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Nondestructive Evaluation of Alkali-Silica Reaction in High-Strength Concrete for Aging Structures Sustainability

Concrete is a multiphase geo-material, which is utilized extensively in passive supporting and shielding structures at nuclear facilities. Chemo-mechanical degradation of concrete in old structures is a challenge to sustainability of aging commercial light water reactors. Alkali-silica reaction (ASR) is a common slowly evolving chemo-mechanical damage mechanism of concrete, which could take tens of years to reach the threshold stage when visible cracks appear in a concrete structure. In ASR, concrete constituents react with each other, namely the alkalis in the pore solution of hydrated cement paste (mostly K{sup +}OH{sup -} and Na{sup +}OH{sup -}) react with non-crystalline silica (SiO{sub 2}) of the aggregates to form highly hydrophilic gel. At sufficient levels of ambient relative humidity (typically above 85%), imbibition of water causes expansion of the ASR gel, which results in cracking of constrained reinforced concrete and ultimate structural weakening below safety margin levels. Stability and functional performance of concrete structures potentially suffering from chemo-mechanical deterioration due to ASR is evaluated in a multi-stage process involving material evaluation and structural engineering analysis. Existing methods used by industry for concrete material evaluation are based on extrusion of cores from multiple locations in a structure, and destructive laboratory tests on cores. Because each destructive test requires separate core extrusion, the total number of cores taken from the structure at once could be numbering in hundreds. Laboratory tests include petrography (high resolution optical microscopy of core sections) to develop damage rating index (DRI) score of concrete cores. Another test may involve chemical pore solution extraction from cores, and solution speciation analysis using inductively coupled plasma and mass spectroscopy (ICP/MS). Other tests may consist of mechanical evaluation of cores strength and fracture toughness. The DRI score of concrete material as well as other information obtained from the laboratory tests is subsequently used in structural engineering calculations, where stresses in the entire structure are modeled to evaluate its safety and mechanical stability. Extrusion of a large number of cores is highly undesirable for evaluation of nuclear facility concrete structures. The amount of destructive material testing could be minimized by developing methods for in-situ NDE of ASR to quantify the amount of deterioration that is occurring in the structure, and to identify areas in the structure where more deterioration may be occurring.

36 MATERIALS SCIENCE↗

2024 JISEA Annual Meeting: Session 1

This is the presentation for the 2024 JISEA Annual Meeting Session 1: Hard-to-Decarbonize Industries, which took place on February 26, 2024. The presentation includes slides from Chad Reese, Environmental Affairs Manager at the San Diego County Regional Airport Authority, on sustainability efforts at the San Diego International Airport; Jordan Lambert, Director of Ag Innovation at Colorado State University, on agricultural decarbonization; Ana Aday, Materials Science Researcher at NREL, on decarbonizing the cement and concrete industry; and Rolf Weberg, Director of the Natural Resource Research Institute at the University of Minnesota Duluth, on integrated industrial decarbonization.

agriculture decarbonization↗

Mineralogy, provenance, and diagenesis of a potassic basaltic sandstone on Mars: CheMin X-ray diffraction of the Windjana sample (Kimberley area, Gale Crater)

The Windjana drill sample, a sandstone of the Dillinger member (Kimberley formation, Gale Crater, Mars), was analyzed by CheMin X-ray diffraction (XRD) in the MSL Curiosity rover. From Rietveld refinements of its XRD pattern, Windjana contains the following: sanidine (21% weight, ~Or 95 ); augite (20%); magnetite (12%); pigeonite; olivine; plagioclase; amorphous and smectitic material (~25%); and percent levels of others including ilmenite, fluorapatite, and bassanite. From mass balance on the Alpha Proton X-ray Spectrometer (APXS) chemical analysis, the amorphous material is Fe rich with nearly no other cations—like ferrihydrite. The Windjana sample shows little alteration and was likely cemented by its magnetite and ferrihydrite. From ChemCam Laser-Induced Breakdown Spectrometer (LIBS) chemical analyses, Windjana is representative of the Dillinger and Mount Remarkable members of the Kimberley formation. LIBS data suggest that the Kimberley sediments include at least three chemical components. The most K-rich targets have 5.6% K 2 O, ~1.8 times that of Windjana, implying a sediment component with >40% sanidine, e.g., a trachyte. A second component is rich in mafic minerals, with little feldspar (like a shergottite). A third component is richer in plagioclase and in Na 2 O, and is likely to be basaltic. The K-rich sediment component is consistent with APXS and ChemCam observations of K-rich rocks elsewhere in Gale Crater. The source of this sediment component was likely volcanic. Finally, the presence of sediment from many igneous sources, in concert with Curiosity's identifications of other igneous materials (e.g., mugearite), implies that the northern rim of Gale Crater exposes a diverse igneous complex, at least as diverse as that found in similar-age terranes on Earth.

