Article(id=1322164610417930793, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164546295410919, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1734883200000, receivedDateStr=2024-12-23, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793158207754, onlineDateStr=2026-10-28, pubDate=1764000000000, pubDateStr=2025-11-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793158207754, onlineIssueDateStr=2026-10-28, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793158207754, creator=13701087609, updateTime=1793158207754, updator=13701087609, issue=Issue{id=1322164546295410919, tenantId=1146029695717560320, journalId=1225396423026438145, year='2025', volume='45', issue='11', pageStart='1', pageEnd='284', issueExtLink='null', onlineDate='null', pubDate='1764000000000', pubDateStr='2025-11-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793158192465, creator='13701087609', updateTime=1793158905697, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322167537857573862, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164546295410919, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322167537861768167, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164546295410919, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=88, endPage=96, ext={EN=ArticleExt(id=1322164610623451690, articleId=1322164610417930793, tenantId=1146029695717560320, journalId=1225396423026438145, language=EN, title=Influence of Compound Additive Ratio on the Performance of Fly Ash-Based Mine Filling Material, columnId=null, journalTitle=Mining Research and Development, columnName=null, runingTitle=null, highlight=null, articleAbstract=

To address the problems of low filling body strength and large surface subsidence in the current filling mining process of a coal mine in Jining, filling materials were prepared with fly ash as the main material and lime, β-gypsum, cement, sodium hydroxide, and compound additives (slag A, AEA-type expansive agent B, cement clinker C) as auxiliary materials. The influence of additive ratio on slurry flow performance, uniaxial compressive strength of filling body, hydration products, and microstructure was explored. The study shows that the flow performance of slurry has no linear relationship with changes in the content of each component in the additive. Under different additive ratios, the initial fluidity of the filling slurry is ≥22.2 cm and the dynamic viscosity is ≤218 mPa•s, which meets the self-flow requirement. When the content of other components is constant, with the increase in the content of components A, B, and C, the filling body strength at different curing ages all shows a trend of first increasing and then decreasing. Under different additive ratios, the hydration products of the filling body cured for 28 days are basically consistent, but there are differences in the intensity of diffraction peaks. The increase in the content of components A, B, and C can effectively improve the compactness and pore development of the filling body. However, when their content is excessive, the microstructure deteriorates. When the content of components A, B, and C is 14%, 6%, and 8% respectively, the mechanical properties of the filling body are optimal. Its early-age (8 h) strength and long-term (28 d) strength reach 0.75 MPa and 4.33 MPa respectively, with the highest compactness and excellent flow performance.

, authors=Guozhi HE1, Guolei LIU1, Qiufeng MA1, Xiqing HAO2, Haibin HU2, Xinyu LIU1, Bingzhe BAI1, authorsList=Guozhi HE, Guolei LIU, Qiufeng MA, Xiqing HAO, Haibin HU, Xinyu LIU, Bingzhe BAI, authorCompany=null, correspAuthors=Guolei LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322164617191731783, articleId=1322164610417930793, tenantId=1146029695717560320, journalId=1225396423026438145, language=CN, title=复合添加剂配比对粉煤灰基矿用充填材料性能的影响研究, columnId=1226462294490657775, journalTitle=矿业研究与开发, columnName=采矿与矿山充填, runingTitle=null, highlight=null, articleAbstract=

针对济宁某煤矿当前充填开采工艺充填体强度低、地表沉降量较大的问题,以粉煤灰为主料,石灰、β-石膏、水泥、片碱、复合添加剂(矿渣A、AEA型膨胀剂B、水泥熟料C)为辅料制备充填材料,探究了添加剂配比对料浆流动性能、充填体单轴抗压强度、水化产物及微观结构的影响。研究表明,料浆流动性能与添加剂中各组分掺量的变化无线性关系,不同添加剂配比下,充填料浆初始流动度≥22.2 cm,动力黏度≤218 mPa•s,满足自流要求。当其他组分掺量一定时,随着A、B、C组分掺量的增加,不同养护龄期的充填体强度均呈现先升高后降低的趋势。不同添加剂配比下,养护28 d的充填体水化产物基本一致,但衍射峰强度存在差异。A、B、C组分掺量的增加能够有效改善充填体密实度及孔隙发育情况,过量时微观结构出现劣化。当A、B、C组分掺量分别为14%、6%、8%时,充填体力学性能最优,早期(8 h)强度及长期(28 d)强度分别达到0.75 MPa和4.33 MPa,充填体密实度最高,流动性能优异。

