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At least 199 records · Page 11

Effect of temperature curing on properties and hydration of wollastonite blended magnesium potassium phosphate cements

K-struvite, the main hydrate of magnesium potassium phosphate (MKP) cements, dehydrates at ~50 °C, thus elevated temperatures at service conditions could affect cement properties and durability. In this study, properties and hydration of MKP cement without and with wollastonite were investigated at 20 and 50 °C. In hydrated pure MKP cement K-struvite decomposes progressively over time to MgKPO{sub 4}·H{sub 2}O at 50 °C, which leads to a strong reduction of solid volume and severe strength loss. The presence of wollastonite significantly slows down the decomposition rate of K-struvite, which is still observed after 393 days at 50 °C. K-struvite together with amorphous hydroxyapatite, M-(C)-S-H and CaK{sub 3}H(PO{sub 4}){sub 2} from the wollastonite reaction result in a cement with good short and long-term strength at both 20 and 50 °C.

36 MATERIALS SCIENCE↗

Effects of blended cements and carbonation on chloride-induced corrosion propagation

Highlights: • Corrosion propagation of blended cements was investigated for 1 year. • Carbonated and non‑carbonated mortars were evaluated. • Galvanostatic pulse and ER sensors were used to monitor corrosion. • Mortar properties were correlated with corrosion rates and corrosion damage. • Relationships between mortar properties and corrosion behaviour were established. Supplementary cementitious materials are known to refine the pore structure of concrete and accelerate the carbonation progress. The combination of the two processes can have both beneficial and disadvantageous effects on corrosion, especially when chlorides are also involved. In this study the corrosion properties of multiple blended cements were evaluated in carbonated and non‑carbonated states, with chlorides introduced through cyclic ponding. The examination involved monitoring the propagation phase, determining the microstructural properties of cements, and assessing the final corrosion damage. The results showed that the steel in the blended cements initially had a relatively high corrosion activity, which later decreased compared to the OPC. This stabilisation was presumably due to the beneficial changes to the pore structure. Carbonation had a significant impact on the corrosion, with carbonated mortars revealing shallower damage over a larger surface area. This effect was more pronounced for blended cements that exhibited greater susceptibility to carbonation.

36 MATERIALS SCIENCE↗

Characterization of reactive MgO-modified calcium sulfoaluminate cements upon carbonation

This study characterizes reactive MgO-modified calcium sulfoaluminate (CSA) cement upon carbonation. Paste samples were fabricated by replacing CSA cement with reactive MgO at levels of 0, 5, 10, and 20 wt%. The samples were cured for 56 days and further cured at a CO{sub 2} concentration of 3% for 28 days. MgO incorporation into the CSA cement favored the formation of monosulfate over ettringite. Externally supplied MgO in the CSA cement reduced Al uptake in C-A-S-H and formed hydrotalcite as a secondary phase, which is associated with a reduction in the carbonation degree. In addition, the incorporated MgO inhibited the carbonation of ettringite and monosulfate, while more C-A-S-H and aluminum hydroxide were formed in neat CSA cement upon carbonation, showing the nearly full decomposition of ettringite and monosulfate. The tetrahedral Al network of the MgO-modified sample was not altered upon carbonation, indicating that MgO modified the route of carbonation.

36 MATERIALS SCIENCE↗

Impact of downhole pressure and fluid-access on the effectiveness of wellbore cement expansion additives

Autogenous shrinkage of wellbore cement widely impairs zonal isolation. MgO-based cement expansion additives (CEAs) can mitigate this shrinkage, or even impart net expansion, by creating porosity through displacive crystal growth-processes. However, both MgO hydration and autogenous shrinkage behaviour depend strongly on stress state. Evaluation of CEA performance in wellbore cements therefore requires testing under elevated pressures representative for subsurface environments. We report experiments addressing the chemical and bulk volume changes that occur in cement hydrating at 10 MPa confining pressure and 90 °C. Volumetric response was investigated as function of MgO concentration, external water supply, and pore pressure decrease through water consumption during reaction. Results show the bulk expansion achieved using MgO-based CEAs diminishes markedly with increasing effective confining pressure or, equivalently, upon restricting fluid supply. This reduced expansion-potential under pressure has profound implications for slurry design, notably regarding CEA-concentrations required to counteract micro-annulus formation while maintaining low cement permeability.

