CN104271793B - 高表面积涂层 - Google Patents
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- CN104271793B CN104271793B CN201380010776.5A CN201380010776A CN104271793B CN 104271793 B CN104271793 B CN 104271793B CN 201380010776 A CN201380010776 A CN 201380010776A CN 104271793 B CN104271793 B CN 104271793B
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Abstract
本发明涉及一种将涂层涂布到制品的方法和具有所述涂层的制品。该涂层具有至少一个层,该层的表面积大于所述涂层的所述层的表观面积或投影面积。这种高表面积的涂层是在相对较高的气体压力中涂布的,在一个实施方案中,可以使用磁控溅射离子镀系统涂布。
Description
本申请的主题涉及涂层的生成,该涂层具有或者包括至少一个具有相对高的表面积的层,其中所述表面的面积比该表面的表观面积或投影面积更大。
在制品上设置涂层以对制品提供保护和/或特定的特征或特性是公知的,并且可以选择涂层的特定的组成和/或特征以实现特定的功能和/或性能。
在许多情况下,涂布涂层的主要目的是确保涂层的厚度和/或组成满足预定的要求,但是已知难以有效地涂布涂层,其中涂层的表面积可以增大以提供要获得的涂层的更有效的特征。
本发明的目的是提供一种具有外表面的涂层,形成该外表面以在涂层和已经涂布涂层的制品的使用中提供特定的优势。另一个目的是提供一种涂布这样的涂层的方法,其能够实现外表面的特性的形成的所需控制。
在本发明的第一方面,提供了一种制品,其具有涂布到其至少一部分上的涂层,所述涂层包括至少一个层,该层的表面积大于所述涂层的所述层的表观面积或投影面积。
在一个实施方案中,所述表面积至少比所述表观面积或投影面积大30倍。
在一个实施方案中,所述层的表观面积或投影面积使用所述层的长度和宽度来计算。当基本上平滑的时候,所述表观面积或投影面积通常可以被视为表面积。
在一个实施方案中,设置有高表面积的所述涂层的至少一个层形成所述涂层的外表面。
在一个实施方案中,所述涂层包括至少一个另外的层,其比设置有高表面积的材料的层更致密。
在另一个实施方案中,在所述涂层内设置有具有高表面积的所述层以及涂布在所述层上的至少一个材料的另外的层。
在一个实施方案中,所述涂层的晶粒尺寸在3至100nm的范围内,所述层厚度在50nm至10μm的范围内,优选在50nm至3.0μm范围内。
在一个实施方案中,所述涂层由单一元素组成。在另一个可选实施方案中,所述涂层由金属、半金属、陶瓷及其混合物的多种组合组成。
在一个实施方案中,将所述涂层涂布到所述制品以启用和/或改善所述制品在催化、光催化、抗反射、抗菌、传感器、过滤器、引火装置、疏水表面、生物医学假体和/或热屏障功能的任一种或任意组合中的用途。
在一个实施方案中,提供表面精加工以改善用于形成涂层的材料的特性。
在一个实施方案中,涂布的材料是氧化物,如氧化钛、氧化镍或氧化铜,且控制表面积,以提高涂层的亲水性。
在本发明的另一个方面,提供了涂布涂层的方法,所述方法包括以下步骤:将待涂布的制品放在固定器上,选择性地操作一个或多个材料沉积构件,以将材料从所述材料沉积构件上沉积到所述制品上以形成涂层,并且其中在涂布所述涂层的至少一个层的过程中,操作所述材料沉积构件以产生表面积大于所述层的表面的表观面积或投影面积的所述至少一个层。
在一个实施方案中,使用物理气相沉积涂布所述涂层。
在另一个实施方案中,通过使用磁控溅射以高速率沉积材料来形成涂层,从而涂布所述涂层。
