CN107841741A - A kind of aluminium base surface biological handles oxidation technology - Google Patents
A kind of aluminium base surface biological handles oxidation technology Download PDFInfo
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- CN107841741A CN107841741A CN201710953775.4A CN201710953775A CN107841741A CN 107841741 A CN107841741 A CN 107841741A CN 201710953775 A CN201710953775 A CN 201710953775A CN 107841741 A CN107841741 A CN 107841741A
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- aluminium base
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
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Abstract
The method that the present invention relates to the use of biological oxidation, aluminium base is handled under sour environment using acidophil, with circulating water flushing, fine and close pellumina is generated on aluminium base.Avoid inorganic chemistry oxidation and the electroxidation of high pollution high energy consumption, again in the fine and close alundum (Al2O3) layer of surface of aluminum plate generation, with higher insulation and thermal conduction characteristic, fine and close oxide layer have uniformly, stably, it is consistent the characteristics of, the heat conductive insulating characteristic of aluminum-based copper-clad plate greatly improved, and do not produce industrial pollution and energy loss.
Description
Technical field
The present invention relates to a kind of surface of aluminum plate processing method.
Background technology
, it is necessary to carry out oxidation processes to aluminium surface in aluminium base production process, alundum (Al2O3) oxide layer is formed.Aluminium closes
The anodic oxidation of gold surface processing generally use, chemical conversion treatment, plating and differential arc oxidation etc..Al and Al-alloy is through chemistry
Oxide-film obtained by oxidation, thickness about at 0.5-4 μm, wear no resistance, and corrosion resistance is lower than anode oxide film, should not individually make
With；But it is the good bottom painted with certain anti-corrosion and preferable physical absorption ability.
CN1039626A discloses a kind of aluminium and alloy method for oxidation, and a, chemical oxidation solution are by 3.7-6.7 g/l
Chromic anhydride, 1-3 g/l of fluoride, the 0.5-0.05 g/l of potassium ferricyanide, 0.5-3 g/l of surfactant, 0.05-0.05 grams/
Rare element composition is risen, b, chemical oxidation process flow are that (1) uses aqueous cleaning agent situation, and (2) use 40 DEG C of -50 DEG C of hot water
Wash, (3) wash (4) in flowing cool water and carry out pickling, and (5), which are placed in flowing cool water, to be cleaned, and (6) are cleaned with deionized water, and (7) are entered
The dip-coating of row chemical oxidation or brushing, (8) are dried under 50 DEG C of -60 DEG C of states.Although its chemical oxidation solution chromium used
Content is decreased, but still serious pollution can be produced to environment.
CN1047114A discloses a kind of method in one layer of fastening protective clear layer of metallized film Surface Creation, is included in base
Aluminium plating membrane is prepared on bottom material, in aluminium plating membrane surface oxidation, generation protective layer, finished product cleaning and drying, in aluminium plating membrane
The method of surface oxidation uses chemical oxidation treatment method, and its chemical solution is formulated as follows：H3PO425-80mL/L、CrO310-75g/
L、NH4HF21-9g/L、H3BO30.5-6g/L、C4H6O61-8g/L、(HO)C6H3(COOH)SO3H·2H2O 1-8g/L、
C6H8O7·H2O 1-8g/L.The technique uses more organic substance, and pollution of chromium environment.
CN101892478B discloses a kind of method and chemically blackening solution in aluminum alloy surface generation black film layer, the party
Method uses first carries out oxidation processes to form oxidation film layer to aluminium alloy；Then aluminum alloy surface is entered with chemically blackening solution
The processing of row chemically blackening, wherein, chemically blackening solution is by nickel nitrate, ammonium molybdate, nitric acid, 2-amino-2-methyl-1-propanol, height
Potassium manganate and water composition, wherein containing nickel nitrate 0.5-1.8g/L, ammonium molybdate 30-60g/L, nitric acid 10-20g/L, 2- amino-
2- methyl isophthalic acids-propyl alcohol 30-80g/L, potassium permanganate 5-7g/L, the chemically blackening processing are carried out at -85 DEG C of temperature 45 C, located
The reason time is 3-16 minutes；Seal treatment finally is carried out to aluminum alloy surface with aluminum chemistry oxidation sealer.The technique use compared with
Strong nitric acid, potassium permanganate, very big pollution is brought to environment.
