CN113416437A - 一种耐腐蚀耐磨不粘锅涂层及其制备方法 - Google Patents
一种耐腐蚀耐磨不粘锅涂层及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种耐腐蚀耐磨不粘锅涂层,包含底层和面层材料,所述底层材料包括如下各组分:镍铝合金粉末15‑30份、碳化硼3‑6份、硼化钛4‑7份、氮化硅2‑5份、氧化镧0.5‑2.5份、二硼化锆1‑3份;所述面层材料成梯度荷叶式结构,包括有机硅树脂30‑50份、聚醚醚酮8‑12份、乙醇25‑45份、短切纤维3‑7份、纳米银4‑8份、纳米二氧化硅10‑15份;通过合金/氧化物底层+梯度性面层结构,得到了耐腐蚀性好、耐磨性高、不粘锅性能好的涂层。
Description
技术领域
本发明涉及涂层制备技术领域,具体涉及一种耐腐蚀耐磨不粘锅涂层及其制备方法。
背景技术
金属材质的锅作为食品烹饪工具,容易导致食物出现粘锅、烧焦等问题,产生苯并芘、丙烯酰胺等有害成分,危害人体健康。从20世纪60年代起,不粘锅开始进入家庭生活中,其主要原理是:在锅体表面上喷涂一层以聚四氟乙烯为主要原材料的不粘涂料,通过420℃的高温烧结,使不粘涂层与基材紧密结合,利用不粘涂层的强化学惰性将食物和锅体分开,从而起到不粘作用。然而,在聚四氟乙烯的生产过程中会使用PFOA作为原料,可能对人体和环境有害,一度引起消费者的恐慌。为此,有必要研究开发对人体和环境无害的绿色环保不粘炊具涂层。
申请号为201110316124.7的中国专利文献报道了一种炊具用防粘连涂料,由聚醚砜、聚苯硫醚、抗粘连剂、颜料、水和溶剂组成,改善了涂层的硬度、耐磨性和耐腐蚀性,然而其抗粘连剂仍然使用的是特富龙或其他氟涂层,氟涂层与铁等基材,易闪蚀,不能很好保护基材。申请号为201310015258.4的中国专利文献报道了一种纳米SiO2杂化聚酯改性有机硅的不粘涂料,该涂层具有不粘性好、耐温性好、耐化学性能优、耐腐蚀、硬度高等特点,然而其使用的有机溶剂大都对环境有害且施工上不太方便,成本也较高。
发明内容
本发明的目的是针对现有技术中不粘锅涂层在耐腐蚀、耐摩等方面存在的不足,提供一种耐腐蚀耐磨不粘锅涂层的制备方法,通过合金/氧化物底层+梯度性面层结构,得到了耐腐蚀性好、耐磨性高、不粘锅性能好的涂层。
为了实现上述目的,本申请采用如下技术方案:
一种耐腐蚀耐磨不粘锅涂层,包含底层和面层材料,所述底层材料包括如下各组分:镍铝合金粉末15-30份、碳化硼3-6份、硼化钛4-7份、氮化硅2-5份、氧化镧0.5-2.5份、二硼化锆1-3份;所述面层材料成梯度荷叶式结构,包括有机硅树脂30-50份、聚醚醚酮8-12份、乙醇25-45份、短切纤维3-7份、纳米银4-8份、纳米二氧化硅10-15份。
进一步的,所述底层材料包括镍铝合金粉末23份、碳化硼5份、硼化钛6份、氮化硅3份、氧化镧1.5份、二硼化锆2份;所述面层材料包括有机硅树脂42份、聚醚醚酮10份、乙醇35份、短切纤维5份、纳米银6份、纳米二氧化硅13份。
上述一种耐腐蚀耐磨不粘锅涂层的制备方法,包括如下步骤:
S1:对不粘锅锅体前处理;
S2:按份数比将镍铝合金粉末、碳化硼、硼化钛、氮化硅、氧化镧、二硼化锆充分混合得底层粉末;将步骤S1前处理后的不粘锅锅体预热,使温度维持在200-300℃,采用等离子喷涂粉末方式在锅体内表面预置底层粉末,干燥后得到底层材料;
S3:按份数比将有机硅树脂、聚醚醚酮和乙醇混合,边升温边加入短切纤维、纳米银、纳米二氧化硅,待温度到100-120℃,搅拌反应1-2h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为180-220℃,采用等离子喷涂粉末方式在步骤S2底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构;所述面层结构的中心到边缘的角度为1-5°;
S4:将步骤S3所得面层结构干燥即可得到所述耐腐蚀耐磨不粘锅涂层。
