CN101575703A - Surface treatment aluminum product, method for manufacturing the surface treatment aluminum product and aluminum product surface treating method - Google Patents
Surface treatment aluminum product, method for manufacturing the surface treatment aluminum product and aluminum product surface treating method Download PDFInfo
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- CN101575703A CN101575703A CNA2008101255962A CN200810125596A CN101575703A CN 101575703 A CN101575703 A CN 101575703A CN A2008101255962 A CNA2008101255962 A CN A2008101255962A CN 200810125596 A CN200810125596 A CN 200810125596A CN 101575703 A CN101575703 A CN 101575703A
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Abstract
The present invention provides a surface treatment aluminum product with low dusty effect, as well as a method for manufacturing the surface treatment aluminum product with low dusty effect and the aluminum product surface treating method. The solution of the invention adopts a method for manufacturing surface treatment aluminum product, as well as aluminum product surface treating method and surface treatment aluminum product, which is characterized in that the aluminum product surface is processed by phosphoric acid with the weight percent of more than 50% and less than 100% and dissolved aluminium with the weight percent from 0 .001 % to 5 %, and then ultrasonic cleaning is performed on.
Description
Technical field
[0001] the present invention relates to the manufacture method of surface treated aluminum material and the surface treatment method of aluminium, relate in particular to the manufacture method of the surface treated aluminum material that can obtain having hanged down the dirt surface treated aluminum material, also relate to the surface treatment method that the second phase compound that can suppress aluminium material surface breaks away from the aluminium that plays dirt that is caused in addition.
Background technology
[0002] in recent years, be will equip hard disk drive on the various portable units of representative with the computer, more and more need to improve the performance of hard disk drive.Usually, for hard disk drive, in order to make dish (disk) not influenced by koniology, to coat with shell, but for this shell, for the needs of hard disk drive miniaturization and lighting, mainly use lightweight and physical strength excellence, and excellent aluminium such as processibility and cost-effectivenes.In addition, as the magnetic head that is used for reproducing at the enterprising line item of disk, from disk, usually carry out position control by driving stem (actuator arm) (rocking arm), but driving stem itself is high speed and need carries out the high precision driving, therefore same lightweight and the high aluminium of physical strength of using.
[0003] on the other hand, along with the raising that the hard disk drive high performance requires, people study the influence of particulates such as dust.Especially, if these puberty of employed aluminium such as shell or driving stem play dirt, then hard disk drive and other precision apparatus on every side may produce mishandle.Therefore, having proposed driving stem surface after forming process does not have electrolysis NiP plating and handles and form the hard disk drive cartridge that is provided with resin molding on the method (being the example of the driving stem that formed by magnesium class alloy, for example referring to patent documentation 1) of overlay film and the aluminium material surface outside the shell with schemes such as resin-coated aluminium (for example referring to patent documentation 2 and 3).
[0004] still, do not play dirt effect excellence though there is the inhibition of electrolysis NiP plating processing, but the cost of employed no electrolysis NiP plating solution has accounted for the only about half of of hard disk shell manufacturing cost, the zincate that aluminium material surface is replaced with zinc as pre-treatment is handled and need be carried out repeatedly pickling usually in addition, exists therefore that treatment process is various, the big problem of cost cost.And, apply no electrolysis Ni P plating after, in order to make the plated film stabilization, also attempted carrying out the method for chromate treating, but this processing may influence environment.On the other hand, for above-mentioned resin-coated aluminium, owing on the aluminium material surface of disk one side, resin molding is not set when storing disk, therefore for example may cause the aluminium material surface of disk one side to play dirt from the impact of outside.If form resin molding on the aluminium material surface of disk one side, then the temperature rising that this moment, the disk rotation caused can cause producing gas from resin molding, might cause the mishandle and the fault of hard disk drive.In addition, except there was the deterioration with age problem in resin molding, if form resin molding on the aluminium material surface, then press process etc. may cause peeling off of resin molding, therefore also existed the shape of shell and the problem that processing is restricted.
[0005] for this situation, the inventor has proposed to be suitable for the novel dirt surface treated aluminum material scheme (referring to patent documentation 4) of having hanged down as precision equipment component materials such as the shell of this precision equipments such as hard disk drive and driving stems.The inventor at first observes the condition of surface of aluminium, finds out that the second phase compound that aluminium material surface exists has been the dirt source.The second phase compound that exists in the aluminium is the material that is formed phase by substrate metal aluminium (Al) material (other impurity such as Fe, Si, Cu, Mg, Zn) in addition, for example is Al
3Fe, α AlFeSi, Al
3Mg
2, Mg
2Compounds such as Si and Al-Mg-Zn compound.These second phase compounds for aluminium material surface exists can utilize the reflected electron image of scanning electron microscope (SEM) to check its size and distribution, in addition, also can identify this material by X-ray diffraction.The inventor uses the oxygen acid treatment solution that is made of the oxygen acid that contains element-specific that aluminium is handled, and prevents that the second phase compound from from the film that aluminium material surface breaks away from, successfully having obtained having hanged down the dirt surface treated aluminum material thereby formed.But when the shape of hard disk shell and driving stem etc. was more complicated, the effect that has suppressed dirt was still waiting further improvement.
