JPH01172588A - Alloy plating bath - Google Patents
Alloy plating bathInfo
- Publication number
- JPH01172588A JPH01172588A JP33328987A JP33328987A JPH01172588A JP H01172588 A JPH01172588 A JP H01172588A JP 33328987 A JP33328987 A JP 33328987A JP 33328987 A JP33328987 A JP 33328987A JP H01172588 A JPH01172588 A JP H01172588A
- Authority
- JP
- Japan
- Prior art keywords
- chromium
- alloy
- bath
- iron
- alloy plating
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 17
- 239000000956 alloy Substances 0.000 title claims abstract description 17
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract 2
- 239000006172 buffering agent Substances 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 229910000599 Cr alloy Inorganic materials 0.000 abstract description 9
- 239000000788 chromium alloy Substances 0.000 abstract description 8
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- VQYBJJWZTGPLRX-UHFFFAOYSA-N [P].[Cr].[Fe] Chemical compound [P].[Cr].[Fe] VQYBJJWZTGPLRX-UHFFFAOYSA-N 0.000 abstract description 3
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 3
- 239000004471 Glycine Substances 0.000 abstract description 2
- 229910001096 P alloy Inorganic materials 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 235000007831 chromium(III) chloride Nutrition 0.000 abstract 1
- 239000011636 chromium(III) chloride Substances 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005280 amorphization Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアモルファス鉄−クロムーリン合金めつき浴に
関するものであり、耐食性がよく、光沢を有する電流密
度範囲の広いアモルファス鉄−クロムーリン合金めっき
を得るためのものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an amorphous iron-chromium alloy plating bath, and provides an amorphous iron-chromium alloy plating with good corrosion resistance, gloss, and a wide current density range. It is for.
鉄とクロムの合金に半金属を混入させ三元、四元の合金
にすることにより、アモルファス化を容易にし六り、ク
ロムの不動態皮膜の生成を促進させるということが言わ
れている。（増本健、深道和明：アモルファス合金、ア
グネ、１９８１）本発明では鉄−クロム合金の塩化浴に
、次亜リン酸塩添加することにより耐食性がよく、光沢
を有する電流密度範囲の広いアモルファス鉄−クロムー
リン合金めっきを得るための合金めっき浴を提供するも
のである。It is said that by mixing metalloids into an alloy of iron and chromium to form a ternary or quaternary alloy, it is possible to facilitate amorphization and promote the formation of a passive film of chromium. (Ken Masumoto, Kazuaki Fukamichi: Amorphous Alloy, Agne, 1981) In the present invention, by adding hypophosphite to the chloride bath of the iron-chromium alloy, an amorphous alloy with good corrosion resistance, luster, and a wide current density range is produced. The present invention provides an alloy plating bath for obtaining iron-chromium alloy plating.
従来鉄とクロムのアモルファス合金めっき皮膜に関する
報告はあったが、（青柳義臣、′″金属表面技術協会
第７３回学術講演大会要旨果′”、３４．１９８６）め
っき皮膜中に半金属を混入させ三元、四元の合金にする
ことにより、アモルファス化を容易にしたり、クロムの
不動態皮膜の生成を促進するという試みはｆｌわれなか
った。There have been reports on amorphous alloy plating films of iron and chromium (Yoshiomi Aoyagi, ``Metal Surface Technology Association
73rd Academic Conference Abstracts', 34. 1986) By mixing metalloids into the plating film to create ternary or quaternary alloys, it is possible to facilitate amorphization and to form a passive film of chromium. Attempts to promote this were unsuccessful.
従来の鉄とクロムのアモルファス合金めっき浴では光沢
を白する電流密度範囲が狭くしかもアモルファス化しに
くかったり、めっき皮膜表面のりロムの不動態皮膜生成
が不十分で耐食性に問題がでることがあるなどの問題点
があった。Conventional iron and chromium amorphous alloy plating baths have a narrow current density range that whitens the luster and are difficult to turn into amorphous, and the formation of a passive film of laminate on the surface of the plating film is insufficient, resulting in problems with corrosion resistance. There was a problem.
