CN1065690A - Nickel electroplated cold-rolled steel sheet and preparation method thereof - Google Patents
Nickel electroplated cold-rolled steel sheet and preparation method thereof Download PDFInfo
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- CN1065690A CN1065690A CN92100427A CN92100427A CN1065690A CN 1065690 A CN1065690 A CN 1065690A CN 92100427 A CN92100427 A CN 92100427A CN 92100427 A CN92100427 A CN 92100427A CN 1065690 A CN1065690 A CN 1065690A
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating 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
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Abstract
A kind of cold-rolled steel sheet that has excellent punching formation property and bonderizing, electroplated nickel, it comprises a kind of cold-rolled steel sheet.
A kind of nickel electrolytic coating that generates at least one surface of this cold-rolled steel sheet, the nickel particle is with at least 1 * 10 in this layer
12/ rice
2Distribution density precipitation, the coating weight of this nickel electrolytic coating is at 5～60 milligrams/meter
2Cold-rolled steel sheet; With
The nickel oxide film that one deck generates on this nickel electrolytic coating surface, its mean thickness is in 0.0005～0.003 micrometer range.
Above-mentioned cold-rolled steel sheet can further contain the most nearly 0.15% (weight) titanium (Ti) and reach in 0.15% (weight) niobium (Nb) at least a most.Under the situation of adding titanium and/or niobium, also can further add the most nearly 0.003% (weight) boron (B).
Description
The present invention relates to have the nickel electroplated cold-rolled steel sheet and the manufacture method thereof of excellent press formability and bonderizing.
In general, the cold-rolled steel sheet material (thin plate) that is used for automobile or electrical equipment is all made the regulation shape by means of the large vol press.For make large-scale car body, reduce automobile during travelling atmidometer and obtain style outward appearance preferably, present regular practice is that protective shield, door and tail of the body are made circle.
On the other hand,, also making great efforts to reduce car body weight, thereby reducing oil consumption from the viewpoint of economical advantage and environment protection.In order to reduce car body weight, be necessary to reduce the thickness of the steel sheet of making car body; For the steel sheet that should be subjected to deep draw (as exposing plate) situation also is like this.Anti-depression performance and the shape stability that need be satisfied with as the steel sheet that exposes plate.Therefore, be necessary to use thin high-strength steel to make and expose plate.In order to adopt deep draw that thin high strength cold-rolled steel sheet is shaped, be necessary to utilize in advance powerful press to increase the wrinkle restraint of steel sheet, thereby prevent from cold-rolled steel sheet, to produce wrinkle during the drawing.
Can adopt continuous annealing or pack annealing, make cold-rolled steel sheet annealing, to reach the purpose of the crystal grain recrystallization that makes gross distortion during it is cold rolling.
A kind of common low carbon aluminium killed steel has been used as the material of the soft cold-rolled steel sheet of deep draw.The carbon aluminium-killed steel of a kind of siliceous, manganese and phosphorus has been used as the material of deep draw high-strength steel thin plate.Pack annealing has been used to soft cold-rolled steel sheet of above-mentioned deep draw and the annealing of deep draw high-strength steel thin plate.The feature of pack annealing be heat-up time long, cooling time long, crystal grain is easily grown, and can obtain having the cold-rolled steel sheet of high Lankford value.
It is longer that the steel sheet of pack annealing is exposed to the pyritous time than the steel sheet of continuous annealing.As a result, contained silicon, manganese and phosphorus concentrates on the surface of steel sheet in the steel sheet of pack annealing with oxide form.These concentrate on the lip-deep oxide compound of steel sheet plays lubricant film during drawing effect.In addition, the steel sheet of pack annealing has higher Lankford value than the steel sheet of continuous annealing.Therefore, in the steel sheet of pack annealing, take place hardly such as the such trouble of pressure break.
When the steel sheet of pack annealing carry out drawing, when carrying out bonderizing then, contained element and (for example be enriched to the lip-deep element of steel sheet in the steel sheet, manganese) just make the reaction activation that forms phosphate layer, thereby on the steel sheet surface, form the thin phosphate layer of one deck densification.This layer phosphate layer has the function that improves lacquer bounding force and corrosion resistance nature in this steel sheet japanning back.
Yet, owing to reasons such as simplified manufacturing technique, raising productive rate and saving labor forces, carry out steel sheet annealing with the continuous annealing method and becoming conventional way day by day recently.Knownly be suitable for using the cold-rolled steel sheet that continuous annealing handles and comprise a kind of ultra low-carbon steel or a kind of steel (being designated hereinafter simply as " IF steel ") that are called no gap steel.
In order to improve Lankford value as the index of ultra low-carbon steel thin plate punching, following measures have been taked: during making steel, carry out the steel degassing, so that carbon content is reduced to below the 100PPm, and makes other impurity content drop to bottom line, thereby crystal grain can be grown fast.
The IF steel is by at least a the adding in the ultra low-carbon steel in titanium and the niobium produced, and by means of the element of these interpolations the carbon of solid solution element interaction and nitrogen is fixed, thereby makes and might obtain high Lankfora value with the continuous annealing of short period of time.
Because the development of above-mentioned ultra low-carbon steel and IF steel is even now utilize the continuous annealing method also might make the cold-rolled steel sheet with high Lankford value.
Yet the Lankford value of carrying out the deep draw cold-rolled steel sheet (hereinafter to be referred as " continuous annealing cold-rolled steel sheet ") of continuous annealing equals or even surpasses the Lankford value of the deep draw cold-rolled steel sheet (hereinafter to be referred as " pack annealing cold-rolled steel sheet ") that carries out common pack annealing.But, the continuous annealing cold-rolled steel sheet breaks during drawing easily, and when being processed into complicated shape, than the easier wearing and tearing of pack annealing cold-rolled steel sheet.According to for finding out the result of former thereby the various researchs carried out, as shown in table 1, the friction co-efficient value that has disclosed steel sheet surface between continuous annealing cold-rolled steel sheet and pack annealing cold-rolled steel sheet has very big-difference.Table 1 shows numerical value, Lankford value (r value) and the ultimate extension of the skin friction coefficient (μ) of common continuous annealing and pack annealing cold-rolled steel sheet than (LDR), and table 2 is listed the chemical constitution of employed continuous annealing and pack annealing cold-rolled steel sheet in these researchs.
Fig. 1 be the Lankford value of explanation continuous annealing cold-rolled steel sheet and pack annealing cold-rolled steel sheet and ultimate extension than between the graphic representation that concerns.In Fig. 1, mark " zero " is represented the pack annealing cold-rolled steel sheet, and mark " △ " is represented the continuous annealing cold-rolled steel sheet.As shown in fig. 1, between continuous annealing and the pack annealing cold-rolled steel sheet Lankford value and ultimate extension than aspect difference be considered to cause by the following fact: the great friction coefficient on such steel sheet surface has reduced steel sheet surface and wrinkle and has suppressed oilness between anchor clamps or the mould in the continuous annealing cold-rolled steel sheet, thereby influence material mobile smoothly in press die.
