Coal fly ash-slag-based geopolymers: Microstructure and metal leaching

This study deals with the use of fly ash as a starting material for geopolymeric matrices. The leachable concentrations of geopolymers were compared with those of the starting fly ash to evaluate the retention of potentially harmful elements within the geopolymer matrix. Geopolymer matrices give rise to a leaching scenario characterised by a highly alkaline environment, which inhibits the leaching of heavy metals but may enhance the mobilization of certain oxyanionic species. Thus, fly ash-based geopolymers were found to immobilise a number of trace pollutants such as Be, Bi, Cd, Co, Cr, Cu, Nb, Ni, Pb, Sn, Th, U, Y, Zr and rare earth elements. However, the leachable levels of elements occurring in their oxyanionic form such as As, B, Mo, Se, V and W were increased after geopolymerization. This suggests that an optimal dosage, synthesis and curing conditions are essential in order to obtain a long-term stable final product that ensures an efficient physical encapsulation.     

Geopolymers for immobilization of Cr(6+), Cd(2+), and Pb(2+)

Alkali activation of fly ash by sodium silicate solutions, forming geopolymeric binders, provides a potential means of treating wastes containing heavy metals. Here, the effects on geopolymer structure of contamination of geopolymers by Cr(VI), Cd(II) and Pb(II) in the forms of various nitrate and chromate salts are investigated. The addition of soluble salts results in a high extent of dispersal of contaminant ions throughout the geopolymer matrix, however very little change in geopolymer structure is observed when these materials are compared to their uncontaminated counterparts. Successful immobilization of these species will rely on chemical binding either into the geopolymer gel or into other low-solubility (silicate or aluminosilicate) phases. In the case of Pb, the results of this work tentatively support a previous identification of Pb(3)SiO(5) as a potential candidate phase for hosting Pb(II) within the geopolymer structure, although the data are not entirely conclusive. The addition of relatively low levels of heavy metal salts is seen to have little effect on the compressive strength of the geopolymeric material, and in some cases actually gives an increase in strength. Sparingly soluble salts may undergo some chemical conversion due to the highly alkaline conditions prevalent during geopolymerization, and in general are trapped in the geopolymer matrix by a simple physical encapsulation mechanism. Lead is in general very effectively immobilized in geopolymers, as is cadmium in all except the most acidic leaching environments. Hexavalent chromium is problematic, whether added as a highly soluble salt or in sparingly soluble form.     

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.     

壳聚糖改性地聚合物的力学及吸附性能

采用壳聚糖增韧改性矿渣基地聚合物,研究了壳聚糖掺量对矿渣基地聚合物强度与弯曲韧性、吸附重金属离子性能的影响规律,采用FTIR、NMR、SEM及EDS等测试手段揭示了壳聚糖对矿渣基地聚合物的改性机制。结果表明,与空白样相比,壳聚糖掺量（与矿粉质量比）为2%的矿渣基地聚合物28天弯曲韧性系数提高497.22%,对Pb2+、Cr3+的吸附效率分别提高68.89%、81.45%。壳聚糖在分子层面（C—O—Si键的形成及[SiO₄]聚合度的降低）及亚微观层面（三维互穿网络结构的形成）对矿渣基地聚合物进行增韧改性。壳聚糖自身较高的吸附性及低Ca/Si比C—S—H凝胶数量的增加,是矿渣基地聚合物吸附性能显著提升的关键。      

Immobilization of heavy metals (Pb, Cu, Cr, Zn, Cd, Mn) in the mineral additions containing concrete composites

The presented work determines the level of heavy metals (Pb+2, Cu+2, Zn+2, Cr+6, Cd+2, Mn+2) immobilization in the composites produced using Ordinary Portland Cement (OPC) as well as of binders containing large amount of mineral additives in its composition-siliceous fly ash (FA), fluidized bed combustion ash (FFA) and ground granulated blast furnace slag (GGBFS). Heavy metals were introduced to cementitious materials in the form of soluble salts as well as components of hazardous wastes (medical ash, metallurgical dust). It has been stated, that the level of heavy metals immobilization is combined with composites composition. Majority of analyzed heavy metals, added to binders' composition in the form of heavy metal salts achieves high level of immobilization, in mortar based on binder with 85% GGBFS and 15% OPC. The lowest immobilization level was reached for chromium Cr+6 added to hardening mortars as Na2Cr2O72H2O. The level ranges from 85.97% in mortars made on blended binder (20% OPC, 30% FFA and 50% GGBFS) to 93.33% in mortar produced on OPC. The increase of the so-called immobilization degree with time of hardened material maturing was found. This should be attributed to the pozzolanic or pozzolanic/hydraulic properties of components used; their effect on microstructure of hardened material is also important. Mineral additions enter the hydration reactions in the mixtures and favor the formation of specific microstructure promoting the immobilization of hazardous elements.     

