Article(id=1149773878186172439, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149773869357167407, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2404614, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1718812800000, receivedDateStr=2024-06-20, revisedDate=1738684800000, revisedDateStr=2025-02-05, acceptedDate=null, acceptedDateStr=null, onlineDate=1752057054318, onlineDateStr=2025-07-09, pubDate=1746633600000, pubDateStr=2025-05-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752057054318, onlineIssueDateStr=2025-07-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752057054318, creator=13701087609, updateTime=1752057054318, updator=13701087609, issue=Issue{id=1149773869357167407, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='13', pageStart='5273', pageEnd='5704', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752057052207, creator=13701087609, updateTime=1768456769392, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1218559268744253990, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149773869357167407, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1218559268744253991, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149773869357167407, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=5544, endPage=5551, ext={EN=ArticleExt(id=1149773878488162328, articleId=1149773878186172439, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Molecular Dynamics Simulation of C-S-H/γ-FeOOH Interfacial Bonding Behaviour in an Erosive Environment, columnId=1156262729917780302, journalTitle=Science Technology and Engineering, columnName=Papers·Architectural Science, runingTitle=null, highlight=null, articleAbstract=

Molecular dynamics method is adopted to investigate the effect of different NaCl solutions concentrations on the bonding properties of the calcium silicate hydrate/γ-FeOOH(C-S-H/γ-FeOOH) interface. The effect mechanism of NaCl solution concentration is revealed from the interface ion evolution, radial distribution function, particle strength distribution, interaction energy and mechanical properties. The results show that as the concentration of NaCl solution increases, interlayer Ca h 2 + ions separate from the surface of C-S-H and diffuse to the interlayer solution, Na+ ions enter the C-S-H layer. Ca h 2 + ions adsorb Cl- ions in the solution, resulting in the ion clusters of Ca h 2 + and Cl- on the surface of C-S-H. In addition, the γ-FeOOH surface hydroxyl oscillation provides adsorption points for Na + ions, resulting in the increase of Na+ ions on the γ-FeOOH surface. When the NaCl solution concentration increased, the RDF peak of Cah—Os gradually decreased and the radial distribution function(RDF) peak of Cah—Ow, Cah—Cl, and Na—Os gradually increases, consistent with the ionic strength distribution. Where, Os is the oxygen on the silicon chain in C-S-H, and Ow is the oxygen in the interlayer solution water. Ca h 2 + ions form ionic bonds with Ow in water, leading to a reduction of Cah—Os ionic bonds on the C-S-H surface. Since the strength and stability of Cah—Os ionic bond are better than that of Cah—Ow,therefore, the C-S-H/γ-FeOOH interfacial interaction energy and peak stress both show a decreasing trend with the increase of NaCl solution concentration.

, correspAuthors=Bin MA, 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=Yan-qi CHEN, Bin MA, Yan-feng WEI, Yun-fan CHU), CN=ArticleExt(id=1149773907613410145, articleId=1149773878186172439, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=侵蚀环境下C-S-H/γ-FeOOH界面黏结性能的分子动力学模拟, columnId=1156262730517565784, journalTitle=科学技术与工程, columnName=论文·建筑科学, runingTitle=null, highlight=null, articleAbstract=

采用分子动力学研究了不同浓度NaCl溶液对水化硅酸钙(calcium silicate hydrate, C-S-H)和钢筋钝化膜(γ-FeOOH)(下文简称为C-S-H/γ-FeOOH)界面黏结性能的影响,从界面处离子演化、径向分布函数、粒子强度分布、相互作用能和力学性能等方面揭示了NaCl溶液浓度的影响机理。研究结果显示,随着NaCl溶液浓度升高,层间 Ca h 2 +离子从C-S-H表面脱离扩散至层间溶液,Na+离子进入C-S-H层中, Ca h 2 +离子对溶液中Cl-离子具有吸附作用,导致C-S-H表面出现 Ca h 2 +和Cl-的离子团。此外,由于γ-FeOOH表面羟基振荡,为Na+离子提供吸附点位,致使γ-FeOOH表面Na+离子增多。当NaCl溶液浓度升高时,Cah—Os的径向分布函数(radial distribution function,RDF)峰值逐渐降低,Cah—Ow、Cah—Cl和Na—Os的RDF峰值均逐渐升高,该结果与离子强度分布一致,其中Os为C-S-H中硅链上的氧,Ow为层间溶液水中的氧。 Ca h 2 +离子与水中Ow形成离子键,导致C-S-H表面Cah—Os离子键减少。Cah—Os离子键的强度和稳定性优于Cah—Ow,故随着NaCl溶液浓度的升高,C-S-H/γ-FeOOH界面相互作用能和峰值应力均呈下降趋势。

