聚合物水泥基防水涂料的制备及涂膜性能、显微结构的研究
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摘要
建筑渗漏已成为建设工程的质量通病，它不仅扰乱人们的正常生活、工作生产秩序，而且给国家造成巨大的经济损失。因此，建筑防水在建设工程中占有十分重要的地位，对保证与发挥建筑物的使用功能与寿命具有不可低估的作用。
聚合物水泥基防水涂料是由聚合物乳液和无机填料复合而成的水乳型双组分防水涂料。涂料涂覆后，复合体系中水泥遇到乳液中的水即发生水化反应，形成一定量的水泥凝胶体；而聚合物乳液本身属于胶体分散体，其中的聚合物颗粒向料浆中分散，吸附在水泥及其水化产物和其它填料的表面。随着水分的消耗和逸失，聚合物颗粒之间慢慢地靠拢而相互凝聚在一起，进一步固化即形成连续的涂膜结构。该涂膜弥补了水泥基材料柔性不足以及聚合物乳液涂膜再溶胀，防水性差的缺陷，提高了聚合物涂料的拉伸强度。既有有机涂料高韧高弹性能，又有无机材料耐久性好等优点，达到了二者性能上的优势互补，起到“复合叠加”效应。同时它还具有粘结强度高、无毒、无味、无大气污染等优点。
本文从防水涂料料浆稳定性的研究出发，分析了影响聚合物水泥基防水涂膜性能的各种因素。它们分别是：①液粉比；②灰聚比；③成膜助剂用量；④增塑剂用量；⑤分散剂用量；⑥填料的种类；⑦水泥的品种；⑧养护龄期及制度；⑨成膜方法及厚度。结果表明：合理的液粉比和灰聚比关系到涂膜的刚性与柔性；成膜助剂有利于改善涂膜的成膜性能，提高涂膜的柔韧性；适当的增塑剂可以提高涂膜的低温柔性；分散剂能使无机填料的二次粒子充分解聚，使涂料更加均匀和稳定；不同的填料或水泥对涂膜性能也有一定程度的影响；同时，养护龄期和制度及成膜方法和厚度也影响着涂膜的拉伸性能。通过对几种防水涂料的对比，水泥的水化有利于涂膜结构的发展，使其更加致密，从而提高涂膜的耐久性。进而利用扫描电子显微镜观察了涂膜的结构和形貌；X—射线确定了水泥水化相的组成；红外光谱跟踪涂膜成膜前后各种基团的变化；对聚合物水泥基防水涂料的成膜过程和机理作出一定的假定。
The leakage has become a common fault in the construction quality. It not only disturbs people normal living,working and production order,but also leads to enormous economic loss. Therefore,the building waterproofing plays an important role in the construction. In that it can effectively guarantees the construction's function and prolongs lifespan.
The polymer modified cementitious waterproofing coating,which is an emulsion and double ingredient paint,is made up of the polymer latex and inorganic fillers. After coated,the hydration will take place as soon as cement in the composite system contacts with water of the latex. Because the polymer latex is colloid dispersoid,the polymer particles disperse into slurry and absorb on cement,hydrate and other fillers. Along with the water depletes and escapes,the polymer particles close slowly and agglomerate with each other. At last,a continuous film structure comes into being. The film offsets the traditional polymer-cement composite material's defects,such as lack of flexibility and the film's re-solution,and enhances the tensile strength of the coating. It integrates the advantages of organic material as toughness and flexibility and advantage of inorganic material as good durability,so makes composite effect. Moreover,it has other merits,such as high bond strength,innocuity,insipidity and no atmosphere poll
ution.
