Toward Self-Healing Concrete Infrastructure: Review of Experiments and Simulations across Scales.

Cement and concrete are vital materials used to construct durable habitats and infrastructure that withstand natural and human-caused disasters. Still, concrete cracking imposes enormous repair costs on societies, and excessive cement consumption for repairs contributes to climate change. Therefore, the need for more durable cementitious materials, such as those with self-healing capabilities, has become more urgent. In this review, we present the functioning mechanisms of five different strategies for implementing self-healing capability into cement based materials: (1) autogenous self-healing from ordinary portland cement and supplementary cementitious materials and geopolymers in which defects and cracks are repaired through intrinsic carbonation and crystallization; (2) autonomous self-healing by (a) biomineralization wherein bacteria within the cement produce carbonates, silicates, or phosphates to heal damage, (b) polymer-cement composites in which autonomous self-healing occurs both within the polymer and at the polymer-cement interface, and (c) fibers that inhibit crack propagation, thus allowing autogenous healing mechanisms to be more effective. In all cases, we discuss the self-healing agent and synthesize the state of knowledge on the self-healing mechanism(s). In this review article, the state of computational modeling across nano- to macroscales developed based on experimental data is presented for each self-healing approach. We conclude the review by noting that, although autogenous reactions help repair small cracks, the most fruitful opportunities lay within design strategies for additional components that can migrate into cracks and initiate chemistries that retard crack propagation and generate repair of the cement matrix.

Impact of chitin nanofibers and nanocrystals from waste shrimp shells on mechanical properties, setting time, and late-age hydration of mortar.

Every year ~ 6-8 million tonnes of shrimp, crab, and lobster shell wastes are generated, requiring costly disposal procedures. In this study, the chitin content of shrimp shell waste was oxidized to produce chitin nanocrystals (ChNC) and mechanically fibrillated to obtain chitin nanofibers (ChNF) and evaluated as additives for mortar. ChNF (0.075 wt%) and ChNC (0.05 wt%) retarded the final setting time by 50 and 30 min, likely through cement dispersion by electrostatic repulsion. ChNF (0.05 wt%) with a larger aspect ratio than ChNC resulted in the greatest improved flexural strength and fracture energy by 24% and 28%. Elastic modulus increased by up to 91% and 43% with ChNC and ChNF. Solid-state nuclear magnetic resonance (NMR) showed ChNF (0.05 wt%) enhanced calcium-silicate-hydrate structure with a 41% higher degree of polymerization, 9% more silicate chain length, and a 15% higher degree of hydration at 28 days. Based on the findings, chitin seems a viable biomass source for powerful structural nanofibers and nanocrystals for cementitious systems to divert seafood waste from landfills or the sea.

High-temperature high-pressure microfluidic system for rapid screening of supercritical CO2 foaming agents.

CO2 foam helps to increase the viscosity of CO2 flood fluid and thus improve the process efficiency of the anthropogenic greenhouse gas's subsurface utilization and sequestration. Successful CO2 foam formation mandates the development of high-performance chemicals at close to reservoir conditions, which in turn requires extensive laboratory tests and evaluations. This work demonstrates the utilization of a microfluidic reservoir analogue for rapid evaluation and screening of commercial surfactants (i.e., Cocamidopropyl Hydroxysultaine, Lauramidopropyl Betaine, Tallow Amine Ethoxylate, N,N,N' Trimethyl-N'-Tallow-1,3-diaminopropane, and Sodium Alpha Olefin Sulfonate) based on their performance to produce supercritical CO2 foam at high salinity, temperature, and pressure conditions. The microfluidic analogue was designed to represent the pore sizes of the geologic reservoir rock and to operate at 100 °C and 13.8 MPa. Values of the pressure drop across the microfluidic analogue during flow of the CO2 foam through its pore network was used to evaluate the strength of the generated foam and utilized only milliliters of liquid. The transparent microfluidic pore network allows in-situ quantitative visualization of CO2 foam to calculate its half-life under static conditions while observing if there is any damage to the pore network due to precipitation and blockage. The microfluidic mobility reduction results agree with those of foam loop rheometer measurements, however, the microfluidic approach provided more accurate foam stability data to differentiate the foaming agent as compared with conventional balk testing. The results obtained here supports the utility of microfluidic systems for rapid screening of chemicals for carbon sequestration or enhanced oil recovery operations.

