CN101457354B - Environment friendly room temperature non-slag colorful chemical conversion solution and process - Google Patents
Environment friendly room temperature non-slag colorful chemical conversion solution and process Download PDFInfo
- Publication number
- CN101457354B CN101457354B CN200910076288XA CN200910076288A CN101457354B CN 101457354 B CN101457354 B CN 101457354B CN 200910076288X A CN200910076288X A CN 200910076288XA CN 200910076288 A CN200910076288 A CN 200910076288A CN 101457354 B CN101457354 B CN 101457354B
- Authority
- CN
- China
- Prior art keywords
- chemical conversion
- solution
- temperature
- film
- grams per
- 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.)
- Expired - Fee Related
Links
Abstract
The invention relates to an environment-friendly room temperature no-slag colorful chemical conversion solution and a process thereof; the process is characterized in that the carbon steel is arranged and treated in bath solution with the temperature of 10-31 DEG C which contains 3.8-10.3g/L of zinc phosphate, 4.0-15.0mL/L of phosphoric acid, 0.6-2.8g/L of manganese salt, 1.8-6.0g/L of sodium phosphate, 4.1-8.4g/L of organic acid salt and 0.6-4.6g/L of accelerator and has the pH value of 2.5-3.2 for 8-30 minutes, washed by tap water and dried, thus forming a uniform and compact colorful chemical conversion film on the surface of the carbon steel; the conversion film has excellent decoration performance, anti-corrosion performance and subsequent manufacturability. The conversion solution and the process excellently solve the problem of heavy pollution and large energy dissipation during phosphating at high and intermediate temperature and bluing at high temperature, and also solve the problems of environment pollution, harm on the health of operators, bad anti-corrosion performance of the blued film, bad adhesion of the substrate and the blued film, and the like due to selenious acid and copper ions in blued solution at normal temperature and hexavalent chromium ions in oxidation passivation solution.
Description
Technical field
The present invention relates to a kind of in steel surface carries out normal temperature phosphating, passivation and the chemical conversion of turn blue (blackout) is handled prescription and technology, by phosphatization, passivation and the chemical conversion of turn blue (blackout) handle, form to cover homogeneously crystallized careful colour film at steel surface, with the corrosion resisting property that strengthens steel surface and ornamental and with surperficial subsequent disposal performance.Be a kind of novel steel surface anti-corrosion and combination with decorative surfaces treatment process and technology of energy-conserving and environment-protective, belong to field of fine chemical.
Background technology
The chemical conversion processing is meant immerses solidity to corrosion and the subsequent disposal performance that improves matrix surface in the chemical tank liquor through certain chemical treatment with metalwork.Chemical conversion is handled and to be comprised phosphatization, passivation, oxidation usually and conversion processing technology such as turn blue.For phosphatization, before the middle nineteen seventies, phosphatization adopts the high-temperature technology of 70-80 ℃ (sometimes up to 90-100 ℃) more, and the phosphatize phosphate coat crystallization of gained is thick, and bonderizing tank liquor sediment is many, and tank liquor is unstable and seriously polluted; After the middle nineteen seventies, people are for save energy and reduce pollution, competitively low temperature (＜70 ℃) phosphating process in the exploitation.Enter after 21 century, phosphating process and technology are had higher requirement, exploitation low temperature (or very low temperature), the conversion processing prescription of ultralow heavy metal metal ionic concn and the emphasis that technology becomes research.
The iron and steel oxidation also claims to turn blue or turn black.In order to obtain blue rete attractive in appearance at steel surface, generally adopt alkaline oxygenated, the normal temperature technology of turning blue.Alkaline oxygenatedly in containing the alkaline tank liquor of the high temperature of oxygenant (130～150 ℃), carry out usually, generally contain sodium hydroxide (55～85g/L) and Sodium Nitrite (150～200g/L), even partially disposed liquid also contains sodium phosphate and potassium bichromate in this conversion treating solution.Thereby this oxidation is turned blue to handle and is had that energy consumption is big, environmental pollution serious and to fatal shortcomings such as human health damage are strong.Turn blue and handle the big problem of energy consumption in order to solve high temperature oxidation, people have developed room temperature turn blue treatment formulations and technology, liquid is mainly by cupric nitrate (1～3g/L) yet normal temperature turns blue, Resorcinol (2～4g/L), selenous acid (3～5g/L), (30～40ml/L) wait composition to nitric acid, treatment technology and technology preferably resolve energy consumption problem though this room temperature is turned blue, but be very restricted owing to highly toxic substances such as containing a large amount of selenous acid and Resorcinol in the treatment solution uses, room temperature is turned blue and is handled resulting rete to have sticking power low in addition, solidity to corrosion with shortcoming such as wear no resistance.
