Properties of MSW fly ash-calcium sulfoaluminate cement matrix and stabilization/solidification on heavy metals

In this paper, investigations were undertaken to formulate the properties of fly ash-calcium sulfoaluminate (CSA) cement matrix by blending MSW fly ash with CSA cement. The compressive strength, pore structure, hydration phases, and leaching behavior of Zn and Pb doped MSW fly ash-CSA cement matrices were determined by XRD, MIP, DSC, FTIR, EDX, TCLP leaching test and other experiments. The results showed that the addition of MSW fly ash to form fly ash-CSA cement matrix reduced the compressive strengths of matrices and made the pore distribution of matrices coarser, compared to that of pure CSA cement matrix. However, fly ash-CSA cement matrix could effectively immobilize high concentration of heavy metal such as lead and zinc with much lesser leaching of TCLP. Besides ettringite AFt, Friedel phase was a new hydration phase formed in the matrix. The formation of these hydration phases was responsible for huge reservoir of heavy metal stabilization by chemical fixing. Therefore, it could be postulated that MSW fly ash-CSA cement matrix was a potential new constituent of S/S matrix for high concentration of heavy metals such as Zn and Pb ions.     

Microstructure determination of cement pastes by NMR and conventional techniques

Applicability of NMR relaxation analysis to the characterization of pore structure in hydrating white cement pastes has been investigated. Measurements of transverse magnetization relaxation were made in specimens saturated and partially filled with water for periods of hydration between 1 and 28 days. The fast diffusion model successfully accounts for all relaxation measurements. The transverse surface relaxation rate was determined. A two-component pore volume size distribution was found. Comparison was made with mercury porosimetry and nitrogen sorption experiments and the results were correlated with compressive strength.     

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.     

高强度三掺复合水泥的强度及孔结构性能研究

分别将30%、40%、50%混合材与水泥熟料复合,制备高强度复合水泥.混合材主要为矿渣、活化粉煤灰和活化煤矸石.通过砂浆强度测试及孔结构测试等技术,对复合水泥的力学性能、水化过程和水化机理进行了分析研究.试验结果表明,当3种混合材复掺时,制备的复合水泥的强度较高.复合水泥28d抗压强度最高达到65MPa,各试样的抗压强度均超过50MPa,且后期强度继续增大.从孔结构结果可看出,制备的复合水泥的水泥石有较多的凝胶孔和较低的总孔隙率.     

Improvement of ground granulated blast furnace slag on stabilization/solidification of simulated mercury-doped wastes in chemically bonded phosphate ceramics

This paper investigated the effectiveness of (ground granulated blast furnace slag) GGBFS-added chemically bonded phosphate ceramic (CBPC) matrix on the stabilization/solidification (S/S) of mercury chloride and simulated mercury-bearing light bulbs (SMLB). The results showed that the maximal compressive strength was achieved when 15% and 10% ground GGBFS was added for HgCl(2)-doped and SMLB-doped CBPC matrices, respectively. The S/S performances of GGBFS-added matrices were significantly better than non-additive matrices. As pore size was reduced, the leaching concentration of Hg(2+) from GGBFS-added CBPC matrix could be reduced from 697 microg/L to about 3 microg/L when treating HgCl(2). Meanwhile, the main hydrating product of GGBFS-added matrices was still MgKPO(4).6H(2)O. The improvement of S/S effectiveness was mainly due to physical filling of fine GGBFS particles and microencapsulation of chemical cementing gel.     

Improvement of early-age properties for glass-cement mortar by adding nanosilica

Poor early-age performance (e.g. lower early strength, longer setting time) is an important technical challenge for the application of blended cementitious materials containing low reactivity or high volumes of supplementary cementing materials. In this study, the mechanism of using nanosilica (NS) to improve the early-age properties for cement mortars blended with glass powder (GP) and glass aggregates has been investigated. The results indicate that the addition of NS into glass-based cement mortar largely improved the early stiffening which was dependent on high specify surface area of the NS rather than cement hydration. Combining the use of NS and GP was conducive to compensate the delayed setting times and the strength losses caused by the incorporation of GP. These beneficial behaviors were associated with the physical, acceleration, pozzolanic and pore refinement effects of NS. In terms of heat of hydration, the inclusion of NS intensified and accelerated the appearance of the third exothermic peak (AFt to AFm) due to the absorption of sulfate ions by the increased C-S-H formation. Also, the total hydration heat liberated was found to correlate linearly with the corresponding early-age compressive strength. Microstructural analysis suggest that NS significantly helped to densify the microstructure of the GP blended cement matrix and improved the interface between the GP particle and the binder matrix. This was verified by the contribution of NS on refining the coarse pore size caused by the use of GP as a replacement of cement.     