更进一步的,步骤S1具体为:将不粘锅锅体依次放入浓度为30-60%去污粉水溶液,饱和Na2CO3水溶液、丙酮、无水乙醇、去离子水中各超声清洗10-20min,然后在温度为80-100℃的干燥箱里鼓风干燥1-2h。
更进一步的,步骤S2具体为:所述等离子喷涂粉末工艺参数如下:喷枪角度:60-80°,电流为300-500A,喷枪枪口与容器体内表面之间距离为30-60cm,喷枪移动速度40-70cm/s,氩气流量为30-60L/min,氦气流量为20-50L/min,送气压力为15-35L/min,底层粉末流量为20-40g/min。
更进一步的,所述等离子喷涂粉末工艺参数如下:喷枪角度:70°,电流为450A,喷枪枪口与容器体内表面之间距离为45cm,喷枪移动速度55cm/s,氩气流量为40L/min,氦气流量为35L/min,送气压力为30L/min,底层粉末流量为25g/min。
更进一步的,步骤S3具体为:按份数比将有机硅树脂、聚醚醚酮和乙醇混合,边升温边加入短切纤维、纳米银、纳米二氧化硅,待温度到110℃,搅拌反应1.5h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为210℃,所述面层结构的中心到边缘的角度为5°。
更进一步的,所述等离子喷涂粉末工艺参数如下:喷枪角度:40-70°,电流为200-400A,喷枪枪口与容器体内表面之间距离为20-40cm,喷枪移动速度35-55cm/s,氩气流量为40-80L/min,氦气流量为30-60L/min,送气压力为20-40L/min,面层粉末流量为30-70g/min。
更进一步的,所述等离子喷涂粉末工艺参数如下:喷枪角度:55°,电流为350A,喷枪枪口与容器体内表面之间距离为25cm,喷枪移动速度40cm/s,氩气流量为60L/min,氦气流量为40L/min,送气压力为30L/min,面层粉末流量为50g/min。
有益效果:
1. 本发明以合金+氧化物组成的底层材料和荷叶式面层结构制备得到不粘锅涂层,该涂层具备良好的耐高温、耐腐蚀、耐磨、不粘、抗菌等性能。
2. 以镍铝合金粉末和碳化硼、硼化钛、氮化硅、氧化镧、二硼化锆等混合沉积得底层材料,采用镍铝熔点低且润湿性佳的特性,更易于锅具基体结合,附着性能好,无需加入硅烷偶联剂等增加基体结合力;镍铝合金和碳化硼、硼化钛、氮化硅、氧化镧、二硼化锆协同作用,赋予底层材料优良的耐腐蚀、耐磨、硬度和耐高温等性能。
3. 本发明采用等离子喷涂粉末工艺,底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构,采用渐进式混合,结合性能佳,不易脱落,涂层的微观结构沿特定方向呈连续变化,力学性能和组织沿厚度方向逐步变化,消除了底层和面层等之间由于物性参数巨大差异而在涂层内部产生的热应力界面,达到了缓和热应力的目的,避免裂纹产生;涂层致密均匀,孔隙较少,具备良好的耐磨、耐腐蚀、不粘、抗菌等性能。
具体实施方式
以下结合下述实施方式进一步说明本发明,下述实施方式仅用于说明本发明,而非限制本发明。
实施例1
S1:将不粘锅锅体依次放入浓度为40%去污粉水溶液,饱和Na2CO3水溶液、丙酮、无水乙醇、去离子水中各超声清洗15min,然后在温度为90℃的干燥箱里鼓风干燥2h;
S2:将15g镍铝合金粉末、3g碳化硼、4g硼化钛、2g氮化硅、0.5g氧化镧、1g二硼化锆充分混合得底层粉末;将步骤S1前处理后的不粘锅锅体预热,使温度维持在200℃,采用等离子喷涂粉末方式在锅体内表面预置底层粉末,干燥后得到底层材料;所述等离子喷涂粉末工艺参数如下:喷枪角度:60°,电流为300A,喷枪枪口与容器体内表面之间距离为30cm,喷枪移动速度40cm/s,氩气流量为30L/min,氦气流量为20L/min,送气压力为15L/min,底层粉末流量为20g/min;
