CN1697888A - Aluminum alloy sheet excellent in formability and hardenability during baking of coating and method for production thereof - Google Patents
Aluminum alloy sheet excellent in formability and hardenability during baking of coating and method for production thereof Download PDFInfo
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Abstract
A sheet of a 6000 type aluminum alloy containing Si and Mg as main alloy components and having excellent formability sufficient to allow flat hemming, excellent resistance to denting, and good hardenability during baking a coating, which exhibits an anisotropy of Lankford values of more than 0.4 or the strength ratio for cube orientations of the texture thereof of 20 or more, and exhibits a minimum bend radius of 0.5 mm or less at 180 DEG bending even when the offset yield strength thereof exceeds 140 MPa through natural aging; and a method for producing the sheet of the aluminum alloy, which comprises subjecting an ingot to a homogenization treatment, cooling to a temperature lower than 350 DEG C. at a cooling rate of 100 DEG C./hr or more, optionally to room temperature, heating again to a temperature of 300 to 500 DEG C. and subjecting it to hot rolling, cold rolling the hot rolled product, and subjecting the cold rolled sheet to a solution treatment at a temperature of 400 DEG C. or higher, followed by quenching.
Description
Technical field
The present invention relates to a kind of formability and coating sintering hardening good, be applicable to that transportation equipment parts, particularly automobile are with the aluminium alloy plate and the manufacture method thereof of outside plate.
Background technology
As the automobile outside plate, require to have: erosion resistance, 5 anti-indenture, 4 1) formability, 2) conformality (can correctly obtain the characteristic of the shape of press tool during punch process), 3))) products surface quality etc.In the past, as the automobile outside plate, use 5000 series (Al-Mg) aluminium alloy or 6000 series (Al-Mg-Si) aluminium alloy, but in order to obtain good coating sintering hardening, high intensity, can expect that thin-walled property, light-weighted 6000 series alloys are attracted attention, and it is being carried out various improvement more.
In the above-mentioned characteristic that requires with outside plate as automobile, for conformality, the yield-point of material is the smaller the better, with respect to this, for anti-indenture, then yield-point is the bigger the better, both requirements of relevant yield-point just are opposite, but in 6000 series alloys, solve above-mentioned opposite problem by such method, promptly carry out punch process in the low stage of the good yield-point of conformality, make its sclerosis improve yield-point then in the coating sintering operation, (spy opens flat 5-247610 communique thereby improve anti-indenture, Te Kaiping 5-279822 communique, Te Kaiping 6-17208 communique etc.).
For the products surface quality after the forming process, the situation that surface irregularity or protuberance trace (because plastic working and the muscle shape defective of the length that generates at rolling direction) etc. take place is arranged also in 6000 series alloys.For the products surface quality defective, can solve by the adjustment of alloying constituent and the management of creating conditions, for example, in order to suppress to swell trace, following scheme is proposed, promptly, homogenize under the temperature more than 500 ℃ handle after, be cooled to 450~350 ℃, begin hot rolling and prevent the generation (spy opens flat 7-228956 communique) of thick precipitate in this temperature province, but when if the speed of cooling when the treatment temp that homogenizes more than 500 ℃ is cooled to 450 ℃ hot-rolled temperature is slack-off, then generate the condensation product of Mg-Si compound, for this reason, in the operation afterwards, need long solution treatment, exist and reduce the problem of making efficient.
For formability, automobile with the lamina rara externa (outer panel) of outside plate with material with inner plating (innerpanel) when assembling with material, need carry out ratio (R/t) 180 ° of bending machining little, the processing conditions strictness (dull and stereotyped crimping processing: flat hemming) of flexural center radius (R) and thickness of slab (t), but 6000 series alloys are poorer than 5000 series alloys bendabilities, and the position big for the punch process degree has problems on dull and stereotyped crimping processibility.
Disclosure of an invention
Present inventors study at the method for formability, the particularly bendability of further improvement 6000 series alloys materials, found that, in 6000 series alloys, bendability is subjected to the influence of the azimuth difference of the precipitation state of Mg-Si compound and adjacent crystal grain.In addition, bendability is relevant with Lankford value, in order to improve bendability, the anisotropy of Lankford value is strengthened, and then, bendability also with the cubes orientation (Cube orientation) of set tissue 100}<001〉and strength ratio (the degree of randomness ratio: random ratio) relevant, in order to improve bendability, also need to make the high set tissue of integrated level that cubes is orientated.And, in order to obtain above-mentioned characteristic, proterties, seek the Si amount as the main adding elements of 6000 series alloys, the optimum amount of Mg amount, and suitably to control the optimumization of manufacturing process, the particularly speed of cooling that homogenizes after handling of suitable control ingot bar be important.
The present invention just is based on that above-mentioned opinion forms, its purpose is to provide a kind of aluminium alloy plate and manufacture method thereof, this aluminium alloy plate have can be dull and stereotyped the excellent formability of crimping processing, surface irregularity or protuberance trace do not take place after the moulding, have the good coating sintering hardening that can solve conformality and anti-indenture problem, and then the particularly anti-thread rust of erosion resistance is also good.
Aluminium alloy plate of the present invention in order to achieve the above object is to contain the 6000 series alloys calendering plate that Si and Mg form as main alloying constituent, it is characterized in that the has excellent bending properties after solution treatment and quench treatment, even because room-temperature aging and yield-point and then when improving, the inboard limit bending radius of 180 ° of bending machining, for example also be below 0.5mm, its concrete embodiment is as described below.
(1) aluminium alloy plate, contain Si:0.5~1.5%, Mg:0.2~1.0%, and constitute by surplus Al and impurity, perhaps, be to contain Si:0.8~1.2%, Mg:0.4~0.7%, Zn:0.1~0.3%, and constitute by surplus Al and impurity, the maximum diameter that it is characterized in that the Mg-Si compound is below the 10 μ m, the quantity of the Mg-Si compound of 2~10 μ m diameters is 1000/mm
2Below.
(2) aluminium alloy plate contains Si:0.4~1.5%, Mg:0.2~1.2%, Mn:0.05~0.3%, and is made of surplus Al and impurity, and the azimuth difference that it is characterized in that the crystal grain of adjacency is that the following crystal boundary proportion of 15 degree is more than 20%.
(3) aluminium alloy plate contains Si:0.5~2.0%, Mg:0.2~1.5%, satisfies 0.7Si%+Mg%≤2.2%, Si%-0.58Mg% 〉=0.1%, and is made of surplus Al and impurity, it is characterized in that the anisotropy of Lankford value surpasses 0.4.Lankford value r is the amount of tension test sheet, the ratio of the logarithmic strain of the logarithmic strain of plate width direction and thickness of slab direction when for example giving 15% tensile deformation, promptly, r=(logarithmic strain of plate width direction)/(logarithmic strain of thickness of slab direction), the anisotropy of Lankford value=(r0+r90-2 * r45)/2 (r0: the tension test sheet of 0 degree direction of r value, r90 get to(for) rolling direction: the tension test sheet of 90 degree directions of r value, r45 get to(for) rolling direction: get 45 for rolling direction and spend the r value of the tension test sheet of directions).
(4) aluminium alloy plate contains Si:0.5~2.0%, Mg:0.2~1.5%, satisfies 0.7Si%+Mg%≤2.2%, and is made of surplus Al and impurity, it is characterized in that the strength ratio (Cube orientation) of the cubes orientation of the set tissue that forms is more than 20.
In addition, the concrete embodiment of the manufacture method of above-mentioned aluminium alloy plate is as follows.
(1) manufacture method of aluminium alloy plate, it is characterized in that after the ingot bar that will have the aluminium alloy of above-mentioned composition under the temperature more than 450 ℃ homogenizes processing, be cooled to the temperature of regulation of 350~500 ℃ temperature range with the speed of cooling more than 100 ℃/hour, the hot rolling that under the temperature of this regulation, begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quenching.
(2) manufacture method of aluminium alloy plate, it is characterized in that the ingot bar that the temperature more than 450 ℃ will have an aluminium alloy of above-mentioned composition homogenize handle after, be cooled to be lower than 300 ℃ temperature with the speed of cooling more than 100 ℃/hour, then, the hot rolling that begins to roll after the temperature of reheat to 350~500 ℃, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quenching.
(3) manufacture method of aluminium alloy plate, it is characterized in that the ingot bar that the temperature more than 450 ℃ will have an aluminium alloy of above-mentioned composition homogenize handle after, be cooled to be lower than 300 ℃ temperature with the speed of cooling more than 100 ℃/hour, and then cool to room temperature, then, after the temperature of reheat to 350~500 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quenching.
(4) manufacture method of aluminium alloy plate, it is characterized in that the ingot bar that the temperature more than 450 ℃ will have an aluminium alloy of above-mentioned composition homogenize handle after, be cooled to be lower than 350 ℃ specified temperature with the speed of cooling more than 100 ℃/hour, under this specified temperature, carry out hot rolling, and then carry out cold rolling after, under the temperature more than 450 ℃, carry out solution treatment, quenching.
(5) manufacture method of aluminium alloy plate, it is characterized in that the ingot bar that the temperature more than 450 ℃ will have an aluminium alloy of above-mentioned composition homogenize handle after, be cooled to be lower than 350 ℃ temperature with the speed of cooling more than 100 ℃/hour, then, the temperature of reheat to 300~500 ℃, the hot rolling that begins to roll, so carry out cold rolling after, under the temperature more than 450 ℃, carry out solution treatment, quenching.
(6) manufacture method of aluminium alloy plate, it is characterized in that the ingot bar that the temperature more than 450 ℃ will have an aluminium alloy of above-mentioned composition homogenize handle after, be cooled to be lower than 350 ℃ temperature with the speed of cooling more than 100 ℃/hour, and then cool to room temperature, then, the temperature of reheat to 300~500 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 450 ℃, carry out solutionizing and handle, quench.
The optimised form that carries out an invention
For the meaning of the alloying constituent of Al-Mg-Si alloy sheets of the present invention and limit reason and describe.
Si: be the function that improves intensity behind the Mg-Si compound in order to obtain intensity and high BH is necessary, to have forming.Preferred content is 0.5~2.0% scope, is lower than at 0.5% o'clock, can not get full intensity under the heating when coating sintering, and then the formability variation, in addition, if above 2.0% o'clock, yield-point height during punch process, formability and conformality are poor, and the erosion resistance after the coating is deterioration also.Preferred content is 0.4~1.5%, again so preferred content is 0.5~1.5%, again and then preferred content is 0.6~1.3%, most preferred content is 0.8~1.2% scope.
Mg: have the function that improves intensity in the same manner with Si.Preferred content is 0.2~1.5% scope, is lower than at 0.2% o'clock, can not get full intensity under the heating when coating sintering.In addition, if surpass at 1.5% o'clock, after the solution treatment or the yield-point height of final thermal treatment after being over, formability and conformality are poor.Preferred content is 0.2~1.2%, again so preferred content is 0.2~1.0%, again and then preferred content is 0.3~0.8%, most preferred content is 0.4~0.7% scope.
The anisotropy of Lankford value is for surpassing 0.4, and in order to improve bendability, the relation of Si and Mg preferably content satisfies 0.7Si%+Mg%≤2.2%, Si%-0.58Mg% 〉=0.1%.In addition, the strength ratio for the cubes that adds the big collection tissue is orientated obtains good bendability, and the pass of preferred Si and Mg is 0.7Si%+Mg%≤2.2%.
Zn: the property handled of the zinc phosphate when improving surface treatment, but preferred content is the scope below 0.5%, if surpass at 0.5% o'clock, corrosion-resistant.And then preferably 0.1~0.3% the interior interpolation of scope.
Cu: improve intensity, formability.Preferred content is below 1.0%, if surpass at 0.1% o'clock, corrosion-resistant.And then preferably in 0.3~0.8% scope, add.If pay attention to erosion resistance, then preferably below 0.1%.
