JPH03247796A - Steel sheet having silica combined coating and its production - Google Patents
Steel sheet having silica combined coating and its productionInfo
- Publication number
- JPH03247796A JPH03247796A JP4369690A JP4369690A JPH03247796A JP H03247796 A JPH03247796 A JP H03247796A JP 4369690 A JP4369690 A JP 4369690A JP 4369690 A JP4369690 A JP 4369690A JP H03247796 A JPH03247796 A JP H03247796A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- steel sheet
- silica
- composite coating
- silica particles
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 55
- 239000010959 steel Substances 0.000 title claims abstract description 55
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 11
- -1 nitrate ions Chemical class 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract 2
- 239000002131 composite material Substances 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 238000009751 slip forming Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims 1
- 238000006263 metalation reaction Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 15
- 238000007747 plating Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、耐食性および耐摩耗性に優れた、シリカ複
合被膜を有する鋼板およびその製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a steel plate having a silica composite coating, which has excellent corrosion resistance and wear resistance, and a method for manufacturing the same.
鋼板の耐食性および耐摩耗性を向上させるために、例、
えば・、亜鉛系めっき被膜中にシリカ粒子などの酸化物
粒子を分散させる試みが、近年盛んに行なわれている。To improve the corrosion resistance and wear resistance of steel plates, e.g.
For example, attempts have been made in recent years to disperse oxide particles such as silica particles in zinc-based plating films.
このような、めっき被膜中に分散されている酸化物粒子
の有する、化学的安定性、電気的絶縁性および硬度によ
って、めっき被膜に優れた耐食性および耐摩耗性が付与
される。The chemical stability, electrical insulation, and hardness of the oxide particles dispersed in the plating film provide the plating film with excellent corrosion resistance and wear resistance.
例えば、特開昭５４−１４’６２２８号公報には、２〜
１５＋＋＋ｔ、％の量のシリカ粒子が均一に分散してい
る亜鉛系めっき被膜を有する、亜鉛−シリカ複合めっき
鋼板が開示されており、従来の亜鉛めっき鋼板に比べて
、耐食性が１．５〜３倍に向上する旨が述べられている
（以下、「先行技術１」という）。For example, in Japanese Patent Application Laid-open No. 54-14'6228, 2-
A zinc-silica composite coated steel sheet is disclosed that has a zinc-based plating film in which silica particles in an amount of 15+++t,% are uniformly dispersed, and has a corrosion resistance of 1.5 to 3% compared to conventional galvanized steel sheets. It is stated that the improvement is doubled (hereinafter referred to as "prior art 1").
また、特開昭５４−４５６３４号公報には、酸化物、炭
化物およびフッ化黒鉛等の粒子が均一に分散しているめ
っき被膜を有するめっき鋼板が開示されており、従来の
亜鉛めっき鋼板に比べて、耐摩耗性が向上する旨が述べ
られている（以下、「先行技術２」という。Furthermore, JP-A No. 54-45634 discloses a galvanized steel sheet having a plating film in which particles of oxides, carbides, graphite fluoride, etc. are uniformly dispersed, and compared to conventional galvanized steel sheet. It is stated that the wear resistance is improved (hereinafter referred to as "prior art 2").
〔発明が解決しようとする課題〕
上述した先行技術１および２においては、めっき被膜中
における、シリカ粒子などの酸化物粒子の結合力は極め
て弱く、従って、鋼板の表面は、これらの酸化物粒子に
よって完全には覆われていない。この結果、耐食性、耐
摩耗性の向上は不完全であり、特に、めっき鋼板に成形
加工を施した後の耐食性および耐摩耗性は、成形加工を
施す前に比べて顕著に劣化する。[Problems to be Solved by the Invention] In the above-mentioned prior arts 1 and 2, the bonding force of oxide particles such as silica particles in the plating film is extremely weak, and therefore the surface of the steel sheet is coated with these oxide particles. not completely covered by. As a result, improvements in corrosion resistance and abrasion resistance are incomplete, and in particular, the corrosion resistance and abrasion resistance after forming a plated steel sheet are significantly worse than before forming.
