Calcium Aluminate Cement Research Articles

Stabilization and Solidification of Beryllium Waste: Influence of the Cement Composition on the Corrosion of Be Metal

Beryllium metal is used as neutron moderator and reflector or multiplier in certain types of fission or fusion reactors. Dismantling of these reactors will produce radioactive beryllium waste, classified as low- or intermediate-level waste, that will need to be stabilised and solidified before being sent to disposal. The cementation process is under consideration because it may offer a good compromise between simplicity of implementation, cost, and quality of the final cemented wasteform. Nevertheless, knowledge of the corrosion behaviour of Be metal in a cement-based matrix is still limited, partly due to the high toxicity of Be that complicates testing. This study thus investigates Be corrosion in cement suspensions using potentiometry, voltammetry, and electrochemical impedance spectroscopy. Among the five different investigated systems (Portland cement blended without or with 40 wt.% silica fume, calcium sulfoaluminate clinker blended without or with 15% anhydrite, and calcium aluminate cement), Portland cement blended with 40% silica fume and calcium sulfoaluminate cement comprising 15% anhydrite are the most effective in mitigating beryllium corrosion. They allow reduction in the corrosion current by factors of 4 and 50, respectively, as compared to Portland cement.

Preparing porous calcium hexaluminate (CA6) ceramics with calcium aluminate cement (CAC) as the gelling agent and sole calcia source

Preparing porous calcium hexaluminate (CA6) ceramics with calcium aluminate cement (CAC) as the gelling agent and sole calcia source

Functionalizing heavy metal contained incinerated sewage sludge ash in recycled glass-based alkali-activated materials for sewer environment

This study evaluates the performance of alkali-activated cement (AAC) mortars in an artificial sewage environment. The mortars, initially prepared with waste glass powder (GP) and ground granulated blast furnace slag (GGBS) in a 50:50 mass ratio, were modified by replacing 10 wt% of GGBS with incinerated sewage sludge ash (ISSA) with the goal of offering a biocidal effect. Comparisons were made with calcium aluminate cement (CAC), metakaolin (MK), and MK combined with zinc ferrite nanoparticles, each at a similar GGBS replacement level. The results showed that only incorporating CAC improved the strength development, achieving compressive and flexural strengths of 62.7 MPa and 7.4 MPa, respectively, at 28 days, while introducing ISSA or MK reduced the compressive strength to 47 MPa and flexural strength to 4.5 MPa. Although heavy metal ions from ISSA or zinc ferrite nanoparticles minimized biofilm thickness, they could not compensate for the reduced strength and increased alkalis leaching. Among all the tested mixtures, the 50GP40GGBS10CAC mixture exhibited superior biogenic acid resistance, possibly due to its Al-rich C-N-A-S-H gel phases (Ca/Si = 0.4, Na/Al = 0.8, Si/Al = 3.4) and refined pore structure (porosity = 3.4 %), making it the most microbial acid-resistant option for sewer rehabilitation.

Experimental Study on the Effect of Calcium Aluminate Cement Addition on the Drying and Physical Properties of Refractory Castables Containing Colloidal Silica.

Colloidal silica-bonded castables offer several advantages compared to traditional calcium aluminate cement (CAC)-bonded castables, including lower torque values during mixing, superior drying properties, and a lower CaO content. Nevertheless, information on the combination of CAC and colloidal silica is limited, and the effect of CAC additions on the drying properties of colloidal silica-bonded castables remains unknown. In this study, these drying properties were measured by rapidly heating 400 kg samples to 500 °C and assessing the resulting damage to each sample. Additionally, the physical and chemical properties of small-scale samples were analyzed to evaluate the impact of CAC addition. The analyzed properties included cold crushing strength (CCS), density, permanent linear change (PLC) and weight loss. The microstructure of the samples was investigated by FESEM and EDS. The results indicate that adding 1.5 wt.% increased the cold crushing strength at 20 °C, while lower CAC amounts had no noticeable effect. A mullite phase was observed in the sample without CAC, and correspondingly, anorthite was found in those with CAC additions. The samples exhibited significant differences in the drying tests, with the degrees of damage increasing with the CAC addition.

