Effect of Zn,Cu,Cr and Pb Chlorides on the Formation of Tricalcium Aluminate Trisulfate Hydrate

The effect of addition of Zn, Cu, Pb and Cr chlorides as admixtures on the hydration reaction of the system 3CaO·Al2O3-gypsum with molar ratio 1：3 was studied. Different ratios of each salt were used, namely 0.5%, 2% and 4% by weight of the solid mixture. Hydration reaction was carried out at 35℃ for various time intervals from 0.5 h to up to 7 d. Hydration rate of the system 3CaO·Al2O3-CaSO4·2H2O in absence and presence of different salts was studied via the determination of the combined water contents. X-ray diffraction analysis showed that the ettringite was the only hydration product formed in the different mixes. The hydration products were investigated by scanning electron microscopy （SEM） and thermal gravimetric analysis. The results indicated that the rate of formation of ettringite and its microstructure depend on the admixture and its dosage.     

Hydrothermal Characteristics of Blended Cement Pastes Containing Silica Sand Using Cement Kiln Dust as an Activator

The hydrothermal reactivity of silica sand was studied using cement kiln dust (CKD) as an activator in addition to the portland cement fraction of El-Karnak cement (a blend of ordinary Portland cement and ground sand).Autoclaved El-Karnak cement pastes were studied at pressures of 0.507,1.013 and 01.520 MPa of saturated steam with respect to their compressive strength,kinetics of hydrothermal reaction and the phase composition of the formed hydrates.The role of CKD in affecting the physicochemical and mechanical properties of El-Karnak cement pastes was studied by autoclaving of several pastes containing 5,7.5,10 and 20% CKD at a pressure of 1.013 MPa of saturated steam.CKD was added either as a raw CKD (unwashed) or after washing with water (washed CKD).The results of these physicochemical studies obtained could be related as much as possible to the role of CKD (raw or washed) in affecting the hydrothermal reactivity of silica sand in El-Karnak cement pastes.     

Effect of Some Heterocyclic Derivatives on the Removal of Copper Ions from Wastewater by Cementation

Removal of copper ions from copper sulphate solutions on a rotating zinc rod in absence and in presence of 3(2H)-furanones and 4H-pyran-4-one derivatives was investigated experimentally. Variables studied were initial copper ions concentration, rotational speed of the zinc rod, temperature and concentration of organic additives. It was found that cementation reaction is first order in presence and in absence of additives. Increasing concentration of initial copper ions, rotational speed of the zinc rod and temperature were found to increase the rate of cementation. In presence of organic additives an enhancement of the rate was observed, except in presence of methoxyfuranone the rate was found to decrease by an amount ranging from 11.74% to 33.79%. Rate acceleration or inhibition is associated mainly with changes in the structure of the additives as well as its concentration. The apparent activation energy for the cementation process in presence of different additives was estimated and was found to be r     

Alumina Effect on the Phase Transformation of 3Y-TZP Ceramics

The isothermal tetragonal-to-monoclinic phase transformation of 3 mol fraction Y2O3-ZrO2 ceramics contain- ing different amounts of Al2O3 during ageing in water at 130℃ for periods of time up to 40 h was investigated to explore the effect of Al2O3 addition on this transformation. The propagation of the transformation into the specimen interiors was suppressed by the addition of Al2O3. The transformation kinetics showed a nucleation and growth mechanism on the specimen surface to be dominant in the low temperature ageing in water environment.     

Corrosion of AISI 4130 Steel Alloy under Hydrodynamic Condition in Ethylene Glycol+Water+NO2- Solution

The electrochemical behavior of steel alloy in ethylene glycol-water mixture at different solution rotating speeds was investigated by polarization curves and AC impedance measurements (EIS). The results obtained showed that corrosion rate was not changed significantly at different rotating speeds and was decreased with increasing ethylene glycol concentration. The effect of nitrite as an inhibitor was studied and high inhibition efficiency was obtained. It was found that surface passivation occurred in the presence of inhibitor. The inhibiting effect of the nitrite was explained on the basis of the competitive adsorption between the inorganic anions and the aggressive Cl- ions and the adsorption isotherm basically obeys the Flory-Huggins adsorption isotherm. Thermodynamic parameters for steel corrosion and inhibitor adsorption were determined, which revealed that the adsorption process is spontaneous.     

