CN116875088A - 低温诱导具有光催化活性的硅钛复合超亲水涂层及其制备 - Google Patents
低温诱导具有光催化活性的硅钛复合超亲水涂层及其制备 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 55
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
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- 239000002243 precursor Substances 0.000 claims description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- VNRWTCZXQWOWIG-UHFFFAOYSA-N tetrakis(trimethylsilyl) silicate Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C VNRWTCZXQWOWIG-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 34
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 1
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- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及极端浸润表面制备技术领域,公开了低温诱导具有光催化活性的硅钛复合超亲水涂层及其制备,该涂层采用溶胶凝胶法利用二氧化硅的本征亲水性与二氧化钛的光致亲水性协同作用达到超亲水效果,具体通过低温诱导热处理工艺克服了传统Sol‑gel法制备薄膜需要高温烧结才能获得理想晶型的缺点,同时还能适用于热敏基材。本发明经低温诱导热处理工艺制备得到的涂层低碳环保、具有较好的光催化活性和超亲水效果,具有良好的应用前景。
Description
技术领域
本发明涉及极端浸润表面制备技术领域,具体涉及一种低温诱导具有光催化活性的硅钛复合超亲水涂层制备方法。
背景技术
超亲水表面是指液体能在其表面完全扩散,且接触角接近或等于0°的表面。作为一种极端润湿现象,超亲水表面具有自清洁、高效热传导和优良的生物相容性等优点,在很多领域都表现出潜在的应用前景,如:自清洁耐沾污、防雾防冰、生物医学设备及材料、油水分离等,备受学者关注。
传统超亲水表面的制备多使用溶胶凝胶法制备SiO2或TiO2膜,该方法操作简单易大面积制备,但得到的凝胶膜需要经高温烧结致晶化、致密化才能达到使用要求,这带来了极大的能耗问题也限制了其在热敏基材上的使用。不同于SiO2,亲水性是自身特性,对晶型并无要求;TiO2是因为其晶体具有光催化性能,从而光致亲水,且几种晶型中又以锐钛矿型的晶格中含有最多的缺陷和空位,而具有更高的光催化活性。因此低温制备硅钛溶胶并获得锐钛矿晶型,从而得到具有光催化性能并与基材良好附着的超亲水溶胶膜具有重要的现实意义。
