Superplasticized portland cement: production and compressive strength of mortars and concrete

This paper deals with the effect of intergrinding different percentages of a naphthalene-based superplasticizer with Portland cement clinker and gypsum on the fineness of the product, and on the water requirement and the compressive strength of the mortars made with the superplasticized cement. The properties of the fresh and hardened concrete made with the superplasticized cements were also investigated. The results showed that the intergrinding of a given amount of a naphthalene-based superplasticizer with Portland clinker and gypsum reduced the grinding time required for obtaining the same Blaine fineness as that of the control Portland cement without the superplasticizer. The water requirement of the mortars made with the superplasticized cements was similar to that of the mortars made with the control Portland cements when the same amount of the superplasticizer was added at the mortar mixer; for a given grinding time and a Blaine fineness of 4500 cm²/g, the mortars made with the superplasticized cement had higher compressive strength than those made with the control Portland cement. For a given grinding time or Blaine fineness of cement ≥5000 cm²/g, the slump loss, air content stability, bleeding, autogenous temperature rise, setting times, and compressive strength of the concrete made with the superplasticized cements were generally comparable to those of the concrete made with the control Portland cements when the superplasticizer was added at the concrete mixer.     

Clay content of argillites: Influence on cement based mortars

The pozzolanic activity of four heated powders containing different clays has been tested. Mineral transformations during calcination from 20 to 900 °C have been followed by X-ray diffraction (XRD) and Differential Scanning Calorimetry (DSC). Compressive strength tests were performed at 1, 7 and 28 days on cement–clay mortars using 30% of pozzolanic material as a replacement by mass for cement. Calcination temperatures corresponded to the stages of potentially high reactivity identified by XRD. Results indicated that there exists incompatibility between clay minerals which can not be activated at the same temperatures. Products of recrystallisation of the earlier activated clay were already formed when the second clay type was activated. Concerning the type and the abundance of clay minerals in the raw material, this study evidences that the compressive strength is, at first approximation, correlated with the percentage of activated clay and less with the nature of the clay assemblage.     

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.     

Effects of aluminate and sulfate contents on the hydration and strength of Portland cement pastes and mortars

Evaluation of effects of C₃A and SO₃ contents in Portland cement on its compressive strength, hydration rate and products. Three cement samples varying in C₃A content and one varying in SO₃ content were used, hydrated initially at three temperatures. Compressive strength, bound water content, free lime content and Differential Scanning Calorimeter curves were determined during the progression of hydration. In interpretation bound water was used as a measure of quantity of binding material and Free Lime to Bound Water Ratio (FLWR) - of chemical constitution and quality.     

铝酸三钙和碳酸钙对硅酸盐水泥早期力学强度及凝结时间的协同作用研究

本文研究了协同掺加铝酸三钙(C3 A)和碳酸钙(CaCO3)对硅酸盐水泥早期水化及硬化性能的影响.用X射线衍射(XRD)、热重分析(TG)、扫描电子显微镜(SEM)等技术分析水化产物及显微结构.结果表明,协同掺加C3 A和CaCO3会显著提高硅酸盐水泥的早期力学强度.当硅酸盐水泥中掺加15％(质量分数,下同)的C3 A...     

碱性和无碱液体速凝剂促凝早强作用机理对比研究

碱性和无碱速凝剂掺入水泥后的水化机理不同,导致应用性能存在明显差异。本文通过测试凝结时间和砂浆抗压强度等宏观性能对比了两种速凝剂的应用性能,并通过水化放热分析、XRD定量分析、热重分析和SEM微观形貌观察等微观方法综合分析了两者的早期水化历程。结果表明:碱性速凝剂加入水泥后,[Al(OH)₄]^-加快了水泥中石膏的消耗速度,水化初期生成大量钙矾石(AFt),促进了硅酸三钙(C₃S)矿物的水化,缩短了水泥浆体的凝结时间并提高了砂浆的早期抗压强度,但石膏的加速消耗也使得单硫型水化硫铝酸钙(AFm)和水化铝酸钙(C-A-H)等水化产物提前生成,影响了水泥基材料的后期抗压强度发展;无碱速凝剂加入水泥后,[Al(OH)₄]^-和SO^2-₄在液相中生成了大量AFt,促进了铝酸三钙(C₃A)和C₃S矿物的水化,影响了氢氧化钙(CH)的结晶析出。值得注意的是,SO^2-₄不仅促进了C₃A生成AFt的过程,也延缓了水泥中石膏的消耗及AFm和C-A-H等产物的生成,因此无碱速凝剂的加入除了明显提高早期抗压强度外,后期28 d抗压强度也不受影响。     

