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In order to investigate the properties of seawater mixing alkali-activated materials, the development law of hydration reaction, mechanics and corrosion resistance of seawater alkali-activated materials based on multi-component composite cementitious materials was studied. The results show that seawater mixing has a certain inhibitory effect on the hydration reaction of alkali-activated slag, and the compressive strength of SLCM at different ages also shows a decreasing trend to a certain extent, which is not conducive to the development of strength. Fly ash and silica fume can reduce the hydration reaction rate, early strength and toughness of the seawater alkali-activated materials, but their strength and toughness increase potential is significant in the later period, in which the strength and toughness growth rate of the silica-fly ash-slag terpolymer system from 7 days to 28 days reaches 50.9% and 86.7%, respectively. Compared with alkali-activated slag, adding fly ash and silica fume can improve the electric flux permeability and chloride ion mobility coefficient of alkali excited materials in seawater to a certain extent, which is consistent with their microstructure, but the three still belong to the same chloride ion permeability grade, i.e., medium permeability grade (electric flux method).

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赵计辉(1985—),男,汉族,陕西咸阳人,博士,副教授。研究方向:绿色低碳建材及固废资源化利用。E-mail:

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赵计辉(1985—),男,汉族,陕西咸阳人,博士,副教授。研究方向:绿色低碳建材及固废资源化利用。E-mail:

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赵计辉(1985—),男,汉族,陕西咸阳人,博士,副教授。研究方向:绿色低碳建材及固废资源化利用。E-mail:

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Construction and Building Materials, 2013, 48: 1187-1201., articleTitle=Influence of fly ash on the water and chloride permeability of alkali-activated slag mortars and concretes, refAbstract=null)], funds=[Fund(id=1205914227437536046, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, awardId=52378280, language=CN, fundingSource=国家自然科学基金(52378280), fundOrder=null, country=null), Fund(id=1205914227496256305, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, awardId=2019A1515011981, language=CN, fundingSource=广东省自然科学基金(2019A1515011981), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1205914221137691289, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, xref=null, ext=[AuthorCompanyExt(id=1205914221150274202, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, companyId=1205914221137691289, language=EN, 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Chemical composition of raw materials

, figureFileSmall=null, figureFileBig=null, tableContent=
成分 含量/%
Na2O MgO Al2O3 SiO2 SO3 K2O CaO Fe2O3
矿渣粉 0.1 9.3 14.9 35.0 1.1 0.4 36.3 0.6
粉煤灰 1.0 1.1 20.4 51.0 0.6 3.3 6.1 13.4
硅灰 0.6 0.5 0.2 96.2 0.8 0.8 0.4 0.1
珊瑚砂 1.0 1.1 2.5 41.9 0.7 0.9 45.8 3.2
), ArticleFig(id=1205914226649006870, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=CN, label=表1, caption=

原材料化学组成

, figureFileSmall=null, figureFileBig=null, tableContent=
成分 含量/%
Na2O MgO Al2O3 SiO2 SO3 K2O CaO Fe2O3
矿渣粉 0.1 9.3 14.9 35.0 1.1 0.4 36.3 0.6
粉煤灰 1.0 1.1 20.4 51.0 0.6 3.3 6.1 13.4
硅灰 0.6 0.5 0.2 96.2 0.8 0.8 0.4 0.1
珊瑚砂 1.0 1.1 2.5 41.9 0.7 0.9 45.8 3.2
), ArticleFig(id=1205914226732892953, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=EN, label=Table 2, caption=

Basic physical properties of coral sand

, figureFileSmall=null, figureFileBig=null, tableContent=
粒径范
围/mm
表观密度/
(kg·m-3)
堆积密度/
(kg·m-3)
空隙
率/%
饱和面干
观密度/
(kg·m-3)
饱和面
吸水
率/%
1.18~2.36 2 788.4 1 152.7 15.9 2 344.5 5.3
2.36~4.75 2 607.7 1 089.1 10.1 2 343.7 8.4
4.75~9.50 2 451.8 1 022.6
), ArticleFig(id=1205914226800001820, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=CN, label=表2, caption=