The bonderizing of continuous annealing cold-rolled steel sheet is described now.Continuous annealing cold-rolled steel sheet to drawing carries out bonderizing, just forms one deck phosphate layer on the surface of this continuous annealing cold-rolled steel sheet.Because the continuous annealing cold-rolled steel sheet has only the very low impurity element of content, and this steel sheet surface is exposed to the pyritous time and far is shorter than the pack annealing steel sheet during annealing, so element contained in this steel sheet is enriched on its surface hardly.As a result, the precipitation of having only the only a few negative electrode to form phosphoric acid salt crystal grain on the surface of continuous annealing cold-rolled steel sheet is examined, thereby the phosphate layer that generates on the steel sheet surface comprises coarse crystal grain.
Fig. 5 is a width of cloth SEM(scanning electronic microscope) Photomicrograph, be presented at the phosphate layer crystalline structure that generates on the pack annealing cold-rolled steel sheet surface, Fig. 6 is the SEM Photomicrograph of the phosphate layer crystal gold phase structure that forms on continuous annealing cold-rolled steel sheet surface of width of cloth explanation.As shown in Figure 6, the phosphate layer crystal grain that forms on continuous annealing cold-rolled steel sheet surface is thicker than the phosphate layer crystal grain that forms on the pack annealing cold-rolled steel sheet surface shown in Fig. 5.Therefore, the continuous annealing cold-rolled steel sheet is at bonderizing, and the erosion resistance aspect after paint adhesion and the japanning all is inferior to the pack annealing cold-rolled steel sheet.
The above-mentioned inferior position of continuous annealing cold-rolled steel sheet aspect bonderizing just can be observed when with mineral acid this steel sheet being carried out pickling, not only in ultra low-carbon steel so, it also is like this going in the situation of aluminum steel and capped steel at the common low carbon gold.
As a kind of way of the inferior bonderizing problem that solves the sulfuric acid refining continuous annealing cold-rolled steel sheet, proposed on the cold-rolled steel sheet surface, to form the few metal plating of a kind of quantity, for example, and nickel coating, specific practice is as follows:
(1) Japanese patent provisional publication thing № .56-116,833(1981 September 12) a kind of method that is used to improve the cold-rolled steel sheet bonderizing is disclosed, this method comprises: forming one deck coating weight on the cold-rolled steel sheet surface is 0.3-10mg/dm
2Nickel coating (hereinafter being referred to as " prior art 1 ").
(2) cold-rolled steel sheet of metal that Japanese patent provisional publication thing № .56-116,833(1981 September 12) discloses a kind of plating with excellent bonderizing, it comprises:
Cold-rolled steel sheet; The coating that is selected from following at least a metal that forms on described cold-rolled steel sheet surface: titanium, manganese, nickel, cobalt, copper, molybdenum and tungsten, its coating weight are 1～500mg/m
2(hereinafter being referred to as " prior art 2 ").
According to aforementioned prior art 1 and 2, the cold-rolled steel sheet that the nickel that can obtain having excellent bonderizing has been electroplated.This is attributable to the following fact: because the above-mentioned nickel that forms on described cold-rolled steel sheet surface and the metal plating of other metals, at the phosphoric acid salt film formation reaction of the sedimentary part surface formation of metal (as: nickel) activation of cathode.
But prior art 1 and 2 has following problems.
In order to improve the phosphorization treatment performance of cold-rolled steel sheet, it is considerable that calcium phosphate precipitation check figure order is adjusted to certain distribution density.But according to prior art 1 and 2, the coating weight scope of nickel and other metal plating is very wide, can reach 1-500mg/m
2When the coating weight of nickel and other metal plating too big, when exceeding its necessary level, perhaps when nickel and other metallic particles do not distribute according to certain distribution density, just can't obtain to form thin, the required crystallite size of fine and close phosphate layer, therefore, just can't after japanning, reach excellent japanning binding property and excellent erosion resistance.Otherwise if the coating weight of nickel and other metal plating is too light, the number of calcium phosphate precipitation nuclear just is not enough to form coarse, thick phosphate layer, and, also just can't reduce the frictional coefficient on steel sheet surface fully.
Both just the coating weight of nickel and other metal plating was within the scope of regulation, if on coating, there is not the oxide film of nickel and other metals, oxide film had perhaps both just been arranged, but it is very thin, the frictional coefficient on described cold-rolled steel sheet surface increases, and this can cause the press formability of steel sheet to reduce.In order to prevent that press formability from reducing, need make the upper limit of the coating weight of metal plating near open amount in prior art 1 and 2.But this can destroy the bonderizing of steel sheet again.
As the technology of improving cold-rolled steel sheet bonderizing and erosion resistance, following cold-rolled steel sheet is proposed:
Japanese patent provisional publication thing № 2-101,200(1990 April 12) the nickel-plated cold-rolled thin plate with excellent bonderizing and erosion resistance is disclosed, it comprises: a kind of cold-rolled steel sheet; With the nickel layer that forms on described cold-rolled steel sheet surface, in this layer, the nickel particle is with 1 * 10
12-5 * 10
14/ m
2The distribution density deposition, said nickel coating is 1-50mg/m in the coating weight scope on described cold-rolled steel sheet surface
2, include metallic nickel and nonmetal nickel in the said nickel particle, its thickness is 0.0009-0.03 μ m, and adheres to the surface of said metallic nickel, and said nickel particulate size range is that 0.001-0.3 μ m(hereinafter is referred to as " prior art 3 ").
According to aforementioned prior art 3, can form crystallite size phosphate layer within the specific limits, fine and close, even, the cold-rolled steel sheet that can obtain having excellent bonderizing and erosion resistance thus.In addition, prior art 3 can make the frictional coefficient on continuous annealing cold-rolled steel sheet surface reduce.
But our studying in great detail shows: prior art 3 has following problems.
In prior art 3, when the coating weight of nickel coating is lower than 5mg/m
2The time, then can't obtain to have the cold-rolled steel sheet of excellent bonderizing.Reason is as follows: more particularly, be since the number (representing) of phosphoric acid salt initial precipitation nuclear with distribution density 1 * 10
10To 5 * 10
11/ m
2Scope within.And phosphoric acid salt initial precipitation check figure order is to form densification, even phosphate layer and its crystallite size is within certain scope desired by means of bonderizing.