[0006] still, the burr that the bight that the driving stem forming process is caused generates, can peel off as small tinsel after in being assembled into disk, cause read failure, in order to address this problem, proposed driving stem to be carried out the surface-treated method (referring to patent documentation 5 and 6) of chemical grinding with the mixed aqueous solution of phosphoric acid and nitric acid.But, this surface treatment method is to utilize the mixed aqueous solution that has added nitric acid in the phosphoric acid of low concentration to form chemical grinding liquid, remove cutting from the bight thus and suppress burr about tens of μ m that the forming process of a class causes, this is to suppress the sort of aluminium that the second phase compound causes with purpose, and to play the technology of dirt different.In addition, also proposed to remove deburring from driving stem equally, then by in containing the acidic aqueous solution of fluoride ion, flooding, the method (referring to patent documentation 7) that Si oxide contained in the aluminium of driving stem etc. is removed will be formed, though the chemical grinding of the mixed aqueous solution that this method can not be by adopting phosphoric acid and nitric acid is handled, but remove Si oxide etc. by other acidic aqueous solution, handle but aluminium will be immersed in the acidic aqueous solution that contains fluoride ion, therefore may dissolve base material aluminium simultaneously, the second new phase compound may expose from the teeth outwards.
[patent documentation 1] TOHKEMY 2004-27304 communique
[patent documentation 2] Japanese kokai publication hei 10-249994 communique
[patent documentation 3] Japanese kokai publication hei 11-25653 communique
[patent documentation 4] TOHKEMY 2005-336605 communique
[patent documentation 5] TOHKEMY 2004-131757 communique
[patent documentation 6] TOHKEMY 2004-216480 communique
[patent documentation 7] TOHKEMY 2006-342413 communique
Summary of the invention
[0007] inventor has carried out more detailed research to the relation that plays dust quantity that obtains having hanged down the aluminium that the shape of the surface treatment method of aluminium of surface treated aluminum material of dirt and hard disk shell or driving stem etc. causes of previous report, the result has obtained new discovery, promptly, applying cut-out, cutting, compacting, perforate, the place of incision of the aluminium of forming process such as perforation, formed and had the surface of fracture that to observe the fine concave-convex surface of confirming as shown in Figure 1 by SEM, compare with other position that does not have surface of fracture, the surface of fracture with this concave-convex surface is easy to generate the disengaging of the second phase compound.That is, the increasing of the surface of fracture that causes along with forming process, the dirt that rises that the second phase compound that exists on the surface of fracture of aluminium causes increases.In addition, on the SEM photo of Fig. 1 (a), the zone in left side (I) is surface of fracture, and the zone on right side (II) is shear surface.In addition, Fig. 1 (b) is the situation after surface of fracture amplifies.
[0008] therefore, the inventor is for need obtaining some forming process, and need to have hanged down dirt, the method of surface treated aluminum material that is suitable as the material of the shell of precision equipment or precision equipment parts is furtherd investigate, found that the surface smoothing treatment solution that contains the phosphoric acid of normality by use, eliminate the small concave-convex surface that surface of fracture occurs equably, handle the face of surface of fracture is coarse, use ultrasonic cleaning again, can prevent that the second phase compound breaks away from from surface of fracture, further improve and suppressed the effect of dirt, thereby finished the present invention.
[0009] therefore, the object of the present invention is to provide and for example possess identical with the aluminium of handling through no electrolysis NiP plating or better manufacture method of having hanged down the surface treated aluminum material of dirt.
[0010] another object of the present invention is to provide the surface treatment method of aluminium, can obtain to suppress that the disengaging of the second phase compound causes plays dirt, possess for example identical with the aluminium of handling through no electrolysis NiP plating or the better surface treated aluminum material that has hanged down dirt.
Promptly, content of the present invention is the manufacture method of surface treated aluminum material, it is characterized in that surface for aluminium, with contain more than the 50 weight % and the phosphoric acid of less than 100 weight % and more than the 0.001 weight % and the surface smoothing treatment solution of the dissolved aluminum below the 5 weight % handle, and carry out ultrasonic washing.
In addition, content of the present invention is the surface treatment method of aluminium, it is characterized in that surface for aluminium, with contain more than the 50 weight % and the phosphoric acid of less than 100 weight % and more than the 0.001 weight % and the surface smoothing treatment solution of the dissolved aluminum below the 5 weight % handle, and carry out ultrasonic washing.
Another content of the present invention is a surface treated aluminum material, it is characterized in that is with the phosphoric acid that contains the above and less than 100 weight % of 50 weight % and 0.001 weight % is above and the surface smoothing treatment solution of the dissolved aluminum that 5 weight % are following is handled the surface of aluminium, and carries out ultrasonic washing and obtain.
[0014] in the present invention, at first as the surface smoothing treatment solution of principal constituent chemical smoothing is carried out on the surface of aluminium, thereby coarse (the fine concave-convex surface) of the surface of fracture of the aluminium that generates because of forming process such as cut-out, cutting, compacting, perforate, perforation handled with containing phosphoric acid.Promptly, as shown in Figure 1, produced on the surface of fracture and can observe the fine concave-convex surface of confirming by SEM, the second phase compound produces from this concave-convex surface easily and breaks away from, therefore by handling as the surface smoothing treatment solution of principal constituent with containing phosphoric acid, just make this fine concave-convex surface smoothing, removed the dirt source of rising of aluminium.Utilize the smooth surface of using this smooth surface treatment solution to handle, can prevent effectively that the second phase compound breaks away from from the fine concave-convex surface of surface of fracture, and can prevent that also fine concave-convex surface (surface of fracture) from itself having become the dirt source.
