水滑石复合水泥基材料氯离子吸附能力的研究进展

摘要/Abstract

摘要： 以氯离子为诱导的钢筋锈蚀是造成混凝土耐久性问题的主要原因,其本质是氯离子通过材料基体的多孔结构在水泥基材料中扩散,并逐步迁移到钢筋表面,发生不利的物理化学反应。水滑石即层状双金属氢氧化物(LDHs)是一种新型延缓钢筋锈蚀的外掺材料,具有独特的层状结构和离子交换性质,可在特定的介质溶液中将客体阴离子与层间阳离子进行交换,达到吸附氯离子、延长混凝土结构服役寿命的目的。本文介绍了水滑石的结构性质、制备方法及氯离子吸附机理,总结了不同类型水滑石的氯离子吸附能力及相关研究成果。研究结果表明:水滑石复合水泥基材料的氯离子吸附性能受LDHs材料制备工艺、水泥基材料中孔隙液pH值及氯离子浓度影响,高温焙烧处理的水滑石对氯离子吸附效果更好;当LDHs掺量控制在1%~3%(质量分数)时,有利于改善水泥基材料的抗氯离子渗透性能。

关键词: 氯离子侵蚀, 水滑石, 水泥基材料, 氯离子吸附, 钢筋锈蚀, 离子交换

Abstract: Chloride ions induced corrosion of reinforcing steel is a major cause of concrete durability problems. The essence is that chloride ions diffuse through the porous structure of the material matrix in the cementitious material and gradually migrate to the surface of the reinforcing steel, where adverse physicochemical reactions occur. Hydrotalcite, known as layered double hydroxides (LDHs), is a new type of admixture to delay the corrosion of reinforcement. It has unique layered structure and ions exchange properties which ensures ion exchange between chloride ions and interlayer cations of LDHs and reaches the purpose of adsorption of chloride ions, thus extending the service life of concrete structures. This paper introduces the structural properties, modification method of hydrotalcite as well as its adsorption mechanisms on chloride ions, and summarizes the research results of recent years on the adsorption capacity of chloride ions through different modified hydrotalcite systems to improve the corrosion of steel reinforcement. The results indicate that the chloride ions adsorption capacity of hydrotalcite-based composite materials is mainly affected by LDHs preparation procedure, pH value of the pore solution and the chloride ions concentration. The chloride ions adsorption of calcined LDHs is more effective. When the addition of LDHs is 1%~3% (mass fraction), the resistance to chloride ions permeability of cement-based materials will be obviously improved.

Key words: chloride ions erosion, hydrotalcite, cement-based material, chloride ion adsorption, steel corrosion, ion exchange

中图分类号:

TU528

周丽娜, 蔡颖, 马财龙, 罗玲. 水滑石复合水泥基材料氯离子吸附能力的研究进展[J]. 硅酸盐通报, 2023, 42(4): 1137-1147.

ZHOU Lina, CAI Ying, MA Cailong, LUO Ling. Research Progress on Adsorption Capacity of Hydrotalcite for Chloride Ions in Cement-Based Materials[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2023, 42(4): 1137-1147.

