CN102758205B - Aluminum alloy polishing solution and preparing method thereof - Google Patents
Aluminum alloy polishing solution and preparing method thereof Download PDFInfo
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- CN102758205B CN102758205B CN201210245355.8A CN201210245355A CN102758205B CN 102758205 B CN102758205 B CN 102758205B CN 201210245355 A CN201210245355 A CN 201210245355A CN 102758205 B CN102758205 B CN 102758205B
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Abstract
The invention relates to an aluminum alloy polishing solution, which includes the following components according to mass percent: 50 to 80wt% of phosphoric acid, 10 to 30wt% of sulfuric acid, 0.7 to 5wt% of glycerin, 0.05 to 3wt% of corrosion inhibitor, and 1 to 12wt% of surfactant. The aluminum alloy polishing solution has low corrosivity, excellent polishing effect and good market prospect, and produces no toxic nitrogen dioxide.
Description
Technical field
The present invention relates to polishing technology, relate in particular to a kind of aluminium alloy polishing fluid and preparation method thereof.
Background technology
Aluminium and alloy product are because having special character, apply quite extensive, in hardware market, occupy extremely important status, aluminum products will carry out polishing in surface treatment, this not only makes the outward appearance of aluminum products have bright appearance, and uniform and smooth surface can disperse to reduce the absorption of corrosive medium, raising etch resistant properties.
Polishing refers to and utilizes machinery, chemistry or electrochemical effect, workpiece surface roughness is reduced, to obtain the working method of light, flat surface.Main polishing technology is three acid polishing at present.
The application of polishing technology that aluminium alloy three acid polishing technology has had following four large drawbacks limit:
1. can not dusting, remove mechanical line.In aluminium alloy moulding process, there are many mechanical lines on surface, and after three acid polishing is processed, lines is more obvious, has a strong impact on aluminium alloy visual appearance.Except with the lower mechanical means of efficiency (as sandblast, machine throw) etc. carry out outside pre-treatment, in recent decades, do not develop the mature technology that goes line and the supporting processing of dusting and then row polishing by chemical process, restricted the popularization of polishing technology.
2. dripping time is too short, reagent consumption is too large, yield rate is too low.The current mark problem of polishing material is the world-famous puzzle of puzzlement aluminium processing industry.Aluminium alloy leaves after polishing fluid, and aloft dripping time generally must not exceed 30 seconds, otherwise there will be current mark, produces waste product.So short dripping time, certainly will cause two large serious consequences: first reagent consumption is too large, unexpectedly up to 400-600kg/ ton material, will be also that so high spent acid is processed the about 800Kg sheet alkaline purification waste water of increase.It two is that yield rate is too low, and generally less than 70%, most of waste product is to cause due to current mark or flower material, has further increased production cost.Therefore, although glossing is so simple and direct, cost be all oxidation pretreatment technologies, up to 6000-8000 yuan/ton of material.
3. nitric acid decomposition is too fast, and a large amount of tobacco are seriously polluted, processing cost costliness.Nitric acid is strong oxidizer, under hot conditions, runs into the very strong metal of this reductibility of aluminium, and the making us soon of decomposition rate is difficult to the imagination: a large amount of tobacco overflowed as the same moment of catching fire, and exhausting is difficulty all, and thoroughly absorption is more difficult.In addition, the fluctuation up and down of concentration of nitric acid, certainly will cause polished aluminum alloy surface bright alternately dark, and yield rate is low.
4. the serious loss of gloss of oxidation, quality is had a greatly reduced quality.Three acid polishing, generally can form minute surface, and once anodic oxidation, gloss is had a greatly reduced quality.How reducing oxidation loss of gloss, is again a world-famous puzzle.Between mirror polish and anodizing tank, newly establish and protect photoxidation groove, polishing material is first protected to photochemical oxidation processing, and then enter anodizing tank, effectively reduce luminance loss.
Traditional aluminium alloy polishing fluid uses nitric acid because of metropolitan, in the time producing, can produce a large amount of poisonous nitrogen peroxide (being commonly called as Huanglong), must spend a large amount of funds to build exhausting and exhaust system for reducing the harm of nitrogen peroxide, and the nitrogen peroxide of discharging is huge to environmental hazard.
