CN102312233B - Aluminum alloy plate after surface treatment and manufacturing method thereof - Google Patents
Aluminum alloy plate after surface treatment and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides an aluminum alloy plate after surface treatment and the manufacturing method thereof. The aluminum alloy plate has excellent degreasing performances, chemical conversion processing performances and caking property even if a period before a manufacturing process from the aluminum alloy plate manufacturing to locomotive panel entering is prolonged. The aluminum alloy plate after surface treatment comprises a substrate composed of aluminum alloy, an oxidation overlay film formed on the surface of the substrate, and a surface treating overlay film formed on the surface of an oxidation overlay film and comprising zirconium, wherein, the thickness of the oxidation overlay film ranges from 1 nm to 30 nm. The surface treating overlay film does not comprise halogen and phosphor and has an adhesion quantity ranging from 0.01 mg/m2 to 100 mg/m2 on the oxidation overlay film if converted into zirconium dioxide. Furthermore, the aluminum alloy plate after surface treatment comprises an aluminum alloy plate and an overlay film formed on the surface of the aluminum alloy plate, wherein, the thickness of the overlay film ranges from 1 nm to 30 nm. The magnesium concentration is 1-20 atom%. The zirconium concentration is 0.2-10 atom%. The halogen concentration and the phosphor concentration are respectively lower than 0.1 atom%.
Description
Technical field
The present invention relates to implement the surface-treated aluminium alloy plate, relate to automobile-use, especially can be fit to be used in surface treated aluminium alloy plate and the manufacture method thereof of vehicle panels.
Background technology
As member or the parts usefulness of the conveyors such as motor vehicle, boats and ships, aircraft or vehicle, machinery, electronic product, building, works, optical device, implements, utilize various aluminium alloy plates according to each characteristic of each alloy.And the lightweight of pursuing in recent years motorcar body replaces the ferrous materials that in the past used to improve fuel availability, and proportion to be about 1/3 and the use to motorcar body with aluminium alloy plate of good energy absorption of iron constantly increase.
When using aluminium alloy plate as vehicle panels, pursue solidity to corrosion after plasticity, weldability, cohesiveness, chemical convertibility, the application, attractive in appearance etc.The situation of making the method for vehicle panels and use steel plate in the past with aluminium alloy plate is basic identical, 1) is shaped (to cutting out of specified dimension, to stipulating the stamping of shape), 2) engage (welding and/or bonding), 3) (based on the degreasing of clean-out system → surface adjustment → zinc phosphate processing), 4 are processed in chemical conversion) application (based on the primary coat of electro dipping → in be coated with → on be coated with).
On the other hand, the modularization development of automotive component.Thus owing to need to make aluminium alloy plate self, therefore enter before the manufacturing process of described vehicle panels or the vehicle body manufacturing process during exist than in the past elongated tendency.To be parts company should be directly installed on all parts on the vehicle body with vehicle manufacturers to the modularization of automotive component assists in advance the method that is installed in after the assembling on the vehicle body.Modular purpose is to make the difficult operation of vehicle manufacturers simplify and enhance productivity, and also has the production process of shortening and cuts down half-finished effect.Modularization helps this Xiao of Cheng Minus of motor vehicle.
From make aluminium alloy plate self to enter before the described manufacturing process during than prolong in the past, therefore from the viewpoint of the surface protection of aluminium alloy plate, need to apply antirust oil handling to aluminium alloy plate.Yet, in any case the surface property of aluminium alloy plate all rheological parameters' change with time can occur, thereby can produce bad impact to degreasing, the chemical convertibility of aluminium alloy plate.Follow the rheological parameters' change with time of the surface property of aluminium alloy plate, the degreasing deterioration when chemical conversion is processed, chemical conversion are processed overlay film and are difficult to adhere to, and the result is the solidity to corrosion that affects after the application.And, in aluminium alloy vehicle panels processed that engages by binding agent, invade the junction surface because moisture, oxygen or salt grade, and the interface of binding agent and aluminium alloy plate occur through the time deteriorated and generation interface peel, thereby have the problem of cohesive strength decline.
Therefore, in the past, the oxidation overlay film by clean waiting the surface of removing aluminium alloy plate to form, especially contained the oxidation overlay film of Mg, and improved degreasing, chemical convertibility and cohesiveness (for example, with reference to patent documentation 1～5).Yet, be difficult to the oxidation overlay film is removed fully, and be difficult to obtain the few aluminium alloy plate that has superior surface performance of rheological parameters' change with time of surface property.And, fully need strongly to clean except the deoxidation overlay film, so productivity is poor, uneconomical.
The Mg amount and the OH that adjust the oxidation overlay film of aluminium alloy plate measure, rear 14 days of the adjustment of oxidation overlay film with interior coating slushing oil (for example, with reference to patent documentation 6).And, form the surface coating that is consisted of by phosphoric acid salt overlay film and the pellumina that forms on the surface of aluminium alloy plate thereon, and apply slushing oil (for example, with reference to patent documentation 7) at this surface coating (pellumina).
Patent documentation 1: Japanese kokai publication hei 06-256980 communique
Patent documentation 2: Japanese kokai publication hei 06-256881 communique
Patent documentation 3: Japanese kokai publication hei 05-070741 communique
Patent documentation 4: Japanese kokai publication hei 04-214835 communique
Patent documentation 5: Japanese kokai publication hei 02-115385 communique
Patent documentation 6: TOHKEMY 2006-200007 communique
Patent documentation 7: No. 2744697 communique of Japanese Patent
The rheological parameters' change with time of the surface property of aluminium alloy plate variable quantity to about the week after the firm manufacturing of aluminium alloy plate is maximum, and variation afterwards is fewer.Therefore; in the aluminium alloy plate that patent documentation 6 is put down in writing; owing to adjust rear 14 days with interior coating slushing oil on the surface, so the surface protection of aluminium alloy plate is insufficient, can have degreasing, chemical convertibility and the close-burning problem that can't obtain as target.And in the aluminium alloy plate that patent documentation 7 is put down in writing, the structure of its surface coating has been placed the sample evaluation result in a week after by oiling and has been determined, therefore can have degreasing, chemical convertibility and the close-burning problem that can't obtain target.
Summary of the invention
The present invention is used for solving above-mentioned problem, even its problem be to provide a kind of from make aluminium alloy plate self before the manufacturing process that enters vehicle panels etc. during prolong, degreasing, chemical convertibility and cohesiveness is excellent surface treated aluminium alloy plate and manufacture method thereof also.