Alkali-activated cements and mortars based on blast furnace slag and red clay brick waste

This study investigates the effects of adding various concentrations, sources and compositions of ground red clay brick waste (RCBW) on the properties of fresh and hardened pastes and mortars of alkali-activated slag. The method used to grind the granulated blast furnace slag (GBFS) and RCBW (separate and conjoint) is also assessed, along with the fineness (300–900 m²/kg) of the blended alkali-activated GBFS-RCBW cement, the alkali activator (sodium carbonate or sodium silicate) and the curing conditions (normal conditions or steam curing). The water requirement and setting time for the fresh pastes are also considered; and in the case of the hardened paste and mortar, the water absorption, density and compressive/flexural strength are measured after 1, 3, 7 and 28 days of aging. From the results obtained, it is demonstrated that the addition of 40% RCBW improves the 7- and 28-day strength of blended alkali-activated slag pastes and mortars, and can replace up to 60% of the slag without losing strength.     

Drying-induced changes in the structure of alkali-activated pastes

Drying of cement paste, mortar, or concrete specimens is usually required as a pre-conditioning step prior to the determination of permeability-related properties according to standard testing methods. The reaction process, and consequently the structure, of an alkali-activated slag or slag/fly ash blend geopolymer binder differs from that of Portland cement, and therefore there is little understanding of the effects of conventional drying methods (as applied to Portland cements) on the structure of the geopolymer binders. Here, oven drying (60 °C), acetone treatment, and desiccator/vacuum drying are applied to sodium silicate-activated slag and slag/fly ash geopolymer pastes after 40 days of curing. Structural characterization via X-ray diffraction, infrared spectroscopy, thermogravimetry, and nitrogen sorption shows that the acetone treatment best preserves the microstructure of the samples, while oven drying modifies the structure of the binding gels, especially in alkali-activated slag paste where it notably changes the pore structure of the binder. This suggests that the pre-conditioned drying of alkali activation-based materials strongly affects their microstructural properties, providing potentially misleading permeability and durability parameters for these materials when pre-conditioned specimens are used during standardized testing.     

Characterisation of ground hydrated Portland cement-based mortar as an additive to alkali-activated slag cement

The sustainable development of cement manufacturing requires extension of the raw material base, including large-tonnage waste. Hydrated mortar waste is a promising mineral resource for the production of Portland cements and alternative binders, such as alkali-activated slag cement. The influences of ground-hydrated mortar aged for 3 months on the properties of alkali-activated slag fresh and hardened pastes were performed. The results show that the properties are dependent on the concentration (2.5–60%), cement:sand ratio (1:1–3) and fineness (200–600 m²/kg) of the ground hydrated mortar; the alkali activator (sodium carbonate and sodium silicate); and the curing conditions (normal conditions and steam curing). The fresh paste properties that we considered in this study included the water requirement and the setting time; the hardened paste properties we considered were the water absorption, the density, and the compressive strength after 2, 7, 14, 28, 180 and 360 days of ageing. The ground hydrated mortar improved the early strength and the long-term strength of the alkali-activated slag paste and replaced the slag up to 50%. The factors that affecting the strength of the alkali-activated slag cement with ground hydrated mortar as an additive were, in order of influence, alkali activator type > curing conditions > cement:sand ratio > ground-hydrated mortar fineness.     

Reuse of cement-solidified municipal incinerator fly ash in cement mortars: physico-mechanical and leaching characteristics

The reuse of cement-solidified Municipal Solid Waste Incinerator (MSWI) fly ash (solidified/stabilised (S/S) product) as an artificial aggregate in Portland cement mortars was investigated. The S/S product consisted of a mixture of 48 wt.% washed MSWI fly ash, 20 wt.% Portland cement and 32 wt.% water, aged for 365 days at 20 degrees C and 100% RH. Cement mortars (water/cement weight ratio=0.62) were made with Portland cement, S/S product and natural sand at three replacement levels of sand with S/S product (0%, 10% and 50% by mass). After 28 days of curing at 20 degrees C and 100% RH, the mortar specimens were characterised for their physico-mechanical (porosity, compressive strength) and leaching behaviour. No retardation in strength development, relatively high compressive strengths (up to 36 N/mm2) and low leaching rates of heavy metals (Cr, Cu, Pb and Zn) were always recorded. The leaching data from sequential leach tests on monolithic specimens were successfully elaborated with a pseudo-diffusional model including a chemical retardation factor related to the partial dissolution of contaminant.     

