JPS6372864A - Stainless steel sheet coated with copper compound - Google Patents
Stainless steel sheet coated with copper compoundInfo
- Publication number
- JPS6372864A JPS6372864A JP21593486A JP21593486A JPS6372864A JP S6372864 A JPS6372864 A JP S6372864A JP 21593486 A JP21593486 A JP 21593486A JP 21593486 A JP21593486 A JP 21593486A JP S6372864 A JPS6372864 A JP S6372864A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- stainless steel
- film
- patina
- steel sheet
- 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.)
- Pending
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 24
- 239000010935 stainless steel Substances 0.000 title claims abstract description 24
- 239000005749 Copper compound Substances 0.000 title claims description 20
- 150000001880 copper compounds Chemical class 0.000 title claims description 20
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052802 copper Inorganic materials 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 241001311547 Patina Species 0.000 abstract description 9
- 238000004544 sputter deposition Methods 0.000 abstract description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 abstract description 5
- 239000005750 Copper hydroxide Substances 0.000 abstract description 5
- 239000005751 Copper oxide Substances 0.000 abstract description 5
- 229940116318 copper carbonate Drugs 0.000 abstract description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 5
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 abstract description 5
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 238000007733 ion plating Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000336 copper(I) sulfate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は皮膜をコーティングしたステンレス板、より詳
しくは緑色系銅化合物をコーティングすることによって
、ステンレス板のもつ特性を損なうことなく、緑青の発
生した銅板と同じ装偽性をもつステンレス板に関するも
のである。[Detailed Description of the Invention] Industrial Application Field The present invention is a stainless steel plate coated with a film, more specifically, a copper plate coated with a green copper compound to produce a patina without impairing the characteristics of the stainless steel plate. This relates to a stainless steel plate that has the same camouflage properties as .
従来の技術
特定の条件のもとで金属銅上に発生する緑色系のさびは
、塩基性炭酸銅、水酸化銅、酸化銅、硫酸銅などの混合
物で緑青（ろくしよう）と総称される。緑青は化学的に
安定でかつ緻密な物質なので、これが表面に存在すると
材料に耐腐食性を与えるものであり、かつ緑系統の特有
の色を示す物質であるので、古来から屋根材、壁材など
に緑青が表面に自然発生した銅板が用いられてきた。Prior Art The greenish rust that forms on metallic copper under certain conditions is a mixture of basic copper carbonate, copper hydroxide, copper oxide, copper sulfate, etc. and is collectively called verdigris. Patina is a chemically stable and dense substance, so when it exists on the surface, it gives materials corrosion resistance.It is also a substance that exhibits a characteristic green color, so it has been used as roofing and wall materials since ancient times. Copper plates with a naturally occurring patina on their surfaces have been used for such purposes.
このような、緑青の自然発生を待つ銅板の使用法に加え
、近年、あらかじめ積極的に緑青を発生させた銅板が外
装用材料として用いられるようになってきた。このよう
な緑青つき銅板を積極的に作成する手段としては、表面
を清浄にした銅板に塩類水溶液等の薬品を塗布した後大
気中で暴露し、銅板表面でさび発生の化学反応を進行さ
せて緑青様の物質を発生させ、さらに表面が安定状態に
なるまで放置するのが従来の技術であった。In addition to the use of copper plates that wait for patina to develop naturally, in recent years copper plates that have been actively patinaed in advance have come to be used as exterior materials. One way to proactively create such a copper plate with a patina is to apply a chemical such as a salt solution to a copper plate whose surface has been cleaned, and then expose it to the atmosphere to allow a chemical reaction that causes rust to occur on the surface of the copper plate. The conventional technique was to generate a verdigris-like substance and then leave it until the surface became stable.
一方では近年、材料の高付加価値化、高槻ｆｌＥ化の要
求から、真空蒸着法、スパッタリング法、イオンブレー
ティング法、プラズマＣＶＤ法などの真空ドライコーテ
ィング技術が発達してきている。On the other hand, in recent years, vacuum dry coating techniques such as vacuum evaporation, sputtering, ion blasting, and plasma CVD have been developed in response to demands for higher value-added materials and Takatsuki FLE.
