CN101048527A - Hot-dip galvanized steel sheet and manufacturing method therefor - Google Patents
Hot-dip galvanized steel sheet and manufacturing method therefor Download PDFInfo
- Publication number
- CN101048527A CN101048527A CN 200580036387 CN200580036387A CN101048527A CN 101048527 A CN101048527 A CN 101048527A CN 200580036387 CN200580036387 CN 200580036387 CN 200580036387 A CN200580036387 A CN 200580036387A CN 101048527 A CN101048527 A CN 101048527A
- Authority
- CN
- China
- Prior art keywords
- comparative example
- hot
- steel
- steel plate
- dip galvanizing
- 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
Images
Landscapes
- Coating With Molten Metal (AREA)
Abstract
A hot dip zinc plated steel sheet which comprises a steel sheet containing 0.1 to 3.0 mass % of Si, a hot dip zinc plating layer, and, formed between said steel sheet and said hot dip zinc plating layer, a layer enriched in at least one component of selected from the group consisting of S, C, Cl, Na, K, B, P, F and N which contains an oxide containing Si and has a thickness of 0.01 to 100 [mu]m. Said hot dip zinc plated steel sheet is free from the non-plating phenomenon, exhibits fine surface appearance and is excellent in the adhesion of a plating layer and sliding characteristics, although it uses a base steel sheet having a relatively great Si content. Further, an alloyed hot dip zinc plated steel sheet produced by alloying said hot dip zinc plated steel sheet is excellent also in the resistance to powdering.
Description
Technical field
The present invention relates to a kind of hot-dip galvanizing sheet steel and manufacture method thereof, described hot-dip galvanizing sheet steel can be fit in fields such as automobile, building materials and household electrical appliances use.Even particularly relate to a kind ofly when being starting material with the many steel of Si content, also having both has the good adherence of coating and the hot-dip galvanizing sheet steel of sliding.And relate to and a kind of this hot-dip galvanizing sheet steel is carried out the alloyed zinc hot dip galvanized of alloying.
Background technology
In recent years, in fields such as automobile, building materials and household electrical appliances, used the surface treated steel plate of sheet stock having been given rust-preventing characteristic usually.Wherein, the hot-dip galvanizing sheet steel that usually use can be made at an easy rate and rust-preventing characteristic is good or it has been carried out the alloyed hot-dip galvanized steel sheet of alloying.
In general, hot-dip galvanizing sheet steel is by following operation manufacturing.After steel billet carried out hot rolling, further implement cold rolling or thermal treatment, obtain steel sheet.With pretreatment procedure degreasing and/or pickling are carried out in this steel-sheet surface and wash, or after omitting pretreatment procedure and removing the oil content of surface of thin steel sheet in the preheating oven internal combustion, in non-oxidizable environment or reductibility environment, implement recrystallization annealing, make the base steel sheet that coating is used.Then, in non-oxidizable environment or reductibility environment, base steel sheet is cooled to the temperature that is suitable for coating after, do not contact during pot galvanize that atmosphere impregnated in the Al (being generally about 0.1～0.2 quality %) that is added with trace bathes, make thus.In addition, by the steel plate after the pot galvanize is continued to heat-treat alloying heat-transmission steel plate galvanized in alloying furnace.
But, in recent years,, sought the high strength of base steel sheet itself for slimming (lightweight) and the high strength equilibrium that makes steel plate.Implement pot galvanize in such base steel sheet, the usage quantity that has both the high-strength hot-dip zinc-coated steel sheet of rust-preventing characteristic increases.
As steel plate high strength method, in steel, add Si and solution strengthening elements such as Mn, P.Wherein, because Si has the advantage of the ductility ground high strength that can not damage steel, be hopeful as high tensile steel plate so contain the Si steel plate.
But there are the following problems to contain hot-dip galvanizing sheet steel that the Si high tensile steel plate is substrate and alloyed hot-dip galvanized steel sheet.
As mentioned above, the base steel sheet of pot galvanize is implemented pot galvanize in the reductibility environment, after annealing under the temperature about 600～900 ℃.But, because the Si in the steel is the easily oxidizable element, so in the general reductibility environment that uses, optionally carry out on the base steel sheet surface enrichment taking place in the surface oxidation formation oxide compound.The wettability of the fused zinc when making such Si oxide compound and electroplating processes reduces, and produces the situation of not plating.Therefore, make the Si concentration in the steel high more for high strength, wettability reduces more, and the situation of not plating often takes place.In addition, the problem of existence is, even under the situation that does not reach the degree that plating do not go up, also can make the adherence of coating deterioration.
And, when the Si in the steel optionally carries out surface oxidation when being enriched in the surface, because the oxide compound of Si hinders the alloying reaction of Zn and Fe, so the alloying process interalloyization after pot galvanize postpones significantly.Its result hinders productive rate significantly.On the other hand, when under high temperature more, carrying out Alloying Treatment, take place easily because of crossing the powdered that alloying causes in order to ensure productive rate.Therefore, be difficult to make high yield and good chalking resistance equilibrium.
To this problem, motion has following resolution policy.
For example, motion is in No. 2587724 communique of Japanese Patent, in the preoxidation environment steel plate is heated, and after the surface forms ferric oxide, carries out reduced anneal, improves the wettability with pot galvanize thus.
This technology is by forming this ferric oxide at surface of steel plate, the surface enrichment of the Si during in the hope of the inhibition reduced anneal.But, as is generally known, follow the increase of the Si concentration in the steel, the oxidation rate of the iron of surface of steel plate significantly reduces.For example, be steel plate more than the 0.1 quality % for the Si concentration in the steel, only can not fully carry out the oxidation of iron with the disclosed method for oxidation of this communique, be difficult to obtain ferric oxide for the surface enrichment requirement that suppresses Si.
Its result, the generation that situation is not gone up in the plating in the time of can not fully suppressing pot galvanize.In addition, when alloying is carried out in this pot galvanize, can not fully solve the problem that the alloying that might take place significantly postpones and so in alloying process.
When alloying speed is slow,, just must improve the alloying temperature if want in the CGL of the furnace superintendent that limits alloying furnace, to maintain certain productive rate.But,, will cause the deterioration of aforesaid chalking resistance inevitably if at high temperature carry out alloying.
In addition, during Si surface enrichment when not having fully to suppress reduced anneal, can significantly hinder the homogeneity of the alloying reaction of Zn and Fe.Its result, coating surface is caused the concavo-convex remarkable of zn-fe alloy layer, the remarkable deterioration of the sliding during extrusion molding by heterogeneous alloyization.
In addition, for example, in Japanese kokai publication hei 11-50223 communique, disclose following method: before hot dip, make sulphur or sulphur compound count 0.1～1000mg/m with the S amount
2After adhering to, under weak acid environment, carry out preheating procedure, then, in containing the non-oxidizable environment of hydrogen, anneal.
And, in TOHKEMY 2001-279410 communique, disclose following technology: on the surface of the high-tensile steel that contains Mn, P, Si, by making the ammonium salt that contains S in S conversion 0.1～1000mg/m
2Adhere to the back and implement thermal treatment, in the base steel of steel plate, make the diffusion of S composition, with the sulphur compounds such as Mn reaction generation MnS in the steel.Utilize this method, in the surface enrichment that suppresses Mn, by the existence of sulphur enriched layer, blocking suppresses the surface enrichment of Si to the diffused line of the surface of steel plate of Si.
These technology all are to utilize sulfurized layer that surface of steel plate forms in the hope of improving with the wettability of fused zinc.But the inventor understood, when this technology being applied to the high steel plate of Si concentration in the steel, only uses the effect that is produced by sulfurized layer can not fully suppress the surface enrichment of Si.Therefore, same with above-mentioned situation, can not solve the problem of the performance of coating.In addition, still same during the high steel plate of the Si concentration in being applied to steel even under the weak oxide environment, carry out preheating procedure with above-mentioned situation, can not solve the problem of chalking resistance and sliding.
And, because these technology made sulphur or sulphur compound be attached to surface of steel plate before thermal treatment, so in ensuing heat treatment step, the sulphur composition is emitted in a large number with corrosive gasess such as sulfurous gas and hydrogen sulfide in process furnace.Therefore, the corrosion damage of equipment is serious in heating furnace body and the stove, except the frequent repairing of needs and deterioration are upgraded, when furnace gas is discharged into the atmosphere, considers from the viewpoint of air conservation, also desulfurizer must be set.Therefore, in order to realize the explained hereafter of these technology, be necessary further improvement.
The present invention develops in view of above-mentioned practical situation, its purpose is, a kind of hot-dip galvanizing sheet steel and manufacture method thereof are provided, when even described hot-dip galvanizing sheet steel is substrate to contain high Si steel plate, automotive sheet as requiring strict especially composite coating properties also has both good adherence of coating and the sliding that can restrain oneself fully.And, a kind of alloyed hot-dip galvanized steel sheet that has both good chalking resistance also is provided.
Summary of the invention
That is, the present invention relates to a kind of hot-dip galvanizing sheet steel, it has: steel plate, and it contains the Si of 0.1～3.0 quality %; Hot galvanized layer; And enriched layer, between this steel plate and this hot galvanized layer, containing the oxide compound of Si, thickness is 0.01～100 μ m, and has at least a kind of composition that is selected among S, C, Cl, Na, K, B, P, F and the N.
Need to prove that this hot-dip galvanizing sheet steel is preferred: the concentration of this composition of this steel plate of concentration ratio of this composition of this enriched layer is high more than 10%.
In addition, these hot-dip galvanizing sheet steels are preferred: the amount of the oxide compound that contains this Si of this enriched layer converts with oxygen and counts 0.01～1g/m
2
And above-mentioned any hot-dip galvanizing sheet steel is preferred: also have the Fe layer under this hot galvanized layer.
In addition, above-mentioned any hot-dip galvanizing sheet steel is preferred: this enriched layer is that the compound of the composition of this composition and this steel plate disperses to form, especially more preferably this composition is S, as the granulous MnS more than the particle diameter 50nm of this compound, the per 20 μ m on the direction at the interface that is parallel to this pot galvanize and this steel plate exist more than 5 for arbitrary section.
In addition, in above-mentioned any hot-dip galvanizing sheet steel, preferably this pot galvanize is alloyed zinc hot dip galvanized.
And, the present invention relates to a kind of manufacture method of hot-dip galvanizing sheet steel, it has following operation successively: at the surface of steel plate that contains Si 0.1～3 quality %, adhere to the operation of at least a kind of material that is selected from S, C, Cl, Na, K, B, P, F, N and their compound; The steel plate that is attached with this material is heated, and forming rhombohedral iron ore content at this surface of steel plate is the operation of the oxide film thereon below the 70 quality %; With this oxide film thereon reductive operation; And will reduce the operation that good steel plate carries out pot galvanize.
Need to prove, in this manufacture method, for Fe, preferably under oxidative environment, carry out this heating under surpassing 500 ℃ at the Da Wendu that is up to of steel plate.
And, in above-mentioned any method, preferably after this pot galvanize operation, further carry out Alloying Treatment.
In addition, the present invention relates to a kind of manufacture method of hot-dip galvanizing sheet steel, it is characterized in that, with the steel plate that contains Si 0.1～3.0 quality % is substrate, before pot galvanize is implemented on the surface of this steel plate, form rhombohedral iron ore content on the surface of base steel sheet and be the oxide film thereon below the 70 quality %, then reduce and handle the back and implement pot galvanize.
Description of drawings
The figure of one example of Fig. 1 depth profile (Depth Profile) that to be expression obtain by the linear analysis that utilizes EPMA the cross section of alloyed hot-dip galvanized steel sheet.
The figure of one example of Fig. 2 depth profile that to be expression obtain by GDS the top layer of alloyed hot-dip galvanized steel sheet.
Embodiment
Below, specifically describe the present invention.
The present inventor painstakingly studies repeatedly in order to address the above problem.It found that: in order to stop Si in the steel at surface enrichment, by under hot galvanized layer, generating the enriched layer of element-specific, and in this enriched layer, generate the oxide compound that contains Si, also improve greatly even the many steel plates of Si content have been implemented the tack of hot galvanized layer.But also find that the existence of the oxide compound by containing described Si and the enriched layer of this element-specific can promote uniform alloying, and suppressing the concavo-convex formation of coating and smoothing, the result also significantly improves sliding.
The present inventor to the Si concentration that is used for suppressing steel be the steel plate more than the 0.1 quality % plating not, after the method for promotion alloying is painstakingly studied repeatedly when seeking adherence of coating, obtain as drawing a conclusion: under the high situation of the Si of steel plate concentration, even only form the ferric oxide of q.s that can promotes oxidn, the wettability with fused zinc can not be improved fully, the situation of not plating can not be suppressed fully.
Therefore, further study repeatedly, found that: on the basis of the ferric oxide that is formed with q.s, the composition of its ferric oxide also is important.That is, under the high situation of the Si of steel plate concentration, the composition of the ferric oxide that the surface forms when making the steel plate oxidation by being controlled at can achieve the above object, and then finish the present invention.
Promptly, invented a kind of manufacture method of hot-dip galvanizing sheet steel, it has following operation successively: containing the surface that Si is the steel plate of 0.1～3 quality %, adhering to the operation that is selected from least a kind of material in the family that is made of S, C, Cl, Na, K, B, P, F, N and their compound; The steel plate that is attached with this material is heated, and forming rhombohedral iron ore content at this surface of steel plate is the operation of the oxide film thereon below the 70 quality %; With this oxide film thereon reductive operation; And will reduce the operation that good steel plate carries out pot galvanize.
At first, the one-tenth of the coating raw sheet (base steel sheet) among the present invention is grouped into describes.
In the present invention, the Si content in the base steel sheet is defined in the scope of 0.1～3.0 quality %.Its reason is that when being base steel sheet with the many steel of Si content, adherence of coating and sliding are a problem, but in order to improve the intensity of steel plate, needs the Si amount of this degree.Other reason also is, in order to generate the oxide compound of the aforesaid Si of containing, needs to contain in the basis Si.If the Si content in the steel is lower than 0.1 quality %, then below coating, can not form the oxide compound of the aforesaid Si of containing fully, can not obtain effect of the present invention.
Need to prove, in the present invention, the element beyond the Si is not particularly limited, can utilize present known composition to be.The representative composition is carried out following narration.
