CN113025969A - 制造装饰表面的方法 - Google Patents

制造装饰表面的方法 Download PDF

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CN113025969A
CN113025969A CN202011417956.3A CN202011417956A CN113025969A CN 113025969 A CN113025969 A CN 113025969A CN 202011417956 A CN202011417956 A CN 202011417956A CN 113025969 A CN113025969 A CN 113025969A
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C·默讷斯特尔斯基
M·格斯塔尔特
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Abstract

本发明涉及一种方法，包括在基底，例如不锈钢手表表盘上沉积化学计量LaBx的硼化镧的层，其中x在9至12之间，随后用激光处理，以使激光处理过的层的部分根据激光功率改变颜色。这种方法有可能制造具有高耐腐蚀性和耐磨性的多色表面。优选地，使用紫红色LaB6靶通过PVD(物理气相沉积)和通过阴极溅射沉积LaBx层，以致沉积层的颜色不同于靶的颜色。在特定功率下的激光处理改变该层的处理部分中的化学计量，以致这些部分的颜色根据所得化学计量而变。在较高功率下，激光基本除去LaBx层，以致处理部分的颜色取决于基底的材料。

Description

制造装饰表面的方法
技术领域
本发明涉及奢侈品，如手表或首饰的装饰表面的制造领域。本发明更特别涉及六硼化镧(LaB6)用于制造这些装饰表面的用途。
背景技术
六硼化镧属于稀土类。考虑到其极低的功函数，即大约2.4eV，这种材料常用于电子领域。主要用途之一是热阴极的制造。
化学计量LaB6具有浓烈的紫红色(purple-violet)，邻近的化学计量(adjacentstoichiometries)可呈现例如蓝色或绿色。这种陶瓷具有极高硬度值(大约2500HV)和高耐腐蚀性。
发明内容
根据本发明，在基底，例如不锈钢手表表盘上沉积化学计量LaBx的硼化镧的层，随后用激光处理，以将经受激光处理的层的所述部分的所述化学计量LaBx改变成LaBy并赋予其颜色，获得的所述颜色取决于激光参数。通过调节激光参数发生从LaBx到LaBy的变化。激光参数特别是脉冲持续时间、平均激光束功率、每脉冲的能量、重复频率、光斑直径、在纵向和横向上的光斑重叠和每脉冲的注量(fluence)。
有利地，通过激光处理将LaBx层转化成LaBy，其中y在9至12之间。
这种方法有可能制造具有高耐腐蚀性和耐磨性的多色表面。优选地，使用紫红色LaB6靶通过PVD(物理气相沉积)和优选通过阴极溅射沉积LaBx层，以致沉积层的颜色不同于靶的颜色。在特定功率下的激光处理改变该层的处理部分中的化学计量，以致这些部分的颜色根据所得化学计量而变。在较高功率下，激光基本除去LaBx层，以致处理部分的颜色取决于基底的材料。
本发明还涉及使用本发明的方法制成的装饰物体，特别是包括带有层的基底的物体，所述层包含至少两个彼此不同颜色的部分，这些部分至少在其表面上由硼化镧组成，硼化镧在不同部分中取决于不同的硼化镧化学计量。优选地，所述层的表面的一个部分包含LaBy，其中y在9至12之间。
具体实施方式
下面描述本发明的详细实施方案。这种实施方案不限制本发明的范围，而是仅充当根据本发明的方法的使用示例。
通过将紫红色粉末形式的x＝6的LaBx沉积在底座上制备靶，底座优选由铜制成。将所述粉末烧结和硬焊在底座上，以在底座上形成仍为紫红色的固体层，其可充当用于通过阴极溅射施加PVD沉积的靶。通常，该固体层的厚度约为500nm(0.5μm)。可获得用于PVD应用的带有LaB6并预先制备的底座。在下文描述的方法的实例中，发明人使用带有直径大约75mm的圆形LaB6层的底座。
将20mm X 30mm的不锈钢基底引入RF-CCP(射频电容耦合等离子体)型反应器，并放在反应室内的平台上。该反应器包括适用于固定靶的载体和标准RF源。该反应器带有用于降低和调节该室内的压力的装置和用于将气态流体流，如氩气流引入该室的装置。
在本实例中，该反应器以共焦模式运行。这意味着靶相对于中轴成优选30°角并垂直于平台放置。平台可旋转安装并可围绕该中轴旋转。
在安装靶后，首先进行清洁基底的步骤，通过对其施以蚀刻工艺进行，例如借助在反应室内形成的氩等离子体。这种蚀刻步骤的参数例如如下：压力1.5 10-2毫巴；持续时间5min；加速电压600V。
然后，使用在载体中的靶以在PVD沉积过程中充当阴极，并使得靶与基底中心之间的距离典型地为110mm。厚度为大约500mm的硼化镧层的沉积通过在氩气中的PVD、借助靶的阴极溅射在下列典型条件下进行：
·施加于阴极的功率:250W(即在DC模式中在0.62A下404V)
·Ar压力:3微巴(μbar)
·沉积温度:430℃(该温度是在机器上程序控制的设定点，而非在基底上测量的实际温度)
·相对于基底施加在阴极上的偏压:-150V DC
·沉积时间:1500秒，以获得300nm(0.2至0.25nm/s)
·基底的旋转速度:大约10rpm
观察到，沉积层的颜色不同于靶的紫红色。沉积层的颜色是瓦灰蓝。通过该层的SEM-EDX分析提供这种颜色差异的解释。化学计量LaB6的层不再是靶，而是化学计量LaB9至LaB12，下文称为LaBy。确实，镧和硼的溅射速率不同，这产生富硼和因此贫镧的层。
根据本发明，通过PVD沉积的层的局部激光处理再次改变该层的颜色。使用在红外范围内运行的标刻激光。控制激光以在LaBx层的表面的预定部分上扫描光斑。根据施加的参数，可在同一基底的相邻区域上获得三种不同颜色：蓝色、紫色和灰白色，从而在基底上获得多色图案。下表公开了在这三种情况下施加的典型参数。
Figure BDA0002820843480000031
观察到，激光功率主要决定获得的颜色。频率、重叠和脉冲持续时间的差异几乎不影响或不影响颜色，但可导致相同颜色的不同色度(shade)。
SEM-EDX分析确认，蓝色和紫色层由特定化学计量的硼化镧组成，其决定相关颜色。另一方面，灰白色含有很少的硼和镧，但其颜色取决于不锈钢基底的Fe和Ni的存在。这意味着基本已除去或部分除去LaBy层并且颜色主要取决于基底的颜色。
一系列纳米压痕证实通过PVD沉积的层具有大约2500HV的硬度值，并在激光处理后其保持紫色1500HV和蓝色1000HV的硬度值，这对经受磨损的钟表应用是足够的。此外，“热带气候”试验，即在室中暴露于60℃的温度、90％的％RH 7天，证实该涂层完全不受影响。
因此，非限制性地，一旦激光光斑并不穿透LaBx层，则有可能根据这种方法装饰钟表组件，如钟表表盘、指针、表壳、卡扣元件(clasp element)或表带连接(bracelet link)。
显然，本发明不限于所举的实例，而是适用于本领域技术人员显而易见的各种变体和修改。特别地，本发明不限于外部钟表部件或甚至不限于钟表领域。因此，例如，不妨碍本发明的方法用于餐具、首饰、皮革制品或甚至书写工具领域的应用。

