Determination of activation effect of Ca(OH)<Subscript>2</Subscript> upon the hydration of BFS and related heat by isothermal calorimeter

Isothermal conduction calorimetry, differential thermal analysis (DTA)–thermogravimetric analysis (TG) analysis, and SEM observations have proved the activation effect of Ca(OH)₂ released from the C₃S hydration upon blast furnace slag (BFS). Five sample mixtures of BFS and C₃S and two samples of pure BFS and C₃S were submitted to reaction with water inside the calorimeter at room temperature. The values of hydration heat were recorded up to 7 days. Samples were stored in humidity during 28 days and then were submitted to DTA–TG and SEM analysis. The effect of Ca(OH)₂ upon heat evolution of sample mixtures has been quantified and its influence upon the formation of new hydrates and microstructure of pastes was evidenced.     

Crystallization and Phase Stability of CaSO<Subscript>4</Subscript> and CaSO<Subscript>4</Subscript> – Based Salts

Summary.  Calcium sulfate occurs in nature in form of three different minerals distinguished by the degree of hydration: gypsum (CaSO₄·2H₂O), hemihydrate (CaSO₄·0.5H₂O) and anhydrite (CaSO₄). On the one hand the conversion of these phases into each other takes place in nature and on the other hand it represents the basis of gypsum-based building materials. The present paper reviews available phase diagram and crystallization kinetics information on the formation of calcium sulfate phases, including CaSO₄-based double salts and solid solutions. Uncertainties in the solubility diagram CaSO₄–H₂O due to slow crystallization kinetics particularly of anhydrite cause uncertainties in the stable branch of crystallization. Despite several attempts to fix the transition temperatures of gypsum–anhydrite and gypsum–hemihydrate by especially designed experiments or thermodynamic data analysis, they still vary within a range from 42–60°C and 80–110°C. Electrolyte solutions decrease the transition temperatures in dependence on water activity. Dry or wet dehydration of gypsum yields hemihydrates (α-, β-) with different thermal and re-hydration behaviour, the reason of which is still unclear. However, crystal morphology has a strong influence. Gypsum forms solid solutions by incorporating the ions HPO₄ ²⁻, HAsO₄ ²⁻, SeO₄ ²⁻, CrO₄ ²⁻, as well as ion combinations Na⁺(H₂PO₄)⁻ and Ln³⁺(PO₄)³⁻. The channel structure of calcium sulfate hemihydrate allows for more flexible ion substitutions. Its ion substituted phases and certain double salts of calcium sulfate seem to play an important role as intermediates in the conversion kinetics of gypsum into anhydrite or other anhydrous double salts in aqueous solutions. The same is true for the opposite process of anhydrite hydration to gypsum. Knowledge about stability ranges (temperature, composition) of double salts with alkaline and alkaline earth sulfates (esp. Na₂SO₄, K₂SO₄, MgSO₄, SrSO₄) under anhydrous and aqueous conditions is still very incomplete, despite some progress made for the systems Na₂SO₄–CaSO₄ and K₂SO₄–CaSO₄–H₂O. Corresponding author. E-mail: daniela.freyer@chemie.tu-freiberg.de Received December 17, 2002; accepted January 10, 2003 Published online April 3, 2003     

Hydration mechanisms of supersulfated cement

Considerable attention has been given to special cements, capable of reducing CO₂ emissions, energy and limestone consumption. Supersulfated cements are made of blast furnace slag (GBFS), calcium sulfate (CS), and small quantities of activator, but achieving their optimal proportions is complex. In this paper, the effects of the both CS and alkali activator (KOH) contents were studied. The main results showed that the compressive strength, heat of hydration, and consumption of anhydrite phase were strongly influenced by the alkaline content, while low calcium sulfate or alkaline content increased the formation of CSH. The instability of ettringite was verified: with low CS, the probable hypothesis was its conversion into monosulfate due to the scarcity of sulfate; with high CS, it was associated with intense, rapid consumption of anhydrite with high KOH content, followed by the precipitation of ettringite on the surface of slag grains and its conversion into monosulfate.     