通常材料从其中沉积出来的磁控管的靶和材料将被沉积到其上的制品使得溅射材料在冲击制品时的行进方向与制品的表面不为90度。在一个实施方案中冲击角度在50-70度的范围内。
通常,至少当涂布用于形成涂层的高表面积层的材料时,涂层设备中磁控管的设置以开放场或所谓的“镜像场”方式操作。
在一个实施方案中,所涂布的涂层包括镍,其中产生高表面积。在一个实施方案中,所述涂层是镍和钼的合金,例如NiMo。
在一个实施方案中,用于形成涂层的至少高表面积层的材料是金属合金,并随后对其进行处理,以除去金属合金中的元素以在高表面积涂层上产生迷宫效应,与所谓的Raney金属(M.Raney,美国专利1628190(1927)方法相似。
在一个实施方案中,所述涂层是通过在选定的气体、连续气体或气体混合物中沉积材料而涂布,从而形成所需的涂层。优选地,形成至少所述涂层的至少高表面积层的材料在存在氦气的涂布环境中涂布。
在一个实施方案中,以2.0×10-3毫巴和1.5×10-2毫巴之间的范围内的总压力提供所述气体,所述压力优选在1.0×10-2毫巴至1.5×10-2毫巴的范围内。
在一个实施方案中,在沉积材料以形成涂层的过程中所述气体压力保持为恒定值。
在一个实施方案中,在沉积材料以形成涂层的过程中所述气体压力是变化的。
在一个实施方案中,在沉积过程中基板的温度保持在100~1000℃的范围内,以促进涂层材料扩散入基板表面中。
典型地,在沉积期间控制上述参数,以确保涂层附着到其涂布的制品的表面上,获得涂层的外表面的所需的高表面积。
在一个实施方案中,选择所述涂层以在优选具有高熔点的金属中产生成核(“种子”)密度,以获得每μm2的成核颗粒在10,000至25000的范围内的涂层。
在一个实施方案中,另一涂层,例如,作为连续的共形层或作为催化材料的离散颗粒,例如铂族金属(PGM),或它们的化合物,也可以沉积在高表面积的涂层上面,以进一步提高涂布表面的整体的催化性能。
在一个实施方案中,将所述涂层涂布到由钢、不锈钢、铝及其合金、钛及其合金、聚合物、陶瓷、碳布、玻璃、橡胶和/或木头中的任一种或任意组合形成的制品上。
典型地,所述制品可以是导电的,并且在这种情况下,所述涂层一般包括一层或多层较致密的涂层材料。
在一个实施方案中,涂布所述涂层的制品以适合于其目的的形式提供,如平坦的表面、网状结构、粉末、纤维和/或颗粒的任一种或任意组合。
在本发明的另一个方面中,提供了一种用于涂布涂层的方法,所述方法包括以下步骤:将待涂布的制品放置在固定器上,选择性地操作一个或多个磁控管,以将材料从所述材料沉积构件上沉积到所述制品上以形成涂层,其中至少在涂布所述涂层的一个层的过程中设置使用的磁控管以产生 开放场溅射环境,以产生表面积大于所述层的表面的表观面积或投影面积的所述层。
现在参考附图描述本发明的具体实施方案;其中,
图1a和1b示出了可在根据本发明的涂层的涂布中使用的开放和闭合场磁控溅射设备的类型;
图2a和2b示出了I型和II型不平衡磁控管的磁场分布的模拟;
图3a和3b示出了根据本发明的一个实施方案涂布的高表面积镍合金涂层的视图;
图4a和4b示出了根据本发明的另一个实施方案的高表面积的镍合金涂层的视图,其具有致密的底层和高表面积的顶层;
图5a-5c以图表和照片示出了根据本发明的另一实施方案的具有高表面积的TiO2涂层。
图6a和6b示出了根据本发明的具有~3至10nm尺寸的Ni合金纳米簇;且
图7a和7b示出了根据本发明的具有通常小于或等于~3nm的尺寸的Ni合金纳米簇。
在本发明的一个实施方案中,使用图1a和1b中所示类型的磁控溅射离子镀系统2沉积高表面积的涂层。被选定作为形成涂层所需的四种金属、合金、碳或化合物靶,4,6,8,10,被分布安装在位于腔室中的各个磁控管12,14,16,18中。选择性地操作磁控管以从选定靶溅射沉积材料,以在被固定在可绕中心轴22如箭头24所示那样旋转的固定器20上的制品上形成涂层。在材料溅射期间,将氩气或氩气加氦气引入到所述腔室中,以进行纯磁控溅射沉积;将氧、氮或烃气体引入腔室中作为反应性气体,以进行反应溅射沉积。
