from a mixture of oxides. Their structures were compared. The infrared spectra suggest that the gel derived glass has a different structure than the corresponding melt quenched glass, having a more uniform distribution of non-bridging oxygens among the SiO₄ tetrahedra. Owing to its porosity, the gel derived glass is more prone to devitrify than the melt quenched glass is. The infrared spectra relative to samples soaked in a fluid simulating the composition of the human blood plasma suggest that the gel derived glass is more bioactive than the melt quenched glass is.