58 GEOSCIENCES↗

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. Here, we performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. The data then indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. Our results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Circular Economy Contributions to Decarbonizing the US Steel Sector

The potential benefits of the circular economy (CE) for decarbonization have recently attracted much attention in the academic and grey literature. The department of energy (DOE) industrial decarbonization roadmap highlight that in addition to the four pillars (energy efficiency, electrification, low-carbon fuels, feedstocks, and energy sources, and carbon capture, utilization, and storage (CCUS)) identified in the roadmap, "scenarios [...] will need to be developed that incorporate materials efficiency and circular economy strategies". Moreover, the roadmap identifies hard-to-abate CO2 emissions across the five industrial subsectors included in the analysis (iron & steel, chemical, food & beverage, refining, and cement manufacturing). Thus, additional options to decarbonize the industrial sector, like the CE, could prove beneficial to address those hard-to-abate emissions. Moreover, they may be less costly, require less R&D or incentives, and be more readily adopted than other strategies such as energy efficiency and CCUS. While the Industrial Decarbonization Roadmap includes some CE strategies (e.g., the increasing market share of steel from electric arc furnaces - which incorporate steel scrap), a deeper dive into what role the CE could play in the United States (US) industrial decarbonization is needed. In this work, we present several industrial decarbonization scenarios that incorporate materials efficiency and circular economy strategies for the iron & steel subsector. The scenarios identify barriers (including technical limits and constraints), opportunities, and R&D needs.Moreover, we estimate the contribution of those scenarios to reducing the industrial sector's CO2 emissions and their potential synergies with the Industrial Decarbonization Roadmap's four pillars. Iron & steel manufacturing was responsible for 90 million tons of industrial CO2 emissions in 2020 - 7% of the industrial sector's total process- related emissions. Besides recycling - which presents technical limitations due to trace contaminants - CE strategies on the demand side could lower iron & steel manufacturing emissions (e.g., the development of lighter products or business models that encourage a more intensive use). This study reviews barriers, opportunities, and trade-offs for 5 material efficiency strategies. Many topics explored in the review call for further research.

barriers↗

Detection and Signal Processing for Near-Field Nanoscale Fourier Transform Infrared Spectroscopy

Researchers from a broad spectrum of scientific and engineering disciplines are increasingly using scattering-type near-field infrared spectroscopic techniques to characterize materials non-destructively with nanoscale spatial resolution. However, a sub-optimal understanding of a technique's implementation can complicate data interpretation and act as a barrier to entering the field. Here the key detection and processing steps involved in producing scattering-type near-field nanoscale Fourier transform infrared spectra (nano-FTIR) are outlined. The self-contained mathematical and experimental work derives and explains: i) how normalized complex-valued nano-FTIR spectra are generated, ii) why the real and imaginary components of spectra qualitatively relate to dispersion and absorption respectively, iii) a new and generally valid equation for spectra which can be used as a springboard for additional modeling of the scattering processes, and iv) an algebraic expression that can be used to extract an approximation to the sample's local extinction coefficient from nano-FTIR. The algebraic model for weak oscillators is validated with nano-FTIR and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra on samples of polystyrene and Kapton and further provides a pedagogical pathway to cementing some of the technique's key qualitative attributes.

36 MATERIALS SCIENCE↗

CO 2 -induced chemo-mechanical alteration in reservoir rocks assessed via batch reaction experiments and scratch testing

