CN101274494A - Aluminum alloy material having superior surface performance - Google Patents
Aluminum alloy material having superior surface performance Download PDFInfo
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- CN101274494A CN101274494A CNA2007100889716A CN200710088971A CN101274494A CN 101274494 A CN101274494 A CN 101274494A CN A2007100889716 A CNA2007100889716 A CN A2007100889716A CN 200710088971 A CN200710088971 A CN 200710088971A CN 101274494 A CN101274494 A CN 101274494A
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Abstract
The invention provides an aluminium alloy material having excellent surface stability to the aging change to surface characteristics and being applied to modules of automotive parts. The surface of the aluminium alloy material is provided with hydrated hydrophosphate such as monohydric phosphate, dihydric phosphate, etc., and the hydrated hydrophosphate can be aluminium monohydric phosphate and aluminium dihydrogen phosphate, etc. and has no adverse effect on formation, adhesion, chemical processing, coating, corrosion resistance of the aluminium alloy material so as to optimize the surface stability of the aging change to surface characteristics of the aluminium alloy material.
Description
Technical field
The present invention relates to a kind of automobile that is applicable to, particularly car panel, have an excellent aluminium alloy material that changes into surface stabilities such as the wet stability of water when handling, coating, adhesion durability, welding stability.In the present invention, so-called aluminium alloy material is meant the calendering plate made by various manufacture methods, calendering paper tinsel, extruding shape material, forges material, casting material etc.
Background technology
As everyone knows, in the past as the member and the parts of the conveyer of automobile, boats and ships, aircraft or vehicle etc., machinery, electric product, building, structures, optical device, equipment, general various aluminium alloy material (below be also referred to as aluminium or Al), the various characteristics of the corresponding every kind of alloy of these aluminium alloy materials.
In recent years, at the earth environment problem of initiations such as vehicle exhaust, the lightweight that automobile production producer is generally pursued by realizing car body reduces fuel consumption.Therefore, replace the original ferrous materials that uses, proportion is about 1/3 of iron, the producer that the aluminium alloy material with excellent energy absorption is used for car body increases day by day.
When aluminium alloy is used for car panel, the corrosion resistance after requiring it to have formability, weldability, cementability, chemical treatability, application, aesthetic property etc.The method of use aluminium alloy manufacturing car panel and the situation of existing employing steel plate are basic identical, are divided into 1) (size, the shape of drawing for stipulating that cut into regulation) is shaped; 2) engage (welding and/or bonding); 3) change into processing (carrying out surface adjustment → trbasic zinc phosphate processing such as degreasing → glue titanate processing with cleaning agent); 4) application (priming paint, finish paint, the lac varnish that are undertaken by the electrolytic deposition application).
On the other hand, automobile component is realized modularization just day by day, from aluminium alloy plate self be made into the back to enter till above-mentioned car panel and the car body manufacturing process during the tendency of prolongation is arranged before relatively.
The modularization of so-called automobile component is meant each parts that will directly be installed at auto producer on the car body, is installed in the method on the car body after parts company carries out partial assembled more in advance.Its main purpose is to simplify the operation of auto producer and enhances productivity.Also have the production process of shortening, reduce half-finished effect.Though increased the burden of parts companies, have the effect of the whole cost that reduces auto producer and parts company, the result helps to cut down the cost of automobile.
Up to now automobile is a direct method of supplying from the aluminum material factory to the auto producer with the main flow of the carrying approach of aluminium alloy plate, but along with modular progress is had to via parts factory, therefore, from aluminium alloy plate be made into the back to enter into till the above-mentioned operation during elongated than before.
Along with the variation of this situation, the aluminium alloy of use particularly its surface characteristic take place through the time change, problems such as formability, cementability, chemical treatability, coating appear influencing.Wherein know be follow through the time change, change into the degreasing variation when handling, cause changing into and handle epithelium and be difficult to adhere to, the result has influence on corrosion resistance.
Therefore, all tend to up to now improve (with reference to Patent Document 1-5) such as chemical treatabilities by the magnesium of removing aluminum alloy surface.But the magnesium of only removing aluminum alloy surface can not obtain with respect to surface characteristic through the time stability that changes.
In addition, particularly have the excellent hygroscopicity and the aluminium alloy plate of cementability after the degreasing, proposed the body of a motor car that the Mg amount and the OH amount of its surperficial epithelium are adjusted is used the scheme (with reference to Patent Document 6) of aluminium alloy plate in order to obtain.But, carrying out needing coating antirust oil that the surface is protected in the surface adjusts back 14 days, and can not realize obtaining for surface characteristic through the time stability that changes purpose.
