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The invention relates to a method of making fluoropolymers without excessive degradation of the polymer backbone. The invention also relates to the fluoropolymers made by this method, and method of using the fluoropolymers.
Chemically modified plastics have emerged as practical solutions to plastic waste increases. Here, the inherent novelty of decorating polymer chains with chemical functionality results in distinct properties that expand the available application space. Nevertheless, developing designer materials for specific applications beyond compatibilization or mild property enhancement is difficult due to the synergistic effects of both the polar functionality imparted and the parent materials' intrinsic properties. By incorporating perfluoro-alkyl side-chains onto the backbone of dehydrogenated waste HDPE, unique surface properties intermediate between polytetrafluoroethylene (PTFE, the model fluoropolymer) and HDPE become apparent, while the overall material mechanical and thermal properties result in more LLDPE-like materials. This is demonstrated through moderate decreases in the surface free energy of the perfluoroalkylated polyolefin surface (increase in H 2 O contact angle of ~ 6°) and increased ordering under shear when blended with PTFE nanoparticles where the crossover point occurred at higher strains. Critically, perfluoroalkylated HDPE possesses improved rheological modification properties at elevated temperatures with PTFE nanoparticles, resulting in more thermally robust and stable composite materials.
Thermosetting fluoropolymer foams are made by mixing fluid from thermosetting fluoropolymer components having a substantial fluoride content, placing the mixture in a pressure tight chamber, filling the chamber with a gas, at a relatively low pressure, that is unreactive with the fluoropolymer components, allowing the mixture to gel, removing the gelled fluoropolymer from the chamber and therafter heating the fluoropolymer at a relatively low temperature to simultaneously cure and foam the fluoropolymer. The resulting fluoropolymer product is closed celled with the cells storing the gas employed for foaming. The fluoropolymer resins employed may be any thermosetting fluoropolymer including fluoroepoxies, fluoropolyurethanes and fluoroacrylates.
This report focuses on the use of fluoropolymers in infrastructure materials (building construction materials, transportation, and electrical transmission and distribution); renewable energy generation components (specifically wind and solar); and energy storage components (lithium-ion batteries and fuel cells) and product lifespan impacts if fluoropolymers were no longer available or allowed in commerce. Additionally, environmental considerations for fluoropolymer manufacture, use, and end-of-life disposal are discussed. This document is the second of two companion reports. The first report, Assessment of Fluoropolymer Production and Use With Analysis of Alternative Replacement Materials, contained an analysis of use of fluoropolymers and their potential replacement technologies in aerospace, automotive, battery, building construction, chemical processing, electronics, infrastructure, semiconductor, solar panel, and wind energy industries sectors, along with qualitative life cycle assessment (LCA) and cost-benefit analysis of replacing fluoropolymers. This report does not focus on the lifecycle aspects of use of fluoropolymer or alternatives in the designated applications. For more information on those topics, see aforementioned report.
Methods for manufacturing electrodes include applying a fluoropolymer film to a lithium-based host material, defluorinating the fluoropolymer film by heating to produce a lithium electrode having a solid electrolyte interface (SEI) layer including defluorinated fluoropolymers and at least about 5 wt. % LiF. The fluoropolymers can include one or more of fluorinated ethylenepropylene, perfluoroalkoxy alkanes, vinylidenefluoride, and copolymers of perfluoromethylvinylether and tetrafluoroethylene. The fluoropolymers can include one or more fluorinated monomers, including hexafluoropropylene, tetrafluoroethylene, ethylene-tetrafluoroethylene, perfluoroethers, and vinylidene fluoride. The —CF 3 functional groups of the defluorinated fluoropolymers can be about 3 wt. % to about 10 wt. % of the SEI layer. The SEI layer can include about 30 wt. % to about 50 wt. % LiF. The method can include assembling a battery cell by disposing a battery separator between a cathode and the electrode, and disposing the battery separator, the cathode, and the electrode in an electrolyte.
This report focuses on fluoropolymers, which are a subgroup of the much larger class of fluorinated chemicals known as per- and polyfluoroalkyl substances (PFAS). Clearly distinguishing fluoropolymers is important to understanding their distinctive chemical properties, associated risks and benefits, and roles in commerce. In this report, the factors that are considered in a lifecycle assessment (LCA) of fluoropolymers will be discussed. These include the manufacturing of fluoropolymers, their use in industry, and available replacement technologies. Emphasis is placed on fluoropolymer plastics because of their extensive use in the commerce sectors considered here, specifically aerospace, automotive, battery, building construction, chemical processing, electronics, infrastructure, semiconductor, solar panel, and wind energy industries.
An electron bombardment argon ion source was used to ion etch various metals and fluoropolymers. The metal and fluoropolymers were exposed to (0.5 to 1.0) keV Ar ions at ion current densities of (0.2 to 1.5) mA/sq cm for various exposure times. The resulting surface texture is in the form of needles or spires whose vertical dimensions may range from tenths to hundreds of micrometers, depending on the selection of beam energy, ion current density, and etch time. The bonding of textured surfaces is accomplished by ion beam texturing mating pieces of either metals or fluoropolymers and applying a bonding agent which wets in and around the microscopic cone-like structures. After bonding, both tensile and shear strength measurements were made on the samples. Also tested, for comparison's sake, were untextured and chemically etched fluoropolymers. The results of these measurements are presented.
