JPS6253588B2 - - Google Patents
Info
- Publication number
- JPS6253588B2 JPS6253588B2 JP59118004A JP11800484A JPS6253588B2 JP S6253588 B2 JPS6253588 B2 JP S6253588B2 JP 59118004 A JP59118004 A JP 59118004A JP 11800484 A JP11800484 A JP 11800484A JP S6253588 B2 JPS6253588 B2 JP S6253588B2
- Authority
- JP
- Japan
- Prior art keywords
- chromic acid
- zinc
- nickel
- layer
- resistant
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 239000000463 material Substances 0.000 claims description 44
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 43
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 43
- 229910052759 nickel Inorganic materials 0.000 claims description 34
- 238000007747 plating Methods 0.000 claims description 34
- 229910000831 Steel Inorganic materials 0.000 claims description 33
- 239000010959 steel Substances 0.000 claims description 33
- 238000009713 electroplating Methods 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000011282 treatment Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 26
- 238000005260 corrosion Methods 0.000 claims description 26
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 25
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010306 acid treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- -1 it was dried at 50°C Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
〔産業上の利用分野〕
本発明は、例えば内熱機関における機関周囲で
の各種部品或いはこれら部材として250℃程度以
下の加温雰囲気状態にあつて使用される板、管、
棒或いは線材等からなる鉄鋼材の表面に施して成
る耐熱・耐食性を同時に要求される重合被覆鋼材
およびその重合被覆形成方法の改善に関するもの
である。
〔従来技術の問題点〕
従来、機関周囲に使用される各種部品或いはこ
れら部材として耐熱・耐食性の被覆構造を有する
鉄鋼材としては、一般に電鍍法或いは浸漬法によ
つて形成した鉄鋼材表面の亜鉛の鍍金層上に、単
に通常のクロメート被膜を有して成るか、或いは
外観での品質価値の要求に関連して、鉄鋼材表面
の前記亜鉛の鍍金層上に、黒色クロメート被膜を
形成するかして実用に供していた。
しかしながらこれら従来のものにあつては、長
時間の走行等による機関からの連続した或いは断
続繰返しによる熱影響によつて、前記クロメート
被膜或いは黒色クロメート被膜ともいずれも概し
て短時間に変色し、強いては消失、剥離等を生ず
る等、未だ耐熱性の要求を充分に満足できない状
況にあり、同時に耐熱性の劣化に起因して耐食性
をも損つてその低下を招く問題を有し、従つて広
くその改善が望まれる現状にある。
〔発明の目的〕
本発明は、従来の前記問題を、特に亜鉛−ニツ
ケル合金による鍍金層と黒色ニツケルの電鍍層と
のなす相互の被着重合面での密着性を著しく向上
し、更に外側表面にクロム酸被膜を形成し、それ
ぞれの前記鍍金層、電鍍層およびクロム酸被膜の
有する耐食性と、これら簡易な重合被覆形成方法
に関連して効果的に解決せしめ、前記温度以下の
加温雰囲気における使用状態下にあつても、耐熱
性と耐食性とを共に満足することのできる耐熱・
耐食性重合被覆鋼材および重合被覆形成方法を提
案することを目的とするものである。