Relative therewith, for obtain surface characteristic through the time aluminium alloy plate with low uncertainty, proposed a kind ofly to possess: the metallic aluminium matrix that contains the aluminium alloy plate of 2～10 weight %Mg; Phosphate coating with the aluminium that on this matrix, forms; And the body of a motor car of the pellumina that on phosphate coating, forms aluminium alloy plate (with reference to Patent Document 7).
Patent Document 1 spy opens flat 06-256980 communique (in full)
Patent Document 2 spies open flat 06-256881 communique (in full)
Patent Document 3 spies open flat 06-220564 communique (in full)
Patent Document 4 spies open flat 04-214835 communique (in full)
Patent Document 5 spies open flat 02-115358 communique (in full)
But, in the embodiment of Patent Document 7, be benchmark with the material of placing week age after the sample preparation, evaluation result is compared.As described later, the surface characteristic of described aluminium alloy through the time change, the week age left and right sides variable quantity maximum after sample preparation, variable quantity thereafter is less.The scheme of above-mentioned Patent Document 7 that hence one can see that can not obtain the stable aluminium alloy material of surface characteristic.
Particularly in the purposes of automobile etc., as with respect to surface characteristic through the time surface stability that changes, require aluminium alloy material to have to change into the wet stability of water, coating, adhesion durability, welding stability etc. when handling.More particularly be exactly to require to have to aluminium alloy material change into the wet stability of water when handling (stable change into processings), when aluminium alloy material is carried out application coatings such as the connecting airtight property of filming, with bonding agent to aluminium alloy material carry out when bonding adhesion durability (adhesion strength), by welding welding stability (bond strength) when aluminium alloy material engaged etc.
Summary of the invention
The present invention designs in order to solve these problems just, and its purpose is, provide a kind of for surface characteristic through the time change aluminium alloy material with excellent surface stability.
In order to reach this purpose, the main points with aluminium alloy material of excellent surface stability of the present invention are to have the hypophosphite monohydrate hydrogen salt on the surface of aluminium alloy material.
At this, hydrophosphate of the present invention is meant and comprises phosphoric acid hydrogen (HPO in salt
4, H
2PO
4) the general name of salt, representational have a dibasic alkaliine (HPO
4), dihydric phosphate (H
2PO
4) wait ackd salt.This hydrophosphate is preferably at least a slaine of selecting from Al, K, Ca, Mn, Li etc.In addition, this hydrophosphate is preferably dihydric phosphate.
Hypophosphite monohydrate hydrogen salt of the present invention is meant on the above-mentioned hydrophosphate and combines the crystallization water, has the OH base in the salt.
So hypophosphite monohydrate hydrogen salt of the present invention contains on phosphoric acid hydrogen this point and the hydration this point, tangible difference is arranged with phosphate in the described Patent Document 6 in salt.For example, compare with object lesson, the phosphate in the described Patent Document 6 is sodium phosphate, and hydrophosphate of the present invention is dibastic sodium phosphate or sodium dihydrogen phosphate, and the dibastic sodium phosphate among the present invention or sodium dihydrogen phosphate have also carried out hydration.
In addition, on the aluminium alloy material surface, be formed with the oxide scale film of aluminium inevitably, hypophosphite monohydrate hydrogen salt of the present invention, exist or be dispersed on this alumina epithelium and oxide scale film in.So so-called among the present invention have hypophosphite monohydrate hydrogen salt, specifically a surface state that comes to this of Zhiing on the aluminium alloy material surface.
In addition, when the hypophosphite monohydrate hydrogen salt attached to the aluminium alloy material surface on the time because the pre-treatments such as cleaning of following etching to carry out, there is no need to remove at all and be formed on lip-deep alumina epithelium of aluminium alloy material and magnesium.But, in the manufacturing process of described aluminium alloy material, for example, allow the hypophosphite monohydrate hydrogen salt attached on the aluminium alloy material surface certainly because other purpose of operation by pre-treatment, is removed after lip-deep alumina epithelium of aluminium alloy material and the magnesium.In this case, the oxide scale film of aluminium also is formed on the aluminium alloy material surface soon, thus hypophosphite monohydrate hydrogen salt of the present invention, exist or be dispersed on the oxide scale film of this aluminium and oxide scale film in.
