CN112739849A - 包含具有防银变色防护的银表面的基底和制造这种基底的方法 - Google Patents

包含具有防银变色防护的银表面的基底和制造这种基底的方法 Download PDF

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CN112739849A
CN112739849A CN201980062075.3A CN201980062075A CN112739849A CN 112739849 A CN112739849 A CN 112739849A CN 201980062075 A CN201980062075 A CN 201980062075A CN 112739849 A CN112739849 A CN 112739849A
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coating
substrate
silver
thickness
final
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M·C·马纳斯特斯基
M·V·斯帕索夫
M·C·福雷
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Swatch Group Research and Development SA
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Abstract

本发明涉及基底(1),其包含通过具有1nm至200nm的厚度的保护涂层(4)防止银变色的最终镀银表面。所述保护涂层(4)包含沉积在所述最终镀银表面上并具有0.5nm至100nm的厚度的第一Al2O3涂层(4a)和在第一Al2O3涂层(4a)上的具有0.5nm至100nm的厚度的第二TiO2涂层(4b)。本发明还涉及制造这样的基底的方法。

Description

包含具有防银变色防护的银表面的基底和制造这种基底的 方法
技术领域
本发明涉及包含通过保护涂层防止银变色的最终镀银表面的基底。这种包含镀银表面的基底特别是能被薄银涂层涂布的钟表元件,如表盘、镶嵌体(applique)或指针。本发明还涉及制造这样的基底的方法。
背景技术
在钟表领域中,常见的是通过用优选电镀沉积的薄银涂层涂布基底来制造钟表元件,以赋予钟表元件非常白和独特的银外观。这样的钟表元件是例如被薄银层涂布的由黄铜或金制成的表盘。
但是,银具有随时间变色的缺点。为了解决这一问题,钟表元件的敏感镀银表面已知通过Zapon上漆法来保护。Zapon清漆是一种纤维素清漆,其可在溶剂中稀释。Zapon上漆是包括如下步骤的方法:在要保护的表面上施加(例如通过喷涂施加)纤维素清漆的几个涂层、然后将它们放置在炉中以加速其硬化。最终涂层具有大约8至15μm的总厚度。
但是,这种纤维素清漆仅不完美地保护敏感金属。此外,所需的纤维素清漆的沉积厚度掩盖精细的结构细节,如常用于装饰表盘的玑镂纹(guillochage)。因此,玑镂纹的细节在清漆涂层下未被增强,甚至可能消失。最后,纤维素清漆的涂层通过改变(CIE L*a*b*颜色空间的)L*参数而改变受保护的镀银表面的覆盖(cover)和外观。
为了替代Zapon上漆法,如专利EP 1 994 202中所述,已经提出借助ALD法在敏感镀银表面上沉积保护涂层。这种方法有可能沉积极薄(50nm和100nm)和高保护性的涂层,获得的保护高于用通常10μm的纤维素清漆涂层获得的保护。
但是,这种ALD的缺点在于沉积在基底的镀银表面上的不当保护涂层的使用降低了银的亮度并改变镀银表面的美学呈现。
此外,ALD法的缺点还在于,在基底的镀银表面上形成对所述镀银表面的附着力不佳的保护涂层,以致通过ALD沉积的所述保护涂层例如在使用移印或其他工艺的最终装饰操作的过程中在最轻微的应力下层离。
发明内容
本发明的目标在于通过提出一种具有有效防止银变色的镀银表面,同时保持所述镀银表面的最终外观,特别是银的亮度和颜色的基底,补救这些缺点。
为此,本发明涉及一种基底,其包含通过具有1nm至200nm的厚度的保护涂层防止银变色的最终镀银表面。
根据本发明,所述保护涂层包含沉积在所述最终镀银表面上并具有0.5nm至100nm的厚度的第一Al2O3涂层和在第一Al2O3涂层上的具有0.5nm至100nm的厚度的第二TiO2涂层。