Here, the injection of carbon dioxide (CO 2 ) into geological formations results in a chemical re-equilibration between the mineral assemblage and the pore fluid, with ensuing mineral dissolution and re-precipitation. Hence, target rock formations may exhibit changes of mechanical and petrophysical properties due to CO 2 exposure. We conducted batch reaction experiments with Entrada Sandstone and Summerville Siltstone exposed to de-ionized water and synthetic brine under reservoir pressure (9–10 MPa) and temperature (80°C) for up to four weeks. Samples originate from the Crystal Geyser field site, where a naturally occurring CO 2 seepage alters portions of these geologic formations. We conducted micro-scratch tests on rock samples without alteration, altered under laboratory conditions, and naturally altered over geologic time. Scratch toughness and hardness decrease as a function of exposure time and water salinity up to 52% in the case of Entrada and 87% in the case of Summerville after CO 2 -induced alteration in the laboratory. Imaging of altered cores with SEM-EDS and X-ray microCT methods show dissolution of carbonate and silica cements and matrix accompanied by minor dissolution of Fe-oxides, clays, and other silicates. Parallel experiments using powdered samples confirm that dissolution of carbonate and silica are the primary reactions. The batch reaction experiments in the autoclave utilize a high fluid to rock volume ratio and represent an end member of possible alteration associated with CO 2 storage systems. These types of tests serve as a pre-screening tool to identify the susceptibility of rock facies to CO 2 -related chemical-mechanical alteration during long-term CO 2 storage.

54 ENVIRONMENTAL SCIENCES↗

Synthesis and property of EPEG ‐based polycarboxylate ether superplasticizers via RAFT polymerization

Abstract Polycarboxylate ether superplasticizers (PCEs) with comb‐shaped molecular structures have attracted considerable attention in the area of admixtures for construction engineering. However, there are some contradictions in studying the relationship between the molecular structure and property of PCE due to its random structure based on traditional free radical polymerization, which is confused for designing and developing novel PCEs. In this article, a series of reversible addition fragmentation chain transfer (RAFT) polymerization‐based polycarboxylate ether superplasticizers (RPCs) were prepared by the copolymerization of acrylic acid (AA) and ethylene‐glycol monovinyl polyethylene glycol (EPEG). The chemical structure and composition of RPCs were characterized and their adsorption behavior and dispersion properties were conducted. The results demonstrate that the molecular weights of RPCs do not vary significantly with prolonging reaction time, and the actual monomer ratio in RPCs displays a significant change to the feed one due to the monomer reactivity and conversion at higher reaction temperature, which is different from conventional free radical polymerization. The dispersion and adsorption properties of RPCs to cement were evaluated by slurry fluidity tests and total organic carbon (TOC) experiments. The effect of polymerization temperature and time on the dispersion ability has been systematically studied. The results indicate that the dispersion ability and adsorption capacity of RPCs are closely related to their molecular structures. The dispersion ability of RPCs were enhanced with increasing carboxyl group density in a certain range of monomer molar ratios (≤6:1). This study will provide a new platform for designing and developing high‐performance and rational cost‐effective superplasticizers with well‐defined structure and controlled molecular weight.

Chen, Xiaodong↗

Recycling Perspectives of Electric Arc Furnace Slag in the United States: A Review

This article presents a comprehensive review of electric arc furnace (EAF) slag recycling in the United States, examining its classification and the associated challenges and opportunities of its industrial use. The study affirms EAF slag's nonhazardous status. Here, the main challenges identified in EAF slag applications include substantial variations in composition and volume instability during/after hydration. Analysis of the U.S. recycling practices reveals that EAF slag is predominantly reused, with minimal landfill disposal. However, its prevalent use as a low value-added aggregate in construction applications underscores the industry's ongoing challenge to get additional value from EAF slag recycling. Despite these challenges, the study highlights a great potential for increased value extraction from EAF slag recycling. Beyond conventional applications as a clinker material for the cement industry, the review explores modern technologies for steelmaking slag recycling, revealing options for recovering valuable metals such as Cr, V, Mo, and Fe through methods such as leaching, reduction, and oxidation.

42 ENGINEERING↗

An exploration of benchtop X–ray emission spectroscopy for precise characterization of the sulfur redox state in cementitious materials

The evolution of sulfur chemistry in cements is best known in the bailiwick of failure mechanisms via sulfate attack but is equally important for its contributions to the reduction capacity of cementitious materials often used for immobilizing nuclear waste streams destined for long-term storage, e.g., cementitious waste forms (CWF). The total reduction capacity of CWFs, encompassing contributions from both S and Fe reductants, and its implications toward radionuclide immobilization is most often studied by destructive wet chemistry methods requiring acid digestion in the presence of Ce(IV) and subsequent titration and colorimetric interpretation. Here, we investigate a similarly analytical but nondestructive alternative, benchtop high resolution wavelength-dispersive x-ray fluorescence spectroscopy, most commonly known as x-ray emission spectroscopy (XES), for probing the bulk sulfur oxidation state distribution. We present here an initial investigation of S XES, including an improved experimental protocol for lab XES of inhomogeneous samples, both as a complement to the Ce(IV) test and for new scientific opportunities that it enables for observing changes in sulfur chemistry. We discuss future improvements and opportunities, including: (1) the practical challenges associated with coordinating XES and Ce(IV) liquid extraction for a more comprehensive perspective on reduction capacity and for a high-precision evaluation of uncertainties in the Ce(IV) test; and (2) new opportunities, due to the nondestructive nature of XES, for controlled evolution studies aimed at elucidating specific chemical responses of CWF’s exposed to invasive gas or liquid species or to accelerated aging by radiative dose or thermal treatment.