Crystallization of the molten phase in portland cement clinker

Crystallization of a liquid similar to that present in Portland cement at clinkering temperatures has been studied. Its composition (in wt %) is CaO = 54.8, Aℓ₂O₃ = 22.7, Fe₂O₃ = 16.5, SiO₂ = 6.0. Prolonged crystallization or slow cooling yields the equilibrium phases: C₃A, ferrite close to C₄AF, and C₂S. With more rapid cooling or with static crystallization at lower temperatures, metastable phases form. The most important is a hitherto-unreported cubic polymorph of C₃A having a_o 3.9 Å. It is designated “proto-C₃A’ to distinguish it from ordinary cubic C₃A.     

CCUS环境下水泥单矿C3S的CO2腐蚀动力学研究

在碳捕集、利用和封存(CCUS)井下,油井水泥因长期受井下高温、高压和高酸性流体的作用会遭受碳化腐蚀导致水泥环失效。为了模拟CO₂地质封存井下碳化腐蚀环境,本文将油井水泥的主要单相矿物硅酸三钙(C₃S)置于不同温度(30 ℃、60 ℃、90 ℃),并密封在8.0 MPa的气相或液相的CO₂碳化环境下,采用XRD和TGA相结合的分析方法,分析水泥单矿C₃S受CO₂腐蚀环境的影响规律。根据非稳态Fick扩散的渗透理论模型,建立腐蚀产物定量分析结果与腐蚀龄期的数学模型,拟合得到C₃S受CO₂腐蚀后的产物生成系数,以此评价不同CO₂腐蚀因素对C₃S的影响程度。结果表明:在CO₂气相环境中,温度升高将显著加剧对C₃S的腐蚀且产生溶蚀现象;而在CO₂液相环境下,高温(90 ℃)使C₃S水化反应加剧并形成阻滞层,降低CO₂对C₃S的腐蚀速率。     

海水对高贝利特硫铝酸盐水泥水化过程和力学性能的影响

研究了海水拌和与海水养护条件下高贝利特硫铝酸盐水泥(HB-CSA)和普通硅酸盐水泥(OPC)胶砂的抗压强度和抗折强度,采用等温量热法、X射线衍射分析法和热重分析法表征了两种水泥的水化过程和水化产物,分析了海水对HB-CSA水化过程和力学性能的影响。结果表明:海水拌和未明显影响HB-CSA的早期水化过程,海水拌和与海水养护未改变其主要水化产物类型;海水拌和显著加快了OPC的早期水化,海水中的氯盐与OPC的水化产物反应,导致水化氯铝酸钙(Friedel盐)的生成。海水拌和与海水养护对HB-CSA的抗压强度影响较小,但降低了OPC的后期抗压强度。海水养护对HB-CSA和OPC抗折强度的提高较为明显,钙矾石(AFt)含量的增加是抗折强度提高的主要原因。HB-CSA的水化产物中未见Ca(OH)₂和单硫型水化硫铝酸钙(AFm),避免了海水侵入后过量CaSO₄·2H₂O和AFt生成造成的混凝土膨胀开裂和强度下降的危害。     

The influence of air content by assessing the pozzolanic activity of fly ash by strength testing

The pozzolanic activity of fly ash and natural pozzolans are generally assessed by a compressive strength test with Portland cement in a mortar. A test mix in which part of the Portland cement is replaced by fly ash is compared with a control mix with pure Portland cement. When testing cement according to such procedures the influence of varying air contents in the test mortars can be comparable to that of other factors, hence complicating the interpretation of results. Fly ash seems to affect the air void content in mortar in two ways: By a direct contribution from hollow or porous particles in the fly ash and by reducing the amount of entrained air, an effect which is apparently caused by the residual carbon present in the fly ash.These aspects are elucidated by examples from laboratory experiments with fly ash.     