〔発明の構成〕
本発明は、鉄鋼材の表面に亜鉛−ニツケル合金
の鍍金層を下層とし、該鍍金層の表面に黒色ニツ
ケルの電鍍層を上層として被着重合し、更に該電
鍍層の表面にクロム酸被膜を有する耐熱・耐食性
重合被覆鋼材を要旨とするものであり、更に該重
合被覆鋼材の重合被覆形成方法として、予め脱
脂、脱錆等の前処理を施した鉄鋼材の表面に電鍍
法による亜鉛−ニツケル合金の鍍金層を形成し、
更に該亜鉛−ニツケル合金の鍍金層の表面に、電
鍍法により亜鉛30重量％乃至50重量％からなり硫
化ニツケル中に金属亜鉛が共析して外観黒色を呈
した黒色ニツケルの電鍍層を形成せしめ、次いで
該黒色ニツケルの電鍍層の表面に、クロム酸水溶
液による浸漬、水洗及び乾燥のこれら一連からな
るクロム酸処理を１回以上施してクロム酸被膜を
形成するか、或いは前記クロム酸処理を、クロム
酸水溶液による浸漬、乾燥及び加熱からなるこれ
ら一連の処理を１回以上施してクロム酸被膜を形
成するか、或いは又、クロム酸処理をクロム酸水
溶液による浸漬、水洗及び乾燥のこれら一連から
なるクロム酸処理を１回以上施すとともに、更に
再度クロム酸水溶液による浸漬、乾燥及び加熱か
らなるこれら一連の処理を１回以上施してクロム
酸被膜を形成するかして成る重合被覆形成方法を
要旨とするものであり、以下本発明を図面に基づ
いて説明すれば次の通りである。
第１図及び第２図はいずれも本発明の重合被覆
形成方法によつて構成された耐熱・耐食性重合被
覆鋼材として板材（第１図）および管材（第２
図）にそれぞれ施した要部の一部切欠による拡大
断面図であつた、１は予め脱脂、脱錆等の前処理
を施した表面１′に電鍍法によつて亜鉛−ニツケ
ル合金からなる鍍金層２を形成した鉄鋼材、３は
亜鉛−ニツケル合金からなる鍍金層２の表面２′
に電鍍法により被着重合した黒色ニツケルの電鍍
層、４は更に黒色ニツケルの電鍍層３の表面３′
に形成したクロム酸被膜である。
尚前記亜鉛−ニツケル鍍金層は、塩化亜鉛、塩
化ニツケル及び塩化アンモニウムを主成分とする
PH5.8乃至6.8の電鍍浴によつて施されるもので、
又ニツケルを７重量％乃至15重量％の範囲に含有
した状態で形成されるもので、当然ニツケルのこ
れら含有によつて耐熱・耐食性を効果的となすも
のである。一方前記黒色ニツケルの電鍍層３の被
着重合に際しては、硫酸ニツケル、硫酸亜鉛、硫
酸ニツケルアンモニウム及びチオシアン化カリウ
ムからなるPH5.6乃至5.9の電鍍浴をもつて使用で
きることとなり、且つ亜鉛を30重量％乃至50重量
％の範囲に含有したニツケル−亜鉛の合金層から
なる外観黒色を呈して形成されるもので、前記下
層の亜鉛−ニツケルの鍍金層に類似した同種金属
の組成によつて被着重合してなるため、相互の被
着重合面での密着性を著しく向上することとな
る。又同時に被着重合に際して使用する前記PH
5.6乃至5.9の範囲にある電鍍浴を使用するため、
その中間での前処理に制限をうけることなく、こ
れら処理作業を簡易とし、密着性と充分な耐熱性
を有して被着重合し、更に又黒色ニツケルの電鍍
層３の表面３′に構成したクロム酸被膜４に相乗
して耐食性をも充分に発揮することができるので
ある。
尚クロム酸被膜４の形成に際しては、無水クロ
ム酸の水溶液に前記被着重合した鉄鋼材１を約20
秒乃至60秒間浸漬し、水洗した後に常温乃至150
℃の範囲で乾燥を行い、これら浸漬、水洗及び乾
燥の一連の処理を１回以上施すか、或は無水クロ
ム酸の水溶液に前記鉄鋼材１を同様に浸漬し、引
き上げた後そのままの状態で乾燥せしめ、その後
約300℃以下において１分乃至５分間の加熱を行
い、これら浸漬、乾燥及び加熱からなる一連の処
理を１回以上施すか、或いは又、前記浸漬、水洗
及び乾燥の一連の処理を１回以上施した後に、更
に再度前記浸漬、乾燥及び加熱からなる一連の処
理を１回以上施すかして形成されるものである。
又無水クロム酸の濃度としては、20ｇ／乃至
900ｇ／の範囲が望まれるところであり、20
ｇ／未満では被膜効果に乏ぼしく、又900ｇ／
を越えると水溶液の粘度を増して著しく作業性
を低下せしめ、同時に不経済となす理由によるも
のである。
〔発明の作用〕
本発明は、前記の重合被覆構造およびその形成
方法を要旨とするため、亜鉛−ニツケル合金から
なる鍍金層２に、硫化ニツケル中に金属亜鉛が共
析した黒色ニツケルの電鍍層３を被着重合して優
れた密着性を発揮し、更に、上層の黒色ニツケル
電鍍層３によつて250℃以下の加温雰囲気状態下
での耐熱性を、又下層の亜鉛−ニツケル合金から
なる鍍金層２によつて耐熱性と同時に耐食性をそ
れぞれ発揮せしめる結果となり、更に黒色ニツケ
ルの電鍍層３の被着重合に際しての前記電鍍浴の
PH値の範囲で処理するため、その中間での前処理
が至極簡単で、従つて生産性を向上して廉価に形
成することは勿論のこと、特に黒色ニツケルの電
鍍層３の表面３′に前記一連の処理を施すことに
