CN108456878B - 一种纳米颗粒表面改性提升转化膜性能方法 - Google Patents
一种纳米颗粒表面改性提升转化膜性能方法 Download PDFInfo
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Abstract
本发明涉及一种纳米颗粒表面改性提升转化膜性能方法，属于金属材料的表面处理技术领域。本发明所述的方法包括：先对试样表面经过打磨处理，随后利用硅烷偶联剂水解在镁合金表面通过自组装的形式形成硅烷膜，随后加入纳米颗粒最终经过磷化处理得到耐蚀性良好的磷化膜。具体包括：硅烷溶液的配制，溶胶法制备纳米颗粒，试样的预处理，转化膜的制备。与现有技术相比，本发明的膜层制备操作简单，成本低廉，制备出的磷化膜表面均一致密，颗粒细小且排列紧密，有着良好的耐蚀性能，对基体耐蚀性能的提高很明显。
Description
技术领域
本发明属于金属材料表面化学处理技术领域，特别涉及化学转化膜前处理的方法。
背景技术
随着科学技术的发展，各类金属及其合金在国民生产生活当中起着越来越重要的作用。与此同时，腐蚀所引起的材料失效问题也愈发的突出，据不完全统计，单就钢铁行业而言，其每年因腐蚀原因导致报废的材料占其年产量的30％，提升金属材料的耐蚀性能已成为当下工程材料防护技术中的一个重要环节。
在众多的防腐蚀手段中，表面处理因其简单经济快捷被人们所广泛青睐。常用的表面腐蚀防护方法有，阳极氧化处理，微弧氧化处理，化学气相沉积，物理气相沉积，化学镀，电镀和化学转化膜等。在此当中，化学转化膜价格低廉，操作简单，能耗较低，应用范围广泛，是金属腐蚀防护技术一个极为良好的选择。对于化学转化膜技术来说，在成膜前的基体的表面状态直接影响到了随后成膜的质量以及膜层的耐蚀性能，前处理是一项行之有效的提升转化膜性能的步骤。
纳米材料因为其具有的众多出色性能,使它在材料领域一直倍受重视。尤其在于因为其有着小尺寸效应，表界面效应等，导致其与众不同的表界面特性使其在表面改性方面有着广泛地应用，诸如用于陶瓷制品、人造莫来石材料、新型橡胶材料、粘结剂和密封胶、新型有机玻璃、功能纤维、新型塑料、抗老化涂料、纸张表面涂层等各个领域。
硅烷偶联剂是应用最广泛的一类偶联剂，是一类具有特殊结构的低分子有机硅化合物，其可以同时与无机物中的羟基和有机聚合物中的长分子链相互作用，使两种不同性质的材料偶联起来。其用于金属腐蚀防护方面的应用，主要是通过硅烷偶联剂水解生成硅醇与金属表面的羟基结合，形成涂层，提高其抗腐蚀性。
发明内容
为了克服现有技术的不足，本发明提供一种纳米颗粒表面改性提升转化膜性能方法，前处理中形成硅烷膜，将硅烷膜作为预处理膜，同时在之后的步骤中引入纳米颗粒进行表面改性处理，目的是利用硅烷偶联剂使得金属基体与纳米粒子充分结合，进而在成膜过程中形核位点增加，进一步使得膜层晶粒细化，减少膜层的孔隙率，降低其裂缝产生的概率，从而达到提升膜层耐蚀性能的目的。
本发明的上述目的是通过以下技术方案来实现的：
一种纳米颗粒表面改性提升转化膜性能方法，包括步骤如下：
步骤1，硅烷溶液的配制：配制硅烷偶联剂：C2H5OH：H2O质量比为8～9:1～0.5:1～0.5的溶液，然后静置5～60min，使得硅烷溶液充分水解，随后进一步稀释，稀释浓度比为1～10％；
步骤2，试样的预处理：将金属试样用砂纸打磨，随后用丙酮超声除油，酒精清洗，去离子水冲洗后干燥；
步骤3，试样的制备：将步骤2预处理后的试样在步骤1配制得到的硅烷溶液中提拉浸泡1～2min，随后在80～120℃的烘箱中烘干5～15min；
步骤4，在加入纳米颗粒的溶液中，先搅拌2～3h，随后超声10～30min，再将步骤3处理得到的试样提拉浸没30～60s，再用蒸馏水浸洗；
步骤5，通过转化膜工艺成膜，随后取出在蒸馏水中浸洗，常温下老化。
进一步地，上述步骤1中水解静置时间为10～15min，进一步稀释浓度比为1～3％。
进一步地，上述步骤2砂纸打磨按照240目、400目、800目、1000目的砂纸依次打磨。
进一步地，上述步骤2金属试样为镁合金、不锈钢或铝合金中的一种。
进一步地，上述步骤4中的纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒或三氧化二铝纳米颗粒中的一种。
