JPH04198491A - Treatment of metal surface - Google Patents

Treatment of metal surface

Info

Publication number
JPH04198491A
JPH04198491A JP2325750A JP32575090A JPH04198491A JP H04198491 A JPH04198491 A JP H04198491A JP 2325750 A JP2325750 A JP 2325750A JP 32575090 A JP32575090 A JP 32575090A JP H04198491 A JPH04198491 A JP H04198491A
Authority
JP
Japan
Prior art keywords
parts
treatment
zinc
alloy
silica
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.)
Granted
Application number
JP2325750A
Other languages
Japanese (ja)
Other versions
JP2950481B2 (en
Inventor
Keiichi Ishizuka
石塚 啓一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON DAKURO SHAMROCK KK
Original Assignee
NIPPON DAKURO SHAMROCK KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NIPPON DAKURO SHAMROCK KK filed Critical NIPPON DAKURO SHAMROCK KK
Priority to JP2325750A priority Critical patent/JP2950481B2/en
Priority to EP91120491A priority patent/EP0488353B1/en
Priority to DE69106678T priority patent/DE69106678T2/en
Priority to AT91120491T priority patent/ATE117026T1/en
Publication of JPH04198491A publication Critical patent/JPH04198491A/en
Application granted granted Critical
Publication of JP2950481B2 publication Critical patent/JP2950481B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/06Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/06Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48Chemical 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 using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53Treatment of zinc or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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 using aqueous solutions
    • C23C22/68Chemical 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 using aqueous solutions using aqueous solutions with pH between 6 and 8
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/18After-treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Chemically Coating (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

PURPOSE:To obtain the corrosion resistance being not inferior to a chromate treatment by forming a zinc (alloy) film by projecting a prescribed blast material on a metal material surface and subsequently treating with an aqueous silica suspension solution and an aqueous solution incorporating a prescribed metal ion. CONSTITUTION:The blast material consisting of an assembly of double layered coated particles with adhered a zinc (alloy) layer through an iron-zinc alloy layer on the circumstance of a core being iron (alloy) particles as the core, is projected on a metal surface to form a zinc (alloy) coating film. Next this is conducted a contact treatment such as dipping, coating in an aqueous solution containing one kind or more metallic ions among Ti, Zr, Mg, Ba, Sr, W, Ni, Co, Sn, Mo, Mn and the aqueous silica suspension solution. The silica concentration in the silica suspension solution is about 0.1-20 parts for 100 wt. parts of water and also the metal ion concentration in the aqueous metallic ion solution is preferably about 0.01-20 parts for 100 parts of water.

Description

【発明の詳細な説明】 (産業上の利用分野) この発明は金属表面の防蝕処理に関する。[Detailed description of the invention] (Industrial application field) This invention relates to anti-corrosion treatment of metal surfaces.

(従来技術とその問題点) 従来の金属表面の防食処理として、1llj ’jXi
を溶融めっきまたは電気めっきしてからクロメ−1・処
理するという方法はよく知られている。またプラスト亜
鉛めっき法も知られている。最近鉄または鉄合金の粒子
を核として、その周囲に鉄亜鉛合金層を介して亜鉛また
は亜鉛合金層を被着してなる独立した複数粒子の欠合体
からなる改良されたプラスト材料を鉄または鉄合金表面
に投射することからなる改良されたフラスト亜鉛被覆法
が開発された(特公昭59−931.2)。 この方法
を木明細計ては改良プラス1〜亜鉛被覆法と呼ぶ。
(Prior art and its problems) As a conventional anticorrosion treatment for metal surfaces, 1llj 'jXi
The method of hot-dipping or electroplating and then treating with chrome-1 is well known. A plasto galvanizing method is also known. Recently, an improved plastic material consisting of a disjoint body of multiple independent particles is made of iron or iron alloy particles as a core, and a zinc or zinc alloy layer is coated around the core through an iron-zinc alloy layer. An improved method of coating zinc frusto, which consists of spraying onto the alloy surface, was developed (Japanese Patent Publication No. 59-931.2). This method is called improved plus 1 to zinc coating method.