Enhancement in early strengths of slag-cement mortars by adjusting basicity of the slag prepared from fly-ash of MSWI

The insufficient early strengths of cement mortars in which partial cement had been replaced by pulverized slag melted from municipal solid waste incinerator (MSWI) fly-ash were tackled in this study by adjusting the basicity of the slag through the addition of various amounts of CaCO₃ into MSWI fly-ash, melted into a ‘modified slag’, pulverized to partially replace cement. Increased basicity in the modified slag manifestly improves the early compressive strengths of cement mortar with 20% Portland cement replaced by the modified slag powder (20 wt.% CaCO₃ added). The 14-day and 28-day compressive strengths of the mortars evidently increased to nearly that of the reference specimen made of only Portland cement mortar. The 90-day compressive strength is even higher than that of the reference specimen. Porosity and Fourier transform infrared spectra (FTIR) analyses evidenced the improvement in early strengths by hydration while the enhancement in long-term strength by pozzolanic reaction in the CaCO₃ added slag-cement mortar.     

Structural investigation relating to the cementitious activity of bauxite residue — Red mud

The cementitious behavior of red mud derived from Bauxite-Calcination method was investigated in this research. Red mud were calcined in the interval 400–900 °C to enhance their pozzolanic activity and then characterized in depth through XRD, FTIR and ²⁹Si MAS-NMR techniques with the aim to correlate phase transitions and structural features with the cementitious activity. The cementitious activity of calcined red mud was evaluated through testing the compressive strength of blended cement mortars. The results indicate that red mud calcined at 600 °C has good cementitious activity due to the formation of poorly-crystallized Ca₂SiO₄. The poorly-crystallized Ca₂SiO₄ is a metastable phase which will transform into highly-crystallized Ca₂SiO₄ with the increase of calcination temperature from 700 °C moving to 900 °C. It is the metastable phase that mainly contributes to the good cementitious activity of red mud. This paper points out another promising direction for the proper utilization of red mud.     

Use of recycled copper slag for blended cements

Copper slag is a by‐product generated during smelting to extract copper metal from the ore. The copper slag obtained may exhibit pozzolanic activity and may therefore be used in the manufacture of addition‐containing cements. In this paper the effect of the incorporation of the copper slag in cement is measured. Blends of copper slag with Portland cement generally possess properties equivalent to Portland cement containing fly ash, but very different to the silica fume incorporation. Copper slag and fly ash reduce the heat of hydration more effectively than silica fume in mortars. The replacement of 30% cement by copper slag reduces the flexural and compressive strength in a similar way to fly ash; however, after 28 days, the reduction is less than the percentage of substitution. Hydrated calcium aluminate phases were analysed using scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The pozzolanic activity of copper slag is similar to that of fly ash and higher than silica fume. In the presence of low water/cement ratios, certain pozzolanic materials produce a very compact cement paste that limits the space available for hydration products, a determining factor in the formation of hydrated calcium aluminates. SEM was found to be a useful analytical technique when aluminates are formed and can be clearly detected by XRD. Copyright © 2008 Society of Chemical Industry     