Below the C:0.5 quality %
C is the element that contains in the steel, and its content is in the scope of 0.0001～0.5 quality % usually.The C that also can in base steel sheet, contain in the present invention, this scope.In addition, C is not only useful to high strength, and, balanced and also be useful element when generating retained austenite etc. and carrying out organizational controls in order to improve strength-ductility.In order to manifest their effect, preferably contain more than the 0.05 quality %.On the other hand, C content is that the following steel plate of 0.25 quality % is because weldability is also good, so preferred.
Below the Mn:5 quality %
Mn is the element useful to high strength, can contain the Mn of this scope in the scope below 5 quality % in base steel sheet.Particularly, can bring into play its effect by containing the Mn more than the 0.1 quality %, more than the preferred 0.5 quality %.Mn is also same with Si, is the element that forms oxide film in when annealing, and its content is the following steel plates of 3.0 quality %, and the enriched layer of formation element-specific and when containing the oxide compound of Si below coating might improve adherence of coating.In addition, also help and guarantee its weldability and strength-ductility equilibrium.Therefore, preferred Mn content is below the 3.0 quality %.The scope of 0.5～3.0 quality % more preferably.
Below the Al:5.0 quality %
Al replenishes the element that adds with Si, preferably contains more than 0.01%.On the other hand, Al amount is the following steel plates of 5.0 quality %, and the enriched layer of formation element-specific and when containing the oxide compound of Si below coating might improve adherence of coating.In addition, also help and guarantee its weldability and strength-ductility equilibrium.Therefore, preferred Al is below the 5.0 quality %.The scope of 0.01～3.0 quality % more preferably.
More than in the steel beyond the illustrative element element for example have: Ti, Nb, V, Cr, S, Mo, Cu, Ni, B, Ca, N, P and Sb etc.The content of these elements is just confirmed to obtain effect of the present invention so long as reach Ti:1 quality %, Nb:1 quality %, V:1 quality %, Cr:3 quality %, S:0.1 quality %, Mo:1 quality %, Cu:3 quality %, Ni:3 quality %, B:0.1 quality %, Ca:0.1 quality %, N:0.1 quality %, P:1 quality %, Sb:0.5 quality %.
So long as amount to content is the following scopes of 5 quality %, just can contain a kind or 2 kinds that is selected from these elements.Remainder is Fe and unavoidable impurities.
Secondly, in the present invention, before the annealing operation of CGL (coating line continuously), be selected from least a kind of material in the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound in the surface attachment of above-mentioned steel plate (base steel sheet).
Such material can the following material of illustration.
Phosphoric acid (H
3PO
4), potassiumphosphate (K
3PO
4), ammonium phosphate ((NH
4)
3PO
4), sodium phosphate (Na
3PO
4), sodium hydrogen phosphate (Na
2HPO
4), tertiary iron phosphate (FePO
4), phosphonic acids (H
3PO
3) and phospho acid (H
3PO
2) wait contain P-compound,
Sodium hydroxide (NaOH), sodium sulfate (Na
2SO
4), sodium sulphite (Na
2S), Sulfothiorine (Na
2S
2O
3), sodium-chlor (NaCl), yellow soda ash (Na
2CO
3), Trisodium Citrate (Na
3C
6H
5O
7), Zassol (NaCNO), sodium-acetate (CH
3COONa), sodium hydrogen phosphate (Na
2HPO
4), sodium phosphate (Na
3PO
4), Sodium Fluoride (NaF), sodium bicarbonate (NaHCO
3), SODIUMNITRATE (NaNO
3), sodium oxalate ((COONa)
2), sodium tetraborate (Na
2B
4O
7) and sodium oxide (Na
2O) etc. contain the Na compound,
Potassium hydroxide (KOH), Potassium ethanoate (CH
3COOK), potassium borate (K
2B
4O
7), salt of wormwood (K
2CO
3), Repone K (KCl), potassium cyanate (KCNO), hydrogen citrate potassium (KH
2C
6H
5O
7), Potassium monofluoride (KF), potassium molybdate (K
2MoO
4), saltpetre (KNO
3), potassium permanganate (KMnO
4), potassiumphosphate (K
3PO
4), vitriolate of tartar (K
2SO
4), potassium sulfocyanate (KSCN) and potassium oxalate ((COOK)
2) wait contain the K compound,
Hydrochloric acid (HCl), sodium-chlor (NaCl), ammonium chloride (NH
4Cl), antimony chloride (SbCl
3), Repone K (KCl), iron(ic) chloride (FeCl
2, FeCl
3), titanium chloride (TiCl
4), cupric chloride (CuCl), bariumchloride (BaCl
2), molybdenum chloride (MoCl
5) and sodium chlorate (NaClO
3) wait contain the Cl compound,
Sulfuric acid (H
2SO
4), sodium sulfate (Na
2SO
4), S-WAT (Na
2SO
3), sodium sulphite (Na
2S), ammonium sulfate ((NH
4)
2SO
4), ammonium sulfide ((NH
4)
2S), Sulfothiorine (Na
2S
2O
3), sodium pyrosulfate (NaHSO
4), monoammonium sulfate (NH
4HSO
4), vitriolate of tartar (K
2SO
4), ferric sulfate (FeSO
4, Fe
2(SO
4)
3), ammonium sulfate iron (Fe (NH
4)
2(SO
4)
2, FeNH
4(SO
4)
2), barium sulfate (BaSO
4), antimony sulfide (Sb
2S
3), iron sulphide (FeS), thiocarbamide (H
2NCSNH
2), thiourea peroxide ((NH
2)
2CSO
2), the thenoic acid salt of SCH base and thiocyanic acid salt etc. with SCN base contain the S compound,
Antimonic fluoride (SbF
3), Neutral ammonium fluoride (NH
4F), Potassium monofluoride (KF), ammonium bifluoride (NH
4HF
2), hydrogen fluoride (HF), Sodium Fluoride (NaF), barium fluoride (BaF
2) and cobaltous fluoride (CoF
3) wait contain the F compound,
Boric acid (H
3BO
3), potassium borate (K
2B
4O
7), sodium tetraborate (Na
2B
4O
7), lead borate (Pb (BO
2)
2) and manganese borate (MnH
4(BO
3)
2) wait contain the B compound,
Can use to contain C, N compound etc. headed by oxalic acid and Oxalates, citric acid and citric acid salt, nitric acid and the Nitrates.
To making above-mentioned substance attached to the method on the steel plate, be not particularly limited, physical attachment gets final product.Can use for example to use above-mentioned substance is mixed in solution or the suspension liquid that water or organic solvent etc. form, in such solution or suspension liquid, make the method for steel plate dipping; The method of such solution or suspension liquid being sprayed etc. with atomizer etc.; With the method for coating such as roller coating machine etc.In addition, even make its drying, do not change effect of the present invention thereafter yet.In addition, even directly apply compound, also can obtain same effect.
Making before above-mentioned substance adheres to, also can implement the pre-treatment that electrolytic degreasing or pickling etc. are used at present as required.In addition, after above-mentioned substance is adhered to,,, also can obtain effect of the present invention so long as above-mentioned substance is attached to steel plate even implement this pre-treatment.And, also can use the method that when use contains the ROLLING OIL rolling of above-claimed cpd, it is adhered to.
In any case, when making the steel plate oxidation, it is important making above-mentioned substance be attached to surface of steel plate.
The amount of the element of the adhesion amount conversion cost invention regulation of above-mentioned substance, so long as amount to (below, be also referred to as the element-specific amount) at 0.01～1000mg/m
2Scope just be fit to.Its reason is that adhesion amount is controlled at rhombohedral iron ore content below the 70 quality % easily for this scope steel plate.Other reason also is, so long as the element-specific amount is 0.01mg/m
2More than, below coating, just form this enriched layer easily.Reason on the other hand is, the element-specific amount is controlled at 1000mg/m
2Below, rather than be because of effect of the present invention, favourable economically.
Need to prove, make its quantivative approach that is attached to this material of steel plate, can utilize the wet analysis method to measure.That is the element-specific amount in the total amount of element-specific amount that, can be by from base steel sheet, also containing this material in the deduction base steel sheet and easily obtaining.
Secondly, in the present invention, heat being attached with the steel plate that is selected from least a kind of material in the family that is made of S, C, Cl, Na, K, B, P, F, N and their compound, forming rhombohedral iron ore content at this surface of steel plate is oxide film thereon below the 70 quality %.
For example, heat, can easily finish by the steel plate that will be attached with this material.Need to prove that the difference of method for oxidation is to not influence of effect of the present invention, as long as steel plate can be carried out oxidation, which kind of method can.
Heating means can be the type of heating that roasting kiln heating, induction heating, radiation heating and energising heating etc. are used at present, are not particularly limited.For example, the roasting kiln type of heating can use process furnace such as the oxidized still of present use and non-oxidation furnace.
Under the situation of non-oxidation furnace, for example be set at above 1.0 by air-fuel ratio with the updraft roasting kiln, can be easily with the steel plate oxidation.
In addition, this oxidation is preferably carried out under the oxidative environment of iron.Under the situation of induction heating mode, radiation type of heating and energising type of heating, be oxidative environment by near the environment set the steel plate that will heat, can be easily with the steel plate oxidation.Oxidative environment generally is at least a kind the environment that contains in the oxidizing gas such as oxygen, water vapour and carbonic acid gas, so long as steel plate can be carried out oxidation, just is not particularly limited.
Need to prove that above-mentioned is the example of expression representative, in any case, gets final product so long as can make steel plate carry out oxidation, its method is not particularly limited.
By making at least a kind of material that is selected from the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound be attached to surface of steel plate, rhombohedral iron ore content can be controlled at below the 70 quality %, its reason is as described below.
That is, the occasion of the steel plate that the Si concentration in the steel is high, in existing method for oxidation, the Si in the steel forms the oxide film of the Si of stratiform densification in the enrichment of the interface of ferric oxide and base steel sheet.Because the oxide compound of this lamellated Si hinders the diffusion from the Fe on basis,, therefore, generate rhombohedral iron ore (Fe as the oxide compound of metal ion excess type (n type) so suppress iron significantly at surface oxidation
2O
3) ferric oxide that content is high.
On the other hand, when this material is attached to surface of steel plate, because the generation of the Si oxide compound at the interface of aforementioned ferric oxide of obstruction and base steel sheet, so spread easily from the Fe on basis.Its result, iron is easy oxidation on the surface, generates the magnetite (Fe as the oxide compound of metal ion deficiency (p type)
3O
4) and the high ferric oxide of wustite (FeO) content, its result may reduce rhombohedral iron ore content.
Need to prove, in the present invention, to be attached with the steel plate that is selected from least a kind of material in the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound when carrying out oxidation, preferably under oxidative environment, be up to the heat treated that temperature surpasses 500 ℃.This is up to temperature for example can measure this surface of steel plate with radiation thermometer or contact thermometer etc.Its reason is, as long as heat treated surpasses 500 ℃, just easy content with the rhombohedral iron ore in the oxide film thereon is controlled at below the 70 quality %, suppresses the surface enrichment of Si, improves the wettability with fused zinc.On the other hand, its upper limit is not particularly limited.But practical ceiling temperature is that reduction is continuously handled below the steel billet temperature that needs, for example is to be both economical about 750～800 ℃.
In general, known have when making the steel plate oxidation, generates by wustite (FeO), magnetite (Fe
3O
4) and rhombohedral iron ore (Fe
2O
3) oxide film thereon that constitutes, the situation of the steel plate more than Si concentration height to the 0.1 quality % in the steel, the rhombohedral iron ore content in the oxide film thereon raise (for example, with reference to Japanese new system steel skill and technique No.77, p.1 (1998)).By the rhombohedral iron ore content in this oxide film thereon is set at below the 70 quality %, can improve with the back operation in the wettability of the fused zinc implemented, can suppress the situation of not plating fully.And, after this coating, when alloying is carried out in this steel plate and pot galvanize, also promote steel plate and zinc-plated 's alloying easily.On the other hand, when rhombohedral iron ore content surpassed 70 quality %, the wettability reduction with fused zinc can not suppress the situation of not plating fully.Need to prove, because the rhombohedral iron ore in the preferred extremely strong inhibited oxidation tunicle, so rhombohedral iron ore content certainly is 0 quality %.But, preferred usually the use about rhombohedral iron ore content 10～70 quality %.
By the rhombohedral iron ore content in the oxide film thereon of surface of steel plate is suppressed at below the 70 quality %, improvement is not clear and definite as yet with the reason of the wettability of fused zinc.But, it has been generally acknowledged that the surface enrichment behavior of the Si the when composition of oxide film thereon is handled thereafter reduction brings influence, it has been generally acknowledged that, when rhombohedral iron ore content is 70 quality % when following, can suppress the surface enrichment of Si fully, realize good adherence of coating.
Need to prove that so-called oxide film thereon is not limited to FeO, the Fe of aforementioned mistake among the present invention
3O
4And Fe
2O
3Even, comprise the oxide compound that for example contains as the Si that adds element in the steel etc., do not influence effect of the present invention yet.
Need to prove that available use has the x-ray diffraction method of rotational vibration sample bench, and (Cu manages ball, tube voltage: 50kV and tube current: 250mA) measure rhombohedral iron ore content.That is, prepare rhombohedral iron ore (Fe in addition in advance
2O
3), magnetite (Fe
3O
4) and the standard powdered sample of wustite (FeO), make 3 kinds of different samples of these blending ratios (quality %), be provided in the X-ray diffraction.Measure rhombohedral iron ore (Fe
2O
3): (104) face, magnetite (Fe
3O
4): (400) face, wustite (FeO): the diffraction peak intensity (cps) of (200) face, obtain the relation of blending ratio (quality %) and diffraction peak intensity (cps), production standard curve.Based on this typical curve, can obtain rhombohedral iron ore content (quality %) by the diffraction peak intensity that obtains.
The oxide film thereon of utilizing aforesaid method to obtain preferably converts with the oxygen amount and counts 0.01～5g/m
2Ferric oxide.This oxygen amount is 0.01g/m
2Oxide film thereon because the ferric oxide amount is abundant, suppress the surface enrichment of Si easily.On the other hand, this oxygen amount is 5g/m
2Following oxide film thereon, the reduction of back operation is easy, and, can promote alloying in the Alloying Treatment process after the pot galvanize of carrying out thereafter.