In the present invention, as described in above-mentioned main points because on the aluminium alloy material surface, have hydrophosphate, thus can provide a kind of for surface characteristic through the time change aluminium alloy material with excellent surface stability.
Be known that the difference of hypophosphite monohydrate hydrogen salt self, used as medicament and additive in the past according to every kind of salt.But as the present invention, the hypophosphite monohydrate hydrogen salt make aluminium alloy material with respect to surface characteristic through the time change that to have excellent surface stability this point not open, why can make as the present invention aluminium alloy material for surface characteristic through the time change and to have excellent surface stability, present stage still indeterminate its principle.But, can infer the micro-content organism that exists in the environment, especially carboxylate etc. caused the aluminium alloy material surface characteristic through the time change.That is, the micro-content organism that exists in the environment, particularly carboxylate etc., gradually through the time be accumulated on aluminium alloy material (oxide scale film) the most surperficial, though only in micro-scope, this accumulation surpasses when a certain amount of, can infer that the surface characteristic of aluminium alloy material can significantly descend.
Relative therewith, if on the aluminium alloy material surface, have the hypophosphite monohydrate hydrogen salt, even carboxylate etc. through the time be accumulated on aluminium alloy material (oxide scale film) the most surperficial, this hypophosphite monohydrate hydrogen salt also can to should carboxylate through the time accumulate further " from bulk-growth " (self-propagation).Thus, hydrophosphate is broken through the accumulating layer of carboxylate, perhaps eliminates the accumulating layer of carboxylate, is present on aluminium alloy material (oxide scale film) the most surperficial, gets rid of the influence of carboxylate, keep for surface characteristic through the time surface stability that changes.
So, the above-mentioned effect of hypophosphite monohydrate hydrogen salt much less of the present invention, mechanism, and be present in the organic matter of the trace in the above-mentioned environment and aluminium alloy material surface characteristic through the time relation that changes, not known up to now.Yet, as described later, also have a part of data that can prove this hypothesis.
Phosphate in the described Patent Document 6 does not have this effect.Can infer that this is because the phosphate in the described Patent Document 6 does not comprise phosphoric acid hydrogen and do not carry out hydration, can not as hypophosphite monohydrate hydrogen salt of the present invention, carry out described " from bulk-growth ", thereby can not get rid of the influence of carboxylate.
In addition, according to the present invention, also can obtain desired effects even omit the removal operation of surperficial magnesium.Lip-deep Mg residual quantity, with the atomic ratio (Mg/Al) of the Al that measures by XPS (X linear light electronic spectroscopy) be also to have effect more than 0.1, to by all producing effect till the higher limit of the alloy material of common hot rolling, cold rolling acquisition (5000 be about 1.5,6000 be about 0.5).
Description of drawings
Fig. 1 represents that the example 2 of table 1 is at the infrared absorption spectroscopy of moist environment after indoor 2 weeks of placement.
Fig. 2 represents that the example 2 of table 1 is at the infrared absorption spectroscopy of the indoor placement of moist environment during the 1st week.
Fig. 3 represents the infrared absorption spectroscopy of example 2 after just having carried out the present invention's processing of table 1.
Fig. 4 represents that the comparative example 29 of table 2 is at the infrared absorption spectroscopy of moist environment after indoor 2 weeks of placement.
Fig. 5 represents that the comparative example 29 of table 2 is at the infrared absorption spectroscopy of the indoor placement of moist environment during the 1st week.
Fig. 6 represents that the comparative example 29 of table 2 is at the infrared absorption spectroscopy that just compares after example is handled.
Fig. 7 represents that the comparative example 31 of table 2 is at the infrared absorption spectroscopy of moist environment after indoor 2 weeks of placement.
Fig. 8 represents that the comparative example 31 of table 2 is at the infrared absorption spectroscopy of the indoor placement of moist environment during the 1st week.
Fig. 9 represents that the comparative example 31 of table 2 is at the infrared absorption spectroscopy that just compares after example is handled.
The specific embodiment
(hypophosphite monohydrate hydrogen salt)
The concrete kind of hypophosphite monohydrate hydrogen salt of the present invention is as described below.
(1) phosphoric acid hydrogen zinc:
Phosphoric acid one hydrogen zinc: ZnHPO
4Zinc dihydrogen phosphate: at Zn (H
2PO
4)
2In combine the crystallization water.
(2) phosphoric acid hydrogen aluminium:
Phosphoric acid one hydrogen aluminium: Al
2(HPO
4)
3Aluminium dihydrogen phosphate: at Al (H
2PO
4)
3In combine the crystallization water.
