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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Oxygen Isotope Microanalysis By Secondary Ion Mass Spectrometry Suggests Continuous 300-million-year History of Calcite Cementation and Dolomitization in the Devonian Bakken Formation

Calcite cementation and dolomitization are key diagenetic processes in many sedimentary systems. Unravelling detailed histories and timescales of cementation and replacement is, however, often compromised by the limited spatial resolution of many analytical techniques; in some cases multiple grains are co-analyzed so that diagenetic histories are blurred and reaction periods are difficult to establish. In this study we have used 10-micrometer-resolution, in situ secondary ion mass spectrometry to determine the oxygen isotope composition of 197 individual, 10–50-micrometer-size crystals of dolomite and calcite from six samples in a single core of Upper Devonian middle Bakken Member siltstones and sandstones, the major tight oil formation of the Williston basin, USA. This amount of data places important constraints on the range of temperatures and times that carbonate cementation and replacement occurred. Petrographic data show that microcrystalline calcite cement is an early phase, and combined with mineralogical data suggest that much of the dolomite replaces calcite. Over spatial scales of less than a centimeter, analyses of individual calcite crystals have a range of 5‰ for δ 18 O in the group of crystals, and for the group of individual dolomite crystals, 10‰. These sub-centimeter ranges are as great as those observed in previous studies of carbonate cements sampled over many meters and remind us that previous low-resolution studies may have inadvertently analyzed mixed phases. There is no relationship between dolomite texture and isotopic composition at this spatial scale; microscale backscattered electron imagery and scanning electron microscopy cathodoluminescence zoning is seen, but cannot be resolved with a 10-micrometer spot size. Assuming, since it is an early cement, that calcite precipitated from seawater (δ 18 O = –1.5‰), it formed at ca. 15–40°C, mainly at the lower temperatures. Present-day formation waters in Devonian rocks in this region have oxygen isotope compositions of 7–8‰ VSMOW. Using these values as a likely dolomitizing fluid, we suggest that dolomitization occurred continuously between 40 and 140°C over 150–200 million years, most likely in a fluid with a high Mg/Ca ratio resulting from gypsum formation in local evaporites. Finally, we suggest that this exceptionally low rate of dolomitization was controlled by the low rate of supply of Mg in a very sluggish flow regime; dolomitization is incomplete because of a limited supply of Mg.

58 GEOSCIENCES↗
DOE OSTI2019

Self-Healing, Re-adhering, and Corrosion-Mitigating Inorganic Cement Composites for Geothermal Wells at 270°-300°C: Final Report

Under the DOE EERE Geothermal Technologies Office (GTO)-funding project in FY 2016- 2018, the scope of work at Brookhaven National Laboratory (BNL) aimed 1) to conduct the screening of qualified candidates for self-healing cement composites reinforced with microcarbon fiber (MCF), 2) to obtain the fundamental understanding of self-healing mechanism, to develop self-healing aides, 3) to evaluate re-adhering performance of debonded self-healing composites to carbon steel (CS) casing or granite rock formation, 4) to evaluate bond durability of composite/CS joint in acid and thermal shock environments, 5) to assess the corrosion mitigation of CS by composites adhering and re-adhering to CS surfaces, and 6) to investigate the maintenance of pumpability at 85° and 100°C of optimized composite slurry as well as to evaluate self-healing and re-adhering ability of pumpable composite formulation at hydrothermal temperatures, ranging from 270° to 300°C. In this work, three different cementitious material groups, 1) Ordinary Portland Cement (OPC)-based cements, 2) alkali (sodium metasilicate, SMS)-activated cements, and 3) phosphate (sodium hexametaphosphate, SHMP)-bonded cements, were evaluated to meet the following ten material criteria suitable for inorganic cement composites in six different environments, the plain water, alkali carbonate, geo-brine, thermal shock, pH 0.6 H 2 SO 4 /brine, and pH 5.5 scCO 2 /brine.

