Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed and that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.     

The role of alumina on performance of alkali-activated slag paste exposed to 50 °C

The strength and microstructural evolution of two alkali-activated slags, with distinct alumina content, exposed to 50 °C have been investigated. These two slags are ground-granulated blast furnace slag (containing 13% (wt.) alumina) and phosphorous slag (containing 3% (wt.) alumina). They were hydrated in the presence of a combination of sodium hydroxide and sodium silicate solution at different ratios. The microstructure of the resultant slag pastes was assessed by X-ray diffraction, differential thermogravimetric analysis, and scanning electron microscopy. The results obtained from these techniques reveal the presence of hexagonal hydrates: CAH₁₀ and C₄AH₁₃ in all alkali-activated ground-granulated blast-furnace slag pastes (AAGBS). These hydrates are not observed in pastes formed by alkali-activated ground phosphorous slag (AAGPS). Upon exposure to 50 °C, the aforementioned hydration products of AAGBS pastes convert to C₃AH₆, leading to a rapid deterioration in the strength of the paste. In contrast, no strength loss was detected in AAGPS pastes following exposure to 50 °C.     

Mechanical performance and microstructure of the calcium carbonate binders produced by carbonating steel slag paste under CO2 curing

Calcium carbonate binders were prepared via carbonating the paste specimens cast with steel slag alone or the steel slag blends incorporating 20% of Portland cement (PC) under CO₂ curing (0.1 MPa gas pressure) for up to 14 d. The carbonate products, mechanical strengths, and microstructures were quantitatively investigated. Results showed that, after accelerated carbonation, the compressive strengths of both steel slag pastes and slag-PC pastes were increased remarkably, being 44.1 and 72.0 MPa respectively after 14 d of CO₂ curing. The longer carbonation duration, the greater quantity of calcium carbonates formed and hence the higher compressive strength gained. The mechanical strength augments were mainly attributed to the formation of calcium carbonate, which caused microstructure densification associated with reducing pore size and pore volume in the carbonated pastes. In addition, the aggregated calcium carbonates exhibited good micromechanical properties with a mean nanoindentation modulus of 38.9 GPa and a mean hardness of 1.79 GPa.     

Hydration studies of calcium sulfoaluminate cements blended with fly ash

The main objective of this work is to study the hydration and properties of calcium sulfoaluminate cement pastes blended with fly ash (FA) and the corresponding mortars at different hydration ages. Laboratory X-ray powder diffraction, rheological studies, thermal analysis, porosimetry and compressive strength measurements were performed. The analysis of the diffraction data by Rietveld method allowed quantifying crystalline phases and overall amorphous contents. The studied parameters were: i) FA content, 0, 15 and 30 wt.%; and ii) water addition, water-to-CSA mass ratio (w/CSA = 0.50 and 0.65), and water-to-binder mass ratio (w/b = 0.50). Finally, compressive strengths after 6 months of 0 and 15 wt.% FA [w/CSA = 0.50] mortars were similar: 73 ± 2 and 72 ± 3 MPa, respectively. This is justified by the filler effect of the FA as no strong evidences of reactivity of FA with CSA were observed. These results support the partial substitution of CSA cements with FA with the economic and environmental benefits.     

Fabrication and properties of thermal insulating material using hollow glass microspheres bonded by aluminum–chrome–phosphate and tetraethyl orthosilicate

Thermal insulation material made by hollow glass microspheres (HGM) with different content of aluminum–chrome–phosphate solution (ACP) and tetraethyl orthosilicate (TEOS) as binders was formed, dried and sintered at 250 °C, 450 °C or 650 °C for 2 h. Properties such as density, compressive strength, thermal conductivity and microstructure of the specimens were determined. It is found that TEOS improved the distribution of ACP and increased the compressive strength of the specimens. HGM bonded by appropriate amount of ACP and TEOS achieved preferable value of density, compressive strength and thermal conductivity which were significant for thermal insulation materials. The compressive strength of specimens sintered at 450 °C and 650 °C was higher than that of the specimens sintered at 250 °C.     

Effect of substitution of granulated slag by air-cooled slag on the properties of alkali activated slag

This article assesses the mechanical and durability performance of replacement of GBFS by ACS activated by 3:3 NaOH:Na₂SiO₃ (3:3 SH:SSL) wt% (at optimum value 6 wt%) mixed with sea water (SW) and cured at 100% R.H. at room temperature. The kinetic behavior of activated GBFS-ACS mixes was measured by determination of setting time, combined water, bulk density and compressive strength up to 90 days. The rate of activation of the AAS has been studied from some selected samples by FT-IR, TGA, DTG analysis and SEM techniques. The compressive strength of dried activated GBFS-ACS pastes in comparison with saturated GBFS-ACS pastes up to 90 days was determined. The results revealed that the blended pastes of 80% GBFS+20% ACS gives the higher combined water, bulk density and compressive strength than those of 40/60 and 60/40% GBFS/ACS and lower than the 100% GBFS up to 90 days. Also, the compressive strength of dried samples at 105 °C for 24 h activated by (3:3 SH:SSL) mixed with SW and cured in 100% R.H. at room temperature up to 90 days is greater than saturated samples cured at the same conditions. On increasing the amount of ACS up to 40%, the setting time decreases then increases at 60% but still shorter than 100% GBFS. Finally, ACS can be used as partial substitution of GBFS in AAS.     

