Properties and mechanism of mine tailings solidified and filled with fluorgypsum-based binder material

The properties and microscopic structure of tailings solidification bodies, the hardening mechanism of the fluorgypsum-based binder material (FBBM) and tailings solidification mechanism were investigated. FBBM consisted of 40% fluorgypsum,25%-50% blast furnace slag,10%-35% ordinary Portland cement clinker(OPCC) and 1% activator, which was good material in binding iron ore tailings.XRD analysis showed that the properties of tailings solidification bodies was related to its ettringite content.SEM and XRD analyses of tailings solidification bodies showed that the chemical reaction was produced between FBBM and tailings in the whole hydration process. The hydration of the resulting gel material covered the surface of the tailings particles and formed a gel structure. A large number of ettringite crystals and the remaining board-like gypsum crystals took each end and constituted the structural skeleton. The filamentous network-like calcium-silicate-hydrate(C-S-H) gel bonded firmly together with ettringite crystals, dehydrated gypsum crystals and granular tailings, and formed an extremely dense whole.     

矿渣-粉煤灰-氟石膏胶结材激发及毒性

研究了激发剂对氟石膏的激发效果和机理,复合氟石膏胶结材的强度、软化系数和浸出毒性。通过NaOH、Na2SO4和NaF对氟石膏激发试验,确定最优掺量均为1％。在此基础上,采用矿渣、粉煤灰、熟料对用量80％以上氟石膏进一步改性,发现Na2SO41％、矿渣2．5％、粉煤灰5％和氟石膏89％复合胶结材性能最好,28d抗压强度可达12．25MPa,软化系数可达0．70,浸出氟离子浓度降低到0．7485mg／L。SEM和XRD分析发现水化形成的二水石膏晶体与少量水化硅酸钙、钙矾石及氟化钙互相填充包裹,阻碍了水分进入,改善了复合胶结材耐水性能和降低了浸出毒性。     

Mechanical property and microstructure of alkali-activated Yellow River sediment-coal slime ash composites

This work focuses on the production of a new composite material using Yellow River sediment and coal slime ash via alkali-activating method. XRD, FTIR and SEM/EDS were used to characterize the alkali-activated products and microstructure of the composite material. Compressive strength was tested to characterize the mechanical property of the composite material. It is found that the compressive strength of the Yellow River sediment-coal slime ash composites increases as the added Ca(OH)₂ content grows. The compressive strength increases fast in the early stage but slowly after 28 days. The strength of the composites can be significantly improved via the addition of small amount of NaOH and gypsum. The products (C-S-H, ettringite and CaCO₃), especially C-S-H, make much contribution to the enhancement of strength. The highest strength of the composites can reach 14.4 MPa after 90 days curing with 5% Ca(OH)₂, 0.2% NaOH and 7.5% gypsum. The improved properties of the composites show great potential of utilizing Yellow River sediment for inexpensive construction materials.     

钢渣-杂填土基层材料配合比优化试验研究

以杂填土、钢渣、矿渣微粉为原料,采用土体固化技术混拌制备钢渣-杂填土基层材料。开展钢渣、混凝土破碎料、素土等主料对基层材料强度的耦合影响试验,构建回归模型,得到主料最优掺入比例,试验验证表明,回归模型预测值误差小于2%;以钢渣、混凝土破碎料、水泥、固化剂为因素开展正交试验,得到的最优结果与强度耦合影响试验基本一致,从而确定钢渣-杂填土最优配合比。最优配合比试件试验结果表明：钢渣-杂填土强度随龄期增长显著提升,30 d高温水浴膨胀率仅为1.03%。X射线衍射分析（XRD）及扫描电子显微镜（SEM）测试表明：矿渣微粉中SiO₂与钢渣中f-CaO反应生成水化硅酸钙（C-S-H）凝胶,同时发现土壤固化剂对土体的改性可有效抑制钢渣膨胀;C-S-H凝胶填充于混凝土破碎料、钢渣、土颗粒间,增加了钢渣-杂填土基层材料密实度,使其强度得以提高。     

Modification of waste fluorgypsum and its applications as a cement retarder

The waste fluorgypsum was modified and applied as a cement retarder. The main chemical composition and mineral structure of the waste fluorgypsum were analyzed. Scanning electron microscopy (SEM) and eight-channel micro-calorimeter (TAM Air) were employed to analyze the changes in morphology and study the application performance of the modified fluorgypsum, respectively. Experimental results indicate that the flexural strength and compressive strength of the modified fluorgypsum are roughly equal to those of the natural gypsum. The morphology of the crystal of the fluorgypsum changes from block particle into trimetric short column. The fluorgypsum crystals stagger mutually and improve the strength of the hardened body. The modified fluorgypsum as cement retarder could delay the hydration, reduce the heat of the hydration and make the setting time, volume stability, and the SO3 content of the cement meet the national standards. The modified fluorgypsum is a good substitute for the natural gypsum.     

