CN1089996A - 有淡玫瑰红色调的物品 - Google Patents
有淡玫瑰红色调的物品 Download PDFInfo
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- CN1089996A CN1089996A CN93112662A CN93112662A CN1089996A CN 1089996 A CN1089996 A CN 1089996A CN 93112662 A CN93112662 A CN 93112662A CN 93112662 A CN93112662 A CN 93112662A CN 1089996 A CN1089996 A CN 1089996A
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- palladium
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
Abstract
本物品有一个覆盖层,包括第一层为从Ti、Zr、
Hf或这些元素的混合物组成的这一组中选择的一种
元素的氮化物,这个第一层包括从Al、C和Vb族与
VIb族元素中选择的至少一种元素,和第二层为钯
(pd)和铟(In)构成的混合物。某些第三元素如Al
或Cu可以添加到混合物PdIn中。
这种覆盖层可以用于珠宝、光学仪器
(optimotery)或钟表制造业。
Description
本发明涉及一种在构成其本体的基质上有一个淡玫瑰红色覆盖层的物品,所述覆盖层包含第一层,其组成为从包括Ti、Zr、Hf或这些元素的混合物的这一组中选择的一种元素的氮化物,所述第一层包括从Al、C和Ⅴb族与Ⅵb族元素中选择的至少一种元素。
已经有人提出一种淡玫瑰红色覆盖层,属于如上所定义的单一氮化物层。这一方面可以参阅Leybold AG公司(德国)于1991年2月出版的资料,题为“What you ever wanted to know about deco coatings”(关于deco涂层,你曾经想要知道什么),PartⅢ。这个出版物中有一章涉及所谓“淡玫瑰红”(rosy pink)的色调对照,这是一种有淡红色调的桃红,也是一种目前流行用来覆盖观览物支座的桃红。直至现在,还没有人提出这样一种足够硬以致能耐磨损和耐划伤的覆盖层,已提出的合金都相当软并包含诸如金属间组合物(主要包括钯和铟),这种组合物的颜色各异,从浅黄色到金色或玫瑰金色。这样一种组合物的硬度几乎不大于350HV1,其描述详见US-A-4804517。
一种颜色可以用其色泽,其清晰度及其饱和程度来表征。诸如Minolta CR200比色仪和配备了积分球的Perkin-Elmer 555分光光度计等仪器能把人类知觉范围内的所有颜色转换成一种数字代码,使人们能非常精确地表达他们所讨论的颜色。这种代码是在国际照明委员会的建议(CIE.1976)中定义的。这个系统表达了色空间L*a*b*。当用这个系统表达一种颜色时,清晰度用L*值表示,而色泽和饱和程度则用a*和b*指出2个色轴,a*是红-绿轴,b*是黄-蓝轴。a*的正值对应于红色,负值对应于绿色,而b*的正值对应于黄色,负值对应于蓝色。清晰度L*的数值可在0(黑)至100(白)之间变化。
以上提到的Leybold公司的出版物用下列数值定义“淡玫瑰红”色调:L*=73,a*=8,b*=5。为了达到这种色调,已经提出了若干种组合物,它们全都是用物理蒸气沉积(PVD)法沉积到基质上的一层硬(>600HV1)氮化物,其中每一层都只略微接近于对淡玫瑰红所指出的颜色定义。这些组合物连同对应色调给出如下:
Ti90Al10NxTi95Al5NxTi80Al10V10NxZr80Al20NxTi80Cr20NxTiCxNy | L*=57,a*=9,b*=5L*=57,a*=10,b*=8L*=60,a*=7,b*=7L*=53,a*=6,b*=6L*=63,a*=4,b*=9L*=61,a*=7,b*=5 |
除这些组合物外,本申请者还将加上已经成功地生产出的下列组合物:
Zr80Ti20CxN1-x | L*=62,a*=7,b*=7 |
如果已知钛的氮化物(TiN)有接近于金色的黄色,那么,添加铝或铬或碳到这种氮化物中就会引起红色势头的出现,最后产生一种接近于所希望的淡玫瑰红的色泽。然而,在上述所有情况下都要注意的是,清晰度L*低得太多,会导致一种不醒目的、黯淡的颜色。现在已经注意到,要使这种色调引人注目,清晰度L*有至少70的数值是绝对必要的。
为了达到这一点,本发明设想在第一层氮化物上涂上由钯(Pd)和(In)的混合物构成的第二层。
现在将详细解释本发明。
把一个淡玫瑰红色覆盖层沉积在物品的本体上,该物品可以是观览物支座或表壳构造另件(肩宽、月牙形饰物、棱边等)。这个覆盖层包括第一层,其组成是选自包含钛(Ti)、锆(Zr)和铪(Hf)或这些元素的其它混合物的这一组中的一种元素的氮(N)化物,这第一层包括从铝(Al)、碳(C)和Ⅴb族与Ⅵb族元素中选择的至少一种元素。这一层较好通过PVD步骤沉积,其厚度可以在0.1-2.5μm之间变化。元素的选择取决于人们希望得到的颜色(见上表)。要注意的是,在沉积期间可以加氧,这样可以进一步增强淡红倾向。所得到的这一层非常硬,其硬度超过600HV1,使得该物品能耐磨损,而最重要的是耐划伤。
在这个第一层上,沉积了第二层由钯(Pd)和铟(In)构成的混合物。这个第二沉积层旨在增加前面所说的清晰度L*,并提高可以得到的色泽a*和b*的精确度。
如以上也已经说过的,其厚度可限制在0.05-1μm之间的这个第二层并非特别耐划伤。如果这个第二层不是在第一层之后进行,就会有必要使其厚度增加(例如)到大于10μm,以确保它具有合理的寿命。不过,要理解的是,厚层中的划伤比在薄层中更容易看得见,在薄层的情况下划痕不会那样深。结果,在本发明的第二薄层上划出的伤痕不会很深,因而不太容易看得见,因为它们受到基本上不会划伤的第一个氮化物层的限制。至于正常磨损,例如摩擦引起的磨损,这在本发明的覆盖层中也不太容易看得见,因为一旦第二层消失,基本上不会磨损的第一层依然存在,其颜色与第二层的颜色是相匹配的。