CN101463476B discloses a kind of oxidized aluminum alloy techniques of, including following steps are completed：(1) removed with neutrality
Oil solution removes the grease on articles made of aluminium alloy surface；(2) water cleaning aluminum alloy article surface is used；(3) acid solution method is used
Remove the oxide-film on articles made of aluminium alloy top layer；(4) water cleaning aluminum alloy article surface is used；(5) aoxidized in oxidation treatment solution
Processing, treatment temperature are higher than 45 DEG C, and processing time is 5-20 minutes；Oxidation treatment solution wherein described in step (5) by with
Under several steps form：(51) aluminate, citric acid or citrate, metavanadate and fluoride are mixed to form with water and mixed
Solution；(52) above-mentioned mixing is adjusted with nitric acid, hydrochloric acid or other inorganic acids for not influenceing articles made of aluminium alloy superficial oxidation film quality
Oxidation treatment solution is made between 1.2-1.6 in solution ph；(53) in the solution aluminate content 0.01-20g/L it
Between, citric acid or citrate content between 5-50g/L, metavanadate content is between 0.1-20g/L, content of fluoride
Between 1.0-2.0g/L；(6) water cleaning aluminum alloy article surface is used；(7) sealer is aoxidized to cleaning using OY-61 aluminum chemistries
Articles made of aluminium alloy carry out Seal treatment, 90-95 DEG C for the treatment of temperature, processing time is 8-12 minutes.The processing step complexity compared with
It is more, and more acidic materials are used, cost is high.
CN104313560A discloses a kind of surface of aluminum plate processing method, comprises the following steps：(1) surface of aluminum plate is cleaned：It is right
Surface of aluminum plate is cleaned, and removes the impurity and grease of surface of aluminum plate；(2) surface of aluminum plate is roughened：Aluminium sheet is immersed in alkali lye, alkali
Liquid temperature degree is 50-80 DEG C, soak time 2-4min；(3) surface of aluminum plate aoxidizes：Aluminium sheet is immersed in 30-45 DEG C of weak acid solution
3-5min, weak acid solution include the raw material of following parts by weight；(4) water-filling cleaning is entered to aluminium sheet；(5) aluminium sheet is dried.Should
Technique needs to use alkali lye, and effect on environment is serious.
CN102174695A discloses a kind of aluminium conductive chemical oxidation method, and method and step is:(1) will prepare to prepare solution body
The deionized water of product half is added in container；(2) by chromium trioxide/chromic anhydride 2.5-4.0g/L, sodium fluoride 3.0-4.0g/L and phosphorus
Sour 11.0-13.0g/L is added in deionized water, and stirring is uniformly dissolved it；(3) deionized water is added to required volume；(4)
The temperature control of oxidation solution at 16-38 DEG C；(5) aluminium to be oxidized is put into the oxidation solution 15-30 seconds.The technique into
This height, power consumption is big, and equally there is also problem of environmental pollution.
Traditional solution method is the method using chemical oxidation and electroxidation, but both techniques exist high pollution,
The problem of high energy consumption, will slowly it be eliminated.The main deficiency of existing process is：(1) low production efficiency, oxidation solution temperature are difficult
With control；(2) oxidization time is grown, and power consumption is big, and water consumption is also big；(3) highly basic, strong acid casualty accident easily occurs.How should
Oxidation processes are carried out to aluminium base and do not produce high pollution, high energy consumption again, are current problems faceds.
The content of the invention
The present invention is directed to the problem of existing aluminium base surface oxidation technological effect is bad, there is provided a kind of aluminium base plate surface life
Thing handle oxidation technology, technique is simple, and cost is low, no chemical contamination problem, and the pellumina of aluminium base plate surface have compared with
Good adhesion.
Technical scheme, inorganic chemistry oxidation and the electroxidation of high pollution high energy consumption are avoided, and in aluminium sheet table
The fine and close alundum (Al2O3) layer of face generation, has higher insulation and a thermal conduction characteristic, fine and close oxide layer have it is uniform, stably,
The characteristics of consistent, the heat conductive insulating characteristic of aluminum-based copper-clad plate greatly improved, and do not produce industrial pollution and energy loss.
The method that technical scheme utilizes biological oxidation, aluminium base is carried out under sour environment using acidophil
Processing, with circulating water flushing, fine and close pellumina is generated on aluminium base.
Technical scheme is specially：A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried.
It is further preferred that the oil removal treatment of step 1) is to handle 1-2h, alkaline degreasing liquid at room temperature with alkaline degreasing liquid
For sodium hydroxide solution or potassium hydroxide solution.