Yet, for nickel particulate distribution density in the nickel coating is limited in aforesaid 1 * 10
12～5 * 10
14/ rice
2In the scope, the coating weight of nickel coating must be at least 5 milligrams/meters
2But, according to prior art 2, the coating weight of disclosed nickel coating is at 1～50 milligram/meter
2In the scope.So, when the coating weight of nickel coating is at 5 milligrams/meter
2When following, can not reach nickel particle at least 1 * 10
12/ rice
2Distribution density.Therefore, phosphoric acid salt initial precipitation check figure order can't remain in the above prior art 2 described desired extents in some cases, in this case, can't make this steel sheet have excellent bonderizing.
In addition, in prior art 2, the purpose that forms nonmetal nickel film on the nickel coating surface is to improve the cold-rolled steel sheet alramenting property handled and reduce frictional coefficient.Yet, nonmetal nickel is a kind of metal oxide basically, and as disclosed in the example of prior art 3, when by making steel sheet carry out in alkaline tank liquor that anode electrolysis is handled and when forming one deck mean thickness on the steel sheet surface, not having the steel sheet surface of nickel coating to form mean thickness than above-mentioned bigger nonmetal nickel oxide film in a part at least 0.005 micron nonmetal nickel oxide film.As a result, although the drawing property improvement, the part that phosphate layer deposition weight is little is more, thus the back paint adhesion power that causes painting reduces the corrosion resistance nature variation.
When by using mild steel sheet as material and it is carried out continuous annealing handle when making the deep draw cold-rolled steel sheet, need solve bonderizing reduction and press formability simultaneously and reduce this two problems.
In this case, very be necessary to develop a kind of be suitable for that continuous annealing is handled, in deep draw processing press formability and the cold-rolled steel sheet bonderizing excellence, that electroplated nickel, but at present also nobody a kind of like this cold-rolled steel sheet and manufacture method thereof are proposed.
Therefore, an object of the present invention is to provide a kind of be suitable for that continuous annealing is handled, in deep draw processing press formability and the cold-rolled steel sheet bonderizing excellence, that electroplated nickel.
According to one of feature of the present invention, provide a kind of press formability and bonderizing excellence, electroplated the cold-rolled steel sheet of nickel, it comprises:
A kind of cold-rolled steel sheet, it basic composition is:
Carbon (C): mostly be 0.06%(weight most)
Silicon (Si): mostly be 0.5%(weight most)
Manganese (Mn): mostly be 2.5%(weight most)
Phosphorus (P): mostly be 0.1%(weight most)
Sulphur (S): mostly be 0.025%(weight most),
Soluble aluminum (Soi.Al): mostly be 0.10%(weight most),
Nitrogen (N): mostly be 0.05%(weight most),
Remaining sum is iron (Fe) and follows impurity;
A kind of nickel electrolytic coating that forms at least one surface of described cold-rolled steel sheet, the nickel particle is with at least 1 * 10 in this layer
12/ rice
2Distribution density precipitation, the coating weight of described nickel electrolytic coating is that every square metre of described cold-rolled steel sheet surface is coated with 5～60 milligrams; With
A kind of nickel oxide film that forms on described nickel electrolytic coating surface, its mean thickness is in 0.0005～0.003 micron scope.
According to another feature of the present invention, provide a kind of method of making press formability and bonderizing excellence, having electroplated the cold-rolled steel sheet of nickel, comprise the steps:
Prepare a kind of steel ingot, it basic composition is:
Carbon (C): mostly be 0.06%(weight most),
Silicon (Si): mostly be 0.5%(weight most),
Manganese (Mn): mostly be 2.5%(weight most),
Phosphorus (P): mostly be 0.1%(weight most),
Sulphur (S): mostly be 0.025%(weight most),
Soluble aluminum (Sol.Al): mostly be 0.10%(weight most),
Nitrogen (N): mostly be 0.005%(weight most),
Remaining sum is iron (Fe) and follows impurity; Then
The described steel ingot of hot rolling is to prepare a kind of hot-rolled steel thin plate; Then
Cold rolling described hot-rolled steel thin plate, rate of compression are within 60～85% scopes, to prepare a kind of cold-rolled steel sheet; Then
Described cold-rolled steel sheet is carried out continuous annealing handle, comprise described cold-rolled steel sheet is heated to recrystallization temperature, then with its slow cooling; Then
Cold-rolled steel sheet to described continuous annealing in the acid electroplating groove carries out continuous nickel electroplating processes, and to form a nickel electrolytic coating, the nickel particle is with at least 1 * 10 in this layer
12/ rice
2Distribution density be deposited at least one surface of described cold-rolled steel sheet, the coating weight of described nickel electrolytic coating is that every square metre of described cold-rolled steel sheet surface is coated with 5～60 milligrams; Then
On its described at least one surface, there being the described cold-rolled steel sheet of described nickel electrolytic coating to immerse in a kind of neutral tank liquor or the alkaline tank liquor, so that on described nickel electrolytic coating, form the nickel oxide film of a mean thickness within 0.0005～0.003 micrometer range.
In the above-mentioned cold-rolled steel sheet and manufacture method thereof of having electroplated nickel, described cold-rolled steel sheet can further contain any in the column element down.
(1) titanium (Ti), quantity is 0.15%(weight the most nearly);
(2) niobium (Nb), quantity is 0.15%(weight the most nearly);
(3) titanium (Ti), quantity is 0.15%(weight the most nearly), and niobium (Nb), quantity is 0.15%(weight);
(4) titanium (Ti), quantity is 0.15%(weight the most nearly), and boron (B), quantity is 0.003%(weight the most nearly);
(5) niobium (Nb), quantity is 0.15%(weight the most nearly), and boron (B), quantity is 0.003%(weight the most nearly); And
(6) titanium (Ti), quantity is 0.15%(weight the most nearly), niobium (Nb), quantity is 0.15%(weight the most nearly), and boron (B), quantity is 0.003%(weight the most nearly).
Fig. 1 be illustrate the Lankford value of the common continuous annealing cold-rolled steel sheet that all do not have coating and common pack annealing cold-rolled steel sheet and ultimate extension than between the graphic representation of relation;
Fig. 2 is the graphic representation of the coating weight of explanation nickel electrolytic coating to the influence of phosphoric acid salt initial precipitation check figure order, nickel size distribution density, frictional coefficient and phosphate layer crystal size, and what its reflected is example of the present invention and the outer comparison example of the scope of the invention;
Fig. 3 is the graphic representation of relation between explanation Lankford value and the ultimate extension ratio, and what its reflected is example of the present invention and the outer comparison example of the scope of the invention;
Fig. 4 is the graphic representation of the mean thickness of explanation nickel oxide film to the influence of phosphate layer crystal size and frictional coefficient, and what its reflected is example of the present invention and the outer comparison example of the scope of the invention;
Fig. 5 is width of cloth scanning electronic microscope (SEM) Photomicrograph, and the phosphate layer crystalline structure that forms on pack annealing cold-rolled steel sheet surface is described;
Fig. 6 is width of cloth scanning electronic microscope (SEM) Photomicrograph, and the phosphate layer crystalline structure that forms on continuous annealing cold-rolled steel sheet surface is described;
Fig. 7 is width of cloth scanning electronic microscope (SEM) Photomicrograph, and the phosphate layer crystalline structure that forms on the sample surfaces of invention NO.7 is described, the coating weight of its nickel electrolytic coating is 23 milligrams/meter
2, the mean thickness of nickel oxide film is 17
(dust); With
Fig. 8 is width of cloth scanning electronic microscope (SEM) Photomicrograph, and the phosphate layer crystalline structure that forms on the sample surfaces of the Comparative Examples NO.10 outside the scope of the invention is described, the coating weight of its nickel coating is 23 milligrams/meter
2, the mean thickness of nickel oxide film is 75
(dust).