Recycled granulate obtained from waste alumina-rich refractory powder by the cold bonding process

Within the scope of the present study the cold-bonding process was used for the recycling of waste filter powder which was mixed with two different binders in different concentrations; alumino-silicate cement and potassium water glass, and combinations of these two materials, and hardened at room temperature. Selected samples were also fired at 1200 °C. Tests to determine tensile and compressive strength, density and porosity, as well as dilatometry and SEM analyses, were performed. As expected, compressive strength increased as a function of the concentration of the potassium water glass. When combinations of both binders were used, compressive strengths were higher, but a significant increase in strength was also achieved by firing the samples. The compressive strengths of the non-fired samples were in the range from 0.8 to 2.4 MPa, whereas after firing strengths of up to 36 MPa were obtained. During the firing density increased, and porosity was reduced, while the average pore size increased. The results of dilatometric analysis showed that the granulate produced with cement shrink upon firing up to 300 °C, but then start slowly to expand, whereas the granulate produced by water glass first expanded on firing up to 800 °C, and then began to shrink swiftly. In the case of combinations of the two binders, shrinkage as well as expansion on firing was less pronounced. Selected granulate prepared using potassium water glass were also tested in a refractory concrete matrix in order to verify their usability.     

New insights into water bonding during early tricalcium silicate hydration with quasielastic neutron scattering

New information on the water bonding during the first 36 h of hydration of tricalcium silicate was obtained using the high neutron flux at the sample position of the time-of-flight spectrometer (TOFTOF), FRM II in Garching, Germany, together with ²⁹Si NMR and X-ray diffraction measurements. A rapid increase in the amount of constrained water was observed at the beginning of the induction period. This is attributed to the formation of an early C-S-H with a large specific surface area (around 800 m²/g). During subsequent hydration, the amount of constrained water, as given by the total surface area of the hydration products, is controlled by (a) the formation of new metastable early C-S-H which increases total surface area and (b) polymerisation processes which reduce total surface area. The relative contribution of these processes varies during hydration.     

Reactivity and phase composition of Ca2SiO4 binders made by annealing of alpha-dicalcium silicate hydrate

This study investigates the production of highly reactive dicalcium silicate Ca₂SiO₄ (C₂S).To that end, binders were synthesised by annealing of alpha-dicalcium silicate hydrate (α-C₂SH) between 400 and 800 °C. Two different heating sequences were tested. The phase compositions were determined by means of XRD. Depending on the annealing temperature and the heating conditions the cementitious materials consist of an X-ray-amorphous content as well as x-Ca₂SiO₄ (x-C₂S) and γ-Ca₂SiO₄ (γ-C₂S). The hydration kinetics of some selected binders were investigated by means of isothermal calorimetry. The specific reactivity of the phases produced by means of annealing was determined during the first 40 h of hydration by use of XRD and TGA.The resulting binders show the highest reactivity when low annealing temperatures (< 500 °C) were used. After 72 h, degrees of hydration of about 89% are achieved. The most reactive component is the X-ray-amorphous content, followed by x-C₂S.     

Properties and durability of alkali-activated slag pastes immersed in sea water

This paper represents the experimental trials to activate blast-furnace slag to produce cementless binding materials. The aims of the work is to study the properties of activated slag mixed with sodium hydroxide and sodium silicate liquid 6 wt% of granulated slag. Also, studying the effect of mixing water (tap and sea water) on the kinetic of activation. The rate of activation of the alkali activated slag (AAS) has been studied by FTIR, TGA, DTG and SEM techniques. The results revealed that the increase of NaOH content and mixing with sea water increase the combined water up to 90 days. On the other hand, the bulk density and compressive strength was increased by increasing Na₂SiO₃ content in presence of NaOH. The activated granulated slag showed good durability in sea water, i.e., the compressive strength increased gradually with immersing time up to 12 months. Whereas, the strength of sulfate resisting cement (SRC) pastes immersed in sea water increases up to 6 months then decreases up to one year. Therefore, it can be concluded that alkali activated slag are more durable in sea water than SRC pastes.     