(3) potassium hydrogen phosphate:
Potassium phosphate,monobasic: K
2HPO
4Potassium dihydrogen phosphate: at KH
2PO
4In combine the crystallization water.
(4) calcium monohydrogen phosphate:
Calcium monohydrogenphosphate: CaHPO
4Calcium dihydrogen phosphate: at Ca (H
2PO
4)
2In combine the crystallization water.
(5) phosphoric acid hydrogen tin:
Phosphoric acid one hydrogen tin: SnHPO
4Biphosphate tin: at Sn (H
2PO
4)
2In combine the crystallization water.
(6) strontium monophosphate:
Phosphoric acid one hydrogen strontium: SrHPO
4Strontium biphosphate: at Sr (H
2PO
4)
2In combine the crystallization water.
(7) phosphoric acid hydrogen thallium:
Biphosphate thallium: at TlH
2PO
4In combine the crystallization water.
(8) phosphoric acid hydrogen thorium:
Phosphoric acid one hydrogen thorium: at Th (HPO
4)
2In combine the crystallization water.
(9) dibastic sodium phosphate:
Disodium-hydrogen: Na
2HPO
4Sodium dihydrogen phosphate: at NaH
2PO
4In combine the crystallization water.
(10) magnesium monohydrogen phosphate:
Phosphoric acid one hydrogen magnesium: MgHPO
4Magnesium dihydrogen phosphate: at Mg (H
2PO
4)
2In combine the crystallization water.
(11) manganese hydrogen phosphate:
Phosphoric acid one hydrogen manganese: MnHPO
4Phosphate dihydrogen manganese: at Mn (H
2PO
4)
2In combine the crystallization water.
(12) lithium hydrogen phosphate:
Phosphoric acid one hydrogen lithium: Li
2HPO
4Lithium dihydrogen phosphate: at LiH
2PO
4In combine the crystallization water.
Though by having the hypophosphite monohydrate hydrogen salt that exemplifies above on the surface that makes aluminium alloy material, can provide a kind of for surface characteristic through the time change aluminium alloy material with excellent surface stability, but consider the easily property obtained, the cost of hydrophosphate, the conditions such as stability of the aqueous solution, be preferably at least a slaine of from Al, K, Ca, Mn, Li, selecting (above-mentioned 2,3,4,11,12 compound).In these slaines, the hygroscopicity of dihydric phosphate is high especially, can further promote hydration.In addition, being preferably hydrophosphate is dihydric phosphate.The many more solubility for water of hydrogen contained in the hydrophosphate are big more, thereby make the possibility that is treated as under the higher concentration.
Also have, according to the hydrophosphate of selecting, the element (metal) that constitutes this salt might be the element of not sneaking into usually in its manufacturing process.Therefore, the risk of existence is that this element may change into described in the automobile making and handles and coating process, and operations such as perhaps bonding, welding produce bad or negative influence.So, be preferably and will do not cause the hydrophosphate of element bad or negative effect (metal) as the standard of selecting this manufacturing process.From this point, in the manufacturing process that uses aluminium,, be preferably and select phosphoric acid hydrogen aluminium for fear of above-mentioned risk.
(amount of hypophosphite monohydrate hydrogen salt)
Even on the surface of aluminium alloy material, there is the hypophosphite monohydrate hydrogen salt of denier, also can give play to for surface characteristic through the time change and keep the effect (the following surface stability effect that also only is called) of surface stability.So the concentration of the hypophosphite monohydrate hydrogen salt in the aqueous solution of processing aluminium alloy material also can be denier.
The lower limit amount of the lip-deep hypophosphite monohydrate hydrogen salt amount of aluminium alloy material is more than the 0.03at%, and the lower limit amount of the hydrophosphate concentration of the aqueous solution of processing (dipping) aluminium alloy material is more than the 0.001g/l.But the hypophosphite monohydrate hydrogen salt of trace decomposes in the aqueous solution easily, can cause the problem of aqueous solution deficient in stability in addition.In order to prevent the generation of this problem, really and play consistently the effect of hypophosphite monohydrate hydrogen salt, the lip-deep hypophosphite monohydrate hydrogen salt amount that is preferably aluminium alloy material is more than the 0.3at%, and the hydrophosphate concentration of handling the aqueous solution of (dipping) aluminium alloy material is more than the 0.01g/l.
