CN1074062C - Converting agent of iron rust - Google Patents
Converting agent of iron rust Download PDFInfo
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- CN1074062C CN1074062C CN99125516A CN99125516A CN1074062C CN 1074062 C CN1074062 C CN 1074062C CN 99125516 A CN99125516 A CN 99125516A CN 99125516 A CN99125516 A CN 99125516A CN 1074062 C CN1074062 C CN 1074062C
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- agent
- rust
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Abstract
The present invention belongs to the field of rust prevention and protection of metal chemistry. The present invention is especially suitable for metal components of ships, bridges, buildings, etc. of various low-alloy products. The converting agent of iron rust of the present invention uses phosphonic acid as main materials and uses water as solvents. The converting agent of iron rust of the present invention is prepared from organic acid, catalysts, anti-rust agents, corrosion inhibitors, activating agents, penetrating agents and alloy powder. Compared with the prior art, the converting agent has the characteristics of reasonable design of ingredients, wide application range, favorable combination properties, economical use, etc.
Description
The invention belongs to corrosion protection field in the metallochemistry.More be applicable to hardwares for building such as steamer in various carbon steels, the low alloy steel goods, basin, iron tower, bridge.
At present, developed out polytype " on rust paint " both at home and abroad, this class coating can directly be coated in the steel surface that gets rusty; by infiltration, conversion or stable to rusty scale; play a protective role, thereby save rust cleaning work, realized that rust cleaning and painted are unified.But this series products have many deficiencies as: (1) this class coating is to practical application conditional request harshness, and is very big to its performance impact as rusty scale thickness, homogeneity etc.; (2) existence of resin film forming matter and organic solvent in this class coating has influenced the function performance that in the coating rust is produced working substance, and is not exclusively thorough to the effect of rust, thereby do not reach expected effect.In the prior art, there is the water system of employing treatment solution to carry out antirust processing.This class treatment solution has two types at present basically, i.e. tannin acid type (as Australian EXIT RUST) and phosphatic type (as the KO-99 of the U.S.), and the former can only be used under the very uniform ideal conditions of rusty scale, and phenomenons such as whiting, efflorescence then appear in the latter easily.Australian Ke Laisimo company provide a kind of converting agent of iron rust (phosphatic type) (Chinese patent: publication number CN1049871A), it is by two phase composites, use inconvenient, and with deionized water preparation, cost height.
It is reasonable in design to the objective of the invention is to propose a kind of composition, and the scope of application is wide, good combination property, economic converting agent of iron rust.
By existence to organic solvent (thinner) and resene film forming matter in the band rust result discovery on rust paint of steel surface, to with the performance of the material normal function of rust effect very big influence being arranged in the coating, it is relatively poor that the effect of becoming rusty often only is confined to the top layer penetrating quality, can not make rusty scale obtain handling fully, up hill and dale, thereby just not reaching expected effect yet, this is the ubiquitous problem of on rust paint in the market.From to the rust be used for, on rust paint has osmosis type, transformant, stable form, the used transforming agent of this class coating mainly contains two kinds, i.e. tannic acid and phosphoric acid.By test, we find tannic acid really can with the iron rust effect, generate the black product, but there are the following problems:
(1) this product some be water miscible, so once the surface has moisture content to exist, must reduce the resistance of surface electrolyte, this protection against corrosion to iron and steel is disadvantageous.
(2) character of black conversion coating is relevant with the lot number that uses tannic acid, though products that may different batches, structure is to some extent due to the difference.This also gives the stable difficulty of bringing of test work and quality product.
(3) tannic acid can only react with iron rust, and metallic iron itself is not produced effect.
For above-mentioned reasons, converting agent of iron rust of the present invention then is the treatment solution based on phosphoric acid, according to the converting agent of iron rust that the object of the invention proposed, it is characterized in that this transforming agent is a kind of based on phosphoric acid, with water is solvent, and containing the treatment solution that organic acid, catalyzer, rust-preventive agent, inhibiter, promoting agent, permeate agent and alloy powder are formed, its concrete Chemical Composition is (weight %): phosphoric acid (H
3PO
4, 85%) and be 35-50%, organic acid is 8-10%, and tap water is 35-45%, and catalyzer is 1.0-2.0%, and rust-preventive agent is 0.2-0.8%, and inhibiter is 0.05-0.5%, and promoting agent is 0.01-1.0%, and permeate agent is 0.05-2.0%, alloy powder is 4-9%.Other features of converting agent of iron rust of the present invention also have in composition, and catalyzer should be MnCO
3, ZnCO
3, any one or two kinds among the ZnO and two or more sum form.Inhibiter should be that any one or two kinds and the two or more sum in Sodium Benzoate, tartrate and the citric acid formed.Rust-preventive agent should be MoO
3And KNO
2In any one.Permeate agent should be that any one or two kinds and the two or more sum in glycerol, Sorbitol Powder and the polyoxyethylene glycol formed.Promoting agent should be that any one or two kinds and the two or more sum in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, dodecanol sodium sulfate, dodecyl alcohol phosphoric acid ester and the alkyl polyoxyethylene phosphoric acid fat formed.Organic acid should be any one acid in formic acid, acetate, propionic acid, butyric acid, the valeric acid.But be best especially with acetate.Effect to each chemical composition in the converting agent of iron rust composition of the present invention is described in detail below.