, correspAuthors=马彬, authorNote=null, correspAuthorsNote=
* 马彬(1986—),男,汉族,河南驻马店人,博士,副教授。 研究方向:建筑节能材料。E-mail:
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=iOOz1shqyAYQaXPxA4OQ0Q==, magXml=RSNFgbw28xa4COyLW7R9jw==, pdfUrl=null, pdf=q3vx3195YFmhFewPo8tJzg==, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=crwKf04sJP9W53ttzDRjwQ==, mapNumber=null, authorCompany=null, fund=null, authors=

陈彦齐(1998—),男,汉族,广东茂名人,硕士研究生。研究方向:无机非金属材料。E-mail:

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陈彦齐(1998—),男,汉族,广东茂名人,硕士研究生。研究方向:无机非金属材料。E-mail:

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陈彦齐(1998—),男,汉族,广东茂名人,硕士研究生。研究方向:无机非金属材料。E-mail:

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红色球为氧;黄色球为硅;绿色球为钙;白色球为氢;紫色球为钠;浅绿色球为氯;蓝紫色球为铁

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Cah为层间钙;Os为C-S-H中硅链上的氧;Ow为层间溶液水中的氧

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1 kcal/mol=4.19 kJ/mol

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侵蚀环境下C-S-H/γ-FeOOH界面黏结性能的分子动力学模拟
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陈彦齐 , 马彬 * , 魏燕锋 , 楚云帆
科学技术与工程 | 论文·建筑科学 2025,25(13): 5544-5551
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科学技术与工程 | 论文·建筑科学 2025, 25(13): 5544-5551
侵蚀环境下C-S-H/γ-FeOOH界面黏结性能的分子动力学模拟
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陈彦齐 , 马彬* , 魏燕锋, 楚云帆
作者信息
  • 桂林电子科技大学建筑与交通工程学院, 桂林 541004
  • 陈彦齐(1998—),男,汉族,广东茂名人,硕士研究生。研究方向:无机非金属材料。E-mail:

通讯作者:

* 马彬(1986—),男,汉族,河南驻马店人,博士,副教授。 研究方向:建筑节能材料。E-mail:
Molecular Dynamics Simulation of C-S-H/γ-FeOOH Interfacial Bonding Behaviour in an Erosive Environment
Yan-qi CHEN , Bin MA* , Yan-feng WEI, Yun-fan CHU
Affiliations
  • School of Architecture and Transportation Engineering, Guilin University of Electronic Technology, Guilin 541004, China
出版时间: 2025-05-08 doi: 10.12404/j.issn.1671-1815.2404614
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采用分子动力学研究了不同浓度NaCl溶液对水化硅酸钙(calcium silicate hydrate, C-S-H)和钢筋钝化膜(γ-FeOOH)(下文简称为C-S-H/γ-FeOOH)界面黏结性能的影响,从界面处离子演化、径向分布函数、粒子强度分布、相互作用能和力学性能等方面揭示了NaCl溶液浓度的影响机理。研究结果显示,随着NaCl溶液浓度升高,层间 Ca h 2 +离子从C-S-H表面脱离扩散至层间溶液,Na+离子进入C-S-H层中, Ca h 2 +离子对溶液中Cl-离子具有吸附作用,导致C-S-H表面出现 Ca h 2 +和Cl-的离子团。此外,由于γ-FeOOH表面羟基振荡,为Na+离子提供吸附点位,致使γ-FeOOH表面Na+离子增多。当NaCl溶液浓度升高时,Cah—Os的径向分布函数(radial distribution function,RDF)峰值逐渐降低,Cah—Ow、Cah—Cl和Na—Os的RDF峰值均逐渐升高,该结果与离子强度分布一致,其中Os为C-S-H中硅链上的氧,Ow为层间溶液水中的氧。 Ca h 2 +离子与水中Ow形成离子键,导致C-S-H表面Cah—Os离子键减少。Cah—Os离子键的强度和稳定性优于Cah—Ow,故随着NaCl溶液浓度的升高,C-S-H/γ-FeOOH界面相互作用能和峰值应力均呈下降趋势。