The oxidation passivation is to improve the corrosion proof another kind of method of steel surface, normally in oxidizing acidic solution, carry out, usually the oxidation passivating solution by potassium bichromate (50～80g/L), chromic anhydride (～82g/L) and phosphoric acid (～formation such as 81g/L), 60～90 ℃ of treatment temps, time 5～10min.Has excellent corrosion resisting property though handle resulting passive film, because treatment solution contains a large amount of hypertoxic 6 valency chromium and has gradually by the displaced trend of treatment solution of low toxicity with this class conversion fluid.
In sum, low, the eco-friendly steel surface chemical conversion of research energy consumption technology is extremely urgent with prescription.
Summary of the invention
The object of the invention provides superloy surface normal temperature non-slag colorful chemical and transforms prescription and technology.Solved following five problems:
1) power consumption of medium and high temperature phosphatization is big, pollutes to weigh, and the tank liquor sediment is many and unstable, and phosphatize phosphate coat is coarse and solidity to corrosion is poor;
2) normal temperature phosphating contains nitrite ion and a large amount of metallic nickel heavy ions etc.;
3) the high temperature energy consumption of turning blue is big, pollutes heavy and contains carcinogenic substance such as a large amount of nitrite;
4) it is poor to contain a large amount of selenium elements and the normal temperature binding force of membrane that turns blue during normal temperature turns blue;
5) contain the sexavalence heavy metal chromium ion of a large amount of strong toxicities in the oxidation passivating solution.
This prescription gained conversion film is thin crystal formation colorful film, can improve the solidity to corrosion and the ornamental and subsequent treatment process of steel surface greatly.
The object of the invention provides a kind of eco-friendly room temperature non-slag colorful chemical conversion solution, it is characterized in that: every liter of solution phosphoric acid zinc 3.8～10.3 grams per liters, phosphatase 24 .0～15.0 milliliter/liter, manganese salt 0.6～2.8 grams per liter, sodium phosphate 1.8～6.0 grams per liters, organic carboxylate 4.1～8.4 grams per liters, promotor 1.6～4.6 grams per liters, all the other are water, and regulate pH value to 2.5～3.2.
Further manganese salt is Mazhev salt.
Further promotor is zinc nitrate, cupric nitrate or SODIUMNITRATE.
Use the technology that described chemical conversion solution carries out chemical conversion, it is characterized in that: carbon steel is placed described chemical conversion solution, in the tank liquor of 10～30 ℃ of temperature behind treatment time 8～30min, after the water flushing and drying up, can form a kind of colorful chemical conversion film of even compact at steel surface.
The concrete treatment process of the present invention is achieved through the following technical solutions: and electrochemical deoiling → hot tap water washes → cold running water flushing → pickling → cold running water washes → neutralize → cold running water washes → activate → cold running water washes → and chemical conversion → cold running water washes → dries up.
Above-mentioned master operation is described as follows:
(1) electrochemical deoiling
Place 65～90 ℃ of electrochemical deoiling treatment solutions to get final product in 5～10 minutes pending carbon steel.The electrochemical deoiling prescription is: sodium hydroxide 20g/L, sodium phosphate 20g/L, yellow soda ash 20g/L, water glass 3020g/L, tensio-active agent 1～2g/L, tap water surplus.
(2) pickling
It is that 1: 1 hydrochloric acid soln was handled 60～120 seconds that pending carbon steel is placed volume ratio.
(3) neutralization
Under 5% aqueous sodium carbonate room temperature, soak 30～60s.
(4) activation
Place the room temperature mixed acid solution to soak 20～40s the carbon steel after the neutralization.The proportioning of nitration mixture consists of: hydrochloric acid 100ml/L, HF 10～20ml/L.
(5) chemical conversion
Place 10～30 ℃, pH2.5～3.2 chemical conversion solutions to handle 8～30min the carbon steel after activation and the washing, can obtain thin crystal formation colorful film.
The chemical conversion liquid formula is: zinc phosphate 3.8～10.3g/L, phosphatase 24 .0～15.0ml/L, manganese salt 0.6～2.8g/L, sodium phosphate 1.8～6.0g/L, organic acid salt 4.1～8.4g/L, promotor 1.6～4.6g/L.
The relative prior art of the present invention has following characteristics:
1. the chemical conversion film of Sheng Chenging is a kind of by the colored composite membrane that phosphoric acid salt and oxide compound constituted, characteristics such as have that the careful color and luster of crystallization is even, solidity to corrosion good, ornamental strong and subsequent treatment process is good.