この方法は、設備が低順で、エネルギー消費が少なく環
境汚染要素゛が少ない画期的な方法であるが、この方法
によって形成された亜鉛被覆は耐食性においてなお充分
でなく、100mg/dm2の付着量で、塩水噴霧試験
において、24時間以内に赤錆が発生する。これは、こ
の方法によって形成された亜鉛被覆が鉄亜鉛合金である
ことによると考えられる。
This method is an innovative method that requires less equipment, consumes less energy, and has fewer environmental pollutants.However, the zinc coating formed by this method still has insufficient corrosion resistance, and has a coating of 100 mg/dm2. In the salt spray test, red rust occurs within 24 hours. This is believed to be because the zinc coating formed by this method is an iron-zinc alloy.

一方金属の表面処理の面からみると亜鉛めっき、亜鉛合
金めっきおよび改良プラス1〜亜鉛被覆法による処理の
みでは充分な耐食性が得らオしないというのが実状であ
る。従ってこの被処理物を耐食性の用途で使用する場合
には、後処理を施す必要がある。
On the other hand, from the viewpoint of surface treatment of metals, the actual situation is that sufficient corrosion resistance cannot be obtained only by zinc plating, zinc alloy plating, and treatments using improved plus 1 to zinc coating methods. Therefore, when this treated material is used for corrosion-resistant purposes, it is necessary to perform post-treatment.

そのための比較的簡単な方法はクロメート処理である。A relatively simple method for this is chromate treatment.

改良プラスト亜鉛被覆法による処理後に適切なりロメー
ト処理を施した場合は240〜1000時間以上でも白
錆及び赤錆とも発生しない(特開昭61−67773、
特開平2−19477)。したがって耐食性用途で金属
に改良プラスト亜鉛被覆法を適用する場合は、後処理と
してクロメ−1〜処理を行うことが不可欠であると考え
られている。
If appropriate romate treatment is applied after treatment with the improved plasto zinc coating method, neither white rust nor red rust will occur for 240 to 1000 hours or more (Japanese Patent Application Laid-Open No. 67773/1983).
JP-A-2-19477). Therefore, when applying the improved plasto zinc coating method to metals for corrosion resistance purposes, it is considered essential to perform chromate-1 treatment as a post-treatment.

しかしながら後処理であるクロメ−1へ処理はいずれも
溶液中に6価のクロl、化合物を含有している。6価の
クロム化合物は安全衛生上および公害問題上有害な化合
物である。したがって産菜上6価のクロム化合物を利用
する場合には、その取扱いについて細心の注意が必要で
ある。
However, the post-treatment of chromate-1 contains a hexavalent chlorine compound in the solution. Hexavalent chromium compounds are harmful compounds in terms of safety and health and pollution problems. Therefore, when using hexavalent chromium compounds for production, great care must be taken in handling them.

しかし耐食性に優れた後処理法としては種々の方θモが
研究されているが、クロメート処理にまさるものは開発
できなかった。
However, although various methods have been studied as post-treatment methods with excellent corrosion resistance, no method superior to chromate treatment has been developed.

(問題点を解決するための手段) 本発明者らは改良フラスr−!lf鉛被鉛被覆土る処理
物の後処理法を鋭意研究した結果、耐食性の面において
クロメ−1へ処理に劣らない後処理を開発した。即ち、
改良プラスト亜鉛被覆法を金属4A料に適用した後、シ
リカ懸濁液と1゛」、Zr、 Mg、Ba、Sr、\V
、 Nj、 Co、Sn、No、 Mnの少くとも1種
のイオン含む水溶液で処理することによって、クロメ−
1へ処理に劣らぬ結果が得られることを見出した。
(Means for solving the problems) The present inventors have developed an improved frass r-! As a result of intensive research on post-treatment methods for lf-lead and lead-coated soil, we have developed a post-treatment method that is comparable to the treatment for chromate-1 in terms of corrosion resistance. That is,
After applying the modified plasto zinc coating method to metal 4A materials, silica suspension and 1'', Zr, Mg, Ba, Sr, \V
, Nj, Co, Sn, No, Mn by treatment with an aqueous solution containing at least one kind of ion.
It has been found that results comparable to those obtained by processing No. 1 can be obtained.