在该实施例中,当固定在固定器上时,靶和制品之间的距离在100-170毫米的范围内。在涂布过程中,基板可以保持静止或以受控的旋转速度旋转穿过靶。
优选地,在涂布之前将基板在专用的清洗溶剂中清洗,使用或不使用超声波搅拌,并完全干燥。将它们置于涂布室中,然后将涂布室抽空至通常低于2.5×10-5毫巴的压力。
然后在沉积之前对基板进行等离子体离子清洗,在4.0×10-3毫巴氩气压力,平均约为-400伏的偏压下,使用脉冲直流(DC)功率250kHz的脉冲频率,500ns的脉冲持续时间,即约87.5%的占空比。
优选在高沉积压力下,例如60~130毫巴;使用氩气和氦气的混合物作为工作气体,例如使用Ar/He=1∶1~1∶2(其为气体流量的比率,通过各质量流量控制器控制)。在涂层室中使用相对高压力的气体可以有效地并以受控的方式形成涂层的高表面积层。在腔室中还提供磁控管12,14,16,18,所述磁控管通常以一种可以在开放的磁场方式操作的类型提供,如图1a中所示。根据本发明的一个实施方案,使用这种形式的设备涂布具有高表面积的涂层。优选使用I型不平衡磁控管,这些磁控管设置在磁场中,如图2a所示。对设置在固定器上的制品施加偏压浮动电位,这些是优选的沉积条件,以获得根据本发明的具有高表面积的表面的涂层。
图3a和3b中示出了使用所述设备涂布的一个这样的涂层,该涂层具有多孔高表面积结构,图3a和3b中示出已涂布到制品上的具有高表面积的镍合金涂层的表面和断截面。
可以发现,通过控制使用所述设备的材料的沉积的过程,可以获得20nm到几十微米的涂层厚度,并且这样的涂层的表面积大于已涂布了涂层的制品的表面的表观面积或投影面积30倍。
在某些情况下,可能希望将具有高表面积的涂层涂布在其外表面上,并且还具有其他所需的性能,例如,为了保护已经被涂布的制品免受腐蚀和其他物理和化学劣化过程。这样的涂层的一个实例在图4a和4b中示出。在这种情况下,该涂层包括致密底层和具有高表面积的顶层的结合。该涂层可在一个过程中沉积,使用先前描述的设备涂布致密底层,但在闭合场配置中操作,如图1b所示,并使用II型磁控管来创建图2b中所示的闭合场。在这种情况下,致密底层可用氩气作为工作气体在1~7毫巴的压力和-35~-55V偏压下沉积,接着在先前所描述的开放场配置中操作设备涂布具有高表面积的顶层。
可以将上述两种沉积环境结合在一个单一的过程中,无论是通过采用具有可变磁配置的磁控管,例如通过将这些磁体放在可移动的支撑体上,增加或减少中央磁极的强度,或通过设置单独的沉积室,所述沉积室分别 配备有两个不同的沉积环境,以沉积一层或多层致密的涂层和一层或多层高表面积的多孔层。
在一个实施方案中,根据本发明的高表面积的涂层的涂布,可被集成到在单独的涂布腔室中提供和使用的具有不同的磁控管配置的大规模生产环境中,例如,闭合场磁控配置与II型不平衡磁控管结合被用于制品的等离子体离子清洗和较致密的涂层的沉积;具有I型不平衡的磁控管的开放场磁控管系统用于另一个腔室中的一层或多层高表面积层的沉积。
可以涂布氧化物、氮化物、碳化物或其他具有高表面积的复合涂层,为了提高涂层的附着性,可先用直流磁控溅射以氩气或氩气加氦气作为工作气体沉积薄金属层。涂布的金属层可以是致密或多孔的,如上所示,取决于特定的涂布要求。然而,应当注意,可以应用氧化物、氮化物或碳化物形成不含金属粘接层的涂层,尤其是当涂层粘附不是问题或者不需要金属夹层时。
最终的氧化物、氮化物或碳化物涂层可以与存在于所述腔室中的氧、氮或丁烷气体通过反应性溅射沉积,在一个实施方案中经由与快速压电阀连接的光学发射监控(OEM)系统控制反应性气体的流量。在沉积过程中,脉冲直流电源在基板上提供-45V~-70V的偏压,参照所要求的涂层厚度控制沉积时间的持续时间。
图5a示出了根据本发明获得的结晶化TiO2涂层的两个典型的XRD图谱。
