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At least 919 records · Page 51

Casing Annulus Monitoring of CO 2 Injection Using Wireless Autonomous Distributed Sensor Networks

Effective and secure carbon subsurface storage, involving the deep underground injection of CO 2 into geological formations where it is permanently trapped, is paramount to mitigating CO 2 emissions (Figure I). Ensuring the integrity of these storage sites and detecting potential leakage through the casing annulus necessitates robust monitoring. This work provides the first integrated demonstration of a wireless casing-annulus monitoring architecture that can operate in highly attenuating cement-brine environments relevant to CO 2 storage. This project focused on developing and validating a novel sensor system for integration with autonomous monitoring near the cement reservoir interface. The goal was a fully integrated Technology Readiness Level (TRL) 4/5 field validation of a distributed wireless intelligent sensor system providing real-time, direct subsurface formation measurements to enhance fluid movement monitoring in the cemented casing annulus. Achieving this objective required the development and integration of 1) wireless autonomous microsensor technology by California Institute of Technology (Caltech); 2) sensor packaging and emplacement technology by Research Triangle Institute (RTI); and 3) smart well completions using wireless active casing collars and NOV pipe by the Sandia National Lab (SNL). The collaboration with the Caltech team in this project aimed to develop millimeter-scale radio frequency identification (RFID) sensors capable of detecting CO 2 , pH, and/or methane levels. These sensors are engineered to be impervious to fluids, allowing them to be mixed with cement and installed within the casing annulus. They operate using RFID protocols at frequencies of 902–928 MHz for both power and communication. A Sandia National Laboratories’ team engaged their expertise in the development of a Smart Collar system designed for the wireless data collection from these RFID sensors embedded in the cement annulus and transmission of this information to the ground surface via IntelliPipe/IntelliServ NOV drill pipe. This is accomplished through inductive coupling at the collar, which facilitates data transfer through each segment of the pipe. Because the system cannot transmit a direct current signal to power the Smart Collar, both power and communication were implemented using alternating current and electromagnetic signals at varying frequencies. Furthermore, the developed microsensor technology had to be demonstrated and validated in comparison with reference transducer measurements in a field test site at The University of Texas at Austin (UT-Austin). Although the full sensor suite did not reach field-deployment readiness, the system-level integration achieved in this project establishes a validated pathway for future incorporation of advanced microsensors.

47 OTHER INSTRUMENTATION↗

Development Of Thermodynamic and Kinetic Simulation Tools and Testing Procedures for Enhanced Durability of Concrete Containing Industrial By-Products

This project developed screening tools that enable evaluation of alternative cementitious binders that create concretes to significantly reduce energy and emissions while remaining cost competitive on both initial and long-term costs. The team began with the viewpoint that acceptance of new cementitious binder products has a substantially greater chance of successful implementation when capital investment is not excessive and the end product has customers that have experience and resources to use this. As such, a binder system that is based on portland cement with blended using industrial by-products (alternative cementitious materials) has the potential for dramatic and meaningful impact. The team has focused on developing implementable solutions in specifications and current practice. This however requires three main factors: 1) ability to screen byproducts and alternative materials for success, 2) ability to ‘treat’ materials chemically to enhance kinetics, and 3) ability to provide predictions of performance of both binders and concrete from first principles. The project developed/refined a state of the art and scientifically based screening test for SCM called the pozzolanic reactivity test. The team developed kinetic models to simulate these materials as well as experimental approaches to alter selected reactions. Simulation tools were developed that enable the performance of concrete to be predicted based on the chemistry and reactivity of the cement and alternative SCM. Specifically, this project: • enhanced the kinetic reactivity models for use in multi-scale computational programs that use thermodynamics to predict reaction products. 2 • developed scaling models to extend thermodynamic modeling to link these models with pore structure. This enables strength, transport property, and coupled transport prediction. • developed tools to predict performance of cementitious materials using the pozzolanic reactivity test and chemical composition. The predicted properties are consistent with AASHTO R101 and the CEB-FIP model code and can be measured using associated test procedures. • demonstrated mechanical and fracture based modeling tools that thermodynamic predictions and inputs to predict concrete service life. These results have been used to demonstrate the value of enabling specifications to include ASTM C 595 cement as well ASTM C150 cement. In addition, these products are being used to expedite the evaluation of alternative SCM to aide in determining which materials have potential value and what ‘compositions’ of blended cements merit further investment.

