热浸镀锌层在不同pH值饱和Ca（OH）_2溶液中的腐蚀行为
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摘要
钢筋混凝土结构的过早失效大多是由于其中的钢筋腐蚀所致。混凝土中存在孔隙,孔隙液主要为饱和的Ca(OH)_2溶液,pH值一般在12~13.5之间,钢筋处于钝化状态。当混凝土碳化(空气中的二氧化碳通过混凝土中的毛细孔道,与混凝土孔隙液中的Ca(OH)_2进行中和反应生成CaCO3)时,孔隙液pH值下降,钢筋处于非钝化状态,腐蚀加快。热浸镀锌是保护混凝土钢筋的重要方法之一,在国内外已有较多的应用和研究,但对孔隙液pH值变化后,热镀锌层和植入混凝土时生成保护作用的锌酸钙(CaHZn)膜层的变化及其腐蚀规律的细节尚不太清楚。
本文以pH值9~13.5的饱和Ca(OH)_2溶液模拟混凝土孔隙液,系统地研究了热浸镀锌层在这些模拟孔隙液中的腐蚀行为,对浸泡后的试样进行塔菲尔线性极化和电化学阻抗谱测试分析,同时对不同状态下的腐蚀产物进行SEM观察微观组织形貌、EDS成分测定及X射线相分析分析,系统地研究了热浸镀锌层和覆盖锌酸钙的热镀锌层在不同pH值模拟混凝土孔隙液中浸泡过程中的腐蚀产物的形成规律、显微结构、溶解转化规律和电化学腐蚀特点。研究表明:
热镀锌层在pH为12.5的模拟孔隙液中生成致密的锌酸钙保护层,锌酸钙的稳定性与孔隙液的pH值密切相关。当pH值为9~12时,随着pH降低和浸泡时间增加,锌层上CaHZn减少而Zn(OH)_2增加(Zn(OH)_2经干燥脱水可转变为ZnO),当pH值为9时,覆盖层可全部转化为Zn(OH)_2;当pH为12~13时,锌层表面生成少量片状的锌酸钙膜;试样的自腐蚀电流icorr随锌酸钙增多而减小;上述情况下锌层均处于钝化状态, icorr小于或接近0.1μA/cm2;随着CaHZn减少和Zn(OH)_2增加,极化电阻(Rp)、膜层电阻(Rc)、穿透电阻(Rct)和扩散电阻(Ws)均降低;当pH值为12.5~ 13.5时,随pH升高和浸泡时间增加,锌酸钙溶解但不生成Zn(OH)_2覆盖,残留的锌酸钙随pH升高而迅速减少,当pH值为13.5,锌层表面不生成保护膜,icorr显著增到102μA/cm2,腐蚀显著加快。
对于在上述模拟孔隙液中浸泡的已覆盖锌酸钙的热镀锌层,随pH降低和浸泡时间增加,锌层上锌酸钙减少而Zn(OH)_2增加,当pH值为9时,覆盖层可全部转化为Zn(OH)_2;随着锌酸钙减少和Zn(OH)_2增加,极化电阻(Rp)、膜层电阻(Rc)、穿透电阻(Rct)和扩散阻抗(Ws)均降低,而自腐蚀电流密度icorr增大,但icorr仍接近钢筋钝化临界值0.1μA/cm2。当pH值大于12.5,锌酸钙逐渐溶解,腐蚀加快情况与热镀锌层相似。
当混凝土发生碳化,混凝土孔隙液pH值降低,只要pH值小于13,热浸镀锌层和覆盖锌酸钙的热镀锌层均具有很高的耐蚀性,能够保护钢筋数十年免遭腐蚀破坏;但在采用高碱度水泥,pH值大于13的混凝土孔隙液中,热浸镀锌层和覆盖锌酸钙的热镀锌层的耐蚀性显著下降,不能对钢筋提供有效地防腐保护。故热浸镀锌钢筋在采用非高碱度水泥的混凝土时具有低成本、高抗蚀防腐保护的特点,值得在实际生产中推广。
Premature failure of reinforced concrete structures are mostly caused by the corrosion of rebars embedded in the concrete. There are some pores exsited in the concrete, with the pore solution mainly composed of saturated Ca(OH)_2, and has the pH value ranges from 12 to 13.5, the rebars is passivation. If the pore solution is carbonized by carbon dioxide via conversing Ca(OH)_2 to CaCO3, the pH value will decrease, the rebars is depassivation, and the corrosion rate is increased. Hot-dip galvanizing is one of the most effective ways to protect rebars from corrosion, and has been gained much application and study home and obroad. However, detailes on the affection caused by diversification of pH value on galvanizing layer and protective calcium hydroxyzincate (CaHZn) which formed during the process of the dipping in the saturated Ca(OH)_2 have not been clearly reported.
