CN1701130A - Steel sheet plated by hot dipping with alloyed zinc with excellent adhesion and process for producing the same - Google Patents
Steel sheet plated by hot dipping with alloyed zinc with excellent adhesion and process for producing the same Download PDFInfo
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- CN1701130A CN1701130A CN 200480001145 CN200480001145A CN1701130A CN 1701130 A CN1701130 A CN 1701130A CN 200480001145 CN200480001145 CN 200480001145 CN 200480001145 A CN200480001145 A CN 200480001145A CN 1701130 A CN1701130 A CN 1701130A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 231
- 239000010959 steel Substances 0.000 title claims abstract description 231
- 238000000034 method Methods 0.000 title claims description 45
- 239000011701 zinc Substances 0.000 title claims description 29
- 229910052725 zinc Inorganic materials 0.000 title claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 16
- 238000007598 dipping method Methods 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims description 189
- 239000011248 coating agent Substances 0.000 claims description 187
- 239000000463 material Substances 0.000 claims description 125
- 238000007747 plating Methods 0.000 claims description 76
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- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 46
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- 238000005275 alloying Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
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- 238000010301 surface-oxidation reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 43
- 238000012360 testing method Methods 0.000 description 38
- 239000002184 metal Substances 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 25
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- 238000000137 annealing Methods 0.000 description 21
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001953 recrystallisation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
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- 230000000007 visual effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
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Abstract
The present invention provides a galvannealed steel sheet excellent in the adhesion with a base steel sheet and a manufacturing method thereof. The galvannealed steel sheet according to the invention has, in an interface between a galvannealed layer and the base steel sheet thereon the galvannealed layer is formed, an irregularity that has a depth of 10 nm or more at a pitch of 0.5 mu m or less at least one per 5 mu m of a length of the interface.
Description
Technical field
The present invention relates to the good alloyed hot-dip galvanized steel sheet and the manufacture method thereof of adherence of coating of a kind of former relatively material steel plate (mother metal).
Background technology
In recent years, use surface treated steel plate from rust-preventing characteristic to former material steel plate that give in fields such as automobile, household electrical appliances, building materials.Wherein also use can make at a low price and application after the good alloyed hot-dip galvanized steel sheet of rust-preventing characteristic.At automotive field, in the high strength of former material steel plate, lightweight is also in development especially.The usage quantity that has the high strength alloyed hot-dip zinc-coated steel plate of rust-preventing characteristic concurrently has the tendency of increase.
Yet, because the coating of alloyed hot-dip galvanized steel sheet and the interface fragility of former material steel plate, for example when using metal die to carry out drawing, coating is peeled off, because the coating of peeling off makes the quality product variation, thereby need clean metal die continually attached on the metal die.Have and carrying out bonding adhesive bond portion with subsidiary material, coating is peeled off, the situation of the bonding strength that can not get expecting.Perhaps have to splash breaking that stone etc. causes when advancing owing to automobile in the winter time and cause coating to be peeled off, can not keep the problem of the rust-preventing characteristic of expectation.
Usually, hot-dip galvanizing sheet steel, in pretreatment procedure, degreasing and/or pickling are carried out in the surface of former material steel plate and clean, perhaps omit pretreatment procedure and remove the oil content of former material surface of steel plate in the preheating oven internal combustion after, in slightly acidicization or reducing atmosphere, carry out preheating, in reducing atmosphere, carry out recrystallization annealing.By in reducing atmosphere former material steel plate be cooled to the temperature that be fit to plating, with atmosphere contact and be impregnated in the pot galvanize bath of adding trace of Al (about 0.1～0.2 quality %) after, thickness of coating adjusted and make thereafter.
The coating of alloyed hot-dip galvanized steel sheet, the Fe-Zn alloy phase that is formed by the mutual diffusion mutually of Fe and Zn constitutes.At the near interface of coating and former material steel plate, form the high Fe-Zn alloy phase of Fe containing ratio, along with near coating top layer side, form the low Fe-Zn alloy phase of Fe containing ratio.(for example Γ mutually or Γ 1 phase) is hard and more crisp because the Fe-Zn alloy phase that the Fe containing ratio that forms at the near interface of coating and former material steel plate is high, if thereby blocked up formation, then encouraged the vulnerability at the interface of coating and former material steel plate.And, because the coating of alloyed hot-dip galvanized steel sheet is the Fe-Zn alloy phase, also exist the tack of the coating on the interface of coating and former material steel plate poor, the shortcoming of on the interface of coating and steel plate, peeling off easily.
In the past, in alloyed hot-dip galvanized steel sheet, method to the adherence of coating that improves former relatively material steel plate has been carried out all research, for example, in patent documentation 1, following technology is disclosed: during extremely low carbon IF steel (Interstitial FreeSteel) below mother metal uses C:0.006 quality %, by an amount of Si, the P etc. of adding in steel, and the diffusion of the Zn in the promotion coating on the crystal boundary of mother metal improves adherence of coating.Yet to the requirement of in recent years high strength, extremely low carbon IF steel is because intensity is low, the performance that can not be met.In addition, at the steel plate that uses high strength (for example, more C and other alloying elements of containing make the steel plate of tensile strength more than 440MPa in mother metal) time, there is the problem of the tack of the coating tunicle that the method with record in the above-mentioned patent documentation 1 not necessarily can be met.
In addition, in patent documentation 2, record mother metal and use and to contain P:0.010～0.10 quality %, Si:0.05～0.20 quality %, and the P that satisfies Si 〉=P improves the technology of the tack of coating tunicle when adding steel.Yet, exist in and be applicable to when above-mentioned P adds steel plate beyond the steel, the problem of the tack of the coating tunicle that is met surely of differing.
And, in patent documentation 3, following technology is disclosed: when mother metal adds the high strength residual austenite steel of Si, Al for the soft steel that uses C:0.05～0.25 quality % is also an amount of, add fixedly crystal boundary C such as Ti, Nb by an amount of in steel, and raising plating boundary strength.Yet this is the technology about the residual austenite steel, has the method with record in the patent documentation 3, does not have the high tensile steel plate of residual austenite phase not necessarily can obtain the problem of enough performances to other.
In addition, for the method for the tack at the interface of coating that improves alloyed hot-dip galvanized steel sheet and steel plate, the shape that is conceived to the interface of coating and former material steel plate had been carried out all research in the past.For example in patent documentation 4 and 5, disclose a kind of roughness that makes except that the surface of steel plate after the de-plating, counted technology more than the 6.5 μ m with 10 mean roughness Rz.In addition, in patent documentation 6, disclose and a kind of P has been added steel, making roughness Rz except that the steel surface behind the de-plating tunicle is 12 〉=Rz 〉=0.0075Sm+6.7 (wherein, Rz (μ m): 10 mean roughness, Sm (μ m): technology concavo-convex equispaced).Yet, present inventors are through wholwe-hearted research, the result obtains following new opinion: for the shape at the interface of coating that helps adherence of coating and base steel sheet, very important with the micro concavo-convex that 10 mean roughness Rz that explain in the opinion in the past can not define, the remarkable good alloyed hot-dip galvanized steel sheet of the adherence of coating that can in the past not had thus.
Patent documentation 1: specially permit communique No. 3163986
Patent documentation 2: specially permit communique No. 2993404
Patent documentation 3: the spy opens the 2001-335908 communique
Patent documentation 4: specially permit communique No. 2638400
Patent documentation 5: specially permit communique No. 2932850
Patent documentation 5: specially permit communique No. 2976845
Summary of the invention
The present invention, purpose is to provide a kind of and compares with product in the past, and adherence of coating is good alloyed hot-dip galvanized steel sheet and manufacture method thereof significantly.
Main points of the present invention are as follows:
(I) the good alloyed hot-dip galvanized steel sheet of a kind of adherence of coating, it is characterized in that, at the alloyed hot-dip zinc coating with form on the interface of former material steel plate of this alloyed hot-dip zinc coating, spacing be 0.5 μ m following and have an above degree of depth of 10nm concavo-convex in existence on the interface length of per 5 μ m more than 1.
(II) the good alloyed hot-dip galvanized steel sheet of a kind of adherence of coating, it is characterized in that, the surface shape of the former material steel plate of observing for peeling off the alloyed hot-dip zinc coating, use cutoff wavelength are that the expanded area ratio Sdr that the Hi-pass filter of 0.5 μ m is measured is more than 2.0%.
(III) as above-mentioned (I) or (II) the good alloyed hot-dip galvanized steel sheet of described adherence of coating, it is characterized in that, above-mentioned former material steel plate is in quality %, contains that C:0.25% is following, Si:0.03～2.0% and P:0.005～0.07%, and for satisfying the composition of following (1) formula.
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
(IV) as the good alloyed hot-dip galvanized steel sheet of above-mentioned (III) described adherence of coating, it is characterized in that, coating was attached in the tight last stage of above-mentioned former material steel plate, before above-mentioned coating is adhered to, former material steel plate is heat-treated, so that the Si that contains in this former material steel plate not selected oxidation on the surface.
(V) as above-mentioned (III) or (IV) the good alloyed hot-dip galvanized steel sheet of described adherence of coating, it is characterized in that having the oxide compound of Si in the base steel below above-mentioned interface is tight.
(VI) as above-mentioned (III), (IV) or (V) the good alloyed hot-dip galvanized steel sheet of described adherence of coating, it is characterized in that above-mentioned former material steel plate is for also containing the composition below the Mn:5%, below the S:0.01% and below the Al:0.08% in quality %.
(VII) as the good alloyed hot-dip galvanized steel sheet of each described adherence of coating in above-mentioned (III)～(VI), it is characterized in that above-mentioned former material steel plate is for also to contain the composition more than a kind or 2 kinds that is selected from below the Ti:0.2%, below the Nb:0.2% and in below the V:0.2% in quality %.
(VIII) manufacture method of the good alloyed hot-dip galvanized steel sheet of a kind of adherence of coating, it is characterized in that, to containing below the C:0.25% in quality %, Si:0.03～2.0% and P:0.005～0.07%, and be that the former material steel plate that satisfies the composition of following (1) formula is heat-treated, so that the not selected surface oxidation of the Si in the steel, be cooled to plating temperature in the atmosphere below oxygen concentration is 0.005 volume % afterwards, should impregnated in the pot galvanize bath and form coating by former material steel plate, then be heated to 460～600 ℃ temperature range, remain on the Alloying Treatment of implementing coating in this Heating temperature scope with the above heat-up rate of 20 ℃/s.
