CN107460467A - Application aluminium Low-Temperature Phosphate Liquid - Google Patents
Application aluminium Low-Temperature Phosphate Liquid Download PDFInfo
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- CN107460467A CN107460467A CN201710593859.1A CN201710593859A CN107460467A CN 107460467 A CN107460467 A CN 107460467A CN 201710593859 A CN201710593859 A CN 201710593859A CN 107460467 A CN107460467 A CN 107460467A
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- parts
- acid
- water
- zinc oxide
- diethylentriamine
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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
- C23C22/07—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 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
Abstract
The invention discloses application aluminium Low-Temperature Phosphate Liquid, including diethylentriamine penta-methylene base phosphonic acids, 0.7~2 part of phytic acid, 120~160 parts of phosphoric acid, 32~48 parts of zinc oxide, 20~40 parts of nitric acid, 1~6 part of nickel nitrate and 1400~2000 parts of the water that parts by weight are 3~6 parts.This phosphating solution is free of noxious material nitrite, and the aluminium after phosphatization rolls up corrosion stability and wearability is preferable；Phosphatization temperature is low, saves the energy, phosphating time is short, improves production efficiency；Formula material is simple, is easily controlled during actual production.
Description
Technical field
The present invention relates to application aluminium Low-Temperature Phosphate Liquid.
Background technology
Application aluminium also known as spraying aluminium, application aluminium volume, spraying aluminium volume.Its preparation process, which is generally cleaned, (to be removed aluminium volume rolling
One layer of lubricating oil, anti-oxidation grease and the various dirts of surface attachment when processed) → chemical conversion (add industrial chemicals with aluminium roll up surface shape
Into oxide-film) → application → baking.It is more at present to form phosphatization on aluminium volume surface by the way of phosphatization in formation process
Film, normal low temperature phosphor turn into trend, mainly have physics promotion law, chemically assist in method and electrochemistry promotion law；Physics promotion law has
Immersion phosphorating treatment and spray phosphorating treatment.Compared with immersion operation, strength spray webbing faster, the time it is shorter (1.0~
1.5min) concentration and temperature are relatively low, and equipment and space are further reduced, it is easy to accomplish automatically control, but the phosphorus of gained
It is nearly all H films [Zn to change film3(PO4)2〃4H2O], and it is mainly P films [Zn to impregnate rule2Fe(PO4)2〃4H2O].In phosphating solution
Addition accelerator is that often low temperature phosphor handles one of wide variety of method at present, normal temperature phosphating can not spontaneous progress, it is necessary to plus
Enter certain accelerator and just can guarantee that phosphating reaction is smoothed out.But current phosphating solution typically contains noxious material nitrous acid
Salt, and aluminium is rolled up after phosphatization corrosion stability and wearability be not high.
Authorization Notice No. is CN 102817027B patent：A kind of Low-Temperature Phosphate Liquid, configured by weight by following raw material
Form：Phosphatase 11 70-180, zinc oxide 48-52, sodium molybdate 2-3, citric acid 4-6, sodium perborate 1-2, sodium carbonate 2-2.5, chromic acid
0.8-1.2, water 1700-1800；Its operating temperature is low, and the time is short, and energy consumption is small, can generate a kind of function admirable in steel surface
Fine and close phosphatization crystalline film；But the steel corrosion resistance after phosphatization and wearability are general.Authorization Notice No. is the B of CN 102418094
Patent：Low temperature phosphor technique is used in cold forming processing, and it includes：Phosphate radical, zinc ion, nitrate anion and dissolving metallic element, matter
Amount proportioning is as follows：The mass ratio of zinc ion and phosphate radical：0.5-1.3；The mass ratio of nitrate anion and phosphate radical：1-2；Dissolving
The mass ratio of metallic element ion and phosphate radical：0-0.015, its accelerator are natrium nitrosums.
The content of the invention
Present invention mainly solves technical problem be, there is provided application aluminium Low-Temperature Phosphate Liquid, without noxious material nitrous acid
Salt, and the aluminium after phosphatization rolls up corrosion stability and wearability is preferable；Phosphatization temperature is low, saves the energy, phosphating time is short, improves life
Produce efficiency；Formula material is simple, is easily controlled during actual production.