[0015] phosphoric acid concentration of surface smoothing treatment solution is the above and less than 100 weight % of 50 weight %, is preferably 70～90 weight %.If the content of phosphoric acid is less than 50 weight %, then as following formula (1) showed, the phosphoric acid that helps to implement smoothing tailed off, and therefore may make the micro concavo-convex of surface of fracture can not obtain enough smoothings.And, the viscosity step-down of surface smoothing treatment solution, therefore the surface smoothing treatment solution forms on the fine concave-convex surface of surface of fracture equably and spreads, so the concave-convex surface of surface of fracture dissolves equably by the concavo-convex former state that it has, and surface of fracture may not smoothing.If be more than the 50 weight %, the phosphoric acid amount that then helps to carry out smoothing is enough, and the viscosity brought of phosphoric acid causes the surface smoothing treatment solution slack-off in the recess diffusion of surface of fracture, and the dissolving of protuberance is preferentially carried out, so the micro concavo-convex of surface of fracture is able to smoothing.Also have, the upper limit about phosphoric acid concentration, concentrate if make the moisture evaporation in the commercially available phosphoric acid solution (85 weight %), phosphatase 11 00 weight % is possible in theory, but the upper limit less than 100 weight % of phosphoric acid from the following aspect: cause from the concave-convex surface dissolving of the surface of fracture of aluminium that the aluminium component amount increases the treatment solution, therefore phosphatase 11 00 weight % can not realize outside when system liquid, in addition system during liquid shown in following formula (2) the interior dehydration reaction of phosphoric acid molecules cause generating water, thereby phosphatase 11 00 weight % can not realize.But therefore the concentrated spended time of wanting of the phosphoric acid of above record is being preferably in the practicality below the 90 weight %.
2Al+6H
3PO
4→2Al(H
2PO
4)
3+3H
2 ......(1)
2H
3PO
4→H
4P
2O
7+H
2O ......(2)
[0016] in addition, in the present invention, must under containing the state of dissolved aluminum, the surface smoothing treatment solution carry out the surface smoothing processing to aluminium.It is the reasons are as follows.If aluminium is handled with the surface smoothing treatment solution, then shown in above-mentioned formula (1), the solubilizing reaction of aluminium begins immediately, and the smoothing of the micro concavo-convex of surface of fracture begins to carry out, but the aluminium beyond the surface of fracture also dissolves simultaneously, therefore is difficult to guarantee the dimensional precision of aluminium.Particularly need under the situation of micron order or submicron order dimensional precision, can produce big problem at hard disk parts such as driving stem or precision equipment parts and so on.Therefore, the surface smoothing treatment solution that contains dissolved aluminum by use is handled aluminium, has just suppressed the excessive dissolution reaction of aluminium, reaction is controlled at the micro concavo-convex that optionally makes surface of fracture carries out smoothing.In addition, because the existence of dissolved aluminum, the viscosity of surface smoothing treatment solution increases, so the protuberance optimum solvation that is produced on the surface of fracture, can expect that the level and smooth reaction of surface of fracture is carried out effectively.
[0017] herein, the concentration that make the dissolved aluminum of the surface smoothing treatment solution of handling aluminium be 0.001 weight % above, below the 5 weight %, be preferably 0.01 weight % above, below the 3 weight %, more preferably 0.1 weight % above, below the 3 weight %.If the concentration of contained dissolved aluminum is less than 0.001 weight % in the surface smoothing treatment solution, then can not expect to control fully effectively al dissolution reaction as described above, for handled aluminium, be difficult for guaranteeing dimensional precision.Otherwise if contain dissolved aluminum with the amount that surpasses 5 weight %, the reaction that then is used to make the micro concavo-convex of the surface of fracture of aluminium to carry out smoothing may be carried out insufficient.Consider that from the treatment solution control aspect of surface smoothing treatment solution the lower value of above-mentioned dissolved aluminum concentration is preferably 0.01 weight %, if consider cost-effectivenes etc., then more preferably lower value is 0.1 weight %.In addition, consider that from the aspect that the smoothing reaction of the micro concavo-convex of surface of fracture can effectively be carried out the upper limit of concentration of above-mentioned dissolved aluminum is preferably below the 3 weight %.About making in the surface smoothing treatment solution means of dissolved aluminum in advance, have no particular limits, for example can illustration prepare aluminium sheet in addition and impregnated in the surface smoothing treatment solution, make it to dissolve and reach the method etc. of the dissolved aluminum concentration of regulation.In this case, preferably prepare and the identical aluminium sheet of enforcement surface-treated target aluminium material of the present invention, dissolve.
[0018] wants to add man-hour to having the such glossy aluminium of minute surface, can make in the surface smoothing treatment solution among the present invention and contain other acid such as nitric acid, sulfuric acid, hydrochloric acid, acetic acid, oxalic acid, boric acid, hydrofluoric acid, can make 1～30 weight % that adds up to of these acid this moment.Wherein, if contain nitric acid, then may produce nitric acid gas (NO
X), when therefore in the surface smoothing treatment solution, adding nitric acid, and then can make the urea that wherein contains 0.2～10 weight %.That is,, then shown in following formula (3), produce NO like that if handle aluminium with the surface smoothing treatment solution that contains phosphoric acid and nitric acid
X, but because the existence of urea can suppress NO as following formula (4)
XGeneration.Therefore, concentration of nitric acid is 1 weight % when above, can on purpose make it to contain urea.
7Al+7H
3PO
4+5HNO
3→7AlPO
4+2N
2+NO
2+13H
2O ......(3)
10Al+10H
3PO
4+6HNO
3→10AlPO
4+3N
2+18H
2O ......(4)
[0019] about using the surface smoothing treatment solution to handle the concrete means of aluminium, have no particular limits, can illustration make aluminium be immersed in the treatment solution dip treating or with the means such as spraying processing of treatment solution spraying, but under the situation of dip treating, can be 60～110 ℃ of temperature, in preferred 65～105 ℃ surface smoothing treatment solution, aluminium was flooded 10 seconds～20 minutes preferred 30 seconds～5 minutes treatment time.If the temperature of surface smoothing treatment solution is lower than 60 ℃, then speed of response is slack-off, treatment time is elongated, efficient is low, if instead above 110 ℃, then the moisture evaporation quantitative change in the surface smoothing treatment solution is big, and their steam output also becomes greatly when particularly containing nitric acid or sulfuric acid etc., therefore is difficult to control the composition of treatment solution.Also have, for the fine concave-convex surface that makes surface of fracture reaches smoothly, speed of response is constant preferably, and the treatment solution temperature is constant preferably also.On the other hand, if the treatment time is less than 10 seconds, then aluminium material surface almost can not reach smoothing, so removing of the fine concave-convex surface of surface of fracture becomes difficult.Otherwise if surpass 20 minutes, then meltage is too much, and the dimensional precision of aluminium is difficult to guarantee.