スパッタリング法では、グロー放電で電離したＡｒ＋イ
オンがターゲット（ソース物質でできたカソード電極）
に衝突し、運動量の交換によってはじきとばされたター
ゲット表面の原子が基板に付着して皮膜となる。In the sputtering method, Ar+ ions ionized by glow discharge are used as a target (cathode electrode made of source material).
The atoms on the target surface that collide with the substrate and are repelled by the exchange of momentum attach to the substrate, forming a film.
イオンブレーティング法ではＡｔガスのプラズマ放電中
でソース物質を加熱融解し、蒸気として飛び出した原子
をプラズマによってイオン化、活性化したのち基板上に
堆積させる。In the ion blating method, a source material is heated and melted in a plasma discharge of At gas, and the atoms released as vapor are ionized and activated by the plasma, and then deposited on a substrate.
プラズマＣＶＤ法では気体状の原料物質を真空槽内に導
入しグロー放電をおこさせて原料分子を分解し、あるい
は他の反応性ガスと反応させて基板上に化合物の皮膜を
析出させる。In the plasma CVD method, a gaseous raw material is introduced into a vacuum chamber and a glow discharge is caused to decompose the raw material molecules or react with other reactive gases to deposit a compound film on the substrate.
これらの真空ドライコーティング技術を利用した製品の
例として、金色のＴｉＮ （窒化チタン）をコーティン
グした装飾性材料に関する出願がすでになされている。As an example of a product using these vacuum dry coating techniques, an application has already been filed for a decorative material coated with golden TiN (titanium nitride).
発明が解決しようとする問題点
前項で述べたように、緑青（ろくしよう）と呼ばれる緑
色系の銅化合物は古来から装飾性の屋根、壁材などに利
用されてきた。Problems to be Solved by the Invention As mentioned in the previous section, a greenish copper compound called verdigris has been used for decorative roofing and wall materials since ancient times.
近年ではあらかじめ積極的に緑青を発生させた銅板が用
いられるようになってきているが、表面を清炸にした銅
板に塩類水溶液等の薬品を塗布した後大気中で５ｋ”ｉ
ｌ＆シ、銅板表面でさび発生の化学反応を進行させて緑
青様の物質を発生させ、さらに表面が安定な状態になる
まで放置する従来の緑青つき銅板作成法では、以下のよ
うな問題点があった。In recent years, copper plates that have been actively given a patina have come into use, but after coating a copper plate with a clean surface and applying a chemical such as an aqueous salt solution, it is exposed to 5k”i in the atmosphere.
The conventional method for producing copper plates with patina, in which a rust-producing chemical reaction progresses on the surface of the copper plate to generate a patina-like substance, and is then left until the surface becomes stable, has the following problems. there were.
（１）銅板の表面に薬品を塗布した後、安定な緑青が発
生するまでの時間がかかる（１日以上）。(1) After applying a chemical to the surface of a copper plate, it takes time (more than one day) for a stable patina to develop.
（２）基板が銅板であるため、比較的強度が弱い。(2) Since the board is a copper plate, its strength is relatively low.
（３）基板が銅板であるため、コストが高い。(3) Since the substrate is a copper plate, the cost is high.
問題点を解決するための手段
本発明者は、前項に述べたような３つの問題点を解決す
べく研究を重ねた結果、真空ドライコーティング技術を
利用して、従来技術による緑青発生銅板と同じ外観を持
ち、しかもその問題点が解消もしくは軽減されている、
ステンレス板を基板とする新しい複合材料を発明したも
のである。Means for Solving the Problems As a result of repeated research in order to solve the three problems mentioned in the previous section, the inventor of the present invention has found that by using vacuum dry coating technology, the same as the patina-generating copper plate produced by the conventional technology. It has a good appearance, and its problems have been eliminated or reduced.
This is a new composite material that uses a stainless steel plate as a substrate.