In the present invention, phosphoric acid not only can react with the steel surface rusty scale, makes it change into stable protective film, and can produce phosphorization to rusty part not, generates protective film equally, thereby has guaranteed the continuity and the globality of protective film.
In the present invention, catalyzer mainly is MnCO
3, ZnCO
3, any one or two kinds of above sum among the ZnO.The existence of catalyzer can be reacted with the vitriol in the iron rust, helps generating a kind of phosphoric acid salt and is fixed up.
In the present invention, alloy powder is the iron filings in iron powder or the machining, and alloy powder can assist iron rust is changed into magnetite.X-ray diffraction test also shows, contains the phosphoric acid salt of the iron, manganese, zinc etc. of multiple crystalline form in the rete after the conversion.
In the present invention, organic acid can be any one in formic acid, acetate, propionic acid, butyric acid, the valeric acid organic acid, but best with acetate especially.
In the present invention, inhibiter mainly is any one or two kinds of above sum in Sodium Benzoate, tartrate and the citric acid.Rust-preventive agent mainly is MoO
3And KNO
2In any.Inhibiter and rust-preventive agent can make the do not become rusty surface passivation of part of steel, the defective that simultaneously also can seal the phosphoric acid salt rete, and promote the deposition of phosphorization membrane, thus improved the corrosion resisting property of protection rete, further strengthen rust-proof effect.
In the present invention, permeate agent mainly is any one or two kinds of and two or more sums in glycerol, Sorbitol Powder and the polyoxyethylene glycol.The effect of permeate agent is to make treatment solution more complete, more thorough to the effect of rusty scale.
In the present invention, activator is any one or two kinds of and two or more sums in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, dodecanol sodium sulfate, dodecyl alcohol phosphoric acid ester, the alkyl polyoxyethylene phosphoric acid fat.The existence of promoting agent can improve the affinity on treatment solution and steel surface, and a small amount of greasy dirt on the energy treat surface, brings convenience to actually operating.
The production method of converting agent of iron rust of the present invention is similar to prior art, after at first each chemical composition being pressed set amount and being taken out, by production sequence put to mix heat mixing in the molten device after, can use.Also can pour into and seal long storage in the bottle.
Converting agent of iron rust of the present invention has following characteristics compared with prior art:
1, has multiple function: normal temperature phosphating agent, passivator, converting agent of iron rust are combined together.
2, with the process water be base, the non-volatile organism of drying process, free from environmental pollution, reduced cost simultaneously again.
3, operational safety is reliable, and base steel is not produced hydrogen embrittlement, does not fire not quick-fried and stable performance, and storage period is long.
4, practical, good combination property, to all even uneven corrosion situation is all applicable, labour intensity is low, work efficiency is high.The membranous layer corrosion resistance that is coated with back formation can be good, can be used as one deck priming paint and use.And great majority such as this rete and epoxy, alkyd, phenolic aldehyde lacquer class has good compatible matching capacity.
Embodiment:
The composition scope of converting agent of iron rust according to the present invention, we have prepared the transforming agent of the present invention of six kinds of different component content altogether, see Table 1.In order to contrast us, dip test and CuSO have been carried out also with reference to GB GB/T12612-90
4Spot test.For further checking film forming corrosion resisting property, indoor accelerated corrosion test and lacing film light exposure test have also been carried out.Testing used steel plate is common cold-rolled steel sheet, and test-results sees the following form.Table 1 is the component content table of the embodiment of the invention.Table 2 is the dip test contrast table, and table 3 is CuSO
4The contrast table of spot test, table 4 are the contrast table of salt-fog test.Be comparative test result below.
Test 1 is a dip test, sees Table 2, and priming paint is red lead primer in table 2, and finish paint is alkyd titanium dioxide lacquer.
Test 2 is CuSO
4Simultaneous test sees Table 3, carries out with reference to GB GB6807-86, with the CuSO for preparing
4The time that metals copper color appears in steel surface is observed and write down to drips of solution at different sites.By table 3 as seen, corrosion resistance of surface after treatment improves greatly, and performance is better than external like product EXITRUST and KO-99.
Test 3 salt-fog tests
Undertaken by ASTMB117.At 35 ℃, under the condition of PH=7,, observe the changing conditions of rete in the test piece with the 5%NaCl certain hour of spraying continuously.Found that all test pieces are through 150 hours salt fogs, film itself is in conjunction with intact, no peeling, loosening, dropping situations.Test is also found, the rete that obtains is handled in the test piece of different corrosion situations, and corrosion resisting property is also different.Rusty scale conversion film solidity to corrosion is good uniformly, and under the similarity condition, the conversion film corrosion resisting property that thicker rusty scale obtains is also strong.If rusty scale blocked up (＞100 μ m), then pass through the salt-fog test of certain hour after, transform rete and loosening skin effect phenomenon occurs.