36 MATERIALS SCIENCE↗

Clinical Outcome and Safety of Multilevel Vertebroplasty: Clinical Experience and Results

To compare safety and efficacy of percutaneous vertebroplasty (PVP) when treating up to three vertebrae or more than three vertebrae per session. We prospectively compared two groups of patients with symptomatic vertebral fractures who had no significant response to conservative therapy. Pathologic substrate included osteoporosis (n = 77), metastasis (n = 24), multiple myeloma (n = 13), hemangioma (n = 15), and lymphoma (n = 1). Group A patients (n = 94) underwent PVP of up to three treated vertebrae (n = 188). Group B patients (n = 36) underwent PVP with more than three treated vertebrae per session (n = 220). Decreased pain and improved mobility were recorded the day after surgery and at 12 and 24 months after surgery per clinical evaluation and the use of numeric visual scales (NVS): the Greek Brief Pain Inventory, a linear analogue self-assessment questionnaire, and a World Health Organization questionnaire. Group A presented with a mean pain score of 7.9 {+-} 1.1 NVS units before PVP, which decreased to 2.1 {+-} 1.6, 2.0 {+-} 1.5 and 2.0 {+-} 1.5 NVS units the day after surgery and at 12 and 24 months after surgery, respectively. Group B presented with a mean pain score of 8.1 {+-} 1.3 NVS units before PVP, which decreased to 2.2 {+-} 1.3, 2.0 {+-} 1.5, and 2.1 {+-} 1.6 NVS units the day after surgery and at 12 and 24 months after surgery, respectively. Overall pain decrease and mobility improvement throughout the follow-up period presented no statistical significance neither between the two groups nor between different underlying aetiology. Reported cement leakages presented no statistical significance between the two groups (p = 0.365). PVP is an efficient and safe technique for symptomatic vertebral fractures independently of the vertebrae number treated per session.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Feasibility Study of Needle Placement in Percutaneous Vertebroplasty: Cone-Beam Computed Tomography Guidance Versus Conventional Fluoroscopy

ObjectiveTo investigate the accuracy, procedure time, fluoroscopy time, and dose area product (DAP) of needle placement during percutaneous vertebroplasty (PVP) using cone-beam computed tomography (CBCT) guidance versus fluoroscopy.Materials and MethodsOn 4 spine phantoms with 11 vertebrae (Th7-L5), 4 interventional radiologists (2 experienced with CBCT guidance and two inexperienced) punctured all vertebrae in a bipedicular fashion. Each side was randomization to either CBCT guidance or fluoroscopy. CBCT guidance is a sophisticated needle guidance technique using CBCT, navigation software, and real-time fluoroscopy. The placement of the needle had to be to a specific target point. After the procedure, CBCT was performed to determine the accuracy, procedure time, fluoroscopy time, and DAP. Analysis of the difference between methods and experience level was performed.ResultsMean accuracy using CBCT guidance (2.61 mm) was significantly better compared with fluoroscopy (5.86 mm) (p < 0.0001). Procedure time was in favor of fluoroscopy (7.39 vs. 10.13 min; p = 0.001). Fluoroscopy time during CBCT guidance was lower, but this difference is not significant (71.3 vs. 95.8 s; p = 0.056). DAP values for CBCT guidance and fluoroscopy were 514 and 174 mGy cm{sup 2}, respectively (p < 0.0001). There was a significant difference in favor of experienced CBCT guidance users regarding accuracy for both methods, procedure time of CBCT guidance, and added DAP values for fluoroscopy.ConclusionCBCT guidance allows users to perform PVP more accurately at the cost of higher patient dose and longer procedure time. Because procedural complications (e.g., cement leakage) are related to the accuracy of the needle placement, improvements in accuracy are clinically relevant. Training in CBCT guidance is essential to achieve greater accuracy and decrease procedure time/dose values.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Comparison of Percutaneous Cementoplasty with and Without Interventional Internal Fixation for Impending Malignant Pathological Fracture of the Proximal Femur