Microstructural characteristics,porosity and strength development in ceramic-laterized concrete

Interfacial bonding between constituent materials and pore sizes in a concrete matrix are major contributors to enhancing the strength of concrete. In a bid to examine how this phenomenon affects a laterized concrete, this study explored the relationship between the morphological changes, porosity, phase change, compressive, and split tensile strength development in a ceramic-laterized concrete. Varying proportions of ceramic aggregates, sorted from construction and demolition wastes, and lateritic soil were used as substitutes for natural aggregates. Strength properties of the concrete specimens were evaluated after 7, 14, 28 and 91 days curing, but morphological features, using secondary electron mode, were examined only at 7 and 28 days on cured specimens, using Scanning electron microscope (SEM). From all the mixes, selected samples with higher 28 day crushing strength, and the reference mix, were further characterized with more advanced analysis techniques, using the mercury intrusion porosimetry (MIP), thermogravimetric analysis (TGA), X-ray Diffractometer, and SEM (backscatter electron mode-for assessment of the interfacial transition properties between aggregates and paste).The reference mix yielded higher mechanical properties than the concrete containing secondary aggregates, this was traced to be as a result of higher peaks of hydration minerals of the concrete, coupled with its low tortuosity and compactness. However, a laterized concrete mix containing both 90% of ceramic fine and 10% of laterite as fine aggregate provided the optimal strength out of all the modified mixes. Although, the strength reduction was about 9% when compared with the reference case, however, this reduction in strength is acceptable, and does not compromise the use of these alternative aggregates in structural concrete.     

Creep analysis of concrete containing rice husk ash

This paper presents an experimental study on the mechanical properties of concrete added with rice husk ash (RHA) as a supplementary cementitious material. The compressive strength, modulus of elasticity and creep were obtained experimentally from specimens with different RHA contents (0%, 10%, 15% and 20% of binder). The results show that the addition of RHA in concrete can improve both the compressive strength and modulus of elasticity and reduce the creep of concrete. The examination of pore micro-structure of hardened concrete using both the mercury intrusion porosimetry and scanning electron microscope techniques demonstrates that RHA particles can react with calcium hydroxide originated from cement hydration to produce additional C-S-H, which can fill voids and large pores and thus reduces the porosity related to capillary pores and voids. In addition, the release of absorbed water, which is retained in the small pores of RHA particles at early days, can improve cement hydration and thus reduce the porosity related to gel pores.     

温度对含模拟α-高放核废液的磷酸镁水泥固化体性能的影响

利用磷酸镁水泥(Magnesium potassium phosphate cement,MPC)对模拟α-高放核废液(HLW)进行固化,研究温度对固化体力学性能、物相组成、微观形貌及核素Cs~+浸出率的影响。BET、XRD、SEM及AAS等测试结果表明,室温下MgO、KH2PO4与高放核废液反应形成致密结构;随着温度的升高,固化体脱水,400℃时孔道结构增多,平均孔径增大,抗压强度降低,Cs~+浸出率增加;温度继续升高,磷酸镁水泥烧结陶瓷化,平均孔径逐渐减小,抗压强度增大;900℃时固化体表现出良好的陶瓷结构特征,晶粒完全熔融,晶粒间没有明显界线,Cs~+的28d浸出率为7.21×10~(-6) g/(cm~2·d)。不同温度下高放核废液的磷酸镁水泥固化体核素Cs~+的浸出率均能达到玻璃固化体的性能要求,表明磷酸镁水泥用于固化高放核废液具有明显优势。     

A new Schiff's base ligand immobilized agarose membrane optical sensor for selective monitoring of mercury ion

A highly selective optical sensor was developed for the Hg(2+) determination by chemical immobilization of 2-[(2-sulfanylphenyl)ethanimidoyl]phenol (L), on an agarose membrane. Spectrophotometric studies of complex formation between the Schiff's base ligand L and Hg(2+), Sr(2+), Mn(2+), Cu(2+), Al(3+), Cd(2+), Zn(2+), Co(2+) and Ag(+) metal ions in methanol solution indicated a substantially larger stability constant for the mercury ion complex. Consequently, the Schiff's base L was used as an appropriate ionophore for the preparation of a selective Hg(2+) optical sensor, by its immobilization on a transparent agarose film. A distinct color change, from yellow to green-blue, was observed by contacting the sensing membrane with Hg(2+) ions at pH 4.5. The effects of pH, ionophore concentration, ionic strength and reaction time on the immobilization of L were studied. A linear relationship was observed between the membrane absorbance at 650 nm and Hg(2+) concentrations in a range from 1×10(-2) to 1×10(-5) mol L(-1) with a detection limit (3σ) of 1×10(-6) mol L(-1). No significant interference from 100 times concentrations of a number of potentially interfering ions was detected for the mercury ion determination. The optical sensor was successfully applied to the determination of mercury in amalgam alloy and spiked water samples.     