The technical solution adopted for the present invention to solve the technical problems is：Application aluminium Low-Temperature Phosphate Liquid, including parts by weight are 3
~6 parts of diethylentriamine penta-methylene base phosphonic acids, 0.7~2 part of phytic acid, 120~160 parts of phosphoric acid, 32~48 parts
Zinc oxide, 20~40 parts of nitric acid, 1~6 part of nickel nitrate and 1400~2000 parts of water.Due to phytic acid molecule
In have can be with 24 oxygen atoms of metal combination, 12 hydroxyls and 6 phosphates, therefore phytic acid is that metal is multiple tooth
Chelating agent, with easily forming one layer of fine and close unimolecule diaphragm in metal surface during metal complex, it can effectively prevent O2Deng entrance
Metal surface, so as to resist corrosion of metal.Because the unimolecule diaphragm with organic coating has similar chemical property, together
When due also to organic coating chemical action can occur for the hydroxyl and phosphate isoreactivity group contained in film layer, therefore through inositol
There is very high corrosion resistance the treated metal surface of six phosphate esters, and has stronger cementability with organic coating.And diethylene
Triamine penta-methylene base phosphonic acids can be with Zn2+Chelate attached collection and form one layer of corrosion resistant film on aluminium volume surface, therefore it can improve phosphorus
The corrosion resistance and wearability that aluminium is rolled up after change.The collective effect of diethylentriamine penta-methylene base phosphonic acids and phytic acid is then significantly
Enhance the corrosion resistance and wearability of the volume of the aluminium after phosphatization.Aluminium is rolled up at 20-30 DEG C and carries out phosphating coat obtained by phosphorating treatment
The resistance to copper sulphate time, phosphatization area reached 150-170m more than 18 minutes2/ kg, film weight is up to 4.3-5g/m2。
As the further improvement of application aluminium Low-Temperature Phosphate Liquid of the present invention, the preparation of diethylentriamine penta-methylene base phosphonic acids
Journey is as follows：1mol diethylentriamine and 5mol phosphorous acid and 36% hydrochloric acid 100ml and 100ml water, are stirred, then after mixing
80 DEG C are warming up to, 5mol formaldehyde is added dropwise, is kept after 110 DEG C~120 DEG C are warming up to after being added dropwise 2 hours, then decompression is steamed
The 150ml aqueous solution is distillated, cooling and standings, after waiting crystal to separate out, filters out crystal, and will be filtered with water with after ethanol washing and drying
The crystal gone out is diluted to concentration 60%.
As the further improvement of application aluminium Low-Temperature Phosphate Liquid of the present invention, diethylentriamine penta-methylene base phosphonic acids is 4 parts, flesh
The phosphate ester of alcohol six is 1 part, 50 parts of phosphatase 11,38 parts of zinc oxide, 40 parts of nitric acid, the water of 3 parts and 1900 parts of nickel nitrate；Described phosphorus
Change liquid preparation method be：Stirring after 150 parts of phosphoric acid and 40 parts of nitric acid are dissolved in 1900 parts of water, it is small to place 12~24
When；The zinc oxide of formula rate is added, is sufficiently stirred, 9-11 hours is cooled down, obtains the mixed liquor of phosphoric acid and zinc oxide；Will formula
In other compositions be sufficiently mixed after, be added in foregoing mixed liquor, be sufficiently stirred.
Beneficial effects of the present invention have：
1st, without noxious material nitrite, and the aluminium after phosphatization rolls up corrosion stability and wearability is preferable；
2nd, phosphatization temperature is low, saves the energy, phosphating time is short, improves production efficiency；
3rd, formula material is simple, is easily controlled during actual production；
4th, the corrosion resistance of the aluminium volume after phosphatization and wearability are very high；Aluminium is rolled up at 20-30 DEG C and carried out obtained by phosphorating treatment
The resistance to copper sulphate time of phosphating coat, phosphatization area reached 150-170m more than 18 minutes2/ kg, film weight is up to 4.3-5g/m2。
Embodiment
With reference to embodiment, the embodiment of the present invention is further described.Following examples are only used for more
Add and clearly demonstrate technical scheme, and can not be limited the scope of the invention with this.