Mn, Cr, V, Zr: have and improve intensity, crystal grain miniaturization and shaggy function when preventing forming process.Preferred content is: Mn is 1.0% below, Cr is 0.3% below, V is 0.2% below and Zr is a scope below 0.2%, as if prescribing a time limit above last respectively, then generates thick intermetallics, the formability deterioration.The content of preferred Mn and Zr is below 0.3% and 0.15% following scope, adds in the scope of Mn:0.05~0.3%, Cr:0.05~0.15%, V:0.05~0.15%, Zr:0.05~0.15% again and then preferably.
For the azimuth difference of the crystal grain that makes adjacency is that the ratio that the following crystal boundary of 15 degree accounts for is more than 20%, and improve bendability, as containing Mn:0.05~0.3% by composition.
Ti, B: make cast structure's miniaturization, improve formability.Preferred content is: Ti is 0.1% below, B is the following scope of 50ppm, if content surpasses respectively and upward then increases thick intermetallics in limited time, the formability reduction.In addition, as other impurity, preferably Fe is limited in below 0.5%, more preferably below 0.3%.
Below, describe for the manufacturing process of aluminium alloy plate of the present invention.
Treatment condition homogenize: must carry out under the temperature more than 450 ℃, during for 450 ℃ of Heating temperature less thaies, remove the ingot bar segregation and homogenize insufficiently, give the Mg of intensity
2Whether the solid solution of Si composition or not, insufficient formability.Processing preferably homogenizes under the temperature more than 480 ℃.
Cooling after handling homogenizes: by with speed of cooling more than 100 ℃/hour, more preferably the speed of cooling more than 300 ℃/hour is cooled off and can be obtained excellent characteristic.Owing to need large-scale equipment in order to accelerate speed of cooling, so in fact preferably manage with 300~1000 ℃/hour.If when speed of cooling was slow, the Mg-Si compound was separated out, aggegation.For method of cooling in the past, under the situation of large-scale core, speed of cooling is about 30 ℃/hour, for low like this speed of cooling, the Mg-Si compound is separated out in cooling, thickization of aggegation, the bendability that material for solution treatment, after quenching can not improve.
Control by above-mentioned speed of cooling, 1. obtain the suitable distribution of Mg-Si compound, 2. the azimuth difference of the crystal grain of adjacency is that the ratio that the following crystal boundary of 15 degree accounts for becomes more than 20%, 3. the anisotropy of Lankford value is big, in addition, 4. the integrated level of cubes orientation uprises, and has improved bendability.
Cooling after handling homogenizes, be necessary with more than 100 ℃/hour, preferably more than 150 ℃/hour, more preferably the speed of cooling more than 300 ℃/hour be cooled to below 350 ℃, the temperature below 300 ℃ more preferably, if local have the situation more than 350 ℃ also can influencing characteristic.For this reason, with above-mentioned speed will all be cooled to below 300 ℃, preferably below 250 ℃.The homogenize method of cooling of the ingot bar handled, can adopt water-cooled, air-cooled, mist is cold, with modes such as interchanger contacts, as long as can obtain the speed of cooling of necessity, be not particularly limited.
It not necessarily must be the treatment temp that homogenizes that refrigerative begins temperature, even slow cooling after cause the temperature of separating out indistinctively, begins to cool down with the speed of cooling more than 100 ℃/hour, also can obtain same effect.For example, when homogenizing processing with the temperature more than 500 ℃, also can be cooled to 500 ℃ lentamente.
Hot rolling: hot rolling is that ingot bar is cooled to the specified temperature of 350~500 ℃ or 300~450 ℃ from the treatment temp that homogenizes, and begins under this specified temperature.Perhaps, also ingot bar can be cooled to specified temperature below 350 ℃ from the treatment temp that homogenizes, under this specified temperature, begin.
After the temperature that is cooled to below 350 ℃, can be heated to 300~500 ℃ temperature once more after, the beginning hot rolling also can be cooled to the temperature below 350 ℃, and then cool to room temperature, then, be heated to 300~500 ℃ temperature once more after, the beginning hot rolling.
Beginning temperature for hot rolling is below 300 ℃ the time, and the distortion impedance becomes big, and the calendering degradation in efficiency is so be unfavorable.If when surpassing 500 ℃, then the crystal grain in the calendering is thick, becomes the material of easy generation protuberance trace, so calendering beginning temperature preferably is limited in 300~500 ℃.If consider the homogeneity of distortion impedance or worked structure, calendering beginning temperature, more preferably 380~450 ℃.
The hot rolled end temp is preferably below 300 ℃.If when the hot rolling end temp surpasses 300 ℃, then cause separating out of Mg-Si compound easily, formability reduces easily, and the recrystallization grain is thick simultaneously, becomes the reason that the protuberance trace takes place.If when the distortion impedance when considering hot rolling, the residual oil mark that refrigerant causes etc., preferably end temp is more than 200 ℃.
Solution treatment: preferred solid solution temperature is more than 450 ℃, more preferably more than 500 ℃.When 500 ℃ of less thaies, the solid solution of Mg-Si precipitate is insufficient, can not get full intensity, formability, in order to obtain necessary strength, formability, must carry out the thermal treatment of very long time, and industrial is unfavorable.The solution treatment time is not particularly limited as long as in the scope that can obtain intensity, but industrial generally remaining on usually in 120 seconds (s).
Cooling temperature during quenching: need be to be cooled to preferably cool off below 120 ℃ from solid solution temperature more than 5 ℃/second with the speed of cooling more than 10 ℃/second.If quenching velocity is slow excessively, then cause separating out of wash-out element, in the time of intensity, BH, formability deterioration, erosion resistance also reduces.
Final thermal treatment: in back 60 minutes of quenching, under 40~120 ℃, carry out 50 hours with interior thermal treatment.Handle raising BH voltinism by this.When being lower than 40 ℃, the raising of BH is insufficient, surpasses 120 ℃ temperature or surpasses 50 hours time, and then the in the initial stage of that yield-point is too high, and formability reduces or the coating sintering hardening reduces.
After the final thermal treatment, can handle with interior recovery in 60 seconds with interior carrying out under with 170~230 ℃ temperature, restore to handle by this and further improve the coating sintering hardening on 7th.
For aluminium alloy, after by using above-mentioned manufacturing process, carrying out solution treatment, quenching, can obtain having the sheet material of good bendability with above-mentioned composition.This aluminium alloy plate is applicable to that the automobile that for example carries out crimping processing is with complex-shaped and light automobile parts such as hood, case cover, doors, in addition, when promptly being used in the splash pan that do not carry out crimping processing, roof etc., bendability is also good, after so punch process becomes complicated shape, can carry out the big processing of the little difficulty of bending radius, enlarge the use range of aluminium aspect materials used in auto manufacturing, can make the car body lightweight.
In order more positively to improve formability, particularly improve bendability, preferably create conditions by adjusting alloying constituent, particularly Si, Mg amount and adjustment, the anisotropy that makes Lankford value is more than 0.6, and making the strength ratio of the cubes orientation of set tissue is more than 50.
Below, embodiments of the invention and comparative example are described contrastively, confirm its effect according to these.In addition, these embodiment are used to illustrate a preferred embodiment of the present invention, and the present invention is not limited.
Embodiment 1
Have the Al alloy block of forming shown in the table 1 with the manufacturing of DC casting, the ingot bar that obtains is homogenized under 540 ℃ temperature handled 6 hours, with 300 ℃/hour speed of cooling cool to room temperature.Then, the temperature with this ingot bar reheat to 400 ℃ begins hot rolling under this temperature, and rolling to thickness is 4.0mm, and then, through cold rolling, and become thickness 1mm.
At the cold-reduced sheet that obtains, after carrying out 5 seconds solution treatment under 540 ℃ the temperature, quench up to 120 ℃ temperature with 30 ℃/second speed of cooling, after 5 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment.
With the final thermal treatment plate that obtains as test sample, with following method, evaluation is measured the maximum diameter of Mg-Si compound, the compound number of 2~10 μ m diameters from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days.In addition, for the limit bending radius in tensile properties, the formability, estimate after 4 months from final thermal treatment.The result is shown in table 2~3.
Tensile properties: carry out tension test, measure tensile strength (σ
B), yield-point (σ
0.2), elongation (δ).
Formability: carry out Erichsen test (EV), with moulding highly be lower than 10mm as defective.In addition,, measure 180 ° of pliability tests of the limit bending radius after the 10% stretching prestrain in order to estimate the crimping processibility, with inboard limit bending radius be below the 0.5mm as qualified.
Erosion resistance: at test sample, carrying out zinc phosphate with commercially available chemical conversion treatment solution handles and electrodeposition coating, impose the crosscut that reaches the aluminium base, carried out salt-fog test 24 hours according to JIS Z2371, then, after placing 1 month under 50 ℃-95% the wet condition, measure the maximum thread rust length that takes place from crosscut portion, with the thread rust length of maximum be below the 4mm as qualified.
Coating sintering hardening (BH): impose 2% tensile deformation, be determined at and carry out the yield-point (σ of heat treated (BH) after 20 minutes under 170 ℃
0.2), with yield-point be more than the 200Mpa as qualified.
The mensuration of Mg-Si compound: measure the maximum diameter of compound by observation by light microscope, for the distribution of the compound of 2~10 μ m diameters, use the image analysis device, investigation adds up to 1 square millimeter of (1mm under the condition of 1 pixel=0.25 μ m
2) scope.Being with the difference of Al-Fe compound, is to be undertaken by the light and shade of compound, with point analysis in advance, confirms compound particles, only detects selected testing conditions on the level of Mg-Si compound not detecting the Al-Fe compound.
Table 1
Alloy | Form (quality %) | ||||||||||
??Si | ??Mg | ??Cu | ??Mn | ????Cr | ??V | ??Zr | ?Fe | ?Zn | ?Ti | ????B | |
??1 ??2 ??3 ??4 ??5 ??6 ??7 | ??1.0 ??0.8 ??1.1 ??1.0 ??1.2 ??1.1 ??1.1 | ??0.5 ??0.6 ??0.5 ??0.6 ??0.4 ??0.5 ??0.5 | ??-- ??0.02 ??0.01 ??0.7 ??0.01 ??0.01 ??0.4 | ??-- ??0.08 ??0.08 ??0.1 ??-- ??0.15 ??0.07 | ????-- ????-- ????-- ????-- ????0.1 ????-- ????-- | ??-- ??-- ??-- ??-- ??-- ??0.12 ??-- | ??-- ??-- ??-- ??-- ??-- ??-- ??0.08 | ?0.17 ?0.17 ?0.17 ?0.17 ?0.17 ?0.13 ?0.15 | ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.04 ?0.03 | ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 | ????5 ????5 ????5 ????5 ????5 ????5 ????5 |
Annotate: B is ppm
Table 2
Test sample | Alloy | Tensile properties | Formability | Erosion resistance | BH | |||
????σ B????MPa | ???σ 0.2????MPa | ????δ ????% | ????EV ????mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ?? ????MPa | ||
????1 ????2 ????3 ????4 ????5 ????6 ????7 | ????1 ????2 ????3 ????4 ????5 ????6 ????7 | ????242 ????245 ????243 ????274 ????257 ????259 ????268 | ????125 ????131 ????127 ????134 ????135 ????132 ????136 | ????31 ????30 ????32 ????31 ????32 ????30 ????30 | ????10.8 ????10.4 ????10.6 ????10.5 ????10.6 ????10.2 ????10.3 | ????0.1 ????0.2 ????0.1 ????0.2 ????0.2 ????0.3 ????0.2 | ????0 ????1.5 ????0.5 ????3.5 ????1.0 ????1.0 ????2.5 | ????211 ????220 ????214 ????221 ????217 ????208 ????223 |
Table 3
Test sample | Alloy | The maximum diameter μ m of Mg-Si compound | 2~10 μ m diameter compounds several/mm 2 | Characteristic after 4 months room-temperature agings | |
???σ 0.2? ? ????MPa | Inboard limit bending radius mm | ||||
????1 ????2 ????3 ????4 ????5 ????6 ????7 | ????1 ????2 ????3 ????4 ????5 ????6 ????7 | ????6 ????8 ????6 ????9 ????5 ????5 ????6 | ????550 ????800 ????650 ????720 ????580 ????520 ????600 | ????143 ????147 ????142 ????150 ????152 ????151 ????155 | ????0.2 ????0.3 ????0.2 ????0.3 ????0.4 ????0.4 ????0.3 |
Shown in table 2~3, in the evaluation of BH, all surpass 200Mpa according to test sample No.1~7 of condition of the present invention, shown good BH, for formability, moulding under EV highly also surpasses 10mm, and inboard limit bending radius also is below the 0.5mm, has good formability.In addition, maximum thread rust length also is below the 4mm, shows superior corrosion resistance.
