CN110117787B - 二氧化钛薄膜的制备方法 - Google Patents
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Abstract
本发明属于金属材料表面处理领域，涉及一种二氧化钛薄膜的制备方法，对原材料进行清洁后放置于可通入流动性气体的石英反应炉内，通入氩气，烘干，然后根据欲获得不同反应产物与表面结构的需要，将炉温升至240℃‑1400℃之间特定的温度，将纯净水均匀喷涂在钛材料表面；纯水喷涂需要一定时间间隔，间隔时间长度根据反应需求选择在1秒至120秒之间。本发明提供的二氧化钛薄膜的制备方法，采用纯水在高温下直接与钛表面进行反应，通过控制反应温度、反应时间与反应间歇时间的长度，可较为准确的控制钛表面生成TiO2层的厚度、形貌、相、针状孔隙结构与金红石型TiO2的体积与长度，从而根据材料应用目标满足材料的使用性能。
Description
技术领域
本发明属于金属材料表面处理领域，涉及一种二氧化钛薄膜的制备方法，具体是一种在特定条件下采用特殊工艺使液态水与钛表面进行反应，来实现钛材料表面二氧化钛化合物的生成并实现二氧化钛化产物有序受控定向生长的表面处理工艺。
背景技术
二氧化钛薄膜的制备方法，目前主要使用以下几种工艺：
磁控溅射法，是薄膜物理气相沉积(PVD)的一种方法,该法制备的薄膜质量高、密度大、结合性能好、强度大,而且生产重复性好,适于大面积沉积成膜,便于连续和半连续生产,缺点是薄膜活性较低。磁控溅射沉积将金属靶作阴极，导电玻璃(如ITO)作阳极，在Ar和O2氛围下溅射沉积到导电玻璃基片上，得到TiO2薄膜。该TiO2薄膜能够牢固地附着在基底上，易于进行大面积的均匀镀膜。但是磁控溅射得到的薄膜太致密，孔隙率相对较低且分布不均匀。
水热合成法，通过水解钛的醇盐或氯化物前驱体得到无定形沉淀，然后在酸性或碱性溶液中胶溶得到溶胶物质，将溶胶在高压釜中进行水热熟化。熟化后的溶胶涂覆在导电玻璃基片上，经高温(500℃左右)煅烧，即得到纳米晶TiO2薄膜。也可以使用TiO2的醇溶液与商业Ti02(P25，30nm)混合以后得到的糨糊来代替上面提到的溶胶。反应中为了防止颗粒团聚，通常采用化学表面改性的方法，如加有机螫合剂、表面活性剂、乳化剂等，以降低粉末表面能，增加胶粒问静电排斥，或产生空问位阻作用而使胶体稳定。该方法主要在于加入了一个水热熟化过程，由此控制产物的结晶和长大，继而控制半导体氧化物的颗粒尺寸和分布，以及薄膜的孔隙率，得到的TiO2颗粒是锐钛矿型还是锐钛矿型与金红石型的混合物由反应条件(如煅烧温度)决定。局限性是它必须进行高温和高压处理，水热合成法需时较长。
阳极氧化法，将工业纯钛片浸入于电介质溶液，适当控制氧化电压、溶液温度,得到非晶氧化膜，再进行控制条件下的晶化处理,得到锐钛矿相纳米TiO2薄膜,其晶粒度约为10～30nm。该方法成本较高，但存在环境污染等问题。
喷射高温分解沉积法，是将羟乙酰丙酮化钛溶于2-丁醇中作为初始源溶液，通过SPD设备将源溶液在空气压力下呈喷雾状间歇地喷射到被加热的玻璃基底上形成TiO2薄膜。所得TiO2薄膜表面形态为大约宽100nm的叶片状结构，粗糙因子为50，薄膜厚度为1μm。这种方法制得的TiO2薄膜孔隙率较低，颗粒尺寸较大。喷射高温分解沉积法制备工艺大大简化，可以在空气中和常压下进行，但是所得到的TiO2薄膜的颗粒尺寸分布不均匀，孔隙率低，且无法控制氧化物颗粒的尺寸和形态。
冷压法，是将纳米TiO2粉体加入有机溶剂中制成悬浮液，然后将其刮涂到导电基片上。待有机溶剂挥发之后，将基片放到两块钢压板之间施以压力，如果基片是玻璃，压力一般为1000kg/cm2；如果基片是塑料，则采用滚动挤压的方式，压力一般为400kN/m。冷压法制得的TiO2薄膜颗粒细小，分布均匀，平均粒径为23nm，孔隙率为50～55％，膜厚度为8μm左右。但该薄膜与基片界面间的连接并不牢固，容易随外界环境条件如温度、湿度、机械作用等因素而发生Ti层与基片的剥离。