Need to prove that the quantivative approach of this oxygen amount in this oxide film thereon can the following method of illustration.That is, utilize the wet analysis method, can easily carry out quantitatively by the oxygen amount in the deduction base steel sheet in the total oxygen demand from hot-dip galvanizing sheet steel of the present invention.If the production standard curve also can utilize simple and easy quantivative approachs such as X fluorescence and GDS in advance.
Need to prove, after adhering at least a kind of material that is selected from the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound, obtain carrying out oxide treatment in the method that rhombohedral iron ore content is the oxide film thereon below the 70 quality %, this material does not discharge in well-oxygenated environment, and enters in the oxide film thereon or the amount in the base steel sheet increases.Therefore, also has following effect: can suppress to be used in the process furnace of oxide treatment and sneaking into from the obnoxious flavour of the exhaust of process furnace.
Secondly, in the present invention, the oxide film thereon that forms at surface of steel plate is as mentioned above reduced.This method of reducing is not particularly limited as long as use the method for using at present.
For example, generally implementing reduction with the annealing furnace of radiation type of heating in containing the reductibility environment of hydrogen, under the temperature about 600～900 ℃ handles.But, be not particularly limited, as long as the zone of oxidation of surface of steel plate can be reduced, any method can.
And, in the present invention, will impregnated in the coating bath and implement pot galvanize by above-mentioned base steel sheet of having carried out the reduction processing.The method that needs only according to present implementation is handled in this pot galvanize.For example, this base steel sheet in non-oxidizable or reductibility environment, be cooled to the temperature that is suitable for coating, usually to coating bath temperature temperature about equally.On the other hand, the temperature of usually coating being bathed is set at about 440～520 ℃, the Al concentration in bathing is set at about 0.1～0.2%.
Need to prove, bathe coating conditions such as composition according to the use variation coating temperature of goods and coating sometimes, but coating condition difference to effect of the present invention without any influence, be not particularly limited.For example, except that Al, even sneak into elements such as Pb, Sb, Fe, Mg, Mn, Ni, Ca, Ti, V, Cr, Co, Sn, effect of the present invention was also without any change during coating was bathed.
And, the method for adjusting the thickness of coating behind the coating also is not particularly limited.In general, the using gas wiping by distance between gaseous tension, wiping nozzle and the steel plate of adjustments of gas wiping etc., is adjusted the thickness of coating.At this moment, the thickness of coating is not particularly limited, about preferred 3～15 μ m.Its reason is, as long as it is more than the 3 μ m, just can obtain sufficient rust-preventing characteristic.On the other hand, it is below the 15 μ m, and is favourable to processibility and economy.
In addition, in the present invention, also can after above-mentioned pot galvanize, implement Alloying Treatment.
As previously mentioned, according to the present invention, Si carries out surface enrichment when annealing owing to can be suppressed at, so can solve the problem that the alloying of the many steel plates of the Si content of prior art existence significantly postpones.Its result can not hinder productive rate ground and make the good alloyed hot-dip galvanized steel sheet of chalking resistance.
Any heating means that alloying processing method can the using gas heating, induction heating and energising heating etc. are used at present are not particularly limited.
As mentioned above, the inventor has developed following technology: on the base steel sheet surface of the Si that contains 0.1～3 quality %, after adhering at least a kind of material that is selected from the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound, preferably in the annealing furnace of CGL with this steel plate oxidation, form oxide film thereon, next carry out reduced anneal, with this oxide film thereon reduction, then, carry out fusion coating.
In the present invention, by before base steel sheet annealing, promptly before this oxidation, make this material be attached to base steel sheet, even the steel plate that Si content is many, owing in oxidation operation, can form oxide film thereon than the iron of present volume, therefore, can suppress the generation of the surface enrichment thing of the present Si that after the reduced anneal of proceeding, occurs effectively on the base steel sheet surface.Its result when the base steel sheet after the reduced anneal that will continue to use the inventive method is carried out pot galvanize, can obtain not having the good coating of appearance of the situation of not plating, and obtains the good hot-dip galvanizing sheet steel of adherence of coating and sliding.
And when suppressing the surface enrichment of Si by above-mentioned oxide treatment, this material that adheres to can invade the top layer of steel plate by thermal treatments such as oxide treatment.Its result, after the pot galvanize or after the Alloying Treatment thereafter, existence is selected from the enriched layer of at least a kind of composition in the family that is made of S, C, Cl, Na, K, B, P, F and N below coating.
Need to prove, the so-called enriched layer of the present invention, be meant the high zone more than 10% of this constituent concentration of the concentration ratio base steel sheet of at least a kind of composition being selected from the family that constitutes by S, C, Cl, Na, K, B, P, F and N (below, be also referred to as the enrichment composition).
Such enriched layer as shown in the Examples, use GDS to obtain the depth profile of the enrichment composition (element) of depth direction by the surface of this Coated Steel, or by by use EPMA the depth profile that linear analysis obtains being carried out in the cross section of this Coated Steel, the peak strength that near interface occurs is expressed as the high zone more than 10% of this composition intensity than base steel sheet.
At this, the peak strength that enriched layer is defined as the enrichment composition of near interface is than the reason in this high zone more than 10% of composition intensity of base steel sheet, if this increment is lower than 10%, and the Si surface enrichment in the time of then can not fully suppressing reduced anneal.
Need to prove, the mensuration of the depth profile of this enriched layer, can use above-mentioned GDS, also can use the linear analysis in the cross section that utilizes EPMA, but as described later, when utilizing EPMA to carry out linear analysis, should be noted that this enriched layer preferably the compound of this composition of this enrichment composition and base steel sheet disperse the enriched layer that forms.That is, this enriched layer be the compound with this composition of base steel sheet disperse to form enriched layer the time, utilizing EPMA to carry out in the linear analysis of cross section, sometimes also may the non-existent part of analysis of compounds.Therefore, when use utilizes EPMA to carry out linear analysis, measure at 5 places the optional position in steel plate cross section, obtain the thickness in the high zone more than 10% of intensity of this composition of the strength ratio base steel sheet of this enrichment composition, by obtaining the average thickness value that 5 times are measured, be set at the thickness of measuring this enriched layer.
In addition, when carrying out oxide treatment, when the growing amount of ferriferous oxide increases, at the interface and/or the inner oxide compound that forms Si of base steel side of this ferriferous oxide and base steel when material of the present invention is adhered to.And, owing to handle with this ferriferous oxide restoring transformation Cheng Tie, so the oxide compound of Si remains in base steel inside by follow-up reduction.After pot galvanize thereafter, there is the layer of (being reduced) iron in its result below this coating, have this enriched layer that comprises the oxide compound that contains Si in its lower section.
Need to prove that what is called of the present invention " oxide compound that contains Si " must contain Si and oxygen.But, owing to the situation that contains the oxide compound of composition in the steel is wherein also arranged and contain the situation of their double salt and complex salt etc., so not only be defined in the oxide compound of Si, unqualified to its kind." oxide compound that contains Si " of representative can illustration SiO
2, FeSiO
3, Fe
2SiO
4, MnSiO
3Or their mixture etc.
That is, hot-dip galvanizing sheet steel of the present invention has: steel plate, and it contains the Si of 0.1～3.0 quality %; Hot galvanized layer; And enriched layer, between this steel plate and this hot galvanized layer, containing the oxide compound of Si, thickness is 0.01～100 μ m, and has at least a kind of composition that is selected among S, C, Cl, Na, K, B, P, F and the N.
The adherence of coating of hot-dip galvanizing sheet steel exhibit excellent of the present invention and the reason of sliding do not have clearly as yet to be explained, but the present inventor is presumed as follows.
Promptly, consider that its reason is, when generating the enriched layer of mentioned component on the surface of base steel sheet as the present invention, when pot galvanize, the adaptability that the intermetallic compound of the Fe-Al that generates at the interface of zinc-plated and steel plate and base steel sheet have taken place helps tack like this and changes.
In addition, when generating the enriched layer of this composition on the surface of base steel sheet, this composition is separated out in coating dissolving in the pot galvanize operation inevitably, and its part is present in the coating with the near interface of steel plate.Therefore, consider to compare with the common hot-dip galvanizing sheet steel that does not have this enriched layer, its sliding improves.
And, can improve adherence of coating and sliding by in this enriched layer, there being the oxide compound that contains Si, its reason is considered as follows.
That is, when existence in this enriched layer contained the oxide compound of Si, the shape at the interface of coating and steel plate became concavo-convex, can improve tack by this fixed effect.Its result, the sliding that adds man-hour also improves.Need to prove that this effect is no matter in the occasion of hot-dip galvanizing sheet steel, and is still all identical in the occasion of alloyed hot-dip galvanized steel sheet.
As mentioned above, when the enriched layer of this composition of formation below coating, and exist when containing the oxide compound of Si in this enriched layer, utilize both synergies, its tack improves greatly, and its sliding also improves.
The thickness of this enriched layer of the present invention need be controlled at the scope of 0.01～100 μ m.Its reason is, when the thickness less than 0.01 μ m of this enriched layer, can not manifest the effect that improves adherence of coating fully, on the other hand, when it surpasses 100 μ m, its fatigue characteristic deterioration.More preferably greater than 1 μ m, the scope below 50 μ m.
In addition, in the present invention, the concentration of this composition of this enriched layer preferably concentration than this composition of this base steel sheet is high more than 10%.
Its reason is, when being this this enriched layer, and the surface enrichment of Si when fully suppressing reduced anneal easily.
Need to prove, such enriched layer as shown in the Examples, by using the depth profile that GDS obtains by the cross section of this Coated Steel or use EPMA to carry out the depth profile that linear analysis obtains, the peak strength that manifests near interface is shown as the high zone more than 10% of peak strength than base steel.
At this, the enriched layer preferably compound of this composition of this enrichment composition and base steel sheet disperses the enriched layer that forms.This composition of so-called base steel sheet has iron certainly, estimates to also have Si, Mn, Ti, Nb, V, Cr, S, Mo, Cu, Ni, B, Ca, N, P and Sb etc.Consider that its reason is, in order to form the enriched layer of desirable material, can be when generating the compound with this composition of base steel sheet more fixing enrichment composition.In addition, think that the advantage that this compound disperses to bring is that owing to the grain boundary that is present in base steel sheet according to this compound of analytical results mostly, so this compound can effectively suppress the surface enrichment of Si in the steel by stopping up the diffused line of Si.
And, as long as this compound of this enriched layer is set at MnS, just can more stably obtain effect of the present invention.Its reason is that in all cpds of estimating, MnS is a compound highly stable in the steel, generates easily, creates conditions easily.
In order to form MnS, as long as select S as the element that before above-mentioned oxide treatment, is attached to steel plate, in oxide treatment and reduction treatment process, S in steel plate top layer (behind coating under the coating) with steel in Mn chemical combination, carry out enrichment.
At this moment, the growing amount of this suitable compound is preferred: the above MnS of particle diameter 50nm exists more than 5 at per 20 μ m of the arbitrary section of the direction at the interface that is parallel to coating and base steel sheet.In addition, be meant at this said MnS and utilize main component Mn and S to form, exist, also be out of question even the element beyond the Fe etc. mixes.
The judgement of the evaluation of compound, dispersion state and number, except the SEM in the cross section of Coated Steel observe or tem observation, can be undertaken by utilizing EDS and transmitted electron line diffraction (TED) to wait as required.
In addition, the amount of the oxide compound that contains Si that contains in the enriched layer preferably converts with oxygen and counts 0.01～1g/m
2Scope.As long as this amount that contains the Si oxide compound is 0.01g/m
2More than, just can significantly improve adherence of coating and sliding.On the other hand, this amount that contains the Si oxide compound is 1g/m
2Both economical when following.
Need to prove, when such oxide compound being carried out when specific, the sample that can form with the adjustment of TEM replica plating in EDX analysis confirmation oxide compound, contain Si.
Need to prove, when the hot-dip galvanizing sheet steel with the invention described above carries out alloying, except can be implementing under the lower alloying temperature, can also obtain that not only adherence of coating and sliding are good, but also have both the alloyed hot-dip galvanized steel sheet of good chalking resistance.
When existing hot-dip galvanizing sheet steel is carried out alloying, generate at the interface of zinc-plated and base steel sheet than base steel sheet hardness high " mutually, should " mutually and the difference of hardness of steel plate can cause the deterioration of adherence of coating inevitably.But, when hot-dip galvanizing sheet steel of the present invention is carried out alloying, owing to below coating, have the enriched layer of this composition, so the hardness of mechanical characteristics, the particularly base steel sheet of the near interface of zinc-plated and base steel sheet becomes near " value of hardness reduces effectively so give the distortion at this interface when base steel sheet is out of shape mutually.It has been generally acknowledged that, its result, adherence of coating improves.
Need to prove, in the situation of pot galvanize of the present invention, because the surface enrichment of the Si can suppress to anneal the time, so than carrying out alloying under the lower temperature, its result also has and can suppress the disadvantageous " advantage of the generation of phase of adherence of coating.
In general, alloyed zinc hot dip galvanized sliding manifests by the variation of alloying behavior.That is, as previously mentioned, in when annealing, the surface enrichment thing of the Si that produces on the surface of the base steel sheet alloying speed that slows down.Its reason is, after annealing, carries out selective oxidation on the surface, and the surface enrichment thing of enrichment suppresses the alloying reaction of Zn and Fe.Its result, the coating after alloying finishes hinders the homogeneous reaction of Zn and Fe, becomes concavo-convex serious coating.In addition, also thickization of the crystallization of the alloy of Zn and Fe.Owing to, caused the sliding deterioration of coating by thickization of the concavo-convex and crystal grain that suppresses the coating that this alloying causes.
But hot-dip galvanizing sheet steel of the present invention is identical with the situation of the tack of front, and owing to the enriched layer of this composition of existence below coating, so compare with common situation, the Si surface enrichment in the time of can suppressing to anneal promotes alloying.Its result, the reaction of Zn and Fe is also even, and it is level and smooth that coating becomes.In addition, it is fine that crystal grain also becomes, and compares with the Si steel that contains with aforesaid existing method for making manufacturing, shows good sliding.
