The sCO2 system located in 916/160A, Sandia National Laboratories, CA, was constructed in 2014, for testing of materials in the presence of supercritical carbon dioxide (sCO2) at high pressures (up to 3500 psi) and temperatures (up to 650°C). The basic design of the system consists of a thermally insulated IN625 autoclave, a high-pressure supercritical CO2 compressor, autoclave heaters, temperature controllers, gas manifold, and temperature and pressure diagnostics. This system was modified in 2016 (sCO2 compressor was removed) to enable corrosion studies with metal alloys in gaseous CO2 at lower pressure (up to 300 psi) at 500°C. The capability was not used much afterwards until 2020, when preliminary tests using this capability (again without the supercritical CO2 compressor) involved the exposure of fatigue and tensile specimens of HN 230 and 800H alloys to CO2 gas for 168 hours in gaseous CO2. Using this capability, we finished experiments with low pressure (450 psi/ 3 MPa), high temperature (650°C) exposure of fatigue and tensile specimens of HN 230 and 800H alloys to CO2 gas for 168 hours. The data from these experiments will be compared to that gathered from experiments performed in 2020 using the tube furnace and presented in a future report. It is to be noted that the tube furnace experiments ran 500-1500 hours, unlike the 168 hours of exposure in the recent experiment. This can help validate the use of the sCO2 autoclave for both CO2 and sCO2 experiments.
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 CO2 (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.
Polymeric materials have played a significant role in the adoption of a multi-materials approach towards the development of a safe and cost-effective solution for hydrogen fuel storage in Fuel Cell Vehicles (FCVs). Numerous studies exist with regards to the exposure of polymeric materials to gaseous hydrogen as applicable to the hydrogen infrastructure and related compression, storage, delivery, and dispensing operations of hydrogen at fueling stations. However, the behavior of these soft materials under high pressure hydrogen environments has not been well understood. This study involves exposure of select thermoplastic and elastomeric polymers to high pressure hydrogen (70-100 MPa) under static, isothermal, and isobaric conditions followed by characterization of physical properties and mechanical performance. Special attempt has been made to explain hydrogen effects on polymer properties in terms of polymer structure-property relationships, and also understand the influential role played by additives such as fillers, plasticizers, and processing AIDS in polymers exposed to hydrogen. Efforts have also been focused on deriving suitable conditions of static testing in high pressure hydrogen environments as a valuable part of developing a suitable test methodology for such systems. Understanding the relationships between polymer composition and microstructure, time of exposure, rate of depressurization, purge and exposure conditions, etc. in this simple study will help better define the test parameters for upcoming high pressure cycling experiments in hydrogen.