[0020] for the aluminium that uses after the surface smoothing treatment solution carries out the surface smoothing processing, carry out ultrasonic washing.With possibility is residual on the aluminium material surface after the processing of surface smoothing treatment solution the fine concave-convex surface of a clean part that do not eliminate be arranged, and the second phase compound, therefore by ultrasonic washing, just physically removed these parts.In addition, if aluminium material surface residual the surface smoothing treatment solution, may corrode aluminium after then, therefore thisly remove the surface smoothing treatment solution with ultrasonic washing and made contribution by improving solidity to corrosion, this effect also doubles.
[0021] about this ultrasonic washing, consider from above-mentioned purpose, aluminium material surface is carried out more even washing, the frequency of ultrasonic of using can suitably be selected from the high frequency of 100kHz～1MHz usually, if but the vibration as the washing object aluminium and shine ultrasonic wave equably, even then for example the low frequency about 40kHz also can.In addition, general method as ultrasonic washing, when aluminium is immersed in that the irradiation ultrasonic wave is carried out the ultrasonic wave washing in the pure water etc., if use the high frequency of 100kHz～1MHz, then can on purpose carry out about 3～5 minutes, if 40kHz, power 100W then can on purpose carry out 1～3 minute.And, also can utilize identical or different frequency to repeat carrying out washing treatment more than 2 times.Also have, the aluminium after preferably surperficial smoothing being handled carries out ultrasonic washing rapidly.Because the period before ultrasonic washing is if the difficulty that becomes is then removed in the residue that adheres on the aluminium material surface (smut) oxidation.At this moment, before ultrasonic washing,, can go residue treatment by handling with acidic aqueous solutions such as nitric acid, sulfuric acid, hydrochloric acid because of removing the purpose of residue.In addition, the aluminium after can handling surperficial smoothing is washed, and after remaining surface smoothing treatment solution is removed, washs with ultrasonic wave.
[0022] in the present invention,, also can handle, carry out heat treated again, on aluminium material surface, to form film with the oxygen acid treatment solution that contains oxygen acid for the aluminium behind the ultrasonic washing.Described oxygen acid contains more than one oxygen acid that are selected from phosphorus, silicon and the chromium and constitutes element.By chemical treatment that utilizes the surface smoothing treatment solution and the physical treatment that utilizes ultrasonic washing, removed the second phase compound on the aluminium material surface as much as possible, otherwise, even the inexpungible second phase compound exists, the processing and the heat treated of oxygen acid treatment solution by regulation, formed firm film (oxygen acid aluminium film) on the aluminium material surface, can prevent that the second phase compound breaks away from.In addition, by forming this film, can also give aluminium simultaneously with erosion resistance.
[0023] about the oxygen acid treatment solution, get final product so long as contain by being selected from the aqueous solution that more than one oxygen acid in phosphorus, silicon and the chromium constitute the oxygen acid that element constitutes, specifically can illustration phospho acid (HPH
2O
2), phosphorous acid (H
3PO
3), phosphonic acids (H
2PHO
3), phosphoric acid (H
3PO
4), tetra-sodium (H
4P
2O
7), metaphosphoric acid ((HPO
3)
n), Hypophosporous Acid, 50 ((HO)
2OP-PO (OH)
2), orthosilicic acid (H
4SiO
4), positive silicic acid ((H
2SiO
3)
n), inclined to one side two silicic acid (H
2Si
2O
5), chromic acid (H
2CrO
4), dichromic acid (H
2Cr
2O
7) aqueous solution that waits, be preferably the aqueous solution of phospho acid, phosphorous acid, phosphonic acids, phosphoric acid, tetra-sodium, metaphosphoric acid and Hypophosporous Acid, 50.By handling, can form the aluminum phosphate film that constitutes by aluminum phosphate, phosphoric acid one hydrogen aluminium, aluminium dihydrogen phosphate etc. from the teeth outwards with these phosphoric acid class aqueous solution.Also have, oxygen acid can use any a kind, also can be mixed with two or more.
[0024] about the content of the formation of the oxygen acid in oxygen acid treatment solution element, its total amount can be 10～10000ppm, is preferably 25～500ppm.If be less than 10ppm, then film forms the possibility deficiency, otherwise if surpass 10000ppm, then unreacted oxygen acid can remain in the surface of aluminium, might cause acid corrosion.Also having, is more than the 10ppm if oxygen acid constitutes the content of element, then can form the film that can prevent that the second phase compound breaks away from, then more effective if be more than the 25ppm, if taking cost into account, and then can be for below the 500ppm.
[0025] in addition, the oxygen acid treatment solution does not need to contain above-mentioned oxygen acid in fact and constitutes oxygen acid other oxygen acid in addition that element constitutes, and oxygen acid constitutes the metal-salt of the oxygen acid of element formation.Herein, other oxygen acid is meant the oxygen acid that contains phosphorus, silicon and chromium element in addition, and in addition, oxygen acid constitutes the metal-salt of the oxygen acid of element formation can enumerate for example oxysalts such as zinc phosphate, zirconium phosphate, Plessy's green.