The people such as Sun Hongbo, the harm for traditional three acid polishing to environmental and human health impacts, has developed taking phosphoric acid-sulfuric acid as basal liquid, and adds the smokeless surface with chemical polishing technology of additive.First studied not containing the additive impact of various factors on quality of finish constantly, and selected on this basis optimal processing parameter, determined the mass concentration of composite additive.Result shows: at H
3pO
4(volume fraction is 85%): H
2sO
4(volume fraction is 98%)=2:1, Al
3+8～10g/L, WYZ-1 type composite additive 10g/L, 9-110 DEG C, under 1-2min processing condition, can improve quality of finish, and inhibiting point corrosion, obtains good polishing effect, has successfully solved the tobacco pollution problem in chemical rightenning, meets industrial needs.(research of the smokeless surface with chemical polishing technology of aluminum alloy environment-friendly type, Sun Hongbo etc. electroplate and environmental protection 2009.9,29(5): 20-23)
On the other hand, those skilled in the art have also developed corresponding diacid (phosphoric acid-sulfuric acid) type aluminium alloy polishing fluid, but polishing effect is but all unsatisfactory, does not reach the polishing effect of nitric acid type polishing fluid far away.
Therefore, how to develop one and do not contain nitric acid, in production, do not produce nitrogen peroxide, the aluminium alloy polishing fluid lower to environment and direct labor's harm, polishing effect is simultaneously this area technical problem urgently to be resolved hurrily not second to nitric acid type polishing fluid without nitric acid polishing fluid again.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of aluminium alloy polishing fluid, described polishing fluid, not containing nitric acid composition, does not have nitrogen peroxide and produces in production, can will drop to minimum aluminium alloy polishing fluid to environment and direct labor's harm.Aluminium alloy polishing fluid of the present invention can apply to five metals processing, for example aluminum connector, capacitance shell or other aluminum handwares in a large number.
The present invention is achieved through the following technical solutions:
A kind of aluminium alloy polishing fluid, comprises following component by quality percentage composition:
The quality percentage composition sum of described each component is 100wt%.
Nitric acid is strong oxidizer, has the effect of good polishing and surfacing, if there is no nitric acid in rumbling compound, polishing effect can obviously weaken.In the formula of aluminium alloy polishing fluid provided by the invention, although do not contain nitric acid, by coordinating the ratio of phosphoric acid and sulfuric acid, and add inhibiter and tensio-active agent in aluminium alloy polishing fluid, and allocate its ratio, and obtain polishing effect good, can not produce the aluminium alloy polishing fluid of tobacco.
Phosphoric acid (H
3pO
4), another name ortho-phosphoric acid, is a kind of common mineral acid, is middle strong acid, is dissolved in hot water and can be obtained by Vanadium Pentoxide in FLAKES.Ortho-phosphoric acid is industrial with vitriolization phosphatic rock and get final product.Phosphoric acid is easy deliquescence in air, and heating meeting dehydration obtains tetra-sodium, obtains metaphosphoric acid in further dehydration, and phosphoric acid is mainly used in the industry such as pharmacy, food, fertilizer, also can be used as chemical reagent.Pure phosphoric acid is clear crystal, and 42.3 DEG C of fusing points, belong to high boiling point acid, soluble in water.Commercially available phosphoric acid is thickness, nonvolatile strong solution, phosphorus acid content 83-98%, and density is 1.685g/mL.
Preferably, phosphoric acid volume fraction of the present invention is 80-88%, for example 80.1%, 80.5%, 80.8%, 81.6%, 82.4%, 83.6%, 84.1%, 84.6%, 85.7%, 86.8%, 87.2%, 87.7%, 87.9%, and preferably 83-86%, further preferably 85%.
Sulfuric acid, chemical formula is H
2sO
4, be a kind of colorless and odorless oily liquids, be the strong acid of the difficult volatilization of a kind of high boiling point (boiling point: 338 DEG C), soluble in water, can be with arbitrarily than miscible with water.Sulfuric acid is one of staple product in basic chemical industry, and he is not only as the raw material of many Chemicals, but also is widely used in other sector of the national economy.Sulfuric acid concentration >=70% is called the vitriol oil, and 98% vitriol oil relative density is 1.84g/mL.The vitriol oil has strong oxidisability, and under normal temperature, the vitriol oil can make the metal such as iron, aluminium generation passivation.
Preferably, sulfuric acid of the present invention is the vitriol oil, and described vitriol oil volume fraction is 95-99%, for example 95.1%, 95.3%, 95.8%, 96.3%, 96.9%, 97.5%, 98.0%, 98.1%, 98.4%, 98.8% etc., and preferably 96%-99%, further preferably 98%.
