Engineering topics

Scrivener, Karen

Publications and source records attributed to Scrivener, Karen.

17 records

DOE OSTI2021

Factors affecting the reactivity of slag at early and late ages

This study investigates the difference between the reactivity of slag in NaOH solution (w/s = 100) and in cement paste (w/b = 0.4). The reactivity of slag is much higher in NaOH solution than in cement paste. When the NaOH solution is saturated with portlandite, the rate of reaction of slag decreases to approach that in cement paste. This suggests that the slower reaction of slag in cement paste might be due to the presence of calcium ions released by the clinker phases. At 28 days, relative humidity measurements indicate that water is only present in pores less than 6 nm. Above 6 nm, hydration cannot take place due to the lack of water. From a thermodynamic point of view, the small size of water filled pores may slow down the slag reaction due to the high concentration of species in solution required for hydrate growth to balance the increase of the surface energy.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Limestone calcined clay cement and concrete: A state-of-the-art review

This article reviews the rapidly developing state-of-the-art literature available on the subject of the recently developed limestone calcined clay cement (LC{sup 3}). An introduction to the background leading to the development of LC{sup 3} is first discussed. The chemistry of LC{sup 3} hydration and its production are detailed. The influence of the properties of the raw materials and production conditions are discussed. The mixture design of concrete using LC{sup 3} and the mechanical and durability properties of LC{sup 3} cement and concrete are then compared with other cements. At the end the economic and environmental aspects of the production and use of LC{sup 3} are discussed. The paper ends with suggestions on subjects on which further research is required.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Impact of limestone fineness on cement hydration at early age

This study compares the influence of two limestone fineness on strength development and cement hydration. The replacement of clinker by 20% of fine limestone (d{sub v,50} = 2 μm and SSA = 4,21 m{sup 2}/g) gives similar strength development to PC up to 7 days. Fine limestone enhances cement hydration and offsets the dilution effect caused by the decrease of clinker amount. The accelerating effect of the limestone was explained by a higher degree of undersaturation with respect to C{sub 3}S. The influence of coarse limestone (d{sub v,50} = 130 μm and SSA = 0,46 m{sup 2}/g) on cement hydration is limited to dilution effect. The combination of fine and coarse limestone was also studied. A linear correlation was obtained between strength and gel space ratio for all investigated systems. Furthermore, the results showed that despite the similarity of specific surface area, limestone is more effective than quartz for the enhancement of cement hydration.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Strength-promoting mechanism of alkanolamines on limestone-calcined clay cement and the role of sulfate

This paper reports the strength-promoting mechanism of alkanolamines on limestone-calcined clay cement (LC{sup 3}). The hydration kinetics, phase formation and microstructure of LC{sup 3} with triethanolamine (TEA) or triisopropanolamine (TIPA) were investigated. TEA enhanced the strength of LC{sup 3}, while TIPA was effective at 28 days, and a correct sulfate addition promoted their effects. Alkanolamines accelerated the aluminate reaction of LC{sup 3} during early hydration, increased sulfate slowed this reaction by producing more ettringite. TIPA favoured the hydration of ferrite in clinker, not only accelerated the silicate reaction of metakaolin, but also resulted in a rapid limestone reaction. Alkanolamines altered the morphology and chemical composition of the aluminate hydrates and C-A-S-H. Alkanolamines enabled the reduction of porosity of hardened pastes and the increased sulfate further refined them. It was the large pores being induced by TIPA at early ages that were considered to have an adverse impact on the early strength of LC{sup 3}.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Understanding of the factors slowing down metakaolin reaction in limestone calcined clay cement (LC3) at late ages

Factors which could explain the slowing down of the metakaolin reaction in LC{sup 3} blends are investigated. Portlandite availability and the presence of aluminium ions in the pore solution are shown not to be limiting factors. Hydrates can only precipitate in solution filled pores. Internal relative humidity measurements indicate that at 28 days solution is present only in pores with radii below 13 nm. An enhancement of metakaolin reaction was obtained at late ages when the larger capillaries are filled with solution. The lower limit of the water filled pores was more difficult to analyse since there is a lack of precision in determining interfacial energies of hydrates and pore solution of the system. However, this study gives an indication of order of magnitude where the growth of hydrates could be slowed down.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Efficacy of SCMs to mitigate ASR in systems with higher alkali contents assessed by pore solution method

This study demonstrates the efficacy of supplementary cementitious materials (SCMs) to mitigate alkali-silica reaction (ASR) even when used in conjunction with cement of higher alkali contents (up to 1% Na{sub 2}O{sub eq}). The expansion of concrete prisms was studied immersed in simulated pore solution in order to address the limitations of conventional ASR testing methods, accelerated mortar bar test (AMBT) and concrete prism test (CPT). Expansion results demonstrate that 25% fly ash and 50% slag are both sufficient to mitigate ASR even with cements with alkali content up to 1% Na{sub 2}O{sub eq} and that the pore solution method is a viable alternative ASR testing method. Massive amounts of ASR products (~20 μm thickness) were observed in concretes without SCMs consistent with high degree of expansion and extensive cracking. Small amounts of ASR products (≤5 μm thickness) were also observed in concrete with SCMs despite absence of significant expansion.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Unravelling chloride transport/microstructure relationships for blended-cement pastes with the mini-migration method