[0026] if the oxygen acid treatment solution contains the metal-salt that oxygen acid constitutes the oxygen acid of element formation, then can form zinc phosphate or zirconium phosphate film on the aluminium material surface, a little less than these films and the bonding force as the aluminium of base material, therefore can not prevent the disengaging of the second phase compound fully, in addition, also can separate out on aluminium material surface, film itself has just become the dirt source.Equally, constitute other oxygen acid beyond the oxygen acid that element constitutes, then can not form firm combination, therefore can on the aluminium material surface after the processing, separate out and become the dirt source with aluminium as base material if contain specific oxygen acid.Therefore, about the oxygen acid treatment solution, essence does not contain oxygen acid and constitutes the metal-salt that other oxygen acid beyond the oxygen acid that element constitutes or oxygen acid constitute the oxygen acid that element constitutes and be advisable, preferred do not contain in the metal-salt that other oxygen acid and oxygen acid constitute the oxygen acid that element constitutes any in fact, based on above-mentioned identical reason, do not contain the metal of fluorochemicals such as hydrofluoric acid ammonium, Potassium monofluoride, zirconium, titanium, zinc, nickel etc. 3～12 and their salt, basic metal and alkaline-earth metal and their salt, hydrofluoric acid etc. in the oxygen acid treatment solution and be advisable.Also have, even the above-mentioned various materials that can not contain in fact, material that can not be below the detected 1ppm for for example by ICP luminescence analysis, atom absorption photometry or ion-chromatographic determination metallic element, non-metallic element, anionic species the time does not have special problem even contain in the oxygen acid treatment solution of the present invention yet.
[0027] means about utilizing the oxygen acid treatment solution that aluminium material surface is handled, for example can adopt dip treating, spray handle, with coatings such as brushes etc., preferably aluminium is immersed in and carries out dip treating in the oxygen acid treatment solution.About the treatment condition of dip treating, can in preferred 25～80 ℃ oxygen acid treatment solution, flood aluminium 10 seconds～30 minutes, preferred 1 minute～15 minutes 10～100 ℃ of temperature.If the temperature of oxygen acid treatment solution is lower than 10 ℃, then oxygen acid and aluminium are not easy reaction, otherwise if be higher than 100 ℃, then the dissolving quantitative change of aluminium is big.If dipping time is less than 10 seconds, the aluminium material surface oxygen acid quantity not sufficient of adhering to then, the formation of heat treated caudacoria is insufficient, and the second phase compound may break away from, on the contrary if surpass 30 minutes, then the dissolving quantitative change of aluminium is many, is difficult to guarantee dimensional precision.
[0028] heat treated about carrying out after handling with the oxygen acid treatment solution will be 80～400 ℃ of temperature, carry out under preferred 100～300 ℃.If the heat treated temperature is lower than 80 ℃, may not can form film fully on the aluminium material surface after then handling, otherwise if be higher than 400 ℃, then softening as the aluminium of base material, intensity may step-down with the oxygen acid treatment solution.The heat treated time is 0.5～120 part, is preferably 3～60 fens.If the heat treated time is less than 0.5 fen, then the film of aluminium material surface forms insufficiently, and the second phase compound may break away from, otherwise if be longer than 120 minutes, then the strength of materials of surface treated aluminum material may reduce.Also have,, can in air, carry out about the atmosphere gas of heat treated.
[0029] in addition, also can in the oxygen acid treatment solution, add alcoholic solvent or varsols such as acetone and toluene such as ethanol, Virahol.By adding these solvents, can promote the evaporation of solvent composition in the oxygen acid treatment solution, the dyeing of one of bad order that may occur when preventing as heat treated.And these solvents can make the surface go up residual a part of pollutant dissolution, are evaporated containing under the situation of pollutent then, have therefore improved surface clearness, can form the surface with lower dirt.In order to obtain identical therewith effect, also can use the aluminium material surface after the varsols washing heat treated such as alcoholic solvent such as ethanol, Virahol or acetone and toluene.
[0030] carry out heat treated after, can carry out ultrasonic washing again.That is, can think in a series of surface treatment, attached on the aluminium, or form oxide compound on the aluminium material surface,, can wash with ultrasonic wave once more for the purpose of removing them from pollutent contained in the dust of outside and the various treatment solution etc.About the wash conditions of this moment, can be according to carrying out with the identical mode of the ultrasonic washing after the processing of surface smoothing treatment solution with above-mentioned.
[0031] in the present invention, about carrying out the surface-treated aluminium, so long as the material that aluminum or aluminum alloy constitutes gets final product, its size and shape have no particular limits, and can carry out appropriate selection according to purposes.For example except raffinal (JIS H4170; 1N99), the aluminium that also can use various aluminium alloys such as A1100, A5052, A6063 to constitute, in addition, also can be the extrusion profile that forms by extrusion moulding, the heavy wall that forms by rolling processing or injection molding or thin-wall boards, these sheet materials are carried out bending machining material that suitable bending machining obtains etc.
[0032] in addition,, can carry out perhaps considering, suitably select the surface of aluminium to handle from the cost aspect with to carrying out the various processing that surface smoothingization is treated to representative as the whole surface of the aluminium of base material about surface treatment method of the present invention.When selecting the treating part, can observe the surface of aluminium, handle the zone that has applied forming process such as cut-out, cutting, compacting, perforate, perforation at least.