本発明は上記のような問題点を改善するため行った種々
の実験と研究をもとに、耐食性がよく、光沢を有する電
流密度範囲の広いアモルファス鉄−クロムーリン合金め
っきを可能にする添加剤を含む合金めっき浴を提供する
ものである。The present invention is based on various experiments and research conducted in order to improve the above-mentioned problems, and has developed an additive that enables amorphous iron-chromium alloy plating with good corrosion resistance, high gloss, and a wide current density range. The present invention provides an alloy plating bath containing:
本発明は鉄−クロム合金の塩化浴において、次亜リン酸
塩を添加することを特徴とする合金浴である。ここで鉄
−クロム合金の塩化浴とは二価の鉄、三価のクロムの塩
化物、錯化剤としてグリシン、伝導塩として塩化アンモ
ニウム、塩化ナトリウム、塩化カリウム等、緩衝剤とし
てホウ酸、ギ酸とその塩、酢酸とその塩等を含むもので
ある。The present invention is an alloy bath characterized in that hypophosphite is added to a chlorination bath for an iron-chromium alloy. Here, the chloride bath for iron-chromium alloys consists of chlorides of divalent iron and trivalent chromium, glycine as a complexing agent, ammonium chloride, sodium chloride, potassium chloride, etc. as conductive salts, boric acid, formic acid as buffering agents, etc. and its salts, acetic acid and its salts, etc.
この浴に次亜リン酸塩を０．０５ｍｏ１〜数ｍ０１／１
添加することにより耐食性がよく、光沢を有する電流密
度範囲の広いアモルファス鉄−クロムーリン合金めっき
を得ることができる。Hypophosphite is added to this bath from 0.05 mo1 to several m01/1
By adding it, it is possible to obtain an amorphous iron-chromulin alloy plating with good corrosion resistance, gloss, and a wide current density range.
次亜リン酸塩の添加量を調整することにより合金めっき
皮膜中に数ａｔ％〜数士ａｔ％のリンを混入させること
ができる。リンのような半金属が混入することにより皮
膜のアモルファス化が容易になり、光沢を有する電流密
度範囲が広がる。さらに皮膜の表面においてリンは溶は
出し易くクロムの濃縮を速め緻密で強固な不動態皮膜の
生成を促進する働きがある。また、次亜リン酸塩は還元
剤として働くものであるため、電流−電位曲線を測定し
たところ次亜リン酸塩を添加した後の陽極反応において
は３価のクロムが６価のクロムに酸化されるピークがほ
とんど観測できなかった。このことは６価クロムを含ま
ない低公害のめつき浴として工業的にも利用し得るもの
であることを示している。By adjusting the amount of hypophosphite added, several at % to several at % of phosphorus can be mixed into the alloy plating film. By mixing a semimetal such as phosphorus, the film becomes amorphous easily, and the current density range in which it has luster is widened. Furthermore, phosphorus is easily soluble on the surface of the film and has the function of accelerating the concentration of chromium and promoting the formation of a dense and strong passive film. Additionally, since hypophosphite acts as a reducing agent, current-potential curve measurements revealed that trivalent chromium was oxidized to hexavalent chromium in the anodic reaction after adding hypophosphite. Almost no peaks could be observed. This shows that it can be used industrially as a low-pollution plating bath that does not contain hexavalent chromium.
以下実施例により本発明をさらに詳細に説明する。 The present invention will be explained in more detail with reference to Examples below.
塩化クロム ｌ ｍ ｏ ｌ ／ １塩
化第一鉄 ０．１ｍｏｆ／１グリシｙ
１ 、２ ｍ ｏ ｌ ／ １塩化アンモニウム
２．０ｍｏｌ／１酢酸 ０．２ｍ
ｏｌ／１酢酸ナトリウム ０．２ｍｏｌ／１次亜
リン酸ナトリウム １．０ｍｏｌ／１上記のようにめっ
き浴を調整し、浴温２５度、陽極に白金板、陰極に銅板
を用いて電流密度１０ｍＡ／ｃｍ”めっきを行った。次
にできた試料を下記のような方法により分析した。Chromium chloride l mol / 1 ferrous chloride 0.1 mof / 1 glycy
1,2 mol/1 ammonium chloride 2.0 mol/1 acetic acid 0.2 m
ol/1 Sodium acetate 0.2 mol/1 Sodium hypophosphite 1.0 mol/1 The plating bath was adjusted as above, the bath temperature was 25 degrees, the current density was 10 mA/1 using a platinum plate for the anode and a copper plate for the cathode. cm'' plating was performed.Then, the resulting sample was analyzed by the method described below.