〔発明の構成〕[Structure of the invention]

本発明は鉄または鉄合金を核としてこの核の周囲に鉄亜
鉛合金属を介して亜鉛または亜鉛合金を被覆してなる複
層被覆粒子の集合体からなるブラスト材料を金属表面に
投射して亜鉛または亜鉛合金の被覆皮膜を形成し;この
ように形成された表面を、水性シリカJ111i濁液お
よびT」、Zr、MB、 Ba、Sr、 W、 Nj、
 Co、Sn、 No、Mnの少くとも1種の金属イオ
ンを含む水溶液と接触させることからなる金属表面処理
方法を提供する。
In the present invention, a blasting material consisting of an aggregate of multilayer coated particles made of iron or iron alloy as a core and zinc or zinc alloy coated around this core via an iron-zinc alloy metal is projected onto the metal surface. or form a coating film of zinc alloy; the surface thus formed is treated with an aqueous silica J111i suspension and
Provided is a metal surface treatment method comprising contacting with an aqueous solution containing at least one metal ion of Co, Sn, No, and Mn.

本発明方法の前段階の処理は、基本的に特公昭59−9
312号に開示されている方法であり、その公知の改良
方法を含む。
The pre-stage treatment of the method of the present invention is basically
No. 312, including known improvements thereto.

本発明の方法に使用されるシリカは沈降性シリカでも気
相加水分解シリカでもよく、要するに水性懸濁液を形成
するものなら何でもよい。シリカは、水100重量部に
対して0.1〜20重量部を含有される。0.1重量部
以下では処理物表面に充分な耐食性を発揮する皮膜が形
成されず、また20重量部以上では処理物表面に分厚い
ケル状皮膜ができてしまい実用的ではない。
The silica used in the process of the invention may be a precipitated silica or a gas-phase hydrolyzed silica, in short anything that forms an aqueous suspension. Silica is contained in an amount of 0.1 to 20 parts by weight per 100 parts by weight of water. If it is less than 0.1 part by weight, a film exhibiting sufficient corrosion resistance will not be formed on the surface of the treated product, and if it is more than 20 parts by weight, a thick shell-like film will be formed on the surface of the treated product, which is not practical.

シリカ懸濁液単独で処理される場合、処理液の温度は、
5〜40℃の範囲が最適である。5℃未満では処理後の
乾燥に時間がかかり実用的ではなく、40℃を超える温
度では処理液中のSj O,力噛1期にケル化してしま
う。
When the silica suspension is treated alone, the temperature of the treatment liquid is
A range of 5 to 40°C is optimal. If the temperature is lower than 5°C, it will take a long time to dry after the treatment, which is not practical, and if the temperature exceeds 40°C, the SjO in the treatment solution will turn into kelp in the first stage.

また浸漬時間は10〜250秒までの範囲が最適である
。10秒以下では処理物表面に完全な皮膜が形成されず
、250秒を超える時間では処理プロセスを考える場合
実用的な長さではない。
Moreover, the optimum immersion time is in the range of 10 to 250 seconds. If it is less than 10 seconds, a complete film will not be formed on the surface of the treated object, and if it is more than 250 seconds, it is not a practical length when considering the treatment process.

処理液は、Ti、 Zr、Mg、llr+、 Sr、W
、Ni、Co、Sn、 Mo、Mnイオンの1種または
2種以上を含有する水溶液である。
The treatment liquid is Ti, Zr, Mg, llr+, Sr, W
, Ni, Co, Sn, Mo, and Mn ions.

金属イオン源は、金属の水溶性塩ならば何でもよい。そ
の溶液のpuは特に問題にならない。甲、に水溶液であ
ればよい。
The metal ion source may be any water-soluble salt of a metal. The pu of the solution is not particularly problematic. An aqueous solution is sufficient.