珊瑚砂的基本物理性质

, figureFileSmall=null, figureFileBig=null, tableContent=
粒径范
围/mm
表观密度/
(kg·m-3)
堆积密度/
(kg·m-3)
空隙
率/%
饱和面干
观密度/
(kg·m-3)
饱和面
吸水
率/%
1.18~2.36 2 788.4 1 152.7 15.9 2 344.5 5.3
2.36~4.75 2 607.7 1 089.1 10.1 2 343.7 8.4
4.75~9.50 2 451.8 1 022.6
), ArticleFig(id=1205914226862916383, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=EN, label=Table 3, caption=

Chemical composition in artificial seawater

, figureFileSmall=null, figureFileBig=null, tableContent=
成分 NaCl MgCl2 Na2SO4 CaCl2 KCl NaHCO3
含量/
(g·L-1)
24.5 5.2 4.1 1.2 0.7 0.2
), ArticleFig(id=1205914226946802465, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=CN, label=表3, caption=

人工海水中的化学成分

, figureFileSmall=null, figureFileBig=null, tableContent=
成分 NaCl MgCl2 Na2SO4 CaCl2 KCl NaHCO3
含量/
(g·L-1)
24.5 5.2 4.1 1.2 0.7 0.2
), ArticleFig(id=1205914227030688547, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=EN, label=Table 4, caption=

The mix ratio of seawater mixing alkali-activated slag material

, figureFileSmall=null, figureFileBig=null, tableContent=
试样类型 拌合水 原材料 激发剂模数(物质的量比)
[n(SiO2)∶n(Na2O)]
碱掺量(质量比)
[m(Na2O)∶m(原材料)]/%
水胶比 胶砂比
净浆 SW、DI 矿渣粉 1.3 4.0 0.4
砂浆 SW、DI 0.5 1∶3
), ArticleFig(id=1205914227101991717, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=CN, label=表4, caption=

海水拌合碱矿渣材料的配合比

, figureFileSmall=null, figureFileBig=null, tableContent=
试样类型 拌合水 原材料 激发剂模数(物质的量比)
[n(SiO2)∶n(Na2O)]
碱掺量(质量比)
[m(Na2O)∶m(原材料)]/%
水胶比 胶砂比
净浆 SW、DI 矿渣粉 1.3 4.0 0.4
砂浆 SW、DI 0.5 1∶3
), ArticleFig(id=1205914227177489192, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=EN, label=Table 5, caption=

The mix ratio of seawater mixing composite alkali-activated material

, figureFileSmall=null, figureFileBig=null, tableContent=
编号 矿渣粉/% 粉煤灰/% 硅灰/% 激发剂模数 水胶比 碱掺量/% 胶砂比
SLCM 100 0 0 1.3 0.5 4.0 0.8
FA30 70 30 0
FA30SF05 65 30 5
), ArticleFig(id=1205914227261375273, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1156908307576345356, language=CN, label=表5, caption=

海水拌合多元复合碱激发材料的配合比

, figureFileSmall=null, figureFileBig=null, tableContent=
编号 矿渣粉/% 粉煤灰/% 硅灰/% 激发剂模数 水胶比 碱掺量/% 胶砂比
SLCM 100 0 0 1.3 0.5 4.0 0.8
FA30 70 30 0
FA30SF05 65 30 5
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基于多元复合胶凝材料的海水碱激发材料的性能
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赵计辉 , 吴坤润 , 杨刚强
科学技术与工程 | 论文·一般工业技术 2025,25(1): 103-111
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科学技术与工程 | 论文·一般工业技术 2025, 25(1): 103-111
基于多元复合胶凝材料的海水碱激发材料的性能
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赵计辉 , 吴坤润, 杨刚强
作者信息
  • 中山大学土木工程学院, 广州 510275
  • 赵计辉(1985—),男,汉族,陕西咸阳人,博士,副教授。研究方向:绿色低碳建材及固废资源化利用。E-mail:

Properties of Seawater Alkali-activated Materials Based on Multi-component Composite Cementitious Materials
Ji-hui ZHAO , Kun-run WU, Gang-qiang YANG
Affiliations
  • School of Civil Engineering, Sun Yat-sen University, Guangzhou 510275, China
出版时间: 2025-01-08 doi: 10.12404/j.issn.1671-1815.2310037
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为了研究海水拌合碱激发材料性能,探讨了基于多元复合胶凝材料的海水拌合碱激发材料水化反应过程、力学与抗侵蚀等性能发展规律。结果表明:海水拌合对碱激发矿渣的水化反应过程具有一定的抑制作用,宏观上不同龄期的抗压强度也在一定程度上呈现降低趋势,不利于强度发展;粉煤灰和硅灰会降低海水拌合碱激发材料的水化反应速率、早期强度和韧性,但其后期强度及韧性增长潜力显著,其中硅灰-粉煤灰-矿渣三元体系7~28 d的强度与韧性增长率分别达到50.9%和86.7%。与碱激发矿渣相比,粉煤灰和硅灰的掺入会在一定程度上提高海水碱激发材料的电通量渗透性和氯离子迁移系数,这与其微观结构表现一致,但三者仍同属于一个氯离子渗透性等级,即中等渗透性等级(电通量法)。
海水  /  复合胶凝材料  /  碱激发材料  /  水化反应热  /  力学性能  /  氯离子渗透

In order to investigate the properties of seawater mixing alkali-activated materials, the development law of hydration reaction, mechanics and corrosion resistance of seawater alkali-activated materials based on multi-component composite cementitious materials was studied. The results show that seawater mixing has a certain inhibitory effect on the hydration reaction of alkali-activated slag, and the compressive strength of SLCM at different ages also shows a decreasing trend to a certain extent, which is not conducive to the development of strength. Fly ash and silica fume can reduce the hydration reaction rate, early strength and toughness of the seawater alkali-activated materials, but their strength and toughness increase potential is significant in the later period, in which the strength and toughness growth rate of the silica-fly ash-slag terpolymer system from 7 days to 28 days reaches 50.9% and 86.7%, respectively. Compared with alkali-activated slag, adding fly ash and silica fume can improve the electric flux permeability and chloride ion mobility coefficient of alkali excited materials in seawater to a certain extent, which is consistent with their microstructure, but the three still belong to the same chloride ion permeability grade, i.e., medium permeability grade (electric flux method).