Influence of Silica Fume on Corrosion Behaviour of Reinforced Steel in Different Media

Electrochemical and corrosion behaviour of reinforced steel embedded in cement pastes incorporating different amounts of silica fume as a partial replacement of cement has been studied in chloride and sulphate solutions by using different electrochemical techniques. The results indicate that, while steel passivity degree is low in the control samples' upon soaking in the corrosive media, it has been high in samples incorporating silica fume and increased with increasing silica fume content. The improvement effect of silica fume may be attributed to the pore solution structure of the cement paste, which limits the mobility of aggressive ions near the surface of the steel. The mechanism of steel corrosion due to chloride and sulphate attack and passivation effect of silica fume are discussed.     

Influece of Silica Fume on Corrosion Behaviour of Reinforced Steel in Different Media

Electrochemical and corrosion behaviour of reinforced steel embedded in cement pastes incorporating different amounts of silica fume as a partial replacement of cement has been studied in chloride and sulphate solutions by using different electrochemical techniques.The results indicate that ,while steel passivity degree is low in the control samples‘upon soaking in the corrosive media,it has been high ih samples incorporating silica fume and increased with increasing silica fume content.The improvement effect of silica fume may be attributed to the pore solution structure of the cement paste,which limits the mobility of aggressive ions near the surface of the steel.The mechanism of steel corrosion due to chloride and sulphate attack and passivation effect of silica fume are discussed.     

Synthesis and Characterization of ZnO Nanowires and ZnO–CuO Nanoflakes from Sputter-Deposited Brass(Cu_(0.65)–Zn_(0.35)) Film and Their Application in Gas Sensing

A novel method was presented for synthesis of ZnO and ZnO–CuO composites in the form of nanowires,nanorods and nanoflakes on oxidized silicon substrates. Further, the use of the synthesized nanostructures for gas sensing was demonstrated. Pure brass(Cu0.65–Zn0.35) films were deposited on oxidized Si substrate by radio frequency(RF) diode sputtering. Subsequently, these films having thickness in the range of 100–200 nm were oxidized in different oxidizing ambient in the temperature range of 300–550 °C.The effect of temperature, time and oxidizing ambient on the growth of nanostructures was investigated by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD) and photoluminescence(PL) techniques. The nanostructures surface was analyzed by X-ray photoelectron spectroscopy(XPS). The synthesized nanowires had diameter in the range of 60–100 nm and length up to 50 μm. Based on these observations, the growth mechanism has been suggested. For the nanorods, the diameter was observed to be ~150 nm. Samples having dense nanowires, nanorods and nanoflakes were used as a gas sensing material. The performance of the sensor was investigated for different nanostructured materials for various volatile organic compounds(VOCs). It was observed that ZnO–CuO nanoflakes were more sensitive to VOC sensing compared to ZnO nanowires and nanorods.     

Solvothermal Synthesis of Boehmite and γ-Alumina Nanorods

Boehmite nanorods were synthesized by a solvothermal method using AICl3·6H2O in mixed solvents of water and aniline. The solvothermal time, heating temperature and the concentration of aniline have effects on the morphology of boehmite. γ-alumina nanorods were prepared by a simple thermal transformation of boehmite nanorods. A rational mechanism based on the oriented attachment is proposed for the formation of boehmite nanorods. The products were characterized by X-ray powder diffraction （XRD） and transmission electron microscopy （TEM）. Photoluminescence （PL） spectrum of the boehmite nanorods was also investigated.     