よつて形成したこれら方法に関連したクロム酸被
膜４によつて白錆の発生を抑制し、亜鉛とクロム
酸との反応によつて生ずるクロム化合物により、
存在するピンホールを封孔するとともに、表面に
不働態被膜を形成して安定化させる作用を発揮し
て一層耐食性を向上させ、同時にクロム酸被膜４
での変色、消失或いは剥離等をも軽減、防止する
結果となるのである。
〔発明の実施例〕
実施例 １
・ 鉄鋼材…材質STPG38、外径10.0m／ｍ、肉
厚0.7m／ｍ、長さ500m／ｍの管材を常法によ
り脱脂、脱錆の前処理を行う。
・ 亜鉛−ニツケル合金鍍金処理…塩化亜鉛45
ｇ／、塩化ニツケル75ｇ／、塩化アンモニ
ウム250ｇ／、硼酸20ｇ／の組成からなる
PH5.8の鍍金浴を使用し、前記管材を陰極と
し、一方ニツケル板を陽極として浴温38℃で陰
極電流密度2A／ｄm2で10分間通電した後、水
洗を行い、層厚５μからなる亜鉛−ニツケル合
金の鍍金層を得た。
・ 中間での前処理…10％の硫酸水溶液に５秒間
浸漬した後、水洗を行う。
・ 黒色ニツケル電鍍処理…硫酸ニツケル75ｇ／
、硫酸亜鉛38ｇ／、硫酸ニツケルアンモニ
ウム45ｇ／、チオシアン化カリウム15ｇ／
の組成からなるPH5.6の電鍍浴を使用し、前記
亜鉛−ニツケル合金の鍍金層を有した管材を陰
極とし、一方ニツケル板を陽極として浴温50
℃、陰極電流密度1A／ｄm2で５分間通電した
後、水洗を行つた結果、前記鍍金層上に層厚４
μからなる黒色ニツケルの電鍍層を被着重合し
た得た。
・ クロム酸処理…無水クロム酸750ｇ／の水
溶液に前記被着重合した管材を30秒間浸漬し、
水洗した後、50℃で乾燥し、これら一連の処理
によりクロム酸被膜を形成した。
実施例 ２
・ 鉄鋼材…実施例１に同じ。
・ 亜鉛−ニツケル合金鍍金処理…塩化亜鉛60
ｇ／、塩化ニツケル85ｇ／、塩化アンモニ
ウム200ｇ／、アンモニア水50ml／、硼酸
20ｇ／の組成からなるPH6.5の鍍金浴を使用
し、前記管材を陰極とし、一方ニツケル板を陽
極として浴温40℃で陰極電流密度2.5A／ｄm2
で８分間通電した結果層厚５μからなる亜鉛−
ニツケル合金の鍍金層を得た。
・ 中間での前処理…実施例１に同じ。
・ 黒色ニツケル電鍍処理…実施例１に同じ。
・ クロム酸処理…無水クロム酸50ｇ／の水溶
液に前記被着重合した管材を40秒間浸漬し、水
洗した後、120℃で炉中乾燥し、これら一連の
処理を２回行つてクロム酸被膜を形成した。
実施例 ３
鉄鋼材、亜鉛−ニツケル合金鍍金処理、中間で
の前処理および黒色ニツケル電鍍処理は、いずれ
も実施例１に同じ。
・ クロム酸処理…無水クロム酸500ｇ／の水
溶液に前記被着重合した管材を30秒間浸漬し、
90℃で乾燥した後、260℃で５分間加熱し、こ
れら一連の処理によりクロム酸被膜を形成し
た。
実施例 ４
鉄鋼材、亜鉛−ニツケル合金鍍金処理、中間で
の前処理および黒色ニツケル電鍍処理は、いずれ
も実施例１に同じ。
・ クロム酸処理…無水クロム酸250ｇ／の水
溶液に前記被着重合した管材を25秒間浸漬し、
常温で乾燥した後、230℃で５分間加熱し、こ
れら一連の処理を２回行つてクロム酸被膜を形
成した。
実施例 ５
鉄鋼材、亜鉛−ニツケル合金鍍金処理、中間で
の前処理および黒色ニツケル電鍍処理は、いずれ
も実施例１に同じ。
・ クロム酸処理…無水クロム酸750ｇ／の水
溶液に前記被着重合した管材を30秒間浸漬し、
水洗した後、60℃で乾燥し、更に再度無水クロ
ム酸250ｇ／の水溶液に30秒間浸漬し、60℃
で乾燥した後、250℃で３分間加熱してクロム
酸被膜を形成した。
比較例
実施例１と同じ鉄鋼材を用いて酸化亜鉛30ｇ／
、青化ソーダ50ｇ／、苛性ソーダ60ｇ／の
組成からなる鍍金浴を使用し、前記管材を陰極と
し、一方亜鉛板を陽極として常温下で陰極電流密
度3A／ｄm2で15分間通電した後、水洗を行つて
層厚９μからなる亜鉛の鍍金層を得た後に、黒色
クロメート浴に常温下で20秒間浸漬し、その後水
洗、乾燥して黒色クロメート被膜を得た。
尚前記本発明品（実施例１乃至５）と従来品
（比較例）との耐熱・耐食性試験に係る比較特性
結果については、下記の表−１及び表−２に記載
するところである。
・ 耐熱性試験結果
加温雰囲気200℃で24時間連続一定加熱した
後、大気中に放冷して大気温度まで温度降下し、
その後再び250℃の昇温雰囲気で24時間連続一定
加熱してそれぞれの外観状態を目視により観察し
た。
[Industrial Field of Application] The present invention relates to plates, pipes, etc. used in a heated atmosphere of about 250°C or less as various parts or parts around an internal heat engine, for example.