C-S-H  /  γ-FeOOH  /  NaCl溶液  /  黏结性能  /  分子动力学

Molecular dynamics method is adopted to investigate the effect of different NaCl solutions concentrations on the bonding properties of the calcium silicate hydrate/γ-FeOOH(C-S-H/γ-FeOOH) interface. The effect mechanism of NaCl solution concentration is revealed from the interface ion evolution, radial distribution function, particle strength distribution, interaction energy and mechanical properties. The results show that as the concentration of NaCl solution increases, interlayer Ca h 2 + ions separate from the surface of C-S-H and diffuse to the interlayer solution, Na+ ions enter the C-S-H layer. Ca h 2 + ions adsorb Cl- ions in the solution, resulting in the ion clusters of Ca h 2 + and Cl- on the surface of C-S-H. In addition, the γ-FeOOH surface hydroxyl oscillation provides adsorption points for Na + ions, resulting in the increase of Na+ ions on the γ-FeOOH surface. When the NaCl solution concentration increased, the RDF peak of Cah—Os gradually decreased and the radial distribution function(RDF) peak of Cah—Ow, Cah—Cl, and Na—Os gradually increases, consistent with the ionic strength distribution. Where, Os is the oxygen on the silicon chain in C-S-H, and Ow is the oxygen in the interlayer solution water. Ca h 2 + ions form ionic bonds with Ow in water, leading to a reduction of Cah—Os ionic bonds on the C-S-H surface. Since the strength and stability of Cah—Os ionic bond are better than that of Cah—Ow,therefore, the C-S-H/γ-FeOOH interfacial interaction energy and peak stress both show a decreasing trend with the increase of NaCl solution concentration.