Claims (14)

1.在基底上制造装饰表面的方法，其特征在于该方法包括下列步骤：
·在基底上沉积具有第一化学计量的LaBx的层，
·对LaBx层的至少一个部分施以激光处理，以将经受激光处理的LaBx层的所述部分的所述化学计量LaBx改变成LaBy并赋予其颜色，获得的所述颜色取决于激光源的类型以及激光参数。
2.根据权利要求1的方法，其特征在于通过PVD(物理气相沉积)沉积所述层。
3.根据权利要求2的方法，其特征在于通过包含烧结和硬焊在底座上的粉末形式的LaB6的靶的阴极溅射沉积所述层。
4.根据权利要求3的方法，其特征在于在RF-CCP(射频电容耦合等离子体)型反应器中进行所述PVD沉积。
5.根据前述权利要求任一项的方法，其特征在于通过激光处理将LaBx层转化成LaBy，其中y在9至12之间。
6.根据前述权利要求任一项的方法，其进一步包括在沉积LaBx层之前蚀刻基底的步骤。
7.根据前述权利要求任一项的方法，其特征在于用不同功率的激光处理所述层的几个相邻部分，以在基底上获得多色图案。
8.根据前述权利要求任一项的方法，其特征在于所述激光处理使用在红外范围内运行的标刻激光，并通过在沉积层的表面的至少一个部分上扫描激光光斑进行。
9.根据前述权利要求任一项的方法，其特征在于用激光处理的所述部分的颜色通过在激光影响下的LaBx层的化学计量的变化获得且随激光功率变化，或通过完全或部分去除LaBx层以使所得颜色取决于基底的颜色而获得。
10.具有多色表面的装饰物体，其包括带有层的基底，其特征在于所述层包含至少两个彼此不同颜色的部分，这些部分至少在其表面上由硼化镧组成，硼化镧在不同部分中取决于不同的硼化镧化学计量。
11.根据权利要求10的装饰物体，其特征在于所述层的表面的一个部分包含LaBy，其中y在9至12之间。
12.根据权利要求10或11的物体，其特征在于不同颜色的部分是相邻部分。
13.根据权利要求10至12之一的物体，其特征在于所述基底的表面进一步包括一个或多个附加部分，其颜色取决于基底本身。
14.手表，其特征在于所述手表包含一个或多个根据权利要求10至13任一项的组件。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116288173A (zh) * 2021-12-21 2023-06-23 奥米加股份有限公司 在基底上沉积涂层的方法
CN116288183A (zh) * 2021-12-21 2023-06-23 奥米加股份有限公司 在基底上沉积涂层的方法
WO2024016182A1 (zh) * 2022-07-19 2024-01-25 得利钟表制品厂有限公司 表面改性和颜色改变方法以及物品

