Glass transition phenomena Semiannual status report
Multiple transitions in polymer systems and equation of state properties for glass transition phenomena
Simha, R.↗
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Temperature Evolution of the Activation Barriers Leads to Meyer−Neldel Rules for Structural Relaxation and Transport in Polymers
Understanding activation barriers controlling structural relaxation in glass-forming liquids, molecular transport, and ionic conductivity in amorphous polymers is a grand challenge of fundamental scientific and materials engineering interest across disciplines. Over decades, intriguing but puzzling empirical correlations between the elementary time scale of activated barrier crossing and the apparent Arrhenius activation energy, the so-called Meyer−Neldel (MN) rules, have been discovered in diverse liquids and glasses. Here, in this study, we formulate and successfully apply a new experimental analysis and an explicitly dynamical theoretical framework which provides an understanding of the origin, validity, and failure of such correlations, that bridge and unify the three fields of structural relaxation, molecular transport, and ionic conductivity in liquids and quenched glasses. Distinct quasi-universal laws are predicted in equilibrated liquids and nonequilibrium glasses, consistent with experiments. Our analysis reveals that even if the relaxation appears Arrhenius over a limited temperature range, the physical activation barrier is generally temperature-dependent in polymeric systems even below glass transition temperature. In addition, we show that the approximate validity of classical MN rules hinges on a linear temperature dependence of this barrier and the temperature range probed in experiments. Our findings are relevant for controlling the activation barrier in functional soft polymeric materials relevant to molecular separations, barrier coatings, and charge transport, and also provide new constraints on the theoretical understanding of the mechanism underlying slow activated dynamics in glass-forming condensed matter.
Meyer-Neldel rules↗
Near Surface Vapor Bubble Layers in Buoyant Low Stretch Burning of Polymethylmethacrylate
Large-scale buoyant low stretch stagnation point diffusion flames over solid fuel (polymethylmethacrylate) were studied for a range of aerodynamic stretch rates of 2-12/ sec which are of the same order as spacecraft ventilation-induced stretch in a microgravity environment. An extensive layer of polymer material above the glass transition temperature is observed. Unique phenomena associated with this extensive glass layer included substantial swelling of the burning surface, in-depth bubble formation, and migration and/or elongation of the bubbles normal to the hot surface. The bubble layer acted to insulate the polymer surface by reducing the effective conductivity of the solid. The reduced in-depth conduction stabilized the flame for longer than expected from theory neglecting the bubble layer. While buoyancy acts to move the bubbles deeper into the molten polymer, thermocapillary forces and surface regression both act to bring the bubbles to the burning surface. Bubble layers may thus be very important in low gravity (low stretch) burning of materials. As bubbles reached the burning surface, monomer fuel vapors jetted from the surface, enhancing burning by entraining ambient air flow. Popping of these bubbles at the surface can expel burning droplets of the molten material, which may increase the fire propagation hazards at low stretch rates.
Olson, Sandra L.↗
Strain-Based Chemiresistive Polymer-Coated Graphene Vapor Sensors
Suspended chemiresistive graphene sensors have been fabricated using well-established nanofabrication techniques to generate sensors that are highly sensitive to pyridine and with excellent discrimination between polar and nonpolar analytes. When coated with a polymer surface layer and suspended on 3-D patterned glass electrodes, a hybrid combination of polymer and graphene yields chemiresistive vapor sensors. Expansion and contraction of the polymer layer produces strain on the suspended graphene (Gr). Hence, when organic vapors permeate into the polymer layer, the high gauge factor of the graphene induces substantial electrical resistive changes as folds and creases are induced in the graphene. The hybrid suspended polymer/Gr sensor exhibits substantial responses to polar organic vapors, especially pyridine, while also exhibiting reversibility and increased discrimination between polar and nonpolar analytes compared to previous approaches. This sensor design also allows for potential tunability in the types of polymers used for the reactive surface layer, allowing for use in a variety of potential applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Biobased chemical recycling: aminolysis of PET using renewable reagents and monomers to synthesize new semi-aromatic polyamides
Chemical recycling of PET is a method of depolymerizing polymer chains to monomeric components enabling the synthesis of second-generation materials with virgin-like quality. Commercial chemical recycling techniques rely upon high pressure methanolysis to create precursors capable of synthesizing a second-generation PET resin. However, despite the circular approach of methanolysis, a product with a very short lifespan and similar value is created. The approach of the current study is to utilize aminolysis as an ambient pressure technique to create precursors for higher value materials with longer lifespans to address the current crisis in plastic waste. Semi-aromatic polyamides (SAP) are desired in this circumstance because of their high melting point and heat resistance combined with good melt-processability similar to aliphatic polyamides. In this study SAPs were synthesized using precursors recovered from the aminolysis of PET employing biobased diamines and dicarboxylic acids. While aminolysis has been explored in previous studies, this work investigated the use of biobased components from castor oil: decamethylene diamine during recycling and sebacic acid during polymerization. Polymer synthesis resulted in the formation of SAPs similar to polyphthalamides (PPA) with novel structures given the aromatic portion from terephthalic acid (TPA) and aliphatic portion from the diamines and diacids. The synthesized materials exhibited excellent thermal stability with high glass transition temperatures. Novel polymers were created with varying aliphatic chain length to understand fundamental parameters needed to produce a valuable polymer from post-consumer waste.
