CN104694915A - Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material - Google Patents
Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material Download PDFInfo
- Publication number
- CN104694915A CN104694915A CN201410739754.9A CN201410739754A CN104694915A CN 104694915 A CN104694915 A CN 104694915A CN 201410739754 A CN201410739754 A CN 201410739754A CN 104694915 A CN104694915 A CN 104694915A
- Authority
- CN
- China
- Prior art keywords
- base material
- titanium alloy
- organic
- alloy base
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The organic-inorganic a passivating liquid for the surface treatment of a ship titanium alloy base material, which comprises the following main active ingredients: zirconate, phosphate, silicate and an N-containing organic heteroaromatic compound, an organic-inorganic passivating film can be formed on the surface of the titanium alloy base material by dip-coating or brush-coating construction for twice or three times, the compatibility between the base material and the organic coating can be enhanced, the adhesion strength of epoxy primer on the surface of titanium alloy base material can be improved to 10MPa from 7MPa, and the interfacial destruction rate is reduced to 1% from 30%. The organic-inorganic passivating liquid can be used for surface treatment of a ship titanium alloy base material, the adhesion strength of the surface coating can be effectively enhanced, and the organic-inorganic passivating liquid plays an important role in prolonging the service life of the coating, and has the wide application prospects.
Description
[technical field]
The present invention relates to chemical material technical field, be specifically related to a kind of for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution.
[background technology]
Known, titanium alloy surface very easily forms layer oxide film, non-activity group, and roughness is low, and organic coating is more difficult forms high-strength attachment on its surface.Therefore, for strengthening the bonding strength of coating, modification need be carried out to titanium alloy surface, to improve base surface roughness and activity.For a long time, titanium alloy surface treatment technology mainly adopts chromate conversion coating and phosphatize phosphate coat etc., and result of use is fine.Wherein, chromate conversion membrane technology is most effective means, but its strong toxicity and carinogenicity impel people to be devoted to research and develop treatment technology that is novel, environmental protection.
Carry out the more research about titanium alloy surface treatment solution abroad, as United States Patent (USP), US 7018486 [P] disclose a kind of non-hexavalent chromium, and the conversion film that solidity to corrosion is high, mainly comprise solubility chromic salt, fluorochemical and a kind of additive in its solution.Additive contains sequestrant or multichain ligand, is mainly salt acids and the ester class of phosphoramidic acid, as hydroxyl, alkyl, phosphoramidic acid, diethylaminomethyl phosphoric acid etc.The best in quality concentration of trivalent chromium compound is 0.5 ~ 8.0 g/L, and the best in quality concentration of fluorochemical is 0.5 ~ 18g/L, and the best in quality concentration of additive is 15 ~ 30 mg/L, and solution ph is 2.5 ~ 4.0; United States Patent (USP), US 5322870 [P] disclose a kind of Chrome-free In situ phosphatization treatment solution, primarily of amine and phosphorization agent composition.Phosphorization agent can be alkyl, phenyl or aryl phosphate ester, also can be alkyl, phenyl or aryl phosphoric acids.Form phosphate coating surface at substrate surface, top coat adhesion strength can be strengthened; United States Patent (USP), US 4988396 [P] disclose a kind of permanganate conversion film, and main component is permanganate, muriate and phosphoric acid salt etc., can obtain the conversion film with good corrosion resistance.The metal be suitable for has Al and Alalloy, titanium or titanium alloy, through suitable pre-treatment, can obtain the conversion film that solidity to corrosion is good, improves the adhesion strength of organic coating.
Find through retrieval, the people such as the Chen Yichi of BJ University of Aeronautics & Astronautics develop a kind of improvement titanium system surface conditioner, primarily of activeconstituents (titanium phosphate), composition such as basic metal (alkaline-earth metal) positively charged ion and dispersion stabilizer etc., solidity to corrosion can be formed good, and evenly, fine and closely woven phosphatize phosphate coat.The people such as the Tao Jie of Nanjing Aero-Space University adopt the method for differential arc oxidation to prepare porous TiO at titanium alloy surface
2rete, have studied the relation etc. of pore size and anchoring strength of coating, domesticly has no the relevant patent application of titanium alloy surface treatment solution and relevant report.
