CN100410422C - Nanometer alumina composite phosphatized film and preparation method thereof - Google Patents
Nanometer alumina composite phosphatized film and preparation method thereof Download PDFInfo
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- CN100410422C CN100410422C CNB2006100456537A CN200610045653A CN100410422C CN 100410422 C CN100410422 C CN 100410422C CN B2006100456537 A CNB2006100456537 A CN B2006100456537A CN 200610045653 A CN200610045653 A CN 200610045653A CN 100410422 C CN100410422 C CN 100410422C
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- phosphate coating
- al2o3
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Abstract
The present invention adopts nano alpha-Al2O3 powder to modify a phosphate coating; nano alpha-Al2O3(100 to 120 nm) is added in phosphorizing liquids of a zinc-calcium-manganese tertiary cation system; proper dispersing agents AOS are selected so that the nano alpha-Al2O3 is uniformly dispersed in the phosphorizing liquids; the nano alpha-Al2O3 and the phosphate coating are together deposited on steel surfaces in a certain temperature range after carbon steel test samples are phosphated, and a nano alpha-Al2O3 phosphate coating is formed. The results of scanning electron microscopes, energy spectrums, electron microprobes and X-ray diffraction show that the alpha-Al2O3 is uniformly distributed in the composite coating; the phosphate coating layer comprises the main ingredients of alpha-Al2O3, Zn3(PO4)2.4H2O, Mn3(PO4)2.2H2O, ZnMn2(PO4)2.4H2O and Fe. The nano alpha-Al2O3 is added to the phosphate coating, so the wear resistance of the phosphate coating is obviously improved. Under the optimal prescription conditions, the number of the times of the wear resistance of the phosphate coating is enhanced to 150 from 72 which is the number of times of the wear resistance of the phosphate coating when the nano alpha-Al2O3 is not added, the lost weight is reduced by 2.5 times, and meanwhile, the wear coefficient is reduced to 0.14 from 0.65.
Description
Technical field
The invention belongs to Materials science and sufacing field.
Background technology
Phosphatization is one of process for treating surface that extensively adopts, and is applied to the every field of industry, as automobile making, space flight and aviation, mechanical workout, household electrical appliance etc.Its purposes can be divided into the preceding bottoming phosphatization of lacquer; Antirust, the anti-corrosion phosphatization of using; Lubricated, wear resistant friction reducing phosphatization; Electrical isolation and ornamental phosphatization.In the past the bonderizing of steel surface was used for more anticorrosion, about attrition resistant applied research seldom.For the phosphatization such as a lot of motion bearing parts such as gear, piston ring, valve, usually adopt simple zinc system or manganese-series phosphorized processing, for example the Wear-resistance Medium Temperature Mananese Phosphating Process take Mazhev salt or manganese nitrate as Phosphating Solution master composition.And manganese-series phosphorized film has better wear resistance than zinc phosphating film, but there is a lot of disadvantages in actual applications in traditional manganese-series phosphorized technology, and is long as the treatment process time, temperature is high, and the solidity to corrosion of film is poor, and the phosphatization sediment is many etc.Suddenly to be the problem that exists in the phosphating process in order overcoming existing, to have carried out in recent years the research about wear-resisting phosphating coat and wear-resisting complex phosphate coating aspect.Studied multiple metal ion K as Hao Haiyan etc.
