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DOE OSTI2024

Adsorption Thermodynamics for Process Simulation

Adsorption has rapidly evolved in recent decades and is an established separation technology extensively practiced in gas separation industries and others. However, rigorous thermodynamic modeling of multicomponent adsorption equilibrium remains elusive, and industrial practitioners rely heavily on expensive and time-consuming trial-and-error pilot studies to develop adsorption units. Here, this article highlights the need for rigorous adsorption thermodynamic models and the limitations and deficiencies of existing models such as the extended Langmuir isotherm, dual-process Langmuir isotherm, and adsorbed solution theory. It further presents a series of recent advances in the generalization of the classical Langmuir isotherm of single-component adsorption by deriving an activity coefficient model to account for the adsorbed phase adsorbate–adsorbent interactions, substituting adsorbed phase adsorbate and vacant site concentrations with activities, and extending to multicomponent competitive adsorption equilibrium, both monolayer and multilayer. Requiring a minimum set of physically meaningful model parameters, the generalized Langmuir isotherm for monolayer adsorption and the generalized Brunauer–Emmett–Teller isotherm for multilayer adsorption address various thermodynamic modeling challenges including adsorbent surface heterogeneity, isosteric enthalpies of adsorption, BET surface areas, adsorbed phase nonideality, adsorption azeotrope formation, and multilayer adsorption. Also discussed is the importance of quality adsorption data that cover sufficient temperature, pressure, and composition ranges for reliable determination of the model parameters to support adsorption process simulation, design, and optimization.

09 BIOMASS FUELS↗
DOE OSTI2023

Comparison of Heterogeneous Langmuirian Models for Mixed-Gas Adsorption Equilibria

Mixed-gas adsorption remains a very active area of research, where newly proposed adsorption equilibrium models need to be compared to standards in the field. The generalized Langmuir (gL) isotherm, proposed by Hamid et al. to address adsorption of different size molecules on heterogeneous adsorbents without requiring evaluation of the Gibbs isotherm, has thus far been tested mainly against the adsorbed solution theory (AST). The gL isotherm was shown to be thermodynamically consistent and gave either better or similar representation than AST models. Here, the gL isotherm is contrasted with the Dual-Process Langmuir isotherm popularized by Ritter and his co-workers and the Loading Ratio Correlation popularized for simple mixtures, both of which are considered the “standard” models for process simulation. Furthermore, the comparison is based on their theoretical roots, interpretations, and representation of the equilibrium loading and the isosteric enthalpy of adsorption of unary, binary, and ternary mixtures of various gaseous adsorbates on different adsorbents over a range of experimental pressures and temperatures.

42 ENGINEERING↗
DOE OSTI2023

Towards a heat- and mass-balanced kinetic model of TATB decomposition

We report TATB (1,3,5-triamino-2,4,6-trinitrobenzene) was thermally degraded by two small-scale analytical methods – simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) and a hot-stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. SDT used ramped heating, isothermal soaking, and thermal pretreatment at various conditions. The heat flow and mass loss were monitored during various treatment conditions to derive chemical decomposition kinetics and Arrhenius parameters. FTIR experiments used isothermal heating, and changes were monitored spectroscopically. Solid samples generated at specific conditions were collected from both methods and were analyzed by DMSO extraction followed by chemical speciation by optical and mass spectrometric methods. Characterization provided the following reaction insights: TATB decreases in a sigmoidal pattern in isothermally heated samples. Other soluble products gradually increase in concentration and then abruptly decline in concentration during the second exotherm, such as diamino-dinitro-benzofurazan and amino-nitro-benzodifurazan. FTIR showed gradual changes in the amino and nitro functionality, shifting positions and decreasing intensity for the first 40 min. Then the solid gradually appeared more like an amorphous C with N incorporated, similar to previous studies on thermally degraded TATB-type materials. Extracted residues (DMSO-soluble components removed) examined by FTIR showed an abrupt change in chemical composition between 40- and 45-min isothermal treatment, indicating early forming solids are different than later forming residues. A reliable mass- and energy-balanced global reaction network must include at least two autocatalytic reactions, either in parallel or series, and at least one must have an explicit initiation reaction having a low activation energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