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
As the manufacture method of the good alloyed hot-dip galvanized steel sheet of above-mentioned (VIII) described adherence of coating, it is characterized in that (IX) above-mentioned former material steel plate is for also containing the composition below the Mn:5%, below the S:0.01% and below the Al:0.08% in quality %.
(X) as above-mentioned (VIII) or (IX) manufacture method of the good alloyed hot-dip galvanized steel sheet of described adherence of coating, it is characterized in that, above-mentioned former material steel plate is for also to contain the composition more than a kind or 2 kinds that is selected from below the Ti:0.2%, below the Nb:0.2% and in below the V:0.2% in quality %, and the Si content in above-mentioned heat-up rate and the former material steel plate satisfies following (2) formula.
ST≥3.25/[Si]……??(2)
Wherein, the ST in the formula be heat-up rate (℃/s), [Si] is the content (quality %) of the Si in the steel plate.
Description of drawings
Fig. 1 is in the alloyed hot-dip galvanized steel sheet of the present invention, and dissolving removes the SEM photo of the surface of steel plate after the de-plating.
Fig. 2 is the section S EM photo of alloyed hot-dip galvanized steel sheet of the present invention.
Fig. 3 is in the explanation alloyed hot-dip galvanized steel sheet of the present invention, the figure of the micro concavo-convex that forms at the interface of coating and steel plate.
Fig. 4 is illustrated in the chart of the relation of micro concavo-convex proportion that the interface of coating and steel plate forms and plating boundary strength.
Fig. 5 is the chart of the relation of expression expanded area ratio Sdr and plating boundary strength.
Fig. 6 is to containing the steel plate more than a kind or 2 kinds among Ti, Nb and the V, representing Si content and the heat-up rate chart to the influence of the area occupation ratio of micro concavo-convex.
Fig. 7 is the figure that is illustrated in the summary of the test sample that the tension test that is used for estimating adherence of coating 1 uses.
Fig. 8 is the figure of summary that expression is used to estimate the test (bending-replication processing experiment) of adherence of coating 2.
Fig. 9 be expression in order to estimate adherence of coating 4, to be arranged in the metal die with stiffening web, be configured as the figure of summary of the test of コ shape.
Figure 10 is a 3D-SEM image of removing the former material surface behind the coating of alloyed hot-dip galvanized steel sheet, (a) is the bad material of tack (comparative example), (b) is tack good material (example).
In the explanation of representing the symbol in each accompanying drawing down.
1: concavo-convex curve, 2: paddy portion, 3,4: peak portion, 5: test materials, 6: caking agent, 7: spacer, 8: arrow, 9: test materials, 10: concavity metal die, 11: convex metal die, 12: arrow, 13: test materials, 14: punch die, 15: blank holder 16: the metal die, 17 with stiffening web: drift
Embodiment
Below, the present invention is described in detail
First invention of the present invention is the good alloyed hot-dip galvanized steel sheet of a kind of adherence of coating, at the alloyed hot-dip zinc coating with form on the interface of former material steel plate of this alloyed hot-dip zinc coating, spacing be 0.5 μ m following and have an above degree of depth of 10nm concavo-convex in existence on the interface length of per 5 μ m more than 1.
Present inventors found that through wholwe-hearted research: by form successive micro concavo-convex portion on the interface of coating and steel plate, owing to the cementation effect, can significantly improve the tack at the interface of coating and former material steel plate.
Fig. 1 and Fig. 2 be expression as the continuous jog at the interface of the coating of one embodiment of the present of invention and former material steel plate, by the SEM photo of scanning electronic microscope (SEM) when observing.Fig. 1 grants ultrasonic wave and dissolves to remove the alloyed hot-dip zinc coating in alkaline solution, the former material surface of steel plate at the interface of coating and former material steel plate is exposed, the surperficial SEM photo when observing by scanning electronic microscope.Fig. 2 grinds the cross section of alloyed hot-dip galvanized steel sheet, after in 0.1 quality % nital, corroding, and the section S EM photo when observing by scanning electronic microscope.The spacing of this jog is more little, and the concavo-convex degree of depth is dark more good more.Present inventors study the relation of the concavo-convex state at adherence of coating and plating interface, found that: concavo-convex the exist ratio of the degree of depth more than 10nm that exists with the spacing below the 0.5 μ m has very big relation with the adhesion strength of coating.The jog at the interface of coating and former material steel plate by using scanning electronic microscope (SEM) or using transmission electron microscope (TEM) that the cross section of coating is observed, can be measured the spacing and the degree of depth, under represent measuring method.
The mensuration of the spacing and the degree of depth can followingly be carried out: as shown in Figure 3, use concavo-convex curve 1 by the confirmable interface of above-mentioned cross-section, on this concavo-convex curve 1, on certain datum length L (for example 0.5 μ m), see the paddy portion 2 that is in the height extreme lower position, be in highly 2 peak portions 3 of extreme higher position respectively with both sides in this paddy portion 2,4, to measure this 2 peak portions 3 in the longitudinal direction, slant range between 4 will be measured above-mentioned 2 peak portions 3 as spacing P on short transverse, slant range in 4 between a lower peak portion 3 and the paddy portion 2 is as depth D.Use this measuring method, if in datum length L (for example 0.5 μ m), depth D becomes then that to have spacing P be that the following and depth D of 0.5 μ m is the situation of the above micro concavo-convex of 10nm more than 10nm.
Yet in the present invention, spacing is that 0.5 μ m is following and have the concavo-convex interface length at per 5 μ m of the above depth D of 10nm (here so-called interface length is meant on the thickness direction cross section, the slant range between 2 on the interface.) on need to exist more than 1.This is because if do not exist with this ratio, then can not help to improve adherence of coating.This concavo-convex measuring method carries out as described below.Promptly, the coating cross section that 10 μ m are long is divided into each datum length L (0.5 μ m), in 20 visuals field, observe (each visual field is measured more than 5000 times in multiplying power at least), wherein, to have above-mentioned spacing P be that 0.5 μ m is following and have a visual field of the micro concavo-convex of the above depth D of 10nm to counting.Above-mentioned steps is carried out in any coating cross section 5 times, the visual field number that will have an above-mentioned micro concavo-convex relatively all visuals field number (percentage of 20 * 5=100) visual field number is as the shared ratio of micro concavo-convex, this ratio taken as in the situation more than 10% satisfy above-mentioned condition.
The relation of representing the adhesion strength of ratio that the above-mentioned micro concavo-convex measured like this is shared and coating at Fig. 4.As shown in Figure 4, if the shared ratio of micro concavo-convex more than 10%, then the adhesion strength of coating shows high value.At this, the adhesion strength of coating, the method that is to use the aftermentioned embodiment evaluation of adherence of coating 1 () to be put down in writing is carried out tension test, removes tensile strength and the value of trying to achieve with bond area.
From the above mentioned, in the present invention, on the interface of alloyed hot-dip zinc coating and former material steel plate, spacing be 0.5 μ m following and have the concavo-convex of the above degree of depth of 10nm need be more than 1 in existence on the interface length of per 5 μ m.
As shown in Figure 1, concavo-convex formation has directivity, but just passable as long as satisfy this condition on the cross section of the direction of concavo-convex the closeest existence.
Then, second invention of the present invention is described.
Second invention of the present invention is the good alloyed hot-dip galvanized steel sheet of a kind of adherence of coating, it is characterized in that, the surface shape of the former material steel plate of observing for removing the alloyed hot-dip zinc coating, use cutoff wavelength are that the expanded area ratio Sdr that the Hi-pass filter of 0.5 μ m is measured is more than 2.0%.
Present inventors, as can be by the surface to as the index measured of the continuous concavo-convex degree at above-mentioned Fig. 1 and steel plate interface shown in Figure 2, be conceived to expanded area ratio Sdr.The ratio that the area that has actual concavo-convex surface on the zone does not have concavo-convex planar area is relatively measured in expanded area ratio (Developed interfacial area ratio) expression, is by the expressed value of following formula.
Expanded area ratio (Sdr)=(A-B)/B * 100 (%)
A: measure the surface-area that has actual concavo-convex interface on the zone
B: measuring on the zone does not have concavo-convex planar area
Therefore, on concavo-convex big, interface that surface-area is bigger, Sdr becomes bigger value.Because plating interface shape of the present invention is very small concavo-convex, thereby is difficult to carry out quantitative evaluation.Yet, can obtain its high magnification SEM image by presenting good interface, calculate above-mentioned evaluation number accurately and to small concavo-convex the evaluation.Promptly, to the former material surface behind the coating of removing alloyed hot-dip steel plate, be coated with the thick Au of tens of nm to avoid the influence of surface composition, use the electron beam three-dimensional roughness analytical equipment ERA-8800FE of エ リ オ ニ Network ス company to measure, carry out shape analysis, obtain expanded area ratio Sdr.Shape analysis is carried out under the 15V acceleration voltage, and (visual field area: 12 μ m * 9 μ m), the line data of going forward side by side is handled to accommodate 10000 times the visual field with 1200 * 900 resolution.The value of expanded area ratio Sdr is measured optional zone, averages and tries to achieve.And, use the correction of this height of devices direction, use the contact pin type in NIST, be used, VLSI ス Application ダ one De company is produced, optical profile type surface roughness measurement machine SHS film difference of altitude standard (three kinds of difference of altitude 18nm, 88nm, 450nm) as object as the state-run research institute of the U.S..The Hi-pass filter that re-uses cutoff wavelength and be 0.5 μ m is for the 3D shape calculation of parameter.This handles for removing the influence that long period rises and falls, and target size concavo-convex is estimated very important.Cutoff wavelength also needs the concavo-convex size that will estimate relatively and suitably selects.By all results of study as can be known, based on the result of the high pass filter, processes of 0.5 μ m cutoff wavelength, be good for dependency and reproducibility with boundary strength.Thereby handle with this understanding.Example is measured in expression in Figure 10.Figure 10 (a) is the 3D-SEM image of the bad material of tack (comparative example), Figure 10 (b) is the 3D-SEM image of tack good material (example), the value of expanded area ratio Sdr is 1.7% in comparative example, be 2.5% in example, in image and Sdr value, show evident difference.On the other hand, the Ra in this image is 0.00531 μ m in comparative example, is 0.00547 μ m in example, can not use general Ra commonly used to make this difference value as can be known, can confirm the validity of evaluation assessment.
Fig. 5 is the chart of the relation of the plating boundary strength on the interface of expression expanded area ratio Sdr value and coating and former material steel plate.As shown in Figure 5, expanded area ratio Sdr can obtain high boundary strength 2.0% when above.In the present invention, though using the expanded area comparison shape be considered to the three-dimensional parameter that is suitable for estimating most stipulates, but also can after carrying out same high pass filter, processes, use the RSm (mean length of roughness curve key element) of two-dimensional parameter to estimate.
