JPH03264693A - Production of zinc-silica composite electroplated steel sheet - Google Patents
Production of zinc-silica composite electroplated steel sheetInfo
- Publication number
- JPH03264693A JPH03264693A JP6196090A JP6196090A JPH03264693A JP H03264693 A JPH03264693 A JP H03264693A JP 6196090 A JP6196090 A JP 6196090A JP 6196090 A JP6196090 A JP 6196090A JP H03264693 A JPH03264693 A JP H03264693A
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- silica particles
- silica
- plating layer
- bath
- 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 silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 26
- 239000010959 steel Substances 0.000 title claims abstract description 26
- 239000000377 silicon dioxide Substances 0.000 title claims description 30
- 239000002131 composite material Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011701 zinc Substances 0.000 claims abstract description 33
- 238000009713 electroplating Methods 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- -1 nitrate ions Chemical class 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000003139 buffering effect Effects 0.000 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 abstract description 53
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000006174 pH buffer Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 35
- 239000000872 buffer Substances 0.000 description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 10
- 239000004317 sodium nitrate Substances 0.000 description 5
- 235000010344 sodium nitrate Nutrition 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 230000002542 deteriorative effect Effects 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000012733 comparative method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、耐食性に優れた亜鉛−シリカ複合電気めっ
き鋼板の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a zinc-silica composite electroplated steel sheet having excellent corrosion resistance.
亜鉛系電気めっき鋼板の耐食性を更に向上させるために
、亜鉛または亜鉛合金からなる亜鉛系めっき層中にシリ
カ粒子を均一に分散させることによって、めっき層の耐
食性を改善する試みが、近年盛んに行なわれている。In order to further improve the corrosion resistance of zinc-based electroplated steel sheets, many attempts have been made in recent years to improve the corrosion resistance of the coating layer by uniformly dispersing silica particles in the zinc-based coating layer made of zinc or zinc alloy. It is.
このように、亜鉛系めっき層中にシリカ粒子を均一に分
散させることによって、亜鉛系めっき層の耐食性は向上
する。しかしながら、亜鉛系めっき層中にシリカ粒子を
均一に分散させることは、容易ではない。その理由は、
シリカ粒子は、他の酸化物粒子と同様に、亜鉛電気めっ
き浴中で負に帯電し、そして、陰極としての鋼板の表面
上に析出しにくい傾向があるからである。In this way, by uniformly dispersing silica particles in the zinc-based plating layer, the corrosion resistance of the zinc-based plating layer is improved. However, it is not easy to uniformly disperse silica particles in the zinc-based plating layer. The reason is,
This is because silica particles, like other oxide particles, tend to be negatively charged in zinc electroplating baths and are less likely to deposit on the surface of the steel sheet serving as the cathode.
上述した問題を解決し、亜鉛系めっき層中にシリカ粒子
が均一に分散する亜鉛−シリカ複合電気めっき鋼板を製
造するための方法として、例えば特開昭６３−１９９８
９９号公報には、下記からなる方法が開示されている。As a method for solving the above-mentioned problems and producing a zinc-silica composite electroplated steel sheet in which silica particles are uniformly dispersed in the zinc-based plating layer, for example, Japanese Patent Laid-Open No. 63-1998
No. 99 discloses a method consisting of the following.
シリカ粒子および硝酸イオンを含有する亜鉛または亜鉛
合金酸性電気めっき浴を使用し、鋼板を陰極として、電
気めっきにより、前記鋼板の表面上に、シリカ粒子が分
散した亜鉛系めっき層を形成する。（以下、「先行技術
」という）。A zinc-based plating layer in which silica particles are dispersed is formed on the surface of the steel plate by electroplating using a zinc or zinc alloy acidic electroplating bath containing silica particles and nitrate ions and using the steel plate as a cathode. (hereinafter referred to as "prior art").