In addition, the hypophosphite monohydrate hydrogen salt is saturated even the volume effect also can produce.In addition, its upper limit is by the meltage decision that is attached to the hydrophosphate in the lip-deep aqueous solution of aluminium alloy material.In this, the lip-deep hypophosphite monohydrate hydrogen salt amount of aluminium alloy material need not to surpass 20at%, and the hydrophosphate concentration of handling the aqueous solution of (dipping) aluminium alloy material need not to surpass 7g/l.
(the hypophosphite monohydrate hydrogen salt is at the lip-deep adherence method of aluminium alloy material)
These hypophosphite monohydrate hydrogen salts attached on the aluminium alloy material surface, can be passed through the manufacturing process at aluminium alloy material, and perhaps the aqueous solution that contains the hypophosphite monohydrate hydrogen salt beyond the manufacturing process is handled and is carried out.In the manufacturing process of aluminium alloy material, for example can be with the cooling water after the heat treatments such as solution processing and annealing, perhaps the rinse water in the matting is handled as the aqueous solution that contains (making its dissolving) these hypophosphite monohydrate hydrogen salts.
The temperature of the aqueous solution of hypophosphite monohydrate hydrogen salt can be a room temperature, also can heat etc.Processing time is not particularly limited, can be according to other treatment conditions such as the concentration of the aqueous solution and temperature, perhaps according to suitably selecting at the lip-deep expectation adhesion amount of aluminium alloy material.
In addition, when the hypophosphite monohydrate hydrogen salt attached to the aluminium alloy material surface on the time, need not pre-treatments such as cleaning by following etching to carry out at all, remove oxide scale film and the magnesium be formed on the lip-deep aluminium of aluminium alloy material.But, in the manufacturing process of described aluminium alloy material, because other purpose of operation allows to make on the surface of hypophosphite monohydrate hydrogen salt attached to aluminium alloy material after the oxide scale film and magnesium by the lip-deep aluminium of pre-treatment removal aluminium alloy material certainly.In this case, can on the aluminium alloy material surface, form at once the oxide scale film of aluminium, therefore, hypophosphite monohydrate hydrogen salt of the present invention exist or be dispersed on the oxide scale film of this aluminium and oxide scale film in.
(Al alloy)
The Al alloy that the present invention uses, according to the purposes of Al alloy material, can use comprise pure Al interior AA or JIS defined or with AA or the approximate various Al alloys of JIS.In addition, according to purposes, aluminium alloy material used in the present invention also can use by calendering plate, calendering paper tinsel extruding shape material, forge various manufacture methods aluminium alloys preparation, different shape such as material, casting material.
Just when being used for automobile making, being preferably and using yield point is 0.2%, the high-intensity aluminium alloy material that 170MPa is above.As the aluminium alloy material that satisfies this specific character, be common to the parts purposes of this structure usually, this aluminium alloy material be 5000 be, 6000 be, 7000 the higher general-purpose alloy of yield point such as be, preferably use as required by modified aluminium alloy.Less from the age-hardening energy and the alloying element amount of excellence, and have excellent materials recycling usability and formability, be preferably and use 6000 aluminium alloys that are.
Embodiment
Below embodiments of the invention are described.Two kinds of cold-rolled aluminum alloy sheets (thickness of slab 1mm) of 6022 specifications that to 5,000 5182 specifications and 6000 that are are apply various hydrophosphates and handle, and it is estimated at the ageing stability of moist environment after indoor two weeks of placement.
5182 aluminium alloy plates contain the Mg of 4.5 quality %, and 0.2% yield point is 150Mpa, and 6022 aluminium alloy plates contain the Mg of 0.55 quality % and the Si of 0.95 quality %, and 0.2% yield point is 230MPa.
As the pre-treatment of handling prior to hydrophosphate, dipping flooded for 10 seconds in 60 ℃ 15 quality % aqueous solution of nitric acid after 10 seconds in the sodium hydrate aqueous solution of 60 ℃ 5 quality %, and water cleans by force afterwards.In this test,, carry out above-mentioned pre-treatment by force for the surface condition that makes processed material (former material) is identical.
Under above-mentioned pre-treatment condition, the oxide scale film and the magnesium that have been formed on the lip-deep aluminium of aluminium alloy material are removed.But, owing to can be at once on aluminum alloy surface, form the oxide scale film of aluminium, handle being attached by hydrophosphate at the lip-deep hypophosphite monohydrate hydrogen salt of aluminium alloy material, exist or be dispersed on the oxide scale film of this aluminium and oxide scale film in.