中国发明专利申请CN108483936A,公开了一种玻璃表面超亲水、高附着力处理剂及其制备方法,由硅溶胶及Si-PEG聚合物溶液制备而成。中国发明专利申请CN106492774A,公开了一种玻璃负载纳米光催化膜的制备方法,由纳米二氧化钛水溶胶和纳米二氧化硅水溶胶复配,在500℃高温下灼烧制备。中国发明专利申请CN114381149A,公开了一种超亲水涂层材料组合物及其应用方法,由纳米二氧化钛和可水解硅烷以及纳米二氧化硅组成。单一组分的超亲水涂层易被污染破坏;如果将纳米二氧化钛粉体直接分散在涂料中,其遮盖力强,严重影响涂料透明度和透明基材使用;溶胶制备的涂层则需在高温灼烧下使用,能耗高危险系数大。因此,迫切需要寻求一种耐久性好、附着力强、透明度高、制备简单、能耗低的超亲水涂层。
发明内容
有鉴于此,本发明旨在提供一种能够在低温环境下制备得到且具有光催化活性的硅钛复合超亲水涂层。
为了实现上述目的,本发明的技术方案具体如下:
一种低温诱导的具有光催化活性的硅钛复合超亲水涂层的制备方法,包括以下步骤:
1)将可水解硅烷与无水乙醇混合,加入水解催化剂调节pH至1-3,滴加水并搅拌反应,得到二氧化硅前驱体溶液;
2)将钛源与无水乙醇混合后,滴加入步骤1)制备的二氧化硅前驱体溶液中,搅拌反应得到硅钛复合前驱体溶液;其中,钛源为钛酸四乙酯、钛酸四丙酯和钛酸四丁酯中的一种或多种的组合;
3)向硅钛复合前驱体溶液加入PEG混匀,陈化后得到硅钛复合溶胶;
4)将硅钛复合溶胶稀释后涂覆在基材上,然后置于热水环境中处理,取出基材干燥。
在上述制备方法中,可水解硅烷具体为四乙氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、四(三甲基硅氧基)硅烷中的一种或多种的组合。
在上述制备方法中,步骤1)中的可水解硅烷与无水乙醇混合的最佳摩尔比为1∶5。
在上述制备方法中,水解催化剂优选为盐酸、硝酸、硫酸、醋酸、柠檬酸中的一种或两种的组合。
在上述制备方法中,步骤1)中搅拌反应的时间优选为0.5~2h。
在上述制备方法中,步骤2)中钛源与步骤1)中可水解硅烷的摩尔比为1∶1-10,且钛源与步骤1)中滴加的水的摩尔比为1:10-100。
在上述制备方法中,步骤2)中的钛源与无水乙醇混合的最佳摩尔比为1∶20。
在上述制备方法中,步骤2)中将钛源滴加至二氧化硅前驱体溶液的时间优选为≤10min。
在上述制备方法中,步骤2)中搅拌反应的时间优选为0.5~2h。
在上述制备方法中,PEG的分子量优选为200-1500,其与硅钛复合溶胶中所含的SiO2-TiO2氧化物的质量比优选为0.1-3∶1;而且试验数据表明,在此范围内,随着PEG添加量的增加,使得硅钛复合溶胶的稳定性先增后减。
在上述制备方法中,PEG与硅钛复合前驱体溶液混匀搅拌的时间优选为1-2h,陈化时间可以为12h。
在上述制备方法中,在步骤4)优选采用醇类、醇醚类、酯类溶剂稀释硅钛复合溶胶,具体为乙醇、异丙醇、正丙醇、乙二醇醚、丙二醇醚、乙酸甲酯、乙酸乙酯、乙酸正丙酯中的一种或多种组合;根据实际需求,利用稀释剂可调整硅钛复合溶胶浓度,且稀释比例优选为1∶1-10。
在上述制备方法中,所述基材的材质为玻璃、聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)中的一种。
在上述制备方法中,在涂覆复合溶胶前,可以对基材表面进行预处理,以利于溶胶与基材充分接触并附着;另外,将复合溶胶涂覆至基材表面后,推荐在室温条件下干燥5-10min后再置于热水环境中处理。
在上述制备方法中,热水环境优选为热水蒸气环境或热水水煮环境,且其温度优选为50-100℃,处理时长优选为1-8h。
在上述制备方法中,热水环境处理后的基材在氮气处理下干燥。
通过本发明上述制备方法获得的具有光催化活性的硅钛复合超亲水涂层也属于本发明的保护范围。
与现有技术相比,上述方案的突出效果是:
1)本发明中用溶胶凝胶法将硅钛溶胶进行原位复配,协同了二氧化硅上的本征亲水性与二氧化钛的光致亲水性,使涂层具备超亲水性;而且,通过低温诱导热处理工艺克服了传统Sol-gel法制备薄膜需要高温烧结才能获得理想晶型的缺点,适用于热敏基材。
2)本发明调整了传统溶胶凝胶工艺,将钛酸四丁酯的乙醇溶液滴加到二氧化硅前驱体溶液中,使钛酸四丁酯在过量水中水解,而非将水加入到钛酸四丁酯中,因水解不充分出现有机中间产物。充分水解可以使溶胶跨越凝胶化过程直接得到无机粒子,这些无机粒子更容易在后期热水环境的处理下发生重排,从而形成稳定的具有晶体结构的纳米TiO2。
3)本发明引入聚乙二醇(PEG),PEG作为有机高分子可以辅助成膜,避免无机组分在缩聚成膜时产生开裂;还含有羟基和醚键两种亲水基而无疏水基,因此水溶性、稳定性极好,易与胶粒表面建立较强的氢键,形成一层高分子保护膜,包围胶体粒子呈现空间位阻效应,有效地抑制了胶体粒子的团聚,位阻效应随添加量和分子量的增加而增强。且因其在水中有较高的溶解度,热水处理过程中很容易从薄膜中溶解渗出,从而在基体表面易形成多孔薄膜结构,不仅有利于二氧化钛纳米微晶在基体表面的均匀分散发挥光催化作用,还能增加表面粗糙度。
4)本发明未按照传统工艺先各自制备二氧化硅二氧化硅溶胶和二氧化钛溶胶,再将二者混合、陈化。相较于溶液和固体粉末,溶胶体系的不稳定性更高,混合很容易破坏二者原本的稳定状态,发生凝胶或沉淀。而本发明的实验数据表明,将钛酸四丁酯加入到二氧化硅体系中一起水解,并通过调整工艺参数,可以直接形成一个稳定的复合溶胶体系。
5)本发明制得的超亲水涂层为无机膜层,其耐久性和耐磨性更佳、零VOC排放、透明性好、超亲水性能优异。
附图说明
图1为实施例1中提供的涂层的接触角图。
图2为实施例1中提供的涂层在紫外光下的光催化效果图。
图3为实施例2中提供的涂层的接触角图。
图4为实施例1与实施例2中提供的涂层的实际防雾效果图。
图5为实施例1与对比例1所制得的溶胶和涂层的对比图。
图6为不同水量对涂层中二氧化钛晶型影响的XRD图。
图7为热水环境处理对涂层中二氧化钛晶型影响的XRD图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明部分实施例,而不是全部的实施例。
需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
下述实施例中,若无特殊说明,均为常规方法;所述试剂和材料,若无特殊说明,均可从商业途径获得。
实施例1
本例具体通过以下步骤制备低温诱导的具有光催化活性的硅钛复合超亲水涂层:
1)将四乙氧基硅烷、无水乙醇以1∶5的摩尔比混合,加入HCl(36.5%)调节溶液pH为1,滴加一定量去离子水,其与步骤2)中的钛酸四丁酯摩尔比为50∶1,室温下搅拌水解30min得到二氧化硅前驱体溶液;
2)将钛酸四丁酯、无水乙醇以1∶20的摩尔比进行混合稀释,其中钛酸四丁酯与四乙氧基硅烷的摩尔比为1∶5,10分钟内逐滴加入定量步骤1)制得的二氧化硅前驱体溶液,搅拌反应1h得到硅钛复合前驱体溶液;
3)将PEG 600加入定量步骤2)制得的硅钛复合溶胶中混合均匀,添加量为硅钛复合溶胶中所含的SiO2-TiO2氧化物的质量和的2倍,搅拌2小时后静置陈化12小时,得到硅钛复合溶胶;
4)将步骤3)制得的硅钛复合溶胶经乙醇稀释6倍,涂覆在已清洁好的玻璃片上,室温下干燥5min;
5)将干燥后的玻璃片放入100℃热水中水煮处理2h,取出基材在氮气环境下吹干即得。