上述した問題を改善する手段として、特開昭６３−２０
３７７８号公報には、鋼板の表面上に形成された、酸化
物粒子が分散している下・層としてのめっき層と、前記
めっき層の表面上に形成された、表面被覆率が５０％以
上であって、、 ０．０１〜１μｍの厚さを有する。
上層としてのセラミック凝集体層とからなる、２層のめ
っき層を有するめっき鋼板が開示されている（以下、「
先行技術３」という）。As a means to improve the above-mentioned problems, Japanese Patent Laid-Open No. 63-20
Publication No. 3778 describes a plating layer as a lower layer formed on the surface of a steel sheet in which oxide particles are dispersed, and a plating layer formed on the surface of the plating layer with a surface coverage of 50% or more. and has a thickness of 0.01 to 1 μm.
A plated steel sheet is disclosed that has two plating layers, including a ceramic aggregate layer as an upper layer (hereinafter referred to as "
Prior Art 3).
しかしながら、先行技術３において、セラミツ４
り凝集体層を電気めっきによって形成すると、形成され
たセラミック凝集体層は綿状になり且つその厚さも不均
一になる。従って、信頼し得るめっき層を工業的に形成
することはできない。However, in Prior Art 3, when the ceramic aggregate layer is formed by electroplating, the formed ceramic aggregate layer becomes flocculent and non-uniform in thickness. Therefore, a reliable plating layer cannot be industrially formed.
セラミック凝集体層を、公知のゾルゲル法によって形成
すれば、形成されたセラミック凝集体層は、比較的密で
且つその厚さも均一になる。しかしながら、この方法の
場合には、通常、有機溶媒を使用するために作業環境が
悪化し、且つ、後処理として加熱工程を必要とする。従
って、作業環境の整備や加熱工程のために多額の費用を
必要とし、製造コストが上昇する。If the ceramic aggregate layer is formed by a known sol-gel method, the formed ceramic aggregate layer will be relatively dense and have a uniform thickness. However, in the case of this method, the working environment is generally deteriorated due to the use of an organic solvent, and a heating step is required as a post-treatment. Therefore, a large amount of money is required for preparation of the working environment and heating process, which increases manufacturing costs.
従って、この発明の目的は、耐食性および耐摩耗性に優
れ、これらの性能が成形加工を施した後においても劣化
することのない、自動車用、家庭電気製品用および建材
用等として好適な、シリカ複合被膜を有する鋼板および
その製造方法を提供することにある。Therefore, an object of the present invention is to develop a silica which has excellent corrosion resistance and abrasion resistance, and whose properties do not deteriorate even after molding, and which is suitable for use in automobiles, home appliances, building materials, etc. An object of the present invention is to provide a steel plate having a composite coating and a method for manufacturing the same.
本発明者等は、上述した問題を解決すべく鋭意研究を重
ねた。その結果、シリカ粒子凝集被膜中において、シリ
カ粒子を、バインダーとしての金属、その水酸化物また
はその酸化物によって互いに強固に結合させれば、耐食
性および耐摩耗性に優れたシリカ複合被膜が安定して得
られることを知見した。The present inventors have conducted extensive research in order to solve the above-mentioned problems. As a result, if silica particles in a silica particle agglomeration coating are strongly bonded to each other by metal as a binder, its hydroxide, or its oxide, a silica composite coating with excellent corrosion resistance and wear resistance can be stabilized. We found that it can be obtained by
この発明は、上記知見に基いてなされたものであって、
この発明のシリカ複合被膜を有する鋼板は、金属、前記
金属の水酸化物および前記金属の酸化物の少なくとも１
つによって互いに結合されたシリカ粒子からなるシリカ
複合被膜が、鋼板の最表面上に連続的に形成されている
ことに特徴を有するものであり、そして、この発明の方
法は、シリカ粒子、金属イオンおよび硝酸イオンを含有
する酸性電解液を使用し、鋼板を陰極とする陰極電解に
より、前記鋼板の最表面上に、金属、前記金属の水酸化
物および前記金属の酸化物のうちの少なくとも１つによ
って互いに結合されたシリカ粒子からなるシリカ複合被
膜を連続的に形成することに特徴を有するものである。This invention was made based on the above findings, and
A steel sheet having a silica composite coating of the present invention comprises at least one of a metal, a hydroxide of the metal, and an oxide of the metal.