+, Na
+, Ca
2+, Mn
2+, Ni
+Content, temperature, acid the influence of processing parameter to phosphorization filming such as compare, developed the high-efficiency abrasion-proof composite phosphorized liquid, its phosphatize phosphate coat has good thermostability and wear-resisting abrasion resistance (material protection, 2003,36 (1): 37-38).Li Jingang has been studied different promotor, additive, and processing parameter has been developed wear-resisting composite phosphorized liquid (Shenyang Engineering College's journal, 2005,1 (4): 79-81,87) to the influence of phosphatize phosphate coat.Prime minister Lee adds a certain amount of Ni in conjunction with Zinc phosphating and manganese-series phosphorized advantage
2+And special auxiliary agent, by regulate processing method obtain composite phosphorized liquid (mechanical engineer, 2005,2:76-77).The result shows: part is through the more effective running-in wearing-in period that shortened of the more common manganese-series phosphorized processing of composite phosphorized processing, and significant prolongation is stablized wearing-in period, effectively reduces about 1 times of coefficient of friction.Yuan Qiang makes PTFE and the manganous phosphate salt surperficial common deposited at steel by add tetrafluoroethylene (being called for short PTFE) emulsion FL in common manganese phosphating liquor, forms composite membrane.Experiment shows: FL content reaches 8ml/l in solution, and when treatment temperature was 65 ℃, wearability the best of skin covering of the surface will improve about 6 times than it single manganese phosphate coating.Scanning electron microscope analysis finds that PTFE is in the space that pencil evenly is embedded in manganous phosphate salt (journal of Zhejiang university, 1998,1).
However, in production application, most wear-resisting phosphatization temperature height need lot of energy, and the solution evaporation capacity is big, and composition changes fast, causes the Phosphating Solution instability, and the Phosphating Solution life-span is short, the product quality inequality, and contain poisonous additive etc.Therefore reduce phosphatization temperature, reduce the sediment growing amount, the research of developing nontoxic high abrasion phosphatization is still a brand-new problem.
Because nano particle has skin effect, the characteristics such as small-size effect, the in recent years research of nano material and application is a focus of at present domestic and international material science research.As people such as Zhao Lulu research through nanometer SiO
2The Ni-P-nanometer SiO that deposits after the modification
2Composite deposite has better hardness, wear resistance (Liaoning Normal University's journal 2004,9 (27): 3).The wear resistance of adding nano SiC brushing coating and hardness all have raising by a relatively large margin in quick electronickelling liquid, frictional coefficient reduces, the nano SiC that adds mainly is distributed in the fault location of coating and the coating (Xu Longtang between the nickel crystallite, Xu Binshi, Zhou Meiling etc. Chinese Surface Engineering 1999,12 (3): 7).
Because nanometer Al
2O
3The volume that has, surface interface, quantum size, and the effect such as macroscopical tunnel make it show unique performance at aspects such as power, heat, light, magnetic, catalysis, electricity, have broad prospects.α type nanometer Al particularly
2O
3Have that crystalline phase is stable, hardness is high, good stability of the dimension, high strength, the characteristic such as heat-resisting, corrosion-resistant. can be widely used in the strengthening and toughening of the products such as various plastics, rubber, pottery, refractory material, the anti-wear performance of compactness, fineness, cold and hot fatigability, fracture toughness, creep-resistant property and macromolecular material product that particularly improves pottery is particularly remarkable.
The objective of the invention is to add granularity in Phosphating Solution is α-Al of 100-120nm
2O
3Powder makes it and the surperficial codeposition of phosphating coat at steel, forms nanometer α-Al
2O
3Complex phosphate coating utilizes α-Al
2O
3With the characteristic of nano material, wearability enhancing, the coefficient of friction of film are reduced, to strengthen wear resistant friction reducing and the lubrication of phosphating coat.This is a kind of ways and means of new enhancing phosphatize phosphate coat wear resistance.
Summary of the invention
Technical solution of the present invention is achieved like this:
Chosen a kind of zinc calcium manganese triple cationic system phosphorization liquid as basic phosphatization liquid, its main component is:
ZnO 15-20g/l, H
3PO
425-30ml/l, HNO
315-20ml/l, Mn (H
2PO
4)
25-10g/l, Ni (NO
3)
21-5g/l, Ca (NO
3)
22-3g/l, HAS 2-5g/l, sodium nitrate 1-3g/l, tartaric acid 2-5g/l, citric acid 1-5g/l;
Xiang Yisheng adds dried dispersant A OS 0.5-4.0 gram in should the basis Phosphating Solution, utilize mechanical agitation after, add again α-Al that dried granularity is 100-120nm
2O
3Powder 0.1-5.0 gram fully stirs again, under 50 ℃ of-90 ℃ of temperature, phosphatization 9-12 minute, makes nanometer α-Al
2O
3In parkerizing process, with the phosphating coat codeposition, form nanometer α-Al
2O
3Complex phosphate coating.Utilize nano material and Al
2O
3Characteristic, strengthen phosphating coat wear resistant friction reducing and lubrication.
