Respective Glass Transition Research Articles

Effect of Chain Orientation on Coupling of Optical and Mechanical Anisotropies of Polymer Films

Polymer films have broad applications in different industries with specific requirements for their optical and mechanical properties. In mass production, processing conditions during film formation that apply forces and motions in various directions to the film tend to manifest preferred molecular chain orientation in the film microstructure, which unavoidably produces optical and mechanical anisotropies. In this paper, we investigate the effect of such macromolecular orientations on the optical and mechanical anisotropies of several polymer films, including polystyrene, poly(methyl methacrylate), poly(ethylene terephthalate), poly(ethylene naphthalate), poly(ether ether ketone), poly(ether sulfones), poly(ethylene chlorotrifluoroethylene), poly(phenylsulfone), and polycarbonate, at temperatures well below their respective glass transitions (Tg). The film mechanical responses, including elasticity, yielding, and post-yield behaviors, were obtained for the in- and out-of-plane directions utilizing tensile and nanoindentation testing methods, respectively. In addition, the net chain orientation within the films was evaluated by birefringence through analyzing the film optical refractive indices, which were verified and complemented by wide-angle X-ray scattering (WAXS) measurements. The results reveal a considerable quantitative correlation between the birefringence and the degree of elastic anisotropy and a qualitative correlation between the chain orientation and the film post-yield tensile instability (necking). These observations corroborate the interrelationship between the microstructure of polymer films and their optical and mechanical properties. In addition, they emphasize that process conditions can be selected to tune the optical and mechanical anisotropies to best serve the material performance in specific devices. We also propose an empirical equation to approximate the out-of-plane film stiffness based upon the optical and in-plane mechanical properties.

Mechanical Characterization of Vial Strain During Freezing and Thawing Operations Using Amorphous Excipients

The purpose of this study was to investigate the mechanical stresses and strains acting on pharmaceutical glass tubing vials during freezing and thawing of model pharmaceutical formulations. Strain measurements were conducted inside of a laboratory-scale freeze-dryer using a custom wireless sensor. In both sucrose and trehalose formulations at concentrations between 5 % and 20 % w/v, the strain measurements initially increased before peaking in magnitude at temperatures close to the respective glass transition temperatures of the maximally freeze concentrated solutes, Tg’. We attribute this behavior to a shift in the mechanical properties of the frozen system from a purely elastic glass below Tg’ to a viscoelastic rubber-like material above Tg’. That is, when the interstitial region becomes mechanically compliant at temperature above Tg’. The outputs were less predictable below 5 % w/v and tended to exhibit two separate peaks in strain output, one near the equilibrium melting temperature of pure ice and the other near Tg’. The peaks merged at concentrations between 4 and 5 % w/v where the largest strain magnitude was observed. The strain on primary packaging has traditionally been applied to evaluate the risk of damage or breakage due to, for example, crystallization of excipients. However, data collected during this study suggest there may be utility in formulation design or as a process analytical technology to minimize potentially destabilizing stresses and strains in the frozen formulation.

Thermal conductivity of CaO-B2O3 system as functions of temperature including glass transition

The study aims to investigate the possible effect of glass transition firstly on the thermal conductivity of the CaO-B2O3 system. The addition of CaO was varied in the range of 0 to 40 mass %. The transient hot-wire method, transient hot-strip method, laser flash method and the thermoreflectance method were applied for the investigation in the temperature range of 298 K to 1175 K. Positive temperature dependence was found for the 38mass %CaO-B2O3 sample, which is the same as reported for B2O3. However, slopes of the temperature dependence change just above the respective glass transition temperature. The addition of CaO to B2O3 leads to the increase of thermal conductivity. The study discusses the possible structural change of B2O3.