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。     

Influence of pH, curing time and environmental stress on the immobilization of hazardous waste using activated fly ash

The current work is related to inorganic species in sludge generated from Common Effluent Treatment Plant contaminated with hazardous wastes at relatively high concentration. The environmental sensitive metals studied in the sludge are Pb, Fe, Ni, Zn and Mn. The solidification/stabilization (S/S) of heavy metals within fly ash-cement-based matrix was conducted for low cost treatment and reuse of sludge. The study examines the strength of the S/S product by predicting the effect of supplementary cementing material from efficiency factor (k) at 60 degrees C curing temperature. The leaching test was performed at two different pH 7 and 4 to determine the efficiency of heavy metal immobilization. It was observed that replacing 76% OPC by 56% fly ash and 20% sludge for 28 days curing period shows increase in strength as well as rate of stabilization for zinc, iron and manganese at pH 7, lead and nickel were stabilized by 79 and 82%, respectively. Environmental stress test was performed to evaluate the tolerance of extreme adverse environmental condition.     

Studies on potential of Portland cement mortar for binding of waterworks sludge to reduce heavy metal leaching

The investigation of heavy metal leaching and physicochemical properties of cement-solidified waterworks sludge (CMWWS) formed by incorporating waterworks sludge (WWS) into cement mortar was carried out. The chemical composition, compressive strength and other physicochemical properties of the CMWWS cube specimens were determined using field emission scanning electron microscopy (FESEM), X-ray diffractometry (XRD) and Fourier transform-infrared spectroscopy (FTIR). The major type of chemical components present in CMWWS was found to be Al and Fe. The increasing amount of WWS added to cement mortar resulted in the increasing of organic matter, urchin-like morphology and clear peak intensity. At the end of 28 days of curing, the soaking solution became strongly basic and CMWWS cube specimens leached out higher amount of heavy metals. The compressive strength of CMWWS increased up to a WWS percentage of 10%, and basic (pH > 7) curing solution was found to be better than water for curing purposes. It is concluded that solidification–stabilisation (S/S) technique is able to effectively reduce the leaching of heavy metals from the WWS and CMWWS containing up to 10% WWS can be used as construction material.     

Bond strength of PCC pavement repairs using metakaolin-based geopolymer mortar

In order to use geopolymer mortar as a pavement repair material, a splitting test and a slant shear test are performed to characterize the bond strength of the geopolymer and conventional cement mortar interfaces. Effect of curing time, degradation of the cement mortar under different acid conditions on the bond strength of geopolymer with conventional cement mortar, and comparison of the metakaolin geopolymer with other pavement repair materials are analyzed. It was found that curing time affects the interface bond strength greatly. Metakaolin geopolymer reaches 80% of its 28 day strength in 3 days curing, but shows low strength in 24 h curing. Curing temperature affects the strength of metakaolin geopolymer, however metakaolin geopolymer cured in ambient temperature and the bond strength of 3 days curing through splitting and slant shear tests reaches 3.63 MPa and 16.32 MPa, respectively. Degradation of cement mortar negatively affects the bond strength of geopolymer and conventional cement mortar. Possibility of using metakaolin geopolymer as a repair material is discussed by comparison of this experimental result with these of other repair materials.     

Leaching characteristics of slag from the melting treatment of municipal solid waste incinerator ash

This study investigated the composition and leaching characteristics of municipal solid waste incinerator (MSWI) ash and slag. The modified slags were characterized after the melting of MSWI ash mixtures at 1400 degrees C for 30 min. The ash mixtures were composed of different types of MSWI ash, including cyclone ash, scrubber ash and bottom ash, in various proportions. The results indicate that the Cd leaching concentration of the cyclone ash and the Pb leaching concentration of the scrubber ash reached 1.82 and 8.7 mg/L, respectively, which exceeds the ROC EPA's current regulatory thresholds, and can thus be classified as hazardous. The results of the analysis of the metal content and the leaching behavior of heavy metals, showed high concentrations of Cu and Zn, but a low leaching ratio of these metals. Concerning the characteristics of the modified slags, the X-ray diffraction patterns of the MSWI fly ash slag showed that it contained large amounts of glass. The toxicity characteristic leaching procedure (TCLP) leaching concentrations of the target metals of all the slags, met the ROC EPA's regulatory thresholds. The leaching concentrations of heavy metals in the F- and B1-slag were lower than those in the cyclone and the bottom ash, because there was a high amount of SiO(2), which formed a net-like structure in the bottom ash.     