Wherein dispersant A OS can to nanoparticulate dispersed, prevent its agglomerate in Phosphating Solution.The pre-treatment of carbon steel test specimen adopts weak base except grease, the watery hydrochloric acid rust cleaning, and washing is adopted in post processing.
In addition, once used the tensio-active agent of being other as dispersion agent in the experimentation of the present invention, they are: Sodium dodecylbenzene sulfonate, OP-10, sodium laurylsulfonate.Simultaneously also attempted the method for mechanical stirring, ultrasonic dispersing.
The method that the present invention examines or check the phosphatize phosphate coat wear resistance is in phosphatize phosphate coat surface friction method with silicon carbide paper, implementation method is the intercepting one piece size No. 600 water mill fine sandpapers close with the test specimen area, 50 gram counterweights bear a heavy burden on sand paper, rub on the phosphatize phosphate coat surface then, till seeing the metal polish matrix, calculate the weightless numerical value before and after its friction, and choose 4 of tow sides and weigh its wear resistance with the average friction number of times.
In Phosphating Solution, add nanometer α-Al
2O
3Front and back phosphating coat Performance Ratio sees Table 1.
Observe the microscopic appearance of Fig. 1 and Fig. 2 phosphating coat, can find out, not plus nano α-Al
2O
3The phosphating coat grain contours obvious, and plus nano α-Al
2O
3The phosphating coat intergranule surrounded, fill by small nano particle.
To plus nano α-Al
2O
3Complex phosphate coating carry out electron probing analysis, investigate nanometer α-Al
2O
3Distribution situation in phosphating coat is seen Fig. 3.White point represents aluminium element among the figure, can find out Al
2O
3Distributing in phosphating coat is uniformly basically, and in fact also this uniform distribution can effectively strengthen the wearability of phosphating coat just.
Nanometer α-Al
2O
3Composite phosphorized film component EDAX results is seen Fig. 4.EDAX results shows that the phosphide composite film that adds nanometer contains O, P, Fe, Zn, Ca, Mn, Al, and the elementary composition content of complex phosphate coating sees Table 2.
With nanometer α-Al
2O
3Complex phosphate coating carries out X-ray diffraction analysis, learns that the main component of phosphorization membrane has: α-Al
2O
3, Zn
3(PO
4)
24H
2O, Mn
3(PO
4)
22H
2O, ZnMn
2(PO
4)
24H
2O and Fe see Fig. 5.
Two kinds of phosphating coats are done abrasion test at UMT-2 type abrasion wear test machine, and the coefficient of friction-time changing curve that obtains is seen Fig. 6 and Fig. 7.Can find out from two figure, along with the time changes, plus nano Al
2O
3After, the coefficient of friction ratio of phosphating coat is plus nano Al not
2O
3As seen phosphating coat low add nanometer Al
2O
3Can also play antifriction function.
Description of drawings
Fig. 1 is plus nano Al not
2O
3Phosphating coat SEM microscopic appearance figure, multiplication factor is 1000 times
Fig. 2 plus nano Al
2O
3Complex phosphate coating SEM microscopic appearance figure, multiplication factor is 1000 times
Fig. 3 plus nano Al
2O
3The electron probe scintigram of complex phosphate coating Al element, multiplication factor is 3000 times
Fig. 4 plus nano Al
2O
3Complex phosphate coating energy spectrum analysis figure, abscissa is energy (energy), ordinate is photoelectron intensity (cps)
Fig. 5 plus nano Al
2O
3The complex phosphate coating X-ray spectrogram, abscissa is angle (2 θ), ordinate is intensity (I)
Fig. 6 is plus nano Al not
2O
3Phosphating coat coefficient of friction-time changing curve, abscissa is time (second), ordinate is coefficient of friction
Fig. 7 plus nano Al
2O
3Complex phosphate coating coefficient of friction-time changing curve, abscissa is time (second), ordinate is coefficient of friction
At present, Application of micron in phosphorization technology, be there is not yet report both at home and abroad. The present invention is with nanometer α-Al2O
3Powder (100-120nm) joins in the Phosphating Solution, adopts surfactant as dispersant, makes nanometer α-Al2O
3Be dispersed in the Phosphating Solution, after phosphatization is processed, obtain nanometer α-Al2O
3At rete In equally distributed complex phosphate coating. The wearability of this complex phosphate coating is than plus nano Al not2O
3Phosphating coat, Greatly increase under same condition, the antifriction number of times is increased to 150 times by 72 times; Weight loss reduces 2.5 times; Coefficient of friction (COF.F) is reduced to 0.14 from 0.65. Increased the lubricity of complex phosphate coating.