S3:将30g有机硅树脂、8g聚醚醚酮和25g乙醇混合,边升温边加入3g短切纤维、4g纳米银、10g纳米二氧化硅,待温度到100℃,搅拌反应1h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为180℃,采用等离子喷涂粉末方式在步骤S2底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构;所述面层结构的中心到边缘的角度为3°;所述等离子喷涂粉末工艺参数如下:喷枪角度:40°,电流为200A,喷枪枪口与容器体内表面之间距离为20cm,喷枪移动速度35cm/s,氩气流量为40L/min,氦气流量为30L/min,送气压力为20L/min,面层粉末流量为30g/min;
S4:将步骤S3所得面层结构干燥即可得到所述耐腐蚀耐磨不粘锅涂层。
实施例2
S1:将不粘锅锅体依次放入浓度为40%去污粉水溶液,饱和Na2CO3水溶液、丙酮、无水乙醇、去离子水中各超声清洗15min,然后在温度为90℃的干燥箱里鼓风干燥2h;
S2:将30g镍铝合金粉末、6g碳化硼、7g硼化钛、5g氮化硅、2.5g氧化镧、3g二硼化锆充分混合得底层粉末;将步骤S1前处理后的不粘锅锅体预热,使温度维持在300℃,采用等离子喷涂粉末方式在锅体内表面预置底层粉末,干燥后得到底层材料;所述等离子喷涂粉末工艺参数如下:喷枪角度:80°,电流为500A,喷枪枪口与容器体内表面之间距离为60cm,喷枪移动速度70cm/s,氩气流量为60L/min,氦气流量为50L/min,送气压力为35L/min,底层粉末流量为40g/min;
S3:将50g有机硅树脂、12g聚醚醚酮和45g乙醇混合,边升温边加入7g短切纤维、8g纳米银、15g纳米二氧化硅,待温度到120℃,搅拌反应2h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为220℃,采用等离子喷涂粉末方式在步骤S2底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构;所述面层结构的中心到边缘的角度为7°;所述等离子喷涂粉末工艺参数如下:喷枪角度:70°,电流为400A,喷枪枪口与容器体内表面之间距离为40cm,喷枪移动速度55cm/s,氩气流量为80L/min,氦气流量为60L/min,送气压力为40L/min,面层粉末流量为70g/min;
S4:将步骤S3所得面层结构干燥即可得到所述耐腐蚀耐磨不粘锅涂层。
实施例3
S1:将不粘锅锅体依次放入浓度为40%去污粉水溶液,饱和Na2CO3水溶液、丙酮、无水乙醇、去离子水中各超声清洗15min,然后在温度为90℃的干燥箱里鼓风干燥2h;
S2:将23g镍铝合金粉末、5g碳化硼、6g硼化钛、3g氮化硅、1.5g氧化镧、2g二硼化锆充分混合得底层粉末;将步骤S1前处理后的不粘锅锅体预热,使温度维持在260℃,采用等离子喷涂粉末方式在锅体内表面预置底层粉末,干燥后得到底层材料;所述等离子喷涂粉末工艺参数如下:喷枪角度:70°,电流为450A,喷枪枪口与容器体内表面之间距离为45cm,喷枪移动速度55cm/s,氩气流量为40L/min,氦气流量为35L/min,送气压力为30L/min,底层粉末流量为25g/min;
S3:将42g有机硅树脂、10g聚醚醚酮和35g乙醇混合,边升温边加入5g短切纤维、6g纳米银、13g纳米二氧化硅,待温度到110℃,搅拌反应1.5h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为210℃,采用等离子喷涂粉末方式在步骤S2底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构;所述面层结构的中心到边缘的角度为5°;所述等离子喷涂粉末工艺参数如下:喷枪角度:55°,电流为350A,喷枪枪口与容器体内表面之间距离为25cm,喷枪移动速度40cm/s,氩气流量为60L/min,氦气流量为40L/min,送气压力为30L/min,面层粉末流量为50g/min;
S4:将步骤S3所得面层结构干燥即可得到所述耐腐蚀耐磨不粘锅涂层。
对比例1
与实施例1的区别在于,步骤S2中不使用镍铝合金粉末,其他步骤与条件不变。
比照对比例1和实施例1的数据可知,由于步骤S2中缺少镍铝合金粉末,底层材料与锅具基体结合力下降,附着性能减弱;硬度和耐磨性等有所降低。