The method of the present invention is characterized in that a silica composite coating consisting of silica particles bonded to each other by silica particles is continuously formed on the outermost surface of a steel plate. and at least one of a metal, a hydroxide of the metal, and an oxide of the metal by cathodic electrolysis using an acidic electrolyte containing nitrate ions and a steel plate as a cathode. This method is characterized in that a silica composite coating consisting of silica particles bonded to each other is continuously formed.
この発明において、被膜を形成する酸化物粒子としてシ
リカ粒子を選んだ理由は、シリカ粒子の粒度分布その他
の性状は安定しており、そして、シリカ粒子は、安価で
且つ取扱いやすく、めっき被膜に優れた耐食性を付与し
得るからである。シリカ粒子の粒径は５〜１１００ｎの
範囲内が好ましい。粒径が５層ｍ未満では電解液中にお
いて不安定であり、一方、粒径が］−００ｎｍを超える
と、強固な凝集層を作りにくくなる。薄くても緻密なシ
リカ被膜を得るためには、上記範囲内において小粒径の
シリカ粒子を使用することがよく、一方、厚いシリカ被
膜を得るためには、」二記範囲内において大粒径のシリ
カ粒子を使用することがよい。In this invention, the reason why silica particles were selected as the oxide particles forming the coating is that the particle size distribution and other properties of silica particles are stable, and silica particles are inexpensive, easy to handle, and have excellent plating coating properties. This is because it can provide additional corrosion resistance. The particle size of the silica particles is preferably within the range of 5 to 1100 nm. If the particle size is less than 5 m, it will be unstable in the electrolytic solution, while if the particle size exceeds -00 nm, it will be difficult to form a strong cohesive layer. In order to obtain a thin but dense silica coating, it is best to use silica particles with a small particle size within the above range, while in order to obtain a thick silica coating, it is recommended to use silica particles with a large particle size within the range specified in 2. It is preferable to use silica particles of
この発明においては、被膜中のシリカ粒子を互いに結合
させるためのバインダーとして、金属、前記金属の水酸
化物および前記金属の酸化物の少なくとも１つを含有さ
せる。このような、金属等を含有させることによって、
シリカ粒子の結合は強化され、被膜の耐食性および耐摩
耗性は飛躍的に向上し、成形加工を施した後においても
これらの性能が劣化することはない。In the present invention, at least one of a metal, a hydroxide of the metal, and an oxide of the metal is contained as a binder for bonding the silica particles in the coating to each other. By including such metals,
The bonds between the silica particles are strengthened, and the corrosion resistance and abrasion resistance of the coating are dramatically improved, and these properties do not deteriorate even after molding.
前記金属としては、亜鉛、ニッケル、コバルト、銅、錫
、鉄、クロム等、陰極電解により、酸性電解液中から析
出し得る金属を使用する。As the metal, a metal such as zinc, nickel, cobalt, copper, tin, iron, chromium, etc., which can be deposited from an acidic electrolyte by cathodic electrolysis, is used.
被膜中における前記金属等の含有割合は、０，１〜２０
ｔｙｔ、％の範囲内とし、そして、シリカ粒子の含有割
合は、 ８０〜９９ 、９臀ｔ、％の範囲内とすること
が好ましい。前記金属等の含有割合が０．ｌｌ１ｔ。The content ratio of the metal etc. in the coating is 0.1 to 20
The content of silica particles is preferably within the range of 80 to 99%. The content ratio of the metal etc. is 0. ll1t.
％未満では、シリカ粒子を強固に結合させることができ
ない。一方、金属等の含有割合が２Ｑｔｉｔ、％を超え
ると、耐食性および耐摩耗性が低下する。If the amount is less than %, silica particles cannot be firmly bonded. On the other hand, if the content of metals, etc. exceeds 2Qtit,%, corrosion resistance and wear resistance decrease.
シリカ複合被膜の厚さは、 ５０ｎｍ〜５μｍの範囲内
とすることが好ましい。被膜の厚さが５０ｎｍ未満では
、所望の耐食性および耐摩耗性が得られない。被膜の厚
さが５μｍを超えると、被膜が脆くなり月つ製造コス１
〜が上昇して不経済になる。The thickness of the silica composite coating is preferably within the range of 50 nm to 5 μm. If the thickness of the coating is less than 50 nm, desired corrosion resistance and wear resistance cannot be obtained. When the thickness of the coating exceeds 5 μm, the coating becomes brittle and the manufacturing cost is 1.
