Hydration characteristics of waste sludge ash that is reused in eco-cement clinkers

The study reports on the hydration characteristics of eco-cement clinkers produced with waste sludge ash as raw components. The tested mixtures were composed of different types of waste sludge ash, including sewage sludge ash, water purification sludge ash, limestone, and ferrate, prepared using the optimum proportioning method. The mixtures were burned at 1400 °C for 6 h. The clinkers thus obtained were quantified and the hydration characteristics of the eco-cement pastes prepared from the waste sludge ashes. The setting time, compressive strength, hydrates and porosity distribution were examined at various ages. The 28-day compressive strength of the early high strength developing of eco-cement C paste outperformed that of ordinary Portland cement paste by 3 MPa. It is supposed that the large quantity of limestone used provided CaO, which in turn enhanced the formation of C₃S, leading to the greater compressive strength development in the eco-cement C paste. From the porosity distribution, shown by the Mercury Intrusion Porosimetry results, it was found that, with increasing curing ages, the gel pores (<0.01 μm) increased and the total porosity and capillary pores (>0.01 μm) decreased—a result that shows that hydrates had filled the pores. This resulting densification and enhanced later strength were caused by the shifting of the pore size distribution to a smaller diameter range.     

Effect of waste aluminosilicate material on cement hydration and properties of cement mortars

The effect of waste material (catalyst used previously in catalytic cracking of petroleum in fluidized bed—fluidized bed cracking catalyst denoted as FBCC) on cement hydration kinetics was investigated in terms of fineness of this admixture. The compressive strength and microstructure of cement mortars were also examined. Variable percentage of this aluminosilicate admixture, originating from batches of quite different grain size composition, was introduced to cement pastes. Further on, cement mortars were produced using the material of higher activity, as it has been found in admixtured cement investigations. The waste was added as cement replacement or, partially, as sand replacement. The activity of waste catalyst was strongly related to the fineness—finer grains indicate better activity. In the presence of a FBCC admixture, the Ca(OH)₂ content decrease in cement pastes due to the pozzolanic reaction is observed. The surface area of hydrated paste becomes higher and, simultaneously, the mean pore diameter decreases, as compared to reference sample, without admixture. The strength improvement is observed particularly when the aluminosilicate material is introduced as partial sand replacement.     

Hydration of fly ash cement

It is necessary to establish the material design system for the utilization of large amounts of fly ash as blended cement instead of disposing of it as a waste. Cement blended with fly ash is also required as a countermeasure to reduce the amount of CO₂ generation. In this study, the influences of the glass content and the basicity of glass phase on the hydration of fly ash cement were clarified and hydration over a long curing time was characterized. Two kinds of fly ash with different glass content, one with 38.2% and another with 76.6%, were used. The hydration ratio of fly ash was increased by increasing the glass content in fly ash in the specimens cured for 270 days. When the glass content of fly ash is low, the basicity of glass phase tends to decrease. Reactivity of fly ash is controlled by the basicity of the glass phase in fly ash during a period from 28 to 270 days. However, at an age of 360 days, the reaction ratios of fly ash show almost identical values with different glass contents. Fly ash also affected the hydration of cement clinker minerals in fly ash cement. While the hydration of alite was accelerated, that of belite was retarded at a late stage.     

Hydration reactions of cement combinations containing vitrified incinerator fly ash

One treatment option for municipal solid waste incinerator fly ash (IFA) is vitrification. The process yields a material containing reduced levels of trace metals relative to the original ash. The material is glassy and potentially suitable as a cement component in concrete. This paper examines the vitrification of an IFA and studies the hydration reactions of combinations of this vitrified material and Portland cement (PC). Isothermal conduction calorimetry, powder X-ray diffraction (XRD), thermogravimetry (TG) and scanning electron microscopy were employed to study the hydration reactions. As the levels of vitrified ash increase, the quantities of AFt phase produced decrease, whilst quantities of AFm phase increase, due to the reduced levels of sulfate in the vitrified ash. The levels of calcium silicate hydrate (CSH) gel (inferred from estimates of quantities of gel-bound water) remain constant at 28 days regardless of vitrified ash content, indicating that the material is contributing toward the formation of this product.     