, authors=何国志1, 刘国磊1, 马秋峰1, 郝喜庆2, 胡海滨2, 刘歆瑜1, 白秉哲1, authorsList=何国志, 刘国磊, 马秋峰, 郝喜庆, 胡海滨, 刘歆瑜, 白秉哲, authorCompany=null, correspAuthors=刘国磊, authorNote=

何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

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刘国磊(1985—),男,山东淄博人,博士,教授,博士生导师,研究方向为矿山安全与绿色开采。E-mail:
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何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

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何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

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Zibo: Shandong University of Technology, 2021., articleTitle=Macro and meso response mechanism of early mechanical behavior of backfill based on slag-based cementitious material, refAbstract=null)], funds=[Fund(id=1322164623764206219, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, awardId=52474104, language=CN, fundingSource=国家自然科学基金面上项目(52474104), fundOrder=null, country=null), Fund(id=1322164623881646732, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, awardId=51904178, language=CN, fundingSource=国家自然科学基金资助项目(51904178), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1322164617435001416, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, xref=1., ext=[AuthorCompanyExt(id=1322164617443390025, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, companyId=1322164617435001416, language=EN, country=null, 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Results of main chemical composition analysis of test materials

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试验材料SiO2Al2O3CaOMgOFe2O3Na2OTiO2SO3K2OMnO
粉煤灰30.50023.400 01.610.020 02.4400.4580.7720.5220.8530.020
矿渣28.00015.700 041.008.780 00.5100.7860.5973.2000.3100.336
生石灰0.7940.403 084.803.500 00.2130.028—0.3090.026—
β-石膏0.3270.084 541.900.013 80.029——57.6000.016—
水泥4.75017.600 042.501.200 02.8300.3930.54514.6000.2980.030
), ArticleFig(id=1322164623466410632, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, language=CN, label=表1, caption=

试验材料主要化学成分分析结果

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试验材料SiO2Al2O3CaOMgOFe2O3Na2OTiO2SO3K2OMnO
粉煤灰30.50023.400 01.610.020 02.4400.4580.7720.5220.8530.020
矿渣28.00015.700 041.008.780 00.5100.7860.5973.2000.3100.336
生石灰0.7940.403 084.803.500 00.2130.028—0.3090.026—
β-石膏0.3270.084 541.900.013 80.029——57.6000.016—
水泥4.75017.600 042.501.200 02.8300.3930.54514.6000.2980.030
), ArticleFig(id=1322164623571268233, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164610417930793, language=EN, label=Table 2, caption=

Additive ratio test schemes

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试验序号ABC
110212
212212
314212
416212
51408
61428
71468
81488
914210
1014216
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添加剂配比试验方案

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试验序号ABC
110212
212212
314212
416212
51408
61428
71468
81488
914210
1014216
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复合添加剂配比对粉煤灰基矿用充填材料性能的影响研究
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何国志 1 , 刘国磊 1 , 马秋峰 1 , 郝喜庆 2 , 胡海滨 2 , 刘歆瑜 1 , 白秉哲 1
矿业研究与开发 | 采矿与矿山充填 2025,45(11): 88-96
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矿业研究与开发 |采矿与矿山充填 2025 , 45 (11) : 88 -96
复合添加剂配比对粉煤灰基矿用充填材料性能的影响研究
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何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

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何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

