Thermal analysis of borogypsum and its effects on the physical properties of Portland cement

Borogypsum, which consists mainly of gypsum crystals, B₂O₃ and some impurities, is formed during the production of boric acid from colemanite, which is an important borate ore. In this study, the effect of borogypsum and calcined borogypsum on the physical properties of ordinary Portland cement (OPC) has been investigated. The calcination temperature and transformations in the structures of borogypsum and natural gypsum were determined by differential thermal analysis (DTA), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) techniques. Thermal experiments were carried out between ambient temperature and 500 °C in an air atmosphere at a heating rate of 10 °C min⁻¹. After calculation of enthalpy and determination of conversion temperatures, borogypsum (5% and 7%), hemihydrate borogypsum (5%) and natural gypsum (5%) were added separately to Portland cement clinker and cements were ground in the laboratory. The final products were tested for chemical analysis, compressive strength, setting time, Le Chatelier expansion and fineness properties according to the European Standard (EN 196). The results show that increasing the borogypsum level in Portland cement from 5% to 7% caused an increase in setting time and a decrease in soundness expansion and compressive strength. The cement prepared with borogypsum (5%) was found to have similar strength properties to those obtained with natural gypsum, whereas a mixture containing 5% of hemihydrate borogypsum was found to develop 25% higher compressive strength than the OPC control mixtures at 28 days. For this reason, utilization of calcined borogypsum in cement applications is expected to give better results than untreated borogypsum. It is concluded that hemihydrate borogypsum could be used as a retarder for Portland cement as an industrial side. This would play an important role in reducing environmental pollution.     

脱硫石膏的热处理及其对矿渣水泥若干性能的影响

研究了在不同温度下处理的脱硫石膏对矿渣水泥若干性能的影响，确定其在水泥基材料中循环利用的可行性。研究结果表明，经低温烘干焙烧处理的脱硫石膏，掺入到矿渣水泥中并控制适当的SO3掺量，水泥凝结时间正常，强度略有提高，并且明显降低了硬化水泥浆体的失水率和干缩率，可以有效防止收缩裂缝的产生：并进一步探讨了脱硫石膏对矿渣水泥性能的影响机理。     

Mineralogical and chemical properties of FGD gypsum from Florina,Greece

BACKGROUND: The aim of this work is to define the chemical and mineralogical composition of the fuel gas desulphurization (FGD) gypsum produced from the Meliti thermal power plant in the region of Florina in North West Greece, in order to investigate potential uses in the cement industry. Mineralogical and microprobe analyses were carried out on FGD gypsum samples collected from the Meliti 330 MW lignite‐fired power plant. RESULTS: Results show that the main component of the FGD gypsum is pure mineral gypsum (CaSO₄·2H₂O). The particle size of the gypsum ranges from 5 to 50 µm and the crystals are mainly of rhomboid shape. Microprobe analysis shows that the concentration of CaO and SO₃, which are the main components, range from 31.9%–32.5% and from 45.90–46.40%, respectively. CONCLUSION: This FGD gypsum can easily substitute the natural gypsum used in the production of cement. Copyright © 2007 Society of Chemical Industry     

Utilization of borogypsum as set retarder in Portland cement production

Boron ores are used in the production of various boron compounds such as boric acid, borax and boron oxide. Boric acid is produced by reacting colemanite(2CaO·3B₂O₃·5H₂O) with sulphuric acid and a large quantity of borogypsum is formed during this production. This waste causes various environmental problems when discharged directly to the environment. Portland cement is the most important material in the building industry. This material is produced by adding about 3-5% gypsum (CaSO₄·2H₂O) to clinker as a set retarder. The aim of this study was to stabilize borogypsum, and to produce cements by adding borogypsum instead of natural gypsum to clinker. Concrete using cement produced with borogypsum was tested to find the mechanical properties and the test values were compared with those of concrete from cement with natural gypsum. Compressive strength of concrete from cement produced with borogypsum was found to be higher than that of natural gypsum. Also, the setting time of cement with borogypsum was longer than that of the Portland cement.     

