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Article(id=1149781962673578954, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149781952959574654, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2403638, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1715788800000, receivedDateStr=2024-05-16, revisedDate=1735228800000, revisedDateStr=2024-12-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1752058981817, onlineDateStr=2025-07-09, pubDate=1743091200000, pubDateStr=2025-03-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752058981817, onlineIssueDateStr=2025-07-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752058981817, creator=13701087609, updateTime=1752058981817, updator=13701087609, issue=Issue{id=1149781952959574654, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='9', pageStart='3529', pageEnd='3967', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752058979501, creator=13701087609, updateTime=1776333392421, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1251596220226027613, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149781952959574654, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1251596220226027614, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149781952959574654, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=3813, endPage=3820, ext={EN=ArticleExt(id=1149781963072037835, articleId=1149781962673578954, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Effect of Nano-silica on Concrete Properties under Low-temperature Environment, columnId=1156262729917780302, journalTitle=Science Technology and Engineering, columnName=Papers·Architectural Science, runingTitle=null, highlight=null, articleAbstract=

To solve the problem of deterioration of concrete performance caused by low temperature in cold regions. Based on the theory of nanomaterials to improve the properties of concrete, the effect of nano-silica on the properties of concrete was studied from the macro and micro scales. The results of the compressive strength test show that the compressive strength of ordinary concrete is attenuated by about 10% under low temperature curing. After being mixed with nano silica, the compressive strength of concrete is increased by about 20%, and the optimal dosage is 2%. The improvement mechanism of nano-silica on concrete properties was explored through microscopic test data such as mercury intrusion, X-ray diffraction and scanning electron microscopy. The results show that nano-silica can promote cement hydration at room temperature and low temperature curing, consume calcium hydroxide generated by hydration, and produce more hydrated calcium silicate and hydrated calcium aluminate gel, thereby reducing the porosity of concrete, optimizing the microstructure of concrete, and improving the performance of concrete. Compared with the room temperature environment, the improvement effect of nano-silica on concrete at low temperature is slightly reduced, but it completely overcomes the adverse effects of low temperatures on the performance of ordinary concrete.

, correspAuthors=Chun-qing LI, 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, authorCompany=null, fund=null, authors=null, authorsList=Chang-zhi LIU, Chun-qing LI, Dun CHEN, Shan-zhi FAN, Qing-long ZHANG), CN=ArticleExt(id=1149781999801557253, articleId=1149781962673578954, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=低温环境下纳米二氧化硅对混凝土性能的影响, columnId=1156262730517565784, journalTitle=科学技术与工程, columnName=论文·建筑科学, runingTitle=null, highlight=null, articleAbstract=

为了解决寒冷地区低温导致混凝土性能劣化的问题。基于纳米材料改善混凝土性能的理论,从宏观和微观两个尺度研究了纳米二氧化硅对混凝土性能的影响。抗压强度试验结果发现,低温养护下普通混凝土的抗压强度衰减10%左右;掺入纳米二氧化硅后混凝土的抗压强度提升20%左右,最佳掺量是2%。通过压汞、X射线衍射和扫描电镜等微观试验数据探讨了纳米二氧化硅对混凝土性能的改良机理。结果表明,常温和低温养护下纳米二氧化硅都能促进水泥水化,消耗水化生成的氢氧化钙,产生更多的水化硅酸钙和水化硅铝酸钙凝胶,从而降低混凝土的孔隙率,优化混凝土的微观结构,提升混凝土的性能。相比常温环境,低温下纳米二氧化硅对混凝土性能的提升效果略有下降,但其完全可以弥补低温对混凝土性能造成的不利影响。

, correspAuthors=李春清, authorNote=null, correspAuthorsNote=
* 李春清(1987—),男,汉族,甘肃永靖人,博士,讲师。研究方向:水泥混凝土材料。E-mail:。
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=YhLOBIgqc6SusntsKfv0gA==, magXml=sXVOCuAglSeu5ZxkUgygcg==, pdfUrl=null, pdf=e/lhVfNtedP280MPRvd6VQ==, pdfFileSize=17068395, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=B9JFRH2I3gbiEqVIiHov/Q==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=YXVIoWmYy5j8iqk7wInYSQ==, mapNumber=null, authorCompany=null, fund=null, authors=