seawater  /  composite cementitious materials  /  alkali-activated materials  /  heat of hydration reaction  /  mechanical property  /  chloride penetration
赵计辉, 吴坤润, 杨刚强. 基于多元复合胶凝材料的海水碱激发材料的性能. 科学技术与工程, 2025 , 25 (1) : 103 -111 . DOI: 10.12404/j.issn.1671-1815.2310037
Ji-hui ZHAO, Kun-run WU, Gang-qiang YANG. Properties of Seawater Alkali-activated Materials Based on Multi-component Composite Cementitious Materials[J]. Science Technology and Engineering, 2025 , 25 (1) : 103 -111 . DOI: 10.12404/j.issn.1671-1815.2310037
众所周知,水泥在生产过程中排出的大量CO2加剧了全球气候变暖,采用绿色环保的碱激发材料替代水泥具有深远意义。同时,中国在推进海洋经济建设中,工程材料所用的河砂、淡水等资源严重短缺,已远远不能满足海洋工程建设的需求。为了解决淡水资源短缺,有研究提出使用海水制备混凝土。Etxeberria等[1]研究表明,海水拌合可以改善水泥的力学性能,缩短水泥的凝结时间,增加水泥的干燥收缩率;Younis等[2]研究发现,使用海水制备混凝土会显著降低混凝土的和易性,减少初凝时间。一些研究表明海水会增加混凝土的早期强度,但对其长期强度有不利影响[3]。针对河砂骨料的匮乏,有一些学者提出采用丰富的海砂作为骨料来替代河砂。海砂是未来工程建设的重要资源[4]。宁博等[5]研究表明,相对于天然河砂,使用海砂制备的同等级高性能混凝土的早期强度发展迅速,工作性能更加优异。李田雨等[6]研究发现,海水、海砂中的氯离子可以加速水泥水化,使混凝土具备较高的早期强度。此外,还有一些学者提出使用珊瑚砂骨料来替代天然河砂。苏丽等[7]认为珊瑚砂的基本性能可以满足其作为混凝土骨料的基本要求。王建平等[8]研究表明,以珊瑚砂为细骨料制备的混凝土性能良好,珊瑚砂与水泥净浆结合紧密。这些学者的研究为海洋工程材料提供了新的思路,未来很有必要利用沿海及海洋中资源丰富的海砂、海水制备建筑工程材料。
使用海洋资源制备混凝土必须要考虑其抗腐蚀性能,对于岛礁工程在海洋环境中的腐蚀问题,有研究发现碱激发胶凝材料相比于普通硅酸盐水泥具有更好的耐久性,细化孔隙结构有助于碱激发胶凝材料抗腐蚀能力的提升。Roy等[9]和Ravikumar等[10]研究表明,随着碱激发矿渣体系中矿渣掺量的增加,抗氯离子渗透性能逐渐增强。Ismail等[11]研究表明,在碱激发矿渣体系中加入粉煤灰会使氯化物渗透性增加。Li等[12]研究表明,粉煤灰的掺入提高了碱矿渣的和易性,但降低了其强度和耐久性。陈乔等[13]研究表明,当掺入5%~15%的硅灰时,碱矿渣混凝土抗氯离子渗透性提高。Zheng等[14]研究表明,钠长石能促进碱矿渣的水化程度和C-A-S-H凝胶的生成。因此,多元复合的碱激发体系有可能达到更加优异的抗腐蚀性能,进行相关方面的研究十分必要。
目前,国内外学者对提升碱激发材料的性能作出了丰富的研究,但对于以珊瑚砂作为骨料的海水碱激发体系的研究相对较少。基于此,现以海水为拌合水、珊瑚砂为骨料,配制基于矿渣-粉煤灰-硅灰的多元复合碱激发材料体系,探究多元复合碱激发体系的水化过程、力学性能和抗腐蚀性能。
研究所用矿渣粉、粉煤灰、硅灰和珊瑚砂的化学组成和矿物组成分别如图1表1所示,其中珊瑚砂作为骨料使用,其经过破碎和筛分,形成D级配砂,即Ⅰ区中砂,细度模数为2.8,其基本物理性质如表2所示。
人工海水(sea water,SW)依据美国ASTM D1141-98 (2013)标准配制而成,具体化学成分如表3所示。
将固体颗粒的NaOH(纯度≥95%)、硅酸钠溶液(即水玻璃溶液,模数M=3.3,SiO2质量分数27.5%,Na2O质量分数8.25%)以及去离子水(deionized water,DI)或海水混合制备出所需模数下的碱激发剂。
试验的配合比设计分为两个部分。第一部分试验旨在探究海水拌合对碱激发材料水化反应过程与力学性能的影响,选用海水(SW)、去离子水(DI)作为拌合水制备碱激发矿渣胶凝材料,对照组为去离子水(DI)组。第一部分试验配合比设计如表4所示,以净浆试样测定48 h水化放热速率与放热总量曲线,以砂浆试样测试宏观力学强度。