36 MATERIALS SCIENCE↗

Near-field infrared microscopy: A novel analytic mapping technique to nanocharacterize calcium silicate-based cement materials

Infrared imaging via scattering-type scanning near-field optical microscopy (s-SNOM) allows chemical mapping of organic and inorganic materials with nanoscale spatial resolution. However, its potential adaptation to the complex multiphase structure of Portland cement is yet to be explored. Here we demonstrate the successful implementation of s-SNOM to spatially resolve coexisting chemical phases in tricalcium silicate, Portland cement's main compound, with 20-nm resolution. We found that s-SNOM is sensitive to different anhydrous polymorphic phases, revealing nanoscale domains that are ‘invisible’ to other microscopic techniques. Furthermore, s-SNOM's ability to distinguish the unhydrated and hydrated phases signifies its great promise as an analytical tool to study the complex hydration process of cement. The key to s-SNOM's application was nano-modifying the surface roughness of the cement samples, allowing nanoscale infrared imaging without topographical artifacts. Our study opens a window for infrared spectral microscopy in cement and other porous inorganic materials.

36 MATERIALS SCIENCE↗

Modeling the corrosion of steel casing and the damage of well cement in a borehole system

This work presents the effect of chloride-induced corrosion in an underground borehole system, specifically considering the steel casing and further damage to the surrounding cement. In the past four decades, oil well cement has been successfully used for underground construction. However, high concentrations of chloride ions gradually degrade the functionality and durability of well cement. Gasses and liquids can leak from deterioration caused by chloride ions, and thus motivate this study. The chemo-mechanical coupling diffusion model and a classical fracture mechanics model are applied. The model is validated with OPC concrete corrosion data from literature, and then applied to well cement using experimentally obtained material property data. The time when crack initiation, peak pressure, and complete fracture is reached in the model of the cement sheath provides a quantification of the expected service life of the borehole system.

36 MATERIALS SCIENCE↗

Wellbore cement fracture permeability as a function of confining stress and pore pressure

Cemented annulus fractures are a major leakage path in a wellbore system, and their permeability plays an important role in the behavior of fluid flow through a leaky wellbore. The permeability of these fractures is affected by changing conditions including the external stresses acting on the fracture and the fluid pressure within the fracture. Laboratory gas flow experiments were conducted in a triaxial cell to evaluate the permeability of a wellbore cement fracture under a wide range of confining stress and pore pressure conditions. For the first time, an effective stress law that considers the simultaneous effect of confining stress and pore pressure was defined for the wellbore cement fracture permeability. Here the results showed that the effective stress coefficient (λ) for permeability increased linearly with the Terzaghi effective stress ( -p) with an average of λ = 1 in the range of applied pressures. The relationship between the effective stress and fracture permeability was examined using two physical-based models widely used for rock fractures. The results from the experimental work were incorporated into numerical simulations to estimate the impact of effective stress on the interpreted hydraulic aperture and leakage behavior through a fractured annular cement. Accounting for effective stress-dependent permeability through the wellbore length significantly increased the leakage rate at the wellhead compared with the assumption of a constant cemented annulus permeability.

58 GEOSCIENCES↗

Immediate impact on the rim zone of cement based materials due to chemical attack

Cement based materials are in their widespread application fields exposed to various aqueous environments. This can lead to serious chemical changes affecting the durability of the materials. In particular in the context of service life prediction a detailed knowledge of the reaction mechanisms is a necessary base for the evaluation of the aggressivity of an aqueous medium and this is deduced commonly from long term investigations. However, these processes start immediately at the material/water-interface, when a cementitious system comes into contact with an aqueous solution, altering here the chemical composition and microstructure. This rim zone represents the first hurdle that has to be overcome by an attacking aqueous solution. Therefore, the properties of the surface near area should be closely associated with the further course of deterioration processes by reactive transport. In this context short term exposure experiments with hardened cement paste over 4 and 48 h have been carried out with demineralized water, hard tap water and different sulfate solutions. In order to investigate immediate changes in the near-surface region, depth profile cuts have been performed on the cement paste samples by means of focused ion beam preparation techniques. A scanning beam of Gallium ions is applied to cut a sharp edge in the cement paste surface, providing insights into the composition and microstructure of the upper ten to hundred microns. Electron microscopic investigations on such a section of the rim zone, together with surface sensitive X-ray diffraction accompanied by a detailed characterization of the bulk composition confirm that the properties of the material/water interface are of relevance for the durability of cement based systems in contact with aqueous solutions. In this manner, focused ion beam investigations constitute auspicious tools to contribute to a more sophisticated understanding of the reaction mechanisms. - Highlights: • The chemical stability is related to the properties of material/water interface. • Properties of the rim zone readjust quickly, triggered by hydrochemical conditions. • Durability research can be improved by combining FIB techniques and common analytics.