Structural Dependence of Creep/Fatigue Behaviour of Single Crystal Ni-base Superalloy

The effect of different initial microstructures deftned by γ' precipitate morphology has been investigated at the creep/fatigue conditions of 900℃ and 500 MPa. The wave form of stress as a function of time for cyclic load was of trapezoidal shape with a hold time of 10s at the upper stress level. The TEM was employed to examine the deformation process in strengthened γ' matrix in dependence of γ' precipitate morphology. The fracture lifetime and cycle number up to fracture were the criteria to evaluate the additional cyclic component efFect on the course of deformation     

Properties of polyvinyl alcohol cement pastes

Properties of cement pastes containing varying amounts of each of polyvinyl alcohol (PVAL), mixtures of polyvinyl alcohol and phenol formaldehyde (PF) and mixtures of poly vinyl alcohol and borax were studied in this paper. Though the strength parameters of the PVAL-cement pastes are comparable to virgin cement paste their resistance to acid is far superior. Soxhlet extraction with water, done to determine leachability of the polymer from the polymer cement paste, revealed that the percentage of polyvinyl alcohol leached out was less when borax or PF resin was added to the PVAL cement paste. The compressive strength of the poly vinyl alcohol–phenol formaldehyde cement paste was found to be inferior to the other two cases but the retention of compressive strength after immersing in each of acid, base and kerosene was much better. In general, polyvinyl alcohol when added to cement pastes improves the chemical resistance properties in terms of retention of compressive strength after exposure to chemicals.     

Lead leachability in stabilized/solidified soil samples evaluated with different leaching tests

Leaching tests and model calculations were performed to investigate the immobilization mechanisms of Pb and compare different leaching protocols. Stabilization/solidification (S/S) treatments reduced Pb concentrations in the toxicity characteristic leaching procedure (TCLP) leachate from 5.9 mg/L for untreated soil to less than 0.7 mg/L. The results of eight different leaching protocols show that: (1) the main factor controlling the Pb concentration in the leachate is the final pH; (2) the final pH is a function of the leachant acidity; and (3) for a given final pH, the type of leachant has a relatively minor effect on leachability. The diffuse layer adsorption model, aqueous and precipitation reactions were employed in the MINTEQA2 program to describe the Pb leaching behavior. Both leaching tests and model simulations indicate that the Pb leaching behavior can be divided into three stages based on the leachate pH: a high alkalinity leaching stage at pH > 12, where Pb formed soluble hydroxide anion complexes and leached out; a neutral to alkaline immobilization stage in the pH range of 6-12, which was characterized by low Pb leachability caused by adsorption and precipitation; and an acid leaching stage with pH < 6, where the acid neutralizing capacity (ANC) of the S/S materials was totally consumed and therefore free Pb-ion leached out.     

Analysis of calcium leaching behavior of plain and modified cement pastes in pure water

The calcium ion leaching behavior of cement pastes modified with a high-alkali fine glass powder, silica fume, and fly ash, exposed to deionized water, is reported in this paper. Porosity enhancement in pastes subjected to leaching is attributed both to the dissolution of calcium hydroxide (CH) as well as decalcification of C–S–H gel. A methodology that combines the measured porosity increase along with the CH and C–S–H contents remaining after leaching for a particular duration is developed to separate the porosities created due to CH and C–S–H leaching. In order to quantify the influence of leaching on the amounts of Ca ions remaining in the CH and C–S–H phases, solid–liquid equilibrium curves for calcium are developed for the unleached and leached pastes. Leaching depths are also calculated using the CH contents of the leached and unleached specimens. All the modified pastes show better leaching resistance than the plain paste. In addition to the microstructure densification, the lower Ca–Si molar ratio in modified pastes that reduces the equilibrium liquid Ca ion concentration contributes to this observation. For the glass powder modified paste, the presence of higher alkali content in the pore solution further reduces the dissolution of CH due to common ion effect, thus providing it with the highest leaching resistance. Fly ash and silica fume modified pastes demonstrate leaching resistance in between those of the plain and glass powder modified mixtures.     