すなわち、本発明ではステンレス基板上に塩基性炭酸銅
、酸化銅、水酸化銅、硫酸銅などの緑色系銅化合物の皮
膜をコーティングすることにょうて、緑青（ろくしよう
）様の外観を持ち、かつ時間的生産性、強度、価格の点
で従来材料の問題点を解消もしくは軽減する、銅化合物
被覆ステンレス板によって前記の贋題点を解決する。That is, in the present invention, by coating a stainless steel substrate with a film of a greenish copper compound such as basic copper carbonate, copper oxide, copper hydroxide, copper sulfate, etc., it has a verdigris-like appearance. The above-mentioned drawbacks are solved by a copper compound-coated stainless steel plate that eliminates or alleviates the problems of conventional materials in terms of time productivity, strength, and cost.
本発明による被覆ステンレス板は次のようなものである
。基板となるステンレス板はＳ Ｕ Ｓ ３０４系、
４３０系をはじめ、どのような鋼種のものでもよい、板
厚も任意であるが、通常の用途のためには０．３ｍｍ〜
３１程度のものが用いられる。ドライコーティング装置
に装着可使なものであれば形状は自由である。The coated stainless steel plate according to the present invention is as follows. The stainless steel plate that serves as the substrate is SUS 304 series,
It can be made of any type of steel, including 430 series, and the plate thickness can be arbitrary, but for normal use, 0.3 mm ~
A number of about 31 is used. The shape can be any shape as long as it can be attached to a dry coating device.
ステンレス板上にコーティングされた皮膜は塩基性炭酸
銅、酸化銅、水酸化銅、硫酸銅など銅化合物の混合物の
組成を持ち、外部から入射した単色光に対する反射率が
波長５５０ ｎｓ＋近傍の光について比較的大きいこと
によって、太陽光あるいは電球等の光のもとで緑色系統
に見えるものである。The film coated on the stainless steel plate has a composition of a mixture of copper compounds such as basic copper carbonate, copper oxide, copper hydroxide, and copper sulfate, and has a reflectance of monochromatic light incident from the outside at a wavelength of around 550 ns+. Due to its relatively large size, it appears green under sunlight or light from a light bulb.
皮膜の厚さはふつう１〜１０終−程度だが、特に制限は
ない、銅化合物の混合物における各成分化合物の割合を
かえることによって、緑色系統の中でもいろいろな色相
に変化させることが可能である。The thickness of the film is usually about 1 to 10 mm thick, but there is no particular limit, and by changing the ratio of each component compound in the copper compound mixture, it is possible to change the hue to various hues within the green family.
本発明における被覆ステンレス板は次のようにして製造
される。The coated stainless steel plate in the present invention is manufactured as follows.
（＋）厚さ０．３１〜３■層程度のスレンレス板を用意
し、スパッタリング法で緑色系の銅化合物混合物の皮膜
をコーティングすることによって本発明の銅化合物被覆
ステンレス板を作成する。銅化合物被覆を行うには■目
的の皮膜と同じ化学組成をもつ化合物あるいは混合物の
ターゲット（膜のソース物質でできたカソード電極）を
用いスパッターガスにはＡｔ等の不活性ガスを用いてタ
ーゲットの組成そのままの皮膜を得る方法、■ターゲッ
トに金属銅を用い、スパッターガスのＡｒの他にら、Ｃ
Ｏ２、ＳＯ２、Ｈ２などの反応性ガスを流して、いわゆ
る反応性スパッタリングによって塩基性炭酸銅、酸化銅
、水酸化銅、ｖ＆ａｙｓなどの混合物で目的の化学組成
をもつ皮膜を形成する方法のいづれも適用できる。(+) The copper compound coated stainless steel plate of the present invention is prepared by preparing a stainless steel plate with a thickness of about 0.31 to 3 cm and coating it with a film of a greenish copper compound mixture by sputtering. To perform copper compound coating ■ Use a compound or mixture target (cathode electrode made of the film's source material) with the same chemical composition as the target film, and use an inert gas such as At as the sputtering gas to coat the target. Method for obtaining a film with the same composition: ■Using metallic copper as a target, in addition to Ar as a sputtering gas,
Either method involves flowing a reactive gas such as O2, SO2, or H2 to form a film with a desired chemical composition using a mixture of basic copper carbonate, copper oxide, copper hydroxide, v&ays, etc. by so-called reactive sputtering. Applicable.