42 ENGINEERING↗

Selection of Binders for a Reactive Metal (Tungsten) Encapsulation - 17211

Waste containing reactive metals is produced by nuclear activities, and the usual strategy is to encapsulate this waste in ordinary Portland cement (OPC) or alternative binders in a state suitable for storage. However, in the case of tungsten metal, corrosion by the pore solution of the binders could occur with hydrogen release. Based on Potential-pH diagram, tungsten metal corrosion depends on pH conditions. Consequently, studies have been performed with tungsten in a large pH scale relevant for various binders such as ordinary Portland cement (OPC), sodium geo-polymer (Na-Geo), magnesium-phosphate cement (MKP) and wollastonite-based cement (Wo). The influence of representative pore solutions of OPC, Na-Geo, MKP and Wo on tungsten corrosion has been studied by electrochemical methods (Open Circuit Potential and impedance spectroscopy). The corrosion of tungsten encapsulated in OPC, Na-Geo, MKP and Wo has been investigated by measuring the production of hydrogen over time. It is shown that ordinary Portland cement is not a suitable binder for tungsten metal encapsulation while a binder producing a pore solution with a neutral pH such as MKP presents the lowest interaction with tungsten. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Atomic-scale identification of defects in alite

Crystallographic defects play a crucial role in cement hydration, with initial dissolution being dominated by the formation of etch pits that rely on the intersection of defects on surfaces. However, the defects present in cement particles have remained a mystery due to the lack of detailed direct observation at the atomic scale. In this study, we used scanning transmission electron microscopy to unravel the defects in alite particles at the single-atom level. Our observations identified different types of defects, including vacancies, doping, dislocations, rough surfaces, and grain boundaries. Atomic ordering in the alite crystal was further examined based on our single-atom recognition method. Our findings indicate that defects in cement particles may serve as reactive sites during the early hydration stage, facilitating the initial dissolution and providing nucleation sites for hydration products. Finally, this work provides insights into cement defect formation at the single-atom level and offers new opportunities in tuning the hydration process through defect engineering of cement particles.

36 MATERIALS SCIENCE↗

Recent Cryogenic Carbon Capture™ Field Test Results

Sustainable Energy Solutions (SES) has been developing Cryogenic Carbon Capture™ (CCC) since 2008. In that time, two processes have been developed, the External Cooling Loop and Compressed Flue Gas CCC processes (CCC-ECL and CCC-CFG, respectively). The CCC-ECL process cools the flue gas with an external refrigerant loop. This process currently captures up to 1 tonne of CO2 per day (TPD). SES has tested CCC-ECL on real flue gas slip streams from subbituminous coal, bituminous coal, biomass, natural gas, shredded tires, and municipal waste fuels at field sites that include utility power stations, heating plants, cement kilns, and pilot-scale research reactors. The CO2 concentrations from these tests ranged from 5 to 22% on a dry basis. CO2 capture ranged from 95-99+% during these tests. Several other condensable species were also captured including NO2, SO2 and PMxx at 95+%. NO was also captured at a modest rate. The CCC-CFG process has been scaled up to a 0.25 ton per day system. This system has been tested on real flue gas streams including subbituminous coal, bituminous coal, and natural gas at field sites that include utility power stations, heating plants, and pilot-scale research reactors. CO2 concentrations for these tests ranged from 5 to 15% on a dry basis. CO2 capture ranged from 95-99+% during these tests. Several other condensable species were also captured including NO2, SO2, and PMxx at 95+%. NO was also captured at 90+%. Hg capture was also verified and the resulting effluent from CCC-CFG was below a 1ppt concentration. This paper will focus on discussion of the capabilities of CCC generally, the results of CCC-ECL field testing, and future steps surrounding the development of this technology. Test results that will be presented have been collected during 9 months of testing at a commercial power plant under funding from the US Department of Energy (DOE) and the host utility. Testing of one of the systems at a commercial cement plant in the United States will also be discussed. During this testing, the system captured CO2 from the cement plant and stored the CO2 in pressurized tanks. These tanks were provided to a partner company that later used the CO2 in a CO2 utilization demonstration. The CO2 was utilized to cure concrete manufactured using cement from the same plant where the CO2 was captured. This integrated capture and utilization demonstration was the first time that the cement industry has shown in the field that it can sequester its CO2 emissions in its main product stream. This represents a potential game changing solution for industrial CO2 emissions. Operational data and host-site feedback indicate that the CCC process is ideally suited for deployment into a variety of commercial environments. A few areas of de-risking remain to make sure the technology can meet very strict industrial reliability standards. These areas of de-risking are identified and discussed. The product CO2 is shown to meet specification for many uses including industrial and merchant applications. The technology is nearing readiness for deployment at commercial scale and several initial target markets have been identified.