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.     

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.     

Effect of cement substitution by limestone on the hydration and microstructural development of ultra-high performance concrete (UHPC)

The effect of limestone on the hydration and microstructural development of ultra high performance concrete (UHPC) with different levels of replacement (34%, 54% and 74% by volume) was investigated. Up to 54% replacement of cement by limestone the mixes showed better workability and higher compressive strength (170 MPa at 56 days for 54% addition) compared to a classical mix (155 MPa) with no limestone replacement. The kinetics of hydration were compared for different replacement levels using isothermal calorimetry. The phase development was quantified by X-ray diffraction with Rietveld method combined with thermal gravimetric analysis. The pore structure was examined by mercury intrusion porosimetry. The composition of hydration products was determined by scanning electron microscopy with energy dispersive X-ray analysis. The results showed that the hydration degree of the cement is increased from 39% for classical UHPC to 66% for the UHPC with 54% of limestone.     

钙系磷酸盐化学键合材料的制备及其固化重金属研究

利用富含氧化钙的铬铁渣(FS)和磷酸二氢钾(P)反应制备钙系磷酸盐化学键合材料,并用其作为固化重金属离子(Pb~(2+)、Cd~(2+)、Cu~(2+))基体材料。研究了原料配比、缓凝剂及重金属掺量对胶凝材料初凝时间和抗压强度的影响。结果表明:当P/FS(质量比,下同)为1/4及硼砂掺量为2%时,材料性能最好,自然养护28d和常压蒸汽养护24h抗压强度分别可达25.65 MPa和36.86 MPa。随着重金属掺量的增加,材料抗压强度逐渐降低,掺量为3%时,自然养护28d和蒸汽养护24h试块抗压强度均大于10 MPa,满足建筑材料要求。固化体重金属毒性浸出试验表明:磷酸盐化学键合材料对重金属离子(Pb~(2+)、Cd~(2+)、Cu~(2+))均具有很好的固化效果,浸出浓度远低于相应的鉴别标准。通过XRD、SEM和FTIR分析,钙系磷酸盐化学键合材料固化重金属的机理是通过水化产物的化学键合、吸附以及物理包裹作用将Pb~(2+)、Cd~(2+)、Cu~(2+)固化在材料中。     

Effects of CuO nanoparticles on compressive strength of self-compacting concrete

In the present study, the compressive strength, thermal properties and microstructure of self-compacting concrete with different amounts of CuO nanoparticles have been investigated. CuO nanoparticles with an average particle size of 15 nm were added to self-compacting concrete and various properties of the specimens were measured. The results indicate that CuO nanoparticles are able to improve the compressive strength of self-compacting concrete and reverse the negative effects of superplasticizer on compressive strength of the specimens. CuO nanoparticles as a partial replacement of cement up to 4 wt.% could accelerate C–S–H gel formation as a result of the increased crystalline Ca(OH)₂ amount at the early ages of hydration. Increasing CuO nanoparticle content to more than 4 wt.%, causes reduced compressive strength because of unsuitable dispersion of nanoparticles in the concrete matrix. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate that CuO nanoparticles up to 4 wt.% could improve the mechanical and physical properties of the specimens. Finally, CuO nanoparticles improved the pore structure of concrete and caused shifting of the distributed pores from harmless to low harm.     

Immobilization of mercury in field soil and sediment using carboxymethyl cellulose stabilized iron sulfide nanoparticles

Mercury (Hg) is one of the most pervasive and bio-accumulative metals in the environment. Yet, effective in situ remediation technologies have been lacking. This study investigated the effectiveness of a class of soil-deliverable FeS nanoparticles for in situ immobilization of Hg in two field-contaminated soils from a New Jersey site and one sediment from an Alabama site. The nanoparticles were prepared using sodium carboxymethyl cellulose (CMC) as a stabilizer. Transmission electron microscopy measurements revealed a particle size of 34.3 ± 8.3 nm (standard deviation), whereas dynamic light scattering gave a hydrodynamic diameter of 222.5 ± 3.2 nm. Batch tests showed that at an FeS-to-Hg molar ratio of 28:1-118:1, the nanoparticles reduced water-leachable Hg by 79%-96% and the TCLP (toxicity characteristic leaching procedure) based leachability by 26%-96%. Column breakthrough tests indicated that the nanoparticles were deliverable in the sediment/soil columns under moderate injection pressure. However, once the external pressure was removed, the delivered nanoparticles remained virtually mobile under typical groundwater flow conditions. When the Hg-contaminated soil and sediment were treated with 52-95 pore volumes of a 500 mg l(-1) FeS nanoparticle suspension, water-leachable Hg was reduced by 90%-93% and TCLP-leachable Hg was reduced by 65%-91%. The results warrant further field demonstration of this promising in situ remediation technology.     