优选地,该基底包含在保护层下方的具有1至3微米的厚度的基本纯银或合金化银的涂层。这种厚度可以:
-彻底地(cleanly)封闭基本纯银或合金化银的涂层,即具有无孔隙涂层。这种无孔隙涂层形成完美均匀的表面以供沉积保护涂层。因此,在沉积保护涂层后,在基底上,特别是在可能可见的非镀银部件上没有开放区域。
-保持在小于5微米,因为5微米和更大的厚度将使例如表盘的装饰变平整。例如,手工玑镂纹具有30至50微米的深度,如果沉积太厚的涂层,这将变得不清晰。
本发明还涉及一种制造这样的基底的方法,所述基底包含通过保护涂层防止银变色的最终镀银表面,所述方法包括下列步骤:
a)获得具有最终镀银表面的基底
b)在来自步骤a)的所述最终镀银表面的至少一部分上沉积至少一个具有1nm至200nm的厚度的防银变色的保护涂层,所述步骤b)包括第一步骤b1):在来自步骤a)的所述最终镀银表面的至少一部分上沉积具有0.5nm至100nm的厚度的第一Al2O3涂层,和第二步骤b2):在步骤b1)中获得的第一Al2O3涂层上沉积具有0.5nm至100nm的厚度的第二TiO2涂层。
令人惊讶地,第一Al2O3涂层和第二TiO2涂层的顺序和厚度使得有可能获得防银变色的保护涂层,其尽可能增强银的非常白的颜色,因此保持基底的最终表面的银色亮度。
根据本发明,该方法包括步骤a3):在所述基底上沉积基本纯银的涂层以获得所述最终镀银表面,基本纯银的涂层优选具有1000nm至3000nm的厚度。
根据一个备选实施方案,该方法包括步骤a1):在所述基底上沉积包含相对于合金的总重量计0.1重量%至10重量%的铜的银铜合金的涂层以获得所述最终镀银表面,所述银铜合金的涂层优选具有1000nm至3000nm的厚度。
附图说明
将从下文参考附图给出的描述清楚显现进一步的特性和优点,该描述是指示性的并且不以任何方式构成限制,其中:
-图1是根据本发明的基底的第一备选实施方案的示意性视图;
-图2是根据本发明的基底的第二备选实施方案的示意性视图;和
-图3是根据本发明的基底的第三备选实施方案的示意性视图。
具体实施方式
本发明涉及包含通过保护涂层防止银变色的最终镀银表面的基底。
这样的基底是例如钟表或珠宝元件,特别是外部钟表部件。特别地,基底可以是钟表表盘,其在表面上可具有结构化,如玑镂纹,即具有精细细节的一组线条,它们相互交叉以获得装饰效果。基底可以是指数、安装在表盘上的装饰(月相或其它)或指针。
基底优选是金属的。其可由黄铜制成、基于黄金或白金(yellow or white gold)或银或任何其它合适的金属或金属合金(贵金属或非贵金属)。
基底可具有或没有初始镀银表面。
基底可包含初始镀银表面,所述基底因此基于银(纯银或银合金,特别是具有>90重量%的Ag含量的银合金)并固有地具有所述初始镀银表面,其也形成最终镀银表面。然后直接在基于银的基底上沉积保护涂层。
参考图1,显示根据本发明的第一备选实施方案的基底1,其中基底1可没有初始镀银表面,或包含固有的镀银表面。在第一种情况下,基底可以例如由黄铜制成、基于黄金或白金或除银外的任何其它合适的金属或金属合金(贵金属或非贵金属)。在第二种情况下,基底1基于银、由例如纯银(solid silver)制成并固有地具有初始镀银表面。
有利地,基底1包含银铜合金的涂层2,其包含相对于合金的总重量计0.1重量%至10重量%的铜,以形成所述最终镀银表面。可在基底1上直接沉积银铜合金的涂层2,特别是当所述基底1不基于银时,并替代常规使用的高纯银(fine silver)涂层。可通过任何合适的方法沉积银铜合金的涂层2,如PVD(快速沉积)或借助合适的银铜电镀浴电镀沉积。
参考图2,显示根据本发明的第二备选实施方案的基底10,其中基底10不基于银并包含基本纯银的涂层20以形成所述最终镀银表面。这样的涂层20优选电镀沉积。基底10可本身由黄铜制成并被例如电镀沉积的贵金属的涂层,例如金涂层涂布。基底10也可以是纯贵金属,例如由纯金制成。如果必要,可使用本领域技术人员已知的中间金属涂层以防止由热处理或ALD法引起的某些金属之间的任何金属间扩散。
参考图3,显示根据本发明的第三备选实施方案的基底100,其中基底100不基于银并包含银铜合金的涂层2,其包含相对于合金的总重量计0.1重量%至10重量%的铜,以形成所述最终镀银表面。此外,基底100在所述基底100和所述银铜合金的涂层2之间包含基本纯银的涂层20。
无论具有基本纯银的涂层的备选实施方案如何,所述基本纯银的涂层20可具有200nm至3000nm的厚度。