Carry out broad research from above-mentioned viewpoint, processed property excellence, cold-rolled steel sheet and the manufacture method thereof of having electroplated nickel in order to develop a kind of press formability and phosphatization. Obtained following achievement:
By forming the nickel electrodeposited coating that the regulation coating weight is arranged on the continuous annealing cold-rolled steel sheet surface that specific chemical composition is arranged, the nickel particle precipitates with specified distribution density in this layer, form the nickel oxide film with regulation average thickness on nickel electrodeposited coating surface then, at last this cold-rolled steel sheet being carried out phosphatization processes, form phosphate layer on the nickel oxide film surface, this phosphate layer becomes finer and close, has further improved lacquer cohesive and the decay resistance after the japanning.
The present invention carries out on above-mentioned achievement basis. Now, further describe of the present inventionly, have excellent press formability and phosphatization and process cold-rolled steel sheet and manufacture method thereof property, that electroplated nickel.
The chemical composition of cold-rolled steel sheet of the present invention is because of in the following reasons the is limited in above-mentioned scope.
(1) carbon:
Carbon content is higher than 0.06%(weight) understand the ductility of grievous injury cold-rolled steel sheet, thus cause plasticity relatively poor. On the other hand, carbon content is lower than 0.0005%(weight) can cause the steel refining time long, this is economically inadvisable.
(2) silicon and manganese:
Silicon and manganese added to need to be had in the high strength steel of the high press formability thin plate. Silicon and manganese are the elements that can strengthen this solid solution. Add silicon and manganese improved this cold-rolled steel sheet intensity and can its plasticity of grievous injury. Yet, because the easy oxidation of these elements, so silicone content is higher than 0.5%(weight) or manganese content be higher than 2.5%(weight) all can cause the oxidation on steel sheet surface, thereby damage the distinctive appearance of this cold-rolled steel sheet. On the other hand, silicone content is lower than 0.005%(weight) or manganese content be lower than 0.05%(weight) all can cause steel refining time of more growing, this is economically inadvisable.
(3) phosphorus:
Phosphorus has the function that improves cold-rolled steel sheet intensity. Yet phosphorus content is higher than 0.1%(weight) can cause the longitudinal fracture during the cold-rolled steel sheet deep draw. On the other hand, phosphorus content is lower than 0.001%(weight) can cause steel refining time of more growing, this is economically inadvisable.
(4) sulphur and nitrogen:
Lower sulfur content or lower nitrogen content all can improve the press formability of cold-rolled steel sheet. Yet sulfur content is higher than 0.025%(weight) or nitrogen content be higher than 0.005%(weight) economically all inadvisable. On the other hand, sulfur content is lower than 0.005%(weight) or nitrogen content be lower than 0.0005%(weight) all can cause steel refining time of more growing, this is economically inadvisable.
(5) soluble aluminum:
Soluble aluminum is to be contained in the steel as the residual aluminum (Al) as deoxidier. When at least 640 ℃ coil temperature and prepare the hot rolled thin coiled sheet with hot rolling technology, soluble aluminum has fixed nitrogen and improves the function of formability. By soluble aluminum content being adjusted at least 0.01%(weight), can obtain the aluminum killed steel of stabilized deoxy. Yet, along with soluble aluminum content surpasses 0.1%(weight), above-mentioned effect is just saturated.
(6) titanium and niobium:
If require cold-rolled steel sheet to have very high formability, just need to additionally be added into titanium and niobium. Titanium and niobium have the function that makes carbon and nitrogen fixing, therefore, add titanium and/or niobium in the oriented steel and make the IF steel and become possibility so that adopt. The content of titanium and niobium depends on the content of carbon and nitrogen. If the content of titanium and niobium surpasses respectively 0.15%(weight), also just can not obtain making carbon and the fixing intended effect of nitrogen, and run into economically disadvantageous situation. When titanium and niobium are lower than respectively 0.001%(weight) time, aforesaid effect can not be obtained.
(7) boron
The function of boron is to prevent longitudinal fracture, and this must take place in the cold-rolled steel sheet of the IF steel that contains titanium and/or niobium. But add the deep draw performance that boron improves cold-rolled steel sheet. Therefore, boron is additionally to add together with titanium and/or niobium as required. Yet boron content surpasses 0.003%(weight) can cause the ductility of cold-rolled steel sheet lower. On the other hand, if boron content is lower than 0.0002%(weight), just can not obtain aforesaid intended effect.
In the present invention, the nickel electrodeposited coating is to form on the continuous annealing cold-rolled steel sheet surface that above-mentioned chemical composition is arranged. The nickel particle is with at least 1 * 1012/ rice2Distribution density be deposited in the nickel electrodeposited coating, and the coating weight of nickel electrodeposited coating is 5～60 milligrams on every square metre of cold-rolled steel sheet surface. The reasons are as follows.
For the phosphatization property processed that improves the continuous annealing cold-rolled steel sheet, necessary is to play making salmoite (Zn3（PO
4）
2) and phosphorus chloritoid (Zn2Fe（PO
4）
2) negative electrode of precipitation nuclear effect of these phosphate crystals precipitation with certain Density Distribution on continuous annealing cold-rolled steel sheet surface, in order to generate the phosphate initial precipitation nuclear that is called local structure cell. Being distributed in the lip-deep negative electrode number of steel sheet equals by the element that is enriched in the steel sheet surface and being deposited at steel The local structure cell number that forms under the potential difference effect that nickel particle in the nickel electrodeposited coating that thin sheet surface forms produces.