上述した先行技術によれば、電気めっき浴中に含有して
いる硝酸イオンによって、シリカ粒子に対し亜鉛が活性
化される。この結果、めっき層中へのシリカの共析率が
増加し、鋼板の表面上に、シリカ粒子が均一に分散した
亜鉛系めっき層を形成することができ。According to the prior art described above, zinc is activated on silica particles by nitrate ions contained in the electroplating bath. As a result, the eutectoid rate of silica in the plating layer increases, and a zinc-based plating layer in which silica particles are uniformly dispersed can be formed on the surface of the steel sheet.
しかしながら、上述した先行技術には、次のような問題
がある。However, the above-mentioned prior art has the following problems.
硝酸イオンを含有するＺｎ −ＳｊＯ□酸性電気めっき
浴を使用して電気めっきを行なう際における、Ｚｎ−８
１０，の共析挙動は、次のように推定される。Zn-8 when performing electroplating using a Zn-SjO□ acidic electroplating bath containing nitrate ions.
The eutectoid behavior of 10, is estimated as follows.
Ｚｎ” ＋、２０Ｈ−−＋Ｚｎ（ＯＲ）２＋−・＋＋・
・＋・（１）Ｚｎ （ＯＨ）２＋ ２ｅ−→ｚｎ＋２０
Ｈ−・・・・・・・・・（２）Ｎｏ、−＋９Ｈ＋＋８ｅ
−）ＮＨ３＋３８２０ −（３）上記（１）および（
２）のＺｎ２＋の還元反応によって、陰極界面における
めっき浴のｐＨは約５．６になるが、それ以上には上昇
しない。しかし、上記（３）のＮＯ３−の還元反応によ
って、めっき浴のｐＨは、約５．６以上に上昇する。
この結果、シリカ粒子が亜鉛イオンに吸着され、めっき
層にシリカが亜鉛と共析する。Zn” +, 20H−−+Zn(OR)2+−・++・
・+・(1) Zn (OH)2+ 2e-→zn+20
H-・・・・・・・・・(2) No, -+9H++8e
-)NH3+3820 -(3) Above (1) and (
Due to the reduction reaction of Zn2+ in 2), the pH of the plating bath at the cathode interface becomes approximately 5.6, but does not rise beyond that. However, the pH of the plating bath increases to about 5.6 or more due to the reduction reaction of NO3- in (3) above.
As a result, silica particles are adsorbed by zinc ions, and silica and zinc are eutectoid in the plating layer.
このように、硝酸イオンによってめっき浴のｐｌ＋は上
昇し、シリカの共析率は増加するが、一方、シリカの共
析率が増加し過ぎると、めっき層の加工性が劣化する。In this way, the pl+ of the plating bath increases due to nitrate ions, and the eutectoid rate of silica increases, but on the other hand, if the eutectoid rate of silica increases too much, the workability of the plating layer deteriorates.
硝酸イオンの含有量は、上述しためっき浴のρ■および
シリカの共析率に敏感に反応するため、めっき層の加工
性を劣化させずに、シリカの共析率を増加させ得る、め
っき浴中の硝酸イオンの濃度の適正な範囲は、極めて狭
い。The content of nitrate ions responds sensitively to the above-mentioned plating bath ρ■ and the eutectoid rate of silica, so the plating bath can increase the eutectoid rate of silica without deteriorating the workability of the plating layer. The appropriate range for the concentration of nitrate ions in is extremely narrow.
めっき浴中の硝酸イオンの濃度を、上述した狭一
い適正範囲に保つことは極めて困難なため、その耐食性
を向上させ得るに十分な量のシリカ粒子が均一に分散し
、しかも、加工性の劣化することのないめっき層を有す
る、亜鉛−シリカ複合電気めっき鋼板を、安定して製造
することは極めて困難である。Since it is extremely difficult to maintain the concentration of nitrate ions in the plating bath within the narrow appropriate range mentioned above, it is necessary to uniformly disperse silica particles in sufficient amount to improve the corrosion resistance and to improve processability. It is extremely difficult to stably produce zinc-silica composite electroplated steel sheets that have a plating layer that does not deteriorate.