Properties of Alkali-activated Yellow River Sediment-slag Composite Material

In order to consume the Yellow River sediment as much as possible and improve the longterm stability of the Yellow River, Yellow River sediment was utilized as the main raw material to produce a composite material. Ca(OH)_2 was used as alkali-activator to activate the active SiO_2 and Al_2O_3 compositions in Yellow River sediment. 10 wt% slag was added into the mixture to further improve the strength of the composites. The effect of activity rate of the Yellow River sediment and dosage of Ca(OH) _2 on the compressive strength of the Yellow River sediment-slag composite material at different curing ages was researched. XRD, SEM/EDS, light microscope and FTIR were used to further explore the products and the microstructure of the composite material. Results showed that the active ratio of sediment had a great influence on the compressive strength of specimen. In addition, the compressive strength of specimen increased with the increase of Ca(OH)_2dosage and curing age. When the dosage of Ca(OH)_2 was more than 5 wt% as well as the curing age reached 90 days, the compressive strength of the composite material could meet the engineering requirement. In the alkali-activated process, the main product was hydrated calcium silicate(C-S-H) gel, which filled up the gaps among the sediment particles and decreased the porosity of the specimen. Moreover, the CaCO_3 produced by the carbonization of the C-S-H gel and excess Ca(OH)_2 also played a role on the strength.     

Early hydration of composite cement with thermal activated coal gangue

Composite cement samples were prepared by mixing clinker, gypsum with burnt coal gangues which was calcined at various temperatures. The mechanical strength and Ca(OH)₂ content in the cement paste were tested, and the paste composition and microstructure were analyzed by thermogravimetry-differential thermal analysis (TG-DSC), X-ray diffraction(XRD), scanning electronic microscopy (SEM) and pore structure analysis. Results demonstrate that the thermal activated coal gangue could accelerate the early hydration of cement clinker obviously, which promotes the gangue hydration itself. The early hydrated products of the cement are C-S-H gel, Ca(OH)₂ and AFt. The cement with 30% (in mass) the gangue exhibits higher mechanical strength, and among all the cement samples the one with the gangue burnt at 700 °C displays the highest hydration rate, mechanical strength, the most gel pores and the lowest total porosity.     

石膏与硅灰对钢渣水泥基胶凝材料复合改性效应

以钢渣和水泥为主要原料,加入少量石膏(CaSO4·2H2O)与硅灰,制备钢渣水泥基胶凝材料。探讨了CaSO4·2H2O与硅灰掺量对钢渣水泥基胶凝材料强度的影响,并通过XRD、SEM表征,研究钢渣水泥基胶凝材料的水化性能。结果表明：复掺1% CaSO4·2H2O和4% 硅灰的钢渣水泥基胶凝材料3 d抗压强度较未掺CaSO4·2H2O与硅灰提高了59.0%,28 d抗压强度提高了32.4%;CaSO4·2H2O与硅灰的加入不会影响钢渣水泥基胶凝材料水化产物种类;相同龄期内,加入CaSO4·2H2O与硅灰的钢渣水泥基胶凝材料中水化硅酸钙(C-S-H)凝胶和钙矾石(AFt)含量增多,Ca(OH)2晶体含量、晶体尺寸有所减小。     

Effects of molecular structure of polycarboxylate-type superplasticizer on the hydration properties of C3S

Effects of polycarboxylate-type superplasticizer(PC) molecular structure on the hydration heat of tricalcium silicate(C3S) paste and polymerization degree of hydration products(C-S-H gel) were researched by using TAM AIR isothermal microcalorimetry(TA) and 29Si nuclear magnetic resonance(NMR).Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.     

Durability and micro-structure of reactive powder concrete

Durability of traditional reactive powder concrete (RPC) with rich cement and high volume of fly-ash reactive powder concrete (FRPC) were studied. The X-diffraction and scanning electron microscope (SEM) measurement was imployed to analyze the microstructure. The results show that both types of RPC have higher compressive strength, less volume shrinkage ratio and better carbonation-, chloride-, freezing-resistances than the conventional concrete. The results of X-diffraction indicate that they basically have C-S-H as the main composition without Ca(OH)₂ crystal and ettringite. SEM results show that hydration products of FRPC is mainly III-C-S-H which is piled up closely like densely arranged stone body and it has very compacted structure, in addition, Ca/Si ratio of C-S-H gel is lower than 1.5.     

