程海勇等：高硫膏体强度劣化机理实验研究 ·1497· [8]Fall M,Benzaazoua M.Modeling the effect of sulphate on strength 4结论 development of paste backfill and binder mixture optimization.Ce (1)不同硫含量的膏体强度表现出不同的增长形 ment Concrete Res,2005,35(2):301 式，含硫膏体在一定程度上能促进早期强度，但却抑制 [9]Klein K,Simon D.Effect of specimen composition on the strength development in cemented paste backfill.Can Geotech /2006.43 了后期强度发育，同时疏含量越高，膏体强度劣化现象 (3):310 越显著，通过实验分析将含硫膏体强度发育划分成早 [10]Zhang Q L,Wang X M,Tian M H.The influence of sulfide on 期、中期和后期三个阶段. the strength of filling body.Min Res Dev,2004,24(Suppl 1): (2)X射线物相分析和环境扫描电镜分析发现， 168 引起膏体强度劣化的物相主要为膨胀性钙矾石和石膏 (张钦礼，王新民，田明华.硫化物对充填体强度的影响.矿 类物质.养护过程中硫化物持续氧化造成碱度降低， 业研究与开发，2004,24（增刊1）：168) [11]Xu Y H.Study on influence of sulphide in tailings on quality of 使C-S-H产生脱钙和CH的分解，已形成的胶凝体系 backfill.Min Res Dev,2009.29(5):4 遭到破坏，进一步促进了充填体的劣化. (许毓海.尾砂中硫化物对充填体质量影响研究.矿业研究 (3)通过膨胀应变方程和线弹性应变分析认为， 与开发，2009.29(5)：4) 结晶压的循环积累及释放促进了充填体裂纹的增长发 [12]Han R J,Wang L.Study on tailings filling system for a lead-zinc 育，裂纹的增长为石膏和钙矾石晶体的发育提供了空 mine with high sulfur content.Energ Sa Non-ferr Metall,2014, 30(1):29 间，同时孔隙率的提高为晶体发育提供了材料通道. (韩瑞军，王麒.某铅锌矿高硫尾砂充填系统研究.有色冶 金节能.2014,30(1)：29) 参考文献 [13]Ma J T,Shui Z H,Chen W,et al.Effect of curing humility on carbonation rate of shrinkage-compensating concrete.Concrete, [1]Liu C,Wang HJ,Wu A X,et al.Determination of concentration 2011(1):24 range of fine unclassified tailings paste in copper-molybdenum (马军涛，水中和，陈伟，等.养护湿度对补偿收缩混凝土碳 mine.Chin J Rock Mech Eng,2015,34(Suppl 1):3432 化速率的影响.混凝土，2011(1)：24) (刘超，王洪江，吴爱祥，等.铜钼矿细粒全尾膏体浓度范围 [14]Wang Y T,Yang Z Q.Li M H,et al.Experimental studies of 确定.岩石力学与工程学报，2015,34（增刊1）：3432) the performance characteristic on new filling cementing material [2]Cihangir F,Ercikdi B,Kesimal A,et al.Paste backfill of high- with unclassified tailings.Min Res Dev,2014,34(7):63 sulphide mill tailings using alkali-activated blast fumace slag: (王有团，杨志强，李茂辉，等.新型充填胶凝材料全尾砂浆 effect of activator nature,concentration and slag properties.Miner 工作特性试验研究.矿业研究与开发，2014,34(7)：63) Eng,2015,83:117 [15]Gao J F.Experiment and practice of sulfur-containing tailings ce- [3]Zhang Q L,Kang Q,Xiao F G,et al.Key technology of cemen- mentation filling applied in underground mined-out area.Nonferr ted backfilling with high viscosity sulfur-content tailings.Metal Metal (Min Sect),2014,66(3):9 Mime,2010(11）:39 (高建蜂.含硫尾矿应用于井下空区胶结充填的试验与实 (张钦礼，康度，肖富国，等.含硫高粘性尾矿胶结充填关键 践.有色金属：矿山部分，2014,66(3)：9) 技术.金属矿山，2010(11)：39) [16]Benzaazoua M,Belem T,Bussiere B.Chemical factors that in- [4]Liu Y Q,Hou DD.Strength test of sulphidic tailings backfill. fluence the performance of mine sulphidic paste backfill.Cement Mod Min,2013(11):195 Concrete Res,2002,32(7)1133 (刘允秋，侯大德.含硫尾砂充填体强度试验.