On the Phase with an Unreported Ternary Composition Found in the P-Pt-Rh System

This work reports a ternary structure in the P-Pt-Rh system, which has a composition not reported in the literature. The structure formed in the Pt-6 wt.% Rh alloy which was partially melted in a P-enriched CO environment near 1000 °C isothermally and non-isothermally as part of the type B thermocouple assembly. A composition and a crystal structure of this phase were investigated by utilizing SEM, EPMA, XRD and TEM techniques to discuss the potential of this structure being a true ternary phase. The EPMA indicated chemistries of the ternary structure from both isothermal and non-isothermal samples were about 23P-52Pt-25Rh (at.%) and, 22P-54Pt-24Rh (at.%) respectively. TEM diffraction patterns identified this ternary structure to be crystalline with a complex non-cubic structure, and confirmed it was not amorphous. Finally, by superimposing the compositions in the ternary phase diagram, it was concluded this phase was not extensions of any binary phases known in the respective binary systems.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Probing surface-adsorbate interactions through active particle dynamics

Adsorbate molecules present in a reaction mixture may bind to and block catalytic sites. Measurement of the surface coverage of these molecules via adsorption isotherms is critical for modeling and design of catalytic reactions on surfaces. However, it is challenging to measure isotherms in solution in a way that is directly relevant to catalytic activity under reaction conditions, particularly since adsorbates may bind with an enormous range of surface affinity parameters. Here we used the motion of self-propelled catalytic Janus particles, which employ the decomposition of hydrogen peroxide fuel as a propulsion mechanism, to determine the effective surface coverage of thioglycerol, furfural, and ethanol on a platinum surface as a function of concentration in aqueous solution by measuring the decrease in active motion due to the blocking of active sites. For strongly adsorbing thioglycerol, this effective coverage was compared and contrasted to the total adsorbed amount measured using inductively-coupled plasma analysis. Demonstrating the broad applicability of this approach, the surface affinity of the three adsorbates spanned more than four orders of magnitude. For each species, the adsorbate-mediated attenuation of active motion occurred over a wide concentration range and was well-described by a Langmuir isotherm. The strongly interacting thioglycerol had the highest affinity towards the surface (K a = 15.5 ± 4.3 mM –1 ) and fully deactivated the active particle motion at surface saturation. Furfural had an intermediate affinity (K a = 0.42 ± 0.07 mM –1 ) but did not fully block H 2 O 2 access to the surface at apparent saturation, consistent with a maximum fractional surface coverage of θ max = 0.67. Ethanol exhibited even lower affinity (K a = 0.0025 ± 2x10 -4 mM –1 ) and its coverage saturated at only θ max = 0.38. Analysis of isotherms at elevated temperatures enabled direct extraction of the enthalpies of adsorption. The degree of surface coverage at adsorbate saturation appeared to correlate with the relative energies of adsorption for the different adsorbate species and was consistent with adsorbate saturation of one of multiple active site populations towards H 2 O 2 decomposition. Furthermore, computational investigations into solvent effects on furfural adsorption showed good quantitative agreement with the experimental results. This work leverages unique properties of active particles to explore fundamental catalysis questions and demonstrates a novel paradigm for significant and experimentally accessible multidisciplinary research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Austenite formation and cementite dissolution during intercritical annealing of a medium-manganese steel from a martensitic condition

In the present study, in situ high-energy X-ray diffraction (HEXRD), dilatometry, and metallography were conducted for the purpose of understanding microstructure evolution during intercritical annealing of a Fe-0.19C-4.39Mn steel from a martensitic initial condition. Three different simulations for austenite growth and solute partitioning during isothermal holding were conducted using the DICTRA™ module of Thermo-Calc®. The microstructures after intercritical annealing exhibit film-like retained austenite; however, in situ HEXRD indicates that retained austenite in the initial martensitic microstructure had decomposed upon heating to the isothermal holding temperature, suggesting that film-like austenite may be generated during intercritical annealing via nucleation and growth of new austenite and without necessarily preserving initial retained austenite films in the martensitic microstructure. Metallography and in situ HEXRD also indicate that cementite had formed upon heating but did not readily dissolve during an 1800 s isothermal hold although considerable growth of austenite had occurred during the isothermal hold, suggesting that austenite nucleation and initial growth during intercritical annealing does not solely occur due to carbon partitioning. A simulation incorporating cementite suggests that the increase in austenite fraction during intercritical annealing initially occurs in association with Mn partitioning followed by austenite growth induced by gradual cementite dissolution.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Iodine Removal from Carbonate-Containing Alkaline Liquids Using Strong Base Resins, Hybrid Resins, and Silver Precipitation

