铜渣基草酸盐水泥的制备及其性能
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摘要
以铜渣和草酸为原料,按一定比例混合,通过酸碱反应制备铜渣基草酸盐水泥,考察了铜渣与草酸质量比(CS/OA)、水灰质量比(W/C)、缓凝剂种类及掺量对所制水泥力学性能和凝结时间的影响,用扫描电镜和X射线粉末衍射仪分析了水泥的微观形貌和物相组成。结果表明,随质量比CS/OA和W/C增加,水泥的抗压强度呈先增大后减小的趋势,凝结时间随CS/OA增大而减小,随W/C增大而增大。硼砂和三聚磷酸钠对水泥的抗压强度影响较大,随其掺量增加,水泥的力学性能降低,适量的硼酸可提高水泥的抗压强度,且具有较好的缓凝效果,可将硼酸作为较佳缓凝剂。当质量比CS/OA=4和W/C=0.16～0.17、硼酸掺量为2.5wt%时,材料性能最优,养护28 d抗压强度可达38.5 MPa,凝结时间为24 min。水泥主要水化产物是结构密实、结晶良好的柱形FeC_2O_4·2H_2O,添加硼砂和三聚磷酸钠会使水泥出现孔隙,而硼酸会促进水化反应使水化产物结晶更优,且不会破坏水泥的密实度。
Mixing according to a certain ratio, the copper slag and the oxalic acid were used as raw materials to prepare the copper slag-based oxalate cement by an acid-base reaction. The influence of the mass ratios of copper slag to oxalic acid(CS/OA) and water to cement(W/C), the retarder type and its content on the mechanical properties and setting time of copper slag-based oxalate cement ware discussed. The morphology and phase composition of the copper slag based oxalate cement were analyzed by SEM and XRD. Theresults showed that with the increase of mass ratios of CS/OA and W/C, the compressive strength increased first and then decreased, and the setting time decreased with the increasing of CS/OA and increased with the increasing of W/C. The borax and the sodium tripolyphosphate had a very negative influence on the compressive strength of the material, which lead to a significant decrease in the mechanical properties of the material as the amounts of the borax and the sodium tripolyphosphate increased. The proper amount of the boric acid can improve the compressive strength of the material and had a good retarding effect, therefore, the boric acid was preferred as a retarder. The material properties were optimum when CS/OA was 4, the W/C was 0.16?0.17, and the boric acid content was 2.5 wt%. Its compressive strength reached 38.5 MPa after curing 28 d and the setting time was 24 min. The main hydration product of the copper slag based oxalate cement was a column type FeC2 O4·2 H2 O, which has a dense structure and good crystallization. The addition of the borax and the sodium tripolyphosphate could cause stomata and gap in the copper slag based oxalate cement structure, while the boric acid could promote the hydration reaction to optimize crystallization of the hydrated product without compromising the compactness of the material structure.
Mixing according to a certain ratio, the copper slag and the oxalic acid were used as raw materials to prepare the copper slag-based oxalate cement by an acid-base reaction. The influence of the mass ratios of copper slag to oxalic acid(CS/OA) and water to cement(W/C), the retarder type and its content on the mechanical properties and setting time of copper slag-based oxalate cement ware discussed. The morphology and phase composition of the copper slag based oxalate cement were analyzed by SEM and XRD. Theresults showed that with the increase of mass ratios of CS/OA and W/C, the compressive strength increased first and then decreased, and the setting time decreased with the increasing of CS/OA and increased with the increasing of W/C. The borax and the sodium tripolyphosphate had a very negative influence on the compressive strength of the material, which lead to a significant decrease in the mechanical properties of the material as the amounts of the borax and the sodium tripolyphosphate increased. The proper amount of the boric acid can improve the compressive strength of the material and had a good retarding effect, therefore, the boric acid was preferred as a retarder. The material properties were optimum when CS/OA was 4, the W/C was 0.16?0.17, and the boric acid content was 2.5 wt%. Its compressive strength reached 38.5 MPa after curing 28 d and the setting time was 24 min. The main hydration product of the copper slag based oxalate cement was a column type FeC2 O4·2 H2 O, which has a dense structure and good crystallization. The addition of the borax and the sodium tripolyphosphate could cause stomata and gap in the copper slag based oxalate cement structure, while the boric acid could promote the hydration reaction to optimize crystallization of the hydrated product without compromising the compactness of the material structure.
引文
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[14]朱茂兰,熊家春,胡志彪,等.铜渣中铜铁资源化利用研究进展[J].有色冶金设计与研究,2016,37(2):15-17,27.Zhu M L,Xiong J C,Hu Z B,et al.Research progress in resource utilization of iron and copper in copper smelting slag[J].Nonferrous Metals Engineering&Research,2016,37(2):15-17,27.
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[17]沈敏,田莉,薛爱芳,等.壳聚糖预分离富集-离子色谱法测定痕量草酸根[J].分析科学学报,2008,24(3):299-302.Shen M,Tian L,Xue A F,et al.Preconcentration and separation of trace amounts of oxalate with chitosan and determination by ion chromatography[J].Journal of Analytical Science,2008,24(3):299-302.