In order to solve above-mentioned problem, surface treated aluminium alloy plate of the present invention possesses: the substrate that is made of aluminium alloy; Be formed on the lip-deep oxidation overlay film of this substrate; Be formed on the lip-deep surface treatment overlay film that contains zirconium of this oxidation overlay film, described surface treated aluminium alloy plate is characterised in that, the thickness of described oxidation overlay film is 1～30nm, the not halogen-containing and phosphorus of described surface treatment overlay film is counted 0.01～100mg/m to the adhesion amount of described oxidation overlay film with zirconium dioxide conversion amount
2
In addition, surface treated aluminium alloy plate of the present invention possesses aluminium alloy plate and is formed on the lip-deep overlay film of this aluminium alloy plate, described surface treated aluminium alloy plate is characterised in that, the thickness of described overlay film is 1～30nm, magnesium density is 1～20 atom %, zirconium concentration is 0.2～10 atom %, and halogen concentration and phosphorus concentration are respectively less than 0.1 atom %.
So, oxidation overlay film by possessing the lip-deep regulation thickness that is formed on substrate and be formed on the lip-deep surface treatment overlay film that contains the zirconium of regulation adhesion amount of oxidation overlay film, the acid cleaning that need not in the past carry out etc. and can improve degreasing, chemical convertibility and cohesiveness.Especially in the surface treatment overlay film, by making take the fixed adhesion amount of zirconium dioxide conversion gauge as specialized range, and the surface treatment overlay film suppresses the absorption of slushing oil, therefore during the degreasing in the chemical conversion treatment process, can fully remove slushing oil and press oil, thereby keep good immersion.Consequently, can suppress degreasing bad (immersion property the is bad) chemical conversion that causes and process the generation of inequality.And, because the surface treatment overlay film is combined securely with the oxidation overlay film, therefore can suppress to occur between surface treated aluminium alloy plate and the binding agent situation of interface peel.And, because the not halogen-containing and phosphorus of surface treatment overlay film, thereby when making surface treated aluminium alloy plate, use the surface treatment liquid of not halogen-containing and phosphorus, thereby alleviate the load to producing apparatus, and minimizing is on the impact of environment.
The manufacture method of surface treated aluminium alloy plate of the present invention is characterised in that, comprises: by rolling substrate manufacture operation of making described substrate; With described base plate heating to 400～580 ℃ and form the heating process of described oxidation overlay film on the surface of described substrate; The described substrate that forms described oxidation overlay film is cooled off, and form the refrigerating work procedure of described surface treatment overlay film on the surface of described oxidation overlay film, wherein, in described refrigerating work procedure, using not halogen-containing and phosphorus and concentration is that 0.005～5g/L, pH are that 1～5 the zirconium nitrate aqueous solution is as cooling fluid.And, preferably, in the manufacture method of surface treated aluminium alloy plate of the present invention, described substrate is made of thermal treatment type aluminium alloy, described heating process is described substrate to be implemented the solution treatment operation of solution treatment, and described refrigerating work procedure is the quenching process of the described substrate that is formed with described oxidation overlay film being implemented quench treatment.
According to this kind step, by the heating process of carrying out heating with specified temperature, and stipulate the oxidation overlay film of thickness in the formation of the surface of substrate, and adjust the intensity of surface treated aluminium alloy plate.And, the refrigerating work procedure that cools off by the zirconium nitrate aqueous solution that carries out stipulating, and form the surface treatment overlay film of regulation adhesion amount on the surface of oxidation overlay film.And, in refrigerating work procedure, use the surface treatment liquid of not halogen-containing and phosphorus as cooling fluid, therefore can reduce the load to producing apparatus, and reduce the impact on environment.Need to prove that as thermal treatment type aluminium alloy, the known Al-Cu-Mg of having is that alloy (2000 are), Al-Mg-Si are that alloy (6000 are), Al-Zn-Mg are alloy (7000 are).
[invention effect]
The degreasing of surface treated aluminium alloy plate of the present invention, chemical convertibility and cohesiveness are excellent, and can reduce the load to producing apparatus, and environmental compatibility is good.
In addition, it is excellent that the manufacture method of surface treated aluminium alloy plate of the present invention can be made degreasing, chemical convertibility and cohesiveness, and can alleviate the load to producing apparatus, the surface treated aluminium alloy plate of environmental compatibility excellence.And manufacture method of the present invention can be omitted the acid cleaning in the past carried out etc., can realize that therefore cost descends.
Description of drawings
Fig. 1 is the sectional view of the structure of expression surface treated aluminium alloy plate of the present invention.
Fig. 2 is the sectional view of the structure of expression surface treated aluminium alloy plate of the present invention.
Fig. 3 is the process flow chart of the manufacture method of expression surface treated aluminium alloy plate of the present invention.
[nomenclature]
1 substrate
2 oxidation overlay films
3 surface treatment overlay films
4 overlay films
10 surface treated aluminium alloy plates
S1 substrate manufacture operation
The S2 heating process
The S3 refrigerating work procedure
Embodiment
" surface treated aluminium alloy plate "
Below, with reference to Fig. 1, specify surface treated aluminium alloy plate of the present invention.As shown in Figure 1, surface treated aluminium alloy plate 10 of the present invention possesses: substrate 1; Be formed on the lip-deep oxidation overlay film 2 of this substrate 1; Be formed on the lip-deep surface treatment overlay film 3 that contains zirconium of this oxidation overlay film 2.And, stipulated the thickness of oxidation overlay film 2, the adhesion amount of surface treatment overlay film 3.
Need to prove that at this, the surface of substrate 1 (oxidation overlay film 2) refers at least one side on the surface of substrate 1 (oxidation overlay film 2), comprises so-called surface, the back side.
Below, each structure is described.
＜substrate 〉
Substrate 1 is made of aluminium alloy, and its thickness of slab is suitably set according to the purposes of surface treated aluminium alloy plate 10.And, become the aluminium alloy of material of substrate 1 also according to the purposes of surface treated aluminium alloy plate 10, from the JIS defined be similar to the various non-thermal treatment type aluminium alloy of JIS or thermal treatment type aluminium alloy suitably select.Need to prove, non-thermal treatment type aluminium alloy is that fine aluminium (1000 are), Al-Mn are that alloy (3000 are), Al-Si are that alloy (4000 are) and Al-Mg are alloy (5000 are), and thermal treatment type aluminium alloy is that Al-Cu-Mg is that alloy (2000 are), Al-Mg-Si are that alloy (6000 are) and Al-Zn-Mg are alloy (7000 are).
If enumerate object lesson, then surface treated aluminium alloy plate is being used in the situation of automobile-use, preferred 0.2% endurance is the above high-intensity substrate of 100MPa.Satisfy the aluminium alloy of the substrate of this specific character as formation, usually be fit to use in this kind structural member purposes widely used 5000 be, 6000 be, 7000 the higher general-purpose alloy of endurance such as be, that is, suitable use is as required and modified aluminium alloy.Good age hardening performance or the alloying element amount is fewer and the reproducibility of waste material or the point that has excellent moldability on, preferably use 6000 line aluminium alloys.