The present invention relates to a polymer coated steel material which is applied to the surface of a steel material such as a rod or wire rod and which requires heat resistance and corrosion resistance at the same time, and a method for forming the polymer coat. [Problems with the prior art] Conventionally, various parts used around engines or steel materials with heat-resistant and corrosion-resistant coating structures have generally been coated with zinc on the surface of steel materials formed by electroplating or dipping. Either a regular chromate film is simply formed on the zinc plating layer on the surface of the steel material, or a black chromate film is formed on the zinc plating layer on the surface of the steel material in relation to the requirements for quality value in appearance. and put it into practical use. However, in the case of these conventional products, both the chromate film and the black chromate film generally discolor in a short period of time due to the continuous or intermittent heat effects from the engine during long-term running, etc. It is still not possible to fully satisfy the requirements for heat resistance due to problems such as disappearance and peeling, and at the same time there is a problem that corrosion resistance is also deteriorated due to deterioration of heat resistance. The current situation is that it is desired. [Object of the Invention] The present invention solves the above-mentioned conventional problems by significantly improving the adhesion of a zinc-nickel alloy plating layer and a black nickel electrolytic plating layer at their mutual adhesion polymerization surfaces, and further improves the adhesion of a zinc-nickel alloy plating layer and a black nickel electroplating layer. By forming a chromic acid film on the surface, the corrosion resistance of each of the plating layer, electrolytic plating layer, and chromic acid film is effectively solved in relation to the simple polymerization coating formation method, and the corrosion resistance in a heated atmosphere below the above temperature is effectively solved. Heat-resistant and corrosion-resistant products that can satisfy both heat resistance and corrosion resistance even under usage conditions.
The purpose of this paper is to propose a corrosion-resistant polymer coated steel material and a method for forming the polymer coat. [Structure of the Invention] The present invention comprises forming a zinc-nickel alloy plating layer as a lower layer on the surface of a steel material, depositing and polymerizing a black nickel electroplating layer on the surface of the plating layer, and then depositing and polymerizing a black nickel electroplating layer on the surface of the plating layer. The main feature of this technology is a heat-resistant and corrosion-resistant polymer-coated steel material having a chromic acid coating on the surface of the steel material, and the method for forming the polymer coating of the polymer-coated steel material involves electroplating the surface of the steel material, which has undergone pretreatment such as degreasing and derusting. Forming a plating layer of zinc-nickel alloy by method,
Further, on the surface of the zinc-nickel alloy plating layer, an electroplated layer of black nickel containing 30% to 50% by weight of zinc and having a black appearance is formed by eutectoiding metallic zinc into nickel sulfide. Then, the surface of the electroplated layer of the black nickel is subjected to a chromic acid treatment consisting of a series of immersion in an aqueous chromic acid solution, washing with water, and drying one or more times to form a chromic acid film, or the chromic acid treatment is A chromic acid film is formed by performing a series of treatments consisting of dipping in an aqueous chromic acid solution, drying, and heating one or more times, or alternatively, the chromic acid treatment consists of a series of these treatments consisting of dipping in an aqueous chromic acid solution, washing with water, and drying. The gist is a method for forming a polymeric coating, in which a chromic acid treatment is performed one or more times, and a series of treatments consisting of immersion in an aqueous chromic acid solution, drying, and heating is performed one or more times to form a chromic acid film. The present invention will be explained below based on the drawings. FIGS. 1 and 2 both show a plate material (FIG. 1) and a pipe material (FIG.
1 is an enlarged cross-sectional view with a partial cutaway of the main parts applied to each of the above. 1 is a surface 1' that has been pre-treated by degreasing, derusting, etc., and is plated with a zinc-nickel alloy by electroplating. The steel material on which layer 2 was formed, 3 is the surface 2' of the plating layer 2 made of zinc-nickel alloy.