It is further preferred that the oil removal treatment of step 1) is glass marble bead, globular glass ball is sprayed to aluminium base
Plate surface removes oil mark, and it is 200-300mm to control jet length, and jet angle is 50-55 degree, injection pressure 3-4kg/mm2。
It is further preferred that the oxidation processes of step 2) are to immerse aluminium base in the waterborne liquid containing acidophil, it is thermophilic
The addition of sour bacterium is 5-1000g/L, preferably 50-500g/L, more preferably 300g/L, and the pH of waterborne liquid is 2-6, dip time
For 1-50h, preferably 5-10h, more preferably 8h.
It is further preferred that air is passed through in the oxidation processes of step 2) into steeping liq, the intake of air
For 1-5L/h, preferably 3L/h.
It is further preferred that the drying temperature of step 3) is 50-80 DEG C.
Biological oxidation is carried out using acidophil in technical scheme, acidophil can grow numerous under sour environment
Grow, and most acidophil is aerobic, can obtain energy by aoxidizing.Inventors believe that in technical scheme
In, rational course of reaction is：Acidophil sucks ability to hydrogen ion with certain, and can be carried out by aerobic reaction
To obtain energy, the oxygen evolution in water is produced oxidation reaction with aluminium and produces alundum (Al2O3), with circulation oxidation reaction by acidophil
Water is flushed to filter the thalline reacted, and the Al of densification is generated on aluminium sheet2O3。
With the oxidation technology of the biological treatment of the present invention, its advantage is that the film layer of generation is fine and close, and it is wear-resisting, corrosion resistance is good,
Film surface is bright, bright in luster.This oxide-film has fabulous tack, the performance such as anti-corrosion, wear-resisting, UV resistant, weather-proof.
The reagent polluted without using generation environment, not electricity consumption, technique is also relatively simple, and the requirement to base material is relatively low, cost also compared with
It is low.
The invention has the advantages that：
Chemical oxide film obtained by technical scheme is iris, and it is improve aluminium and aluminium alloy anti-that it, which is acted on,
Corrosive power, and strengthen the adhesion of matrix and coating.
Technical scheme meets environmental requirement.All reagents and raw material are nontoxic or low toxicity compounds, are free of
The heavy metal such as Cr VI and lead cadmium, without using strong acid such as hydrofluoric acid, nitric acid, sulfuric acid.
Technical scheme cost is low, good economy performance, is conventional commercial product, purchases conveniently.
Technical scheme process is simple.Need only to aluminium base pretreatment, oxidation processes, the step of washing and drying
Suddenly, the preprocessing process of aluminium base can be omitted even for preferable aluminium base board raw material, is closed after oxidation processes without increasing
Process, simplify technological process.
Embodiment
The present invention is described below in more detail to contribute to the understanding of the present invention.
It should be appreciated that the term or word that use in the specification and in the claims are not construed as having
The implication limited in dictionary, and be interpreted as on the basis of following principle having and its implication one in the context of the present invention
The implication of cause：The concept of term can be limited suitably by inventor for the best illustration to the present invention.
Embodiment 1
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；Described oil removal treatment is use
Alkaline degreasing liquid handles 2h at room temperature, and alkaline degreasing liquid is sodium hydroxide solution.
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
50g/L, the pH of waterborne liquid is 2, dip time 40h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 50 DEG C.
Embodiment 2
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Described oil removal treatment is to handle 2h at room temperature with alkaline degreasing liquid, and alkaline degreasing liquid is potassium hydroxide solution.
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
500g/L, the pH of waterborne liquid is 4, dip time 10h.
Air is passed through in described oxidation processes into steeping liq, the intake of air is 3L/h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 70 DEG C.
Embodiment 3
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Described oil removal treatment is glass marble bead, and globular glass ball is sprayed to aluminium base plate surface and removes oil mark,
It is 300mm to control jet length, and jet angle is 50 degree, injection pressure 3kg/mm2。
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
300g/L, the pH of waterborne liquid is 2, dip time 8h.Air is passed through in oxidation processes into steeping liq, air
Intake is 3L/h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 80 DEG C.
Embodiment 4
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Described oil removal treatment is glass marble bead, and globular glass ball is sprayed to aluminium base plate surface and removes oil mark,
It is 250mm to control jet length, and jet angle is 55 degree, injection pressure 4kg/mm2。
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
800g/L, the pH of waterborne liquid is 3, dip time 10h.Air, air are passed through in oxidation processes into steeping liq
Intake be 3L/h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 60 DEG C.