2. solution formula does not contain nitrite and toxic substances such as selenium and heavy metallic salt, has advantages such as environmental friendliness, cleaner production.
3. zinc ion concentration content in the solution does not produce sediment in the treating processes, and tank liquor is stable, and process controllability is good.
4. raw material of the present invention is easy to get, and cost is low, is suitable for industrial production.
Embodiment
(1) electrochemical deoiling
Place 65～90 ℃ of electrochemical deoiling treatment solutions to get final product in 5～10 minutes pending carbon steel.The electrochemical deoiling prescription is: sodium hydroxide 20g/L, sodium phosphate 20g/L, yellow soda ash 20g/L, water glass 3020g/L, tensio-active agent 1～2g/L, deionized water surplus.
(2) pickling
At first dispose pickle solution, the concentrated hydrochloric acid of massfraction 36.5% and deionized water were configured to pickle solution in 1: 1 by volume put into containers for future use.Under the room temperature, cold rolling steel disc is put into this pickle solution 60～120s, eliminate surperficial rusty stain and oxide skin.
(3) neutralization
Adopt under the mass percent concentration 5% aqueous sodium carbonate room temperature and soak 30～60s.
(5) activation
Prescription: concentrated hydrochloric acid (1.19g/ml) 100ml/L; HF20ml/L.
Below preceding 5 steps of each embodiment all in above-mentioned processing parameter, carry out.It is because commercially available concentration all is no less than 85% that phosphoric acid adopts mass percent concentration to be no less than 85%, can not be interpreted as the qualification that limits protection domain.
Example 1:
It is stand-by to get the cold rolling steel disc of 40 * 40 * 1mm.
(6) chemical conversion
To put into this chemical conversion solution through the test piece of activation treatment, 20 ℃ of controlled temperature are regulated PH to 2.8 with sodium hydroxide and were handled 15 minutes.The chemical conversion prescription is as follows: zinc phosphate 10.8g/L, phosphoric acid (concentration is no less than 85%) 9.5ml/L, acid manganous phosphate 1.7g/L, sodium phosphate 3.9g/L, adipic acid 6.5g/L, zinc nitrate 3.1g/L.
(7) drying
To from tank liquor, take out through the test piece that chemical conversion solution is handled, and, dry up with hair dryer and to get final product through the tap water flushing.
The gained test piece is the homogeneously crystallized careful colorful chemical conversion film of surface coverage, carries out the anti-corrosion time 110s of cupric sulphate dropping test.
Example 2: the proportioning of handling except that (6) chemical conversion form different, all processing steps (1), (2), (3), (4), (5), (6), (7) are identical with example 1.
Chemical conversion: will put into this chemical conversion solution through the test piece of activation treatment, 10 ℃ of controlled temperature are regulated PH to 2.7 with sodium hydroxide and were handled 30 minutes; Chemical conversion liquid prescription: zinc phosphate 10.3g/L, phosphatase 11 5.0ml/L, acid manganous phosphate 2.8g/L, sodium phosphate 6.0g/L, oxalic acid 8.4g/L, SODIUMNITRATE 4.6g/L.
The gained chemical conversion film is the careful colored rete of crystallization, and the drop of anti-copper sulfate experiment reaches 90s.
Example 3:
The proportioning of handling except that (6) chemical conversion form different, all processing steps (1), (2), (3), (4), (5), (6), (7) are identical with example 1.
Chemical conversion: will put into this chemical conversion solution through the test piece of activation treatment, 30 ℃ of controlled temperature are regulated PH to 2.5 with sodium hydroxide, handle 10 minutes; Chemical conversion liquid prescription: zinc phosphate 3.8g/L, phosphatase 24 .0ml/L, acid manganous phosphate 0.6g/L, sodium phosphate 1.8g/L, acetate 4.1g/L, cupric nitrate 1.6g/L.
The gained chemical conversion film is the careful colored rete of crystallization, and the drop of anti-copper sulfate experiment reaches 100s.
Claims (3)
1. eco-friendly room temperature non-slag colorful chemical conversion solution, it is characterized in that: every liter of solution phosphoric acid zinc 3.8～10.3 grams per liters, phosphatase 24 .0～15.0 milliliter/liter, manganese salt 0.6～2.8 grams per liter, sodium phosphate 1.8～6.0 grams per liters, organic carboxylate 4.1～8.4 grams per liters, promotor 1.6～4.6 grams per liters, all the other are water, and regulate pH value to 2.5～3.2; Promotor is zinc nitrate, cupric nitrate or SODIUMNITRATE.
2. according to the described chemical conversion solution of claim 1, it is characterized in that: manganese salt is Mazhev salt.
