JPS6224500B2 - - Google Patents
Info
- Publication number
- JPS6224500B2 JPS6224500B2 JP6514784A JP6514784A JPS6224500B2 JP S6224500 B2 JPS6224500 B2 JP S6224500B2 JP 6514784 A JP6514784 A JP 6514784A JP 6514784 A JP6514784 A JP 6514784A JP S6224500 B2 JPS6224500 B2 JP S6224500B2
- Authority
- JP
- Japan
- Prior art keywords
- copper alloy
- titanium
- titanium nitride
- nitrogen
- atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 26
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
Description
本発明は、高い硬度と融点を持ち、耐食性にも
すぐれ、更に化学的にも安定であり装飾性にもす
ぐれた窒化チタンを銅合金の表面に形成させるこ
とを特徴とする銅合金の表面処理方法に関するも
のである。
従来、銅合金の表面に窒化チタンを被覆する方
法としては、銅合金に窒化チタンを蒸着又はスパ
ツタリング法で被着する方法、又はチタンを被着
後、窒化させ窒化チタンとする方法があつた。し
かし、これらの方法は高真空の蒸着又はスパツタ
リング装置を必要とし、装置が大型になり操作も
煩雑となる等の欠点があつた。
本発明は、かかる現状に鑑み鋭意研究を行つた
結果、チタンを0.05wt％以上含有する銅合金を特
定の雰囲気で加熱して該合金の表面に窒化チタン
を形成させることを特徴とする表面処理方法を見
出したものである。即ち、本発明方法は窒素ガス
またはアンモニアもしくはアンモニア分解ガスま
たは任意の割合で混合した窒素と水素の混合ガス
雰囲気中で加熱することにより該銅合金の表面に
窒化チタンを形成させることを特徴とする銅合金
の表面処理方法に関するものである。
このようにチタンを含有する銅合金を前記の特
定雰囲気下で加熱するだけで窒化チタンが銅合金
の表面に選択的かつ優先的に形成される現象の機
構は次のように推定される。
すなわち、前記の窒素を含有する雰囲気中でチ
タン含有銅合金を加熱すると該雰囲気中の窒素が
チタン含有銅合金表層部のチタンと反応して窒化
チタンが銅合金表面に形成される。前記窒化チタ
ンの形成により表層部のチタンが消費されて銅合
金中の表層部と内部とで濃度勾配を生ずるが、加
熱された銅合金の内部のチタンは表面に向つて拡
散する。このようにして加熱処理を継続すると銅
合金中に存在するチタンが表面に向つてさらに拡
散し、雰囲気中の窒素と反応して窒化チタン膜が
形成され、この膜は銅合金の表面全体を覆うよう
になる。この結果、黄金色の美麗な窒化チタン膜
を有する銅合金が得られる。
この場合雰囲気中に多量の酸素が混入すると、
銅の酸化物等の複雑な化合物ができて灰黒色の粗
い表面となるので好ましくない。
本発明において銅合金のチタン含有率を0.05wt
％以上としたのは、それよりチタンの含有量が少
ない銅合金では長時間の加熱に対してもチタンの
拡散は起こらず窒化チタンの皮膜の形成という現
象は見出せないからである。
また、拡散の加熱条件としては、温度は500℃
以上必要であり好ましくは800℃以上である。
さらにチタンと同時に他の元素を添加した銅合
金でも窒化チタンの析出を阻害する元素は認めら
れないので本方法はチタンを含有する多元系合金
に適用できるものである。
次に実施例について説明する。
実施例
第１表に示すチタン含有銅合金を窒素ガスまた
はアンモニアもしくはアンモニア分解ガスまたは
任意の割合で混合した窒素と水素の混合ガス雰囲
気中で熱処理を施すと光沢のある美しい黄金色の
表面が得られた。
窒化チタン層はＸ線回折によつて確認すること
ができるが、第１表に示す窒化チタンはASTM
（American Society for Testing ＆
Materials）による標準の窒化チタンの回折角度
と比較対照して行つた。この結果、窒化チタンに
特徴的なCuKα線使用の際の回折角（２θ）の
（111）36.8゜及び（200）42.6゜が確認された。
第１表には熱処理条件と表面の窒化チタン析出
層の厚さとの関係を示す。
第１表でチタン含有量0.02wt％では窒化チタ
ン・皮膜は形成されない。
The present invention is a surface treatment for a copper alloy characterized by forming titanium nitride, which has high hardness and melting point, excellent corrosion resistance, chemical stability, and excellent decorative properties, on the surface of the copper alloy. It is about the method. Conventionally, methods for coating the surface of a copper alloy with titanium nitride include a method of depositing titanium nitride on the copper alloy by vapor deposition or sputtering, or a method of depositing titanium and then nitriding it to form titanium nitride. However, these methods require high-vacuum deposition or sputtering equipment, and have drawbacks such as increased equipment size and complicated operations. As a result of extensive research in view of the current situation, the present invention provides a surface treatment characterized by heating a copper alloy containing 0.05 wt% or more of titanium in a specific atmosphere to form titanium nitride on the surface of the alloy. We have found a way. That is, the method of the present invention is characterized in that titanium nitride is formed on the surface of the copper alloy by heating in an atmosphere of nitrogen gas, ammonia, ammonia decomposition gas, or a mixed gas of nitrogen and hydrogen mixed in an arbitrary ratio. This invention relates to a method for surface treatment of copper alloys. The mechanism of the phenomenon in which titanium nitride is selectively and preferentially formed on the surface of the copper alloy simply by heating the titanium-containing copper alloy in the above-mentioned specific atmosphere is estimated as follows. That is, when a titanium-containing copper alloy is heated in the nitrogen-containing atmosphere, the nitrogen in the atmosphere reacts with titanium in the surface layer of the titanium-containing copper alloy, and titanium nitride is formed on the surface of the copper alloy. The formation of titanium nitride consumes titanium in the surface layer, creating a concentration gradient between the surface layer and the interior of the copper alloy, but titanium inside the heated copper alloy diffuses toward the surface. As the heat treatment continues in this way, the titanium present in the copper alloy further diffuses toward the surface and reacts with nitrogen in the atmosphere to form a titanium nitride film, which covers the entire surface of the copper alloy. It becomes like this. As a result, a copper alloy having a beautiful golden titanium nitride film is obtained. In this case, if a large amount of oxygen is mixed into the atmosphere,
Complex compounds such as copper oxides are formed, resulting in a grayish-black and rough surface, which is undesirable. In the present invention, the titanium content of the copper alloy is reduced to 0.05wt.