在另一实施方案中,本发明可提供一种涂层,高表面积的金属层设置作为底层。这种形式的底层的供应可以用于增加顶部化合物层的催化性能和/或促进沉积的顶部化合物层的结晶。
图5b和5c示出了沉积在高表面积的NiMo底层上的结晶的TiO2涂层。相反,没有NiMo底层的沉积的TiO2涂层是无定形结构。
在沉积期间可在基板上施加额外的加热或正偏压,如果需要,可以使用闭合场磁控系统、高功率II型非平衡磁控管、较高的电源或HIPIMS,以得到结晶化的高表面积化合物涂层。
在某些情况下,所沉积的高表面积化合物涂层可具有无定形结构,并且如果需要,可使用沉积后的热处理获得结晶的结构。
图6a-6b和7a-7b示出了上面所描述的在高表面积沉积条件下生产镍合金纳米簇的实例,粒径通常在3~10nm的范围内。具有可控尺寸的颗粒可以通过改变沉积条件来沉积,其两个实例分别示于图6a-6b和图7a-7b中。这种颗粒可沉积到平坦表面、网格、粉末、纤维和颗粒上,与使用纳米簇束发生器相比,这是产生纳米颗粒的有效方式。
因此,根据本发明,提供了可以以有效的和可重复的方式涂布具有高表面积的至少一个层的涂层的方法和设备。
Claims (45)
1.制品,其具有涂布到其表面的至少一部分上的涂层,所述涂层包括至少一个层,该层的表面积比所述涂层的所述层的表观面积或投影面积至少大30倍,并且所述至少一个层的所述表观面积或投影面积使用其长度和宽度来计算,其中将所述涂层涂布在所述制品的所述表面部分上,并且在沉积以形成所述至少一个层的材料中并通过所述材料产生高表面积特性。
2.根据权利要求1的制品,其中所述涂层的所述至少一个层形成所述涂层的外表面。
3.根据权利要求1的制品,其中所述涂层包括至少一个另外的层,所述另外的层比所述至少一个层的材料更致密。
4.根据权利要求1的制品,其中所述至少一个层设置在所述涂层内,所述至少一个另外的层的材料涂布在所述至少一个层上。
5.根据权利要求1的制品,其中所述涂层的晶粒尺寸在3nm至100nm的范围内。
6.根据前述权利要求任一项的制品,其中所述涂层的层厚度在50nm至10μm的范围内。
7.根据权利要求6的制品,其中所述涂层的层厚度在50nm至3.0μm范围内。
8.根据权利要求1的制品,其中所述涂层由单一元素组成。
9.根据权利要求1的制品,其中所述涂层由金属、半金属和/或陶瓷中的任一种或任意组合组成。
10.根据权利要求1的制品,其中将所述涂层涂布到所述制品以启用和/或改善所述制品在催化、抗反射、抗菌、传感器、过滤器、引火装置、疏水表面、生物医学假体和/或热屏障功能的任一种或任意组合中的用途。
11.根据权利要求10的制品,其中所述催化为光催化。
12.根据权利要求1的制品,其中所述至少一个层包括镍。
13.根据权利要求12的制品,其中所述至少一个层由镍和钼的合金形成。
14.根据权利要求13的制品,其中所述镍和钼的合金为NiMo。
15.根据权利要求1的制品,其中所述至少一个层由金属合金形成。
16.根据权利要求1的制品,其中所述至少一个层设置为迷宫。
17.根据权利要求1的制品,其中在一种或多种气体中在2.0×10-3毫巴和1.5×10-2毫巴之间的范围内的总压力下涂布所述涂层的至少一部分。
18.根据权利要求17的制品,其中所述压力在1.0×10-2毫巴至1.5×10-2毫巴的范围内。
19.根据权利要求1-5和7-18的任一项的制品,其中所述涂层包括底层和具有高表面积的顶层。
20.涂布涂层的方法,所述方法包括以下步骤:将待涂布的制品放在固定器上,选择性地操作多个磁控管形式的一个或多个材料沉积构件,以将材料从所述材料沉积构件上沉积到所述制品上以形成涂层,并且在涂布所述涂层的至少一个层的过程中,操作所述材料沉积构件以产生表面积大于所述层的表面的表观面积或投影面积的所述至少一个层,其中选择性地操作其中至少一个磁控管,以将材料从所述磁控管沉积到所述制品上,并且至少在涂布所述至少一个层的过程中,所述磁控管在开放场或镜像场溅射环境中操作。