[summary of the invention]
For overcoming the deficiency existed in background technology, the invention provides a kind of for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, the present invention is with zirconate, phosphoric acid salt, silicate and contain N organic heterocyclic molecule for main film forming substance, by dip-coating or spraying coating process, the very thin organic-inorganic passive film of one deck can be formed at titanium alloy surface, improve the consistency of base material and surperficial organic coating, effectively strengthen the adhesion strength of coating, extend its work-ing life.
For realizing goal of the invention as above, the present invention adopts technical scheme as described below:
A kind of for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, moiety comprises by mass percentage:
Zirconate 1 ~ 3%;
Phosphoric acid salt 1 ~ 3%;
Silicate 0 ~ 1%;
Containing N organic heterocyclic molecule 2 ~ 3%;
Solvent 92 ~ 94%.
Described for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, described zirconate is potassium fluozirconate, sodium fluozirconate or ammonium fluozirconate.
Described for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, described phosphoric acid salt is Sodium hexametaphosphate 99, tripoly phosphate sodium STPP or SODIUM PHOSPHATE, MONOBASIC.
Described for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, described silicate is Starso, water glass or potassium silicate.
Described for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, described is any one or a few combination in 7-azaindole, PA and 2-mercaptobenzothiazole.
Described for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, described solvent is deionized water.
Adopt technical scheme as above, the present invention has superiority as described below:
One of the present invention is used for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, the present invention is with zirconate, phosphoric acid salt, silicate and containing N organic heterocyclic molecule be main film forming substance, by dip-coating or spraying coating process, together 3 ~ 5 μm of thick organic/inorganic passive films can be formed at titanium alloy substrate surface, the corrosion resisting property of base material can be strengthened, this passive film and surperficial epoxy antirust coating have good consistency, coating adhesive strength significantly improves, interfacial failure rate reduces greatly, the work-ing life of effective prolongation titanium alloy surface antifouling coating system, have broad application prospects.
[accompanying drawing explanation]
Fig. 1 is the electrochemistry Nuquist graphic representation of titanium alloy passive film of the present invention;
Fig. 2 is the analog electrical resistance of titanium alloy passive film of the present invention;
Fig. 3 is that epoxy primer of the present invention is in substrate surface contact angle test result;
Fig. 4 is epoxy primer adhesion strength test result of the present invention.
[embodiment]
Can explain the present invention in more detail by the following examples, the present invention is not limited to the following examples;
One of the present invention is used for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, and moiety comprises by mass percentage:
Zirconate 1 ~ 3%; Phosphoric acid salt 1 ~ 3%;
Silicate 0 ~ 1%; Containing N organic heterocyclic molecule 2 ~ 3%;
Solvent 92 ~ 94%.
Wherein said zirconate is potassium fluozirconate, sodium fluozirconate or ammonium fluozirconate; Described phosphoric acid salt is Sodium hexametaphosphate 99, tripoly phosphate sodium STPP or SODIUM PHOSPHATE, MONOBASIC; Described silicate is Starso, water glass or potassium silicate; Described be in 7-azaindole, PA and 2-mercaptobenzothiazole any one or a few combination; Described solvent is deionized water; Described zirconate, phosphoric acid salt, silicate and containing N organic heterocyclic molecule total concn be 6 ~ 8%.
After utilizing organic-inorganic passivating solution process titanium alloy base material of the present invention, form one deck organic/inorganic passive film on surface, significantly can improve the corrosion resisting property of base material.Electrochemistry Nuquist curve before and after the passivation of titanium alloy base material and analog electrical resistance are as illustrated in fig. 1 and 2.
Organic-inorganic passive film can improve the consistency of epoxy primer and base material, reduces contact angle, is conducive to its wetting and dispersing at substrate surface, as shown in Figure 3.
Epoxy primer is only 6.8MPa at the sticking power of titanium alloy substrate surface, and interfacial failure rate reaches about 30%.Titanium alloy base material is after passivating solution process, and the sticking power of epoxy primer significantly rises to 9.7MPa, and increase rate reaches 43%, and interfacial failure rate is reduced to 1%, as shown in Figure 4.
Specific embodiments of the invention are as follows:
Organic-inorganic passivating solution composition and epoxy primer sticking power test result as shown in the table:
Passivating solution composition and epoxy primer sticking power test result
Titanium alloy base material Passivation Treatment process: first utilize dehydrated alcohol oil removing, decontamination, then utilize sand papering, increases substrate roughness, finally uses washed with de-ionized water, removing substrate surface impurity.Surface treatment is complete, and titanium alloy base material is immersed in passivating solution 5 ~ 10min, and taking-up is dried.