High performance Applications↗
A review of the fabrication methods and mechanical behavior of continuous thermoplastic polymer fiber–thermoplastic polymer matrix composites
Abstract Thermoplastic polymer fiber–thermoplastic polymer matrix composites (PPCs or PRFPs), often recognized as self‐reinforced or single polymer composites, are potential candidates for future advanced polymer composites because of various advantages ( e.g., recyclability, formability, low‐cost, ultra‐lightweight, environmental friendliness, etc.). The manufacturability and mechanical behavior of these composites compared to conventional carbon‐/glass‐/aramid‐fiber‐reinforced polymers is of great interest to the composites community, but there are a limited number of studies in this area. To this end, this paper reviewed fabrication methods with different processing parameters and mechanical behavior of uni‐/multi‐directional thermoplastic PPCs featuring continuous thermoplastic polymer fibers from limited data in the literature. It was shown that most specific behaviors (normalized by density) of these materials in various loading conditions (e.g., quasi‐static tension/shear/flexure, tension‐tension fatigue, and out‐of‐plane impacting, etc.) are comparable to or better than glass‐/aramid‐fiber‐reinforced polymers. Particularly, the specific ductility in the foregoing conditions outperforms all the carbon‐/glass‐/aramid‐fiber‐reinforced polymers. Thermoplastic PPCs with remarkable performance can be achieved through several uncomplicated methods (e.g., film stacking, hot compaction, powder and solution impregnations, matrix infusion and injection molding, additive manufacturing, etc.), which have some similarities to the methods used for carbon‐/glass‐/aramid‐fiber‐reinforced polymers. Moreover, several opportunities and challenging problems of thermoplastic PPCs were summarized at the end of this review paper. Efficient solutions may require countless efforts in the composites community to further strengthen the performance and understanding of thermoplastic PPCs for wide applications in various engineering fields in the future.
36 MATERIALS SCIENCE↗
Mechanical Properties and Durability of "Waterless Concrete"
Waterless concrete consists of molten elementary sulfur and aggregate. The aggregates in lunar environment will be lunar rocks and soil. Sulfur is present on the Moon in Troilite soil (FeS) and by oxidation soil iron and sulfur can be produced. Iron can be used to reinforce the sulfur concrete. Sulfur concrete specimens were cycled between liquid nitrogen (approximately 191 C) and room temperature (approximately 21 C) to simulate exposure to a lunar environment. Cycled and control specimens were subsequently tested in compression at room temperatures (approximately 21 C) and approximately 101 C. Test results showed that due to temperature cycling, compressive strength of cycled specimens was 20% of those non-cycled. Microscopic examination of the fracture surfaces from the cycled samples showed clear de-bonding of the sulfur from the aggregate material whereas it was seen well bonded in those non-cycled. This reduction in strength can be attributed to the large differences in thermal coefficients of expansion of the materials constituting the concrete which promoted cracking. Similar sulfur concrete mixtures were strengthened with short and long glass fibers. The glass fibers from lunar regolith simulant was melted in a 25 cc Pt-Rh crucible in a Sybron Thermoline high temperature MoSi2 furnace at melting temperatures of 1450 to 1600 C for times of 30 min to 1 hour. Glass fibers were cast from the melt into graphite crucibles and were annealed for a couple of hours at 600 C. Glass fibers and small rods were pulled from the melt. The glass melt wets the ceramic rod and long continuous glass fibers were easily hand drawn. The glass fibers were immediately coated with a protective polymer to maintain the mechanical strength. The glass fibers were used to reinforce sulfur concrete plated to improve the flexural strength of the sulfur concrete. Prisms beams strengthened with glass fibers were tested in 4-point bending test. Beams strengthened with glass fiber showed to exhibit an increase in the flexura strength by as much as 45%.
