Three-dimensional printing of flash-setting calcium aluminate cement

Three-dimensional indirect printing of flash-setting calcium aluminate cement (CAC) was investigated. Upon water injection into a biphasic mixture of tricalcium aluminate (3CaO·Al₂O₃) and dodecacalcium heptaaluminate (12CaO·7Al₂O₃) (phase ratio 0.56/0.44) initially a gel formed acting as a bonding phase which stabilizes the printed object geometry. Post-exposure in water finally resulted in the formation of 2CaO·Al₂O₃·8H₂O and 4CaO·Al₂O₃·19H₂O reaction phases as confirmed by SEM, X-ray diffraction, and FTIR analyses. Reduction of porosity by volume expansion upon hydrolysis reaction from 50% after printing to 20% after post-treatment gave rise for an increase of compressive strength from 5 to 20 MPa, respectively. A bone regenerating scaffold for a micro-vascular loop model was fabricated by 3D printing and hydraulic reaction bonding to demonstrate the potential of using flash-setting calcium aluminate cement powder for biomedical ceramic applications.     

Early hydration of quick cements in the system C11A7 · CaF2C2SC2(A,F)

To explain the initial hydration of quick cements of the system C₁₁A₇ · CaF₂C₂SC₂(A,F), their SO₃/Al₂O₃ ratio was varied, Portland cement was added to increase the alcalinity of the pore solution in the cement stone, and setting retarded was used during the tests. The process of hydration was investigated with the help of X-ray diffraction and scanning electron microscopy as well as via the determination of the chemically bound water. The quantity of rapidly growing ettringite crystals increases with a rising SO₃/ Al₂O₃ value. The optimal SO₃/Al₂O₃ value of the system C₁₁A₇ · CaF₂C₂SC₂(A,F) is found between 0.26 and 0.38. The sole addition of setting retarder or Portland cement can distinctly reduce the formation of monocarbonate or even stop it completely. However, the simultaneous addition of both additives (setting retarded and a Portland cement) supports the formation of ettringite and monocarbonate crystals and through this also supports the increase of initial strength of quick cement.     

Effects of crystallinity and silica content on the hydration kinetics of 12CaO · 7Al2O3

The effects of 12CaO₇ · Al₂O₃ crystallinity on the kinetics of hydration reaction were studied by measuring the heat liberated using a conduction calorimeter. The crystallinity of the sample was modified by changing the cooling rate of the sample after synthesis reaction. In addition, the effects of silica addition to 12CaO₇ · Al₂O₃ glass on kinetics were also investigated. The results indicated that the glass underwent a faster initial kinetic hydration reaction compared with that of crystalline calcium aluminate. The addition of silica, on the other hand, decreased the reaction rates. The results are discussed in terms of the solvation rate of the calcium aluminate phases and the precipitation of the hydrate phases.     

Sisal fiber-reinforced cement composite with Portland cement substitution by a combination of metakaolin and nanoclay

This paper reports the partial replacement of Portland cement (PC) by combination of metakaolin (MK) and nanoclay (NC) in sisal fiber-reinforced cement composites by studying the microstructure, mechanical behavior, and the interfacial properties between fiber and cement matrices. The mechanical properties of cement matrix and natural fiber-reinforced composites are studied using compressive strength development and flexural behavior, respectively. The tensile behavior of the natural fiber was also investigated and analyzed by Weibull distribution model. The characteristics of hydration products were analyzed by scanning electron microscope, X-ray diffraction, and thermogravimetry analysis. Our results show that the combination of MK and NC can improve the hydration of cement more effectively, with better microstructure and enhanced mechanical properties, than mixes without them. The calcium hydroxide (CH) contents of matrixes with 50 wt% combined substitutions, containing 1, 3, and 5 wt% of nanoclay, were 58.12, 60.16, and 64.25 % less than that of PC, respectively. The ettringite phase is also effectively removed due to the substitution of MK and NC, which improve both Al/Ca and Si/Ca ratios of calcium silicate hydrates (C–S–H) due to the high content of SiO₂ and Al₂O₃. The interfacial bond between fiber and cement matrix and flexural properties of sisal fiber-reinforced cement composites are also significantly improved. The optimum interface adhesion between sisal fiber and matrix was achieved by replacing cement by 27 % MK and 3 % NC, which increased the bond strength and pull-out energy by 131.46 and 196.35 %, respectively.     