现在来看以上提到的第二层PdIn,测定表明,如果该混合物具有论量组成,就是说Pd的重量为48.3%,In的重量为51.7%,则色调就可定义为L*=70,a*=14且b*=3。
为了得到一种接近于所希望的淡玫瑰红的色调,提出了一种主要由钯和铟构成的混合物,并向其中添加一种选自Mg、Al、Si、Sn、Sb、Zn、Cu、Ag、Au、Zn、Y、Ti、Zr、Hf和Ni的第三元素。
具体地说,包含46-58%(重量)钯、42-54%(重量)铟和0.5-5%(重量)铝的混合物提供了令人满意的结果。更准确地说,47.49%(重量)Pd、51.25%(重量)In和1.26%(重量)Al的混合物给出的硬度为284HV1,色调L*=70、a*=8、b*=5,这非常接近于以上定义的淡玫瑰红色调(L*=73,a*=8,b*=5)。
同样,包含42-52%(重量)钯、42-54%(重量)铟和0.5-6%(重量)铜的混合物也提供令人满意的结果。更准确地说,45.15%(重量)Pd、52.52%(重量)In和2.33%(重量)Cu的混合物给出的硬度为242HV1,色调L*=71,a*=8,和b*=4,这也接近于淡玫瑰红色调,其数值详见前段。
应进一步说明的是,姑且不论对淡玫瑰红色调的追求,PdIn合金,尤其处于金属间化合相β-PdIn的合金,也能产生接近于金色的色调,因此,出于经济上的原因,人们对于它的使用产生了兴趣,也属于贵金属类的钯比金廉价数倍。
这里考虑的第二层同第一层一样也是用PVD工艺沉积的。其原理是用离子,一般是Ar+轰击要沉积的材料靶的表面,这些离子具有足以轰出该靶的一个或若干个原子的能量;而这些原子就这样射向基质,在基质上它们以覆盖层形式沉积。
Claims (6)
1、在形成其本体的基质上有一个淡玫瑰红色覆盖层的物品,所述覆盖层包含第一层其组成为从由Ti、Zr、Hf或这些元素的混合物组成的这一组中选择的一种元素的氮化物,所述第一层包括从Al、C和Ⅴb族与Ⅵb族元素中选择的至少一种元素,其特征在于如下事实:所述第一层被由钯和铟所构成的混合物组成的第二层所覆盖。
2、按照权利要求1的物品,其特征在于如下事实:钯和铟的混合物具有论量组成。
3、按照权利要求1的物品,其特征在于如下事实:该混合物主要由钯和铟以及选自Mg、Al、Si、Sn、Sb、Zn、Cu、Ag、Au、Y、Ti、Zr、Hf和Ni的一种第三元素构成。
4、按照权利要求3的物品,其特征在于如下事实:该混合物包含46-58%(重量)钯、42-54%(重量)铟和0.5-5%(重量)铝。
5、按照权利要求3的物品,其特征在于如下事实:该混合物包含42-52%(重量)钯、42-54%(重量)铟和0.5-6%(重量)铜。
6、按照权利要求1-5之一的物品,其特征在于如下事实:它是一个表壳或者是表壳的一个构成部件。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9215816A FR2699555B1 (fr) | 1992-12-23 | 1992-12-23 | Objet présentant un revêtement de coloration rosée. |
CH9215816 | 1992-12-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1089996A true CN1089996A (zh) | 1994-07-27 |
CN1045478C CN1045478C (zh) | 1999-10-06 |
Family
ID=9437189
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93112662A Expired - Fee Related CN1045478C (zh) | 1992-12-23 | 1993-12-22 | 在形成其本体的基质上有淡玫瑰红色覆盖层的物品 |
Country Status (9)
Country | Link |
---|---|
US (1) | US5445892A (zh) |
EP (1) | EP0603673B1 (zh) |
JP (1) | JPH06228770A (zh) |
KR (1) | KR100319534B1 (zh) |
CN (1) | CN1045478C (zh) |
AT (1) | ATE145017T1 (zh) |
DE (1) | DE69305833T2 (zh) |
ES (1) | ES2096841T3 (zh) |
FR (1) | FR2699555B1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104630710A (zh) * | 2015-03-16 | 2015-05-20 | 广东迪奥应用材料科技有限公司 | 一种玫瑰金色装饰镀涂层及其制备方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19745407C2 (de) * | 1996-07-31 | 2003-02-27 | Fraunhofer Ges Forschung | Verfahren zur Glanzbeschichtung von Kunststoffteilen, vorzugsweise für Fahrzeuge, und danach beschichtetes Kunststoffteil |
US6800326B1 (en) | 1997-01-14 | 2004-10-05 | Seiko Epson Corporation | Method of treating a surface of a surface of a substrate containing titanium for an ornament |
JP3557868B2 (ja) * | 1997-01-14 | 2004-08-25 | セイコーエプソン株式会社 | 装飾品の表面処理方法、装飾品および電子機器 |
US6360423B1 (en) | 1997-12-16 | 2002-03-26 | Clad Metals Llc | Stick resistant coating for cookware |