Also have, it is contemplated that the residual quantity of magnesium on the surface of the aluminium alloy material that has applied this pre-treatment, with the atomic ratio (Mg/Al) of the Al that measures by XPS (X linear light electron spectrometer) all below 0.1.By the way, the result who in fact uses XPS (X linear light electron spectrometer) that the aluminium alloy material surface of comparative example 30 described later is measured shows that described atomic ratio is 0.09 (also have, the back is elaborated to XPS).
Carry out various hydrophosphate of the present invention under the conditions shown in Table 1 and handle,, enumerated and carried out non-processor (only being above-mentioned pre-treatment) and parkerized example under the conditions shown in Table 2 in order to compare.And, the aluminium alloy material after these are handled is placed on the ageing stability of indoor two weeks of 40 ℃, the moist environment of 90%RH during the back estimates.The ageing stability evaluation by the aluminium alloy material surface, place the hygroscopicity test after two weeks, and by infrared spectroscopic analysis to the surface composition between two resting periods in week through the time change the investigation of carrying out.In addition, also the stability of bonding durability and welding is investigated, thereby ageing stability is estimated by test.
(hygroscopicity)
Hygroscopicity is estimated the water wetted surface rate of sample.The numerical value of the good more water wetted surface rate of hygroscopicity is high more.Test method with above-mentioned processing after, the length of taking off from aluminium alloy material is that the sample of 70mm * width 150mm was immersed in 2% aqueous solution (60 ℃ of temperature) of the alkaline defatting agent Riddlin (manufacturing of ippon company) that sells in market after 30 seconds, to having carried out estimating (the good more numerical value of situation is high more) with respect to the water wetted surface rate (only measuring a side) of sample area with visual.The quantity (n) of sample in each example is made as 3, and the hygroscopicity area occupation ratio is got its mean value.Its result is shown in table 1, table 2.
(infrared spectroscopic analysis)
On the same analysis position, after with hydrophosphate or phosphate the oxide scale film on aluminium alloy material surface being handled, it is indoor to be placed on moist environment immediately, state separately during to first week, after second week, the FTIR (Fourier transformation infrared spectrometer) that the parallel polarisation of spending by incidence angle 75 uses analyzes.And, in the hydrophosphate of example is handled, 1150cm
-1Wave number part on whether produce the infrared absorption spectroscopy (absorption peak) of phosphoric acid hydride and in the phosphate treated of comparative example, 1150cm
-1Wave number part on whether produce the infrared absorption spectroscopy (absorption peak) of phosphoric acid, and each time dependent of each absorption spectrum (absorption peak) changes and investigates.Its result is shown in table 1, table 2.
In addition, Fig. 1～Fig. 3 represents that respectively example 2 handling back (Fig. 3), is placed on back each infrared absorption spectroscopies of (Fig. 1) of indoor first when week (Fig. 2) of moist environment and two weeks immediately.Moreover Fig. 4～Fig. 6 represents the example do not handled respectively, i.e. comparative example 29 after having carried out above-mentioned pre-treatment (Fig. 6), when being placed on indoor first week of moist environment immediately (Fig. 5) and two weeks back each infrared absorption spectroscopies of (Fig. 4).In addition, Fig. 7～Fig. 9 represents to have carried out parkerized example respectively, and promptly comparative example 31 is handled back (Fig. 9), is placed on back each infrared absorption spectroscopies of (Fig. 7) of indoor first when week (Fig. 8) of moist environment and two weeks immediately.
(adhesion durability)
Take off the sample of long 100mm * wide 25mm * thick 1mm from aluminium alloy material, make its sclerosis after using the structural bonding agent of 1 liquid type epoxies to paste sample.Sample after pasting was immersed in 50 ℃ of warm water after two weeks, obtains its adhesive strength by tension test.Obtain before pasting the ratio that sample remained on the situation in the moist environment and do not remain on the adhesive strength under the situation in the moist environment (keeping the intensity ÷ in two weeks not have the intensity of maintenance), the strength maintenance rate is measured.Its result is shown in table 1, table 2.
(welding stability)
Take off the sample of long 150mm * wide 30mm * thick 1mm from aluminium alloy material, in moist environment, kept for two weeks after, carry out AC spot-welding.Electrode with one group is got ready continuously, to measuring electrode life.Between electrode, insert heat sensitive paper when whenever getting 50 times continuously ready and weld, the faulted condition of electrode is observed, with confirm to occur damage to get number continuously ready be electrode life.Its result is shown in table 1, table 2.