Example as the composition of preferred aluminium alloy, enumerate the following Cu of Si, 1.0 quality % of the Mg, 0.3～2.3 quality % that contain 0.2～1.5 quality %, and, contain the element more than a kind of selecting Ti, the B below the 0.06 quality % below 0.1 quality %, the Be below the 0.2 quality %, the Mn below the 0.8 quality %, the Cr below the 0.4 quality %, the Fe below the 0.5 quality %, the Zr below the 0.2 quality %, the V below the 0.2 quality %, and the aluminium alloy that consisted of by Al and inevitable impurity of rest part.The numerical definiteness of each element be the reasons are as follows described.
(Mg is 0.2～1.5 quality %)
Mg has and puies forward high-intensity effect.The content of Mg is during less than 0.2 quality %, and the effect that intensity improves is little.On the other hand, when the content of Mg surpasses 1.5 quality %, plasticity is lower easily will.
(Si is 0.3～2.3 quality %)
Si has and puies forward high-intensity effect.The content of Si is during less than 0.3 quality %, and the effect that intensity improves is little.On the other hand, when the content of Si surpasses 2.3 quality %, plasticity, hot rolling are lower easily will.
(Cu is that 1.0 quality % are following)
Cu has and puies forward high-intensity effect.Yet when the content of Cu surpassed 1.0 quality %, solidity to corrosion descended easily.
(element more than a kind of selecting the Ti below 0.1 quality %, the B below the 0.06 quality %, the Be below the 0.2 quality %, the Mn below the 0.8 quality %, the Cr below the 0.4 quality %, the Fe below the 0.5 quality %, the Zr below the 0.2 quality %, the V below the 0.2 quality %)
Ti has makes the crystal grain of ingot bar fine, and improves the effect of plasticity.Yet, when the content of Ti surpasses 0.1 quality %, owing to form thick crystallisate, and plasticity descends easily.
It is fine that B has the crystal grain or the crystallisate that make ingot bar, and improve the effect of plasticity.Yet, when the content of B surpasses 0.06 quality %, owing to form thick crystallisate, and plasticity descends easily.
Be has the effect that improves hot rolling and plasticity.Yet when the content of Be surpassed 0.2 quality %, effect was saturated.
Mn, Cr, Fe, Zr, V have and put forward high-intensity effect.Yet, when content surpasses 0.8 quality %, 0.4 quality %, 0.5 quality %, 0.2 quality %, 0.2 quality % respectively, owing to form thick crystallisate, and plasticity descends easily.
In addition, as inevitable impurity, Ca, Zn, Ni etc. have been enumerated.
＜oxidation overlay film 〉
And oxidation overlay film 2 is because the thermal treatment in the manufacturing processed of surface treated aluminium alloy plate 10 etc., and is formed on inevitably the surface of substrate 1.The thickness of oxidation overlay film 2 is 1～30nm, controls by the Heating temperature in the manufacturing processed (heating process) of surface treated aluminium alloy plate 10.
(thickness is 1～30nm)
The thickness of oxidation overlay film 2 is during less than 1nm, owing to suppress the absorption of the ester composition in slushing oil and the press oil, therefore even without surface treatment overlay film 3, also degreasing, chemical convertibility and cohesiveness can be guaranteed, but acid cleaning etc. need to be carried out for film thickness monitoring is become less than 1nm.Therefore, productivity is poor, and is impracticable.On the other hand, when the thickness of oxidation overlay film 2 surpasses 30nm, even being set, surface treatment overlay film 3 also can't guarantee chemical convertibility.And, the preferred 10～20nm of the thickness of oxidation overlay film 2.
＜surface treatment overlay film 〉
Surface treatment overlay film 3 is formed in the lip-deep zirconium that contains of oxidation overlay film 2, and the adhesion amount of oxidation overlay film is counted 0.01～100mg/m with zirconium dioxide conversion amount
2Overlay film, and be the overlay film of not halogen-containing and phosphorus.And the adhesion amount of surface treatment overlay film 3 is controlled by the cooling conditions in the manufacturing processed (refrigerating work procedure) of surface treated aluminium alloy plate 10.
(adhesion amount is counted 0.01～100mg/m with zirconium dioxide conversion amount
2)
The adhesion amount of surface treatment overlay film 3 is less than 0.01mg/m
2The time, can't cover fully concavo-convex oxidation overlay film 2, and, namely allow to fully capping oxidation overlay film 2, because the Zr composition in the surface treatment overlay film 3 is not enough, therefore also can't guarantee degreasing, chemical convertibility and cohesiveness.On the other hand, surface treatment overlay film 3 adheres to above 100mg/m
2, the raising effect of degreasing is saturated, and adhesion amount is inhomogeneous easily, and chemical convertibility and cohesiveness are descended.And the adhesion amount of surface treatment overlay film 3 is preferably counted 0.1～10mg/m with zirconium dioxide conversion amount
2
(not halogen-containing and phosphorus)
In the present invention, the not halogen-containing and phosphorus of surface treatment overlay film 3 refers to by fluorescent x-ray and high frequency glow discharge emmission spectrometric analysis (Glow Discharge Optical Emission Spectroscopy, hereinafter referred to as GD-OES) when measuring halogen and phosphorus, fluorine is less than 0.1 atom %, chlorine is less than 0.1 atom %, and bromine is less than 0.1 atom %, and iodine is less than 0.1 atom %, astatine is less than 0.1 atom %, and phosphorus is less than 0.1 atom %.When surface treatment overlay film 3 contained halogen, load can act on producing apparatus.And, if surface treatment overlay film 3 is phosphorous, then when discharging surface treatment liquid, produce easily precipitation, easily contaminate environment.
As the measuring method of the thickness of oxidation overlay film 2, for example, can measure by GD-OES.Particularly, the degree of depth of one half of the oxygen peak concentration during the depth direction that can measure by GD-OES distributes is as the compound film laminating total of surface treatment overlay film 3 (the oxidation overlay film 2 with) thickness, and the rule depth gauge with the Zr density loss during to 0.1 atom % is decided to be the thickness of surface treatment overlay film 3.And the value that the thickness from compound film laminating can be deducted the thickness of surface treatment overlay film 3 is defined as the thickness of oxidation overlay film 2.Yet, if measuring method is to have the measuring method with precision with GD-OES, be not defined as GD-OES, also can be AES (Auger electron spectrography), XPS (x-ray PES) etc.
As the measuring method of the adhesion amount of surface treatment overlay film 3, for example, can measure by fluorescent x-ray.Particularly, by fluorescent x-ray the zirconium in the compound film laminating (surface treatment overlay film 3) is carried out quantitatively its value being converted into the zirconium dioxide amount, and as the adhesion amount of surface treatment overlay film 3.Yet, if measuring method is to have and the measuring method of fluorescent x-ray with precision, be not defined as fluorescent x-ray.