Isotopic analysis of243Cm and244Cm by internal conversion electron spectrometry

The electrodeposition of uranium and trace quantities of²³⁹Pu,²³⁴Th,¹⁴⁴Ce on a stainless steel disk has been investigated from 0.5–2.0M NaOH and the two-phase system: extract of actinides in TBP-aqueous solution of NaOH. The electrodeposition yield of the above elements reaches 98–100% in 40 min of electrolysis with current density 0.4–0.5 A/cm². The presence of 0.5M Na₂CO₃, 2.0M NaNO₃, 2.0M NaNO₂, 0.2M NaF in alkaline solutions does not decrease the electrodeposition yield. The electrodeposited films meet all the requirements of -spectrometry. The uranium oxidation states (V) and (IV) have been determined in the electrodeposited films.     

Chromatographic studies of metal complexes. Part VI. Investigation of the effect of electrolytes on thin-layer chromatography

The octahedral cationic Co^III complexes [Co(ida)(bigH)₂]⁺, [Co(glyO)(bigH)₂]²⁺, [Co(α-alanO)(bigH)₂]²⁺, [Co(β-alanO)BigH)₂]²⁺ and Co(PhbigH)₃]³⁺, where idaH₂=iminodiacetic acid, glyOH=glycine, α-alanOH=α-alanine, β-alanOH=β-alanine and PhbigH=phenylbiguanide, were studied by thin-layer chromatography on silica gel in solutions of different electrolytes (NaCl, NaBr, NaI, Na₂SO₄, Na₂S₂O₃, NaNO₂ and NaNO₃). Among other factors, the movement of the cationic complexes was found to be dependent on the surface tension and equivalent conductance of the developer electrolyte.     

Investigations of cement early hydration in the presence of chemically activated fly ash

The paper describes an attempt of chemical activation of fly ash and claims the usefulness of combination of such investigation methods as calorimetry and infrared absorption for investigations of early periods of cement hydration. The research samples were cement pastes made with an addition of fly ash and admixtures of chemical activators, CaCl₂, Na₂SO₄ and NaOH, whereas a cement paste without fly ash addition and a cement-fly ash paste (both without admixtures) were used as reference samples. In order to investigate early periods of cement pastes hydration, the amount and rate of heat release were registered, and IR spectrums were checked at appointed hydration moments. As a result, it was shown that the combination of calorimetric and IR absorption methods in the investigations of early periods of cement hydration was useful. It was confirmed that the use of chemical activators CaCl₂, Na₂SO₄ and NaOH accelerated the hydration of cement pastes containing fly ash additive in early hours after adding water. The action of activators on hydrating cement system is different for each of investigated compounds.     

Sugarcane Bagasse Mild Alkaline/Oxidative Pretreatment for Ethanol Production by Alkaline Recycle Process

In order to decrease the alkali and water consumptions in the sugarcane bagasse alkaline/oxidative pretreatment for ethanol production, an alkaline recycle process was carried out. Two recycles of NaOH/H₂O₂ pretreatment did not decrease the pretreatment and enzymatic hydrolysis efficiencies and the consumptions of NaOH and water would be saved by 26% and 40%, respectively. A simultaneous saccharification and fermentation (SSF) culture with pretreated bagasse as substrate was developed giving 25 g ethanol l⁻¹ with a yield of 0.2 g g⁻¹ bagasse and productivity of 0.52 g l⁻¹ h⁻¹.     

Investigation on mechanical properties, durability and micro-structural development of steel slag blended cements

To improve the properties of steel slag blended cements, a chemical activator was added into blended cements, the mechanical properties and durability of steel slag blended cements were investigated. The results show that steel slag in blended cement pastes presents low hydraulic activity and makes practically no contribution to strength development. After the addition of chemical activator, the mechanical properties and durability of ternary blended cements are increased significantly. The hydration process and micro-structural development of blended cement was investigated by isothermal calorimeter and scanning electric microscope, respectively. Steel slag started hydration in the first 3?days in the presence of chemical activator, steel slag and granulate blast furnace slag reacted with Ca(OH)₂ to form a dense microstructure as curing proceeded. Therefore, both early and late compressive strengths of steel slag blended cement with 35% cement clinker and 30% steel slag can be comparable with those of Portland cement.     