Then, the suitable steel plate that uses as former material steel plate of the present invention is described.
Former material steel plate is preferably in quality %, contains that C:0.25% is following, Si:0.03～2.0% and P:0.005～0.07%, and for satisfying the composition of following (1) formula.
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
At this, composition C, P and Si are above-mentioned scope in the steel of preferred former material steel plate (mother metal), are based on following reason.Below, the content of element (%) is all represented quality %.
Below the C:0.25%
By increasing the intensity that C content can easily improve steel, be the essential element of high strength of former material steel plate (mother metal).If yet C content is too much, the ductility of mother metal or weldability variation, thereby C content is preferably below 0.25%.In addition, be under the situation of deep drawing purposes at steel plate, preferably do not do one's utmost to add C.
Si：0.03～2.0％
Si is the strengthening element of steel, still forms the element of continuous jog simultaneously on the interface of coating and former material steel plate.Though do not know in detail, if but Si contains quantity not sufficient 0.03%, then be difficult to form continuous jog, on the other hand, because Si postpones alloying reaction, thereby does not preferably do one's utmost to add on the viewpoint of alloying, if Si content surpasses 2.0%, the effect that then improves adherence of coating is saturated, is easy to generate the problem that makes the alloying reaction excessive deferral simultaneously.Therefore, Si content is preferably in 0.03～2.0% scope.
P：0.005～0.07％
P is the strengthening element of steel.Yet, owing to be significant grain boundary segregation element, make the alloying reaction excessive deferral, perhaps make the weldability variation, thereby preferably do one's utmost to reduce, P content is preferably below 0.07%.Yet,, have the problem that diminishes economy, thereby preferred P content is more than 0.005% if the degree that will surpass need and reduce P content in the steel needs to use highly purified senior electrolytic iron.
In addition, in the present invention, preferably C, Si in the above-mentioned former material steel plate and the content of P are defined in above-mentioned scope, and for satisfying the composition of following (1) formula.
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
As mentioned above, by in steel, adding Si, can form continuous jog, significantly improve adherence of coating at coating and former material steel plate and interface.Yet if except Si, also compound interpolation C, P in steel suppress the formation of continuous jog at the interface of coating and former material steel plate, hinder the raising of adherence of coating.As mentioned above, C and P are the steel strengthening elements, are the necessary elements of high strength.Just, as implied above in order to be formed with the continuous jog that helps adherence of coating, need the addition of corresponding C and P that the Si addition is also adjusted.When [C]+[P]≤[Si], on the interface of coating and former material steel plate, form continuous jog easily.
In addition, also can contain C, Si and P other elements in addition in the steel.
As other element, can enumerate as Mn, the S and the Al that contain composition in the former material steel plate, the preferable range of these elements is as follows.
Below the Mn:5%
Mn is the strengthening element of steel, can contain as required.Yet, if Mn content surpasses 5%, diminish the processibility and the economy of mother metal, thereby preferred Mn content is below 5%.And in order fully to obtain the strengthening effect of steel, preferred Mn content is more than 0.5%.
Below the S:0.01%
S is the inevitable element that exists in the steel, if S content, then has the tendency that the processibility of former material steel plate reduces greater than 0.01%.Therefore, preferred S content is below 0.01%.
Below the Al:0.08%
Because Al has the effect of reductor, can contain as required.Yet even Al content surpasses 0.08%, its effect is also just saturated, and causes the increase of manufacturing cost, thereby Al content is preferably below 0.08%.And in order to manifest the effect as reductor, preferred Al content is more than 0.02%.
And, as the strengthening element of steel, also can contain be selected among Ti, Nb and the V more than a kind or 2 kinds.Ti, Nb and V can combine and form fine precipitate with C, the N in the steel, make former material steel plate high strength.At this,, then have the tendency that hinders processibility, thereby the content of Ti, Nb and V is preferably respectively below 0.2% if add Ti, Nb and each composition of V above 0.2%.
In addition, if an amount of add be selected among Ti, Nb and the V more than a kind or 2 kinds, then can with the combining of solid solution P, form the fine precipitate of Fe-(Ti, Nb, V)-P, make a part of solid solution P become harmless.Its result, the inter-diffusion reaction of excessive deferral Fe and Zn not, and significantly improve the plating boundary strength.In order to manifest this effect, the P content in the preferred corresponding steel and contain the Ti, the Nb that satisfy following (3) formula and V in more than a kind or 2 kinds.
[Ti]+[Nb]+[V]≥[P]……??(3)
Wherein, [Ti], [Nb], [V] and [P] represent the content (quality %) of Ti, Nb, V and P in the former material steel plate respectively.
No matter whether Cr, Mo, Cu, Ni, Ca, B, compositions such as N, Sb to beyond the composition in the above-mentioned former material steel plate add, and all effect of the present invention are not had help, thereby also can add as required.Separately interpolation reason and preferable range are as follows.
Below the Cr:0.5%
Be the steel strengthening element, can add as required.But owing to can cause the plating reduction, alloying is inhomogeneous, thereby preferably below 0.5%.
Below the Mo:1.0%
Be the steel strengthening element, can add as required.But postpone owing to can produce alloying, diminish processibility and economy, thereby preferably below 1%.
Below the Cu:0.5%
Be the element that improves plating, can add as required.If but surpass 0.5%, then effect is saturated, diminishes economy, thereby preferably below 0.5%.
Below the Ni:0.5%
Be the element that improves plating, can add as required.If but surpass 0.5%, then effect is saturated, diminishes economy, thereby preferably below 0.5%.
Below the Ca:0.01%
Be reductor, can contain as required.If but surpass 0.01% then effect is saturated, thereby preferably below 0.01%.
Below the B:0.003%
Can improve secondary processing brittleness by grain-boundary strengthening.Because it is saturated to surpass 0.003% effect, thereby preferably below 0.003%.
Below the N:0.01%
N sneaks into as impurity.If surpass 0.01%, then ductility reduces, thereby preferably below 0.01%.
Below the Sb:0.05%
Be to improve the uneven element of coating outward appearance, can add as required.If but surpass 0.05% then effect is saturated, diminish economy, thereby preferably below 0.05%.
More than the surplus beyond Shuo Ming the element preferably is made of Fe and unavoidable impurities.
In addition, in the present invention, the tensile strength of former material steel plate, No. 5 test films that use JIS Z2201 to stipulate are measured by the stretching test method of JIS G 3302 regulations, preferably more than 440MPa.This is because of being the high-tensile steel of tensile strength more than 440MPa by making former material steel plate, can satisfy the high strength and/or the light-weighted requirement of former material in fields such as automobile, household electrical appliances, building materials.
Then, below to be used for form on the interface of alloyed hot-dip zinc coating and former material steel plate of the present invention concavo-convex (spacing be 0.5 μ m below and have an above degree of depth of 10nm concavo-convex at concavo-convex more than 1 of existence on the interface length of per 5 μ m, perhaps, the surface shape of the former material steel plate of observing for peeling off the alloyed hot-dip zinc coating, using cutoff wavelength is that expanded area ratio Sdr that the Hi-pass filter of 0.5 μ m is measured is concavo-convex more than 2.0%) create conditions and describe.
Alloyed hot-dip galvanized steel sheet of the present invention for example can be by having steel plate that mentioned component forms as former material steel plate, implement pot galvanize with and subsequent Alloying Treatment and making.At this, former material steel plate can be hot-rolled steel sheet, cold-rolled steel sheet or they are carried out any steel plate in the steel plate after the special thermal treatment, not limit especially.Former material steel plate carries out degreasing and/or pickling to the surface and cleans in pretreatment procedure, perhaps remove the oil content of former material surface of steel plate in the preheating oven internal combustion after, implement the annealing about 750～900 ℃ omitting pretreatment procedure in reducing atmosphere.Make the scale reduction of former material surface of steel plate thus, become the condition of surface that is fit to pot galvanize thereafter.At this, add in the former material steel plate of Si at Xiang Gangzhong, Si even in reducing atmosphere, also may may be formed oxide compound in surface densification by the oxidation of selectivity ground surface for Fe.Wettability with pot galvanize when the Si of surface selectivity oxidation oxide compound is handled plating reduces, and produces the situation of plate not on, thereby the selection surface oxidation in need the inhibition reducing atmosphere.And as mentioned above, the Si in the steel has the effect that forms micro concavo-convex portion at the interface of coating and former material steel plate, but even Si exists as oxide compound, does not also find its effect, thereby need substantially suppress the selection surface oxidation in the reducing atmosphere.
At this, the so-called selection surface oxidation that substantially suppresses Si as mentioned above, means and reduces the plating wettability and do not produce the state that situation is not gone up in plating.So long as it is just no problem not produce the state that plating do not go up situation.
Use is added the steel of Si and is obtained not making in fact in reducing atmosphere Si to select the method for the state of surface oxidation not limit especially in steel, have in reducing atmosphere, anneal before, in weak oxide atmosphere, for example in the inert gas atmosphere that contains the following trace oxygen of 1 volume %, preheat the method that processing or heat temperature raising are handled.Just by in weak oxide atmosphere, making the surface of steel plate oxidation generate thin iron rust skin, then in reducing atmosphere, anneal and generate reduced iron at surface of steel plate, can suppress the selection surface oxidation of Si.So-called weak oxide atmosphere is meant and can reduces the oxidizing atmosphere of the degree handled fully in reducing atmosphere thereafter.Do not limit especially.As weak oxide atmosphere, for example can enumerate and contain oxygen: 0.01～0.5 volume %, dew point :-20 ℃～+ 20 ℃, surplus is made of nitrogen, temperature is 300～500 ℃ a atmosphere, in addition, as reducing atmosphere, for example can enumerate and contain hydrogen: 3～20 volume %, surplus is made of nitrogen, and temperature is 750～900 ℃ a atmosphere.
Generate thin iron rust skin if in weak oxide atmosphere, make the surface of steel plate oxidation, then in reducing atmosphere, anneal and generate reduced iron at surface of steel plate, the Fe oxide compound that generates in weak oxide atmosphere so is reduced by the annealing in the reducing atmosphere thereafter, and the Si oxide compound is owing to also be reduced during annealing in reducing atmosphere, thus in the base steel below the surface of former material steel plate is tight as subscale and residual.This subscale is different from the oxide compound of the selected surface oxidation of Si, suppresses the effect of the selected surface oxidation of Si when having the annealing in reducing atmosphere.This subscale, the pot galvanize operation with and subsequent the alloying engineering after still residual.