Toutanji, Houssam↗
[Results of Simulation Studies]
Lattice Monte Carlo and off-lattice molecular dynamics simulations of h(sub 1)t(sub 4) and h(sub 4)t(sub l) (head/tail) amphiphile solutions have been performed as a function of surfactant concentration and temperature. The lattice and off-lattice systems exhibit quite different self-assembly behavior at equivalent thermodynamic conditions. We found that in the weakly aggregating regime (no preferred-size micelles), all models yield similar micelle size distributions at the same average aggregation number, albeit at different thermodynamic conditions (temperatures). In the strongly aggregating regime, this mapping between models (through temperature adjustment) fails, and the models exhibit qualitatively different micellization behavior. Incipient micellization in a model self-associating telechelic polymer solution results in a network with a transient elastic response that decays by a two-step relaxation: the first is due to a heterogeneous jump-diffusion process involving entrapment of end-groups within well-defined clusters and this is followed by rapid diffusion to neighboring clusters and a decay (terminal relaxation) due to cluster disintegration. The viscoelastic response of the solution manifests characteristics of a glass transition and entangled polymer network.
Source record↗
Some characteristics of polymers in composite materials and as electrical conductors
The characteristics of carbon fibers (CF) made from polyacrylonitrile (PAN) materials are discussed, together with research on conducting polymers. CF materials have better mechanical properties, chemical inertness, and higher stiffness than metallic materials but are subject to environmental instability, flammability, and delamination fatigue. Polymerization procedures for the monopolymer PAN are described, noting the use of SEM and X-ray diffraction techniques for studying the fiber structure. High modulus and strength of CF are caused by covalent sp(2) bonds in hexagonal carbon rings, which are stronger than the same links in diamonds. Details of the molecular chain structures and macroformations, stress-strain as a function of temperature, and thermosetting and glass transition temperatures of polymers are provided. Computational quantum chemistry techniques are being applied to studying electrical conductance in polymers, mainly to discover ways to stabilize the materials. Doped CH(x) has exhibited photovoltaic properties and other polymers have become superconductors at cryogenic temperatures.
Hansen, C. F.↗
Polyimides containing the cyclobutene-3,4-dione moiety
In the present invention, linear aromatic polyimides containing the cyclobutene-3,4-dione moiety were produced from the reaction of a substituted or unsubstituted 1,2-bis(4-aminoanilino) cyclobutene-3,4-dione (SQDA) with various aromatic dianhydrides. These polymers had high molecular weights and their glass transition temperatures (Tgs) were greater than 500 C. Despite the very high Tg, these polymers exhibited excellent adhesion to glass. In addition, the films of these polyimides increased in flexibility with increasing cure temperatures. The novelty of this invention lies in the linear aromatic polyimide containing the cyclobutene-3,4-dione moiety. The presence of this moiety causes such changes in properties as Tgs greater than 500 C, excellent adhesion to glass, and increased flexibility with increasing cure temperatures.
St.clair, Terry L.↗
Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains
The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (T g ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher T g . In this work, the T g s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermally cleavable side chains at 140 °C, is found to remove more than 95% of alkyl side chains in 24 h, and raise the backbone T g from 23 to 75 °C. Coarse grain molecular dynamics simulations are used to understand the T g dependence on side chain cleavage. X-ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. Here, the combined effect of enhancing T g and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Charging of Composites in the Space Environment
Deep dielectric charging and subsequent electrostatic discharge in composite materials used on spacecraft have become greater concerns since composite materials are being used more extensively as main structural components. Deep dielectric charging occurs when high energy particles penetrate and deposit themselves in the insulating material of spacecraft components. These deposited particles induce an electric field in the material, which causes the particles to move and thus changes the electric field. The electric field continues to change until a steady state is reached between the incoming particles from the space environment and the particles moving away due to the electric field. An electrostatic discharge occurs when the electric field is greater than the dielectric strength of the composite material. The goal of the current investigation is to investigate deep dielectric charging in composite materials and ascertain what modifications have to be made to the composite properties to alleviate any breakdown issues. A 1-D model was created. The space environment, which is calculated using the Environmental Workbench software, the composite material properties, and the electric field and voltage boundary conditions are input into the model. The output from the model is the charge density, electric field, and voltage distributions as functions of the depth into the material and time. Analysis using the model show that there should be no deep dielectric charging problem with conductive composites such as carbon fiber/epoxy. With insulating materials such as glass fiber/epoxy, Kevlar, and polymers, there is also no concern of deep dielectric charging problems with average day-to-day particle fluxes. However, problems can arise during geomagnetic substorms and solar particle events where particle flux levels increase by several orders of magnitude, and thus increase the electric field in the material by several orders of magnitude. Therefore, the second part of this investigation was an experimental attempt to measure the continuum electrical properties of a carbon fiber/epoxy composite, and to create a composite with tailorable conductivity without affecting its mechanical properties. The measurement of the conductivity and dielectric strength of carbon fiber/epoxy composites showed that these properties are surface layer dominated and difficult to measure. In the second experimental task, the conductivity of a glass fiber/epoxy composite was increased by 3 orders of magnitude, dielectric constant was increased approximately by a factor of 16, with minimal change to the mechanical properties, by adding conductive carbon black to the epoxy.