20 FOSSIL-FUELED POWER PLANTS↗

Using Radioiodine Speciation to Address Environmental Remediation and Waste Stream Sequestration Problems at the Fukushima Daiichi Nuclear Power Plant and a DOE Site

Iodine-129 ( 129 I), with a half-life of half-life of 16 million years, is commonly considered the single greatest risk driver in high-level and low-level nuclear repositories. This risk stems from several basic properties of 129 I, and under many geochemical conditions, it can move as an anion at nearly the rate of water through the subsurface environment. 129 I is also extremely radiologically toxic because over 90% of body burden accumulates in the thyroid, which weighs only about 14g in an adult. There is also a large worldwide inventory of radioiodine as a result of its high fission yield and this inventory is rapidly increasing as a result of nuclear energy production. Radioiodine is produced at a rate of 40 GBq (1 Ci) per gigawatt of electricity produced by nuclear power. To illustrate how the properties of 129 I magnify its risk, 129 I accounts for only 0.00002% of the radiation released from the Savannah River Site in Aiken, South Carolina, but contributes 13% of the population dose, a six orders of magnitude magnification of risk with respect to its radioactivity. The currently favored solid phase for LLW immobilization is cement, while HLW immobilization is the incorporation of waste into glass (vitrification). However, so far, the incorporation into cement and subsequent leaching of only iodide has been seriously investigated. The major problem with this approach is that it ignores the complex speciation of iodine, i.e., it ignores iodate and organo-iodine which have different chemistries. Most of the past research was devoted to the mechanism of iodide uptake in cement hydrate phases that is sorption and/or incorporation. Very few data exist on iodate and organo-iodine incorporation in cement, even though large quantities of liquid waste containing also radioiodine have already been solidified in cement Iodine-129 from low-level waste is commonly disposed of in cementitious materials. Grout, a dense cementitious fluid, mixed with a reducing slag, is often used to immobilize radionuclides. However, the reducing environment might not be conducive to immobilize iodine. For example, the silver based immobilization technologies (e.g., AgCl, Ag-impregnated granular activated carbon, Ag-mordenite) remove iodine from the aqueous phase by promoting the formation of Ag-iodide precipitates. The solubility of AgI is eight orders of magnitude lower than it is for AgIO 3 . Similarly, coprecipitation of iodine into calcium carbonate phases occurs only with IO 3 - and not with I - and org-I. If one would want to immobilize iodine more effectively, different engineering approaches would need to be used to promote binding of I - , IO 3 - , or organo-I. Using laboratory experiments with grout, slag, and silver-based adsorbents, and GC-MS and I K-edge XANES and EXAFS and C K-edge XANES spectroscopy for identifying iodine speciation, the major problems with these methods have been identified as focused too much on just one of the iodine species for immobilization, while others, especially organo-I, remained mobile. Finally, we established that most of the adsorbents that are used contain sufficient amounts of organic matter to create organo-I . It is anticipated that increased attention directed at understanding and quantifying the speciation of radioiodine, as opposed to simply total radioiodine, will lead to improved remediation results to be used for long-term radioiodine disposal in cementitious waste forms.