This paper studies the stability of the waterproofing coatings' slurry and analyzes the different factors that influence the polymer modified cementitious waterproofing coatings. They include the ratio of liquid to powder(L/P),(2) the ratio of cement to polymer(C/P),(3) the dosage of coalescer,the dosage of plastizer,(5) the dosage of dispersant,the type of filler,(7) the type of cement,(8) curing age and rule,(9) the way of film formation and thickness. The results show that the rational L/P and C/P is related to rigidity and flexibility. The coalescer can improve the ability of film formation of the paint and enhance the flexibility of film. Proper plastizer can improve the low temperature performance. The dispersant makes the particles of inorganic filler disper sufficiently. As a result,the paint becomes more homogeneous and stable. Also the different types of fillers and cements can influence the performance of the coating. Moreover both the curing age,rule and the way,thickness of film-formation determ
ine the tensile performance. By comparison with several waterproofing coatings,we find that the hydrate reinforces the film structure and improves the durability. SEM can be
used to observe the structure and appearance of the film,XRD to determine the hydrate of cement,IR to analyze the variety of polymer group after coating. At last this article discusses the film-form mechanism and preparation of the waterproofing coating.
聚合物水泥基防水涂料是由聚合物乳液和无机填料复合而成的水乳型双组分防水涂料。涂料涂覆后，复合体系中水泥遇到乳液中的水即发生水化反应，形成一定量的水泥凝胶体；而聚合物乳液本身属于胶体分散体，其中的聚合物颗粒向料浆中分散，吸附在水泥及其水化产物和其它填料的表面。随着水分的消耗和逸失，聚合物颗粒之间慢慢地靠拢而相互凝聚在一起，进一步固化即形成连续的涂膜结构。该涂膜弥补了水泥基材料柔性不足以及聚合物乳液涂膜再溶胀，防水性差的缺陷，提高了聚合物涂料的拉伸强度。既有有机涂料高韧高弹性能，又有无机材料耐久性好等优点，达到了二者性能上的优势互补，起到“复合叠加”效应。同时它还具有粘结强度高、无毒、无味、无大气污染等优点。
本文从防水涂料料浆稳定性的研究出发，分析了影响聚合物水泥基防水涂膜性能的各种因素。它们分别是：①液粉比；②灰聚比；③成膜助剂用量；④增塑剂用量；⑤分散剂用量；⑥填料的种类；⑦水泥的品种；⑧养护龄期及制度；⑨成膜方法及厚度。结果表明：合理的液粉比和灰聚比关系到涂膜的刚性与柔性；成膜助剂有利于改善涂膜的成膜性能，提高涂膜的柔韧性；适当的增塑剂可以提高涂膜的低温柔性；分散剂能使无机填料的二次粒子充分解聚，使涂料更加均匀和稳定；不同的填料或水泥对涂膜性能也有一定程度的影响；同时，养护龄期和制度及成膜方法和厚度也影响着涂膜的拉伸性能。通过对几种防水涂料的对比，水泥的水化有利于涂膜结构的发展，使其更加致密，从而提高涂膜的耐久性。进而利用扫描电子显微镜观察了涂膜的结构和形貌；X—射线确定了水泥水化相的组成；红外光谱跟踪涂膜成膜前后各种基团的变化；对聚合物水泥基防水涂料的成膜过程和机理作出一定的假定。
The leakage has become a common fault in the construction quality. It not only disturbs people normal living,working and production order,but also leads to enormous economic loss. Therefore,the building waterproofing plays an important role in the construction. In that it can effectively guarantees the construction's function and prolongs lifespan.
The polymer modified cementitious waterproofing coating,which is an emulsion and double ingredient paint,is made up of the polymer latex and inorganic fillers. After coated,the hydration will take place as soon as cement in the composite system contacts with water of the latex. Because the polymer latex is colloid dispersoid,the polymer particles disperse into slurry and absorb on cement,hydrate and other fillers. Along with the water depletes and escapes,the polymer particles close slowly and agglomerate with each other. At last,a continuous film structure comes into being. The film offsets the traditional polymer-cement composite material's defects,such as lack of flexibility and the film's re-solution,and enhances the tensile strength of the coating. It integrates the advantages of organic material as toughness and flexibility and advantage of inorganic material as good durability,so makes composite effect. Moreover,it has other merits,such as high bond strength,innocuity,insipidity and no atmosphere poll
ution.
