Time-dependent Reactions of the Crystallizing and Solidifying of Linear High Polymers
Polyethylene polymer crystal growth - effects of high pressure, high temperature, and formation time on thermodynamic stability
THERMOSTABILITY↗
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Shear sensitive monomer-polymer laminate structure and method of using same
Monomer cholesteric liquid crystals have helical structures which result in a phenomenon known as selective reflection, wherein incident white light is reflected in such a way that its wavelength is governed by the instantaneous pitch of the helix structure. The pitch is dependent on temperature and external stress fields. It is possible to use such monomers in flow visualization and temperature measurement. However, the required thin layers of these monomers are quickly washed away by a flow, making their application time dependent for a given flow rate. The laminate structure according to the present invention comprises a liquid crystal polymer substrate attached to a test surface of an article. A light absorbing coating is applied to the substrate and is thin enough to permit bonding steric interaction between the liquid crystal polymer substrate and an overlying liquid crystal monomer thin film. Light is directed through and reflected by the liquid crystal monomer thin film and unreflected light is absorbed by the underlying coating. The wavelength of the reflected light is indicative of the shear stress experienced by the test surface. Novel aspects of the invention include its firm bonding of a liquid crystal monomer to a model and its use of a coating to reduce interference from light unreflected by the monomer helical structure.
Singh, Jag J.↗
Novel Microstructures for Polymer-Liquid Crystal Composite Materials
There are a number of interface-dominated composite materials that contain a liquid crystalline (LC) phase in intimate contact with an isotropic phase. For example, polymer- dispersed liquid crystals, used in the fabrication of windows with switchable transparency, consist of micron size LC droplets dispersed in an isotropic polymer matrix. Many other types of liquid crystal composite materials can be envisioned that might have outstanding optical properties that could be exploited in novel chemical sensors, optical switches, and computer displays. This research project was based on the premise that many of these potentially useful LC composite materials can only be fabricated under microgravity conditions where gravity driven flows are absent. In the ground-based research described below, we have focused on a new class of LC composites that we call thermotropic- lyotropic liquid crystal systems (TLLCs). TLLCs consist of nanosize droplets of water dispersed in an LC matrix, with surfactants at the interface that stabilize the structure. By varying the type of surfactant one can access almost an infinite variety of unusual LC composite microstructures. Due to the importance of the interface in these types of systems, we have also developed molecular simulation models for liquid crystals at interfaces, and made some of the first measurements of the interfacial tension between liquid crystals and water.
Magda, Jules J.↗
Skin friction measurement with partially exposed polymer dispersed liquid crystals
Partially exposed polymer dispersed liquid crystal thin film (10-25 microns) deposited on a flat glass substrate has been used for the first time to measure skin friction. Utilizing the shear-stress-induced director reorientation in the partially exposed liquid-crystal droplets, optical transmission under crossed polarization has been measured as a function of the air flow differential pressure. Direct measurement of the skin friction with a skin friction drag balance, under the same aerodynamic conditions, lets us correlate the skin friction with optical transmission. This provides a unique technique for the direct measurement of skin friction from the transmitted light intensity. The results are in excellent agreement with the model suggested in this paper.
Parmar, D. S.↗
Method of determining shear stress employing a monomer-polymer laminate structure
A laminate structure attached to the test surface of an article is presented. The laminate structure is comprised of a liquid crystal polymer substrate. A light absorbing coating is applied to the substrate and is thin enough to permit bonding steric interaction between the liquid crystal polymer substrate and an overlying liquid crystal monomer thin film. Light is directed through and reflected by the liquid crystal monomer thin film and unreflected light is absorbed by the underlying coating. The wavelength of the reflected light is indicative of the shear stress experienced by the test surface.