根据一个实施方案,基本纯银的涂层20可具有200nm至600nm,优选300nm至500nm的厚度以形成薄银涂层。
根据一个优选实施方案,基本纯银的涂层20可具有1000nm至3000nm,优选1500nm至2500nm的厚度以形成厚银涂层。
这样的厚银涂层的优点在于,获得无孔隙的基本纯银的中间或最终涂层,以能够获得无孔隙的基底的最终镀银表面并因此确保提高的防银变色保护涂层在所述最终镀银表面上的附着。
无论具有银铜合金的涂层的备选实施方案如何,银铜合金的涂层2具有200nm至600nm,有利地300nm至400nm的厚度,或优选1000nm至3000nm,更优选1500nm至2500nm的厚度以构成具有上述优点的厚涂层。
优选地,银铜合金包含相对于合金的总重量计0.2重量%至8重量%,优选0.5重量%至7重量%的铜。选择铜相对于银的比例以在表面上建立足够的Cu自由基,这随后确保防银变色的保护涂层的附着力,而不改变银的颜色,因为银铜合金的涂层形成基底的最终镀银表面。
基底的最终镀银表面,基底1或100的银铜合金的涂层2,或者基底10的基本纯银的涂层20,或者如果基底本身基于银,则是表面的初始镀银表面,通过具有1nm至200nm,优选1nm至100nm,更优选40nm至100nm的厚度的保护涂层4保护以防银变色。
根据本发明,所述保护涂层4包含沉积在所述最终镀银表面上并具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层4a,和在第一Al2O3涂层4a上的具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层4b。
特别优选地,第一Al2O3涂层4a具有30nm至50nm的厚度,且第二TiO2涂层4b具有10nm至50nm的厚度。
有利地,已借助选自ALD(原子层沉积)、PVD(物理气相沉积)、CVD(化学气相沉积)和溶胶-凝胶沉积的方法沉积保护涂层4。优选地,已通过ALD沉积保护涂层4。第一Al2O3涂层4a、然后第二TiO2涂层4b的相继ALD沉积使得有可能形成致密涂层并获得极薄和高保护性的涂层,具有特别好的美学呈现。这样的ALD沉积的细节和参数是本领域技术人员已知的。它们例如描述在专利EP 1 994 202中。Al2O3涂层可由TMA(三甲基铝)前体获得,可用H2O、O2或O3进行其氧化。TiO2涂层可由TTIP(异丙醇钛)或TiCl4(三氯化钛)获得,可用用H2O、O2或O3进行其氧化。
特别优选地,通过ALD沉积具有30nm至50nm的厚度的第一Al2O3涂层和具有10nm至50nm的厚度的第二TiO2涂层4b,获得防银变色的保护涂层4。
令人惊讶地,第一Al2O3涂层和第二TiO2涂层的顺序和厚度的组合使得有可能获得防银变色的保护涂层,其尽可能增强银的非常白的颜色,因此保持基底的最终表面的银色亮度。
借助一种制造方法获得根据本发明的基底,所述方法包括下列步骤:
a)获得具有最终镀银表面的基底1,10,100
b)在来自步骤a)的所述最终镀银表面的至少一部分上沉积至少一个具有1nm至200nm,优选1nm至100nm,更优选40nm至100nm的厚度的防银变色的保护涂层4,所述步骤b)包括第一步骤b1):在来自步骤a)的所述最终镀银表面的至少一部分上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层4a,和第二步骤b2):在步骤b1)中获得的第一Al2O3涂层4a上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层4b。
特别优选地,第一Al2O3涂层4a具有30nm至50nm的厚度,且第二TiO2涂层4b具有10nm至50nm的厚度。
有利地,步骤b)借助选自ALD、PVD、CVD和溶胶-凝胶沉积的方法进行。
特别优选地,步骤b)借助ALD沉积进行。
有利地,根据本发明的方法可在步骤b2)之前和/或之后将保护涂层沉积和等离子体处理(典型地,Ar等离子体)组合,以降低沉积的保护涂层的内部张力。这种组合有可能软化保护涂层以使它们在环境应力,如机械、热或其它应力的过程中不那么脆。
有利地,制造根据本发明的基底的方法可在步骤a)和步骤b)之间,包括至少一个对步骤a)中获得的基底的最终镀银表面的等离子体预处理步骤c)。
该等离子体预处理步骤c)包括剥脱(stripping)最终镀银表面以特别除去在暴露于空气的基底的表面上自然形成并阻碍保护涂层4的良好附着的AgS/Ag2S硫化物。