■Ｘ線回折
Ｃｕ Ｋ ａ線により２０〜７０度（２θ）までＸ線回
折を行ったが基板の鋼以外のピークは観測できなかった
。■X-ray diffraction X-ray diffraction was performed using Cu Ka rays from 20 to 70 degrees (2θ), but no peaks other than those due to the steel of the substrate could be observed.
■反口・Ｉ型電子線回折 電子線回折による回折線は観測できなかった。■Soraguchi/I-type electron diffraction No diffraction lines could be observed by electron beam diffraction.
■および、■の分析により皮膜はアモルファスであるこ
とがわかった。Analysis of (2) and (2) revealed that the film was amorphous.
■二次イオン質量分析（Ｓ Ｉ Ｍ Ｓ ）Ｓ Ｉ Ｍ
Ｓにより＋１１成および、深さ方向の分析を行った。■Secondary ion mass spectrometry (SIMS) SIM
+11 formation and depth direction analysis were performed using S.
条件は下記のとおりであり、結果は第１図に示した。The conditions were as follows, and the results are shown in FIG.
１次イオン ０２”１次イオン
エネルギー １２ＫｅＶ１次イオン電流
２００μＡラスタ一面積 ２００
μｍ第１図からめっき皮膜表面では鉄（図中のａ）とリ
ン（図中のｂ）が溶は出し、クロム（図中のＣ）の濃度
が高くなっていることがわかる。つまり、表面でクロム
が濃縮され不動態皮膜を作っていることがわかる。また
、鉄に対するクロム、リンの濃度を相対感度係数により
換算したところそれぞれ１０％、６％であった。Primary ion 02” Primary ion energy 12KeV Primary ion current
200μA raster area 200
From Figure 1, it can be seen that iron (a in the figure) and phosphorus (b in the figure) are eluted from the surface of the plating film, and the concentration of chromium (C in the figure) is high. In other words, it can be seen that chromium is concentrated on the surface and forms a passive film. Furthermore, when the concentrations of chromium and phosphorus relative to iron were converted using relative sensitivity coefficients, they were 10% and 6%, respectively.
さらに、常ｌ晶でＩＮ、ＨＣＩ溶液中に浸漬後の重量減
少量から腐食速度を求めたところ３０４スデンレス鋼の
腐食速度のｌ／ｌ Ｏ程度であった。Furthermore, when the corrosion rate was determined from the amount of weight loss after being immersed in the IN and HCI solution for the normal l crystal, it was found to be approximately l/l O of the corrosion rate of 304 stainless steel.
同様の浴組成でハルセル試験を行った結果５〜１５０ｍ
Ａ／ｃｍ″の電流密度範囲で光沢めっきが得られた。こ
の電流密度範囲で作製した試料のＸ線回折および、反射
型電子線回折を行ったところアモルファス構造であるこ
とが確認された。The result of Hull cell test with similar bath composition was 5 to 150 m.
A bright plating was obtained in a current density range of A/cm''. X-ray diffraction and reflection electron beam diffraction of the sample prepared in this current density range confirmed that it had an amorphous structure.
なお、錯化剤、伝導塩、緩衝剤の添加量はその機能を発
揮する添加範囲内であれば何れでもかまわない。Note that the amounts of the complexing agent, conductive salt, and buffering agent may be in any range as long as they can achieve their functions.
以上実施例にも述べてきたように本発明の合金めっき浴
は、耐食性がよく、光沢を有する電流密度範囲の広いア
モルファス鉄−クロムーリン合金めっきが得られるとい
う極めて優秀なめっき浴で工業的にも利用し得るもので
ある。As described in the examples above, the alloy plating bath of the present invention is an extremely excellent plating bath that can provide amorphous iron-chromulin alloy plating with good corrosion resistance, gloss, and a wide current density range, and is also industrially suitable. It is something that can be used.
