Robust, thiol-based 3D printed elastomers for chemically-resistant downhole completions

This Phase I SBIR submitted to the National Energy Technology Laboratory (NETL) aims to improve efficiency in unconventional oil and gas recovery through optimization of the downhole completions process and provide supply chain surety to deliver point-of-need solutions to remote production facilities by commercializing novel, thiol-based 3D printable photo-resins that unlock polymers with materials properties and geometries not previously achievable by any other manufacturing means. Conventional completions processes utilize tools which are manufactured from cast and milled rubber and metal parts, assembled in factories, inventoried, and shipped to locations for use. This generates long lead times for replacement parts, high inventory costs and limited ability to respond to unconventional situations (such as packers for needed for sealing high salinity wells, wells with irregular rock faces, and pausing well production with retrievable packer systems). Additive manufacturing of functional parts made from 3D printable elastomers that are mechanically robust and hydrolytically stable can be rapidly deployed on- site to improve up-time and limit costly inventory overhead. Furthermore, additive manufacturing can enable novel geometries, unattainable by conventional molding and subtractive manufacturing, which leads to improved functionality and decreased cost. Adaptive3D’s proprietary technologies including its photo-Polymerization Induced Phase Separation (photoPIPS) mimic aspects of vulcanization (using sulfur to crosslink rubber although our mechanism is fundamentally different) and enable 3D printing of mechanically robust elastomers suitable for the oil and gas market. During Phase I, we seek to demonstrate the feasibility employing our photoPIPS additive manufacturing technology to create tough, tear-resistant, chemically stable elastomers specifically designed to meet the chemical, mechanical and thermal needs of oil and gas applications and test them through ASTM standard methods for down-hole rubbers including: D7999-15(2019) (CNG applications), F146-12(2019)e1 (fluid resistance) and F38-18 (creep). The specific target of this Phase I NETL feasibility study is a 3D printable rubber which has mechanical and chemical properties similar to NBR, a thermoset elastomer used in a range of oil and gas applications. The elastomer resulting from our proposed efforts will be mechanically robust and chemically resistant. To address these challenges, we will employ a two-step process whereby (1) a nascent rubber is mixed with a reactive/labile scaffold and the scaffold is reacted/fixed through the 3D printing process to form a given geometry, then (2) the rubber will be thermally treated, releasing the labile vulcanizing agent which in turn crosslinks the rubber into its final, chemically robust form. This two- step process will be achieved in an industrially scalable 1-part, 1-pot system, enabling maximal versatility and limiting waste as the excess resin is recycled into the next print (providing for a greener process). Small Lot Manufacturing enables reduced tooling costs, reduced time to manufacture and the ability to provide more customized solutions on a per well or even per fracking zone basis, given recent advances in pre-production modeling and simulation. Novel Geometries possible due to additive manufacturing, enable value added components to capture un-tapped markets such as differentiated parts that could sustain high pressures in saline environments and achieve specific thickness to swell ratios. On-Demand Manufacturing reduces inventory and transportation costs and can improve up-time. Needing to helicopter an $1 O-ring onto a platform in the Gulf of Mexico could lead to millions of dollars in downtime- driven lost revenues and our approach is scalable into other emerging alternative energy technologies.