129-Iodine↗

Model Package Report: Composite Analysis Solid Waste Release Model (CASWR Model)

This document describes the implementation of a solid waste form release model in GoldSim for the Hanford Site Composite Analysis (CA) Update. This Composite Analysis Solid Waste Release model (CASWR model) was designed to generate deterministic radionuclide release rates for Hanford’s Central Plateau solid waste disposal sites using single realizations of release model coefficients. Five generalized waste form types are used for the conceptual model of waste release: surplus reactor block, cement, soil-debris, grouted residual waste, and ancillary equipment. The surplus reactor block waste form consists of radionuclide leaching from surplus production graphite reactor core blocks via unspecified processes (White et al., 1984 as cited in PNNL-15965). The cement waste form represents solidified wastes whose permeability is much lower than that of the surrounding soil. The soil-debris waste form type is defined as unconsolidated waste mixed with soil material. Tanks and canyon complexes comprise the grouted residual waste form such that their solid waste will be grouted and capped with a surface barrier at the completion of their cleanup. Finally, the ancillary equipment waste form constitutes contaminant releases from ancillary and auxiliary waste form residues associated with tank farms at closure. Individual sub-models are implemented to numerically represent a respective waste form within the CASWR Model: Surplus Reactor Block Sub-model, Cement Sub-model, SoilDebris Sub-model, Grouted Residual Waste Sub-model, and Ancillary Equipment Submodel. Advection is assumed to be the primary transport process governing the release of radionuclides in the Ancillary Equipment and Soil-Debris Sub-models. Diffusion is assumed to be the primary release process in the Grouted Residual Waste and Cement Sub-models. An unspecified zero-order release process is considered in the Surplus Reactor Block Sub-model due to the lack of information regarding actual processes involved in irradiated graphite leaching. The Surplus Reactor Block, Cement, and SoilDebris Sub-models were compared against analytical solutions (PNNL-11800, Composite Analysis for Low-Level Waste Disposal in the 200 Area Plateau of the Hanford Site). The agreement between results of these analytical solutions and the corresponding waste form models verified their correct implementation in GoldSim. A 1-D modeling abstraction approach for the Grouted Residual Waste and Ancillary Equipment Sub-models was adopted from existing Performance Assessment (PA) models. Despite the simplifications made in these sub-models, they were found to be appropriate representations of the waste forms, similar to what was used in the Waste Management Area C PA model (RPP-ENV-58782, Performance Assessment of Waste Management Area C, Hanford Site, Washington, Rev. 0). A sensitivity analysis was conducted to identify the most influential parameters in each waste form sub-model. Suggestions for considering pH-dependent and redox-dependent release mechanisms are formulated through the development of a conditional constant approach in GoldSim.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermal contacts between metal and glass for use at cryogenic temperatures

Thermal contacts designed to cool a 50-cm diam fused-silica mirror to 5 K without serious distortion of the optical surfaces were tested. Rubber cement and copper-filled rubber cement were found to be well suited for maintaining thermal contact between the fused-silica and copper straps. A variety of other adhesives proved to be unreliable because they spalled the glass. The thermal resistances of the rubber cement and copper-filled rubber cement were determined. For the copper-filled rubber cement, the thermal resistances varied from 570 K/W at 60 K to 15,000 K/W at 10 K.

Obrien, K.↗

Waste management technology development and demonstration programs at Brookhaven National Laboratory

Two thermoplastic processes for improved treatment of radioactive, hazardous, and mixed wastes were developed from bench scale through technology demonstration: polyethylene encapsulation and modified sulfur cement encapsulation. The steps required to bring technologies from the research and development stage through full scale implementation are described. Both systems result in durable waste forms that meet current Nuclear Regulatory Commission and Environmental Protection Agency regulatory criteria and provide significant improvements over conventional solidification systems such as hydraulic cement. For example, the polyethylene process can encapsulate up to 70 wt pct. nitrate salt, compared with a maximum of about 20 wt pct. for the best hydraulic cement formulation. Modified sulfur cement waste forms containing as much as 43 wt pct. incinerator fly ash were formulated, whereas the maximum quantity of this waste in hydraulic cement is 16 wt pct.

