Article(id=1322164953688159183, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164760943116291, 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=1733328000000, receivedDateStr=2024-12-05, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793158289596, onlineDateStr=2026-10-28, pubDate=1766592000000, pubDateStr=2025-12-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793158289596, onlineIssueDateStr=2026-10-28, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793158289596, creator=13701087609, updateTime=1793158289596, updator=13701087609, issue=Issue{id=1322164760943116291, tenantId=1146029695717560320, journalId=1225396423026438145, year='2025', volume='45', issue='12', pageStart='1', pageEnd='302', issueExtLink='null', onlineDate='null', pubDate='1766592000000', pubDateStr='2025-12-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793158243641, creator='13701087609', updateTime=1793158929367, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322167637195477357, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164760943116291, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322167637199671662, tenantId=1146029695717560320, journalId=1225396423026438145, issueId=1322164760943116291, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=135, endPage=143, ext={EN=ArticleExt(id=1322164953969177552, articleId=1322164953688159183, tenantId=1146029695717560320, journalId=1225396423026438145, language=EN, title=Effect of Plastic Expansion Agent on the Properties of Mine Grouting Materials, columnId=null, journalTitle=Mining Research and Development, columnName=null, runingTitle=null, highlight=null, articleAbstract=

Adding plastic expansion agent is an effective measure to improve the volume stability of mine grouting materials. By preparing mine grouting materials with plastic expansion agent, the influence of plastic expansion agent on its working performance, rheological properties, mechanical properties and volume stability was investigated. Then, the mechanism was elucidated through the analysis of pore structure and microscopic morphology. The results show that with the increase of plastic expansion agent content, the working performance and rheological property of the grouting materials are improved, the compressive strength and flexural strength decrease, the plastic expansion rate increases gradually at 3 h, but the influence on volume deformation is small in the middle and late stages. The total porosity and average pore size of the hardened slurry are increased significantly after the addition of plastic expansion agent. When the addition rate is higher than 0.12%, the proportion of capillary pores and large pores are increased more. Considering the performance parameter requirements of grouting materials, it is more suitable when the plastic expansion rate is in the range of 0.04%-0.08%.

, authors=Qidong SUN1, Ming WANG1, Haiyan XU1, Jin ZHANG1, Sha LU1, Bing HUANG2, authorsList=Qidong SUN, Ming WANG, Haiyan XU, Jin ZHANG, Sha LU, Bing HUANG, authorCompany=null, correspAuthors=Ming WANG, 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=1322164957798577125, articleId=1322164953688159183, tenantId=1146029695717560320, journalId=1225396423026438145, language=CN, title=塑性膨胀剂对矿用注浆材料的性能影响研究, columnId=1226462295417598973, journalTitle=矿业研究与开发, columnName=矿山安全与环保, runingTitle=null, highlight=null, articleAbstract=

掺加塑性膨胀剂是改善矿用注浆材料体积稳定性的有效措施。采用塑性膨胀剂制备矿用注浆材料,探究了塑性膨胀剂对其工作性能、流变性能、力学性能以及体积稳定性等关键参数的影响规律,并通过孔结构和微观形貌分析阐明其作用机理。结果表明:随着塑性膨胀剂掺量的增加,注浆材料的工作性能和流变性能均有所改善,抗压及抗折强度不断降低,3 h竖向膨胀率逐渐增加,但对中后期体积变形影响较小。掺入塑性膨胀剂后,硬化浆体总孔隙率及平均孔径均显著增长,掺量高于0.12%时,毛细孔和大孔比例增长幅度更大。综合考虑注浆材料性能参数要求,塑性膨胀率掺量范围为0.04%~0.08%时较为适宜。

, authors=孙启栋1, 王明1, 许海燕1, 张进1, 鲁莎1, 黄冰2, authorsList=孙启栋, 王明, 许海燕, 张进, 鲁莎, 黄冰, authorCompany=null, correspAuthors=王明, authorNote=

孙启栋(1980—),男,山东枣庄人,工程师,主要研究方向为地质勘探及注浆。E-mail:

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王明(1981—),男,山东枣庄人,高级工程师,主要研究方向为地质勘探及注浆。E-mail:
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孙启栋(1980—),男,山东枣庄人,工程师,主要研究方向为地质勘探及注浆。E-mail:

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Research on expansion performance of cementitious grout[D]. Hangzhou: Zhejiang University, 2020: 36-43., articleTitle=Research on expansion performance of cementitious grout, refAbstract=null), Reference(id=1322164974319939664, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, doi=null, pmid=null, pmcid=null, year=2019, volume=29, issue=5, pageStart=1067, pageEnd=1081, url=null, language=null, rfNumber=[22], rfOrder=34, authorNames=HU Jianhua, REN Qifan, MA Shaowei, journalName=Transactions of Nonferrous Metals Society of China, refType=null, unstructuredReference=HU Jianhua, REN Qifan, MA Shaowei, et al. Macroscopic and microscopic trans-scale characteristics of pore structure of mine grouting materials[J]. Transactions of Nonferrous Metals Society of China, 2019, 29 (5): 1067-1081., articleTitle=Macroscopic and microscopic trans-scale characteristics of pore structure of mine grouting materials, refAbstract=null), Reference(id=1322164974466740305, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, doi=null, pmid=null, pmcid=null, year=2024, volume=null, issue=null, pageStart=48, pageEnd=49, url=null, language=null, rfNumber=[23], rfOrder=35, authorNames=曲佳雯, journalName=null, refType=null, unstructuredReference=曲佳雯. 不同养护温度下硫铝酸钙氧化钙补偿收缩胶凝体系膨胀及力学性能研究[D].泰安:山东农业大学,2024: 48-49., articleTitle=不同养护温度下硫铝酸钙氧化钙补偿收缩胶凝体系膨胀及力学性能研究, refAbstract=null), Reference(id=1322164974584180818, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, doi=null, pmid=null, pmcid=null, year=2024, volume=null, issue=null, pageStart=48, pageEnd=49, url=null, language=null, rfNumber=[23], rfOrder=36, authorNames=QU Jiawen, journalName=null, refType=null, unstructuredReference=QU Jiawen. Study on expansion and mechanical properties of calcium sulphoaluminate-calcium oxide shrinkage-compensating cementitious system at different curing temperatures[D]. 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figureFileBig=NOaCP1BKjSokf760XS1kZg==, tableContent=null), ArticleFig(id=1322164966296236069, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=EN, label=Table 1, caption=

Chemical composition of fast hard sulphoaluminate cement

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SiO2Al2O3CaOSO3MgOR2O烧失量
9.8521.6847.8110.651.621.456.94
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快硬硫铝酸盐水泥化学成分

, figureFileSmall=null, figureFileBig=null, tableContent=
SiO2Al2O3CaOSO3MgOR2O烧失量
9.8521.6847.8110.651.621.456.94
), ArticleFig(id=1322164966451425319, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=EN, label=Table 2, caption=

Physical properties of fast hard sulphoaluminate cement

, figureFileSmall=null, figureFileBig=null, tableContent=
物理性能标准稠度用水量/%凝结时间/min抗压强度/MPa
初凝时间终凝时间1 d3 d28 d
水泥26.5122333.942.647.3
), ArticleFig(id=1322164966535311400, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=CN, label=表2, caption=

快硬硫铝酸盐水泥物理性能

, figureFileSmall=null, figureFileBig=null, tableContent=
物理性能标准稠度用水量/%凝结时间/min抗压强度/MPa
初凝时间终凝时间1 d3 d28 d
水泥26.5122333.942.647.3
), ArticleFig(id=1322164966606614569, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=EN, label=Table 3, caption=

Test mix proportion of grouting materials for mine

, figureFileSmall=null, figureFileBig=null, tableContent=
序号胶凝材料/(kg•m-3)塑性膨胀剂掺量/%
水泥硅灰微珠矿渣粉石英砂聚羧酸减水剂
17001001001001 00080.00
27001001001001 00080.04
37001001001001 00080.08
47001001001001 00080.12
57001001001001 00080.16
), ArticleFig(id=1322164966698889258, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=CN, label=表3, caption=

矿用注浆材料试验配合比

, figureFileSmall=null, figureFileBig=null, tableContent=
序号胶凝材料/(kg•m-3)塑性膨胀剂掺量/%
水泥硅灰微珠矿渣粉石英砂聚羧酸减水剂
17001001001001 00080.00
27001001001001 00080.04
37001001001001 00080.08
47001001001001 00080.12
57001001001001 00080.16
), ArticleFig(id=1322164966778581035, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=EN, label=Table 4, caption=

Pore structure parameters of hardened paste of grouting material at 3 d age with different plastic expansion agent contents

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塑性膨胀剂掺量/%孔结构参数
总进汞体积/(mL•g-1)总孔表面积/(m•g-1)平均孔径/nm孔隙率/%
0.000.137 913.14741.9522.712 1
0.040.152 214.17142.9523.521 1
0.080.158 815.43541.1524.096 4
0.120.169 114.33247.1926.220 3
0.160.209 517.71247.3229.389 4
), ArticleFig(id=1322164966875050028, tenantId=1146029695717560320, journalId=1225396423026438145, articleId=1322164953688159183, language=CN, label=表4, caption=