Mechanical, physical and durability performance of engineered cementitious composites prepared with calcium aluminate cement

This research aims to fill a gap in existing studies by exploring the use of calcium aluminate cement (CAC) as an eco-friendly substitute for Ordinary Portland Cement (OPC) in Engineered Cementitious Composites (ECC). The study investigates the impact of CAC, both with and without the presence of fly ash (FA), on the mechanical, physical, durability, and microstructural properties of ECC-CAC mixtures. Various proportions of FA-to-CAC up to 1.5 were considered, while assessing different engineering parameters of compressive and flexural strengths, ductility, ultrasonic measurements, chloride penetrability, and drying shrinkage. Moreover, scanning electron microscopy (SEM) coupled with energy dispersive X-ray analysis (EDX) and X-Ray diffraction (XRD) were utilized to analyze the reaction products related to CAC and/or FA in selected mixtures. Higher strengths of CAC-ECC were achieved at earlier curing ages, though the transformation of CAC’s metastable phases led to reduced strengths in ECC-CAC mixtures compared to the control ECC during extended curing periods. Furthermore, the combination of FA with CAC played a crucial role in avoiding the hydrates conversion and minimizing the shrinkage in CAC-ECC, achieving even lower shrinkage levels than those observed in control OPC-ECC.

Service life prediction model for biogenic acid corrosion: Advancement of life factor method for concrete sewer design

Current service life prediction models for concrete sewer design, including the widely used Life Factor Method (LFM), do not efficiently incorporate certain key corrosion contributing factors, such as material selection, concrete mix design, and sewer environment. This paper describes an advancement of the LFM model to cover these factors, broaden its usage, and improve concrete sewer design and applications. By integrating the first principles of the original LFM model, advanced knowledge from the literature, and results from field performance studies of various sewer concretes, a practical and relatively simple LFM model was advanced. With concrete mix design, oxide composition of all concrete ingredients, and sewer environmental and hydraulic conditions, the so-called ‘advanced LFM model’ could predict the corrosion rate of various concrete mixes. The model emphasised the influence of various modern binders, including calcium aluminate and calcium sulpho-aluminate cements, and various aggregate types including siliceous, calcareous, and alumina-based aggregates, when subjected to different sewer environments.

Synthesis of silane-modified styrene-acrylic ester emulsion and its inhibition mechanism on whitening of calcium aluminate cement mortar

A new polymer, triethoxyvinylsilane-modified styrene-acrylic ester emulsion (TMSA), was synthesized through emulsion polymerization. The effect of TMSA on the whitening of calcium aluminate cement (CAC) mortar was investigated. The results showed that TMSA had an excellent inhibition effect on the whitening of the CAC mortar with only 0.8 % - 1.6 % addition. Analysis of the micro-morphology and Raman spectra revealed that the white deposits on the surface of the mortar were C4AC(_)H11 and CaCO3, whereas TMSA addition effectively inhibited the formation of C4AC(_)H11 and reduced the occurrence of CaCO3. Through investigating the hydration, Ca2+ concentration, capillary water absorption and pore structure, it was found that the effect of the CAC hydration on the whitening of the mortars was inessential, whereas there was a strong link among whitening, capillary water absorption and macro-capillary pores. The addition of TMSA not only reduced the concentration of Ca2+ which was the source of the whitening, but also reduced the formation of macro-capillary pores in the CAC mortar that led to a significant reduction in the capillary water absorption, thus weakening the mobility of pore solution in the mortar and hindering the migration of Ca2+ to the mortar surface. Based on these two aspects, TMSA effectively inhibited the whitening of the CAC mortar.

The effect of the alumina-rich spinel exsolution on the microstructure of CAC-bonded castables

According to the magnesia-alumina phase diagram, the alumina-rich spinel may undergo exsolution of corundum during firing when incorporated into the castable. This research aimed to explore the phenomenon of alumina-rich spinel exsolution and its subsequent impact on the distribution of CaO·6Al2O3 inside the spinel and the strength of the castables when subjected to a firing temperature of 1600 °C. The results indicated that the amount of exsolved corundum escalated as the alumina content within the spinel rose after heat treatment, and this exsolved corundum was predominantly found within the original spinel particle. The CaO·2Al2O3, which formed when calcium aluminate cement was heated above 1200 °C, reacted preferentially with the exsolved corundum rather than with pre-added α-Al2O3 leading to the formation of CaO·6Al2O3 inside the spinel after firing at temperatures exceeding 1400 °C. This reaction formed an interpenetrated "spinel-CaO·6Al2O3" structure during firing, which enhanced the strength of the castables.

