CN116144254A - 一种用于增强低表面能树脂附着力的仿生梯度材料 - Google Patents
一种用于增强低表面能树脂附着力的仿生梯度材料 Download PDFInfo
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Abstract
本发明提出了一种用于增强低表面能树脂附着力的仿生梯度材料,属于仿生材料技术领域。本发明受自然界中的树木通过在土壤中扎根策略启发,提出了一种用于增强低表面能树脂附着力的仿生梯度材料,该材料由低表面能的树脂和高表面能树脂构成,以高表面能树脂模拟泥土,其上部带有多孔结构,利用低表面能树脂模拟树干和树根,使其下部融合进高表面能树脂的多孔结构中,通过物理结合的方式形成用于增强低表面能树脂附着力的仿生梯度材料,即顶部低表面能,底部高表面能;弹性模量的分布为顶部弹性模量低、中间次之,底部弹性模量高。本发明的仿生梯度材料显著提升了PDMS与金属基底的附着力,在304不锈钢基底表面,其附着力为纯PDMS的6.38倍。
Description
技术领域
本发明属于仿生材料技术领域。
背景技术
硅树脂(如硅橡胶、聚二甲基硅氧烷等)具有优异的物理、化学特性,在电绝缘、涂料、塑料、日用品等领域广泛应用。然而,由于硅树脂通常具有低表面能特性,作为涂料使用时,其与基底材料的结合力差,从而容易从基底脱落,降低使用寿命。传统的方法是对硅树脂表面进行化学改性提升其表面能,但由于原子的迁移特性,这种表面化学改性提升的表面能不够持久;另一方面,对于海洋防污涂料,提升其表面能会使防污性能下降,这是一个矛盾的地方。
自然界中的树木通过在土壤中扎根,即使风吹雨打也不易从土壤中脱离;如图1所示,软珊瑚在钙化的珊瑚礁(珊瑚礁为死亡珊瑚的尸体,为多孔结构)上扎根生长,在水流作用下,也不会被冲走,这些现象表明生物进化出了独特的附着策略,也为解决上述问题提供了一种新的思路。
发明内容
本发明受上述生物扎根策略启发,提出了一种用于增强低表面能树脂附着力的仿生梯度材料,该材料由低表面能的树脂和高表面能树脂构成,
以高表面能树脂模拟泥土,其上部带有多孔结构,利用低表面能树脂模拟树干和树根,使其下部融合进高表面能树脂的多孔结构中,通过物理结合的方式形成用于增强低表面能树脂附着力的仿生梯度材料,即顶部低表面能,底部高表面能;顶部弹性模量低、中间次之,底部弹性模量高的梯度材料。
其中低表面能的树脂优选为聚二甲基硅氧烷(PDMS),高表面能树脂优选为聚氨酯(PU)
本发明中一种用于增强低表面能树脂附着力的仿生梯度材料的制备方法,具体步骤如下:
步骤一、在金属基底上制备聚氨酯底层;
步骤二、在聚氨酯底层上制备多孔聚氨酯;
步骤三、在多孔聚氨酯上制备聚二甲基硅氧烷。
步骤一的具体步骤如下:
(1)按照质量比10:1:4的比例称取聚氨酯、固化剂和乙酸乙酯,向聚氨酯中加入固化剂和乙酸乙酯搅拌均匀获得聚氨酯稀释液;
(2)将充分搅拌后的聚氨酯稀释液置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(3)取0.8mL聚氨酯稀释液均匀涂附在基底上,放置24h待聚氨酯固化,得到聚氨酯底层。
步骤二的具体步骤如下:
(1)按照质量比10:1:6:(50~110)称取聚氨酯、固化剂、乙酸乙酯和氯化钠,将固化剂、乙酸乙酯与氯化钠加入聚氨酯中,搅拌均匀获得PU-氯化钠混合液;
(2)取1mL的PU-NaCl混合液均匀涂附在步骤一获得的聚氨酯底层上,放置24h待其固化;
(3)待PU-NaCl混合液表面固化后,将其放置在60℃条件下水浴加热24h以溶解NaCl颗粒,为加快溶解效率,每2h左右换一次水;
(4)待NaCl溶解析出后,将产品放入60℃烘箱中烘干,在聚氨酯底层上制备得到多孔聚氨酯。
步骤三的具体步骤如下:
(1)按照质量比10:1的比例称取聚二甲基硅氧烷和固化剂,将固化剂加入聚二甲基硅氧烷中,搅拌均匀后,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失,;
(2)取1.5mL步骤(1)中混有固化剂的聚二甲基硅氧烷均匀涂附在步骤二制备得到的多孔聚氨酯表面,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(3)将步骤(2)的产品置于90℃环境下加热6h,使聚二甲基硅氧烷固化,获得所述用于增强低表面能树脂附着力的仿生梯度材料。
本发明的有益效果:
由于聚氨酯与金属基底的附着力较高,本发明的仿生梯度材料显著提升了PDMS与金属基底的附着力,在304不锈钢基底表面,其附着力为纯PDMS的6.38倍,本发明为硅树脂类涂料的应用提供了参考。
附图说明
图1受生物扎根泥土启发的仿生梯度材料
图2本发明的制备流程示意图
图3本发明对制备的仿生梯度材料进行附着力试验的照片
图4本发明对制备的仿生梯度材料进行附着力试验的结果图
具体实施方式
下面以具体实施例的形式对本发明技术方案做进一步解释和说明。
本实施例中整体制备流程采用自下而上的方式,即先制备PU底层,然后制备多孔层,最后制备PDMS顶层(图2),具体流程如下:
(1)称取10g的PU,加入1g固化剂与4g乙酸乙酯搅拌均匀获得聚氨酯稀释液;