各イオンの濃度ば水100重址部に対して0.01〜2
0重量部である。0601重量部未満では1反応の進行
が遅く処理時間が長大となり、20重足部を超えると処
理後に処理物表面にスラッジ状の生成物が付着する。
The concentration of each ion is 0.01 to 2 per 100 parts of water.
It is 0 parts by weight. If it is less than 0.601 parts by weight, the progress of one reaction is slow and the processing time becomes long, and if it exceeds 20 parts by weight, a sludge-like product will adhere to the surface of the treated product after treatment.

処理液の温度は、5℃〜沸点の範囲が最適である。5℃
未満では処理後の乾燥に時間がかがり実用的ではない。
The temperature of the treatment liquid is optimally in the range of 5° C. to the boiling point. 5℃
If it is less than that, it will take a long time to dry after treatment, which is not practical.

また浸漬時間は3〜250秒までの範囲が最適である。Moreover, the optimal immersion time is in the range of 3 to 250 seconds.

3秒未満、 もしくは250秒を超える浸漬は処理プロ
セス上実用的ではない。
Immersion for less than 3 seconds or for more than 250 seconds is not practical in the treatment process.

それぞれの液中に改良プラスト亜鉛被覆法による被処理
物を処理する。
The objects to be treated by the modified plasto zinc coating method are placed in each solution.

この二つの処理を同−媒質中で同時に行う場合は、処理
液の温度は、5℃〜40℃の範囲である。
When these two treatments are performed simultaneously in the same medium, the temperature of the treatment liquid is in the range of 5°C to 40°C.

5℃未満では処理後の乾燥に時間がかかり実用的でない
。40℃を超えるとシリカが早期にゲル化してしまう。
If it is less than 5°C, it will take a long time to dry after treatment, which is not practical. If the temperature exceeds 40°C, silica will gel early.

また浸漬時間は10〜250秒の範囲が適当である。Further, the appropriate immersion time is in the range of 10 to 250 seconds.

10秒未満では処理物表面に完全な皮膜が形成されず、
250秒を超えると処理プロセスとして実用的でない。
If it takes less than 10 seconds, a complete film will not be formed on the surface of the treated object,
If the time exceeds 250 seconds, it is not practical as a treatment process.

接触処理は、浸漬、塗布、スプレー等に実施されている
が浸漬が最も実際的である。
Contact treatment is carried out by dipping, coating, spraying, etc., but dipping is the most practical.

本発明の方法による改良プラス1〜亜鉛被覆と組み合せ
た湿式表面処理はクロメ−1へ処理に劣らぬ効果を有し
、クロメート処理のように公害問題が少ない。
Wet surface treatment in combination with Modified Plus 1 to Zinc coating by the method of the present invention is as effective as Chromate-1 treatment and has fewer pollution problems than chromate treatment.

本発明の効果は、シリカが亜鉛被覆相に、そのボアを埋
めて吸着し、金属イオンが該シリカと結合してアモルフ
ァス状皮膜を形成するためと推定されている。
It is presumed that the effect of the present invention is due to the fact that silica is adsorbed to the zinc-coated phase by filling its pores, and metal ions combine with the silica to form an amorphous film.

(発明の具体的開示) 以下本発明を実施例及び比較例によって具体的に開示す
る。本発明はこれら実施例によって限定されるものでは
ない。
(Specific Disclosure of the Invention) The present invention will be specifically disclosed below with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

試験には100 X 50 X 2.Om+nの軟鋼テ
スI・パネルを用いた。このテストパネルをトリクロロ
エタンで蒸気脱脂したのち、特公昭59J3]2号明細
書に記載されている改良プラス1〜亜鉛被覆法による処
理を行い表面に亜鉛−鉄合金被覆を生成させた。このテ
ストパネルに実施例および比較例の後処理を施した。テ
ストパネルの耐食性試験は、JTS−Z237]1に規
定される塩水噴霧試験を行ない、白銹発召−の状況を経
時的に調査した。
The test is 100 x 50 x 2. Om+n mild steel test I panel was used. After vapor degreasing this test panel with trichloroethane, it was treated according to the improved plus 1 to zinc coating method described in Japanese Patent Publication No. 59 J3 [2] to form a zinc-iron alloy coating on the surface. This test panel was subjected to post-treatment of Examples and Comparative Examples. For the corrosion resistance test of the test panel, a salt spray test specified in JTS-Z237]1 was conducted, and the state of white rust formation was investigated over time.

