CN107778007A - 获得具有金属外观的氧化锆基制品的方法 - Google Patents

获得具有金属外观的氧化锆基制品的方法 Download PDF

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CN107778007A
CN107778007A CN201710733755.6A CN201710733755A CN107778007A CN 107778007 A CN107778007 A CN 107778007A CN 201710733755 A CN201710733755 A CN 201710733755A CN 107778007 A CN107778007 A CN 107778007A
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gas
resistive element
chamber
nitrogen
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CN107778007B (zh
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C·福雷
L·屈尔绍
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Swatch Group Research and Development SA
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Abstract

本发明涉及获得成品或半成品氧化锆基制品(1)的方法，所述制品的表面具有金属外观和非零表面电导率，其特征在于所述方法包括以下步骤：‑取得至少一个以其成品或半成品形式预成形的氧化锆制品；‑将所述制品置于其中氢和碳/氮气体混合物被加热的腔室中；‑使用至少一个电流穿过的电阻元件将所述制品和气体混合物加热以达到所述氢和碳/氮基气体分子的解离和所述制品温度的增加；‑将所述制品保持在所产生的反应性气氛中以达到碳/氮原子在所述制品外表面中的扩散。

Description

获得具有金属外观的氧化锆基制品的方法
技术领域
本发明涉及氧化锆基制品，特别是烧结制品，尤其是其化学结构沿着其厚度转变以为所述制品赋予具有金属外观和非零电导率的外表面的制品。本发明还涉及此种制品的用途，其作为诸如腕表的制品、一件珠宝或任何其它可以使用这种类型的产品的奢侈工业制品的外部元件，尤其是用于制造表壳或手镯的结构元件。本发明最后涉及获得此种制品的方法。
发明背景
在所有已知的材料当中，金属得到非常广泛地使用，原因在于某些非常有利的性能：高机械耐性、高韧性、导电性等。另外，它们的特性光泽是装饰性应用渴求的。然而，金属的硬度低于陶瓷，这可能导致在许多常规使用条件中的显著磨损和腐蚀，例如当这些材料用来制造外部时钟元件，例如表壳或腕带时。
存在已知的将陶瓷成形和抛光以获得其硬度和耐磨性和耐腐蚀性远高于金属的外界元件的方法。
存在改进这种类型的氧化锆基陶瓷(ZrO2)部件以赋予其金属性能的已知方法，包括接近于铂的灰色颜色和亮度和非零表面电导率，同时维持与金属相比更高的硬度和耐磨和耐腐蚀性。这种方法使得可以获得具有部分还原的ZrO2芯和金属外观的成品或半成品氧化锆制品。它包括以下步骤：
-取得至少一个以其成品或半成品形式预成形的氧化锆制品；
-将所述制品置于腔室内部，在其中由氢气、中性气体和痕量碳的混合物产生等离子体，和
-维持所述制品在所述等离子体附近保持大约15-240分钟的时期，所述制品的平均温度设置在大约600-1,300℃的这些条件中，以达到碳原子在所述制品中的扩散。
此种方法因此使得可以制备这样的氧化锆部件，其具有碳化锆ZrC外层，具有金属外观和性能，即明亮且导电的表面，同时与金属部件相比保持其有利的性能。
因此，与通过PVD或CVD或其它沉积方法沉积金属外观的薄装饰性膜的方法相比有利的是，通过这种碳化方法制备的金属外观外层与部件的芯是整体，实现了层的完美结合而没有脱层风险。