Alkali activation of a novel calcium‐silicate hydraulic binder with CaO/SiO2 = 1.1

A quasi‐amorphous low‐calcium‐silicate hydraulic binder, with an overall CaO/SiO₂ (C/S) molar ratio of 1.1, was produced. This cementitious material was then hydrated with aqueous solutions containing 3 wt% alkalis (either NaOH, Na₂CO₃ or Na₂SiO₃). The evolution of the hydration processes of the samples were monitored by compressive strength testing, XRD, FTIR, ²⁹Si and ²⁷Al MAS NMR, isothermal calorimetry and TGA. It was found that the nearly exclusive hydration product formed was a C‐S‐H phase with a semi‐crystalline structure. More importantly, the paste prepared with the Na₂SiO₃ solution developed compressive strength values similar to those of ordinary portland cements (OPC) with faster early age kinetics. In addition, the isothermal calorimetry results indicated that these new hydraulic binders present much lower heat of hydration values compared with a traditional OPC. The results presented here open the possibility of producing cement with a compressive strength comparable to that of OPC but with lower CO₂ emissions during the production process and with lower hydration heat related problems during the production of concrete structures.     

Chemistry of cement hydration in polymer-modified pastes containing lead compounds

The role of polymeric additives on the hydration process of cement pastes admixed with a lead compound (Pb₃O₄) was investigated. Three series of pastes were prepared: the reference series, mixing water with Ordinary Portland Cement (OPC), and two series in which whether a styrene–butadiene rubber latex or a superplasticiser based on acrylic-modified polymer was added to the pastes. For each series, 5 and 10 wt% of Pb were mixed with the pastes. Phase analysis and microstructural characterisation were carried out by means of X-ray powder diffraction and SEM–EDX. Thermogravimetric analysis was performed to monitor the hydration degree of the three pastes; indeed, quantitative determination of portlandite and calcite was performed.Dynamic leach tests were performed on solidified monoliths to evaluate the effective immobilisation of Pb₃O₄. After 384 h leaching, excellent results were obtained by pastes mixed with superplasticiser that showed a cumulative release of Pb equal to 0.62 mg/l for samples containing 5 wt% of Pb, and equal to 0.84 mg/l for samples bearing 10 wt% of Pb.     

Evidence for anomalous water vapor sorption kinetics in cement based materials

We used dynamic sorption balance measurements to evaluate the diffusivity for cement pastes with three different binders (OPC, OPC + 70% slag, OPC + 10% silica fume). The diffusion of water vapor in cement based materials is normally assumed to follow Fick's law of diffusion, but our results clearly show that Fick's law cannot completely describe the sorption process in our materials. In this paper we report the evidence for this anomalous sorption behavior and discuss a possible method to evaluate diffusivities from such measurements.     

C4A3Š hydration in different alkaline media

This study explored the behaviour of laboratory-synthesised calcium sulphoaluminate (C₄A₃Š) in alkaline media. C₄A₃Š was hydrated in three liquid media: water, 8-M NaOH and 4 (wt.%) Na₂CO₃ added to the C₄A₃Š + water mix. Hydration kinetics were studied via isothermal conduction calorimetry and 2- and 28-day mechanical strength values were found. The reaction products were characterised with XRD and FTIR. The findings showed that whilst C₄A₃Š hydration kinetics were accelerated in the presence of alkalis, the resulting pastes had lower mechanical strength than the pastes hydrated with water and exhibited severe decay in some cases. An analysis of the hydration products revealed the presence of ettringite in the water-hydrated C₄A₃Š pastes, whereas under alkaline conditions the main calcium sulphoaluminate hydrate detected was U phase.     

Clay reactivity: Production of alkali activated cements

This study has assessed the suitability of dehydroxylated (5 h at 750 °C) red, white and ball clays for the use as prime materials in the production of alkaline cements. The analytical methodology applied to quantify their potentially reactive phases included selective chemical attack, which was also used in conjunction with subsequent ICP analysis of the resulting leachate to determine their reactive SiO₂/Al₂O₃ ratios. These results were compared with compressive strength values of the respective pastes activated with an 8-M NaOH solution and cured at 85 °C and 90% RH for 20 h. It was observed that when the reactive phase content was above 50%, the reactive SiO₂/Al₂O₃ ratio in the starting materials had a larger impact than the amount of reactive phase on the developed strength of the cement material. In this context, fly ash was used as the reference material. Finally, to verify the accuracy of the results, a binder consisting of 70 wt.% fly ash and 30 wt.% dehydroxylated clay was activated with an 8-M NaOH solution. The reactivity of this cement was determined by chemical attack with 1:20 HCl (v/v) and the reaction products were characterised by powder X-ray diffraction and ²⁹Si MAS NMR spectroscopy.     