Effect of barium on the structure and dielectric properties of multicomponent ceramics based on ferroelectric relaxors

High-density ceramic samples of mPb(Mg_1/3Nb_2/3) · yPb(Zn_1/3Nb_2/3) · nPb(Ni_1/3Nb_2/3) · xPbTiO₃ (m = 0.4541, y = 0.0982, n = 0.1477, x = 0.3) solid solutions, unmodified and barium-modified, with the composition lying in a morphotropic phase region, have been prepared by a conventional ceramic processing technique. We demonstrate that barium substitution for 5% of the lead on the A site allows one to obtain ceramics containing no pyrochlore phase. Modification with barium shifts the solid solution from the morphotropic to a tetragonal phase region. In addition, barium doping increases the average grain size of the ceramic from 2–3 to 3–4 μm and changes the type of fracture from intergranular to mixed (intergranular and transgranular). Modification with barium increases the relative dielectric permittivity ?/?₀ (at E = 0) of the material by more than a factor of 2 (from 4300 to 9100). We conclude that materials based on the ceramics studied can find practical application and examine ways of further improving their piezoelectric performance.     

Effect of fluid flow on the hydration of a sodium-calcium-silicate glass

The effect of rotating a 0.2Na₂O·0.1CaO·0.7SiO₂ glass sample during hydration was studied at 90°C using sputter-induced photon spectrometry (SIPS). Concentration-versus-depth profiles for hydrogen, sodium, and calcium were measured. The resulting depth profiles show an increase in hydralion depth and a change in profile shape as the rate of rotation was increased.     

Influence of pozzolana on sulfate attack of cement stone affected by chloride ions

This study investigated the influence of natural pozzolana (opoka) additive on the hydration of Portland cement and the effects of pozzolana on sulfate attack of cement stone affected by chloride ions. In the samples, 25 % (by weight) of the Portland cement was replaced with pozzolana. The specimens were hardened for 28 days in water, and then one batch was soaked in a saturated NaCl solution and another in a 5 % Na₂SO₄ solution for 3 months at 20 °C. After being kept for 3 months in a saturated NaCl solution, samples were transferred to a 5 % Na₂SO₄ solution and kept under these conditions for 3 months. It was estimated that under normal conditions, pozzolana additive accelerated the hydration of calcium silicates and initiated the formation of CO₃ ^2?–AFm; opoka also decreased the threshold pore diameter of hardened Portland cement paste. It was found that Cl^– ions penetrate to monosulfoaluminate, form Friedel’s salt, and release SO₄ ^2? ions, which react with unaffected monosulfoaluminate and form extra ettringite; when samples were transferred to the 5 % Na₂SO₄ solution, a greater quantity of new ettringite was formed. Meanwhile, pozzolana additive reduced the penetration of chloride and sulfate ions into the structure of Portland cement hydrates and inhibited sulfate attack of cement stone treated in a saturated NaCl solution.     

碱激发和复合激发下建筑垃圾砖粉活性研究

为提高建筑垃圾废砖再生利用率,采用砂浆力学测试手段研究了建筑垃圾砖粉活性和碱激发、复合激发对建筑垃圾砖粉活性的影响,并借助扫描电镜和热分析方法对建筑垃圾砖粉、建筑垃圾复合粉体材料的颗粒形貌、水化产物组成等进行了研究。结果表明:建筑垃圾砖粉活性较小,当掺量大于20%时,砂浆强度随其掺量的增加直线下降;不同碱激发剂对建筑垃圾砖粉有不同的激发效果,Ca(OH)2激发效果最好,NaOH次之,Na2SiO3·9H2O激发效果最差;复合形成的建筑垃圾复合粉体材料具有较好的活性,当其掺量不超过40%时,砂浆28d抗压强度高达50 MPa。微观分析结果表明:建筑垃圾复合粉体材料比砖粉具有更好的颗粒级配,在其水化过程中降低了稳定性较差的Ca(OH)2含量,提高了水泥石密实度,是一种经济、环保的新材料。     