US7093340B2 (en) | 1997-12-16 | 2006-08-22 | All-Clad Metalcrafters Llc | Stick resistant ceramic coating for cookware |
EP3220212A1 (fr) * | 2016-03-16 | 2017-09-20 | The Swatch Group Research and Development Ltd. | Procédé de décoration d'un composant horloger |
KR102099203B1 (ko) * | 2018-04-20 | 2020-04-09 | 한국과학기술연구원 | 이온 주입 발색 합금체 및 이의 제조방법 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3304598C2 (de) * | 1983-02-10 | 1986-05-22 | Institut metallurgii imeni A.A. Bajkova Akademii Nauk SSSR, Moskau/Moskva | Legierungen auf der Basis von Palladium |
JPS61127863A (ja) * | 1984-11-22 | 1986-06-16 | Seiko Instr & Electronics Ltd | 外装部品 |
FR2589484A1 (fr) * | 1985-11-04 | 1987-05-07 | Asulab Sa | Objet pourvu d'un revetement en metal precieux resistant a l'usure |
US4804517A (en) * | 1986-03-06 | 1989-02-14 | Williams Dental Company, Inc. | Gold colored palladium - indium alloys |
JPS6465274A (en) * | 1987-09-04 | 1989-03-10 | Seiko Epson Corp | Production of antiqued external parts for timepiece |
US4902535A (en) * | 1987-12-31 | 1990-02-20 | Air Products And Chemicals, Inc. | Method for depositing hard coatings on titanium or titanium alloys |
US5015537A (en) * | 1988-09-12 | 1991-05-14 | Seiko Epson Corporation | Ornamental member |
JP2716186B2 (ja) * | 1989-02-08 | 1998-02-18 | 住友金属鉱山株式会社 | ブロンズ色を呈する物品 |
-
1992
- 1992-12-23 FR FR9215816A patent/FR2699555B1/fr not_active Expired - Fee Related
-
1993
- 1993-12-03 KR KR1019930026300A patent/KR100319534B1/ko not_active IP Right Cessation
- 1993-12-10 DE DE69305833T patent/DE69305833T2/de not_active Expired - Fee Related
- 1993-12-10 EP EP93119938A patent/EP0603673B1/fr not_active Expired - Lifetime
- 1993-12-10 AT AT93119938T patent/ATE145017T1/de not_active IP Right Cessation
- 1993-12-10 ES ES93119938T patent/ES2096841T3/es not_active Expired - Lifetime
- 1993-12-10 US US08/164,542 patent/US5445892A/en not_active Expired - Fee Related
- 1993-12-22 JP JP5345585A patent/JPH06228770A/ja active Pending
- 1993-12-22 CN CN93112662A patent/CN1045478C/zh not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104630710A (zh) * | 2015-03-16 | 2015-05-20 | 广东迪奥应用材料科技有限公司 | 一种玫瑰金色装饰镀涂层及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ES2096841T3 (es) | 1997-03-16 |
DE69305833D1 (de) | 1996-12-12 |
FR2699555B1 (fr) | 1995-02-03 |
JPH06228770A (ja) | 1994-08-16 |
EP0603673A1 (fr) | 1994-06-29 |
US5445892A (en) | 1995-08-29 |
ATE145017T1 (de) | 1996-11-15 |
FR2699555A1 (fr) | 1994-06-24 |
KR940014906A (ko) | 1994-07-19 |
CN1045478C (zh) | 1999-10-06 |
DE69305833T2 (de) | 1997-05-28 |
KR100319534B1 (ko) | 2002-03-20 |
EP0603673B1 (fr) | 1996-11-06 |
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