发明内容
针对上述技术问题，本发明提供一种二氧化钛薄膜的制备方法，解决现有水热法制备TiO2需进行涂覆与煅烧等工艺，涉及到高温和高压处理，存在涂覆层与基体层结合牢固性不高，合成时间相对较长等问题。
具体的技术方案为：
二氧化钛薄膜的制备方法，包括以下步骤：
(1)对原材料进行清洁
钛材料为纯钛/钛合金材料，去除表面杂质与氧化膜后，依次采用丙酮、酒精、去离子水对钛材料表面进行反复清洗；
(2)钛材料的烘干与加热
将钛材料放置于可通入流动性气体的石英反应炉内，通入氩气，排除炉内空气，并保持氩气的持续通入；将炉温升高烘干钛材料，然后根据欲获得不同反应产物与表面结构的需要，将炉温升至特定的温度；
进一步的，步骤(2)具体过程为，对石英反应炉内以2ml-1500ml/s的速率通入氩气，排除炉内空气，并保持氩气的持续通入以保证炉内氩气正压力，防止空气倒流；将炉温升至140℃并保温1小时烘干，然后根据欲获得不同反应产物与表面结构的需要，将炉温升至240℃-1400℃之间特定的温度。
(3)钛表面的水淬处理
炉温升至特定温度后，打开纯净水喷头阀门，以1ml/m2-1000ml/m2的流速将纯净水均匀喷涂在钛材料表面；纯水喷涂需要一定时间间隔，间隔时间长度根据反应需求选择在1秒至120秒之间。
进一步的，步骤(3)，具体过程为，根据对所需获得的TiO2层厚度、相及形貌的不同需合理选择反应温度、喷涂流量、与喷涂时间，具体为：
240℃-350℃，纯水喷涂流量为1ml/m2-200ml/m2，时间间隔1秒至30秒，喷涂次数1-200次，获得100nm-240μm厚度，颗粒状锐钛矿型TiO2薄膜层；
350℃-740℃，纯水喷涂流量为1ml/m2-400ml/m2，时间间隔1秒至60秒，喷涂次数1-200次，获得1μm-2㎜厚度，颗粒状锐钛矿/金红石混晶型TiO2薄膜层；
740℃-1400℃，纯水喷涂流量为1ml/m2-1000ml/m2，时间间隔1秒至120秒，喷涂次数1-200次，获得1μm-10mm厚度，表面出现针状结构的金红石型TiO2薄膜层。通过增加喷涂次数，提高该针状金红石型TiO2的数量；通过提高反应温度与喷涂纯水的流量，提高该针状金红石型TiO2的体积与长度。
本发明提供的二氧化钛薄膜的制备方法，采用纯水在高温下直接与钛表面进行反应，通过控制反应温度、反应时间与反应间歇时间的长度，可较为准确的控制钛表面生成TiO2层的厚度、形貌、相、针状孔隙结构与金红石型TiO2的体积与长度，从而根据材料应用目标满足材料的使用性能。
附图说明
图1为实施例针状结构的金红石型TiO2薄膜层的宏观形貌图；
图2为实施例800℃，纯水喷涂流量为10ml/㎡时获得的针状结构的金红石型TiO2薄膜层的宏观形貌图；
图3为实施例1100℃，纯水喷涂流量为50ml/㎡时获得的针状结构的金红石型TiO2薄膜层的宏观形貌图；
图4为实施例针状TiO2层的厚度情况图；
图5为实施例采用的石英反应炉结构示意图。
具体实施方式
结合实施例说明本发明的具体技术方案。
(1)对原材料进行清洁，具体流程为：以纯钛/钛合金材料为原材料，原材料形态包括钛膜、钛片、钛板、钛块等，去除表面杂质与氧化膜后，采用丙酮、酒精、去离子水对其进行反复清洗3次。
(2)钛材料的烘干与加热，具体工艺为：将钛材料放置于可通入流动性气体的石英反应炉内，如图4所示，以2ml-1500ml/s的速率通入氩气，排除炉内空气，并保持氩气的持续通入以保证炉内氩气正压力，防止空气倒流。将炉温升至140℃并保温1小时后，根据欲获得不同反应产物与表面结构的需要，将炉温升至240℃-1400℃之间。