15 GEOTHERMAL ENERGY↗
DOE OSTI2023

Analysis of Carbon Capture Retrofits for Cement Plants

The objective of this study is to provide an estimate of the cost to capture CO 2 in retrofit applications at cement plants. The cement plant configurations considered in this study include natural gas and solid fuel (coal and coke) cases, and both wet- and dry kiln-fed plant designs, however the base cement plants in this study were not evaluated other than characterization of their kiln off-gas stream and high-level quantification of heat integration potential at the existing plant. In each case, the base cement plant produces 1.5 M tonnes per year of finished cement, assuming 91.4 percent clinker content. This analysis includes a 10 percent retrofit cost increase for process integration and low grade heat recovery, when compared to the analogous non-heat integration case. Heat integration is considered as a potential offset to capture system heating demands (i.e., as a percentage reduction). Recovery and reuse of excess heat from the base cement plant can provide economic benefits—primarily by reducing the need to purchase supplemental natural gas for CO 2 solvent regeneration—but any process improvement must be great enough to overcome the cost increases (i.e., capital and O&M) necessary to realize those benefits. With heat integration potential of 10 percent and 30 percent, that benefit wasn’t significant enough to offset the increase in capital and operating costs, and a cost of capture increase was observed based on the assumptions in this report. Benefits of heat integration potential may be realized when natural gas prices are higher, as demonstrated in the sensitivity to natural gas price where crossover points exist between heat integration cases and their respective non-heat integration cases. Four of the base cases were further evaluated to explore the cost implications of deeper levels of gas pre-treatment to remove oxides of nitrogen (NOx) and oxides of sulfur (SOx) from the kiln off-gas stream prior to CO 2 capture, purification, and compression. The results of these additional case analyses showed a 7.4–18.8 percent increase in cost of capture over the respective base case (i.e., analogous cases without SOx/NOx removal).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

An assessment of gas-side fouling in cement plants

The cement industry is the most energy-intensive industry in the United States in terms of energy cost as a percentage of the total product cost. An assessment of gas-side fouling in cement plants with special emphasis on heat recovery applications is provided. In the present context, fouling is defined as the buildup of scale on a heat-transfer surface which retards the transfer of heat and includes the related problems of erosion and corrosion. Exhaust gases in the cement industry which are suitable for heat recovery range in temperature from about 100 to 1300 K, are generally dusty, may be highly abrasive, and are often heavily laden with alkalies, sulfates, and chlorides. Particulates in the exhaust streams range in size from molecular to about 100 micrometers in diameter and come from both the raw feed as well as the ash in the coal which is the primary fuel used in the cement industry. The major types of heat-transfer equipment used in the cement industry include preheaters, gas-to-air heat exchangers, waste heat boilers, and clinker coolers. At the present time, the trend in this country is toward suspension preheater systems, in which the raw feed is heated by direct contact with the hot kiln exit gases, and away from waste heat boilers as the principal method of heat recovery. The most important gas-side fouling mechanisms in the cement industry are those due to particulate, chemical reaction, and corrosion fouling.

Marner, W. J.↗
NASA NTRS2019

Experimental Investigation of Cement Hydration in Gravity-Free Environment

In this work, cement hydration in terrestrial and microgravity environment was compared. This was for the first time, when the International Space Station was utilized to fully investigate the complex process of cement solidification. Microstructural development of hydrating cement occurs in stages during the hydration reaction and hardening process, which results in elaborate combinations of amorphous and crystalline phases. The morphology, volume fraction, and distribution of these phases ultimately determine the hardened cement’s material properties. Minimizing gravity-driven phenomena, such as thermosolutal convective flow and sedimentation ensures crystal growth strictly by diffusion and a microstructure forms differently from that observed in typical laboratory conditions on Earth. A test matrix was developed that includes samples with various w/c ratio and various compositions; incorporating alite, pure water and cement system, cement with chemical admixtures, as well as commercial products. This paper reports on main changes initially observed in the microstructural development of hydrated pure compound of tricalcium silicate (C3S).

Neves, Juliana↗
DOE OSTI2021

Self-re-adhering alkali-activated cement composite and its ability to mitigate corrosion of carbon steel in 300 °C hydrothermal environment