刘昌智(1979—),男,汉族,甘肃白银人,高级工程师。研究方向:公路工程。E-mail:。

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刘昌智(1979—),男,汉族,甘肃白银人,高级工程师。研究方向:公路工程。E-mail:。

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刘昌智(1979—),男,汉族,甘肃白银人,高级工程师。研究方向:公路工程。E-mail:。

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V表示孔容,一定意义上相当于吸附量;d表示直径;dV/dlgd表示孔容随孔径变化率的规律

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Physical properties of cement

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/
(m2·kg-1)		 初凝
时间/min		 终凝
时间/min		 细度/%
345 178 224 1.2
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水泥的物理特性

, figureFileSmall=null, figureFileBig=null, tableContent=
比表面积/
(m2·kg-1)		 初凝
时间/min		 终凝
时间/min		 细度/%
345 178 224 1.2
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Chemical component of cement

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成分 质量分数/%
CaO 69.89
SiO2 17.30
Al2O3 3.14
Fe2O3 3.76
MgO 2.09
K2O 0.64
TiO2 0.18
), ArticleFig(id=1251249374924321644, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149781962673578954, language=CN, label=表2, caption=

水泥的化学成分

, figureFileSmall=null, figureFileBig=null, tableContent=
成分 质量分数/%
CaO 69.89
SiO2 17.30
Al2O3 3.14
Fe2O3 3.76
MgO 2.09
K2O 0.64
TiO2 0.18
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Physical properties of nano-SiO2

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纯度/% 比表面积/(m2·g-1) 直径/nm 密度/(g·cm-3)
99.9 220 20 0.06
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纳米二氧化硅的物理特性

, figureFileSmall=null, figureFileBig=null, tableContent=
纯度/% 比表面积/(m2·g-1) 直径/nm 密度/(g·cm-3)
99.9 220 20 0.06
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Mix proportions of concrete samples

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试样编号 水灰比 添加量/(kg·m-3)
水泥 纳米二氧化硅 减水剂 细骨料 粗骨料
OPC*/OPC 0.4 440.0 0.0 4.4 678.0 1 106.0
NS1*/NS1 0.4 435.6 4.4 4.4 678.0 1 106.0
NS2*/NS2 0.4 431.2 8.8 4.4 678.0 1 106.0
NS3*/NS3 0.4 426.8 13.2 4.4 678.0 1 106.0
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混凝土配合比

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试样编号 水灰比 添加量/(kg·m-3)
水泥 纳米二氧化硅 减水剂 细骨料 粗骨料
OPC*/OPC 0.4 440.0 0.0 4.4 678.0 1 106.0
NS1*/NS1 0.4 435.6 4.4 4.4 678.0 1 106.0
NS2*/NS2 0.4 431.2 8.8 4.4 678.0 1 106.0
NS3*/NS3 0.4 426.8 13.2 4.4 678.0 1 106.0
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低温环境下纳米二氧化硅对混凝土性能的影响
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刘昌智 1 , 李春清 2, * , 陈敦 3 , 范善智 4, 5 , 张青龙 4, 5
科学技术与工程 | 论文·建筑科学 2025,25(9): 3813-3820
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科学技术与工程 | 论文·建筑科学 2025, 25(9): 3813-3820
低温环境下纳米二氧化硅对混凝土性能的影响
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刘昌智1 , 李春清2, * , 陈敦3, 范善智4, 5, 张青龙4, 5
作者信息
  • 1 甘肃省公路交通建设集团有限公司, 兰州 730000
  • 2 西北民族大学土木工程学院, 兰州 730030
  • 3 中国科学院西北生态环境资源研究院冰冻圈科学与冻土工程全国重点实验室, 兰州 730000
  • 4 甘肃省交通科学研究院集团有限公司, 兰州 730000
  • 5 甘肃省桥梁隧道健康监测与安全评估技术创新中心, 兰州 730000