従って、この発明の目的は、シリカ粒子および硝酸イオ
ンを含有する亜鉛または亜鉛合金電気めっき浴を使用し
、鋼板の表面上に、シリカ粒子が分散した亜鉛系めっき
層を形成する際における上述した問題を解決し、耐食性
を向上させ得るに十分な量のシリカ粒子が均一に分散し
、しかも、加工性の劣化することがないめっき層を有す
る、亜鉛−シリカ複合電気めっき鋼板を、安定して製造
するための方法を提供することにある。Therefore, an object of the present invention is to solve the above-mentioned problems when forming a zinc-based plating layer in which silica particles are dispersed on the surface of a steel sheet by using a zinc or zinc alloy electroplating bath containing silica particles and nitrate ions. Stable production of zinc-silica composite electroplated steel sheets that have a sufficient amount of silica particles uniformly dispersed to improve corrosion resistance and have a plating layer that does not deteriorate workability. The goal is to provide a way to do so.
［課題を解決するための手段〕
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、シリカ粒子および硝酸イオンを含有す
る亜鉛または亜鉛合金酸性電気めっき浴中に、ρ１１が
５〜１２の範囲内においてρ１１緩衝作用を有するｐＨ
緩衝剤を添加し、このめっき浴を使用して電気めっきを
行なえば、耐食性を向上させ得るに十分な量のシリカ粒
子が均一に分散し、しかも、加工性の劣化することがな
いめっき層に有する、亜鉛−シリカ複合電気めっき鋼板
を、安定して製造し得ることを知見した。[Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above-mentioned problems. As a result, in a zinc or zinc alloy acidic electroplating bath containing silica particles and nitrate ions, a pH that has a ρ11 buffering effect within the range of 5 to 12 was found.
If a buffer is added and electroplating is performed using this plating bath, a sufficient amount of silica particles will be uniformly dispersed to improve corrosion resistance, and the plating layer will not deteriorate in processability. It has been found that it is possible to stably produce a zinc-silica composite electroplated steel sheet having the following properties.
この発明は、上記知見に基いてなされたものであって、
シリカ粒子および硝酸イオンを含有する亜鉛または亜鉛
合金酸性電気めっき浴を使用し、鋼板を陰極として、電
気めっきにより、前記鋼板の表面上に、シリカ粒子が分
散した亜鉛系めっき層を形成することからなる、亜鉛−
シリカ複合電気めっき鋼板の製造方法において、
前記酸性電気めっき浴中に、前記シリカ粒子および前記
硝酸イオンと共に、ｐＨが５〜１２の範囲内においてｐ
Ｈ緩衝作用を有するｐＨ緩衝剤を含有させ、このような
酸性電気めっき浴を使用して電気めっきを行なうことに
特徴を有するものである。This invention was made based on the above findings, and
Forming a zinc-based plating layer in which silica particles are dispersed on the surface of the steel plate by electroplating using a zinc or zinc alloy acidic electroplating bath containing silica particles and nitrate ions and using the steel plate as a cathode. Zinc-
In the method for producing a silica composite electroplated steel sheet, in the acidic electroplating bath, together with the silica particles and the nitrate ions, pH is within a range of 5 to 12.
The method is characterized in that it contains a pH buffering agent having an H buffering effect, and electroplating is performed using such an acidic electroplating bath.
この発明において、シリカ粒子および硝酸イオンを含有
するめっき浴中に、ｐｌ（が５〜１２の範囲６−
内においてｐＨ緩衝作用を有するｐＨ緩衝剤を添加する
理由は、次の通りである。即ち、前記めっき浴中に、上
述したｐＨ緩衝剤が含有されていると、前述の（３）の
反応によって生ずる、 めっき浴のｐｏの過剰な上昇が
抑制される。従って、めっき層中のシリカの共析率が過
剰に増加することなく、めっき層の加工性の劣化を防止
することができる。In this invention, the reason why a pH buffering agent having a pH buffering effect within the range of 5 to 12 is added to the plating bath containing silica particles and nitrate ions is as follows. When the above-mentioned pH buffer is contained in the plating bath, an excessive increase in po of the plating bath caused by the reaction (3) described above is suppressed. Therefore, the silica in the plating layer is Deterioration of workability of the plating layer can be prevented without excessively increasing the eutectoid rate.