36 MATERIALS SCIENCE↗

Photocatalytic activities and chemically-bonded mechanism of SiO2@ TiO2 nanocomposites coated cement-based materials

Highlights: • Two samples have different deposited density of TiO{sub 2} nanoparticles on each SiO{sub 2} nanosphere, which depend on the difference of the water dosage. • When the curing time is 28 days, water adsorption rates of mortar-2 at 270 min have decreased by 17.8%, which may be attributed to pozzolanic reactivity of SiO{sub 2} on cement-based materials. • The formation of C-S-H gels via pozzolanic reaction of SiO{sub 2} on cement-based materials has been demonstrated by XPS and NMR spectra. • Cem-1 and cem-2 show excellent photocatalytic property. - Abstract: Photocatalytic technology has been studied in building materials, especially for the surface. However, the drawback of surface-treatment application is weak adhesion between coatings and the substrates resulting poor durability in outdoor environments. In the study, two SiO{sub 2}@TiO{sub 2} core-shell nanocomposites were synthetized and coated cement-based materials, and the photocatalytic activity (rhodamine B removal efficiency) and surface modification/densification performances of coated cement-based materials were studied. The two samples have different deposited densities of TiO{sub 2} nanoparticles on each SiO{sub 2} nanosphere. Water adsorption rates of coated mortar measured at 270 min decreased by 17.8% when curing time was 28 days. Reaction experiments of SiO{sub 2}@TiO{sub 2} nanocomposites and Ca(OH){sub 2} with different dosages were carried out to investigate the reaction mechanism. The formation of C-S-H gel was confirmed due to the pozzolanic reaction of samples and Ca(OH){sub 2}. The coated cement pastes show excellent photocatalytic activity for rhodamine B removal.

36 MATERIALS SCIENCE↗

A comprehensive review on the loss of wellbore integrity due to cement failure and available remedial methods

With the recent abrupt fluctuations in oil pricing and the need of complying with environmental and social requirements, nowadays it is an urgent call for the oil and gas industry to produce the hydrocarbon without any loss as well as in a safe manner. Cements are placed in the annular space of casing to provide zonal isolation in between wellbore and surface during the operational life cycle of the well or even after the abandonment. But this is not what happens most of the time. Cement degrades or loses its integrity through debonding either from the casing or formation and generates cracks or fractures due to varied reasons throughout the life of the well. Multiple causes contribute to the loss of wellbore integrity – either by physical, mechanical, or chemical processes. These failures lead to sustained casing pressure (SCP) and contamination of surrounding environment. To combat this issue or to restore the well integrity, multiple remedial actions have also been either implemented in the industry or proposed based on experimental research to prevent the damage or to seal the leakage in the cement sheath. Here, this paper will provide an extensive review of the underlying reasons of cement failure and the available remedial actions to minimize the loss of well integrity issue. These information are not only useful to know about the different corrective options available for us to implement in industry but also it will provide us a knowledge base regarding how we can enhance the performance of the exiting systems to battle the cement integrity problem more efficiently.