C-S-H  /  γ-FeOOH  /  NaCl solution  /  bonding properties  /  molecular dynamics
陈彦齐, 马彬, 魏燕锋, 楚云帆. 侵蚀环境下C-S-H/γ-FeOOH界面黏结性能的分子动力学模拟. 科学技术与工程, 2025 , 25 (13) : 5544 -5551 . DOI: 10.12404/j.issn.1671-1815.2404614
Yan-qi CHEN, Bin MA, Yan-feng WEI, Yun-fan CHU. Molecular Dynamics Simulation of C-S-H/γ-FeOOH Interfacial Bonding Behaviour in an Erosive Environment[J]. Science Technology and Engineering, 2025 , 25 (13) : 5544 -5551 . DOI: 10.12404/j.issn.1671-1815.2404614
钢筋混凝土是土木工程中最常见的复合材料,广泛应用于各种侵蚀工程环境,其耐久性面临严峻挑战。钢筋混凝土材料由钢筋与混凝土材料组成,且存在混凝土-钢筋界面[1],该界面的黏结性能直接影响钢筋混凝土的耐久性。因此,为提高钢筋混凝土的耐久性,需要深入了解侵蚀环境下混凝土-钢筋界面的黏结性能。
目前许多学者对钢筋与混凝土的黏结性能进行了试验研究。其中,陈梦成等[2]研究了在氯盐环境下钢筋混凝土简支梁的承载性能,指出随着腐蚀率的增加,钢筋与混凝土的极限承载能力呈现先增加后降低的趋势。Shang等[3]在持续荷载和氯化物侵蚀耦合作用下研究了钢筋与混凝土的黏结性能,发现相同荷载下受氯离子侵蚀的钢筋与混凝土的黏结应力高于未受侵蚀的钢筋与混凝土的黏结应力。刘柯楠等[4]研究了不同聚乙烯醇纤维掺量和硫酸盐冻融次数对纤维钢筋混凝土黏结滑移性能的影响,指出纤维增加了钢筋混凝土黏结的峰值滑移和塑性应变,钢筋在混凝土中的峰值滑移随硫酸盐冻融次数的增加而减少。然而,目前大多数试验研究对操作技术的要求比较严格,且会受到环境等因素的影响。
分子动力学作为一种数值模拟计算方法,已广泛用于混凝土复合材料的微观特性研究[5]。Wu等[6]分析了不同温度对钢筋钝化膜(γ-FeOOH)纳米孔道中氯化钠溶液吸附的影响,结果表明随着温度升高,增强了γ-FeOOH纳米孔道中水和离子的运输和吸附能力,加速了钢筋钝化膜的破坏。Tu等[7]研究了水化硅酸钙(calcium silicate hydrate, C-S-H)和γ-FeOOH界面氯离子和硫酸根离子的传输和吸附行为,发现硫酸根离子与阳离子易形成离子簇,阻碍溶液传输和原子运动,而氯离子参与较少。可见,目前关于C-S-H/γ-FeOOH界面的研究仍处于初期阶段且多关注于界面离子扩散与传输等,然而对于侵蚀环境下C-S-H/γ-FeOOH界面黏结性能的研究尚未系统开展。
现采用分子动力学研究不同浓度NaCl溶液对C-S-H/γ-FeOOH界面黏结性能的影响,并从界面处离子演化、径向分布函数、粒子强度分布、相互作用能和力学性能等方面揭示NaCl溶液对C-S-H/γ-FeOOH界面的影响机理,以期为解决钢筋混凝土的耐久性问题提供理论指导。
C-S-H/γ-FeOOH界面模型由C-S-H、γ-FeOOH和NaCl溶液组成。选用单斜Tobermorite-11 Å层状结构,其中1 Å=10-10 m,依照Pellenq等[8]的方法,构建C-S-H模型,化学式为 (CaO)1.67(SiO2)(H2O)1.68,密度为2.45 g/cm3。硅酸盐链分布如下:单体(Q0)占比为11.63%,二聚体或长链的端部(Q1)占比为67.44%,硅链中间的Si(OH)4(Q2)占比为20.93%,平均链长为2.62,与已有的模拟结果[8]和实验结果[9]相吻合,如图1(a)所示。将C-S-H模型进行扩胞,最终尺寸为a = 43.38 Å,b = 43.22 Å,c = 43.22 Å,其中,abc分别为晶胞的三组棱长。
混凝土水化过程会产生氢氧化钙,使钢筋周围呈碱性环境。钢筋在碱性环境下,会生成纳米厚的钝化膜[10]。目前,研究人员通过X射线光电子能谱和X射线衍射研究了钝化膜的结构[11],发现钝化膜主要由γ-FeOOH和γ-Fe2O3组成,其中γ-FeOOH为外部锈层的主要成分。因此,采用前期研究人员模拟使用的γ-FeOOH模型构建钢筋钝化膜[12],其晶体结构参数为a = 3.05 Å,b = 12.30 Å,c = 3.93 Å,α = β = γ = 90°。首先,沿γ-FeOOH结构的[0 1 0]方向进行切割,使羟基在γ-FeOOH表面和层间规则排列[9]。然后,将γ-FeOOH初始模型进行扩胞,使其与C-S-H模型相匹配,最终γ-FeOOH模型尺寸为a = 43.25 Å,b = 42.76 Å,c = 32.32 Å,α = β = γ =90°,如图1(a)所示,其中αβγ分别为棱间交角。最后将C-S-H和γ-FeOOH组合成界面模型。