The ability of several material types to remove aqueous iodine from a mildly alkaline, carbonate-rich nuclear waste stream was evaluated: strong base anion exchange resins (SBAR), hybrid resins, Ag-containing materials and Bi-containing hybrid resins. A combination of batch testing and flow through column testing were used in the evaluation. In batch testing, hybrid resins CHM-20, SIR-110-CE and RTBI were shown to have high efficiency for the removal of both iodide and iodate simultaneously, while Ag-containing materials and SBAR demonstrated high capacity for iodide removal. One example of each material type (CHM-20, A532E and Ionex 400) were further evaluated for their sorption isotherms and column performance. The Langmuir isotherm, or a Langmuir-Freundlich hybrid isotherm, best described the sorption of iodide to the CHM-20 hybrid resin and Purolite A532E. The Freundlich isotherm best described the uptake of iodate to CHM-20 and A532E and for both iodide and iodate to the Ag-containing Ionex-400. In column testing the Purolite A532E had exceptional performance for overall iodide removal. With the capacity demonstrated the A532E resin would exceed Class C waste classification before breakthrough initiated, and column change outs in processing would be dictated by eventual waste classification, not breakthrough. The Ionex 400, a Ag-zeolite, was observed to degrade over time in the column in the mild alkaline conditions whereas the hybrid CHM-20 was limited in the single pass through design and would be best suited for applications where iodide and iodate are present and recirculation of the column effluent is feasible. Here this work highlights the feasibility of commercially available materials to separate radioiodine from liquid environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Oxidation kinetics of SPS-densified U 3 Si 2 fuels—Microstructure impact

Here, U 3 Si 2 is a potential candidate for accident tolerant fuels because of its high uranium density and excellent thermal conductivity in comparison to UO 2 . However, U 3 Si 2 suffers from oxidation, steam corrosion, and subsequent disintegration/pulverization. The detailed investigation of kinetics that incorporates fundamental treatment of oxidation of U 3 Si 2 is scarcely reported, and the oxidation mechanisms have not been fully elucidated. In this paper, the oxidation behavior of microcrystalline (mc - ) and nanocrystalline (nc - ) U 3 Si 2 have been systematically investigated using a thermogravimetric analysis (TGA) apparatus through a series of isothermal and non-isothermal kinetic studies. The isothermal kinetic study with a model-fitting approach indicates oxidation activation energy of 85 kJ/mol for dense mc - U 3 Si 2 and 96.4 kJ/mol for nc - U 3 Si 2 pellets, while the isoconversional approach leads to an activation energy in the range of 70–85 kJ/mol for mc - U 3 Si 2 and 75–86 kJ/mol for nc - U 3 Si 2 with three most common model-free methods, including Kissinger–Akahira–Sunose, Flynn–Wall–Ozawa, and Friedman methods. The derivation of oxidation activation energies using both isothermal and isoconversional methods highlights the approach to evaluate the oxidation resistance of nuclear materials using TGA quantitatively and makes it possible to compare among various nuclear fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Performance Restoration of a Tritium-Aged LaNi 4.25 Al 0.75 Sample

Hydride beds containing LaNi 4.25 Al 0.75 (LANA.75) are used to store significant quantities of tritium. These hydride beds have a limited service life due to radiolytic decay of tritium to 3He within the metal matrix. The crystal structure of the hydride is altered by trapped 3 He, which has a very low solubility in the metal. The altered structure induces the formation of a heel of trapped hydrogen isotopes and diminishes the reversible capacity of the hydride. With sufficient tritium exposure, the bed loses the ability to deliver 3He-free tritium, and replacement is needed. Demonstration of a means to regenerate tritium-aged LANA.75 in situ would delay or even eliminate the need to replace lanthanum nickel aluminum (LANA) hydride beds. This paper presents test results obtained during regeneration testing. The efficacy of regeneration testing was evaluated by comparing tritium desorption isotherms collected on the hydride before and after exposure to regeneration conditions. Testing was performed on a bench-scale tritium-aged LANA.75 sample that was previously isotopically exchanged (from tritium to deuterium), passivated, and recovered. Once transferred to a high-temperature test cell, the deuterium heel of the sample was isotopically exchanged with tritium, and a baseline desorption isotherm was collected for comparison purposes. The sample was then heated under vacuum, and comparative isotherms were gathered between regeneration evolutions. Shifts in isotherms show progressive improvements with higher-temperature exposure over the tritium-aged baseline. The heel was significantly reduced, and the reversible capacity of the hydride was essentially restored to near virgin values. For all tested conditions, the plateau pressure remained higher than virgin LANA.75.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