Kalb, Paul D.↗

Transient Liquid Water as a Mechanism for Induration of Soil Crusts on Mars

The Viking and the Mars Exploration Rover missions observed that the surface of Mars is encrusted by a thinly cemented layer tagged as "duricrust". A hypothesis to explain the formation of duricrust on Mars should address not only the potential mechanisms by which these materials become cemented, but also the textural and compositional components of cemented Martian soils. Elemental analyzes at five sites on Mars show that these soils have sulfur content of up to 4%, and chlorine content of up to 1%. This is consistent with the presence of sulfates and halides as mineral cements. . For comparison, the rock "Adirondack" at the MER site, after the exterior layer was removed, had nearly five times lower sulfur and chlorine content , and the Martian meteorites have ten times lower sulfur and chlorine content, showing that the soil is highly enriched in the saltforming elements compared with rock.Here we propose two alternative models to account for the origin of these crusts, each requiring the action of transient liquid water films to mediate adhesion and cementation of grains. Two alternative versions of the transient water hypothesis are offered, a top down hypothesis that emphasizes the surface deposition of frost, melting and downward migration of liquid water and a bottom up alternative that proposes the presence of interstitial ice/brine, with the upward capillary migration of liquid water.

Landis, G. A.↗

Application of Interparticle Spacing Model to Maximize Filler Content in Cementitious Pastes

One of the most impactful ways to reduce embodied carbon of concrete in the near term is by partially replacing Portland cement with supplementary cementitious materials and/or fillers. This article describes an approach to reduce cement content in concrete through the development of high filler, low water (HFLW) cementitious pastes. Pastes with cement content as low as 50% (% weight of fines) were designed by applying models that maximize the packing density of the granular system and that consider the characteristics of the materials to calculate interparticle spacing (IPS), thereby allowing to obtain pastes with higher solids concentration and lower water demand. Strong correlations were found between IPS, the consistency index of the Herschel-Bulkley rheological model, and cement hydration kinetic parameters of binary and ternary pastes containing a Portland limestone cement and up to two different types of ground limestone. The approach showed to be feasible for the design of HFLW concrete paste fraction.

Antunes da Silva, Denise↗

Update on Construction Planning for the Bulgarian Low and Short-Lived Intermediate Level Radioactive Waste Repository - 16159

The Bulgarian State Enterprise for Radioactive Waste Management (SERAW) is planning the construction of a near-surface repository for low and short-lived inter-mediate level radioactive waste, the National Disposal Facility (NDF), at the Radiana Site adjacent to the Kozloduy Nuclear Power Plant (KNPP). This paper presents an update on construction planning activities that were originally presented at the 2015 Waste Management Conference. The Site, a rectangular area approximately 1.2 km east-west by 0.4 north-south, is located on a slopping area between the second and sixth loess terraces above the River Danube with elevations ranging from approximately +40 m to elevation +95 m. Construction of the NDF will be divided into three phases separated by approximately 20 years each. The first phase will see the construction of the primary support facilities, referred to as the Auxiliary Buildings and including the Waste Reception and Buffer Storage (WRBS) Building, and the first set of 22 reinforced concrete disposal cells and supporting infrastructure, including a network of subsurface observation galleries, the Infiltration Network Control (ICN) Galleries. Each disposal cell will be 20.15 m long by 17.05 m wide by 9.45 m in height. The disposal cells will be arranged in two parallel rows. Disposal activities will be conducted using overhead cranes installed inside of track mounted mobile roofs. Each row of disposal cells will be serviced by one mobile roof. The mobile roofs will be supported by massive concrete foundations. Construction at the site will present several logistical challenges that will need to be overcome to fully realize the NDF. First in order to begin construction of these facilities nearly 1 million m{sup 3} of soil will require excavation and handling. Consistent with requirements to minimize potential environmental impacts identified in the site Environmental Safety Assessment (EIA) excavated soil will, to the extent possible, remain onsite. Approximately three quarters of the soil can be accommodated within the site boundaries. Another challenge results from requirements imposed by the ground conditions. The sub-grade at the site, which consists primarily of loess, will require considerable improvement. To this end a 5 m thick loess-cement cushion will be constructed across much of the site. Specifically, the cushion will be required beneath the disposal cells and the WRBS Building. The cushion beneath the disposal cells also contains embedded structures, including the ICN Galleries as well as the massive concrete foundation beams required for the two mobile roofs. Construction of these structures will require planned interruptions in the construction of the loess-cement cushion. Specific cement types and strict quality requirements will be required for completion of the loess-cement cushion as well as for the completion of the ICN Galleries. The construction planning will need to account for the large volumes of soil to be excavated as well as ensuring sufficient material supplies in terms of both quality as well as quantity. Large quantities of materials including both dry cement for mixing with the loess, and wet concrete for pouring of the mobile roof foundations are ac-counted for by the plan. However, even after completion of these activities additional challenges are addressed by the plan related to the contemporaneous construction management of the auxiliary buildings and the disposal cells. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Alkali-activated materials