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何国志1 , 刘国磊1 , 马秋峰1, 郝喜庆2, 胡海滨2, 刘歆瑜1, 白秉哲1
作者信息
  • 1.山东理工大学 资源与环境工程学院,山东 淄博市 255049
  • 2.枣庄矿业集团高庄煤业有限公司,山东 济宁市 272200
通讯作者:
刘国磊(1985—),男,山东淄博人,博士,教授,博士生导师,研究方向为矿山安全与绿色开采。E-mail:
作者简介:

何国志(1998—),男,云南南华人,硕士研究生,研究方向为矿山动力灾害控制与充填开采。E-mail:

Influence of Compound Additive Ratio on the Performance of Fly Ash-Based Mine Filling Material
Guozhi HE1 , Guolei LIU1 , Qiufeng MA1, Xiqing HAO2, Haibin HU2, Xinyu LIU1, Bingzhe BAI1
Affiliations
  • 1.School of Resources and Environmental Engineering, Shandong University of Technology, Zibo, Shandong 255049, China
  • 2.Zaozhuang Mining Group Gaozhuang Coal Co., Ltd., Jining, Shandong 272200, China
出版时间: 2025-11-25
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针对济宁某煤矿当前充填开采工艺充填体强度低、地表沉降量较大的问题,以粉煤灰为主料,石灰、β-石膏、水泥、片碱、复合添加剂(矿渣A、AEA型膨胀剂B、水泥熟料C)为辅料制备充填材料,探究了添加剂配比对料浆流动性能、充填体单轴抗压强度、水化产物及微观结构的影响。研究表明,料浆流动性能与添加剂中各组分掺量的变化无线性关系,不同添加剂配比下,充填料浆初始流动度≥22.2 cm,动力黏度≤218 mPa•s,满足自流要求。当其他组分掺量一定时,随着A、B、C组分掺量的增加,不同养护龄期的充填体强度均呈现先升高后降低的趋势。不同添加剂配比下,养护28 d的充填体水化产物基本一致,但衍射峰强度存在差异。A、B、C组分掺量的增加能够有效改善充填体密实度及孔隙发育情况,过量时微观结构出现劣化。当A、B、C组分掺量分别为14%、6%、8%时,充填体力学性能最优,早期(8 h)强度及长期(28 d)强度分别达到0.75 MPa和4.33 MPa,充填体密实度最高,流动性能优异。

粉煤灰基矿用充填材料  /  复合添加剂  /  流动性能  /  抗压强度  /  水化产物  /  微观结构

To address the problems of low filling body strength and large surface subsidence in the current filling mining process of a coal mine in Jining, filling materials were prepared with fly ash as the main material and lime, β-gypsum, cement, sodium hydroxide, and compound additives (slag A, AEA-type expansive agent B, cement clinker C) as auxiliary materials. The influence of additive ratio on slurry flow performance, uniaxial compressive strength of filling body, hydration products, and microstructure was explored. The study shows that the flow performance of slurry has no linear relationship with changes in the content of each component in the additive. Under different additive ratios, the initial fluidity of the filling slurry is ≥22.2 cm and the dynamic viscosity is ≤218 mPa•s, which meets the self-flow requirement. When the content of other components is constant, with the increase in the content of components A, B, and C, the filling body strength at different curing ages all shows a trend of first increasing and then decreasing. Under different additive ratios, the hydration products of the filling body cured for 28 days are basically consistent, but there are differences in the intensity of diffraction peaks. The increase in the content of components A, B, and C can effectively improve the compactness and pore development of the filling body. However, when their content is excessive, the microstructure deteriorates. When the content of components A, B, and C is 14%, 6%, and 8% respectively, the mechanical properties of the filling body are optimal. Its early-age (8 h) strength and long-term (28 d) strength reach 0.75 MPa and 4.33 MPa respectively, with the highest compactness and excellent flow performance.