参考文献

[1] 杨长辉, 晏宇, 欧忠文. 偏高岭土水泥净浆结合氯离子性能的研究[J]. 混凝土, 2010(10): 1-3+7.
YANG C H, YAN Y, OU Z W. Capability of cement paste binding chloride ions with metakaolin as admixture[J]. Concrete, 2010(10): 1-3+7 (in Chinese).
[2] TANG S W, YAO Y, ANDRADE C, et al. Recent durability studies on concrete structure[J]. Cement and Concrete Research, 2015, 78: 143-154.
[3] OTIENO M, BEUSHAUSEN H, ALEXANDER M. Chloride-induced corrosion of steel in cracked concrete-part I: experimental studies under accelerated and natural marine environments[J]. Cement and Concrete Research, 2016, 79: 373-385.
[4] XIONG C S, LI W H, JIN Z Q, et al. Preparation of phytic acid conversion coating and corrosion protection performances for steel in chlorinated simulated concrete pore solution[J]. Corrosion Science, 2018, 139: 275-288.
[5] JIN Z Q, CHANG H L, DU F Y, et al. Influence of SAP on the chloride penetration and corrosion behavior of steel bar in concrete[J]. Corrosion Science, 2020, 171: 108714.
[6] CHEN C, JIANG L H, GUO M Z, et al. Effect of sulfate ions on corrosion of reinforced steel treated by DNA corrosion inhibitor in simulated concrete pore solution[J]. Construction and Building Materials, 2019, 228: 116752.
[7] GOMES C, MIR Z M, BASTOS A C, et al. Effect of layered double hydroxides on the performance and service life of reinforced concrete[C]// Conference on Durable Concrete for Infrastructure under Severe Conditions-Smart Admixtures, Self-Responsiveness and Nanoadditions, Ghent, Belgium, September, 2019, 10-11.
[8] MIR Z M, BASTOS A, HÖCHE D, et al. Recent advances on the application of layered double hydroxides in concrete-a review[J]. Materials (Basel, Switzerland), 2020, 13(6): 1426.
[9] TATEMATSU H, SASAKI T. Repair materials system for chloride-induced corrosion of reinforcing bars[J]. Cement and Concrete Composites, 2003, 25(1): 123-129.
[10] RAKI L, BEAUDOIN J J, MITCHELL L. Layered double hydroxide-like materials: nanocomposites for use in concrete[J]. Cement and Concrete Research, 2004, 34(9): 1717-1724.
[11] HONG S X, QIN S F, LIU Z M, et al. Enhanced corrosion resistance and applicability of Mg/Al-CO^2-₃ layered double hydroxide film on Q235 steel substrate[J]. Construction and Building Materials, 2021, 276: 122259.
[12] CHEN M Z, WEI Y N, ZHENG H B, et al. Ca-LDH-modified cementitious coating to enhance corrosion resistance of steel bars[J]. Journal of Building Engineering, 2022, 51: 104301.
[13] OESTREICHER V, JOBBÁGY M, REGAZZONI A E. Halide exchange on Mg(II)-Al(III) layered double hydroxides: exploring affinities and electrostatic predictive models[J]. Langmuir: the ACS Journal of Surfaces and Colloids, 2014, 30(28): 8408-8415.
[14] SJÅSTAD A O, ANDERSEN N H, VAJEESTON P, et al. On the thermal stability and structures of layered double hydroxides Mg_1-xAl_x(OH)₂(NO₃)_x·mH₂O (0.18≤x≤0.38)[J]. European Journal of Inorganic Chemistry, 2015, 2015(10): 1775-1788.
[15] YANG Z X, FISCHER H, CEREZO J, et al. Aminobenzoate modified MgAl hydrotalcites as a novel smart additive of reinforced concrete for anticorrosion applications[J]. Construction and Building Materials, 2013, 47: 1436-1443.
[16] 孙远. 不同形貌水滑石及其焙烧产物的离子吸附性能研究[D]. 哈尔滨: 哈尔滨工业大学, 2019.