[0033] in addition, in the present invention, before carrying out the surface smoothing processing, can implement skimming treatment, etch processes, go any processing in residue treatment or the electrolytic polishing processing with the surface smoothing treatment solution.Wherein, about skimming treatment, can use the common degreasing fluid that constitutes by sodium hydroxide, yellow soda ash, sodium phosphate, tensio-active agent etc. to carry out, as treatment condition, dipping temperature is 15～55 ℃ usually, preferred 25～40 ℃, dipping time is 1～10 minute, preferred 3～6 minutes.In addition, about etch processes, can use alkali aqueous solutions such as sodium hydroxide, potassium hydroxide, yellow soda ash, its concentration is 20～200g/L, preferred 50～150g/L, as treatment condition, dipping temperature is 30～70 ℃, preferred 40～60 ℃, dipping time is 0.5～5 minute, preferred 1～3 minute.
[0034] about going residue treatment, for example can carry out in bathing at the residue that goes that constitutes by 1～30% nitric acid, as treatment condition, usually, dipping temperature is 15～55 ℃, preferred 25～40 ℃, dipping time is 1～10 minute, preferred 3～6 minutes.In addition, handle, for example can carry out at the mixed treating liquid that constitutes by perchloric acid 20 weight % and ethanol 80 weight % about electrolytic polishing, as treatment condition, can be at current density 1～10A/dm
2, bath voltage 20～30V handled 1～5 minute down.
[0035] surface treated aluminum material that obtains by the present invention handle by the surface smoothing treatment solution of regulation and ultrasonic washing removed as much as possible as rise the dirt source second mutually compound, have the treat surface of utmost point cleaning, so be to have got rid of the possible material of a dirt as much as possible.As being immersed in the pure water, the above population of particle diameter 0.5 μ m that the ultrasonic irradiation of usefulness frequency 120kHz produced in the time of 1 minute if measure with alpha counter in the liquid, with the unit surface conversion of surface treated aluminum material, is 1000/cm then
2Below, 500/cm more preferably
2Below.
[0036] surface treatment method in according to the present invention, even for the aluminium that forms by forming process such as cut-out, cutting, compacting, perforate, perforation with a plurality of surface of fracture, also can carry out the fine concave-convex surface that surface of fracture is removed in the surface smoothing processing by surface smoothing treatment solution with regulation, therefore can be to taking precautions against in possible trouble as the disengaging of the second phase compound that plays the dirt source.In addition, according to surface treatment method of the present invention, can obtain the good above-mentioned surface treated aluminum material of dimensional precision.
[0037] in addition, the identical or higher levels of dirt that hanged down of aluminium after the surface treated aluminum material tool being and not being electrolysis NiP plating that is obtained by the present invention is handled, therefore also be favourable on operation and cost, and the excellent corrosion resistance of the surface treated aluminum material that obtains, applicable to various uses.
Brief description of drawings
[Fig. 1] Fig. 1 (a) is the SEM photo that shows the state of the surface of fracture (I) of aluminium and shear surface (II), (b) is the enlarged view of a surface of fracture part.
Embodiment
Below based on embodiment and comparative example etc. the present invention is carried out more specific description.
Embodiment
＜test the making of surface treated aluminum material 〉
By cutting the square plate of commercially available A5052 aluminium (thickness of slab 1.0mm) is cut into vertical 100mm, horizontal 70mm, preparation has the aluminium of surface of fracture.Ready aluminium is completely infused in the surface smoothing treatment solution of being made up of phosphoric acid 80 weight %, dissolved aluminum (dissolving Al) 1 weight % and water 19 weight %, flooded 2 minutes down for 90 ℃, carry out the surface smoothing processing in surface smoothing treatment solution temperature.In addition, this surface smoothing treatment solution prepares in the following manner, that is, will the aluminium sheet identical with the aluminium material used in the present embodiment be immersed in and dissolve in the phosphate aqueous solution, reaches the dissolved aluminum concentration of regulation.
[0041] will put into the washing container that has added pure water through the aluminium after the surface smoothing processing then, under frequency 40kHz and power 100W, carry out ultrasonic washing 3 minutes (ultrasonic washing for the first time).Behind the ultrasonic washing, take out aluminium, obtain the test surface treated aluminum material.
[0042]＜play the evaluation of dirt 〉
In the following manner the test of above-mentioned acquisition is estimated with the dirt that rises of surface treated aluminum material.To put in the commercially available pyrex system beaker (1L) as the 600ml ultrapure water of experimental liquid, will test with surface treated aluminum material to be immersed in the ultrapure water with the discontiguous vacant state of container with silk thread.Then, in possessing the sonic washing machine in ultrasonic emitting source, the rinse bath bottom takes in above-mentioned glass beaker, in rinse bath, add entry his-and-hers watches face then and handle aluminium and carry out ultrasonic irradiation, under this state to the test in the ultrapure water with the ultrasonic wave of surface treated aluminum material irradiation frequency 120kHz, power 100W 1 minute.Then, with the particle diameter that exists in alpha counter in the liquid (the NP 500T that Japanese electric look industrial society makes) the determination test liquid is the above population of 0.5 μ m, the increase number of particle from ultrapure water is obtained the dust quantity of testing with on the surface treated aluminum material unit surface that rises.The results are shown in the table 1.Herein, the dust quantity on the unit surface is 1000/cm
2When following, be evaluated as zero, surpass 1000/cm
2The time, be evaluated as *.Also have, with the population in the experimental liquid (ultrapure water) before the surface treated aluminum material, measure with alpha counter in the liquid according to mode same as described above in advance for dip test.
[0043]＜evaluation of erosion resistance 〉
Above-mentioned test was placed 500 hours in the environment of 85 ℃ of temperature and humidity 90% with surface treated aluminum material, carry out corrosion resistance test, the evaluation test surface discolouration situation of surface treated aluminum material.Especially, by following third-class the evaluation: being zero during no change, is △ when changing slightly, when having significant change for *.The results are shown in the table 1.