Epoxy primer sticking power test process: passive film gets final product application epoxy primer at normal temperature after dry 1 ~ 4h, after the dry 5 ~ 7d of epoxy primer solidification, the method testing coating sticking power specified by 9.4.3 in GB/T 5210-2006.
Titanium alloy base material passivation pre-treatment of the present invention mainly comprises: (1) dehydrated alcohol deoiling; (2) sand papering, improves roughness; (3) dehydrated alcohol decontamination; (4) washed with de-ionized water.
Passive film of the present invention 25 DEG C, can application epoxy primer after dry 2h under 50% humidity condition.
Titanium alloy base material organic-inorganic passivating solution of the present invention can form the thick organic/inorganic passive film of one deck 3 ~ 5 μm at titanium alloy substrate surface, strengthen the corrosion resisting property of titanium alloy base material, good consistency is had with surperficial epoxy organic coating, coating adhesive strength can be made can be significantly increased to 10 MPa from 7 MPa, and interfacial failure rate is reduced to 0 from 30%.Therefore, organic-inorganic passivating solution of the present invention is used for the surface treatment of boats and ships titanium alloy base material, the attachment of effects on surface coating has obvious enhancement.
Part not in the detailed description of the invention is prior art.
The embodiment selected in this article in order to open object of the present invention, currently thinks to be suitable for, but it is to be understood that the present invention is intended to comprise all changes belonging to the embodiment in this design and invention scope and improvement.
Claims (6)
1., for a boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: moiety comprises by mass percentage:
Zirconate 1 ~ 3%;
Phosphoric acid salt 1 ~ 3%;
Silicate 0 ~ 1%;
Containing N organic heterocyclic molecule 2 ~ 3%;
Solvent 92 ~ 94%.
2. according to claim 1 for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: described zirconate is potassium fluozirconate, sodium fluozirconate or ammonium fluozirconate.
3. according to claim 1 for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: described phosphoric acid salt is Sodium hexametaphosphate 99, tripoly phosphate sodium STPP or SODIUM PHOSPHATE, MONOBASIC.
4. according to claim 1 for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: described silicate is Starso, water glass or potassium silicate.
5. according to claim 1 for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: described is any one or a few combination in 7-azaindole, PA and 2-mercaptobenzothiazole.
6. according to claim 1 for boats and ships titanium alloy base material surface-treated organic-inorganic passivating solution, it is characterized in that: described solvent is deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410739754.9A CN104694915A (en) | 2014-12-08 | 2014-12-08 | Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410739754.9A CN104694915A (en) | 2014-12-08 | 2014-12-08 | Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104694915A true CN104694915A (en) | 2015-06-10 |
Family
ID=53342451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410739754.9A Pending CN104694915A (en) | 2014-12-08 | 2014-12-08 | Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104694915A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824717A (en) * | 2016-12-31 | 2017-06-13 | 马鞍山市川金属科技有限公司 | A kind of car door process of surface treatment for lifting paint adhesion |
| CN106868489A (en) * | 2016-12-31 | 2017-06-20 | 马鞍山市川金属科技有限公司 | A kind of surface treatment method of the automotive hub of anti-depainting |
| CN107354492A (en) * | 2017-06-30 | 2017-11-17 | 常州思宇环保材料科技有限公司 | A kind of coating corrosion resistant protecting agent |
| WO2019084987A1 (en) * | 2017-11-06 | 2019-05-09 | 常熟市欧迪管业有限公司 | Titanium tube for tubular heat exchanger |
| CN114232000A (en) * | 2021-12-16 | 2022-03-25 | 深圳市纳明特科技发展有限公司 | Titanium alloy surface treatment process |
| CN116411269A (en) * | 2023-04-07 | 2023-07-11 | 浙江小铱环保科技有限公司 | A kind of phosphorus-free chemical conversion coating film-forming liquid on iron and steel metal surface and application thereof |