不同塑性膨胀剂掺量下注浆材料3 d龄期硬化浆体的孔结构参数

, figureFileSmall=null, figureFileBig=null, tableContent=
塑性膨胀剂掺量/%孔结构参数
总进汞体积/(mL•g-1)总孔表面积/(m•g-1)平均孔径/nm孔隙率/%
0.000.137 913.14741.9522.712 1
0.040.152 214.17142.9523.521 1
0.080.158 815.43541.1524.096 4
0.120.169 114.33247.1926.220 3
0.160.209 517.71247.3229.389 4
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塑性膨胀剂对矿用注浆材料的性能影响研究
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孙启栋 1 , 王明 1 , 许海燕 1 , 张进 1 , 鲁莎 1 , 黄冰 2
矿业研究与开发 | 矿山安全与环保 2025,45(12): 135-143
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矿业研究与开发 |矿山安全与环保 2025 , 45 (12) : 135 -143
塑性膨胀剂对矿用注浆材料的性能影响研究
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孙启栋1 , 王明1 , 许海燕1, 张进1, 鲁莎1, 黄冰2
作者信息
  • 1.山东中兴建安建工有限公司,山东 枣庄市 277099
  • 2.济南大学 自动化与电气工程学院,山东 济南 250022
通讯作者:
王明(1981—),男,山东枣庄人,高级工程师,主要研究方向为地质勘探及注浆。E-mail:
作者简介:

孙启栋(1980—),男,山东枣庄人,工程师,主要研究方向为地质勘探及注浆。E-mail:

Effect of Plastic Expansion Agent on the Properties of Mine Grouting Materials
Qidong SUN1 , Ming WANG1 , Haiyan XU1, Jin ZHANG1, Sha LU1, Bing HUANG2
Affiliations
  • 1.Shandong Zhongxing Jian'an Construction Engineering Co., Ltd., Zaozhuang, Shandong 277099, China
  • 2.School of Electrical Engineering, University of Jinan, Jinan, Shandong 250022, China
出版时间: 2025-12-25
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掺加塑性膨胀剂是改善矿用注浆材料体积稳定性的有效措施。采用塑性膨胀剂制备矿用注浆材料,探究了塑性膨胀剂对其工作性能、流变性能、力学性能以及体积稳定性等关键参数的影响规律,并通过孔结构和微观形貌分析阐明其作用机理。结果表明:随着塑性膨胀剂掺量的增加,注浆材料的工作性能和流变性能均有所改善,抗压及抗折强度不断降低,3 h竖向膨胀率逐渐增加,但对中后期体积变形影响较小。掺入塑性膨胀剂后,硬化浆体总孔隙率及平均孔径均显著增长,掺量高于0.12%时,毛细孔和大孔比例增长幅度更大。综合考虑注浆材料性能参数要求,塑性膨胀率掺量范围为0.04%~0.08%时较为适宜。

塑性膨胀剂  /  注浆材料  /  流变性能  /  力学性能  /  体积稳定性

Adding plastic expansion agent is an effective measure to improve the volume stability of mine grouting materials. By preparing mine grouting materials with plastic expansion agent, the influence of plastic expansion agent on its working performance, rheological properties, mechanical properties and volume stability was investigated. Then, the mechanism was elucidated through the analysis of pore structure and microscopic morphology. The results show that with the increase of plastic expansion agent content, the working performance and rheological property of the grouting materials are improved, the compressive strength and flexural strength decrease, the plastic expansion rate increases gradually at 3 h, but the influence on volume deformation is small in the middle and late stages. The total porosity and average pore size of the hardened slurry are increased significantly after the addition of plastic expansion agent. When the addition rate is higher than 0.12%, the proportion of capillary pores and large pores are increased more. Considering the performance parameter requirements of grouting materials, it is more suitable when the plastic expansion rate is in the range of 0.04%-0.08%.