This paper studies the stability of the waterproofing coatings' slurry and analyzes the different factors that influence the polymer modified cementitious waterproofing coatings. They include the ratio of liquid to powder(L/P),(2) the ratio of cement to polymer(C/P),(3) the dosage of coalescer,the dosage of plastizer,(5) the dosage of dispersant,the type of filler,(7) the type of cement,(8) curing age and rule,(9) the way of film formation and thickness. The results show that the rational L/P and C/P is related to rigidity and flexibility. The coalescer can improve the ability of film formation of the paint and enhance the flexibility of film. Proper plastizer can improve the low temperature performance. The dispersant makes the particles of inorganic filler disper sufficiently. As a result,the paint becomes more homogeneous and stable. Also the different types of fillers and cements can influence the performance of the coating. Moreover both the curing age,rule and the way,thickness of film-formation determ
ine the tensile performance. By comparison with several waterproofing coatings,we find that the hydrate reinforces the film structure and improves the durability. SEM can be
used to observe the structure and appearance of the film,XRD to determine the hydrate of cement,IR to analyze the variety of polymer group after coating. At last this article discusses the film-form mechanism and preparation of the waterproofing coating.
引文
【1】金孝权，杨承忠主编．建筑防水，东南大学出版社，1998年．
【2】项桦太，杨扬，张文华编．建筑防水工程技术．中国建筑工业出版社，1998年．
【3】徐益超．上海地区高层住宅外墙渗水情况及对策．建筑技术，1999，28(6)：400—402．
【4】邓大宁．建筑外墙防水问题探讨．中国建筑防水，1999—3．
【6】张沂．聚合物水泥类防水涂料综述．中国建筑防水，2001(4)：10—12．
【6】张大科．改性沥青防水卷材的现状、问题及对策．化学建材，2000(1)；37—39．
【7】梁乃兴．聚合物改性水泥混凝土．北京：人民交通出版社，1995年．
【8】Ohama, Y.: Principle of Latex Modification and Some Typical Properties of Latex Modified Mortars and Concretes. ACI Materials Journal, Nov. ～Dec. 1987. p. 511 518.
【9】Etsuo Sakai and Jun Sugita. Composite Mechanism of Polymer Modified Cement. Cement and Concrete Research, Vol. 25, No. 1, pp. 127-135, 1995.
【10】Chen, Z. and Tan, M. Progress of Polymer Concrete Composite, Proceedings of the First East Asia Symposium Polymers in Concrete, Korea, pp. 25-40, May 2-3, 1994.
【11】契尔金斯基著，张留城，夏巨敏译，聚合物水泥混凝土．北京：中国建筑工业出版社，1987．
【12】邓超．日本聚合物水泥防水涂料概况．中国建筑防水，2001(4)：25—27．
【13】叶林标．国内外环保型防水材料的开发与应用．建筑技术，2001，32(7)：442—444．
【14】李谷云等．聚合物水泥防水涂料标准的制度，中国建筑防水，2001(4)：6—9．
【15】黄金荣．福建省建筑防水现状与发展对策．中国建筑防水，2000(4)：38．
【16】周昌盛等．新型聚合物改性水泥基复合材料的应用前景．中国建材，2000(12)：79—80．
【17】袁大伟．聚合物水泥若干问题探讨，中国建筑防水，2001(4)：22—24．
【18】翟红．参照美国标准检测水乳型防水涂料的耐水浸泡性．化学建材，2001(3)：41—42．
【19】徐峰编著．建筑涂料与涂装技术．北京：化学工业出版社，1998年．
【20】陈宗淇，王光信，徐桂英编．胶体与界面化学．北京：高等教育出版社，2001年．
【21】Tatsuo Sato. Stability of Dispersion. Journal of Coatings Technology, 1993,825(65): 113-121.
【22】余樟清，陈焕钦，潘祖仁等．聚合物乳液的稳定性．涂料工业，1998(11)：41—44．
【23】Taylor, H. F. W.: Cement Chemistry. Academic Press Limited, London, 1990.