Calcium aluminate cement blended to bioactive glass and strontium: in vitro and in vivo evaluation studies

Calcium aluminate cement blended to bioactive glass and strontium: in vitro and in vivo evaluation studies

Study on the microstructure and impermeability of calcium aluminate cement containing metakaolin for development of high-performance marine engineering materials

To provide a high-performance marine engineering material, the microstructure and impermeability of calcium aluminate cement (CAC) containing metakaolin (MK) were studied. The chloride penetration resistance of the CAC-MK and Portland cement (PC) mortars was assessed based on physical and chemical barrier effects. The results show that the alumina in MK is more easily dissolved than silica, which inhibits the transformation of CAH10 and prevents microstructural deterioration. Adding 7.5% and 15.0% MK reduces the volume of large pores in the 3-day-old CAC paste by 49.8% and 69.1% while increasing the volume of pores smaller than 50 nm by 175.6% and 242.5%, respectively. Moreover, the microstructure of MK-containing CAC pastes becomes denser with age when cured at 40 °C, enhancing the mechanical strength and water penetration resistance. The CAC mortar containing MK exhibits better resistance to chloride attack than PC mortar, due to the stronger chloride binding capacity and migration resistance.

Snapshot on 3D printing with alternative binders and materials: Earth, geopolymers, gypsum and low carbon concrete

The rapid development of 3D concrete printing now offers mechanical efficiency and freedom to push the limits of construction design. The digital manufacturing process holds potential for reducing carbon footprints through design optimization. Printable concrete, which is a mix of cement (based on ordinary Portland cement), aggregates, and admixtures, is attractive due to widespread and cost-effective constituents. However, many common formulations omit gravel, requiring higher cement paste volumes and inducing significant embodied carbon. Assessing the potential of low-carbon cements like Limestone Calcined Clay Cement (LC3), calcium aluminate cement (CAC), or magnesium-based cement for 3D printing is a current challenge that can address this issue. Tailoring these construction materials to printing applications and environmental needs now drives scientific exploration. This paper comprehensively reviews alternative materials and binders such as earthen materials, geopolymers, low carbon binders or gypsum-based materials, addressing fresh and hardened properties, developed digital processes, targeted applications, and discussing advantages and drawbacks of each alternative.

Resource utilization of sulfidic copper tailings in calcium aluminate cement: Mechanical property, hydration process and environmental impact

Sulfidic copper tailings (STs) is a byproduct generated from mineral processing activities. To address this environmental burden, calcium aluminate cement (CAC) was used to utilize STs as cementitious materials. The influence of STs on the hydration process, mechanical properties and life-cycle assessment of STs blended CAC were investigated. Results show that the initial setting time of the samples is significantly shortened with the presence of STs. Moreover, the addition of STs greatly accelerates cement hydration and promotes the formation of ettringite, which is caused by the dissolution of sulfidic-rich STs. Hence, the hardened cement paste containing 5 wt.% STs with dense microstructure and high elastic modulus is achieved, which enhances the compressive strength for STs blended CAC. From an environmental point of view, the utilization of STs can save energy and reduce CO2 emissions. Such work may provide new insights into the application of sulfidic copper tailings in low-carbon cementitious materials.

Performance of high-strength green strain-hardening cementitious composites incorporating CSA/CAC cements and GGBS