对比例2
与实施例1的区别在于,步骤S2中不使用氧化镧、二硼化锆,其他步骤与条件不变。
比照对比例2和实施例1的数据可知,由于步骤S2中缺少氧化镧、二硼化锆,底层材料耐腐蚀、耐磨等性能有所下降。
对比例3
与实施例1的区别在于,步骤S2中不使用硼化钛、氮化硅,其他步骤与条件不变。
比照对比例3和实施例1的数据可知,由于步骤S2中缺少硼化钛、氮化硅,底层材料耐腐蚀、耐磨等性能有所下降。
对比例4
与实施例1的区别在于,步骤S2中采用普通涂覆方法,而非等离子喷涂粉末工艺,其他步骤与条件不变。
比照对比例4和实施例1的数据可知,普通涂覆方法相比,底层材料与锅体基体的结合力和涂层本身致密性均有所下降。
对比例5
与实施例1的区别在于,步骤S2中采用等离子喷涂粉末方式在步骤S2底层材料上表面直接喷涂,而非从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构,其他步骤与条件不变。
比照对比例5和实施例1的数据可知,对比例5中未形成梯度荷叶式面层结构,涂层会产生一定的裂纹,分布不够均匀;且耐磨、耐腐蚀、不粘、抗菌等性能均有所下降。
性能测试方法:
涂层的附着力测试方法为GB9286-1998,硬度的方法为GB/T6739-耐冲击性的测试方法为GB1732-93,耐磨性的测试方法为GB1768-1979,以250g砝码下砂轮打磨200圈后失重作为耐磨性的评价标准。涂层的热稳定性通过测定其5%热失重温度来表征,所用仪器为梅特勒公司的同步热分析仪TGA/DSC1进行测试表征,样品测试条件为:在空气气氛下。耐腐蚀性能测试:将不粘锅涂层浸泡于10%盐酸溶液、10%的氢氧化钠溶液或1mol/L的氯化钠溶液中,共浸泡10天,观察膜表面。
对上述各实施例和对比例进行测试,结果如下:
试验 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 | 对比例4 | 对比例5 |
附着力 | 0级 | 0级 | 0级 | 2级 | 1级 | 1级 | 2级 | 2级 |
硬度 | 5H | 6H | 6H | 3H | 4H | 4H | 4H | 4H |
耐冲击性(kg·cm) | 271 | 278 | 282 | 238 | 247 | 253 | 231 | 216 |
耐磨性(g) | 0.0018 | 0.0016 | 0.0012 | 0.0045 | 0.0031 | 0.0035 | 0.0047 | 0.0061 |
耐热性(℃) | 645 | 652 | 663 | 610 | 617 | 625 | 637 | 636 |
抗菌率(%) | 99.8 | 99.9 | 99.9 | 99.2 | 98.3 | 98.5 | 98.9 | 96.1 |
耐腐蚀性(盐) | 10天无变化 | 10天无变化 | 10天无变化 | 9天出现溶出 | 7天出现溶出 | 7天出现溶出 | 8天出现溶出 | 8天出现溶出 |
耐腐蚀性(酸) | 10天无变化 | 10天无变化 | 10天无变化 | 9天出现溶出 | 7天出现溶出 | 7天出现溶出 | 8天出现溶出 | 8天出现溶出 |
耐腐蚀性(碱) | 10天无变化 | 10天无变化 | 10天无变化 | 9天出现溶出 | 7天出现溶出 | 7天出现溶出 | 8天出现溶出 | 8天出现溶出 |
以上所述仅为本发明的较佳实施方式,本发明的保护范围并不以上述实施方式为限,但凡本领域普通技术人员根据本发明所揭示内容所作的等效修饰或变化,皆应纳入权利要求书中记载的保护范围内。
Claims (9)
1.一种耐腐蚀耐磨不粘锅涂层,其特征在于,包含底层和面层材料,所述底层材料包括如下各组分:镍铝合金粉末15-30份、碳化硼3-6份、硼化钛4-7份、氮化硅2-5份、氧化镧0.5-2.5份、二硼化锆1-3份;所述面层材料成梯度荷叶式结构,包括有机硅树脂30-50份、聚醚醚酮8-12份、乙醇25-45份、短切纤维3-7份、纳米银4-8份、纳米二氧化硅10-15份。