Because equipment is former thereby can not carry out that preheating in weak oxide atmosphere handled or heat temperature raising when handling, after in reducing atmosphere, carrying out 800～900 ℃ a heat treated of comparatively high temps, remove oxide on surface by processing such as pickling or grindings.Then, after the second-heating of carrying out the lesser temps below 800 ℃ in reducing atmosphere is handled, carry out plating and handle, can substantially suppress the selection surface oxidation of Si by not contacting atmosphere.As mentioned above, obtain in reducing atmosphere, not making in fact Si to select the method for the state of surface oxidation not limit especially, and use any method not hinder effect of the present invention.
Former material steel plate after the annealing is cooled to be fit to the temperature of plating in above-mentioned reducing atmosphere, preferably be cooled to 440～540 ℃, contact with atmosphere and impregnated in the pot galvanize bath and implement plating.At this moment, making the tight preceding atmosphere of plating is the atmosphere of oxygen concentration below 0.005 volume %.This is because particularly oxygen makes the reactivity of former material surface of steel plate reduce the formation of the micro concavo-convex at the interface of obstruction coating and former material steel plate.Because the balance gas beyond the oxygen does not influence the formation of micro concavo-convex is special, thereby does not do qualification.For example, can enumerate hydrogen is that 3～20 volume %, surplus are the atmosphere of nitrogen.In addition, cause plate not on, thereby content hangs down that some are relatively good from this point owing to oxygen makes to reduce with the wettability of pot galvanize.
Pot galvanize is handled and can be carried out according to the method for being carried out in the past, and for example making and bathing temperature is about 450～500 ℃, and the Al concentration in the plating bath is that 0.10～0.15 quality % is more suitable.But need change above-mentioned plating condition according to composition in the steel is different, and the difference of plating condition to effect of the present invention without any help, thereby do not limit especially.
Adjust that the method for thickness of coating does not limit especially behind the plating, but generally use the wind brush, adjust by the distance between air pressure, wind brush and the steel plate of wind brush etc.At this moment, the thickness of coating is preferably in 3～15 mu m ranges.If less than 3 μ m then can not fully obtain rust-preventing characteristic.On the other hand, if surpass 15 μ m, the effect that not only improves rust-preventing characteristic is saturated, also has the tendency that processibility and economy reduce, thereby not preferred.
Alloying heating treatment method after the adjustment thickness of coating can be undertaken by methods such as gas heating or induction heating.But the average heating speed when being warming up to the alloying temperature need 20 ℃/more than the s.This is because if 20 ℃/s of less than is then elongated in the residence time of low-temperature region, produces alloying reaction and postpone, the formation of the micro concavo-convex at the interface of obstruction coating and former material steel plate.
In addition, in former material steel plate, when containing Ti, Nb and V with above-mentioned scope, the Si content in intensification temperature in the time of need making the heating in the Alloying Treatment and the former material steel plate satisfies following (2) formula.
ST≥3.25/[Si]……??(2)
Wherein, the ST in the formula be heat-up rate (℃/s), [Si] is the content (quality %) of Si in the steel plate.
According to inventors' research as can be known, if in steel, contain Ti, Nb and V, when Si content is low in steel, even the heat-up rate when making Alloying Treatment be 20 ℃/more than the s, also there is the situation of the micro concavo-convex at the interface that does not form coating of the present invention and former material steel plate, need improves heat-up rate according to Si content.
Fig. 6 is in the scope that satisfies above-mentioned (3) formula, and to containing a kind of among Ti, Nb and the V or the steel plate more than 2 kinds, expression Si content and heat-up rate are to the chart of the influence of the area occupation ratio of micro concavo-convex.Owing to satisfy above-mentioned (2) formula, the area occupation ratio of micro concavo-convex becomes more than 10% as can be known.
The Alloying Treatment time is not particularly limited, and preferably the Fe containing ratio in the coating is adjusted to 8～13 quality %.If the Fe containing ratio less than 8 quality % in the coating then can not fully generate above-mentioned Fe-Zn alloy phase, owing to residual soft η-Zn phase is arranged, thereby bring obstacle may for processibility, cementability on the coating top layer.On the other hand, if the Fe containing ratio in the coating surpasses 13 quality %, then blocked up formation hard and crisp Fe-Zn alloy phase (for example Γ mutually, Γ 1 phase) on the interface of coating and former material steel plate have encouraged the vulnerability at the interface of coating and steel plate, thereby have become problem.
In the mass percent that this said " the Fe containing ratio in the coating " is the whole relatively coating of Fe in the coating, be mean F e containing ratio.Measure the method for the Fe containing ratio in the coating, for example can in the hydrochloric acid that adds inhibitor, make the dissolving of alloyed hot-dip zinc coating, measure by ICP (Inductively Coupled Plasma) Emission Spectrophotometer method.
The method that Fe containing ratio in the coating is adjusted into 8～13 quality % does not limit especially, but generally adjusts by plate temperature in the alloy heat treated stove and time inside furnace etc.Time inside furnace is preferably shorter from productive viewpoint, specifically operates with about 5～30 seconds.In addition, plate temperature basis is selected with the relation of time inside furnace, but generally operates under 460～600 ℃.Under the situation of 460 ℃ of less thaies, for the Fe containing ratio in the coating is adjusted into 8～13 quality %, must carry out long Alloying Treatment, need make steel plate speed extremely slack-off, perhaps need long and big Alloying Treatment stove.Therefore, there is the problem of the huge cost of equipment of productivity reduction or needs, thereby preferably more than 460 ℃.On the other hand, if above 600 ℃, there are the problem of the vulnerability at the interface that encourages coating and former material steel plate in easy blocked up formation hard and crisp Fe-Zn alloy phase at the coating and the interface of former material steel plate (for example Γ mutually, Γ 1 phase), thereby preferably below 600 ℃.
After Alloying Treatment, cool off immediately.Method of cooling does not limit especially, but 420 ℃ of carrying out preferably that chilling more than 30 ℃/second finishes until alloying reaction, for example can use air cooling, the mist method of in the past carrying out such as cold and carries out.
Foregoing has just been represented an example of embodiment of the present invention, can be in invention scope all in addition changes.
Embodiment 1
The steel ingot that will have chemical constitution shown in the table 1 is heated to 1250 ℃, carries out hot rolling, removes surface scale, makes the hot-rolled steel sheet that thickness is 2.0mm.The rate that then is rolled be 50% cold rolling, make the cold-rolled steel sheet that thickness is 1.0mm, cut out wide: 70mm, length: 180mm, dew point for-30 ℃, contain in the process furnace in the nitrogen atmosphere of 3 volume % hydrogen, carry out a heat treated of 830 ℃, behind the clean surface, make former material steel plate.Former material steel plate be impregnated in 60 ℃ 5% hydrochloric acid 10 seconds and after carrying out pickling, use laboratory plating simulator to carry out recrystallization annealing and pot galvanize (following is called " plating ").Recrystallization annealing condition and plating condition are as follows.
Table 1
| Steel No. | It is Fe and inevitable impurity that steel is formed (quality %) surplus | Remarks | |||||
| ??C | ??Si | ??Mn | ??P | ??sol.Al | ??S | ||
| ??1A | ??0.03 | ??0.1 | ??2.2 | ??0.065 | ??0.03 | ??0.003 | Embodiment |
| ??1B | ??0.08 | ??0.1 | ??0.5 | ??0.01 | ??0.029 | ??0.003 | |
| ??1C | ??0.08 | ??0.25 | ??2 | ??0.01 | ??0.042 | ??0.003 | |
| ??1D | ??0.08 | ??0.2 | ??2.6 | ??0.015 | ??0.035 | ??0.003 | |
| ??1E | ??0.03 | ??0.6 | ??2 | ??0.01 | ??0.05 | ??0.003 | |
| ??1F | ??0.08 | ??0.2 | ??2 | ??0.01 | ??0.041 | ??0.003 | |
| ??1G | ??0.08 | ??0.6 | ??1.95 | ??0.01 | ??0.045 | ??0.003 | |
| ??1H | ??0.15 | ??0.8 | ??2.6 | ??0.012 | ??0.065 | ??0.003 | |
| ??1I | ??0.1 | ??0.25 | ??2 | ??0.015 | ??0.029 | ??0.003 | |
| ??1J | ??0.03 | ??0.25 | ??1.6 | ??0.03 | ??0.033 | ??0.003 | |
| ??1K | ??0.16 | ??0.2 | ??0.8 | ??0.01 | ??0.041 | ??0.003 | |
| ??1L | ??0.25 | ??0.3 | ??0.8 | ??0.012 | ??0.041 | ??0.003 | |
| ??1M | ??0.03 | ??0.5 | ??1.5 | ??0.02 | ??0.036 | ??0.003 | |
| ??1N | ??0.003 | ??0.02 | ??0.28 | ??0.02 | ??0.031 | ??0.003 | Comparative example |
| ??1O | ??0.002 | ? 0.02 | ??0.09 | ??0.014 | ??0.04 | ??0.003 | |
| ??1P | ??0.15 | ??0.05 | ??1.2 | ??0.012 | ??0.039 | ??0.003 | |
| ??1Q | ??0.15 | ??0.1 | ??1.2 | ??0.012 | ??1.5 | ??0.003 | |
| ??1R | ??0.05 | ??0.02 | ??0.8 | ??0.008 | ??0.055 | ??0.003 | |
| ??1S | ??0.018 | ??0.02 | ??0.18 | ??0.01 | ??0.033 | ??0.003 | |
| ??1T | ??0.01 | ??0.1 | ??1 | ? 0.075 | ??0.035 | ??0.003 | |
| ??1U | ??0.004 | ??0.02 | ??0.14 | ??0.021 | ??0.045 | ??0.003 | |
| ??1V | ??0.08 | ??0.07 | ??2 | ??0.01 | ??0.06 | ??0.003 | |
| ??1W | ??0.002 | ??0.02 | ??0.3 | ??0.035 | ??0.033 | ??0.003 | |
| ??1X | ??0.12 | ??0.1 | ??3 | ??0.015 | ??1.5 | ??0.003 | |
| ??1Y | ??0.08 | ??0.05 | ??1.5 | ??0.03 | ??0.041 | ??0.003 | |
Recrystallization annealing
Atmosphere: 5 volume % hydrogen+nitrogen (dew point :-35 ℃)
Temperature: 750 ℃
Hold-time: 20 seconds
The plating condition
Plating bath is formed: Zn+0.14 quality %Al (Fe is saturated)
Bathe temperature: 460 ℃
Plate temperature during plating: 460 ℃
The plating time: 1 second
Oxygen concentration in the atmosphere before plating is tight: the condition that table 2 is put down in writing (surplus 5 volume % hydrogen+nitrogen (dew point :-35 ℃))
The steel plate that obtains contains Al:0.2～0.5 quality %, Fe:0.5～2 quality % in coating.After above-mentioned plating is handled, in the energising process furnace, in atmosphere, implement Alloying Treatment.Heat-up rate when making Alloying Treatment and alloying temperature are the condition that table 2 is put down in writing.