最后，这种方法使得可以获得在表面上具有有利的碳化锆ZrC性能而不必制备固体ZrC部件的成品或半成品部件，而固体ZrC部件要求高温烧结方法，可能在压力下高温烧结。此外，ZrC密度比ZrO2高10％，以致通过上述方法碳化的ZrO2部件比由固体ZrC构成的同样几何结构的部件轻。最后，因为ZrC(典型地，25GPa)比ZrO2(典型地，13GPa)硬得多，所以固体ZrC部件在烧结后与由ZrO2构成的相同部件相比对机器加工和抛光而言硬得多。上述方法克服这些问题，尤其是通过使得可以将ZrC部件的表面转变延迟到在ZrO2部件的机械加工和抛光后。
可以调整这种方法以获得仍具有金属外观、非零电导率和完美粘附，但是颜色是接近于金的黄色的氮化锆层。为了实现这一点，等离子体由氢气、中性气体和痕量氮气的混合物获得。
然而，所使用的等离子体方法具有产生烟炱的缺点。这种烟炱认为是脏的和磨损性的，因为它由来自等离子体处理的颗粒构成。此类颗粒在其上沉积了烟炱的氧化锆部件的加工期间可能对所述部件有害。
发明内容
本发明目的是通过提供获得由氧化锆构成的制品的方法克服现有技术中的缺点，所述方法允许在制品表面的厚度上形成碳化锆或氮化锆层，其具有与通过等离子体方法获得的层相同的美感、电性能和机械性能和耐化学性能，但是不形成磨损性烟炱。
为此，本发明涉及获得成品或半成品氧化锆基制品的方法，所述制品具有金属外观和非零表面电导率，其特征在于它包括以下步骤：
-取得至少一个以其成品或半成品形式预成形的氧化锆制品；
-将所述制品置于腔室中，在其中，通过至少一个由高熔点金属构成并被电流穿过的电阻元件，例如至少一个纤丝来加热由氢和碳/氮构成的气体混合物，和
-加热所述气体混合物以达到氢和碳或氮基气体的分子的解离并保持所述制品在含所述经加热气体的腔室内部以加热所述制品并达到碳/氮原子在所述制品中的扩散。
根据本发明的方法有利地使用防止烟炱形成的加热装置，而所述烟炱可能在经处理制品的操作期间导致刮痕。
在第一有利的实施方案中，所述方法还包括，在加热包含在所述腔室内部的气体的步骤期间，以及随后在实际的碳化/氮化处理步骤期间，包含在所述氧化锆制品中的氧朝所述表面扩散和释放。
在第二有利的实施方案中，所述方法还包括在加热包含在所述腔室内部的气体的步骤之前的还原步骤，该还原步骤包括将所述制品置于其中注入氢气(dihydrogen)的第二腔室内部和包括加热所述氢气(dihydrogen)和置于该腔室内部的制品，从而允许所述氢气解离和包含在所述氧化锆制品中的氧朝表面扩散和释放。
在第三有利的实施方案中，在所述制品的外表面上转变的层的厚度是大约10至1,000nm。
在第四有利的实施方案中，所述外表面的厚度是20-200nm。
在第五有利的实施方案中，所述至少一个电阻元件由高熔点金属构成，所述高熔点金属选自包括铌、钼、钽、钨和铼的组。
在第六有利的实施方案中，所述由高熔点金属构成的至少一个电阻元件是纤丝。
在第七有利的实施方案中，所述腔室包括单一电阻元件，其布置在所述腔室内部用于以均匀方式加热所述工艺气体和待处理制品。
在第八有利的实施方案中，所述腔室包括分布在所述腔室内部的多个电阻元件用于以均匀方式加热所述工艺气体和待处理制品。
在第九有利的实施方案中，所述工艺气体中的至少一种经由被穿过的电流加热的电阻元件注入并且所述电阻元件则在它们的体积中包括用于所述工艺气流的管网，而不是经由专用注射系统围绕着所述电阻元件注入，以便增加所述工艺气体的解离效率和利用电阻元件在所述腔室内部的配置以确保所述反应性气体注射的分布导致整个制品的均匀方法。
在第十实施方案中，通过本领域技术人员已知的任何方法使所述工艺气体中的至少一种单独地离解，然后注入主腔室中以与其它工艺气体混合而产生所述方法所要求的反应性气氛。
附图说明
根据本发明的设计的目的、优点和特征将通过以下详细描述的本发明至少一个实施方案而变得更加清楚，所述实施方案仅仅作为非限制性实例给出并通过附图说明，其中：
-图1示意性地表示根据本发明的制品；
-图2示意性地表示进行根据本发明的方法的腔室；
-图3和4示意性地表示根据本发明的在腔室内部的纤丝布置。
具体实施方式
例如在图1中，提供了通过氧化锆制品1形成的起始物体，所述氧化锆制品具有四方结晶构型(氧化锆，ZrO2)，白色，通过常规的陶瓷制品制造技术例如烧结制备。
这种制品可以是具有其将使用的最终形状的成品，例如已经被镜面抛光并旨在形成手表的外部元件的一般平行六面体形状的部件，例如手表带节。当然，如果需要，制品可以是半成品，其可进行后续机械加工以使得制品适合其最终应用。制品1可能是手表的部件或一件珠宝的部件或与可以使用这种外部元件的奢侈品工业相关的任何制品的部件。