[18]张静,沈国良,马晓雨,等.草酸镁的合成与应用研究[J].化学工程师,2013,27(3):43-46,50.Zhang J,Shen G L,Ma X Y,et al.Study on synthesis and application of magnesium oxalate[J].Chemical Engineer,2013,27(3):43-46,50.
[19]何欢,周新涛,罗中秋,等.铜渣基铁系磷酸盐化学键合材料的制备及其固化Pb2+的研究[J].材料导报,2016,30(9):117-121.He H,Zhou X T,Luo Z Q,et al.Preparation of iron based chemically bonded phosphate ceramics using copper slag and its utilization on immobilization of Pb2+[J].Materials Review,2016,30(9):117-121.
[20]杜海云.用铜渣制备无机胶凝材料及其高温性能研究[D].昆明:昆明理工大学,2017:33-40.Du H Y.Performance of cementitious material containing copper slag after exposure to high temperatures[D].Kunming:Kunming University of Science and Technology,2017:33-40.
[21]孙春景,林旭健,季韬.磷镁比、水灰比、硼砂掺量对磷酸钾镁水泥耐水性的影响[J].福州大学学报(自然科学版),2016,44(6):856-862.Sun C J,Lin X J,Ji T.Influence of the ratio of KH2PO4 to MgO,ratio of water to bind,content change of borax on water resistance of magnesium-potassium phosphate cement[J].Journal of Fuzhou University(Natural Science Edition),2016,44(6):856-862.
[22]齐召庆,徐哲,孙运亮,等.原材料及配比对磷酸镁水泥强度的影响[J].当代化工,2015,44(11):2581-2584.Qi Z Q,Xu Z,Sun Y L,et al.Effect of raw materials and their ratio on compressive strength of magnesium phosphate cement[J].Contemporary Chemical Industry,2015,44(11):2581-2584.
[23]徐选臣,邵云霞.水灰比对磷酸钾镁水泥性能的影响[J].硅酸盐通报,2013,32(2):236-241.Xu X C,Shao Y X.The effect of ratio of water to binder on the properties of magnesium potassium phosphate cement paste[J].Bulletin of the Chinese Ceramic Society,2013,32(2):236-241.
[24]Soudée E,Péra J.Mechanism of setting reaction in magnesiaphosphate cements[J].Cement and Concrete Research,2000,30(2):315-321.
[25]Sugama T,Kukacka L E.Magnesium monophosphate cement derived from diammoniun phosphate solutions[J].Cement and Concrete Research,1983,13(3):407-416.
[26]Papo A,Piani L,Riceceri R.Sodium tripolyphosphate and polyphosphate as dispersing agents for kaolin suspensions:rheological characterization[J].Journal of Engineering,2013,201(1):219-230.
[2]汪宏涛,丁建华,张时豪,等.磷酸镁水泥水化热的影响因素研究[J].功能材料,2015,46(22):22098-22102.Wang H T,Ding J H,Zhang S H,et al.Study on the influent factors of magnesium phosphate cement hydration heat[J].Journal of Functional Materials,2015,46(22):22098-22102.
[3]Sun D S,Sun P,Wang A G,et al.Research of magnesium phosphate cement and its development prospects[J].Materials Review,2013,27(5):70-75.
[4]陈兵,雒亚莉,王菁.磷酸镁水泥性能试验研究[J].水泥,2010,(7):14-18.Chen B,Luo Y L,Wang J.Study on performance of magnesium phosphate cement[J].Cement,2010,(7):14-18.
[5]Li Y,Sun J,Chen B.Experimental study of magnesia and M/P ratio influencing properties of magnesium phosphate cement[J].Construction and Building Materials,2014,65(13):177-183.
[6]Bansal N P,Singh J P,Lamon J,et al.Influence of particle size distribution of wollastonite on the mechanical properties of CBPCs(chemically bonded phosphate ceramics):processing and properties of advanced ceramics and composites III,volume 225[M].New York:John Wiley&Sons,2011:85-98.
[7]毛敏,王智,贾兴文.磷酸镁水泥耐水性能改善的研究[J].非金属矿,2012,35(6):1-3.Mao M,Wang Z,Jia X W.Researching on water resistance improvement of magnesium phosphate cement[J].Non-Metallic Mines,2012,35(6):1-3.
[8]Yang Q,Zhu B,Wu X.Characteristics and durability test of magnesium phosphate cement-based material for rapid repair of concrete[J].Materials and Structures,2000,33(4):229-234.
[9]Neiman R,Sarma A C.Setting and thermal reactions of phosphate investments[J].Journal of Dental Research,1980,59(9):1478-1485.
[10]胡华洁,杜骁,陈兵.原料配比参数对磷酸镁水泥性能的影响[J].四川建筑科学研究,2015,41(4):73-78.Hu H J,Du X,Chen B.Factors influencing properties of magnesium phosphate cement[J].Sichuan Building Science,2015,41(4):73-78.
