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Printable Fiber Reinforced Cement Composites – Feasibility Study

Additive manufacturing is enabling the manufacturability of structures with previously unattainable complexity or functionality, and there is growing interest in additive manufacturing of “printed” concrete structures. The focus of this Phase 1 Technical Collaboration (TC) project was to evaluate feasibility of printing hybrid cement composite structures reinforced with textile carbon fibers (tCF). This project leverages other (non-IACMI) projects on cement formulation and printing process development, as well as on the production process for tCF. This project’s primary focus was to explore cement composite mix design with textile carbon fibers to be manufactured by MonteFibre (TC partner) and evaluate suitable fiber-matrix interface or sizing for cement composites working with Michelman (TC Partner). This project supports IACMI’s goal of reducing the cost and embodied energy of carbon fiber composites. Cost is one of the fundamental challenges to carbon fiber reinforced cement composites. Cement is an extremely inexpensive material (approximately $\$$0.05/lb). Adding 1 wt% of conventional carbon fiber to cement quadruples its cost. Therefore, the need to use low-cost carbon fiber and ensure that the additional cost of the carbon fiber has a greater cost benefit to the final product. This was the first preliminary evaluation to integrate tCF reinforcement in cement composites, and such potential tCF utilization should significantly reduce materials cost. Cement composite production is energy and emissions intensive, thus by strengthening it less material will be required. Hence, the embodied energy and production time of the resulting structures will be reduced. Additionally, integrating these new materials into additive processes can enable selective use of the material in high load or stress areas. It is noteworthy that past work in this field of fiber reinforced cement composites did not consider the optimization of fiber-matrix interface using suitable sizing. Carbon fiber reinforcement offers potential added benefits of thermal conductivity (which affects cure rate) and flow behavior that could provide opportunities for site specific utilization of carbon fiber on hybrid cement structures (e.g. use the fiber reinforcement on outer surfaces to enhance strength and modulus and then infiltrating the internal structures with conventional concrete). MonteFibre was the industry lead and planned on supplying the tCF for this project. However, during the short Phase-1 duration of this project, MonteFibre was unable to produce tCF for this project due to manufacturing plant being off-line throughout the course of the project. The project team decided to pursue an alternate option which involved demonstrating printable concrete with steel fibers by the ORNL lead, Dr. Brian Post. The University of Tennessee collaboration team focused on evaluating the suitable chemical sizing for carbon fibers working with Michelman and also developed methods for material characterization of cement-based composites to evaluate the material response for compression, shear, flexure, and tension. The two milestones for University of Tennessee, Knoxville were realized related to identification of one sizing suitable for carbon fiber reinforced cement composite and developing data associated with mechanical behavior of unreinforced (neat) and carbon fiber reinforced cement composites. ORNL could not complete the task of carbon fiber reinforced printed cement composites due to the reasons mentioned earlier, but was able to replace tCF with steel fibers to demonstrate the feasibility of printing with fiber reinforced cement composites. The Project team reviewed possible sizing chemistry available in collaboration with Michelman for use on carbon fiber reinforcement in cement composites and concrete applications. Our initial goal was to identify a sizing most promising for formulation with textile carbon fibers (tCF) to deliver excellent mechanical properties in composite material state. Since tCF was not available for this project as originally envisioned, the team continued this task to identify a suitable sizing for carbon fiber applications by applying such sizing to lower cost carbon fibers currently available commercially from Zoltek called Panex fibers. At a future time this can be optimized for textile carbon fibers from Montefibre. The bulk of previous work on carbon fiber reinforced cement has neglected the importance of fiber-matrix adhesion on mechanical properties of the cement composite and identifying this missing link was an important accomplishment for future research. Tensile behavior of fiber reinforced concrete is important to evaluate in order to realize the dream of concrete products that do not need reinforcing steel. Important sample preparation and testing procedures were addressed in this study and it was concluded that substantial improvements in tensile behavior, without compromising compressive strength, and improved ductility can result from the use of carbon fiber reinforcement.