石膏对石灰石粉水泥基材料水化及硬化性能的影响

针对我国目前非荷载作用下混凝土严重开裂的问题,以"比表面积较低的水泥熟料-比表面积较高的掺合料-足够掺量的石膏"构成的胶凝材料体系为研究对象,通过水化热速率、X射线衍射(XRD)、扫描电子显微镜(SEM)、压汞法(MIP)及热重-差示扫描量热法(TG-DSC)等手段,研究石膏对石灰石粉水泥基材料水化及硬化体微结构的影响。结果表明,石灰石粉能够加速C3A与石膏作用生成钙矾石相,在足量石膏存在的条件下,能够阻碍钙矾石向低硫型硫铝酸钙转变;石灰石粉的掺入与石膏一起延缓了C3A的水化;在石灰石粉和足够石膏同时存在的情况下,C3A水化生成具有膨胀性的水化碳铝酸钙和高硫型硫铝酸钙,补偿了收缩,提高了水泥基材料的抗裂性能;熟料粗磨、掺合料细磨及较高石膏掺量的胶凝材料体系配制的C30和C50等级混凝土,强度能持续增大,从28d到180d,强度分别提高了36.7%和33.3%,混凝土结构紧密、孔隙率低、有害孔含量少。     

Influence of curing temperatures on the hydration of calcium aluminate cement/Portland cement/calcium sulfate blends

In this paper, the effects of curing temperature on the hydration of calcium aluminate cement (CAC) dominated ternary binders (studied CAC: Portland cement: calcium sulfate mass ratio were 22.5: 51.7: 25.8) were estimated at 0, 10, 20 and 40 °C, respectively. Both α-hemihydrate and natural anhydrite were employed as the main source of sulfate. The impacts of temperature on the phase assemblages, morphology and pore structure of pastes hydrated up to 3 days were determined by using X-ray diffraction (XRD), backscattered electron imaging (BEI) and mercury intrusion porosimetry (MIP). Results reveal that the main hydration products are firmly related to calcium sulphoaluminate based phases. Increasing temperature would result in a faster conversion from ettringite to plate-like monosulfate for both calcium sulfate doped systems. When the temperature increases to 40 °C, an extraordinary formation of strätlingite (C₂ASH₈) and aluminium hydroxide is observed in anhydrite doped pastes. Additionally, increased temperature exerts different effects on the pore structure, i.e. the critical pore diameter shifts to finer one for pastes prepared with α-hemihydrate, but changes to coarser one for those made with anhydrite. From the mechanical point of view, increased temperature accelerates the 1-day strength development prominently, while exerts marginal influence on the development of 3-day strength.     

Effect of further water curing on compressive strength and microstructure of CO2-cured concrete

This study aims to investigate the effects of further water curing on the compressive strength and microstructure of CO₂-cured concrete. The results showed that concrete with a residual w/c ratio of 0.25 showed the most rapid strength development rate upon further water curing due to hydration of uncarbonated cement particles. Thermogravimetric, IR-spectrophotometric and scanning electron microscope examinations indicated that further hydration of the cement particles could form C-S-H gel and ettringite crystals. The results showed that the calcite formed during the initial CO₂ curing was consumed during the further hydration of C₃A, and produced calcium monocarbonaluminate hydrate. Also, Ca(OH)₂ was not detected due to its reaction with the formed silica gel. Mercury intrusion porosimetry test results indicated that the porosity and pore size of the CO₂ cured mortar decreased further after water curing.     

Reaction of sodium calcium borate glasses to form hydroxyapatite

This study investigated the transformation of two sodium calcium borate glasses to hydroxyapatite (HA). The chemical reaction was between either 1CaO · 2Na₂O · 6B₂O₃ or 2CaO · 2Na₂O · 6B₂O₃ glass and a 0.25 M phosphate (K₂HPO₄) solution at 37, 75 and 200 °C. Glass samples in the form of irregular particles (125–180 μm) and microspheres (45–90 and 125–180 μm) were used in order to understand the reaction mechanism. The effect of glass composition (calcium content) on the weight loss rate and reaction temperature on crystal size, crystallinity and grain shape of the reaction products were studied. Carbonated HA was made by dissolving an appropriate amount of carbonate (K₂CO₃) in the 0.25 M phosphate solution. X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy were used to characterize the reaction products. The results show that sodium calcium borate glasses can be transformed to HA by reacting with a phosphate solution. It is essentially a process of dissolution of glass and precipitation of HA. The transformation begins from an amorphous state to calcium-deficient HA without changing the size and shape of the original glass sample. Glass with a lower calcium content (1CaO · 2Na₂O · 6B₂O₃), or reacted at an elevated temperature (75 °C), has a higher reaction rate. The HA crystal size increases and grain shape changes from spheroidal to cylindrical as temperature increases from 37 to 200 °C. Increase in carbonate concentration can also decrease the crystal size and yield a more needle-like grain shape.     