Use of gypsum/brucite mixed precipitate instead of gypsum in Portland cement

The possibility of replacing the natural gypsum used in cement production by a chemical precipitate consisting of gypsum (CaSO₄ ·2H₂O) and brucite (Mg(OH)₂), was investigated. This precipitate is a by‐product of a new hydrometallurgical process, which was developed in order to treat economically low‐grade nickel oxide ores. More specifically, it is obtained by hydrolytic precipitation of magnesium at temperatures not exceeding 80 °C, from sulfate solutions which result from heap leaching of nickel oxide ores with dilute sulfuric acid at ambient temperature, using calcium hydroxide as a neutralizing agent. The mixture generally consists of 20–30% non‐fibrous magnesium hydroxide, 60–75% gypsum and any excess of calcium hydroxide, depending on the precipitation conditions. In the present work, a mixture was produced by hydrolytic precipitation at 25 °C, using 1.1 times the stoichiometric quantity of Ca(OH)₂ required to precipitate all of the magnesium. The possibility of using the above precipitate as a substitute for gypsum in cement was examined by testing four different cement mixtures, one reference sample, containing 4.5% gypsum and 0.5% anhydrite ((PC)_Ref) and another three with 4.1%, 5.2% and 6.3% of gypsum/brucite mixed precipitate ((PC)_B/G), in the place of gypsum. All samples were tested by determining the grindability, setting time, expansion and compressive strength. The results of the physico‐mechanical tests showed that the replacement of natural gypsum by the above precipitate did not affect negatively the quality of the produced cements. Copyright © 2005 Society of Chemical Industry     

Effect of MgO on the composition and properties of alite-sulphoaluminate cement

The effect of MgO on the composition and properties of alite-sulphoaluminate cement clinker with commercial-grade raw materials such as limestone, clay, gypsum and fly ash as starting materials has been investigated in order to confirm results previously obtained with pure raw materials. The experiment results confirm that the addition of MgO at about 2-5% can improve the burnability of raw meal, promote the absorption of free lime and the formation of C₃S and C₄A₃S¯. In addition, it is shown that this can also increase the strength development of the cement and shorten the setting time. When the content of MgO reaches about 8%, the strength of the cement decreases slightly and the setting time is extended.     

Effects of flue gas desulphurization sludge on the pozzolanic reaction of reject-fly-ash-blended cement pastes

Reject fly ash (rFA), a coarse portion of the pulverized fuel ash (PFA) produced from coal-fired power plants and rejected from the ash classifying process, has remained unused due to its high carbon content and large particle size (>45 μm). However, the reject ash may have potential uses in chemical stabilization/solidification (S/S) processes that require relatively low strength and low chemical reactivity. Flue gas desulphurization (FGD) sludge is a by-product of the air pollution control process in coal-fired power plants. Its chemical composition is mainly gypsum. As there is no effective usage of both of these materials, it was of interest to conduct research on the possible activation of rFA using FGD. This paper presents experimental results of the effect of FGD on the pozzolanic reaction of rFA-blended cement pastes with or without Ca(OH)₂ and chemical activators. The results show that FGD take effect as an activator only at late curing ages. Adding Ca(OH)₂ activates the hydration of rFA. Chemical activator, such as alkali sulphate, is more effective in enhancing the strength development and degree of hydration of rFA than CaCl₂ in the rFA-Ca(OH)₂-cement system. But CaCl₂ is more effective in the rFA-Ca(OH)₂-FGD-cement system. The chemical activators speed up the reaction of the rFA through the formation new hydration products and elevating the pH value.     

Production of expansive additive to portland cement

The expansive additive was produced from sulfate–calcium component and aluminate clinker, containing 60% Al₂O₃. The sulfate–calcium component is prepared by flue gas desulphurization gypsum and calcareous raw material mixture burning. The ground sulfate component, mixed with ground aluminate clinker transforms into the effective expansive addition to portland cement. The following main phases were present in this expansive material: anhydrite, calcium oxide and monocalcium aluminate.The expansive substance was added to CEM I 42.5 cement as 7 and 12% addition. The mixtures were subjected to the hydration process; the expansion was measured as a function of varying conditions. The linear changes, as well as the compressive/flexural strength were determined after 1, 3, 7 and 28 days. The initial and final setting time was also measured.The cement with 7% (by weight) expansive additive is a shrinkage-less material, while the mixture with 12% (by weight) expansive additive is an expansive binder.The samples were examined by XRD and SEM-EDS.     