Singh, Jag J.↗
Fundamentals of Scalable Nanoparticle Assembly in Engineering Polymres
Systematically improving the properties of polymer nanocomposites is contingent on effectively controlling nanoparticle (NP) dispersion; further, it is necessary to attain this at scale if these methods are to impact practical applications. While most past work has focused on amorphous polymers, ≈ 70% of all polymers sold annually are semicrystalline. Inspired by this apparent disconnect, our work in the current DOE funded grant and this renewal proposal employs a novel handle, polymer crystallization, to organize NPs into the various amorphous zones of the lamellar semicrystalline morphology (interlamellar, interfibrillar and interspherulitic domains) of stereoregular polymers. We hypothesize that the isothermal crystallization rate of a polymer host, G, and NP diffusivity, are the two relevant control parameters in this context. In the case where the NPs are miscible in the melt, they remain spatially well-dispersed when the polymer is crystallized at a rate that is fast relative to NP diffusion. In contrast, monolayer-thick NP sheets with intersheet spacing of ~10-100nm form in slowly crystallized samples. This sheet stacking is remarkably similar to that seen in natural materials, e.g., Nacre. There is also ordering of the NPs at the larger interfibrillar scale. Importantly, the relative fraction of engulfed, interlamellar and interfibrillar NPs is determined by G. Further, the modulus of these materials can increase by a factor of 2-3 due to the organization state of the NPs, while leaving fracture toughness unaffected. We have established the broad applicability of this approach in two polymers, polyethylene (PE) and polyethyleneoxide (PEO). To achieve this goal we developed a method for grafting long PE chains from NPs with controlled graft density and molecular weight, giving us the ability to tailor their dispersion in the PE melt prior to crystallization. In this renewal proposal, we will develop the fundamental, quantitative understanding that will allow us to independently tailor polymer crystallization rate, NP diffusivity and NP agglomeration state in semicrystalline polymers so as to facilely control NP ordering and hence properties. A program that tightly integrates experiment and theory is proposed, and a key outcome of this research will be a three-dimensional design map for different regimes of NP organization (and hence properties) that can be achieved by polymer crystallization. A second independent outcome is the role of directional solidification and how it competes with the rates of polymer crystallization and NP mobility to affect the organization of the NP.
36 MATERIALS SCIENCE↗
Investigation of Polymer Liquid Crystals
The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.
Han, Kwang S.↗
Microgravity polymer and crystal growth at the Advanced Materials Center for the Commercial Development of Space
The microgravity research programs currently conducted by the Advanced Materials Center for the Commercial Development of Space (CCDS) are briefly reviewed. Polymer processing in space, which constitutes the most active microgravity program at the Advanced Materials CCDS, is conducted in three areas: membrane processing, multiphase composite behavior, and plasma polymerization. Current work in microgravity crystal growth is discussed with particular reference to the development of the Zeolite Crystal Growth facility.
Mccauley, Lisa A.↗
Wholly aromatic liquid crystalline polyetherimide (LC-PEI) resins
The benefits of liquid crystal polymers and polyetherimides are combined in an all-aromatic thermoplastic liquid crystalline polyetherimide. Because of the unique molecular structure, all-aromatic thermotropic liquid crystal polymers exhibit outstanding processing properties, excellent barrier properties, low solubilities and low coefficients of thermal expansion in the processing direction. These characteristics are combined with the strength, thermal, and radiation stability of polyetherimides.
Weiser, Erik S.↗
Some new avenues in polymer single crystal studies
Growing, visualizing polyethylene single crystals
Keller, A.↗
Shear-Sensitive Monomer/Polymer Liquid Crystal System
Report describes preliminary investigation of new monomer/polymer liquid crystal system, thin film of shear-sensitive cholesteric monomer liquid crystal (TI 511) on Xydar (STR800) (or equivalent) liquid crystal polymer substrate. Monomer/polymer liquid crystal films applied to surfaces provide quantitative indications of shear stresses caused by winds blowing along surfaces. Effects of shear stresses reversible in new coating system. System provides quantitative data on flows in wind tunnels.
Singh, Jag J.↗
Advanced Embedded Active Assemblies for Extreme Space Applications
This work describes the development and evaluation of advanced technologies for the integration of electronic die within membrane polymers. Specifically, investigators thinned silicon die, electrically connecting them with circuits on flexible liquid crystal polymer (LCP), using gold thermo-compression flip chip bonding, and embedding them within the material. Daisy chain LCP assemblies were thermal cycled from -135 to +85degC (Mars surface conditions for motor control electronics). The LCP assembly method was further utilized to embed an operational amplifier designed for operation within the Mars surface ambient. The embedded op-amp assembly was evaluated with respect to the influence of temperature on the operational characteristics of the device. Applications for this technology range from multifunctional, large area, flexible membrane structures to small-scale, flexible circuits that can be fit into tight spaces for flex to fit applications.
lead bonding↗
Shear-induced surface alignment of polymer dispersed liquid crystal microdroplets on the boundary layer
Polymer dispersed liquid crystal thin films have been deposited on a glass substrate, utilizing the processes of polymerization and solvent evaporation induced phase separation. Liquid crystal microdroplets trapped on the upper surface of the thin film respond to the shear stress due to air or gas flow on the surface layer. Response to an applied step shear stress input on the surface layer has been measured by measuring the time response of the transmitted light intensity. Initial results on the measurements of the light transmission as a function of the air flow differential pressure indicate that these systems offer features suitable for boundary layer and gas flow sensors.