Embodiment one：
Application aluminium Low-Temperature Phosphate Liquid, including the diethylentriamine penta-methylene base phosphonic acids that parts by weight are 4 parts is, phytic acid
Fat is 1 part, 50 parts of phosphatase 11,38 parts of zinc oxide, 40 parts of nitric acid, the water of 3 parts and 1900 parts of nickel nitrate；The system of described phosphating solution
Preparation Method is：Stirring after 150 parts of phosphoric acid and 40 parts of nitric acid are dissolved in 1900 parts of water, is placed 12~24 hours；Add
The zinc oxide of formula rate, is sufficiently stirred, and cools down 9-11 hours, obtains the mixed liquor of phosphoric acid and zinc oxide；By its in formula
After its composition is sufficiently mixed, it is added in foregoing mixed liquor, is sufficiently stirred.Wherein diethylentriamine penta-methylene base phosphonic acids
Preparation process is as follows：1mol diethylentriamine and 5mol phosphorous acid and 36% hydrochloric acid 100ml and 100ml water, are stirred after mixing
Mix, then heat to 80 DEG C, 5mol formaldehyde is added dropwise, keep 2 hours after 110 DEG C~120 DEG C are warming up to after being added dropwise, then
It is evaporated under reduced pressure out the 150ml aqueous solution, cooling and standings, after waiting crystal to separate out, filters out crystal, and with using water after ethanol washing and drying
The crystal that will filter out is diluted to concentration 60%.
Embodiment two：
It is with the difference of embodiment one：Application aluminium Low-Temperature Phosphate Liquid, including the first of diethylentriamine five that parts by weight are 3 parts
Support group phosphonic acids is, phytic acid is 0.7 part, 20 parts of phosphatase 11,32 parts of zinc oxide, 20 parts of nitric acid, 1 part of nickel nitrate and 1400
The water of part；The preparation method of described phosphating solution is：Stirred after 120 parts of phosphoric acid and 20 parts of nitric acid are dissolved in 1400 parts of water
Mix.
Embodiment three：
It is with the difference of embodiment one, application aluminium Low-Temperature Phosphate Liquid, including the first of diethylentriamine five that parts by weight are 6 parts
Support group phosphonic acids is, phytic acid is 2 parts, 60 parts of phosphatase 11,48 parts of zinc oxide, 40 parts of nitric acid, 6 parts and 2000 parts of nickel nitrate
Water；The preparation method of described phosphating solution is：Stirred after 160 parts of phosphoric acid and 40 parts of nitric acid are dissolved in 2000 parts of water
Mix.
Example IV：
It is with the difference of embodiment one, application aluminium Low-Temperature Phosphate Liquid, including the first of diethylentriamine five that parts by weight are 3 parts
Support group phosphonic acids is, phytic acid is 2 parts, 20 parts of phosphatase 11,40 parts of zinc oxide, 30 parts of nitric acid, 4 parts and 1500 parts of nickel nitrate
Water；The preparation method of described phosphating solution is：Stirred after 120 parts of phosphoric acid and 30 parts of nitric acid are dissolved in 1500 parts of water
Mix.
Aluminium volume after phosphatization in embodiment one to four is respectively taken one section, sand for surface paper is polished, and is then placed in 60% salt
20~30min of soaking at room temperature in acid solution, 1min is rinsed with circulating water after taking-up, puts into the phosphating solution prepared and locates immediately
Reason, 25~30 DEG C of temperature, time 30min, then takes out naturally dry.After being placed in the workpiece after phosphatization indoors air,
Phosphatization film properties are tested.
Test result such as following table：
After tested, most preferred embodiment is embodiment one, and its copper-bath titrates 18min to be occurred without soil Red, and other are each
Item index is also preferable.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (3)
1. application aluminium Low-Temperature Phosphate Liquid, it is characterised in that including parts by weight be 3~6 parts diethylentriamine penta-methylene base phosphonic acids,
0.7~2 part of phytic acid, 120~160 parts of phosphoric acid, 32~48 parts of zinc oxide, 20~40 parts of nitric acid, 1~6 part
Nickel nitrate and 1400~2000 parts of water.