PurposeTo compare the efficacy of percutaneous cementoplasty (PCP) with and without interventional internal fixation (IIF) on malignant impending pathological fracture of proximal femur.MethodsA total of 40 patients with malignant impending pathological fracture of proximal femur were selected for PCP and IIF (n = 19, group A) or PCP alone (n = 21, group B) in this non-randomized prospective study. Bone puncture needles were inserted into the proximal femur, followed by sequential installation of the modified trocar inner needles through the puncture needle sheath. Then, 15–45 ml cement was injected into the femur lesion.ResultsThe overall excellent and good pain relief rate during follow-ups were significantly higher in group A than that in group B (89 vs. 57 %, P = 0.034). The average change of VAS, ODI, KPS, and EFES in group A were significantly higher than those in group B at 1-, 3-, 6-month, 1-year (P < 0.05). Meanwhile, The stability of the treated femur was significantly higher in group A than that in group B (P < 0.05).ConclusionPCP and IIF were not only a safe and effective procedure, but resulted in greater pain relief, bone consolidation, and also reduced the risk of fracture than the currently recommended approach of PCP done on malignant proximal femoral tumor.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Efficacy of the Vertebral Body Stenting System for the Restoration of Vertebral Height in Acute Traumatic Compression Fractures in a Non-osteoporotic Population

Introduction: To evaluate the effectiveness of percutaneous image-guided vertebral body stenting (VBS) at restoring vertebral height in acute, stable, traumatic thoracolumbar fractures in a young, non-osteoporotic population. Materials and Methods: A single-centre retrospective review of all traumatic non-osteoporotic fractures treated with VBS between 2010 and 2017 was performed. Inclusion criteria included patients with recent (< 10 days), symptomatic and stable thoracolumbar compression fractures. Patients with low-energy fractures, osteoporosis and age > 60/50 years (male/female) were excluded. Primary outcomes included: correction of vertebral height, correction of kyphosis angle and Beck Index on reconstructed pre- and post-procedural CBCT images. Secondary outcomes included intra-procedural stent recoil, complications, cement leakage and factors predicting height restoration. Results: Thirty-nine patients (26 men, 13 women; mean age 33.6 years, range 15–57 years) underwent VBS 5 days post-trauma on average (range 1–10), for stable compression fractures located between T5 and L5. Mean vertebral height gain, vertebral kyphosis angle correction and Beck index improvement were 3.8 mm (95% CI 3.36–4.50; P(> 3 mm) = 99.9%), 4.3° (95% CI 3.50–5.20; P(> 3°) = 99.9%) and 0.07 [95% CI 0.053–0.11], respectively (all statistically significant). Technical success was 92%, with 3 “major” stent recoils resulting in loss of vertebral height correction. No symptomatic complications were observed. No predictive factors for procedural success were identified. Conclusion: VBS can significantly restore vertebral height in young patients with traumatic vertebral compression fractures.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Microscale mechanical modeling of deformable geomaterials with dynamic contacts based on the numerical manifold method

Abstract Micromechanical modeling of geomaterials is challenging because of the complex geometry of discontinuities and potentially large number of deformable material bodies that contact each other dynamically. In this study, we have developed a numerical approach for micromechanical analysis of deformable geomaterials with dynamic contacts. In our approach, we detect contacts among multiple blocks with arbitrary shapes, enforce different contact constraints for three different contact states of separated, bonded, and sliding, and iterate within each time step to ensure convergence of contact states. With these features, we are able to simulate the dynamic contact evolution at the microscale for realistic geomaterials having arbitrary shapes of grains and interfaces. We demonstrate the capability with several examples, including a rough fracture with different geometric surface asperity characteristics, settling of clay aggregates, compaction of a loosely packed sand, and failure of an intact marble sample. With our model, we are able to accurately analyze (1) large displacements and/or deformation, (2) the process of high stress accumulated at contact areas, (3) the failure of a mineral cemented rock samples under high stress, and (4) post-failure fragmentation. The analysis highlights the importance of accurately capturing (1) the sequential evolution of geomaterials responding to stress as motion, deformation, and high stress; (2) large geometric features outside the norms (such as large asperities and sharp corners) as such features can dominate the micromechanical behavior; and (3) different mechanical behavior between loosely packed and tightly packed granular systems.

58 GEOSCIENCES↗