In order to guarantee the rear excellent corrosion resistance of excellent lacquer cohesive and japanning, the granularity of the crystal grain of phosphate layer should be in certain scope, and for this reason, phosphate initial precipitation check figure purpose distribution density should be 1 * 1010～5×10
11/ rice2 In order to make phosphate initial precipitation check figure order reach above-mentioned distribution density, the distribution density that is deposited in the nickel particle in the nickel electrodeposited coating should be 1 * 1012～5×10
14/ rice2 In addition, in order to reach above-mentioned coprecipitated nickel hydroxide distribution of particles density, be necessary the coating weight of nickel electrodeposited coating is limited in the scope on 5～60 milligrams on every square meter cold-rolled steel sheet surface. By the coating weight of nickel electrodeposited coating is limited in the above-mentioned scope, just might be adjusted at least 1 * 10 to the distribution density that is deposited in the nickel particle in the nickel electrodeposited coating12/ rice2Thereby, guarantee that phosphatization processes necessary phosphate initial precipitation check figure order, thereby reduced coefficient of friction.
Therefore, the coating weight by restriction nickel electrodeposited coating and the distribution density of coprecipitated nickel hydroxide particle and getable phosphate crystal particle mean size is 1～3 micron, this equals the particle mean size of the phosphate crystal that forms on coffin annealing cold-rolled steel sheet surface. This is so that can reach gratifying lacquer bonding force and decay resistance after japanning.
Yet, if the coating weight of nickel electrodeposited coating is lower than 5 milligrams on every square metre of cold-rolled steel sheet surface, just can not adjust at least 1 * 10 to the distribution density of nickel particle12/ rice2, thereby can not guarantee that also phosphatization processes necessary initial precipitation check figure order. In addition, can not be reduced the intended effect of steel sheet skin-friction coefficient. On the other hand, if the coating weight of every square metre of nickel electrodeposited coating surpasses 60 milligrams, just above-mentioned effect reaches capacity, this can only cause waste. In addition, the coating weight of nickel electrodeposited coating is above 60 milligrams/meter2Can cause phosphate initial precipitation check figure order to reduce, this is a kind of ill-effect.
In the present invention, formed average thickness range on nickel electrodeposited coating surface at 0.0005～0.003 micron nickel oxide film. The reasons are as follows.
When forming the nickel electrodeposited coating on continuous annealing cold-rolled steel sheet surface, it is quite low that the hardness on steel sheet surface becomes. In order to increase the hardness on steel sheet surface, need to increase the coating weight of nickel electrodeposited coating. Yet, when increasing the coating weight of nickel electrodeposited coating, the distribution density of the nickel particle that wherein precipitates is remained in the appropriate scope. Therefore, in the present invention, the coating weight of nickel electrodeposited coating does not increase, but form one deck nickel oxide film on nickel electrodeposited coating surface, its average thickness range is 0.0005～0.003 micron, or more preferred scope is 0.001～0.002 micron, thereby increases the lubricity on steel sheet surface. This has just reduced the coefficient of friction on steel sheet surface. The average thickness of nickel oxide film is lower than 0.0005 micron just can not reach the intended effect that reduces coefficient of friction.
On the other hand, because nickel oxide film is a kind of electrical insulator, its average thickness can hinder flowing smoothly be used to the electric current that causes the phosphate crystal precipitation greater than 0.003 micron. Therefore, when processing to form one deck nickel oxide film by the anode electrolysis in neutral or alkaline tank liquor, if tank liquor concentration height or Faradaic current are big, then form the nickel oxide film of thick layer, not only on nickel electrodeposited coating surface so, and do not cover on the steel sheet surface portion of nickel electrodeposited coating also like this. The number that this has reduced phosphate initial precipitation nuclear causes more coarse phosphate crystal grain, thus the formation of the fine and close phosphate layer of overslaugh. For this reason, the average thickness of nickel oxide film should be limited in 0.0005～0.003 micron scope, or more preferably 0.001～0.002 micron.
Above-mentioned cold-rolled steel sheet manufacture method of having electroplated nickel of the present invention is as follows.
Prepare the steel ingot of a kind of chemical composition in the above-mentioned scope of the present invention. Then, with this steel ingot hot rolling, prepare a kind of hot-rolled steel thin plate.
Then, this hot-rolled steel thin plate is carried out cold rolling with the compression ratio in 60～85% scopes, prepare a kind of cold-rolled steel sheet. The cold-rolled compression ratio should be limited in 60～85% scopes. If the cold-rolled compression ratio is lower than 60% or be higher than 85%, this cold-rolled steel sheet does not possess sufficient deep draw.
Then, the cold-rolled steel sheet for preparing is thus carried out continuous annealing process, comprise this cold-rolled steel sheet is heated to recrystallization temperature, make it then Slow cooling.
Illustrating now continuous annealing of the present invention processes. More particularly, cold-rolled steel sheet is heated to recrystallization temperature, and keeps in this temperature a period of time of 3～10 minutes scopes. Then, the cold-rolled steel sheet with like this heating arrives about 50 ℃ temperature with the most nearly 5 ℃/second the cooling velocity Slow cooling according to the appropriate selection of steel grade.
Another embodiment that continuous annealing of the present invention is processed is as follows. Cold-rolled steel sheet is heated to recrystallization temperature, and kept 3～10 minutes in this temperature. Then, the cold-rolled steel sheet of like this heating being cooled to rapidly with at least 10 ℃/seconds cooling velocity can be up to 450 ℃ temperature. Then, the overaging of the temperature of this steel sheet in 250～400 ℃ of scopes being carried out 1～3 minute is processed. Then, this steel sheet being cooled to can be up to 50 ℃ temperature.
Why like this cold-rolled steel sheet being carried out continuous annealing and process, is owing to might reduce the operating time, can obtain qualitative uniformity, might improve product yield and productivity.
Subsequently, cold-rolled steel sheet through such continuous annealing is carried out continuous nickel electroplating processes in the acid electroplating tank liquor, at least one surface at this cold-rolled steel sheet forms the nickel electrodeposited coating, and its coating weight is 5～60 milligrams of every square meter cold-rolled steel sheets, and the nickel particle is with at least 1 * 10 in this layer12/ rice2Distribution density precipitation.
Can utilize displacement method to make the nickel solids precipitation on this cold-rolled steel sheet surface, this method comprises this cold-rolled steel sheet is immersed in the acidic bath, but for the nickel particle is stably precipitated with constant distribution density, should adopt electroplating processes.
Then, the cold-rolled steel sheet that has just formed the nickel electrolytic coating at least one surface like this is immersed in a kind of neutral tank liquor or the alkaline tank liquor, perhaps in this neutrality tank liquor or alkaline tank liquor, carries out anode electrolysis and handle.Like this, having formed one deck average thickness range on this nickel electrolytic coating surface is 0.0005～0.003 micron nickel oxide film.10 grams per liter yellow soda ash (Na
2CO
3) aqueous solution is applicable to as alkaline tank liquor.