2.根据权利要求1所述的一种耐腐蚀耐磨不粘锅涂层,其特征在于,所述底层材料包括镍铝合金粉末23份、碳化硼5份、硼化钛6份、氮化硅3份、氧化镧1.5份、二硼化锆2;所述面层材料包括有机硅树脂42份、聚醚醚酮10份、乙醇35份、短切纤维5份、纳米银6份、纳米二氧化硅13份。
3.根据权利要求1或2所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,包括如下步骤:
S1:对不粘锅锅体前处理;
S2:按份数比将镍铝合金粉末、碳化硼、硼化钛、氮化硅、氧化镧、二硼化锆充分混合得底层粉末;将步骤S1前处理后的不粘锅锅体预热,使温度维持在200-300℃,采用等离子喷涂粉末方式在锅体内表面预置底层粉末,干燥后得到底层材料;
S3:按份数比将有机硅树脂、聚醚醚酮和乙醇混合,边升温边加入短切纤维、纳米银、纳米二氧化硅,待温度到100-120℃,搅拌反应1-2h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为180-220℃,采用等离子喷涂粉末方式在步骤S2底层材料上表面从内向外逐渐递减喷涂面层粉末,形成荷叶式面层结构;所述面层结构的中心到边缘的角度为1-5°;
S4:将步骤S3所得面层结构干燥即可得到所述耐腐蚀耐磨不粘锅涂层。
4.根据权利要求3所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,步骤S1具体为:将不粘锅锅体依次放入浓度为30-60%去污粉水溶液,饱和Na2CO3水溶液、丙酮、无水乙醇、去离子水中各超声清洗10-20min,然后在温度为80-100℃的干燥箱里鼓风干燥1-2h。
5.根据权利要求3所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,步骤S2具体为:所述等离子喷涂粉末工艺参数如下:喷枪角度:60-80°,电流为300-500A,喷枪枪口与容器体内表面之间距离为30-60cm,喷枪移动速度40-70cm/s,氩气流量为30-60L/min,氦气流量为20-50L/min,送气压力为15-35L/min,底层粉末流量为20-40g/min。
6.根据权利要求5所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,步骤S2具体为:所述等离子喷涂粉末工艺参数如下:喷枪角度:70°,电流为450A,喷枪枪口与容器体内表面之间距离为45cm,喷枪移动速度55cm/s,氩气流量为40L/min,氦气流量为35L/min,送气压力为30L/min,底层粉末流量为25g/min。
7.根据权利要求3所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,步骤S3具体为:按份数比将有机硅树脂、聚醚醚酮和乙醇混合,边升温边加入短切纤维、纳米银、纳米二氧化硅,待温度到110℃,搅拌反应1.5h;后经干燥粉碎得面层粉末;控制不粘锅锅体温度为210℃,所述面层结构的中心到边缘的角度为3°。
8.根据权利要求7所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,所述等离子喷涂粉末工艺参数如下:喷枪角度:40-70°,电流为200-400A,喷枪枪口与容器体内表面之间距离为20-40cm,喷枪移动速度35-55cm/s,氩气流量为40-80L/min,氦气流量为30-60L/min,送气压力为20-40L/min,面层粉末流量为30-70g/min。
9.根据权利要求8所述的一种耐腐蚀耐磨不粘锅涂层的制备方法,其特征在于,所述等离子喷涂粉末工艺参数如下:喷枪角度:55°,电流为350A,喷枪枪口与容器体内表面之间距离为25cm,喷枪移动速度40cm/s,氩气流量为60L/min,氦气流量为40L/min,送气压力为30L/min,面层粉末流量为50g/min。
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