3. application rights requires the technology that 1 described chemical conversion solution carries out chemical conversion, it is characterized in that: carbon steel is placed described chemical conversion solution, in the tank liquor of 10～30 ℃ of temperature behind treatment time 8～30min, after the water flushing and drying up, can form a kind of colorful chemical conversion film of even compact at steel surface.'
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910076288XA CN101457354B (en) | 2009-01-09 | 2009-01-09 | Environment friendly room temperature non-slag colorful chemical conversion solution and process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910076288XA CN101457354B (en) | 2009-01-09 | 2009-01-09 | Environment friendly room temperature non-slag colorful chemical conversion solution and process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101457354A CN101457354A (en) | 2009-06-17 |
| CN101457354B true CN101457354B (en) | 2011-03-16 |
Family
ID=40768469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910076288XA Expired - Fee Related CN101457354B (en) | 2009-01-09 | 2009-01-09 | Environment friendly room temperature non-slag colorful chemical conversion solution and process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101457354B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699887A (en) * | 2017-09-28 | 2018-02-16 | 国营芜湖机械厂 | A kind of phosphorization membrane part room temperature restorative procedure of high strength steel workpiece |
| CN108517517B (en) * | 2018-04-16 | 2019-09-20 | 江苏科技大学 | A method of titanium phosphate zinc chemical conversion film is prepared on titanium surface |
| CN112323052A (en) * | 2020-10-20 | 2021-02-05 | 安徽华飞机械铸锻有限公司 | Method for improving corrosion resistance of marine carbon steel |
| CN114134496B (en) * | 2021-09-28 | 2023-09-05 | 河南北方红阳机电有限公司 | Alkali-free oxidation process suitable for high-strength steel and copper alloy combination |
| CN114324740B (en) * | 2021-12-30 | 2024-01-30 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Method for analyzing mixed acid solution of tri-acid deoxidization |
-
2009
- 2009-01-09 CN CN200910076288XA patent/CN101457354B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101457354A (en) | 2009-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103184446B (en) | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof | |
| CN101457354B (en) | Environment friendly room temperature non-slag colorful chemical conversion solution and process | |
| DE3031270C2 (en) | ||
| CN102912338B (en) | Aluminium alloy trivalent chromium passivation solution as well as preparation method and passivation technology thereof | |
| CN1858302B (en) | High anti-corrosion zinc coating trivalent chromium lue-white passivating agent and its preparing method | |
| CN101487116B (en) | Use of passivation film forming liquid on steel surface | |
| CN103352216B (en) | The coloring treatment process of a kind of copper or copper alloy surface | |
| CN102002698A (en) | Anti-rust treating agent for nickel-plated battery steel shell and using method thereof | |
| CN1986883A (en) | Environment friendly no-chromium conversion treating solution | |
| CN105779988A (en) | Chromate-free passivation solution for electroplated zinc and passivation technology thereof | |
| CN102851660A (en) | Phosphorus-free and chromium-free passive film-forming solution for steel surfaces and usage method thereof | |
| CN101356301A (en) | Aqueous reaction solution and method of passivating workpieces having zinc or zinc alloy surfaces | |
| CN103572273A (en) | Color passivated galvanized steel plate and manufacturing method thereof | |
| WO2016201935A1 (en) | Method for forming golden yellow film layer on surface of aluminum alloy | |
| CN103194742B (en) | Inorganic-resin black coating agent applied to metal surface treatment, as well as preparation method and application of black coating agent | |
| CA2124977C (en) | Non-chromium passivation method and composition for galvanized metal surfaces | |
| TW201026894A (en) | Aqueous solution for blackened chemical conversion treatment of zinc or zinc alloy surface and method of forming black anti-corrosion coating using aqueous solution for the said treatment | |
| CN102965655A (en) | Method for improving corrosion resistance of phosphate coating on surface of neodymium-iron-boron permanent magnet | |
| CN102268664A (en) | Chromium-free passivating solution used for black passivation treatment of zinc plating and preparation method thereof | |
| CN101525747B (en) | Clean rare-earth salt passivation solution | |
| CN101660156B (en) | Silicate color passivation solution used for zinc-plating material | |
| CN101565828A (en) | Organic and inorganic composite magnesium alloy non-chromium passivation treatment fluid | |
| US3032435A (en) | Process for improving the corrosion resistance of pieces of light metals and light metal alloys | |
| CN104593759A (en) | Aluminum passivating agent | |
| CN101200799B (en) | Medium-low temperature high corrosion resistant black phosphating solution on steel surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110316 Termination date: 20140109 |