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Nissen, April

Publications and source records attributed to Nissen, April.

STUDIES ON PIPELINE POLYETHYLENES IN HYDROGEN GAS ENVIRONMENTS USING IN-SITU AND EX-SITU CHARACTERIZATION METHODS

Polymeric materials are commonplace in the natural gas infrastructure as distribution pipes, coatings, seals, and gaskets. Under the auspices of the U.S. Department of Energy HyBlend program, one of the means to reduce greenhouse gas emissions is with replacing natural gas, either partially or completely, with hydrogen. This approach makes it imperative that we conduct near-term and long-term materials compatibility research in these relevant environments. Insights into the effects of hydrogen and hydrogen gas blends on polymer integrity can be gained through both ex-situ and in-situ analytical methods. Our work represented here highlights a study of the behavior of pipeline polyethylene (PE) materials, including HDPE (Dow 2490 and GDB50) and MDPE (Ineos and legacy Dupont Aldyl A), when exposed to hydrogen by means of in-situ X-ray scattering and ex-situ Raman spectroscopy techniques. Samples were tested in ex-situ hydrogen and argon gas environments and in-situ hydrogen environments to identify differences due to permeation and solubility of these gases. These methods complemented each other because Raman spectroscopy could capture permanent effects after materials were removed from gaseous environments, and in-situ X-ray scattering analysis collected real-time data to elucidate the impact of the gas environment on polymer microstructure. Data collected revealed that the aforementioned polymers did not show significant changes in crystallinity and microstructure under the exposure conditions tested. Our findings from these studies will help establish real-time effects caused by hydrogen gas transport through pipeline polyethylenes by way of its influence on polymer structure and chemistry, which is directly related to pipeline mechanical strength and longevity of service.

Hydrogen materials compatibility, Natural gas pipe↗

Evaluation of Common Thermoplastic Polymers in High-Pressure Cycling Hydrogen Under Ambient and Cold Environments as Applicable to the Hydrogen Infrastructure

Thermoplastic polymers are required to perform unfailingly under stringent conditions of changing pressures (35 MPa to 70 MPa) and temperatures (-40°C to +85°C) in storage and fueling operations. Although diffusivity in glassy polymers appear to be an order of magnitude lower than elastomers, polymer microstructural attributes such as degree of crystallinity and presence of polar and non-polar groups on the main chain with and without branching can play a substantial role in influencing their behaviors in hydrogen environments. In the work described here, the effect of high-pressure hydrogen cycling on PEEK, PTFE, PA11, HDPE, POM (and different commercial grades of these polymers) under ambient and cold (-40°C) conditions is addressed. Ex-situ characterization for polymer changes included density measurements for impact of hydrogen retention, hardness changes using nanoindentation, storage modulus and glass transition changes using dynamic mechanical and thermal analysis (DMTA), degree of crystallization with Differential Scanning Calorimetry (DSC) and tensile testing following ASTM D412. In other evaluations, solid-state nuclear magnetic resonance (NMR), attenuated total reflectance Fourier transform infra-red spectroscopy (ATRFTIR), X-ray diffraction (XRD), and X-ray CT results are presented. The overall impact of these evaluations is to establish a technical basis for the behaviors of common thermoplastics in cycling hydrogen environments under ambient and cold temperatures while establishing the relationship between polymer structure-based properties and hydrogen transport effects.

Menon, Nalini C.↗

Collective Summary of sCO2 Materials Development (Supercritical Transformational Electric Power Generation (STEP) Level 2 Milestone Report) (Parts I - II)

Polymers such as PTFE (polytetrafluorethylene or Teflon), EPDM (ethylene propylene diene monomer) rubber, FKM fluoroelastomer (Viton), Nylon 11, Nitrile butadiene (NBR) rubber, hydrogenated nitrile rubber (HNBR) and perfluoroelastomers (FF_202) are commonly employed in super critical CO 2 (sCO2) energy conversion systems. O-rings and gaskets made from these polymers face stringent performance conditions such as elevated temperatures, high pressures, pollutants, and corrosive humid environments. In FY 2019, we conducted experiments at high temperatures (100°C and 120°C) under isobaric conditions (20 MPa). Findings showed that elevated temperatures accelerated degradation of polymers in sCO2, and that certain polymer microstructures are more susceptible to degradation over others. In FY 2020, the focus was to understand the effect of sCO2 on polymers at low (10 MPa) and high pressures (40 MPa) under isothermal conditions (100°C). It was clear that the same selectivity was observed in these experiments wherein certain polymeric functionalities showed more propensity to failure over others. Fast diffusion, supported by higher pressures and long exposure times (1000 hours) at the test temperature, caused increased damage in sCO2 environments to even the most robust polymers. We also looked at polymers under compression in sCO2 at 100°C and 20 MPa pressure to imitate actual sealing performance required of these materials in sCO2 systems. Compression worsened the physical damage that resulted from chemical attack of the polymers under these test conditions. In FY 2021, the effect of cycling temperature (from 50°C to 150°C to 50°C) for polymers under a steady sCO2 pressure of 20 MPa was studied. The aim was to understand the influence of cycling temperatures of sCO2 for typical polymers under isobaric (20 MPa) conditions. Thermoplastic polymers (Nylon, and PTFE) and elastomers (EPDM, Viton, Buna N, Neoprene, FF202, and HNBR) were subjected to 20 MPa sCO2 pressure for 50 cycles and 100 cycles in separate experiments. Samples were extracted for ex-situ characterization at 50 cycles and upon the completion of 100 cycles. Each cycle constituted of 175 minutes of cycling from 50°C to 150°C. The polymer samples were examined for physical and chemical changes by Dynamic Mechanical and Thermal Analysis (DMTA), Fourier Transform Infrared (FTIR) spectroscopy, and compression set. Density and mass changes immediately after removal from test were measured for degree of swell comparisons. Optical microscopy techniques and micro computer tomography (micro CT) images were collected on select specimens. Evaluations conducted showed that exposures to super-critical CO2 environments resulted in combinations of physical and/or chemical changes. For each polymer, the dominance of cycling temperatures under sCO2 pressures, were evaluated. Attempts were made to qualitatively link the permanent sCO2 effects to polymer micro- structure, free volume, backbone substitutions, presence of polar groups, and degree of crystallinity differences. This study has established that soft polymeric materials are conducive to failure in sCO2 through mechanisms of failure that are dependent on polymer microstructure and chemistry. Polar pendant groups, large atom substitutions on the backbone are some of the factors that are influential structural factors.

36 MATERIALS SCIENCE↗

Arathane 5753 HVB: An Alternative to EN-7/EN-8 Encapsulants

Conathane EN-7 (referred to as EN-7) has been used for decades to pot electrical connectors, providing mechanical support for solder joints in cables. Unfortunately, the EN-7 formulation contains a suspect carcinogen and chemical sensitizer, toluene diisocyanate (TDI). Because of this, various groups have been formulating replacement materials, but all have come up short in final properties or in processing. We propose Arathane 5753 HVB as a replacement for EN-7. The properties compare very well with EN-7 and the processing has both advantages and disadvantages over EN-7 as discussed in detail below.

36 MATERIALS SCIENCE↗