Need to prove, as mentioned above, in hot-dip galvanizing sheet steel of the present invention, below this coating, have the layer of (being reduced) iron, have this enriched layer that comprises the oxide compound that contains Si in its lower section.But, when hot-dip galvanizing sheet steel of the present invention is carried out Alloying Treatment, also carry out zinc-plated certainly and alloying (being reduced) iron.Therefore, in the hot-dip galvanizing sheet steel of the alloying that obtains, below this zinc coating, can not confirm the iron layer sometimes.But, even this alloyed hot-dip galvanized steel sheet, owing to below this coating, have " enriched layer that includes this composition of the oxide compound that contains Si ", so belong to technical scope of the present invention.
Embodiment
Embodiment A:
With 8 kinds of cold-rolled steel sheets shown in the table 1 and hot-rolled steel sheet as for the examination material, with 5 quality %NaOH solution carry out electrolytic degreasing (80 ℃ * 5 seconds, 5A/dm
2), as this material, (a) phosphoric acid (100g/l) will be contained respectively, (b) hydrochloric acid (1g/l), (c) Sodium Fluoride (2g/l), (d) Sulfothiorine (20g/l), (e) potassium hydroxide (100g/l), (f) ammonium thiocyanate (50g/l), (g) sulfuric acid (50g/l), (h) ammonium sulfate (30g/l), (i) thiocarbamide (20g/l), (j) sodium sulfate (50g/l), (k) ferric sulfate (20g/l), (l) sulfuric acid (10g/l), (m) ammonium sulfate (5g/l), (n) thiocarbamide (1g/l) and (o) aqueous solution of ammonium sulfate (150g/l), utilize the coating of line rod, as show 2-1, shown in table 3-1 and the table 4-1, change adhesion amount and after being coated in surface of steel plate, make its drying with drying machine.
These are heated for the process furnace of examination material with oxidative environment, after the disposable taking-up, after annealing, carry out coating with the hot dip simulator.Oxide treatment condition etc. is also remembered in the lump in table 2-1, table 3-1 and table 4-1.
In addition, as a comparison, implement not carry out heat treated ground annealing carrying out coating.
Heating condition is steel plate to be changed to be up to temperature.Need to prove, be set at 1 second, carry out quenching with nitrogen then in the hold-time that is up under the temperature.
Annealing conditions is: (dew point :-35 ℃), plate temperature are that 830 ℃, hold-time are to carry out under 45 seconds the condition in 10 volume % hydrogen+nitrogen environments.
The coating condition is: use 460 ℃ the zinc-plated bath that contains 0.14 quality %Al (Fe is saturated), invading the plate temperature is 460 ℃, and dipping time is 1 second, the appearance behind the evaluation coating.Behind the coating, adhesion amount is adjusted into single face 45g/m with the nitrogen wiping
2
To the hot-dip galvanizing sheet steel that obtains, according to method described later carry out the mensuration of the thickness of enrichment composition and enrichment, under the coating the oxide compound that contains Si quantitatively, simultaneously, further carry out the evaluation of coating outward appearance and adherence of coating according to judgement criteria described later.The proterties of enriched layer is shown in table 2-2, table 3-2 and table 4-2.
And a part of Coated Steel carries out the hold-time with the energising process furnace behind coating be that (heat-up rate: 40 ℃/s) is that the alloying temperature of 10 ± 0.5 quality % is estimated alloying speed by obtaining Fe content in the coating for 10 seconds Alloying Treatment.Judgement criteria as described later.In addition, using Fe content in the coating is that the sample of 10 ± 0.5 quality % carries out 90 ° of pliability tests, estimates chalking resistance according to judgement criteria described later.And, also carry out for the evaluation of sliding according to judgement criteria described later.
These evaluation results are remembered in the lump in table 2-3, table 3-3 and table 4-3.
Table 2-1～table 4-3 as can be known by above-mentioned, contain the compound that is selected from least a kind of material in the family that constitutes by S, C, Cl, Na, K, B, P, F, N and their compound by adhering at surface of steel plate, carry out oxide treatment then, after to form rhombohedral iron ore content be oxide film thereon below the 70 quality %, under reductive condition, anneal, even be under the situation of substrate with the higher steel plate of the Si content that obtains, there is not the situation of not plating yet, do not have significant alloying to postpone, demonstrate good chalking resistance and sliding.But also as can be known: in hot-dip galvanizing sheet steel that obtains or alloyed hot-dip galvanized steel sheet, under this coating, have enriched layer, simultaneously, in this enriched layer, have the oxide compound that contains Si.Need to prove, the oxide film thereon that after oxide treatment, forms, the remainder beyond the rhombohedral iron ore is confirmed to be the tissue based on magnetite, wustite.
Embodiment B:
As this material, reach (s) sodium tetraborate (3g/l) with adhesion amount application (o) Repone K (50g/l), (p) ammonium oxalate (100g/l), (q) sulfuric acid (50g/l), (r) sodium hydroxide (30g/l) shown in the table 5-1, as heating condition, under 0.1 volume % oxygen+nitrogen environment, handle, in addition, with the same condition of embodiment A under make Coated Steel, estimate equally.The proterties of enriched layer is shown in table 5-2.The evaluation result of the Coated Steel that obtains is like this remembered in the lump in table 5-3.
Table 5-1～table 5-3 as can be known by above-mentioned, by adhere to this material at surface of steel plate, carry out oxide treatment then, after to form rhombohedral iron ore content be oxide film thereon below the 70 quality %, under reductive condition, anneal, the higher base steel sheet of the Si content that obtains does not have the situation of not plating behind this coating, do not have significant alloying to postpone yet, and demonstrates good chalking resistance and sliding.But also as can be known: in hot-dip galvanizing sheet steel that obtains or alloyed hot-dip galvanized steel sheet, under this coating, have enriched layer, simultaneously, in this enriched layer, have the oxide compound that contains Si.Need to prove, the oxide film thereon that after oxide treatment, forms, the remainder beyond the rhombohedral iron ore is confirmed to be the tissue based on magnetite, wustite.
Embodiment C:
As this material, adhesion amount shown in the 6-1 is used (t) antimony chloride (20g/l), (u) ammonium sulfate (30g/l), (v) lead chloride (1g/l), (w) thiocarbamide (20g/l) reach (x) sodium-chlor (25g/l) to show, as the heat treated condition, using air-fuel ratio is that 1.15 updraft roasting kiln carries out heat treated, in addition, with the same condition of embodiment A under make Coated Steel, estimate equally.The proterties of enriched layer is shown in table 6-2.The evaluation result of the Coated Steel that obtains is like this remembered in the lump in table 6-3.
By among above-mentioned table 6-1～table 6-3 as can be known, adhere to this material at surface of steel plate, carry out oxide treatment then, after to form rhombohedral iron ore content be oxide film thereon below the 70 quality %, under reductive condition, anneal, the higher base steel sheet of the Si content that obtains does not thus have the situation of not plating behind this coating, do not have significant alloying to postpone yet, and demonstrates good chalking resistance and sliding.But also as can be known: in hot-dip galvanizing sheet steel that obtains or alloyed hot-dip galvanized steel sheet, under this coating, have enriched layer, simultaneously, in this enriched layer, have the oxide compound that contains Si.Need to prove, the oxide film thereon that after oxide treatment, forms, the remainder beyond the rhombohedral iron ore is confirmed to be the tissue based on magnetite, wustite.
Need to prove that each judgement criteria of coating quality is as described below.
The thickness of＜enrichment composition and the mensuration of enrichment 〉
For hot-dip galvanizing sheet steel and alloyed hot-dip galvanized steel sheet, pair cross-section utilizes the linear analysis of EPMA and/or GDS to measure under the condition below, by the depth profile that obtains (for example Fig. 1, Fig. 2), to this side of base steel, will be enriched layer thickness than the raise thickness setting in the zone more than 10% of the congruent intensity in the base steel part from the interface of this coating and base steel sheet in the peak strength of the enrichment composition (element) that near interface manifests.In addition, will be set at enrichment with respect to the increasing amount of the peak strength A of this composition of the enriched layer of the peak strength B of this composition in the base steel measures.That is enrichment (%)=(intensity A-intensity B)/intensity B * 100%.At this, enrichment is lower than 10% situation, the thickness in the zone that enrichment thickness will be more some than the intensity B height of the enrichment composition in the base steel in depth profile is recorded in the table.In addition, for utilizing the linear analysis of EPMA, 5 places to the optional position in steel plate cross section measure, obtain the thickness in the high zone more than 10% of intensity of the strength ratio base steel of enrichment composition, by the average thickness value of obtaining 5 mensuration, the mean value of peak strength A, be set at this enriched layer thickness and enrichment.In utilizing the mensuration of GDS, by the conversion of sputtering time to enriched layer thickness, by the sputtering rate under the GDS condition below: 0.04 μ m/sec. converts.
(EPMA condition determination)
Acceleration voltage: 20kV
Line: 0.05 μ A
(GDS condition determination)
Tube current: 30mA
Argon flow amount: 400ml
The quantitative method that contains the oxide compound of Si under the＜coating 〉
For hot-dip galvanizing sheet steel or alloyed hot-dip galvanized steel sheet, in that being dissolved in alkaline solution as follows, removes coating, obtain the amount of oxide compound by this steel plate and the difference of oxygen analytical value of the steel plate two sides mechanically being ground the steel plate of the 100 μ m that disappear.In addition, the sample that forms with the adjustment of TEM replica plating is analyzed through EDX and can be confirmed to contain Si in this oxide compound.
(alkaline solution)
NaOH：8.2％
Trolamine: 2.1%
H
2O
2：1.2％
＜coating outward appearance 〉
The hot-dip galvanizing sheet steel that use obtains, range estimation and carry out the outward appearance observation with 10 times magnifying glass, the situation that does not have fully not plate is made as nothing does not plate, to can observe situation that small plating do not go up with 10 times magnifying glass and be made as small plating and do not go up, the situation of can visual observations not plating has been made as plating and has not gone up.
Zero: do not have and do not plate
△: have small plating not go up
*: there is plating not go up
＜adherence of coating 〉
The hot-dip galvanizing sheet steel that use obtains carries out pellet impact test, and the coating when carrying out tape stripping is peeled off state evaluation.Test conditions is: on the hot-dip galvanizing sheet steel that loads on the hemispherical protuberances of 1/2 inch of diameter, the weight that makes 2.8kg is implemented tape stripping at convex side after falling from the eminence of 1m.
Zero: no coating is peeled off
*: there is coating to peel off
＜alloying speed 〉
Zero: the alloying temperature: finish 500 ℃ of following alloyings
*: alloying temperature: surpassing 500 ℃ of following alloyings end
＜chalking resistance 〉
Cutting width from alloyed hot-dip galvanized steel sheet is that 25mm, length are the test film of 40mm, (ニ チ バ Application is made with glass ribbon, width: 24mm) be attached to the position that length is 20mm, after zone face bent to 90 ° to the inside, carry out flexion torsion, the Zn amount conduct counting that when peeling off glass ribbon, utilizes the X fluorometric assay to adhere to.The Zn counting that records is adjusted into the counting that the test film width is per unit length (1m), estimates according to following standard.
Zero: good (counting: 0～5000)
*: bad (counting: more than 5000)
＜sliding test 〉
With regard to sliding, under following condition, use the sliding test of the instrument of shape shown below.Obtain coefficientoffriction from the ratio of drawing force F and pressing load P by following formula, estimate with following standard.
μ＝2P/F
Surface pressure: 9.8MPa, sliding distance: 100mm, sliding velocity: 10mm/s, specimen width: 20mm
Model: the contact area of flat tool (shoulder R5, #1200 grind) and sample: 10 * 20mm
Oiling condition ノ Star Network ス ラ ス ト 550KH:1.0g/m
2Oiling
Zero: good (μ: be lower than 0.12)
*: bad (μ: more than 0.12)
Embodiment D:
With the same condition of embodiment A under make Coated Steel.Evaluation method also with embodiment A much at one, to meticulousr poor of chalking resistance evaluation, be set at
◎: outstanding (counting: be lower than 4000)
Zero: good (counting: 4000～5000)
*: bad (counting: surpass 5000).
And, for the examination materials, utilize SEM and TEM to carry out the evaluation of enriched fractions of coating near interface and the affirmation of distribution situation to various.The sample of analyzing usefulness supplies the examination material by the cross section processing and fabricating that utilizes focused ion beam (FIB).Utilize SEM to observe the size and the number of the compound of judging the enrichment composition that generates, utilize TEM-EDS and transmitted electron line diffraction to carry out the evaluation of compound.The evaluation of the number of compound is in utilizing the cross-section visual field of SEM, with the interface parallel direction of coating and base steel sheet, to the number of the compound more than the particle diameter 50nm of the near interface in the zone that is present in wide 20 μ m, the mean number at 5 places at random selected is set at evaluation index.
Attachment material, oxide treatment, enriched layer proterties are shown in table 7 with the result who obtains.
Show by table 7, form aptly in the material of enriched layer, particularly fully disperse the state that forms, can obtain more excellent characteristic by the compound that enriched layer is set at composition in enrichment composition and the basic steel at the coating near interface.