Fly ash-based mine filling material  /  Compound additive  /  Flow performance  /  Compressive strength  /  Hydration product  /  Microstructure
何国志, 刘国磊, 马秋峰, 郝喜庆, 胡海滨, 刘歆瑜, 白秉哲. 复合添加剂配比对粉煤灰基矿用充填材料性能的影响研究. 矿业研究与开发, 2025 , 45 (11) : 88 -96 .
Guozhi HE, Guolei LIU, Qiufeng MA, Xiqing HAO, Haibin HU, Xinyu LIU, Bingzhe BAI. Influence of Compound Additive Ratio on the Performance of Fly Ash-Based Mine Filling Material[J]. Mining Research and Development, 2025 , 45 (11) : 88 -96 .
粉煤灰是燃煤电厂产生的主要固体废弃物之一,随着电力工业的发展,其排放量逐年增加,成为我国主要大宗固废之一[1]。因粉煤灰具有较好的火山灰效应、形态效应和微集料效应,且价格低廉、来源广[2-3],在废水处理[4-5]、建筑材料[6-8]、矿山充填等领域得到广泛应用[9-11]。当前,诸多矿山从业者和科研人员针对粉煤灰充填胶凝材料制备、粉煤灰基膏体充填材料流变性能和力学性能等开展了大量研究,如周林邦等[12]探究了大掺量粉煤灰下水胶比、外加剂、骨料类型对充填材料流变性能、力学性能及其稳定性的影响,研究表明:粉煤灰掺量为60%、水胶比为1.0时,力学性能最优,再加入0.2%的减水剂,流变性能得到较好的提升;在相同条件下,以煤矸石为骨料的充填体稳定性始终优于以风积砂为骨料的充填体。李晓磊等[13]研究表明,当粉煤灰掺量能够改变水泥粉煤灰基矸石胶结充填体的破坏形态和脆延性时,即粉煤灰掺量由0增加至90%时,充填体破坏形态由剪切破坏向拉剪破坏、拉伸破坏转变,脆延性破坏模式由脆延性破坏变为延性破坏,揭示了粉煤灰占比与充填体破坏特征之间的响应关系。王小勇等[14]采用粉煤灰和水泥制备复合胶凝材料,探究了粉煤灰掺量和料浆质量浓度对胶结矸石充填材料流动性能、力学性能的影响,研究表明,充填体强度、料浆屈服应力均与粉煤灰掺量和料浆质量浓度成正比。李明等[15]通过正交试验得到了粉煤灰替代水泥对粉煤灰基膏体充填材料流动性能和力学强度的影响规律。乔龙腾等[16]开展了碱激发粉煤灰基胶凝材料性能研究,指出相较于Na2SiO3,使用NaOH作为激发剂时,对改善充填体抗压强度效果更明显。赵茂平等[17]以粉煤灰为主料,以NaOH、钠水玻璃、外加剂制备专用辅料,采用靶向激发制备浓度为55%的自流充填浆液,同时提出沟谷山地自流充填技术,并在某矿4604(1)工作面进行应用,经测量,工作面倾向、走向最大下沉量分别为-156 mm、-111 mm,保障了地面建筑的安全使用。上述文献对粉煤灰资源化利用提供了大量研究基础,但更多的研究聚焦于将粉煤灰作为一种活性掺合料替代或部分替代水泥制备矿山膏体充填胶凝材料,即将粉煤灰作为一种辅料进行研究;而对粉煤灰作为主要原料制备充填材料的报道相对较少。
本文在前人的研究基础上,根据济宁某矿“三下”充填开采充填体早期强度(8 h)、长期强度(28 d)分别不低于0.2 MPa、2.72 MPa的要求,以粉煤灰为主料,石灰、石膏、水泥、复合添加剂、片碱为辅料,制备新型早强矿用充填材料,分析复合添加剂的配比变化对料浆流动性能及充填体力学性能的影响,同时借助扫描电子显微镜(SEM)、X射线衍射(XRD)等技术探究粉煤灰基矿用充填材料的微观结构和水化机理。