As shown in Figure 2, surface treated aluminium alloy plate 10 of the present invention possesses substrate 1 and the lip-deep overlay film 4 that is formed on this substrate 1.Need to prove, as described later, in the manufacture method of overlay film 4, at first form the oxidation overlay film, then, zirconium nitrate (formal name: dinitric acid zirconium white, trivial name: contain oxygen zirconium nitrate, zirconium nitrate, the nitric acid zircon etc.) aqueous solution is contacted with the surface of the oxidation overlay film of formation, by cooling off and implement surface treatment, and the whole overlay film 4 that forms.
The structure of＜overlay film 〉
Overlay film 4 is in order to improve degreasing, to reduce the uneven of chemical conversion processing and improve cohesiveness, and be formed on the lip-deep film of substrate 1 with the composition of regulation with the thickness of regulation.Need to prove, at this, the formation of overlay film 4 is after having made the oxidation overlay film by heating process, carries out surface treatment by the refrigerating work procedure that has used the zirconium nitrate aqueous solution at the oxidation overlay film, and at the on the whole formation overlay film 4 that has carried out this surface-treated oxidation overlay film.
(thickness)
The scope of this overlay film 4 take its thickness as 1～30nm is formed on the substrate 1.Overlay film 4 need to carry out acid cleaning etc. for film thickness monitoring is become less than 1nm.Therefore, productivity is poor, and is impracticable.On the other hand, when the thickness of overlay film surpassed 30nm, the overlay film amount was superfluous and form concavo-convexly on the surface, and the result is that chemical conversion occurs is uneven, chemical conversion decline.
The thickness of overlay film 4 is mainly determined by the formed oxidation overlay film of heating process described later.Therefore, in the surface treatment that the zirconium nitrate aqueous solution that uses as cooling fluid by refrigerating work procedure described later carries out, owing to become the state that zirconium dioxide adheres to or enter the oxidation overlay film, therefore most of thickness by the oxidation overlay film determines.
(magnesium density)
Overlay film 4 forms magnesium density the scope of 1～20 atom %.When overlay film 4 comprises magnesium component in substrate 1, be difficult to its magnesium density is suppressed to less than 1 atom %, therefore need to process.On the other hand, when magnesium density surpasses 20 atom %, even used the processing of the present invention of the zirconium nitrate aqueous solution also can't guarantee degreasing, chemical conversion etc.Need to prove that the preferred scope of the magnesium density in the overlay film 4 is 2～15 atom %.And, the magnesium amount that magnesium density in the overlay film 4 contains by substrate 1 or create conditions and control, at this, especially control the magnesium amount (0.2～1.5 quality %) that substrate 1 contains, and be controlled in the scope of 1～20 atom % by the magnesium density of manufacture method described later with overlay film 4.
Overlay film 4 has the zirconium concentration of the scope of 0.2～10 atom %.The zirconium concentration of overlay film 4 can't suppress the absorption of the ester composition in the press oil, and can't obtain the desirable performances such as degreasing, chemical conversion during less than 0.2 atom %.On the other hand, when the zirconium concentration of overlay film 4 surpassed 10 atom %, surperficial zirconium was too much, and the obstruction chemical conversion is processed reaction and produced chemical conversion processing inequality, chemical conversion decline.Need to prove that the preferred scope of zirconium concentration is 0.4～8 atom %.The control of zirconium concentration can be by the zirconium nitrate aqueous solution that uses in the refrigerating work procedure described later concentration etc. carry out.
And overlay film 4 is the zirconium concentration combination with the magnesium density of afore mentioned rules and afore mentioned rules, and the film of not halogen-containing and phosphorus.For example, when measuring halogen and phosphorus, fluorine is less than 0.1 atom %, and chlorine is less than 0.1 atom %, and bromine is less than 0.1 atom %, and iodine is less than 0.1 atom %, and astatine is less than 0.1 atom %, and phosphorus is less than 0.1 atom %.When the surface treatment overlay film contained halogen, effect had load on the producing apparatus corresponding with halogen.And, in the phosphorous situation of surface treatment overlay film, when discharging surface treatment liquid, produce easily precipitation, easily contaminate environment.
In addition, overlay film 4 is except containing above-mentioned element (magnesium, zirconium, halogen and phosphorus), and rest part is made of oxygen, aluminium and impurity.The preferred content of oxygen, aluminium is respectively 20～65 atom %.As impurity, C, Si, Ca, Fe, Cu, Mn, Ti, Zn, Ni etc. have been enumerated, if C then allows the content less than 5 atom %, if other impurities are then allowed the content less than 0.5 atom %.
Need to prove that the oxidation overlay film that the heating process by overlay film 4 forms is formed in the Porous overlay film of the lip-deep convex-concave shape of substrate 1, when substrate 1 is alloy when consisting of by 6000, is the overlay film take magnesium oxide as main component.At this, the thickness of oxidation overlay film is 1～30nm, and the Heating temperature of the manufacturing processed (heating process) by surface treated aluminium alloy plate 10 is controlled.The thickness of oxidation overlay film is during less than 1nm, can suppress the absorption of the ester composition in slushing oil and the press oil, therefore even without the surface treatment overlay film, also degreasing, chemical convertibility and cohesiveness can be guaranteed, but acid cleaning etc. need to be carried out for film thickness monitoring is become less than 1nm.Therefore, productivity is poor, and is impracticable.On the other hand, when the thickness of oxidation overlay film surpasses 30nm, even being set, the surface treatment overlay film also can't guarantee chemical convertibility.And, the preferred 10～20nm of the thickness of oxidation overlay film.
In addition, the surface treatment of the surface of oxidation overlay film being carried out is carried out the surface of oxidation overlay film by the use zirconium nitrate aqueous solution not halogen-containing and phosphorus in refrigerating work procedure.And in surface treatment, zirconium concentration is controlled by the cooling conditions in the manufacturing processed (refrigerating work procedure) of surface treated aluminium alloy plate 10.When zirconium concentration is less than 0.2 atom % by surface treatment, can't cover fully concavo-convex oxidation overlay film, and, namely allow to abundant capping oxidation overlay film, because the Zr composition in the oxidation overlay film is not enough, therefore also can't guarantee degreasing, chemical convertibility and cohesiveness.On the other hand, when surface-treated zirconium concentration surpassed 10 atom %, the raising effect of degreasing was saturated, and the distribution of zirconium is inhomogeneous easily, and chemical convertibility and cohesiveness are descended.And, preferred 0.4～0.8 atom % of surface-treated zirconium concentration.