Copper-impregnated Al–Ce-pillared clay for selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by hydrocarbon is an efficient way to remove NO emission from lean-burn gasoline and diesel exhaust. In this paper, a thermally and hydrothermally stable Al–Ce-pillared clay (Al–Ce-PILC) was synthesized and then modified by SO₄²⁻, whose surface area and average pore diameter calcined at 773 K were 161 m²/g and 12.15 nm, respectively. Copper-impregnated Al–Ce-pillared clay catalyst (Cu/SO₄²⁻/Al–Ce-PILC) was applied for the SCR of NO by C₃H₆ in the presence of oxygen. The catalyst 2 wt% Cu/SO₄²⁻/Al–Ce-PILC showed good performance over a broad range of temperature, its maximum conversion of NO was 56% at 623 K and remained as high as 22% at 973 K. Furthermore, the presence of 10% water slightly decreased its activity, and this effect was reversible following the removal of water from the feed. Py-IR results showed SO₄²⁻ modification greatly enhanced the number and strength of Brönsted acidity on the surface of Cu/SO₄²⁻/Al–Ce-PILC, which played a vital role in the improvement of NO conversion. TPR and XPS results indicated that both Cu⁺ and isolated Cu²⁺ species existed on the optimal catalyst, mainly Cu⁺, as Cu content increased to 5 wt%, another species CuO aggregates which facilitated the combustion of C₃H₆ were formed.     

Catalytic reduction of SO2 over supported transition-metal oxide catalysts with C2H4 as a reducing agent

This work investigates performances of supported transition-metal oxide catalysts for the catalytic reduction of SO₂ with C₂H₄ as a reducing agent. Experimental results indicate that the active species, the support, the feed ratio of C₂H₄/SO₂, and pretreatment are all important factors affecting catalyst activity. Fe₂O₃/γ-Al₂O₃ was found to be the most active catalyst among six γ-Al₂O₃-supported metal oxide catalysts tested. With Fe₂O₃ as the active species, of the supports tested, CeO₂ is the most suitable one. Using this Fe₂O₃/CeO₂ catalyst, we found that the optimal Fe content is 10 wt.%, the optimal feed ratio of C₂H₄/SO₂ is 1:1, and the catalyst presulfidized by H₂+H₂S exhibits a higher performance than those pretreated with H₂ or He. Although the feed concentrations of C₂H₄:SO₂ being 3000:3000 ppm provide a higher conversion of SO₂, the sulfur yield decreases drastically at temperatures above 300 °C. With higher feed concentrations, maximum yield appears at higher temperatures. The C₂H₄ temperature-programmed desorption (C₂H₄-TPD) and SO₂-TPD desorption patterns illustrate that Fe₂O₃/CeO₂ can adsorb and desorb C₂H₄ and SO₂ more easily than can Fe₂O₃/γ-Al₂O₃. Moreover, the SO₂-TPD patterns further show that Fe₂O₃/γ-Al₂O₃ is more seriously inhibited by SO₂. These findings may properly explain why Fe₂O₃/CeO₂ has a higher activity for the reduction of SO₂.     

粉煤灰掺量对氯氧镁水泥混凝土物理力学性能的影响

为了拓展氯氧镁水泥(MOC)材料的应用领域,以盐湖提钾肥副产物水氯镁石、轻烧氧化镁和粉煤灰为胶凝材料,制备了不同粉煤灰掺量的氯氧镁水泥混凝土(MOCC)。研究了粉煤灰掺量对MOCC抗压强度、物相组成、微观形貌和孔结构的影响。结果表明:随着粉煤灰掺量的增加,MOCC的抗压强度逐渐降低,当粉煤灰掺量为40%(质量分数)时,其300 d抗压强度降低至39.99 MPa,降低了22.52%。MOCC的主要水化产物为5Mg(OH)₂·MgCl₂·8H₂O(5·1·8)和Mg(OH)₂,掺加粉煤灰并没有产生新的晶相。掺入粉煤灰增加了MOCC的孔隙率和有害孔体积,从而降低了其抗压强度。采用相同水灰比制备了普通硅酸盐水泥混凝土,抗压强度对比测试结果表明:掺40%的粉煤灰MOCC的抗压强度虽然比未掺粉煤灰MOCC抗压强度低,但仍比普通硅酸盐水泥混凝土300 d龄期的抗压强度(33.42 MPa)高出19.66%,说明MOCC比普通硅酸盐水泥混凝土具有较高的抗压强度。     