采用二级粉煤灰作为主要原料,通过X射线荧光光谱仪(XRF)分析其化学成分,结果见表1。基于氧化物含量计算其碱性率M0,M0 = (CaO+MgO)/(SiO2+Al2O3)=0.03<1,表明该粉煤灰呈酸性;质量系数K,K = (CaO+MgO+Al2O3)/(SiO2+TiO2+MnO)=0.80<1.8,CaO含量仅为1.61%<10%,为低钙粉煤灰[18]。原材料的XRD图谱如图1所示。图1(a)为粉煤灰的XRD图谱,可知主要物相为莫来石、石英、硅线石、亚硫酸钙、硅酸二钙、氧化铝、氧化铁等,图中大量弥散峰通常被认为是硅铝玻璃相物质。
辅料由生石灰、β-石膏、水泥、复合添加剂(由矿渣、AEA型膨胀剂、水泥熟料组成)组成。生石灰中CaO含量为84.8%;β-石膏呈白色,其主要化学成分为SO3和CaO,二者总含量为99.5%。水泥主要成分为CaO和Al2O3,含量分别为42.5%和17.6%,其次是SO3和SiO2,含量分别为14.6%和4.75%。该水泥初凝时间为0.5 h,终凝时间为3 h。24 h抗压强度、抗折强度分别不低于30.0 MPa、6.0 MPa。
矿渣外观呈灰色,其主要成分为CaO、SiO2、Al2O3,经计算,该矿渣微粉质量系数K=2.26,碱性率M0=1.14,为碱性高活性矿渣。图1(b)为矿渣的XRD图谱,主要结晶相为硅酸三钙、硅酸二钙、镁黄长石、硅镁钙石、镁橄榄石等,此外存在大量弥散峰,表明其具有较高的活性。矿渣能够较好地改善料浆和易性,降低料浆泌水率,同时有助于提高充填体的耐久性和长期强度。AEA型膨胀剂和水泥熟料的XRD图谱分别如图1(c)和图1(d)所示。由图1(c)和图1(d)可以看出,AEA型膨胀剂和水泥熟料中的主要物相均为无水硫铝酸钙。
本研究采用NaOH纯度≥95%的片碱作为激发剂,试验用水为自来水。
基于前期大量探索性试验,将料浆质量浓度控制在55%,粉煤灰、生石灰、β-石膏、水泥、NaOH配比已确定,试验通过调整添加剂中矿渣、AEA型膨胀剂、水泥熟料(分别记为A、B、C)3种组分的掺量(占粉煤灰质量百分比),以探究添加剂的配比对粉煤灰基矿用充填材料性能的影响。添加剂配比试验方案见表2。
试验过程如下:按比例准确称量烘干后的粉煤灰、生石灰、石膏、水泥、复合添加剂,倒入JJ-5型搅拌机中搅拌5 min形成均匀的充填料浆,随后浇灌至涂有脱模油、尺寸为70.7 mm×70.7 mm×70.7 mm的三联模具中,振实料浆排除内部气泡,静置2 min后刮平上表面并编号,室温条件下6 h后脱模。为模拟井下充填环境,将脱模后的试块放入密封袋后,置于YH-90B型养护箱中养护,养护温度为25 ℃,湿度为95%。使用AEC-201型水泥强度试验机测试养护龄期分别为8 h、1 d、3 d、7 d、14 d、28 d试块的单轴抗压强度(UCS),试验机加载速率为2.4 kN/s,每组检测3个试块,取平均值。将破碎的试块放入无水乙醇中浸泡24 h,终止其水化反应,取出后放入鼓风干燥箱中干燥,选取断面平整、尺寸适宜的碎块进行喷金处理,随后通过SEM分析其微观结构,对剩余样品经磨碎筛分后进行XRD分析。
为探究不同添加剂配比的料浆流动性能,使用NDJ-8S数显旋转黏度计(3#转子,转速为60 r/min)检测料浆黏度,使用尺寸为36 mm×60 mm×60 mm的净浆流动度试模检测其流动度。
添加剂配比对料浆流动性能的影响如图2所示。