このように、めっき浴中へのｐＨ緩衝剤の添加によって
、めっき層の加工性を劣化させずに、シリカの共析率を
増加させ、耐食性を向上し得る。めっき浴中の硝酸イオ
ンの濃度の適正範囲が、大幅に拡大する。In this way, by adding a pH buffer to the plating bath, the eutectoid rate of silica can be increased and the corrosion resistance can be improved without deteriorating the workability of the plating layer. The appropriate range of nitrate ion concentration in the plating bath is greatly expanded.
ｐＨ緩衝剤は、室温〜６０℃の温度のめっき浴における
ρ１１が、５〜１２の範囲内においてＰ）Ｉ緩衝作用を
有するものであることを必要とする。ｐＨ緩衝作用が５
未満または１２超においてのみ生ずるＰ）Ｉ緩衝剤では
、前述の（３）の反応によって生ずる、めっき浴のｐＨ
の過剰な上昇を抑制することはできない。The pH buffer is required to have a P)I buffering effect in a plating bath at a temperature of room temperature to 60°C, with ρ11 in the range of 5 to 12. pH buffering effect is 5
For P)I buffers that occur only at temperatures below or above 12, the pH of the plating bath caused by the reaction in (3) above
It is not possible to suppress the excessive rise in
下記に、この発明において使用する好適なｐＨ緩衝剤の
一例を示す。An example of a suitable pH buffer for use in this invention is shown below.
Ａ ： ｃｌａｒｋ−Ｌｕｂｓの緩衝液Ｂｕｓφｒｅｎ
ｓの緩衝液
Ｃ： Ｋｏｌｔｏｆｆの緩衝液
Ｄ＝阿１ｃｈａｅｌｉｓの緩衝液
Ｅ ： Ａｔｋｉｎｓ−Ｐａｎｔｉｎの緩衝液Ｆ ：
Ｐａ１ｉｔｚｓｃｈの緩衝液
Ｇ ： Ｍｃｌｌｖａｉｎｅの緩衝液
Ｈ： Ｍｅｎｚｅｌの緩衝液
Ｉ ： １ｄａｌｐｏｌｅの緩衝液
Ｊ ： Ｈａｓｔｊ、ｎｇ−３ｅｎｄｒｏｙの緩衝液Ｋ
： Ｂｒ１ｔｔｏｎ−Ｒｏｂｉｎｓｏｎの緩衝液Ｌ
： Ｇｏｍｏｒｉの緩衝液
Ｍ：等張緩荷液
ＮＵＮ−エチルモルホリン−塩酸の緩衝液シリカ粒子は
、めっき浴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。シリカ粒子の粒
径は、１１００ｎ以下に限定することが好ましい。粒径
が１１００ｎを超えると、シリカ粒子をめっき層中に均
一に分散さ７−
＝８−
せることか困難になる。めっき浴中のシリカ粒子の含有
量は、 ０．５〜１００ ｇ ／ Ｑの範囲内が好まし
い。シリカ粒子の含有量が０ 、５ ｇ／ １未満では
、シリカの共析効率が低下して、めっき層に高い耐食性
が得られない。一方、１００ｇ／Ｑを超えると、電解効
率が低下する。A: Clark-Lubs buffer Busφren
s buffer C: Koltoff's buffer D = Chaelis' buffer E: Atkins-Pantin's buffer F:
Palitzsch's buffer G: Mcllvaine's buffer H: Menzel's buffer I: 1dalpole's buffer J: Hastj, ng-3endroy's buffer K
: Br1tton-Robinson buffer L
: Gomori's buffer M: isotonic buffer solution NUN-ethylmorpholine-hydrochloric acid buffer As the silica particles, colloidal silica is preferably used from the viewpoint of ease of handling when added to the plating bath. The particle size of the silica particles is preferably limited to 1100 nm or less. When the particle size exceeds 1100 nm, it becomes difficult to uniformly disperse the silica particles in the plating layer. The content of silica particles in the plating bath is preferably in the range of 0.5 to 100 g/Q. If the content of silica particles is less than 0.5 g/1, the eutectoid efficiency of silica decreases, and high corrosion resistance cannot be obtained in the plating layer. On the other hand, if it exceeds 100 g/Q, the electrolytic efficiency will decrease.