Effect of fly ash on the kinetics of Portland cement hydration at different curing temperatures

This paper describes the effect of fly ash on the hydration kinetics of cement in low water to binder (w/b) fly ash-cement at different curing temperatures. The modified shrinking-core model was used to quantify the kinetic coefficients of the various hydration processes. The results show that the effect of fly ash on the hydration kinetics of cement depends on fly ash replacement ratios and curing temperatures. It was found that, at 20 °C and 35 °C, the fly ash retards the hydration of cement in the early period and accelerates the hydration of cement in the later period. Higher the fly ash replacement ratios lead to stronger effects. However, at 50 °C, the fly ash retards the hydration of the cement at later ages when it is used at high replacement ratios. This is because the pozzolanic reaction of the large volumes of fly ash is strongly accelerated from early in the aging, impeding the hydration of the cement.     

Replacement of raw mix in cement production by municipal solid waste incineration ash

The feasibility of municipal solid waste incineration (MSWI) ash utilized as the replacement of raw mix in cement production is investigated. Result shows that sieving, self-grinding, and magnet separation processes are necessary to remove the debris, salt, and metallic contents that existed in the MSWI ash. By using the pretreated MSWI ashes, the produced cement specimens were in compliance with the unconfined compression strength (UCS) standard in Taiwan at small replacement percentage (<5%). When ash replacement percentage is large (more than 10%), the strength development of specimens would be hindered due to the deficient formation of the calcium silicate. Calculation on lime saturation factor (LSF) also shows a descending trend in consequence of the increase in replacement percentage. Thus, compositional effect should be taken into consideration for promoting the calcium silicate formation at the case of large ash replacement. In this research, adjustment of chemical composition was achieved by adding 183 g calcium oxide per kilogram of cement raw mixture with 15% ash replacement. After adjustment, the produced cement could develop seven- and fivefold increase on UCS compared with those without calcium oxide supplement at 3 and 7 days of curing, respectively. Results concluded that the MSWI ash was suitable in reuse for cement production under a well-conditioned situation.     

Reactive pozzolana from Indian clays—their use in cement mortars

Studies were undertaken to produce reactive pozzolana i.e. metakaolin from four kaolinitic clays collected from different sources in India. The metakaolin produced from these clays at 700-800 °C show lime reactivity in between 10.5 to 11.5 N/mm² which is equivalent to commercially available calcined clay Metacem-85. The microstructure of the metakaolin has been reported. The effect of addition of metakaolin up to 25% in the Portland cement mortars was investigated. An increase in compressive strength and decrease of porosity and pore diameter of cement mortars containing metakaolin (10%) was noted over the cement mortars without metakaolin. The hydration of metakaolin blended cement mortars was investigated by differential thermal analysis (DTA) and scanning electron microscopy (SEM). The major hydraulic products like C-S-H and C₄AH₁₃ have been identified. Durability of the cement mortars with and without metakaolin was examined in different sulphate solutions. Data show better strength achievement in cement mortars containing 10% MK than the OPC mortars alone.     

Early-age deformation, drying shrinkage and thermal dilation in a new type of dental restorative material based on calcium aluminate cement

Dimensional changes during the first hour of hydration for small specimens of a dental material based on calcium aluminate cement (CAC) was examined. The study was conducted on specimens prepared in two different ways. First, intact tablets (three pieces per test) dipped in water were measured. Second, compacted specimens from four tablets were measured after 10 min of hydration. The dimensional changes were studied in both wet and dry conditions at 37 °C and in a dry condition at 25 °C. In the wet environment at 37 °C no dimensional change of the samples was observed. At normal room humidity (RH 55%) at both temperatures, shrinkage of 0.35-0.40% was observed. For comparison to the early-age drying shrinkage, a study of the drying shrinkage in mature material, hydrated for 50 and 100 days, respectively, was conducted. Furthermore the thermal expansion coefficient was determined and found to be close to that of tooth substance.     