In the system of phosphoric acid-sulfuric acid, the concentration of phosphoric acid is larger, the bright property of aluminum alloy surface is poorer, and sulfuric acid is in the polishing process of aluminium alloy, because making the surface of aluminium alloy, its oxidation-passivation there is very good planarization and bright property, when but the concentration of sulfuric acid is excessive, can cause on the contrary the excessive corrosion of aluminium alloy, unfavorable on the contrary for polishing.Particularly, if when the amount of phosphoric acid is less than 50wt%, the content of sulfuric acid is large (being greater than 30wt%), and serious corrosion can occur aluminum alloy surface, and bright planarization all shows poor; In the time that phosphorus acid content is greater than 80wt% (content of sulfuric acid is less than 10wt%), phosphorus acid content is high, and the light effect performance of sulfuric acid is not outstanding, causes the polishing effect of polishing fluid bad.
Glycerine plays in the present invention and makes aluminium alloy glazed surface finer and smoother, improves the effect of the smooth finish of product.
Preferably, inhibiter of the present invention is selected from organic acid, benzotriazole (BTA), thiocarbamide, imidazolines inhibiter, hydramine phosphoric acid ester, the combination of any a kind or at least 2 kinds in Aksu-28, described organic acid example has acetic acid, oxalic acid or succsinic acid etc., the example of described imidazolines inhibiter has glyoxal ethyline quinoline, 2-ethyl imidazol(e) quinoline or 2 isopropyl imidazole quinoline etc., the example of described hydramine phosphoric acid ester has 2-hydroxyethylidene diphosphonic acid guanidine-acetic acid, hexanediamine four methylenephosphonic acids or polyamino polyether base methylenephosphonic acid etc., described combination is acetic acid/glyoxal ethyline quinoline for example, 2 isopropyl imidazole quinoline/thiocarbamide, benzotriazole (BTA)/Aksu-28, succsinic acid/Aksu-28/ hexanediamine four methylenephosphonic acids etc., preferably Aksu-28.
Described Aksu-28 are a kind of high-efficient corrosion inhibitor that Dutch Aksu-Nobel company produces, and its effect is to prevent that aluminum alloy surface excessive erosion from improving smooth finish.
Preferably, tensio-active agent of the present invention is selected from the combination of any a kind or at least 2 kinds in sodium diphenylaminesulfonate, Witco 1298 Soft Acid, HF-600, and described combination is sodium diphenylaminesulfonate/Witco 1298 Soft Acid, Witco 1298 Soft Acid/HF-600/ sodium diphenylaminesulfonate etc. such as.
Described HF-600 is the tensio-active agent purchased from Shenzhen Rong Qiang Science and Technology Ltd., and its 25 DEG C of left and right are colourless to faint yellow thick liquid; The pH value of water solution of the 3wt% of HF-600 is 6.5-8.5; HLB value is 12.5-14.5.The use temperature of HF-600 is 60-100 DEG C, there is excellent degreasing power, dedust power ability, lubricating oil Vaseline (butter) class is mixed to greasy dirt to be had strong cleaning force, wax dirt is also had to strong cleaning paraffin removal power, there are good water-soluble and washing property, acid and alkali-resistance, have good compatibleness, coordinate and just become high-quality grease-removing agent, clean-out system with conventional auxiliary agent.
In the present invention, HF-600 is as a kind of tensio-active agent, and its Main Function is the black dirt of removing aluminium alloy glazed surface, the generation of acid mist while simultaneously suppressing polishing.
As optimal technical scheme, polishing fluid of the present invention comprises following component by quality percentage composition:
The quality percentage composition sum of described each component is 100wt%.
Preferably, polishing fluid of the present invention comprises following component by quality percentage composition:
As optional technical scheme, polishing fluid of the present invention comprises following component by mass percentage:
Two of object of the present invention is to provide a kind of preparation method of aluminium alloy polishing fluid of the present invention, and described method is in reactor, first to drop into the phosphoric acid of formula ratio, and then drops into successively sulfuric acid, glycerine, Aksu-28, HF-600; Continue to stir 10min, pack out product;
Described reactor is the reactor with whipping appts, for example liquid stirrers.
Three of object of the present invention is to provide a kind of using method of aluminium alloy polishing fluid of the present invention, and described method comprises successively oil removing, washing, aluminium alloy polishing, washing, striping (being the black film of removing glazed surface), washing, dries;
Described aluminium alloy polishing step uses aluminium alloy polishing fluid stoste provided by the invention;
Preferably, the temperature of described aluminium alloy polishing step is 90-110 DEG C, and the typical but non-limiting example of described polish temperature has 91 DEG C, 92 DEG C, 97 DEG C, 101 DEG C, 105 DEG C, 107 DEG C, 109 DEG C etc.Polish temperature is less than 90 DEG C, and polishing effect is bad, and profile pattern and bright property are poor; Polish temperature is greater than 110 DEG C, and excessive erosion easily occurs polishing workpiece, easily causes workpiece to cancel.