（２）イオンブレーティング方法によっても、同様の皮
膜を得ることができる。この場合は蒸発源にＣｕを用い
、反応ガスとしテ０２、ＣＯ２、ＳＯ２、Ｈ２等を用い
る。(2) A similar film can also be obtained by the ion blating method. In this case, Cu is used as the evaporation source, and Te02, CO2, SO2, H2, etc. are used as the reaction gas.
（３）プラズマＣＶＤ法によっても、同様の皮膜を得る
ことができる。この場合は、原料として宥機銅化合物ガ
スを用いる。(3) A similar film can also be obtained by plasma CVD. In this case, a soothing copper compound gas is used as the raw material.
以上のような方法で作成した本発明の緑青（ろくしよう
）様の外観を示す銅化合物被覆ステンレス板は、使用目
的に応じて緑青様皮膜の厚さを自由に制御して作成する
ことができる。またコーティング条件を１１節すること
により皮膜の化学組成も自由にコントロールできる。The copper compound-coated stainless steel plate of the present invention that exhibits a patina-like appearance produced by the method described above can be produced by freely controlling the thickness of the patina-like film depending on the purpose of use. . Furthermore, the chemical composition of the film can be freely controlled by setting the coating conditions in 11 sections.
実施例１
スパッタリング法によって本発明の銅化合物被覆板を作
成した。ターゲットには、無水硫酸銅ＣｕＳＯ４と酸化
銅（ＩＩ）ＣｕＯの各粉末を重量比ｌ対ｌで混合し、高
圧焼結法によって厚さ６ｍｍ、直径１５２．４ｍ−の円
板を作成して使用した。スパッターガスとしてアルゴン
を用い、５Ｘ１０−３Ｔｏｒｒのアルゴン分圧下でＲＦ
スパッタリングを行なった。Example 1 A copper compound coated plate of the present invention was created by a sputtering method. For the target, powders of anhydrous copper sulfate CuSO4 and copper(II) oxide CuO were mixed at a weight ratio of 1 to 1, and a disk with a thickness of 6 mm and a diameter of 152.4 m was created using a high-pressure sintering method. did. RF using argon as sputtering gas under argon partial pressure of 5X10-3 Torr.
Sputtering was performed.
基板には５ＵＳ４３０ステンレスのＢＡ（光輝焼鈍）処
理板で厚さ０．７層層、８０ｓ＋ｍ角のものを用い、基
板は室温のままｌｐｍのコーティングを行ない、未発１
４の銅化合物被覆ステンレス板を作成した０作成した板
の表面は緑青と同様の緑色をしており、基板に対する密
着性は良好であった。The substrate used was a 5US430 stainless steel BA (bright annealing) plate with a thickness of 0.7 layers and an 80s+m square.
A copper compound-coated stainless steel plate was prepared in No. 4. The surface of the plate prepared in No. 0 had a green color similar to verdigris, and its adhesion to the substrate was good.
実施例２
イオンブレーティング法によって本発明の銅化合物被覆
板を作成した。真空槽内にプラズマ発生用のアルゴンガ
スおよび二酸化炭素ガス（ＣＯ２）酸素（））を５対２
対ｌの割合の流量で導入して圧力を５ＸＩＯ−３↑ｏｒ
ｒに保ち、ＲＦコイルによってプラズマを発生させた状
態で、石英るつぼ中に入れた粒状の金属銅を電子ビーム
加熱によって蒸発させて成膜させた。Example 2 A copper compound coated board of the present invention was produced by an ion blating method. Argon gas for plasma generation, carbon dioxide gas (CO2), oxygen ()) are mixed in a 5:2 ratio in a vacuum chamber.
Introduce the pressure at a flow rate of 5XIO-3↑or
While maintaining the temperature at r and generating plasma using an RF coil, granular metallic copper placed in a quartz crucible was evaporated by electron beam heating to form a film.