Before continuous nickel electroplating processes, this cold-rolled steel sheet surface will be cleaned with acid wash on request.Why carry out pickling, be because there is direct heat oven the ingress of continuous annealing apparatus under many circumstances, at the rapid cooling zone middle part quick cooling apparatus such as water-chilling plant and air/water refrigerating unit are arranged, thereby, the atmospheric gas dew point rises and can produce the ferric oxide film on the steel sheet surface between heating period, and this may hinder the nickel particle to precipitate with perfect condition.Though adopt hydrochloric acid tank liquor immersion method to carry out pickling in these embodiments, utilize sulfuric acid tank liquor immersion method or in the dilute sulphuric acid tank liquor electrolysis treatment carry out pickling and do not damage essence of the present invention.
Now, by means of example, with the comparative example contrast, further describe the present invention simultaneously.
Example
B～G level steel that each chemical constitution of refining is as shown in table 2 is equipped with plate slab from B～G level steel respectively with continuous casting process then.Then, with the plate slab hot rolling of making thus, preparation has the hot-rolled steel thin plate of specific thickness respectively.Wherein the finishing temperature of every kind of hot-rolled steel thin plate is to be at least the wherein Ar of every kind of steel
3The temperature of transition point, and the temperature of coiling in the hot rolling is 730 ℃ to B～E and G level steel, is 560 ℃ to F level steel.Then, this hot-rolled steel thin plate is carried out pickling, to remove the scale of this hot-rolled steel thin sheet surface with the chlorohydric acid pickling method.
Then, under condition as shown in table 4, the hot-rolled steel thin plate through overpickling is carried out cold rolling, prepare thickness range respectively and be 0.8～1.0 millimeter cold-rolled steel sheet.Then, under condition as shown in table 4 this cold-rolled steel sheet being carried out continuous annealing handles.Then, the cold-rolled steel sheet of like this continuous annealing is immersed in the acid tank liquor that contains hydrochloric acid as shown in table 3, so that carry out pickling under condition as shown in table 3.
Then, the cold-rolled steel sheet of wherein each pickling is placed nickel bath solution as shown in table 3, handle according to carrying out continuous electroplating under the condition shown in the table 3.Then, the cold-rolled steel sheet that has formed the nickel electrolytic coating is thereon placed sodium bicarbonate (NaHCO
3) in the aqueous solution, under condition as shown in table 3, carry out anode electrolysis and handle, so that on this nickel electrolytic coating surface, form nickel oxide film.It is cold rolling that all cold-rolled steel sheets that formed nickel electrolytic coating and nickel oxide film on its surface are hardened with about 1.0% ratio of elongation, electroplated cold-rolled steel sheet sample (hereinafter to be referred as " the sample of the present invention ") № 1～12 of nickel in the preparation scope of the invention.
For relatively, utilize the D and the E level steel that respectively have chemical constitution in the scope of the invention as shown in table 2, prepared cold-rolled steel sheet sample (hereinafter to be referred as " comparative sample ") № .1～13 that the scope of the invention has been electroplated nickel outward.Comparative sample № .1～13 are as shown in table 5, and the coating weight of its nickel electrolytic coating or the mean thickness of nickel oxide film are all outside scope of the present invention.
To sample NO.1 of the present invention～12 of preparation thus and each in comparative sample NO.1～13, all according to following Study on Test Method the frictional coefficient (μ) on steel sheet surface, ultimate extension is than (LDR), Lankford value (r value), bonderizing, the mean thickness of nickel particulate distribution density and nickel oxide film in the nickel electrolytic coating.The results are shown in table 4 and 5.
The testing method of steel sheet skin friction coefficient:
Every kind of sample from sample NO.1 of the present invention～12 and comparative sample NO.1～13 downcuts and is of a size of 30 millimeters * 200 millimeters test piece.Test piece is placed on the deflector roll, then under the pressure of 400 kgfs a pressurizing member that is of a size of 3 millimeters * 10 millimeters from being pressed onto the surface of test piece.Then, in this state, test piece is extracted out, measure this tensile force f (kgf) constantly, and calculate coefficientoffriction=400/F from the tensile force f of measuring thus with 1000 meters/minute speed.By means of the about 3 microns bort of granularity with the rectangular direction of slip direction on make the lower surface of pressurizing member have surfaceness in advance.
The testing method of ultimate extension ratio:
Respectively downcut a plurality of disks from sample NO.1 of the present invention～12 and comparative sample NO.1～13 with different diameter.Then, utilizing a diameter is drift and these disks of die stamping of 50 millimeters.The disk maximum diameter that produces fracture on the disk as yet is defined as the ultimate extension ratio with the ratio of punch diameter.When measure this ultimate extension than the time, commercially available rust-proof oil is coated on disk, drift and the mould as lubricant.
The testing method of Lankford value:
To each sample in sample NO.1 of the present invention～12 and comparative sample NO.1～13, before forming the nickel electrolytic coating, measure Lankfod value (r value) with a kind of currently known methods.
The testing method of bonderizing:
Each sample in sample NO.1 of the present invention～12 and comparative sample NO.1～13 a kind of bonderizing solution (Japan PerkeriZing Co., Ltd. makes; PB-3030) submergence is 15 seconds in, then rinsing and drying.Observe the surface of each sample in the sample of the present invention of above-mentioned submergence in bonderizing solution and the comparative sample by means of scanning electron microscope, to measure phosphoric acid salt initial precipitation check figure order.In addition, in each sample in sample of the present invention and the comparative sample 120 seconds of submergence in above-mentioned bonderizing solution, so that on this steel sheet surface, be completed into phosphate layer, and observe by means of scanning electron microscope, so that measure the granularity of phosphoric acid salt crystal grain and the outward appearance of phosphate layer.The phosphate layer outward appearance is assessed according to following standard:
◎: the granularity of phosphoric acid salt crystal grain is in 1.5～2.5 microns scope, and the deposition of phosphate layer is abundant;
⊙: the granularity of phosphoric acid salt crystal grain 1.0～＜1.5 microns or＞2.5～3.0 microns scope in, and the deposition of phosphate layer is abundant;
△: the granularity of phosphoric acid salt crystal grain＞3.0 micron, and the deposition of phosphate layer is abundant;
*: the granularity of phosphoric acid salt crystal grain＞3.0 micron, and the deposition of phosphate layer is insufficient.
Phosphate layer is peeled off with contrary electrolytic process, so that determine the deposition of phosphate layer according to the weight difference between before and after peeling off.
The measuring method of the mean thickness of nickel particulate distribution density and nickel oxide film in the nickel electrolytic coating:
Nickel particulate distribution density is by utilizing extraction transfer printing (extraction replica method) extraction precipitation to measure at the lip-deep nickel of this steel sheet, observe by means of transmission electron microscope then.The mensuration of nickel oxide film mean thickness is undertaken by using Anger electronics optical spectroscopy.