Preferably, the time of described aluminium alloy polishing step is 10-20s, and the typical but non-limiting example of described polishing time has 10.1s, 10.4s, 10.7s, 11.3s, 12.2s, 13.6s, 14.5s, 15.6s, 17.1s, 18.7s, 19.3s, 19.8s etc.Polishing time is less than 10s, and polishing effect is bad, and profile pattern and bright property are poor; Polishing time is greater than 20s, and excessive erosion easily occurs polishing workpiece, easily causes workpiece to cancel.
Compared with prior art, the present invention has following beneficial effect:
(1) aluminium alloy polishing fluid provided by the invention, not containing nitric acid composition, does not have nitrogen peroxide and produces in production, drops to minimum to environment and direct labor's harm.
(2) aluminium alloy polishing fluid provided by the invention selects phosphoric acid and sulfuric acid as the main component of polishing fluid, chooses most suitable ratio, the simultaneously corresponding auxiliary agent of compatibility, thus ensure the polishing effect of aluminium alloy polishing fluid.
(3) in aluminium alloy polishing fluid provided by the invention, phosphoric acid and sulfuric acid are the main raw materials of polishing, glycerine is to make aluminium alloy glazed surface finer and smoother, improve the smooth finish of product, the effect of Aksu-28 is to prevent that aluminum alloy surface excessive erosion from improving smooth finish, the effect of HF-600 is that the black dirt of aluminium alloy glazed surface is removed, and the generation of acid mist can suppress polishing time.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
A kind of polishing fluid comprises following component by quality percentage composition:
Wherein, the volume fraction of phosphoric acid is 80%, and the volume fraction of sulfuric acid is 95%;
Preparation method is:
In liquid stirrers, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, thiocarbamide, Witco 1298 Soft Acid; Continue to stir 10min, pack out product;
Using method:
By the polishing-washing-striping-washing-oven dry of Al alloy parts process oil removing-washing-aluminium alloy; Wherein, aluminium alloy polish temperature is 90 DEG C, and polishing time is 20s.
Embodiment 2
A kind of polishing fluid comprises following component by quality percentage composition:
Wherein, the volume fraction of phosphoric acid is 88%, and the volume fraction of sulfuric acid is 99%;
Preparation method is:
In liquid stirrers, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, BTA, HF-600; Continue to stir 10min, pack out product;
Using method:
By the polishing-washing-striping-washing-oven dry of Al alloy parts process oil removing-washing-aluminium alloy; Wherein, aluminium alloy polish temperature is 110 DEG C, and polishing time is 10s.
Embodiment 3
A kind of polishing fluid comprises following component by quality percentage composition:
Wherein, the volume fraction of phosphoric acid is 85%, and the volume fraction of sulfuric acid is 98%;
Preparation method is:
In liquid stirrers, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, Aksu-28, sodium diphenylaminesulfonate; Continue to stir 10min, pack out product;
Using method:
By the polishing-washing-striping-washing-oven dry of Al alloy parts process oil removing-washing-aluminium alloy; Wherein, aluminium alloy polish temperature is 100 DEG C, and polishing time is 13s.
Embodiment 4
A kind of polishing fluid comprises following component by quality percentage composition:
Wherein, the volume fraction of phosphoric acid is 83%, and the volume fraction of sulfuric acid is 96%;
Preparation method is:
In liquid stirrers, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, Aksu-28, HF-600; Continue to stir 10min, pack out product;
Using method:
By the polishing-washing-striping-washing-oven dry of Al alloy parts process oil removing-washing-aluminium alloy; Wherein, aluminium alloy polish temperature is 97 DEG C, and polishing time is 17s.
Embodiment 5
A kind of polishing fluid comprises following component by mass percentage:
Wherein, the volume fraction of phosphoric acid is 86%, and the volume fraction of sulfuric acid is 99%;
Preparation method is:
In liquid stirrers, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, Aksu-28, HF-600; Continue to stir 10min, pack out product;
Using method:
By the polishing-washing-striping-washing-oven dry of Al alloy parts process oil removing-washing-aluminium alloy; Wherein, aluminium alloy polish temperature is 90-110 DEG C, and polishing time is 10-20s.
Comparative example 1
Choose commercially available aluminium alloy polishing fluid and carry out simultaneous test.
Comparative example 2
Choose commercially available diacid aluminium alloy polishing fluid and carry out simultaneous test.