To the steel plate that obtains, after table 2 expression recrystallization annealing until the cooling atmosphere of plating; The thickness of coating; The heat-up rate of Alloying Treatment, temperature and hold-time; Fe containing ratio in the coating; The micro concavo-convex that forms at the interface of coating and former material steel plate have a ratio; And expanded area ratio Sdr.In addition, below the evaluation method of the adherence of coating 1 of the steel plating plate that obtains is illustrated in, and evaluation result charged to table 2 in the lump.
The concavo-convex ratio in interface
Use SEM (also using TEM simultaneously), in arbitrary section, with 5 visuals field the cross section at the interface of coating in the steel plating plate that obtains and steel plate is observed on the length of 10 μ m, the ratio that micro concavo-convex (spacing is below the 0.5 μ m and has the above degree of depth of 10nm) whole relatively coating cross section is shared is as the concavo-convex ratio in interface (%).
Expanded area ratio Sdr
Remove de-plating by in the basic solution that contains NaOH, NaCl, trolamine, carrying out potentiostatic deposition, the interface of coating and former material steel plate is exposed, use electron beam three-dimensional roughness analytical equipment ERA-8800FE (manufacturing of エ リ オ ニ Network ス company) that surface shape measuring is carried out on this surface.Test sample is coated with the thick Au of tens of nm avoiding the influence of surface composition, and for measuring.Shape analysis is determined under the acceleration voltage 15V to be carried out, and accommodates 10000 times the visual field (visual field area is 12 μ m * 9 μ m) with 1200 * 900 resolution, carries out data processing.The value of expanded area ratio Sdr, the results averaged that obtains measuring optional 3 zones and trying to achieve.Use the correction of this height of devices direction, use the contact pin type in NIST, be used, VLSI ス Application ダ one De company is produced, optical profile type surface roughness measurement machine SHS film difference of altitude standard (three kinds of difference of altitude 18nm, 88nm, 450nm) as object as the state-run research institute of the U.S..The Hi-pass filter that re-uses cutoff wavelength and be 0.5 μ m is for the 3D shape calculation of parameter.
The thickness of coating
Use opticmicroscope that (multiplying power: 400 times) observed in the cross section of the steel plating plate that obtains, measure the thickness of any coating at 3, with their mean value as the thickness (μ m) of coating.
The containing ratio of Fe in the coating
The coating that makes the steel plating plate that obtains dissolves in the hydrochloric acid that adds inhibitor, uses ICP Emission Spectrophotometer method that Zn in the coating and Fe are carried out quantitative analysis, with Fe relatively the mass percent (quality %) of (Zn+Fe) as the Fe containing ratio in the coating.
(evaluation of adherence of coating 1)
From the steel plating plate that obtains cut out 2 wide: the test film of 25mm, length: 80mm, in slushing oil: 550KH (パ one カ one emerging producing made) behind the dipping, lean to and be placed in the atmosphere 24 hours, make test sample.As shown in Figure 7, behind coating adhesive 6 on the bonding surface portion of test sample 5, the length X that makes intersection is that 20mm makes it overlapping.Caking agent 6 uses E-56 (サ system ラ イ ズ MSI manufacturing), uses spacer 7 (the SUS304 system metal wire of φ 0.15mm), makes the caking agent thickness of each test film all keep certain.Behind the coating adhesive, in drying oven, implement 20 minutes, 170 ℃ thermal treatment, use autoplotter (Shimadzu Seisakusho Ltd.'s manufacturing) to be implemented on the direction of arrow 8 afterwards and carry out the tensile tension test, measure tensile shear strength and peel off form, estimate according to following standard.Tensile shear strength, the ratio (%) of the intensity the when cold-rolled steel sheet (non-plating material) that has same steel composition and a size with relative use is implemented above-mentioned tension test is estimated.
The judgement criteria of tensile shear strength
◎: good especially (intensity contrast: surpass 90%)
Zero: good (intensity contrast: surpass below 80%, 90%)
△: bad a little (intensity contrast: surpass below 60%, 80%)
*: bad (intensity contrast: below 60%)
Peel off the judgement criteria of form
◎: good (aggegation is peeled off in the caking agent)
△: bad a little (a part of coating/former material steel plate interface peel)
*: bad (whole coating/former material steel plate interface peel)
In peeling off the judgement criteria of form, so-called coating/former material steel plate interface peel, be meant interface peel at coating and former material steel plate, but owing to peel off the form difference, situation about not peeling off at the interface of coating and former material steel plate is unevenly also arranged, thereby from the interface of coating and former material steel plate, situation about peeling off in coating side or the following scope of former material steel plate side 2 μ m also belongs to the interface peel at coating and former material steel plate.
Table 2-1
| Test sample No. | Steel No. | After the recrystallization annealing in the cooling atmosphere of plating oxygen concentration (volume %) | The Alloying Treatment condition | Alloyed hot-dip galvanized steel sheet | Evaluation result | Remarks | ||||||
| Coating | Former material steel plate | Interface micro concavo-convex ratio (%) | Adherence of coating 1 | |||||||||
| Heat-up rate (℃/s) | The alloying temperature (℃) | Hold-time (s) | Thickness (μ m) | Fe containing ratio (quality %) | Expanded area ratio Sdr (%) | Tensile shear strength | Peel off form | |||||
| ??1 | ??1A | ??0.002 | ??25 | ??490 | ??15 | ??7 | ??10.8 | ??2.2 | ??15 | ??○ | ??◎ | Embodiment |
| ??2 | ??1B | ??0.002 | ??20 | ??480 | ??10 | ??6 | ??9.2 | ??2.1 | ??15 | ??◎ | ??◎ | |
| ??3 | ??1C | ??0.001 | ??25 | ??490 | ??9 | ??3 | ??10.3 | ??2.5 | ??50 | ??◎ | ??◎ | |
| ??4 | ??1C | ??0.002 | ??25 | ??490 | ??15 | ??7 | ??9.9 | ??2.5 | ??45 | ??◎ | ??◎ | |
| ??5 | ??1C | ??0.002 | ??25 | ??490 | ??22 | ??6 | ??12.5 | ??2.8 | ??75 | ??◎ | ??◎ | |
| ??6 | ??1C | ??0.003 | ??30 | ??510 | ??20 | ??14 | ??11.2 | ??2.6 | ??60 | ??◎ | ??◎ | |
| ??7 | ??1D | ??0.002 | ??25 | ??500 | ??16 | ??9 | ??11.8 | ??2.6 | ??55 | ??◎ | ??◎ | |
| ??8 | ??1E | ??0.002 | ??35 | ??520 | ??20 | ??8 | ??10.6 | ??2.6 | ??65 | ??◎ | ??◎ | |
| ??9 | ??1F | ??0.002 | ??25 | ??490 | ??15 | ??10 | ??11.0 | ??2.3 | ??30 | ??◎ | ??◎ | |
| ??10 | ??1G | ??0.002 | ??30 | ??520 | ??15 | ??6 | ??11.3 | ??2.5 | ??50 | ??◎ | ??◎ | |
| ??11 | ??1H | ??0.004 | ??30 | ??520 | ??20 | ??6 | ??10.6 | ??2.3 | ??25 | ??◎ | ??◎ | |
| ??12 | ??1I | ??0.002 | ??20 | ??460 | ??12 | ??4 | ??9.1 | ??2.1 | ??10 | ??○ | ??◎ | |
| ??13 | ??1J | ??0.002 | ??25 | ??490 | ??20 | ??7 | ??10.6 | ??2.8 | ??70 | ??◎ | ??◎ | |
Table 2-2
| ??14 | ??1K | ??0.002 | ??30 | ??510 | ??15 | ??6 | ??11.2 | ??2.8 | ??75 | ??◎ | ??◎ | |
| ??15 | ??1L | ??0.004 | ??25 | ??480 | ??18 | ??8 | ??11.0 | ??2.8 | ??65 | ??◎ | ??◎ | |
| ??16 | ??1M | ??0.002 | ??35 | ??540 | ??6 | ??5 | ??9.2 | ??2.8 | ??70 | ??◎ | ??◎ | |
| ??17 | ??1N | ??0.003 | ??20 | ??520 | ??8 | ??7 | ??10.0 | ??1.6 | ??0 | ??× | ??△ | Comparative example |
| ??18 | ??1O | ??0.002 | ??30 | ??470 | ??15 | ??10 | ??9.5 | ??1.5 | ??0 | ??× | ??× | |
| ??19 | ??1P | ??0.002 | ??20 | ??500 | ??20 | ??6 | ??12.3 | ??1.7 | ??0 | ??△ | ??× | |
| ??20 | ??1Q | ??0.002 | ??20 | ??490 | ??15 | ??6 | ??10.0 | ??1.9 | ??0 | ??△ | ??△ | |
| ??21 | ??1R | ??0.002 | ??35 | ??490 | ??7 | ??7 | ??8.2 | ??1.8 | ??0 | ??△ | ??△ | |
| ??22 | ??1S | ??0.003 | ??20 | ??520 | ??15 | ??8 | ??12.8 | ??1.4 | ??0 | ??× | ??× | |
| ??23 | ??1T | ??0.002 | ??20 | ??520 | ??22 | ??9 | ??11.5 | ??1.7 | ??0 | ??× | ??△ | |
| ??24 | ??1U | ??0.002 | ??20 | ??510 | ??12 | ??10 | ??11.5 | ??1.6 | ??0 | ??× | ??× | |
| ??25 | ??1V | ??0.001 | ??20 | ??500 | ??9 | ??8 | ??9.9 | ??1.8 | ??0 | ??× | ??△ | |
| ??26 | ??1W | ??0.002 | ??30 | ??490 | ??12 | ??10 | ??9.6 | ??1.9 | ??0 | ??△ | ??△ | |
| ??27 | ??1X | ??0.002 | ??20 | ??520 | ??15 | ??11 | ??11.6 | ??1.7 | ??0 | ??× | ??× | |
| ??28 | ??1Y | ??0.002 | ??20 | ??470 | ??18 | ??9 | ??11.1 | ??1.7 | ??0 | ??△ | ??△ | |
| ??29 | ??1B | ??0.007 | ??20 | ??480 | ??10 | ??6 | ??9.2 | ??1.9 | ??5 | ??△ | ??△ |
By the evaluation result of table 2 as can be known, alloyed hot-dip galvanized steel sheet of the present invention (embodiment) is compared with steel plate (comparative example) in the past, significantly improves the boundary strength of coating and steel plate, improves adherence of coating.