Comparative example 1
Has the Al alloy block of forming shown in the table 4 with the manufacturing of DC casting, handle the ingot bar that obtains with the operation identical with embodiment 1, make the cold-reduced sheet that thickness is 1mm, for the cold-reduced sheet that obtains, carry out solution treatment, quenching with embodiment 1 the same terms, after 5 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment.
With the final thermal treatment plate that obtains as test sample, with the method identical with embodiment 1, evaluation is measured the maximum diameter of Mg-Si compound, the number of 2~10 μ m diameter compounds from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days.In addition, for the inboard limit bending radius in tensile properties, the formability, estimate after 4 months from final thermal treatment.The result is shown in table 5~6.
Table 4
Alloy | Form (quality %) | ||||||||||
?Si | ?Mg | ?Cu | ????Mn | ????Cr | ????V | ????Zr | ????Fe | ????Zn | ????Ti | ????B | |
???8 ???9 ???10 ???11 ???12 ???13 ???14 ???15 ???16 | ?0.3 ?1.9 ?1.1 ?1.1 ?1.1 ?1.1 ?1.1 ?1.1 ?1.1 | ?0.6 ?0.6 ?0.1 ?1.4 ?0.5 ?0.5 ?0.5 ?0.5 ?0.5 | ?0.01 ?0.01 ?0.01 ?0.01 ?1.5 ?0.02 ?0.02 ?0.02 ?0.02 | ????0.05 ????0.05 ????0.05 ????0.05 ????0.05 ????0.5 ????0.02 ????0.02 ????0.02 | ????0.01 ????0.01 ????0.01 ????0.01 ????0.01 ????0.01 ????0.4 ????0.01 ????0.01 | ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????0.4 ????-- | ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????0.3 | ????0.20 ????0.20 ????0.20 ????0.20 ????0.20 ????0.20 ????0.20 ????0.20 ????0.20 | ????0.03 ????0.03 ????0.03 ????0.03 ????0.03 ????0.03 ????0.03 ????0.03 ????0.03 | ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 | ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 |
Annotate: B is ppm
Table 5
Test sample | Alloy | Tensile properties | Formability | Erosion resistance | BH | |||
??σ B? ? ? ? ? ??MPa | ?σ 0.2? ? ? ? ? ??MPa | ??δ ? ? ? ? ??% | ????EV ? ? ? ? ????mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ????MPa | ||
??8 ??9 ??10 ??11 ??12 ??13 ??14 ??15 ??16 | ??8 ??9 ??10 ??11 ??12 ??13 ??14 ??15 ??16 | ??163 ??265 ??157 ??280 ??294 ??247 ??246 ??247 ??245 | ??70 ??139 ??65 ??141 ??132 ??130 ??128 ??129 ??132 | ??30 ??31 ??32 ??29 ??30 ??28 ??29 ??28 ??27 | ????10.7 ????10.5 ????10.8 ????10.2 ????10.6 ????9.7 ????9.6 ????9.8 ????9.5 | ??0 ??0.5 ??0 ??0.6 ??0.4 ??0.6 ??0.4 ??0.5 ??0.7 | ????0.5 ????1.0 ????1.5 ????1.0 ????5.0 ????1.0 ????1.0 ????1.0 ????1.5 | ????125 ????224 ????118 ????229 ????228 ????217 ????214 ????212 ????213 |
Table 6
Test sample | Alloy | The maximum diameter μ m of Mg-Si compound | 2~10 μ m diameter compounds several/mm 2 | Characteristic after 4 months room-temperature agings | |
?σ 0.2? ? ? ?MPa | Inboard limit bending radius mm | ||||
?8 ?9 ?10 ?11 ?12 ?13 ?14 ?15 ?16 | ?8 ?9 ?10 ?11 ?12 ?13 ?14 ?15 ?16 | ?4 ?15 ?3 ?18 ?9 ?12 ?8 ?12 ?14 | ?300 ?1350 ?260 ?2430 ?880 ?1250 ?940 ?1120 ?1290 | ?85 ?158 ?79 ?159 ?154 ?146 ?143 ?146 ?148 | ?0 ?0.7 ?0 ?0.7 ?0.5 ?0.7 ?0.5 ?0.6 ?0.7 |
Shown in table 5~6, because the Si of test sample No.8 amount is few, the Mg amount of test sample No.10 is few, so their BH is poor.Because the Si of test sample No.9 amount is many, the Mg amount of test sample No.11 is many, so their bendability is all poor.Because the Cu of test sample No.12 amount is many, so anti-thread rust is poor, because Mn amount, Cu amount, V amount, Zr amount are many respectively in test sample No.13~16, so the moulding of EV is highly little, bendability is also insufficient.
Embodiment 2, comparative example 2
Use the alloy No.1 of embodiment 1 and 3 ingot bar, carrying out under 540 ℃ after 8 hours homogenize handle, under condition as shown in table 7, cool off, hot rolling and to make thickness be 4.5mm, after being cold rolled to 1mm thickness, under condition as shown in table 7, carry out solution treatment, then, carry out being cooled to 120 ℃ quenching with 15 ℃/second speed of cooling, quench after 10 minutes, under 90 ℃, carry out 5 hours final thermal treatment.In addition, homogenize after the processing, be cooled to hot-rolled temperature, begin hot rolling at this point.
With the final thermal treatment plate that obtains as test sample, with the method identical with embodiment 1, evaluation is measured the maximum diameter of Mg-Si compound, the number of 2~10 μ m diameter compounds from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days.In addition, for the limit bending radius in tensile properties, the formability, estimate after 4 months from final thermal treatment.And then, after giving 10% tensile deformation on 90 ° of directions, carry out electrodeposition coating with respect to rolling direction, have or not with visual observation and swell the generation of trace.The result is shown in table 8~9.
Table 7
Test sample | Alloy | Speed of cooling ℃/h after handling homogenizes | Hot rolling begins temperature ℃ | Solution treatment condition temperature-time (℃) (s) |
??17 ??18 ??19 ??20 ??21 | ????1 ????1 ????3 ????3 ????3 | ????150 ????800 ????200 ????600 ????2000 | ????370 ????450 ????400 ????440 ????470 | ????550-3 ????520-5 ????530-7 ????550-5 ????560-3 |
??22 ??23 ??24 ??25 ??26 | ????1 ????1 ????1 ????3 ????3 | ????30 ????70 ????200 ????150 ????20 | ????420 ????400 ????550 ????410 ????450 | ????550-3 ????550-3 ????520-7 ????450-3 ????520-5 |
Table 8
Test sample | Alloy | Tensile properties | Formability | Erosion resistance | BH | ||||
????σ B? ? ? ? ? ????MPa | ???σ 0.2? ? ? ? ? ????MPa | ????δ ? ? ? ? ? ????% | ?????EV ? ? ? ? ? ?????mm | Inboard limit bending radius mm | Have or not the protuberance trace to take place | Maximum thread rust length m m | σ behind the BH 0.2? ? ? ????MPa | ||
?17 ?18 ?19 ?20 ?21 | ????1 ????1 ????3 ????3 ????3 | ????243 ????248 ????244 ????249 ????252 | ????123 ????126 ????125 ????127 ????129 | ????30 ????31 ????31 ????30 ????31 | ????10.7 ????10.6 ????10.5 ????10.4 ????10.5 | ????0.1 ????0 ????0 ????0 ????0.1 | Do not have | ????1.0 ????1.5 ????0.5 ????0.5 ????0.5 | ????210 ????218 ????215 ????216 ????215 |
?22 ?23 ?24 ?25 ?26 | ????1 ????1 ????1 ????3 ????3 | ????195 ????207 ????245 ????201 ????210 | ????80 ????92 ????127 ????92 ????105 | ????30 ????30 ????31 ????32 ????31 | ????10.8 ????10.7 ????10.5 ????10.5 ????10.7 | ????0 ????0 ????0.2 ????0 ????0 | Do not have | ????1.0 ????1.0 ????0.5 ????2.0 ????1.5 | ????180 ????188 ????220 ????162 ????185 |
Table 9
Test sample | Alloy | The maximum diameter μ m of Mg-Si compound | 2~10 μ m diameter compounds several/mm 2 | Characteristic after 4 months room-temperature agings | |
???σ 0.2? ? ????MPa | Inboard limit bending radius mm | ||||
??17 ??18 ??19 ??20 ??21 | ????1 ????1 ????3 ????3 ????3 | ????8 ????7 ????6 ????6 ????6 | ????470 ????630 ????570 ????660 ????750 | ????141 ????143 ????142 ????142 ????142 | ????0.2 ????0.1 ????0 ????0.1 ????0.1 |
??22 ??23 ??24 ??25 ??26 | ????1 ????1 ????1 ????3 ????3 | ????22 ????17 ????8 ????15 ????26 | ????1800 ????1520 ????1360 ????2520 ????2400 | ????97 ????108 ????146 ????106 ????127 | ????0 ????0 ????0.3 ????0 ????0 |
Shown in table 8~9, according to test sample No.17 of the present invention~21, good tensile strength, BH, formability, erosion resistance have been shown, even also keep good bendability after 4 months in room-temperature aging.On the other hand, test sample No.22, No.23, No.26, because the speed of cooling that homogenizes after handling is little, so tensile strength is low, BH is also poor.Test material No.24 is because the hot-rolled temperature height, so take place because the protuberance trace that the organizational growth during hot rolling causes.Test sample No.25 is because solid solution temperature is low, so tensile strength is low, BH is also poor.
Embodiment 3, comparative example 3
Have the aluminium alloy agglomeration of forming shown in the table 10 with the manufacturing of DC casting, the ingot bar that the processing that homogenizes under 540 ℃ temperature obtains 6 hours is with 300 ℃/hour speed of cooling cool to room temperature.Then, the temperature with this ingot bar reheat to 400 ℃ begins hot rolling under this temperature, and rolling to thickness is 4.0mm, and then, through cold rolling and to make thickness be 1mm.
For the cold-reduced sheet that obtains, after carrying out 5 seconds solution treatment under 540 ℃ the temperature, quench up to 120 ℃ temperature with 30 ℃/second speed of cooling, after 5 minutes after the quenching, under 90 ℃, carry out 3 hours thermal treatment.
With the final thermal treatment plate that obtains as test sample, with the method identical with embodiment 1, evaluation is from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days, measures the number of compound of maximum diameter, 2~10 μ m diameters of Mg-Si compound.In addition, for the limit bending radius in tensile properties, the formability, estimate after 4 months from final thermal treatment.The result is shown in table 11~12.