~ rises and becomes uneconomical.
この発明において、上述したシリカ複合被膜をその上に
形成すべき鋼板は、冷延鋼板または熱延鋼板などの表面
処理を施されていない鋼板でも、亜鉛、ニッケル、クロ
ムなどのめっき層を有する従来のめっき鋼板でもよい。In this invention, the steel sheet on which the above-mentioned silica composite coating is to be formed may be a steel sheet without surface treatment such as a cold rolled steel sheet or a hot rolled steel sheet, or a conventional steel sheet having a plating layer of zinc, nickel, chromium, etc. A plated steel sheet may also be used.
次に、この発明のシリカ複合被膜を有する鋼板の製造方
法を説明する。Next, a method for manufacturing a steel plate having a silica composite coating according to the present invention will be explained.
シリカ粒子、金属イオンおよび硝酸イオンを含有する酸
性電解液を使用し、鋼板に陰極電解を施すことにより、
鋼板の表面上に、当該金属イオンの還元による金属リッ
チの被膜と、この金属リッチの被膜の表面上の、前記金
属、その水酸化物およびその酸化物のうちの少なくとも
１つによって互いに結合されたシリカ粒子からなる、シ
リカリンチのシリカ複合被膜とからなる２層の被膜を形
成することができる。最表面のシリカ複合被膜によって
、鋼板の表面は完全に被覆される。By applying cathodic electrolysis to the steel plate using an acidic electrolyte containing silica particles, metal ions, and nitrate ions,
A metal-rich coating formed by reduction of the metal ions on the surface of the steel sheet, and a metal-rich coating bonded to each other by at least one of the metal, its hydroxide, and its oxide on the surface of the metal-rich coating. A two-layer coating consisting of silica particles and a silica composite coating of silica lynch can be formed. The surface of the steel plate is completely covered by the outermost silica composite coating.
シリカ粒子は、電解液に添加する上での取り扱い易さか
ら、コロイダルシリカを使用することが好ましい。電解
液中のシリカ粒子の含有量は、１０〜２００ ｇ／ｆｌ
の範囲内が好ましい。 シリカ粒子の含有量が１０ｇ／
ｌ未満では、シリカの凝集、析出効率が低下して、高い
耐食性が得られない。As the silica particles, it is preferable to use colloidal silica because it is easy to handle when added to the electrolytic solution. The content of silica particles in the electrolyte is 10 to 200 g/fl
It is preferably within the range of . The content of silica particles is 10g/
If it is less than 1, the efficiency of agglomeration and precipitation of silica decreases, making it impossible to obtain high corrosion resistance.
一方、２００ｇ／１１を超えると、電解液が不安定にな
る。On the other hand, if it exceeds 200 g/11, the electrolyte becomes unstable.
金属イオンは、その金属の硫酸塩または塩化物として電
解液中に添加する。電解液中の金属イオンの含有量は、
０．０２〜２モル／ｌ、の範囲内が好ましい。金属イオ
ンの含有量が０．０２モル／ｌ未満では、シリカ粒子を
強固に結合させることができない。一方、金属イオンの
含有量が２モルＩＱを超えると、電解液が不安定になる
。The metal ion is added to the electrolyte as a sulfate or chloride of the metal. The content of metal ions in the electrolyte is
It is preferably within the range of 0.02 to 2 mol/l. If the metal ion content is less than 0.02 mol/l, the silica particles cannot be firmly bonded. On the other hand, if the metal ion content exceeds 2 mol IQ, the electrolyte becomes unstable.
硝酸イオンは、シリカ粒子の凝集、析出補助剤である。Nitrate ion is an aggregation and precipitation aid for silica particles.
硝酸イオンは、電解時に鋼板の表面で還元されて浴のＰ
Ｈを上昇させる。この結果、電解液中の金属イオンは、
単に還元析出するだけではなく、その金属の水酸化物を
形成する。同時に、シリカ粒子は、その表面のシラノー
ル基が解離して、不安定になる。このようにして不安定
化したシリカ粒子は、鋼板の表面」二において相互に凝
集し、そして、凝集したシリカ粒子の表面に金属水酸化
物が吸着する。Nitrate ions are reduced on the surface of the steel plate during electrolysis and become P in the bath.