基板として実施例１と同じものを用い、ｌｐｍのコーテ
ィングを行なって本発明の銅化合物被覆ステンレス板を
作成した０作成した板の表面は緑青と類似した緑色系統
の外観をもち、基板に対する密着性は良好であった。銅
化合物皮膜部を削りとって粉末とし、Ｘ線回折パターン
を測定した結果、孔雀石Ｃｕ２ＳＯ４・（ＯＨ）２と同
じスポー２トが見られた。Using the same substrate as in Example 1, the copper compound-coated stainless steel plate of the present invention was prepared by coating with lpm. The surface of the prepared plate had a green appearance similar to verdigris, and its adhesion to the substrate was poor. was in good condition. The copper compound coating was scraped off to form a powder, and the X-ray diffraction pattern was measured. As a result, the same spor2 as malachite Cu2SO4.(OH)2 was observed.
発明の効果
未発１１は、強度、密着性、装飾性、耐食性にすぐれた
緑青様表面を有する銅化合物被覆ステンレス板で、この
ものはドライコーティング法によって生産性良く製造す
ることができる。Effect of the Invention No. 11 is a copper compound-coated stainless steel plate having a patina-like surface with excellent strength, adhesion, decorativeness, and corrosion resistance, and can be manufactured with high productivity by a dry coating method.
Claims (1)
ングした、装飾性、耐食性にすぐれる銅化合物被覆ステ
ンレス板。A copper compound-coated stainless steel plate with excellent decorative properties and corrosion resistance, made by coating a green copper compound film on a stainless steel substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21593486A JPS6372864A (en) | 1986-09-16 | 1986-09-16 | Stainless steel sheet coated with copper compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21593486A JPS6372864A (en) | 1986-09-16 | 1986-09-16 | Stainless steel sheet coated with copper compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6372864A true JPS6372864A (en) | 1988-04-02 |
Family
ID=16680678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21593486A Pending JPS6372864A (en) | 1986-09-16 | 1986-09-16 | Stainless steel sheet coated with copper compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372864A (en) |
-
1986
- 1986-09-16 JP JP21593486A patent/JPS6372864A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS58153776A (en) | Method for preparing ornamental parts and ion plating apparatus used therein | |
| US3503787A (en) | Method of making refractory aluminum nitride coatings | |
| Wolf et al. | Ion bombardment during thin film deposition and its influence on mechanical and chemical surface properties | |
| JPH07103461B2 (en) | Method for forming black film and film thereof | |
| JP6426726B2 (en) | Decorative HIPIMS Hard Material Layer | |
| WO2008028355A1 (en) | Method for making surface antibacterial products utilizing physical vapor deposition technology | |
| JPH045750B2 (en) | ||
| CN110418857B (en) | Cylindrical titanium oxide sputtering target and preparation method thereof | |
| JPS6372864A (en) | Stainless steel sheet coated with copper compound | |
| Shimpi et al. | Decorative coatings produced using combination of reactive arc evaporation and magnetron sputtering | |
| JPS6196721A (en) | Film forming method | |
| Yue et al. | Structure of nanometer-size crystalline Ti film | |
| JPS62253762A (en) | Vapor deposition method for zn alloy | |
| JPS6334222B2 (en) | ||
| JPH04103754A (en) | Ceramic-coated material and its production | |
| CN109487223A (en) | The preparation method of calcium silicate hydrate nano film | |
| JPS6372866A (en) | Decorative coating method with titanium nitride | |
| JPH03226562A (en) | Color coating method | |
| RU2039127C1 (en) | Method for making corrosion resistant gold-colored plating on substrates | |
| JP2005290426A (en) | Method for producing polymer thin film of triazinedithiole derivative | |
| JPH03226563A (en) | Color coating method | |
| JPH03226560A (en) | Color coating method | |
| JPH03226561A (en) | Color coating method | |
| CN117488245A (en) | Antibacterial ceramic tile based on magnetron sputtering technology and preparation method thereof | |
| RU2249061C2 (en) | Corrosion resistant tantalum-based coating and method for production thereof |