Cement-steel interface is a weak point of cement sheath integrity under the environments of high-temperature geothermal wells. This paper presents carbon steel (CS) adherence behaviors of 300 °C-autoclaved alkali-activated Calcium-Aluminate-Cement (CAC)/fly ash F (FAF) (Thermal Shock Resistant Cement, TSRC), granulated blast furnace slag (GBFS)/SiO 2 , and Ordinary Portland Cement (OPC)/SiO 2 blends. The composites’ ability to preserve the bond under the conditions of thermal shock (TS) and strong acid attack (pH 0.6 H 2 SO 4 /brine at 90 °C) as well as their ability to recover the damaged bond and provide steel corrosion protection after additional short-time 5-day curing at 300 °C were evaluated. GBFS/SiO 2 sheath underwent catastrophic failure in the first TS cycle; OPC/SiO 2 lost 78 % and TSRC 51 % of the bond strength in 6 cycles. Only TSRC-CS bond survived 30 days of strong acid exposure; OPC/SiO 2 bond failed after 18 days and GBFS/SiO 2 after 20 days. Addition of micro-glass fibers (MGF) to TSRC further improved its bond strength and CS corrosion protection. Samples of TSRC-CS cured for 30 days at 300 °C before the bond damage recovered 49 % of the damaged bond strength after additional short-time curing. The CS protected by the re-adhered TSRC showed low corrosion rate of 0.13 mm/year (TSRC-MGF), 0.2 mm/year (TSRC) vs. 0.64 mm/year for OPC/SiO 2 protected CS.

15 GEOTHERMAL ENERGY↗
DOE OSTI2014

A modified ASTM C1012 procedure for qualifying blended cements containing limestone and SCMs for use in sulfate-rich environments

Blended Portland cements containing up to 15% limestone have recently been introduced into Canada and the USA. These cements were initially not allowed for use in sulfate environments but this restriction has been lifted in the Canadian cement specification, provided that the “limestone cement” includes sufficient SCM and that it passes a modified version of the CSA A3004-C8 (equivalent to ASTM C1012) test procedure run at a low temperature (5 °C). This new procedure is proposed as a means of predicting the risk of the thaumasite form of sulfate attack in concretes containing limestone cements. The goal of the present study was to better understand how this approach works both in practice and in theory. Results from three different laboratories utilizing the CSA A3004-C8 test procedure are compared and analyzed, while also taking into account the results of thermodynamic modeling and of thaumasite formation experiments conducted in dilute suspensions.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Utilization of rice husk ash in green natural fiber-reinforced cement composites: Mitigating degradation of sisal fiber

This study aims to explore a novel approach to improve the durability of sisal fiber in cement composites by using by-products of biomass power plant: rice husk ash (RHA). The effects of two RHAs on the fiber's degradation were investigated indirectly by testing flexural behavior of sisal fiber-cement composite beams and directly by means of uniaxial tensile properties, thermal decomposition, crystallinity indices and microstructures of embedded fibers, after exploring up to 30 wetting and drying cycles. Allowing the distinction between pozzolanic activities, the efficiency of RHA was compared with two fly ashes and combinations of two clay minerals (metakaolin and nanoclay) with a cement substitution level of 30 wt.%. The durability of composites was improved considerably by incorporating RHA owing to the mitigation of fiber's degradation: the ultimate tensile strength and cellulose fraction of embedded fibers were improved by 384% and 45%, respectively. Fine RHA and the combination of metakaolin and nanoclay yield similar efficiency in mitigating degradation of sisal fiber, and are better than the coarse RHA and fly ashes. The correlations between cement hydration and sisal fiber degradation were analyzed. The results indicate that degree of hydration, calcium hydroxide content and alkalinity of the cement matrix play decisive roles in alkali attacks and mineralization of fiber's cell walls.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Interactions between fluoride ions and cement paste containing superplasticizer

Fluoride compounds are used as fluxes in the low-temperature calcination of cement. Elution of fluoride ions after calcination decreases the fluidity of cement paste containing superplasticizers, but the mechanism of fluidity decrease is unclear. Authors investigated the effects of fluoride on cement pastes containing superplasticizers and the fluidity decrease mechanism. KF addition to cement paste containing a polycarboxylate- or naphthalenesulfonate-based superplasticizer increased the yield stress, the amount of adsorbed superplasticizer, and the solid-phase specific surface area. KF addition increased the amount of adsorbed superplasticizer for alite paste but not for Ca{sub 3}Al{sub 2}O{sub 6}-CaSO{sub 4} paste. Transmission electron microscopy found SiO{sub 2} fine particles after KF addition. In the absence of water, the increase in specific surface area with fluoride was larger in hydrated than in unhydrated cement. It is supposed that the fluidity decrease results from the preferential adsorption of superplasticizer on SiO{sub 2} particles generated by reactions between hydrated calcium silicate and fluoride ions.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Production of H{sub 2} by water radiolysis in cement paste under electron irradiation: A joint experimental and theoretical study