02 PETROLEUM↗

Air Emissions Impacts of Fuel Substitution in the United States Cement Industry

High-heat industrial processes cannot be easily electrified, often rely on comparatively high-emitting solid fuels, and are essential for economic growth. Cement production in particular is critical to supporting construction and the expansion and maintenance of infrastructure systems in countries around the world. Fuels for cement production include petcoke, coal, and waste solvents, and their combustion contributes approximately 40% of the CO 2 emissions from global cement production. Broadening the fuel resources to include agricultural residues and other wastes can reduce emissions and divert waste from landfills. We assess the potential to use 16 different alternative fuels across the 88 integrated cement plants in the United States. The share of alternative fuels in the cement production sector could increase from the current level of 17% to as high as 73%. Fuel substitution can reduce the current fuel-related life-cycle emissions (28.6 ± 5.7 Mton CO 2 /year) by 19–45%. The greatest national-scale human health cobenefits occur when alternative fuels are prioritized at facilities currently using coal and petcoke. NO x emissions outcomes from this strategy are mixed, but SO x and particulate matter emissions reductions drive net human health benefits. These results suggest that targeted fuel substitution in heavy industries can yield outsized emissions benefits.

alternative fuels↗

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of composite materials based on cement-ceramic powder blended binder

Characterization of newly developed composite mortars with incorporated ceramic powder coming from precise brick cutting as partial Portland cement replacement up to 40 mass% is presented in the paper. Fine ceramic powder belongs to the pozzolanic materials. Utilization of pozzolanic materials is accompanied by lower request on energy needed for Portland clinker production which generally results in lower production costs of blended binder and lower CO{sub 2} emission. In this paper, the ceramic powder is used in cement based mortar composition in amount of 8, 16, 24, 32, and 40 mass% of cement. Chemical composition of ceramic powder is analyzed by X-Ray Fluorescence and X-Ray Diffraction. The particle size distribution of ceramics is accessed on laser diffraction principle. For 28 days cured mortar samples, basic physical and mechanical properties are experimentally determined. The obtained results demonstrate that ceramic powder has potential to replace a part of Portland cement in composition of cement based composites and to reduce negative environmental impact of their production.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Carbon Nanofiber Clustering on the Micromechanical Properties of a Cement Paste

The use of carbon nanofibers (CNFs) in cement systems has received significant interest over the last decade due to their nanoscale reinforcing potential. However, despite many reports on the formation of localized CNF clusters, their effect on the cement paste micromechanical properties and relation to the mechanical response at the macroscopic scale are still not fully understood. In this study, grid nanoindentation coupled with scanning electron microscopy and energy dispersive spectroscopy was used to determine the local elastic indentation modulus and hardness of a portland cement paste containing 0.2% CNFs with sub-micro and microscale CNF clusters. The presence of low stiffness and porous assemblage of phases (modulus of 15–25 GPa) was identified in the cement paste with CNFs and was attributed primarily to the interfacial zone surrounding the CNF clusters. The CNFs favored the formation of higher modulus C–S–H phases (>30 GPa) in the bulk paste at the expense of the lower stiffness C–S–H. Nanoindentation results combined with a microscale–macroscale upscaling homogenization method further revealed an elastic modulus of the CNF clusters in the range from 18 to 21 GPa, indicating that the CNF clusters acted as compliant inclusions relative to the cement paste.

36 MATERIALS SCIENCE↗

Proposal of a Descriptive Modeling of Portland Cement Behavior under Radioactive Waste Repository Environment - 17267

Storage and disposal of DSRS is a problem in many countries over the world. Brazilian inventory is about 300,000 sources (in use or stored), many of them with high activity and long lived radionuclides. Our proposal to deposition of DSRS: Dispose of the DSRS in a deep borehole repository. The IPEN concept was adapted from the BOSS Concept, developed by the NECSA/IAEA. Cementitious materials are intended to be used as a backfill material between the steel casing and the geological formation around the borehole and Casing. The required service life of the installation is counted in thousands of years. Issues to be addressed: Assessment of cement paste long-term durability and its behavior under radiation, high pressure and temperature and penetration of groundwater containing chemically aggressive species. The present study aims at defining the relevant external factors and their influence on the durability of hydrated cement. This study will be helpful on modeling the long-term reactions in the cement matrix and can improve the safety assessment. The synergism between all factors that can affect the cement is hard to predict and have to take into account many processes. For example, the calcium ion content in a cementitious matrix can be altered by many factors and depends on the cement mix designs and environmental factors that will prevail at the repository.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of Cement Solidification Technique for Sodium Borate Waste Produced in PWR Plants - 16061