Table 10
Alloy | Form (quality %) | ||||||||||
????Si | ????Mg | ????Zn | ????Cu | ????Mn | ????Cr | ????V | ??Zr | ?Fe | ?Ti | ????B | |
????17 ????18 ????19 ????20 ????21 ????22 | ????1.0 ????0.9 ????1.1 ????1.0 ????1.1 ????1.2 | ????0.5 ????0.6 ????0.45 ????0.5 ????0.6 ????0.7 | ????0.18 ????0.28 ????0.2 ????0.15 ????0.2 ????0.25 | ????-- ????-- ????0.01 ????0.03 ????0.02 ????0.01 | ????-- ????-- ????0.01 ????0.04 ????0.03 ????0.05 | ????-- ????-- ????-- ????0.1 ????-- ????0.2 | ????-- ????-- ????-- ????-- ????0.1 ????-- | ??-- ??-- ??-- ??-- ??-- ??0.08 | ?0.17 ?0.17 ?0.14 ?0.15 ?0.17 ?0.14 | ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 | ????5 ????5 ????5 ????5 ????5 ????5 |
????23 ????24 ????25 ????26 ????27 ????28 ????29 | ????0.3 ????1.6 ????1.1 ????1.1 ????1.1 ????1.1 ????1.1 | ????0.6 ????0.6 ????0.1 ????1.4 ????0.5 ????0.5 ????0.5 | ????0.2 ????0.2 ????0.2 ????0.2 ????0.04 ????0.6 ????0.2 | ????0.02 ????0.02 ????0.01 ????0.01 ????0.02 ????0.01 ????0.02 | ????0.08 ????0.07 ????0.15 ????0.08 ????-- ????0.10 ????0.07 | ????-- ????-- ????-- ????-- ????-- ????0.1 ????-- | ????-- ????-- ????-- ????-- ????-- ????-- ????-- | ??-- ??-- ??-- ??-- ??-- ??-- ??-- | ?0.16 ?0.16 ?0.16 ?0.16 ?0.16 ?0.16 ?0.5 | ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 ?0.02 | ????5 ????5 ????5 ????5 ????5 ????5 ????5 |
Annotate: B is ppm
Table 11
Test sample | Alloy | Tensile properties | Formability | Erosion resistance | BH | |||
??σ B? ? ? ??MPa | ?σ 0.2? ? ? ??MPa | ??δ ? ? ? ??% | ?????EV ? ? ? ?????mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ????MPa | ||
??27 ??28 ??29 ??30 ??31 ??32 | ??17 ??18 ??19 ??20 ??21 ??22 | ??243 ??247 ??246 ??247 ??249 ??251 | ??124 ??126 ??128 ??125 ??127 ??129 | ??30 ??30 ??31 ??31 ??30 ??29 | ????10.8 ????10.6 ????10.8 ????10.6 ????10.6 ????10.5 | ????0 ????0.1 ????0 ????0 ????0.1 ????0.2 | ????0.5 ????1.5 ????1.0 ????1.5 ????1.5 ????1.5 | ????208 ????210 ????213 ????209 ????211 ????214 |
??33 ??34 ??35 ??36 ??37 ??38 ??39 | ??23 ??24 ??25 ??26 ??27 ??28 ??29 | ??186 ??254 ??182 ??280 ??245 ??247 ??252 | ??75 ??137 ??77 ??142 ??128 ??132 ??134 | ??31 ??30 ??32 ??29 ??30 ??29 ??28 | ????10.8 ????10.9 ????11 ????10.2 ????10.4 ????10.6 ????9.4 | ????0 ????0.3 ????0 ????0.6 ????0 ????0 ????0.4 | ????0 ????1.0 ????1 ????1.0 ????2.0 ????3.0 ????1.5 | ????149 ????216 ????172 ????229 ????215 ????218 ????221 |
Table 12
Test sample | Alloy | The maximum diameter μ m of Mg-Si compound | 2~10 μ m diameter compounds several/mm 2 | Characteristic after 4 months room-temperature agings | |
???σ 0.2? ? ? ????MPa | Inboard limit bending radius mm | ||||
??27 ??28 ??29 ??30 ??31 ??32 | ??17 ??18 ??19 ??20 ??21 ??22 | ????8 ????9 ????7 ????8 ????8 ????9 | ????560 ????820 ????540 ????810 ????820 ????830 | ????142 ????144 ????145 ????145 ????144 ????146 | ????0.1 ????0.2 ????0.1 ????0.1 ????0.1 ????0.2 |
??33 ??34 ??35 ??36 ??37 ??38 ??39 | ??23 ??24 ??25 ??26 ??27 ??28 ??29 | ????6 ????12 ????5 ????18 ????8 ????7 ????8 | ????380 ????890 ????250 ????2430 ????710 ????860 ????1140 | ????93 ????156 ????94 ????158 ????144 ????150 ????150 | ????0 ????0.5 ????0 ????0.7 ????0.1 ????0.2 ????0.5 |
Shown in table 11~12,, in the evaluation of BH, all shown the good BH that surpasses 200Mpa according to test sample No.27 of the present invention~32, for formability, moulding at EV has highly also all surpassed 10mm, and inboard limit radius also all is below the 0.2mm, to have good formability.In addition, maximum thread rust length also all below 2mm, has shown superior corrosion resistance.
In contrast, because the Si of test sample No.33 amount is few, the Mg amount of test sample No.35 is few, so BH is poor.Because the Si of test sample No.34 amount is many, the Mg amount of test sample No.36 is many, so bendability is all low.Because the Zn of test sample No.37 amount is few, the Zn amount of test sample No.38 is many, so anti-thread rust is all poor.Because the Fe of test sample No.39 amount is many, so the moulding of EV is highly little, bendability is also insufficient.
Embodiment 4, comparative example 4
Use the ingot bar of the alloy No.17 of embodiment 3, after the processing that homogenizes in 5 hours under 540 ℃ the temperature, under the represented condition of table 13, cool off, to make its thickness be 5.0mm in hot rolling, after being cold-rolled to 1.0mm thickness again, under the described condition of table 13, apply solution treatment, then carry out being cooled to 120 ℃ quenching with 150 ℃/second speed of cooling, quench after 5 minutes, final thermal treatment is 2 hours under 80 ℃.Homogenize and handle postcooling, and begin hot rolling at this point to hot-rolled temperature.
With the final thermal treatment plate that obtains as test sample, begin tensile properties, formability, erosion resistance, coating sintering hardening after 10 days with the method evaluation identical from final thermal treatment, measure the maximum diameter of Mg-Si compound, the quantity of 2~10 μ m diameter compounds with embodiment 1.In addition, for the limit bending radius in tensile properties, the formability, be to estimate after 4 months from final thermal treatment.And then, giving to carry out electrodeposition coating after 10% the tensile deformation on the directions that become 90 degree with rolling direction, observe to have or not with eyes and swell the generation of trace.Its result is illustrated in table 14~15.
Table 13
Test sample | Alloy | Speed of cooling ℃/h after handling homogenizes | Hot rolling begins temperature ℃ | Solution treatment condition temperature-time (℃) (s) |
??40 ??41 ??42 | ??17 ??17 ??17 | ????300 ????200 ????600 | ??400 ??470 ??440 | ????550-5 ????530-10 ????540-10 |
??43 ??44 ??45 | ??17 ??17 ??17 | ????40 ????300 ????250 | ??450 ??540 ??420 | ????550-5 ????520-10 ????450-10 |
Table 14
Test sample | Alloy | Tensile properties | Formability | Erosion resistance | BH | ||||
??σ B? ? ? ??MPa | ?σ 0.2? ? ? ??MPa | ??δ ? ? ? ??% | ???EV ? ? ? ???mm | Inboard limit bending radius mm | Have or not the protuberance trace to take place | Maximum thread rust length m m | σ behind the BH 0.2? ? ??MPa | ||
??40 ??41 ??42 | ??17 ??17 ??17 | ??245 ??240 ??247 | ??125 ??124 ??128 | ??30 ??31 ??30 | ??10.7 ??10.8 ??10.7 | ????0 ????0 ????0 | Do not have | ????0.5 ????1.0 ????1.0 | ??207 ??208 ??207 |
??43 ??44 ??45 | ??17 ??17 ??17 | ??205 ??248 ??195 | ??97 ??129 ??84 | ??30 ??31 ??31 | ??10.8 ??10.5 ??11.0 | ????0 ????0.1 ????0 | Do not have | ????1.0 ????0.5 ????0.5 | ??175 ??209 ??162 |
Table 15
Test sample | Alloy | The maximum diameter μ m of Mg-Si compound | 2~10 μ m diameter compounds several/mm 2 | Characteristic after 4 months room-temperature agings | |
???σ 0.2? ? ????MPa | Inboard limit bending radius mm | ||||
??40 ??41 ??42 | ??17 ??17 ??17 | ????7 ????8 ????7 | ????620 ????750 ????580 | ????141 ????140 ????144 | ????0.1 ????0.1 ????0.1 |
??43 ??44 ??45 | ??17 ??17 ??17 | ????15 ????7 ????18 | ????1360 ????1550 ????2420 | ????111 ????146 ????97 | ????0 ????0.2 ????0 |
Shown in table 14~15, shown good tensile strength, BH, formability, erosion resistance according to test sample No.40 of the present invention~42, also keep excellent in vending workability after 4 months in room-temperature aging.On the other hand, test sample No.43 is because the speed of cooling of the processing that homogenizes is little, so tensile strength is low, BH is also poor.Test sample No.44 is because the hot-rolled temperature height, so take place because the protuberance trace that the tissue growth during hot rolling causes.Test sample No.45 is because solid solution temperature is low, so tensile strength is low, the BH characteristic is also poor.
Embodiment 5
Have the aluminium alloy ingot bar of the represented composition of table 16 with the manufacturing of DC casting, the ingot bar that obtains is homogenized under 540 ℃ temperature handled 6 hours, with 300 ℃/hour speed of cooling cool to room temperature.Then, under this temperature, begin hot rolling with this ingot bar reheat to 400 ℃, roll be 4.0mm to thickness till, and then, be 1mm through the cold rolling thickness that makes.
For the cold rolling calendering plate that obtains, after applying 5 seconds solution treatment under 540 ℃ the temperature, quench up to 120 ℃ temperature with 30 ℃/second speed of cooling, after 5 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment.
With the final thermal treatment plate that obtains as test sample, with the method identical with embodiment 1, evaluation is from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days, and then the azimuth difference of measuring crystal boundary with following method distributes.Its result is illustrated in the table 17.
The azimuth difference Determination of distribution of crystal boundary: behind the plate surface with emery paper grinding test sample, and then carry out mirror polish, be contained on the scanning electron microscope (SEM) by electrolytic polishing.Making and observing multiplying power is 100 times, to be installed on the EBSP device on the SEM, measures the grain arrangement with the spacing of 10 μ m, measures the tilt profiles of crystal boundary, calculates the ratio of the crystal boundary below 15 °.
Table 16
Alloy | Form (quality %) | ||||||||||
????Si | ????Mg | ?Cu | ?Mn | ?Cr | ?V | ?Zr | ?Fe | ?Zn | ?Ti | ????B | |
????30 ????31 ????32 ????33 ????34 ????35 ????36 ????37 | ????1.0 ????0.8 ????1.2 ????1.1 ????1.0 ????1.1 ????1.1 ????1.1 | ????0.5 ????0.6 ????0.4 ????0.5 ????0.5 ????0.4 ????0.5 ????0.5 | ?-- ?0.02 ?0.01 ?0.01 ?0.7 ?0.01 ?0.01 ?0.5 | ?0.05 ?0.08 ?0.08 ?0.08 ?0.10 ?0.05 ?0.15 ?0.07 | ?-- ?-- ?-- ?-- ?-- ?0.10 ?-- ?-- | ?-- ?-- ?-- ?-- ?-- ?-- ?0.13 ?-- | ?-- ?-- ?-- ?-- ?-- ?-- ?-- ?0.08 | ?0.13 ?0.15 ?0.16 ?0.19 ?0.16 ?0.17 ?0.13 ?0.15 | ?0.01 ?0.01 ?0.02 ?0.28 ?0.02 ?0.02 ?0.04 ?0.03 | ?0.02 ?0.03 ?0.02 ?0.02 ?0.03 ?0.03 ?0.02 ?0.02 | ????5 ????7 ????6 ????4 ????5 ????6 ????5 ????4 |
Annotate: B is ppm
Table 17
Test sample | Alloy | The ratio % of the crystal boundary below 15 ° | Tensile properties | Formability | Erosion resistance | BH | |||
?σ B? ? ? ?MPa | ?σ 0.2? ? ? ??MPa | ??δ ? ? ? ??% | ??EV ? ? ? ??mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ????MPa | |||
?46 ?47 ?48 ?49 ?50 ?51 ?52 ?53 | ?30 ?31 ?32 ?33 ?34 ?35 ?36 ?37 | ????38 ????35 ????42 ????41 ????36 ????43 ????46 ????42 | ?242 ?247 ?242 ?242 ?278 ?261 ?258 ?265 | ??125 ??134 ??125 ??126 ??139 ??136 ??129 ??135 | ??32 ??31 ??32 ??30 ??30 ??32 ??29 ??30 | ?10.5 ?10.2 ?10.7 ?10.5 ?10.4 ?10.5 ?10.4 ?10.5 | ????0.1 ????0.2 ????0.1 ????0.1 ????0.1 ????0.2 ????0.2 ????0.2 | ????0 ????1.3 ????0.4 ????0 ????3.2 ????1.2 ????1.1 ????2.7 | ????213 ????222 ????213 ????216 ????225 ????218 ????210 ????222 |
Shown in table 17, test sample No.46~53 of condition have all shown the good BH that surpasses 200Mpa in the BH evaluation according to the present invention, for formability, moulding at EV has highly all surpassed 10mm, and inboard limit bending radius also all is below the 0.2mm, to have good formability.In addition, maximum thread rust length also is below the 4mm, to have shown superior corrosion resistance.
