Synthesis and heavy metal immobilization behaviors of fly ash based gepolymer

Two aspects of studies were carried out: 1) synthesis of geopolymer by using fly ash and metakaolin; 2) Immobilization behaviors of fly ash based geopolymer in a presence of Pb and Cu ions. As for the synthesis of fly ash based geopolymer, 4 different fly ash content (10%, 30%, 50%, 70%) and 3 types of curing regimes (standard curing, steam curing and autoclave curing) were investigated to obtain the optimum synthesis condition based on the compressive and flexural strength. The experimental results show that geopolymer, containing 30% fly ash and synthesized at steam curing (80° for 8 h), exhibits higher mechanical strengths. The compressive and flexural strengths of fly ash based geopolymer reach 32.2 MPa and 7.15 MPa, respectively. Additionally, Infrared (IR) and X-ray diffraction (XRD) techniques were used to characterize the microstructure of the fly ash geopolymer. IR spectra shows that the absorptive band at 1086 cm⁻¹ shifts to lower wave number around 1033 cm⁻¹, and the 6-coordinated Al transforms into 4-coordination during the synthesis of fly ash based geopolymer. The resulting geopolymeric products were X-ray amorphous materials. As for immobilization of heavy metals, the leaching tests were employed to investigate the immobilization behaviors of the fly ash based geopolymer synthesized under the above optimum condition. The leaching tests showed that fly ash based geopolymer can effectively immobilize Cu and Pb heavy metal ions, and the immobilization efficiency reached 90% greater when heavy metals were incorporated in the fly ash geopolymer in the range of 0.1% to 0.3%. The Pb exhibits better immobilization efficiency than the Cu, especially in the case of large dosages of heavy metals.     

Activation of rejected fly ash using flue gas desulphurization (FGD) sludge

Low-grade fly ash (rejected fly ash, rFA), a significant portion of the pulverized fuel ash (PFA) produced from coal-fired power plants and rejected from the ash classifying process, remains unused due to its high carbon content and large particle size (>45 μm). But it is thought that the rejected ash may have potential uses in chemical stabilization solidification (S/S) processes which need relatively lower strengths and a lower chemical reactivity. Flue Gas Desulphurisation (FGD) sludge is a by-product of air pollution control equipment in coal fired power plants whose chemical composition is mainly gypsum. As there is no effective usage of both of these two materials, it is of interest to research on the possible activation of rFA using FGD. This paper presents experimental results of a study on the properties of rFA activated by the FGD in rFA-cement pastes. Different percentages of FGD were added into the mix to study the effects of the FGD on the reaction of the rFA blended cement pastes. The results show that FGD takes effect as an activator only at late curing ages. Adding Ca(OH)₂ enhances the effect of FGD on activating the hydration of rFA. Also, 10% FGD by weight of rFA is the optimal addition in the rFA-cement pastes. The results of the compressive strength measurements correlate well with the porosity results. QIAO Xiu-chen : Born in 1973 Funded by the Research Grants Council of Hong Kong (Project No. PolyU 5056/00E)     

Influence of Thermally Treated Flue Gas Desulfurization （FGD） Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.     

Preparation and mechanical properties of polypropylene fiber reinforced calcined kaolin-fly ash based geopolymer

To improve the environmental benefits and solve the problems of large shrinkage and high brittleness, the partial replacement of calcined kaolin by fly ash as a raw material for geopolymer synthesis and the influences of polypropylene (PP) fiber on the mechanical properties and volume stability were investigated. The results show that compressive strength of the geopolymer containing 33.3%(mass fraction) fly ash by steam curing at 80 °C for 6 d is improved by 35.5%. The 3-day compressive strength, flexural strength and impacting energy of geopolymers containing 0.05%PP fiber increase by 67.8%, 36.1% and 6.25%, while the shrinkage and modulus of compressibility decrease by 38.6% and 31.3%, respectively. The results of scanning electron microscopy (SEM) and the appearances of crack growths confirm that PP fiber can offer a bridging effect over the harmful pores and defects and change the expanding ways of cracks, resulting in a great improvement of strength and toughness. Foundation item: Project(2006AA06Z225) supported by the National High-Tech Research and Development Program of China     