Czepiela, Steven A.↗
Structures and Properties of Polymers Important to Their Wear Behavior
The wear and transfer of various semicrystalline polymers sliding against smooth steel or glass surfaces were examined. The effects of structures, and properties of polymers on their wear behavior are discussed. It is found that the high wear characteristics of PTFE is due to the easy destruction of the banded structure of PTFE. The size of spherulites and the molecular profile are closely related to the magnitude of wear rates of typical semicrystalline polymers. The effects of these factors on the wear rate on the basis of the destruction or melting of spherulites at the frictional surface are discussed. Although the fatigue theory of wear indicates that some mechanical properties are important to wear behavior, it is shown that the theory does not always explain the experimental result obtained on a smooth surface.
Tanaka, K.↗
Thermogravimetric Analysis (TGA) for Carbon Fiber and Glass Fiber Epoxy Composites and their Constituents
In this work, thermogravimetric analysis (TGA) was performed on samples of a carbon fiber epoxy composite, a glass fiber epoxy composite, and a mixed carbon fiber/glass fiber epoxy composite, as well on each constituent material (polymer epoxy, carbon fibers and glass fibers). TGA was conducted for heating rates from 1-20 C/min with purified purge gases of nitrogen and dry air. For the fiberglass composite, we find that ~70% of the material remains after heating in air to 1200 C. For the carbon fiber epoxy composite, we observe greater mass loss as the carbon fibers can oxidize, leaving little material by the end of the test. The mixed composite, which has a 2:1 ratio of glass fibers to carbon fibers, experienced a total mass loss between the two other composites. By determining the relationship between the thermal decomposition of a composite material and its constituent materials, we can predict the fire behavior of novel composites during the material design phase.
36 MATERIALS SCIENCE↗
Dielectric determination of the glass transition temperature (T sub g)
The objective is to determine the glass transition temperature of a polymer using a dielectric dissipation technique. A peak in the dissipation factor versus temperature curve is expected near the glass transition temperature T sub g. It should be noted that the glass transition is gradual rather than abrupt, so that the glass transition temperature T sub g is not clearly identifiable. In this case, the glass transition temperature is defined to be the temperature at the intersection point of the tangent lines to the dissipation factor versus temperature curve above and below the transition region, as illustrated.
Ries, Heidi R.↗
Videos of Chemically Activated Frontal Polymerization of Thermosets
Video recordings of the frontal ring-opening metathesis polymerization (FROMP) of thermoset polymer specimens in 10mm glass test tubes were collected in order to measure the front speed resulting from varied front initiation methods. Maximum front temperature was also measured. Polymerization resins comprised of dicyclopentadiene (DCPD) with 5 wt% 5-ethylidene-2-norbornene (ENB) added, grubbs’ second generation catalyst, and tributyl phosphite (TBP) inhibitor (8000:1:1 monomer:initiator:inhibitor ratio). Polymerization fronts were triggered using concentrated solutions of grubbs’ third generation catalyst in various solvents.
Cramblitt, Anna C.↗
Low-temperature radiation-resistant material for ball-bearing retainers
Radiation resistant material, made of polyimide polymers and S-glass cloth, is used in ball bearing retainers for extreme environments. Material displays satisfactory wear resistance, lubricity, and stability. Results of comparative tests with fluorocarbon materials are given.
Desau, P. O.↗