SR19021 Tritium Aging of Regenerated LANA.75 (Final Project Report)

The Savannah River Tritium Enterprise (SRTE) has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. LANA.75 beds store significant quantities of tritium but have a limited service life due to the radiolytic decay of tritium to He-3 within the metal matrix. It has been shown that heating tritium-aged LANA.75 under vacuum can reverse tritium aging effects, eliminating the heel of trapped hydrogen, and restoring the reversible capacity. Additional investigation is needed to ensure there are no unexpected changes to the hydride before this restoration technique is employed in full scale beds in the Tritium Facilities. This project was to be comprised of three distinct scopes: obtain tritium aging data on the sample regenerated in 2018, regenerate a tritium-aged sample at 600 °C, and perform thermal stability testing on a non-tritiated sample. Isotherms were collected on the previously regenerated sample after approximately two years of tritium aging. Isotherms were collected at 80, 100, and 120 °C. As expected, there was a decrease in the plateau pressure, an increase in plateau slope, and a portion of the “heel” of tritium trapped in the metal had been reestablished. Unexpectedly, it appeared that the plateau had shortened at the higher tritium to metal ratios as well. This is typically seen in older samples. The second scope, to regenerate a second tritium-aged LANA.75 sample, was not completed. A Task Technical and Quality Assurance Plan was written and approved, a high temperature test cell was fabricated, several pre-job briefs were held, and the hydride sample was passivated with air. Despite these successes, the hydride sample was not recovered from the legacy test cell. The third scope was to perform thermal stability testing on a “cold” LANA.75 sample. A non-tritiated sample of LANA.75 was held at 750 °C under vacuum for 200 hours to simulate exposure to multiple regeneration evolutions. Hydride isotherm performance, chemical composition, crystallinity, particle size, and morphology are compared between the pre- and post-regeneration samples. No significant changes were observed in composition, crystallinity, or particle size. Comparison of before and after isotherms showed that performance improved rather than deteriorated during the evolution. Scanning Electron Microscopy (SEM) analysis showed small growths on the particle surface after exposure to regeneration conditions. Additional testing will be required to determine the cause of these growths.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2024

Development of a Cure Model for Unsaturated Polyester Resin Systems Based on Processing Conditions

Unsaturated polyester resin (UPR) systems are extensively used in composite materials for applications in the transportation, marine, and infrastructure sectors. There are continually evolving formulations of UPRs that need to be evaluated and optimized for processing. Differential Scanning Calorimetry (DSC) provides valuable insight into the non-isothermal and isothermal behavior of UPRs within a prescribed temperature range. In the present work, non-isothermal DSC tests were carried out between temperatures of 0.0 °C and 250 °C, through different heating and cooling ramp rates. The isothermal DSC tests were carried out between 0.0 and 170 °C. The instantaneous rate of cure of the tested temperatures were measured. The application of an autocatalytic model in a calculator was used to simulate curing behaviors under different processing conditions. As the temperature increased from 10 °C up to 170 °C, the rate of cure reduced, and the heat of reaction increased. The simulated cure behavior from the DSC data showed that the degree of cure (α) maximum value of 71.25% was achieved at the highest heating temperature of 85 °C. For the low heating temperature, i.e., 5 °C, the maximum degree of cure (α) did not exceed 12% because there was not enough heat to activate the catalyst to crosslink further.

Polymer Science↗
DOE OSTI2020

As a Matter of State: The Role of Thermodynamics in Magnetohydrodynamic Turbulence