The steel ingot that will have chemical constitution shown in the table 3 is heated to 1250 ℃, carries out hot rolling, removes surface scale, makes the hot-rolled steel sheet that thickness is 2.0mm.The rate that then is rolled be 50% cold rolling, make the cold-rolled steel sheet that thickness is 1.0mm, cut out wide: 70mm, length: 180mm, clean surface and make former material steel plate.Former material steel plate be impregnated in 60 ℃ 5% hydrochloric acid 10 seconds and after carrying out pickling, in the nitrogen atmosphere that contains 0.1 volume % oxygen (dew point :+20 ℃), carry out 400 ℃, keep a heat treated of 1 second, in the nitrogen atmosphere that contain 5 volume % oxygen (dew point :+20 ℃) implement 750 ℃, maintenance 1 second second-heating processing thereafter.Use the former material steel plate of above-mentioned heat treated, carry out recrystallization annealing and plating with laboratory plating simulator.Recrystallization annealing condition and plating condition are as follows.
Table 3
| Steel No. | It is Fe and inevitable impurity that steel is formed (quality %) surplus | ??3.25/Si | Remarks | ||||||
| ??C | ??Si | ??Mn | ??P | ??Ti | ??Nb | ??V | |||
| ??2A | ??0.025 | ??0.13 | ??2 | ??0.03 | ??0.02 | ??0.01 | ??0.01 | ??25 | Embodiment |
| ??2B | ??0.08 | ??0.1 | ??0.5 | ??0.01 | ??0.02 | ??0.01 | ??- | ??33 | |
| ??2C | ??0.08 | ??0.25 | ??2 | ??0.01 | ??0.02 | ??0.06 | ??- | ??13 | |
| ??2D | ??0.08 | ??0.2 | ??2.6 | ??0.015 | ??0.02 | ??0.05 | ??- | ??16 | |
| ??2E | ??0.075 | ??0.6 | ??2 | ??0.01 | ??- | ??0.03 | ??- | ??5 | |
| ??2F | ??0.08 | ??0.2 | ??2 | ??0.01 | ??0.02 | ??- | ??- | ??16 | |
| ??2G | ??0.08 | ??0.6 | ??1.95 | ??0.01 | ??0.01 | ??0.01 | ??- | ??5 | |
| ??2H | ??0.15 | ??0.8 | ??2.6 | ??0.012 | ??0.01 | ??0.01 | ??- | ??4 | |
| ??2I | ??0.1 | ??0.3 | ??2 | ??0.015 | ??- | ??0.02 | ??0.02 | ??11 | |
| ??2J | ??0.08 | ??0.25 | ??1.6 | ??0.03 | ??- | ??0.025 | ??0.05 | ??13 | |
| ??2K | ??0.16 | ??0.2 | ??0.8 | ??0.01 | ??0.01 | ??0.01 | ??- | ??16 | |
| ??2L | ??0.25 | ??0.3 | ??0.8 | ??0.012 | ??0.02 | ??0.03 | ??- | ??11 | |
| ??2M | ??0.04 | ??0.16 | ??3 | ??0.04 | ??0.02 | ??0.03 | ??0.01 | ??20 | |
| ??2N | ??0.003 | ? 0.02 | ??0.28 | ??0.02 | ??0.02 | ??0.01 | ??- | ??163 | Comparative example |
| ??2O | ??0.002 | ? 0.02 | ??0.09 | ??0.014 | ??0.02 | ??0.01 | ??- | ??163 | |
| ??2P | ??0.15 | ??0.1 | ??1.2 | ??0.012 | ??0.01 | ??- | ??- | ??33 | |
| ??2Q | ??0.15 | ? 0.02 | ??1.2 | ??0.012 | ??0.02 | ??0.01 | ??0.01 | ??163 | |
| ??2R | ??0.05 | ? 0.02 | ??0.8 | ??0.008 | ??0.02 | ??0.05 | ??- | ??163 | |
| ??2S | ??0.018 | ? 0.02 | ??0.18 | ??0.01 | ??0.02 | ??0.01 | ??- | ??163 | |
| ??2T | ??0.01 | ??0.12 | ??1 | ? 0.075 | ??0.02 | ??0.05 | ??- | ??27 | |
| ??2U | ??0.004 | ??0.03 | ??0.14 | ??0.04 | ??0.01 | ??0.01 | ??- | ??108 | |
| ??2V | ??0.08 | ??0.07 | ??2 | ??0.01 | ??0.02 | ??0.01 | ??- | ??46 | |
| ??2W | ??0.002 | ? 0.02 | ??0.1 | ??0.01 | ??0.01 | ??0.01 | ??- | ??163 | |
| ??2X | ??0.002 | ??0.03 | ??0.3 | ??0.035 | ??0.02 | ??0.01 | ??0.02 | ??108 | |
| ??2Y | ??0.12 | ? 0.02 | ??1.5 | ??0.015 | ??0.02 | ??0.01 | ??- | ??163 | |
| ??2Z | ??0.08 | ??0.05 | ??1.5 | ??0.03 | ??0.02 | ??0.03 | ??- | ??65 | |
Recrystallization annealing
Atmosphere: 5 volume % hydrogen+nitrogen (dew point :-35 ℃)
Temperature: 830 ℃
Hold-time: 20 seconds
The plating condition
Plating bath is formed: Zn+0.13 quality %Al (Fe is saturated)
Bathe temperature: 460 ℃
Plate temperature during plating: 460 ℃
The plating time: 1 second
Oxygen concentration in the atmosphere before plating is tight: the condition that table 4 is put down in writing (surplus 5 volume % hydrogen+nitrogen (dew point :-35 ℃))
The steel plating plate that obtains contains Al:0.2～0.5 quality %, Fe:0.5～2 quality % in coating.After above-mentioned plating is handled, in the energising process furnace, in atmosphere, implement Alloying Treatment.Heat-up rate when making Alloying Treatment and alloying temperature are condition shown in the table 4.
To the steel plating plate that obtains, with the method for explanation in the foregoing description 1 in the same manner to after the recrystallization annealing until the cooling atmosphere of plating; The thickness of coating; Heat-up rate in the Alloying Treatment, temperature and hold-time; Fe containing ratio in the coating; The micro concavo-convex that forms at the interface of coating and former material steel plate have a ratio; And expanded area ratio Sdr studies.And, in the evaluation of carrying out above-mentioned adherence of coating 1, also carry out the evaluation of adherence of coating shown below 2.These results are shown in table 4.In addition, the evaluation method of the adherence of coating of the steel plating plate that obtains is represented below, and evaluation result is charged to table 4 in the lump.
(evaluation of adherence of coating 2)
Cut out wide from the steel plating plate that obtains: the test film of 22mm, length: 180mm, remove burrs on edges, after among slushing oil: 550KH (パ one カ one emerging producing made), flooding, lean to and be placed in the atmosphere 24 hours, make test sample.Test sample 9 is arranged in the concavity metal die 10 shown in Figure 8, implements the following test that applies bending-replication processing: convex metal die 11 is descended, with the surface of load W indentation test sample 9.The each test in the surface of metal die all uses the pouncing paper of #1200 to grind, and cleans adhering to foreign matter.Make metal die be pressed into the load P be 8kN, the speed of pulling out that makes test sample is 20mm/s.After the test, after test sample carried out slight degreasing, (ニ チ バ Application is made, width: 24mm), the Zn amount that is attached in the time of will taking off by fluorescent X-ray on the glass ribbon is measured as counting, estimates according to following standard to stick glass ribbon at the sliding part with metal die.