Comparative example 5
Have the aluminium alloy ingot bar of the represented composition of table 18 with the manufacturing of DC casting, handle the ingot bar that obtains with the operation identical with embodiment 5.Make the cold-reduced sheet that thickness is 1mm.The cold-reduced sheet that obtains is carried out solution treatment, quenching with embodiment 1 the same terms, under 100 ℃, carry out 3 hours thermal treatment after 5 minutes after the quenching.
As test sample, use the method evaluation identical from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days, and then the azimuth difference of measuring crystal boundary distribute with the final thermal treatment plate that obtains with embodiment 5.Its result is illustrated in the table 19.
Table 18
Alloy | Form (quality %) | ||||||||||
????Si | ????Mg | ????Cu | ??Mn | ??Cr | ????V | ??Zr | ??Fe | ??Zn | ??Ti | ????B | |
????38 ????39 ????40 ????41 ????42 ????43 ????44 ????45 ????46 ????47 ????48 | ????0.3 ????1.7 ????1.0 ????1.1 ????1.0 ????1.1 ????1.0 ????1.0 ????1.1 ????1.1 ????1.0 | ????0.5 ????0.5 ????0.1 ????1.5 ????0.5 ????0.6 ????0.5 ????0.5 ????0.6 ????0.6 ????0.6 | ????0.02 ????0.02 ????0.02 ????0.02 ????0.02 ????1.3 ????0.01 ????0.01 ????0.01 ????0.01 ????0.02 | ??0.06 ??0.05 ??0.04 ??0.05 ??0.06 ??0.05 ??0.5 ??0.06 ??0.05 ??0.06 ??0.02 | ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.4 ??0.01 ??0.01 ??0.01 | ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????0.4 ????-- ????-- | ??-- ??-- ??-- ??-- ??-- ??-- ??-- ??-- ??-- ??0.23 ??-- | ??0.15 ??0.14 ??0.17 ??0.16 ??0.13 ??0.15 ??0.17 ??0.16 ??0.14 ??0.16 ??0.14 | ??0.02 ??0.03 ??0.02 ??0.03 ??0.6 ??0.03 ??0.03 ??0.02 ??0.02 ??0.03 ??0.02 | ??0.03 ??0.02 ??0.03 ??0.03 ??0.02 ??0.02 ??0.03 ??0.02 ??0.03 ??0.02 ??0.03 | ????5 ????6 ????4 ????5 ????4 ????6 ????4 ????5 ????4 ????5 ????5 |
Annotate: B is ppm
Table 19
Test sample | Alloy | The ratio % of the crystal boundary below 15 ° | Tensile properties | Formability | Erosion resistance | BH | |||
??σ B? ? ? ??MPa | ???σ 0.2? ? ? ????MPa | ????δ ? ? ? ????% | ?????EV ? ? ? ?????mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ????MPa | |||
??54 ??55 ??56 ??57 ??58 ??59 ??60 ??61 ??62 ??63 ??64 | ??38 ??39 ??40 ??41 ??42 ??43 ??44 ??45 ??46 ??47 ??48 | ????27 ????42 ????31 ????39 ????41 ????35 ????46 ????51 ????48 ????43 ????17 | ??161 ??268 ??160 ??279 ??248 ??291 ??245 ??244 ??251 ??244 ??243 | ????68 ????142 ????68 ????140 ????125 ????129 ????128 ????126 ????131 ????130 ????124 | ????29 ????31 ????32 ????30 ????31 ????29 ????27 ????29 ????28 ????27 ????30 | ????10.8 ????10.6 ????10.7 ????10.2 ????10.6 ????10.5 ????9.5 ????9.6 ????9.8 ????9.5 ????10.3 | ????0 ????0.6 ????0 ????0.7 ????0.2 ????0.4 ????0.7 ????0.8 ????0.8 ????0.7 ????0.8 | ????0.4 ????1.1 ????1.6 ????1.1 ????6.8 ????5.5 ????0.9 ????1.1 ????1.0 ????1.3 ????0.4 | ????123 ????226 ????119 ????228 ????220 ????226 ????215 ????213 ????214 ????214 ????210 |
Shown in table 19, because the Si of test sample No.54 amount is few, the Mg amount of test sample No.56 is few, so BH is poor.Because the Si of test sample No.55 amount is many, the Mg amount of test sample No.57 is many, so bendability is all low.Because the Zn of test sample No.58 amount is many, the Cu amount of test sample No.59 is many, so anti-thread rust is poor.Because Mn amount, Cr measure respectively, V measures, the Zr amount is many in test sample No.60~63, so the moulding of EV is highly little, bendability is insufficient.Because the Mn of test sample No.64 amount is few, so being 15 proportions of spending following crystal boundary, the azimuth difference of adjacent crystal grain is lower than 20%, bendability is poor.
Embodiment 6
The ingot bar of the alloy 30 shown in that use is used in embodiment 5, the table 16, test sample No.65~71 are made in the processing that homogenizes under the conditions shown in Table 20, hot rolling, cold rolling, solution treatment, final thermal treatment and restore and handle.At this moment, the treatment time that homogenizes is 6 hours, and the thickness of slab after the hot rolling is 4.0mm, and the thickness of slab after cold rolling is 1.0mm, and the back of quenching is 5 minutes to heat treatment period.For test sample No.65, after thermal treatment, the recovery of carrying out under 200 ℃ 3 seconds is handled.In addition, the fate of handling to recovery after the thermal treatment is 1 day.
The test sample that use obtains uses the method evaluation identical with embodiment 5 from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days, and then the azimuth difference of measuring crystal boundary distributes.Its result is illustrated in the table 21.In addition, become with rolling direction give on the 90 degree directions with 10% tensile deformation after, carry out electrodeposition coating, observe with eyes and have or not when swell the generation of trace, do not see fully and swell the generation of trace.
Table 20
Test sample | Alloy | Processing homogenizes | Hot rolling | Solution treatment | Thermal treatment | ||||
Temperature ℃ | Cooling temperature after the processing ℃/h | Beginning temperature ℃ | Temperature ℃ | Time s | Speed of cooling ℃/s | Temperature ℃ | Time s | ||
??65 ??66 ??67 ??68 ??69 ??70 ??71 | ??30 ??30 ??30 ??30 ??30 ??30 ??30 | ??540 ??520 ??540 ??540 ??540 ??540 ??540 | ????300 ????300 ????300 ????300 ????300 ????300 ????300 | ??400 ??400 ??400 ??450 ??400 ??400 ??400 | ??550 ??550 ??550 ??550 ??520 ??550 ??550 | ????5 ????5 ????5 ????5 ????30 ????5 ????10 | ????30 ????30 ????30 ????30 ????30 ????10 ????30 | ????100 ????100 ????100 ????100 ????100 ????100 ????60 | ????3 ????3 ????3 ????3 ????3 ????3 ????5 |
Table 21
Test sample | Alloy | The ratio % of the crystal boundary below 15 ° | Tensile properties | Formability | Erosion resistance | BH | |||
??σ B? ? ? ??MPa | ?σ 0.2? ? ? ??MPa | ??δ ? ? ? ??% | ???EV ? ? ? ???mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ? ??MPa | |||
??65 ??66 ??67 ??68 ??69 ??70 ??71 | ??30 ??30 ??30 ??30 ??30 ??30 ??30 | ????41 ????47 ????24 ????27 ????48 ????37 ????35 | ??237 ??238 ??241 ??245 ??235 ??239 ??245 | ??122 ??117 ??124 ??126 ??118 ??122 ??126 | ??31 ??30 ??31 ??31 ??31 ??31 ??31 | ??10.8 ??10.4 ??10.7 ??10.9 ??10.6 ??10.7 ??10.7 | ????0.1 ????0.3 ????0.3 ????0 ????0 ????0.2 ????0.1 | ????0.3 ????0.6 ????0.5 ????0.2 ????0.4 ????0.6 ????0.2 | ??226 ??206 ??206 ??215 ??207 ??208 ??204 |
Shown in table 21, according to test sample No.65 of the present invention~71, shown good tensile strength, BH, formability, erosion resistance.Do not see the generation of protuberance trace fully yet.
Comparative example 6
The ingot bar of the alloy 30 shown in that use is used in embodiment 5, the table 16, test sample No.72~80 are made in the processing that homogenizes under the conditions shown in Table 22, hot rolling, cold rolling, solution treatment, final thermal treatment and restore and handle.At this moment, the treatment time that homogenizes is 6 hours, and the thickness of slab after the hot rolling is 4.0mm, and the thickness of slab after cold rolling is 1.0mm, and the back of quenching is 5 minutes to carrying out final heat treatment period.For test sample No.80, and then the recovery of carrying out under 300 ℃ of temperature 30 seconds is handled.At this moment, the fate of handling to recovery after the final thermal treatment is 1 day.
For the test sample that obtains, use the method evaluation identical from tensile properties, formability, erosion resistance, the coating sintering hardening of final thermal treatment after 10 days, and then the azimuth difference of measuring crystal boundary distribute with embodiment 5.Its result is illustrated in the table 23.In addition, become with rolling direction give on the 90 degree directions with 10% tensile deformation after, carry out electrodeposition coating, observe with eyes and have or not when swell the generation of trace, see having on the test sample No.74 and swell the generation of trace.