36 MATERIALS SCIENCE↗

TCF - Sustainable Well Cement for Geothermal, Thermal Recovery, and Carbon Storage wells

Primary cementing is the most important operation performed on a subterranean well. Cement, placed in the annulus between the casing and the formations, serves as a hydraulic seal preventing fluids and gas migrations, protecting steel casing from corrosion, and supporting the well structure. Poor cementing jobs can be directly responsible for wells not reaching their full capacity, casing corrosion, compromised well integrity and, in the worst-case scenarios, well collapse. Geothermal, thermal recovery, and carbon storage wells offer environments that are especially difficult for cements to survive while the required lifespan of these wells can be years. In these wells currently used cements cannot provide durable well integrity, and new solutions are necessary. The necessity of stabilizing the electric grid, increasing its flexibility, and providing energy on demand will further expand the market of durable cement solutions for applications in high-temperature underground reservoir thermal energy storage wells (HT RTES). The design challenges of special cement systems for such wells originate from chemistry limitations of currently used well cements, aggressive environments, temperature and repeated shock conditions associated with them, and very weak formations that are not uncommon in these wells. During the last 70 years the most common systems for thermal-well construction have been Ordinary Portland Cement (OPC) (absolute majority of the wells), silica-lime system, and high aluminum cement-containing formulations. The major issues of calcium-silicate hydrates, that form during the hydration of OPC resulting in hardened material, are their poor chemical resistance to acids due to the calcium interactions with acid anions followed by its eventual dissolution, even in mild acids, such as carbonic acid from CO 2 dissolution, and inadequate bonding to the steel causing serious casing corrosion problems (Sugama & Pyatina, 2019). Performance of OPC-based cement may be significantly improved with organic additives; however, those are limited by their temperature stability. An alternative to calcium-silicate cement was developed by BNL and commercialized by Halliburton as ThermaLock TM cement. Calcium-aluminate-phosphate-based chemistry of the material allowed overcoming acid-resistance problems of OPC, especially in CO 2 -rich geothermal environments. In 2012-2015, building upon this experience, BNL developed Thermal Shock Resistant Cement (TSRC) with the support of Geothermal Technology Office (GTO) of DOE. TSRC has high-temperature stable chemistry, superior properties of cement-metal casing bond and corrosion protection (4-times better than currently used OPC-based formulation), significantly outperforms common well-cements in thermal-shock tests, has self-healing properties, and like ThermaLock TM is CO 2 resistant incorporating carbonate ions into stable hydrates (Gill et al., 2012).

15 GEOTHERMAL ENERGY↗

Cementation of Nuclear Wastes: From Past to Future in a Sustainable Approach - 18266

Cementation of nuclear wastes is a widespread technology due to several factors such as excellent feedback from past experience, simplicity of implementation and versatility. Indeed, as nuclear wastes come in many physical states (bulk wastes, powders, sludges), cementation is the immobilisation process that can easily accommodate this large range of wastes provided the appropriate mixing technology is used: heterogenous cementation (grouting of bulky wastes) or homogenous cementation (intermixing process between the powder or the sludge and the cementitious material). However, nuclear wastes equally present an important chemical variability. This is especially true as New Areva's range of nuclear activities covers the entire fuel cycle: mining, conversion, enrichment and recycling and dismantling and decommissioning. The chemical interactions between the waste and the cement matrix are carefully studied by New Areva's R and D teams in order to provide comprehensive solutions by developing cement formulations which are adapted to wastes characteristics. The aim of the studies is to obtain cement waste-forms that meet the waste acceptance criteria, the final product being thus in perfect adequacy with the disposal requirements. For over 30 years New Areva has been developing cement formulations adapted to the physical and chemical specificities of the wastes accounting for constrains imposed by waste characteristics. The overall approach includes the definition of the appropriate cement composition at laboratory scale, engineering design, equipment manufacturing, testing and commissioning of the cementation facilities. With this strong technical background, a specific methodology has been developed by New Areva teams in order to allow a rapid screening of possible solutions for a given waste (in terms of cement chemistry adapted to the waste) in a learn-fast approach that is based on theoretical analysis and small-scale tests. The methodology was applied for wastes presenting a complex nature (such as reactive metals, ion exchange resins, oils and solvents, mercury, etc), known to interact with Portland cement from a chemical point of view and leading to durability issues of the wasteform (swelling, strength reduction, leaching) and thus reducing the final waste loading. Once the screening process is over, the main drivers for choosing the most appropriate solution to be further developed at pilot scale are: reducing the overall volume and the impact of the final waste package, ensure the waste package performance as defined by the disposal requirements and control the long-term behaviour in final disposal. Moreover, a modelling approach is addressed, aiming to develop a thermo-chemo-mechanical (THM) concrete models that are able to predict the behaviour of the structure (waste form) in time. The aim of the present paper is to describe the main principles within the developed methodology and illustrate it by using a few specific examples. Several distinct cement formulations are developed for complex wastes, limiting the chemical interaction between the cement matrix and the given wastes, obtaining better waste loadings and better overall durability behaviour which facilitates long term behaviour demonstration. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