Simultaneous test
Embodiment 1-5 and comparative example 1,2 are carried out to simultaneous test, and test event has: whether have tobacco generation, minute surface reflecting rate and aluminium alloy rate of weight loss.
Wherein, whether there is tobacco to produce by visual judgement;
Minute surface reflecting rate is measured the aluminum alloy sheet after polishing on UV, visible light-infrared spectrophotometer;
Aluminium alloy rate of weight loss by test the workpiece quality before polishing (meter is made m
0) and polishing after workpiece quality (meter is made m
1) measure, calculation formula is rate of weight loss=[(m
0-m
1)/m
0] * 100%.
Table 1 is the performance test results of embodiment 1-5 and comparative example 1,2.
The performance test results of table 1 embodiment 1-5 and comparative example 1,2
| Whether there is tobacco to produce | Minute surface reflecting rate (%) | Rate of weight loss (%) | |
| Embodiment 1 | Nothing | 63 | 25 |
| Embodiment 1 | Nothing | 65 | 24 |
| Embodiment 1 | Nothing | 67 | 23 |
| Embodiment 1 | Nothing | 68 | 22 |
| Embodiment 1 | Nothing | 70 | 20 |
| Comparative example 1 | Have | 71 | 23 |
| Comparative example 2 | Nothing | 40 | 30 |
As can be seen from Table 1, the polishing effect of aluminium alloy polishing fluid provided by the invention can match in excellence or beauty with the polishing effect of commercially available nitric acid type polishing fluid (comparative example 1), but but there is no the generation of poisonous nitrogen dioxide gas.Compared with commercially available two acid type aluminium alloy polishing fluids (comparative example 2), no matter be on polishing effect, still again in the corrodibility of aluminium alloy, show all very excellent, after commercially available two acid type aluminium alloy polishing fluid polishings, the rate of weight loss of aluminium alloy is 30%, and after polishing fluid polishing provided by the invention, the rate of weight loss of aluminium alloy is only 20-25%; Aspect reflecting rate, the aluminium alloy reflecting rate after commercially available two acid type aluminium alloy polishing fluid polishings is only 40%, and after polishing fluid polishing provided by the invention the reflecting rate of aluminium alloy up to 70%.
This shows, the corrodibility of aluminium alloy polishing fluid provided by the invention is low, and polishing effect is good and can not produce poisonous nitrogen peroxide, has solved the technical barrier of this area, has good market outlook.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. an aluminium alloy polishing fluid, is characterized in that, described polishing fluid comprises following component by quality percentage composition:
Described phosphoric acid volume fraction is 80-88%; Described sulfuric acid is the vitriol oil, and described vitriol oil volume fraction is 95-99%; Described inhibiter is Aksu-28; Described tensio-active agent is HF-600;
Described aluminium alloy polishing fluid prepares by the following method:
In reactor, first drop into the phosphoric acid of formula ratio, and then drop into successively sulfuric acid, glycerine, Aksu-28, HF-600; Continue to stir 10min, pack out product.
2. polishing fluid as claimed in claim 1, is characterized in that, described phosphoric acid volume fraction is 83-86%.
3. polishing fluid as claimed in claim 2, is characterized in that, described phosphoric acid volume fraction is 85%.
4. polishing fluid as claimed in claim 1, is characterized in that, described vitriol oil volume fraction is 96%-99%.
5. polishing fluid as claimed in claim 4, is characterized in that, described vitriol oil volume fraction is 98%.
6. a preparation method for the aluminium alloy polishing fluid as described in one of claim 1-5, is characterized in that, described method is in reactor, first to drop into the phosphoric acid of formula ratio, and then drops into successively sulfuric acid, glycerine, Aksu-28, HF-600; Continue to stir 10min, pack out product;
Described reactor is the reactor with whipping appts.
7. method as claimed in claim 6, is characterized in that, described reactor is liquid stirrers.
8. a using method for the aluminium alloy polishing fluid as described in one of claim 1-5, is characterized in that, described method comprises oil removing, washing, aluminium alloy polishing, washing, striping, washing, oven dry successively;
Described aluminium alloy polishing step is the stoste of the described aluminium alloy polishing fluid of one of right to use requirement 1-5.
9. method as claimed in claim 8, is characterized in that, the temperature of described aluminium alloy polishing step is 90-110 DEG C.
10. method as claimed in claim 8, is characterized in that, the time of described aluminium alloy polishing step is 10-20s.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109440113A (en) * | 2018-12-06 | 2019-03-08 | 北京动力机械研究所 | A kind of high temperature alloy chemical polishing agent and preparation method thereof |
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