| CN117187815A (en) * | 2022-05-30 | 2023-12-08 | 中国石油天然气集团有限公司 | Corrosion inhibitor suitable for titanium alloy products |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312855A (en) * | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
| CN101743210A (en) * | 2007-04-18 | 2010-06-16 | 恩索恩公司 | Metal surface enhanced |
| CN102061465A (en) * | 2010-12-31 | 2011-05-18 | 大连工业大学 | Chrome-free sealing agent |
-
2014
- 2014-12-08 CN CN201410739754.9A patent/CN104694915A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312855A (en) * | 1940-09-07 | 1943-03-02 | Parker Rust Proof Co | Method of coating aluminum |
| CN101743210A (en) * | 2007-04-18 | 2010-06-16 | 恩索恩公司 | Metal surface enhanced |
| CN102061465A (en) * | 2010-12-31 | 2011-05-18 | 大连工业大学 | Chrome-free sealing agent |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824717A (en) * | 2016-12-31 | 2017-06-13 | 马鞍山市川金属科技有限公司 | A kind of car door process of surface treatment for lifting paint adhesion |
| CN106868489A (en) * | 2016-12-31 | 2017-06-20 | 马鞍山市川金属科技有限公司 | A kind of surface treatment method of the automotive hub of anti-depainting |
| CN107354492A (en) * | 2017-06-30 | 2017-11-17 | 常州思宇环保材料科技有限公司 | A kind of coating corrosion resistant protecting agent |
| WO2019084987A1 (en) * | 2017-11-06 | 2019-05-09 | 常熟市欧迪管业有限公司 | Titanium tube for tubular heat exchanger |
| CN114232000A (en) * | 2021-12-16 | 2022-03-25 | 深圳市纳明特科技发展有限公司 | Titanium alloy surface treatment process |
| CN114232000B (en) * | 2021-12-16 | 2023-12-26 | 深圳市纳明特科技发展有限公司 | Titanium alloy surface treatment process |
| CN117187815A (en) * | 2022-05-30 | 2023-12-08 | 中国石油天然气集团有限公司 | Corrosion inhibitor suitable for titanium alloy products |
| CN116411269A (en) * | 2023-04-07 | 2023-07-11 | 浙江小铱环保科技有限公司 | A kind of phosphorus-free chemical conversion coating film-forming liquid on iron and steel metal surface and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104694915A (en) | Organic-inorganic passivating liquid for surface treatment of ship titanium alloy base material | |
| Becker | Chromate-free chemical conversion coatings for aluminum alloys | |
| CN107790360A (en) | The preparation method of composite coating that marine anticorrosion uses | |
| CN102942863A (en) | Non-aromatic corrosion prevention method for metal surface | |
| CN103952691A (en) | Rare earth metal salt passivating solution and method for passivating surface coating of galvanized steel wire | |
| CN101525747A (en) | Clean rare-earth salt passivation solution | |
| CN107384121A (en) | A kind of anticorrosive paint and spraying method of water conservancy gate protective coating | |
| CN102942868A (en) | Non-aromatic corrosion prevention method for metal structure | |
| CN105038580A (en) | Self-curing chemically bonded phosphate zinc-rich coating | |
| CN103665975A (en) | Organic silicon anti-rust paint for ship and preparation method thereof | |
| CN104099009A (en) | Urea-containing aluminum alloy surface treatment agent | |
| CN108221016B (en) | A kind of zinc-plated sealer and its application method | |
| CN102942855A (en) | Corrosion prevention technology for metal structure | |
| CN103469196A (en) | Phosphatization film sealing fluid and sealing technology | |
| CN102942813A (en) | Non-aromatic corrosion prevention technology for metal surface | |
| CN102964994A (en) | Coating scheme of anti-corrosion coating | |
| CN102964992A (en) | Coating scheme of anti-corrosion coating | |
| CN102942869A (en) | Environment-friendly paint coating method for metal surface | |
| CN102942844A (en) | Non-aromatic corrosion prevention technology for metal structure | |
| CN103214955A (en) | Anticorrosion technology of metal surface | |
| CN103045088A (en) | Environment-friendly paint coating flow for metal surface | |
| CN102942847A (en) | Corrosion prevention process of metal structure | |
| CN102942846A (en) | Coating scheme of anti-corrosion paint | |
| CN103214938A (en) | Coating method of anticorrosion coating material | |
| CN103938247A (en) | Preparation method of metal complex-perfluorpolyether oil complex phase coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150610 |
|
| RJ01 | Rejection of invention patent application after publication |