[11]薛明,曹巨辉,蒋江波,等.硼砂对磷酸镁水泥性能影响及微观作用机理分析[J].后勤工程学院学报,2011,27(6):52-55.Xue M,Cao J H,Jiang J B,et al.Influence of borax on properties of magnesium phosphate cement and its microscopic mechanism[J].Journal of Logistical Engineering University,2011,27(6):52-55.
[12]王二强,王冬,刘兴华.磷酸镁水泥缓凝剂的研究[J].混凝土,2012,(9):86-88.Wang E Q,Wang D,Liu X H.Research on retarders of magnesia phosphate cement[J].Concrete,2012,(9):86-88.
[13]Hall D A,Stevens R,El-Jazairi B.The effect of retarders on the microstructure and mechanical properties of magnesia-phosphate cement mortar[J].Cement and Concrete Research,2001,31(3):455-465.
[14]朱茂兰,熊家春,胡志彪,等.铜渣中铜铁资源化利用研究进展[J].有色冶金设计与研究,2016,37(2):15-17,27.Zhu M L,Xiong J C,Hu Z B,et al.Research progress in resource utilization of iron and copper in copper smelting slag[J].Nonferrous Metals Engineering&Research,2016,37(2):15-17,27.
[15]周占兴,周春芳.铜渣的新型资源化处理工艺[J].冶金设备,2015,(1):51-54,24.Zhou Z X,Zhou C F.A new resourceful treatment-technology for copper slag[J].Metallurgical Equipment,2015,(1):51-54,24.
[16]王东方.草酸市场前景及生产应用[J].化工技术经济,2003,21(3):20-22.Wang D F.Processes and market of oxilic acid[J].Chemical Technology Economy,2003,21(3):20-22.
[17]沈敏,田莉,薛爱芳,等.壳聚糖预分离富集-离子色谱法测定痕量草酸根[J].分析科学学报,2008,24(3):299-302.Shen M,Tian L,Xue A F,et al.Preconcentration and separation of trace amounts of oxalate with chitosan and determination by ion chromatography[J].Journal of Analytical Science,2008,24(3):299-302.
[18]张静,沈国良,马晓雨,等.草酸镁的合成与应用研究[J].化学工程师,2013,27(3):43-46,50.Zhang J,Shen G L,Ma X Y,et al.Study on synthesis and application of magnesium oxalate[J].Chemical Engineer,2013,27(3):43-46,50.
[19]何欢,周新涛,罗中秋,等.铜渣基铁系磷酸盐化学键合材料的制备及其固化Pb2+的研究[J].材料导报,2016,30(9):117-121.He H,Zhou X T,Luo Z Q,et al.Preparation of iron based chemically bonded phosphate ceramics using copper slag and its utilization on immobilization of Pb2+[J].Materials Review,2016,30(9):117-121.
[20]杜海云.用铜渣制备无机胶凝材料及其高温性能研究[D].昆明:昆明理工大学,2017:33-40.Du H Y.Performance of cementitious material containing copper slag after exposure to high temperatures[D].Kunming:Kunming University of Science and Technology,2017:33-40.
[21]孙春景,林旭健,季韬.磷镁比、水灰比、硼砂掺量对磷酸钾镁水泥耐水性的影响[J].福州大学学报(自然科学版),2016,44(6):856-862.Sun C J,Lin X J,Ji T.Influence of the ratio of KH2PO4 to MgO,ratio of water to bind,content change of borax on water resistance of magnesium-potassium phosphate cement[J].Journal of Fuzhou University(Natural Science Edition),2016,44(6):856-862.
[22]齐召庆,徐哲,孙运亮,等.原材料及配比对磷酸镁水泥强度的影响[J].当代化工,2015,44(11):2581-2584.Qi Z Q,Xu Z,Sun Y L,et al.Effect of raw materials and their ratio on compressive strength of magnesium phosphate cement[J].Contemporary Chemical Industry,2015,44(11):2581-2584.
[23]徐选臣,邵云霞.水灰比对磷酸钾镁水泥性能的影响[J].硅酸盐通报,2013,32(2):236-241.Xu X C,Shao Y X.The effect of ratio of water to binder on the properties of magnesium potassium phosphate cement paste[J].Bulletin of the Chinese Ceramic Society,2013,32(2):236-241.
[24]Soudée E,Péra J.Mechanism of setting reaction in magnesiaphosphate cements[J].Cement and Concrete Research,2000,30(2):315-321.
[25]Sugama T,Kukacka L E.Magnesium monophosphate cement derived from diammoniun phosphate solutions[J].Cement and Concrete Research,1983,13(3):407-416.
[26]Papo A,Piani L,Riceceri R.Sodium tripolyphosphate and polyphosphate as dispersing agents for kaolin suspensions:rheological characterization[J].Journal of Engineering,2013,201(1):219-230.