The judgement criteria of adherence of coating 2
◎: good especially (counting: below 25)
Zero: good (counting: surpass below 25,50)
△: bad a little (counting: surpass below 50,150)
*: bad (counting: surpass 150)
Table 4-1
| Test sample No. | Steel No. | After the recrystallization annealing in the cooling atmosphere of plating oxygen concentration (volume %) | The Alloying Treatment condition | Alloyed hot-dip galvanized steel sheet | Evaluation result | Remarks | |||||||
| Coating | Former material steel plate | Interface micro concavo-convex ratio (%) | Adherence of coating 1 | Adherence of coating 2 | |||||||||
| Heat-up rate (℃/s) | The alloying temperature (℃) | Hold-time (s) | Thickness (μ m) | Fe containing ratio (quality %) | Expanded area ratio Sdr (%) | Tensile shear strength | Peel off form | ||||||
| ??1 | ??2A | ??0.001 | ??30 | ??520 | ??15 | ??6 | ??10.5 | ??2.6 | ??60 | ??○ | ??◎ | ??◎ | Embodiment |
| ??2 | ??2B | ??0.002 | ??35 | ??180 | ??12 | ??7 | ??9.5 | ??2.6 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??3 | ??2C | ??0.001 | ??25 | ??490 | ??10 | ??3 | ??10.5 | ??2.6 | ??55 | ??◎ | ??◎ | ??◎ | |
| ??4 | ??2C | ??0.001 | ??25 | ??490 | ??15 | ??7 | ??9.9 | ??2.5 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??5 | ??2C | ??0.002 | ??25 | ??490 | ??25 | ??6 | ??12.8 | ??2.8 | ??70 | ??◎ | ??◎ | ??○ | |
| ??6 | ??2C | ??0.002 | ??25 | ??520 | ??25 | ??14 | ??11.0 | ??2.7 | ??65 | ??◎ | ??◎ | ??◎ | |
| ??7 | ??2D | ??0.002 | ??25 | ??500 | ??15 | ??9 | ??11.6 | ??2.6 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??8 | ??2E | ??0.003 | ??25 | ??520 | ??17 | ??8 | ??10.4 | ??2.5 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??9 | ??2F | ??0.002 | ??25 | ??490 | ??15 | ??11 | ??11.2 | ??2.6 | ??60 | ??◎ | ??◎ | ??◎ | |
| ??10 | ??2G | ??0.002 | ??25 | ??500 | ??20 | ??6 | ??10.9 | ??2.6 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??11 | ??2H | ??0.004 | ??25 | ??520 | ??15 | ??6 | ??9.9 | ??2.5 | ??45 | ??◎ | ??◎ | ??◎ | |
| ??12 | ??2I | ??0.002 | ??25 | ??460 | ??8 | ??4 | ??8.9 | ??2.1 | ??15 | ??○ | ??◎ | ??◎ | |
| ??13 | ??2J | ??0.001 | ??25 | ??490 | ??20 | ??7 | ??10.6 | ??2.5 | ??50 | ??◎ | ??◎ | ??◎ | |
| ??14 | ??2K | ??0.002 | ??25 | ??460 | ??30 | ??7 | ??11.2 | ??2.6 | ??60 | ??◎ | ??◎ | ??◎ | |
Table 4-2
| ??15 | ??2L | ??0.002 | ??25 | ??480 | ??20 | ??8 | ??11.1 | ??2.5 | ??55 | ??◎ | ??◎ | ??◎ | |
| ??16 | ??2M | ??0.002 | ??25 | ??560 | ??5 | ??6 | ??9.2 | ??2.1 | ??25 | ??◎ | ??◎ | ??◎ | |
| ??17 | ??2N | ??0.002 | ??10 | ??520 | ??8 | ??9 | ??10.0 | ??1.9 | ??8 | ??△ | ??△ | ??◎ | Comparative example |
| ??18 | ??2O | ??0.002 | ??35 | ??530 | ??5 | ??5 | ??9.6 | ??1.6 | ??0 | ??△ | ??△ | ??◎ | |
| ??19 | ??2P | ??0.002 | ??15 | ??490 | ??12 | ??6 | ??10.0 | ??1.9 | ??7 | ??△ | ??× | ??◎ | |
| ??20 | ??2Q | ??0.003 | ??25 | ??490 | ??8 | ??6 | ??9.0 | ??1.5 | ??0 | ??△ | ??△ | ??◎ | |
| ??21 | ??2R | ??0.002 | ??25 | ??490 | ??7 | ??7 | ??8.2 | ??1.6 | ??0 | ??△ | ??△ | ??○ | |
| ??22 | ??2S | ??0.002 | ??25 | ??500 | ??15 | ??6 | ??12.4 | ??1.7 | ??3 | ??× | ??× | ??× | |
| ??23 | ??2T | ??0.002 | ??25 | ??480 | ??18 | ??7 | ??11.2 | ??1.8 | ??8 | ??× | ??△ | ??○ | |
| ??24 | ??2U | ??0.002 | ??25 | ??510 | ??8 | ??9 | ??10.4 | ??1.6 | ??0 | ??× | ??× | ??△ | |
| ??25 | ??2V | ??0.002 | ??25 | ??500 | ??9 | ??8 | ??9.9 | ??1.7 | ??6 | ??△ | ??△ | ??◎ | |
| ??26 | ??2W | ??0.002 | ??25 | ??490 | ??15 | ??7 | ??10.3 | ??1.9 | ??9 | ??△ | ??○ | ??△ | |
| ??27 | ??2X | ??0.002 | ??25 | ??520 | ??7 | ??10 | ??9.5 | ??1.8 | ??5 | ??△ | ??△ | ??◎ | |
| ??28 | ??2Y | ??0.002 | ??25 | ??480 | ??15 | ??8 | ??10.5 | ??1.4 | ??0 | ??× | ??× | ??△ | |
| ??29 | ??2Z | ??0.002 | ??25 | ??470 | ??18 | ??9 | ??11.1 | ??1.6 | ??2 | ??△ | ??△ | ??× | |
| ??30 | ??2B | ??0.010 | ??35 | ??480 | ??12 | ??7 | ??9.5 | ??1.9 | ??5 | ??△ | ??△ | ??△ |
By the evaluation result of table 4 as can be known, alloyed hot-dip galvanized steel sheet of the present invention (embodiment) is compared with steel plate (comparative example) in the past, and the boundary strength of coating and steel plate significantly rises, and adherence of coating improves.
The steel ingot that will have chemical constitution shown in the table 5 is heated to 1250 ℃, carries out hot rolling, removes surface scale, makes the hot-rolled steel sheet that thickness is 2.0mm.The rate that then is rolled be 65% cold rolling, make the cold-rolled steel sheet that thickness is 0.7mm, cut out wide: 70mm, length: 180mm, dew point for-30 ℃, contain in the process furnace in the nitrogen atmosphere of 3 volume % hydrogen, carry out a heat treated of 830 ℃, behind the clean surface, make former material steel plate.Former material steel plate be impregnated in 60 ℃ 5% hydrochloric acid 10 seconds and after carrying out pickling, use laboratory plating simulator to carry out recrystallization annealing and plating.Recrystallization annealing condition and plating condition are as follows.
Table 5
| Steel No. | It is Fe and inevitable impurity that steel is formed (quality %) surplus | Other | Remarks | |||
| ??C | ??Si | ??Mn | ??P | |||
| ??3A | ??0.002 | ??0.1 | ??1.5 | ??0.02 | ??- | Embodiment |
| ??3B | ??0.01 | ??0.3 | ??1 | ??0.07 | ??- | |
| ??3C | ??0.007 | ??0.1 | ??2.2 | ??0.05 | ??- | |
| ??3D | ??0.03 | ??0.06 | ??2 | ??0.01 | ??Cu：0.2，Ni：0.1 | |
| ??3E | ??0.002 | ??0.5 | ??1.5 | ??0.07 | ??- | |
| ??3F | ??0.08 | ??0.1 | ??2 | ??0.01 | ??Cr：0.05 | |
| ??3G | ??0.05 | ??0.3 | ??0.5 | ??0.06 | ??Mo：0.15 | |
| ??3H | ??0.15 | ??0.3 | ??0.7 | ??0.02 | ??- | |
| ??3I | ??0.1 | ??0.25 | ??2.6 | ??0.06 | ??Ca：0.005 | |
| ??3J | ??0.003 | ??0.25 | ??2 | ??0.01 | ??B：0.001 | |
| ??3K | ??0.16 | ??0.3 | ??0.8 | ??0.01 | ??- | |
| ??3L | ??0.25 | ??0.5 | ??2 | ??0.012 | ??Mo：0.3，B：0.002 ??，Ti：0.02 | |
| ??3M | ??0.04 | ??0.07 | ??3 | ??0.01 | ??Sb：0.01 | |
| ??3N | ??0.003 | ? 0.02 | ??0.56 | ??0.01 | ??- | Comparative example |
| ??3O | ??0.003 | ??0.04 | ??0.34 | ??0.065 | ??B：0.002 | |
| ??3P | ??0.003 | ??0.03 | ??0.5 | ??0.04 | ??- | |
| ??3Q | ??0.002 | ? 0.02 | ??0.5 | ??0.04 | ??- | |
| ??3R | ??0.008 | ??0.05 | ??0.75 | ? 0.09 | ??- | |
| ??3S | ??0.08 | ??0.05 | ??2 | ??0.01 | ??Cr：0.05 | |
| ??3T | ??0.008 | ??0.09 | ??1 | ? 0.09 | ??- | |
| ??3U | ??0.004 | ? 0.02 | ??0.14 | ??0.021 | ??- | |
| ??3V | ??0.08 | ??0.07 | ??2 | ??0.01 | ??Ca：0.005 | |
| ??3W | ??0.002 | ? 0.01 | ??0.1 | ??0.01 | ??Mo：0.15 | |
| ??3X | ??0.01 | ? 0.02 | ??0.45 | ??0.01 | ??- | |
| ??3Y | ??0.12 | ? 0.02 | ??1.5 | ??0.015 | ??- | |
| ??3Z | ??0.08 | ??0.06 | ??1.5 | ??0.03 | ??Sb：0.01 | |
Recrystallization annealing
Atmosphere: 5 volume % hydrogen+nitrogen (dew point :-35 ℃)
Temperature: 750 ℃
Hold-time: 20 seconds
The plating condition
Plating bath is formed: Zn+0.14 quality %Al (Fe is saturated)
Bathe temperature: 460 ℃
Plate temperature during plating: 460 ℃
The plating time: 1 second
Oxygen concentration in the atmosphere before plating is tight: the condition that table 6 is put down in writing (surplus 5 volume % hydrogen+nitrogen (dew point :-35 ℃))
The steel plating plate that obtains contains Al:0.2～0.5 quality %, Fe:0.5～2 quality % in coating.After above-mentioned plating is handled, in the energising process furnace, in atmosphere, implement Alloying Treatment.Heat-up rate when making Alloying Treatment and alloying temperature are condition shown in the table 6.
To the steel plating plate that obtains, with the method for explanation in the foregoing description 1 in the same manner to after the recrystallization annealing until the cooling atmosphere of plating; The thickness of coating; Heat-up rate in the Alloying Treatment, temperature and hold-time; Fe containing ratio in the coating; The micro concavo-convex that forms at the interface of coating and former material steel plate have a ratio; And expanded area ratio Sdr studies.And, in the evaluation of carrying out above-mentioned adherence of coating 1, also carry out the evaluation of adherence of coating shown below 3 and 4.These results are shown in table 6.
(evaluation of adherence of coating 3)
Cut out wide from the steel plating plate that obtains: the test film of 40mm, length: 100mm, be to stick glass ribbon on the position of 50mm (ニ チ バ Application is made, width: 24mm) in length, after 90 ° of zone face bendings to the inside, carry out replication, the Zn amount of adhering in the time of will taking glass ribbon off by fluorescent X-ray is measured as counting.Counting when becoming the test film width to be unit length (1m) the Zn counting revisal of measuring is estimated according to following standard.
The judgement criteria of adherence of coating 3
◎: good especially (counting: below 500)
Zero: good (counting: surpass below 500,1000)
△: bad a little (counting: surpass below 1000,3000)
*: bad (counting: surpass 3000)
(evaluation of adherence of coating 4)
Cut out wide from the steel plating plate that obtains: the test film of 70mm, length: 150mm, in slushing oil: 550KH (パ one カ one emerging producing made) behind the dipping, lean to and be placed in the atmosphere 24 hours, make test sample.Be held on as shown in Figure 9 formation at both ends and have under the punch die 14 and the state between the blank holder 15 of metal die 16 of stiffening web, implement following test: be pressed into drift 17 from the back side of testing all product 13, be configured as コ shape test sample 13.The surface of metal die, each test all uses the pouncing paper of #1000 to grind, and cleans adhering to foreign matter.Making wrinkle resistant pressure P is 12kN, and making drift speed is 100mm/min.After the test, after test sample carried out slight degreasing, (ニ チ バ Application is made, width: 24mm), measure as counting attached to the amount of the Zn on the glass ribbon in the time of will taking off by fluorescent X-ray, estimate according to following standard to stick glass ribbon in protruding side.