Densification of Sodium Borosilicate Glasses at Ambient Temperature: Structural Investigations by Solid-State Nuclear Magnetic Resonance and Raman Scattering

Alkali-borosilicate glasses with composition (80-x)SiO2-xB2O3-20Na2O (10 ≤ x ≤ 30) were subjected to a 25 GPa compression and decompression at room temperature, resulting in density increases between 1.4% and 1.9%. The structural changes associated with this process have been investigated and compared with uncompressed glasses having the same thermal history. Systematic trends are identified, using Raman scattering and multinuclear solid-state Nuclear Magnetic Resonance (ssNMR). Perhaps counterintuitively, pressurization tends to increase the concentration of three-coordinated boron species (B(III) units) at the expense of four-coordinated boron (B(IV) units). 23Na NMR spectra show a systematic shift toward higher frequencies in the pressurized glasses, consistent with shorter average Na-O distances. The results are consistently explained in terms of a breakage of Si-O-B4 linkages resulting in the formation of nonbridging oxygen species. Pressure effects on the spectra are reversed by annealing the glasses at their respective glass transition temperatures.

Flexural, impact, and dynamic mechanical analysis of glass fiber/ABS and glass fiber/carbon fiber/ABS composites

AbstractIn this study, a hybrid manufacturing technique was proposed to fabricate composites of acrylonitrile butadiene styrene (ABS) with Bidirectional woven glass fiber mat (GF)/ABS and GF/Bidirectional woven carbon fiber mat (CF)/ABS. The composites were fabricated using fused deposition modeling 3D printing, followed by hot compression molding, and their flexural, impact, and dynamic mechanical behaviors were examined. Results indicated that composites with GF and ABS combinations had shown the highest maximum flexural strength (64.46 MPa) and impact strength (0.089 J/mm2). The hybrid composites showed intermediate performance between ABS and GF/ABS composites, with higher flexural strain before failure than ABS and GF/ABS. A comprehensive analysis utilizing scanning electron microscopy was carried out to evaluate the adhesion characteristics of the fiber‐matrix interface in impact‐tested samples. Dynamic mechanical analysis showed that GF/ABS composites had offered superior E′, E″, and tanδ than the hybrid configuration. The peak tan delta values obtained from ABS, GF/ABS, and GF/CF/ABS composites were utilized to determine their respective glass transition temperatures. The observed values for ABS, GF/ABS, and GF/CF/ABS composites were 109.65, 69.95, and 71.5°C, respectively. Some potential applications for the composites fabricated in this study could include the development of lightweight and strong components for aerospace or automotive industries.

Accelerated physical aging of four PET copolyesters: Enthalpy relaxation and yield behaviour

Assessing suitability of amorphous polymers in durable products requires understanding of long-term effects of physical aging on the material properties. This work shows four polyesters with varying diol composition (poly(ethylene-co-1,4-cyclohexylenedimethylene terephthalate) (PETG1 and PETG2 with ∼30 and ∼60% 1,4-cyclohexylenedimethylene (CHDM), respectively), poly(ethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate) (PETT) with ∼30% 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and poly(1,4-cyclohexylenedimethylene-co-2,2,4,4-tetramethyl-1,3-cyclobutanediol terephthalate) (PCTT) with ∼80% CHDM and ∼20% TMCD) exposed to thermal treatment at 20, 30 and 40 °C below their respective glass transition temperatures for up to 504 h to accelerate physical aging. The enthalpy relaxation was investigated by differential scanning calorimetry and compared to mechanical changes manifested as tensile yield strength increase. The physical aging rates were found to depend on both chemical structure and composition of CHDM and TMCD segments, where the introduction of TMCD inhibited physical aging. Arrhenius and Vogel-Fulcher-Tamman models were used to fit horizontal shift factors and evaluate the time and temperature dependencies for each polyester. From this study, the two models showed no significant differences in ability to describe the effects of physical aging. The Arrhenius activation energies, Ea, were all in the range 118–244 kJ mol−1, were both PETG1 and PETG2 showed no significant difference between Ea for enthalpy relaxation and yield strength increase, whereas PETT and PCTT showed ∼19 and ∼107% difference between the two, respectively, suggesting that the relationship between the two phenomena is not independent of chemical structure. The difference between the activation energies suggests that the time scales for physical aging are different when observed as enthalpy relaxation and yield strength.

Variability in the inorganic composition of colored acrylonitrile-butadiene-styrene and polylactic acid filaments used in 3D printing.