Differentiating seawater and groundwater sulfate attack in Portland cement mortars

The study reported in this article deals with understanding the physical, chemical and microstructural differences in sulfate attack from seawater and groundwater. Portland cement mortars were completely immersed in solutions of seawater and groundwater. Physical properties such as length, mass, and compressive strength were monitored periodically. Thermal analysis was used to study the relative amounts of phases such as ettringite, gypsum, and calcium hydroxide, and microstructural studies were conducted by scanning electron microscopy. Portland cement mortars performed better in seawater solution compared to groundwater solution. The difference in performance could be attributed to the reduction in the quantity of the expansive attack products (gypsum and ettringite). The high Cl concentration of seawater could have played an important role by binding the C₃A to form chloroaluminate compounds, such as Friedel's salt (detected in the microstructural studies), and also by lowering the expansive potential of ettringite. Furthermore, the thicker layer of brucite forming on the specimens in seawater could have afforded better protection against ingress of the solution than in groundwater.     

Effects of the secondary minerals of the natural pozzolans on their pozzolanic activity

Natural pozzolans have been widely used as substitutes for Portland cement, because of their binding properties. Some of them are natural volcanic rocks which contain secondary minerals such as clays and zeolites corresponding to products of the alteration of the rock. The objective of this study was to document the potential effect of the secondary minerals on the strength development of pozzolanic mortars. We chose to investigate this effect by thermally destabilising these minerals in three different pozzolanic deposits (poz-1, poz-2 and poz-3). We first did a detailed mineralogical study, to identify the occurrence and the nature of the different secondary minerals. Kaolinite is abundant in poz-1 and different types of zeolite were identified in poz-2 and poz-3. Thermal treatments were monitored by X-ray Diffraction (XRD) analysis, in order to document mineralogical transformations. The effect on the pozzolanic activity has been tested by strength measurements on normalised mortars at 1, 7 and 28 days. Strength of all blended cements is enhanced while destabilising secondary alteration minerals. For kaolinite, we showed that a strength improvement occurs as soon as it is destructured, even if it is not transformed in metakaolin. For zeolites, destabilisation takes place at low temperature (350 °C), but as recrystallisation products are easily formed, activation temperature window is narrow. Endly, we have evidence that the presence of calcite in pozzolans has an effect on early strength. Therefore this study is giving new perspectives for a better use of natural pozzolanic materials in the cement industry.     

The effect of MgSO4 and HCL solutions on the strength and durability of pozzolan cement mortars

Pozzolan cements are produced by adding pozzolans such as silica fume, rice husk ash, blast furnace slag, fly ash, trass in 20% replacement for Portland cement. On the 28th day of production, the produced specimens are stored in water, in MgSO₄·7H₂O (5%) solution and in HCl (pH = 2) solution. The strengths and weights were determined after the mortars are stored in solutions for 56 days. Compressive strengths of the mortars stored in water for 28 days are silica fume, rice husk ash, and control, 43.3, 40.1, and 31.0 MPa, respectively. The highest loss of compressive strength is 20% and the highest gain of weight is 4.2%, occurring in blast furnace slag mortar in MgSO₄.     

Hydration of cement paste and concrete from raw mix containing metallic particles

A comparative analysis of the hydration kinetics of cement paste and mortar from raw mix containing finely dispersed metallic particles and of natural origin was performed using the most rational methods of investigation. These methods include the differential thermal, X-ray, IR-spectroscopy, chemical and electrochemical analyses. Results of the different analyses showed that the kinetics of chemical reaction in hardening cement mortars produced from raw mix containing metallic particles differ from those of ordinary Portland cement of natural origin. The increased presence of Fe₂O₃ in the clinker minerals to a great extent negatively influenced their solubility, thus increasing the induction, setting and hardening periods. This research also to some extent revealed the effect of wearing of grinding balls and metallic lining surfaces of grinding mills (especially during preparation of raw mix), on the chemical-mechanical properties of cement of natural origin.