また電気亜鉛めっきパネルとしては、めっき膜厚8ミク
ロンの電気亜鉛めっきを施した100 X 50X2.
Ommの軟鋼テストパネルを試験に供した。
In addition, the electrogalvanized panel is 100 x 50 x 2.0 mm, electrogalvanized with a plating film thickness of 8 microns.
Omm mild steel test panels were tested.

以下の実施例においてlliに「部」と記すのは「重量
部」のことである。
In the following examples, "parts" in lli means "parts by weight."

実施例」 脱イオン水100部に対して、シリカ0.5部を加えて
、均一に攪拌して、この処理液中に改良ブラスト亜鉛被
覆法により処理したテストパネルを30秒間浸漬した後
、温風乾燥した。次に脱イオン水100部に対して、K
2ZrF、をZrイオンとして0.5部を加えて、均一
に攪拌して、前記の被処理物を常温で60秒間浸漬した
。その後温風乾燥した。この試料について耐食試験を行
った。結果を表1に示す。
Example 0.5 part of silica was added to 100 parts of deionized water, stirred uniformly, and a test panel treated by the improved blast zinc coating method was immersed in this treatment solution for 30 seconds, and then heated. Air dried. Next, for 100 parts of deionized water, K
0.5 part of 2ZrF as Zr ion was added, stirred uniformly, and the object to be treated was immersed for 60 seconds at room temperature. It was then dried with warm air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

実施例2 実施例1のシリカ懸濁液を刷毛を用いて塗布したのち、
温風乾燥した。次に実施例1のに2ZrF、含有液を刷
毛を用いて塗布したのち、温風乾燥した。
Example 2 After applying the silica suspension of Example 1 using a brush,
Dry with warm air. Next, a solution containing 2ZrF was applied to the surface of Example 1 using a brush, and then dried with warm air.

この試料について耐食試験を行った。結果を表1に示す
A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

実施例3 脱イオン水100部に対し、シリカ5部を加え、さらに
Nj、 (SO3)2・411.0をN1イオンとして
1部を加えて均一に攪拌して、この処理液中に改良プラ
ス1〜亜鉛被覆法により処理したテストパネルを60秒
浸漬したのち、温風に燥した3、この試料に一〕いて耐
食試験を行った。結果を表1に示す。
Example 3 5 parts of silica was added to 100 parts of deionized water, and 1 part of Nj, (SO3)2.411.0 was added as N1 ion, and the mixture was stirred uniformly to inject improved plus into this treatment liquid. Test panels treated by the zinc coating method were immersed for 60 seconds and then dried in hot air.3 The samples were then subjected to a corrosion resistance test. The results are shown in Table 1.

実施例4 実施例3のシリカおよびNJ、(SO3)2・41シo
含右液を刷毛を用いて塗布したのち、温風乾燥した。こ
の試料について耐食試験を行った3、結果を表1に示す
Example 4 Silica of Example 3 and NJ, (SO3)2.41sio
After applying the liquid containing the liquid with a brush, it was dried with warm air. A corrosion resistance test was conducted on this sample3, and the results are shown in Table 1.

実施例5 脱イオン水100部に対し、シリカ10部を加え、さら
にMnCO3・411□0をMnイオンとして1部を加
えて均一に攪拌して、この処理液中に改良プラス1〜亜
鉛被覆法により処理したナス1−パネルを60秒浸漬し
たのち、温風乾燥した。この試料について耐食性試験を
行った。結果を表1に示す。
Example 5 To 100 parts of deionized water, 10 parts of silica was added, and 1 part of MnCO3.411□0 as Mn ion was added and stirred uniformly. The treated eggplant 1-panel was immersed for 60 seconds and then dried with warm air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

実施例6 実施例5の5jO2及びMnCQ、2・411□0溶液
をスプレーで塗布したのち、温風乾燥した。この試料に
ついて耐食試験を行った。結果を表1に示す。
Example 6 The 5jO2 and MnCQ, 2·411□0 solution of Example 5 was applied by spray and then dried with hot air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