【24】季永新，胡明．丙烯酸乳液稳定的研究．林产化工通讯，1997(2)：25—26．
【25】王涛，许仲梓．聚合物改性水泥砂浆性能的影响因素．混凝土与水泥制品，1996(5)：23—26．
【26】肖雪平．苯丙乳液的钙离子稳定性．化学建材，1991(5)：12—14．
【27】雷生山．适合JS防水涂料的聚合物乳液．涂料工业，2002(2)：40—41．
【28】陈建奎编著．混凝土外加剂的原理与应用．北京：中国计划出版社，1997年．
【29】David J. Lundberg and J. Edward Glass. Pigment Stabilization Through Mixed Associative Thickener Interactions. Journal of Coatings Technology. 1992, 807(64): 53-61.
【30】Tan, M.;Roy, D. m.:An Investigation of the effect of organic solvent on the rheological properties and hydration of cement paste. Cement and Concrete Research, 17. 1987. pp. 983-994.
【31】蔡永泰，邱聪等．(Point-JS991)聚合物水泥基复合防水涂料的研制．化学建材，2001(6)：35—37．
【32】室井宗一著．高分子乳液在建筑涂料中的应用．北京：化学工业出版社，1988年．
【33】王春久．水泥的改性与水泥基防水材料．中国建筑防水，1999(1)：26—28．
【34】杨永锋．也谈聚合物—水泥基复合防水材料的刚性—柔性突变．中国建筑防水，2000(4)：14—15．
【35】Tan Meng Kwang．成膜助剂在水性乳胶涂料中的作用及其选择方法．涂料工业，1996(4)：32—35．
【36】谢云林．增塑剂DBP对VAE乳液粘度的影响．中国胶粘剂，1999，9(2)：30—31．
【37】Wick Z W Jr. Free Volume and the Coatings Formulator. Journal of Coatings Technology, 1986, 58(743): 23-32.
【38】夏冬．柔性聚合物水泥防水卷材．新型建筑材料，2002(2)：39—42．
【39】Jorg Schmitz. A new concept for dispersing agents in aqueous coating. Progress in Organic Coatings, 1999, (35): 191-196.
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【41】R. Ollitrault-Fichet, C. Gauthier, .et. Microstructural Aspects in a Polymer-Modified Cement. Cement and Concrete Research. Vol. 28, No. 12, pp. 1687-1693, 1998.
【42】Joachim Schulze. Influence of water-cement ratio and cement content on the properties of polymer-modified mortars. Cement and Concrete Research. Vol. 29, pp. 909-915,
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【43】Joachim Schulze and Otmar Killermann. Long-term performance of redispersible powders in mortars. Cement and Concrete Research. Vol. 31, pp. 357-362, 2001.
【44】Musarrat Ullah Khan Afridi. A note on the formation Ca(OH)_2 crystals in polymer-modified mortars. Cement and Concrete Research. Vol. 23, pp. 484-485, 1993
【45】I. Janotka, J. Madejova,. et. Behaviour of Ca(OH)_2 in the presence of the set styrene-acrylate dispersion. Cement and Concrete Research. Vol. 26, No. 1, pp. 1727-1735, 1996.
【46】F. A. Shaker and M. M. Reda. Durability of styrene-butadiene latex modified concrete. Cement and Concrete Research. Vol. 27, No. 5, pp. 771-720, 1997.
【47】ChongY. Rha, Chang E. Kim,. et. Preparation and characterization of absorbent polymer-cement composites. Cement and Concrete Research. Vol. 29, pp. 231-236, 1999.
【48】卢涌泉、邓振华编．实用红外光谱解析．北京：电子工业出版社，1985年
【49】Chandra. S.;Flodin, P.:Interactions of polymers and organic admixture on Portland cement hydrations. Cement and Concrete Research. Vol. 17, pp. 875-890, 1987.
【50】T.Sugama and L. E. Kukacka.:Products formed in aged Ca-polymer complexed polymer concrete containing cement paste. Cement and Concrete Research. Vol. 12, pp. 789-796, 1982.