现代矿业， [17]Wang B,Zhang H Y,Dong X L,et al.Long-term deterioration 2013(11):195) of cemented paste backfill due to sulphide oxidation.Ind Miner [5]Yin J D,Song J P.Sulfide coagulation mechanism and its applica- Process,2007,36(10):29 tion in the paste filling.Mod Min,2015(1):183 (王宝，张虎元，董兴玲，等.硫化物氧化对充填体长期强度 (尹建东，宋军平.硫化物促凝机理及其在膏体充填中的应 的影响.化工矿物与加工，2007,36(10)：29) 用.现代矿业，2015(1)：183) [18]Hansen T C.Physical structure of hardened cement paste.A [6]Zhang Y,Tang M L.Yang S M,et al.Status and progress of ex- classical approach.Mater Struct,1986,19(6):423 ploiting pyrites resources in China.Bull Chin Ceramic Soc,2013, [19]Ibrahim R E H,Roziere E,Grondin F,et al.Influence of sul- 32(5):895 phate solution concentration on the performance of cementitious (张跃，唐明林，扬守明，等.我国硫铁矿资源开发利用现状 materials during external sulphate attack.Meditsinskaia Sestra, 和进展.硅酸盐通报，2013,32(5)：895) 2009,43(10):63 [7]Ayora C,Chinchon S,Aguado A,et al.Weathering of iron sul- [20]Guo Z H,Shi X D.Reinforced Concrete Principle and Analysis. fides and concrete alteration:thermodynamic model and observa- Beijing:Tsinghua University Press,2003 tion in dams from Central Pyrenees,Spain.Cement Concrete Res, (过镇海，时旭东.钢筋混凝土原理和分析.北京：清华大学 1998,28(4):591 出版社，2003)程海勇等: 高硫膏体强度劣化机理实验研究 4 结论 (1) 不同硫含量的膏体强度表现出不同的增长形 式,含硫膏体在一定程度上能促进早期强度,但却抑制 了后期强度发育,同时硫含量越高,膏体强度劣化现象 越显著,通过实验分析将含硫膏体强度发育划分成早 期、中期和后期三个阶段. (2) X 射线物相分析和环境扫描电镜分析发现, 引起膏体强度劣化的物相主要为膨胀性钙矾石和石膏 类物质. 养护过程中硫化物持续氧化造成碱度降低, 使 C鄄鄄 S鄄鄄H 产生脱钙和 CH 的分解,已形成的胶凝体系 遭到破坏,进一步促进了充填体的劣化. (3) 通过膨胀应变方程和线弹性应变分析认为, 结晶压的循环积累及释放促进了充填体裂纹的增长发 育,裂纹的增长为石膏和钙矾石晶体的发育提供了空 间,同时孔隙率的提高为晶体发育提供了材料通道. 参 考 文 献 [1] Liu C, Wang H J, Wu A X, et al. Determination of concentration range of fine unclassified tailings paste in copper鄄molybdenum mine. Chin J Rock Mech Eng, 2015, 34(Suppl 1): 3432 (刘超, 王洪江, 吴爱祥, 等. 铜钼矿细粒全尾膏体浓度范围 确定. 岩石力学与工程学报, 2015, 34(增刊 1): 3432) [2] Cihangir F, Ercikdi B, Kesimal A, et al. Paste backfill of high鄄 sulphide mill tailings using alkali鄄activated blast furnace slag: effect of activator nature, concentration and slag properties. Miner Eng, 2015, 83: 117 [3] Zhang Q L, Kang Q, Xiao F G, et al. Key technology of cemen鄄 ted backfilling with high viscosity sulfur鄄content tailings. Metal Mine, 2010(11): 39 (张钦礼, 康虔, 肖富国, 等. 含硫高粘性尾矿胶结充填关键 技术. 金属矿山, 2010(11): 39) [4] Liu Y Q, Hou D D. Strength test of sulphidic tailings backfill. Mod Min, 2013(11): 195 (刘允秋, 侯大德. 含硫尾砂充填体强度试验. 现代矿业, 2013(11): 195) [5] Yin J D, Song J P. Sulfide coagulation mechanism and its applica鄄 tion in the paste filling. Mod Min, 2015(1): 183 (尹建东, 宋军平. 硫化物促凝机理及其在膏体充填中的应 用. 现代矿业, 2015(1): 183) [6] Zhang Y, Tang M L, Yang S M, et al. Status and progress of ex鄄 ploiting pyrites resources in China. Bull Chin Ceramic Soc, 2013, 32(5): 895 (张跃, 唐明林, 扬守明, 等. 