进一步地，上述二氧化硅纳米颗粒溶液的制备：在室温下，将5～10ml TEOS(正硅酸乙酯)在100～150ml乙醇中溶解，加入5～10ml去离子水以及2～3ml氨水，磁力搅拌器混合10～15min，静置。
进一步地，上述步骤5所述的转化膜工艺为磷化膜工艺或稀土转化膜工艺中的一种。
本发明的有益效果：
1)前处理制备纳米颗粒操作简单，成本低廉，耐用可靠
2)纳米颗粒能够在成膜过程中作为形核中心，有效降低晶粒尺寸
3)可以制备出有机无机相紧密结合的复合涂层
4)通过硅烷偶联剂KH550制备的硅烷预处理层能够有效增强与金属基体的附着力，同时使得纳米颗粒与有机涂层紧密结合，让其在有机层表面均匀分布
5)磷化膜表面排列紧密，颗粒较小，孔隙率较小，能够有效防止腐蚀介质进入，能够有效提升基体的耐蚀性。
附图说明
附图1为通过溶胶法制得的二氧化硅纳米颗粒扫描电镜照片。
附图2为经过硅烷偶联剂KH550处理后，制得基体表面制得的硅烷膜扫描电镜照片。
附图3为将经过KH550+SiO2处理后的试样经过溶胶溶液处理的扫描电镜照片。
附图4为经过上述前处理后，磷酸盐转化膜的表面形貌。
附图5为该种镁合金基体，磷化膜以及本专利处理后磷化膜集氢结果。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
本发明中KH550水解机理如下：
硅烷偶联剂的水解：R-Si-O-R'+H2O→R-Si-OH+R'-OH
硅醇基在金属表面的吸附：R-Si-OH+HO-Metal→R-Si-O-Metal+H2O
硅醇基在金属表面的交联：R-Si-OH+HO-Si-R→R-Si-O-Si-R+H2O
硅烷偶联剂水解后生成硅醇(R-Si(OH)3)，硅醇与金属表面的羟基发生化学键合生成Si-O-Metal键，同时硅醇本身也会发生自缩合的交联反应在金属表面生成一层保护膜，该处理方法不仅能改善金属表面性质，同时还可以提高金属的耐腐蚀性。
实例1
溶胶的制备：在室温下，将5ml TEOS在100ml乙醇中溶解，加入5ml去离子水以及2ml氨水，磁力搅拌器混合，10min。静置5h
图1中可看到，制得的纳米二氧化硅颗粒直径约在100nm左右
实例2
A.硅烷溶液的配制：配制KH550:C2H5OH:H2O质量比为8:1:1的溶液，然后静置5min，使得硅烷溶液充分水解，稀释成1％的溶液。
B.试样的预处理：将镁合金分别用240目，400目，800目，1000目的砂纸打磨，随后用丙酮超声除油，酒精清洗用去离子水冲洗后干燥待用
C.试样的制备：将试样在配制得硅烷溶液中提拉浸泡1min，随后在80℃的烘箱中烘干5min
D.溶胶的制备：在室温下，将10ml TEOS在100ml乙醇中溶解，加入10ml去离子水以及2ml氨水，磁力搅拌器混合，10min。静置5h。
E.纳米颗粒的附着：将D中制备的溶胶搅拌2h，随后超声30min，将经过硅烷处理的试样在溶胶中提拉浸没30s用蒸馏水浸洗。
F.在已配置的磷化液中成膜10min，随后取出在蒸馏水中浸洗30s，常温下老化24h。
从图2中可以看到，在试样表面制得较为均匀的硅烷覆盖层。
实例3
A.硅烷溶液的配制：配制KH550:C2H5OH:H2O质量比为8:1:1的溶液，然后静置30min，使得硅烷溶液充分水解，稀释成5％的溶液。
B.试样的预处理：将镁合金分别用240目，400目，800目，1000目的砂纸打磨，随后用丙酮超声除油，酒精清洗用去离子水冲洗后干燥待用
C.试样的制备：将试样在配制得硅烷溶液中提拉浸泡1min，随后在100℃的烘箱中烘干10min
D.溶胶的制备：在室温下，将10ml TEOS在100ml乙醇中溶解，加入10ml去离子水以及2ml氨水，磁力搅拌器混合，10min。静置5h。
E.纳米颗粒的附着：将D中制备的溶胶搅拌2h，随后超声30min，将经过硅烷处理的试样在溶胶中提拉浸没30s用蒸馏水浸洗。
F.在已配置的磷化液中成膜10min，随后取出在蒸馏水中浸洗30s，常温下老化24h。
图3中看到，纳米二氧化硅颗粒较为均匀地分布在基体表面
实例4
A.硅烷溶液的配制：配制KH550:C2H5OH:H2O质量比为8:1:1的溶液，然后静置60min，使得硅烷溶液充分水解，稀释成10％的溶液。
B.试样的预处理：将镁合金分别用240目，400目，800目，1000目的砂纸打磨，随后用丙酮超声除油，酒精清洗用去离子水冲洗后干燥待用
C.试样的制备：将试样在配制得硅烷溶液中提拉浸泡2min，随后在120℃的烘箱中烘干15min