Static and dynamic leaching experiments of heavy metals from fly ash-based geopolymers

The feasibility of high calcium fly ash (CFA)-based geopolymers to fix heavy metals were studied. The CFA-based geopolymers were prepared from CFA, flue gas desulfurization gypsum (FGDG), and water treatment residual (WTR). The static leaching showed that heavy metals concentrations from CFAbased geopolymers were lower than their maximum concentration limits according to the U.S. environmental protection law. And the encapsulated and fixed ratios of heavy metals by the CFA-based geopolymers were 96.02%–99.88%. The dynamic real-time leaching experiment showed that concentration of Pb (II) was less than 1.1 μg / L, Cr (VI) less than 3.25 mg / L, while Hg (II) less than 4.0 μg / L. Additionally, dynamic accumulated leaching concentrations were increased at the beginning of leaching process then kept stable. During the dynamic leaching process, heavy metals migrated and accumulated in an area near to the solid-solution interface. When small part of heavy metals in “the accumulated area” breached through the threshold value of physical encapsulation and chemical fixation they migrated into solution. The dynamic leaching ratios and effective diffusion coefficients of heavy metals from CFA-based geopolymer were very low and the long-term security of heavy metals in CFA-based geopolymer was safe.     

Preparation of fly ash and rice husk ash geopolymer

The geopolymer of fly ash (FA) and rice husk ash (RHA) was prepared. The burning temperature of rice husk, the RHA fineness and the ratio of FA to RHA were studied. The density and strength of the geopolymer mortars with RHA/FA mass ratios of 0/100, 20/80, 40/60, and 60/40 were tested. The geopolymers were activated with sodium hydroxide (NaOH), sodium silicate, and heat. It is revealed that the optimum burning temperature of RHA for making FA-RHA geopolymer is 690℃. The as-received FA and the ground RHA with 1%-5% retained on No.325 sieve are suitable source materials for making geopolymer, and the obtained compressive strengths are between 12.5-56.0 MPa and are dependent on the ratio of FA/RHA,the RHA fineness, and the ratio of so dium silicate to NaOH. Relatively high strength FA-RHA geopolymer mortars are obtained using a sodium silicate/NaOH mass ratio of 4.0, delay time before subjecting the samples to heat for 1 h, and heat curing at 60℃ for 48 h.     

粉煤灰-矿渣基地聚物混凝土力学性能与微观结构

为考察不同配合比对地聚物混凝土性能的影响,开展了粉煤灰与矿渣比例、水玻璃模数以及水玻璃掺量(质量分数)对其宏观力学性能影响的实验研究,并从微观层次扫描电子显微镜(SEM)、能量弥散X射线分析(EDS)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)以及压汞实验(MIP)对微观结构进行研究.结果表明:养护龄期的增加,...     

脱硫石膏－粉煤灰活性掺合料设计及水化特性

针对电厂两大工业废渣--烟气脱硫石膏及粉煤灰,通过试验研发用于混凝土的活性复合矿物掺合料.以适当比例复合后的脱硫石膏及粉煤灰等量取代水泥掺入到水泥砂浆中,通过活性激发措施,以胶砂流动度、早期强度以及强度发展规律等作为控制指标探索脱硫石膏及粉煤灰的最优配比,同时通过微细观结构的SEM观测评价脱硫石膏-粉煤灰活性矿物掺合料在水泥基材料中的作用效应.结果表明,脱硫石膏及粉煤灰以1:2的比例复合等量取代水泥30%掺入水泥砂浆中,可获得较为优异的胶砂流动度、早期强度,而后期强度能赶上甚至超过基准水泥胶砂;SEM表明由于脱硫石膏及其它外加组分的活性激发效应,粉煤灰的活性得到有效激发,早期有明显的钙矾石生成.脱硫石膏-粉煤灰复合矿物掺合料的研发可大量消纳燃煤电厂的工业废渣,且在水泥基材料体系中具有优异的水化及低成本特性,具有显著的"绿色"效应,符合中国"可持续发展"的战略要求.     