Table 3
| Method | Tank liquor is formed | Temperature | Current density |
| Pickling | HCl 50g/l | 50±5℃ | _____ |
| The Ni plating | NiSO 4?·6H 2O 240g/l NiCl 2·6H 2O 45g/l H 3BO 3 30g/l PH 2.5-3.5 | 40±5℃ | -1.0-3.0 A/dm 2 |
| The nickel oxide film forming | NaHCO 3 20g/l | 25±5℃ | 0.1-1.0 A/dm 2 |
As shown in table 4 and 5, the mean thickness of the coating weight of its nickel electrolytic coating, nickel particulate distribution density and nickel oxide film all within the scope of the present invention sample № .1 of the present invention～12 is gratifying test result, and has excellent press formability and bonderizing.
On the contrary, the low coating weight of its nickel electrolytic coating is outside the scope of the invention and the also comparative sample № .1 outside the scope of the invention of the low distribution density of nickel particulate, present great friction coefficient and big phosphate crystal granularity, cause inferior press formability and bonderizing.
Comparative sample № .2～5 that the nickel oxide film mean thickness hangs down scope of the present invention show as the high and ultimate extension ratio deficiency of frictional coefficient, have caused inferior press formability thus.
The nickel oxide film mean thickness hangs down the comparative sample 6～11 of scope of the present invention, and its phosphate crystal granularity is big, and phosphate layer deposition deficiency, and this has also caused inferior phosphorization treatment performance.
The coating weight of nickel electrolytic coating is big, and nickel size distribution density is low, and both have all exceeded the comparative sample 12 and 13 of scope of the present invention, and it is big to show as the phosphate crystal granularity, therefore causes bonderizing inferior.
Fig. 2 is the graphic representation of the coating weight of width of cloth explanation nickel electrolytic coating to the influence of phosphoric acid salt initial precipitation check figure order, nickel particulate distribution density, frictional coefficient and phosphate layer crystal size, is used to explain example of the present invention and the outer Comparative Examples of the scope of the invention.In Fig. 2, symbol " zero " is represented sample of the present invention, symbol "
" represent comparative sample.In Fig. 2, pointed out in the scope of the phosphate layer crystal size that forms from H level steel cold-rolled steel sheet that be equipped with, that electroplated nickel surface and the scope of frictional coefficient with arrow.Fig. 2 shows, if the coating weight of this nickel electrolytic coating within the scope of the invention, its phosphoric acid salt initial precipitation check figure order, nickel particulate distribution density, frictional coefficient and phosphate crystal granularity all can reach the gratifying result as in the pack annealing cold-rolled steel sheet.
Fig. 3 be the Lankford value of width of cloth explanation example of the present invention and the outer Comparative Examples of the scope of the invention and ultimate extension than between the graphic representation of relation.In Fig. 3, symbol " zero " is represented sample of the present invention, and " ● " represents comparative sample, and " △ " representative does not have the continuous annealing cold-rolled steel sheet of electronickelling.Fig. 3 shows that Lankford value and ultimate extension are than all there being difference between example of the present invention and comparison example.
Fig. 4 is the graphic representation of the mean thickness of width of cloth explanation sample of the present invention and the outer comparison example nickel oxide film of the scope of the invention to the influence of phosphate layer crystal size and frictional coefficient.In Fig. 4, symbol " zero " is represented sample of the present invention, and symbol " ● " is represented comparative sample.In Fig. 4, the scope at the phosphate layer crystal size that forms from F level steel cold-rolled steel sheet surface that be equipped with, that electroplated nickel and the scope of frictional coefficient have been pointed out with arrow.Fig. 4 shows, though the coating weight of this nickel electrolytic coating within the scope of the invention, if the mean thickness of nickel oxide film is lower than scope of the present invention, it is higher that frictional coefficient also can become.On the other hand, if the mean thickness of nickel oxide film is lower than scope of the present invention, it is bigger that the granularity of phosphate crystal will become, thereby cause inferior bonderizing.
According to the present invention as detailed above, might obtain being suitable for using continuous annealing processing, press formability and bonderizing excellence, be used for deep draw processing, electroplated the cold-rolled steel sheet of nickel, and manufacture method, thereby industrial useful effect obtained.
Claims (18)
1, a kind of plating with excellent press formability and bonderizing the cold-rolled steel sheet of nickel, comprising:
A kind of cold-rolled steel sheet that following essentially consist is arranged:
Carbon (C): reach 0.06% (weight) most,
Silicon (Si): reach 0.5% (weight) most,
Manganese (Mn): reach 2.5% (weight) most,
Phosphorus (P): reach 0.1% (weight) most,
Sulphur (S): reach 0.025% (weight) most,
Soluble aluminum (Sol, Al): reach 0.10% (weight) most,
Nitrogen (N): reach 0.005% (weight) most,
Remaining sum is iron (Fe) and follows impurity;
A kind of nickel electrolytic coating that forms at least one surface of described cold-rolled steel sheet, the nickel particle is with at least 1 * 10 in this layer
12/ rice
2Distribution density precipitation, the coating weight of described nickel electrolytic coating is that every square metre of described cold-rolled steel sheet surface is 5～60 milligrams; With
The nickel oxide film that forms on described nickel electrolytic coating surface, its mean thickness is at 0.0005～0.003 micron.
2, according to the plating of claim 1 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) titanium (Ti) of quantity.
3, according to the plating of claim 1 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) niobium (Nb) of quantity.
4, according to the plating of claim 2 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) niobium (Nb) of quantity.
5, according to the plating of claim 2 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
6, according to the plating of claim 3 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
7, according to the plating of claim 4 cold-rolled steel sheet of nickel, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
8, according to the plating of claim 1 cold-rolled steel sheet of nickel, wherein:
The mean thickness of described nickel oxide film is in 0.001～0.002 micrometer range.
9, a kind ofly be used to make the method that has excellent press formability and bonderizing, electroplated the cold-rolled steel sheet of nickel, comprise the following steps:
Prepare a kind of steel ingot that following essentially consist is arranged:
Carbon (C): reach 0.06%(weight most),
Silicon (Si): reach 0.5%(weight most),
Manganese (Mn): reach 2.5%(weight most),
Phosphorus (P): reach 0.1%(weight most),
Sulphur (S): reach 0.025%(weight most),
Soluble aluminum (Sol.Al): reach 0.10%(weight most),
Nitrogen (N): reach 0.005%(weight most),
Remaining sum is iron (Fe) and incidental impurities; Then
The described steel ingot of hot rolling is to prepare a kind of hot-rolled steel thin plate; Then
With the cold rolling described hot-rolled steel thin plate of the compression ratio in 60～85% scopes, to prepare a kind of cold-rolled steel sheet; Then
Described cold-rolled steel sheet is carried out continuous annealing handle, comprise that described cold-rolled steel sheet is heated to recrystallization temperature makes it slow cooling then; Then
Cold-rolled steel sheet to described continuous annealing in the acid electroplating tank liquor carries out continuous nickel electroplating processes, so that form the nickel electrolytic coating at least one surface of described cold-rolled steel sheet, the nickel particle is with at least 1 * 10 in this layer
12/ rice
2Distribution density precipitation, the coating weight of described nickel electrolytic coating is that every square metre of described cold-rolled steel sheet surface is 5～60 milligrams, then
The described cold-rolled steel sheet that described nickel electrolytic coating is arranged at least one surface is immersed in a kind of neutral tank liquor or the alkaline tank liquor, and formation one deck average thickness range is 0.0005～0.003 micron a nickel oxide film on described nickel electrolytic coating.