Plastic expansion agent  /  Grouting material  /  Rheological property  /  Mechanical property  /  Volume stability
孙启栋, 王明, 许海燕, 张进, 鲁莎, 黄冰. 塑性膨胀剂对矿用注浆材料的性能影响研究. 矿业研究与开发, 2025 , 45 (12) : 135 -143 .
Qidong SUN, Ming WANG, Haiyan XU, Jin ZHANG, Sha LU, Bing HUANG. Effect of Plastic Expansion Agent on the Properties of Mine Grouting Materials[J]. Mining Research and Development, 2025 , 45 (12) : 135 -143 .
在当前矿山开采作业中,矿山开采深度的增加、巷道复杂程度的增大均对围岩力学性质稳定性具有显著影响,进而导致地表塌陷、地下水污染和生态环境破坏等一系列严重问题频发[1-3]。注浆技术因其具有良好的适应性和治理效果,目前已成为矿山充填、岩体堵水防渗、巷道围岩加固等领域应用最广泛的加固措施[4-5]。注浆材料是注浆技术的核心组成部分,其性能直接决定注浆加固的安全性和耐久性。理想的注浆材料应具有良好的可注性和优异的体积稳定性。然而,传统水泥基注浆材料通常存在流动性低、体积稳定性较差等缺点,工程应用中容易出现空鼓、开裂等缺陷,严重影响其加固效果[6-7]。因此,开发新型高性能矿用注浆材料是当前矿业安全开采的关键所在,对改善注浆加固效果,提升采矿安全性,实现绿色、科学采矿具有重要战略意义。
掺加膨胀剂是改善注浆材料性能的有效措施,常用膨胀剂包括氧化钙类、氧化镁类、硫铝酸钙类和塑性膨胀剂,国内外学者已对此进行了许多研究[8-9]。刘云霄等[10]研究发现,硫铝酸盐膨胀剂会显著提升水泥基材料后期膨胀效果,但早期膨胀速率较低;与硫铝酸盐膨胀剂相比,掺加氧化钙膨胀剂后,水泥基材料膨胀速率和竖向膨胀率都有所提升,但浆体流动度和力学性能降低幅度均增大。焦茂鹏等[11]对掺低活性氧化镁膨胀剂的混凝土开展了研究,结果表明,氧化镁膨胀剂的掺加可以反应生成膨胀性水化产物Mg(OH)2,从而改变混凝土孔径分布,有效改善混凝土的自收缩性能,但氧化镁膨胀剂对胶凝体系的早期水化进程和水化产物影响较小。宋普涛等[12]研究了塑性膨胀剂种类及掺量对灌浆材料的性能影响,研究发现,随着塑性膨胀剂掺量的增加,灌浆材料的竖向膨胀率也随之增加;孔结构分析表明,塑性膨胀剂掺量与灌浆材料的孔隙率和平均孔径存在正相关关系。ZHENG G F等[13]、程平阶等[14]调研发现,与塑性膨胀剂相比,氧化钙、氧化镁、硫铝酸钙等其他各类膨胀剂早期反应相对缓慢,其膨胀作用主要集中在中后期阶段,并且膨胀应力和体积变形程度也相对较小,难以满足矿用注浆材料快速产生膨胀支护效果的要求。塑性膨胀剂可以在胶凝体系中碱金属催化下,分解产生氮气,持续产生微小气泡,从而实现浆体塑性阶段膨胀,是注浆材料3~24 h产生膨胀变形的核心因素[15]。
近年来,注浆材料用膨胀剂相关研究主要集中于氧化钙及硫铝酸盐类膨胀剂等,关于塑性膨胀剂对注浆材料的性能改善作用研究较少。此外,针对掺塑性膨胀剂后注浆材料的流变性能和干燥收缩影响也有待进一步研究。本文采用多种测试手段研究了塑性膨胀剂对矿用注浆材料工作性能、力学性能、体积稳定性以及相关微观特性的影响规律,分析其微观作用机理,旨在确定塑性膨胀剂的最佳掺量范围,为矿用注浆材料的性能优化提供理论依据和应用参考。
水泥:快硬硫铝酸盐水泥(42.5级),比表面积为350 m2/kg,化学成分见表1,物理性能见表2。硅灰:浅灰色粉末,SiO2≥95%,密度为350 kg/m3,比表面积为2 200 m2/kg,烧失量为2.2%。微珠:灰白色粉末,颗粒粒径约为0.8~1.5 μm,比表面积为3 400 m2/kg,28 d活性指数约为102%。粒化高炉矿渣粉:S95级,白色粉末,28 d活性指数为102%,比表面积为425 m2/kg,密度为2.92 kg/m3。石英砂:目数分别为40~80目和80~120目的水洗烘干无泥石英砂,按4∶6的质量比混合,淡黄色近球形颗粒,SiO2≥98%,莫氏硬度为7。减水剂:白色粉体,高性能聚羧酸系减水剂,减水率为30%。塑性膨胀剂:偶氮化合物类塑性膨胀剂,明黄色超细粉末,活性成分≥90%,堆积密度为450~550 kg/m3,颗粒粒径为3~15 μm。