Parmar, D. S.↗
Dynamic Time Multiplexing Fabrication of Holographic Polymer Dispersed Liquid Crystals for Increased Wavelength Sensitivity
Described herein is a new holographic polymer dispersed liquid crystal (HPDLC) medium with broadband reflective properties, and a new technique for fabrication of broadband HPDLC mediums. The new technique involves dynamic variation of the holography setup during HPDLC formation, enabling the broadening of the HPDLC medium's wavelength response. Dynamic variation of the holography setup may include the rotation and/or translation of one or more motorized stages, allowing for time and spatial, or angular, multiplexing through variation of the incident angles of one or more laser beams on a pre-polymer mixture during manufacture. An HPDLC medium manufactured using these techniques exhibits improved optical response by reflecting a broadband spectrum of wavelengths. A new broadband holographic polymer dispersed liquid crystal thin film polymeric mirror stack with electrically-switchable beam steering capability is disclosed. XXXX Described herein is a new holographic polymer dispersed liquid crystal (HPDLC) medium with broadband reflective properties, and a new technique for fabrication of broadband 10 HPDLC mediums. The new technique involves dynamic variation of the holography setup during HPDLC formation, enabling the broadening of the HPDLC medium's wavelength response. Dynamic variation of the holography setup may include the rotation and/or translation of one or more 15 motorized stages, allowing for time and spatial, or angular, multiplexing through variation of the incident angles of one or more laser beams on a pre-polymer mixture during manufacture. An HPDLC medium manufactured using these techniques exhibits improved optical response by reflecting 20 a broadband spectrum of wavelengths. A new broadband holographic polymer dispersed liquid crystal thin film polymeric mirror stack with electrically switchable beam steering capability is disclosed.
Fontecchio, Adam K.↗
Partially exposed polymer dispersed liquid crystals for boundary layer investigations
A new configuration termed partially exposed polymer dispersed liquid crystal in which the liquid crystal microdroplets dispersed in a rigid polymer matrix are partially entrapped on the free surface of the thin film deposited on a glass substrate is reported. Optical transmission characteristics of the partially exposed polymer dispersed liquid crystal thin film in response to an air flow induced shear stress field reveal its potential as a sensor for gas flow and boundary layer investigations.
Parmar, Devendra S.↗
Gas flow-field induced director alignment in polymer dispersed liquid crystal microdroplets deposited on a glass substrate
Polymer dispersed liquid crystal thin films have been deposited on glass substrates by the processes of polymerization and solvent evaporation induced phase separation. The electron and the optical polarization microscopies of the films reveal that PDLC microdroplets formed during the process of phase separation near the top surface of the film remain exposed and respond to shear stress due to air or gas flow on the surface. Optical response of the film to an air flow-induced shear stress input on the free surface has been measured. Director orientation in the droplets changes with the applied shear stress leading to time varying transmitted light intensity. Director dynamics of the droplet for an applied step shear stress has been discussed from free energy considerations. Results on the measurement of light transmission as a function of the gas flow parameter unambiguously demonstrate the potential of these systems for use as boundary layer and gas flow sensors.
Parmar, D. S.↗
Production of crystalline polymers via liquid crystal monomers
Method produces crystalline polymers through a liquid crystalline phase of monomers. The monomer is polymerized while held in the liquid crystalline phase either thermally, photolytically, catalytically, or by X-ray or gamma ray irradiation, and can be performed in an electric or magnetic field that influences the molecular orientation.
Labes, M.↗
In Situ Alloying Enabled by Active Liquid Metal Filler for Self‐Healing Composite Polymer Electrolytes
Abstract Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga 62.5 In 21.5 Sn 16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self‐healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li‐ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li‐LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid‐state Li/LiFePO 4 battery achieves promising full‐cell functionality with notable rate performance and stable cycle life. This active filler‐mediated self‐healing approach could bring new insights into the battery design in versatile solid‐state systems.
Wu, Kai↗