根据前人在侵蚀环境下的界面脱附模拟研究[13],构建不同NaCl浓度的溶液模型,模型厚度为8.0 Å,密度为1.05 g/cm3,浓度分别为0、1、2 mol/L,如图1(b)所示。最后,将溶液放置层间之中,形成了3种不同的C-S-H/γ-FeOOH界面模型,如图1(c)所示。
在C-S-H/γ-FeOOH界面模型中,力场选用Cygan等提出的Clayff力场[14]。该力场因良好的可传递性和可靠性已成功用于水泥水化产物、多组分矿物、氧化物和氢氧化物材料等体系的模拟[15]
采用LAMMPS 软件进行分子动力学模拟。模拟过程分为平衡态模拟和单轴拉伸模拟两个部分。首先,采用周期性边界条件并将时间步长设置为1 fs,在NVT系统下进行1 000 ps的动力学弛豫,温度控制为300 K,压力控制为0 kPa,使结构达到平衡状态。然后,沿Z轴方向对结构进行拉伸,控制XY方向的压力,Z轴方向的压力不受限制。其中,拉伸速率设定为0.008 ps-1,系统温度和模拟时间步长均与平衡过程一致。其中,1 fs=10-15 s,1 ps=10-12 s。
图2为不同C-S-H/γ-FeOOH模型界面处层间 Ca h 2 +离子分布。可见,当NaCl溶液浓度为0 mol/L时, Ca h 2 +离子大部分位于C-S-H表面,仅有少量 Ca h 2 +离子进入层间溶液[图2(a)]。随着NaCl溶液浓度增加,由于C-S-H层与NaCl溶液之间存在Na-Ca阳离子交换, Ca h 2 +离子从C-S-H表面脱离,扩散至层间溶液且分布比较均匀[图2(b)]。这是由C-S-H表面的 Ca h 2 +离子会平衡暴露在硅酸盐链中带负电的Os原子,且硅酸盐链中Os原子数量多于 Ca h 2 +离子,所以未被阳离子完全配位的Os原子从溶液中吸附更多的Na+离子,导致C-S-H表面对 Ca h 2 +离子的约束(静电吸附)变得更弱[16]。当NaCl溶液浓度为2 mol/L时,随着溶液中 Ca h 2 +离子的增多,层间溶液中的 Ca h 2 +离子出现团聚现象[图2(c)]。这是由于 Ca h 2 +离子对Cl-离子有较强的静电吸附,导致 Ca h 2 +离子和Cl-离子形成离子对,从而限制了 Ca h 2 +离子往层间溶液的迁移[17]
图3为不同C-S-H/γ-FeOOH模型界面处Na+离子的分布图。可见,随着NaCl溶液浓度的增加,Na+离子聚集在C-S-H层和γ-FeOOH层的数量逐渐增加。这是由于随着NaCl溶液浓度增加, Ca h 2 +离子有更大的可能离开C-S-H表面,C-S-H与NaCl溶液之间Na与Ca阳离子交换数量增多,故大量Na+离子侵入C-S-H。此外,由于在弛豫过程中γ-FeOOH表面羟基振荡,导致氧原子暴露在层间溶液中,为Na+离子提供吸附点位,所以Na+离子可以渗透到γ-FeOOH基底与羟基之间的空位,并与邻近的氧原子形成离子键[18]
图4为不同C-S-H/γ-FeOOH模型界面处Cl-离子分布。由图4(a)可知,当浓度为1 mol/L时,由于Cl-离子与C-S-H表面释放的 Ca h 2 +离子之间存在静电吸引,导致Cl-离子会在C-S-H表面附近处被 Ca h 2 +离子吸附。可以观察到 Ca h 2 +离子与Cl-离子的位置相吻合。随着NaCl溶液浓度的增加,当浓度为2 mol/L时,由于C-S-H层与溶液之间的相互作用增强,从C-S-H表面脱离的 Ca h 2 +离子增多, Ca h 2 +离子对Cl-离子吸附现象更加显著,在C-S-H层附近形成离子团簇,导致聚集在C-S-H层附近的Cl-离子的数量增多[图4(b)]。此外,随着NaCl溶液浓度的增加,由于γ-FeOOH表面阳离子增多,其阳离子与Cl-离子存在相互作用,导致γ-FeOOH表面附近Cl-离子的数量逐渐增多。
径向分布函数(radial distribution function,RDF)是描述粒子系统中相距参考粒子处粒子密度的一种方法,可以准确量化不同原子的空间关联性,反映原子间的化学键合情况,RDF的计算公式[19]
g(r)= d N 4 π r 2 ρ
式(1)中:dN为dr范围的薄壳内包含的原子数;r为半径;dN/(4πr2)为区域密度;ρ为系统的平均密度。体系结构的差异会导致径向函数的取值和趋势不同,进而判断体系的状态。粒子排列或分布无规律性的非晶体系,其径向分布函数仅在近程具有波峰,且随着半径的增大趋向于1[20]