有利地,这一步骤c)由Ar等离子体或Ar/H2等离子体预处理组成。
根据制造根据本发明的基底的方法的一个实施方案,步骤b)直接在步骤c)之后实施,没有任何其它附加预处理。
根据进一步实施方案,制造根据本发明的基底的方法在步骤c)和步骤b)之间包括附加中间氧化预处理步骤d),从而建立AgO/Ag2O位点,以在第一涂层4a中存在的Al2O3和基底的最终镀银表面的银之间形成共价键以促进保护涂层4附着在基底上。
根据一个备选实施方案,步骤d)的氧化预处理可包括用氧化剂如氧气或Ar/O2的氧化等离子体预处理,从而建立AgO/Ag2O位点。
等离子体中的O2剂量必须精确以建立足够的AgO/Ag2O位点(但这倾向于使银变黄),同时确保银的白度。
等离子体处理参数是本领域技术人员已知的,在此不需要进一步细节。
根据另一备选实施方案,步骤d)的氧化预处理可包括将水或过氧化氢以液体形式注入在真空中的预处理室,以使水或过氧化氢蒸发,其在与基底接触时形成AgO/Ag2O位点。注入的水或过氧化氢的量为几十微摩尔级。
特别有利地,步骤d)在步骤c)和所述步骤d)之间没有通风的情况下进行。为此,根据步骤c)预处理的基底在没有破坏真空的情况下经历根据步骤d)的附加预处理。
此外,获自步骤a)并仅根据步骤c)或根据步骤c)和d)预处理的基底随后有利地在真空中转移到沉积室中,有利地通过ALD沉积,以在获自步骤c)或步骤c)和d)的预处理基底上直接实施步骤b),而没有将基底的最终镀银表面通风。
为此,预处理步骤c)和d)和沉积保护涂层(优选通过ALD沉积)的步骤b)有利地在同一个综合处理机中实施,其中将用于根据步骤c)或根据步骤c)和d)的预处理的装置并入用于沉积保护涂层4(优选通过ALD沉积)的装置中,以使用于实施步骤c)、任选d)(如果存在)和b)的整个处理能够在没有将基底的最终镀银表面通风的情况下进行,优选在真空中进行。
步骤a)的基底1,10,100是金属的,优选基于金或银。
步骤a)的所述基底可包含初始镀银表面,所述基底因此基于银并固有地具有所述初始镀银表面,其也形成最终镀银表面。然后根据步骤b)直接在基于银的基底上沉积保护涂层4。
根据另一备选实施方案,如果基底由纯银制成,其颜色不像高纯银(fine silver)那样白,随后可能想要在沉积保护涂层前借助电铸法或真空法在纯银上沉积高纯银涂层。
根据进一步优选的备选实施方案,无论来自步骤a)的基底1,100是否具有初始镀银表面,制造根据本发明的基底的方法可包括在所述基底1,100上沉积银铜合金涂层2的步骤a1),所述银铜合金包含相对于合金的总重量计0.1重量%至10重量%的铜,以获得所述最终镀银表面,如图1中所示。
根据进一步优选的备选实施方案,如果来自步骤a)的基底100没有初始镀银表面,制造根据本发明的基底的方法可包括在所述基底100和银铜合金的涂层2之间沉积基本纯银的涂层20的中间步骤a2),如图3中所示。
根据进一步优选的备选实施方案,如果来自步骤a)的基底10没有初始镀银表面,制造根据本发明的基底的方法可包括在所述基底10上沉积基本纯银的涂层20的步骤a3),以获得所述最终镀银表面,如图2中所示。如果来自步骤a)的基底没有初始镀银表面,这同样适用。
有利地,基底1,10,100可在步骤a1)、a2)或a3)的至少一个之前和/或在步骤b)之前热处理以放松与先前的机械加工或涂层沉积步骤相关的任何内应力。处理温度和持续时间取决于基底和涂层的性质并且绝不能在由步骤b)沉积保护涂层之前影响部件的美观性。热处理参数是本领域技术人员已知的,在此不需要进一步细节。
无论具有基本纯银的涂层的备选实施方案如何,所述基本纯银的涂层20具有200nm至3000nm的厚度。
根据一个实施方案,基本纯银的涂层20可具有200nm至600nm,优选300nm至500nm的厚度以形成薄银涂层。
根据另一优选实施方案,如上文解释,基本纯银的涂层20可具有1000nm至3000nm,优选1500nm至2500nm的厚度以形成厚银涂层。
无论具有银铜合金的涂层的备选实施方案如何,所述银铜合金的涂层2具有200nm至600nm,有利地300nm至400nm的厚度,或优选1000nm至3000nm,更优选1500nm至2500nm的厚度以形成如上文解释的厚涂层。
优选地,银铜合金包含相对于合金的总重量计0.2重量%至8重量%,优选0.5重量%至7重量%的铜。
当基底在其表面上具有结构化,如玑镂纹时,制造根据本发明的基底的方法的步骤a)包括在基底的表面上制造所述结构化的子步骤。