硝酸イオンとしては、ＮａＮ０．、 ＨＮＯ３，にＮＯ
３゜Ｚｎ （Ｎｏ、 ）２等を使用することができる。As the nitrate ion, NaN0. , HNO3, niNO
3°Zn (No, )2 etc. can be used.
めっき浴中の硝酸イオンの含有量は、 １００〜３００
０ｐｐｍの範囲内が好ましい。硝酸イオンの含有量が１
１００ｐｐ未満では、シリカの共析効率が低下して、
めっき層に高い耐食性が得られない。一方、３０００ｐ
ＰｒＬｌを超えると緻密なめっき層が得られない。The content of nitrate ions in the plating bath is 100-300
It is preferably within the range of 0 ppm. Nitrate ion content is 1
If it is less than 100 pp, the eutectoid efficiency of silica decreases,
High corrosion resistance cannot be obtained from the plating layer. On the other hand, 3000p
If it exceeds PrLl, a dense plating layer cannot be obtained.
めっき層中のシリカの共析率は、０．２ｗｔ、％以上で
あることが好ましい。 シリカの共析率が０ 、２ ｕ
ｔ、％未満では、めっき層に高い耐食性が得られない。The eutectoid rate of silica in the plating layer is preferably 0.2 wt% or more. The eutectoid rate of silica is 0, 2 u
If it is less than t,%, high corrosion resistance cannot be obtained in the plating layer.
シリカの共析率が増加するに従って、めっき層の耐食性
は向上するが、一方、めっき層の加工性は劣化する。従
って、シリカの共析率の上限は、通常の亜鉛めっき鋼板
（めっき量４０ｇ／、（）の加工性（ＯＴ曲げ）よりも
劣化しない、１．５ｗｔ、％とすることが好ましい。As the eutectoid rate of silica increases, the corrosion resistance of the plating layer improves, but on the other hand, the workability of the plating layer deteriorates. Therefore, the upper limit of the eutectoid rate of silica is preferably 1.5 wt.%, which does not deteriorate the workability (OT bending) of a normal galvanized steel sheet (coating amount: 40 g/).
この発明において、シリカ粒子が均一に分散しているめ
っき層中に、金属成分として、亜鉛のみを含有させるほ
か、必要に応じて、鉄、ニッケル、コバルトおよびクロ
ムのうちの少なくとも１つの成分を含有させることがで
きる。In this invention, the plating layer in which silica particles are uniformly dispersed contains only zinc as a metal component and, if necessary, at least one component of iron, nickel, cobalt, and chromium. can be done.
基本の亜鉛めっき浴としては、通常の硫酸浴、塩化浴ま
たは両者の混合浴を使用することができる。これらの基
本浴に、電導度補助剤、光沢剤等を含有させてもよい。As the basic galvanizing bath, a conventional sulfuric acid bath, a chloride bath, or a mixed bath of both can be used. These basic baths may also contain conductivity aids, brighteners, and the like.
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.
下記からなる酸性亜鉛電気めっき浴を基本浴として使用
した。An acidic zinc electroplating bath consisting of the following was used as the base bath.