D.溶胶的制备：在室温下，将10ml TEOS在100ml乙醇中溶解，加入10ml去离子水以及2ml氨水，磁力搅拌器混合，10min。静置5h。
E.纳米颗粒的附着：将D中制备的溶胶搅拌2h，随后超声30min，将经过硅烷处理的试样在溶胶中提拉浸没30s用蒸馏水浸洗。
F.在已配置的磷化液中成膜10min，随后取出在蒸馏水中浸洗30s，常温下老化24h。
图4中可看到，在基体表面覆盖了颗粒细小，排列紧密的膜层
上述硅烷溶液的配制：乙醇与水体积比值范围可选为9-1/9。
上述KH550型硅烷偶联剂质量分数可选为2％-10％。
上述KH550型硅烷偶联剂水解时间可选为1-2小时
上述KH550型硅烷偶联剂需在水解完成后1h以内用完
上述试样置入硅烷溶液可选0.5-2分钟
上述试样可在80-120℃环境下烘干。
上述烘干时间可选为10-15min。
上述溶胶溶液可反复利用。
上述磷化膜能够有效提升镁稀土合金的耐蚀性能。
表1不同处理集氢量
| 48h析氢量(ml·cm<sup>-2</sup>) | |
| 基体 | 21.3 |
| 磷化膜 | 2.7 |
| 本专利处理后磷化膜 | 0.4 |
如表1和图5所示集氢是常用的耐蚀性能测试的方法，48h析氢量越少，表示该涂层耐蚀性能越好。
以上所述内容为本发明构思下的基本说明，而依据本发明所做的任何等效变换，均应属于本发明的保护范围。
Claims (9)
1.一种纳米颗粒表面改性提升转化膜性能方法，其特征在于，包括步骤如下：
步骤1，硅烷溶液的配制：配制硅烷偶联剂：C2H5OH：H2O质量比为8～9:1～0.5:1～0.5的溶液，然后静置5～60min，使得硅烷溶液充分水解，随后进一步稀释，稀释浓度比为1～10％；
步骤2，试样的预处理：将金属试样用砂纸打磨，随后用丙酮超声除油，酒精清洗，去离子水冲洗后干燥；
步骤3，试样的制备：将步骤2预处理后的试样在步骤1配制得到的硅烷溶液中提拉浸泡1～2min，随后在80～120℃的烘箱中烘干5～15min；
步骤4，在加入纳米颗粒的溶液中，先搅拌2～3h，随后超声10～30min，再将步骤3处理得到的试样提拉浸没30～60s，再用蒸馏水浸洗；所述的纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒或三氧化二铝纳米颗粒中的一种；
步骤5，通过转化膜工艺成膜，随后取出在蒸馏水中浸洗，常温下老化。
2.根据权利要求1所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤1中水解静置时间为10～15min，进一步稀释浓度比为1～3％。
3.根据权利要求1或2所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤2砂纸打磨按照240目、400目、800目、1000目的砂纸依次打磨。
4.根据权利要求1或2所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤2金属试样为镁合金、不锈钢或铝合金中的一种。
5.根据权利要求3所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤2金属试样为镁合金、不锈钢或铝合金中的一种。
6.根据权利要求1或2或5所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，二氧化硅纳米颗粒溶液的制备：在室温下，将5～10ml TEOS在100～150ml乙醇中溶解，加入5～10ml去离子水以及2～3ml氨水，磁力搅拌器混合10～15min，静置。
7.根据权利要求1或2或5所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤5所述的转化膜工艺为磷化膜工艺或稀土转化膜工艺中的一种。
8.根据权利要求3所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤5所述的转化膜工艺为磷化膜工艺或稀土转化膜工艺中的一种。
9.根据权利要求4所述的纳米颗粒表面改性提升转化膜性能方法，其特征在于，步骤5所述的转化膜工艺为磷化膜工艺或稀土转化膜工艺中的一种。
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