然后将这种制品引入腔室10，其将在该腔室内部被处理，如图2所示。要施加的处理是碳化或氮化处理。该方法的必要特征是它包括所述制品的表面在10-1,000nm量级的小厚度上的转变，其中由图1中看出的外部区域2中的氧化锆转变成具有金属外观的碳化锆/氮化锆。因此存在的是氧化锆结构的表面改性成为对应于碳化锆/氮化锆的新结晶结构，而不是添加的能够从制品表面除去或分离的涂层，尤其是当制品表面经历高磨损条件时。更具体地说，表面层的具有碳化锆/氮化锆结构的外部区域2从表面延伸到20-200nm的深度。
为了进行碳化或氮化处理，腔室10必须含有含氢和碳或氮的充气气氛A并装备有加热装置20，这些加热装置使得可以激活该处理。
根据本发明，加热装置包括至少一个电阻元件。在第一实施方案中，这种电阻元件是由高熔点金属构成的纤丝21。这种高熔点金属选自包括铌、钼、钽、钨和铼的组。事实上，加热装置20可以包括大尺寸的，布置在所述腔室内部以便以均匀方式加热工艺气体和待处理制品的单纤丝21，或可以包括经布置确保热均匀分布的多个独立纤丝，分别如图3和4所示。
所述纤丝被电流穿过，通过焦耳效应使所述纤丝温度增加。这种温度增加理想地经布置以达到超过1500℃的纤丝温度。
腔室内部的气氛中的温度增加使得发生氧化锆制品的处理。实际上，腔室内部气氛中的这种温度增加导致气体解离使得氢H和碳C或氮N的原子自由，和导致氧化锆部件的温度增加。在热和氢气氛的作用下，包含在氧化锆中的氧的一部分朝表面扩散并从氧化锆释放。
通过氧化锆的氧的一部分朝其表面扩散引起的这种部分氧化锆还原伴随着碳或氮原子从表面朝制品芯部的扩散。实际上，在热影响下，从腔室气体混合物离解的碳或氮原子将扩散在所述部分还原的氧化锆中。碳或氮原子的这种扩散导致出现与部分还原的氧化锆结合的这些原子的表面层而获得碳化锆或氮化锆层。
根据本发明的制品的特征，表面层包括位于部分还原的氧化锆芯部和碳化/氮化外部区域之间的过渡区，所述过渡区包括锆氧碳化物/氧氮化物。因此应指出，表面层的化学组成随着从制品表面测量的深度而变化并从表面处的化学计量碳化锆/氮化锆(ZrC/ZrN)连续地变化到包括锆氧碳化物/氧氮化物的过渡区，然后最终变化到亚化学计量氧化锆(还原的氧化锆)部分的芯部。
根据本发明的另一个优选的特征，过渡区中的锆氧碳化物/氧氮化物的碳/氮含量随深度降低，而它们的氧含量随深度增加。过渡区因此包括其碳/氮含量朝着制品的芯部逐渐降低的锆氧碳化物/氧氮化物，而氧的存在以ZrOxCy/ZrOxNy型化合物形式逐渐地增加并逐渐地达到基本上由ZrO2-x型的部分还原氧化锆形成的制品芯部。当然应该理解的是这些不同区域之间的过渡逐渐地发生。
通过这种方法获得的制品获得一些新颖性能，尤其是非零表面电导率、接近于铂(碳化)或黄金(氮化)的颜色和金属闪光，同时维持陶瓷性能，尤其是它们的非常高的硬度和耐磨和耐腐蚀性。
这种通过电流加热的电阻元件的使用具有不像等离子体方法那样产生烟炱的优点。使用等离子体方法产生的烟炱是脏的和磨损性的，以致处理烟炱覆盖的制品可能导致在所述制品上出现刮痕。
在第二个实施方案中，电阻元件为由电阻材料构成的管子形式，用于该方法中的气体的至少一种在其中流动，用于该方法中的气体的其余部分可以通过第二分配系统注入。当管子被电流穿过时，它开始加热腔室中的气氛和流入所述管子中的所述至少一种工艺气体。所述管子中的开口允许所述工艺气体释放/注入腔室中。
该第二实施方案可以提高该方法中使用的气体的解离效率和利用腔室内部的电阻元件的构造以确保反应性气体的注射分布达到在整体负荷内均匀的方法。在一个变型中，可以提供初步氧化锆还原步骤。该还原步骤在碳化/氮化步骤之前进行并包括将所述制品置于向其中注入氢气H2的气氛腔室。加热所述腔室中的气氛以致制品显示温度增加，从而引起包含在氧化锆中的氧朝其表面扩散以离开氧化锆。
这种还原步骤可以在特定腔室中或在与碳化/氮化操作相同的腔室中进行。在此情况下，所述腔室包括改变所述腔室内部的气氛的性质的装置。
清楚的是，在不脱离由所附权利要求书限定的本发明范围的情况下，可以对上面给出的本发明的各种实施方案作出对本领域技术人员明显的各种改变和/或改进。