Strain-hardening cementitious composites (SHCCs) possess crack control and durability properties. In the pursuit of reducing CO2 emissions and addressing potential issues of slow strength development for SHCCs with pozzolans, the objective of this study was to develop high-strength green SHCCs (HSG-SHCCs) that exhibit improved early strength, drying shrinkage, and environmental friendliness. A ternary binder system was proposed, comprising of ground granulated blast furnace slag (GGBS), ordinary Portland cement (OPC), and either calcium sulfoaluminate cement (CSA) or calcium aluminate cement (CAC). The fresh, mechanical, and durability properties of the proposed HSG-SHCCs were experimentally investigated. Additionally, the microstructures and chemical phases of the developed CSA/CAC-GGBS-OPC ternary binder system were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results revealed that the developed HSG-SHCCs demonstrated 6-hour and 28-day strengths of up to 11 MPa and 110 MPa, respectively. The CSA/CAC-based ternary binder system also exhibited enhanced durability and improved drying shrinkage. However, the inclusion of CSA and CAC in HSG-SHCCs could lead to a reduction in tensile performance, specifically in strain capacity. The main hydration products of the CSA/CAC-GGBS-OPC ternary binder system were C-S-H, ettringite, gibbsite, and calcium hydrate. In addition to the fresh, mechanical, and durability properties, the environmental impact of the developed HSG-SHCCs was also assessed. The results indicated that a 30 % replacement of OPC with CSA cement in the HSG-SHCC mix notably improved the trade-off among CO2 emissions, compressive strength, and tensile cracking resistance.

Influence of silica fume addition and content on the early hydration of calcium aluminate cement – The role of soluble silicon

Hydration of a commercial white calcium aluminate cement (CAC) at 23 °C was modified by silica fume (SF) addition in varying amounts. The process was followed by heat flow calorimetry, quantitative in-situ XRD analysis and Gillmore needle experiments supplemented by pore solution analysis, thermodynamic modelling, and 1H-TD-NMR measurements. Lower SF/cement ratios accelerate the hydration of CAC. Higher ratios trigger an intermediate heat flow event, which is correlated to increased setting rates. This intermediate event (IE) initiates an induction period of constant duration, which appears later with increasing SF/cement ratios. Results show the IE is caused by an initially hindered CA dissolution, in which dissolved silicon provided by SF plays a crucial role. Increasing the [Si] concentration in the pore solution leads to a further retardation of the IE and eventually prevents the entire hydration reaction if a critical amount is reached. A detailed model explaining the observed behavior is proposed.

The influence of low calcium sulfate contents on early calcium aluminate cement–calcite hydration kinetics and pore solution chemistry

A binder mix consisting of CAC, calcite and H2O was investigated to clarify the influence of the addition of low amounts of calcium sulfate in the form of gypsum, hemihydrate or anhydrite on the hydration at 23 °C. Based on experimental data, a model for the hydration of CAC + calcite in the presence of sulfate ions could be developed. Using heat flow calorimetry at 23 °C, it was shown that hydration is accelerated depending on the solubility rates of the different sulfates. In addition, early hydration is characterized by a sequential reaction in which the calcium sulfate must be consumed completely from the pore solution by the precipitation of ettringite before the already known course of CAC + Cc hydration can occur. Monocarbonate and AH3 precipitate as the stable dominant hydrate phases during the main reaction, but conversion-sensitive hydrate phases such as CAH10 are not stable.

Link between the Reactivity of Slag and the Strength Development of Calcium Aluminate Cement.

The problem of loss of strength caused by the conversion reaction with calcium aluminate cements (CAC) is well known. It has been shown that the addition of ground granulated blast furnace slag (GGBS) to CAC inhibits the conversion process. Different slags can have a different chemical and mineralogical composition depending on their origin and production process, which can significantly influence their reactivity. This work investigated the extent to which the R3 test, developed for Portland cement and based on isothermal calorimetry and/or bound water, was used to predict the reactivity of ground granulated blast furnace slag in a CAC. Mortars and cement pastes with a 30% replacement of slag were tested to evaluate their compressive strength and microstructure. The results show that slags with higher reactivity due to their hydraulic properties lead to a lower compressive strength loss within the first 6 h, a higher strength loss after 24 h due to stratlingite formation and a lower strength loss after 28 days due to pozzolanic reaction and stratlingite formation. The results also confirm that the R3 test was used as a rapid method to predict the effects of slag on the compressive strength of CAC.

Influence of CaCO3 on Density and Compressive Strength of Calcium Aluminate Cement-Based Cementitious Materials in Binder Jetting.