Long-term confinement of nuclear waste is one of the main challenges faced by the nuclear industry. Fission products such as {sup 90}Sr and {sup 137}Cs, both β{sup −} emitters known to induce serious health hazards, represent the largest fraction of nuclear waste. Cement is a good candidate to store them, provided it can resist the effects of irradiation over time. Here, we have investigated the effects of β{sup −} decay on cement by performing electron irradiation experiments on different samples. We show that H{sub 2} production in cement, the main effect of water radiolysis, depends strongly on composition and relative humidity. First-principles calculations indicate that the water-rich interlayer regions with Ca{sup 2+} ions act as electron traps that promote the formation of H{sub 2}. They also show that holes localize in water-rich regions in low Ca content samples and are then able to participate in H{sub 2} production. This work provides new understanding of radiolysis effects in cements. - Graphical abstract: H{sub 2} produced by radiolysis in cement paste is investigated by experimental and computational studies.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Influence of MWCNT/surfactant dispersions on the rheology of Portland cement pastes

This work studies the effect of MWCNT/surfactant aqueous dispersions on the rheology of cement paste. Three types of surfactants (sodium dodecyl sulfate, cetylpyridinium chloride and triton TX-100) were used to prepare cement pastes with and without MWCNT. Three rheological parameters were determined for each sample: static yield stress, yield stress, and viscosity. The first was measured directly, while the other two were obtained by fitting a Bingham model to the descending portion of a flow curve. Additionally, X-ray diffraction and isothermal calorimetry were used to follow the hydration reaction of cement during the first hour. It was found that the MWCNT/surfactant dispersions generate an overall shift to higher yield stress values while maintaining viscosity, suggesting a modification of the interparticle attraction. It was concluded that the triple interaction MWCNT-surfactant-cement governs the rheology of cement pastes.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The effect of calcium lignosulfonate on ettringite formation in cement paste

The effect of a softwood calcium lignosulfonate, LSs, on the ettringite formed in cement paste was investigated. Two Portland cements, mainly differing in surface area and C{sub 3}A content, were used. The effect of LSs addition time was studied, by adding either the LSs immediately with the mixing water or after 10 min of hydration. After 30 min of hydration of both cement pastes, the immediate addition of LSs caused the formation of numerous small ettringite crystals. The ettringite crystals had similar shape in pastes with and without LSs addition: cubic or cuboidal shape with length between 0.1 and 0.4 μm. These small particles caused an increase in surface area, which in turn increased the LSs adsorption by the cement paste. This could potentially lead to incompatibility issues between cement and plasticizer.

36 MATERIALS SCIENCE↗
DOE OSTI2018

May reversible water uptake/release by hydrates explain the thermal expansion of cement paste? ÔÇö Arguments from an inverse multiscale analysis

Quasi-instantaneous thermal expansion of cement pastes is governed by the relative humidity (RH) within their air-filled pores and by the decrease/increase of this internal RH resulting from a temperature decrease/increase. The latter effect is traced back to quasi-instantaneous water uptake/release by cement hydrates, using microporomechanics and a three-scale representation of mature cement pastes. Partially saturated gel and capillary pores are considered to be connected and spherical, with radii following exponential distributions. The Mori-Tanaka scheme provides the scale transition from effective pore pressures to eigenstrains at the cement paste level. This modeling approach, together with considering mass conservation of water, allows for downscaling macroscopic thermal expansion coefficients, so as to identify the molecular water uptake/release characteristics of the hydrates. The latter characteristics are mixture-independent, as shown by their use for predicting the thermal expansion coefficients of different mature cement pastes, with w/c-ratios ranging from 0.50 to 0.70.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of the hydration temperature on the pore structure of cement paste: Experimental investigation and micromechanical modelling