Hydration products of alkali-activated slag-red mud cementitious material

A new kind of alkali-slag-red mud cementitious material, abbreviated as ASRC, with both high early and ultimate strength and excellent resistance against chemical attacks has been developed by the application of composite solid alkali activator into slag-red mud mixture system. The hydration products of this cement at ambient temperature have been investigated by means of XRD, IR, TG-DTA, TEM, EDXA, etc. The results showed that the hardened cement paste was mostly consisted of C-S-H gel, being very low in Ca/Si ratio, very fine in size and extremely irregular in its shape. Neither Ca(OH)₂ and AFt, which are usually present in the hardened Portland cement paste, nor zeolite-like products have been detected. These characteristics are considered to be the chemical reasons for the high early and ultimate strength and good resistance against chemical attacks of the hardened ASRC cement paste.     

掺垃圾焚烧飞灰烧制的水泥熟料对水泥性能影响的试验研究

研究了城市生活垃圾焚烧飞灰的性质以及其用于水泥生料配料对水泥力学性能、工作性能和水泥制品环境安全性的影响,探讨了水泥工业协同处置城市生活垃圾焚烧炉渣的技术及其可行性。研究结果表明：掺烧飞灰的熟料的安定性、标准稠度用水量、凝结时间、抗折强度都和基准样相差不大,但是3d和28d抗压强度略微下降;由于掺入飞灰后生料的易烧性得到改善,因此可以稍微调高KH值来抵消强度下降;飞灰掺量为4．62％时,烧制的水泥熟料其制品的重金属极限溶出能够达到Ⅲ类地表水标准,重金属的长期浸渍溶出主要集中在早期,0—3d、3～7d龄期重金属浸渍液能够达到Ⅲ类地表水标准;7—28d、28～60d龄期重金属浸渍液能够达到Ⅱ类地表水标准。     

Mechanical properties and micro-structures of calcium aluminate based ultra high strength cement

This paper describes the mechanical properties and microstructure of calcium aluminate based ultra high strength cement at early age. By using silica fume, polycarboxylate based superplasticizers and a hybrid defoaming mixer, which is anon-contact mixer, cement paste with water to powder ratio of 0.1 can be cast in a mold. When the water to powder ratio is 0.1, the bending strength of hardened samples can be obtained over 30 MPa. Samples were cured at 40 or 60 °C for 7 days. At 60 °C, C₃AH₆ is mainly produced, whereas C₃AH₆ and C₂AH₈ are produced at 40 °C. The mechanical properties of hardened samples with low water to powder ratio are related to the pore volume and pore size distribution.     

Hydration of cementitious materials, present and future

This paper is a keynote presentation from the 13th International Congress on the Chemistry of Cement. It discusses the underlying principles of hydration and recent evidence for the mechanisms governing this process in both Portland cements and other cementitious materials. Given the overriding imperative to improve the sustainability of cementitious materials, routes to reducing CO₂ emissions are discussed and the impact of supplementary materials on hydration considered.     

废弃混凝土中基质胶凝组分作原料煅烧水泥熟料的研究

每年拆除建筑物所产生的废弃混凝土数量巨大,因此废弃混凝土中基质胶凝组分作原料煅烧水泥熟料的再利用研究具有重要的意义。采用热处理和加入表面活性剂与机械粉碎相结合的方法将废弃混凝土中的骨料与基质胶凝组分进行了分离。将分离出的基质胶凝组分按不同配合比制备生料,分别在1400℃,1450℃下进行了熟料煅烧试验,并进行了结构和力学性能测定。试验结果表明,水泥净浆试体的抗压强度随基质胶凝组分配合比的增大而降低,但适当掺入(小于25%)时降低幅度不大;XRD和SEM分析结果表明,1450℃煅烧的熟料矿物结构与常规原料煅烧的熟料基本相同。根据晶种理论和水化物脱水相的反应活性分析了熟料烧成机理。     

Reactions of fly ash with calcium aluminate cement and calcium sulphate

The hydration processes in the ternary system fly ash/calcium aluminate cement/calcium sulphate (FA/CAC/C$) at 20 °C were investigated; six compositions from the ternary system FA/CAC/C$ were selected for this study. The nature of the reaction products in these pastes were analysed by X-ray diffraction (XRD) and infrared spectroscopy (FTIR). At four days reaction time, the main hydration reaction product in these pastes was ettringite and the samples with major initial CAC presented minor ettringite but calcium aluminates hydrates. The amount of ettringite developed in the systems has no direct relation with the initial components.     