    • 刘昌智(1979—),男,汉族,甘肃白银人,高级工程师。研究方向:公路工程。E-mail:。

通讯作者:

* 李春清(1987—),男,汉族,甘肃永靖人,博士,讲师。研究方向:水泥混凝土材料。E-mail:。
Effect of Nano-silica on Concrete Properties under Low-temperature Environment
Chang-zhi LIU1 , Chun-qing LI2, * , Dun CHEN3, Shan-zhi FAN4, 5, Qing-long ZHANG4, 5
Affiliations
  • 1 Gansu Highway Traffic Construction Group Co., Ltd., Lanzhou 730000, China
  • 2 School of Civil Engineering, Northwest Minzu University, Lanzhou 730030, China
  • 3 State Key Laboratory of Cryospheric Science and Frozen Soil Engineering, Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, China
  • 4 Gansu Provincal Transportation Research Institute Group Co., Ltd., Lanzhou 730000, China
  • 5 Gansu Provincial Center of Technology Innovation for Health Monitoring and Security Assessment in Bridge and Tunnel, Lanzhou 730000, China
出版时间: 2025-03-28 doi: 10.12404/j.issn.1671-1815.2403638
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摘要
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为了解决寒冷地区低温导致混凝土性能劣化的问题。基于纳米材料改善混凝土性能的理论,从宏观和微观两个尺度研究了纳米二氧化硅对混凝土性能的影响。抗压强度试验结果发现,低温养护下普通混凝土的抗压强度衰减10%左右;掺入纳米二氧化硅后混凝土的抗压强度提升20%左右,最佳掺量是2%。通过压汞、X射线衍射和扫描电镜等微观试验数据探讨了纳米二氧化硅对混凝土性能的改良机理。结果表明,常温和低温养护下纳米二氧化硅都能促进水泥水化,消耗水化生成的氢氧化钙,产生更多的水化硅酸钙和水化硅铝酸钙凝胶,从而降低混凝土的孔隙率,优化混凝土的微观结构,提升混凝土的性能。相比常温环境,低温下纳米二氧化硅对混凝土性能的提升效果略有下降,但其完全可以弥补低温对混凝土性能造成的不利影响。

混凝土  /  纳米二氧化硅  /  抗压强度  /  孔隙率  /  微观结构

To solve the problem of deterioration of concrete performance caused by low temperature in cold regions. Based on the theory of nanomaterials to improve the properties of concrete, the effect of nano-silica on the properties of concrete was studied from the macro and micro scales. The results of the compressive strength test show that the compressive strength of ordinary concrete is attenuated by about 10% under low temperature curing. After being mixed with nano silica, the compressive strength of concrete is increased by about 20%, and the optimal dosage is 2%. The improvement mechanism of nano-silica on concrete properties was explored through microscopic test data such as mercury intrusion, X-ray diffraction and scanning electron microscopy. The results show that nano-silica can promote cement hydration at room temperature and low temperature curing, consume calcium hydroxide generated by hydration, and produce more hydrated calcium silicate and hydrated calcium aluminate gel, thereby reducing the porosity of concrete, optimizing the microstructure of concrete, and improving the performance of concrete. Compared with the room temperature environment, the improvement effect of nano-silica on concrete at low temperature is slightly reduced, but it completely overcomes the adverse effects of low temperatures on the performance of ordinary concrete.