SUN Y. Research on ion adsorption properties of hydrotalcite with different morphologies and its calcined products[D]. Harbin: Harbin Institute of Technology, 2019 (in Chinese).
[17] BALONIS M, GLASSER F P. Calcium nitrite corrosion inhibitor in Portland cement: influence of nitrite on chloride binding and mineralogy[J]. Journal of the American Ceramic Society, 2011, 94(7): 2230-2241.
[18] YE H L. Autogenous formation and smart behaviors of nitrite- and nitrate-intercalated layered double hydroxides (LDHs) in Portland cement-metakaolin-dolomite blends[J]. Cement and Concrete Research, 2021, 139: 106267.
[19] COSTA D G, ROCHA A B, SOUZA W F, et al. Comparative structural, thermodynamic and electronic analyses of Zn-Al-Aⁿ- hydrotalcite-like compounds (A^n-=Cl^-, F^-, Br^-, OH^-, CO^2-₃ or NO^-₃): an ab initio study[J]. Applied Clay Science, 2012, 56: 16-22.
[20] NEVILLE A. Chloride attack of reinforced concrete: an overview[J]. Materials and Structures, 1995, 28(2): 63-70.
[21] JUSTNE H. A review of chloride binding in cementitious systems[J]. Nordic Concrete Research, 1998, 21: 48-63.
[22] PROVIS J L, BERNAL S A. Geopolymers and related alkali-activated materials[J]. Annual Review of Materials Research, 2014, 44: 299-327.
[23] BERNAL S A, SAN NICOLAS R, MYERS R J, et al. MgO content of slag controls phase evolution and structural changes induced by accelerated carbonation in alkali-activated binders[J]. Cement and Concrete Research, 2014, 57: 33-43.
[24] 许闯, 张祖华, 陈慕翀, 等. 层状双金属氢氧化物在水泥混凝土中的形成、作用机制及应用[J]. 材料导报, 2022, 36(11): 99-105.
XU C, ZHANG Z H, CHEN M C, et al. Formation, interaction mechanisms and application of layered double hydroxides in cement concrete[J]. Materials Reports, 2022, 36(11): 99-105 (in Chinese).
[25] VACCARI A. Layered double hydroxides: present and future[J]. Applied Clay Science, 2002, 22(1/2): 75-76.
[26] DUAN X, EVANS D G. Layered double hydroxides: application of layered double hydroxides[J]. Structure and Bonding, 2006, 119: 193-223.
[27] 朱清, 李成胜, 周建成. 镁铝水滑石的共沉淀法制备及表征[J]. 化工时刊, 2017, 31(4): 1-3+17.
ZHU Q, LI C S, ZHOU J C. The Co-precipitation preparation and properties of inorganic hydrotalcite[J]. Chemical Industry Times, 2017, 31(4): 1-3+17 (in Chinese).
[28] CAO L, GUO J T, TIAN J H, et al. Preparation of Ca/Al-layered double hydroxide and the influence of their structure on early strength of cement[J]. Construction and Building Materials, 2018, 184: 203-214.
[29] LIU Z P, MA R Z, OSADA M, et al. Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies[J]. Journal of the American Chemical Society, 2006, 128(14): 4872-4880.
[30] 张骄佼, 田森林, 周键. 镁铝水滑石的合成与应用研究进展[J]. 材料导报, 2013, 27(7): 144-148.
ZHANG J J, TIAN S L, ZHOU J. Study on synthesis and application of Mg-Al hydrotalcite[J]. Materials Review, 2013, 27(7): 144-148 (in Chinese).
[31] 吴波. 阻锈阴离子插层改性水滑石的制备及其在水泥砂浆中的应用[D]. 深圳: 深圳大学, 2019.
WU B. Preparation of inhibitor ions intercalation modified hydrotalcite and its application in cement mortar[D]. Shenzhen: Shenzhen University, 2019 (in Chinese).
[32] CHEN M Z, WU F, YU L W, et al. Chloride binding capacity of LDHs with various divalent cations and divalent to trivalent cation ratios in different solutions[J]. CrystEngComm, 2019, 21(44): 6790-6800.