In this paper, the corrosion product forming mechanism, microstructure, and transformation of corrosion product dissolving and corrosion resistance have been detected by the systemic work below: the samples of hot dip galvanizing and covered with protective calcium hydroxyzincate layer have respectively been put into the saturated Ca(OH)_2 solution deploying in different pH value; after dipping, the samples were investigated with the electrochemical test analysis using a three-electrode system; the morphology of corrosion product formed under different pH conditions were observed by SEM, the composite and phase were analysed by EDS and XRD. The results have shown that:
The surface of galvanizing samples dipped in the saturated Ca(OH)_2 solution with pH value of 12.5 will be covered with stable protective CaHZn layer after a period, the property of which is influenced also by the pH value. As the pH value decreases from 12 to 9 and as the immersion time increases, the CaHZn decreases while Zn(OH)_2 (changes to ZnO when dried and dehydrated) increases on the surface. The cover is totally composed of Zn(OH)_2 when pH=9; When the pH value is in the range of 12~13, there is few chip CaHZn on the zinc layer, and icorr decreases as the amount of CaHZn increases; The zinc layer is passivate under both condition above, and icorr is less than or close to 0.1μA/cm2; As the CaHZn becomes fewer and the Zn(OH)_2 getting more and more, the value of polarization resistance (Rp), film resistance (Rc), penetration resistance (Rct) and the diffusion resistance (Ws) become lower, meanwhile, the corrosion current density increases; From 12.5~13.5, as the increase of pH value and dipping time, the CaHZn gets dissolved quickly without Zn(OH)_2 existed. When pH value is 13.5, no protective corrosion products can be found on the surface, and the self-corrosion current grows ripidly to 100μA/cm~2, the corrosion rate is accelerated remarkably.
For the above zinc layer coverd by CaHZn immersed in the saturated solution, CaHZn decreases and Zn(OH)_2 increases as the increase of pH value and dipping time. The cover is Zn(OH)_2 when the pH value reachs 9; As the CaHZn becomes fewer and the Zn(OH)_2 getting more and more, the value of polarization resistance (Rp), film resistance (Rc), penetration resistance (Rct) and the diffusion resistance (Ws) become lower, meanwhile, the corrosion current density increases, but is still close to the threshold value of 10-1μA/cm~2. CaHZn is dissoluted gradually, and the corrosion rate is increased when pH>12.5, which is similar to that of hot-dipped steel.
Carbonization can decrease the pH value, but the galvanizing layer with and without CaHZn still have better corrosion resistance to protect steel from corrosion damage; high alkalinity cement using can increase the pH value of pore solution, and the corrosion resistance of the surface cover on the steel sharply decreases which can not provide effective protection to steel anymore. Therefore, if hot-dip galvanizing steel is not used in high alkalinity cement concrete, it is worth being promoted in practical products with low cost, strong corrosion resistance.
本文以pH值9~13.5的饱和Ca(OH)_2溶液模拟混凝土孔隙液,系统地研究了热浸镀锌层在这些模拟孔隙液中的腐蚀行为,对浸泡后的试样进行塔菲尔线性极化和电化学阻抗谱测试分析,同时对不同状态下的腐蚀产物进行SEM观察微观组织形貌、EDS成分测定及X射线相分析分析,系统地研究了热浸镀锌层和覆盖锌酸钙的热镀锌层在不同pH值模拟混凝土孔隙液中浸泡过程中的腐蚀产物的形成规律、显微结构、溶解转化规律和电化学腐蚀特点。研究表明:
热镀锌层在pH为12.5的模拟孔隙液中生成致密的锌酸钙保护层,锌酸钙的稳定性与孔隙液的pH值密切相关。当pH值为9~12时,随着pH降低和浸泡时间增加,锌层上CaHZn减少而Zn(OH)_2增加(Zn(OH)_2经干燥脱水可转变为ZnO),当pH值为9时,覆盖层可全部转化为Zn(OH)_2;当pH为12~13时,锌层表面生成少量片状的锌酸钙膜;试样的自腐蚀电流icorr随锌酸钙增多而减小;上述情况下锌层均处于钝化状态, icorr小于或接近0.1μA/cm2;随着CaHZn减少和Zn(OH)_2增加,极化电阻(Rp)、膜层电阻(Rc)、穿透电阻(Rct)和扩散电阻(Ws)均降低;当pH值为12.5~ 13.5时,随pH升高和浸泡时间增加,锌酸钙溶解但不生成Zn(OH)_2覆盖,残留的锌酸钙随pH升高而迅速减少,当pH值为13.5,锌层表面不生成保护膜,icorr显著增到102μA/cm2,腐蚀显著加快。
对于在上述模拟孔隙液中浸泡的已覆盖锌酸钙的热镀锌层,随pH降低和浸泡时间增加,锌层上锌酸钙减少而Zn(OH)_2增加,当pH值为9时,覆盖层可全部转化为Zn(OH)_2;随着锌酸钙减少和Zn(OH)_2增加,极化电阻(Rp)、膜层电阻(Rc)、穿透电阻(Rct)和扩散阻抗(Ws)均降低,而自腐蚀电流密度icorr增大,但icorr仍接近钢筋钝化临界值0.1μA/cm2。当pH值大于12.5,锌酸钙逐渐溶解,腐蚀加快情况与热镀锌层相似。
当混凝土发生碳化,混凝土孔隙液pH值降低,只要pH值小于13,热浸镀锌层和覆盖锌酸钙的热镀锌层均具有很高的耐蚀性,能够保护钢筋数十年免遭腐蚀破坏;但在采用高碱度水泥,pH值大于13的混凝土孔隙液中,热浸镀锌层和覆盖锌酸钙的热镀锌层的耐蚀性显著下降,不能对钢筋提供有效地防腐保护。故热浸镀锌钢筋在采用非高碱度水泥的混凝土时具有低成本、高抗蚀防腐保护的特点,值得在实际生产中推广。