硫酸亜鉛 ： ３００ｇハＬ
硫酸ソーダ ： ３０ｇＩＱ、
酢酸ソーダ ： １２ｇ／（１，、コロイダルシ
リカ： ７０ｇ／（１、硝酸ナトリウム ： １．６
ｇ／Ｒ１
ｐＨ： ２
上記基本浴に、第１表に示すこの発明の範囲内の方法（
以下、「本発明法」という）Ｎα１〜２２に従ってｐＨ
緩衝剤を添加し、□亜鉛電気めっき浴を調製した。この
ように調製された亜鉛電気めっき浴を使用し、冷延鋼板
を陰極として、 ５０Ａ／ｄｒｒｉの電流密度の電気め
っきにより、前記鋼板の表面上に、シリカ粒子が均一に
分散している、４０ｇ／イの量の亜鉛−シリカ複合電気
めっき層を形成した。Zinc sulfate: 300g/L Sodium sulfate: 30gIQ, Sodium acetate: 12g/(1, Colloidal silica: 70g/(1, Sodium nitrate: 1.6)
g/R1 pH: 2 To the above basic bath, the methods within the scope of this invention shown in Table 1 (
pH according to Nα1-22 (hereinafter referred to as “method of the present invention”)
A buffer was added to prepare a □ zinc electroplating bath. Using the zinc electroplating bath prepared in this way and using the cold-rolled steel plate as a cathode, electroplating was carried out at a current density of 50 A/drri to produce 40 g of silica particles uniformly dispersed on the surface of the steel plate. A zinc-silica composite electroplating layer was formed in an amount of /A.
比較のために、この発明の範囲外である、第１表に併せ
て示す方法（以下、「比較法Ｊという）Ｈａ １に従っ
て、冷延鋼板の表面上に、上記と同じ条件の亜鉛−シリ
カ複合電気めっき層を形成した。For comparison, according to method Ha 1 shown in Table 1 (hereinafter referred to as "comparative method J"), which is outside the scope of this invention, zinc-silica was applied on the surface of a cold rolled steel sheet under the same conditions as above. A composite electroplated layer was formed.
上述した本発明法および比較法により、冷延鋼板の表面
上にめっき層を形成する際における。硝酸ナトリウム（
ＮａＮＯｊの適正な濃度範囲（△×）、即ち、亜鉛−シ
リカ複合電気めっき層の加工性（０７曲げ）が、通常の
亜鉛めっき鋼板（めっき量：４０ｇ／ｒｒｒ）の加工性
よりも劣化したときの硝酸ナトリウムの含有量と、シリ
カの共析率が、耐食性を向上させ得るに十分な０．２す
し０％以上になるときの硝酸ナトリウムの含有量との差
を調べ、これを、第１表に併せて示した。When forming a plating layer on the surface of a cold rolled steel sheet by the above-mentioned method of the present invention and comparative method. Sodium nitrate (
The appropriate concentration range of NaNOj (△×), that is, when the workability of the zinc-silica composite electroplated layer (07 bending) is worse than the workability of a normal galvanized steel sheet (coating amount: 40 g / rrr) The difference between the sodium nitrate content of It is also shown in the table.
第１表から明らかなように、ｐＨ緩衝剤が添加されてい
ないめっき浴を使用した比較法Ｈａ Ｌにおいては、硝
酸ナトリウムの適正な濃度範囲（△×）が０．０２ｇＩ
Ｑで極めて狭く、従って、鋼板の表面上に、耐食性を向
上させ得るに十分な量のシリカ粒子が均一に分散し、し
かも、加工性の劣化することのない亜鉛−シリカ複合電
気めっき層を安定して形成することが極めて困難であっ
た。As is clear from Table 1, in the comparative method HaL, which uses a plating bath to which no pH buffer is added, the appropriate concentration range (△×) of sodium nitrate is 0.02 gI.
Q is extremely narrow, so that a sufficient amount of silica particles are uniformly dispersed on the surface of the steel sheet to improve corrosion resistance, and the zinc-silica composite electroplating layer is stabilized without deteriorating workability. It was extremely difficult to form this structure.
これに対して、この発明の方法により、ｐＨ緩衝剤が添
加されているめっき浴を使用して、めっきを行なった本
発明法Ｎα１〜２２においては、硝酸ナトリウムの適正
な濃度範囲（△Ｘ）が０．０６〜Ｑ 、 ５ ｇ／ Ｑ
で広く、従って、鋼板の表面上に、耐食性を向上させ得
るに十分な量のシリカ粒子が均一に分散し、しかも、加
工性の劣化することがなく、品質の優れた亜鉛−シリカ
複合電気めっき層を、安定して形成することができた。On the other hand, in the method Nα1 to Nα22 of the present invention, in which plating was performed using a plating bath to which a pH buffer was added, the appropriate concentration range (ΔX) of sodium nitrate is 0.06~Q, 5 g/Q
Therefore, a sufficient amount of silica particles are uniformly dispersed on the surface of the steel sheet to improve corrosion resistance, and the zinc-silica composite electroplating has excellent quality without deteriorating workability. The layer could be stably formed.