Table 1 (quality %)
| The steel grade class | Steel plate | C | Si | Mn | P | S | Al | Other |
| A | Cold-rolled steel sheet | 0.002 | 0.15 | 1.5 | 0.07 | 0.004 | 0.03 | - |
| B | 0.1 | 0.25 | 2.0 | 0.05 | 0.002 | 0.70 | - | |
| C | 0.5 | 0.5 | 2.0 | 0.01 | 0.003 | 0.04 | - | |
| D | 0.002 | 0.75 | 1.5 | 0.06 | 0.007 | 0.04 | - | |
| E | 0.1 | 1.0 | 3.5 | 0.01 | 0.003 | 0.05 | - | |
| F | 0.003 | 1.1 | 0.3 | 0.05 | 0.008 | 0.02 | - | |
| G | 0.15 | 1.5 | 2.5 | 0.01 | 0.003 | 0.03 | - | |
| H | 0.1 | 2.9 | 1.5 | 0.01 | 0.003 | 0.03 | - | |
| I | Hot-rolled steel sheet | 0.15 | 0.3 | 1.5 | 0.03 | 0.005 | 0.05 | - |
| J | 0.1 | 2.0 | 1.0 | 0.10 | 0.005 | 0.03 | - | |
| K | Cold-rolled steel sheet | 0.15 | 0.5 | 2.0 | 0.01 | 0.003 | 0.04 | Ti：0.02 |
| L | 0.1 | 0.25 | 1.6 | 0.05 | 0.002 | 0.30 | Nb：0.03 | |
| M | 0.002 | 0.25 | 1.5 | 0.07 | 0.004 | 0.03 | V：0.03 | |
| N | 0.08 | 0.5 | 2.0 | 0.01 | 0.01 | 0.02 | Cr：0.1 | |
| O | 0.15 | 1.5 | 2.1 | 0.01 | 0.003 | 0.03 | Mo：0.2 | |
| P | 0.1 | 2.8 | 0.8 | 0.01 | 0.003 | 0.03 | Cu：0.2 | |
| Q | 0.07 | 0.3 | 1.5 | 0.09 | 0.005 | 0.05 | Ni：0.2 | |
| R | 0.18 | 1.5 | 2.5 | 0.01 | 0.003 | 0.3 | B：0.002 | |
| S | 0.003 | 1.1 | 1.5 | 0.05 | 0.008 | 0.02 | Ca：0.02 | |
| T | 0.003 | 0.8 | 1.9 | 0.01 | 0.008 | 0.02 | N：0.01 | |
| U | 0.1 | 1.0 | 4.5 | 0.01 | 0.003 | 0.8 | Sb：0.02 | |
| V | 0.2 | 1.9 | 1.2 | 0.10 | 0.005 | 0.03 | Ti：0.03，Nb： 0.04 | |
| W | 0.08 | 0.35 | 2.2 | 0.02 | 0.002 | 0.70 | Nb：0.03， Mo：0.25 | |
| X | 0.1 | 2.9 | 2.5 | 0.06 | 0.003 | 0.03 | Cu：0.15 |
Table 2-1
| No. | The steel grade class | Attachment material | Oxide treatment | ||||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Oxygen amount (g/m in the oxide film thereon 2) | Rhombohedral iron ore content (%) | |||
| Embodiment 1 | A | Phosphoric acid | 100 | 70 | Have | 650 | 0.62 | 50 | |
| Embodiment 2 | B | 0.58 | 50 | ||||||
| Embodiment 3 | C | 0.59 | 55 | ||||||
| Embodiment 4 | D | 0.6 | 60 | ||||||
| Embodiment 5 | G | 0.55 | 60 | ||||||
| Embodiment 6 | H | 0.57 | 65 | ||||||
| Embodiment 7 | B | Hydrochloric acid | 1 | 0.1 | Have | 550 | 0.45 | 0 | |
| Embodiment 8 | C | 0.48 | 0 | ||||||
| Embodiment 9 | G | 0.52 | 5 | ||||||
| Embodiment 10 | H | 0.45 | 5 | ||||||
| Embodiment 11 | I | 0.49 | 10 | ||||||
| Embodiment 12 | J | 0.5 | 10 | ||||||
| Embodiment 13 | A | Sodium Fluoride | 2 | 1 | Have | 700 | 0.75 | 0 | |
| Embodiment 14 | B | 0.71 | 0 | ||||||
| Embodiment 15 | C | 0.68 | 0 | ||||||
| Embodiment 16 | E | 0.77 | 0 | ||||||
| Embodiment 17 | F | 0.69 | 0 | ||||||
| Embodiment 18 | H | 0.69 | 0 | ||||||
| Embodiment 19 | A | Sulfothiorine | 20 | 70 | Have | 600 | 0.55 | 0 | |
| Embodiment 20 | B | 0.52 | 0 | ||||||
| Embodiment 21 | C | 0.54 | 0 | ||||||
| Embodiment 22 | D | 0.5 | 0 | ||||||
| Embodiment 23 | G | 0.52 | 5 | ||||||
| Embodiment 24 | H | 0.53 | 5 | ||||||
| Embodiment 25 | A | Potassium hydroxide | 100 | 100 | Have | 600 | 0.51 | 0 |
| Embodiment 26 | B | 0.49 | 0 | |||||
| Embodiment 27 | C | 0.48 | 5 | |||||
| Embodiment 28 | E | 0.45 | 5 | |||||
| Embodiment 29 | F | 0.45 | 10 | |||||
| Embodiment 30 | H | 0.45 | 20 | |||||
| Comparative example 1 | B | Do not have | Do not have | Do not have | Have | 600 | 0.18 | 90 |
| Comparative example 2 | C | 0.12 | 90 | |||||
| Comparative example 3 | G | 0.07 | 90 | |||||
| Comparative example 4 | H | 0.05 | 95 | |||||
| Comparative example 5 | I | 0.2 | 90 | |||||
| Comparative example 6 | J | 0.08 | 95 | |||||
| Comparative example 7 | A | Sodium Fluoride | 2 | 1 | Do not have | - | - | - |
| Comparative example 8 | B | - | - | |||||
| Comparative example 9 | C | - | - | |||||
| Comparative example 10 | E | - | - | |||||
| Comparative example 11 | F | - | - | |||||
| Comparative example 12 | H | - | - | |||||
| Comparative example 13 | A | Sulfothiorine | 20 | 70 | Have | 500 | 0.07 | 75 |
| Comparative example 14 | B | 0.07 | 80 | |||||
| Comparative example 15 | C | 0.07 | 80 | |||||
| Comparative example 16 | D | 0.05 | 85 | |||||
| Comparative example 17 | G | 0.06 | 85 | |||||
| Comparative example 18 | H | 0.05 | 85 | |||||
| Comparative example 19 | A | Hydrochloric acid | 1 | 0.1 | Have | 400 | 0.006 | 80 |
| Comparative example 20 | B | 0.007 | 80 | |||||
| Comparative example 21 | C | 0.006 | 75 | |||||
| Comparative example 22 | D | 0.006 | 80 | |||||
| Comparative example 23 | G | 0.005 | 80 |
| Comparative example 24 | H | 0.002 | 75 | |||||
| Comparative example 25 | A | Phosphoric acid | 100 | 70 | Have | 400 | 0.01 | 85 |
| Comparative example 26 | B | 0.02 | 85 | |||||
| Comparative example 27 | C | 0.02 | 85 | |||||
| Comparative example 28 | D | 0.01 | 85 | |||||
| Comparative example 29 | G | 0.005 | 90 | |||||
| Comparative example 30 | H | 0.005 | 90 | |||||
| Comparative example 31 | A | Ammonium thiocyanate | 50 | 70 | Have | 500 | 0.01 | 80 |
| Comparative example 32 | B | 0.02 | 80 | |||||
| Comparative example 33 | C | 0.02 | 80 | |||||
| Comparative example 34 | D | 0.01 | 80 | |||||
| Comparative example 35 | G | 0.005 | 90 | |||||
| Comparative example 36 | H | 0.005 | 90 |
Table 2-2
| No. | The enriched layer proterties | |||||
| Enrichment composition under the coating | Enrichment composition thickness (μ m) | Enrichment (%) | Contain Si oxide amount (g/m 2) | |||
| GDS | EPMA | GDS | EPMA | |||
| Embodiment 1 | P | 7 | - | 400 | - | 0.1 |
| Embodiment 2 | 7 | - | 400 | - | 0.1 | |
| Embodiment 3 | 7 | - | 400 | - | 0.15 | |
| Embodiment 4 | 7 | - | 400 | - | 0.12 | |
| Embodiment 5 | 7 | - | 400 | - | 0.5 | |
| Embodiment 6 | 7 | - | 400 | - | 0.7 | |
| Embodiment 7 | Cl | 1.1 | - | 100 | - | 0.05 |
| Embodiment 8 | 1.2 | - | 100 | - | 0.05 | |
| Embodiment 9 | 1.1 | - | 100 | - | 0.05 | |
| Embodiment 10 | 1.1 | - | 100 | - | 0.05 | |
| Embodiment 11 | 1.1 | - | 100 | - | 0.05 | |
| Embodiment 12 | 1.1 | - | 100 | - | 0.04 | |
| Embodiment 13 | F，Na | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.12 |
| Embodiment 14 | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.13 | |
| Embodiment 15 | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.12 | |
| Embodiment 16 | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.12 | |
| Embodiment 17 | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.14 | |
| Embodiment 18 | F：1.5，Na：1.4 | - | F：100，Na：100 | - | 0.13 | |
| Embodiment 19 | S，Na | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.1 |
| Embodiment 20 | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.15 | |
| Embodiment 21 | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.1 | |
| Embodiment 22 | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.11 | |
| Embodiment 23 | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.12 | |
| Embodiment 24 | S：3.0，Na：2.0 | - | S：400，Na：400 | - | 0.1 | |
| Embodiment 25 | K | 3.0 | - | 500 | - | 0.12 |
| Embodiment 26 | 3.0 | - | 500 | - | 0.13 | |
| Embodiment 27 | 3.0 | - | 500 | - | 0.11 | |
| Embodiment 28 | 3.0 | - | 500 | - | 0.1 | |
| Embodiment 29 | 3.0 | - | 500 | - | 0.12 | |
| Embodiment 30 | 3.0 | - | 500 | - | 0.13 | |
| Comparative example 1 | Do not have | - | - | - | - | 0.001 |
| Comparative example 2 | - | - | - | - | 0.001 | |
| Comparative example 3 | - | - | - | - | 0.001 | |
| Comparative example 4 | - | - | - | - | 0.001 | |
| Comparative example 5 | - | - | - | - | 0.001 | |
| Comparative example 6 | - | - | - | - | 0.001 | |
| Comparative example 7 | F，Na | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.002 |
| Comparative example 8 | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.003 |
| Comparative example 9 | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.002 | |
| Comparative example 10 | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.002 | |
| Comparative example 11 | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.003 | |
| Comparative example 12 | (F：0.004， Na：0.003) | - | F：5，Na：5 | - | 0.002 | |
| Comparative example 13 | S，Na | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.004 |
| Comparative example 14 | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.005 | |
| Comparative example 15 | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.004 | |
| Comparative example 16 | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.003 | |
| Comparative example 17 | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.003 | |
| Comparative example 18 | (S：0.004， Na：0.004) | - | S：6，Na：6 | - | 0.003 | |
| Comparative example 19 | Cl | (0.003) | - | 5 | - | 0.002 |
| Comparative example 20 | (0.003) | - | 5 | - | 0.003 | |
| Comparative example 21 | (0.003) | - | 5 | - | 0.004 | |
| Comparative example 22 | (0.003) | - | 5 | - | 0.003 | |
| Comparative example 23 | (0.003) | - | 5 | - | 0.003 | |
| Comparative example 24 | (0.003) | - | 5 | - | 0.004 | |
| Comparative example 25 | P | (0.004) | - | 5 | - | 0.002 |
| Comparative example 26 | (0.004) | - | 5 | - | 0.004 | |
| Comparative example 27 | (0.004) | - | 5 | - | 0.003 | |
| Comparative example 28 | (0.004) | - | 5 | - | 0.002 |
| Comparative example 29 | (0.004) | - | 5 | - | 0.004 | |
| Comparative example 30 | (0.004) | - | 5 | - | 0.003 | |
| Comparative example 31 | S，C，N | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.004 |
| Comparative example 32 | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.005 | |
| Comparative example 33 | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.004 | |
| Comparative example 34 | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.004 | |
| Comparative example 35 | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.003 | |
| Comparative example 36 | (S：0.004， C：0.003， N：0.004) | - | S：5，N5 | - | 0.004 |
Table 2-3
| No | The coating quality | ||||
| The coating outward appearance | Adherence of coating | Alloying speed | Chalking resistance | Sliding | |
| Embodiment 1 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 4 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 5 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 6 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 7 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 8 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 9 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 10 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 11 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 12 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 13 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 14 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 15 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 16 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 17 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 18 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 19 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 20 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 21 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 22 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 23 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 24 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 25 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 26 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 27 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 28 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 29 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 30 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 1 | △ | × | × | × | × |
| Comparative example 2 | × | × | × | × | × |
| Comparative example 3 | × | × | × | × | × |
| Comparative example 4 | × | × | × | × | × |
| Comparative example 5 | △ | × | × | × | × |
| Comparative example 6 | × | × | × | × | × |
| Comparative example 7 | × | × | × | × | × |
| Comparative example 8 | × | × | × | × | × |
| Comparative example 9 | × | × | × | × | × |
| Comparative example 10 | × | × | × | × | × |
| Comparative example 11 | × | × | × | × | × |
| Comparative example 12 | × | × | × | × | × |
| Comparative example 13 | △ | × | × | × | × |
| Comparative example 14 | △ | × | × | × | × |
| Comparative example 15 | × | × | × | × | × |
| Comparative example 16 | × | × | × | × | × |
| Comparative example 17 | × | × | × | × | × |
| Comparative example 18 | × | × | × | × | × |
| Comparative example 19 | × | × | × | × | × |
| Comparative example 20 | × | × | × | × | × |
| Comparative example 21 | × | × | × | × | × |
| Comparative example 22 | × | × | × | × | × |
| Comparative example 23 | × | × | × | × | × |
| Comparative example 24 | × | × | × | × | × |
| Comparative example 25 | × | × | × | × | × |
| Comparative example 26 | × | × | × | × | × |
| Comparative example 27 | × | × | × | × | × |
| Comparative example 28 | × | × | × | × | × |
| Comparative example 29 | × | × | × | × | × |
| Comparative example 30 | × | × | × | × | × |
| Comparative example 31 | × | × | × | × | × |
| Comparative example 32 | × | × | × | × | × |
| Comparative example 33 | × | × | × | × | × |
| Comparative example 34 | × | × | × | × | × |
| Comparative example 35 | × | × | × | × | × |
| Comparative example 36 | × | × | × | × | × |
Table 3-1