Concentration of element in the＜overlay film and film thickness measuring 〉
Concentration of element in the overlay film 4 on the plate surface of aluminum alloy materials (substrate 10) (concentration of magnesium density, zirconium concentration, halogen, phosphorus etc.) is measured by GD-OES, after the film thickness of having measured overlay film 4, can in distributing, depth direction calculate the mean value of regulation concentration of element.And GD-OES can measure the thickness of overlay film 4.That is the degree of depth of a half value of the maximum zirconium concentration on the depth direction that, can measure by GD-OES distributes is as the thickness of overlay film.Need to prove that concentration of element and thickness can form the mean value of the measurement result at overlay film 4 lip-deep several positions certainly.
In addition, about surface-treated zirconium concentration, also can use the measuring method same with magnesium density.And zirconium concentration also can be obtained according to the zirconium dioxide concentration of overlay film 4.That is, obtain zirconium dioxide concentration, and obtain zirconium concentration according to this zirconium dioxide of obtaining by the computing of regulation.
" manufacture method of surface treated aluminium alloy plate "
Next, the manufacture method of surface treated aluminium alloy plate of the present invention is described with reference to Fig. 3.The structure of surface treated aluminium alloy plate is described with reference to Fig. 1 in addition.
The manufacture method of surface treated aluminium alloy plate 10 comprises substrate manufacture operation S1, heating process S2, refrigerating work procedure S3.And, stipulated Heating temperature among the heating process S2 and concentration and the pH of the zirconium nitrate aqueous solution among the refrigerating work procedure S3.
Below, each operation is described.
＜substrate manufacture operation 〉
Substrate manufacture operation S1 is the operation of making substrate 1 by rolling.Particularly, preferably make substrate 1 by following step.
Aluminium alloy by continuous casting to composition with regulation melts, casts, thereby makes ingot bar (melt-casting operation), and the described ingot bar that produces is implemented to homogenize thermal treatment (heat treatment step homogenizes).Next, the ingot bar after the described thermal treatment that homogenizes is implemented hot rolling and make heat and prolong plate (hot-rolled process).Then, with 300～580 ℃ heat is prolonged plate and carry out black annealing or process annealing, implement at least once cold rolling 5% or more of final cold rolling rate, thereby make the cold plate (substrate 1) (cold rolling process) that prolongs of the thickness of slab of stipulating.Be more than 300 ℃ by the temperature that makes black annealing or process annealing, can further bring into play the effect that improves plasticity, by forming below 580 ℃, suppress easily the decline of the plasticity that causes of burning.Be more than 5% by making final cold rolling rate, can further bring into play the effect that improves plasticity.Need to prove that the condition of the thermal treatment that homogenizes, hot rolling also is not particularly limited, so long as the condition usually can obtain heat and prolong plate the time gets final product.And, also can not carry out process annealing.
＜heating process 〉
Heating process S2 is heated to 400～580 ℃ with substrate 1, and forms the operation of oxidation overlay film 2 on the surface of substrate 1.And heating process S2 also is the operation of adjusting the intensity of surface treated aluminium alloy plate 10.Need to prove the instant heating of preferred 100 ℃/minutes above rate of heating of heating process S2.
And heating process S2 is the solution treatment operation when substrate 1 is made of thermal treatment type aluminium alloy, is the heating process in the annealing operation (final annealing operation) when substrate 1 is made of non-thermal treatment type aluminium alloy.
(Heating temperature: 400～580 ℃)
Arrive Heating temperature more than 400 ℃ by instant heating, and the intensity behind the application post-heating (curing) of the intensity of surface treated aluminium alloy plate 10 and surface treated aluminium alloy plate 10 thereof raises further.Arrive Heating temperature below 580 ℃ by instant heating, and suppress the decline of the plasticity that causes of burning.And, by under 400～580 ℃ of Heating temperatures, heating, and form regulation thickness (1～30nm) oxidation overlay film 2 on the surface of substrate 1.Need to prove, from putting forward high-intensity viewpoint, preferred 3～30 seconds of hold-time.
＜refrigerating work procedure 〉
Refrigerating work procedure S3 cools off the substrate 1 that is formed with oxidation overlay film 2, and forms surface treatment overlay film 3 on the surface of oxidation overlay film 2,, carries out simultaneously cooling process and surface-treated operation that is.Need to prove that refrigerating work procedure S3 preferably is cooled to 100 ℃ rapidly with 100 ℃/minutes above speed of cooling.Form more than 100 ℃/minutes by the speed of cooling that will be cooled to 100 ℃, can further suppress the decline of plasticity, and further improve the intensity after curing.
And refrigerating work procedure S3 is the quench treatment operation when substrate 1 is made of thermal treatment type aluminium alloy, when substrate 1 is made of non-thermal treatment type aluminium alloy, is the refrigerating work procedure in the annealing operation (final annealing operation).
In refrigerating work procedure S3, as cooling fluid, use not halogen-containing and phosphorus, concentration is 0.005～5g/L, and pH is 1～5 the zirconium nitrate aqueous solution.And, in refrigerating work procedure S3, preferred 1～30 second of cooling time.In this refrigerating work procedure S3, for example, the substrate 1 that is formed with the oxidation overlay film is utilized spray or spraying and the ejection zirconium nitrate aqueous solution, or it is passed through in the zirconium nitrate aqueous solution, and carry out the cooling of substrate 1.
(not halogen-containing and phosphorus)
In the present invention, not halogen-containing and phosphorus refers to as mentioned above as the zirconium nitrate aqueous solution of cooling fluid, when measuring halogen and phosphorus by fluorescent x-ray and GD-OES, can't measure, that is, and less than measuring boundary.And, when cooling fluid contains halogen, can load be arranged in the producing apparatus effect.And, in the phosphorous situation of cooling fluid, produce easily precipitation, easily contaminate environment when discharging surface treatment liquid.(concentration: 0.005～5g/L)
Use the zirconium nitrate aqueous solution of normality as cooling fluid, and the adhesion amount of surface treatment overlay film 3 to be specialized range (count 0.01～100mg/m with zirconium dioxide conversion amount
2).And the zirconium concentration of overlay film 4 becomes specialized range (0.2～10 atom %).The concentration of the zirconium nitrate aqueous solution is during less than 0.005g/L, and the adhesion amount of surface treatment overlay film 3 is few (in zirconium dioxide conversion amount less than 0.01mg/m
2), or the zirconium concentration of overlay film 4 few (less than 0.1 atom %) can't be guaranteed degreasing, chemical convertibility and the cohesiveness of surface treated aluminium alloy plate 10.On the other hand, when concentration surpassed 5g/L, the adhesion amount of surface treatment overlay film 3 was many (in zirconium dioxide conversion amount above 100mg/m
2) or the zirconium concentration of overlay film 4 large (zirconium concentration surpasses 10 atom %), degreasing, chemical convertibility and close-burning raising effect are saturated.Preferred 0.05～the 0.5g/L of the concentration of the zirconium nitrate aqueous solution.