Carry out various parkerized examples 1～28 as can be known from table 1 is clear, had the absorption peak of the phosphoric acid hydroxide of the existence of representing the hypophosphite monohydrate hydrogen salt, on the aluminium alloy material surface, had the hypophosphite monohydrate hydrogen salt.The result shows with the kind of each hydrophosphate irrelevant, and water wetted surface rate is the value up to 95%～100%, has good hygroscopicity.In addition, strength retention has good adhesion durability also up to 91%-96%.Moreover, get ready the number also up to 900 times～1300 times, have good welding stability.
The result shows, even, perhaps place for a long time because the modularization of described automobile component etc. are placed on the aluminium alloy material that uses in the moist environment, its surface characteristic kept and can not take place through the time change.
In contrast, the carrying out in the table 2 various parkerized comparative examples 29～34, have the absorption peak that expression phosphoric acid exists.In addition, the absorption peak of not representing the phosphoric acid hydroxide that the hypophosphite monohydrate hydrogen salt exists certainly.The result compares with example, occurs water wetted surface rate unlimitedly below 85%, the situation of hygroscopicity difference.In addition, also all below 90%, adhesion durability is inferior to example to strength retention.Moreover, get number ready also all below 750 times, its welding stability also is inferior to example.
This result shows when the aluminium alloy material that uses is placed on to obtain for a long time in the moist environment and places, its surface characteristic can take place big through the time change.
And these are true by in the hydrophosphate of example is handled, 1150cm
-1The phosphoric acid hydride that partly produces of wave number infrared absorption spectroscopy and in the phosphate treated of comparative example, at 1150cm
-1The time dependent separately of infrared absorption spectroscopy of the phosphoric acid that partly go up to produce of wave number change prove.
That is, as shown in table 1, the height of the INFRARED ABSORPTION peak value of the phosphoric acid hydroxide of the existence of the hypophosphite monohydrate hydrogen salt of expression example is time dependent to be increased.These are true by Fig. 1～3 confirmation of representative (illustrative) example 2.As can be known along with the passage of time of Fig. 3 to Fig. 1,1150cm
-1The height of INFRARED ABSORPTION peak value of the phosphoric acid hydride that partly produces of wave number increase.
That is, can confirm that " from bulk-growth " (self-propagation) has taken place this hypophosphite monohydrate hydrogen salt if having the hypophosphite monohydrate hydrogen salt on the surface of aluminium alloy material.In addition, can confirm that thus the hypophosphite monohydrate hydrogen salt often is present on aluminium alloy material (oxide scale film) the most surperficial, keep with respect to surface characteristic through the time surface stability that changes.
By the way, in Fig. 1～Fig. 3,2930cm
-1INFRARED ABSORPTION peak value and the 1640cm of the CH that partly produces of wave number
-1The COO that partly produces of wave number
-Infrared absorption peak value representation hydroxy acid.And, along with the temporal passing of Fig. 3 to Fig. 1, INFRARED ABSORPTION peak value height and the COO of CH
-INFRARED ABSORPTION peak value height increase, be accumulated on aluminium alloy material the most surperficial time dependents such as the alleged occurrence micro-content organism in environment, especially carboxylate.Same situation appears in the comparative example of Fig. 4～Fig. 6.
Therefore, described as can be known from these results hypothesis is set up, and, is present in the micro-content organism in the environment that is, is accumulated on aluminium alloy material (oxide scale film) the most surperficial especially time dependent such as carboxylate, causes surface characteristic significantly to descend.In addition, in contrast, if on the surface of aluminium alloy material, have the hypophosphite monohydrate hydrogen salt, even be accumulated on aluminium alloy material (oxide scale film) the most surperficial time dependents such as carboxylate, this hypophosphite monohydrate hydrogen salt also can be accumulated time dependent that should carboxylate, further " from bulk-growth " (self-propagation).Thus, this hypophosphite monohydrate hydrogen salt is broken through the accumulating layer of carboxylate, perhaps the accumulating layer of carboxylate is got rid of, thereby is present on aluminium alloy material (oxide scale film) the most surperficial, get rid of the influence of carboxylate, keep for surface characteristic through the time surface stability that changes.