Fused filament fabrication is a 3D printing technique that has gained widespread use from homes to schools to workplaces. Thermoplastic filaments, such as acrylonitrile-butadiene-styrene (ABS) and polylactic acid (PLA), are extruded at temperatures near their respective glass transition temperature or melting point, respectively. Little has been reported on the inorganic elemental composition and concentrations present in these materials or the methods available for extracting that information. Because inorganic constituents may be included in the aerosolized particulates emitted during the printing process, identifying elements that could be present and at what specific concentrations is critical. The objective of the current research is to determine the range of metals present in thermoplastic filaments along with their relative abundance and chemical speciation as a function of polymer type, manufacturer, and color. A variety of filaments from select manufacturers were digested using a range of techniques to determine the optimal conditions for metal extraction from ABS and PLA polymers. The extraction potential for each method was quantified using by ICP-MS analysis. When possible, further characterization of the chemical composition of the filaments was investigated using X-ray Absorption spectroscopy to determine chemical speciation of the metal. Optimal digestion conditions were established using a high temperature, high pressure microwave-assisted acid digestion method to produce the most complete and repeatable extraction results. The composition and abundance of metals in the filaments varied greatly as a function of polymer, manufacturer, and color. Potential elements of concern present in the filaments at elevated concentration included that could pose a respiratory risk included Si, Al, Ti, Cu, Zn, and Sn. XAS analysis revealed a mixture of metal oxides, mineral, and organometallic compounds were present in the filaments that were being used to increase opaqueness impart color (dyes), polymeric catalysts, and flame retardants. This work shows that a variety of metals are present in the starting materials used for 3D printing and depending on their partitioning into 3D printed products and byproducts as well as the exposure route, may pose a health risk which merits further investigation.

Microstructural Evolution of Viscoelastic Properties of Underfills Under Sustained High Temperature Operation

Abstract Automotive underhood electronics are subjected to high operating temperatures in the neighborhood of 150 to 200? for prolonged periods in the neighborhood of 10-years. Consumer grade off-the shelf electronics are designed to operate at 55 to 85? with a lower use-life of 3 to 5 years. Underfill materials are used to provide supplemental restraint to fine-pitch area array electronics and meet the reliability requirements. In this paper, a number of different underfill materials are subjected to automotive underhood temperatures to study the effect of long time isothermal exposure on microstructure and dynamic-mechanical properties. It has been shown that isothermal aging oxidizes the underfill, which can change the mechanical properties of the material significantly. The oxidation of underfill was studied experimentally by measuring oxidation layer thickness using polarized optical microscope. The effect on the mechanical properties was studied using the dynamic mechanical properties of underfill with DMA (Dynamic Mechanical Analyzer). Two different underfill materials were subjected to three different isothermal exposure, which are below, near and above the glass transition temperature of the underfills. The dynamic mechanical viscoelastic properties like storage modulus, loss modulus, tan delta and their respective glass transition temperatures were investigated. Three point bending mode was used in the DMA with a frequency of 1 Hz operating at 3?/min.

Fast Surface Dynamics on a Metallic Glass Nanowire.

The dynamics near the surface of glasses can be much faster than in the bulk. We studied the surface dynamics of a Pt-based metallic glass using electron correlation microscopy with sub-nanometer resolution. Our studies show an ∼20 K suppression of the glass transition temperature at the surface. The enhancement in surface dynamics is suppressed by coating the metallic glass with a thin layer of amorphous carbon. Parallel molecular dynamics simulations on Ni80P20 show a similar temperature suppression of the surface glass transition temperature and that the enhanced surface dynamics are arrested by a capping layer that chemically binds to the glass surface. Mobility in the near-surface region occurs via atomic caging and hopping, with a strong correlation between slow dynamics and high cage-breaking barriers and stringlike cooperative motion. Surface and bulk dynamics collapse together as a function of temperature rescaled by their respective glass transition temperatures.