包含根据本发明受到保护涂层保护的最终镀银表面的基底,特别是当防银变色的保护涂层通过ALD沉积时,具有尽管存在防银变色的保护涂层但仍得以保存的银的外观和非常白的亮度。如果基底已具有玑镂纹,尽管存在所述防银变色的保护涂层,但玑镂纹的精细细节仍清楚可见。
此外,根据本发明的基底具有完全不欠缺附着力的防银变色的保护涂层。
根据本发明的基底也可用于制造珠宝首饰、书写工具、眼镜相关产品和皮革产品。

Claims (41)

1.基底(1,10,100),其包含通过具有1nm至200nm,优选1nm至100nm的厚度的保护涂层(4)防止银变色的最终镀银表面,所述保护涂层(4)包含沉积在所述最终镀银表面上并具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层(4a)和在第一Al2O3涂层(4a)上的具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层(4b),所述基底的特征在于其包含银铜合金的涂层(2)以形成所述最终镀银表面,该合金含有相对于合金的总重量计0.1重量%至10重量%的铜。
2.基底(1,10,100),其包含通过具有1nm至200nm,优选1nm至100nm的厚度的保护涂层(4)防止银变色的最终镀银表面,所述保护涂层(4)包含沉积在所述最终镀银表面上并具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层(4a)和在第一Al2O3涂层(4a)上的具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层(4b),其特征在于所述基底包含基本纯银的涂层(20),以形成所述最终镀银表面。
3.根据权利要求1或2的基底,其特征在于第一Al2O3涂层(4a)具有30nm至50nm的厚度且第二TiO2涂层(4b)具有10nm至50nm的厚度。
4.根据前述权利要求之一的基底,其特征在于所述保护涂层(4)已通过ALD沉积。
5.根据前述权利要求之一的基底,其特征在于其基于银。
6.根据权利要求1至4之一的基底,其特征在于其不是基于银。
7.根据权利要求1的基底,其特征在于所述基底没有初始镀银表面并且其包含在所述基底和所述银铜合金的涂层(2)之间的基本纯银的涂层(20)。
8.根据权利要求2至7之一的基底,其特征在于所述基本纯银的涂层(20)具有200nm至3000nm的厚度。
9.根据权利要求8的基底,其特征在于所述基本纯银的涂层(20)具有200nm至600nm,优选300nm至500nm的厚度。
10.根据权利要求8的基底,其特征在于所述基本纯银的涂层(20)具有1000nm至3000nm,优选1500nm至2500nm的厚度。
11.根据权利要求1和3至7之一的基底,其特征在于所述银铜合金的涂层(2)具有200nm至600nm,优选300nm至400nm的厚度。
12.根据权利要求1和3至7之一的基底,其特征在于所述银铜合金的涂层(2)具有1000nm至3000nm的厚度。
13.根据权利要求1和3至7和11至12之一的基底,其特征在于所述银铜合金包含相对于合金的总重量计0.2重量%至8重量%,优选0.5重量%至7重量%的铜。
14.根据前述权利要求之一的基底,其特征在于基底(1,10,100)是钟表元件。
15.根据前述权利要求之一的基底,其特征在于其具有表面结构化。
16.制造包含通过保护涂层(4)防止银变色的最终镀银表面的基底(1,10,100)的方法,其特征在于所述方法包括下列步骤:
a)获得具有最终镀银表面的基底(1,10,100)
b)在来自步骤a)的所述最终镀银表面的至少一部分上沉积至少一个具有1nm至200nm,优选1nm至100nm的厚度的防银变色的保护涂层(4),所述步骤b)包括第一步骤b1):在来自步骤a)的所述最终镀银表面的至少一部分上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层(4a),和第二步骤b2):在步骤b1)中获得的第一Al2O3涂层(4a)上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层(4b),
其特征在于所述方法包括在所述基底(1,100)上沉积包含相对于合金的总重量计0.1重量%至10重量%的铜的银铜合金的涂层(2)以获得所述最终镀银表面的步骤a1)。