我国硫铁矿资源开发利用现状 和进展. 硅酸盐通报, 2013, 32(5): 895) [7] Ayora C, Chinchon S, Aguado A, et al. Weathering of iron sul鄄 fides and concrete alteration: thermodynamic model and observa鄄 tion in dams from Central Pyrenees, Spain. Cement Concrete Res, 1998, 28(4): 591 [8] Fall M, Benzaazoua M. Modeling the effect of sulphate on strength development of paste backfill and binder mixture optimization. Ce鄄 ment Concrete Res, 2005, 35(2): 301 [9] Klein K, Simon D. Effect of specimen composition on the strength development in cemented paste backfill. Can Geotech J, 2006, 43 (3): 310 [10] Zhang Q L, Wang X M, Tian M H. The influence of sulfide on the strength of filling body. Min Res Dev, 2004, 24( Suppl 1): 168 (张钦礼, 王新民, 田明华. 硫化物对充填体强度的影响. 矿 业研究与开发, 2004, 24(增刊 1): 168) [11] Xu Y H. Study on influence of sulphide in tailings on quality of backfill. Min Res Dev, 2009, 29(5): 4 (许毓海. 尾砂中硫化物对充填体质量影响研究. 矿业研究 与开发, 2009, 29(5): 4) [12] Han R J, Wang L. Study on tailings filling system for a lead鄄zinc mine with high sulfur content. Energ Sav Non鄄ferr Metall, 2014, 30(1): 29 (韩瑞军, 王麒. 某铅锌矿高硫尾砂充填系统研究. 有色冶 金节能, 2014, 30(1): 29) [13] Ma J T, Shui Z H, Chen W, et al. Effect of curing humility on carbonation rate of shrinkage鄄compensating concrete. Concrete, 2011(1): 24 (马军涛, 水中和, 陈伟, 等. 养护湿度对补偿收缩混凝土碳 化速率的影响. 混凝土, 2011(1): 24) [14] Wang Y T, Yang Z Q, Li M H, et al. Experimental studies of the performance characteristic on new filling cementing material with unclassified tailings. Min Res Dev, 2014, 34(7): 63 (王有团, 杨志强, 李茂辉, 等. 新型充填胶凝材料全尾砂浆 工作特性试验研究. 矿业研究与开发, 2014, 34(7): 63) [15] Gao J F. Experiment and practice of sulfur鄄containing tailings ce鄄 mentation filling applied in underground mined鄄out area. Nonferr Metal (Min Sect), 2014, 66(3): 9 (高建峰. 含硫尾矿应用于井下空区胶结充填的试验与实 践. 有色金属: 矿山部分, 2014, 66(3): 9) [16] Benzaazoua M, Belem T, Bussiere B. Chemical factors that in鄄 fluence the performance of mine sulphidic paste backfill. Cement Concrete Res, 2002, 32(7): 1133 [17] Wang B, Zhang H Y, Dong X L, et al. Long鄄term deterioration of cemented paste backfill due to sulphide oxidation. Ind Miner Process, 2007, 36(10): 29 (王宝, 张虎元, 董兴玲, 等. 硫化物氧化对充填体长期强度 的影响. 化工矿物与加工, 2007, 36(10): 29) [18] Hansen T C. Physical structure of hardened cement paste. A classical approach. Mater Struct, 1986, 19(6): 423 [19] Ibrahim R E H, Rozi侉re E, Grondin F, et al. Influence of sul鄄 phate solution concentration on the performance of cementitious materials during external sulphate attack. Meditsinskaia Sestra, 2009, 43(10):63 [20] Guo Z H, Shi X D. Reinforced Concrete Principle and Analysis. Beijing: Tsinghua University Press, 2003 (过镇海, 时旭东. 钢筋混凝土原理和分析. 北京: 清华大学 出版社, 2003) ·1497·