Study of the hydration of Portland cement blended with blast-furnace slag by calorimetry and thermogravimetry

The hydration of ordinary Portland cement (OPC) blended with blast-furnace slag (BFS) is a complex process since both materials have their own reactions which are, however, influenced by each other. Moreover, the effect of the slag on the hydration process is still not entirely known and little research concerning the separation of both reactions can be found in the literature. Therefore, this article presents an investigation of the hydration process of mixes in which 0–85% of the OPC is replaced by BFS. At early ages, isothermal, semi-adiabatic and adiabatic calorimetric measurements were performed to determine the heat of hydration. At later ages, thermogravimetric (TG) analyses are more suitable to follow up the hydration by assessment of the bound water content w _b. In addition, the microstructure development was visualized by backscattered electron (BSE) microscopy. Isothermal calorimetric test results show an enhancement of the cement hydration and an additional hydration peak in the presence of BFS, whilst (semi-)adiabatic calorimetric measurements clearly indicate a decreasing temperature rise with increasing BFS content. Based on the cumulative heat production curves, the OPC and BFS reactions were separated to determine the reaction degree Q(t)/Q _∞ (Q = cumulative heat production) of the cement, slag and total binder. Moreover, thermogravimetry also allowed to calculate the reaction degree by w _b(t)/w _b∞. The reaction degrees w _b(t)/w _b∞, Q(t)/Q _∞ and the hydration degrees determined by BSE-image analysis showed quite good correspondence.     

Effect of wet spinning parameters on the properties of novel cellulosic fibres

Novel cellulose fibres (Biocelsol) were spun by traditional wet spinning technique from the alkaline solution prepared by dissolving enzyme treated pulp directly into aqueous sodium zincate (ZnO/NaOH). The spinning dope contained 6 wt.% of cellulose, 7.8 wt.% of sodium hydroxide (NaOH) and 0.84 wt.% of zinc oxide (ZnO). The fibres were spun into 5% and 15% sulphuric acid (H₂SO₄) baths containing 10% sodium sulphate (Na₂SO₄). The highest fibre tenacity obtained was 1.8 cNdtex⁻¹ with elongation of 15% and titre of 1.4 dtex. Average molecular weights and shape of molecular weight distribution curves of the celluloses from the novel wet spun cellulosic fibre and from the commercial viscose fibre were close to each other.     

Retention of phosphates from aqueous solutions with in sol–gel-derived amorphous CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system as a model of blast furnace slag

The article proposes new possibilities for the estimation of the maximum phosphate retention capacities (PRC) in blast furnace slags using their modeling. The amorphous blast furnace slag model (BFS–SG) and slag samples along the joining of the CaO:SiO₂ = 1 and (CaO + MgO):SiO₂ = 1 of the CaO–MgO–Al₂O₃–SiO₂ phase diagram were prepared by the sol–gel method. The surface analysis of BFS–SG was performed and the results were compared with real BFS. Batch adsorption experiments were performed to evaluate the phosphate removal of slags. SEM analysis and Raman spectroscopy were used to identify phosphate adsorbed forms. Phosphate retention is realized by the surface reactions of hydration products resulting in a nanostructured Ca-hydroxyapatite. The acid–base properties of the model samples in the selected cross-sections were characterized by the values of the optical basicity. An excellent linear relation between the phosphorus retention capacity (PRC) and the optical basicity of the model samples was found, which allows an estimation of slag retention capacities and the forms of adsorbed phosphorus.     

Deposition of cesium and cobalt sorbed on zeolite in matrices of blast furnace slag

¹³⁷Cs and⁶⁰Co were sorbed from model solutions and waste water on chemically treated granular zeolite. The zeolite was incorporated into cement slurries based on blast furnace slag (BFS). The compressive and bending strength were measured after different times of hydration. The leaching tests were performed in water, base and acid solutions. The leachability was more pronounced only for samples in acidic solutions.     