Relative therewith, as shown in table 1, the INFRARED ABSORPTION peak value that the phosphoric acid of expression comparative example exists do not take place through the time change, do not increase yet.This true Fig. 7～Fig. 9 by the comparative example 31 of representative (illustration) comparative example confirms.That is, along with the passage of time from Fig. 9 to Fig. 7,1150cm
-1The height of INFRARED ABSORPTION peak value of the phosphoric acid that partly go up to produce of wave number do not change.Therefore the carboxylate in the comparative example does not as can be known have the function of as hypophosphite monohydrate hydrogen salt of the present invention time dependent ground " from bulk-growth ".The situation of the aluminium hydroxide among Fig. 4～Fig. 6 of the comparative example of certainly, not handling 29 is identical therewith.
Above result proves, hypophosphite monohydrate hydrogen salt of the present invention, have raising for the aluminium alloy material surface through the time surface stability that changes effect.
[table 1]
[table 2]
Secondly, describe carrying out the embodiment that hydrophosphate do not carry out pre-treatment before handling.In this embodiment, identical with described embodiment, two kinds of cold-rolled aluminum alloy sheets (thickness of slab 1mm) of 6022 specifications that to 5,000 5182 specifications and 6000 that are are apply various hydrophosphates and handle, and the ageing stability of placing in moist environment after two weeks is estimated.
Hydrophosphate of the present invention is handled and is carried out under the conditions shown in Table 3, and in order to compare, the example that does not carry out the hydrophosphate processing carries out under the conditions shown in Table 4.And the aluminium alloy material after will handling is placed in 40 ℃, the moist environment of 90%RH after two weeks, and its ageing stability is estimated.By the hygroscopicity test and the bonding endurancing on the aluminium alloy material surface after enforcement two weeks of placement, and the stability test of welding is estimated ageing stability.In addition, the implementation condition of each test is all identical with described embodiment.
Known to table 3, even handle the example 35～62 do not carry out pre-treatment prior to hydrophosphate, water wetted surface rate also up to 90%～100% numerical value, has good hygroscopicity.In addition, strength retention also up to 91%～96% numerical value, has good adhesion durability.Moreover, get ready the number also up to 900 times～1300 times, have good welding stability.
With the result of the test shown in the table 3 with only carried out pre-treatment, and the embodiment 30 (atomic ratio of Mg/Al is 0.09) of table 2 that the lip-deep Mg amount that remains in aluminium alloy material has been carried out actual measurement is when comparing, and the former has significantly with respect to the latter's water wetted surface rate, strength retention, adhesion durability and improves.Even this comparative result shows the atomic ratio that carries out not reducing in advance after the pre-treatment Mg/Al,, also can obtain excellent ageing stability if apply hydrophosphate.
In addition, though with the result of the test shown in the table 3 with before hydrophosphate is handled, carry out pre-treatment, will remaining in the lip-deep Mg amount of aluminium alloy material, to be made as atomic ratio (Mg/Al) be that the result of the test shown in the table 1 below 0.1 compares also not a halfpenny the worse.This comparative result shows, even remain under the many situations of the lip-deep Mg amount of aluminium alloy material, that is, atomic ratio (Mg/Al) is under 0.37 and 1.26 the state, to handle if apply hydrophosphate, also can obtain excellent ageing stability.
In contrast, under the situation of not carrying out the comparative example 63～65 that hydrophosphate handles of table 4, water wetted surface rate is below 33%, and its hygroscopicity is inferior to example.In addition, strength retention is all below 53%, and adhesion durability also is inferior to example.Moreover, get number ready also below 450 times, welding stability also is inferior to example.
In addition, by XPS (X linear light electronic spectroscopy) atomic ratio of described Mg and Al is measured.XPS has used Perkin-Elmer PHI 5400system in measuring.X-ray source is the MgK alpha ray, 10
-9Vacuum condition under measure.The ratio of Mg/Al is by the Al (2p) of observation and the strength ratio of Mg (2p) are converted to concentration of element than obtaining.
Table 3
[table 4]
Claims (4)
1. an aluminium alloy material that has superior surface performance is characterized in that, has the hypophosphite monohydrate hydrogen salt on the surface of aluminium alloy material.
2. the aluminium alloy material that has superior surface performance according to claim 1 is characterized in that, described hydrophosphate is the salt of at least a metal selected from Al, K, Ca, Mn, Li.
3. the aluminium alloy material that has superior surface performance according to claim 1 is characterized in that described hydrophosphate is a dihydric phosphate.
4. the aluminium alloy material that has superior surface performance according to claim 2 is characterized in that described hydrophosphate is a dihydric phosphate.
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| US11725287B2 (en) | 2015-12-25 | 2023-08-15 | Nihon Parkerizing Co., Ltd. | Method for manufacturing a magnesium material or magnesium alloy material with a coating |
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