CN107512928B - 环境友好的钢筋混凝土除氯防腐专用材料及钢筋混凝土除氯防腐方法 - Google Patents
环境友好的钢筋混凝土除氯防腐专用材料及钢筋混凝土除氯防腐方法 Download PDFInfo
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
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- C04B41/4944—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing atoms other than carbon, hydrogen, oxygen, silicon, alkali metals or halogens, e.g. N-silyldisilazane: Image
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Abstract
本发明提供了一种环境友好的钢筋混凝土除氯防腐专用材料及钢筋混凝土除氯防腐方法,属于钢筋混凝土保护材料技术领域。该材料包括结构式为R1R2R3R4N+X‑的有机硅季铵盐,其中:R1为C1至C20的饱和直链烷烃取代基或C3至C20环烷烃取代基,R2为C1至C20的饱和直链烷基,R3为C1至C20的三甲氧基硅基取代的饱和直链烷烃取代基,R4为C1至C20的三甲氧基硅基取代的饱和直链烷烃取代基或C1至C20的饱和直链烷烃取代基,X‑为NO3 ‑、BF4 ‑、PF6‑或PO4 3‑。本发明的材料能够进入钢筋混凝土内部形成保护涂层,同时氯离子能够迁移出混凝土内部,保护与除氯同时进行,一举两得。
Description
技术领域
本发明属于钢筋混凝土保护材料技术领域,涉及一种防腐材料及使用方法,具体的说是一种环境友好的钢筋混凝土除氯防腐专用材料及钢筋混凝土除氯防腐方法。
背景技术
钢筋混凝土的保护与加固技术,特别是沿海地区的钢筋混凝土的防护,不论在理论界与实际应用中,历来都是一个难点与热点。
钢筋混凝土破损,老化和腐蚀的原因有钢筋锈蚀,混凝土碳化,冻融循环,氯离子腐蚀,硫酸盐腐蚀,碱骨科反应等,在实际操作过程中,往往分为钢筋的腐蚀和混凝土的腐蚀分别进行具体的修复工作。
造成钢筋混凝土中钢筋腐蚀的最主要原因是氯离子腐蚀,在钢筋混凝土的建造过程中,原料就含有氯离子,而酸雨,海水,盐湖盐碱地等和钢筋混凝土接触都会造成非常严重的腐蚀,氯离子的存在会降低混凝土的pH,使钢筋和混凝土变得极易发生腐蚀,其具体的损伤机理包括破坏钝化膜,形成腐蚀电池,去极化作用和导电作用,并且钢筋锈蚀后体积会膨胀数倍,从而导致混凝土的开裂。
针对钢筋混凝土中钢筋的腐蚀,人们采取了在钢筋表面涂抹环氧树脂,用不锈钢代替普通碳钢,向混凝土中掺加火山灰质掺合料,对混凝土进行憎水处理和使用阻锈剂等多种方法,其中又以阻锈剂防止混凝土内部钢筋腐蚀的效果最好。
钢筋阻锈剂是通过降低钢筋的腐蚀速率来实现延缓,遏制或阻止钢筋腐蚀的物质,几十年来,人们思考和尝试了从有机物到无机物的大量物质,并且有很多都表现出了良好的阻锈性能,许多都已经被应用到了冷却系统,炼油装置,锅炉等工业设备,这些物质从无机物到杂环化合物到天然的植物提取物都有,牵涉到极其复杂的作用机理,并且有些阻锈剂很难指出其活性成分,于此同时,非常多的阻锈剂由于其毒性,或者太过昂贵,或者存在安全隐患,实用性大打折扣,因此研究出一种低廉,无毒,环境友好的阻锈剂并不容易。
发明内容
本发明的目的是针对上述问题,提供一种环境友好的钢筋混凝土除氯防腐专用材料。
本发明的另一目的是提供一种钢筋混凝土除氯防腐方法。
为达到上述目的,本发明采用了下列技术方案:一种环境友好的钢筋混凝土除氯防腐专用材料,其特征在于,该材料包括结构式为R1R2R3R4N+X-的有机硅季铵盐,其中:
R1为C1至C20的饱和直链烷烃取代基或C3至C20环烷烃取代基,
R2为C1至C20的饱和直链烷基,
R3为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基,
R4为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基或C1至C20的饱和直链烷烃取代基,
X-为NO3 -、BF4 -、PF6-或PO4 3-。
在上述的环境友好的钢筋混凝土除氯防腐专用材料中,R1为C1至C3饱和直链烷烃取代基或C3至C6环烷烃取代基,R2为 C1至C3饱和直链烷烃取代基,R3为C1至C6三甲氧基硅基或三乙氧基硅基取代的饱和直链烷基,R4为C1至C6三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基或C1至C6饱和直链烷烃取代基,X-为NO3 -或PO4 3-。
在上述的环境友好的钢筋混凝土除氯防腐专用材料中,还包括水,且有机硅季铵盐的水溶液浓度为0.01-1mol/L。
在上述的环境友好的钢筋混凝土除氯防腐专用材料中,有机硅季铵盐的水溶液浓度为0.1-0.2mol/L。
一种钢筋混凝土除氯防腐方法,将混凝土放入到电解液中,在电解液中加入权利要求1-4任意一项所述的环境友好的钢筋混凝土除氯防腐专用材料,在电解液中构件一个阳极,用直流电通电,直流电负极连接混凝土内的钢筋使钢筋成为阴极,在-10℃ -50℃下通电1-90天,电流密度为1-5A/m2。
在上述的钢筋混凝土除氯防腐方法中,在20℃-35℃下通电 10-30天,电流密度为2-3A/m2。
一种钢筋混凝土除氯防腐方法,以Na2CO3溶液为电解质溶液,在Na2CO3溶液中加入权利要求1-4任意一项所述的环境友好的钢筋混凝土除氯防腐专用材料,用直流电的负极连接混凝土中的钢筋,用直流电的正极连接电解质溶液,Na2CO3溶液没过混凝土内的钢筋并使钢筋裸露在Na2CO3溶液中,在-10℃-50℃下通电1-90 天,电流密度为1-5A/m2。
在上述的钢筋混凝土除氯防腐方法中,在20℃-35℃下通电 10-30天,电流密度为2-3A/m2。
在上述的钢筋混凝土除氯防腐方法中,直流电的正极通过导线连接钛网,导线与钛网的连接处采用绝缘处理,直流电的负极通过导线连接钢筋,Na2CO3溶液浸润钢筋。
在上述的钢筋混凝土除氯防腐方法中,钢筋与钛网分别作为阴极与阳极,在通直流电的条件下形成双向电渗。
双向电渗是指在一个电解池中,利用通入直流电后阴离子向阳极移动,阳离子向阴极移动的原理,同时实现阳离子和阴离子向不同方向迁移的技术,由于钢筋混凝土的钢筋四周都是混凝土,不直接和外界接触,一般方法无法使阻锈剂到达钢筋表面,而季铵盐在水溶液中以阳离子的形式存在,若外加电场,则季铵盐阳离子就会一直向阴极移动,同时钢筋混凝土中的氯离子则会离开混凝土,向电解池中的阳极移动。季铵盐其N原子上的孤对电子会填充到钢筋上Fe的空轨道上,从而降低钢筋的电位,达到阻锈的效果。同时其分子链段取代基中含有烷基硅氧烷基团,兼具有机硅的特性,能够在钢筋表面形成致密的保护层。
本发明的材料既可用于现代大型基础设施的保护,如:跨海大桥、大型输变电桩基、沿海高速铁路路基、水利枢纽等;也可以用于“一带一路”沿海地区水泥历史文物建筑的保护与加固。
与现有的技术相比,本发明的优点在于:
1、材料能够进入钢筋混凝土内部形成保护涂层,同时氯离子能够迁移出混凝土内部,保护与除氯同时进行,一举两得。
2、工艺简单,保护效果显著,作用持久,过程环境友好,对人以及环境没有毒害作用。
具体实施方式
实施例1