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336672A2 (en) * 1988-04-04 1989-10-11 Xerox Corporation Epitaxial deposition of thin films
WO2006029677A1 (de) * 2004-09-16 2006-03-23 Merck Patent Gmbh Lasermarkierbare und laserschweissbare polymere materialien
CN101045645A (zh) * 2006-03-28 2007-10-03 柯马杜股份有限公司 装饰陶瓷部件的方法
CN101405146A (zh) * 2006-03-20 2009-04-08 巴斯夫欧洲公司 纳米颗粒状金属硼化物组合物以及其用于识别标记塑料部件的用途
US20090209420A1 (en) * 2005-12-05 2009-08-20 3M Innovative Properties Company Hyperabsorptive nanoparticle compositions
KR100964574B1 (ko) * 2009-07-23 2010-06-21 주식회사 에스코넥 금속 소재의 표면에 대한 레이저 컬러 마킹방법

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT344617B (de) * 1973-06-22 1978-08-10 Plansee Metallwerk Schmuckstueck, zum beispiel uhrenschale, aus metallischem oder keramischem grundwerkstoff
FR2623790B1 (fr) * 1987-11-26 1990-11-30 Rhone Poulenc Chimie Procede de preparation de borures de terres rares
US8702919B2 (en) * 2007-08-13 2014-04-22 Honeywell International Inc. Target designs and related methods for coupled target assemblies, methods of production and uses thereof
WO2009031232A1 (ja) * 2007-09-07 2009-03-12 Canon Anelva Corporation スパッタリング方法および装置
WO2009157087A1 (ja) * 2008-06-27 2009-12-30 キヤノンアネルバ株式会社 電子放出素子の製造法及びそのための記憶媒体又は記録媒体
JP4763857B2 (ja) * 2008-12-29 2011-08-31 キヤノンアネルバ株式会社 均一膜厚分布のためのスパッタ装置の磁界制御
US9346715B2 (en) * 2010-03-29 2016-05-24 Sumitomo Osaka Cement Co., Ltd. Lanthanum hexaboride sintered body, target and lanthanum hexaboride film each comprising same, and process for production of the sintered body
US20140227457A2 (en) * 2011-12-16 2014-08-14 Centro De Investigacion Cientifica Y De Educacion Superior De Ensenada, Baja California Process for obtaining metaloxides by low energy laser pulses irradiation of metal films
RU2621229C2 (ru) * 2012-05-30 2017-06-01 Те Свотч Груп Рисерч Энд Дивелопмент Лтд Керамический элемент, инкрустированный по меньшей мере одним декорированием из композиционной керамики
DE102012017809A1 (de) * 2012-09-10 2014-03-13 Oerlikon Trading Ag, Trübbach Verfahren zur Herstellung einer Metallborocarbidschicht auf einem Substrat
EP3035129B1 (fr) * 2014-12-19 2020-11-04 The Swatch Group Research and Development Ltd Procede de realisation d'un element decore d'une piece d'horlogerie ou de bijouterie
CH714234B1 (fr) * 2017-10-13 2021-05-14 Horlaser Sa Procédé de fabrication d'une pièce et une pièce pour l'horlogerie ou la joaillerie, avec une surface comprenant du titane coloré par oxydation.

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0336672A2 (en) * 1988-04-04 1989-10-11 Xerox Corporation Epitaxial deposition of thin films
WO2006029677A1 (de) * 2004-09-16 2006-03-23 Merck Patent Gmbh Lasermarkierbare und laserschweissbare polymere materialien
US20090209420A1 (en) * 2005-12-05 2009-08-20 3M Innovative Properties Company Hyperabsorptive nanoparticle compositions
CN101405146A (zh) * 2006-03-20 2009-04-08 巴斯夫欧洲公司 纳米颗粒状金属硼化物组合物以及其用于识别标记塑料部件的用途
CN101045645A (zh) * 2006-03-28 2007-10-03 柯马杜股份有限公司 装饰陶瓷部件的方法
JP2007261938A (ja) * 2006-03-28 2007-10-11 Comadur Sa セラミック製部品に装飾を施す方法
KR100964574B1 (ko) * 2009-07-23 2010-06-21 주식회사 에스코넥 금속 소재의 표면에 대한 레이저 컬러 마킹방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.MITTERER: ""Decorative boride coatings based on LaB6"", 《SURFACE AND COATINGS TECHNOLOGY》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116288173A (zh) * 2021-12-21 2023-06-23 奥米加股份有限公司 在基底上沉积涂层的方法
CN116288183A (zh) * 2021-12-21 2023-06-23 奥米加股份有限公司 在基底上沉积涂层的方法
WO2024016182A1 (zh) * 2022-07-19 2024-01-25 得利钟表制品厂有限公司 表面改性和颜色改变方法以及物品

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