图5为不同C-S-H/γ-FeOOH模型中不同离子对的径向分布函数。可见,离子对之间的RDF在近程(2~3 Å)具有显著的峰值,且随着半径的增大趋向于1,表明短程有序和长程无序的无定形结构特征是一致的。此外,相同离子对的峰值在同一位置,即具有相同的键长,表明NaCl溶液的浓度并不影响离子对的键长。
图5(a)图5(b)可知,Cah—Os和Cah—Ow的RDF在2.55 Å和2.75 Å到达峰值,说明Os与Ow和Cah之间有显著的相互作用,该结果与Richardson[21]的实验数据(Ca—O: 2.2~2.9 Å)相吻合。当NaCl溶液浓度从0 mol/L增加到2 mol/L时,Cah—Os的径向分布函数峰值逐渐降低,Cah—Ow的径向分布函数峰值逐渐升高,这是由于 Ca h 2 +离子从C-S-H表面脱离进入层间溶液,与H2O分子中的O原子与成键,导致C-S-H内Os原子附近的 Ca h 2 +离子数量逐渐减少。该结果与C-S-H/γ-FeOOH界面模型中C-S-H表面区域的 Ca h 2 +离子分布一致。
图5(c)可知,Na—Os的RDF在2.55 Å到达峰值,表明Na+离子与C-S-H中的Os原子存在显著的相互作用。当NaCl溶液浓度从1 mol/L增加到2 mol/L时,Na—Os的径向分布函数峰值逐渐增加,表明硅酸盐链附近的Na+离子增加。这是由于硅酸盐链上的Os原子对Na+离子有很强的吸附作用,硅酸盐链上的Os将Na+离子固定,导致Na+离子在C-S-H层聚集。
图5(d)可知,Cah—Cl的RDF在2.75 Å处有第一个峰值,表明Cl-离子与 Ca h 2 +离子之间存在显著的空间相关性。当NaCl溶液浓度从1 mol/L增加到2 mol/L时,Cah-Cl的径向分布函数峰值显著增加,表明在层间溶液中的Cl-离子附近 Ca h 2 +离子增加,Cl-离子能与 Ca h 2 +离子更紧密地结合。此外,在3.81 Å附近还有另一个峰值,表明Cl-离子通过桥接水分子与 Ca h 2 +离子配位,即存在Cah—Ow—Cl相互作用[22]
离子强度分布曲线能直观地反映不同类型离子与基底表面之间的关系。图6为不同NaCl溶液浓度下 Ca h 2 +、Na+和Cl-离子在Z方向离子强度分布曲线图。由图6(a)可知,随着NaCl溶液浓度上升,由于C-S-H表面发生阳离子交换, Ca h 2 +离子会扩散到层间溶液中,导致 Ca h 2 +离子的强度峰从C-S-H层移动到溶液区域。
图6(b)可知,当NaCl溶液浓度为1 mol/L时,由于C-S-H层表面的电负性以及硅酸盐链中Os原子能与Na+离子形成稳定的Na—Os离子键,导致Na+离子在C-S-H区域出现明显的强度峰。当NaCl溶液浓度为2 mol/L时,由于Na+离子的数量增多,Na+离子与 Ca h 2 +离子交换更加剧烈,导致更多的Na+离子在C-S-H区域内聚集,形成更高的强度峰。此外,由于γ-FeOOH表面中的羟基会暴露在溶液中,Na+离子会渗透到γ-FeOOH表面羟基之间的空位,并与邻近的氧原子形成离子键,导致γ-FeOOH表面也出现Na+离子强度峰。
图6(c)可知,当NaCl溶液浓度为1 mol/L时,由于C-S-H表面对阳离子具有亲和性,而对阴离子具有排斥性,故大部分Cl-离子强度峰位于区域溶液内。此外,在C-S-H表面附近的Cl-离子强度峰接近 Ca h 2 +离子强度峰,表明Cl-离子受库伦效应被C-S-H表面脱离的 Ca h 2 +离子吸引,并与Cl-离子形成Ca-Cl离子对。当NaCl溶液浓度为2 mol/L时,由于Cl-离子的数量增加,Cl-离子与 Ca h 2 +离子之间存在相对稳定的作用,导致Cl-离子在区域溶液内的强度峰上升,且C-S-H表面附近的Cl-离子强度峰也上升。
为充分了解NaCl溶液浓度对C-S-H/γ-FeOOH界面黏结性能的影响,进一步计算了C-S-H/γ-FeOOH界面的相互作用能,具体计算公式[23]
Einterface=Etotal-Elayers-Esolution
式(2)中:Etotal为C-S-H/γ-FeOOH体系的总势能; E l a y e r s为C-S-H层和γ-FeOOH层的势能;Esolution为层间溶液的势能。此外,若相互作用能为负值,则说明两相相互吸引;反之说明两相相互排斥[24]
图7为不同C-S-H/γ-FeOOH模型的界面相互作用能。可见,3种结构的界面相互作用能分别为-1 018.579 9、-941.237 5和-928.000 1 kcal/mol,且相互作用能均为负值,表明 C-S-H/γ-FeOOH与层间溶液存在相互吸引作用。此外,随着NaCl溶液浓度增加,界面相互作用能逐渐减小。