Kinetic studies on the dehydration of trans-dichlorotetrammine-cobalt (III) iodate dihydrate

Summary The dehydration of trans-[Co(NH₃)₄Cl₂)IO₃·2H₂O was studied isothermally by t.g.a. In the 0.1 < α < 0.8 range, where α is the fraction of the reaction complete, most of the runs gave the best fit to a second order rate law. Early stages of the reaction appear to follow a rate law based on reaction order while later stages (0.3 < α < 0.5) appear to be controlled by diffusion of H₂O. The reaction in the 0.1 < α < 0.3 range gave a best fit to a third order rate law, while the 0.3 < α < 0.5 range gave the best fit to a three dimensional control rate law. The activation energy for the overall reaction was ca. 103 kJ mol⁻¹. For α < 0.3 the activation energy was ca. 79.9 kJ mol⁻¹, but for 0.3 < α < 0.5 it was ca. 110 kJ mol⁻¹.     

Dispersion behavior of oleic acid in aqueous media: from micelles to emulsions

 Dispersion behavior of aqueous solutions containing oleic acid (RH), sodium oleate (R^-Na⁺), and NaCl was investigated by turbidity and dynamic light-scattering measurements. Changes of the size of scattering particles in solution composed of 1 mM oleic acid and 100 mM NaCl were traced as a function of the degree of ionization α, in terms of radius of the equivalent hydrodynamic sphere. Large associated micelles with a radius of 30 nm appeared by a slight decline of α and existed at α higher than 0.75. They were responsible for the three-phase equilibrium (solution, micelle and aggregated micelle, and acid–soap, (R^-Na⁺)₃RH) characterized by a constant pH of 9.75. The appearance of a new phase, (R^-Na⁺)₃RH, contributed to increase both the turbidity and averaged scattering particle size. As the breakdown of the three-phase equilibrium, radius of scattering particles increased significantly. Finally, oleic acid oil droplets were separated from aqueous phase at low α. When the system was buffered by tris(hydroxymethyl)aminomethane (Tris), scattering particles with a weight-averaged hydrodynamic radius of 75 nm existed in a wide range of α from 0.85 to 0.65. In Tris buffered solution, turbidity formation was induced by the increase in the number of aggregated particles. Received: 12 November 1996 Accepted: 4 April 1997     

Capillary zone electrophoresis to study the humic fraction in organic soils and its relationship with radiocaesium mobility

Humic acids and associated radionuclides were extracted from several soil samples with a significant organic matter content, such as peaty soils and forest soil layers. Extractions were made using two alkaline solutions (Na₄P₂O₇ 0.1 mol·1^–1 and NaOH 0.1 mol·1^–1 under N₂). The humic acid content in the extract was determined by the capillary zone electrophoresis technique (CZE) and associated radiocaseium was determined by gamma spectrometry. After analizing a large number of samples and studying the relationship between humic acid and organic matter content it was possible to conclude that the CZE technique may be a good alternative to classical techniques in humic acid determinations, with NaOH extractions leading to higher results than Na₄P₂O₇. Furthermore, the quantification of the radiocaseium desorbed by applying different extractant reagents (NaOH, Na₄P₂O₇, NH₄AcO and CaCl₂) showed that there may be some organic matter-radionuclide interations, other than those originated by humic acids. which may govern radionuclide retention in soils with a high content of organic matter.     

Kinetic Analysis of Thermal Decomposition of Ca(OH)2 Formed During Hydration of Commercial Portland Cement by DSC

In this paper, evaluation of kinetic parameters (the activation energy – E,the pre-exponential factor – A and the reaction order – n) with simultaneous determination of the possible reaction mechanism of thermal decomposition of calcium hydroxide (portlandite), Ca(OH)₂ formed during hydration of commercial Portland-slag cement, by means of differential scanning calorimetry (DSC) in non-isothermal conditions with a single heating–rate plot has been studied and discussed. The kinetic parameters and a mechanism function were calculated by fitting the experimental data to the integral, differential and rate equation methods. To determine the most probable mechanism, 30 forms of the solid-state mechanism functions, f(α_c) have been tried. Having used the procedure developed and the appropriate program support, it has been established that the non-isothermal thermal decomposition of calcium hydroxide in the acceleratory period (0.004<α_c<0.554) can be described by the rate equation: d α_c/dT=A/βexp(−E/RT)f(α_c), which is based on the concept of the mechanism reaction:f(α_c)=2(α_c)^1/2. The mechanism functions as well as the values of the kinetic parameters are in good agreement with those given in literature. This revised version was published online in August 2006 with corrections to the Cover Date.     