Two-Step Adsorption of a Switchable Tertiary Amine Surfactant Measured Using a Quartz Crystal Microbalance with Dissipation.

The adsorption of a switchable cationic surfactant, N, N, N'-trimethyl- N'-tallow-1,3-diaminopropane (DTTM, Duomeen TTM), at the silica/aqueous solution interface is characterized using a quartz crystal microbalance with dissipation (QCM-D). The adsorption isotherms reveal that changes in the solution pH or salinity affect surfactant adsorption in competing ways. In particular, the combination of the degree of protonation of the surfactant and electrostatic interactions is responsible for surfactant adsorption. The kinetics of adsorption is carefully measured using the real-time measurement of a QCM-D, allowing us to fit the experimental data with analytical models. At pH values of 3 and 5, where the DTTM is protonated, DTTM exhibits two-step adsorption. This is representative of a fast step in which the surfactant molecules are adsorbed with head-groups orientated toward the surface, followed by a slower second step corresponding to formation of interfacial surfactant aggregates on the silica surface.

Characterizing adsorption of associating surfactants on carbonates surfaces.

HYPOTHESIS: The adsorption of anionic surfactants onto positively charged carbonate minerals is typically high due to electrostatic interactions. By blending anionic surfactants with cationic or zwitterionic surfactants, which naturally form surfactant complexes, surfactant adsorption is expected to be influenced by a competition between surfactant complexes and surfactant-surface interactions. EXPERIMENTS: The adsorption behavior of surfactant blends known to form complexes was investigated. The surfactants probed include an anionic C15-18 internal olefin sulfonate (IOS), a zwitterionic lauryl betaine (LB), and an anionic C13-alcohol polyethylene glycol ether carboxylic acid (L38). An analytical method based on high-performance liquid chromatography evaporative light scattering detector (HPLC-ELSD) was developed to measure three individual surfactant concentrations from a blended surfactant solution. The adsorption of the individual surfactants and surfactant blends were systematically investigated on different mineral surfaces using varying brine solutions. FINDINGS: LB adsorption on calcite surfaces was found to be significantly increased when blended with IOS or L38 since it forms surfactant complexes that partition to the surface. However, the total adsorption of the LB-IOS-L38 solution on dolomite decreased from 3.09 mg/m2 to 1.97 mg/m2 when blended together compared to summing the adsorption values of individual surfactants, which highlights the importance of mixed surfactant association.

Static Adsorption of an Ethoxylated Nonionic Surfactant on Carbonate Minerals.

The static adsorption of C12-14E22, which is a highly ethoxylated nonionic surfactant, was studied on different minerals using high-performance liquid chromatography (HPLC) combined with an evaporative light scattering detector (ELSD). Of particular interest is the surfactant adsorption in the presence of CO2 because it can be used for foam flooding in enhanced oil recovery applications. The effects of the mineral type, impurities, salinity, and temperature were investigated. The adsorption of C12-14E22 on pure calcite was as low as 0.01 mg/m2 but higher on dolomite depending on the silica and clay content in the mineral. The adsorption remained unchanged when the experiments were performed using a brine solution or 0.101 MPa (1 atm) CO2, which indicates that electrostatic force is not the governing factor that drives the adsorption. The adsorption of C12-14E22 on silica may be due to hydrogen bonding between the oxygen in the ethoxy groups of the surfactant and the hydroxyl groups on the mineral surface. Additionally, thermal decomposition of the surfactant was severe at 80 °C but can be inhibited by operating in a reducing environment. Under reducing conditions, adsorption of C12-14E22 increased at higher temperatures.