Increase H. As a result, the metal ions in the electrolyte are
Rather than simply being reduced and precipitated, a hydroxide of the metal is formed. At the same time, the silanol groups on the surface of the silica particles dissociate and become unstable. The silica particles thus destabilized aggregate with each other on the surface of the steel sheet, and metal hydroxide is adsorbed on the surface of the aggregated silica particles.
このようにして、鋼板の最表面上に、シリカ複合被膜が
連続的に形成される。シリカ複合被膜中の金属水酸化物
は、鋼板の表面上で部分的に還元され脱水されて、金属
または前記金属の酸化物となり、シリカ粒子の結合を強
固になし、そして、シリカ複合被膜と鋼板との密着力を
高める。上記過程において、電解反応の初期にすばやく
還元された金属イオンにより、最表面のシリカ複合被膜
の下に、金属リッチの被膜が形成される。この金属リッ
チの被膜によって、最表面のシリカ複合被膜の密着力は
高められる。In this way, a silica composite coating is continuously formed on the outermost surface of the steel plate. The metal hydroxide in the silica composite coating is partially reduced and dehydrated on the surface of the steel sheet to become a metal or an oxide of the metal, which strengthens the bond between the silica particles and the silica composite coating and the steel sheet. Increases adhesion with. In the above process, a metal-rich film is formed under the outermost silica composite film by the metal ions that are quickly reduced in the early stage of the electrolytic reaction. This metal-rich coating enhances the adhesion of the outermost silica composite coating.
硝酸イオンとしては、ＮａＮ、Ｏａ＋にＮ０３等を使用
することができる；電解液中の硝酸イオンの含有量は、
０．１〜２０ｇ／［の範囲内が好ましい。硝酸イオンの
含有量が０．１ｇ／［未満では、シリカの析出効率が低
下して、高い耐食性が得られない。As nitrate ions, NaN, Oa+, N03, etc. can be used; the content of nitrate ions in the electrolyte is as follows:
It is preferably within the range of 0.1 to 20 g/[. If the content of nitrate ions is less than 0.1 g/[, the silica precipitation efficiency decreases and high corrosion resistance cannot be obtained.
一方、２０ｇ／ｆｌを超えると金属の水酸化物が過剰に
生成して、被膜が脆くなる。On the other hand, if it exceeds 20 g/fl, metal hydroxide will be excessively produced and the film will become brittle.
次に、この発明を、実施例により１本発明の範囲外の比
較例と対比しながら説明する。Next, the present invention will be explained by way of examples while comparing with comparative examples which are outside the scope of the present invention.
コロイダルシリカが、シリカ粒子の含有量が１１１
〜２０．ＯｇＩＱの範囲内となるように添加され、金属
の硫酸塩または塩化物が、金属イオンの含有量が０．０
２〜２モル／ｌの範囲内となるように添加）れ、そして
、硝酸ナトリウムが、硝酸イオンの含有量が０．１〜２
０ｇＩＱの範囲となるように添加され、更に、塩酸また
は硫酸によりρ■が１〜５に調整された電解液を調製し
た。Colloidal silica has a silica particle content of 111 to 20. The metal sulfate or chloride is added so that the metal ion content is within the OgIQ range of 0.0.
2 to 2 mol/l), and sodium nitrate has a nitrate ion content of 0.1 to 2 mol/l.
An electrolytic solution was prepared in which ρ■ was added in a range of 0 g IQ and ρ■ was adjusted to 1 to 5 with hydrochloric acid or sulfuric acid.
このようにして調製された電解液を使用し、鋼板を陰極
とする陰極電解により、鋼板の表面上に、下層としての
金属リッチの被膜と、前記金属リッチの被膜の上に形成
された、金属、前記金属の水酸化物および前記金属の酸
化物の少なくとも１つによって互い１こ結合されたシリ
カ粒子からなる、上層としてのシリカ複合被膜とからな
る２層の被膜を形成し、かくして、本発明鋼板Ｎｏ １
〜９を調製した。By cathodic electrolysis using the electrolyte prepared in this way and using the steel plate as a cathode, a metal-rich film is formed as a lower layer on the surface of the steel plate, and a metal-rich film is formed on the metal-rich film. , and a silica composite coating as an upper layer consisting of silica particles bonded to each other by at least one of the metal hydroxide and the metal oxide, and thus the present invention Steel plate No. 1
~9 was prepared.