将制得的具有光催化活性的硅钛复合超亲水涂层进行测试。该涂层的水接触角如图1所示,达到8°。在紫外光照射下,检测涂层的催化活性,具体方法为:将0.5ml的有机染液罗丹明B(10mg/L)滴在制得的涂层样品片上,在功率为48W、波长为351nm的紫外光照射装置下放置2h。对染液的降解效果如图2所示,可见涂层体现了光催化降解作用。
实施例2
本例具体通过以下步骤制备低温诱导的具有光催化活性的硅钛复合超亲水涂层:
1)将四乙氧基硅烷、无水乙醇以1∶5的摩尔比混合,加入HCl(36.5%)调节溶液pH为1,滴加一定量去离子水,与步骤2)中的钛酸四丁酯摩尔比为20∶1,室温下搅拌水解30min得到二氧化硅前驱体溶液;
2)将钛酸四丁酯、无水乙醇以1∶20的摩尔比进行混合稀释,其中钛酸四丁酯与四乙氧基硅烷的摩尔比为1∶3,10min内逐滴加入定量步骤1)制得的二氧化硅前驱体溶液,搅拌反应1h得到硅钛复合前驱体溶液;
3)将PEG 1000加入定量步骤2)制得的硅钛复合溶胶中混合均匀,添加量为硅钛复合溶胶中所含的SiO2-TiO2氧化物的质量和的1倍,搅拌2h后静置陈化12h,得到硅钛复合溶胶;
4)将步骤3)制得的硅钛复合溶胶经乙醇稀释10倍,涂覆在已清洁好的玻璃片上,室温下干燥5分钟;
5)将干燥后的玻璃片放入100℃热水中水煮处理2h,取出基材在氮气环境下吹干得低温诱导具有光催化活性的硅钛复合超亲水涂层。
将制得的具有光催化活性的硅钛复合超亲水涂层进行测试,其水接触角如图3所示,达到9°;将实施例1、实施例2制备的涂层以及未处理的玻璃片放入冰箱1h后取出,其防雾性如图4所示,可见本发明制备的涂层具有良好的防雾效果。
对比例1
本例提供了一种硅钛复合涂层,且其制备方法具体如下:
1)将四乙氧基硅烷、无水乙醇以1∶5的摩尔比混合,加入HCl(36.5%)调节溶液pH为1,滴加一定量去离子水,室温下搅拌水解30min得到二氧化硅前驱体溶液;
2)将钛酸四丁酯、无水乙醇以1∶20的摩尔比进行混合稀释,其中钛酸四丁酯与四乙氧基硅烷的摩尔比为1∶5,10分钟内逐滴加入到过量去离子水中,搅拌反应1小时得到二氧化钛前驱体溶液;
3)将PEG 600分别加入定量步骤1)、2)制得的二氧化硅前驱体溶液、二氧化钛前驱体溶液中并混合均匀,添加量为前驱体溶液中所含的SiO2或TiO2的质量的2倍,搅拌2小时后静置陈化12小时,得到硅溶胶和钛溶胶;
4)将步骤3)制得的硅溶胶、钛溶胶混合,并经乙醇稀释6倍,涂覆在已清洁好的玻璃片上,室温下干燥5分钟;
5)将干燥后的玻璃片放入100℃热水中水煮处理2h,取出基材在氮气环境下吹干得到硅钛复合涂层。
对比例1制备的复合溶胶(步骤4)和涂层以及实施例1制备的复合溶胶和涂层的外观对比如图5所示,从图可知:实施例1制得的溶胶透明稳定,而对比例制得的溶胶稳定性极差,易出现沉降;实施例1制得的涂层均匀完整,对透明基材的透明性影响极小,对比例1制得的涂层大量脱落开裂,无法形成有效涂层。
对比例2
本例提供了一种硅钛复合涂层,且其制备方法具体如下:
与实施例1不同的是,步骤1)中滴加的去离子水与步骤2)中的钛酸四丁酯摩尔比为5∶1,其他步骤和条件则同实施例1一致。
取实施例1与对比例2制备的涂层进行XRD测试,结果如图6所示:水酯比50∶1所制得的胶体粉末出现了与锐钛矿标准卡片pdf 21-1272符合的强烈衍射峰,证明锐钛晶体的出现,而水酯比5∶1所制得的胶体粉末未出现衍射峰。其原因可能在于,当水酯比为5∶1时,理论上钛前驱体水解需要4摩尔比的水参与,由于复合溶胶中硅前驱体和钛前驱体均需要水参与水解,钛前驱体并不能得到足够的水参与反应,无法达到充分水解,从而生成大量有机产物;在水酯比50∶1时,所提供的水量远超硅前驱体和钛前驱体所需,二者均能充分水解,从而直接得到更易诱导重排结晶的无机粒子。