(pH：1～5)
Less than 1 o'clock, do not form surface treatment overlay film 3 as the pH of the zirconium nitrate aqueous solution of cooling fluid, can't guarantee degreasing, chemical convertibility and the cohesiveness of surface treated aluminium alloy plate 10.On the other hand, pH surpasses at 5 o'clock, and the stability decreases of cooling fluid produces precipitation easily in cooling fluid.When producing precipitation in cooling fluid, precipitation is surperficial as the plate that foreign matter is pressed into surface treated aluminium alloy plate 10, and bad order is therefore not preferred.PH preferred 2～4 as the zirconium nitrate aqueous solution of water coolant.
So, in refrigerating work procedure, use the zirconium nitrate aqueous solution as cooling fluid, to the substrate 1 after the heating, be that substrate 1 that effects on surface is formed with oxidation overlay film 2 cools off and carries out surface treatment, thereby need not to remove by acid cleaning etc. the oxidation overlay film 2 on surface, the acid cleaning of therefore in the past carrying out etc. no longer needs, and can economize the production line of disacidify cleaning etc.In addition, owing to can carry out cooling process and surface treatment by same operation, therefore can further cut down manufacturing cost.
The manufacture method of surface treated aluminium alloy plate 10 has been described as mentioned above, but when carrying out the manufacturing of surface treated aluminium alloy plate 10, can not apply in the scope of bad impact described each operation, between described each operation or front and back, can comprise other operations yet.For example, the preliminary aging treatment operation of implementing preliminary aging treatment also can be set behind described refrigerating work procedure.Preliminary aging treatment preferably at 72 hours with the interior low-temperature heat of under 40～120 ℃, carrying out 8～36 hours.Under this condition by carrying out preliminary aging treatment, and can realize plasticity and cure after intensity improve.
In addition, also can comprise the defective products of removing operation or removing the defective products that produces in each operation such as the foreign matter of the foreign matter on the plate surface of removing surface treated aluminium alloy plate 10 and remove operation etc.
And the surface treated aluminium alloy plate 10 of manufacturing applies press oil before shaping.Press oil mainly uses the oil that contains the ester composition.
Next, the method that applies press oils at surface treated aluminium alloy plate 10 of the present invention is described.
As the method for coating press oil, for example, only surface treated aluminium alloy plate 10 is immersed in to contain in the press oil of ethyl oleate as the ester composition and gets final product.Coating contain the ester composition press oil method or condition and be not particularly limited, and can extensively be suitable for method or the condition of common coating press oil.And the ester composition is not limited to ethyl oleate, also can utilize the various compositions such as butyl stearate or sorbitan monolaurate.
[embodiment 1]
Next, contrast the embodiment that satisfies important document of the present invention and the comparative example of being discontented with foot important document of the present invention and specify surface treated aluminium alloy plate of the present invention.
Using composition is 6022 specifications (Cu of the Mg of the Si of 0.8～1.5 quality %, 0.45～0.7 quality %, 0.01～0.11 quality %), 6016 specifications (Cu of the Mg of the Si of 1.0～1.5 quality %, 0.25～0.6 quality %, 0.2 quality %), three kind of 6000 line aluminium alloy plate of the commercially available product of 6111 specifications (Cu of the Mg of the Si of 0.6～1.1 quality %, 0.5～1.0 quality %, 0.5～0.9 quality %), by above-mentioned manufacture method, made the base material (with reference to table 1) that is of a size of 70mm width * 150mm length * 1mm thickness.
Next, this base material heating is arrived 480～580 ℃ of temperature to entity, then not heating be the nitric acid of normal temperature and pH is adjusted to flood cooling in 5～20 seconds in the zirconium nitrate aqueous solution that 2～4 concentration is 0.05～0.5g/L after, carry out washing and drying, thereby made the surface treated aluminium alloy plate that is formed with oxidation overlay film and surface treatment overlay film on the two sides.Two sides coating 0.1～2g/m to this surface treated aluminium alloy plate
2Commercially available automobile-use clean press oil (Dormant oils system, kinetic viscosity 1～7cSt) be as for examination material (No.1～22).
Need to prove, for the examination material (No.1～16) making in, in described scope to suitably adjusting the Heating temperature (entity arrival temperature) of substrate, the concentration of the zirconium nitrate aqueous solution, the duration of contact of the zirconium nitrate aqueous solution.In the making for examination material (No.17), do not implement the cooling (surface treatment) based on the zirconium nitrate aqueous solution, and cool off by water-cooled, the surface treatment overlay film is not set.In the making for examination material (No.18,19), under the concentration 0.004g/L of 590 ℃ of the Heating temperatures of substrate, the zirconium nitrate aqueous solution, carry out.In the making for examination material (No.20,21), after heat treated, carry out acid and clean, the surface treatment overlay film is not set.In the making for examination material (No.22), replace the zirconium nitrate aqueous solution and used the aluminium dihydrogen phosphate aqueous solution of concentration 0.5g/L.
About the confession examination material that obtains as mentioned above, measured the thickness of oxidation overlay film by high frequency glow discharge emmission spectrometric analysis (GD-OES (HORIBA JOBIN YVON society system, pattern JY-5000RF)).And, measured the adhesion amount (zirconium dioxide conversion amount) of surface treatment overlay film by fluorescent x-ray (society of Shimadzu Corp system, pattern XRF1800).Its result is as shown in table 1.
In addition, measure the content of halogen of surface treatment overlay film by fluorescent x-ray, and measured phosphorus content by GD-OES.The surface treatment overlay film of confession examination material (No.1～16,18,19) is not halogen-containing, phosphorus.Surface treatment overlay film for examination material (No.22) is not halogen-containing, and it is 5 atom % that the depth direction of overlay film divides the mean value of the phosphorus content that plants.
Next, use above-mentioned supplying to try material, carried out following evaluation.Its result is as shown in table 1.
[table 1]
(notes) are for trying material No.17: based on the cooling of water-cooled
(notes) are for trying material No.22: examination material No.23 is cleaned, supplies in acid: the strong acid cleaning
(notes) are for trying material No.24: based on the cooling of aluminium dihydrogen phosphate aqueous solution
(notes) alloying constituent, A:6022 specification, B:6016 specification, C:6111 specification
＜degreasing (wetted surface area rate) 〉
Each was placed 6 months in the environmental chamber of 50～90%RH with 15～35 ℃ for the examination material.Then, after 6 months, yellow soda ash at commercially available automobile-use is to have flooded 40 ℃ * 2 minutes (stirring based on agitator is arranged) during degreasing is bathed, measured after the washings in 30 seconds (flowing water) with respect to for the wetted surface area rate of examination material area (the table back of the body average) (become good degree, high numerical value, the situation of immersion is 100% fully).Thus, the immersion in the time of can the evaluating chemical conversion processing, i.e. degreasing.Each is 3 for the examination material, and the wetted surface area rate is their mean value.Need to prove that remaining on the indoor initial value before of moist environment all is 100%.The area occupation ratio that will leak is good as degreasing more than 80%, will be bad as degreasing less than 80%.