在前期文献调研及试验基础上,确定矿用注浆材料基准配合比。水胶比固定为0.3,硫铝酸盐水泥掺量为700 kg/m3,硅灰、微珠、粒化高炉矿渣粉的掺量均为100 kg/m3,石英砂掺量为1 000 kg/m3,减水剂掺量为8 kg/m3。以上述基准配合比为基础,分别掺入不同掺量的塑性膨胀剂,塑性膨胀剂掺量为胶凝材料的0.04%、0.08%、0.12%、0.16%(均为质量分数)。具体试验配合比设计见表3。
(1)流出时间。参照《公路工程水泥及水泥混凝土试验规程》(JTG 3420—2024)中倒锥法测试。注浆材料拌合完成后注入体积为(1 725±5)mL的倒锥中,开启阀门使浆体自由流出,测试注浆材料的初始流出时间和30 min流动时间,精确到0.1 s。
(2)流变性能。采用Kinexus lab流变仪测试,流变仪测试程序如图1所示,采用测试程序下行段数据进行模型拟合,测试注浆材料剪切应力剪切速率、表观黏度剪切速率的流变关系曲线。
(3)力学性能。参照《水泥胶砂强度检验方法(ISO法)》(GB/T 17671—1999)测试。试件尺寸为40 mm×40 mm×160 mm,试件标准养护至2 h拆模测试其力学性能,其余样品放置于(20±1)℃水中分别养护至3 d、7 d、28 d龄期测试其抗压和抗折强度,精确到0.1 MPa。
(4)竖向膨胀率。参照《水泥基灌浆材料应用技术规范》(GB/T 50448—2015)测试注浆材料3 h竖向膨胀率,试件尺寸为100 mm×100 mm×100 mm,成型养护温度为(20±2)℃。注浆材料拌合完成后立即灌入试模内,并记录此时百分表读数为初始读数,此后每隔15 min读取千分表读数,计算得到注浆材料竖向膨胀率,精确到0.001%。
(5)自由膨胀率。参照《膨胀水泥膨胀率试验方法》(JC/T 313—2009)测试注浆材料硬化阶段体积稳定性,注浆材料试件尺寸为25 mm×25 mm× 280 mm,试件成型后养护2 h后脱模,使用比长仪测试其初始长度,将试件放入干缩养护箱中继续养护至相应龄期测试试件长度,计算得到注浆材料膨胀率,精确至0.001%。
(6)孔隙率。采用Autopore Ⅳ 9500压汞仪对注浆材料水化3 d的硬化浆体孔结构进行分析。
(7)微观形貌。采用TESCAN MIRA LMS扫描电子显微镜对注浆材料水化3 d的硬化浆体微观形貌进行测试。
注浆材料的工作性能直接影响注浆过程中的注浆速率、注浆深度和灌注率,注浆材料的工作性能以流出时间表征,不同塑性膨胀剂掺量对注浆材料的工作性能影响如图2所示。由图2可知,随着塑性膨胀剂掺量的增加,注浆材料的初始流出时间和30 min流出时间均随之下降,工作性能提升。其中,塑性膨胀剂掺量从0提升至0.08%时,流出时间快速下降,掺量0.08%时注浆材料初始流出时间和30 min流出时间分别为14.2 s和17.1 s,相较基准组下降了11.80%、7.07%。塑性膨胀剂掺量继续提升,流出时间缩短速率变缓,掺量为0.16%时,注浆材料的初始流出时间和30 min流出时间最短,相较掺量0.08%时分别缩短了7.75%、5.26%,此时初始流出时间和30 min流出时间分别为13.1 s和16.2 s。相较而言,塑性膨胀剂对于初始流出时间的影响更为显著。适量的塑性膨胀剂可以显著改善注浆材料工作性能,这主要是由于掺入塑性膨胀剂后,其胺基氮原子上的未共用电子对在浆体内部碱性条件下断裂反应产生氮气,这些微小、均匀气泡可以起到一定的“滚珠”作用,降低胶凝体系内部颗粒之间的摩擦力,从而有效降低浆体稠度,改善浆体流动性。随着水化反应的进行,浆体中水泥颗粒之间相互作用力增强,塑性膨胀剂的改善效果也随之减弱。
流出时间测试可以有效表征注浆材料流动度及其经时损失,然而,实际工程应用中现场工况较为复杂,单一的流出时间测试无法完整、准确地表征注浆材料的工作性能。为全面了解塑性膨胀剂对注浆材料工作性能的影响,本文采用流变学手段开展测试。