[33] 杨成梅, 谢竺. 水滑石/粉煤灰对注浆早强性能的影响研究[J]. 化学与粘合, 2021, 43(1): 48-51.
YANG C M, XIE Z. Research on the effect of hydrotalcite/fly ash on the early strength of cement grouting[J]. Chemistry and Adhesion, 2021, 43(1): 48-51 (in Chinese).
[34] VON HOESSLE F, PLANK J, LEROUX F. Intercalation of sulfonated melamine formaldehyde polycondensates into a hydrocalumite LDH structure[J]. Journal of Physics and Chemistry of Solids, 2015, 80: 112-117.
[35] YANG Z, FISCHER H, CEREZO J, et al. Modified hydrotalcites for improved corrosion protection of reinforcing steel in concrete-preparation, characterization, and assessment in alkaline chloride solution[J]. Materials and Corrosion, 2016, 67(7): 721-738.
[36] 段平. 层状双氢氧化物改善混凝土耐久性能的机理及其应用研究[D]. 武汉: 武汉理工大学, 2014.
DUAN P. Research on modification mechanism and the application of layered double hydroxides for durability of concrete[D]. Wuhan: Wuhan University of Technology, 2014 (in Chinese).
[37] SHUI Z H, YU R, CHEN Y X, et al. Improvement of concrete carbonation resistance based on a structure modified layered double hydroxides (LDHs): experiments and mechanism analysis[J]. Construction and Building Materials, 2018, 176: 228-240.
[38] HANG T T X, TRUC T A, DUONG N T, et al. Layered double hydroxides as containers of inhibitors in organic coatings for corrosion protection of carbon steel[J]. Progress in Organic Coatings, 2012, 74(2): 343-348.
[39] NAKAYAMA H, WADA N, TSUHAKO M. Intercalation of amino acids and peptides into Mg-Al layered double hydroxide by reconstruction method[J]. International Journal of Pharmaceutics, 2004, 269(2): 469-478.
[40] ZUO J D, WU B, LUO C Y, et al. Preparation of MgAl layered double hydroxides intercalated with nitrite ions and corrosion protection of steel bars in simulated carbonated concrete pore solution[J]. Corrosion Science, 2019, 152: 120-129.
[41] XU J X, SONG Y B, ZHAO Y H, et al. Chloride removal and corrosion inhibitions of nitrate, nitrite-intercalated MgAl layered double hydroxides on steel in saturated calcium hydroxide solution[J]. Applied Clay Science, 2018, 163: 129-136.
[42] XU J X, TAN Q P, MEI Y J. Corrosion protection of steel by Mg-Al layered double hydroxides in simulated concrete pore solution: effect of SO^2-₄[J]. Corrosion Science, 2020, 163: 108223.
[43] CHEN Y X, SHUI Z H, CHEN W, et al. Chloride binding of synthetic Ca-Al-NO₃ LDHs in hardened cement paste[J]. Construction and Building Materials, 2015, 93: 1051-1058.
[44] YOON S, MOON J, BAE S, et al. Chloride adsorption by calcined layered double hydroxides in hardened Portland cement paste[J]. Materials Chemistry and Physics, 2014, 145(3): 376-386.
[45] 唐聿明, 牛乐, 左禹. 焙烧水滑石对含氯中性化混凝土孔隙液中钢筋腐蚀行为的影响[J]. 电化学, 2010, 16(4): 368-372.
TANG Y M, NIU L, ZUO Y. Effect of CLDH on rebar corrosion behavior in chloride contaminated neutral pore solutions[J]. Electrochemistry, 2010, 16(4): 368-372 (in Chinese).
[46] 牛乐. 焙烧水滑石(CLDH)对氯离子存在下钢筋腐蚀行为的影响[D]. 北京: 北京化工大学, 2010.
NIU L. Effect of calcined hydrotalcite (CLDH) on the corrosion of rebar by chloride[D]. Beijing: Beijing University of Chemical Technology, 2010 (in Chinese).