Influence of silica fume content on microstructure development and bond to steel fiber in ultra-high strength cement-based materials (UHSC)

The use of silica fume can significantly enhance mechanical properties of concrete given its beneficial filling and pozzolanic effects. In this study, a simple and effective double-side pullout testing method was adopted to characterize the interfacial bond properties, which include pullout load-slip relationship, bond strength, and pullout energy, of steel fiber-matrix in ultra-high strength cement-based material (UHSC) with 0–25% silica fume by the mass of binder. The effects of silica fume content on flowability, heat of hydration, compressive and flexural strengths, hydration products, and pore structure of matrix at different curing time were evaluated as well. Backscatter scanning electron microscopy (BSEM) and micro-hardness measurement were used to examine the quality of interfacial transition zone (ITZ) around the fiber. In terms of the results, the optimal silica fume content could be in the range of 15%–25%. UHSC mixtures with these dosages of silica fume showed significant improvement in pullout behavior. Its bond strength and pullout energy at 28 d could increase by 170% and 250% compared to the reference samples without any silica fume. The microstructural observation verified the findings on the macro-properties development. Formation of more and higher strength of hydration products and refinement of ITZ around the fiber ensured higher micro-hardness, and thus improved the bond to fiber.     

Mechanisms of hydration reactions in high volume fly ash pastes and mortars

This paper describes investigations of high-volume fly ash (HVFA)-Portland cement (PC) binders, the physical and chemical properties of which have been characterized up to 365 days of curing. Physical investigations were made of compressive strength development, pore structure by porosimetry, and morphology by scanning electron microscopy. Chemical examination was conducted for solid phase composition and degree of hydration by X-ray diffraction and thermal analysis, and for pore-fluid composition by high pressure extraction and analysis.

Up to 365d the cement in the HVFA pastes is not fully hydrated. However, the ash participates in both early (sulpho-pozzolanic) and late (alumino-silicate) hydration reactions. In addition to the usual products of cement hydration, ettringite (AFt) has been identified as a product of the early hydration of the fly ash. It has not been possible to identify long term hydration products of fly ash which appear to be non-crystalline. A two-step mechanism for pozzolanic reaction between fly ash and Portland cement has been proposed involving: (a) depolymerization/silanolation of the glassy constituents of the ash by the highly alkaline pore fluids, followed by (b) reaction between solubilized silicate and calcium ions in solution to form C---S---H.     

Blended cements containing high volume of natural zeolites: Properties, hydration and paste microstructure

In this study, properties and hydration characteristics as well as paste microstructure of blended cements containing 55% by weight zeolitic tuff composed mainly of clinoptilolite mineral were investigated. Free Ca(OH)₂ content, crystalline hydration products and decomposition of zeolite crystal structure, pore size distribution and microstructural architecture of hydrated cement pastes were examined. Superplasticizer requirement and compressive strength development of blended cement mortars were also determined. The blended cements containing high volume of natural zeolites were characterized with the following properties; (i) no free Ca(OH)₂ in hardened pastes at the end of 28 days of hydration, (ii) less proportion of the pores larger than 50 nm when compared to portland cement paste, (iii) complete decomposition of crystal structure of zeolite at the end of 28 days of hydration, (iv) presence of tetra calcium aluminate hydrate as a crystalline product of pozzolanic reaction, (v) more compatibility with the melamine-based superplasticizer when compared to the naphthalene based product, and (vi) similar 28 days compressive strength of mortars to that of reference portland cement.     

Investigation of properties of fluorogypsum-slag composite binders – Hydration,strength and microstructure

A composite binder of high strength and low water absorption has been developed using industrial by-products fluorogypsum, granulated blast furnace slag and Portland cement. The development of strength in the binder at an early age is attributed to the conversion of anhydrite into gypsum and at later age is due to the formation of ettringite and tobermorite, as a reaction of slag with lime produced during the hydration of cement. These cementitious phases fill in pores and voids of the hydrating gypsum crystals to form a dense and compact structure of low porosity and low pore volume. The reaction products formed during the hydration period were confirmed by scanning electron microscopy and X-ray diffraction. The reduction in porosity and low pore volume of binders, as studied by mercury intrusion porosimetry, are responsible for attainment of high strength and better stability towards water in composite binders than the conventional gypsum plaster.