Mechanisms of bulk and surface diffusion in metallic glasses determined from molecular dynamics simulations

The bulk and surface dynamics of Cu50Zr50 metallic glass were studied using classical molecular dynamics (MD) simulations. As the alloy undergoes cooling, it passes through liquid, supercooled, and glassy states. While bulk dynamics showed a marked slowing down prior to glass formation, with increasing activation energy, the slowdown in surface dynamics was relatively subtle. The surface exhibited a lower glass transition temperature than the bulk, and the dynamics preceding the transition were accurately described by a temperature-independent activation energy. Surface dynamics were much faster than bulk at a given temperature in the supercooled state, but surface and bulk dynamics were found to be very similar when compared at their respective glass transition temperatures. The manifestation of dynamical heterogeneity, as characterized by the non-Gaussian parameter and breakdown of the Stokes-Einstein equation, was also similar between bulk and surface for temperatures scaled by their respective glass transition temperatures. Individual atom motion was dominated by a cage and jump mechanism in the glassy state for both the bulk and surface. We utilize this cage and jump mechanisms to separate the activation energy for diffusion into two parts: (i) cage-breaking barrier (Q1), associated with the rearrangement of neighboring atoms to free up space and (ii) the subsequent jump barrier (Q2). It was observed that Q1 dominates Q2 for both bulk and surface diffusion, and the difference in activation energies for bulk and surface diffusion mainly arose from the differences in cage-breaking barrier Q1.

Dynamic Moduli of Polybutylene Terephthalate Glass Fiber Reinforced in High-Temperature Environments.

The aim of this work was to show the evolution over time of the dynamic moduli in components made of Polybutylene Terephthalate reinforced with glass fiber when they are held to temperatures close to the glass transition temperature over time. For this purpose, PBT samples reinforced with short, glass fibers of Ultradur® material with 0%, 20%, and 50% in weight content were tested. Dynamic moduli showed an increment with glass fiber content showing a nonlinear behavior with the temperature. The evolution of storage modulus was depicted by means of a modified law of mixtures with an effectiveness factor depending on temperature and fiber content, whereas the evolution over time was obtained with a time–temperature transformation generated with the TTS Data Analysis software of TA-instruments for a given temperature. Storage modulus showed a linear relationship with glass fiber content when components were held to temperatures near to their respective glass transition temperature, obtained from the maximum of loss modulus curve with temperature. In summary, the value and evolution of dynamic moduli of PBT samples improved with glass fiber content, allowing us to increase the durability of components when they are submitted to high-temperature environments.

Influence of filler hybridization on thermomechanical properties of hemp/silver epoxy composite

The polymer composite material’s thermomechanical properties with fiber as reinforcement material have been widely studied in the last few decades. However, these fiber-based polymer composites exhibit problems such as fiber orientation, delamination, fiber defect along the length and bonding are the matter of serious concern in order to improve the thermomechanical properties and obtain isotropic material behavior. In the present investigation filler-based composite material is developed using natural hemp and high thermal conductive silver nanoparticles (SNP) and combination of dual fillers in neat epoxy polymer to investigate the synergetic influence. Among various organic natural fillers hemp filler depicts good crystallinity characteristics, so selected as a biocompatible filler along with SNP conductive filler. For enhancing their thermal conductivity and mechanical properties, hybridization of hemp filler along with silver nanoparticles are conducted. The composites samples are prepared with three different combinations such as sole SNP, sole hemp and hybrid (SNP and hemp) are prepared to understand their solo and hybrid combination. From results it is examined that, chemical treated hemp filler has to maximized its relative properties and showed, 40% weight % of silver nanoparticles composites have highest thermal conductivity 1.00 W/mK followed with hemp filler 0.55 W/mK and hybrid 0.76 W/mK composites at 7.5% of weight fraction and 47.5% of weight fraction respectively. The highest tensile strength is obtained for SNP composite 32.03 MPa and highest young’s modulus is obtained for hybrid composites. Dynamic mechanical analysis is conducted to find their respective storage modulus and glass transition temperature and that, the recorded maximum for SNP composites with 3.23 GPa and 90°C respectively. Scanning electron microscopy examinations clearly illustrated that formation of thermal conductivity chain is significant with nano and micro fillers incorporation.