concrete  /  nano-silica  /  compressive strength  /  porosity  /  microstructure
刘昌智, 李春清, 陈敦, 范善智, 张青龙. 低温环境下纳米二氧化硅对混凝土性能的影响. 科学技术与工程, 2025 , 25 (9) : 3813 -3820 . DOI: 10.12404/j.issn.1671-1815.2403638
Chang-zhi LIU, Chun-qing LI, Dun CHEN, Shan-zhi FAN, Qing-long ZHANG. Effect of Nano-silica on Concrete Properties under Low-temperature Environment[J]. Science Technology and Engineering, 2025 , 25 (9) : 3813 -3820 . DOI: 10.12404/j.issn.1671-1815.2403638
正文
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混凝土是一种性能优良的人造材料,广泛应用于建筑行业,混凝土已成为建筑行业的基石,但随着科技的发展,普通混凝土的性能已经难以满足现代社会可持续发展的要求。现在普遍使用各种添加剂来提升普通混凝土的物理力学性能和耐久性,这一举措有利于实现节能减排的目标[1-2]。纳米科技的出现推动了纳米材料制备技术的发展,大规模生产纳米材料变为了现实,也为纳米材料的实际应用奠定了基础。使用具有独特物理和化学性质的纳米材料改良混凝土已引起了研究者广泛的关注[3],并进行了大量的研究[4-7]。研究结果表明,纳米材料的颗粒能填充混凝土中的有害孔隙,使混凝土的微结构变得更加致密。此外,纳米材料与水化产物反应生成的凝胶材料能提升混凝土的强度和耐久性,从而提高混凝土结构物的质量和使用寿命。然而,这些改良性能通常是在室温养护或正常施工温度条件下(约20 ℃)被获得的。
寒区是指最冷月平均气温在-10~0 ℃,一年中90~145 d内日均气温不超过5 ℃的地区。寒区属于多年冻土区或季节性冻土区,世界上许多这样的地区的工程建设经常在低温环境中进行。一般情况下,温度在0 ℃以下统称为“负温”,温度在0~10 ℃统称为“低温”,温度在10~25 ℃统称为“常温”。5 ℃是全球大多数国家标准规定的低温阈值[8-9],因此现采用20 ℃和5 ℃作为固化养护温度。中国黑龙江、吉林、辽宁、内蒙古等地的混凝土结构工程(工业与民用建筑、桥梁隧道、机场、水坝、车站码头及特种结构)经常在低温环境施工,浇筑成型的混凝土结构往往内部多孔不密实、表面起皮易开裂,导致力学性能降低、使用寿命缩短、维护成本增加,主要原因在于低温环境中混凝土毛细孔中液体结冰,导致混凝土内部产生残余应变并诱发裂缝。以往研究成果亦表明,低温条件下的养护显著影响混凝土的性能,如降低早期水化速率和力学强度[10-11],并对和易性、开裂潜能、电通量和抗氯离子渗透等产生不利影响[12-15]。 同样,改良混凝土的性能也受到低温养护条件的影响。例如,低温养护会降低含有10%硅粉水泥石的抗压强度[16]。相反,Bentz等[17]发现低温养护会增加含有石灰粉水泥石的强度。虽然已开展通过添加不同掺合料(粉煤灰、硅灰、矿渣等)来提升低温下混凝土性能的研究,但改良效果并不明显。对于掺入纳米材料后是否具有良好效果,相关研究目前缺少。
纳米材料改良混凝土性能的研究主要集中于水泥基材料在常温下的水化过程[18-19],如常温下在混凝土中添加纳米颗粒(SiO2、TiO2、Al2O3、Fe2O3、Fe3O4)可以提升混凝土的性能[20-23]。与常温养护条件相比,在低温养护条件下是否有同样的提升作用,仍需研究证明。现采用纳米二氧化硅作为混凝土的掺合料,研究纳米二氧化硅掺量(1%、2%和3%,相对于水泥的质量分数)在常温和低温养护下对混凝土抗压强度、孔隙率、物相组分和微观结构的影响。研究结果对在低温环境下施工的混凝土提供改良方法,为纳米材料的广泛应用奠定基础,可供低温养护混凝土试验参考。