第二部分试验旨在进行海水拌合多元复合碱激发材料的性能研究,设置三组试样分别表示纯矿渣体系(SLCM)、矿渣-粉煤灰二元复合体系(FA30)和矿渣-粉煤灰-硅灰三元复合体系(FA30SF05),配合比设计如表5所示。
1)单轴应力压缩试验法
采用岩石力学万能试验机开展单轴压缩试验,其型号为MTS E45.105。根据标准《岩石物理力学性能试验方法标准》,试件的尺寸为ϕ50 mm×100 mm的圆柱体试块,试验按照规范实施,位移控制的加载方式速率为0.5 mm/min。
2)电通量法
根据《普通混凝土长期性能和耐久性能试验方法标准》(GB/T 50082—2009)规程,采用电通量测定仪测定试样电通量,如图2所示。在标准养护室[温度为(20±2) ℃、湿度为95%±2%]养护至所需龄期后,将圆柱形试样切割成尺寸为ϕ100 mm×50 mm的试块。在测定电通量之前,使用去离子水以及利用真空饱水机对试块进行24 h的真空饱水处理。电通量测定仪器由固定好的饱水试块以及两侧的夹具组成,其中正电极注满0.3 mol/L NaOH溶液,负电极注满3% NaCl溶液。试件两侧布置有60 V的直流电压,每隔一段时间系统自动保存一次电流,以测得的6 h内的电量来评价渗透性高低。
3)快速电迁移法
根据NT Build 492规程,进行快速氯离子迁移试验(rapid chloride migration test,RCM),如图3所示。首先,准备尺寸为ϕ100 mm×50 mm的试样,养护至规定龄期。之后,在饱和氢氧化钙溶液中真空饱和24 h。在装好的试样和装置中,内槽内含有0.3 mol/L NaOH溶液,外槽内含有10% NaCl溶液,测试持续时间为13 h。在压力机上将试样劈裂成两半圆柱块,在断面上喷涂0.1 mol/L AgNO3溶液。
由于Ag+与Cl-和OH-离子分别反应生成白色的AgCl和深褐色的Ag2O,当氯离子存在时,白色氯化银与褐色氧化银在碱性孔溶液中析出,出现清晰可见的边界,由此可以观察并测定氯化物渗透深度,并通过式(1)计算氯离子迁移系数。
$\begin{aligned} D_{\mathrm{nssm}}= & \frac{0.0239(273+T) L}{(E-2) t} \times \\ & {\left[X_{\mathrm{d}}-0.0238 \sqrt{\frac{(273+T) L X_{\mathrm{d}}}{E-2}}\right] } \end{aligned}$
式(1)中:Dnssm为氯离子非稳态迁移系数,10-12m2/s;T为温度,℃;L为试件的厚度,mm;Xd为平均渗透深度,mm;E为电压,V;t为持续时间,h。
(1)等温量热分析法。为了表征浆体的凝结和硬化特点,预计水化升温情况,采用等温量热仪记录浆体放热情况。称取试样的原材料与装好的激发剂溶液,使用搅拌棒充分混合,然后将瓶置于等温量热仪中,记录48 h的水化放热情况。
(2)X射线衍射分析法(X-ray diffraction,XRD)。采用X射线多晶衍射仪对试样水化产物进行XRD扫描以进行定性分析,扫描范围为5°~90°,扫描速率为1(°)/ min,使用来自国际衍射数据中心和无机晶体结构数据库的数据分析XRD图谱。
(3)压汞法。采用压汞仪器进行测试,可以得到能够体现试样孔隙结构的相应参数,通常包括孔径分布、孔隙率以及平均孔径等。
(4)超景深三维可视化分析法。测试所用的仪器为DVM6超景深视频显微镜。测试原理是在z轴方向逐层采集图像并进行图像堆叠,渲染生成密度图或高度图, 最后达到试样表面微细观形貌的可视化效果。
以海水和去离子水分别作为拌合水,测定碱激发矿渣浆体的水化反应放热量,结果如图4所示。碱激发材料的放热过程也具有两个放热峰,前几分钟,矿渣与激发剂接触后迅速溶解,产生尖锐放热峰(A峰),铝硅酸盐前驱体逐渐溶解破坏,形成不稳定的[Si(OH)5]-和[Al(OH)4]-等初期产物。当铝硅酸盐的溶解过程发生到一定程度时,由于溶液中相关盐类物质的存在或离子浓度过高,溶解过程被抑制,水化放热速率下降[15]。由于发生了凝胶产物的缩聚、成核与扩展过程,水化放热速率在10 h左右达到第二个高峰(B峰)。B峰之后水化放热速率下降并趋于稳定,浆体逐渐硬化,形成致密的孔结构[16]
图4(a)所示,当使用海水作为拌合水时,A峰峰值有所降低,出峰时间在矿渣与激发剂接触3 min左右;B峰峰值由2.90 mW/g减弱为2.82 mW/g,出峰时间延长。从图4(b)可以看出,当使用海水作为拌合水时,0~48 h内的总放热量由133.97 J/g降低为127.14 J/g。该结果说明海水拌合对碱激发矿渣体系的水化反应具有一定的抑制作用。
