Hexavalent chromium in tricalcium silicate: Part I Quantitative X-ray diffraction analysis of crystalline hydration products

The hydration products of CrVI-doped tricalcium silicate (C3S) have been investigated. C3S is the main constituent of Portland cement responsible for the strength and stability of hardened Portland cement paste. Chromium trioxide (CrO3), added as a dopant to C3S, simulates hexavalent chromium waste that may be stabilized in ordinary Portland cement. X-ray diffraction was used to monitor the development of the hydration reaction products from the early stages to the late reaction stages. Leaching studies were carried out to evaluate the stability of the CrVI-containing phases in the hydrated C3S matrix.In monolithic waste forms containing hexavalent chromium, CaCrO4·2H2O was found to form within a few minutes of the hydration reaction. With increasing concentration of Ca2+ in the pore solution, Ca2CrO5·3H2O became the stable species. The chromium in this phase was found to be very mobile in a standard acetic acid leaching test.     

Solidification/stabilization of arsenic containing solid wastes using portland cement, fly ash and polymeric materials

Stabilization/solidification (S/S) is used as a pre-landfill waste treatment technology that aims to make hazardous industrial wastes safe for disposal. Cement-based solidification/stabilization technology is widely used because it offer assurance of chemical stabilization of many contaminants and produce a stable form of waste. The leaching behavior of arsenic from a solidified/stabilized waste was studied to obtain information about their potential environmental risk. Activated alumina (AA) contaminated with arsenic was used as a waste, which was stabilized/solidified (S/S) using ordinary portland cement (C), fly ash (FA), calcium hydroxide (CH) and various polymeric materials such as polystyrene and polymethyl methacrylate (PMMA). Toxicity characteristics leaching procedure (TCLP) and semi-dynamic leach tests were conducted to evaluate the leaching behavior of arsenic. Formations of calcite along with precipitate formation of calcium arsenite were found to be responsible for low leaching of arsenic from the stabilized/solidified samples. Effective diffusivity of arsenic ion from the matrix and leachablity index was also estimated. Minimum leaching of the contaminant was observed in matrix having AA+C+FA+CH due to the formation of calcite.     

Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.     

Investigation of the stability of hardened slag paste for the stabilization/solidification of wastes containing heavy metal ions

We have studied the effect of chromium ions and lead ions on the chemical stability of hardened slag paste with toxic wastes during the stabilization/solidification process. The influences of Cr and Pb ions on the hydration of slag were also investigated. Sodium silicate (Na(2)SiO(3)), 5 wt.% of slag, was used as an alkali activator for slag hydration. The physical stability of hardened paste containing partial replacement of slag with fly ash and gypsum was also examined.When gypsum was added to slag, the compressive strength of hardened slag paste developed, accompanying the activation of alumino-ferrite-tricalciumsulfate (Al(2)O(3)-Fe(2)O(3)-3CaSO(4), AFt) and alumino-ferrite-monocalciumsulfate (Al(2)O(3)-Fe(2)O(3)-CaSO(4), AFm) phase generation. Those phases caused densification of the microstructure. Concurrently, the leaching amount of heavy metal ions was decreased. When fly ash was added to slag, the compressive strength increased and the leaching amount decreased with both active formation of aluminate hydrates and ion substitution. Lead ions were mostly stabilized through physical encapsulation by the hardened slag paste's hydrate matrix. In the case of chromium ions, we observed that it was mainly solidified through the formation of a substitutional solid solution with aluminum atoms in the structure of aluminate hydrates.     

Stabilization/solidification of a municipal solid waste incineration residue using fly ash-based geopolymers

The stabilization/solidification (S/S) of a municipal solid waste incineration (MSWI) fly ash containing hazardous metals such as Pb, Cd, Cr, Zn or Ba by means of geopolymerization technology is described in this paper. Different reagents such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, kaolin, metakaolin and ground blast furnace slag have been used. Mixtures of MSWI waste with these kinds of geopolymeric materials and class F coal fly ash used as silica and alumina source have been processed to study the potential of geopolymers as waste immobilizing agents. To this end, the effects of curing conditions and composition have been tested. S/S solids are submitted to compressive strength and leaching tests to assess the results obtained and to evaluate the efficiency of the treatment. Compressive strength values in the range 1-9 MPa were easily obtained at 7 and 28 days. Concentrations of the metals leached from S/S products were strongly pH dependent, showing that the leachate pH was the most important variable for the immobilization of metals. Comparison of fly ash-based geopolymer systems with classical Portland cement stabilization methods has also been accomplished.     