Chemical activation of calcium aluminate cement composites cured at elevated temperature

The influence of sodium sulfate, as an activator, on the hydration of calcium aluminate cement (CAC)–fly ash (FA)–silica fume (SF) composites was investigated. Different mixes of CAC with 20% pozzolans (20% FA, 20% SF and 10% FA + 10% SF) were prepared and hydrated at 38 °C for up to 28 days. The hydration products were investigated by XRD, DSC and SEM. The results showed that sodium sulfate accelerated the hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH₁₀ and C₂AH₈ to form the strätlingite (C₂ASH₈). The later reactions prevent the strength loss by preventing the conversion of CAH₁₀ and C₂AH₈ to the cubic C₃AH₆ phase. The acceleration effect of Na₂SO₄ on the reactivity of fly ash was more pronounced than on the reactivity of silica fume with respect to reaction with CAH₁₀ and C₂AH₈ phases.     

Incorporation of coal combustion residuals into calcium sulfoaluminate-belite cement clinkers

In recent years, calcium sulfoaluminate-belite (CSAB) cement has been promoted as a sustainable alternative to Portland cement due to lower energy used and less CO₂ emitted during production, while providing comparable performance. However, a potential problem facing the widespread adoption and production of CSAB cement is the cost and availability of raw materials and it is therefore desirable to find alternative raw materials to keep costs competitive. In this study, two CSAB cement clinkers with a similar target phase composition were synthesized from combinations of natural and waste materials (coal combustion residuals). The two CSAB cement clinkers were compared against a CSAB clinker made from reagent-grade chemicals, enabling examination of the effects of impurities on performance. Cements made from the clinkers were examined for hydration rate, hydration product formation, dimensional stability, and compressive strength.     

Chemical activation of calcium aluminate cement composites cured at elevated temperature

The influence of sodium sulfate, as an activator, on the hydration of calcium aluminate cement (CAC)–fly ash (FA)–silica fume (SF) composites was investigated. Different mixes of CAC with 20% pozzolans (20% FA, 20% SF and 10% FA + 10% SF) were prepared and hydrated at 38 °C for up to 28 days. The hydration products were investigated by XRD, DSC and SEM. The results showed that sodium sulfate accelerated the hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH₁₀ and C₂AH₈ to form the strätlingite (C₂ASH₈). The later reactions prevent the strength loss by preventing the conversion of CAH₁₀ and C₂AH₈ to the cubic C₃AH₆ phase. The acceleration effect of Na₂SO₄ on the reactivity of fly ash was more pronounced than on the reactivity of silica fume with respect to reaction with CAH₁₀ and C₂AH₈ phases.     

Fixation of alkyl phosphate using waste incineration fly ash

Waste incineration fly ash (Fa), pretreated by washing with distilled water and heating at 1000°C in air, was treated with various concentrations of octyl phosphate [C₈H₁₇OPO₃H₂(OP)] aqueous solution by stirring at 25°C for 3 h and aging at 85°C for 24 h. X-ray fluorescence and X-ray diffraction measurements indicated that the major element of Fa is Ca which exists as CaO and gehlenite (2CaO · Al₂O₃ · SiO₂). Treating Fa in OP solutions dissolved the CaO and gehlenite to form calcium octyl phosphate (C₈H₁₇OPO₃Ca.nH₂O), which is composed of a multilayer alternating dicalcium phosphate dihydrate (CaHPO₄ · 2H₂O)-like phase and a bimolecular layer of octyl groups of the phosphates. Increasing the OP concentration increased the fixed amount of OP and amount of recovery after the treatment. The fixed amount and amount of recovery steeply increased during stirring at 25°C, and were almost unchanged by aging. These facts allow us to infer that Fa is available to fix alkyl phosphate ions such as OP.     