由图2可以看出,料浆黏度与流动度呈反比,当其他组分掺量固定时,随着A、C组分掺量的增加,流动度均呈现先降低后升高的趋势,随着B组分掺量的增加,流动度先升高后降低,黏度变化趋势与流动度相反。由图2(a)可知,A组分从10%增至14%时,流动度降低了11.2%,黏度增加了7.2%,当A掺量为16%,流动度较10%增加了6.8%,黏度降低了7.8%。这说明矿渣掺量的增加,使体系中自由水减少,同时加快了水化体系的反应速率,体系中凝胶物质增多,黏度升高,流动度降低;随着矿渣掺量的进一步增加,改善了料浆和易性,进而提高了流动性。由2(b)可知,B组分掺量为2%较未掺入时流动度提高了9.7%,黏度降低了18.3%,当B掺量由2%增加至8%时,流动度降低了5%,黏度增加了9.6%,但流动度高于未掺入B组分时的流动度。AEA型膨胀剂的加入优化了料浆中颗粒的分散性,随着其掺量的进一步增加,消耗了大量水分,导致黏度增加流动度降低。由2(c)可知,C组分掺量由8%增加至12%时,流动度降低了14.6%,黏度增加了8.4%,当C组分掺量继续增加至16%时,其流动度较掺量为12%时增加了17.6%,黏度相应降低了9.3%。水泥熟料掺量的增加,需要消耗更多的自由水,导致料浆黏度增加,流动度降低,当其掺量增加至16%时,体系中加入更多细小颗粒,这些细小颗粒能够较好地填充大颗粒间的空隙,改善了颗粒间的堆积密度,使得料浆流动度得到提高。料浆流动性能的变化是料浆中各组分共同作用的结果。
同时由图2可知,不同添加剂配比下,充填料浆初始流动度≥22.2 cm,动力黏度≤218 mPa•s,满足文献[17]中充填料浆流动性能相关要求:粉煤灰基自流充填浆液初始流动度≥19.0 cm;似膏体自流充填料浆动力黏度≤1 500 mPa•s,验证了本文研发的粉煤灰基矿用充填材料具有良好的流动性。
添加剂配比对充填体单轴抗压强度的影响如图3所示。图3(a)为当B、C组分掺量分别为2%、12%时,A组分掺量对充填材料单轴抗压强度的影响。当A组分掺量由10%增加至16%时,不同养护龄期试块的抗压强度均呈现先升高后降低的趋势。当A组分掺量为12%、14%、16%时,与掺量为10%的充填试块相比,8 h强度分别增长了36.1%、41.7%、-50.0%,1 d强度分别增长了18.3%、22.5%、-63.4%,7 d强度分别增长了35.3%、10.9%、-26.1%,14 d强度分别增长4.7%、9.5%、-27.3%,28 d强度分别增长了4.6%、5.6%、-22.8%。由此可知,当A组分掺量为14%时,充填试块的强度性能最佳。料浆中石灰的水化提供了一定的碱性环境,同时使用片碱作为碱性激发剂,极大地提高了水化体系中的pH,在OH-的极性作用下,激发了粉煤灰、矿渣微粉的火山灰活性,玻璃相中[SiO4]4-、[AlO4]5-溶出大量活性硅、活性铝,与体系中的Ca2+反应生成钙矾石(AFt)、Ca(OH)2、C-S-H凝胶等产物[19],为充填体提供了力学性能。当A组分掺量增加至16%时,不同龄期的充填试块强度均出现倒缩现象,且充填体早期强度及长期强度均不满足矿山充填需求。一方面,矿渣微粉的增加使得体系中具有火山灰活性的成分增加,但水化体系中原有的碱性物质不足以将其消耗完[20],部分矿渣颗粒以原始的状态赋存于基体中,形成弱面结构,劣化了充填体的强度;另一方面,矿渣微粉表面吸附了大量的游离水,使水化体系中水分减少,抑制了水化反应的进行,水化产物随之减少,强度降低。
图3(b)为当A、C组分掺量分别为14%、8%时,不同B组分掺量下粉煤灰基充填试块不同龄期的抗压强度。从图3(b)可以看出,与未添加B组分时相比,当B组分掺量为2%、6%、8%时,8 h强度分别增长了0、47.1%、-27.5%,1 d强度分别增长了13.6%、110.6%、28.8%,7 d强度分别增长了21.8%、69.0%、19.5%,14 d强度分别增长了20.1%、81.3%、26.5%,28 d强度分别增长了33.8%、87.4%、45.0%。当B组分掺量为0时,7 d强度已达长期强度的75.3%,从14 d到28 d强度仅增长5.5%,且不满足长期强度要求。随着B组分掺量的增加,不同龄期的充填体强度呈先升高后降低的趋势,但均高于掺量为0时的强度,可以看出B组分的掺入能够改善充填体长期强度,且当B组分掺量为6%时增益效果最明显。