以上述べたように、この発明によれば、シリカ粒子およ
び硝酸イオンを含有する亜鉛または亜鉛合金電気めっき
浴を使用し、鋼板の表面上に、シリカ粒子が分散した亜
鉛系めっき層を形成する際における、めっき浴中の硝酸
イオンの濃度の適正範囲が広がり、耐食性を向上させ得
るに十分な量のシリカ粒子が均一に分散し、しかも、加
工性の劣化することがないめっき層を有する、亜鉛−シ
リカ複合電気めっき鋼板を安定して製造することができ
る、工業上有用な効果がもたらされる。As described above, according to the present invention, a zinc or zinc alloy electroplating bath containing silica particles and nitrate ions is used to form a zinc-based plating layer in which silica particles are dispersed on the surface of a steel sheet. Zinc has a plating layer in which the appropriate range of nitrate ion concentration in the plating bath is widened, a sufficient amount of silica particles are uniformly dispersed to improve corrosion resistance, and the processability does not deteriorate. - An industrially useful effect is brought about in which silica composite electroplated steel sheets can be stably produced.
Claims (1)
亜鉛合金酸性電気めっき浴を使用し、鋼板を陰極として
、電気めっきにより、前記鋼板の表面上に、シリカ粒子
が分散した亜鉛系めっき層を形成することからなる、亜
鉛−シリカ複合電気めっき鋼板の製造方法において、 前記酸性電気めっき浴中に、前記シリカ粒子および前記
硝酸イオンと共に、ｐＨが５〜１２の範囲内においてｐ
Ｈ緩衝作用を有するｐＨ緩衝剤を含有させ、このような
酸性電気めっき浴を使用して電気めっきを行なうことを
特徴とする、亜鉛−シリカ複合電気めっき鋼板の製造方
法。[Claims] 1. Zinc with silica particles dispersed on the surface of the steel plate by electroplating using a zinc or zinc alloy acidic electroplating bath containing silica particles and nitrate ions and using the steel plate as a cathode. In the method for manufacturing a zinc-silica composite electroplated steel sheet, which comprises forming a zinc-silica composite electroplating layer, in the acidic electroplating bath, along with the silica particles and the nitrate ions, p is added at a pH within a range of 5 to 12.
1. A method for producing a zinc-silica composite electroplated steel sheet, which comprises containing a pH buffering agent having an H buffering effect and carrying out electroplating using such an acidic electroplating bath.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6196090A JPH03264693A (en) | 1990-03-13 | 1990-03-13 | Production of zinc-silica composite electroplated steel sheet |
| US07/654,065 US5186812A (en) | 1990-03-08 | 1991-02-11 | Method for manufacturing zinc-silica composite electroplated steel sheet |
| CA002036464A CA2036464A1 (en) | 1990-03-08 | 1991-02-15 | Method for manufacturing zinc-silica composite electroplated steel sheet |
| EP91102355A EP0445573A1 (en) | 1990-03-08 | 1991-02-19 | Method for manufacturing zinc-silica composite electroplated steel sheet |
| KR1019910003773A KR910016969A (en) | 1990-03-08 | 1991-03-08 | Manufacturing method of zinc-silica composite electroplated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6196090A JPH03264693A (en) | 1990-03-13 | 1990-03-13 | Production of zinc-silica composite electroplated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03264693A true JPH03264693A (en) | 1991-11-25 |
Family
ID=13186262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6196090A Pending JPH03264693A (en) | 1990-03-08 | 1990-03-13 | Production of zinc-silica composite electroplated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03264693A (en) |
-
1990
- 1990-03-13 JP JP6196090A patent/JPH03264693A/en active Pending
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