An electron-bombardment argon ion source was used to ion-etch various metals and fluoropolymers. The metal and fluoropolymers were exposed to (0.5 to 1.0)-keV Ar ions at ion current densities of 0.2 to 1.5 mA/sq cm for various exposure times. The resulting surface texture is in the form of needles or spires whose vertical dimensions may range from tenths to hundreds of micrometers, depending on the selection of beam energy, ion current density, and etch time. The bonding of textured surfaces is accomplished by ion-beam texturing mating pieces of either metals or fluoropolymers and applying a bonding agent which wets in and around the microscopic conelike structures. After bonding, both tensile and shear strength measurements were made on the samples. Also tested, for comparison's sake, were untextured and chemically etched fluoropolymers. The results of these measurements are presented in this paper.
Co-extruded, non-fluoropolymer backsheet films for photovoltaic (PV) modules have gained popularity in recent years based on their cost competitiveness. However, their viability has been thrown into question as a result of widespread, early-life field-failures of some materials, particularly the polyamide (PA)-based “AAA” backsheet product. Failure to detect weaknesses in those earlier products could be due, in part, to insufficient quality testing practices. New testing protocols have recently been developed to better evaluate such materials. Here we show the testing results for a non-fluoropolymer, co-extruded PA-based backsheet film, which demonstrates greater durability than AAA and some commercial fluoropolymers. Using material characterization techniques including Fourier-transform infrared spectroscopy (FTIR), wide-angle x-ray scattering (WAXS), differential scanning calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), elongation-to-break (ETB), and optical microscopy we perform a comprehensive failure analysis to better understand the materials weaknesses. This analysis can ultimately inform how best to improve the material and extend its lifetime. This work serves as a demonstration that some materials should not be discounted due to a single poorly designed product and that more appropriate qualification testing with subsequent materials analysis can be used to develop better materials.
Fluoropolymer etching and deposition techniques including thermal evaporation, RF sputtering, plasma polymerization, and ion beam sputtering are reviewed. Etching and deposition mechanism and material characteristics are discussed. Ion beam sputter etch rates for polytetrafluoroethylene (PTFE) were determined as a function of ion energy, current density and ion beam power density. Peel strengths were measured for epoxy bonds to various ion beam sputtered fluoropolymers. Coefficients of static and dynamic friction were measured for fluoropolymers deposited from ion bombarded PTFE.
Fluoropolymer etching and deposition techniques including thermal evaporation, RF sputtering, plasma polymerization, and ion beam sputtering are reviewed. Etching and deposition mechanisms and material characteristics are discussed. Ion beam sputter etch rates for polytetrafluoroethylene (PTFE) were determined as a function of ion energy, current density and ion beam power density. Peel strengths were measured for epoxy bonds to various ion beam sputtered fluoropolymers. Coefficients of static and dynamic friction were measured for fluoropolymers deposited from ion bombarded PTFE.
Etching and deposition of fluoropolymers are of considerable industrial interest for applications dealing with adhesion, chemical inertness, hydrophobicity, and dielectric properties. This paper describes ion beam sputter processing rates as well as pertinent characteristics of etched targets and films. An argon ion beam source was used to sputter etch and deposit the fluoropolymers PTFE, FEP, and CTFE. Ion beam energy, current density, and target temperature were varied to examine effects on etch and deposition rates. The ion etched fluoropolymers yield cone or spire-like surface structures which vary depending upon the type of polymer, ion beam power density, etch time, and target temperature. Also presented are sputter target and film characteristics which were documented by spectral transmittance measurements, X-ray diffraction, ESCA, and SEM photomicrographs.
Fires aboard spacecraft have occurred as a result of overheated electrical wires and thermodegradation of their insulation, which is composed of fluoropolymers. The particulate products of polymer thermodegradation are only 20-50 run in diameter and are thought to play a role in "polymer fume fever". Therefore an experimental study of the particulates produced by intense ohmic heating of various fluoropolymer-insulated 20 AWG copper wire (representative of spacecraft materials) was undertaken in normal gravity and in microgravity. The 2.2 s drop facility at NASA LeRC and 1.5 s drop facility at the Colorado School of Mines were used to achieve low gravity conditions. Thermophoretic sampling was used for particulate collection. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) were used to characterize the smoke particulates. It was found that the color of PTFE (Polytetrafluoroethylene) insulation has an overwhelming effect on the size, shape, morphology and, composition of the particulates. Size distributions and shape analyses using computerized image analysis showed that particle size distributions were also dependent on the pigment of the fluoropolymer insulation. The influence of pigment was observed in experiments under both normal and microgravity. Under microgravity conditions, owing to the lack of natural convective transport of particulates, much more particle aggregation was observed, and the nature of the aggregates was dependent on the color of the insulation.