Potential application of coal-fuel oil ash for the manufacture of building materials

In this paper coal-fuel oil ash has been characterized in terms of leaching behaviour and reactivity against lime and gypsum in hydratory systems for the manufacture of building materials. Its behaviour was also compared to that of coal ash. Metal release was measured in a dynamic leaching test with duration up to 16 days. The results have shown that coal-fuel oil ash behaves very similarly to coal ash. The reactivity of coal-fuel oil ash against lime and gypsum was measured in mixtures containing only lime and in mixtures containing both lime and gypsum. These systems were hydrated at 25 and 40 degrees C under 100% R.H. The results have shown that the main hydration products are the same as those that are usually formed in similar coal ash-based systems. That is, calcium silicate hydrate in coal-fuel oil ash/lime systems and calcium silicate hydrate plus calcium trisulphoaluminate hydrate in coal-fuel oil ash/lime/gypsum systems. From the quantitative point of view, hydration runs showed that the amounts of both chemically combined water and reacted lime measured in the case under investigation are very similar to those found in similar coal ash-based systems. Finally, the measurement of unconfined compressive strength proved that the systems have potentiality for the manufacture of pre-formed building blocks.     

Stabilization/solidification of hazardous and radioactive wastes with alkali-activated cements

This paper reviews progresses on the use of alkali-activated cements for stabilization/solidification of hazardous and radioactive wastes. Alkali-activated cements consist of an alkaline activator and cementing components, such as blast furnace slag, coal fly ash, phosphorus slag, steel slag, metakaolin, etc., or a combination of two or more of them. Properly designed alkali-activated cements can exhibit both higher early and later strengths than conventional portland cement. The main hydration product of alkali-activated cements is calcium silicate hydrate (CSH) with low Ca/Si ratios or aluminosilicate gel at room temperature; CSH, tobmorite, xonotlite and/or zeolites under hydrothermal condition, no metastable crystalline compounds such as Ca(OH)(2) and calcium sulphoaluminates exist. Alkali-activated cements also exhibit excellent resistance to corrosive environments. The leachability of contaminants from alkali-activated cement stabilized hazardous and radioactive wastes is lower than that from hardened portland cement stabilized wastes. From all these aspects, it is concluded that alkali-activated cements are better matrix for solidification/stabilization of hazardous and radioactive wastes than Portland cement.     

Thermal activation on calcium silicate slag from high-alumina fly ash: a technical report

The fly ash with alumina composition from 45 to 55 % has been found in China in last 10 years, which attracts great attention from Chinese government and related alumina industry. Chinese government and its state-owned enterprises have successfully extracted the Al as alloy product from the high-alumina fly ash. However, to recycle the calcium silicate slag as residue from the Al industry is still undetermined. In this report, an innovative process is introduced to achieve the regional sustainability for the high-alumina fly ash industry, and it is found that the cementitious material composed of calcium silicate slag met with the mechanical requirements of 32.5 cement for road pavement. The chemical and mineral analysis show that the calcium silicate slag has high CaO content, which reaches up to 48.64 %. C₂S and C₃A are the dominant mineral phases by XRD analysis indicating its potential pozzolanic activity during the hydration process. Thermal activation from 200 to 900 °C was applied to enhance its pozzolanic activity for the calcium silicate slag and it proved that 600 °C is the optimal calcination temperature due to the decomposition of calcite and clay minerals. Also the mineral phase amorphization was also observed during the XRD analysis, which might also contribute to the enhanced pozzolanic properties at 600 °C. Although the designed cementitious material contains a large quantity of solid waste, none of the hazardous heavy metals exceed the EPA limits. This short article originally reported a promising direction for managing solid waste for Al industry and enhancing utilization efficiency for the enterprise internal solid wastes.     

Use of sulfoaluminate cement and bottom ash in the solidification/stabilization of galvanic sludge

Solidification/stabilization (S/S) process can improve the physical characteristics of wastes, reduce their leaching and limit the solubility of their heavy metals. The identification of binders able to assume the fixation of contaminants is essential for the success of the technique. In this study, calcium sulfoaluminate cement was added to another waste, bottom ash, in order to treat galvanic sludge. The properties of the resultant solid matrix (MS) were determined: setting time, compressive strength and products of hydration. Solid matrix composed of 77% waste and only 23% cement presented initial setting time lower than 4 h and 28 day-strength of 6 MPa. SEM investigations showed that contaminants present in the galvanic sludge (Cr) were encapsulated in the hydrated phases and particles of bottom ash.     