なお本発明の合金めっき浴にパルス電解および、超音波
振動を併用することによりめっき皮膜のアモルファス化
がさらに効果的に行われる。さらにｐＨや電流密度を変
化させることによりクロムの混入量をｒｔａｔ％〜数十
ａｔ％に変化させることも可能である。Note that by using pulse electrolysis and ultrasonic vibration in the alloy plating bath of the present invention, the plating film can be made more effectively amorphous. Furthermore, by changing the pH and current density, it is also possible to change the amount of chromium mixed from rtat% to several tens of at%.
第１図は鉄−クロム−リン合金めっき皮膜のＳＥＭＳに
よる測定結果を示した図である。
以上
出願人 セイコー電子工業株式会社
図面ユＹ−１：６−二：更なし）
Ｔ Ｉ Ｍ Ｅ ｆｓｅｃ）
第１図 ＳＩＭＳ＜：よる鉄−７０ム一リン合金めつき
皮膜の泗定手 続 ネ市 正 書（方式）
１６ 事件の表示
昭和６２年 特許願 第３３３２８９号２、発明の名称
合金めっき浴
３、補正をする者
事件との関係 特許出願人
４、補正命令の日付
昭和６３年 ３月２９日
５、補正の対象
図面（第１図）FIG. 1 is a diagram showing the measurement results of an iron-chromium-phosphorus alloy plating film by SEMS. Applicant: Seiko Electronics Co., Ltd. Drawing Y-1:6-2: No changes) TIM E fsec) Fig. 1 Setting procedure for iron-70 mullin alloy plating film by SIMS City official document (method) 16 Indication of the case 1988 Patent application No. 333289 2 Name of the invention Alloy plating bath 3 Person making the amendment Relationship to the case Patent applicant 4 Date of amendment order March 1988 May 29th, drawings subject to amendment (Figure 1)
Claims (1)
、緩衝剤等で構成されるめっき浴において、次亜リン酸
塩添加することを特徴とする合金めっき浴。An alloy plating bath comprising iron chloride, chromium chloride, a complexing agent, a conductive salt, a buffering agent, etc., characterized in that hypophosphite is added thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33328987A JPH01172588A (en) | 1987-12-25 | 1987-12-25 | Alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33328987A JPH01172588A (en) | 1987-12-25 | 1987-12-25 | Alloy plating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01172588A true JPH01172588A (en) | 1989-07-07 |
Family
ID=18264431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33328987A Pending JPH01172588A (en) | 1987-12-25 | 1987-12-25 | Alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01172588A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5694874A (en) * | 1993-08-31 | 1997-12-09 | Juki Corporation | Under thread supply apparatus and method of supplying under thread |
| GB2386907A (en) * | 2002-03-27 | 2003-10-01 | Isle Coat Ltd | Forming ceramic coatings on metals and alloys |
| JP2018508648A (en) * | 2014-12-24 | 2018-03-29 | ポスコＰｏｓｃｏ | Fe-P-Cr alloy sheet and method for producing the same |
-
1987
- 1987-12-25 JP JP33328987A patent/JPH01172588A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5694874A (en) * | 1993-08-31 | 1997-12-09 | Juki Corporation | Under thread supply apparatus and method of supplying under thread |
| GB2386907A (en) * | 2002-03-27 | 2003-10-01 | Isle Coat Ltd | Forming ceramic coatings on metals and alloys |
| US6896785B2 (en) | 2002-03-27 | 2005-05-24 | Isle Coat Limited | Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process |
| GB2386907B (en) * | 2002-03-27 | 2005-10-26 | Isle Coat Ltd | Process and device for forming ceramic coatings on metals and alloys, and coatings produced by this process |
| JP2018508648A (en) * | 2014-12-24 | 2018-03-29 | ポスコＰｏｓｃｏ | Fe-P-Cr alloy sheet and method for producing the same |
| US10563316B2 (en) | 2014-12-24 | 2020-02-18 | Posco | Fe—P—Cr alloy thin plate and method for manufacturing same |
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