Claims (10)

1.获得成品或半成品氧化锆基制品(1)的方法，所述制品具有金属外观和非零表面电导率，其特征在于所述方法包括以下步骤：
-取得至少一个以其成品或半成品形式预成形的氧化锆制品(1)，
-将所述制品置于腔室(10)中，在其中，通过至少一个由导电材料制成并被电流穿过的电阻元件(20)来加热由氢和碳或氮构成的气体混合物，和
-将在所述腔室中的气体混合物加热以达到所述氢和碳或氮基气体分子的解离并将所述制品保持在由此产生的反应性气氛中以加热所述制品并达到碳/氮原子在所述制品的外表面(2)中的扩散，
其中在加热包含在所述腔室中的工艺气体的步骤之前，还原步骤包括将所述制品置于其中注入氢气的腔室内部和包括加热所述氢气，从而允许包含在所述氧化锆制品中的氧朝所述表面扩散和释放。
2.根据权利要求1所述的方法，其特征在于所述方法还包括，在加热包含在所述腔室中的气体的步骤期间，包含在所述氧化锆制品中的氧朝所述表面扩散和释放。
3.根据权利要求1所述的方法，其特征在于所述制品的外表面(2)上的转变层的厚度是10-1,000nm。
4.根据权利要求3的方法，其特征在于所述制品的外表面上的转变层的厚度是20-200nm。
5.根据权利要求1所述的方法，其特征在于所述电阻元件由高熔点金属构成，所述高熔点金属选自包括铌、钼、钽、钨和铼的组。
6.根据权利要求1所述的方法，其特征在于所述电阻元件是纤丝(21)。
7.根据权利要求1所述的方法，其特征在于所述腔室包括单一电阻元件，其布置在所述腔室内部用于加热所述工艺气体和待处理制品从而以均匀方式使所述制品碳化或氮化。
8.根据权利要求1所述的方法，其特征在于所述腔室包括多个分布在所述腔室内部的电阻元件用于加热所述工艺气体和待处理制品从而以均匀方式使所述制品碳化或氮化。
9.根据权利要求1所述的方法，其特征在于将所述工艺气体中的至少一种经由至少一个通过穿过其中的电流而加热的电阻元件注入。
10.根据权利要求1所述的方法，其特征在于使所述工艺气体中的至少一种在被注入主腔室中之前离解。
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US20180057923A1 (en) 2018-03-01
HK1250705A1 (zh) 2019-01-11
US11549170B2 (en) 2023-01-10
EP3287857B1 (fr) 2019-04-03
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