Improvement of metakaolin on radioactive Sr and Cs immobilization of alkali-activated slag matrix

Effects of metakaolin on simulated radioactive Sr or Cs immobilizing behavior of alkali-activated slag (AAS) matrix were evaluated by cation exchange capacity (CEC), distribution ratio of selective adsorption, leaching test and porosity analyses. The results revealed that the additions of metakaolin into the AAS matrixes largely enhanced their distribution ratios K(d) of selective adsorption on Sr and Cs ions. Meanwhile, this new immobilizing matrix M-AAS showed the lowest leaching rate. Hydration product analyzes by XRD, DTA, FTIR and SEM demonstrated that (Na+Al)-substituted calcium silicate hydrate (CSH) and self-generated zeolite were major hydration products in the M-AAS matrix. These products have better Sr and Cs selective adsorption as compared to C-S-H without any substitution and natural zeolite minerals.     

Investigation into the stabilization/solidification performance of Portland cement through cement clinker phases

This research studied the influence of individual heavy metal on the hydration reactions of major cement clinker phases in order to investigate the performance of cement based stabilization/solidification (S/S) system. Tricalcium silicate (C3S) and tricalcium aluminate (C3A) had been mixed with individual heavy metal hydroxide including Zn(OH)2, Pb(OH)2 and Cu(OH)2, respectively. The influences of these heavy metal hydroxides on the hydration of C3S and C3A have been characterized by X-ray diffraction (XRD) and differential scanning calorimetry-thermogravimetry (DSC-TG). A mixture of Zn(OH)2, Pb(OH)2 and Cu(OH)2 was blended with Portland cement (PC) and evaluated through compressive strength and dynamic leach test. XRD and DSC-TG data show that all the heavy metal hydroxides (Zn(OH)2, Pb(OH)2 and Cu(OH)2) have detrimental effects on the hydration of C3A, but only Zn(OH)2 does to the C3S at early curing ages which can completely inhibit the hydration of C3S due to the formation of CaO(Zn(OH)2).2H2O. Cu6Al2O8CO(3).12H2O, Pb2Al4O4(CO3)(4).7H2O and Zn6Al2O8CO(3).12H2O are formed in all the samples containing C3A in the presence of metal hydroxides. After adding CaSO4 into C3A, the detrimental effect of heavy metals increases due to the coating effect of both calcium aluminate sulphates and heavy metal aluminate carbonates. The influence of heavy metal hydroxide on the hydration of C3S and C3A can be used to predict the S/S performance of Portland cement.     

Leaching behavior and immobilization of heavy metals in solidified/stabilized products

Solidification/stabilization (S/S) of hazardous sludge from steel processing plant has been studied. Mechanical strength and leaching behavior test of solidified/stabilized product was performed. Mechanical strength decreases with increase in waste content. Pb, Zn, Cu, Fe and Mn could be considerably immobilized by the solidification/stabilization process. The elements least immobilized were Na, K, and Cl. Leaching of heavy metals in the S/S matrix can be considered as pH dependent and corresponding metal hydroxide solubility controlled process. Geochemical modeling was performed for the prediction of speciation. On the basis of test results, mobility and mechanism of leaching was assessed. Dominant leaching mechanism was surface wash off in the initial stages followed by diffusion for Pb, Zn, Cu, Fe and Mn. Diffusion coefficient was above 11.5 indicating low mobility in the cement matrix.     

Stabilization of Cu in acid-extracted industrial sludge using a microwave process

The leaching concentration of copper ions from the industrial sludge that has been extracted using sulfuric acid may still exceed 15 mg/L, which is the leaching standard of the toxicity characteristic leaching procedure (TCLP) for hazardous waste in Taiwan. Therefore, the acid-extracted industrial sludge is still an important source of hazardous waste. Usually, hazardous waste in Taiwan must be solidified and passed through the TCLP test before it is disposed in a landfill. The aim of this study is to develop a microwave process to stabilize copper ions in the sludge to replace the use of traditional solidification. In this study, two parameters--the reaction time of the microwave process and the additive reagents--were considered. The efficiency of stabilization of the microwave process was evaluated from the result of the TCLP test. The results showed that the stabilization efficiency of copper ions obtained using a microwave process without any added reagent depends highly on the property of the original acid-extracted sludge. Under some conditions, the leaching concentrations were much lower than those of the raw sludge. In additive reagent systems, the results showed that iron powder promoted the stabilization of copper ions more than the other additives such as sodium carbonate and sodium silicate. The leaching concentration of copper ions decreased dramatically from 179.4 to 6.5mg/L below in the iron additive system.     