以海水和去离子水分别作为拌合水的碱激发矿渣砂浆不同龄期的抗压强度如图5所示。由结果可知,去离子水组DI试样在不同龄期的强度比海水组SW试样分别高6.4% (3 d)、5.5%(7 d)、6.1%(28 d)和14.5%(56 d)。28 d龄期之后,SW试样的强度增长基本停止,而DI试样仍有强度增长潜力。由此说明海水拌合相比去离子水拌合不利于碱激发矿渣材料的强度发展,这一结果与早期水化反应放热曲线结果一致,这可能是由于海水中的一些盐类使碱激发矿渣的水化产物趋向于晶体化,使凝胶体形貌及化学组成发生改变[17]
按照表5中的配合比设计,纯矿渣粉(SLCM)、矿渣粉-粉煤灰(FA30)、矿渣粉-粉煤灰-硅灰(FA30SF05)3种胶材的碱激发材料的早期放热规律如图6 所示。在初始的几分钟,由于激发剂与胶凝材料接触,矿物相溶解释放出大量的溶解热;由于粉煤灰富含硅铝质矿物并含有一定的游离CaO,因而在前十几分钟内FA30二元体系放热速率和放热量最大。而FA30SF05三元体系因硅灰中的活性SiO2在早期难以溶解,故而所释放热量的速率最低。
在凝胶成核与扩展的过程中,3种碱激发材料在6~12 h内先后达到第二放热峰,其中相对于SLCM体系(3.6~3.7 mW/g),FA30二元体系的第二放热峰显著下降(仅为2.4~2.5 mW/g),而FA30SF05三元体系第二放热峰最低(仅为2.0~2.1 mW/g),对应的放热总量也是这个趋势,这主要是由于矿渣粉的活性较高,在早期更易与激发剂发生反应,形成较多凝胶产物,产生大量的热量。
SLCM、FA30和FA30SF05的应力-应变曲线如图7所示。由图7(a)图7(b)可以看出,试样在经历压密、弹性及塑性变形过程中其应力-应变曲线先呈现上凹,之后变为斜的直线,而后曲线呈现上凸直至逐渐破坏(弹塑性破坏)或到达极限荷载后立即破坏(脆性破坏),其中SLCM表现出弹塑性破坏,而FA30和FA30SF05基本表现出脆性破坏。由图8(a)可知,FA30在7 d和28 d的抗压强度分别比SLCM低20.4%、10.2%;FA30SF05在7 d和28 d的抗压强度分别比SLCM低48.1%、25.8%。在7~28 d期间, SLCM、FA30和FA30SF05的强度增长分别为5.6%、19.1%和50.9%,说明掺加有粉煤灰、硅灰的二元、三元复合胶凝材料体系的强度后期增长潜力较大。图8(b)为通过应力-应变规律分析求得的试样韧性T参数,其表示材料在塑性变形和断裂过程中吸收能量的能力。一般而言,韧性越好,则发生脆性断裂的可能性越小。由韧性T结果可以看出,SLCM的韧性最高,FA30和FA30SF05依次降低,但SLCM的韧性T随时间的延长为负增长(由123.8降至99.3,7~28 d的增长率为-19.8%),而FA30和FA30SF05的韧性T随时间逐渐提高,尤其是FA30SF05的7~28 d增长率达到86.7%,后期增长潜力显著。
采用DVM6三维超景深显微镜进一步观察SLCM、FA30和FA30SF05试样在力学试验破坏后断裂面的形貌结构,其结果如图9所示。超景深图像显示,很多珊瑚砂被周围浆体紧密地包裹在一起,其中,包裹程度最大的当属SLCM试样,裸露出的珊瑚砂颗粒较少,有着清晰可见的界面过渡区,3D的形貌图也较为平整,水化产物填充密实,这是由于纯矿渣体系在28 d时水化反应较为充分,黏结力强,宏观上也表现为力学性能较高。与此不同的是,FA30和FA30SF05断裂面存在着多孔的微组织和微颗粒,伴随着微裂纹;其中,在FA30SF05中珊瑚砂裸露出的颗粒非常的多,表明水化产物包裹的程度并不明显,其次,三维断裂面形貌图中出现凹凸不平的现象较为明显,这也是整体力学性能不及SLCM的体现。
采用电通量法对28 d龄期的SLCM、FA30和FA30SF05试样的电通量结果如图10所示。一般来说,试样的孔隙越大,可供外界带电荷的离子自由移动的空间就越大。当渗透到试样中的离子通量越多,意味着渗透性越高。由图10(a)可知,在6 h之内电通量随着时间的延长几乎呈线性增加。由图10(b)可知,电通量最高的是FA30SF05,其次是FA30,SLCM的电通量明显最低。
根据《混凝土耐久性检验评定标准》(JGJ/T 193—2009),按照通过电通量的大小,将氯离子渗透性等级可以分为“高”(电通量超过4 000 C)、“中等”(电通量在2 000~4 000 C)、“低”(电通量在1 000~2 000 C)和“很低”(电通量在100~1 000 C),电通量小于100 C的可以忽略。SLCM、FA30和FA30SF05的抗渗透等级均为中等渗透性等级,电通量水平层级并没有大的变化。二元和三元体系较纯矿渣体系会在一定程度上提高氯离子渗透性,这是因为粉煤灰和硅灰的存在使得拥有较好填充能力的C-A-S-H凝胶等水化产物相应减少,导致硬化浆体的不够致密,更多的氯离子可以渗透到基体中,但是总体影响程度并不大。