比較のために、公知のワット浴によってその表面上にニ
ッケルめっき被膜が形成された比較用鋼板Ｎα１．およ
び、コロイダルシリカが添加された公知の各種金属めっ
き浴によってその表面上にシ＝ １？
リカ複合めっき被膜が形成された比較用鋼板Ｎ［１２お
よび３を調製した。For comparison, a comparative steel sheet Nα1. on the surface of which a nickel plating film was formed by a known Watt bath. Then, a coating of 1? Comparative steel plates N[12 and 3 were prepared with a Rica composite plating film formed thereon.
これらの本発明鋼板Ｎα１〜９、および、比較用鋼板Ｎ
α１〜３の、被膜の成分組成、その厚さ、被覆率、耐食
性および耐摩耗性を、第１表に示す。These invention steel plates Nα1 to Nα9 and comparison steel plate N
Table 1 shows the component composition of the coating, its thickness, coverage, corrosion resistance, and abrasion resistance for α1 to α3.
なお、耐食性は、連続１，０００時間の塩水噴霧試験に
おける、赤錆発生までの塩水噴霧時間によって示し、耐
摩耗性は、テーパー摩耗試駆によって測定し、比較用鋼
板Ｎａ １におけるニッケル被膜の摩耗減量を１とした
ときの摩耗減量の相対値によって示した。In addition, corrosion resistance is shown by the salt water spray time until red rust occurs in a continuous 1,000 hour salt water spray test, and wear resistance is measured by a taper wear test. It is expressed as a relative value of wear loss when 1 is taken as 1.
第１表から明らかなように、比較用鋼板Ｎα１における
ニッケル被膜の摩耗減量を１としたときの摩耗減量の相
対値は、比較用鋼板Ｎα２の場合には１．８であり、比
較用鋼板Ｎα３の場合には０．９であるのに対し、本発
明鋼板Ｎｏ、 １は０．２、本発明鋼板Ｎａ ２−６は
く０．１であり、本発明鋼板ＮＣＬ’７〜９の場合でも
０．５〜０．７であって、何れも優れていた。As is clear from Table 1, when the wear loss of the nickel coating on the comparative steel sheet Nα1 is set to 1, the relative value of the wear loss in the case of the comparative steel sheet Nα2 is 1.8, and in the case of the comparative steel sheet Nα3 In the case of the invention steel plate No. 1, it is 0.9, whereas the invention steel sheet No. 1 is 0.2, and the invention steel sheet Na 2-6 is 0.1. 0.5 to 0.7, all of which were excellent.
また、耐食性も、同種金属被膜である、比較用鋼板Ｎα
２と本発明鋼板Ｎα３、および、比較用鋼板Ｎｏ ３と
本発明鋼板Ｎα４を各々比較すれば明らかなように、何
れも本発明鋼板の方が優れていた。In addition, the corrosion resistance of comparative steel sheet Nα, which is a similar metal coating, is
As is clear from comparisons between No. 2 and the steel plate of the present invention Nα3, and comparative steel plate No. 3 and the steel plate of the present invention Nα4, the steel plate of the present invention was superior in both cases.
以上述べたように、この発明によれば、耐食性および耐
摩耗性に優れ、これらの性能が成形加工を施した後にお
いても劣化することのない、自動車用、家庭電気製品用
および建材用等として好適な鋼板が得られる工業上有用
な効果がもたらされる。As described above, according to the present invention, the present invention has excellent corrosion resistance and wear resistance, and these properties do not deteriorate even after being subjected to molding processing, and are suitable for use in automobiles, home appliances, building materials, etc. This brings about an industrially useful effect in that a suitable steel plate can be obtained.