% or more because copper alloys with a lower titanium content do not diffuse titanium even when heated for a long time, and the phenomenon of formation of a titanium nitride film cannot be observed. In addition, the heating conditions for diffusion are 500℃.
The temperature is preferably 800°C or higher. Furthermore, even in copper alloys in which other elements are added at the same time as titanium, no elements that inhibit the precipitation of titanium nitride are found, so this method can be applied to multi-component alloys containing titanium. Next, an example will be described. Example When the titanium-containing copper alloy shown in Table 1 is heat-treated in an atmosphere of nitrogen gas, ammonia, ammonia decomposition gas, or a mixed gas of nitrogen and hydrogen mixed in an arbitrary ratio, a beautiful shiny golden surface can be obtained. It was done. The titanium nitride layer can be confirmed by X-ray diffraction, and the titanium nitride shown in Table 1 is ASTM
(American Society for Testing &
This was done by comparing and contrasting the diffraction angle with the standard titanium nitride diffraction angle. As a result, the diffraction angles (2θ) of (111) 36.8° and (200) 42.6° when using CuKα radiation, which are characteristic of titanium nitride, were confirmed. Table 1 shows the relationship between the heat treatment conditions and the thickness of the titanium nitride precipitated layer on the surface. In Table 1, no titanium nitride film is formed when the titanium content is 0.02wt%.
【表】
以上、本発明の方法は、スパツタリング、蒸着
等の特別な被覆手段を用いることなく、銅合金表
面に美麗かつ耐食性に優れたチタン窒化物の皮膜
を形成することができる画期的な方法である。[Table] As described above, the method of the present invention is an epoch-making method that can form a beautiful and highly corrosion-resistant titanium nitride film on the surface of a copper alloy without using special coating means such as sputtering or vapor deposition. It's a method.
Claims (1)
ガスまたはアンモニアもしくはアンモニア分解ガ
スまたは任意の割合で混合した窒素と水素の混合
ガス雰囲気中で加熱し、該銅合金の表面に窒化チ
タンの皮膜を形成させることを特徴とする銅合金
の表面処理方法。1. A copper alloy containing 0.05 wt% or more of titanium is heated in an atmosphere of nitrogen gas, ammonia, ammonia decomposition gas, or a mixed gas of nitrogen and hydrogen mixed in an arbitrary ratio to form a titanium nitride film on the surface of the copper alloy. A method for surface treatment of a copper alloy, characterized by forming a copper alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6514784A JPS60208476A (en) | 1984-04-03 | 1984-04-03 | Surface treatment of copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6514784A JPS60208476A (en) | 1984-04-03 | 1984-04-03 | Surface treatment of copper alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60208476A JPS60208476A (en) | 1985-10-21 |
| JPS6224500B2 true JPS6224500B2 (en) | 1987-05-28 |
Family
ID=13278473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6514784A Granted JPS60208476A (en) | 1984-04-03 | 1984-04-03 | Surface treatment of copper alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60208476A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63310952A (en) * | 1987-06-11 | 1988-12-19 | Fukuhisa Matsuda | Surface hardened copper alloy |
| US5254183A (en) * | 1991-12-20 | 1993-10-19 | United Techynologies Corporation | Gas turbine elements with coke resistant surfaces |
| US5298091A (en) * | 1991-12-20 | 1994-03-29 | United Technologies Corporation | Inhibiting coke formation by heat treating in nitrogen atmosphere |
| JP4829485B2 (en) * | 2003-06-10 | 2011-12-07 | 有限会社真空実験室 | Vacuum component material, vacuum component, vacuum device, vacuum component material manufacturing method, vacuum component processing method, and vacuum device processing method |
| JP5208555B2 (en) * | 2008-03-31 | 2013-06-12 | Ｊｘ日鉱日石金属株式会社 | Titanium copper for electronic parts |
-
1984
- 1984-04-03 JP JP6514784A patent/JPS60208476A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60208476A (en) | 1985-10-21 |
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