(2)将充分搅拌后的聚氨酯稀释液置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(3)取0.8mL聚氨酯稀释液均匀涂附在10cm×10cm的不锈钢金属板,放置24h待PU固化,得到PU底层;
(4)称取10g的PU,加入1g固化剂、6g乙酸乙酯与70g氯化钠(NaCl)搅拌均匀获得PU-氯化钠混合液,PU:NaCl质量比优化范围为1:5-1:11;
(5)取1mL的PU-NaCl混合液均匀涂附在(3)步骤固化后的PU底层上,放置24h待其固化;
(6)待PU-NaCl表面固化后,将其放置在60℃条件下水浴加热24h以溶解NaCl颗粒,为加快溶解效率,每2h左右换一次水;
(7)待NaCl溶解析出后,取出金属板,放入60℃烘箱中烘干,得到PU底层上覆盖的多孔结构;
(8)取10g的PDMS,加入1g固化剂搅拌均匀,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(9)取1.5mL的PDMS均匀涂附在多孔PU表面,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失,保证PDMS完全渗入到多孔PU中;
(10)将金属板置于90℃环境下加热6h,使PDMS固化,获得PDMS-PU仿生梯度材料(即用于增强低表面能树脂附着力的仿生梯度材料)。
最终获得的PDMS-PU仿生梯度材料:PU底层厚度范围0.10–0.15mm,多孔PU中间层厚度范围0.15-0.20mm,PDMS顶层厚度范围0.3-0.4mm。
效果验证
依据《GB/T5210-2006色漆和清漆拉开法附着力试验》,对本发明制备的仿生梯度材料进行附着力测量。仿生梯度材料a:b定义为中间层中的PU含量a,NaCl含量b。对照组PDMS为纯PDMS,PDMS-PU为PDMS直接覆盖在PU表面,为保证实验的一致性,对照组厚度与仿生梯度材料一致。上述所有样品均涂在304不锈钢基底表面进行实验。
在304不锈钢基底表面,纯PDMS的附着力为0.16±0.02MPa,PDMS-PU的附着力为0.18±0.02MPa,仿生梯度材料1:5的附着力为0.58±0.1MPa,仿生梯度材料1:7的附着力为0.95±0.07MPa,仿生梯度材料1:9的附着力为1.02±0.11MPa,仿生梯度材料1:11的附着力为0.81±0.08MPa。最优值为仿生梯度材料1:9的附着力,比纯PDMS附着力提升了6.38倍。
Claims (6)
1.一种用于增强低表面能树脂附着力的仿生梯度材料,其特征在于,该材料由低表面能的树脂和高表面能树脂构成,
以高表面能树脂模拟泥土,其上部带有多孔结构,利用低表面能树脂模拟树干和树根,使其下部融合进高表面能树脂的多孔结构中,通过物理结合的方式形成用于增强低表面能树脂附着力的仿生梯度材料,即顶部低表面能,底部高表面能;弹性模量分布为顶部弹性模量低、中间次之,底部弹性模量高。
2.根据权利要求1所述的用于增强低表面能树脂附着力的仿生梯度材料,其特征在于,低表面能的树脂为聚二甲基硅氧烷,高表面能树脂为聚氨酯。
3.一种如权利要求2所述用于增强低表面能树脂附着力的仿生梯度材料的制备方法,其特征在于,该方法的具体步骤如下:
步骤一、在金属基底上制备聚氨酯底层;
步骤二、在聚氨酯底层上制备多孔聚氨酯;
步骤三、在多孔聚氨酯上制备聚二甲基硅氧烷。
4.根据权利要求3所述的用于增强低表面能树脂附着力的仿生梯度材料的制备方法,其特征在于,步骤一的具体步骤如下:
(1)按照质量比10:1:4的比例称取聚氨酯、固化剂和乙酸乙酯,向聚氨酯中加入固化剂和乙酸乙酯搅拌均匀获得聚氨酯稀释液;
(2)将充分搅拌后的聚氨酯稀释液置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(3)取0.8mL聚氨酯稀释液均匀涂附在基底上,放置24h待聚氨酯固化,得到聚氨酯底层。
5.根据权利要求3所述的用于增强低表面能树脂附着力的仿生梯度材料的制备方法,其特征在于,步骤二的具体步骤如下:
(1)按照质量比10:1:6:(50~110)称取聚氨酯、固化剂、乙酸乙酯和氯化钠,将固化剂、乙酸乙酯与氯化钠加入聚氨酯中,搅拌均匀获得PU-氯化钠混合液;
(2)取1mL的PU-NaCl混合液均匀涂附在步骤一获得的聚氨酯底层上,放置24h待其固化;
(3)待PU-NaCl混合液表面固化后,将其放置在60℃条件下水浴加热24h以溶解NaCl颗粒,为加快溶解效率,每2h左右换一次水;
(4)待NaCl溶解析出后,将产品放入60℃烘箱中烘干,在聚氨酯底层上制备得到多孔聚氨酯。
6.根据权利要求3所述的用于增强低表面能树脂附着力的仿生梯度材料的制备方法,其特征在于,步骤三的具体步骤如下:
(1)按照质量比10:1的比例称取聚二甲基硅氧烷和固化剂,将固化剂加入聚二甲基硅氧烷中,搅拌均匀后,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(2)取1.5mL步骤(1)中混有固化剂的聚二甲基硅氧烷均匀涂附在步骤二制备得到的多孔聚氨酯表面,置于真空干燥箱中抽真空保持负压0.1MPa的状态,直到气泡消失;
(3)将步骤(2)的产品置于90℃环境下加热6h,使聚二甲基硅氧烷固化,获得所述用于增强低表面能树脂附着力的仿生梯度材料。
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