Novels patterns of hydration and new compounds in the ternary system of CaO-Al2O3-P2O5

 The patterns of hydrating and solidifying with the compositional variation of phosphorus-rich, phosphorus-calcium-rich and aluminum-calcium rich regions in ternary system CaO-Al₂O₃-P₂O₅ has been studied in detail, and two new ternary compounds L and H have been synthesized here. The results indicate that the region of 48–56% P₂O₅ doesn’t present cementitiousness, which contains mainly crystal phases of β-C₂P(2CaO·P₂O₅), α-C₃P(3CaO·P₂O₅) and AlPO₄; the phosphorus-calcium-rich region of 21–35% P₂O₅ exhibits substantial cementitiousness, which contains mainly crystal phase of α-C₃P and certain amount of CA(CaO·Al₂O₃) and new phases L/H; and the aluminum-calcium-rich region of 8–18% P₂O₅ is full of promise for cementitiousness. It contains mainly new crystal phase L and certain amount of α-C₃P and CA. The hydration and solidification mechanisms have been preliminarily analyzed by means of XRD, XPS and DTA. It appears that crystal phase CA might hydrate directly to the stable phase of C₃A·6H₂O in the phosphorus-rich case of 21–35% P₂O₅; new phase H has the behavior of rapid setting; and L, being a dominant phase, can prevent cement pastes from significant strength loss in long curing cycles. Received: 12 March 1998 / Accepted: 29 July 1998     

Calcium silicate cements obtained from rice hull ash: A comparative study

This work describes the utilization of rice hull as raw-material for the preparation of two calcium silicates namely, β-Ca_1.91Ba_0.04SiO₄ and β-Ca_1.96Ba_0.04SiO₄. The synthesis was completed at 800°C. Hydration rate and compressive strength of mortars prepared with the two calcium silicates were studied and compared to mortars prepared with commercial Portland cement. Hydration rates for both silicates, studied by thermogravimetric and FTIR analysis are very similar; after 60 days the hydration rates are around 42–43% and reaches 75% after 270 days. Compressive strength experiments were performed using test specimen prepared with commercial Portland cement as reference, and blends of Portland cement and the two calcium silicates, at replacement levels of 10 and 20%. Results have shown that after a 90 days curing period, the compressive strength of the reference and the blends containing 10% of each of the calcium silicates show the same behavior. Using a replacement level of 20% there is a small decrease in compressive strength. This behavior is attributed to the lower hydration rate of these calcium silicates.     

Report of TC 238-SCM: hydration stoppage methods for phase assemblage studies of blended cements—results of a round robin test

For many microstructural studies it is necessary to “stop” cement hydration—to remove free water. This paper describes the results of a round robin test on the impact of hydration stoppage methods on the composition of hydrated cements. A regular and a fly ash blended Portland cement hydrated for 90 days were selected. Ten laboratories participated in the round robin test. Four common hydration stoppage methods were studied: (1) oven drying at 105 °C, (2) solvent exchange by isopropanol, (3) vacuum drying and (4) freeze drying. After the stoppage of hydration powder samples were studied by thermogravimetry (TG) and X-ray diffraction (XRD). Bound water and Ca(OH)₂ content were determined based on the TG data. Portlandite and ettringite content were quantified by Rietveld analysis of the XRD data. The goal was to establish interlaboratory reproducibility and to identify the best available protocols for research and standardization purposes. Based on the results of the round robin test three recommendations are made. (1) Oven drying at 105 °C is not recommended. This dehydrates, alters and decomposes calcium aluminate hydrates significantly more than other methods and often produced carbonation artefacts. (2) Isopropanol exchange is the most appropriate hydration stoppage method for the study of the complete hydrate assemblage of cements, including calcium aluminate hydrates such as ettringite and AFm phases. (3) For quantification of portlandite (Ca(OH)₂) all tested hydration stoppage protocols are satisfactory, with the exception of oven drying.     

Study of aluminum sulfate and anhydrite on cement hydration process

The influences of aluminum sulfate (AS) introduction and dosage on setting time, hydration heat evolution, hydration product type and pore structure of Portland cement were studied, and the influence of AS on concrete strength was investigated also. The results indicate that AS can effectively accelerate setting time of Portland cement and enhance concrete at early age (1 day) strength. AS can promote hydration process of calcium aluminate but inhibit that of calcium silicate. The effect of AS on hydration process becomes more significant along with the increased dosage; and the introduction of AS can promote the formation of AFt. The research results of this paper favor the opinion of the existence of AFt precursor; and the AFt precursor is amorphous AFm which could not be identified by XRD. With anhydrite as setting regulator, the amorphous AFm retention time is prolonged, and the endothermal peaks produced by amorphous AFm during DSC–MS measurement correspond to 80–160 and 830–910 °C, losing H₂O and SO₂ respectively.