５5
Claims (1)
の少なくとも１つによって互いに結合されたシリカ粒子
からなるシリカ複合被膜が、鋼板の最表面上に連続的に
形成されていることを特徴とする、シリカ複合被膜を有
する鋼板。 ２、前記金属が、亜鉛、ニッケル、コバルト、銅、錫、
鉄およびクロムのうちの何れかである、請求項１記載の
シリカ複合被膜を有する鋼板。 ３、前記シリカ複合被膜中における、金属、前記金属の
水酸化物および前記金属の酸化物の少なくとも１つの含
有割合が、０．１〜２０ｗｔ．％の範囲内である、請求
項１記載のシリカ複合被膜を有する鋼板。 ４、シリカ粒子、金属イオンおよび硝酸イオンを含有す
る酸性電解液を使用し、鋼板を陰極とする陰極電解によ
り、前記鋼板の最表面上に、金属、前記金属の水酸化物
および前記金属の酸化物のうちの少なくとも１つによっ
て互いに結合されたシリカ粒子からなるシリカ複合被膜
を連続的に形成することを特徴とする、シリカ複合被膜
を有する鋼板の製造方法。 ５、前記電解液中における、前記シリカ粒子の含有量が
１０〜２００ｇ／ｌの範囲内であり、前記金属イオンの
含有量が０．０２〜２モル／ｌの範囲内であり、そして
、硝酸イオンの含有量が０．１〜２０ｇ／ｌの範囲内で
ある、請求項４に記載の方法。[Claims] 1. A silica composite coating consisting of silica particles bonded to each other by at least one of a metal, a hydroxide of the metal, and an oxide of the metal is continuously formed on the outermost surface of the steel sheet. A steel plate having a silica composite coating. 2. The metal is zinc, nickel, cobalt, copper, tin,
A steel sheet having a silica composite coating according to claim 1, which is made of either iron or chromium. 3. The content ratio of at least one of the metal, the hydroxide of the metal, and the oxide of the metal in the silica composite coating is 0.1 to 20 wt. A steel sheet having a silica composite coating according to claim 1, wherein the silica composite coating is within the range of %. 4. By cathodic electrolysis using an acidic electrolyte containing silica particles, metal ions, and nitrate ions and using a steel plate as a cathode, metal, hydroxide of the metal, and oxidation of the metal are deposited on the outermost surface of the steel plate. 1. A method for manufacturing a steel sheet having a silica composite coating, the method comprising continuously forming a silica composite coating consisting of silica particles bonded to each other by at least one of the following: 5. The content of the silica particles in the electrolytic solution is within the range of 10 to 200 g/l, the content of the metal ions is within the range of 0.02 to 2 mol/l, and nitric acid 5. The method according to claim 4, wherein the content of ions is in the range of 0.1 to 20 g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4369690A JPH03247796A (en) | 1990-02-23 | 1990-02-23 | Steel sheet having silica combined coating and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4369690A JPH03247796A (en) | 1990-02-23 | 1990-02-23 | Steel sheet having silica combined coating and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03247796A true JPH03247796A (en) | 1991-11-05 |
Family
ID=12670995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4369690A Pending JPH03247796A (en) | 1990-02-23 | 1990-02-23 | Steel sheet having silica combined coating and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03247796A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016188416A (en) * | 2015-03-30 | 2016-11-04 | 新日鐵住金株式会社 | Ultra fine plated steel wire excellent in adhesiveness with rubber, rubber composite using the same and manufacturing method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199899A (en) * | 1987-02-12 | 1988-08-18 | Nkk Corp | Production of dispersion-galvanized steel sheet having high corrosion resistance |
| JPS6462498A (en) * | 1987-08-31 | 1989-03-08 | Nippon Kokan Kk | Production of bright zinc dispersion plated steel sheet having high corrosion resistance |
| JPH01136995A (en) * | 1987-11-20 | 1989-05-30 | Nippon Parkerizing Co Ltd | Composite zinc or zinc-based alloy plating method |
-
1990
- 1990-02-23 JP JP4369690A patent/JPH03247796A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199899A (en) * | 1987-02-12 | 1988-08-18 | Nkk Corp | Production of dispersion-galvanized steel sheet having high corrosion resistance |
| JPS6462498A (en) * | 1987-08-31 | 1989-03-08 | Nippon Kokan Kk | Production of bright zinc dispersion plated steel sheet having high corrosion resistance |
| JPH01136995A (en) * | 1987-11-20 | 1989-05-30 | Nippon Parkerizing Co Ltd | Composite zinc or zinc-based alloy plating method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016188416A (en) * | 2015-03-30 | 2016-11-04 | 新日鐵住金株式会社 | Ultra fine plated steel wire excellent in adhesiveness with rubber, rubber composite using the same and manufacturing method therefor |
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