Examination of durable mortar from Hadrian's Wall

Abstract

Samples of a 1700 year old mortar infill from part of Hadrian's Wall have been analysed using optical and electron probe techniques. The analyses show that considerable quantities of calcium silicate hydrate were formed in the mortar and that much of this has remained uncarbonated. It is suggested that the calcium silicate hydrate is formed from the hydration of β-C₂S, this β-C₂S being formed during the firing of the limestone by the Roman engineers. The CaO/SiO₂ ratio of this hydrate is close to those found in modern calcium silicate hydrates.

MST/688     

SiO2基酸化剂高温消解转炉钢渣中游离CaO的研究

转炉钢渣中游离CaO的水化膨胀是导致转炉钢渣体积安定性不良的重要原因.通过高温配加SiO2基酸化弃,改变w(SiO2)/w(CaO)对转炉钢渣进行稳钙改质处理.利用化学检测分析、X射线衍射和场发射扫描电子显微镜对SiO2基酸化剂高温消解转炉钢渣中游离CaO的效果和特征进行研究.结果表明,改质后的转炉钢渣的w(SiO2)/w(CaO)在0.37以上,就能满足钢渣中f-CaO低于3％的水泥和混凝土行业使用标准,且消解率达到60％以上,而当w(SiO2)/w(CaO)为0.67时,f-CaO低于1％,且消解率达到90％以上;改质前后转炉钢渣的矿相组成有明显差异,改质后转炉钢渣以硅酸二钙、镁黄长石、镁铁尖晶石、磁铁矿和铁铝酸钙相为主,并且镁黄长石相随着w(SiO2)/w(CaO)的增大而增多;转炉钢渣酸化稳钙前f-CaO被紧密包裹在矿相基体中,高温酸化改质后,团簇状聚集的f-CaO颗粒会嵌在硅酸盐相间,无明显包裹现象,尺寸为0.5～2 μm.     

The utilization of thin film transistor liquid crystal display waste glass as a pozzolanic material

This investigation elucidates the pozzolanic behavior of waste glass blended cement (WGBC) paste used in thin film transistor liquid crystal displays (TFT-LCD). X-ray diffraction (XRD) results demonstrate that the TFT-LCD waste glass was entirely non-crystalline. The leaching concentrations of the clay and TFT-LCD waste glass all met the current regulatory thresholds of the Taiwan EPA. The pozzolanic strength activity indices of TFT-LCD waste glass at 28 days and 56 days were 89% and 92%, respectively. Accordingly, this material can be regarded as a good pozzolanic material. The amount of TFT-LCD waste glass that is mixed into WGBC pastes affects the strength of the pastes. The strength of the paste clearly declined as the amount of TFT-LCD waste glass increased. XRD patterns indicated that the major difference was the presence of hydrates of calcium silicate (CSH, 2 theta=32.1 degrees), aluminate and aluminosilicate, which was present in WGBC pastes. Portland cement may have increased the alkalinity of the solution and induced the decomposition of the glass phase network. WGBC pastes that contained 40% TFT-LCD waste glass have markedly lower gel/space ratios and exhibit less degree of hydration than ordinary Portland cement (OPC) pastes. The most satisfactory characteristics of the strength were observed when the mixing ratio of the TFT-LCD waste glass was 10%.     