We investigated the impact of CaCO3 addition on the density and compressive strength of calcium aluminate cement (CAC)-based cementitious materials in binder jetting additive manufacturing (BJAM). To confirm the formation of a uniform powder bed, we examined the powder flowability and powder bed density for CaCO3 contents ranging from 0 to 20 wt.%. Specifically, powders with avalanche angles between 40.1-45.6° formed a uniform powder bed density with a standard deviation within 1%. Thus, a 3D printing specimen (green body) fabricated via BJAM exhibited dimensional accuracy of less than 1% across the entire plane. Additionally, we measured the hydration characteristics of CAC and the changes in compressive strength over 30 days with the addition of CaCO3. The results indicate that the addition of CaCO3 to CAC-based cementitious materials forms multimodal powders that enhance the density of both the powder bed and the green body. Furthermore, CaCO3 promotes the formation of highly crystalline monocarbonate (C4AcH11) and stable hydrate (C3AH6), effectively inhibiting the conversion of CAC and showing compressive strengths of up to 5.2 MPa. These findings suggest a strong potential for expanding the use of BJAM across various applications, including complex casting molds, cores, catalyst supports, and functional architectural interiors.

Effect of pre-hydrated CAC suspensions on the hydration behavior of CAC pastes

The relatively low hydration rate of calcium aluminate cement (CAC) at 15–35 °C leads to retarded setting time and reduced production efficiency of CAC-bonded castables. To accelerate the hydration rate of CAC within this temperature range, the present work proposes the fabrication of nano-hydrates acting as seeds by pre-hydration of CAC in suspensions. CAC powders are dispersed in water with water-to-solid ratio of 4.5 and stirred for varying durations at 25 °C to achieve different pre-hydration degrees. Then the pre-hydrated CAC suspensions replace a small part of cement in the pastes. The influence of the CAC suspensions addition on the hydration heat release and strength development of fresh CAC pastes at 25 °C is investigated. The results indicate that nano-scale hydrates C2AH8 and AH3 form on the surface of pre-hydrated CAC particles in the suspensions and grow rapidly with the extension of stirring duration. The presence of nano-scale hydrates in the pre-hydrated CAC suspensions is found to shorten the induction period of CAC hydration and thus be beneficial to the accelerated hardening of CAC pastes. The pre-hydrated CAC suspension stirred for 3.5 h has the most significant effect on enhancing early strength of the CAC pastes. At this stage, the pre-hydrated CAC within the suspension is in the accelerated period, and has just begun to precipitate large amounts of nano-scale C2AH8 and AH3 acting as seeds to catalyze the hydration and refine the pore structure of CAC pastes.

Study on the electromagnetic transmission properties and mechanical properties of calcium aluminate cement paste by silica fume

Study on the electromagnetic transmission properties and mechanical properties of calcium aluminate cement paste by silica fume

Development of Negative-Temperature Cement Emulsified Asphalt Spraying Materials Based on Spraying Performance and Rheological Parameters.

To develop a cement emulsified asphalt composite (CEAC) that can be sprayed under a plateau negative temperature environment, the effects of the water-solid ratio, calcium aluminate cement substitution rate, emulsified asphalt content, sand-binder ratio, and polyvinyl alcohol (PVA) fiber content on the spraying performance and rheological parameters of CEAC were explored through the controlled variable method. Additionally, the correlation between the spraying performance and rheological parameters of CEAC was established, and the optimal proportion of CEAC was determined. Then, the difference in frost resistance and pore structure between the cement slurry (CS) without emulsified asphalt and CEAC at the optimum proportion was analyzed. The results showed that the optimum proportions for sprayed CEAC were 0.14 water-solid ratio, 0.5 sand-binder ratio, 25% substitution of calcium aluminate cement, 5% emulsified asphalt content, and 1.5% PVA fiber volume mixing. The yield stress and plastic viscosity of CEAC were positively correlated with the build-up thickness, whereas the rebound rate and the latter showed a negative correlation. The spraying performance may be described by the rheological parameters; the ranges of yield stress and plastic viscosity of 2.37-3.95 Pa·s and 77.42-108.58 Pa, respectively, produced the best spray ability. After undergoing an equivalent number of freeze-thaw cycles, CEAC exhibited lower mass and strength loss rates compared to CS, thereby demonstrating superior frost resistance. In addition, the pore structure analysis showed that the difference in capillary and macropore contents was the main reason for the variability in frost resistance between CS and CEAC.