21.根据权利要求20的方法,其中使用物理气相沉积涂布所述涂层。
22.根据权利要求20的方法,其中通过使用磁控溅射沉积材料来涂布所述涂层。
23.根据权利要求20的方法,其中至少在涂布所述至少一个层的过程中,材料从其中沉积出来的磁控管的靶和材料将被沉积到其上的制品被分别布置,使得溅射材料在冲击制品时的行进方向与制品的表面不为90度。
24.根据权利要求23的方法,其中在冲击时,沉积的材料的行进方向相对于制品的表面与制品的表面在50-70度的范围内。
25.根据权利要求21的方法,其中所述至少一个层至少部分通过沉积镍形成。
26.根据权利要求25的方法,其中涂布镍和钼的合金,以形成所述至少一个层。
27.根据权利要求26的方法,其中所述镍和钼的合金为NiMo。
28.根据权利要求20的方法,其中所述至少一个层由金属合金形成,并对其进行处理,以除去金属合金中的至少一种元素以产生具有迷宫效应的所述至少一个层。
29.根据权利要求20的方法,其中通过在选定的气体、连续气体或气体混合物中沉积材料以涂布所述涂层,从而形成所需的涂层。
30.根据权利要求29的方法,其中通过在氦的存在下在涂布环境中涂布材料以形成所述涂层的所述至少一个层。
31.根据权利要求28和30任一项的方法,其中所述气体的总压力设置在2.0×10-3毫巴和1.5×10-2毫巴之间的范围内。
32.根据权利要求31的方法,其中所述压力在1.0×10-2毫巴至1.5×10-2毫巴的范围内。
33.根据权利要求29、30和32任一项的方法,其中在沉积材料以形成涂层的过程中所述气体压力保持为恒定值。
34.根据权利要求29、30和32任一项的方法,其中在沉积材料以形成涂层的过程中所述气体压力是变化的。
35.根据权利要求20的方法,其中在沉积过程中基板的温度保持在100~1000℃的范围内,以促进涂层材料扩散入基板表面中。
36.根据权利要求20的方法,其中涂布所述涂层以在金属中产生成核密度,以获得每μm2的成核颗粒在10,000至25000的范围内的涂层。
37.根据权利要求20-30、32和35-36任一项的方法,其中在所述涂层顶部沉积另一涂层,以提高所涂布的表面的整体催化性能。
38.根据权利要求37的方法,其中所述另一涂层是连续的,共形层的形式。
39.根据权利要求37的方法,其中所述另一涂层是催化材料的离散颗粒的形式。
40.根据权利要求20-30、32、35-36和38-39任一项的方法,其中将所述涂层涂布到制品上,所述制品由钢、铝及其合金、钛及其合金、聚合物、陶瓷、碳布、玻璃和/或木头中的任一种或任意组合形成。
41.根据权利要求40的方法,其中所述聚合物是橡胶。
42.根据权利要求40的方法,其中所述钢为不锈钢。
43.根据权利要求20-30、32、35-36和38-39任一项的方法,其中所述涂层包括底层和具有高表面积的顶层。
44.根据权利要求43的方法,其中使用磁控管沉积设备在闭合场配置中涂布所述底层,并且使用所述设备在开放场配置中涂布所述顶层。
45.用于涂层的涂布的方法,所述方法包括以下步骤:将待涂布的制品放置在固定器上,选择性地操作一个或多个磁控管,以将材料从所述磁控管沉积到所述制品上以形成涂层,其中至少在涂布所述涂层的一层的过程中,设置磁控管以产生开放场溅射环境,以产生表面积大于所述层的表面的表观面积或投影面积的所述层。
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US1628190A (en) | 1926-05-14 | 1927-05-10 | Raney Murray | Method of producing finely-divided nickel |