Cement-based stabilization/solidification of oil refinery sludge: Leaching behavior of alkanes and PAHs

Stabilization/solidification is a process widely applied for the immobilization of inorganic constituents of hazardous wastes, especially for metals. Cement is usually one of the most common binders for that purpose. However, limited results have been presented on immobilization of hydrocarbons in cement-based stabilized/solidified petroleum solid waste. In this study, real oil refinery sludge samples were stabilized and solidified with various additions of I42.5 and II42.5 cement (Portland and blended cement, respectively) and subject to leaching. The target analytes were total petroleum hydrocarbons, alkanes and 16 polycyclic aromatic hydrocarbons of the EPA priority pollutant list. The experiments showed that the waste was confined in the cement matrix by macroencapsulation. The rapture of the cement structure led to the increase of leachability for most of the hydrocarbons. Leaching of n-alkanes from II42.5 cement-solidified samples was lower than that from I42.5 solidified samples. Leaching of alkanes in the range of n-C(10) to n-C(27) was lower than that of long chain alkanes (>n-C(27)), regardless the amount of cement addition. Generally, increasing the cement content in the solidified waste samples, increased individual alkane leachability. This indicated that cement addition resulted in destabilization of the waste. Addition of I42.5 cement favored immobilization of anthracene, benzo[a]anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene, benzo[a]pyrene and dibenzo[a,h]anthracene. However, addition of II42.5 favored 5 out of 16, i.e., naphthalene, anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene and dibenzo[a,h]anthracene.     

Leaching behavior of heavy metals from municipal solid wastes incineration (MSWI) fly ash used in concrete

The characteristics of municipal solid waste incineration (MSWI) fly ash, surface leaching toxicity and successive leaching concentration of heavy metals from MSWI fly ash-cement hardened pastes were studied. And, the relationships between leaching concentrations of heavy metals and leaching time were also discussed. Experimental results showed that immobilization effect of cement on MSWI fly ash is good. Even if MSWI fly ash-cement hardened pastes were damaged, the leaching toxicity is still in a safety range. In early leaching stage, the surface leaching rate is relatively a little high, up to 10(-5)-10(-4)cmd(-1) order of magnitude, in the later time of leaching, its rate rapidly declined, down to 10(-7). Most of leached heavy metals are produced at early ages. The leaching concentration of heavy metals and leaching time has strong positive relationships. In factual utilizing circumstances, heavy metals' leaching from MSWI fly ash-cement hardened pastes is a very slow and gradually diluting process. The leaching toxicity of heavy metals is far lower than that of the National Standard of China, and minimum harmful matters can be contained and released in the environment. Reusing of MSWI fly ash as partial replacement for cement in concrete mixes is potentially feasible.     

Solidification of cement kiln dust using sulfur binder

The present study aims to offer a new methodology for consuming two industrial wastes; sulfur, from petroleum and natural gas industries, and cement kiln dust (CKD), from Portland cement industries, in construction industry. Sulfur solidified cement kiln dust material (SSCKDM) was manufactured by mixing molten sulfur, treated sulfur, CKD and sand at a controlled temperature in excess of 120 °C. The hot mixture was subsequently cast and shaped into the desired mold and was then allowed to solidify at a specified cooling rate. Solidified materials were immersed for time periods up to 28 days in distilled water at different temperatures of 25 and 60 °C, sea water, and acidic and basic universal buffer solutions of pH4 and pH9, respectively. Solidified material performance as function of time and type of aqueous solution exposed to was evaluated in view of compressive strength variations and leachability of metal and heavy metal ions.The results indicated that the solidified articles exhibit homogenous and compact internal microstructure with excellent mechanical properties. However, it showed durability problem upon exposure to aqueous solution environments due to the initial chemical composition of the CKD, whose leached test showed release of relatively high amounts of sulfates and alkali metals. Durability of SSCKDM articles in relation to strength reduction and crack formations control was improved by addition of glass fiber while, the use of anti-leaching agent such as anhydrous sodium sulfide resulted in reduction of leached heavy metals without any measurable decrease in leached amounts of alkali metals and anions from the solidified matrix. Furthermore, based on leachability index method of calculation, potential chemical mobility of metal and heavy metal ions from the solidified matrix was characterized as medium.     