Semi-dynamic leaching tests of nickel containing wastes stabilized/solidified with magnesium potassium phosphate cements

Herein is presented a study on the long-term leaching behaviour of nickel containing wastes stabilized/solidified with magnesium potassium phosphate cements. Two different semi-dynamic leaching tests were carried out on monolithic materials: ANS 16.1 test with liquid-to-solid ratio (L/S) of 10 dm(3) kg(-1) and increasing renewal times, and ASTM C1308 test with liquid-to-solid ratio (L/S) of 100 dm(3) kg(-1) and constant renewal time of 1 day. ASTM C1308 provides a lower degree of saturation of the leachant with respect to the leached material. The effectiveness of magnesium potassium phosphate cements for the inertization of nickel was proved. XRD analyses showed the presence of bobierrite on the monolith's surface after the leaching test, which had not been detected prior to the leaching test. In addition, the calculated cumulative release of the main components of the stabilization matrix (Mg(2+), total P and K(+)) was represented versus time in logarithmic scale and it was determined if the leaching mechanism corresponds to diffusion. Potassium is released by diffusion, while total phosphorous and magnesium show dissolution. Magnesium release in ANS 16.1 is slowed down because of saturation of the leachant. Experimental results demonstrate the importance of L/S ratio and renewal times in semi-dynamic leaching tests.     

Utilization of municipal solid waste incineration (MSWI) fly ash in blended cement Part 1: Processing and characterization of MSWI fly ash

This paper is the first of a series of two articles dealing with the processes applied to MSWI fly ash with a view to reusing it safely in cement-based materials. Part 1 presents two stabilization processes and Part 2 deals with the use of the two treated fly ashes (TFA) in mortars. Two types of binder were used: an Ordinary Portland Cement (OPC) containing more than 95% clinker (CEM I 52.5R) and a binary blend cement composed of 70% ground granulated blast furnace slag and 30% clinker (CEM III-B 42.5N). In this first part, two stabilization processes are presented: the conventional process, called "A", based on the washing, phosphation and calcination of the ash, and a modified process, called "B", intended to eliminate metallic aluminum and sulfate contained in the ash. The physical, chemical and mineralogical characteristics of the two TFA were comparable. The main differences observed were those expected, i.e. TFA-B was free of metallic aluminum and sulfate. The mineralogical characterization of the two TFAs highlighted the presence of large amounts of a calcium aluminosilicate phase taking two forms, a crystalline form (gehlenite) and an amorphous form. Hydration studies on pastes containing mixed TFA and calcium hydroxide showed that this phase reacted with calcium hydroxide to form calcium aluminate hydrates. This formation of hydrates was accompanied by a hardening of the pastes. These results are very encouraging for the reuse of such TFA in cement-based materials because they can be considered as pozzolanic additions and could advantageously replace a part of the cement in cement-based materials. Finally, leaching tests were carried out to evaluate the environmental impact of the two TFAs. The elements which were less efficiently stabilized by process A were zinc, cadmium and antimony but, when the results of the leaching tests were compared with the thresholds of the European landfill directive, TFA-A could nevertheless be accepted at landfills for non-hazardous waste. The modifications of the process led to a significant reduction in the stabilization of chromium, selenium and antimony.     

Effect of barium hydrosilicates on the early hydration rate of Portland cement

We have studied the effect of a barium hydrosilicate-based modifier on the phase composition of Portland cement hydration products. The results demonstrate that the addition of a modifier containing barium hydrosilicates, silicic acid, and calcium carbonate makes it possible to reduce the nucleation rate of crystals of new phases during the induction period of the hydration process, increase alite (3СaO · SiO₂) hydration, and reduce the rate of aluminate phase (3CaO · Al₂O₃) hydration. The use of such a modifier increases the degree of cement hydration and the amount of calcium hydrosilicates and reduces the amount of forming portlandite and ettringite, thereby improving the mechanical properties and durability of the set cement.     

The compositional and molecular character of the calcium silicate hydrates formed in the paste hydration of 3CaO·SiO2

Transmission electron microscopy has been used to determine the composition and characterize the molecular structure of the early calcium silicate hydrates formed in the paste hydration of 3CaO · SiO₂. The initial surface hydrates were found to have a wide range of CaO/SiO₂ compositions, consistent with the rapid and variable rate of dissolution of Ca²⁺ ions from only specific reactive surface sites. The very early surface hydrates appear disordered on a 1 nm scale. At later ages these become microheterogeneous, with more structurally ordered sheet-like fragments and regions developing within the disordered regions. Discrete 3 nm long and 1 nm thick fragments and more structurally ordered assemblies of these were observed. The basic molecular core structure was found to be a 1 nm thick sheet consisting of a protonated CaO _x polyhedral layer sandwiched between short-chain silicate groups. In these paste hydrates, this layer extends for only 3 nm before disordering recurs.