Glass-ceramics made from arc-melting slag of waste incineration fly ash

Grate fly ash and fluidized bed fly ash mixed with glass cullet additive respectively were melted in the electronic arc-furnace. The product, arc-melting slag, was further treated by crushing, pressing and heat treatment in order to make the glass-ceramics. The crystallization behaviors of the produced glass-ceramics were examined by differential thermal analysis (DTA), X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Results show that main crystalline phase of the glass-ceramics from grate fly ash is wollastonite (CaSiO₃) with small amount of diopside (Ca(Mg,Al)(Si,Al)₂O₆), and that from fluidized bed fly ash is diopside (Ca(Mg,Al)(Si,Al)₂O₆). It is found that the glass-ceramics sintered at 850 °C and 1 000 °C from grate fly ash and fluidized bed fly ash respectively have the optimal physical, mechanical and chemical characteristics. Glass-ceramics samples, produced from incinerator fly ash with desirable properties and the low leaching concentration of heavy metals, can be the substitute of nature materials such as marble, granite and porcelain tiles.     

Electrical conductivity and dielectric property of fly ash geopolymer pastes

The electrical conductivity and dielectric property of fly ash geopolymer pastes in a frequency range of 100 Hz-10 MHz were studied.The effects of the liquid alkali solution to ash ratios(L/A) were analyzed.The mineralogical compositions and microstructures of fly ash geopolymer materials were also investigated using X-ray diffraction(XRD) and scanning electron microscopy(SEM).The 10 mol sodium hydroxide solution and sodium silicate solution at a sodium silicate-to-sodium hydroxide ratio of 1.0 were used in...     

Influence of MgO-type expansive agent hydration behaviors on expansive properties of concrete

The hydration behaviors and expansive properties of MgO-type expansive agent curing at different temperatures and environment were investigated.When the curing temperatures changed from 25℃ to 50℃,the conductivities of MgO samples increased from 40 to 80 μs/cm,and the hydrations of MgO were quickened up obviously.Through SEM observation,the hydration product of MgO cured at 50℃ for 28 day was about 2-3μm in length.The expansion of pastes with 5% of the MgO-type expansive agent was from 0.36% to 1.01% when t...     

掺入普通硅酸盐水泥的粉煤灰地聚物混凝土力学性能与微观特征

既有研究表明,在粉煤灰地聚物混凝土（FGC）中掺入少量普通硅酸盐水泥颗粒,能够增强其在常温养护后的力学性能,但这个结果尚未与早期接受高温养护且不含普通硅酸盐水泥的FGC进行力学特征对比,以验证其可实用程度。为更加贴近实际工程需求,将不含水泥颗粒且接受热固化的FGC与含有少量水泥颗粒仅接受室温固化的FGC进行了包括泊松比在内的基本力学性能测试和比较。为了从微观机制上解释力学性能的测试结果,进行了包括SEM、EDS、XRD、FTIR、Micro-CT等的分析。结果表明：常温养护下含有少量水泥颗粒的FGC各项力学性能与不含水泥颗粒并接受热固化的FGC相近,临破坏前的试件横向应变与纵向应变之比均接近1.0,均有突出的横向变形能力;掺量8%的水泥颗粒在室温条件下对FGC聚合反应的促进效果接近FGC接受高温养护,在形成更为合理的微观孔隙结构方面,改进后的FGC在常温养护条件下优于高温养护FGC。     

Optimization of SO<Subscript>3</Subscript> content in blended cementitious materials

Experimental investigation was conducted on the effects of gypsum types and SO₃ content on the fluidity and strengths of different cementitious systems. The experimental results show that influences of gypsum in various cementitious materials are different. For cementitious materials blended with various proportions of slag-fly ash and 5% gypsum content, influences of gypsum and calcined gypsum on the fluidity and flexural/compressive strength are similar. It is revealed that “combination effect” and “synergistic effect” of slag and fly ash play an important role during hydration. For cementitious materials with 45% clinkers, 30% slag, 20% fly ash and 5% limestone, the optimized SO₃ contents in gypsum and calcined gypsum are 3.13% and 3.51% respectively and the optimized gypsum content is 6.5%. While both of them are blended, the optimum ratio of gypsum to calcined gypsum is 40%:60% (total gypsum content 6.5%), correspondingly the optimum ratio of SO₃ is 19.3%:32. 4%. CHEN Mei-zhu : Born in 1974 Funded by Hubei Bureau of Science and Technology of China (981P0202)     