[47] 胡静, 吕亮. 焙烧镁铝碳酸根水滑石对氯离子吸附机理研究[J]. 化学工程与装备, 2008(3): 26-29.
HU J, LV L. Study on adsorption mechanism of chloride ion by calcined Mg-Al-carbonate hydrotalcite[J]. Chemical Engineering & Equipment, 2008(3): 26-29 (in Chinese).
[48] 张琳. 镁铝水滑石的制备及其焙烧产物在水泥净浆中固化氯离子性能研究[D]. 衡阳: 南华大学, 2018.
ZHANG L. Synthesis of Mg-Al layered double hydroxides and their adsorption capabilityof chloride ion in cement paste[D]. Hengyang: University of South China, 2018 (in Chinese).
[49] RAJAMALLU C, CHANDRASEKHAR REDDY T, ARUNAKANTHI E. Service life prediction of self compacted concretes with respect to chloride ion penetration[J]. Materials Today: Proceedings, 2021, 46: 677-681.
[50] 王佩. 焙烧水滑石水泥基复合材料抗盐冻性能研究[D]. 西安: 长安大学, 2020.
WANG P. Study on salt freezing resistance of calcined hydrotalcite cement-based composites[D]. Xi’an: Chang’an University, 2020 (in Chinese).
[51] 段平, 严春杰, 陈伟, 等. 层状双氢氧化物对混凝土抗碳化性能的影响[J]. 硅酸盐学报, 2014, 42(8): 1037-1041.
DUAN P, YAN C J, CHEN W, et al. Influence of layered double hydroxides on carbonation resistance of concrete[J]. Journal of the Chinese Ceramic Society, 2014, 42(8): 1037-1041 (in Chinese).
[52] MA J T, DUAN P, REN D M, et al. Effects of layered double hydroxides incorporation on carbonation resistance of cementitious materials[J]. Journal of Materials Research and Technology, 2019, 8(1): 292-298.
[53] LIU T, CHEN Y X, YU Q L, et al. Effect of MgO, Mg-Al-NO₃ LDH and calcined LDH-CO₃ on chloride resistance of alkali activated fly ash and slag blends[J]. Construction and Building Materials, 2020, 250: 118865.
[54] 冯跃, 耿健, 李东. 焙烧水滑石对砂浆中氯离子渗透的影响[J]. 硅酸盐通报, 2018, 37(4): 1195-1199.
FENG Y, GENG J, LI D. Influence of calcined hydrotalcite on chloride penetration in mortar[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(4): 1195-1199 (in Chinese).
[55] WANG J, HUANG B, MAO Z Y, et al. Study on adsorption properties of calcined Mg-Al hydrotalcite for sulfate ion and chloride ion in cement paste[J]. Materials (Basel, Switzerland), 2021, 14(4): 994.
[56] 宋学锋, 张俊涛, 崔贺龙, 等. 热处理水滑石对普通硅酸盐水泥和碱矿渣水泥抗碳化性能的影响[J]. 硅酸盐通报, 2019, 38(11): 3379-3384.
SONG X F, ZHANG J T, CUI H L, et al. Effect of calcined layered double hydroxides on carbonation resistance of ordinary Portland cement and alkali-activated slag cement[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(11): 3379-3384 (in Chinese).
[57] 李战国, 刘金鹏, 于鹏超, 等. 水滑石类化合物对混凝土物理力学性能影响的探索研究[J]. 建筑技术开发, 2017, 44(17): 95-97.
LI Z G, LIU J P, YU P C, et al. Exploratory research of layered double hydroxides on physical and mechanical properties of concrete[J]. Building Technology Development, 2017, 44(17): 95-97 (in Chinese).
[58] 马军涛. LDHs-MK复合防御体系改性混凝土及其机理研究[D]. 武汉: 武汉理工大学, 2012.
MA J T. Researches on modification and mechanism of LDHs-MK compound defence system in concrete[D]. Wuhan: Wuhan University of Technology, 2012 (in Chinese).
[59] HU Y R, LI H H, WANG Q, et al. Characterization of LDHs prepared with different activity MgO and resisting Cl^- attack of concrete in salt lake brine[J]. Construction and Building Materials, 2019, 229: 116921.
[60] YANG Z X, FISCHER H, POLDER R. Laboratory investigation of the influence of two types of modified hydrotalcites on chloride ingress into cement mortar[J]. Cement and Concrete Composites, 2015, 58: 105-113.