不同塑性膨胀剂掺量下注浆材料流变性能如图3所示,图3(a)和图3(b)分别为不同塑性膨胀剂掺量下注浆材料的剪切应力和表观黏度曲线。由图3(a)可知,注浆材料剪切应力与剪切速率基本呈现线性关系,剪切应力随剪切速率增长而增大。由图3(b)可知,剪切速率从0升至20 s-1时,注浆材料表观黏度迅速降低,继续提升剪切速率后,表观黏度变化趋于稳定。在一定剪切速率下,注浆材料剪切应力和表观黏度均随塑性膨胀剂掺量的增加而下降。当塑性膨胀剂掺量在0.08%以内时,浆体的剪切应力和表观黏度均明显下降,当剪切速率为100 s-1时,掺量为0.08%的注浆材料剪切应力为24.26 Pa,相比基准组降低了14.43%。当塑性膨胀剂掺量高于0.08%时,随着剪切速率的增加,浆体的剪切应力和表观黏度降低速率和幅度均有所减弱。
Bingham模型(见式(1))是目前应用最为广泛的流变拟合模型。
式中:τ为剪切应力,Pa;τ0为屈服应力,Pa;μ为塑性黏度,Pa•s;γ为剪切速率,s-1。
本文通过Bingham流变模型对注浆材料剪切应力曲线进行拟合得到其屈服应力和塑性黏度等主要流变参数,模型拟合系数R2均大于0.96,拟合结果良好。不同塑性膨胀剂掺量下注浆材料的屈服应力和塑性黏度见图4。
塑性黏度是注浆材料浆体内部阻碍其自由流动的性能,可以表征其流动性能的好坏,是注浆材料注浆效率和灌注深度的最相关参数。浆体塑性黏度小的宏观表现为外力作用相同下浆体流动性更佳[16-17]。由图4可知,随着塑性膨胀剂掺量的增加,注浆材料塑性黏度大幅降低。塑性膨胀剂掺量为0.04%、0.08%、0.12%、0.16%时,注浆材料塑性黏度相比基准组分别降低了4.55%、13.64%、22.73%、31.82%。掺量为0.16%时降至最低,此时塑性黏度为0.15 Pa•s。注浆材料塑性黏度的变化规律与其流出时间测试结果基本相印证,这是因为掺加塑性膨胀剂后,反应产生的氮气填充至胶凝体系间隙内,释放出孔隙水,胶凝体系内自由水增加,导致颗粒间水膜厚度增加,注浆材料塑性黏度下降。同时,浆体内气泡的存在有效克服了体系内摩擦力,减少了絮凝结构的团聚,从而降低了材料的塑性黏度。
屈服应力是由胶凝体系颗粒间的表面摩擦与附着力引起的,可以表征浆体产生流动所需要的外力大小,与浆体的填充效果和注浆效率紧密相关[18-19]。塑性膨胀剂掺量增加后,注浆材料浆体屈服应力呈现先降低再趋于稳定并略有下降的趋势。塑性膨胀率掺量从0提升至0.08%时,浆体屈服应力从6.27 Pa降低至2.85 Pa,降低了54.55%;掺量从0.08%提升至0.12%时,屈服应力基本保持稳定,仅降低了2.81%;继续提升掺量至0.16%时,屈服应力小幅下降,此时浆体屈服应力为2.32 Pa,相较基准组降低了63.00%。相较塑性黏度,塑性膨胀剂对屈服应力的影响更为显著。综合考虑塑性膨胀剂对浆体工作性能的作用效果和使用成本,其掺量应控制在0.08%以内为宜。
图5为不同塑性膨胀剂掺量下注浆材料的力学性能变化。如图5所示,随着塑性膨胀剂掺量的增加,注浆材料的抗压强度和抗折强度均不同程度下降,并且早期抗压强度损失更大。塑性膨胀剂掺量低于0.08%时,浆体抗压强度降低幅度较小;掺量为0.08%时,注浆材料2 h、3 d、7 d、28 d的抗压强度分别为24.8 MPa、43.0 MPa、51.7 MPa和61.8 MPa,相比基准组分别降低了6.06%、7.13%、5.14%和4.33%;掺量高于0.08%时,材料力学性能进一步降低,掺入0.16%塑性膨胀剂时,抗压及抗折强度均降至最低,此时2 h、28 d抗压强度相比基准组分别降低了23.11%、15.17%,2 h和28 d抗折强度为4.2 MPa、7.7 MPa,相较基准组分别降低了20.75%、24.51%。
掺加过量塑性膨胀剂会在注浆材料硬化浆体内引入大量气孔,导致注浆材料孔隙率和孔径尺寸增大,密实程度降低,宏观表现为抗压及抗折强度降低。随着龄期的增长,水化反应不断进行,水化产物也随之增多,胶凝体系密实度提升,强度也有所增加,因此,塑性膨胀剂对于材料早期强度影响更为显著。塑性膨胀剂掺加不宜过量,掺量范围限制为0.04%~0.08%较为适宜,此时对注浆材料力学性能负面作用较小。