Remediation and monitoring of abandoned mines

paper describes a recent study on using fly ash for backfilling abandoned room and pillar mines.Detailed investigations on fly ash properties such as the strength and stiffness of settled fly ash, flowability of fly ash grout, as well as chemistry and environmental aspects of fly ash backfill have been undertaken in the laboratory. Numerical modelling was also conducted to quantify the effects of fly ash backfill on the stability of underground pillars. The laboratory tests showed that with a solid concentration of approximate 50%, fly ash grout has an excellent flowability and very low viscosity. It is capable of penetrating and filling almost any voids underground if designed properly and settling as a reasonably stiff solid to provide support to the pillars. Several different types of strength tests proved that a consolidated fly ash should exhibit a friction angle above 42°. 3D numerical modelling on interaction between fly ash backfill and underground pillars has shown that fly ash backfill to 90% roadway height can raise the factor of safety(Fo S) of a marginally stable area to above 1.6, which is the number often used in rock engineering design for long term stability. Chemistry and leachate analysis of representative fly ash samples from a local power station showed that the elemental concentrations in the fly ash solid sample are lower than the allowed contaminant threshold and specific contaminant concentration levels. Geotechnical monitoring in the high risk areas of an abandoned mine has been carried out as part of the risk management and control for potential subsidence. The monitoring has been very helpful in understanding the ground behaviour around the abandoned mine which can provide timely information to the parties concerned in order to make correct decisions to control the subsidence risk.     

纯化粉煤灰的改性及应用研究

为了提高粉煤灰的利用率,扩大应用领域,在Ca（OH）2-H2O-CO2系统,利用化学沉积方法成功地实现了粉煤灰颗粒的表面包覆,包覆后粉煤灰具有较高的白度和表面粗糙度.描述了复合粉煤灰的制备过程,研究了粉煤灰表面的包覆机理,借助SEM,BET,XRD等先进检测技术分析了粉煤灰改性前后的性能变化.试验结果表明：复合粉煤灰的白度由入料的33.54提高到73.13,比表面积由入料的3.07 m^2/g增加到9.77 m^2/g.在25%相同填充量的情况下,PP-复合粉煤灰的力学性能均优于未包覆粉煤灰、重质碳酸钙或轻质碳酸钙作填料的性能.     

Effect of chemical admixtures on properties of high-calcium fly ash geopolymer

Owing to the high viscosity of sodium silicate solution, fly ash geopolymer has the problems of low workability and rapid setting time. Therefore, the effect of chemical admixtures on the properties of fly ash geopolymer was studied to overcome the rapid set of the geo-polymer in this paper. High-calcium fly ash and alkaline solution were used as starting materials to synthesize the geopolymer. Calcium chloride, calcium sulfate, sodium sulfate, and sucrose at dosages of 1wt% and 2wt% of fly ash were selecte...     

Preparation of new cementitious system using fly ash and dehydrated autoclaved aerated concrete

We experimentally studied the interaction between pozzolanic material(fly ash) and dehydrated autoclaved aerated concrete(DAAC). The DAAC powder was obtained by grinding aerated concrete waste to particles fi ner than 75μm and was then heated to temperatures up to 900 ℃. New cementitious material was prepared by proportioning fly ash and DAAC, named as AF. X-ray diffraction(XRD) was employed to identify the crystalline phases of DAAC before and after rehydration. The hydration process of AF was analyzed by the heat of hydration and non-evaporable water content(Wn). The experimental results show that the highest reactivity of DAAC can be obtained by calcining the powder at 700 ℃ and the dehydrated products are mainly β-C2 S and CaO. The cumulative heat of hydration and Wn was found to be strongly dependent on the replacement level of fl y ash, increasing the replacement level of fl y ash lowered them in AF. The strength contribution rates on pozzolanic effect of fl y ash in AF are always negative, showing a contrary tendency of that of cement-fl y ash system.     