2. application aluminium Low-Temperature Phosphate Liquid according to claim 1, it is characterised in that the diethylentriamine penta-methylene base phosphine
The preparation process of acid is as follows：1mol diethylentriamine and 5mol phosphorous acid and 36% hydrochloric acid 100ml and 100ml water, mixing
After stir, then heat to 80 DEG C, 5mol formaldehyde be added dropwise, kept for 2 hours after 110 DEG C~120 DEG C are warming up to after being added dropwise,
Then the 150ml aqueous solution is evaporated under reduced pressure out, cooling and standings, after waiting crystal to separate out, filters out crystal, and with after ethanol washing and drying
The crystal that will filter out with water is diluted to concentration 60%.
3. application aluminium Low-Temperature Phosphate Liquid according to claim 1, it is characterised in that the diethylentriamine penta-methylene base phosphine
Acid is 4 parts, phytic acid is 1 part, 50 parts of phosphatase 11,38 parts of zinc oxide, 40 parts of nitric acid, 3 parts and 1900 parts of nickel nitrate
Water；The preparation method of described phosphating solution is：Stirring after 150 parts of phosphoric acid and 40 parts of nitric acid are dissolved in 1900 parts of water,
Place 12~24 hours；The zinc oxide of formula rate is added, is sufficiently stirred, cools down 9-11 hours, obtains phosphoric acid and zinc oxide
Mixed liquor；After other compositions in formula are sufficiently mixed, it is added in foregoing mixed liquor, is sufficiently stirred.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710593859.1A CN107460467A (en) | 2017-07-20 | 2017-07-20 | Application aluminium Low-Temperature Phosphate Liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710593859.1A CN107460467A (en) | 2017-07-20 | 2017-07-20 | Application aluminium Low-Temperature Phosphate Liquid |
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| Publication Number | Publication Date |
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| CN107460467A true CN107460467A (en) | 2017-12-12 |
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| CN201710593859.1A Pending CN107460467A (en) | 2017-07-20 | 2017-07-20 | Application aluminium Low-Temperature Phosphate Liquid |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061626A (en) * | 1990-11-20 | 1992-06-03 | 新乡市东海配电设备厂 | A kind of new phosphide liquid and preparation method thereof |
| CN102703889A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Low-temperature single-component zinc series phosphating solution and preparation method thereof |
| CN103469190A (en) * | 2013-09-22 | 2013-12-25 | 无锡阳工机械制造有限公司 | Composite type low-temperature phosphating solution |
| CN104250735A (en) * | 2013-06-26 | 2014-12-31 | 无锡洛社科技创业有限公司 | Preparation method of steel plate low-temperature environmental-protection phosphating liquid |
| CN104264142A (en) * | 2014-10-09 | 2015-01-07 | 无锡康柏斯机械科技有限公司 | Normal-temperature wiping phosphating solution and preparation method thereof |
| CN106757280A (en) * | 2016-12-13 | 2017-05-31 | 河南恒星钢缆股份有限公司 | A kind of low temperature On-line electrolytic dissolution Phosphating Solution |
-
2017
- 2017-07-20 CN CN201710593859.1A patent/CN107460467A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061626A (en) * | 1990-11-20 | 1992-06-03 | 新乡市东海配电设备厂 | A kind of new phosphide liquid and preparation method thereof |
| CN102703889A (en) * | 2012-05-28 | 2012-10-03 | 武汉永正科技发展有限公司 | Low-temperature single-component zinc series phosphating solution and preparation method thereof |
| CN104250735A (en) * | 2013-06-26 | 2014-12-31 | 无锡洛社科技创业有限公司 | Preparation method of steel plate low-temperature environmental-protection phosphating liquid |
| CN103469190A (en) * | 2013-09-22 | 2013-12-25 | 无锡阳工机械制造有限公司 | Composite type low-temperature phosphating solution |
| CN104264142A (en) * | 2014-10-09 | 2015-01-07 | 无锡康柏斯机械科技有限公司 | Normal-temperature wiping phosphating solution and preparation method thereof |
| CN106757280A (en) * | 2016-12-13 | 2017-05-31 | 河南恒星钢缆股份有限公司 | A kind of low temperature On-line electrolytic dissolution Phosphating Solution |
Non-Patent Citations (2)
| Title |
|---|
| 唐晖 等: "二乙撑三胺五甲撑基膦酸在低温磷化中的应用", 《材料保护》 * |
| 陈洪希: "肌醇六磷酸脂在低温磷化中的应用", 《电镀与精饰》 * |
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