実施例7 脱イオン水100部に対して、シリカ5部を加えて、均
一に攪拌して、この処理液中に改良プラスト亜鉛被覆法
により処理したナス1〜パネルを30秒間浸漬したのち
、温風乾燥した。次に脱イオン水100部に対して、K
2ZrF、をZrイオンとして、0.5部及び、CoS
O4・811□0をCoイオン濃度として5部加えて、
均一に攪拌して、前記の被処理物を常温浴にて60秒間
浸漬した。その後温風乾燥した。この試料について耐食
試験を行った。結果を表1−に示す。
Example 7 5 parts of silica was added to 100 parts of deionized water, stirred uniformly, and 1 to 1 panel of eggplants treated by the improved plasto zinc coating method were immersed in this treatment solution for 30 seconds. Air dried. Next, for 100 parts of deionized water, K
0.5 part of 2ZrF as Zr ion and CoS
Add 5 parts of O4.811□0 as Co ion concentration,
The object to be treated was immersed in a room temperature bath for 60 seconds while stirring uniformly. It was then dried with warm air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1-.

実施例8 実施例7のシリカ懸濁液を刷毛を用いて塗布したのち、
温風乾燥した。次に実施例7のに2ZrF6およびCo
SO4・8+120含有液を刷毛を用いて塗布したのち
、温風乾燥した。この試料について耐食試験を行った。
Example 8 After applying the silica suspension of Example 7 using a brush,
Dry with warm air. Next, in Example 7, 2ZrF6 and Co
After applying the solution containing SO4.8+120 using a brush, it was dried with warm air. A corrosion resistance test was conducted on this sample.

結果を表1に示す。The results are shown in Table 1.

実施例9− 脱イオン水100部に、シリカ15部を加えて、均一に
攪拌して、この処理液中に改良プラス1〜亜鉛被覆法に
より処理したテスI・パネルを30秒間浸漬した後、温
風乾燥した。次に脱イオン水100部にに2’l’j 
F、を1゛」イオンとして0.5部を加えて、均一に攪
拌した。この試料について耐食試験を行なった。
Example 9 - Add 15 parts of silica to 100 parts of deionized water, stir evenly, and immerse a Tes I panel treated by Modified Plus 1 to zinc coating method in this treatment solution for 30 seconds. Dry with warm air. Then add 2'l'j to 100 parts of deionized water.
0.5 part of F was added as 1" ion, and the mixture was stirred uniformly. A corrosion resistance test was conducted on this sample.

結果を表1に示す。The results are shown in Table 1.

実施例]0 脱イオン水100部に、シリカ15部を加えて、均一に
攪拌して、この処理液中に改良プラスト亜鉛被m法によ
り処理したテストパネルを】0秒間浸漬した後、温風乾
燥した。次に脱イオン水100部に、MgSO4・7H
20iを蝕として0.5部、(N+1. )6Mo70
2.、をMOとして0.5部、およびSrCl2−6H
,OをSrイオンとして0.7部加えて、均一・に攪拌
し、前記被処理物を常温で60秒間浸漬した。この試料
について耐食試験を行なった。結果を表1に示す。
Example] 0 15 parts of silica was added to 100 parts of deionized water, stirred uniformly, and a test panel treated by the modified plasto zinc coating method was immersed in this treatment solution for 0 seconds, and then heated with warm air. Dry. Next, add MgSO4.7H to 100 parts of deionized water.
20i as eclipse, 0.5 part, (N+1.)6Mo70
2. , 0.5 part as MO, and SrCl2-6H
, O were added in an amount of 0.7 parts as Sr ions, and the mixture was stirred uniformly, and the object to be treated was immersed for 60 seconds at room temperature. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