【2】项桦太，杨扬，张文华编．建筑防水工程技术．中国建筑工业出版社，1998年．
【3】徐益超．上海地区高层住宅外墙渗水情况及对策．建筑技术，1999，28(6)：400—402．
【4】邓大宁．建筑外墙防水问题探讨．中国建筑防水，1999—3．
【6】张沂．聚合物水泥类防水涂料综述．中国建筑防水，2001(4)：10—12．
【6】张大科．改性沥青防水卷材的现状、问题及对策．化学建材，2000(1)；37—39．
【7】梁乃兴．聚合物改性水泥混凝土．北京：人民交通出版社，1995年．
【8】Ohama, Y.: Principle of Latex Modification and Some Typical Properties of Latex Modified Mortars and Concretes. ACI Materials Journal, Nov. ～Dec. 1987. p. 511 518.
【9】Etsuo Sakai and Jun Sugita. Composite Mechanism of Polymer Modified Cement. Cement and Concrete Research, Vol. 25, No. 1, pp. 127-135, 1995.
【10】Chen, Z. and Tan, M. Progress of Polymer Concrete Composite, Proceedings of the First East Asia Symposium Polymers in Concrete, Korea, pp. 25-40, May 2-3, 1994.
【11】契尔金斯基著，张留城，夏巨敏译，聚合物水泥混凝土．北京：中国建筑工业出版社，1987．
【12】邓超．日本聚合物水泥防水涂料概况．中国建筑防水，2001(4)：25—27．
【13】叶林标．国内外环保型防水材料的开发与应用．建筑技术，2001，32(7)：442—444．
【14】李谷云等．聚合物水泥防水涂料标准的制度，中国建筑防水，2001(4)：6—9．
【15】黄金荣．福建省建筑防水现状与发展对策．中国建筑防水，2000(4)：38．
【16】周昌盛等．新型聚合物改性水泥基复合材料的应用前景．中国建材，2000(12)：79—80．
【17】袁大伟．聚合物水泥若干问题探讨，中国建筑防水，2001(4)：22—24．
【18】翟红．参照美国标准检测水乳型防水涂料的耐水浸泡性．化学建材，2001(3)：41—42．
【19】徐峰编著．建筑涂料与涂装技术．北京：化学工业出版社，1998年．
【20】陈宗淇，王光信，徐桂英编．胶体与界面化学．北京：高等教育出版社，2001年．
【21】Tatsuo Sato. Stability of Dispersion. Journal of Coatings Technology, 1993,825(65): 113-121.
【22】余樟清，陈焕钦，潘祖仁等．聚合物乳液的稳定性．涂料工业，1998(11)：41—44．
【23】Taylor, H. F. W.: Cement Chemistry. Academic Press Limited, London, 1990.
【24】季永新，胡明．丙烯酸乳液稳定的研究．林产化工通讯，1997(2)：25—26．
【25】王涛，许仲梓．聚合物改性水泥砂浆性能的影响因素．混凝土与水泥制品，1996(5)：23—26．
【26】肖雪平．苯丙乳液的钙离子稳定性．化学建材，1991(5)：12—14．
【27】雷生山．适合JS防水涂料的聚合物乳液．涂料工业，2002(2)：40—41．
【28】陈建奎编著．混凝土外加剂的原理与应用．北京：中国计划出版社，1997年．
【29】David J. Lundberg and J. Edward Glass. Pigment Stabilization Through Mixed Associative Thickener Interactions. Journal of Coatings Technology. 1992, 807(64): 53-61.
【30】Tan, M.;Roy, D. m.:An Investigation of the effect of organic solvent on the rheological properties and hydration of cement paste. Cement and Concrete Research, 17. 1987. pp. 983-994.
【31】蔡永泰，邱聪等．(Point-JS991)聚合物水泥基复合防水涂料的研制．化学建材，2001(6)：35—37．
【32】室井宗一著．高分子乳液在建筑涂料中的应用．北京：化学工业出版社，1988年．
【33】王春久．水泥的改性与水泥基防水材料．中国建筑防水，1999(1)：26—28．
【34】杨永锋．也谈聚合物—水泥基复合防水材料的刚性—柔性突变．中国建筑防水，2000(4)：14—15．
【35】Tan Meng Kwang．成膜助剂在水性乳胶涂料中的作用及其选择方法．涂料工业，1996(4)：32—35．
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