The judgement criteria of adherence of coating 4
◎: good especially (counting: below 50)
Zero: good (counting: surpass below 50,100)
△: bad a little (counting: surpass below 100,300)
*: bad (counting: surpass 300)
Table 6-1
| Test sample No. | Steel No. | After the recrystallization annealing in the cooling atmosphere of plating oxygen concentration (volume %) | The Alloying Treatment condition | Alloyed hot-dip galvanized steel sheet | Evaluation result | Remarks | ||||||||
| Coating | Former material steel plate | Interface micro concavo-convex ratio (%) | Adherence of coating 3 | Adherence of coating 1 | Adherence of coating 2 | |||||||||
| Heat-up rate (℃/s) | The alloying temperature (℃) | Hold-time (s) | Thickness (μ m) | Fe containing ratio (quality %) | Expanded area ratio Sdr (%) | Tensile shear strength | Peel off form | |||||||
| ??1 | ??3A | ??0.002 | ??20 | ??480 | ??15 | ??6 | ??11.0 | ??2.6 | ??65 | ??◎ | ??◎ | ??◎ | ??◎ | Embodiment |
| ??2 | ??3A | ??0.002 | ??25 | ??490 | ??10 | ??3 | ??10.5 | ??2.3 | ??30 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??3 | ??3A | ??0.002 | ??25 | ??490 | ??23 | ??6 | ??12.9 | ??2.7 | ??70 | ??○ | ??◎ | ??◎ | ??○ | |
| ??4 | ??3A | ??0.001 | ??30 | ??520 | ??25 | ??14 | ??11.0 | ??2.6 | ??60 | ??○ | ??◎ | ??◎ | ??◎ | |
| ??5 | ??3B | ??0.001 | ??25 | ??490 | ??10 | ??7 | ??9.2 | ??2.2 | ??15 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??6 | ??3C | ??0.001 | ??30 | ??510 | ??15 | ??11 | ??10.5 | ??2.4 | ??40 | ??○ | ??◎ | ??◎ | ??◎ | |
| ??7 | ??3D | ??0.002 | ??25 | ??490 | ??10 | ??9 | ??10.2 | ??2.2 | ??20 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??8 | ??3E | ??0.002 | ??30 | ??520 | ??9 | ??7 | ??10.2 | ??2.5 | ??50 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??9 | ??3F | ??0.003 | ??25 | ??490 | ??15 | ??9 | ??11.5 | ??2.5 | ??40 | ??○ | ??◎ | ??◎ | ??◎ | |
| ??10 | ??3G | ??0.002 | ??20 | ??470 | ??25 | ??6 | ??10.9 | ??2.6 | ??60 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??11 | ??3H | ??0.002 | ??35 | ??520 | ??15 | ??6 | ??11.9 | ??2.3 | ??20 | ??○ | ??◎ | ??◎ | ??◎ | |
| ??12 | ??3I | ??0.002 | ??20 | ??460 | ??10 | ??4 | ??8.9 | ??2.1 | ??15 | ??◎ | ??○ | ??◎ | ??○ | |
| ??13 | ??3J | ??0.002 | ??25 | ??490 | ??15 | ??7 | ??9.9 | ??2.2 | ??30 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??14 | ??3K | ??0.002 | ??20 | ??460 | ??30 | ??7 | ??10.5 | ??2.1 | ??20 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??15 | ??3L | ??0.002 | ??25 | ??480 | ??20 | ??6 | ??10.8 | ??2.1 | ??20 | ??◎ | ??◎ | ??◎ | ??◎ | |
| ??16 | ??3M | ??0.002 | ??35 | ??560 | ??4 | ??5 | ??9.8 | ??2.1 | ??20 | ??◎ | ??◎ | ??◎ | ??◎ | |
Table 6-2
| ??17 | ??3N | ??0.002 | ??20 | ??520 | ??20 | ??12 | ??12.5 | ??1.8 | ??5 | ??△ | ??△ | ??○ | ??× | Comparative example |
| ??18 | ??3O | ??0.002 | ??20 | ??520 | ??25 | ??10 | ??12.3 | ??1.9 | ??5 | ??△ | ??○ | ??○ | ??× | |
| ??19 | ??3P | ??0.002 | ??20 | ??490 | ??15 | ??6 | ??11.5 | ??1.8 | ??5 | ??△ | ??△ | ??× | ??○ | |
| ??20 | ??3Q | ??0.002 | ??20 | ??520 | ??20 | ??8 | ??12.5 | ??1.8 | ??5 | ??× | ??△ | ??△ | ??△ | |
| ??21 | ??3R | ??0.002 | ??20 | ??490 | ??25 | ??8 | ??11.2 | ??1.5 | ??0 | ??△ | ??× | ??× | ??△ | |
| ??22 | ??3S | ??0.004 | ??30 | ??500 | ??20 | ??10 | ??12.5 | ??1.5 | ??0 | ??× | ??× | ??× | ??× | |
| ??23 | ??3T | ??0.002 | ??20 | ??520 | ??15 | ??7 | ??12.2 | ??1.4 | ??0 | ??△ | ??× | ??△ | ??○ | |
| ??24 | ??3U | ??0.002 | ??30 | ??510 | ??8 | ??7 | ??10.2 | ??1.6 | ??0 | ??× | ??× | ??× | ??△ | |
| ??25 | ??3V | ??0.002 | ??30 | ??480 | ??15 | ??8 | ??9.8 | ??1.5 | ??0 | ??○ | ??△ | ??△ | ??○ | |
| ??26 | ??3W | ??0.002 | ??20 | ??490 | ??20 | ??7 | ??12.8 | ??1.8 | ??5 | ??△ | ??○ | ??◎ | ??△ | |
| ??27 | ??3X | ??0.001 | ??20 | ??480 | ??12 | ??10 | ??9.3 | ??1.5 | ??0 | ??◎ | ??△ | ??△ | ??○ | |
| ??28 | ??3Y | ??0.002 | ??35 | ??490 | ??12 | ??7 | ??10.3 | ??1.6 | ??0 | ??× | ??× | ??× | ??△ | |
| ??29 | ??3Z | ??0.002 | ??30 | ??470 | ??22 | ??9 | ??11.1 | ??1.6 | ??0 | ??× | ??△ | ??△ | ??× | |
| ??30 | ??3D | ??0.008 | ??25 | ??490 | ??10 | ??9 | ??10.2 | ??1.9 | ??5 | ??△ | ??△ | ??△ | ??△ |
By the evaluation result of table 6 as can be known, alloyed hot-dip galvanized steel sheet of the present invention (embodiment) is compared with steel plate (comparative example) in the past, and the boundary strength of coating and steel plate significantly rises, and adherence of coating improves.
Utilize possibility on the industry
Alloyed hot-dip galvanized steel sheet of the present invention, it is the remarkable good alloyed hot-dip galvanized steel sheet that the adherence of coating on the interface of coating and former material steel plate did not have in the past, in the fields such as automobile, household electrical appliances, building materials, do not add the problem that man-hour, coating was peeled off, outward appearance after the processing is good, and can keep sufficient rust-preventing characteristic. Therefore, can bring industrially extremely useful effect: the parts to all shapes can both reach high strength and lightweight.
Claims (10)
1. alloyed hot-dip galvanized steel sheet that adherence of coating is good, it is characterized in that, at the alloyed hot-dip zinc coating with form on the interface of former material steel plate of this alloyed hot-dip zinc coating, spacing be 0.5 μ m following and have an above degree of depth of 10nm concavo-convex in existence on the interface length of per 5 μ m more than 1.
2. alloyed hot-dip galvanized steel sheet that adherence of coating is good, it is characterized in that, the surface shape of the former material steel plate of observing for peeling off the alloyed hot-dip zinc coating, use cutoff wavelength are that the expanded area ratio Sdr that the Hi-pass filter of 0.5 μ m is measured is more than 2.0%.
3. the good alloyed hot-dip galvanized steel sheet of adherence of coating as claimed in claim 1 or 2, it is characterized in that, described former material steel plate is in quality %, contains that C:0.25% is following, Si:0.03～2.0% and P:0.005～0.07%, and for satisfying the composition of following (1) formula;
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
4. the good alloyed hot-dip galvanized steel sheet of adherence of coating as claimed in claim 3, it is characterized in that, coating was attached in the tight last stage of described former material steel plate, before described coating is adhered to, former material steel plate is heat-treated, so that the Si that contains in this former material steel plate not selected oxidation on the surface.
5. as claim 3 or the good alloyed hot-dip galvanized steel sheet of 4 described adherence of coatings, it is characterized in that having the oxide compound of Si in the base steel below described interface is tight.
6. as claim 3, the good alloyed hot-dip galvanized steel sheet of 4 or 5 described adherence of coatings, it is characterized in that described former material steel plate is for also containing the composition below the Mn:5%, below the S:0.01% and below the Al:0.08% in quality %.
7. the good alloyed hot-dip galvanized steel sheet of each described adherence of coating in the claim 3～6 as described, it is characterized in that described former material steel plate is for also to contain the composition more than a kind or 2 kinds that is selected from below the Ti:0.2%, below the Nb:0.2% and in below the V:0.2% in quality %.
8. the manufacture method of the good alloyed hot-dip galvanized steel sheet of an adherence of coating, it is characterized in that, to containing below the C:0.25% in quality %, Si:0.03～2.0% and P:0.005～0.07%, and be that the former material steel plate that satisfies the composition of following (1) formula is heat-treated, so that the not selected surface oxidation of the Si in the steel, be cooled to plating temperature in the atmosphere below oxygen concentration is 0.005 volume % afterwards, should impregnated in the pot galvanize bath and form coating by former material steel plate, then be heated to 460～600 ℃ temperature range, remain on the Alloying Treatment of implementing coating in this Heating temperature scope with the above heat-up rate of 20 ℃/s;
[C]+[P]≤[Si]……??(1)
Wherein, [C], [P] and [Si] represent C, P in the former material steel plate and the content (quality %) of Si respectively.
9. the manufacture method of the alloyed hot-dip galvanized steel sheet that adherence of coating as claimed in claim 8 is good is characterized in that, described former material steel plate is for also containing the composition below the Mn:5%, below the S:0.01% and below the Al:0.08% in quality %.
10. the manufacture method of the good alloyed hot-dip galvanized steel sheet of adherence of coating as claimed in claim 8 or 9, it is characterized in that, described former material steel plate is for also to contain the composition more than a kind or 2 kinds that is selected from below the Ti:0.2%, below the Nb:0.2% and in below the V:0.2% in quality %, and the Si content in described heat-up rate and the former material steel plate satisfies following (2) formula;
ST≥3.25/[Si]……??(2)
Wherein, the ST in the formula be heat-up rate (℃/s), [Si] is the content (quality %) of the Si in the steel plate.
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| JP2003032321 | 2003-02-10 | ||
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