图11所示为试样的氯离子渗透深度示意图,由于氯离子渗透程度均不高,SLCM、FA30和FA30SF05的试件中氯化银的形成并显色不是特别明显,但仍然可以测定。当掺入粉煤灰时,氯离子渗透深度增加;当掺入硅灰时,氯离子渗透深度最深,试样的氯离子渗透深度变化趋势与电通量结果一致。由图12的氯离子迁移系数结果可知,SLCM、FA30和FA30SF05试件的非稳态迁移系数分别为2.3×10-12、4.8×10-12和6.6×10-12 m2/s。
如前文所述,在碱激发矿渣体系中,致密的结构得益于C-A-S-H凝胶的存在;而纯粉煤灰碱激发材料主要以N-A-S-H凝胶为主,N-A-S-H凝胶形成的孔隙结构比C-A-S-H凝胶形成的存在更多孔。一方面,粉煤灰-矿渣二元体系的钙含量降低,Ca/Si比降低,凝胶从致密的C-A-S-H结合凝胶变成了更多孔的(C-N)-A-S-H型凝胶;同时,碱的结合量增加,凝胶从周围孔隙溶液中吸引更多的碱阳离子,如钠离子,降低了孔隙溶液中的碱度。另一方面,由于N-A-S-H凝胶的多孔性,使得凝胶的比表面积增大,在物理吸附(静电或范德华力)氯离子能力比C-A-S-H凝胶要高,凝胶的表面电荷要大;当孔溶液水分蒸发后会留下氯盐沉淀,这也可能是28 d有着更高孔隙结构的原因。硅灰-粉煤灰-矿渣三元体系相比二元体系,钙含量降低,同时硅灰含有大量非晶态的SiO2,因此Ca/Si比进一步降低,C-A-S-H结合凝胶减少。一般来说,N-A-S-H凝胶具有多孔性,SiO2颗粒有助于填充凝胶等孔隙,同时一些SiO2可充当原材料使用,形成富硅的凝胶体。然而,在28 d龄期时,与C-A-S-H凝胶提供的致密性相比,硅灰的填充效果并不明显。同时,氯离子迁移系数有所增加,这与电通量以及体系微观结构变化一致[10,18-19]
(1)海水拌合对碱激发矿渣体系的水化反应进程具有一定的抑制作用,表现为海水拌合碱激发矿渣浆体的水化反应放热速率放缓,放热峰和48 h总热量降低,宏观上不同龄期的抗压强度也在一定程度呈现降低趋势,这与海水中一些盐类离子使产物形貌及组成发生改变有关。
(2)粉煤灰和硅灰的掺入会进一步降低海水拌合碱激发材料的水化反应速率,延缓早期力学强度的发展,表现为:FA30和FA30SF05的7 d抗压强度分别降低20.4%和48.1%;但其后期强度发展增长快,7 d和28 d的强度分别增长19.1%和50.9%,远高于SLCM纯矿渣体系的5.6%。
(3)粉煤灰和硅灰会降低海水拌合碱激发材料的早期韧性,但对照组SLCM的韧性随时间延长的增长率为负,而FA30和FA30SF05的韧性随时间显著增长,尤其FA30SF05的7~28 d增长率达到86.7%,后期增长潜力显著。
(4)与SLCM相比,FA30和FA30SF05会在一定程度上提高28 d龄期的海水拌合碱激发材料的电通量渗透性和氯离子迁移系数,这与其微观结构表现一致,但三者仍同属于一个氯离子渗透性等级,即中等渗透性等级(电通量法)。
  • 国家自然科学基金(52378280)
  • 广东省自然科学基金(2019A1515011981)
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doi: 10.12404/j.issn.1671-1815.2310037
  • 接收时间:2023-12-21
  • 首发时间:2025-07-29
  • 出版时间:2025-01-08
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  • 收稿日期:2023-12-21
  • 修回日期:2024-10-09
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国家自然科学基金(52378280)
广东省自然科学基金(2019A1515011981)
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    中山大学土木工程学院, 广州 510275
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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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