1 原材料及试验方法
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1.1 原材料
试验用水为自来水,水泥为P.O 42.5普通硅酸盐水泥,砂子和碎石均产自甘肃省白银市。砂子为天然河砂,粒径小于4.75 mm,表观密度2.69 g/cm3,含泥量1.0%;碎石为辉绿岩连续级配碎石,粒径5~20 mm,表观密度2.85 g/cm3。减水剂是减水率为25%的聚羧酸高效减水剂,添加量为胶凝材料掺量的1.0%。纳米二氧化硅是苏州远特新材料有限公司生产的,颗粒直径小于20 nm的白色结晶物质。普通硅酸盐水泥的物理特性及化学成分如表1、表2所示,纳米二氧化硅的物理特性如表3所示。
1.2 配合比
混凝土的配合比如表4所示,水胶比为0.4,纳米二氧化硅的添加量分别是水泥质量的1%、2%和3%。每立方米混凝土拌合物中水泥和纳米二氧化硅总量是440 kg,河砂的质量是678 kg,压碎石质量是1 106 kg,减水剂的质量是4.4 kg。
1.3 试验方法
首先,拌制混凝土混合物。把减水剂倒入水中搅拌10 min获得混合溶液;将纳米二氧化硅倒入溶液,用超声波分散处理30 min获得均质悬浮液(图1);把悬浮液倒入放置在试验搅拌机内已按比例配制好的水泥、砂子和碎石混合物中;启动机械搅拌1 min,获得混凝土拌合物(图2)。其次,浇筑所需试样。在100 mm×100 mm×100 mm的试模中浇筑混凝土拌合物,制取试样用于抗压强度试验;在Ф50 mm×60 mm3的试模中浇筑用4.75 cm筛子过滤粗骨料的混凝土拌合物,制取试样用于压汞和扫描电镜试验;在40 mm×40 mm×160 mm的试模中浇筑水胶比0.4的水泥浆液,制取试样用于X射线衍射试验。
最后,按实验需要养护试样。所有试样在试模中成型12 h后脱模,然后分批养护。一批在标准养护室进行养护,温度(20±2) ℃,相对湿度大于95%。另一批先浇水湿润,再用密封袋包裹后放置于温度(5±0.2) ℃恒温冰柜中进行养护。恒温冰柜如图3所示,是由普通冰柜改装而成,增添了温度控制器、温度探头、空气对流器、保温隔热层等,主要目的是保持恒温、均温。
2 纳米二氧化硅对混凝土抗压强度的影响
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图4所示为5 ℃养护条件下,OPC*、NS1*、NS2*和NS3*混凝土试样在第3天、7天、14天和28天的抗压强度。首先,5 ℃条件下养护的混凝土试样抗压强度随养护龄期的增长而逐渐增大,增大效果比较显著。在不同养护龄期,掺入纳米二氧化硅混凝土试样的抗压强度均高于普通混凝土试样,纳米二氧化硅改性混凝土试样的抗压强度随纳米二氧化硅掺量的增加先增大后减小,掺量2%时抗压强度最大。在不同龄期,NS1*试样的抗压强度分别是普通混凝土试样抗压强度的1.10、1.09、1.10和1.17倍;NS2*试样的抗压强度分别是普通混凝土试样的1.26、1.12、1.15和1.22倍;NS3*试样的抗压强度分别是普通混凝土试样的1.08、1.01、1.05和1.12倍。试验结果表明,纳米二氧化硅在低温下可以提高混凝土的抗压强度,但效果随纳米二氧化硅掺量的不同而各异,2%掺量的提升效果最好。纳米二氧化硅的改善作用主要源于二氧化硅纳米颗粒物的物理力学特性,如小尺寸、大比表面积和结合效应。纳米材料颗粒物体积小,其可以填充混凝土中众多的多尺度孔隙,从而降低孔隙率、提高密实度[24]。纳米颗粒物与胶凝基质之间的结合形成裂纹钉和裂纹桥接等,抑制裂纹扩展,确保载荷在空隙和裂纹之间的传递[25]。然而,比表面积大的纳米二氧化硅的表面能很高,大量存在时容易发生团聚,影响混凝土的均质密实度[21]。与其他龄期相比,2%掺量纳米二氧化硅对混凝土早晚期强度的增强均很明显,都在20%(1.26、1.22)以上,这主要归功于纳米材料的填充效应和晶核效应[26]。具体而言,纳米二氧化硅具有高表面能,可以参与水化和二次水化反应来加速水泥的水化过程,从而加速水化硅酸钙凝胶的形成,阻碍钙矾石晶体的早期成长。