10, according to the method for claim 9, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) titanium (Ti) of quantity.
11, according to the method for claim 9, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) niobium (Nb) of quantity.
12, according to the method for claim 10, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.15%(weight) niobium (Nb) of quantity.
13, according to the method for claim 10, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
14, according to the method for claim 11, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
15, according to the method for claim 12, wherein:
Described cold-rolled steel sheet additionally contains the most nearly 0.003%(weight) boron (B) of quantity.
16, according to the method for claim 9, wherein:
There is the described cold-rolled steel sheet of described nickel electrolytic coating in described neutral tank liquor or described alkaline tank liquor, to carry out the anode electrolysis processing.
17, according to the method for claim 9, wherein:
The surface of described cold-rolled steel sheet was cleaned with acid wash before described continuous nickel electroplating processes.
18, according to the method for claim 9, wherein:
The mean thickness of described nickel oxide film is within 0.001～0.002 micrometer range.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3025695A JPH04247849A (en) | 1991-01-25 | 1991-01-25 | Cold rolled steel sheet excellent in press formability and phosphating property and its manufacture |
| JP25695/91 | 1991-01-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1065690A true CN1065690A (en) | 1992-10-28 |
Family
ID=12172930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100427A Pending CN1065690A (en) | 1991-01-25 | 1992-01-25 | Nickel electroplated cold-rolled steel sheet and preparation method thereof |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0496423A1 (en) |
| JP (1) | JPH04247849A (en) |
| KR (1) | KR920014947A (en) |
| CN (1) | CN1065690A (en) |
| AU (1) | AU638371B2 (en) |
| BR (1) | BR9200205A (en) |
| CA (1) | CA2058678A1 (en) |
| ZA (1) | ZA92202B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306056C (en) * | 2003-08-01 | 2007-03-21 | 住友金属工业株式会社 | Low-carbon free cutting steel |
| CN100376707C (en) * | 2003-04-01 | 2008-03-26 | 江苏江南铁合金有限公司 | Ferrotitanium with low silicon and its preparation method |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2810245B2 (en) * | 1991-01-25 | 1998-10-15 | 日本鋼管株式会社 | Cold rolled steel sheet excellent in press formability and phosphatability and method for producing the same |
| JP3300673B2 (en) * | 1998-07-01 | 2002-07-08 | 日本パーカライジング株式会社 | Method and apparatus for quickly forming a phosphate coating on steel wire |
| DE102006029817A1 (en) * | 2006-06-28 | 2008-01-03 | Siemens Ag | Sheet metal and method for producing a metal sheet |
| DE102006035974A1 (en) * | 2006-08-02 | 2008-02-07 | Robert Bosch Gmbh | Process for phosphating a metal layer |
| JP4893540B2 (en) * | 2007-09-03 | 2012-03-07 | 住友金属工業株式会社 | Dull steel plate and manufacturing method thereof |
| US10201953B2 (en) | 2012-04-19 | 2019-02-12 | Nippon Steel & Sumitomo Metal Corporation | Steel foil and method for manufacturing the same |
| DE102013017798A1 (en) * | 2013-10-25 | 2015-04-30 | GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) | Composite steel plate |
| CN108026617B (en) | 2015-09-25 | 2020-03-24 | 日本制铁株式会社 | Steel plate |
| KR102326687B1 (en) * | 2019-12-17 | 2021-11-17 | 주식회사 포스코 | High strength cold steel sheet with good phosphating property and method for manufacturing the same |
| KR102493773B1 (en) * | 2020-12-21 | 2023-01-30 | 주식회사 포스코 | Steel sheet having high phospatability and manufacturing method of the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51151635A (en) * | 1975-06-23 | 1976-12-27 | Nippon Steel Corp | Process for producing chromateetreated steel sheet having nickel diffused underlayer |
| JPS6176621A (en) * | 1984-09-25 | 1986-04-19 | Kawasaki Steel Corp | Manufacture of ultralow carbon cold rolled steel sheet superior in phosphate treatability and formability |
| JPH06104918B2 (en) * | 1988-10-07 | 1994-12-21 | 日本鋼管株式会社 | Cold-rolled steel sheet with excellent phosphatability and corrosion resistance |
| JPH02163344A (en) * | 1988-12-15 | 1990-06-22 | Kawasaki Steel Corp | Cold rolled steel sheet for deep drawing excellent in die galling resistance |
| JPH0756050B2 (en) * | 1989-05-30 | 1995-06-14 | 新日本製鐵株式会社 | Manufacturing method of high strength cold rolled steel sheet for non-aging, high bake hardening and press working by continuous annealing |
| JP2810245B2 (en) * | 1991-01-25 | 1998-10-15 | 日本鋼管株式会社 | Cold rolled steel sheet excellent in press formability and phosphatability and method for producing the same |
-
1991
- 1991-01-25 JP JP3025695A patent/JPH04247849A/en active Pending
-
1992
- 1992-01-02 CA CA002058678A patent/CA2058678A1/en not_active Abandoned
- 1992-01-09 AU AU10137/92A patent/AU638371B2/en not_active Expired - Fee Related
- 1992-01-10 ZA ZA92202A patent/ZA92202B/en unknown
- 1992-01-15 KR KR1019920000473A patent/KR920014947A/en not_active Application Discontinuation
- 1992-01-23 BR BR929200205A patent/BR9200205A/en not_active Application Discontinuation
- 1992-01-24 EP EP92101186A patent/EP0496423A1/en not_active Withdrawn
- 1992-01-25 CN CN92100427A patent/CN1065690A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376707C (en) * | 2003-04-01 | 2008-03-26 | 江苏江南铁合金有限公司 | Ferrotitanium with low silicon and its preparation method |
| CN1306056C (en) * | 2003-08-01 | 2007-03-21 | 住友金属工业株式会社 | Low-carbon free cutting steel |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA92202B (en) | 1992-10-28 |
| JPH04247849A (en) | 1992-09-03 |
| AU638371B2 (en) | 1993-06-24 |
| EP0496423A1 (en) | 1992-07-29 |
| CA2058678A1 (en) | 1992-07-26 |
| KR920014947A (en) | 1992-08-26 |
| AU1013792A (en) | 1992-08-06 |
| BR9200205A (en) | 1992-10-06 |
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