Premature failure of reinforced concrete structures are mostly caused by the corrosion of rebars embedded in the concrete. There are some pores exsited in the concrete, with the pore solution mainly composed of saturated Ca(OH)_2, and has the pH value ranges from 12 to 13.5, the rebars is passivation. If the pore solution is carbonized by carbon dioxide via conversing Ca(OH)_2 to CaCO3, the pH value will decrease, the rebars is depassivation, and the corrosion rate is increased. Hot-dip galvanizing is one of the most effective ways to protect rebars from corrosion, and has been gained much application and study home and obroad. However, detailes on the affection caused by diversification of pH value on galvanizing layer and protective calcium hydroxyzincate (CaHZn) which formed during the process of the dipping in the saturated Ca(OH)_2 have not been clearly reported.
In this paper, the corrosion product forming mechanism, microstructure, and transformation of corrosion product dissolving and corrosion resistance have been detected by the systemic work below: the samples of hot dip galvanizing and covered with protective calcium hydroxyzincate layer have respectively been put into the saturated Ca(OH)_2 solution deploying in different pH value; after dipping, the samples were investigated with the electrochemical test analysis using a three-electrode system; the morphology of corrosion product formed under different pH conditions were observed by SEM, the composite and phase were analysed by EDS and XRD. The results have shown that:
The surface of galvanizing samples dipped in the saturated Ca(OH)_2 solution with pH value of 12.5 will be covered with stable protective CaHZn layer after a period, the property of which is influenced also by the pH value. As the pH value decreases from 12 to 9 and as the immersion time increases, the CaHZn decreases while Zn(OH)_2 (changes to ZnO when dried and dehydrated) increases on the surface. The cover is totally composed of Zn(OH)_2 when pH=9; When the pH value is in the range of 12~13, there is few chip CaHZn on the zinc layer, and icorr decreases as the amount of CaHZn increases; The zinc layer is passivate under both condition above, and icorr is less than or close to 0.1μA/cm2; As the CaHZn becomes fewer and the Zn(OH)_2 getting more and more, the value of polarization resistance (Rp), film resistance (Rc), penetration resistance (Rct) and the diffusion resistance (Ws) become lower, meanwhile, the corrosion current density increases; From 12.5~13.5, as the increase of pH value and dipping time, the CaHZn gets dissolved quickly without Zn(OH)_2 existed. When pH value is 13.5, no protective corrosion products can be found on the surface, and the self-corrosion current grows ripidly to 100μA/cm~2, the corrosion rate is accelerated remarkably.
For the above zinc layer coverd by CaHZn immersed in the saturated solution, CaHZn decreases and Zn(OH)_2 increases as the increase of pH value and dipping time. The cover is Zn(OH)_2 when the pH value reachs 9; As the CaHZn becomes fewer and the Zn(OH)_2 getting more and more, the value of polarization resistance (Rp), film resistance (Rc), penetration resistance (Rct) and the diffusion resistance (Ws) become lower, meanwhile, the corrosion current density increases, but is still close to the threshold value of 10-1μA/cm~2. CaHZn is dissoluted gradually, and the corrosion rate is increased when pH>12.5, which is similar to that of hot-dipped steel.
Carbonization can decrease the pH value, but the galvanizing layer with and without CaHZn still have better corrosion resistance to protect steel from corrosion damage; high alkalinity cement using can increase the pH value of pore solution, and the corrosion resistance of the surface cover on the steel sharply decreases which can not provide effective protection to steel anymore. Therefore, if hot-dip galvanizing steel is not used in high alkalinity cement concrete, it is worth being promoted in practical products with low cost, strong corrosion resistance.
引文
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