高强石膏和脱硫石膏复掺制备家用装修水泥试验研究

利用高强石膏和脱硫石膏单掺及复掺制备家庭装修水泥,通过研究其掺量变化对水泥凝结时间、胶砂强度、砂浆流动度及保水率的影响,根据小磨试验和大磨工业化试生产结果,高强石膏和脱硫石膏复掺可制备具有良好的施工性能的家装水泥。     

激发条件对脱硫石膏-矿渣体系水硬强度的影响

利用正交实验研究了硅酸盐水泥和其他两种矿物组分复合激发对脱硫石膏-矿渣体系强度的影响,用SEM、XRD分析了水化样品的微观结构.研究结果表明:硅酸盐水泥等多组分复合激发下,脱硫石膏-矿渣体系在水中标准条件养护,3 d抗压强度达17 MPa以上,28 d抗压强度达58 MPa以上.复合激发剂3种组分的优化组合为6:6:5,复合激发剂的用量为脱硫石膏-矿渣体系质量的17%左右.脱硫石膏-矿渣体系在复合激发条件下的水化产物主要是钙矾石和C-S-H.大量钙矾石、石膏晶体相互交叉连生,未水化石膏、矿渣颗粒所填充其间,在C-S-H凝胶的胶结下,形成了较为致密的晶胶搭配构成的微观结构.     

Alternative calcium sulfate-bearing materials as cement retarders: Part I. Anhydrite

The hydration process of cement pastes is of great importance to the physicomechanical properties of the hardened material. Thus, substances that regulate the setting of cement, such as natural anhydrite, have attracted significant scientific interest during the past years. This paper briefly describes the results of utilization of natural anhydrite in cement pastes of CEM-I and CEM-II types. The aim of the study has been to inquire the extent of natural gypsum replacement by natural anhydrite. The result of the hydration process has been expressed by the setting time and the compressive strength development, with respect to the SO₃⁻² content of each mixture. The experimental data conclude that natural anhydrite can be a very efficient retarder of the setting of cement, with no significant change in the physicomechanical properties of the hardened pastes.     

改性磷石膏球作缓凝剂对水泥性能的影响

研究了工业化生产的改性磷石膏球对水泥标准稠度用水量、凝结时间、胶砂流动度、胶砂强度及水泥与减水剂相容性的影响,并与原状磷石膏和天然石膏进行对比,结合X-射线衍射、综合热分析等微观测试,分析了改性磷石膏球对水泥水化产物相、水化程度的影响.结果表明:采用改性磷石膏球配制的水泥,其初凝、终凝时间与掺配原状磷石膏水泥相比分别缩短217 min、227 min,1d、3d强度显著高于原状磷石膏配制的水泥,28d强度高于天然石膏配制的水泥,且标准稠度用水量、胶砂流动度、与减水剂的相容性等指标优于天然石膏配制的水泥.改性磷石膏球对水泥早期水化无不良延缓作用,且能提高水泥后期水化程度.综合对比上述三种石膏对水泥性能影响的各项指标,认为改性磷石膏球可以完全替代天然石膏作水泥缓凝剂.     

Studies on high-performance blended/multiblended cements and their durability characteristics

Number of blends were prepared by intergrinding clinker, gypsum, fly ash, calcined clay, microsilica and limestone in laboratory ball mill in varying percentages, and their physical properties such as fineness, consistency, setting time and compressive strength have been determined. The durability tests on selected compositions were also conducted by exposing the mortar cubes separately in 5% Na₂SO₄ and 5% NaCl solutions till the age of 90 and 180 days. The performance was observed by compressive strength development criteria after various length of exposure. Results have been discussed and found that the durability of blended cement is higher than the ordinary Portland cement.     

脱硫石膏对矿渣水泥性能的影响

本文研究了脱硫石膏对矿渣水泥物理性能的影响。试验结果表明,在一定条件下进行热处理后的脱硫石膏掺入矿渣水泥后可以改善水泥的物理性能,提高水泥的强度及有效地调节水泥的凝结时间;不同的热处理条件和脱硫石膏在矿渣水泥中的掺量对试验结果有不同的影响,为获得最优的性能相对应有一个最佳的热处理条件和掺量范围。当矿渣水泥中硫含量在一定的范围内,随着脱硫石膏掺量的增大,水泥强度也随着增大。因此,在矿渣水泥中可以大量地掺入脱硫石膏来改善矿渣水泥的性能,并有效地利用脱硫石膏这种工业废弃物。     