[61] MA J T, WANG D G, CHEN H, et al. Chloride absorption behavior of layered double hydroxides in chloride environment[J]. Journal of Testing and Evaluation, 2020, 48(3): 20190062.
[62] WANG X H, XU J X, TAN Q P. Effect of nitrite intercalated Mg-Al layered double hydroxides on mortar durability under Cl^- and SO^2-₄ coexisting environment[J]. Journal of Central South University, 2022, 29(2): 546-560.
[63] PARKER L M, MILESTONE N B, NEWMAN R H. The use of hydrotalcite as an anion absorbent[J]. Industrial & Engineering Chemistry Research, 1995, 34(4): 1196-1202.
[64] TSUJIMURA A, UCHIDA M, OKUWAKI A. Synthesis and sulfate ion-exchange properties of a hydrotalcite-like compound intercalated by chloride ions[J]. Journal of Hazardous Materials, 2007, 143(1/2): 582-586.
[65] CAO Y H, DONG S G, ZHENG D J, et al. Multifunctional inhibition based on layered double hydroxides to comprehensively control corrosion of carbon steel in concrete[J]. Corrosion Science, 2017, 126: 166-179.
[66] CHEN Z J, YE H L. Sequestration and release of nitrite and nitrate in alkali-activated slag: a route toward smart corrosion control[J]. Cement and Concrete Research, 2021, 143: 106398.
[67] YANG L, CHEN M X, LU Z Y, et al. Synthesis of CaFeAl layered double hydroxides 2D nanosheets and the adsorption behaviour of chloride in simulated marine concrete[J]. Cement and Concrete Composites, 2020, 114: 103817.
[68] GOMES C, MIR Z, SAMPAIO R, et al. Use of ZnAl-layered double hydroxide (LDH) to extend the service life of reinforced concrete[J]. Materials (Basel, Switzerland), 2020, 13(7): 1769.
[69] CAO Y H, ZHENG D J, ZHANG F, et al. Layered double hydroxide (LDH) for multi-functionalized corrosion protection of metals: a review[J]. Journal of Materials Science & Technology, 2022, 102: 232-263.
[70] 田玉琬, 文成, 莫湾湾, 等. Zn-Al-NO₂ LDH对海洋工程中碳钢钢筋的腐蚀抑制规律[J]. 广东海洋大学学报, 2020, 40(3): 122-133.
TIAN Y W, WEN C, MO W W, et al. Corrosion inhibition effect of Zn-Al-NO₂ LDH on carbon steel reinforcement in marine engineering[J]. Journal of Guangdong Ocean University, 2020, 40(3): 122-133 (in Chinese).
[71] KE X Y, BERNAL S A, PROVIS J L. Uptake of chloride and carbonate by Mg-Al and Ca-Al layered double hydroxides in simulated pore solutions of alkali-activated slag cement[J]. Cement and Concrete Research, 2017, 100: 1-13.
[72] KAYALI O, KHAN M S H, SHARFUDDIN AHMED M. The role of hydrotalcite in chloride binding and corrosion protection in concretes with ground granulated blast furnace slag[J]. Cement and Concrete Composites, 2012, 34(8): 936-945.
[73] 陈宇轩, 水中和, 陈伟, 等. LDHs改性偏高岭土基地聚物涂料对混凝土耐久性的影响研究[J]. 硅酸盐通报, 2015, 34(7): 1968-1973.
CHEN Y X, SHUI Z H, CHEN W, et al. Effect of LDHs modified MK-based geopolymer coating on durability of concrete[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(7): 1968-1973 (in Chinese).
[74] 陈国玮, 水中和, 段平, 等. 插层材料-偏高岭土复合改性混凝土抗硫酸盐侵蚀[J]. 武汉理工大学学报, 2014, 36(8): 1-5.
CHEN G W, SHUI Z H, DUAN P, et al. Combination of LDHs and metakaolin for improving the sulfate ion resistance of concrete[J]. Journal of Wuhan University of Technology, 2014, 36(8): 1-5 (in Chinese).