Dynamic Properties of Supercooled Chlorinated Biphenyls.

A study of the dynamics of a series of biphenyl compounds having varying chlorine levels was carried out. Increasing the chlorine content increases the glass transition temperature and makes the dynamics substantially more sensitive to density changes. Nonetheless, in the vicinity of their respective glass transitions, the different liquids display very similar extents of dynamic correlation and dynamic heterogeneity. The slight narrowing of the relaxation peak with increasing chlorine follows the general trend of the effect of increasing molecular polarity. This relationship between the peak breadth and dipole moment was reproduced in molecular dynamics simulations of a simplified model of the Aroclor molecule.

Quantitative estimation of crystallization kinetics in GeGaS and Au‐doped GeGaS glass‐ceramics

AbstractGe26.7Ga8S65.3 (GGS) and 0.1% Au‐doped Ge26.7Ga8S65.3 (GGS‐Au) glasses were prepared and annealed at a temperature that is 20 K higher than their respective glass transition temperature in order to create chalcogenide glass‐ceramics. X‐ray diffraction results showed that, thermal annealing can induce large amount of the crystal growth in the pure glass but this can be significantly suppressed by Au doping in the glass, which is in agreement with the previous results. We further employed various calorimetric methods, together with Mauro‐Yue‐Ellison‐Gupta‐Allan viscosity model, to investigate their crystallization kinetics. The crystal growth rate at annealing temperature of 723 K was quantitatively deduced to be 2.5 × 10−8 μm/s in Au‐doped GGS, which is about 20 times slower than that in the pure GGS with a growth rate of 4.7 × 10−7 μm/s.

Role of Tin Oxide as a Nucleating Agent with Low Solubility in BaO–SrO–ZnO–SiO2 Glasses Studied by Electron and X-ray Microscopy

The crystallization behavior of BaO–SrO–ZnO–SiO2 glasses containing different concentrations of SnO2 was studied using microscopic techniques as well as thermal analyses. It is shown that SnO2 triggers volume crystallization, but at low nucleation rates. During heat treatments near respective glass transition temperatures, nucleation takes place. In the course of this nucleation treatment, SnO2 added leads to the formation of small metallic particles which serve as nuclei for the growth of Ba1–xSrxZn2Si2O7 crystals. The metallic nuclei are composed of metallic Sn and Pt. The latter is introduced into the glass during synthesis in a Pt crucible as a contaminant. Besides scanning electron microscopy, also X-ray microscopy was used to study the microstructure as well as the origin of appearing cracks in three dimensions. It was found that the different morphologies detected via scanning electron microscopy are solely due to different orientations of the crystals within the glassy matrix. Furthermore, evidenc...

Ion Transport in Glassy Polymerized Ionic Liquids: Unraveling the Impact of the Molecular Structure

The impact of molecular structure on ion dynamics and morphology in ammonium- and imidazolium-based glassy polymerized ionic liquids (polyILs) is investigated using broadband dielectric spectroscopy (BDS), wide-angle X-ray scattering (WAXS), and classical molecular dynamics (MD) simulations. It is shown that ammonium-based polyILs exhibit higher dc ionic conductivity at their respective glass transition temperatures (Tg) compared to imidazolium systems. In addition, the length of the alkyl spacer has a more drastic impact on ionic conductivity at comparable time scales of segmental dynamics for ammonium than imidazolium polyILs. Agreement between the characteristic ion diffusion lengths estimated from the dielectric data and the ion-to-ion correlation lengths from the WAXS and all-atom MD simulations is observed. A recently proposed approach is employed to determine ionic mobility in a broad frequency range spanning 5 orders of magnitude below the Tg of polyILs studied, providing access to a regime of dif...