Per- and polyfluoroalkyl substances (PFAS) are a broad class of synthetic chemicals used in a variety of modern technologies and consumer products. PFAS have an alkyl backbone with all or most of the hydrogen (H) atoms replaced with fluorine (F) atoms. PFAS generally fall into one of two categories, they can be non-polymeric with relatively low molecular weights, or long-chain polymers. PFAS are a diverse group of organic compounds that can be solids, liquids, dispersions, or gases. Their mobility and toxicity are influenced by their chain lengths and functional groups. Non-polymeric PFAS are common building blocks for the manufacturing of fluoropolymers. Non-polymeric PFAS are known to be mobile in the environment and some are considered contaminants of emerging concern. Polymeric PFAS, or fluoropolymers, are typically thought to be of low concern, however few systematic investigations into their toxicity have been completed. PFAS, including fluoropolymers and microplastics, have been found in pristine environments and animals located far from site of origin including the arctic and deep ocean.
Compared to other polymers, composite coatings with fluoropolymers as the matrix have attracted considerable interest due to their mechanical performance, chemical stability, and low surface energy. Herein, we present an anticorrosion mechanism of fluoropolymer composite coatings achieved by dispersing varying amounts of polyamide 12 (PA-12) particles over a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The choice of PVDF-HFP as a coating matrix was driven by its superior processability and mechanical properties over Teflon, while PA-12 afforded swelling capacity, preventing electrolyte permeation, and inhibiting matrix stress crack propagation. The corrosion resistance of the coatings was assessed mainly by potentiodynamic polarization and impedance measurements while being immersed in a NaCl solution. Our electrochemical measurement findings showed that 0.75% w/w PA-12 in the PVDF-HFP matrix significantly enhanced corrosion protection even after 21 days of immersion. Microscopy, dielectric spectroscopy, surface analysis, and mechanical testing (American Society for Testing and Materials standards) corroborated the results. PVDF-HFP coatings containing a minimum percolation threshold of 0.75 wt % PA-12 with 1 mil thickness on mild steel exhibited a remarkable increase in resistance and film adhesion, and a notable corrosion rate decrease. Finite element analysis simulation with a bilinear traction-separation law confirmed the swelling mechanism and adhesion behavior. Finally, this study highlights the potential of nylon particle dispersion in PVDF-HFP matrices as a practical approach to developing advanced anticorrosion coatings with promising practical applications in various industries.
The viability of novel coextruded, fluoropolymer-free backsheets for photovoltaic (PV) modules has been questioned as a result of a large number of early-life backsheet failures in PV installations containing one of the earliest co-extruded polyamide (PA)-based backsheet to reach the market, “AAA.” New PV reliability testing protocols have been recently developed and applied to backsheets to reproduce failures observed in the field and evaluate the durability of novel backsheet materials and designs prior to commercialization. A new co-extruded PA-based backsheet was tested using combined-accelerated stress testing (C-AST) and demonstrated a greater lifetime than AAA, and some other fluoropolymer-based backsheets such as polyvinylidene fluoride. The improved PA-based backsheet also eventually failed by through-thickness cracking. Using surface and bulk material characterization techniques, we performed a comprehensive study of material properties before and after the stress testing. Aging of the backsheet resulted in an increase of surface roughness by erosion of the outer PA layer. However the failure is more likely related to an increase in crystallinity of the polyolefin core layer reducing the backsheet tearing energy. The analysis can ultimately inform on the specific weaknesses of the materials so that the manufacturer can improve the backsheet design to extend its lifetime.
Fluoropolymer (FP) binders are commonly only a few percent of polymer bonded explosive compositions but they are essential for the mechanical integrity of the part. Because we are using newly manufactured binders, we need to understand how lot variations might affect processing, aging, and mechanical properties. Time, temperature and radiation induce phase changes in fluoropolymers. These phase changes can rearrange the polymer causing crystalline domains to nucleate and grow that can alter mechanical properties. These studies quantify the aging process so that it may be cross correlated with changes in the adhesion, strength, and other properties important for performance.
This project aims to investigate structural and morphological changes in fluoropolymers induced by both processing and aging phenomena such as heat, time, and irradiation. Fluoropolymers are an important class of thermoplastics that are broadly used in industry as o-rings and seals when chemical resistance and thermal performance are important. They are also often used in thin film geometries as binders in batteries, insulation layers, water barriers, and anti-fouling coatings. For all of these applications, mechanical integrity and aging are important aspects of their use. Changes in the crystalline morphology are known to impact the mechanical properties of the polymer and can lead to failure. The broad goals of this project are to correlate compositional changes, morphological changes, and mechanical changes. report focuses on the morphological changes that are correlated with nuclear magnetic resonance (NMR), calorimetry and mechanical testing. We plan to compare structure and morphology measurements across complementary bulk and surface techniques. We use in situ atomic force microscopy (AFM) to measure domain shape and crystallization kinetics; in situ NMR to measure crystalline composition; and differential scanning calorimetry (DSC) to measure melting temperatures.