Turbulence simulations play a key role in advancing the general understanding of the physical properties of turbulence and in interpreting astrophysical observations of turbulent plasmas. For the sake of simplicity, however, turbulence simulations are often conducted in the isothermal limit. Given that the majority of astrophysical systems are not governed by isothermal dynamics, we aim to quantify the impact of thermodynamics on the physics of turbulence, through varying adiabatic index, γ, combined with a range of optically thin cooling functions. Here, we present a suite of ideal magnetohydrodynamics simulations of thermally balanced stationary turbulence in the subsonic, super-Alfvénic, high ${\beta }_{{\rm{p}}}$ (ratio of thermal to magnetic pressure) regime, where turbulent dissipation is balanced by two idealized cooling functions (approximating linear cooling and free–free emission) and examine the impact of the equation of state by considering cases that correspond to isothermal, monatomic, and diatomic gases. We find a strong anticorrelation between thermal and magnetic pressure independent of thermodynamics, whereas the strong anticorrelation between density and magnetic field found in the isothermal case weakens with increasing γ. Similarly, the linear relation between variations in density and thermal pressure with sonic Mach number becomes steeper with increasing γ. This suggests that there exists a degeneracy in these relations with respect to thermodynamics and Mach number in this regime, which is dominated by slow magnetosonic modes. These results have implications for attempts to infer (e.g.,) Mach numbers from (e.g.,) Faraday rotation measurements, without additional information regarding the thermodynamics of the plasma. However, our results suggest that this degeneracy can be broken by utilizing higher-order moments of observable distribution functions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Calorimetry can detect the early onset of hydrolysis in hybrid supercapacitors with aqueous electrolytes

This study investigates the effect of cation species on the onset of electrolyte hydrolysis in hybrid supercapacitors with aqueous electrolytes using isothermal operando calorimetry. The cells consisted of a positive α-MnO 2 cryptomelane electrode and a negative activated carbon (AC) electrode with either 0.5 M K 2 SO 4 or 0.5 M Cs 2 SO 4 aqueous electrolytes. They were characterized using cyclic voltammetry and galvanostatic cycling. In addition, the instantaneous heat generation rate at each electrode was measured using a custom isothermal operando calorimeter. Heat generation associated with resistive losses (Joule heating) and reversible ion adsorption/desorption was clearly identified. For larger potential windows, an endothermic dip, attributed to the onset of hydrolysis, was observed at the positive α-MnO 2 electrode where K + and Cs + ions engaged in fast surface redox reactions. Interestingly, this endothermic dip appeared at 1.8 V and 2.0 V for K 2 SO 4 and Cs 2 SO 4 aqueous electrolytes, respectively. The difference in the stable operating potential window was attributed to thinner solvation shell around Cs + cation than for K + thus reducing the amount of water present near the electrodes as ions partially shed their solvation shells during adsorption. The early onset of hydrolysis could be observed by isothermal operando calorimetry before it could be observed with conventional electrochemical methods.

42 ENGINEERING↗
DOE OSTI2026

High Pressure X-ray Diffraction and Equation of State of Hydrazine

Synchrotron X-ray diffraction has been used to investigate the structure and equation of state (EOS) of hydrazine (N 2 H 4 ) up to 54.3 GPa at 298 K. The diffraction patterns could be fit to a monoclinic unit-cell structure and put strong constraints on previously reported phase transitions documented by vibrational spectroscopy over this pressure range. Pressure–volume ( P–V ) data were fit using a Vinet EOS, yielding parameters: V 0 = 45.2 Å 3 /molecule (fixed), K 0 = 11.8(7) GPa, and K 0 ′ = 6.5(2). Previously measured high-pressure vibrational frequency shifts were used to estimate the vibrational free energy and model P–V–T isotherms from 0 to 1200 K. The results of the P–V–T isotherms are compared to existing shock Hugoniot data on hydrazine and 298 K isotherms for assemblages of possible decomposition products. This comparison suggests dissociation at high density under shock loading. Good correspondence was found between the static lattice EOS as calculated by the model and the previously reported EOS as calculated by density functional theory. Finally, these results resolve existing uncertainties about the EOS and crystal symmetry of hydrazine at high pressure and provide valuable baseline information on this important energetic material.

diffraction↗
DOE OSTI2022

Measurement of isosteric heat of gas adsorption and Brunauer–Emmett–Teller (BET) surface area using a quartz crystal microbalance

The study of gas adsorption on a solid surface evaluates the affinity between sorbate gas and sorbent substrate and factors that contribute to this. This report presents a test platform for adsorption experiments of various gases on various solid surfaces. Controlled environmental conditions enable investigations in materials surface science and increase the consistency among adsorption data. The system utilizes a quartz crystal microbalance to perform gravimetric analysis of deposition and adsorption, enabling investigation of the interaction of gaseous molecules with solid surfaces. In this study, a quartz crystal microbalance as gas adsorption detector was integrated with an environmental chamber to create a versatile tool for gas adsorption experiments on thin films. Experimental operation of this apparatus was demonstrated via acquisition of the adsorption isotherms of cyclohexane vapor on a gold surface at 55 and 70 °C. The result indicated International Union of Pure and Applied Chemistry Type II adsorption. Consequentially, application of the Brunauer–Emmett–Teller model to the isotherm data subject to predefined criteria for linear region selection yielded a surface area of the sorbent of 0.53 cm2 at 55 °C. From the monolayer region of the isotherms, the isosteric heat of adsorption of the cyclohexane vapor on gold was calculated to be 37 kJ mol-1.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