Naphthyl substituted triphenylamine derivatives as hole transporting materials for efficient red PhOLEDs

Naphthyl substituted triphenylamine and its derivatives with bromine atoms were synthesized and investigated. The respective glass transition temperatures of the materials were estimated to be in a range 65–137 °C, which can provide morphologically-stable amorphous films for applications in organic light emitting diodes. The compounds possess adequate ionization potentials (5.5–5.75 eV), high hole drift mobilities (>10−3 cm2/V·s) and suitable triplet energies (∼2.4 eV), which make them suitable hole transporting materials for use in red phosphorescent organic light-emitting diodes. A superior peak efficiency of 17.9% (31.4 cd/A and 26.9 lm/W) was achieved in a device having hole transporting layer of tris[4-(1-naphthyl)phenyl]amine. Furthermore, the device gave efficiencies of 17.7% and 16.6% recorded at luminance levels of 102 and 103 cd/m2. The efficiency drop from the maximum to the value recorded at the luminance of 103 cd/m2 for the device was only 7%.

Effects of annealing on density, glass transition temperature and structure of tellurite, silicate and borate glasses

Barium tellurite, lead tellurite, molybdenum tellurite, lead silicate and bismuth borate glasses of the compositions: xBaO-(100-x)TeO2 (x = 10, 15 and 20 mol%), xPbO-(100-x)TeO2 (x = 15 and 20 mol%), 25MoO3-75TeO2, xPbO-(100-x)SiO2 (x = 50, 60 and 65 mol%) and 40Bi2O3-60B2O3 were prepared by melt-quenching. The effects of long duration thermal annealing (below the respective glass transition temperature (Tg) values) on the density, thermal properties and the short-range structure of glasses were studied. Density increases on average by about 0.5% to 1% and Tg values show drastic increase in the range of 8 °C-64 °C after annealing. Raman and FTIR studies were performed on glasses before and after annealing, FTIR studies found that bismuth borate glasses show a small but significant increase in the fraction of tetrahedral borons in the borate network with annealing. Raman studies on lead metasilicate glass showed an increase in the concentration of SiO4 units that contain three bridging oxygens. Raman and FTIR spectra of all annealed barium and lead tellurite glasses were indistinguishable from those of the initial samples, however the FTIR spectra of annealed 25MoO3-75TeO2 glass show changes in the relative intensities of the peaks due to MoO vibrations along with the growth and sharpening of low frequency Raman bands, furthermore this glass also showed large differences in its crystallization and melting properties during thermal analysis.

Enthalpy relaxation of low molecular weight amorphous styrene oligomers measured with an adiabatic calorimeter

Herein, we measured the enthalpy relaxation of three styrene oligomers with different molecular weights (styrene oligomer with Mw = 4.53 × 102: PSA-300, styrene oligomer with Mw = 5.89 × 102: PSA-500, and styrene oligomer with Mw = 1.01 × 103: PSA-1000) near their respective glass transition temperatures (Tg) using an adiabatic calorimeter. We determined the relaxation rates and the amounts of configurational enthalpy released from the temperature dependence of the temperature drift rates around Tg. Based on our experimental findings, we found the amounts of configurational enthalpy release per monomer unit to be 0.8, 3.5, and 1.6 kJ mol−1 for PSA-300, PSA-500, and PSA-1000, respectively. These values were 3.9–18 times larger than that of glycerol, which is a typical glass-forming liquid.

(Bi)phenyl substituted 9-(2,2-diphenylvinyl)carbazoles as low cost hole transporting materials for efficient red PhOLEDs

Two low-cost 9-(2,2-diphenylvinyl)carbazole-based derivatives with aryl substitutions were synthesized by simple procedure and then investigated. The respective glass transition temperatures of the materials were estimated to be higher than 90 °C, which can provide morphologically-stable amorphous films for applications in organic light emitting diodes. The compounds possess adequate ionization potentials and suitable triplet energies, which make them suitable hole transporting materials for use in red phosphorescent organic light-emitting diodes. The respective peak efficiencies of the red devices with the p-type dopants were recorded at 8.7% (5.6 cd/A and 3.9 lm/W) and at 8.7% (5.4 cd/A and 3.8 lm/W), correspondingly, demonstrating high potential of the material for applications in light emitting diodes. The characteristics indicated that the devices with the aryl substituted 9-(2,2-diphenylvinyl)carbazoles exhibit better performance than those of widely used hole transporting 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) -based device.