Nanometer α of the present invention-Al2O
3The complex phosphate coating sufacing can be applicable to the requirements such as automobile, valve, piston The phosphatization of wearing piece, application prospect is considerable.
Embodiment
Embodiment
(1) chooses a kind of zinc calcium manganese triple cationic system phosphorization liquid as basic phosphatization liquid, get the pH value that one liter of this phosphatization liquid adds 8 gram sodium carbonate regulating solutions, finish smoothly to guarantee parkerizing process.Then, in one liter of this Phosphating Solution, add dried dispersant A OS2.5 gram, add again dried nanometer α-Al after fully stirring with mechanical agitator
2O
3Powder (100-120nm) 5 gram fully stirs again, and under 80 ℃ of temperature, the carbon steel test specimen that prior pre-treatment has been got well is put into Phosphating Solution and carried out phosphatization, and the time is 12 minutes.Test specimen after the phosphatization is compared with the test specimen that phosphatization under the condition obtains with identical phosphatization liquid phase, and wear resistance is significantly increased, and frictional coefficient reduces.
(2) get one liter of Phosphating Solution, add the pH value of 10 gram sodium carbonate regulating solutions, then, in one liter of this Phosphating Solution, add dried dispersant A OS1.5 gram, add again dried nanometer α-Al after fully stirring with mechanical agitator
2O
3Powder (100-120nm) 3.5 gram fully stirs again, and under 65 ℃ of temperature, the carbon steel test specimen that prior pre-treatment has been got well is put into Phosphating Solution and carried out phosphatization, and the time is 11 minutes.Test specimen after the phosphatization is compared with the test specimen that phosphatization under the condition obtains with identical phosphatization liquid phase, and wear resistance significantly improves, and frictional coefficient reduces.
The comparison of table 1 liang phosphating coat character
System is plus nano Al not2O
3Phosphating coat plus nano Al2O
3Phosphating coat
Film black gray expandable, no color differnece color are slightly darker than the former, no color differnece, structure cause
Outward appearance
Compact structure, close, a small amount of dust of no dust
Thickness (μ m) 16～17 18
Heavy (the g/m of film2) 22.42 24.82
Abrasion resistance (on average) 72 150
Weight loss (g) 0.0488 0.0199
Table 2 plus nano Al2O
3Complex phosphate coating elemental composition EDAX results
Element quality content (%) atom content (%)
O 35.88 62.87
P 17.75 16.07
Mn 1.02 0.52
Fe 4.16 2.09
Zn 39.46 16.92
Al 0.95 0.99
Ca 0.78 0.55
Amount to 100.00 100.00
Claims (2)
1. one kind by Phosphating Solution, nanometer α-Al
2O
3The nanometer α that makes with dispersant-Al
2O
3Complex phosphate coating is characterized in that made nanometer α-Al
2O
3The main component of complex phosphate coating is: α-Al
2O
3, Zn
3(PO
4)
24H
2O, Mn
3(PO4)
22H
2O, ZnMn
2(PO
4)
24H
2O and Fe; Nanometer α-Al
2O
3The quality percentage composition of each element is in the complex phosphate coating: O 35.88%, and P 17.75%, and Mn 1.02%, Fe4.16%, and Zn 39.46%, Al 0.95% and Ca 0.78%.