图5所示为混凝土试样OPC*、NS1*、NS2*和NS3*在低温(5 ℃)和OPC、NS1、NS2和NS3在常温[(20±2) ℃]养护条件下不同龄期的抗压强度及对比。结果表明,常温养护试样的抗压强度明显高于低温养护试样的抗压强度,试样在两种养护条件下的抗压强度的差异随龄期增长在逐渐减小。
如试样OPC*、NS1*、NS2*和NS3*在第3天的抗压强度分别是OPC、NS1、NS2和NS3的0.826、0.872、0.949和0.884倍,在第28天的抗压强度分别是OPC、NS1、NS2和NS3的0.936、0.999、0.999和0.995倍。与其他混凝土试样相比,低温对NS2*试样的抗压强度的影响很弱,早期只衰减5%左右,28 d时已经完全恢复到标准养护状态。由此可以得出,掺入2%纳米二氧化硅的混凝土能克服低温养护造成混凝土强度衰减的问题。该结果对工程建设来说意义重大,可使混凝土工程摆脱低温施工的束缚,即低温降低水化反应速率导致混凝土强度衰减。一般而言,低温会降低水化速率从而减少水化产物数量[27],但具有高表面能的纳米二氧化硅可通过加速水化反应而抵消了低温的不利影响。然而,纳米二氧化硅的用量应限制在水泥质量的2%左右,以防止团聚结块而抑制加速效果。
3 纳米二氧化硅对混凝土微观特性的影响
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选取力学性能最优的纳米二氧化硅改良水泥浆试样和普通水泥浆试样进行微观特性研究,主要对比分析2%纳米二氧化硅掺入水泥浆后在低温和常温养护下孔隙率、微观结构和物质组分的变化情况。
3.1 孔隙率
图6是通过压汞试验获得的水泥砂浆试样OPC*、OPC、NS2*和NS2的孔径分布图,孔径主要分布在7~20 000 nm。根据孔径对水泥砂浆性能的影响,将水泥砂浆中的孔隙分为无害孔(<20 nm)、少害孔(20~50 nm)、有害孔(50~200 nm)和多害孔(>200 nm)四类[28]。可以看出,纳米二氧化硅主要影响砂浆中孔径小于200 nm的孔隙,尤其是少害孔和有害孔。微分曲线上有明显的波峰,与之对应的是砂浆试样的最可几孔径。试样OPC*、OPC、NS2*和NS2的最可几孔径分别是52.9、38.8、33.1和32.9 nm,大小关系为NS2 < NS2* < OPC < OPC*。结果表明,纳米二氧化硅降低了砂浆试样的最可几孔径,但低温养护又增大了砂浆试样的最可几孔径。相比而言,纳米二氧化硅的改良效果强于低温产生的不利影响。
图7展示的是砂浆试样在压汞试验中汞侵入的累积曲线,曲线的高斜率系数区主要分布在20~200 nm,试样OPC*、OPC、NS2*和NS2的临界孔径分别为118.3、90.4、79.3和73.8 nm。结果表明,纳米二氧化硅减小了砂浆中20~200 nm孔隙的临界孔径,低温养护下临界孔径变大。临界孔径的减小表明纳米二氧化硅掺入将砂浆中的大孔隙转化为了小孔隙,使试样更加致密,但低温养护会减弱纳米二氧化硅优化砂浆孔隙的效果。
如图8所示,试样OPC*、OPC、NS2*和NS2的孔隙率分别为13.35%、12.68%、13.07%和11.44%。