A chloride mini-migration method is proposed to estimate effective diffusion coefficients at the scale of the cement paste and to investigate mechanisms with complementary microstructure analyses on the same material. Blended-cement pastes with a wide range of properties were investigated in this study: systems at w/b = 0.3–0.5 including Portland cement, white Portland cement, slag-Portland cement, fly ash, glass powder, and/or limestone and calcined clay. Comparisons showed the relative and combined importance of three main parameters on the effective diffusion coefficient: the porosity, the pore connectivity parameter and the conductivity of the pore solution (low values of the latter two are generally key aspects of the high resistance of blended-cement systems against chloride ingress). Notably, a general correlation for all the investigated systems was established between the effective diffusion coefficient and the bulk conductivity (whereas no simple correlation was observed between the effective diffusion coefficient and the formation factor or the pore connectivity parameter).

36 MATERIALS SCIENCE↗

DOE OSTI2021

The reaction between metakaolin and limestone and its effect in porosity refinement and mechanical properties

In limestone calcined clay cements (LC{sup 3}), more hemicarboaluminate and monocarboaluminate is observed, as compared to other blended cements, from the reaction of metakaolin with limestone. In this study, it is shown that the formation of these carboaluminate phases, predominantly occurs during a “third” hydration peak, after the main alite and aluminate peaks. The influence of the metakaolin content, level of sulfate addition and the water to binder ratio on the position and magnitude of this peak were investigated. This precipitation of hemi and monocarboaluminate has a significant effect on porosity refinement and strength development. It was also observed that alumina from metakaolin can contribute to the precipitation of ettringite if sufficient sulfate is available.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Calcined clay limestone cements (LC3)

The use of supplementary cementitious materials (SCMs) to replace part of the clinker in cement is the most successful strategy to reduce CO{sub 2} emissions in the global cement industry. However, limited supplies of conventional SCMs make it difficult to take this strategy further unless new types of SCMs become available. The only type of material available in the quantities needed to meet demand is clay containing kaolinite, which can be calcined to produce an effective SCM. Such clays are widely available in countries where most growth in demand for cement is forecast. Calcined clays have previously been used as pozzolans, but calcination makes the economics of substitution marginal in a conventional pozzolanic blend. The major innovation presented here is the possibility to make a coupled substitution of cement with calcined clay and limestone. This allows much higher levels of substitution. Blends where calcined clay is used as a pozzolan, typically have clinker contents around 65–70%. Combination of calcined clay with limestone allows higher levels of substitution down to clinker contents of around 50% with similar mechanical properties and improvement in some aspects of durability. The replacement of clinker with limestone in these blends lowers both the cost and the environmental impact.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Changes in microstructure characteristics of cement paste on carbonation

This study investigates the influence of carbonation on the microstructure of cement paste cast with Ordinary Portland Cement (OPC), fly ash based Portland Pozzolana Cement (PPC) and Limestone Calcined Clay Cement (LC{sup 3}) using X-ray diffraction (XRD), thermal analysis (TGA), scanning electron microscope (SEM) and mercury intrusion porosimeter (MIP). A comparison is made between samples exposed to 3% carbon dioxide concentration and those exposed to natural CO{sub 2} concentrations. It is observed that the products formed on carbonation are similar in both the exposure conditions. Distinct rims corresponding to decalcified C-S-H are observed around clinker grains in the carbonated samples. Coarsening of pore structure is observed on carbonation in all the cements and an increase in the total porosity is observed in blended cements. Thermodynamic modeling indicates irrespective of the type of cement the total solid volume is reduced on complete carbonation. The volume change occurring on carbonation obtained from experimental results and thermodynamic modeling are compared.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Laboratory synthesis of C3S on the kilogram scale

An optimized process using amorphous silica for efficient C{sub 3}S synthesis in the laboratory is reported: an estimated production capacity of ~2 kg C{sub 3}S within a week is possible. Amorphous silica (fumed silica) was used as raw material and inter-ground with CaCO{sub 3} and water for C{sub 3}S synthesis, the dried raw mixture has sufficient green strength to be self-supporting, which allows large cylinders to be placed in Platinum crucibles. The mineral composition of the sintered sample was quantified with X-ray powder diffraction using Rietveld analysis. C{sub 3}S with 3 S synthesis was dramatically enhanced because of 1) increased burnability of the raw mix due to amorphous silica and very fine CaCO{sub 3} particles after grinding, 2) simplified sample preparation process avoiding pressing discs and 3) improved capacities of the crucible and furnace.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Determination of the amount of reacted metakaolin in calcined clay blends

This paper presents a comparative study of three methods to determine the amount of reacted metakaolin in calcined clay blends: mass balance, thermodynamic modelling, and the Partial or not Known Crystalline Structure method (PONKCS) based on Rietveld analysis of X-ray diffraction. The methods are applied to Limestone calcined clay cements (LC{sup 3}-50) in this study. Mass balance and thermodynamic modelling results show good agreement, especially at early age. PONKCS method shows globally comparable results, even if it has higher variability. The precision of PONKCS becomes poor for blends with <60% of metakaolin in calcined clay.