実施例11 脱イオン水100部に、シリカ20部を加えて、均一に
攪拌して、この処理液中に改良プラスト亜鉛被覆法によ
り処理したテストパネルを30秒間浸漬した後、温風乾
燥した。次に脱イオン水100部にSnC]、zをSn
イオンとして0.5部およびCoSO4・81120を
Coイオンとして3部加えて、均一に攪拌した。前記の
被処理物を常温で60秒間浸漬し、その後温風乾燥した
。この試料について耐食試験を行なった。
Example 11 20 parts of silica was added to 100 parts of deionized water and stirred uniformly. A test panel treated by the improved plasto zinc coating method was immersed in this treatment solution for 30 seconds, and then dried with hot air. Next, add SnC to 100 parts of deionized water, and replace z with Sn
0.5 parts of ions and 3 parts of CoSO4.81120 were added as Co ions, and the mixture was stirred uniformly. The object to be treated was immersed for 60 seconds at room temperature, and then dried with warm air. A corrosion resistance test was conducted on this sample.

結果を表】に示す。The results are shown in Table.

比較例1 脱イオン水100部に、無水クロム酸1.0部、硫酸0
.1部、硝酸0.1部を均一に溶解した処理液を調製し
た。これに改良プラスト亜鉛被覆法により処理したテス
トパネルを4秒間浸漬した。浸漬後空中放置してから水
洗し、臥風乾燥した。この試料について耐食試験を行っ
た。結果を表1に示す。
Comparative Example 1 100 parts of deionized water, 1.0 part of chromic anhydride, 0 part of sulfuric acid
.. A treatment solution was prepared by uniformly dissolving 1 part of nitric acid and 0.1 part of nitric acid. A test panel treated by the modified plasto zinc coating method was immersed in this for 4 seconds. After soaking, it was left in the air, washed with water, and air-dried. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

比較例2 脱イオン水100部に、無水クロム酸2.0部、硝酸ク
ロム0.1部を均一に溶解した処理液を調製した。
Comparative Example 2 A treatment solution was prepared by uniformly dissolving 2.0 parts of chromic acid anhydride and 0.1 part of chromium nitrate in 100 parts of deionized water.

これに改良プラスト亜鉛被覆法により処理したデス1ヘ
パネルを4秒間浸漬した。浸漬後空中放置し=12− てから水洗し、温風乾燥した。この試料について耐食試
験を行った。結果を表1に示す。比較例31ヘリクロロ
トリフルオロエタン100部に対し、t−ブタノール1
5部、無水り旧ム酸2部、シュウ酸0.01部を均一に
溶解した処理液を調製した。これを上部に凝集装置を有
する槽内て沸1騰させ、−に部の凝集液を槽内に還流し
た。
A Des 1 hepanel treated by the modified plasto zinc coating method was immersed in this for 4 seconds. After immersion, the sample was left in the air for 12 hours, then washed with water and dried with warm air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1. Comparative Example 31 1 t-butanol to 100 parts of helichlorotrifluoroethane
A treatment solution was prepared by uniformly dissolving 5 parts of anhydrous sulfuric acid, 2 parts of anhydrous old muric acid, and 0.01 part of oxalic acid. This was brought to a boil in a tank having a flocculating device at the top, and -1 part of the flocculated liquid was refluxed into the tank.

これに改良プラスト亜鉛被覆法により処理したテストパ
ネルを60秒間浸漬した。浸漬後40°Cの新鮮な空気
中で3分間強制乾燥し、さらにトリクロロトリフルオロ
エタンとt−ブタノールからなる溶液中で洗浄し、その
後軸無させた。この試料について耐食試験を行った。結
果を表1に示す。
Test panels treated by the modified plasto zinc coating method were immersed in this for 60 seconds. After immersion, it was force-dried in fresh air at 40°C for 3 minutes, and then washed in a solution consisting of trichlorotrifluoroethane and t-butanol, and then removed from the shaft. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

比較例4 脱イオン水100部に、タンニン酸1部を均一に溶解し
た処理液を調製した。これに改良プラスト亜鉛被覆法に
より処理したナス1〜パネルを70℃の処理液浴中に4
秒間浸漬した。浸漬後空中放置してから水洗し、温風乾
燥した。この試料について耐食試験を行った。結果を表
1に示す。
Comparative Example 4 A treatment solution was prepared by uniformly dissolving 1 part of tannic acid in 100 parts of deionized water. Then, 1 to 4 panels of eggplant treated using the improved plasto zinc coating method were placed in a treatment solution bath at 70°C.
Immersed for seconds. After immersion, it was left in the air, washed with water, and dried with warm air. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

比較例5 改良プラスト亜鉛被覆法により処理したテストパネルを
、化成処理を施さずそのまま耐食試験を行った。結果を
表1に示す。
Comparative Example 5 A test panel treated by the improved plasto zinc coating method was subjected to a corrosion resistance test without being subjected to any chemical conversion treatment. The results are shown in Table 1.