Melting of municipal solid waste incinerator fly ash by waste-derived thermite reaction

This work describes a novel approach for melting municipal solid waste incinerator (MSWI) fly ash, based on self-propagating reactions, by using energy-efficient simulated waste-derived thermite. The self-propagating characteristics, the properties of the recycled alloy and slag and the partitioning of heavy metals during the process are also studied. Experimental results demonstrate that the mix ratio of fly ash to the starting mixture of less than 30% supports the development of the self-propagating reaction with a melting temperature of 1350-2200 degrees C. Furthermore, metallic iron (or alloy) and the slag were retrieved after activation of the thermite reactions among the starting mixtures. It was noted that more than 91wt.% of iron was retrieved as alloy and the rest of non-reductive oxides as slag. During the thermite reactions, the partition of heavy metals to the SFA and flue gas varied with the characteristics of the target metals: Cd was mainly partitioned to flue gas (75-82%), and partition slightly increased with the increasing fly ash ratio; Pb and Zn, were mainly partitioned to the SFA, and the partition increased with increasing fly ash ratio; Cu was partitioned to the SFA (18-31%) and was not found in the flue gas; and moreover stable Cr and Ni were not identified in both the SFA and flue gas. On the other hand, the determined TCLP leaching concentrations were all well within the current regulatory thresholds, despite the various FA ratios. This suggests that the vitrified fly ash samples were environmental safe in heavy metal leaching. The results of this study suggested that melting of municipal solid waste incinerator fly ash by waste-derived thermite reactions was a feasible approach not only energy-beneficial but also environmental-safe.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Effects of light crude oil contamination on the physical and mechanical properties of geopolymer cement mortar

Fly ash and oil contaminated sand are considered as the two waste materials that may affect environment. This paper investigated the suitability of producing geopolymer cement mortar using oil contaminated sand. A comparison between physical and mechanical properties of mortar produced using geopolymer and Ordinary Portland Cement (OPC), in terms of porosity, hydration and compressive strength, was conducted. The results showed that heat curing can increase the compressive strength of geopolymer mortar up to 54% compared to ambient curing situation. The geopolymer mortar with 1% of light crude oil contamination yielded a 20% higher compressive strength than OPC mortar containing sand with a saturated surface dry condition. Furthermore, the formation of efflorescence decreased as the level of oil contamination decreased. Moreover, the heat curing method increased the kinetic energy and degree of reaction for geopolymer cement mortar, which cause an increment of the density of the pore system and improving the mechanical properties of the resulting composites. From the results of this study, it was demonstrated that geopolymer mortar has the potential of utilizing oil contaminated sand, and reducing its environmental impacts.     

Application of thermally activated municipal solid waste incineration (MSWI) bottom ash fines as binder substitute

Untreated municipal solid waste incineration (MSWI) bottom ash fines (0–2 mm) have poor pozzolanic properties, and contain substances which can pose an environmental risk (e.g. heavy metals and salts). This study investigates combined treatments applied on bottom ash fines (BAF) to increase their reactivity. The treated BAF is compared with both untreated BAF and cement, and its contribution to cement hydration is investigated. Additionally, the utilization of the treated BAF in mortar as cement replacement is tested. Finally, the leaching properties of mortars containing treated and untreated BAF are estimated. According to the results obtained, the 28-day compressive and flexural strengths of mortar with 30% treated bottom ash are about 16% and 6% lower than the reference mortar, respectively. The leaching of contaminants from the crushed mortars with BAF are well under the limit values imposed by Dutch legislation.     

A novel method for preparation of organic resins reinforced geopolymer composites

A novel method for preparation of alkali-activated metakaolin/granulated blast furnace slag (GBFS)-based geopolymer reinforced by organic resins (OR) was reported. The geopolymer composites by doping an amount of 1 wt% OR displayed the highest compressive and flexural strengths at the different curing times. The calorimetry results showed that the reaction heats of the geopolymer composites at the early reaction stage of 1~3d are much higher than that of geopolymer due to the geopolymerization rate to be accelerated by incorporation of OR. A reasonable reinforced mechanism was proposed.     

超细矿渣粉对硅酸盐水泥性能和微观结构的影响

通过掺入不同量的超细矿渣粉,研究其对普通硅酸盐水泥凝结时间、标准稠度用水量以及水泥胶砂流动性和强度的影响。结果表明,水泥浆体的初凝、终凝时间在矿渣粉掺量为5%(质量分数,下同)时有所缩短,而随着超细矿渣粉掺量的增加,初凝时间都有所延长,在掺量为20%时初凝时间最长。然而终凝时间的变化不大,只有掺量为30%时稍有延长;水泥的标准稠度用水量先减少后增加,在掺量为20%时最小;随着超细矿渣粉掺量的增大,水泥胶砂的各龄期抗折强度、3d抗压强度不断提高,7d、28d抗压强度在掺量为20%时达到最大值,之后有所降低。掺入超细矿渣粉后,能通过填充以及与水泥水化产物氢氧化钙发生反应,使水泥中氢氧化钙含量明显降低,水泥微观结构更加密实。