钢筋混凝土样块的制备:使用打磨机打磨钢筋除去钢筋表面的油污和铁锈,从而获得表面较平整光滑的钢筋,然后根据电镀手册进一步进行除油和除锈的预处理。取水泥设计配比(kg/m3) 水泥:标准砂:水=1:2.86:0.86,按此比例称量好水泥和标准砂,置入合金桶中并充分搅拌,再按比例称量好水,同时使用天平称量出质量为水泥质量5%的氯化钠,溶解于水中配置成氯化钠溶液,再将氯化钠溶液倒入合金桶中,使用大功率搅拌器充分搅拌即制得水泥砂浆,将脱模剂喷洒在30mm*30mm*95mm的铸铁模具上,再将经过预处理的钢筋架在模具中央的小孔中,然后使用勺子将水泥砂浆加入模具中,并不断摇晃震动模具,使水泥砂浆均匀分散在模具中,同时赶走砂浆中气泡,最后用铁尺沿模具上表面刮走多余水泥砂浆。
将浇筑好的钢筋混凝土试样放置一天后进行脱模,取出试样,即获得钢筋混凝土试件,在上面铺一层含水至饱和的卫生纸,然后放入标准养护室(T=22℃,相对湿度RH=70%)中,每天向试样表面喷洒水,养护28天,再在自然条件下自然腐蚀至少6个月。
样块制备与养护好后待后续实验:
取适量有机硅季铵盐(R1R2R3R4分别为甲基、甲基、十八烷基, (三甲氧基硅基)丙基;X-为氯离子),用去离子水配置成0.1mol/L 的溶液;0.1mol/L Na2CO3溶液作为电解液。
取一根导线焊接在钛网的一端上,并在连接处涂上环氧树脂并静置至少6h,保证连接处绝缘,再取1个底面积为13cm×18cm 的塑料盒,底部两端各放1个小木块,将钛网架在2个小木块上,另取1根已预处理并完成电化学测试的钢筋混凝土试件平放在钛网上,使未涂上环氧树脂的表面与钛网接触,将电解液缓慢倒入塑料盒中至液面正好未触及裸露的钢筋,然后取一根导线一端夹住已打磨至光滑的裸露的钢筋,另一端连接电源的负极,再使已和钛网焊接上的导线连接电源的正极,接通直流电源,取电流密度大小为1A/m2,通电1d,20℃通电结束后取出钢筋混凝土试件静置。钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
实施例2
本实施例与实施例1基本相同,不同之处在于:R1R2R3R4分别为甲基、甲基、十八烷基,(三甲氧基硅基)丙基;X-为氯离子),用去离子水配置成0.2mol/L的溶液;0.2mol/LNa2CO3溶液作为电解液。电流密度大小为5A/m2,35℃通电10d,通电结束后取出钢筋混凝土试件静置。钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
实施例3
本实施例与实施例1基本相同,不同之处在于:R1R2R3R4分别为环己基、丙基、十八烷基,(三甲氧基硅基)丙基;X-为BF4 -),用去离子水配置成1mol/L的溶液;1mol/L Na2CO3溶液作为电解液。电流密度大小为2.5A/m2,25℃通电25d,通电结束后取出钢筋混凝土试件静置。钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
实施例4
本实施例与实施例1基本相同,不同之处在于:R1R2R3R4分别为丙基、甲基、(三甲氧基硅基)丙基,(三甲氧基硅基)丙基; X-为氯离子),用去离子水配置成0.5mol/L的溶液;0.5mol/L Na2CO3溶液作为电解液。电流密度大小为2A/m2,25℃通电30d,通电结束后取出钢筋混凝土试件静置。钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
实施例5
本实施例与实施例1基本相同,不同之处在于:R1R2R3R4分别为甲基、甲基、(三甲氧基硅基)丙基,(三甲氧基硅基)丙基; X-为氯离子),用去离子水配置成0.01mol/L的溶液;0.01mol/L Na2CO3溶液作为电解液。电流密度大小为3A/m2,30℃通电90d,通电结束后取出钢筋混凝土试件静置。钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
对比例1
采用没有经过本发明所述的材料和方法的钢筋混凝土进行对比实验,即为对照组,钢筋防腐盐雾实验参考国标GB6458-86,结果如下:
实施例6-13
一种环境友好的钢筋混凝土除氯防腐专用材料,该材料包括结构式为R1R2R3R4N+X-的有机硅季铵盐,其中:
R1为C1至C20的饱和直链烷烃取代基或C3至C20环烷烃取代基,
R2为C1至C20的饱和直链烷基,
R3为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基,
R4为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基或C1至C20的饱和直链烷烃取代基,
X-为NO3 -,BF4 -,或PF6-,PO4 3-。
具体见下表:
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
Claims (9)
1.一种环境友好的钢筋混凝土除氯防腐专用材料,其特征在于,该材料包括结构式为R1R2R3R4N+X-的有机硅季铵盐,其中:
R1为C1至C20的饱和直链烷烃取代基或C3至C20环烷烃取代基,
R2为C1至C20的饱和直链烷基,
R3为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基,
R4为C1至C20的三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基或C1至C20的饱和直链烷烃取代基,
X-为NO3 -、BF4 -、PF6-或PO4 3-,
还包括水,且有机硅季铵盐的水溶液浓度为0.01-1mol/L。
2.根据权利要求1所述的环境友好的钢筋混凝土除氯防腐专用材料,其特征在于,R1为C1至C3饱和直链烷烃取代基或C3至C6环烷烃取代基,R2为C1至C3饱和直链烷烃取代基,R3为C1至C6三甲氧基硅基或三乙氧基硅基取代的饱和直链烷基,R4为C1至C6三甲氧基硅基或三乙氧基硅基取代的饱和直链烷烃取代基或C1至C6饱和直链烷烃取代基,X-为NO3 -或PO4 3-,
还包括水,且有机硅季铵盐的水溶液浓度为0.01-1mol/L。
3.根据权利要求1或2所述的环境友好的钢筋混凝土除氯防腐专用材料,其特征在于,有机硅季铵盐的水溶液浓度为0.1-0.2mol/L。
4.一种钢筋混凝土除氯防腐方法,其特征在于,将混凝土放入到电解液中,在电解液中加入权利要求1-3任意一项所述的环境友好的钢筋混凝土除氯防腐专用材料,在电解液中构建一个阳极,用直流电通电,直流电负极连接混凝土内的钢筋使钢筋成为阴极,在-10℃-50℃下通电1-90天,电流密度为1-5A/m2。
5.根据权利要求4所述的钢筋混凝土除氯防腐方法,其特征在于,在20℃-35℃下通电10-30天,电流密度为2-3A/m2。
6.一种钢筋混凝土除氯防腐方法,其特征在于,以0.01-1mol/L Na2CO3溶液为电解质溶液,在Na2CO3溶液中加入权利要求1-3任意一项所述的环境友好的钢筋混凝土除氯防腐专用材料,用直流电的负极连接混凝土中的钢筋,用直流电的正极连接电解质溶液,Na2CO3溶液没过混凝土内的钢筋并使钢筋裸露在Na2CO3溶液中,在-10℃-50℃下通电1-90天,电流密度为1-5A/m2。
7.根据权利要求6所述的钢筋混凝土除氯防腐方法,其特征在于,Na2CO3的浓度为0.1-0.2mol/L,在20℃-35℃下通电10-30天,电流密度为2-3A/m2。
8.根据权利要求6所述的钢筋混凝土除氯防腐方法,其特征在于,直流电的正极通过导线连接钛网,导线与钛网的连接处采用绝缘处理,直流电的负极通过导线连接钢筋,Na2CO3溶液浸润钢筋。
9.根据权利要求8所述的钢筋混凝土除氯防腐方法,其特征在于,钢筋与钛网分别作为阴极与阳极,在通直流电的条件下形成双向电渗。
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