(3)钛表面的水淬处理工艺，具体工艺为：根据欲获得不同反应产物与表面结构的需要，将炉温升至240℃-1400℃之间的特定温度后，打开纯净水喷头阀门，以1ml/m2-1000ml/m2的流速将纯净水均匀喷涂在钛材料表面。纯水喷涂需要一定时间间隔，间隔时间长度根据反应需求选择在1秒至120秒之间。其原因是因为钛材料在纯水喷涂后会受到冷却，造成反应温度的降低。间隔一段时间后再次喷涂的目的是使钛材料的温度重新升高，以满足在特定温度下反应的要求。
根据对所需获得的TiO2层厚度、相及形貌的不同需合理选择反应温度、喷涂流量、与喷涂时间。具体为：240℃-350℃，纯水喷涂流量为1ml/m2-200ml/m2，时间间隔1秒至30秒，喷涂次数1-200次，获得100nm-240μm厚度，颗粒状锐钛矿型TiO2薄膜层；350℃-740℃，纯水喷涂流量为1ml/m2-400ml/m2，时间间隔1秒至60秒，喷涂次数1-200次，获得1μm-2mm厚度，颗粒状锐钛矿/金红石混晶型TiO2薄膜层；740℃-1400℃，纯水喷涂流量为1ml/m2-1000ml/m2，时间间隔1秒至120秒，喷涂次数1-200次，获得1μm-10mm厚度，表面出现针状结构的金红石型TiO2薄膜层；
针状金红石型TiO2生长的调控工艺，可通过增加喷涂次数，提高该针状金红石型TiO2的数量。通过提高反应温度与喷涂纯水的流量，提高该针状金红石型TiO2的体积与长度。如图1所示，为针状结构的金红石型TiO2薄膜层的宏观形貌。
如图2所示，温度采用800℃，纯水喷涂流量为10ml/m2时获得的针状结构的金红石型TiO2薄膜层的宏观形貌。
如图3所示，温度采用1100℃，纯水喷涂流量为50ml/m2时获得的针状结构的金红石型TiO2薄膜层的宏观形貌。
如图4为针状TiO2层的厚度情况。
Claims (3)
1.二氧化钛薄膜的制备方法，其特征在于，包括以下步骤：
（1）对原材料进行清洁
钛材料为纯钛/钛合金材料，去除表面杂质与氧化膜后，依次采用丙酮、酒精、去离子水对钛材料表面进行反复清洗；
（2）钛材料的烘干与加热
将钛材料放置于可通入流动性气体的石英反应炉内，通入氩气，排除炉内空气，并保持氩气的持续通入；将炉温升高烘干钛材料，然后根据欲获得不同反应产物与表面结构的需要，将炉温升至特定的温度；
（3）钛表面的水淬处理
炉温升至特定温度后，打开纯净水喷头阀门，以1ml/m2-1000ml/m2的流速将纯净水均匀喷涂在钛材料表面；纯净水喷涂需要一定时间间隔，间隔时间长度根据反应需求选择在1秒至120秒之间；
具体过程为，根据对所需获得的TiO2层厚度、相及形貌的不同需合理选择反应温度、喷涂流速、与喷涂时间，具体为：
240℃-350℃，纯净水喷涂流速为1ml/m2-200ml/m2，时间间隔1秒至30秒，喷涂次数1-200次，获得100nm-240μm厚度，颗粒状锐钛矿型TiO2薄膜层；
350℃-740℃，纯净水喷涂流速为1ml/m2-400ml/m2，时间间隔1秒至60秒，喷涂次数1-200次，获得1μm-2mm厚度，颗粒状锐钛矿/金红石混晶型TiO2薄膜层；
740℃-1400℃，纯净水喷涂流速为1ml/m2-1000ml/m2，时间间隔1秒至120秒，喷涂次数1-200次，获得1μm-10mm厚度，表面出现针状结构的金红石型TiO2薄膜层。
2.根据权利要求1所述的二氧化钛薄膜的制备方法，其特征在于，步骤（2）具体过程为，对石英反应炉内以2ml-1500ml/s的速率通入氩气，排除炉内空气，并保持氩气的持续通入以保证炉内氩气正压力，防止空气倒流；将炉温升至140℃并保温1小时烘干，然后根据欲获得不同反应产物与表面结构的需要，将炉温升至240℃-1400℃之间特定的温度。
3.根据权利要求1或2所述的二氧化钛薄膜的制备方法，其特征在于，所述的针状结构的金红石型TiO2薄膜层的生长调控，通过增加喷涂次数，提高该针状金红石型TiO2的数量；通过提高反应温度与喷涂纯净水的流速，提高该针状金红石型TiO2的体积与长度。
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