脱硫建筑石膏耐水性能研究

以脱硫建筑石膏为主要胶凝材料,研究无机改性剂粉煤灰和水泥、复合激发剂、有机硅防水剂对脱硫建筑石膏耐水性的影响。实验结果表明,单掺粉煤灰和水泥对脱硫建筑石膏体系的耐水性提高幅度不大。复掺粉煤灰、水泥和复合激发剂后,可以获得6 MPa以上的抗折强度,22 MPa以上的抗压强度,0．6以上的抗折软化系数,但抗压软化系数和吸水率与单掺体系相比差别不大。在复掺最优配方的基础上添加有机硅防水剂,在防水剂掺量为0．8％时,其复合脱硫石膏试块的抗折软化系数0．756,抗压软化系数0．791,分别提高了64．3％和108．1％,吸水率仅为3．7％,显著地提高了脱硫石膏的防水性能。     

鞍钢钢渣矿渣制备人工鱼礁混凝土复合胶凝材料

以81.5％的矿渣、5％的钢渣、12.5％的脱硫石膏以及1％的水泥熟料,制备出了28 d抗压强度为56.75 MPa的低碱度胶凝材料,该胶凝材料可用于制备低碱度人工鱼礁混凝土.通过改变钢渣和脱硫石膏的掺量,研究了其掺量变化与试件强度的影响关系.实验结果表明:在该体系中,当钢渣掺量小于5％时,胶砂试块的强度随着钢渣的增加而提高;当钢渣掺量大于5％时,胶砂试块的强度随着钢渣掺量的增加而降低,并在钢渣掺基大于20％时快速下降.脱硫石膏的掺量对胶砂试块的强度影响更为显著;当脱硫石膏掺量达到12.5％时,与不含脱硫石膏的试样相比,抗压强度和抗折强度分别提高了168％和176％.利用XRD和SEM分析净浆的水化过程,结果表明,体系在早期水化主要生成AFt相和C-S-H凝胶,并对强度的增长起了主要作用.     

Effect of large amounts of natural pozzolan addition on properties of blended cements

In this study, the effects of 35, 45, and 55 wt.% natural pozzolan addition on the properties of blended cement pastes and mortars were investigated. Blended cements with 450 m²/kg Blaine fineness were produced from a Turkish volcanic tuff in a laboratory mill by intergrinding portland cement clinker, natural pozzolan, and gypsum. The cements were tested for particle size distribution, setting time, heat of hydration, compressive strength, alkali-silica activity, and sulfate resistance. Cement pastes were tested by TGA for Ca(OH)₂ content and by XRD for the crystalline hydration products. The compressive strength of the mortars made with blended cements containing large amounts of natural pozzolan was lower than that of the portland cement at all tested ages up to 91 days. Blended cements containing large amounts of pozzolan exhibited much less expansion with respect to portland cement in accelerated alkali-silica test and in a 36-week sulfate immersion test.     

硬石膏对硅酸盐水泥性能的影响

研究了在硅酸盐水泥中使用硬石膏完全代替二水石膏对硅酸盐水泥性能的影响。结果表明硬石膏对硅酸盐水泥的凝结时间无不良影响,对其3d和28d抗压强度的影响也小于5%;当熟料中的w(C3A)<11%时,掺硬石膏不会对水泥凝结时间性能产生不良影响,但w(C3A)>13%时则会引起水泥快凝,此时最好采用硬石膏与二水石膏混掺或只使用二水石膏。     

磷石膏工业化应用的无害化处理

磷石膏是生产磷酸时所排放的工业废渣,其中所含有的磷、氟、有机物等各种杂质对其综合利用造成困难;本文从水泥缓凝剂,建筑石膏,Ⅱ型无水石膏胶结材等工业应用对磷石膏进行无害化处理,磷、氟等杂质对水泥起缓凝时间,延长凝结时间,降低水泥的强度,主要通过石灰中和煅烧方法降低磷、氟的含量。     

脱硫石膏对水泥性能的影响及其品质差异分析

对不同产地脱硫石膏作缓凝剂对水泥物理性能影响进行了研究比较,并分析探讨了脱硫石膏的品质差异及其对水泥性能影响机制。试验结果表明,与天然石膏相比,脱硫石膏对水泥早期和后期强度均有不同程度提高,但水泥凝结时间有不同程度延长。不同产地脱硫石膏对水泥与外加剂相容性、保水性、流变性和干缩率等性能的影响均存在较大差异。研究还发现,亚硫酸钙含量及钙硫比低的脱硫石膏,其水泥凝结时间、干缩性、保水性和砂浆流变性等物理性能均优于或与掺天然石膏的接近;同时,脱硫石膏的结晶程度、晶体形态和石膏溶解速率对水泥凝结时间、与外加剂相容性等也均有较大影响。