| No. | The steel grade class | Attachment material | Oxide treatment | |||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Oxygen amount (g/m in the oxide film thereon 2) | Rhombohedral iron ore content (%) | ||
| Embodiment 31 | A | Sulfuric acid | 50 | 70 | Have | 600 | 0.55 | 0 |
| Embodiment 32 | B | 0.55 | 0 | |||||
| Embodiment 33 | C | 0.53 | 5 | |||||
| Embodiment 34 | D | 0.52 | 5 | |||||
| Embodiment 35 | G | 0.61 | 10 | |||||
| Embodiment 36 | H | 0.51 | 10 | |||||
| Embodiment 37 | B | Ammonium sulfate | 30 | 100 | Have | 650 | 0.56 | 0 |
| Embodiment 38 | C | 0.61 | 0 | |||||
| Embodiment 39 | G | 0.52 | 5 | |||||
| Embodiment 40 | H | 0.54 | 5 | |||||
| Embodiment 41 | I | 0.53 | 10 | |||||
| Embodiment 42 | J | 0.51 | 10 | |||||
| Embodiment 43 | A | Thiocarbamide | 20 | 70 | Have | 700 | 0.64 | 0 |
| Embodiment 44 | B | 0.64 | 0 | |||||
| Embodiment 45 | C | 0.62 | 5 | |||||
| Embodiment 46 | E | 0.71 | 5 | |||||
| Embodiment 47 | F | 0.62 | 10 | |||||
| Embodiment 48 | H | 0.51 | 10 | |||||
| Embodiment 49 | A | Sodium sulfate | 50 | 70 | Have | 600 | 0.55 | 0 |
| Embodiment 50 | B | 0.51 | 0 | |||||
| Embodiment 51 | C | 0.58 | 5 | |||||
| Embodiment 52 | D | 0.54 | 5 | |||||
| Embodiment 53 | G | 0.56 | 10 | |||||
| Embodiment 54 | H | 0.51 | 10 | |||||
| Embodiment 55 | A | Ferric sulfate | 20 | 80 | Have | 550 | 0.41 | 0 |
| Embodiment 56 | B | 0.34 | 0 | |||||
| Embodiment 57 | C | 0.35 | 5 | |||||
| Embodiment 58 | E | 0.41 | 5 | |||||
| Embodiment 59 | F | 0.38 | 10 | |||||
| Embodiment 60 | H | 0.36 | 10 | |||||
| Comparative example 37 | B | Do not have | Do not have | Do not have | Have | 600 | 0.21 | 90 |
| Comparative example 38 | C | 0.25 | 90 | |||||
| Comparative example 39 | G | 0.18 | 90 | |||||
| Comparative example 40 | H | 0.21 | 90 | |||||
| Comparative example 41 | I | 0.24 | 95 | |||||
| Comparative example 42 | J | 0.19 | 90 | |||||
| Comparative example 43 | A | Sulfuric acid | 10 | 5 | Do not have | - | - | - |
| Comparative example 44 | B | - | - | |||||
| Comparative example 45 | C | - | - | |||||
| Comparative example 46 | E | - | - | |||||
| Comparative example 47 | F | - | - | |||||
| Comparative example 48 | H | - | - | |||||
| Comparative example 49 | A | Ammonium sulfate | 5 | 10 | Have | 400 | 0.006 | 80 |
| Comparative example 50 | B | 0.008 | 84 | |||||
| Comparative example 51 | C | 0.004 | 86 | |||||
| Comparative example 52 | D | 0.006 | 82 | |||||
| Comparative example 53 | G | 0.004 | 80 | |||||
| Comparative example 54 | H | 0.003 | 86 | |||||
| Comparative example 55 | A | Thiocarbamide | 1 | 0.1 | Have | 400 | 0.004 | 85 |
| Comparative example 56 | B | 0.003 | 90 |
| Comparative example 57 | C | 0.004 | 89 | |||||
| Comparative example 58 | D | 0.006 | 86 | |||||
| Comparative example 59 | G | 0.004 | 91 | |||||
| Comparative example 60 | H | 0.002 | 90 | |||||
| Comparative example 61 | A | Do not have | Do not have | Do not have | Have | 850 | 3.1 | 75 |
| Comparative example 62 | B | 2.9 | 72 | |||||
| Comparative example 63 | C | 2.6 | 80 | |||||
| Comparative example 64 | D | 2.8 | 85 | |||||
| Comparative example 65 | E | 2.9 | 72 | |||||
| Comparative example 66 | F | 2.8 | 71 | |||||
| Comparative example 67 | G | 2.9 | 75 | |||||
| Comparative example 68 | H | 2.5 | 86 |
Table 3-2
| No. | The enriched layer proterties | |||||
| Enrichment composition under the coating | Enrichment composition thickness (μ m) | Enrichment (%) | Contain Si oxide amount (g/m 2) | |||
| GDS | EPMA | GDS | EPMA | |||
| Embodiment 31 | S | 4.5 | 5 | 300 | 300 | 0.1 |
| Embodiment 32 | 4.6 | 5 | 300 | 300 | 0.1 | |
| Embodiment 33 | 5.1 | 5 | 300 | 300 | 0.9 | |
| Embodiment 34 | 5.1 | 5 | 300 | 300 | 0.9 | |
| Embodiment 35 | 4.9 | 5 | 300 | 300 | 0.7 | |
| Embodiment 36 | 5.3 | 5 | 300 | 300 | 0.7 | |
| Embodiment 37 | S | 10.5 | 10 | 500 | 500 | 0.12 |
| Embodiment 38 | 10.4 | 10 | 500 | 500 | 0.12 | |
| Embodiment 39 | 10.2 | 10 | 500 | 500 | 0.1 | |
| Embodiment 40 | 10.1 | 10 | 500 | 500 | 0.1 | |
| Embodiment 41 | 9.8 | 10 | 500 | 500 | 0.9 | |
| Embodiment 42 | 10.0 | 10 | 500 | 500 | 0.9 | |
| Embodiment 43 | S | 3.1 | 3 | 400 | 400 | 0.08 |
| Embodiment 44 | 3.0 | 3 | 400 | 400 | 0.08 | |
| Embodiment 45 | 3.0 | 3 | 400 | 400 | 0.07 | |
| Embodiment 46 | 2.8 | 3 | 400 | 400 | 0.07 | |
| Embodiment 47 | 3.5 | 3 | 400 | 400 | 0.06 | |
| Embodiment 48 | 3.2 | 3 | 400 | 400 | 0.06 | |
| Embodiment 49 | S | 15.1 | 15 | 100 | 100 | 0.03 |
| Embodiment 50 | 14.8 | 15 | 100 | 100 | 0.03 | |
| Embodiment 51 | 15.0 | 15 | 100 | 100 | 0.03 | |
| Embodiment 52 | 15.8 | 15 | 100 | 100 | 0.02 | |
| Embodiment 53 | 15.3 | 15 | 100 | 100 | 0.02 | |
| Embodiment 54 | 15.4 | 15 | 100 | 100 | 0.02 | |
| Embodiment 55 | S | 20.0 | 20 | 600 | 600 | 0.2 |
| Embodiment 56 | 20.1 | 20 | 600 | 600 | 0.2 | |
| Embodiment 57 | 20.1 | 20 | 600 | 600 | 0.18 | |
| Embodiment 58 | 20.4 | 20 | 600 | 600 | 0.17 | |
| Embodiment 59 | 20.4 | 20 | 600 | 600 | 0.15 | |
| Embodiment 60 | 19.9 | 20 | 600 | 600 | 0.15 | |
| Comparative example 37 | Do not have | - | - | - | - | 0.001 |
| Comparative example 38 | - | - | - | - | 0.001 | |
| Comparative example 39 | - | - | - | - | 0.001 | |
| Comparative example 40 | - | - | - | - | 0.001 | |
| Comparative example 41 | - | - | - | - | 0.001 | |
| Comparative example 42 | - | - | - | - | 0.001 | |
| Comparative example 43 | S | (0.006) | (0.006) | 8 | 8 | 0.006 |
| Comparative example 44 | (0.005) | (0.005) | 8 | 8 | 0.005 | |
| Comparative example 45 | (0.004) | (0.004) | 8 | 8 | 0.004 | |
| Comparative example 46 | (0.004) | (0.004) | 8 | 8 | 0.004 | |
| Comparative example 47 | (0.003) | (0.003) | 8 | 8 | 0.003 |
| Comparative example 48 | (0.003) | (0.003) | 8 | 8 | 0.003 | |
| Comparative example 49 | S | (0.005) | (0.005) | 7 | 7 | 0.005 |
| Comparative example 50 | (0.005) | (0.005) | 7 | 7 | 0.005 | |
| Comparative example 51 | (0.004) | (0.004) | 7 | 7 | 0.004 | |
| Comparative example 52 | (0.004) | (0.004) | 7 | 7 | 0.004 | |
| Comparative example 53 | (0.003) | (0.003) | 7 | 7 | 0.003 | |
| Comparative example 54 | (0.003) | (0.003) | 7 | 7 | 0.003 | |
| Comparative example 55 | S | (0.005) | (0.005) | 5 | 5 | 0.005 |
| Comparative example 56 | (0.004) | (0.004) | 5 | 5 | 0.004 | |
| Comparative example 57 | (0.004) | (0.004) | 5 | 5 | 0.004 | |
| Comparative example 58 | (0.003) | (0.003) | 5 | 5 | 0.003 | |
| Comparative example 59 | (0.003) | (0.003) | 5 | 5 | 0.003 | |
| Comparative example 60 | (0.003) | (0.003) | 5 | 5 | 0.003 | |
| Comparative example 61 | Do not have | - | - | - | - | 0.03 |
| Comparative example 62 | - | - | - | - | 0.03 | |
| Comparative example 63 | - | - | - | - | 0.02 | |
| Comparative example 64 | - | - | - | - | 0.02 | |
| Comparative example 65 | - | - | - | - | 0.03 | |
| Comparative example 66 | - | - | - | - | 0.02 | |
| Comparative example 67 | - | - | - | - | 0.02 | |
| Comparative example 68 | - | - | - | - | 0.04 |
Table 3-3
| No. | The coating quality | ||||
| The coating outward appearance | Adherence of coating | Alloying speed | Chalking resistance | Sliding | |
| Embodiment 31 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 32 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 33 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 34 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 35 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 36 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 37 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 38 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 39 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 40 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 41 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 42 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 43 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 44 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 45 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 46 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 47 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 48 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 49 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 50 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 51 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 52 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 53 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 54 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 55 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 56 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 57 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 58 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 59 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 60 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 37 | × | × | × | × | × |
| Comparative example 38 | × | × | × | × | × |
| Comparative example 39 | × | × | × | × | × |
| Comparative example 40 | × | × | × | × | × |
| Comparative example 41 | × | × | × | × | × |
| Comparative example 42 | × | × | × | × | × |
| Comparative example 43 | × | × | × | × | × |
| Comparative example 44 | × | × | × | × | × |
| Comparative example 45 | × | × | × | × | × |
| Comparative example 46 | × | × | × | × | × |
| Comparative example 47 | × | × | × | × | × |
| Comparative example 48 | × | × | × | × | × |
| Comparative example 49 | × | × | × | × | × |
| Comparative example 50 | × | × | × | × | × |
| Comparative example 51 | × | × | × | × | × |
| Comparative example 52 | × | × | × | × | × |
| Comparative example 53 | × | × | × | × | × |
| Comparative example 54 | × | × | × | × | × |
| Comparative example 55 | × | × | × | × | × |
| Comparative example 56 | × | × | × | × | × |
| Comparative example 57 | × | × | × | × | × |
| Comparative example 58 | × | × | × | × | × |
| Comparative example 59 | × | × | × | × | × |
| Comparative example 60 | × | × | × | × | × |
| Comparative example 61 | ○ | × | ○ | ○ | × |
| Comparative example 62 | ○ | × | ○ | ○ | × |
| Comparative example 63 | ○ | × | ○ | ○ | × |
| Comparative example 64 | ○ | × | ○ | ○ | × |
| Comparative example 65 | ○ | × | ○ | ○ | × |
| Comparative example 66 | ○ | × | ○ | ○ | × |
| Comparative example 67 | ○ | × | ○ | ○ | × |
| Comparative example 68 | ○ | × | ○ | ○ | × |
Table 4-1
| No. | The steel grade class | Attachment material | Oxide treatment | |||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Oxygen amount (g/m in the oxide film thereon 2) | Rhombohedral iron ore content (%) | ||
| Embodiment 61 | K | Ammonium sulfate | 150 | 90 | Have | 650 | 0.82 | 10 |
| Embodiment 62 | L | 0.8 | 10 | |||||
| Embodiment 63 | M | 0.8 | 15 | |||||
| Embodiment 64 | N | 0.8 | 10 | |||||
| Embodiment 65 | O | 0.77 | 15 | |||||
| Embodiment 66 | P | 0.77 | 20 | |||||
| Embodiment 67 | Q | 0.85 | 25 | |||||
| Embodiment 68 | R | 0.82 | 20 | |||||
| Embodiment 69 | S | 0.82 | 10 | |||||
| Embodiment 70 | T | 0.82 | 15 | |||||
| Embodiment 71 | U | 0.77 | 20 | |||||
| Embodiment 72 | V | 0.79 | 15 | |||||
| Embodiment 73 | W | 0.79 | 20 | |||||
| Embodiment 74 | X | 0.8 | 20 | |||||
Table 4-2
| No. | The enriched layer proterties | |||||
| Enrichment composition under the coating | Enrichment composition thickness (μ m) | Enrichment (%) | Contain Si oxide amount (g/m 2) | |||
| GDS | EPMA | GDS | EPMA | |||
| Embodiment 61 | S | 3 | - | 300 | - | 0.15 |
| Embodiment 62 | 3 | - | 300 | - | 0.15 | |
| Embodiment 63 | 3 | - | 300 | - | 0.16 | |
| Embodiment 64 | 3 | - | 300 | - | 0.15 | |
| Embodiment 65 | 3 | - | 300 | - | 0.12 | |
| Embodiment 66 | 3 | - | 300 | - | 0.1 | |
| Embodiment 67 | 3 | - | 300 | - | 0.18 | |
| Embodiment 68 | 3 | - | 300 | - | 0.15 | |
| Embodiment 69 | 3 | - | 300 | - | 0.15 | |
| Embodiment 70 | 3 | - | 300 | - | 0.15 | |
| Embodiment 71 | 3 | - | 300 | - | 0.14 | |
| Embodiment 72 | 3 | - | 300 | - | 0.15 | |
| Embodiment 73 | 3 | - | 300 | - | 0.15 | |
| Embodiment 74 | 3 | - | 300 | - | 0.15 | |
Table 4-3
| No. | The coating quality | ||||
| The coating outward appearance | Adherence of coating | Alloying speed | Chalking resistance | Sliding | |
| Embodiment 61 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 62 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 63 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 64 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 65 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 66 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 67 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 68 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 69 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 70 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 71 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 72 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 73 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 74 | ○ | ○ | ○ | ○ | ○ |
Table 5-1
| No. | The steel grade class | Attachment material | Oxide treatment | |||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Oxygen amount (g/m in the oxide film thereon 2) | Rhombohedral iron ore content (%) | ||