相比而言,低温养护导致试样的孔隙率增大,纳米二氧化硅的掺入降低了试样的孔隙率。可见,纳米二氧化硅的掺入和低温养护环境都对试样的孔隙率产生了影响,纳米二氧化硅的掺入产生了积极作用,而低温养护带来了不利影响,其同时还改变了试样中各孔隙所占的比例。同样,纳米二氧化硅的掺入和低温养护环境改变了试样中无害孔、少害孔、有害孔和多害孔的比例。无害孔对混凝土性能的影响很小,可以忽略不计;多害孔由养护工艺造成,其对混凝土性能影响很大,但按标准要求养护就会避免其影响;少害孔和有害孔是在水泥水化过程中形成的,水化程度直接决定了其含量。从试验结果可以看出,试样中少害孔所占的比例最大,其次是有害孔,无害孔和多害孔所占比例较小。例如,OPC*、OPC、和NS2中少害孔的比例都超过了50%,NS2*中少害孔的比例为44.8%。与常温养护相比,在低温养护下普通试样的有害孔和多害孔的比例增大,无害孔和少害孔的比例减少;纳米二氧化硅改良试样有着类似的规律;这表明低温养护使混凝土的大孔隙增多、小孔隙减少,从而导致其结构密实度下降。常温下试样NS2的少害孔和有害孔的比例小于试样OPC的;低温下试样NS2*的少害孔和有害孔的比例小于试样OPC*的;低温下试样NS2*的无害孔的比例大于试样OPC*的;这些数据充分证明纳米二氧化硅可以优化混凝土的孔隙结构,使混凝土更加密实,尤其在低温环境下。综合而言,纳米二氧化硅和低温环境都会影响水泥水化的过程,纳米二氧化硅会促进水泥水化,而低温会抑制水泥水化,低温施工时在混凝土中掺入纳米二氧化硅可弥补低温对水化带来的不利影响。
3.2 物相组分
为了查明水泥浆体在掺入纳米二氧化硅和低温养护下物相组分的变化,对养护了28 d的水泥浆体试样进行了X射线衍射试验。图9为水泥浆体试样OPC*、OPC、NS2*和NS2的X射线衍射谱,其中水泥石中氢氧化钙(CH)、钙矾石(AFt)、硅酸三钙(C3S)、水化硅酸钙(C-S-H)和水化硅铝酸钙(C-A-S-H)的衍射特征峰用不同的符号标注。所有试样的图谱形状相似,说明纳米二氧化硅的掺入和低温没有导致原本水化产物的消失或其他水化产物的产生。氢氧化钙的特征峰最为突出,试样OPC的最高,试样NS2的最低,试样OPC*低于OPC的,试样NS2*的高于NS2的,说明常温下掺入纳米二氧化硅会促进水化产物氢氧化钙的消耗,低温会抑制水化产物氢氧化钙的生成。同样,低温会减弱纳米二氧化硅对氢氧化钙消耗的促进作用。根源在于纳米材料对水化反应的促进作用,低温对水化反应的抑制作用。相比之下,硅酸三钙、水化硅酸钙、水化硅铝酸钙等物质的衍射峰较弱,但试样之间的图谱差异仍然明显。硅酸三钙一般为水泥未水化充分而残留的矿物质,试样OPC*中最多,其次是OPC和NS2*,试样NS2中最少,说明低温下普通水泥浆水化的很不充分,加入纳米二氧化硅后会促进水泥进一步水化。通过试样中水化硅酸钙和水化硅铝酸钙衍射峰发现,低温和常温下纳米二氧化硅改良水泥浆比普通水泥浆能水化生成更多的水化硅酸钙和水化硅铝酸钙,说明低温和常温下纳米二氧化硅对水泥水化的促进作用都是存在的。试验结果充分证明,纳米二氧化硅的颗粒物不但能填充孔隙,其水化产生的凝胶也能填充孔隙,还能黏结固相物、减少裂缝,从而提升混凝土的密实度。
3.3 微观结构
对养护28 d的砂浆试样OPC*、OPC、NS2*和NS2进行扫描电镜测试,分别放大500倍和10 000倍观察其微观结构形态。如图10(a)所示,在500倍图像中所有试样的结构面特征如颗粒形态、裂缝和孔隙都清晰可见。所有试样中裂缝和孔隙几乎都存在,但结构面密实程度差异明显。相比而言,常温养护试样OPC和NS2的密实性优于低温养护试样OPC*和NS2*的,原因在于低温下水泥水化不充分,导致水化产生的凝胶少,不能将所有的松散颗粒黏结在一起。尤其OPC*试样,结构面中不但有松散颗粒还存在交错裂缝。由于纳米二氧化硅有促进水化反应的作用,所以NS2*的结构面比OPC*的更密实、松散颗粒较少。如图10(b)所示,在10000倍图像中,孔隙和裂缝差异突显。试样OPC*和NS2*的孔隙和裂缝比OPC和NS2多而显著,尤其是OPC*试样,孔隙密布、颗粒松散,整体性极差。