Characterization of pozzolanic reaction and its effect on the C-S-H Gel in fly Ash-cement paste

High resolution solid-state ²⁹Si MAS NMR, combined with XRD, SEM and FTIR were used to characterize the pozzolanic activity of FA, type of main pozzolanic reaction products, and the effect of pozzolanic reaction on the C-S-H microstructure in fly ash-cement (FC) paste. The experimental results indicate that in the hydrated FC paste with 30% dosage of FA at 3 d, FA partially participated in the pozzolanic reaction, while, at 120 d, FA largely reacts. During the hydration of FC paste at laboratory temperature, the pozzolanic reaction products are C-S-H gel rather than zeolitic gel. Moreover, after the covalent bonds of Si-O-Si, Si-O-Al and Al-O-Al in the structure of FA are broken, monosilicates Si-OH and Al-OH groups form, these chemical species can connect C-S-H dimers, thus producing more Al-free C-S-H and aluminous C-S-H than in the plain cement paste. The increased content of Al for Si substitution in the bridging tetrahedra of C-S-H may decrease the stability of C-S-H, which results in a rather obvious loss in the mechanical strength of hardened FC paste.     

Mechanisms of composite agglomeration of fluoric iron concentrate

The effect of composite agglomeration process (CAP) on fluoric iron concentrates sintering was investigated. The yield and quality of the sinter are greatly improved when using CAP assisted with heat airflow and enhancing magnesium oxide (MgO) contents. For conventional sintering of fluoric iron concentrate, due to lower viscosity of binding phase and higher fluidity of liquid phase, the sinter is formed with large thin-walled holes and the strength of the sinter is deteriorated consequently. The novel process forms composite agglomerate in which acid pellets are embedded in basic sinter. The pellets are solid with interconnecting crystals of hematite (Fe₂O₃) and magnetic (Fe₃O₄). For basic sintering, after adding MgO, the viscosity of the melting phase increases and the fluidity decreases; and calcium and aluminum silico-ferrites and magnesium ferrite are formed with perfect crystals and good sintering microstructure.     

Effect of pozzolanic reaction products on alkali-silica reaction

1 IntroductionThe use of fly ashto control the expansion dueto al-kali-silica reaction (ASR) is well established and a num-ber of reviews have been published recently[1-4]. Howflyash brings about this reductionin expansionis not yet un-derstood although a number of theories have been put for-ward to explain its action. For controlling mechanism,they put more emphasis onthe adsorption andresort of al-kali by supplementary cementing material (SCM) , formore acidity oxide in SCM,and the secon…     

Fabrication and Characterization of Nano- CaCO3/Polypropylene Foam Sheets

By applying the reinforcing and toughening effect of calcium carbonate （CaCO3） nanoparticles on polypropylene, foam sheets of good performance were successfully fabricated by extrusion. The equipment and conditions of the extrusion were explored. The mechanical properties of the produced foam sheets were tested. The effect of CaCO3 nano-particles on the mechanical properties and the cellular structure of the sheets was comprehensively studied. The experimental results show that the optimum content of CaCO3 nano-particles in the composite material was -4wt%. At this content, the nano-particles were well dispersed in the substrate, and the composite material had maximum tensile strength and impact strength. Surface treatment of the nano-particles only affected the impact strength of the composite material. CaCO3 micro-particles, on the other hand, showed little effect on the properties of the composite material when the micro-particles content was less than 5 wt%. At a content higher than 5wt%, the properties of the composite material significantly worsened.     

Preparation and properties of alkali activated foam cement reinforced with polypropylene fibers

A new form of foam cement was produced by mixing alkali-activated slag,clay,a small amount of polypropylene fibers with prepared foam during stirring.The preparation of the material is quite different from the normal one,which is produced just at room temperature and without baking.The fabrication of this energy-saving and low-price material can be favorable for lowering carbon emission by using recycled industrial wastes.Thermal conductivity of 0.116 W/(m·k),compressive strength of 3.30 MPa,flexural strength of 0.8 MPa and density of 453 kg/m3 can be achieved after 28 days aging.The hydration product is C-S-H with less Ca(OH)2,calcium aluminum and zeolite,which was characterized by X-ray diffraction(XRD) measurement.This prospective foam cement may be expected to be an excellent economical energy-saving building material.     