图3(c)为当A、B组分掺量分别为14%、2%时,不同C组分掺量下粉煤灰基充填试块不同龄期的抗压强度。从图3(c)可以看出,随着C组分掺量的增加,试块强度先升高后降低,当掺量为10%时强度性能最优。B、C组分主要物相为无水硫铝酸钙(CSA),CSA与体系中的快速反应生成AFt[21],AFt是充填体的主要强度来源。随着B、C组分掺量的增加,体系中的水分难以维持水化反应的进行,出现强度倒缩的现象。此外,试验过程中发现,当C组分掺量为16%时,料浆制备期间,料浆内部温度超过50 ℃,在水化反应初期产生较大的热应力,导致试块基体中生成微裂隙,同时过高的温度导致水化体系中的水分快速蒸发,抑制了水化反应的进行,进一步削弱了充填体的整体强度和稳定性。
图4为不同添加剂配比下充填体养护28 d的XRD衍射图谱。由图4可以看出,主要水化产物为钙矾石(3CaO•Al2O3•3CaSO4•32H2O)、氢氧化钙(Ca(OH)2)、莱粒硅钙石(Ca5(SiO4)2(OH)2)、帕水硅钙石(Ca2Al4Si4O15(OH)2•4H2O);还检测到大量未反应的莫来石(Al6Si2O13)、石英(SiO2)、硅酸二钙(Ca2SiO4)。不同添加剂配比下水化产物基本相同,但衍射峰强度不一致。在衍射角30°、65°附近存在明显的方解石(CaCO3)衍射峰,考虑到试块为密封养护,可能是烘干制备试样过程中发生碳化反应所致。在衍射角25°~30°范围内出现较宽的弥散峰,通常被认为是无定形C-S-H凝胶[22]。
由图4(a)可知,随着A组分掺量的增加,钙矾石、帕水硅钙石、莱粒硅钙石衍射峰增强,莫来石衍射峰强度先降低后升高,石英衍射峰强度先升高后降低。粉煤灰和矿渣中活性SiO2、Al2O3在碱激发作用下溶解生成[SiO4]4-四面体、[AlO4]5-四面体;同时,活性SiO2、Al2O3与生石灰、β-石膏反应生成水化硅酸钙、水化铝酸钙、钙矾石等物质。随着矿渣掺量的增加,活性SiO2、Al2O3含量增多,使水化反应程度增加,水化产物增多。主要反应方程式如下[23]:
由图4(b)可以看出,随着B组分掺量的增加,钙矾石衍射峰增强,莫来石、石英、硅酸二钙等物相的衍射峰强度降低。B组分掺量为6%时,在衍射角25°附近存在明显的钙长石(CaAl2Si2O8)衍射峰。由图4(c)可知,随着C组分掺量的增加,各物相的衍射峰强度呈现先降低后升高的趋势,当C组分掺量为16%时,石英衍射峰强度明显降低。
B、C组分中主要成分Ca4Al6SO16首先与水化体系中的CaSO4•2H2O反应生成钙矾石和铝胶,使得充填体强度提高,反应过程如式(7)所示,同时对矿渣和粉煤灰具有激发作用,进一步消耗了莫来石、石英、硅酸二钙等物质。
图5为不同试验方案下养护龄期为28 d的充填体放大5万倍后的微观相貌,图5中针状、棒状物质为AFt,板状、片状物质为Ca(OH)2,无定形产物为C-S-H凝胶、黑色区域为基体中的微孔洞和裂隙(颜色标识见电子版),上述物质交织在一起,支撑起充填体的力学性能。从图5(a)至图5(c)可以看出,当其他组分掺量固定时,随着A组分掺量的增加,钙矾石变粗,数量增加,微孔洞数量减少,充填体密实度增加;由图5(d)可以看出,当A组分掺量为16%时,钙矾石数量较少,微孔洞较明显。矿渣微粉吸附了大量水分,抑制了水化反应的进行,导致凝胶等产物难以充实充填体中的间隙,基体中微孔洞等弱面结构增加,出现强度倒缩现象。