This paper, which forms part of the UNEP White Papers series on Eco-Efficient Cements, provides a brief discussion of the class of cementing materials known as ‘alkali-activated binders’, which are identified to have potential for utilization as a key component of a sustainable future global construction materials industry. These cements are not expected to offer a like-for-like replacement of Portland cement across its full range of applications, for reasons related to supply chain limitations, practical challenges in some modes of application, and the need for careful control of formulation and curing. However, when produced using locally-available raw materials, with well-formulated mix designs (including in particular consideration of the environmental footprint of the alkaline activator) and production under adequate levels of quality control, alkali-activated binders are potentially an important and cost-effective component of the future toolkit of sustainable construction materials.

36 MATERIALS SCIENCE↗

Fillers in cementitious materials — Experience, recent advances and future potential

The paper discusses the potential of fillers in CO{sub 2} mitigation in the cement industry. A historical overview of the use of fillers is presented as well as the limits of filler use given in cement standards. Globally, limestone filler currently represents only 7% of average worldwide cement composition. The limits of the current route to adding filler in cement by means of intergrinding are discussed. An innovative technology, that compensates binder dilution by a reduction of the water required for good rheological behavior, is presented; this allows clinker replacement rates of up to 70%. The theory that enables the design of such multimodal particle size distributions with high particle packing and low-water demand is presented, and examples of its application in concrete production are given. The efficiency in terms of CO{sub 2} mitigation is demonstrated by comparing concrete formulations designed with this innovative approach with a global benchmark of current technology. New filler minerals, as well as the effects of high-filler content on production processes and on durability are also discussed.

36 MATERIALS SCIENCE↗

Micro- and macroscale coefficients of friction of cementitious materials

Millions of metric tons of cementitious materials are produced, transported and used in construction each year. The ease or difficulty of handling cementitious materials is greatly influenced by the material friction properties. In the present study, the coefficients of friction of cementitious materials were measured at the microscale and macroscale. The materials tested were commercially-available Portland cement, Class C fly ash, and ground granulated blast furnace slag. At the microscale, the coefficient of friction was determined from the interaction forces between cementitious particles using an Atomic Force Microscope. At the macroscale, the coefficient of friction was determined from stresses on bulk cementitious materials under direct shear. The study indicated that the microscale coefficient of friction ranged from 0.020 to 0.059, and the macroscale coefficient of friction ranged from 0.56 to 0.75. The fly ash studied had the highest microscale coefficient of friction and the lowest macroscale coefficient of friction. -- Highlights: •Microscale (interparticle) coefficient of friction (COF) was determined with AFM. •Macroscale (bulk) COF was measured under direct shear. •Fly ash had the highest microscale COF and the lowest macroscale COF. •Portland cement against GGBFS had the lowest microscale COF. •Portland cement against Portland cement had the highest macroscale COF.