17.制造包含通过保护涂层(4)防止银变色的最终镀银表面的基底(1,10,100)的方法,其特征在于所述方法包括下列步骤:
a)获得具有最终镀银表面的基底(1,10,100)
b)在来自步骤a)的所述最终镀银表面的至少一部分上沉积至少一个具有1nm至200nm,优选1nm至100nm的厚度的防银变色的保护涂层(4),所述步骤b)包括第一步骤b1):在来自步骤a)的所述最终镀银表面的至少一部分上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第一Al2O3涂层(4a),和第二步骤b2):在步骤b1)中获得的第一Al2O3涂层(4a)上沉积具有0.5nm至100nm,优选0.5nm至50nm的厚度的第二TiO2涂层(4b),其特征在于所述方法包括在所述基底(10)上沉积基本纯银的涂层(20)以获得所述最终镀银表面的步骤a3)。
18.根据权利要求16或17的方法,其特征在于第一Al2O3涂层(4a)具有30nm至50nm的厚度且第二TiO2涂层(4b)具有10nm至50nm的厚度。
19.根据权利要求16至18之一的方法,其特征在于步骤b)借助选自ALD、PVD、CVD和溶胶-凝胶沉积的方法进行。
20.根据权利要求19的方法,其特征在于步骤b)通过ALD沉积进行。
21.根据权利要求16至20之一的方法,其特征在于其包括,在步骤b2)之前和/或之后,等离子体处理步骤。
22.根据权利要求16至21之一的方法,其特征在于其包括,在步骤a)和步骤b)之间,至少一个对步骤a)中获得的基底的最终镀银表面的等离子体预处理步骤c)。
23.根据权利要求22的方法,其特征在于所述等离子体预处理步骤c)由Ar等离子体或Ar/H2等离子体预处理组成。
24.根据权利要求22至23之一的方法,其特征在于步骤c)在没有将步骤c)和所述步骤b)之间基底的最终镀银表面通风的情况下进行。
25.根据权利要求22至23之一的方法,其特征在于其包括,在步骤c)和步骤b)之间,氧化预处理步骤d)。
26.根据权利要求25的方法,其特征在于所述氧化预处理步骤d)包括用氧化剂的等离子体预处理。
27.根据权利要求25的方法,其特征在于所述氧化预处理步骤d)包括将水或过氧化氢以液体形式注入在真空中的预处理室。
28.根据权利要求25至27之一的方法,其特征在于步骤d)在没有将步骤c)和所述步骤d)之间基底的最终镀银表面通风的情况下进行。
29.根据权利要求25至28之一的方法,其特征在于步骤b)在没有将步骤d)和所述步骤b)之间基底的最终镀银表面通风的情况下进行。
30.根据权利要求29的方法,其特征在于步骤c)、d)和b)在同一个综合处理机中实施。
31.根据权利要求16的方法,其特征在于来自步骤a)的基底(100)没有初始镀银表面,并且所述方法包括在所述基底(100)和所述银铜合金的涂层(2)之间沉积基本纯银的涂层(20)的中间步骤a2)。
32.根据权利要求16至17之一的方法,其特征在于其包括,在步骤a1)、a2)或a3)的至少一个之前和/或在步骤b)之前,基底(1,10,100)的热处理步骤以放松所述基底(1,10,100)中的任何内应力。
33.根据权利要求16至32之一的方法,其特征在于基底(1,10,100)是金属的,优选基于金或银。
34.根据权利要求17至31之一的方法,其特征在于所述基本纯银的涂层(20)具有200nm至3000nm的厚度。
35.根据权利要求34的方法,其特征在于所述基本纯银的涂层(20)具有200nm至600nm,优选300nm至500nm的厚度。
36.根据权利要求34的方法,其特征在于所述基本纯银的涂层(20)具有1000nm至3000nm,优选1500nm至2500nm的厚度。
37.根据权利要求16和31之一的方法,其特征在于所述银铜合金的涂层(2)具有200nm至600nm,优选300nm至400nm的厚度。
38.根据权利要求16和31之一的方法,其特征在于所述银铜合金的涂层(2)具有1000nm至3000nm的厚度。
39.根据权利要求16和31之一的方法,其特征在于所述银铜合金包含相对于合金的总重量计0.2重量%至8重量%,优选0.5重量%至7重量%的铜。
40.根据权利要求16至39之一的方法,其特征在于基底(1,10,100)是钟表元件。
41.根据权利要求40的方法,其特征在于在基底(1,10,100)的表面上制造结构化。
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