本试验中所制备的注浆材料具有优异的早强性能,浆体水化2 h内即可产生终凝强度,因此,本文采用3 h竖向膨胀率表征其体积稳定性。同时为全面表征不同塑性膨胀剂掺量下注浆材料硬化浆体的体积变形,对注浆材料硬化浆体的28 d自由膨胀率进行连续测量,测试结果如图6所示。
由图6(a)可知,塑性膨胀剂可以有效提升注浆材料的微膨胀性能,其作用效果主要集中于浆体初凝开始至终凝结束阶段,掺加塑性膨胀剂后,浆体水化时间在40~70 min范围内时,注浆材料竖向膨胀率急剧增长,随后材料塑性膨胀率变化较小。未掺塑性膨胀剂时,注浆材料3 h竖向膨胀率仅为0.012%。随着塑性膨胀剂掺量的增加,注浆材料3 h竖向膨胀率逐渐增大。塑性膨胀剂掺量范围在0.08%~0.12%时,注浆材料的竖向膨胀率提升幅度相对更大。掺量为0.08%、0.12%、0.16%时,3 h竖向膨胀率分别为1.858%、3.253%、3.872%。这是因为加水拌合1 h左右塑性膨胀剂发气效率最高,发气产生的大量微细孔即为注浆材料早期膨胀源。掺量越高,发气量和发气速率提升越快,宏观表现为塑性膨胀剂掺量与竖向膨胀率呈正相关。
由图6(b)可知,注浆材料硬化浆体28 d体积变形均呈现收缩状态。随着塑性膨胀剂掺量的增加,注浆材料28 d收缩变形程度逐渐降低。掺量为0.16%时,注浆材料28 d膨胀率为-0.109%,相比基准组收缩变形减小了32.30%。这是因为塑性膨胀率主要在浆体塑性阶段发挥膨胀效果,水化硬化后反应虽然已基本结束,但硬化浆体气孔内部仍有膨胀应力的积聚,因此仍具有一定程度补偿收缩的效果[20-21]。单掺塑性膨胀剂时,注浆材料28 d硬化浆体均会产生收缩,无法满足其微膨胀的性能要求,这是因为浆体终凝后,掺加塑性膨胀剂所产生的膨胀应力无法抵消硬化浆体的收缩应力,在中后期难以产生有效膨胀,实际应用中可以考虑搭配氧化镁或硫铝酸盐类膨胀剂复掺以实现注浆材料硬化后的微膨胀效果,提升注浆材料体积稳定性。
矿用注浆材料应具有良好的体积稳定性,考虑到目前关于其体积稳定性尚无此方面的国家标准,因此参考《水泥基灌浆材料应用技术规范》(GB/T 50448—2015)中相关规定,要求注浆材料3 h竖向膨胀率范围应为0.1%~3.5%,同时28 d干燥收缩应尽可能低。结合试验结果,针对竖向膨胀率而言,塑性膨胀剂掺量应控制在0.12%以内。
研究表明,硬化浆体孔隙结构特征可以准确表征其密实程度,同时也对注浆材料力学性能、膨胀性能及耐久性能影响显著[22]。水泥基材料内部孔径划分可以分为4个区间,即凝胶孔(-10 nm)、过渡孔(+10~-100 nm)、毛细孔(+100~-1 000 nm)和大孔(+1 000 nm)[23]。本文采用压汞仪从亚微观角度对注浆材料孔结构进行全面表征,研究不同掺量塑性膨胀剂对硬化浆体孔结构的影响,以揭示其与材料宏观性能的内在关联。不同塑性膨胀剂掺量下注浆材料3 d硬化浆体的孔结构参数见表4,孔径积分曲线和微分曲线如图7所示,孔径分布占比如图8所示。
由表4可知,随着塑性膨胀剂掺量增加,注浆材料的总进汞体积、总孔表面积及总孔隙率均逐渐增加,并且掺量越大,增加幅度越大。与基准组相比,塑性膨胀剂掺量分别为0.04%、0.08%、0.12%、0.16%时,注浆材料总孔隙率分别增加了0.81,1.38,3.51,6.68个百分点。塑性膨胀剂掺量范围在0~0.08%内,注浆材料的平均孔径变化较小;塑性膨胀剂掺量大于0.12%时,平均孔径随其掺量增加而增大;掺量为0.16%时注浆材料平均孔径相比基准组增大了12.80%。
由图7可知,塑性膨胀剂掺量为0.04%~0.12%时,硬化浆体的孔径体积增长较小;掺量范围在0.12%~0.16%时,硬化浆体孔径显著增长,其中孔体积的增加主要集中于凝胶孔和过渡孔,大于100 nm的毛细孔和大孔增加幅度较为平缓;塑性膨胀剂掺量为0.12%时,硬化浆体孔径体积大幅增长,此时孔径体积增加主要集中于对浆体结构不利的毛细孔和大孔,宏观表现为硬化浆体力学性能大幅下降,耐久性降低,这与本文注浆材料力学性能随塑性膨胀剂掺量的变化规律基本一致。图8中孔径分布占比也可佐证上述结论,塑性膨胀剂掺量为0.08%时,孔径在100 nm以内的凝胶孔和过渡孔总占比为42.69%,相较基准组占比提升了7.53%;塑性膨胀剂掺量为0.16%时,孔径在100 nm以上的毛细孔和大孔总占比为66.39%,相较基准组占比增大了10.10%。