Synthesis of fly ash based geopolymer mortar considering different concentrations and combinations of alkaline activator solution

Geopolymerisation is a process that can transform alumina and silica rich waste materials into valuable binding materials, having excellent mechanical properties. The present experimental study shed a light on the variation in compressive strength of fly ash based geopolymer mortar by varying the molarity of sodium hydroxide as 12 M, 14 M, 16 M and accompanying by sodium silicate (Na₂SIO₃) in 2:1 (Na₂SIO₃/ NaOH) with same molarities. All the geopolymer mixes were oven cured at 80 °C for 24 h and after that kept at room temperature up to the time of testing. The compressive strength was checked subsequently at the ages of 3, 7, 14 and 28 days. The experimental results reveal that the addition of sodium silicate enhances the strength development in geopolymer mortar. The ultimate compressive strength of 40.42 MPa was obtained by incorporating sodium silicate along with 16 M concentrated sodium hydroxide. Furthermore, increasing trend of the compressive strength was found with increasing molar concentration of sodium hydroxide and curing period.     

Internal curing by superabsorbent polymers in ultra-high performance concrete

To limit self-desiccation and autogenous shrinkage that may lead to early-age cracking of ultra-high performance concrete (UHPC), internal curing by means of superabsorbent polymers (SAP) may be employed. Cement pastes and UHPC with water-to-cement ratio below 0.25, with or without SAP, were studied. The absorption capacity of a solution-polymerized SAP was first determined on hardened cement pastes by SEM image analysis. It was observed that the SAP cavities become partially filled with portlandite during cement hydration. Isothermal calorimetry showed that water entrainment with SAP delays the main hydration peak, while after a couple of days it increases the degree of hydration in a manner similar to increasing the water-to-cement ratio. Internal curing by SAP is effective in reducing the internal relative humidity decrease and the autogenous shrinkage. Although the mechanical properties are affected by SAP addition, it is possible to reach compressive strengths of almost 150 MPa at 28 days.     

Development of a new rapid,relevant and reliable (R3) test method to evaluate the pozzolanic reactivity of calcined kaolinitic clays

The present paper introduces a new rapid, relevant and reliable (R³) test to predict the pozzolanic activity of calcined clays with kaolinite contents ranging from 0 to 95%. The test is based on the correlation between the chemical reactivity of calcined clays in a simplified system and the compressive strength of blends in standard mortar. The simplified system consists of calcined clay portlandite and limestone pastes with sulfate and alkali levels adjusted to reproduce the reaction environment of hydrating blended cements. The pastes were hydrated for 6 days at 20 °C or for 1 day at 40 °C. The chemical reactivity of the calcined clay can be obtained first by measurement of the heat release during reaction using isothermal calorimetry and second by bound water determination in a heating step between 110 °C and 400 °C.Very good correlations were found between the mortar compressive strength and both measures of chemical reactivity.     

Effect of mechanical activation on the hydraulic properties of stainless steel slags

This work aims to assess the possibility of using ladle metallurgy and argon oxygen decarburization stainless steel slag as a hydraulic binder after mechanical activation. Prolonged milling in ethanol suspension resulted in 10-fold increase of the surface area and increase of the amorphous phase. Calorimetric analysis of slags mixed with water indicated the occurrence of exothermic reactions. XRD results revealed that periclase, merwinite, γ-C₂S and bredigite, decreased with hydration time. Thermogravimetric analyses indicated that the main hydration products are most probably C–S–H, CH and MH. The hydrated products in both slags were similar to C–S–H gel. WDS analysis demonstrated Ca and Si to be widespread in the structure. Formation of M–S–H gel or incorporation of Mg in the C–S–H gel remains uncertain. The 90 days compressive strength of mortars prepared from slags reached approximately 20% for LM and 10% for AOD of the compressive strength of mortars prepared from OPC.     

Hydration of Portland cement with high replacement by siliceous fly ash

The effects of two different low calcium fly ashes on the hydration of ordinary Portland cement (OPC) pastes containing 50 wt.% of fly ash were investigated over a hydration time of 550 days. The results were compared with a reference blend of OPC containing 50 wt.% of inert quartz powder allowing the distinction between "filler effect" and pozzolanic reaction.Until 2 days, no evidence of fly ash reaction was measured and its influence on the hydration is mainly related to the “filler effect”. From 7 days on, the effects of the pozzolanic reaction were observed by the consumption of portlandite, the change of the pore solution chemistry, the formation of a presumably water-rich inner hydration product and the change of the C–S–H composition towards higher Al/Si ratio compared to the C–S–H of neat OPC. Additional strength due to the pozzolanic reaction developed after 28 days of hydration.