A black nickel electroplated layer 3 is coated and polymerized by an electroplating method, and 4 is a surface 3' of the black nickel electroplated layer 3.
This is a chromic acid coating formed on The zinc-nickel plating layer mainly contains zinc chloride, nickel chloride, and ammonium chloride.
It is applied using an electroplating bath with a pH of 5.8 to 6.8.
Also, it is formed in a state containing nickel in the range of 7% to 15% by weight, and naturally, the heat resistance and corrosion resistance are effectively achieved by the content of nickel. On the other hand, when depositing and polymerizing the black nickel electroplating layer 3, it is possible to use an electroplating bath containing nickel sulfate, zinc sulfate, ammonium nickel sulfate, and potassium thiocyanide with a pH of 5.6 to 5.9, and containing 30% by weight of zinc. It is formed with a black appearance and consists of a nickel-zinc alloy layer containing in the range of 50% by weight, and is formed by deposition polymerization due to the composition of the same metal similar to the lower zinc-nickel plating layer. As a result, the adhesion between the mutually adhered and polymerized surfaces is significantly improved. At the same time, the above-mentioned PH used during deposition polymerization
Because we use an electroplating bath in the range of 5.6 to 5.9,
Without being restricted by pre-treatments in the middle, these treatment operations can be simplified, the coating can be polymerized with adhesion and sufficient heat resistance, and the surface 3' of the electroplated layer 3 of black nickel can be further coated. In combination with the chromic acid coating 4, corrosion resistance can be sufficiently exhibited. In addition, when forming the chromic acid film 4, about 20% of the above-described polymerized steel material 1 is added to an aqueous solution of chromic acid anhydride.
After soaking for 60 seconds and rinsing with water, warm to room temperature to 150℃.
Drying is carried out in the temperature range of °C, and a series of treatments of immersion, water washing and drying is performed one or more times, or the steel material 1 is similarly immersed in an aqueous solution of chromic anhydride, and after being pulled out, it is left as is. Dry and then heat at about 300°C or less for 1 to 5 minutes, and perform a series of treatments consisting of dipping, drying, and heating one or more times, or alternatively, a series of treatments consisting of dipping, washing, and drying. It is formed by performing the above-mentioned dipping, drying, and heating series of treatments one or more times again. Also, the concentration of chromic anhydride is 20g/~
A range of 900g/ is desired, and 20
If it is less than 900g/, the coating effect will be poor, and if it is less than 900g/
This is because if it exceeds the viscosity of the aqueous solution, the viscosity of the aqueous solution increases, significantly reducing workability, and at the same time making it uneconomical. [Function of the Invention] Since the gist of the present invention is the above-mentioned polymerized coating structure and method for forming the same, the present invention includes an electroplated layer of black nickel in which metal zinc is co-deposited in nickel sulfide on the plating layer 2 made of a zinc-nickel alloy. 3 is deposited and polymerized to exhibit excellent adhesion, and the upper black nickel electroplated layer 3 provides heat resistance under heated atmosphere conditions of 250℃ or less, and the lower layer zinc-nickel alloy provides excellent adhesion. The result is that the plating layer 2 exhibits both heat resistance and corrosion resistance, and furthermore, when the electroplating layer 3 of black nickel is deposited and polymerized, the electroplating bath
Since the treatment is carried out within the range of PH value, pretreatment in the middle is extremely simple, which not only improves productivity and enables formation at low cost, but also particularly on the surface 3' of the electroplated layer 3 of black nickel. The generation of white rust is suppressed by the chromic acid coating 4 related to these methods formed by performing the above series of treatments, and the chromium compound produced by the reaction between zinc and chromic acid suppresses the occurrence of white rust.
In addition to sealing existing pinholes, a passive film is formed on the surface to exhibit a stabilizing effect, further improving corrosion resistance.
This results in the reduction and prevention of discoloration, disappearance, peeling, etc. [Embodiments of the Invention] Example 1 - Steel material...Material STPG38, outer diameter 10.0 m/m, wall thickness 0.7 m/m, length 500 m/m pipe material is pre-treated to degrease and remove rust by conventional methods. .・ Zinc-nickel alloy plating treatment...Zinc chloride 45
g/, nickel chloride 75g/, ammonium chloride 250g/, boric acid 20g/.