The hydration temperature has a considerable effect on the microstructure of cement paste. The microstructural changes with increasing curing temperature result in a significant decrease of cement mechanical properties. The present work aims at studying these phenomena via micromechanical modelling, based on an experimental characterization of cement microstructure. The pore structure of a class G oil-well cement paste (American Petroleum Institute classification) hydrated at different temperatures, between 7 °C and 90 °C is characterized. Then, the influence of the microstructure variations on the elastic properties of the hardened paste is explored through micromechanical modelling. A previous analysis of the microstructure enabled determining the volume fractions of different phases of a class G cement paste hydrated under different temperatures [1]. A multiscale self-consistent homogenization model is used based on these results to simulate the variations of the mechanical properties with hydration temperature. The results are compared with macro-scale elastic properties obtained from uniaxial compression tests. It is shown that the increasing capillary porosity with elevating hydration temperature, is not sufficient to fully explain this drop of elastic properties. The latter originates mainly from the decrease of the elastic properties of the foam composed of the porous C-S-H intermixed with capillary pores. The pore structure analysis coupled with the micromechanical modelling permitted a back-analysis of the intrinsic porosities of high density and low density C-S-H showing an almost constant LD intrinsic porosity and a significantly decreasing HD intrinsic porosity.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of highly carboxylated colloidal polymers on cement hydration and interactions with calcium ions

Polymer latexes are often found to retard cement hydration. Interaction of polymer particles with Ca{sup 2+} in pore solution and adsorption of polymer on cement were proposed as possible mechanisms for the retardation effect. This paper aims at disclosing the retardation mechanism of colloidal polymers using a highly carboxylated polystyrene latex. Interaction between colloidal particles and Ca{sup 2+} was studied by post-treatment of the latex with Ca(NO{sub 3}){sub 2}. Techniques including calorimetry, adsorption test, ICP-OES, SEM, are involved to investigate effects of the post-treated latexes on hydrations of cement and C{sub 3}S. It is found that enrichment of Ca{sup 2+} on surface of colloidal particles doesn't contribute to the retardation effect of polymer on cement hydration. Furthermore, the acceleration effect of the two-step treated latex using Ca(NO{sub 3}){sub 2} and Na{sub 2}SiO{sub 3} suggests that nucleation inhibition of the adsorbed polymer layer on cement surface is the more conceivable mechanism responsible for the retardation effect of the highly carboxylated latex.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Assessment the leaching characteristics and long-term leaching behavior of some radionuclides from synthesized zeolite cement matrix

Highlights: • Synthesis and characterization of zeolite cement synthesized from fly ash • Leaching tests were used to assess the release rate of {sup 85}Sr and {sup 60}Co radionuclides. • Simple mathematical models were used to detect leaching mechanisms. • Long-term leaching behavior of {sup 85}Sr and {sup 60}Co from cementitious matrix was assessed. The development of cementitious materials remains a vital goal to produce valuable products with good mechanical, physical and chemical properties suitable for the safe disposal of concentrated radionuclides resulted from the treatment of contaminated solutions. In this paper, zeolite cement with good properties was laboratory synthesized from industrial by-products fly ash and characterized using various characterization techniques. The leaching characteristics of strontium and cobalt radionuclides from the synthesized zeolite cement were scrutinized conforming with the standard leaching methodology of International Atomic Energy Authority (IAEA). A mechanical strength assessment was executed to characterize the extent of immobilization process of the solidified matrices. The cumulative leaching fraction (φ) of the two studied radionuclides was found to be less than 5% in all examined conditions, which implies the applicability of the IAEA-recommended methodology for estimating the diffusion coefficient. The experimental leaching data were regressed nonlinearly to various mathematical kinetic models to assess the controlling leaching mechanism and to determine the leaching parameters. The regression results indicated that strontium ({sup 85}Sr) and cobalt ({sup 60}Co) leaching resulted from two succeeding mechanisms: as first order kinetic reaction, and then diffusion. The calculated values of leachability indices signify that the performance of each of the studied matrices is within an acceptable range. A simplified mathematical model, rooted in the first order reaction and diffusion mechanisms, was simulated to predict the radionuclides leaching rates from zeolite cement matrices. By comparing the synthesized zeolite cement with other cementitious materials, it can be concluded that the synthesized material can be classified as an efficient material suitable to immobilize {sup 85}Sr and {sup 60}Co from radioactive wastes. The acquired findings demonstrated that the studied immobilized waste matrices have acceptable mechanical effectiveness.

36 MATERIALS SCIENCE↗
DOE OSTI2021

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↗
DOE OSTI2021

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↗