合成C-S-H凝胶对水泥石-集料界面区的影响

研究了利用硅质材料和钙质材料经常温常压下水热反应制得的合成C-S-H疑胶对水泥石-集料界面区结构和性能的影响,发现这种合成凝胶对界面区的结构和性能有独特的改善作用。本文还探讨了合成C-S-H凝胶对界面区的作用机理。     

Effects of curing systems on properties of high volume fine mineral powder RPC and appearance of hydrates

The effects of different curing systems on the properties of high volume fine mineral powder RPC (reactive powder concrete) and the appearances of hydrates were studied. The experimental results show that dry-heating curing promotes the development of pozzolanic reactivity of fine mineral powder; due to low cement content, 0.20 water-bind ratio and high reactive fine mineral powder content, the strength of RPC increases by around 200% after steam curing and subsequent dry-heating curing. Scanning electron microscopy and energy spectrum diagram showed that: after the high volume fine mineral powder RPC with 0.16 water-bind ratio underwent steam curing and dry-heating curing, there was no significant change in the appearance of hydrates; after the RPC with 0.20 water-bind ratio, the cement content of 150 kg/m³ and more steel slag powder underwent dry-heating curing, there was a certain change in the appearance of C-S-H, the structure of gel was more compact and was uniformly distributed, and the Ca/Si of C-S-H gel decreased from 1.41 to around 1.20.     

Modification of Fluorgypsum as Cement Retarder

The chemical composition and mineral structure of fluorgypsum as well as its harm to application in cement were elaborately analyzed. The primary fluorgypsum was modified and its applications in cement＇s production were studied. The technological flow chart of preparing modified fluorgypsum was given. Experimental results indicate that hydration ratio the modified fluorgypsum through adding compound additive for 14d is about 70%. The modified fluorgypsum as cement retarder has certain stimulation to fly ash and increases the strength of compound cement. In addition, its adding amount is lower than that of natural gypsum. The modified fluorgypsum is a good substitute for natural gypsum.     

Dehydration Characteristics of C-S-H with Ca/Si Ratio 1.0 Prepared Via Precipitation

Calcium silicate hydrate(C-S-H) with Ca/Si ratio 1.0 was prepared via precipitation in solution and heated at various temperatures to investigate its dehydration behavior. The dehydration, structural collapse and recrystallization characteristics of C-S-H and its microstructural change during heating process were investigated by XRD, SEM, Raman and TG-DSC techniques. C-S-H gradually lost non-evaporable water upon heating, about 50% and 80% non-evaporable water was removed below 200 and 400 ℃, respectively, and the rest was removed up to about 1 000 ℃. At 400 ℃, dehydrated C-S-H exhibited the increasing disordering of calcium/silicon environment and the decreasing symmetrical bending vibration of Si-O-Si of Q~2 silicate chains. At 650 ℃ non-bridging oxygen atoms(O_(non)) attached to silicon were almost removed, and significant structural change occurred, and at 815 ℃ C-S-H dehydrated to wollastonite.     

Effect of baking processes on properties of TiB2/C composite cathode material

Pitch and TiB₂/C green composite cathode material were respectively analyzed with simultaneous DSC-TGA, and effects of three baking processes of TiB₂/C composite cathode material, i.e. K25, K5 and M5, on properties of TiB₂/C composite cathode material were investigated. The results show that thermogravimetric behavior of pitch and TiB₂/C green composite cathode is similar, and appears the largest mass loss rate in the temperature range from 200 to 600°C. The bulk density variation of sample K5 before and after baking is the largest (11.9%), that of sample K25 is the second, and that of sample M5 is the smallest (6.7%). The crushing strength of sample M5 is the biggest (51.2 MPa), that of sample K25 is the next, and that of sample K5 is the smallest (32.8 MPa). But, the orders of the electrical resistivity and electrolysis expansion of samples are just opposite with the order of crushing strength. The heating rate has a great impact on the microstructure of sample. The faster the heating rate is, the bigger the pore size and porosity of sample are. Compared with the heating rate between 200 and 600° of samples K25 and K5, that of sample M5 is slower and suitable for baking process of TiB₂/C composite cathode material. Foundation item: Project (2005CB623703) supported by the Major State Basic Research and Development Program of China; Project (2008AA030502) supported by the National High-Tech Research and Development Program of China