The work of Powers and Brownyard revisited: Part 1

Powers and Brownyard [Studies of the physical properties of hardened Portland cement paste. Bull. 22, Res. Lab. of Portland Cement Association, Skokie, IL, U.S. J. Am. Concr. Inst. (Proc.), 43 (1947) 101-132, 249-336, 469-505, 549-602, 669-712, 845-880, 933-992 (reprint)] were the first to systematically investigate the reaction of cement and water and the composition of cement paste. They introduced the concept of nonevaporable (water retained in P-dried state) and gel water (additional water retained upon saturation). Their specific volumes (ν_n and ν_g) are lower than that of free water, causing chemical shrinkage. The retained water was furthermore related to the content of the four most abundant clinker phases, viz alite, belite, aluminate and ferrite.Their work is recapitulated here. Major aspects, such as the specific volume of nonevaporable and gel water, are addressed, as well as the issue of gel water being “compressed”. Subsequently, it will be demonstrated that their water retention data enable the study of the molar reactions of the calcium silicate phases and the reaction products C-S-H (C_1.7SH_3.2 when saturated) and CH, which represents a principal innovation. Using the molar reactions and the specific volumes of nonevaporable (ν_n) and gel water (ν_g), the density of saturated C-S-H and its porosity are derived.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

Hydration and microstructure of ultra high performance concrete incorporating rice husk ash

Rice husk ash (RHA) and silica fume (SF) have a similar chemical composition and a very high specific surface area, but RHA is not an ultra-fine material like SF. The high specific surface area of RHA originates from its internal porosity. For this reason RHA can be expected to behave differently from SF in terms of the hydration and the resulting microstructure of concrete. This still remains unclear in Ultra High Performance Concrete (UHPC). The objective of this research was to study the effect of RHA on the hydration and microstructure development of UHPC. The results are compared to those obtained with a control sample and a sample made with SF.The results show that the addition of RHA can increase the degree of cement hydration in UHPC at later ages. RHA can also refine the pore structure of UHPC and reduce the Ca(OH)₂ content, but less significantly than SF. The thickness of the interface transition zone (ITZ) between sand particles and cement matrix of all samples is very small at the age of 28 days. The compressive strength of the sample made with RHA after 7 days was higher than that of the control sample and the sample made with SF. It is suggested that the porous structure of RHA and the uptake of water in this porous structure results in a kind of is attributable to the internal water curing of the RHA modified mixture.     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Incorporation of trace elements in Portland cement clinker: Thresholds limits for Cu, Ni, Sn or Zn

This paper aims at defining precisely, the threshold limits for several trace elements (Cu, Ni, Sn or Zn) which correspond to the maximum amount that could be incorporated into a standard clinker whilst reaching the limit of solid solution of its four major phases (C₃S, C₂S, C₃A and C₄AF). These threshold limits were investigated through laboratory synthesised clinkers that were mainly studied by X-ray Diffraction and Scanning Electron Microscopy. The reference clinker was close to a typical Portland clinker (65% C₃S, 18% C₂S, 8% C₃A and 8% C₄AF). The threshold limits for Cu, Ni, Zn and Sn are quite high with respect to the current contents in clinker and were respectively equal to 0.35, 0.5, 0.7 and 1 wt.%. It appeared that beyond the defined threshold limits, trace elements had different behaviours. Ni was associated with Mg as a magnesium nickel oxide (MgNiO₂) and Sn reacted with lime to form a calcium stannate (Ca₂SnO₄). Cu changed the crystallisation process and affected therefore the formation of C₃S. Indeed a high content of Cu in clinker led to the decomposition of C₃S into C₂S and of free lime. Zn, in turn, affected the formation of C₃A. Ca₆Zn₃Al₄O₁₅ was formed whilst a tremendous reduction of C₃A content was identified. The reactivity of cements made with the clinkers at the threshold limits was followed by calorimetry and compressive strength measurements on cement paste. The results revealed that the doped cements were at least as reactive as the reference cement.