＜chemical convertibility (whether have chemical conversion to process uneven) 〉
Each is supplied the examination material is 40 ℃ * 2 minutes (stirring based on agitator is arranged) of dipping during degreasing is bathed at yellow soda ash, to having carried out skimming treatment for trying material surface.Next, after the zinc of room temperature is to have flooded 1 minute (stirring based on agitator is arranged) during surface adjustment is bathed, in bathing, 35 ℃ of zinc phosphates flooded 2 minutes (stirring based on agitator is arranged), and to supplying the examination material surface to carry out the chemical conversion processing.Then, visual observation the chemical conversion that for examination material surface produce of chemical conversion after processing process unevenly, and estimated chemical convertibility.In the evaluation of chemical convertibility, with occuring, the uneven situation of chemical conversion processing in table, is not labeled as " nothing ", the expression chemical convertibility is good, is labeled as " having " with the uneven situation of chemical conversion processing has occured in table, and the expression chemical convertibility is bad.
＜cohesiveness (aggegation destructive rate) 〉
(the SUNSTAR skill is ground Co., Ltd.'s system via heat embrittlement type epoxy resin binding agent in the end of two confession examination materials (70mm width) that structure is identical, Penguin cement (the Japanese original text: ペ Application ギ Application セ メ Application ト) #1086), so that overlap joint grows up to the (bond area: 70mm * 13mm=910mm for 13mm
2) mode overlap.Need to prove, the granulated glass sphere (particle diameter 150 μ m) of trace is added in the binding agent and regulate so that the thickness of adhesive layer becomes the mode of 150 μ m.After the coincidence, at room temperature dry 30 minutes, next, make the binding agent sclerosis with 170 ℃ of heating 20 minutes.Then, at room temperature left standstill again 24 hours, thereby formed the adhesion test body.
The adhesion test body that obtains kept 10 days in 50 ℃, the moistening atmosphere of 95%RH after, utilize tensile testing machine to stretch with the speed that 50mm/ divides, based on following formula (1), calculated the aggegation destructive rate (non-interface peel rate) of the adhesive layer of adhesive segment.Need to prove that the aggegation destructive rate is the mean value of three adhesion test bodies.And, in formula (1), with a side of adhesion test body as test film A, with the opposing party as test film B.Be that situation more than 80% is good as cohesiveness with the aggegation destructive rate, will be bad as cohesiveness less than 80% situation.
Aggegation destructive rate (%)=100-{ (bond area of the interface peel area of test film A/test film A) * 100}+{ (bond area of the interface peel area of test film B/test film B) * 100} ... (1)
As shown in table 1, No.1～16 (embodiment) satisfy structure of the present invention, so degreasing, chemical convertibility and cohesiveness are good for the examination material.
On the other hand, for the examination material No.17～discontented foot of 22 (comparative examples) structure of the present invention, become following result.
Supply examination material No.17 because the surface treatment overlay film is not set, so degreasing, chemical convertibility and cohesiveness are bad.Because the thickness of oxidation overlay film surpass higher limit, and the adhesion amount of surface treatment overlay film is less than lower value for examination material No.18,19, so degreasing, chemical convertibility and cohesiveness are bad.For the adhesion amount of the surface treatment overlay film of examination material No.20 within the scope of the invention, but the thickness of oxidation overlay film surpasses higher limit, so chemical convertibility is bad.For the thickness of the oxidation overlay film of examination material No.21 within the scope of the invention, but the adhesion amount of surface treatment overlay film surpasses higher limit, so chemical convertibility and cohesiveness are bad.
Clean and be assumed to be the surface treated aluminium alloy plate in the past that above-mentioned patent documentation etc. is put down in writing although carry out acid for examination material No.22, owing to do not have the surface treatment overlay film, so degreasing, chemical convertibility and cohesiveness are bad.And, owing to carried out sour cleaning, so productivity is also poor.
Although having carried out more powerful cleaning for examination material No.23 is that strong acid cleans, because the thickness of oxidation overlay film is less than lower value, so degreasing, chemical convertibility and cohesiveness are good.Yet, owing to carried out the strong acid cleaning, so productivity is poor.Therefore, this surface treated aluminium alloy plate is uneconomical, and is not suitable for practicality.
For examination material No.24 since aluminium dihydrogen phosphate aqueous solution as cooling fluid, so degreasing and chemical convertibility are good, but cohesiveness is bad.And, cooling fluid precipitate easily and the discharge opeing treatability poor.
[embodiment 2]
It is 6022 specifications that surface treated aluminium alloy plate uses composition as A, as 6016 specifications of B, as three kind of 6000 line aluminium alloy plate of the commercially available product of 6111 specifications of C, by above-mentioned manufacture method, made the base material (with reference to table 2) that is of a size of 70mm width * 150mm length * 1mm thickness.
[table 2]
(notes) alloying constituent, A:6022 specification, B:6016 specification, C:6111 specification
When (notes) overlay film composition does not become 100% in record 4 elements total, contain the micro-impurities such as Si, Ca, Fe, Cu, Mn, Ti, Zn, Ni.
(notes) are for trying material NO.41: based on the cooling of water-cooled
(notes) supply formula material No44: examination material No.45 is cleaned, supplies in acid: the strong acid cleaning
(notes) are for trying material No.48: based on the cooling of aluminium dihydrogen phosphate aqueous solution
(notes) are for trying material No.49: the Zr system of containing halogen processes (environment and machine utilization are high)
Next, this base material heating is arrived 480～580 ℃ of temperature to entity, added do not heat and be the nitric acid of normal temperature and pH is adjusted to flooded cooling in 5～20 seconds in the zirconium nitrate aqueous solution that 2～4 concentration is 0.05～0.5g/L after, carry out washing and drying, thereby produce oxidation overlay film and the surface treated aluminium alloy plate of surface-treated have been carried out in the two sides.Two sides coating 0.1～2g/m to this surface treated aluminium alloy plate
2Commercially available automobile-use clean press oil (Dormant oils system, kinetic viscosity 1～7cSt), and having formed for examination material (No.31～49).
In the making for examination material (No.31～40), in above-mentioned scope to having carried out suitable adjustment the duration of contact of the concentration of the Heating temperature (entity arrival temperature) of substrate, the zirconium nitrate aqueous solution, the zirconium nitrate aqueous solution.For for examination material (No.41), do not implement the cooling (surface treatment) based on the zirconium nitrate aqueous solution, and cool off by water-cooled, do not carry out surface treatment of the present invention.