Using a plating bath with a pH of 5.8, using the tube as the cathode and the nickel plate as the anode, the bath temperature was 38°C and the cathode current density was 2A/dm 2 for 10 minutes, followed by washing with water and forming a layer with a thickness of 5μ. A zinc-nickel alloy plating layer was obtained.・Intermediate pretreatment...Immerse in 10% sulfuric acid aqueous solution for 5 seconds, then rinse with water.・Black nickel electroplating treatment...nickel sulfate 75g/
, zinc sulfate 38g/, nickel ammonium sulfate 45g/, potassium thiocyanide 15g/
An electroplating bath with a pH of 5.6 having a composition of
After applying current for 5 minutes at a cathode current density of 1 A/dm 2 at a temperature of 1 A/dm 2 , a layer thickness of 4
A black nickel electroplated layer consisting of μ was obtained by coating and polymerizing.・Chromic acid treatment: The polymerized pipe material is immersed in an aqueous solution of 750 g of chromic acid anhydride for 30 seconds.
After washing with water, it was dried at 50°C, and a chromic acid film was formed by this series of treatments. Example 2 - Steel material: Same as Example 1.・Zinc-nickel alloy plating treatment…zinc chloride 60
g/, nickel chloride 85g/, ammonium chloride 200g/, ammonia water 50ml/, boric acid
A plating bath of pH 6.5 with a composition of 20g/dm was used, the tube material was used as a cathode, and the nickel plate was used as an anode at a bath temperature of 40°C and a cathode current density of 2.5A/ dm2.
As a result of applying current for 8 minutes at
A plating layer of nickel alloy was obtained. - Intermediate pretreatment...Same as Example 1. - Black nickel electroplating treatment...Same as Example 1.・Chromic acid treatment: The coated and polymerized pipe material is immersed in an aqueous solution of 50 g of chromic acid anhydride for 40 seconds, washed with water, dried in an oven at 120°C, and this series of treatments is performed twice to remove the chromic acid coating. Formed. Example 3 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.・Chromic acid treatment: The polymerized pipe material is immersed in an aqueous solution of 500 g of chromic acid anhydride for 30 seconds.
After drying at 90°C, it was heated at 260°C for 5 minutes, and a chromic acid film was formed by this series of treatments. Example 4 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.・Chromic acid treatment: The polymerized pipe material is immersed in an aqueous solution of 250 g of chromic acid anhydride for 25 seconds.
After drying at room temperature, it was heated at 230° C. for 5 minutes, and this series of treatments was performed twice to form a chromic acid film. Example 5 The steel material, zinc-nickel alloy plating treatment, intermediate pretreatment, and black nickel electroplating treatment were all the same as in Example 1.・Chromic acid treatment: The polymerized pipe material is immersed in an aqueous solution of 750 g of chromic acid anhydride for 30 seconds.
After washing with water, drying at 60°C, immersing again in an aqueous solution of 250g of chromic acid anhydride for 30 seconds, and drying at 60°C.
After drying, it was heated at 250°C for 3 minutes to form a chromic acid film. Comparative example Using the same steel material as Example 1, 30g of zinc oxide/
Using a plating bath with a composition of 50 g of soda cyanide and 60 g of caustic soda, the tube was used as a cathode and the zinc plate was used as an anode, and the current was applied at room temperature for 15 minutes at a cathode current density of 3 A/dm 2 , followed by washing with water. After doing this to obtain a zinc plating layer having a layer thickness of 9 μm, it was immersed in a black chromate bath for 20 seconds at room temperature, and then washed with water and dried to obtain a black chromate coating. The comparative characteristic results of the heat resistance and corrosion resistance tests between the products of the present invention (Examples 1 to 5) and the conventional product (comparative example) are shown in Tables 1 and 2 below.・Heat resistance test results: After being continuously heated at a constant temperature of 200℃ for 24 hours, the product is allowed to cool in the atmosphere and the temperature drops to atmospheric temperature.
Thereafter, the specimens were heated again at a constant temperature of 250° C. for 24 hours, and the external appearance of each specimen was visually observed.
【表】
・耐食性試験結果
前記耐熱性試験の200℃、24時間経過後の試料
について、JISZ−2371による塩水噴霧試験法の
規定によつて行つた。[Table] - Corrosion resistance test results The heat resistance test samples after 24 hours at 200°C were tested according to the salt spray test method according to JISZ-2371.