Table 22
Test sample | Alloy | Processing homogenizes | Hot rolling | Solution treatment | Thermal treatment | ||||
Temperature ℃ | Cooling temperature after the processing ℃/h | Beginning temperature ℃ | Temperature ℃ | Time s | Speed of cooling ℃/s | Temperature ℃ | Time s | ||
??72 ??73 ??74 ??75 ??76 ??77 ??78 ??79 ??80 | ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30 | ??450 ??540 ??540 ??540 ??540 ??540 ??540 ??540 ??540 | ????300 ????100 ????50 ????300 ????300 ????300 ????300 ????300 ????300 | ????400 ????400 ????400 ????500 ????400 ????400 ????400 ????400 ????400 | ????550 ????560 ????560 ????550 ????470 ????550 ????550 ????550 ????550 | ????5 ????10 ????20 ????5 ????10 ????5 ????5 ????5 ????5 | ????30 ????30 ????30 ????30 ????30 ????1 ????30 ????30 ????30 | ????100 ????100 ????100 ????100 ????100 ????100 ????-- ????140 ????100 | ????3 ????3 ????3 ????3 ????3 ????3 ????-- ????72 ????3 |
Table 23
Test sample | Alloy | The ratio % of the crystal boundary below 15 ° | Tensile properties | Formability | Erosion resistance | BH | |||
?σ B? ? ? ? ?MPa | σ 0.2? ? ? ? ?MPa | ?δ ? ? ? ? ?% | ?????EV ? ? ? ? ?????mm | Inboard limit bending radius mm | Maximum thread rust length m m | σ behind the BH 0.2? ? ? ????MPa | |||
??72 ??73 ??74 ??75 ??76 ??77 ??78 ??79 ??80 | ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30 ??30 | ????18 ????15 ????11 ????16 ????43 ????35 ????32 ????38 ????36 | ?215 ?225 ?221 ?243 ?209 ?213 ?241 ?281 ?181 | ?102 ?110 ?107 ?127 ?96 ?99 ?124 ?165 ?82 | ?30 ?31 ?31 ?32 ?27 ?28 ?31 ?29 ?30 | ????9.3 ????10.3 ????10.4 ????10.6 ????9.4 ????9.4 ????10.8 ????9.6 ????9.8 | ????0.8 ????0.7 ????0.8 ????0.7 ????0 ????0.7 ????0.1 ????0.4 ????0.2 | ????1.3 ????0.7 ????0.8 ????0.4 ????1.2 ????6.2 ????0.3 ????0.4 ????0.2 | ????172 ????195 ????191 ????218 ????164 ????183 ????175 ????228 ????153 |
Shown in table 23, because the treatment temp that homogenizes of test sample No.72 is low, so the EV value is low.Bendability is poor, and then BH is also low.Because the speed of cooling that homogenizes after handling of test sample No.73 and 74 is little, so bendability is poor, BH is also low.Because the hot rolled of test sample No.75 begins the temperature height, so bendability is poor, the protuberance trace takes place.Because the solid solution temperature of test sample No.76 is low, so intensity and EV value are low, BH is also low.Because the quenching velocity after the solution treatment of test sample No.77 is slow, so EV value, bendability and corrodibility are poor, intensity and BH are also low.Because test sample No.78 does not carry out final thermal treatment, so BH is low.Because the final thermal treatment temp height of test sample No.79, the treatment time is also long, so the EV value is low.Because the recovery treatment temp height of test sample No.80, so intensity and BH value are low, the EV value is also low.
Embodiment 7
Have shown in the table 24 the aluminium alloy ingot bar of forming with the manufacturing of DC casting, with the ingot bar that obtains homogenize under 550 ℃ handle 6 hours after, be cooled to 200 ℃ with 600 ℃/hour speed of cooling.And then cool to room temperature, the then temperature of reheat to 420 ℃, the beginning hot rolling, roll be 4.5mm to thickness till, the hot rolled end temp is 250 ℃.
Then, carry out cold rolling and make the plate that thickness is 1mm, and then, quench up to 120 ℃, after 3 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment with 30 ℃/second speed of cooling 540 ℃ of solution treatment of implementing 20 seconds down.
For from the aluminium alloy plate of final thermal treatment after 10 days,, estimate tensile property, the anisotropy of Lankford value, coating sintering hardening (BH), bendability with following method.Its result is as shown in Table 25.
Tensile property: take the tension test sheet to carry out tension test from 3 directions (is 0 degree, 45 degree, 90 degree with respect to rolling direction), obtain the mean value of tensile strength as tensile property, yield-point, elongation.
The anisotropy of Lankford value r: take the tension test sheet to carry out tension test from 3 directions (is 0 degree, 45 degree, 90 degree with respect to rolling direction), the Lankford value r when obtaining 15% distortion calculates its anisotropy.
Coating sintering hardening (BH): with respect in addition 2% tensile deformation of rolling direction, 170 ℃ carry out 20 minutes heat treated after, measure yield-point, with more than the 200Mpa as qualified.
Bendability: behind 15% tensile pre-deformation, investigate limit bending radius 180 the degree pliability tests, with inboard limit bending radius be below the 0.1mm as qualified.
Table 24
Alloy | Form (weight %) | ||||||||||
????Si | ?Mg | ????Zn | ????Cu | ??Mn | ???Cr | ??V | ??Zr | ??Fe | ??Ti | ??B | |
????49 ????50 ????51 ????52 ????53 ????54 ????55 | ????1.0 ????1.0 ????0.91 ????1.0 ????1.6 ????1.1 ????0.80 | ?0.65 ?0.48 ?0.53 ?0.40 ?0.34 ?0.54 ?1.1 | ??-- ??-- ??0.18 ??0.02 ??-- ??0.02 ??0.01 | ??-- ??0.02 ??0.01 ??0.72 ??-- ??-- ??0.02 | ??-- ??0.09 ??0.10 ??0.10 ??-- ??0.05 ??0.07 | ???-- ???-- ???-- ???-- ???0.05 ???-- ???-- | ??-- ??-- ??-- ??-- ??-- ??0.08 ??-- | ??-- ??-- ??-- ??-- ??-- ??-- ??0.08 | ??0.25 ??0.17 ??0.18 ??0.18 ??0.18 ??0.13 ??0.15 | ??0.03 ??0.02 ??0.02 ??0.02 ??0.02 ??0.01 ??0.02 | ??10 ??5 ??5 ??5 ??5 ??7 ??5 |
Annotate: B is ppm
Table 25
Test sample | Alloy | Tensile property | Yield-point MPa behind the BH | The anisotropy of Lankford value r | Limit bending radius mm | ||
Tensile strength MPa | Yield-point MPa | Stretching % | |||||
??81 ??82 ??83 ??84 ??85 ??86 ??87 | ??49 ??50 ??51 ??52 ??53 ??54 ??55 | ????246 ????237 ????241 ????266 ????252 ????239 ????254 | ????132 ????122 ????130 ????127 ????141 ????132 ????138 | ????30 ????31 ????30 ????31 ????31 ????30 ????29 | ????212 ????206 ????210 ????220 ????223 ????219 ????226 | ????0.66 ????0.73 ????0.70 ????0.45 ????0.62 ????0.66 ????0.57 | ????0.0 ????0.0 ????0.0 ????0.1 ????0.1 ????0.0 ????0.1 |
As shown in table 2, according to test sample No.81 of the present invention~87, intensity, BH are good, and the anisotropy of Lankford value surpasses 0.4, has good limit curved characteristic.Similarly measure the result of 4 months bendabilities after the room-temperature aging, for the test sample of any alloy, limit bending radius all is 0.0~0.1.
Comparative example 7
Cast manufacturing with DC and have the aluminium alloy ingot bar of forming shown in the table 26, use the operation identical to handle the ingot bar that obtains with embodiment 7, for from the aluminium alloy plate of final thermal treatment after 10 days, with the method identical, estimate tensile property, the anisotropy of Lankford value, coating sintering hardening (BH), bendability with embodiment 7.Its result is shown in table 27.
Table 26
Alloy | Form (weight %) | ||||||||||
?Si | ?Mg | ????Zn | ?Cu | ?Mn | ?Cr | ????V | ??Zr | ??Fe | ??Ti | ????B | |
?56 ?57 ?58 ?59 ?60 ?61 ?62 ?63 ?64 ?65 | ?0.34 ?2.4 ?1.1 ?0.7 ?1.7 ?1.1 ?1.1 ?1.1 ?1.1 ?1.1 | ?0.6 ?0.5 ?0.14 ?1.4 ?1.3 ?0.48 ?0.53 ?0.53 ?0.45 ?0.61 | ????-- ????-- ????-- ????0.1 ????-- ????-- ????-- ????-- ????-- ????-- | ?0.01 ?0.01 ?0.01 ?0.01 ?0.01 ?1.5 ?0.02 ?0.03 ?0.02 ?0.01 | ?0.06 ?0.06 ?-- ?-- ?0.06 ?-- ?1.2 ?-- ?-- ?-- | ?0.01 ?-- ?0.05 ?0.05 ?-- ?-- ?-- ?0.4 ?0.01 ?-- | ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????0.4 ????-- | ??-- ??-- ??-- ??-- ??-- ??0.10 ??-- ??-- ??-- ??0.3 | ??0.20 ??0.18 ??0.15 ??0.15 ??0.18 ??0.18 ??0.15 ??0.17 ??0.22 ??0.14 | ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 | ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 |
Annotate: B is ppm
Table 27
Test sample gold | Alloy | Tensile property | Yield-point MPa behind the BH | The anisotropy of Lankford value r | Limit bending radius mm | ||
Tensile strength MPa | Yield-point MPa | Stretching % | |||||
??88 ??89 ??90 ??91 ??92 ??93 ??94 ??95 ??96 ??97 | ??56 ??57 ??58 ??59 ??60 ??61 ??62 ??63 ??64 ??65 | ????152 ????263 ????162 ????249 ????270 ????283 ????253 ????242 ????239 ????242 | ????83 ????148 ????85 ????138 ????154 ????147 ????141 ????133 ????135 ????141 | ????29 ????31 ????30 ????29 ????28 ????30 ????29 ????28 ????29 ????28 | ????123 ????231 ????132 ????194 ????230 ????243 ????227 ????218 ????217 ????220 | ????0.62 ????0.34 ????0.62 ????0.26 ????0.31 ????0.38 ????0.26 ????0.32 ????0.22 ????0.15 | ????0.0 ????0.6 ????0.0 ????0.6 ????0.6 ????0.7 ????0.6 ????0.5 ????0.6 ????0.7 |
Shown in table 27, because the Si of test sample No.88 amount is few, the Mg amount of test sample No.90 is few, so intensity is all low, BH is poor.Because the Si of test sample No.89 amount is many, so the intensity height, the anisotropy of Lankford value diminishes, and bendability is poor.Because the value of test sample No.91 (Si%-0.58Mg%) is littler than 0.1%, so the anisotropy of Lankford value diminishes, limit bendability is poor.
Because the value of test sample No.92 (0.75Si%+Mg%) surpasses 2.2%, in addition, 93~97 minutes other Cu amounts, Mn amount, Cr amount, V amount, Zr measure too much owing to test sample, so the anisotropy of Lankford value diminishes, bendability is poor.
Embodiment 8, comparative example 8
The represented alloy 50 of DC casting table 24, with the ingot bar that obtains homogenize under 540 ℃ handle 10 hours after, be cooled to 250 ℃ with the speed of cooling shown in the table 28.Then cool to room temperature then is heated to temperature shown in table 28, carries out hot rolling, roll be 4.2mm to thickness till.The hot rolled end temp is 280 ℃.And then, pass through the cold rolling plate that thickness is 1mm that makes, only test sample No.107 is after being cold rolled to thickness 3.0mm, and then 450 ℃ of process annealings of-30 seconds.
Then,, be quenched into 120 ℃, after 3 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment with 30 ℃/second speed of cooling 550 ℃ of solution treatment of implementing 10 seconds down.At the aluminium alloy plate of making by above operation, use the method identical with embodiment 7, estimate tensile property, the anisotropy of Lankford value, BH, bendability.
And then, as the evaluation of protuberance trace, take the tension test sheet on the directions at 90 degree of calendering, in addition 10% tensile deformation has or not the protuberance trace after judging electrodeposition coating.
Its result is shown in table 29.
Table 28
Condition | Speed of cooling ℃/h after handling homogenizes | Hot rolled begins temperature ℃ |
????a ????b ????c ????d ????e ????f ????g ????h ????i ????J | ????550 ????220 ????3000 ????480 ????480 ????380 ????3000 ????50 ????30 ????550 | ????420 ????400 ????430 ????480 ????360 ????550 ????530 ????400 ????520 ????420 |
Table 29
Test sample | Condition | Tensile property | Yield-point MPa behind the BH | The anisotropy of Lankford value r | Limit bending radius mm | Have or not the protuberance trace | ||
Tensile strength MPa | Yield-point MPa | Stretching % | ||||||
??98 ??99 ??100 ??101 ??102 ??103 ??104 ??105 ??106 ??107 | ??a ??b ??c ??d ??e ??f ??g ??h ??i ??J | ????230 ????218 ????234 ????241 ????225 ????236 ????238 ????212 ????231 ????224 | ????121 ????118 ????132 ????130 ????123 ????127 ????131 ????107 ????125 ????118 | ????30 ????31 ????30 ????31 ????32 ????31 ????29 ????31 ????30 ????29 | ????210 ????207 ????226 ????230 ????219 ????227 ????222 ????193 ????214 ????204 | ????0.55 ????0.62 ????0.58 ????0.51 ????0.67 ????0.45 ????0.33 ????0.25 ????0.18 ????0.10 | ????0.0 ????0.0 ????0.1 ????0.1 ????0.0 ????0.3 ????0.3 ????0.5 ????0.6 ????0.4 | Do not have and have or not |
Shown in table 29, according to test sample No.98 of the present invention~102, intensity, BH are good, and the anisotropy of Lankford value all surpasses 0.4, all have good limit curved characteristic.