比較例6 改良ブラスト亜鉛被覆法による被処理物に代わりに、電
気亜鉛めっきを施したデス1−パネルを、実施例1で使
用した処理液を用いて処理をおこなった。この試料につ
いて耐食試験を行った。結果を表1に示す。
Comparative Example 6 Instead of the object to be treated by the improved blast zinc coating method, an electrogalvanized dess 1 panel was treated with the treatment solution used in Example 1. A corrosion resistance test was conducted on this sample. The results are shown in Table 1.

表1Table 1

Claims (5)

【特許請求の範囲】[Claims] 1.鉄または鉄合金を核としてこの核の周囲に鉄亜鉛合
金層を介して亜鉛または亜鉛合金を被覆してなる複層被
覆粒子の集合体からなるブラスト材料を金属表面に投射
して亜鉛または亜鉛合金の被覆皮膜を形成し;このよう
に形成された表面を、水性シリカ懸濁液およびTi,Z
r,Mg,Ba,Sr,W,Ni,Co,Sn,Mo,
Mnの少くとも1種の金属イオンを含む水溶液と接触さ
せることからなる金属表面処理方法。
1. Zinc or zinc alloy is produced by projecting onto the metal surface a blasting material consisting of an aggregate of multi-layer coated particles made of iron or iron alloy as a core and coating the core with zinc or zinc alloy through an iron-zinc alloy layer. the surface thus formed is coated with an aqueous silica suspension and Ti, Z
r, Mg, Ba, Sr, W, Ni, Co, Sn, Mo,
A metal surface treatment method comprising contacting with an aqueous solution containing at least one metal ion of Mn.
2.シリカ懸濁液による処理と金属イオンを含む溶液に
よる処理を同一の媒質で行う請求項1に記載の方法。
2. 2. The method according to claim 1, wherein the treatment with the silica suspension and the treatment with the solution containing metal ions are carried out in the same medium.
3.まずシリカ懸濁液で処理し、次に金属イオン溶液に
よる処理を行う請求項1に記載の方法。
3. 2. A method as claimed in claim 1, characterized in that the treatment is carried out first with a silica suspension and then with a metal ion solution.
4.シリカ懸濁液中のシリカの濃度が水100重量部に
対して、0.1〜20重量部である請求項1、2、3の
いずれかの項に記載の方法。
4. 4. The method according to claim 1, wherein the concentration of silica in the silica suspension is 0.1 to 20 parts by weight per 100 parts by weight of water.
5.金属イオン水溶液中の金属イオンの濃度が、各水1
00重量部に対して0.01〜20重量部である請求項
1、2、3のいずれかの項に記載の方法。
5. The concentration of metal ions in the metal ion aqueous solution is 1
4. The method according to claim 1, wherein the amount is 0.01 to 20 parts by weight based on 0.00 parts by weight.
JP2325750A 1990-11-29 1990-11-29 Metal surface treatment method Expired - Fee Related JP2950481B2 (en)

Priority Applications (4)

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JP2325750A JP2950481B2 (en) 1990-11-29 1990-11-29 Metal surface treatment method
EP91120491A EP0488353B1 (en) 1990-11-29 1991-11-29 Method for treatment of metal surfaces
DE69106678T DE69106678T2 (en) 1990-11-29 1991-11-29 Process for the treatment of metallic surfaces.
AT91120491T ATE117026T1 (en) 1990-11-29 1991-11-29 METHOD FOR TREATING METAL SURFACES.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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JP2950481B2 (en) 1999-09-20
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EP0488353B1 (en) 1995-01-11
DE69106678T2 (en) 1995-06-22
DE69106678D1 (en) 1995-02-23

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