随着NaCl溶液浓度增加, Ca h 2 +离子从C-S-H表面脱离,扩散至层间溶液,同时Na+离子由层间溶液往C-S-H表面聚集并与C-S-H中的Os形成离子键,导致Cah—Os键数量减少,Cah—Ow和Na—Os的数量增多。由于Cah—Os的化学键强度大于Cah—Ow键和Na—Os[25-26],故NaCl溶液的浓度越高,C-S-H与γ-FeOOH的键合相互作用减弱,导致C-S-H/γ-FeOOH界面的相互作用能越小。
图8为不同NaCl溶液浓度的C-S-H/γ-FeOOH模型的应力-应变曲线。可见,所有模型的应力均随拉应变逐渐增加(弹性阶段),然后达到最大峰值,之后应力随应变的进一步增加逐渐减小(失效阶段)。通过计算弹性阶段曲线斜率确定模型的弹性模量分别为37 926.47、32 867.23和30 842.06 MPa。C-S-H与γ-FeOOH之间的结合强度(峰值应力)分别为634.29、578.72和569.36 MPa。此外,峰值应力对应的应变分别为0.028 4、0.022 8、0.019 6。
随着NaCl溶液浓度升高,模型弹性模量、峰值应力、峰值应变均逐渐减小。随着层间NaCl溶液浓度的增加,C-S-H/γ-FeOOH结构模型的失效需要的能量逐渐减少,该结果与相互作用能结论一致。由于在C-S-H表面发生Na-Ca离子交换,Na+离子往C-S-H表面聚集,会吸引更多水分子在界面区域,且水分子参与界面处Cah—Os键的竞争,导致C-S-H与γ-FeOOH界面的成键效率降低[27]。另一方面,由于C-S-H表面脱离的 Ca h 2 +离子与溶液中的Cl-离子产生吸附作用,并形成Ca-Cl离子对,取代了部分Cah—Os化学键,导致C-S-H与γ-FeOOH之间界面的力学性能降低。因此随着层间溶液NaCl溶液浓度的增加,导致结构的键合强度降低。此外,C-S-H与γ-FeOOH之间的结合强度是通过层间溶液传递应力的综合效果[23],故增加NaCl溶液浓度可以加速结构的断裂,从而促进峰值应变的减少。
(1)随着NaCl溶液浓度的升高, Ca h 2 +离子从C-S-H表面脱离扩散至层间溶液,Na+离子进入C-S-H层中, Ca h 2 +离子对溶液中Cl-离子具有吸附作用,导致C-S-H表面出现 Ca h 2 +和Cl-的离子团。此外,由于在弛豫过程中γ-FeOOH表面羟基振荡,表面羟基中氧和氢暴露在层间溶液中,为Na离子提供吸附点位,致使γ-FeOOH表面Na+增多。
(2)Cah—Os和Cah—Ow的RDF在2.55 Å和2.75 Å到达峰值,该结果与实验数据(Ca-O:2.2~2.9 Å)相吻合。当NaCl溶液浓度升高时,Cah—Os的RDF峰值逐渐降低,Cah—Ow、Cah—Cl和Na—Os的RDF峰值均逐渐升高。该结果与离子强度分布一致。
(3)不同C-S-H/γ-FeOOH模型的应力-应变曲线均可分为两个阶段:弹性阶段和失效阶段。溶液中Na+离子与C-S-H表面 Ca h 2 +离子置换, Ca h 2 +离子与水中Ow形成离子键,导致C-S-H表面Cah—Os离子键减少。Cah—Os离子键的强度和稳定性优于Cah—Ow,故随着界面NaCl溶液浓度的升高,C-S-H/γ-FeOOH界面相互作用能和峰值应力均呈下降趋势。从原子尺度揭示了钢筋混凝土的侵蚀机理,为工程中高耐久性钢筋混凝土的设计提供指导。
  • 国家自然科学基金(12162010)
  • 广西科技基地和人才专项(AD19245143)
  • 桂林电子科技大学研究生教育创新计划(2024YCXS194)
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2025年第25卷第13期
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doi: 10.12404/j.issn.1671-1815.2404614
  • 接收时间:2024-06-20
  • 首发时间:2025-07-09
  • 出版时间:2025-05-08
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  • 收稿日期:2024-06-20
  • 修回日期:2025-02-05
基金
国家自然科学基金(12162010)
广西科技基地和人才专项(AD19245143)
桂林电子科技大学研究生教育创新计划(2024YCXS194)
作者信息
    桂林电子科技大学建筑与交通工程学院, 桂林 541004

通讯作者:

* 马彬(1986—),男,汉族,河南驻马店人,博士,副教授。 研究方向:建筑节能材料。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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