[0044] embodiment 2～4
Except adopting the surface smoothing treatment solution that liquid is formed shown in the table 1, obtain test with surface treated aluminum material (embodiment 2,3) by the mode identical with embodiment 1.In addition, making the treatment solution temperature in the surface smoothing processing is 70 ℃, in addition, obtains test with surface treated aluminum material (embodiment 4) by the mode identical with embodiment 1.By the mode identical, the surface treated aluminum material that obtains is played dirt and erosion resistance evaluation respectively with embodiment 1.The results are shown in the table 1.
[0045] embodiment 5
Carry out the surface smoothing processing and for the first time after the ultrasonication by the mode identical, again aluminium is immersed in the 25 ℃ of aqueous solution (oxygen acid treatment solution) that contain phosphoric acid 0.2g/L (content of P is 63ppm) 5 minutes, carry out oxygen acid and handle with embodiment 1.The aluminium that will take out from the oxygen acid treatment solution heats maintenance and carried out heat treated in 5 minutes in 200 ℃ air, obtain the test surface treated aluminum material.By the mode identical, the surface treated aluminum material that obtains is played dirt and erosion resistance evaluation respectively with embodiment 1.The results are shown in the table 1.
[0046] embodiment 6～8
Except adopting the surface smoothing treatment solution that liquid is formed shown in the table 1, obtain test with surface treated aluminum material (embodiment 6,7) by the mode identical with embodiment 5.In addition, making the treatment solution temperature in the surface smoothing processing is 70 ℃, in addition, obtains test with surface treated aluminum material (embodiment 8) by the mode identical with embodiment 5.By the mode identical, the surface treated aluminum material that obtains is played dirt and erosion resistance evaluation respectively with embodiment 1.The results are shown in the table 1.
[0047] embodiment 9
After carrying out heat treated by the mode identical, in the washing container that has added pure water, put into aluminium, carry out frequency 40kHz, the ultrasonic wave washing of power 100W 3 minutes (the 2nd ultrasonic wave washing) with embodiment 5.After the ultrasonic wave washing, take out aluminium, obtain the test surface treated aluminum material.By the mode identical, the surface treated aluminum material that obtains is played dirt and erosion resistance evaluation with embodiment 1.The results are shown in the table 1.
[0048] embodiment 10～13
Except adopting the surface smoothing treatment solution that liquid is formed shown in the table 1, obtain test with surface treated aluminum material (embodiment 10,11,13) by the mode identical with embodiment 9.In addition, making the treatment solution temperature in the surface smoothing processing is 70 ℃, in addition, obtains test with surface treated aluminum material (embodiment 12) by the mode identical with embodiment 9.By the mode identical, the surface treated aluminum material that obtains is played dirt and erosion resistance evaluation respectively with embodiment 1.The results are shown in the table 1.
[0049] comparative example 1～5
Carry out with the situation (comparative example 1,2) of embodiment 1 same operation, similarly to Example 1 not carrying out the situation (comparative example 3) that the 1st ultrasonic wave is washed after the surface smoothing processing for carrying out the surface smoothing treatment solution of forming except liquid shown in the employing table 1, and, obtain the test surface treated aluminum material respectively for the situation (comparative example 4,5) of except the surface smoothing treatment solution that liquid shown in the employing table 1 is formed, carrying out with embodiment 9 same operation.By the mode identical, estimate the test that obtains and play dirt and erosion resistance with surface treated aluminum material with embodiment 1.The results are shown in the table 1.
[0050] reference example 1 and 2
Do not handle for the aluminium that uses among the embodiment 1, directly estimated dirt and erosion resistance (reference example 1) by the mode identical with embodiment 1.In addition, for the aluminium material surface that uses among the embodiment 1, the electroless plating that the plating solution that uses the メ Le プ レ one ト NI-871 that made by メ Le テ Star Network ス Co., Ltd. to constitute carried out 15 minutes under temperature 90 degree applies, and obtains having the aluminium of the NiP coating of 5 μ m.By the mode identical with embodiment 1, the aluminium after this NiP plating handled plays dirt and erosion resistance evaluation (reference example 2).The result is shown in Table 1 respectively.
[0051] can confirm, the test that obtains by the foregoing description 1～3 with the equal tool being and not being of surface treated aluminum material electrolysis NiP plating handle aluminium (reference example 2) equal hang down dirt, while excellent corrosion resistance.
The surface treated aluminum material that is obtained by the present invention has excellent dirt and the erosion resistance of having hanged down, therefore be suitable for as with hard drive materials such as the shell that is installed in the hard disk drive on computer and the word processor etc. as storing device and driving stems being representative, the shell of various precision equipments such as computer-related devices, semiconductor-fabricating device, instrumentation analyzer, electronic apparatus device, Optical devices, medical device and the material of precision equipment parts.In addition, also can be as the building materials of use in material such as the equipment that under dustfree environment, uses and parts and the clean room etc.Not special other restriction of the surface treatment method of the aluminium among the present invention so long as use the material of aluminium, just can be used as process object, therefore for the aluminium that uses in existing device or the parts, also can be suitable for.
Claims (20)
1, the manufacture method of surface treated aluminum material, it is characterized in that surface for aluminium, with containing more than the 50 weight % and the surface smoothing treatment solution of the phosphoric acid of less than 100 weight % and the dissolved aluminum more than the 0.001 weight %, below the 5 weight % is handled, and carry out ultrasonic washing.
2, the manufacture method of the surface treated aluminum material described in the claim 1, the processing that wherein utilizes the surface smoothing treatment solution are that aluminium is immersed in 60～110 ℃ the surface smoothing treatment solution 10 seconds～20 minutes, handle.