通过试样OPC和NS2对比发现,试样中掺入纳米二氧化硅后,原本松散的基体被凝胶连接成了整体。低温导致普通水泥石结构变得更加松散,如试样OPC*。低温会抑制纳米二氧化硅对水泥石结构的优化作用,如试样NS2*中的孔隙比试样NS2中的多很多。综合而言,低温环境下混凝土中的水泥会水化不充分,导致水泥残留物多、水化产生的凝胶少,从而混凝土形成的水泥石中颗粒物多、孔隙多、结构松散。常温和低温下纳米二氧化硅都可以促进水泥水化,从而优化水泥石的微观结构使其更加密实。相比常温环境,低温环境下纳米二氧化硅对混凝土性能的提升略有衰减,但其的掺入完全可以克服低温对混凝土性能带来的不利影响。
4 结论
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混凝土在低温环境中施工会导致其物理力学性能和耐久性衰减,掺入纳米二氧化硅后的混凝土完全可以弥补低温环境带来的不利影响。
(1)低温和常温环境下纳米二氧化硅都可以提升混凝土的抗压强度性能,抗压强度随纳米二氧化硅掺量的增加而先增大后减小,最佳掺量是2%,可提升抗压强度20%左右。
(2)低温环境下施工成型混凝土的物理力学性能衰减,普通混凝土的抗压强度衰减最为明显,初期强度衰减可达17%左右。低温也会造成纳米二氧化硅改良混凝土早期抗压强度的衰减,但不会对其后期强度产生不利影响。
(3)低温和常温下纳米二氧化硅都可以促进水泥水化,消耗更多的氢氧化钙,产生更多的水化硅酸钙和水化硅铝酸钙凝胶,从而降低混凝土的孔隙率,优化混凝土的微观结构,提高混凝土的密实度。与常温相比,低温下纳米二氧化硅对混凝土性能的改良效果略有下降,但完全可以克服低温对普通混凝土性能造成衰减的问题。
研究为纳米材料在寒区混凝土工程中的应用提供了参考,也为低温环境施工中混凝土性能衰减的问题提供了解决思路。建议掺入纳米二氧化硅来提升低温环境下混凝土的性能,最佳掺量控制在水泥质量的2%左右。
基金
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  • 甘肃省交通科学研究院集团有限公司开放基金(JKJTKF202302QS)
  • 甘肃省科技厅中小企业创新基金(22CX3GA073)
文献
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2025年第25卷第9期
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doi: 10.12404/j.issn.1671-1815.2403638
  • 接收时间：2024-05-16
  • 首发时间：2025-07-09
  • 出版时间：2025-03-28
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  • 收稿日期：2024-05-16
  • 修回日期：2024-12-27
基金
甘肃省交通科学研究院集团有限公司开放基金(JKJTKF202302QS)
甘肃省科技厅中小企业创新基金(22CX3GA073)
作者信息
    1 甘肃省公路交通建设集团有限公司, 兰州 730000
    2 西北民族大学土木工程学院, 兰州 730030
    3 中国科学院西北生态环境资源研究院冰冻圈科学与冻土工程全国重点实验室, 兰州 730000
    4 甘肃省交通科学研究院集团有限公司, 兰州 730000
    5 甘肃省桥梁隧道健康监测与安全评估技术创新中心, 兰州 730000

通讯作者:

* 李春清(1987—),男,汉族,甘肃永靖人,博士,讲师。研究方向:水泥混凝土材料。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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