In contrast, test sample No.103,104 is owing to the hot-rolled temperature height, so the protuberance trace has taken place.Test sample No.105 is because the speed of cooling that homogenizes after handling is little, so the anisotropy of Lankford value diminishes, bendability is poor.Test sample No.106 is owing to the hot-rolled temperature height, and the speed of cooling that homogenizes after handling is little, so the protuberance trace takes place, the anisotropy of Lankford value diminishes, and bendability is poor.Test sample No.107 is owing to carry out process annealing, so the anisotropy of Lankford value diminishes, bendability is poor.
Embodiment 9
Alloy 50 shown in the DC casting table 24, with the ingot bar that obtains homogenize under 550 ℃ handle 8 hours after, be cooled to 200 ℃ with 500 ℃/hour speed of cooling.And then cool to room temperature, reheat to 400 ℃, the beginning hot rolling, roll be 4.2mm to thickness till.The hot rolled end temp is 260 ℃.
Then, carry out the cold rolling plate that thickness is 1mm that makes, and then, 550 ℃ of solution treatment of implementing 4 seconds down, till 120 ℃, after 2 minutes after the quenching, under 100 ℃, carry out 2 hours thermal treatment with 40 ℃ of/second quenchings.
Will be with the aluminium alloy plate of above-mentioned operation manufacturing, behind 7 days of final thermal treatment, with the method identical with embodiment 7, obtain with respect to yield-point, limit bending radius after 0 ° of rolling direction, 45 °, 90 ° the tensile strength, yield-point, elongation, Lankford value r, BH of all directions, calculate the anisotropy of Lankford value r, judge to have or not the protuberance trace.Its result is shown in table 30.Shown in table 30, all can obtain excellent characteristic in any direction.
Table 30
Angle with respect to rolling direction | Tensile property | Yield-point MPa behind the BH | The n value | The r value | The anisotropy of r value | Limit bending radius mm | Have or not the protuberance trace | ||
Tensile strength MPa | Yield-point MPa | Stretching % | |||||||
0° | ??241 | ??128 | ??23 | ??227 | ?0.26 | ?0.6 | ????0.61 | ?0.0 | Do not have |
45° | ??225 | ??112 | ??37 | ??205 | ?0.29 | ?0.18 | ?0.0 | Do not have | |
90° | ??234 | ??122 | ??30 | ??221 | ?0.27 | ?0.92 | ?0.0 | Do not have |
Embodiment 10
Makes by DC casting and to have the aluminium alloy ingot bar of forming shown in the table 31, the ingot bar that obtains homogenizing processing under 550 ℃ after 6 hours, is cooled to 200 ℃ with 450 ℃/hour speed of cooling.And then cool to room temperature, the then temperature of reheat to 420 ℃, the beginning hot rolling, roll be 4.5mm to thickness till.The hot rolled end temp is 250 ℃.
And then, carry out cold rolling and make the plate that thickness is 1mm, and then, quench up to 120 ℃ with 30 ℃/second speed of cooling 540 ℃ of solution treatment of implementing 20 seconds down, after 3 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment.
For from the aluminium alloy plate of final thermal treatment after 10 days, carry out tension test, with following method, estimate strength ratio (degree of randomness ratio), the bendability of coating sintering hardening (BH), cubes orientation.Its result is shown in table 32.
The strength ratio of cubes orientation: use the ODF analytical equipment, it is that 22 times, the expansion number of times of odd term are to calculate for 19 times that the Series Expansion Method of advocating according to Bunge makes the expansion number of times of even number item.
Coating sintering hardening (BH): in addition 2% tensile deformation, carry out the heat treated of 170 ℃-20min after, measure yield-point, with more than the 200Mpa as qualified.
Bendability: after 15% stretching prestrain, investigate limit bending radius 180 the degree pliability tests, with inboard limit bending radius be below the 0.2mm as qualified.
Table 31
Alloy | Form (weight %) | ||||||||||
??Si | ?Mg | ??Zn | ??Cu | ??Mn | ??Cr | ??V | ?Zr | ??Fe | ??Ti | ??B | |
?66 ?67 ?68 ?69 ?70 ?71 ?72 | ??1.0 ??1.0 ??0.94 ??1.0 ??1.6 ??1.1 ??0.90 | ?0.62 ?0.46 ?0.53 ?0.42 ?0.36 ?0.54 ?1.1 | ??-- ??-- ??0.18 ??0.04 ??-- ??0.02 ??0.01 | ??-- ??0.01 ??0.01 ??0.75 ??-- ??-- ??0.02 | ??-- ??0.08 ??0.10 ??0.10 ??-- ??0.05 ??0.07 | ??-- ??-- ??-- ??-- ??0.06 ??-- ??-- | ??-- ??-- ??-- ??-- ??-- ??0.09 ??-- | ?-- ?-- ?-- ?-- ?-- ?-- ?0.07 | ??0.24 ??0.16 ??0.15 ??0.15 ??0.15 ??0.12 ??0.14 | ??0.03 ??0.02 ??0.02 ??0.02 ??0.02 ??0.01 ??0.02 | ??10 ??5 ??5 ??5 ??5 ??7 ??5 |
Annotate: B is ppm
Table 32
Test sample | Alloy | Tensile property | Yield point MPa behind the BH | The strength ratio of cubes orientation | Limit bending radius mm | ||
Tensile strength MPa | Yield-point MPa | Stretching % | |||||
??108 ??109 ??110 ??111 ??112 ??113 ??114 | ??66 ??67 ??68 ??69 ??70 ??71 ??72 | ????244 ????238 ????239 ????263 ????252 ????241 ????253 | ????130 ????123 ????128 ????125 ????147 ????134 ????136 | ????31 ????31 ????31 ????30 ????31 ????30 ????30 | ??208 ??207 ??212 ??222 ??226 ??221 ??228 | ??63 ??82 ??57 ??38 ??44 ??78 ??27 | ??0.1 ??0.0 ??0.1 ??0.2 ??0.2 ??0.1 ??0.2 |
Shown in table 32, according to test sample No.108 of the present invention~114, intensity, BH are good, and the strength ratio of cubes orientation all surpasses 20, all has good limit curved characteristic.Similarly measure 4 months bendabilities after the room-temperature aging, consequently, the test sample of any alloy, yield-point all surpasses 160Mpa, and limit bending radius is all below 0.4.
Comparative example 9
Make aluminium alloy ingot bar by the DC casting with composition shown in the table 33, use the operation identical to handle the ingot bar that obtains with embodiment 10, for from the aluminium alloy plate of final thermal treatment after 10 days, with the method identical, estimate strength ratio, the bendability of tensile property, coating sintering hardening (BH), cubes orientation with embodiment 10.Its result is shown in table 34.
Table 33
Alloy | Form (weight %) | ||||||||||
??Si | ??Mg | ????Zn | ????Cu | ??Mn | ?Cr | ????V | ??Zr | ??Fe | ??Ti | ????B | |
??73 ??74 ??75 ??76 ??77 ??78 ??79 ??80 ??81 | ??0.37 ??2.4 ??1.1 ??0.7 ??1.7 ??1.1 ??1.1 ??1.1 ??1.1 | ??0.62 ??0.61 ??0.13 ??1.8 ??0.46 ??0.55 ??0.54 ??0.47 ??0.63 | ????-- ????-- ????-- ????0.1 ????-- ????-- ????-- ????-- ????-- | ????0.01 ????0.01 ????0.01 ????0.01 ????1.5 ????0.02 ????0.03 ????0.02 ????0.01 | ??0.06 ??0.06 ??-- ??-- ??-- ??1.3 ??-- ??-- ??-- | ?0.01 ?-- ?0.05 ?0.05 ?-- ?-- ?0.4 ?0.01 ?-- | ????-- ????-- ????-- ????-- ????-- ????-- ????-- ????0.4 ????-- | ??-- ??-- ??-- ??-- ??0.12 ??-- ??-- ??-- ??0.3 | ??0.22 ??0.17 ??0.14 ??0.14 ??0.17 ??0.14 ??0.17 ??0.24 ??0.13 | ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 | ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 ????5 |
Annotate: B is ppm
Table 34
Test sample | Alloy | Tensile property | Yield-point MPa behind the BH | The strength ratio of cubes orientation | Limit bending radius mm | ||
Tensile strength MPa | Yield-point MPa | Stretching % | |||||
??115 ??116 ??117 ??118 ??119 ??120 ??121 ??122 ??123 | ??73 ??74 ??75 ??76 ??77 ??78 ??79 ??80 ??81 | ????148 ????261 ????155 ????270 ????281 ????251 ????243 ????236 ????238 | ????79 ????147 ????75 ????149 ????145 ????140 ????132 ????133 ????139 | ????30 ????31 ????29 ????29 ????29 ????29 ????27 ????29 ????29 | ????119 ????228 ????127 ????283 ????244 ????228 ????220 ????218 ????222 | ????51 ????16 ????66 ????14 ????8 ????14 ????15 ????12 ????17 | ????0.0 ????0.6 ????0.0 ????0.6 ????0.7 ????0.6 ????0.6 ????0.6 ????0.7 |
Shown in table 34, because the Si of test sample No.115 amount is few, the Mg of test sample No.117 amount is few in addition, so intensity is all low, BH is poor.Because the Si of test sample No.116 amount is many, the Mg of test sample No.118 amount is many in addition, and the value of 0.7Si%+Mg% surpasses 2.2%, so intensity is all high, the integrated level of cubes orientation is low, and bendability is poor.
Since test sample 119~123 each Cu amount, Mn amount, Cr amount, V amount, Zr amount too much, so the integrated level of cubes orientation is low, bendability is poor.
Embodiment 11, comparative example 10
The alloy 67 that DC casting is shown in table 31, with the ingot bar that obtains homogenize under 550 ℃ handle 5 hours after, be cooled to 250 ℃ with the speed of cooling shown in the table 35.Then, be heated to the temperature shown in the table 35, carry out hot rolling, roll be 4.4mm to thickness till.The hot rolled end temp is 250 ℃.And then, pass through the cold rolling plate that thickness is 1mm that makes.Only condition 26 is carried out the process annealing of 400 ℃-2h after hot rolling.
Then,, quench up to 120 ℃, after 3 minutes after the quenching, under 100 ℃, carry out 3 hours thermal treatment with 30 ℃/second cooling temperatures 550 ℃ of solution treatment of implementing 5 seconds down.At the aluminium alloy plate of making by above operation, use the method identical with embodiment 10, estimate strength ratio, the bendability of tensile property, BH, cubes orientation.
And then, as the evaluation of protuberance trace, take the tension test sheet in rolling direction 90 degree directions, the protuberance trace that has or not behind the electrodeposition coating is judged in addition 10% tensile deformation.
These results are shown in table 36.