Ion Exchange of Selected Group II Metals and Lead by Crystalline Silicotitanate and Competition for Cs Exchange Sites

A series of batch contact tests were conducted to evaluate the exchange behavior of Ba, Ca, Pb, and Sr onto crystalline silicotitanate (CST) in support of an expedited Cs removal and pretreatment system at the Hanford site. Binary Na/M 2+ and ternary Na/Cs/M 2+ isotherms were generated to understand selectivity, capacity, and competitive impact of each analyte on Cs uptake from a simple 1 M NaOH/4.6 M NaNO 3 simulant. Analyte loading from a 0.1 M NaOH/5.5 M NaNO 3 simulant was assessed to determine the effect of hydroxide concentration on binary Na/M 2+ isotherms. Finally, results from binary and ternary isotherms indicated that group II metals, and Pb do not impact CST performance toward CST at concentrations expected in Hanford tank waste supernate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Post-process annealing of large-scale 3D printed polyphenylene sulfide composites

Large-scale extrusion-based additive manufacturing of high-performance thermoplastic composites like fiber reinforced polyphenylene sulfide (PPS) is well-suited for tooling applications to lower manufacturing costs and lead times. Autoclave tooling requires good mechanical performance at temperatures even above the glass transition temperature (T g ). In this work, the authors have investigated a post-process isothermal annealing technique to improve the mechanical properties of various grades of carbon fiber reinforced PPS components printed on the Big Area Additive Manufacturing (BAAM) system. Since PPS is a semi-crystalline polymer, crystallinity can change during annealing and affect the mechanical properties of the part. In addition, isothermal annealing can also lead to solid-state structural changes in the form of thermal and oxidative branching and/or crosslinking reactions in some grades of PPS which can alter the crystallization process. This work reports the effect of annealing on dynamic mechanical properties of BAAM printed components, along with studies to determine the effect of annealing on crystallinity and the occurrence of oxidative reactions. Results showed that isothermal annealing at 250 °C for 18 h improved the storage modulus of all selected grades (neat and reinforced) of PPS at temperatures above T g . Annealing led to an overall increase in the degree of crystallinity, with secondary crystallization taking place. Although oxidative structural changes were observed to occur more on the surface of the PPS parts, they primarily influenced the size of crystals formed and did not significantly alter the degree of crystallinity at various regions within the sample.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Dehydroxylation kinetics of kaolinite and montmorillonite examined using isoconversional methods

The use of calcined clays as supplementary cementitious materials (SCMs) in concrete is a promising strategy towards decarbonizing the cement and concrete industry. This is especially relevant considering the ever-increasing demand for concrete. Comprehensive understanding of the kinetics of calcination is essential towards maximizing the potential reactivity of clay minerals while ensuring energy efficiency. In this study, the kinetics of the dehydroxylation of kaolinite and montmorillonite are investigated under non-isothermal conditions at constant heating rate. Activation energies ( E a ) are determined via Friedman differential and advanced Vyazovkin incremental methods over the isoconversional range; these are devoid of computational approximations, thus allowing kinetic analysis without assuming a specific reaction model. Kinetic equations—in the differential form as well as a combination of differential and integral forms are compared against the experimentally determined reaction models to identify the most probable dehydroxylation mechanism for kaolinite and montmorillonite. A reaction order mechanism is established for dehydroxylation of kaolinite, while montmorillonite is noted to undergo dehydroxylation via a single-step reversible diffusion-controlled process. Kinetic triplet—comprising activation energy, reaction model and pre-exponential factor—is used to predict isothermal calcination conditions, which is further verified using analytical techniques. Heat release rates of clay-portlandite blends from isothermal calorimetry are used within a thermodynamic framework to quantify reactivity of the calcined clays. Here, the study demonstrates a general approach based on isoconversional methods to predict calcination conditions for different clays that can be used in efficient and optimized production of blended cements or SCMs.

36 MATERIALS SCIENCE↗