Effect of activator and curing mode on fly ash-based geopolymers

The influences of concentration and modulus of sodium silicate solution and curing mode on the phase composition, microstructure and strength development in the geopolymers prepared using Class F fly ash were investigated. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and MAS NMR were utilized. Results show that the compressive strength increases as sodium silicate solution modulus increases, but when modulus exceeds 1.4, the compressive strength decreases, and it decreases markedly while the modulus is greater than 2.0. The compressive strength was improved by the increase of sodium silicate solution concentration. When the concentration is 32%, the compressive strength reaches the maximum, then it reduces as concentration increasing. Elevated temperature can increase the strength of samples that synthesized from sodium silicate solution with 32% concentration and modulus 1.2. Compared to the strength of the sample cured at 50 °C, the strength of the samples cured at 65 °C and 80 °C are higher at 1 d and 3 d, but the same at 7 d. At high temperature, prolonged curing time will decrease the strength. Long precuring at room temperature before application of heat is beneficial for strength development, and there is about 50% increase in strength of the samples cured at 1 d precuring and 2 d elevated temperature as compared to the strengths of the samples cured for 3 d at elevated temperatures or cured for 28 d at room temperature. The main product of reaction in the geopolymeric material is amorphous alkali aluminosilicate gel.     

Cemented backfill technology based on phosphorous gypsum

Physical-chemical properties of phosphorous gypsum, proportion and cemented mechanism of slurry with gypsum as aggregate were studied to remove the harms of gypsum pile, combining with difficult problems of excessive mined-out gobs, enormous ore body under roadway and low recovery ratio of Yongshaba Mine, Kaiyang Phosphor Mine Group, Guizhou Province, China. An appropriate backfill system and craftwork were designed, using shattering milling method to crush gypsum, double-axles mixing and strong activation mixing way to mix slurry, cemented slurry and mullock backfill alternately process. The results show that gypsum is fit for backfilling afterwards by adding fly ash, though it is not an ideal aggregate for fine granule and coagulate retardation. The suggested dosage (the mass ratio of cement to fly ash to gypsum) is 1:1:6–1:1:8 with mass fraction of solid materials 60%–63%. Slurry is transported in suspend state with non-plastic strength, and then in concretion state after backfilling. The application to mine shows the technology is feasible, and gypsum utilization ratio is up to 100%. Transportation and backfill effect is very good for paste-like slurry and drenching cemented slurry into mullock, and the compressive strength and recovery ratio are 2.0 MPa and 82.6%, respectively, with the maximum subsidence of surface only 1.307 mm. Furthermore, the investment of system is about 7×10⁶ yuan (RMB), only 1/10 of that of traditional paste backfill system. Foundation item: Project (2006BAB02A03) supported by the National Key Technology Research and Development Program; Project (08MX16) supported by Mittal Scientific and Technological Innovation Projects of Central South University during 2008     

Effects of Cr~(3+), Cu~(2+), and Pb~(2+) on Fly Ash based Geopolymer

The effects of Cr~(3+), Cu~(2+), and Pb~(2+) on compressive strength, reaction products, and pore structures of fly ash based geopolymer were studied. In addition, the immobilization and bonding interaction between heavy metal and fly ash based geopolymers were investigated by X-ray photoelectron spectroscopic(XPS) and environmental scanning electron microscope(ESEM) techniques. The experimental results showed that the incorporation of Cr~(3+), Cu~(2+), and Pb~(2+) had a great effect on the later compressive strength and resulted in producing reinhardbraunsite in the solidified body. Moreover, the Pb~(2+) reduced the total pore volume of the solidified body, while Cr~(3+) and Cu~(2+) increased it. The XPS results indicated that O(1 s), Si(2 p), and Al(2 p)bind energy increased due to Cr~(3+) and Cu~(2+) addition, but it did not change significantly due to Pb~(2+) addition.The microstructure of calcium silicate hydrate(C-S-H) gel and sodium silicoaluminate hydrate(N-A-S-H) gel changed in different degree according to the ESEM results. The immobilization of Cr~(3+), Cu~(2+), and Pb~(2+) using fly ash based geopolymer is attributed not only to the physical encapsulation, but also to the chemical bonding interaction.