| Embodiment 75 | A | Repone K | 50 | 100 | Have | 600 | 0.41 | 0 |
| Embodiment 76 | B | 0.43 | 0 | |||||
| Embodiment 77 | C | 0.39 | 0 | |||||
| Embodiment 78 | D | 0.35 | 0 | |||||
| Embodiment 79 | G | 0.42 | 0 | |||||
| Embodiment 80 | H | 0.41 | 0 | |||||
| Embodiment 81 | B | Ammonium oxalate | 100 | 800 | Have | 550 | 0.39 | 20 | |
| Embodiment 82 | C | 0.35 | 25 | ||||||
| Embodiment 83 | G | 0.32 | 40 | ||||||
| Embodiment 84 | H | 0.36 | 60 | ||||||
| Embodiment 85 | I | 0.31 | 20 | ||||||
| Embodiment 86 | J | 0.32 | 55 | ||||||
| Embodiment 87 | A | Sulfuric acid | 50 | 80 | Have | 550 | 0.42 | 0 | |
| Embodiment 88 | B | 0.43 | 0 | ||||||
| Embodiment 89 | C | 0.44 | 0 | ||||||
| Embodiment 90 | E | 0.42 | 0 | ||||||
| Embodiment 91 | F | 0.45 | 0 | ||||||
| Embodiment 92 | H | 0.41 | 0 | ||||||
| Embodiment 93 | A | Sodium hydroxide | 30 | 1 | Have | 600 | 0.51 | 10 | |
| Embodiment 94 | B | 0.52 | 10 | ||||||
| Embodiment 95 | C | 0.53 | 15 | ||||||
| Embodiment 96 | D | 0.5 | 20 | ||||||
| Embodiment 97 | G | 0.49 | 30 | ||||||
| Embodiment 98 | H | 0.56 | 45 | ||||||
| Embodiment 99 | A | Sodium tetraborate | 3 | 0.5 | Have | 650 | 0.59 | 0 | |
| Embodiment 100 | B | 0.58 | 0 | ||||||
| Embodiment 101 | C | 0.6 | 5 | ||||||
| Embodiment 102 | E | 0.57 | 5 | ||||||
| Embodiment 103 | F | 0.55 | 10 | ||||||
| Embodiment 104 | H | 0.6 | 20 | ||||||
| Comparative example 69 | B | Do not have | Do not have | Do not have | Have | 650 | 0.32 | 75 | |
| Comparative example 70 | C | 0.29 | 75 | ||||||
| Comparative example 71 | G | 0.15 | 90 | ||||||
| Comparative example 72 | H | 0.12 | 95 | ||||||
| Comparative example 73 | I | 0.35 | 75 | ||||||
| Comparative example 74 | J | 0.15 | 95 | |||||
| Comparative example 75 | A | Sulfuric acid | 50 | 80 | Do not have | - | - | - |
| Comparative example 76 | B | - | - | |||||
| Comparative example 77 | C | - | - | |||||
| Comparative example 78 | E | - | - | |||||
| Comparative example 79 | F | - | - | |||||
| Comparative example 80 | H | - | - | |||||
| Comparative example 81 | A | Ammonium oxalate | 100 | 800 | Have | 450 | 0.04 | 80 |
| Comparative example 82 | B | 0.04 | 85 | |||||
| Comparative example 83 | C | 0.03 | 85 | |||||
| Comparative example 84 | D | 0.03 | 90 | |||||
| Comparative example 85 | G | 0.02 | 90 |
Table 5-2
| No. | The enriched layer proterties | |||||
| Enrichment composition under the coating | Enrichment composition thickness (μ m) | Enrichment (%) | Contain Si oxide amount (g/m 2) | |||
| GDS | EPMA | GDS | EPMA | |||
| Embodiment 75 | Cl，K | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.15 |
| Embodiment 76 | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.14 | |
| Embodiment 77 | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.16 | |
| Embodiment 78 | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.14 | |
| Embodiment 79 | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.13 | |
| | Cl：3，K：3 | - | Cl：300，K：300 | - | 0.13 | |
| Embodiment 81 | C，N | C：30，N：30 | - | C：500，N：500 | - | 0.06 |
| Embodiment 82 | C：30，N：30 | - | C：300，N：300 | - | 0.06 | |
| Embodiment 83 | C：30，N：30 | - | C：300，N：300 | - | 0.05 | |
| Embodiment 84 | C：30，N：30 | - | C：300，N：300 | - | 0.07 | |
| Embodiment 85 | C：30，N：30 | - | C：300，N：300 | - | 0.06 | |
| Embodiment 86 | C：30，N：30 | - | C：300，N：300 | - | 0.06 | |
| Embodiment 87 | S | 3 | - | 300 | - | 0.04 |
| Embodiment 88 | 3 | - | 300 | - | 0.05 | |
| Embodiment 89 | 3 | - | 300 | - | 0.06 | |
| Embodiment 90 | 3 | - | 300 | - | 0.04 | |
| Embodiment 91 | 3 | - | 300 | - | 0.04 | |
| Embodiment 92 | 3 | - | 300 | - | 0.05 | |
| Embodiment 93 | Na | 2 | - | 100 | - | 0.17 |
| Embodiment 94 | 2 | - | 100 | - | 0.15 | |
| Embodiment 95 | 2 | - | 100 | - | 0.16 | |
| Embodiment 96 | 2 | - | 100 | - | 0.14 | |
| Embodiment 97 | 2 | - | 100 | - | 0.13 | |
| Embodiment 98 | 2 | - | 100 | - | 0.15 | |
| Embodiment 99 | Na，B | Na：2，B：2 | - | Na：100，B：100 | - | 0.14 |
| Embodiment 100 | Na：2，B：2 | - | Na：100，B：100 | - | 0.15 | |
| Embodiment 101 | Na：2，B：2 | - | Na：100，B：100 | - | 0.14 | |
| Embodiment 102 | Na：2，B：2 | - | Na：100，B：100 | - | 0.16 | |
| Embodiment 103 | Na：2，B：2 | - | Na：100，B：100 | - | 0.16 | |
| Embodiment 104 | Na：2，B：2 | - | Na：100，B：100 | - | 0.13 | |
| Comparative example 69 | Do not have | - | - | - | - | 0.001 |
| Comparative example 70 | - | - | - | - | 0.001 | |
| Comparative example 71 | - | - | - | - | 0.001 | |
| Comparative example 72 | - | - | - | - | 0.001 | |
| Comparative example 73 | - | - | - | - | 0.001 | |
| Comparative example 74 | - | - | - | - | 0.001 | |
| Comparative example 75 | S | (0.001) | - | 6 | - | 0.002 |
| Comparative example 76 | (0.001) | - | 6 | - | 0.003 | |
| Comparative example 77 | (0.001) | - | 6 | - | 0.002 | |
| Comparative example 78 | (0.001) | - | 6 | - | 0.002 |
| Comparative example 79 | (0.001) | - | 6 | - | 0.002 | |
| Comparative example 80 | (0.001) | - | 6 | - | 0.002 | |
| Comparative example 81 | C，N | (0.004) | - | C：6，N：6 | - | 0.002 |
| Comparative example 82 | (0.004) | - | C：6，N：6 | - | 0.002 | |
| Comparative example 83 | (0.004) | - | C：6，N：6 | - | 0.003 | |
| Comparative example 84 | (0.004) | - | C：6，N：6 | - | 0.002 | |
| Comparative example 85 | (0.004) | - | C：6，N：6 | - | 0.003 | |
| Comparative example 86 | (0.004) | - | C：6，N：6 | - | 0.002 |
Table 5-3
| No. | The coating quality | ||||
| The coating outward appearance | Adherence of coating | Alloying speed | Chalking resistance | Sliding | |
| Embodiment 75 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 76 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 77 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 78 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 79 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 80 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 81 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 82 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 83 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 84 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 85 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 86 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 87 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 88 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 89 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 90 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 91 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 92 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 93 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 94 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 95 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 96 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 97 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 98 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 99 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 100 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 101 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 102 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 103 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 104 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 69 | △ | × | × | × | × |
| Comparative example 70 | △ | × | × | × | × |
| Comparative example 71 | × | × | × | × | × |
| Comparative example 72 | × | × | × | × | × |
| Comparative example 73 | × | × | × | × | × |
| Comparative example 74 | × | × | × | × | × |
| Comparative example 75 | × | × | × | × | × |
| Comparative example 76 | × | × | × | × | × |
| Comparative example 77 | × | × | × | × | × |
| Comparative example 78 | × | × | × | × | × |
| Comparative example 79 | × | × | × | × | × |
| Comparative example 80 | × | × | × | × | × |
| Comparative example 81 | × | × | × | × | × |
| Comparative example 82 | × | × | × | × | × |
| Comparative example 83 | × | × | × | × | × |
| Comparative example 84 | × | × | × | × | × |
| Comparative example 85 | × | × | × | × | × |
| Comparative example 86 | × | × | × | × | × |
Table 6-1
| No. | The steel grade class | Attachment material | Oxide treatment | |||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Oxygen amount (g/m in the oxide film thereon 2) | Rhombohedral iron ore content (%) | ||
| Embodiment 105 | A | Antimony chloride | 20 | 10 | Have | 550 | 0.35 | 0 |
| Embodiment 106 | B | 0.39 | 0 | |||||
| Embodiment 107 | C | 0.4 | 0 | |||||
| Embodiment 108 | D | 0.36 | 0 | |||||
| Embodiment 109 | G | @ | 10 | |||||
| Embodiment 110 | H | 0.39 | 10 | |||||
| Embodiment 111 | B | Ammonium sulfate | 30 | 50 | Have | 600 | 0.54 | 0 |
| Embodiment 112 | C | 0.52 | 0 | |||||
| Embodiment 113 | G | 0.49 | 0 | |||||
| Embodiment 114 | H | 0.53 | 0 | |||||
| Embodiment 115 | I | 0.51 | 0 | |||||
| Embodiment 116 | J | 0.5 | 0 | |||||
| Embodiment 117 | A | Lead chloride | 1 | 1 | Have | 650 | 0.59 | 45 |
| Embodiment 118 | B | 0.6 | 45 | |||||
| Embodiment 119 | C | 0.62 | 50 | |||||
| Embodiment 120 | E | 0.59 | 60 | |||||
| Embodiment 121 | F | 0.58 | 65 | |||||
| Embodiment 122 | H | 0.59 | 65 | |||||
| Embodiment 123 | A | Thiocarbamide | 20 | 70 | Have | 600 | 0.56 | 0 |
| Embodiment 124 | B | 0.58 | 0 | |||||
| Embodiment 125 | C | 0.55 | 0 | |||||
| Embodiment 126 | D | 0.54 | 0 | |||||
| Embodiment 127 | G | 0.58 | 0 | |||||
| Embodiment 128 | H | 0.56 | 0 | |||||
| Embodiment 129 | A | Sodium-chlor | 25 | 5 | Have | 600 | 0.49 | 0 |
| Embodiment 130 | B | 0.52 | 0 | |||||
| Embodiment 131 | C | 0.51 | 5 | |||||
| Embodiment 132 | E | 0.49 | 5 | |||||
| Embodiment 133 | F | 0.48 | 10 | |||||
| Embodiment 134 | H | 0.51 | 20 | |||||
| Comparative example 87 | B | Do not have | Do not have | Do not have | Have | 550 | 0.12 | 90 |
| Comparative example 88 | C | 0.03 | 90 | |||||
| Comparative example 89 | G | 0.01 | 95 | |||||
| Comparative example 90 | H | 0.005 | 95 | |||||
| Comparative example 91 | I | 0.09 | 90 | |||||
| Comparative example 92 | J | 0.01 | 95 | |||||
| Comparative example 93 | A | Sodium-chlor | 25 | 5 | Do not have | - | - | - |
| Comparative example 94 | B | - | - | |||||
| Comparative example 95 | C | - | - | |||||
| Comparative example 96 | E | - | - | |||||
| Comparative example 97 | F | - | - | |||||
| Comparative example 98 | H | - | - | |||||
| Comparative example 99 | A | Thiocarbamide | 20 | 70 | Have | 450 | 0.05 | 75 |
| Comparative example 100 | B | 0.06 | 75 | |||||
| Comparative example 101 | C | 0.05 | 80 | |||||
| Comparative example 102 | D | 0.03 | 85 | |||||
| Comparative example 103 | G | 0.02 | 95 | |||||
| Comparative example 104 | H | 0.008 | 95 |
Table 6-2
| No. | The enriched layer proterties | |||||
| Enrichment composition under the coating | Enrichment composition thickness (μ m) | Enrichment (%) | Contain Si oxide amount (g/m 2) | |||
| GDS | EPMA | GDS | EPMA | |||
| Embodiment 105 | Cl | 2 | - | 300 | - | 0.08 |
| Embodiment 106 | 2 | - | 300 | - | 0.05 | |
| Embodiment 107 | 2 | - | 300 | - | 0.08 | |
| Embodiment 108 | 2 | - | 300 | - | 0.07 | |
| Embodiment 109 | 2 | - | 300 | - | 0.06 | |
| Embodiment 110 | 2 | - | 300 | - | 0.05 | |
| Embodiment 111 | S | 3 | - | 400 | - | 0.15 |
| Embodiment 112 | 3 | - | 400 | - | 0.14 | |
| Embodiment 113 | 3 | - | 400 | - | 0.13 | |
| Embodiment 114 | 3 | - | 400 | - | 0.14 | |
| Embodiment 115 | 3 | - | 400 | - | 0.14 | |
| Embodiment 116 | 3 | - | 400 | - | 0.15 | |
| Embodiment 117 | Cl | 2 | - | 300 | - | 0.13 |
| Embodiment 118 | 2 | - | 300 | - | 0.12 | |
| Embodiment 119 | 3 | - | 300 | - | 0.14 | |
| Embodiment 120 | 2 | - | 300 | - | 0.12 | |
| Embodiment 121 | 2 | - | 300 | - | 0.12 | |
| Embodiment 122 | 2 | - | 300 | - | 0.13 | |
| Embodiment 123 | S | 5 | - | 600 | - | 0.14 |
| Embodiment 124 | 5 | - | 600 | - | 0.15 | |
| Embodiment 125 | 5 | - | 600 | - | 0.14 | |
| Embodiment 126 | 5 | - | 600 | - | 0.14 | |
| Embodiment 127 | 5 | - | 600 | - | 0.16 | |
| Embodiment 128 | 5 | - | 600 | - | 0.14 | |
| Embodiment 129 | Na，Cl | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.14 |
| Embodiment 130 | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.14 | |
| Embodiment 131 | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.14 | |
| Embodiment 132 | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.15 | |
| Embodiment 133 | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.15 | |
| Embodiment 134 | Na：2，Cl：2 | - | Na：300， Cl：300 | - | 0.14 | |
| Comparative example 87 | - | - | - | - | - | 0.002 |
| Comparative example 88 | - | - | - | - | 0.002 | |
| Comparative example 89 | - | - | - | - | 0.003 | |
| Comparative example 90 | - | - | - | - | 0.002 | |
| Comparative example 91 | - | - | - | - | 0.002 | |
| Comparative example 92 | - | - | - | - | 0.002 | |
| Comparative example 93 | Na，Cl | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.002 |
| Comparative example 94 | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.001 | |
| Comparative example 95 | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.001 | |