36 MATERIALS SCIENCE↗

DOE OSTI2018

A novel method to predict internal relative humidity in cementitious materials by 1H NMR

In sealed cementitious materials, the internal relative humidity (RH) decrease is mainly due to the water activity depression caused by menisci formation in partially-saturated pores. This process can be conveniently described with the evolution of the Kelvin radius. To obtain the Kelvin radius, a novel method based on the evolution of pore volumes quantified by {sup 1}H nuclear magnetic resonance (NMR) and mercury intrusion porosimetry (MIP) was developed. This approach was validated against experimental results for cementitious materials with a range of water to cement ratios from 0.30 to 0.46. A comparison between the Kelvin radius calculated with this approach with a previously published method using data obtained from MIP and chemical shrinkage was presented. A sensitivity analysis for the new prediction method was performed using a bootstrapping technique.

36 MATERIALS SCIENCE↗

DOE OSTI2014

The existence of amorphous phase in Portland cements: Physical factors affecting Rietveld quantitative phase analysis

Rietveld quantitative phase analysis has become a widespread tool for the characterization of Portland cement, both for research and production control purposes. One of the major remaining points of debate is whether Portland cements contain amorphous content or not. This paper presents detailed analyses of the amorphous phase contents in a set of commercial Portland cements, clinker, synthetic alite and limestone by Rietveld refinement of X-ray powder diffraction measurements using both external and internal standard methods. A systematic study showed that the sample preparation and comminution procedure is closely linked to the calculated amorphous contents. Particle size reduction by wet-grinding lowered the calculated amorphous contents to insignificant quantities for all materials studied. No amorphous content was identified in the final analysis of the Portland cements under investigation.

36 MATERIALS SCIENCE↗

DOE OSTI2011

Physical and microstructural aspects of iron sulfide degradation in concrete

The microstructural aspects of iron sulfide degradation in dam concrete were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) in both dam concrete samples and laboratory concrete. The results show that iron sulfide inclusions with a diameter of a few micrometers in the aggregates are reactive and appear to generate expansion first in the aggregates and consequently in the cement paste. The expansion from the iron sulfides is a consequence of the increase in volume of the reaction products formed. The types of iron sulfide present in the aggregate, mainly pyrrhotite (FeS) and pyrite (FeS{sub 2}), show similar reaction behavior in the aggregates. The released sulfate can lead to a secondary ettringite formation in the concrete matrix, but the degradation associated with this appears to be minor. The reaction of the iron sulfides was found to be very slow even when laboratory samples were exposed to elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

Supplementary cementitious materials

The use of silica rich SCMs influences the amount and kind of hydrates formed and thus the volume, the porosity and finally the durability of these materials. At the levels of substitution normally used, major changes are the lower Ca/Si ratio in the C-S-H phase and consumption of portlandite. Alumina-rich SCMs increase the Al-uptake in C-S-H and the amounts of aluminate containing hydrates. In general the changes in phase assemblages are well captured by thermodynamic modelling, although better knowledge of the C-S-H is needed. At early ages, 'filler' effects lead to an increased reaction of the clinker phases. Reaction of SCMs starts later and is enhanced with pH and temperature. Composition, fineness and the amount of glassy phase play also an important role. Due to the diverse range of SCM used, generic relations between composition, particle size, exposure conditions as temperature or relative humidity become increasingly crucial.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2011

The origin of early age expansions induced in cementitious materials containing shrinkage reducing admixtures

Studies on the early-age shrinkage behavior of cement pastes, mortars, and concretes containing shrinkage reducing admixtures (SRAs) have indicated these mixtures frequently exhibit an expansion shortly after setting. While the magnitude of the expansion has been noted to be a function of the chemistry of the cement and the admixture dosage; the cause of the expansion is not clearly understood. This investigation uses measurements of autogenous deformation, X-ray diffraction, pore solution analysis, thermogravimetry, and scanning electron microscopy to study the early-age properties and describe the mechanism of the expansion in OPC pastes made with and without SRA. The composition of the pore solution indicates that the presence of the SRA increases the portlandite oversaturation level in solution which can result in higher crystallization stresses which could lead to an expansion. This observation is supported by deformation calculations for the systems examined.

36 MATERIALS SCIENCE↗