前記したように本発明による耐熱・耐食性重合
被覆鋼材および重合被覆形成方法は、前記相互の
亜鉛−ニツケル合金の鍍金層２と黒色ニツケルの
電鍍層３とをもつて、それぞれに前記加温雰囲気
状態下での耐熱性と耐食性とを同時に満足するこ
とができ、且つこれら相互の被着重合面での密着
性を著しく良好とし、更に前記黒色ニツケル電鍍
層３の表面３′に一連の処理を施すことによつて
形成した前記形成方法に関連して成るクロム酸被
膜４によつて白錆発生を抑制し、亜鉛とクロム酸
との反応によつて生ずるクロム化合物により存在
するピンホールでの封孔を促進するとともに、表
面に不働態被膜を形成して安定化するこれら相乗
効果によつて耐食性を一層向上させることとな
り、同時にクロム酸被膜自体での変色、消失或い
は剥離等をも軽減、防止することができ、更に重
合被覆処理に際して、前記電鍍浴のPH値の使用範
囲に関連した中間での前処理の簡素化により、生
産性を向上して比較的廉価とすることができ、更
に第２層として施した黒色ニツケル電鍍層によつ
て鋼材表面の重合被覆が黒色を呈するため放熱性
も改善される等、多くの特徴を有する極めて有用
な耐熱・耐食性重合被覆鋼材および重合被覆形成
方法のものである。
As described above, the heat-resistant and corrosion-resistant polymer coated steel material and the method for forming the polymer coat according to the present invention have the above-mentioned mutual zinc-nickel alloy plating layer 2 and black nickel electroplating layer 3, respectively, and the heating atmosphere condition. It is possible to simultaneously satisfy the heat resistance and corrosion resistance at the bottom, and to improve the adhesion between these mutually adhered and polymerized surfaces, and further, a series of treatments are applied to the surface 3' of the black nickel electroplated layer 3. In particular, the chromic acid coating 4 formed in connection with the above-mentioned formation method suppresses the generation of white rust, and seals the pinholes that exist due to the chromium compound produced by the reaction between zinc and chromic acid. This synergistic effect, which promotes corrosion and stabilizes the formation of a passive film on the surface, further improves corrosion resistance, and at the same time reduces and prevents discoloration, disappearance, or peeling of the chromic acid film itself. Furthermore, during the polymerization coating process, by simplifying the intermediate pretreatment related to the range of PH value of the electroplating bath, productivity can be improved and the cost can be made relatively low. Extremely useful heat-resistant and corrosion-resistant polymer-coated steel material and method for forming the polymer coating, which have many features such as the black nickel electroplating layer that gives the polymer coating on the surface of the steel material a black color and improved heat dissipation. It is.
第１図は本発明の一実施例に係る耐熱・耐食性
重合被覆を板材に施した要部の一部切欠による拡
大断面図、第２図は同じく管材に施した要部の一
部切欠による拡大断面図である。
１……鉄鋼材、１′……表面、２……亜鉛−ニ
ツケル合金の鍍金層、２′……表面、３……黒色
ニツケルの電鍍層、３′……表面、４……クロム
酸被膜。
Fig. 1 is an enlarged cross-sectional view with a partial notch showing a main part of a plate material coated with a heat-resistant and corrosion-resistant polymer coating according to an embodiment of the present invention, and Fig. 2 is an enlarged view with a partial cutout showing a main part similarly applied to a pipe material. FIG. 1...Steel material, 1'...Surface, 2...Zinc-nickel alloy plating layer, 2'...Surface, 3...Black nickel electroplated layer, 3'...Surface, 4...Chromic acid coating .
Claims (1)
からなる鍍金層２を下層とし、該鍍金層の表面
２′に黒色ニツケルの電鍍層３を上層として被着
重合し、更に黒色ニツケルの電鍍層３の表面３′
にクロム酸被膜４を有して成ることを特徴とする
耐熱・耐食性重合被覆鋼材。 ２ 予め脱脂、脱錆等の前処理を施した鉄鋼材１
の表面１′に、電鍍法による亜鉛−ニツケル合金
の鍍金層２を形成し、更に該亜鉛−ニツケル合金
の鍍金層２の表面２′に電鍍法による黒色ニツケ
ルの電鍍層３を被着重合せしめ、次いで該黒色ニ
ツケルの電鍍層３の表面３′に、クロム酸水溶液
による浸漬、水洗及び乾燥のこれら一連からなる
クロム酸処理を１回以上施してクロム酸被膜４を
形成することを特徴とする耐熱・耐食性重合被覆
鋼材の重合被覆形成方法。 ３ 特許請求の範囲第２項記載の耐熱・耐食性重
合被覆鋼材の重合被覆形成方法において、クロム
酸処理を、クロム酸水溶液による浸漬、乾燥及び
加熱からなるこれら一連の処理を１回以上施して
クロム酸被膜４を形成することを特徴とする耐
熱・耐食性重合被覆鋼材の重合被覆形成方法。 ４ 予め脱脂、脱錆等の前処理を施した鉄鋼材１
の表面１′に、電鍍法による亜鉛−ニツケル合金
の鍍金層２を形成し、更に該亜鉛−ニツケル合金
の鍍金層２の表面２′に電鍍法による黒色ニツケ
ルの電鍍層３を被着重合せしめ、次いで該黒色ニ
ツケルの電鍍層３の表面３′に、クロム酸水溶液
による浸漬、水洗及び乾燥のこれら一連からなる
クロム酸処理を１回以上施すとともに、更に再度
クロム酸水溶液による浸漬、乾燥及び加熱からな
るこれら一連の処理を１回以上施してクロム酸被
膜４を形成することを特徴とする耐熱・耐食性重
合被覆鋼材の重合被覆形成方法。[Scope of Claims] 1 A plating layer 2 made of a zinc-nickel alloy is placed as a lower layer on the surface 1' of a steel material 1, and an electrolytic plating layer 3 of black nickel is deposited and polymerized on the surface 2' of the plating layer as an upper layer. , and the surface 3' of the electroplated layer 3 of black nickel.