2. according to the described nanometer α of claim 1-Al
2O
3The preparation method of complex phosphate coating is characterized in that at first having chosen a kind of zinc calcium manganese triple cationic system phosphorization liquid as basic Phosphating Solution, and its main component is: ZnO 15-20g/l, H
3PO
425-30ml/l, HNO
315-20ml/l, Mn (H
2PO
4)
25-10g/l, Ni (NO
3)
21-5g/l, Ca (NO
3)
22-3g/l, HAS 2-5g/l, sodium nitrate 1-3g/l, tartaric acid 2-5g/l, citric acid 1-5g/l;
Then, Xiang Yisheng adds dried dispersant A OS 0.5-4.0 gram in should the basis Phosphating Solution, utilize mechanical agitation after, adding dry granularity again is α-Al of 100-120nm
2O
30.1-5.0 gram fully stirs again, under 50 ℃ of-90 ℃ of temperature, phosphatization 9-12 minute, makes nanometer α-Al
2O
3In parkerizing process, with the phosphating coat codeposition, form nanometer α-Al
2O
3Complex phosphate coating.
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|---|---|---|---|
| CNB2006100456537A CN100410422C (en) | 2006-01-10 | 2006-01-10 | Nanometer alumina composite phosphatized film and preparation method thereof |
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|---|---|---|---|
| CNB2006100456537A CN100410422C (en) | 2006-01-10 | 2006-01-10 | Nanometer alumina composite phosphatized film and preparation method thereof |
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| CN100410422C true CN100410422C (en) | 2008-08-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104651847A (en) * | 2013-11-25 | 2015-05-27 | 陈克华 | Steel surface rust conversion emulsion |
| CN104087987B (en) * | 2014-06-27 | 2017-01-18 | 哈尔滨工程大学 | Metal-plating composite and preparation method thereof |
| CN109609937B (en) * | 2018-12-06 | 2020-05-22 | 华南理工大学 | Method for preparing composite phosphating film by doping inorganic nanoparticles |
| CN111155076A (en) * | 2020-01-14 | 2020-05-15 | 山东建筑大学 | Process for preparing metal phosphating film based on ultrasonic waves |
| CN111733408A (en) * | 2020-05-29 | 2020-10-02 | 贵州水钢同鑫晟金属制品有限公司 | Steel strand phosphating accelerant and preparation method thereof |
| CN111778499A (en) * | 2020-06-05 | 2020-10-16 | 贵州水钢同鑫晟金属制品有限公司 | Method for manufacturing corrosion-resistant steel strand |
| CN114582618A (en) * | 2022-03-09 | 2022-06-03 | 合肥工业大学 | Nanoparticle-doped composite coating and preparation method and application thereof |
| CN115725964B (en) * | 2022-09-01 | 2023-06-02 | 东莞市颖兴金属表面处理材料有限公司 | Low-temperature slag-less phosphating solution and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000119866A (en) * | 1998-10-15 | 2000-04-25 | Kobe Steel Ltd | Phosphate film, aluminum member having phosphate film and production of phosphate film |
| CN1267691A (en) * | 1999-03-19 | 2000-09-27 | 王国民 | Water soluble rust-dissolving antirust paint and its production process |
| EP1258542A2 (en) * | 2001-05-18 | 2002-11-20 | Robert Bosch Gmbh | Functional coating and process for its production, in particular for wear protection, corrosion protection or for temperature isolation |
-
2006
- 2006-01-10 CN CNB2006100456537A patent/CN100410422C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000119866A (en) * | 1998-10-15 | 2000-04-25 | Kobe Steel Ltd | Phosphate film, aluminum member having phosphate film and production of phosphate film |
| CN1267691A (en) * | 1999-03-19 | 2000-09-27 | 王国民 | Water soluble rust-dissolving antirust paint and its production process |
| EP1258542A2 (en) * | 2001-05-18 | 2002-11-20 | Robert Bosch Gmbh | Functional coating and process for its production, in particular for wear protection, corrosion protection or for temperature isolation |
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| CN1804119A (en) | 2006-07-19 |
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