Peculiarities of the preparation of copolymers of acrylamide with sodium acrylate in inverse emulsions

The polymerization of acrylamide (AA) in inverse emulsions in the presence of saponifying agents (NaOH and Na₂CO₃) and potassium persulphate at 30–50° has been investigated. The rates of the polymerization and alkaline hydrolysis increase with increasing concentration of saponifying agents, AA, initiator and temperature. The molecular weight of copolymers decreases with increasing concentration of saponifying agents for polymerization in water-toluene emulsions and in aqueous solutions. It has been shown that the alkaline hydrolysis in inverse emulsions polymerization of AA is a second-order reaction, with rate proportional to both the amide and the alkaline agent concentrations. The effective overall energies of activation of the alkaline hydrolysis were 57.5 (in the presence of NaOH) and 57.0 kJ/mol (in the presence of Na₂CO₃).     

Influence of alkaline earth oxides on thermal stability of oxyfluoride glass

A new type of glass from the Na₂O–MeO–Al₂O₃–SiO₂–LaF₃ system where MeO = MgO, CaO, BaO and SrO has been studied. The aim of the investigation was to determine, by means of thermal techniques (DTA and DSC), the influence of alkaline earth ions additions on its thermal stability and the ability of LaF₃ phase to crystallization. The effect of LaF₃ crystallization was analyzed in connection with glass composition expressed by the Al₂O₃/(MeO + Na₂O + 3La₂F₆) ratio varying from 0.4 to 0.8 for the alkaline earth admixtures. The compositions of the glasses have been designed so as to make it possible to define the effect of the charge of the ion modifiers (Na⁺, Me²⁺, La³⁺) on the alumina position in the framework of the glass. Two series of glasses were obtained with a different F⁻ content. The formation of LaF₃ depends directly on the strength of the network and can be control by the Al₂O₃/modifiers ratio as well as the content of fluorine ions. Generally, it can be stated that transparent glass-ceramic with nanocrystallization of LaF₃ can be obtained for Al₂O₃/(Na₂O + MeO + 3La₂F₆) ≤0.6 in the examined glasses. The more the ionicity of the alkaline earth ions the greater the tendency for the crystallization of Me₂LaF₇ and MeF₂. In the glass structure the substitution of oxygen ions by F⁻ ions facilitated the crystallization of LaF₃. Simultaneously, it influenced the thermal stability of the aluminosilicate network and induced the crystallization of appropriate silicates during the heat treatment.     

Solubility and Ionic Processes in the Cu X 2? MX ?H2O ( X ?=Cl?, Br?; M +=Li+, Na+, K+, NH4+, Cs+) Systems

 Solubility isotherms in the CuBr₂−MBr−H₂O (M ⁺ = Li⁺, Na⁺, Cs⁺) systems at 298.15 K were measured. The results together with other available literature data for copper chloride and bromide systems were treated by hydration analysis, and comparative discussion of ionic processes taking place in the respective saturated solutions was performed.     

Selective exchange of strontium in an aluminum pillared montmorillonite

The selective uptake of strontium by a specially tailored aluminum pillared montmorillonite was investigated. Selective exchange kinetics revealed a fast component of the order of less than one hour, while exchange isotherms revealed the preference for strontium uptake over sodium and calcium with separation factors α _Na ^Sr =50 and α _Ca ^Sr =2. In an environment of rumen liquid taken from slaughtered sheep, 26% of strontium was removed by 1 g and 40% by 3 g of material.