| Comparative example 96 | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.002 | |
| Comparative example 97 | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.002 | |
| Comparative example 98 | (Cl：0.004， Na：0.003) | - | Cl：5，Na：5 | - | 0.003 |
| Comparative example 99 | S | 0.004 | - | 5 | - | 0.002 |
| Comparative example 100 | 0.004 | - | 5 | - | 0.003 | |
| Comparative example 101 | 0.004 | - | 5 | - | 0.003 | |
| Comparative example 102 | 0.004 | - | 5 | - | 0.002 | |
| Comparative example 103 | 0.004 | - | 5 | - | 0.002 | |
| Comparative example 104 | 0.004 | - | 5 | - | 0.003 |
Table 6-3
| No. | The coating quality | ||||
| The coating outward appearance | Adherence of coating | Alloying speed | Chalking resistance | Sliding | |
| Embodiment 105 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 106 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 107 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 108 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 109 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 110 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 111 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 112 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 113 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 114 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 115 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 116 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 117 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 118 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 119 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 120 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 121 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 122 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 123 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 124 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 125 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 126 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 127 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 128 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 129 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 130 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 131 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 132 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 133 | ○ | ○ | ○ | ○ | ○ |
| Embodiment 134 | ○ | ○ | ○ | ○ | ○ |
| Comparative example 87 | × | × | × | × | × |
| Comparative example 88 | × | × | × | × | × |
| Comparative example 89 | × | × | × | × | × |
| Comparative example 90 | × | × | × | × | × |
| Comparative example 91 | × | × | × | × | × |
| Comparative example 92 | × | × | × | × | × |
| Comparative example 93 | × | × | × | × | × |
| Comparative example 94 | × | × | × | × | × |
| Comparative example 95 | × | × | × | × | × |
| Comparative example 96 | × | × | × | × | × |
| Comparative example 97 | × | × | × | × | × |
| Comparative example 98 | × | × | × | × | × |
| Comparative example 99 | × | × | × | × | × |
| Comparative example 100 | × | × | × | × | × |
| Comparative example 101 | × | × | × | × | × |
| Comparative example 102 | × | × | × | × | × |
| Comparative example 103 | × | × | × | × | × |
| Comparative example 104 | × | × | × | × | × |
Table 7
| No. | The steel grade class | Attachment material | Oxide treatment | The enriched layer proterties | The coating quality | ||||||||||||
| Kind | Concentration (g/l) | Element-specific amount (mg/m 2) | Have or not | Be up to temperature (℃) | Enrichment composition under the coating | Enrichment composition thickness (μ m) | Contain Si oxide amount (g/m 2) | Generate material | Number (individual/20 μ m) | The coating outward appearance | Adherence of coating | Chalking resistance | Sliding | ||||
| GDS | EPMA | ||||||||||||||||
| Embodiment 135 | G | Sulfuric acid | 50 | 70 | Have | 600 | S | 5 | 5 | 0.7 | Granular MnS | 8.8 | ○ | ○ | ◎ | ○ | |
| Embodiment 136 | | 80 | 550 | S | 5 | 5 | 0.8 | 10.6 | ○ | ○ | ◎ | ○ | |||||
| Embodiment 137 | G | 30 | 600 | S | 3 | 3 | 0.5 | 2.4 | ○ | ○ | ○ | ○ | |||||
| Embodiment 138 | E | 30 | 550 | S | 3 | 3 | 0.4 | 3 | ○ | ○ | ○ | ○ | |||||
| Embodiment 139 | G | Ammonium sulfate | 30 | 100 | Have | 650 | S | 10 | 10 | 0.1 | Granular MnS | 6.2 | ○ | ○ | ◎ | ○ | |
| Embodiment 140 | | 80 | 550 | S | 6 | 6 | 0.1 | 8 | ○ | ○ | ◎ | ○ | |||||
| Embodiment 141 | G | 30 | 600 | S | 3 | 3 | 0.06 | 2.2 | ○ | ○ | ○ | ○ | |||||
| Embodiment 142 | E | 30 | 550 | S | 3 | 3 | 0.04 | 2.8 | ○ | ○ | ○ | ○ | |||||
| Embodiment 143 | | Thiocarbamide | 20 | 70 | Have | 700 | S | 2 | 2 | 0.09 | Granular MnS | 6.6 | ○ | ○ | ◎ | ○ | |
| Embodiment 144 | E | 70 | 700 | S | 3 | 3 | 0.07 | 8.4 | ○ | ○ | ◎ | ○ | |||||
| Embodiment 145 | | 20 | 700 | | 1 | 1 | 0.03 | 0.2 | ○ | ○ | ○ | ○ | |||||
| Embodiment 146 | | 20 | 700 | | 1 | 1 | 0.02 | 1.2 | ○ | ○ | ○ | ○ | |||||
The possibility of industrial utilization
Utilize the present invention, even use the many base steel sheet of Si content, also can obtain the good hot-dip galvanizing sheet steel of adherence of coating and sliding. And it is also good that the chalking resistance of the alloyed hot-dip galvanized steel sheet that alloying obtains is carried out in this galvanizing. In addition, two kinds of clad steel sheets can obtain under higher yields.
Claims (11)
1. hot-dip galvanizing sheet steel has:
Steel plate, it contains the Si of 0.1～3.0 quality %;
Hot galvanized layer; With
Enriched layer between described steel plate and described hot galvanized layer, contains the oxide compound of Si, and thickness is 0.01～100 μ m, and has at least a kind of composition that is selected from S, C, Cl, Na, K, B, P, F and N.
2. hot-dip galvanizing sheet steel as claimed in claim 1, wherein, the concentration of the described composition of the described steel plate of concentration ratio of the described composition of described enriched layer is high more than 10%.
3. hot-dip galvanizing sheet steel as claimed in claim 1, wherein, the amount of the oxide compound of the described Si of containing of described enriched layer converts with oxygen and counts 0.01～1g/m
2
4. hot-dip galvanizing sheet steel as claimed in claim 1 wherein, also has the Fe layer under described hot galvanized layer.
5. hot-dip galvanizing sheet steel as claimed in claim 1, wherein, described enriched layer is to be disperseed to form by the compound of the composition of described composition and described steel plate.
6. hot-dip galvanizing sheet steel as claimed in claim 5, wherein, described composition is S, as the granular MnS more than the particle diameter 50nm of described compound, exists more than 5 for arbitrary section at per 20 μ m on the direction at the interface that is parallel to described hot galvanized layer and described steel plate.
7. as each described hot-dip galvanizing sheet steel in the claim 1～6, wherein, described hot galvanized layer is alloyed zinc hot dip galvanized layer.
8. the manufacture method of a hot-dip galvanizing sheet steel, it has following operation successively:
On the surface of the steel plate that contains Si:0.1～3 quality %, adhere to the operation of at least a kind of material that is selected from S, C, Cl, Na, K, B, P, F, N and their compound;
Heating is attached with the steel plate of described material, and forming rhombohedral iron ore content at this surface of steel plate is the operation of the oxide film thereon below the 70 quality %;
With described oxide film thereon reductive operation; With
The steel plate that described reduction is good carries out the operation of pot galvanize.
9. the manufacture method of hot-dip galvanizing sheet steel as claimed in claim 6, wherein, described heating be under the oxidative environment for Fe, the Da Wendu that is up to of steel plate carries out under surpassing 500 ℃.
10. the manufacture method of hot-dip galvanizing sheet steel as claimed in claim 8 or 9 wherein, is further carried out Alloying Treatment after described pot galvanize operation.
11. the manufacture method of a hot-dip galvanizing sheet steel, it is characterized in that, with the steel plate that contains Si:0.1～3 quality % is substrate, before pot galvanize is implemented on the surface of this steel plate, form rhombohedral iron ore content on the surface of base steel sheet and be the oxide film thereon below the 70 quality %, then reduce and handle the back and implement pot galvanize.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004294706 | 2004-10-07 | ||
| JP294706/2004 | 2004-10-07 | ||
| JP101781/2005 | 2005-03-31 | ||
| JP200343/2005 | 2005-07-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101048527A true CN101048527A (en) | 2007-10-03 |
Family
ID=38772226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580036387 Pending CN101048527A (en) | 2004-10-07 | 2005-10-07 | Hot-dip galvanized steel sheet and manufacturing method therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101048527A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827340A (en) * | 2011-09-26 | 2014-05-28 | 杰富意钢铁株式会社 | Alloyed hot-dipped galvanized steel sheet having excellent corrosion resistance after coating |
| CN104040001A (en) * | 2012-01-05 | 2014-09-10 | 杰富意钢铁株式会社 | Hot-dip galvannealed steel sheet |
| CN104508169A (en) * | 2012-08-03 | 2015-04-08 | 新日铁住金株式会社 | Galvanized steel sheet and manufacturing method therefor |
-
2005
- 2005-10-07 CN CN 200580036387 patent/CN101048527A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103827340A (en) * | 2011-09-26 | 2014-05-28 | 杰富意钢铁株式会社 | Alloyed hot-dipped galvanized steel sheet having excellent corrosion resistance after coating |
| CN103827340B (en) * | 2011-09-26 | 2016-03-02 | 杰富意钢铁株式会社 | The alloyed hot-dip galvanized steel sheet of excellent corrosion resistance after application |
| CN104040001A (en) * | 2012-01-05 | 2014-09-10 | 杰富意钢铁株式会社 | Hot-dip galvannealed steel sheet |
| CN104040001B (en) * | 2012-01-05 | 2016-03-09 | 杰富意钢铁株式会社 | Alloyed hot-dip galvanized steel sheet |
| CN104508169A (en) * | 2012-08-03 | 2015-04-08 | 新日铁住金株式会社 | Galvanized steel sheet and manufacturing method therefor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1575348A (en) | Hot press forming method, and a plated steel material therefor and its manufacturing method | |
| RU2621501C1 (en) | Product moulded by hot forming and manufacturing method for product moulded by hot forming | |
| KR101974182B1 (en) | Plated steel plate for hot pressing and hot pressing method of plated steel plate | |
| TWI437122B (en) | Hot dip al-zn coated steel sheet and method for producing the same | |
| US20080070060A1 (en) | Hot-Dip Galvanized Sheet and Method for Manufacturing Same | |
| CN1639376A (en) | Surface treated steel plate and method for production thereof | |
| CN1809650A (en) | Hot press-formed article and method for its manufacture | |
| CN1531604A (en) | High-strength alloyed aluminum-system plated steel sheet and high-strength automotive part excellent in heat resistance and after-painting corrosion resistance | |
| JP5417797B2 (en) | High strength hot dip galvanized steel sheet and method for producing the same | |
| CN103582717B (en) | High-strength hot-dipped galvanized steel sheet having excellent plating adhesion, and method for producing same | |
| JPWO2014171417A1 (en) | Hot-pressed plated steel sheet, hot-pressing method of plated steel sheet, and automotive parts | |
| EP4023787A1 (en) | Hot stamp molded body | |
| JP5020526B2 (en) | Alloyed hot-dip galvanized steel sheet with excellent corrosion resistance, workability, and paintability and method for producing the same | |
| JP4506128B2 (en) | Hot press-formed product and method for producing the same | |
| WO2021106178A1 (en) | Plated steel sheet for hot stamping and hot-stamped member | |
| JP2008144264A (en) | High-strength hot-dip galvannealed steel sheet, and method for manufacturing high-strength hot-dip galvannealed steel sheet | |
| CN101048527A (en) | Hot-dip galvanized steel sheet and manufacturing method therefor | |
| CN103827340B (en) | The alloyed hot-dip galvanized steel sheet of excellent corrosion resistance after application | |
| CN1701130A (en) | Steel sheet plated by hot dipping with alloyed zinc with excellent adhesion and process for producing the same | |
| JP4810980B2 (en) | Method for producing hot-dip galvanized steel sheet and method for producing alloyed hot-dip galvanized steel sheet | |
| EP4268989A1 (en) | Steel sheet for hot stamping and hot-stamped member | |
| JP4747656B2 (en) | Method for producing high-tensile hot-dip galvanized steel sheet and method for producing high-tensile alloyed hot-dip galvanized steel sheet | |
| JP3254160B2 (en) | Alloyed hot-dip galvanized steel sheet with excellent adhesion | |
| JP7288228B2 (en) | HOT STAMP MOLDED PRODUCT AND MANUFACTURING METHOD THEREOF AND ALUMINUM PLATED STEEL STEEL | |
| WO2024166854A1 (en) | Hot-stamping shaped article and manufacturing method for same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20071003 |