For for examination material No.42, use the zirconium nitrate aqueous solution of 590 ℃ of Heating temperatures, concentration 0.05g/L to process.
For for examination material No.43, use the zirconium nitrate aqueous solution of 500 ℃ of Heating temperatures, concentration 0.004g/L to process.
For for examination material (No.44,45), after heat treated, carry out acid cleaning, strong acid cleaning, do not carry out surface treatment of the present invention.
For for examination material No.46, use the zirconium nitrate aqueous solution of 500 ℃ of Heating temperatures, concentration 6g/L to process.
For for examination material No.47, use the zirconium nitrate aqueous solution of 590 ℃ of Heating temperatures, concentration 1g/L to process.
For supplying examination material (No.48), Heating temperature is 500 ℃, replaces the zirconium nitrate aqueous solution, and has used the aluminium dihydrogen phosphate aqueous solution of concentration 0.5g/L.
For supplying examination material No.49, the Zr that contains halogen that has carried out based on concentration 10g/L is the surface treatment of the aqueous solution.Need to prove, at this, consider the load of environment and equipment etc. is processed at normal temperatures, consider on the other hand reactive and set concentration higher.
For obtain as mentioned above for the examination material, by GD-OES (HORIBA JOBIN YVON society system, pattern JY-5000RF)) measured the content of the thickness of overlay film and Mg, Zr, halogen, P.Its result is as shown in table 2.Need to prove, when the total of the content of Mg, Zr, halogen, P does not become 100 atom %, contain O or Al, micro-impurity.
For examination material (No.31～40,41～47) based on surface-treated overlay film not halogen-containing, phosphorus.Supply the not halogen-containing based on the surface-treated overlay film of examination material (No.48), and the mean value of the phosphorus content that the depth direction of overlay film distributes is 10 atom %.And, supply the not phosphorous based on the surface-treated overlay film of examination material No.49, but contain the halogen of 1 atom %.
As shown in table 2, No.31～40 (embodiment) satisfy structure of the present invention, so degreasing, chemical convertibility and cohesiveness are good for the examination material.
On the other hand, for the examination material No.41～discontented foot of 49 (comparative examples) structure of the present invention, therefore become following result.
Supply examination material No.41 owing to do not carry out surface treatment, so degreasing, chemical convertibility and cohesiveness are bad.Surpass higher limit for trying the thickness of material No.42 owing to overlay film, so chemical convertibility is bad.For examination material No.43 based on the zirconium concentration of surface-treated overlay film outside scope of the present invention, so degreasing, chemical convertibility and cohesiveness are bad.For the thickness of the overlay film of examination material No.44 within the scope of the invention, but do not carry out surface treatment of the present invention, therefore can't measure zirconium concentration, and degreasing, chemical convertibility and cohesiveness are bad.
Although for trying material No.45 magnesium density less than lower value, and having carried out than the more powerful cleaning of state that can't measure zirconium concentration is that strong acid cleans, but because the thickness of oxidation overlay film is less than lower value, therefore degreasing, chemical convertibility and cohesiveness are good, but owing to carried out the strong acid cleaning, so productivity is poor.Therefore, based on uneconomical for the surface treated aluminium alloy plate of examination material No.45, and be not suitable for practicality.
Supply examination material No.46 because zirconium concentration surpasses the upper limit, so chemical convertibility is bad.Examination supplies material No.47 because magnesium density surpasses the upper limit, so degreasing, chemical convertibility and cohesiveness are bad.
For examination material No.48 since aluminium dihydrogen phosphate aqueous solution as cooling fluid, so degreasing and chemical convertibility are good, but cohesiveness is bad.And cooling fluid precipitates easily, and the discharge opeing treatability is poor.
Supply examination material No.49 owing to the surface treatment of having carried out based on the Zr system of containing halogen, so degreasing, chemical convertibility and cohesiveness are good, but environment and machine utilization raise.Therefore, based on uneconomical for the surface treated aluminium alloy plate of examination material No.49, and be not suitable for practicality.
More than, embodiment and embodiment are shown and understand in detail surface treated aluminium alloy plate of the present invention, but aim of the present invention is not defined as foregoing, and its interest field must make an explanation based on the record of the scope of patent application.Need to prove that content of the present invention can change change etc. based on above-mentioned record certainly.
Claims (4)
1. surface treated aluminium alloy plate, it possesses: the substrate that is made of aluminium alloy; Be formed on the lip-deep oxidation overlay film of this substrate; Be formed on the lip-deep surface treatment overlay film that contains zirconium of this oxidation overlay film, described surface treated aluminium alloy plate is characterised in that,
The thickness of described oxidation overlay film is 1～30nm,
The not halogen-containing and phosphorus of described surface treatment overlay film is counted 0.01～100mg/m to the adhesion amount of described oxidation overlay film with zirconium dioxide conversion amount
2
2. a surface treated aluminium alloy plate possesses aluminium alloy plate and the lip-deep overlay film that is formed on this aluminium alloy plate, it is characterized in that,
The thickness of described overlay film is 1～30nm, and magnesium density is 1～20 atom %, and zirconium concentration is 0.2～10 atom %, and halogen concentration and phosphorus concentration are respectively less than 0.1 atom %.
3. the manufacture method of a surface treated aluminium alloy plate is made surface treated aluminium alloy plate claimed in claim 1, it is characterized in that, comprising:
By rolling substrate manufacture operation of making described substrate;
With described base plate heating to 400～580 ℃ and form the heating process of described oxidation overlay film on the surface of described substrate;
The described substrate that is formed with described oxidation overlay film is cooled off, and forms the refrigerating work procedure of described surface treatment overlay film on the surface of described oxidation overlay film,
In described refrigerating work procedure, using not halogen-containing and phosphorus and concentration is that 0.005～5g/L, pH are that 1～5 the zirconium nitrate aqueous solution is as cooling fluid.
4. the manufacture method of surface treated aluminium alloy plate according to claim 3 is characterized in that,
Described substrate is made of thermal treatment type aluminium alloy, and described heating process is described substrate to be implemented the solution treatment operation of solution treatment, and described refrigerating work procedure is the quenching process of the described substrate that is formed with described oxidation overlay film being implemented quench treatment.
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| JP6143431B2 (en) * | 2012-09-20 | 2017-06-07 | 株式会社神戸製鋼所 | Aluminum alloy plate, joined body and automobile member using the same |
| JP6283240B2 (en) * | 2013-05-23 | 2018-02-21 | 株式会社神戸製鋼所 | Aluminum alloy plate, joined body and automotive member |
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| CN109536953B (en) * | 2018-12-29 | 2021-02-12 | 安徽鑫铂铝业股份有限公司 | High-strength large-scale vehicle aluminum profile |
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| C06 | Publication | ||
| PB01 | Publication | ||
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