DE69629316T2 (de) * | 1996-04-03 | 2004-05-27 | "Okb" "Titan", Zao | Verfahren und vorrichtung zum aufbringen von porösen schichten und kathodenfilm eines elektrolytischen kondensors |
US5993979A (en) * | 1997-04-29 | 1999-11-30 | E. I. Du Pont De Nemours And Company | Skeletal columnar coatings |
ITMI20031178A1 (it) * | 2003-06-11 | 2004-12-12 | Getters Spa | Depositi multistrato getter non evaporabili ottenuti per |
US7150926B2 (en) * | 2003-07-16 | 2006-12-19 | Honeywell International, Inc. | Thermal barrier coating with stabilized compliant microstructure |
US20070031639A1 (en) * | 2005-08-03 | 2007-02-08 | General Electric Company | Articles having low wettability and methods for making |
EP2113078A4 (en) * | 2007-01-29 | 2013-04-17 | Nanexa Ab | ACTIVE SENSOR SURFACE AND METHOD FOR MANUFACTURING THE SAME |
JP2008274410A (ja) * | 2007-03-30 | 2008-11-13 | Fujifilm Corp | 親水性材 |
US9303322B2 (en) * | 2010-05-24 | 2016-04-05 | Integran Technologies Inc. | Metallic articles with hydrophobic surfaces |
-
2012
- 2012-02-24 GB GBGB1203216.5A patent/GB201203216D0/en not_active Ceased
-
2013
- 2013-02-20 US US14/379,696 patent/US20150252466A1/en not_active Abandoned
- 2013-02-20 CN CN201380010776.5A patent/CN104271793B/zh not_active Expired - Fee Related
- 2013-02-20 EP EP13711099.5A patent/EP2817431A2/en not_active Withdrawn
- 2013-02-20 WO PCT/GB2013/050405 patent/WO2013124647A2/en active Application Filing
Also Published As
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WO2013124647A3 (en) | 2013-11-14 |
US20150252466A1 (en) | 2015-09-10 |
CN104271793A (zh) | 2015-01-07 |
GB201203216D0 (en) | 2012-04-11 |
WO2013124647A2 (en) | 2013-08-29 |
EP2817431A2 (en) | 2014-12-31 |
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