Embodiment 5
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Described oil removal treatment is glass marble bead, and globular glass ball is sprayed to aluminium base plate surface and removes oil mark,
It is 250mm to control jet length, and jet angle is 55 degree, injection pressure 4kg/mm2。
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
300g/L, the pH of waterborne liquid is 3, dip time 8h.Air is passed through in oxidation processes into steeping liq, air
Intake is 3L/h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 60 DEG C.
Embodiment 6
A kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Described oil removal treatment is glass marble bead, and globular glass ball is sprayed to aluminium base plate surface and removes oil mark,
It is 250mm to control jet length, and jet angle is 55 degree, injection pressure 4kg/mm2。
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates oxygen
Change aluminium dense film；
Described oxidation processes are to immerse aluminium base in the waterborne liquid containing acidophil, and the addition of acidophil is
500g/L, the pH of waterborne liquid is 3, dip time 10h.Air, air are passed through in oxidation processes into steeping liq
Intake be 3L/h.
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried, drying temperature is 60 DEG C.
Performance test is carried out to the aluminium base of gained, items test uses the standard method of this area, such as GB/T9792-
1988 film weight, GB/T10125-1997 corrosion resistance, GB/T9286-1988 adhesive force.Test result is as shown in the table.
| Outward appearance (range estimation) | Film weight g/m2 | Corrosion resistance (open-assembly time) | Adhesive force | |
| Embodiment 1 | It is golden yellow | 1.2 | 356 | 1 grade |
| Embodiment 2 | It is golden yellow | 2.0 | 360 | 1 grade |
| Embodiment 3 | Iris | 1.6 | 358 | 1 grade |
| Embodiment 4 | Iris | 2.1 | 380 | 1 grade |
| Embodiment 5 | Iris | 2.2 | 380 | 1 grade |
| Embodiment 6 | Iris | 2.0 | 375 | 1 grade |
The method that the present invention utilizes biological oxidation, is handled aluminium base using acidophil under sour environment, with following
Ring water is rinsed, and the pellumina of densification is generated on aluminium base, and products obtained therefrom is 1.2- for golden yellow or iris, film weight
2.2g/m2, corrosion proof open-assembly time, adhesive force was 1 grade in more than 350h.
The preferred embodiment for the present invention is the foregoing described, so it is not limited to the present invention.Those skilled in the art couple
Embodiment disclosed herein can carry out improvement and the change without departing from scope and spirit.
Claims (6)
1. a kind of aluminium base surface biological handles oxidation technology, including：
Step 1), aluminium base pretreatment, aluminium base plate surface is subjected to oil removal treatment, washing；
Step 2), the oxidation processes of aluminium base, pretreated aluminium base is subjected to biological bacterium processing oxidation, generates aluminum oxide
Dense film；
Step 3), the cleaning-drying of aluminium base, the aluminium base after oxidation processes is washed, dried.
2. oxidation technology according to claim 1, it is characterised in that the oil removal treatment of step 1) is with alkaline degreasing liquid room
The lower processing 1-2h of temperature, alkaline degreasing liquid is sodium hydroxide solution or potassium hydroxide solution.
3. oxidation technology according to claim 1, it is characterised in that the oil removal treatment of step 1) is at glass marble shot-peening
Reason, globular glass ball is sprayed to aluminium base plate surface and removes oil mark, it is 200-300mm, jet angle 50-55 to control jet length
Degree, injection pressure 3-4kg/mm2。
4. oxidation technology according to claim 1, it is characterised in that the oxidation processes of step 2) are to immerse aluminium base to contain
Have in the waterborne liquid of acidophil, the addition of acidophil is 5-1000g/L, preferably 50-500g/L, more preferably 300g/L, water
The pH of property liquid is 2-6, dip time 1-50h, preferably 5-10h, more preferably 8h.
5. oxidation technology according to claim 4, it is characterised in that to steeping liq in the oxidation processes of step 2)
In be passed through air, the intake of air is 1-5L/h, preferably 3L/h.
6. oxidation technology according to claim 1, it is characterised in that the drying temperature of step 3) is 50-80 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110565086A (en) * | 2019-10-23 | 2019-12-13 | 常州澳弘电子股份有限公司 | Aluminum substrate surface biological treatment oxidation process |
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| US20170152603A1 (en) * | 2015-11-30 | 2017-06-01 | Industry-Academic Cooperation Foundation, Yeungnam University | Method for surface treatment of metals using bacteria |
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| CN1924042A (en) * | 2006-10-13 | 2007-03-07 | 中国铝业股份有限公司 | Method of bacterial eliminating sulfur in high sulfur bauxite |
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