总体而言,掺加塑性膨胀剂后,注浆材料平均孔径和总孔隙率均呈现上升趋势。掺量高于0.12%时,塑性膨胀剂掺量越高,孔径分布中毛细孔与大孔级别占比越高。从孔结构特征考虑,应将浆体中塑性膨胀剂掺量限制在0.12%以内。
图9为基准组和掺加0.08%塑性膨胀剂的注浆材料3 d硬化浆体及微细气孔微观形貌图。由图9(a)可以观察到,基准组注浆材料整体结构较为致密,微细孔较少。由图9(b)可发现,掺加0.08%塑性膨胀剂后,硬化浆体内部形成了许多分布均匀、尺寸不一的微细气孔,这类微细气孔即为浆体塑性阶段膨胀源,补偿注浆材料塑性阶段收缩,同时也会导致浆体致密度下降,孔隙率增大,宏观表现为早期塑性阶段注浆材料微膨胀、力学性能下降,这与本文3 h竖向膨胀率及力学性能测试结果一致。图9(c)为该类微细气孔的微观形貌图,从图中可以看出,水化3 d龄期的硬化浆体微细孔洞内部可以观察到大量针棒状钙矾石晶体及絮状C–S–H凝胶等水化产物富集,絮状C–S–H凝胶与针棒状钙矾石晶体相互交织在一起,有助于硬化浆体结构密实度的提升。同时,孔洞内水化产物富集也可以产生膨胀应力,为胶凝体系提供膨胀能,减少硬化浆体内部的孔隙收缩应力,从而实现注浆材料硬化浆体阶段的补偿收缩。
(1)随着塑性膨胀剂掺量增加,注浆材料的初始流出时间和30 min流出时间均不断降低,微观表现为塑性黏度和屈服应力不同程度降低,同时其抗压强度和抗折强度也随之降低。相较而言,掺加塑性膨胀剂后,初始流出时间和早龄期抗压强度降低幅度更大。塑性膨胀剂掺量为0.16%时,初始流出时间和2 h抗压强度较基准组分别下降了18.63%、23.11%。为避免注浆材料力学性能大幅下降,塑性膨胀剂掺量应控制在0.08%以内。
(2)注浆材料3 h竖向膨胀率和28 d自由膨胀率均随塑性膨胀剂掺量增加而增大。其中,塑性膨胀剂对注浆材料早期塑性变形影响更为显著,但对注浆材料硬化浆体阶段体积变形影响较小,这是因为塑性膨胀剂在碱性环境下生成气体的反应主要集中于注浆材料塑性阶段。塑性膨胀剂掺量低于0.12%时,3 h竖向膨胀率满足其工程应用要求,3 h最大竖向膨胀率为3.253%。
(3)孔结构和微观形貌分析可知,掺入塑性膨胀剂后,硬化浆体内部出现尺寸不一的微细气孔,浆体的平均孔径、总孔隙率等孔结构参数均随塑性膨胀剂掺量增加而增大。其中,掺量高于0.12%时,硬化浆体孔径体积增加集中于毛细孔和大孔,掺量为0.16%时毛细孔和大孔孔径占比相较基准组增大了10.10%。
(4)综合考虑掺入塑性膨胀率后注浆材料的工作性能、力学性能和体积稳定性变化规律,得出塑性膨胀剂掺量为0.04%~0.08%时,注浆材料的各项性能参数综合更优。
  • 国家重点研发计划项目(2022YFE0208200)
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2025年第45卷第12期
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  • 接收时间:2024-12-05
  • 首发时间:2026-10-28
  • 出版时间:2025-12-25
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  • 收稿日期:2024-12-05
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国家重点研发计划项目(2022YFE0208200)
作者信息
    1.山东中兴建安建工有限公司,山东 枣庄市 277099
    2.济南大学 自动化与电气工程学院,山东 济南 250022

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王明(1981—),男,山东枣庄人,高级工程师,主要研究方向为地质勘探及注浆。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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