Table 35
Condition | Speed of cooling ℃/h after handling homogenizes | Hot rolled begins temperature ℃ |
??k ??l ??m ??n ??o ??p ??q ??r ??s ??t | ????500 ????200 ????3500 ????500 ????450 ????360 ????2000 ????50 ????25 ????500 | ????420 ????430 ????410 ????470 ????350 ????540 ????520 ????410 ????530 ????420 |
Table 36
Test sample | Condition | Tensile property | Yield-point MPa behind the BH | The strength ratio of cubes orientation | Limit bending radius mm | Have or not the protuberance trace | ||
Tensile strength MPa | Yield-point MPa | Stretching % | ||||||
??124 ??125 ??126 ??127 ??128 ??129 ??130 ??131 ??132 ??133 | ?k ?l ?m ?n ?o ?p ?q ?r ?s ?t | ?232 ?224 ?232 ?241 ?225 ?235 ?230 ?214 ?233 ?226 | ????122 ????120 ????131 ????131 ????123 ????126 ????126 ????109 ????123 ????118 | ??29 ??31 ??30 ??31 ??31 ??30 ??28 ??30 ??30 ??30 | ??213 ??206 ??227 ??232 ??220 ??224 ??218 ??190 ??213 ??208 | ????77 ????85 ????73 ????70 ????83 ????35 ????28 ????11 ????7 ????15 | ????0.0 ????0.0 ????0.1 ????0.1 ????0.0 ????0.3 ????0.3 ????0.5 ????0.6 ????0.4 | Do not have and have or not |
Shown in table 36, according to test sample No.124 of the present invention~128, intensity, BH are good, and the strength ratio of cubes orientation all surpasses 20, all has good limit curved characteristic.
In contrast, test sample No.129,130, owing to improved hot-rolled temperature, so the protuberance trace has taken place.Test sample No.131 is because the speed of cooling that homogenizes after handling is little, so the integrated level of cubes orientation reduces, bendability is poor.Test sample No.132, owing to improved hot-rolled temperature, the speed of cooling that homogenizes after handling is little, so the protuberance trace has taken place, the integrated level of cubes orientation reduces, bendability is poor.Test sample No.133, owing to carried out process annealing, so the integrated level of cubes orientation reduces, bendability is poor.
Industrial utilizability
According to the present invention, provide to have the good flexural property that can carry out the processing of dull and stereotyped crimping and coating sintering is indurative, the aluminium alloy plate of excellent corrosion resistance and manufacture method thereof. This aluminium alloy plate can be applied in the automotive part aspect of and light weight complex-shaped with cover, case cover, door etc. such as the automobile that carries out crimping processing.
Claims (29)
1, a kind of formability and the good aluminium alloy plate of coating sintering hardening, be to contain the aluminium alloy calendering plate that Si and Mg form as main component, it is characterized in that by the room-temperature aging after solution treatment, the quenching, even when yield-point surpassed 140Mpa, the inboard limit bending radius of 180 ° of bending machining after 10% tensile deformation also was below the 0.5mm.
2, formability according to claim 1 and the good aluminium alloy plate of coating sintering hardening, it is characterized in that above-mentioned aluminium alloy calendering plate contains Si:0.5~1.5% (quality %, below identical), Mg:0.2~1.0%, and constitute by surplus Al and impurity.
3, formability according to claim 1 and the good aluminium alloy plate of coating sintering hardening, it is characterized in that it being the aluminium alloy calendering plate that contains Si:0.5~1.5%, Mg:0.2~1.0% and constitute by surplus Al and impurity, the maximum diameter of Mg-Si compound is below the 10 μ m, and the quantity of the Mg-Si compound of 2~10 μ m diameters is 1000/mm
2Below.
4,, it is characterized in that above-mentioned aluminium alloy calendering plate also contains Zn:0.1~0.3% according to claim 2 or 3 described formabilities and the good aluminium alloy plate of coating sintering hardening.
5, a kind of formability and the good aluminium alloy plate of coating sintering hardening, it is the aluminium alloy calendering plate that contains Si:0.8~1.2%, Mg:0.4~0.7%, Zn:0.1~0.3% and constitute by surplus Al and impurity, the maximum diameter that it is characterized in that the Mg-Si compound is below the 10 μ m, and the quantity of the Mg-Si compound of 2~10 μ m diameters is 1000/mm
2Below, the room-temperature aging by solution treatment, after quenching, even when yield-point surpasses 140Mpa, the inboard limit bending radius of 180 ° of bending machining after 1% tensile deformation also is below the 0.2mm.
6, according to any described formability and the good aluminium alloy plate of coating sintering hardening in the claim 1~5, it is characterized in that above-mentioned aluminium alloy calendering plate also contains Mn:0.3% following (do not comprise 0%, below identical), Cr:0.3% is following, V:0.2% is following, Zr:0.15% more than one among following.
7, a kind of formability and the good aluminium alloy plate of coating sintering hardening, be the aluminium alloy calendering plate that contains Si:0.4~1.5%, Mg:0.2~1.2%, Mn:0.05~0.3 and be made of surplus Al and impurity, the azimuth difference that it is characterized in that the crystal grain of adjacency is that the crystal boundary proportion below 15 ° is more than 20%.
8, formability according to claim 7 and the good aluminium alloy plate of coating sintering hardening is characterized in that above-mentioned aluminium alloy calendering plate also contains below the Zn:0.5%.
9,, it is characterized in that above-mentioned aluminium alloy calendering plate contains also that Cr:0.3% is following, V:0.2% is following, Zr:0.15% more than one among following according to claim 7 or 8 described formabilities and the good aluminium alloy plate of coating sintering hardening.
10, a kind of formability and the good aluminium alloy plate of coating sintering hardening are to contain Si and Mg as the aluminium alloy calendering plate that main component forms, and it is characterized in that the anisotropy of Lankford value surpasses 0.4.
11, formability according to claim 10 and the good aluminium alloy plate of coating sintering hardening, it is characterized in that above-mentioned aluminium alloy calendering plate contains Si:0.5~2.0%, Mg:0.2~1.5%, satisfy 0.7Si%+Mg%≤2.2%, Si%-0.58Mg% 〉=0.1%, and constitute by surplus Al and impurity.
12, a kind of formability and the good aluminium alloy plate of coating sintering hardening are to contain Si and Mg as the aluminium alloy calendering plate that main alloying constituent forms, and it is characterized in that the strength ratio that the cubes of the set tissue that forms is orientated is more than 20.
13, formability according to claim 12 and the good aluminium alloy plate of coating sintering hardening, it is characterized in that above-mentioned aluminium alloy calendering plate contains Si:0.5~2.0%, Mg:0.2~1.5%, satisfy 0.7Si%+Mg%≤2.2%, and constitute by surplus Al and impurity.
14,, it is characterized in that above-mentioned aluminium alloy calendering plate also contains below the Zn:0.5% according to claim 11 or 13 described formabilities and the good aluminium alloy plate of coating sintering hardening.
15,, it is characterized in that above-mentioned aluminium alloy calendering plate contains also that Mn:1.0% is following, Cr:0.3% is following, V:0.2% is following, Zr:0.2 more than one among following according to any described formability and the good aluminium alloy plate of coating sintering hardening in the claim 11,13,14.
16,, it is characterized in that above-mentioned aluminium alloy calendering plate also contains below the Cu:1.0% according to any described formability and the good aluminium alloy plate of coating sintering hardening in the claim 2~9,11,13~15.
17,, it is characterized in that above-mentioned aluminium alloy calendering plate contains also that Ti:0.1% is following, at least a among following of B:50ppm according to any described formability and the good aluminium alloy plate of coating sintering hardening in the claim 2~9,11,13~16.
18, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 2~6,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 2~6,16, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 450 ℃ in 17, be cooled to the temperature of regulation of 350~500 ℃ temperature range with the speed of cooling more than 100 ℃/hour, the hot rolling that under the temperature of this regulation, begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
19, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 2~6,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 2~6,16, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 450 ℃ in 17, be cooled to temperature below 350 ℃ with the speed of cooling more than 100 ℃/hour, then, the temperature of reheat to 350~500 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
20, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 2~6,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 2~6,16, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 450 ℃ in 17, be cooled to temperature below 350 ℃ with the speed of cooling more than 100 ℃/hour, and then cool to room temperature, then, the temperature of reheat to 350~500 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
21, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 7~9,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 7~9,16, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 480 ℃ in 17, be cooled to the temperature of regulation of 300~450 ℃ temperature range with the speed of cooling more than 150 ℃/hour, the hot rolling that under the temperature of this regulation, begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
22, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 7~9,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 7~9,16, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 480 ℃ in 17, be cooled to temperature below 300 ℃ with the speed of cooling more than 150 ℃/hour, and then after the temperature of reheat to 300~450 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
23, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 7~9,16, the manufacture method of any described aluminium alloy plate in 17, it is characterized in that to have claim 7~9,16, the aluminium alloy ingot bar of any one described composition is after the processing that homogenizes under the temperature more than 480 ℃ in 17, be cooled to temperature below 300 ℃ with the speed of cooling more than 150 ℃/hour, and then cool to room temperature, then after the temperature of reheat to 300~450 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 500 ℃, carry out solution treatment, quench.
24, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is the manufacture method of any described aluminium alloy plate in the claim 11,13~17, it is characterized in that to have the aluminium alloy ingot bar of any described composition in the claim 11,13~17 after the processing that homogenizes under the temperature more than 450 ℃, be cooled to specified temperature below 350 ℃ with the speed of cooling more than 100 ℃/hour, under this specified temperature, carry out hot rolling, and then carry out cold rolling after, under the temperature more than 450 ℃, carry out solution treatment, quenching.
25, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 11, the manufacture method of any described aluminium alloy plate in 13~17, it is characterized in that to have claim 11, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 450 ℃ in 13~17, be cooled to temperature below 350 ℃ with the speed of cooling more than 100 ℃/hour, and then after the temperature of reheat to 300~450 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 450 ℃, carry out solution treatment, quench.
26, the manufacture method of the aluminium alloy plate that a kind of formability and coating sintering hardening are good, it is claim 11, the manufacture method of any described aluminium alloy plate in 13~17, it is characterized in that to have claim 11, the aluminium alloy ingot bar of any described composition is after the processing that homogenizes under the temperature more than 450 ℃ in 13~17, be cooled to temperature below 350 ℃ with the speed of cooling more than 100 ℃/hour, and then cool to room temperature, then after the temperature of reheat to 300~500 ℃, the hot rolling that begins to roll, and then carry out cold rolling after, under the temperature more than 450 ℃, carry out solution treatment, quench.
27,, it is characterized in that above-mentioned hot rolled end temp is below 300 ℃ according to the manufacture method of the aluminium alloy plate that any described formability and coating sintering hardening are good in the claim 18~26.
28, according to the manufacture method of the aluminium alloy plate that any described formability and coating sintering hardening are good in the claim 18~27, after it is characterized in that above-mentioned solution treatment, carry out being cooled to 120 ℃ quenching with the speed of cooling more than 5 ℃/second, in back 60 minutes of quenching, under 40~120 ℃ temperature, carry out 50 hours with interior thermal treatment.
29, the manufacture method of the aluminium alloy plate that formability according to claim 28 and coating sintering hardening are good, it is characterized in that above-mentioned thermal treatment after, in 7 days, under 170 ℃~230 ℃ temperature, carry out handling with interior recovery in 60 seconds.
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JP091980/2001 | 2001-03-28 | ||
JP2001091979 | 2001-03-28 | ||
JP091979/2001 | 2001-03-28 | ||
JP295633/2001 | 2001-09-27 | ||
JP063118/2002 | 2002-03-08 | ||
JP063119/2002 | 2002-03-08 | ||
JP077794/2002 | 2002-03-20 | ||
JP077795/2002 | 2002-03-20 |
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CN2008100912011A Division CN101260491B (en) | 2001-03-28 | 2002-03-26 | Aluminum alloy sheet with excellent formability and paint bake hardenability, and method for production thereof |
CN2008100916008A Division CN101302592B (en) | 2001-03-28 | 2002-03-26 | Aluminum alloy sheet having excellent bending workability and hardenability in coating/baking, and production method thereof |
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CH480883A (en) * | 1964-08-27 | 1969-11-15 | Alusuisse | Process for the production of hardenable strips and sheets from hardenable aluminum alloys with copper contents below 1% |
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