3, the manufacture method of the surface treated aluminum material described in the claim 1 or 2, wherein behind ultrasonic washing, handle with the oxygen acid treatment solution that contains oxygen acid, carry out heat treated again under 80～400 ℃ temperature, described oxygen acid contains more than one oxygen acid that are selected from phosphorus, silicon and the chromium and constitutes element.
4, the manufacture method of the surface treated aluminum material described in the claim 3, wherein the oxygen acid treatment solution is to constitute by containing the aqueous solution of material more than a kind or 2 kinds that is selected from phospho acid, phosphorous acid, phosphonic acids, phosphoric acid, tetra-sodium, metaphosphoric acid, Hypophosporous Acid, 50, orthosilicic acid, positive silicic acid, inclined to one side two silicic acid, chromic acid and dichromic acid.
5, the manufacture method of the surface treated aluminum material described in the claim 3 or 4, wherein the total content of the formation of the oxygen acid in oxygen acid treatment solution element is 10～10000ppm.
6, the manufacture method of the surface treated aluminum material described in the claim 3 is wherein carried out ultrasonic washing once more after heat treated.
7, the manufacture method of the surface treated aluminum material described in the claim 1 wherein before handling with the surface smoothing treatment solution, is implemented skimming treatment, etch processes, is gone more than in handling any of residue treatment or electrolytic polishing.
8, the surface treatment method of aluminium, it is characterized in that surface for aluminium, with containing more than the 50 weight % and the surface smoothing treatment solution of the phosphoric acid of less than 100 weight % and the dissolved aluminum more than the 0.001 weight %, below the 5 weight % is handled, and carry out ultrasonic washing.
9, the surface treatment method of the aluminium described in the claim 8, the processing that wherein utilizes the surface smoothing treatment solution are aluminium to be immersed in 60～110 ℃ the surface smoothing treatment solution 10 seconds～20 minutes processing.
10, the surface treatment method of the aluminium described in the claim 8 or 9, wherein behind ultrasonic washing, handle with the oxygen acid treatment solution that contains acid, carry out heat treated again under 80～400 ℃ temperature, described oxygen acid contains more than one oxygen acid that are selected from phosphorus, silicon and the chromium and constitutes element.
11, the surface treatment method of the aluminium described in the claim 10, wherein the oxygen acid treatment solution is to constitute by containing the aqueous solution of material more than a kind or 2 kinds that is selected from phospho acid, phosphorous acid, phosphonic acids, phosphoric acid, tetra-sodium, metaphosphoric acid, Hypophosporous Acid, 50, orthosilicic acid, positive silicic acid, inclined to one side two silicic acid, chromic acid and dichromic acid.
12, the surface treatment method of the aluminium described in the claim 10 or 11, wherein the total content of the formation of the oxygen acid in oxygen acid treatment solution element is 10～10000ppm.
13, the surface treatment method of the aluminium described in the claim 10 wherein carries out ultrasonic washing once more after heat treated.
14, the surface treatment method of the aluminium described in the claim 8 wherein before handling with the surface smoothing treatment solution, is implemented skimming treatment, etch processes, is gone more than in handling any of residue treatment or electrolytic polishing.
15, surface treated aluminum material, it is characterized in that, be to handle the surface of aluminium, and carry out ultrasonic washing and obtain with containing the above and phosphoric acid of less than 100 weight % of 50 weight % and the surface smoothing treatment solution of the dissolved aluminum that 0.001 weight % is above, 5 weight % are following.
16, the surface treated aluminum material described in the claim 15, the processing that wherein utilizes the surface smoothing treatment solution are aluminium to be immersed in 60～110 ℃ the surface smoothing treatment solution 10 seconds～20 minutes processing.
17, the surface treated aluminum material described in the claim 15 or 16, it is characterized in that, behind ultrasonic washing, handle with the oxygen acid treatment solution that contains oxygen acid, the heat treated of carrying out under 80～400 ℃ temperature again, described oxygen acid contain more than one oxygen acid that are selected from phosphorus, silicon and the chromium and constitute elements.
18, the surface treated aluminum material described in the claim 17 is characterized in that, has the aluminum phosphate tunicle more than a kind that is selected from aluminum phosphate, phosphoric acid one hydrogen aluminium and the aluminium dihydrogen phosphate on the surface.
19, the surface treated aluminum material described in the claim 17 or 18 wherein carries out ultrasonic washing once more and obtains after heat treated.
20, each described surface treated aluminum material in the claim 15～19, wherein be immersed in the pure water, population more than the particle diameter 0.5 μ m that produces in the time of 1 minute with the ultrasonic irradiation of frequency 120kHz is 1000/cm when alpha counter is measured in the liquid
2Below.
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Cited By (6)
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| CN102652058A (en) * | 2009-12-11 | 2012-08-29 | 日本轻金属株式会社 | Aluminium/resin composite exhibiting excellent weather resistance and manufacturing method for the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3373801B2 (en) * | 1999-02-26 | 2003-02-04 | 日本軽金属株式会社 | Aluminum substrate surface treatment method and surface treatment agent |
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| JP3543194B2 (en) * | 2001-12-21 | 2004-07-14 | 壽男 小田島 | Chrome-free surface treatment agent for metal materials and surface-treated metal materials |
| DE50310042D1 (en) * | 2002-07-10 | 2008-08-07 | Chemetall Gmbh | METHOD OF COATING METALLIC SURFACES |
| JP2005336605A (en) * | 2004-04-27 | 2005-12-08 | Nippon Light Metal Co Ltd | Surface-treated aluminum material, manufacturing method therefor, and cover case for precision instrument formed of the surface-treated aluminum material |
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