对比例3
本例提供了一种硅钛复合涂层,且其制备方法具体如下:
与实施例1不同的是,本例未将涂覆干燥后形成的涂层置于热水环境中处理,即无实施例1中的步骤5),其他步骤和条件则同实施例1一致。
取实施例1与对比例3制备的涂层进行XRD测试,结果如图7所示:实施例1制得的涂层出现了与锐钛矿标准卡片pdf 21-1272符合的强烈衍射峰,证明锐钛晶体的出现,而对比例3所制得的胶体粉末未出现衍射峰,证明热水处理对晶型出现的有效影响。
综上所述,本发明的制备方法有效降低了溶胶膜晶化、致密化所需的温度,提高了与基材的附着力,协同二氧化硅的本征亲水性和二氧化钛的光致亲水性达到超亲水效果。
以上所述仅为本发明较佳的实施例及辅助说明的对比例,并非因此限制本发明的实施方式及保护范围,对于本领域技术人员而言,应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案,均应当包含在本发明的保护范围内。
Claims (10)
1.一种低温诱导的具有光催化活性的硅钛复合超亲水涂层的制备方法,其特征在于,包括以下步骤:
1)将可水解硅烷与无水乙醇混合,加入水解催化剂调节pH至1-3,滴加水并搅拌反应,得到二氧化硅前驱体溶液;
2)将钛源与无水乙醇混合后,滴加入所述二氧化硅前驱体溶液中,搅拌反应得到硅钛复合前驱体溶液;所述钛源为钛酸四乙酯、钛酸四丙酯和钛酸四丁酯中的一种或多种的组合;
3)向硅钛复合前驱体溶液加入PEG混匀,陈化后得到硅钛复合溶胶;
4)将硅钛复合溶胶稀释后涂覆在基材上,然后置于热水环境中处理,取出基材干燥。
2.根据权利要求1所述的制备方法,其特征在于,所述可水解硅烷为四乙氧基硅烷、四甲氧基硅烷、四乙氧基硅烷、四丁氧基硅烷、四(三甲基硅氧基)硅烷中的一种或多种的组合。
3.根据权利要求1所述的制备方法,其特征在于,所述水解催化剂为盐酸、硝酸、硫酸、醋酸、柠檬酸中的一种或两种的组合。
4.根据权利要求1所述的制备方法,其特征在于,步骤2)中所述钛源与步骤1)中所述可水解硅烷的摩尔比为1∶1-10,且所述钛源与步骤1)中水的摩尔比为1:10-100。
5.根据权利要求1所述的制备方法,其特征在于,所述PEG的分子量为200-1500,且其与硅钛复合溶胶中所含的SiO2-TiO2氧化物的质量比为0.1-3∶1。
6.根据权利要求1所述的制备方法,其特征在于,在步骤4)中,采用醇类、醇醚类、酯类溶剂稀释硅钛复合溶胶,具体为乙醇、异丙醇、正丙醇、乙二醇醚、丙二醇醚、乙酸甲酯、乙酸乙酯、乙酸正丙酯中的一种或多种组合。
7.根据权利要求1所述的制备方法,其特征在于,所述基材为玻璃、聚碳酸酯、聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、聚氯乙烯中的一种。
8.根据权利要求1所述的制备方法,其特征在于,所述热水环境为热水蒸气环境或热水水煮环境,其温度为50-100℃,处理时长为1-8h。
9.根据权利要求1所述的制备方法,其特征在于,所述基材在氮气处理下干燥。
10.一种低温诱导的具有光催化活性的硅钛复合超亲水涂层,其特征在于,根据权利要求1-9任一项所述的制备方法获得。
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