A heat-resistant and corrosion-resistant polymer coated steel material, characterized in that it has a chromic acid coating 4 on its surface. 2 Steel material 1 that has been pretreated such as degreasing and derusting
A plating layer 2 of zinc-nickel alloy is formed on the surface 1' of the zinc-nickel alloy by electroplating, and an electroplating layer 3 of black nickel is superimposed on the surface 2' of the zinc-nickel alloy plating layer 2. Then, the surface 3' of the electroplated layer 3 of the black nickel is subjected to a chromic acid treatment consisting of a series of immersion in an aqueous chromic acid solution, washing with water, and drying at least once to form a chromic acid coating 4. A method for forming a polymer coating on heat-resistant and corrosion-resistant polymer coated steel. 3. In the method for forming a polymeric coating on heat-resistant and corrosion-resistant polymeric-coated steel material as described in claim 2, the chromic acid treatment is performed one or more times in a series of treatments consisting of immersion in an aqueous chromic acid solution, drying, and heating. A method for forming a polymeric coating on a heat-resistant and corrosion-resistant polymeric-coated steel material, the method comprising forming an acid coating 4. 4 Steel material 1 that has been pretreated such as degreasing and derusting
A plating layer 2 of zinc-nickel alloy is formed on the surface 1' of the zinc-nickel alloy by electroplating, and an electroplating layer 3 of black nickel is superimposed on the surface 2' of the zinc-nickel alloy plating layer 2. Then, the surface 3' of the electroplated layer 3 of the black nickel is subjected to a chromic acid treatment consisting of a series of immersion in an aqueous chromic acid solution, washing with water, and drying at least once, followed by further immersion in an aqueous chromic acid solution, drying, and heating. A method for forming a polymeric coating on a heat-resistant and corrosion-resistant polymeric-coated steel material, which comprises performing a series of these treatments one or more times to form a chromic acid coating 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11800484A JPS60262976A (en) | 1984-06-08 | 1984-06-08 | Heat and corrosion resistant multiply coated steel material and formation of multilayered coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11800484A JPS60262976A (en) | 1984-06-08 | 1984-06-08 | Heat and corrosion resistant multiply coated steel material and formation of multilayered coat |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4184418A Division JPH0718020B2 (en) | 1992-06-18 | 1992-06-18 | Heat resistant / corrosion resistant polymer coated steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262976A JPS60262976A (en) | 1985-12-26 |
| JPS6253588B2 true JPS6253588B2 (en) | 1987-11-11 |
Family
ID=14725667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11800484A Granted JPS60262976A (en) | 1984-06-08 | 1984-06-08 | Heat and corrosion resistant multiply coated steel material and formation of multilayered coat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017110686A1 (en) * | 2015-12-25 | 2017-06-29 | 新日鐵住金株式会社 | Threaded joint for pipe and manufacturing method of threaded joint for pipe |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5475436A (en) * | 1977-11-29 | 1979-06-16 | Nippon Steel Corp | Zinc-plated steel products for coating |
| JPS55110792A (en) * | 1979-02-15 | 1980-08-26 | Sumitomo Metal Ind Ltd | Surface treated steel plate |
-
1984
- 1984-06-08 JP JP11800484A patent/JPS60262976A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5475436A (en) * | 1977-11-29 | 1979-06-16 | Nippon Steel Corp | Zinc-plated steel products for coating |
| JPS55110792A (en) * | 1979-02-15 | 1980-08-26 | Sumitomo Metal Ind Ltd | Surface treated steel plate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017110686A1 (en) * | 2015-12-25 | 2017-06-29 | 新日鐵住金株式会社 | Threaded joint for pipe and manufacturing method of threaded joint for pipe |
| JPWO2017110686A1 (en) * | 2015-12-25 | 2018-07-05 | 新日鐵住金株式会社 | Threaded joint for pipe and method for manufacturing threaded joint for pipe |
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| Publication number | Publication date |
|---|---|
| JPS60262976A (en) | 1985-12-26 |
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