36 MATERIALS SCIENCE↗

Photovoltaic's silica-rich waste sludge as supplementary cementitious material (SCM)

Waste sludge, a solid recovered from wastewater of photovoltaic-industries, composes of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. This sludge deflocculates in aqueous solutions into nano-particles smaller than 1 μm. Thus, this sludge constitutes a potentially hazardous waste when it is improperly disposed. Due to its high content of amorphous SiO{sub 2}, this sludge has a potential use as supplementary cementitious material (SCM) in concrete. In this study the main properties of three different samples of photovoltaic's silica-rich waste sludge (nSS) were physically and chemically characterized. The characterization techniques included: scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), nitrogen physical adsorption isotherm (BET method), density by Helium pycnometry, particle size distribution determined by laser light scattering (LLS) and zeta-potential measurements by dynamic light scattering (DLS). In addition, a dispersability study was performed to design stable slurries to be used as liquid additives for the concrete production on site. The effects on the hydration kinetics of cement pastes by the incorporation of nSS in the designed slurries were determined using an isothermal calorimeter. A compressive strength test of standard mortars with 7% of cement replacement was performed to determine the pozzolanic activity of the waste nano-silica sludge. Finally, the hardened system was fully characterized to determine the phase composition. The results demonstrate that the nSS can be utilized as SCM to replace portion of cement in mortars, thereby decreasing the CO{sub 2} footprint and the environmental impact of concrete. -- Highlights: •Three different samples of PV nano-silica sludge (nSS) were fully characterized. •nSS is composed of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. •Dispersability studies demonstrated that nSS agglomerates are broken to nano-size. •nSS can be classified as a pozzolanic material with activity index higher than 100. •nSS can be use as a potential SCM to partly replace cement in concrete.

36 MATERIALS SCIENCE↗

Simulation of the properties of MgO-MgfCl{sub 2}-H{sub 2}O system by thermodynamic method

Magnesium oxychloride cement (MOC) has been investigated by many researchers who have studied its hydration products and properties. Previous works mainly concentrated on experimental studies. This study uses a thermodynamic approach to understand the formation conditions of two major hydration products of MOC, Mg{sub 3}(OH){sub 5}Cl · 4H{sub 2}O (phase 5) and Mg{sub 2}(OH){sub 3}Cl · 4H{sub 2}O (phase 3) at room temperature. The hydration reaction equilibrium of MOC phases has been predicted by using the geochemistry speciation code PHREEQC together with the extended ‘Pitzer.dat’ database. The results show that the formation of the hydration products are controlled by MgCl{sub 2} concentration, activity of H{sub 2}O and pH values of the system. The equilibrium of solid phase diagram, the solubility of different hydration phases are consistent with those results obtained from experimental studies, which validates the thermodynamic model. The phase diagram provides qualitative insights on the synthesis of pure phase 3 and phase 5. For MgO-MgCl{sub 2}-H{sub 2}O system, the minimum MgCl{sub 2} concentration for phase 5 and phase 3 to form are 1.47 mol · kg{sup −} {sup 1} and 2.25 mol · kg{sup −} {sup 1}, respectively. Increasing water volume can result in the transformation from phase 5 and phase 3 to brucite. Additionally, the stability analysis suggests that phase 5 prefers to formation at a higher condition of the a{sub Mg}2 +, pH and a{sub H2O} as compared to the phase 3. Phosphate can significantly influence the hydration products composition of MOC during hydration but no new phosphate appears. - Highlights: • A thermodynamic database was established for magnesium oxychloride cement system on the basis of Pitzer.dat. • Thermodynamic behaviors of magnesium oxychloride cement hydration was modeled. • Calculated phase diagram of magnesium oxychloride cement was plotted.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Admixtures and sustainability

Cement additives and concrete admixtures are construction chemicals that reliably improve the sustainability of a broad range of cement-based systems. This improvement can be derived from enhancing durability and strength through water reduction, and catalyzing the cement hydration process to enable replacement of clinker with supplementary cementitious materials. Through current best practices, incorporation of these potent chemicals at a fraction of a percent of the entire concrete mix affords a clinker replacement of about 20% by weight. This replacement amount can be more than doubled with correct mix proportioning. Innovative technologies such as pre-test tools and smart concrete management systems further improve the effectiveness of admixtures applied in both current and new cementitious materials. Provided longer set times, a consequence of SCM incorporations, can be tolerated, further reduction in CO{sub 2} emissions can be attained. Making trade-offs such as this will be essential to optimizing the sustainability of cement-based materials.

36 MATERIALS SCIENCE↗