Oil palm ash as partial replacement of cement for solidification/stabilization of nickel hydroxide sludge

In this study, solidification/stabilization (S/S) of nickel hydroxide sludge using ordinary Portland cement (OPC) and oil palm ash (OPA) was carried out. The effects of increased substitution of OPA wt% in the S/S mix designs on the treated samples' physical and chemical characteristics were investigated. The physical characteristics studied were unconfined compressive strength (UCS) and changes in crystalline phases while chemical characteristics studied were leachability of nickel and leachate pH. Results indicated the optimum mix design for S/S of nickel hydroxide sludge using both OPC and OPA at B/S(d)=1 in terms of cost-effectiveness and treatment efficiency was 15 wt% OPA, 35 wt% OPC and 50 wt% sludge. The sufficient UCS and low leached nickel concentrations shown for this mix design indicate the viability of using OPA as substitute of OPC as it can significantly reduce cost normally incurred by usage of high amounts of OPC.     

Effects of sucrose and sorbitol on cement-based stabilization/solidification of toxic metal waste

The effects of sucrose or sorbitol addition on the hydration, unconfined compressive strength and leachability of Portland cement pastes containing 1% Pb and 1% Zn were studied as a function of time. Whereas Pb and Zn were found to shorten the time to achieve maximum hydration of Portland cement, the combination of these metals with 0.15 wt% sucrose or 0.40 wt% sorbitol retarded the setting of cement by at least 7 and 28 days, respectively, without affecting the strength at 56 days. The leachability of Pb and Zn evaluated by the TCLP 1311 protocol at 56 and 71 days was slightly reduced or unchanged by the addition of sucrose or sorbitol. SEM-EDS and XRD analyses revealed that ettringite precipitation was favored whereas the formation of CSH gel, which accounts for most of the strength of hydrated cement, was delayed in cement pastes containing both metals and sucrose or sorbitol. These results indicate that controlled additions of sucrose or sorbitol can add flexibility to the handling of cement-treated metal waste, particularly when it needs to be transported by truck or pipeline between the treatment plant and the disposal site, without affecting its long-term performance.     

Immobilization and leaching characteristics of arsenic from cement and/or lime solidified/stabilized spent adsorbent containing arsenic

Solidification/stabilization (S/S) of hazardous iron oxide coated cement (IOCC) spent adsorbent containing arsenic (As(III)) was investigated in the present study. Cement and lime-based S/S effectiveness was evaluated by performing semi-dynamic leach tests. The S/S effectiveness was evaluated by measuring effective diffusion coefficients (D(e)) and leachability indices (LX). It was found that though cement or lime alone were efficient in preventing arsenic leaching (D(e) being in range of 10(-10) to 10(-12) for all the matrices) from the solidified matrices, the best combination for arsenic containment in the matrix was obtained when a mixture of cement and lime was used. The LX values for all the matrices were higher than 10, suggesting that the S/S treated arsenic sludge are acceptable for "controlled utilization". Calcite formation along with precipitation and conversion into non-soluble forms (calcium arsenite, calcium hydrogen arsenate hydrates, calcium hydrogen arsenates, etc.) were found to be the responsible mechanism for low leaching of arsenic from the solidified/stabilized samples. A linear relationship between cumulative fraction (CFR) of arsenic leached and square root of leach time (R(2) ranging from 0.90 to 0.94) suggested that the diffusion is the responsible mechanism for arsenic leaching. Thus, cement and lime show effective containment of the As(III) within the matrix thus indicating S/S by cement and lime, which is also a low-cost option, as a suitable management option for the toxic As(III) sludge.     

The effect of high salt concentration on the integrity of silica-fume blended cementitious matrices for waste immobilization applications

Silica Fume is a commonly used pozzolanic additive for cementitious matrices used for immobilization of Low Level Waste (LLW). Cementitious systems containing silica-fume are used to reduce the leachability of various hazardous species. However, during the last years several publications have shown that commercially available densified silica-fume (DSF) does not fully disperse within cementitious pastes and concrete mixes, but rather tends to form agglomerated particles which range in size from tens to hundreds of microns. Cementitious matrices containing such agglomerates are prone to the alkali-silica reaction (ASR). As radioactive waste streams often contain high alkali salt concentrations, the occurrence of ASR, deleterious osmotic pressure or other degradation mechanisms in cementitious waste matrices must be considered. The aim of this research was to study the effect of high salt content in DSF bearing pastes on the integrity of the immobilized waste form and its efficiency to immobilize low level radioactive waste. The dependence of matrix integrity on both salt and silica fume concentration is presented.