A cement solidification process for treating sodium borate waste produced in pressurized water reactor (PWR) plants was studied. It is known that the setting and hardening reaction of cement is retarded by the presence of boron compounds. This technique was developed to obtain high uniaxial compressive strength more than 10 MPa which can satisfy various countries disposal regulations. As examples of disposal regulations, France requires 8 MPa for homogeneous solidified products. The sodium/ boron (Na/B) ratio was controlled to about 1 by adding NaOH to simulated liquid waste for the purpose of improving the workablility and mechanical strength. To obtain high volume reduction, simulated liquid waste was dehydrated and powdered by using a wiped film evaporator. Ordinary portland cement (OPC) was used for the solidification. The viscosity of cement mixture was controlled by the water/cement ratio. The resulting viscosity became less than 25 dPa.s, and it was possible to continuously mix the mixture. Solidified cement with containing 73 kg/m{sup 3} of boron had a uniaxial compressive strength of more than 10 MPa. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Behaviour of Alpha Emitters in Cement - 16139

Alpha emitting radioelements can interact with cements in a number of ways. Alpha-radiolysis of water produces hydrogen that may pressurise and damage the structure, and it is postulated that the intense alpha radiation field around waste particles containing high alpha activity can cause mineralogical changes in the hydration products. In addition, their solubility in cement pore fluid can be increased by complexation with organic materials such as the degradation products of cellulose, which itself may be promoted by alpha irradiation. Analysis of pore fluid expressed from cements containing plutonium and a range of organic materials has demonstrated their effect on plutonium solubility. Calculations of hydrogen pressurisation as a result of alpha radiolysis suggest that radiolytic hydrogen will not exceed tensile strength of the cement. Further work is described in which cements containing high loadings of plutonium will be examined in the NNL Central Laboratory to investigate mineralogical changes during and after hydration. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A machine learning approach for clinker quality prediction and nonlinear model predictive control design for a rotary cement kiln

Abstract Cement manufacturing is energy‐intensive (5Gj/t) and comprises a significant portion of the energy footprint of concrete systems. Incorporating modern monitoring, simulation and control systems will allow lower energy use, lower environmental impact, and lower costs of this widely used construction material. One of the goals of the CESMII roadmap project on the Smart Manufacturing of Cement included developing an analytical process model for clinker quality that includes the chemistry of the kiln feed and accounts for critical process variables. This predictive model will be used in nonlinear model predictive control system designed to significantly reduce process energy use while maintaining or improving product quality. In the cement manufacturing plant used in this study, the kiln feed (meal) is tested every 12 h and used to estimate the mineral composition of the cement kiln output (clinker) using the stoichiometry‐based Bogue's model and the expertise of the plant operators. During kiln operation, kiln output (clinker) is sampled and tested every 2 h to measure its chemical and mineral composition. The predicted and measured values of the clinker composition are used by the plant operators to adjust the kiln input stream and the production process characteristics to maintain stable operation and uniform product quality. However, the time delay between prediction and testing, along with inaccuracies inherent in the Bogue's model have made any process changes designed to minimize energy use problematic, especially in‐light of potential clinker quality issues that process changes often pose. A new analytical model that integrates quality information and process operation information has been developed from data collected from 2 years of production from an operating cement facility. To make the model fuel‐type‐independent, consumed heat energy was computed in the model instead of fuel type and amount. A Feedforward Network was trained and tailored from collected data. Many data‐based simulations were conducted to quantitatively evaluate the proposed model and the 5‐fold cross‐validation procedure was used to test the models. The resulting predictive model was shown to have a low root mean square error (MSE) with respect to the estimated clinker mineral composition compared to that using the industry standard “Bogue’ model”. The end goal of this work was to develop a single machine learning tool that allows the use of quality control data and process control variables to improve energy efficiency of the process in a continuous fashion. The proposed nonlinear model predictive control system (NMPC) can generate predicted kiln production characteristics based on manipulated variables in manner that accurately follows the target product quality values. Simulation results also show that the proposed model produced accurate predictions of kiln outputs that fell within the required constraints, while manipulating control variables within typical operational ranges.

Ali, Asem M.↗