由图5(e)至图5(h)可以看出,当其他组分掺量不变时,B组分掺量对充填体微观结构的影响。从图5(e)可以看出,AFt、Ca(OH)2、C-S-H凝胶等水化产物包裹粉煤灰微珠。随着B组分掺量的增加,基体的微观结构由稀疏的放射状向密实的层状、板状发展,基体致密性先升高后降低[25]。由图5(g)可以看出,当B组分掺量为6%时,生成大量粗棒状的钙矾石,致密性最好,无明显微孔洞和裂隙,使其具备较高的强度性能。由图5(h)可以看出,当B掺量增加至8%时,AFt产状数量增加,但产状呈纤细化,互相交错生长,表面附着零星凝胶产物,致密性降低,宏观表现为强度降低。
图5(f)、图5(i)、图5(c)、图5(j)展示了其他成分含量一定时,C组分掺量分别为8%、10%、12%、16%时充填体的微观结构,充填体致密性随着C掺量的增加先升高后降低。图5(j)中仅有少量细短的AFt,多为层状的Ca(OH)2,尽管产物间密实度较高,但存在明显的裂隙,结合充填料浆制备及养护过程放热情况,水化反应初期大量放热,导致基体中产生热应力,进一步诱发基体中产生初始微裂隙,进而劣化充填体的强度。
(1)随着A、C组分掺量的增加,料浆流动性能先降低后升高,黏度先升高后降低。而随着B组分掺量的增加,料浆流动性先升高后降低,黏度先降低后升高。不同添加剂配比下,充填料浆初始流动度≥22.2 cm,动力黏度≤218 mPa•s,满足自流要求。当复合添加剂中A、B、C组分分别占粉煤灰质量的12%、2%、12%时,流动性能最好。
(2)当其他组分掺量一定时,随着A、B、C组分掺量的增加,充填体不同养护龄期的抗压强度均呈现先升高后降低的趋势。当A、B、C掺量分别占粉煤灰质量的14%、6%、8%时,强度性能最优,充填体8 h、28 d的强分别度为0.75 MPa、4.33 MPa,远超济宁某矿“三下”开采充填体力学性能要求。
(3)不同添加剂配比下,养护28 d的充填体水化产物基本一致,但衍射峰强度存在差异。当其他组分掺量一定时,随着A、B、C组分掺量的增加,充填体密实度先升高后降低,孔隙数量先减少后增多。
  • 国家自然科学基金面上项目(52474104)
  • 国家自然科学基金资助项目(51904178)
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2025年第45卷第11期
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  • 接收时间:2024-12-23
  • 首发时间:2026-10-28
  • 出版时间:2025-11-25
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  • 收稿日期:2024-12-23
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国家自然科学基金面上项目(52474104)
国家自然科学基金资助项目(51904178)
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    1.山东理工大学 资源与环境工程学院,山东 淄博市 255049
    2.枣庄矿业集团高庄煤业有限公司,山东 济宁市 272200

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刘国磊(1985—),男,山东淄博人,博士,教授,博士生导师,研究方向为矿山安全与绿色开采。E-mail:
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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