Test 4, warm test is undertaken by ASTM D1735, at relative temperature PH＞95%, under T=49 ℃ the condition, the test piece after handling among the embodiment is inserted, and observes the corrosion and the changing conditions of rete.Test finds that the back rete is handled in the test piece of different corrosion situations, and through 100 hours humid heat test, surface oxidisation point area was all less than 10%, and rete non-loosening skin effect phenomenon.
Test the test of 5 heatproofs
Under the condition of 150 ℃ of temperature, the test piece after handling among the embodiment is inserted, observe the corrosion and the changing conditions of rete.Test is found, the rete after the test piece of different corrosion situations is handled, process constant temperature 90 minutes, rete non-loosening skin effect phenomenon.Illustrate that converting agent of iron rust of the present invention is applicable to the baking vanish occasion.
Test 6 lacing film light exposure tests: tan by the sun being positioned over indoor and outdoors after each test piece is handled respectively among the embodiment, the result shows that outdoor 2-3 month, indoor more than 1 year, rust was not returned on the test piece surface.
Test the test of 7 paint film matching capacitys
Use various coating, be coated in respectively in the steel plate test piece of the embodiment of the invention after handling respectively, by the matching capacity of salt-fog test and adhesion test check and paint film.The result shows that the present invention all can supportingly use great majority such as alkyd, phenolic aldehyde, epoxy, pitch, Polyurethane, rubber lacquer.The component content table (weight %) of table 1 embodiment of the invention
Table 2 iron rust has transformed or iron rust has transformed corrosion failure test (results after 50 days) behind sample primer coating and/or the finish paint
Annotate: priming paint is red lead primer, and finish paint is an alkyd titanium dioxide
| Composition | Embodiment | |||||
| 1 | ?2 | ?3 | ?4 | ?5 | ?6 | |
| Phosphoric acid | 40 | ?48 | ?40 | ?36 | ?48 | ?45 |
| Organic acid | 10 (acetate) | 8 (acetate) | 9 (acetate) | 10 (formic acid) | 8 (propionic acid) | (8.5 valeric acid) |
| Catalyzer | 1.5(MnCO 3) | 1.8(ZnCO 3) | 1.2(ZnO) | 1.1(MnCO 3?ZnCO 3) | 1.7(MnCO 3) | 1.6(ZnCO 3?ZnO) |
| Rust-preventive agent | 0.6MoO 3 | 0.7MoO 3 | ?0.4MoO 3 | 0.7KNO 2 | ?0.3KNO 2 | 0.5KNO 2 |
| Inhibiter | (0.4 Sodium Benzoate) | (0.2 tartrate) | (0.07 citric acid) | (0.1 Sodium Benzoate, tartrate) | (0.3 Sodium Benzoate, citric acid) | (0.6 tartrate and citric acid) |
| Promoting agent | (0.5 sodium laurylsulfonate) | (0.2 Sodium dodecylbenzene sulfonate) | (0.05 petroleum sodium sulfonate) | (0.05 Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate) | (0.3 petroleum sodium sulfonate, dodecanol sodium sulfate) | (0.1 dodecyl alcohol phosphoric acid ester and alkyl polyoxyethylene phosphoric acid fat) |
| Perviousness | (1.0 glycerol) | (0.5 polyoxyethylene glycol) | (1.0 Sorbitol Powder) | (0.06 glycerol, polyoxyethylene glycol) | (0.1 Sorbitol Powder and polyoxyethylene glycol) | (0.15 glycerol, Sorbitol Powder) |
| Alloy powder | 8 (iron filings) | 5 iron filings) | 6 (iron filings) | 9 (iron filings) | 5 (iron filings) | 7 (iron filings) |
| Tap water | 38 | ?35.6 | ?42.1 | ?42.99 | ?36.3 | ?36.55 |
| Add up to | 100.00 | ?100.00 | ?100.00 | ?100.00 | ?100.00 | 100.00 |
| Handle type | The tap water dipping | The 3%NaCl dipping | |
| The embodiment of the invention | Transforming agent of the present invention | No change | No change |
| Transforming agent+priming paint of the present invention | No change | The minute quantity blister | |
| Comparative Examples | Acid etching+priming paint+finish paint | Individual other places rust staining | The part rustization |
| Hand washing+priming paint+finish paint | A small amount of rust staining | Whole rustization |
Table 3CuSO
4Spot test
Table 4 iron rust has transformed or iron rust has transformed salt-fog test result behind sample primer coating and/or the finish paint
Annotate: priming paint is red lead primer, and finish paint is an alkyd titanium dioxide
| Corrosion place | Rust place not | ||||
| Be untreated | Embodiment 1 handles | EXIT RUST handles (Australia) | Be untreated | Embodiment 1 handles | KO-99 handles) (USA) |
| 20-30min | ＞3h | 1-2h | ＜10s | ＞4min | ?2min |
| Handle type | Test period | Test-results | |
| The embodiment of the invention | Transforming agent of the present invention | 150 hours | No change |
| Transforming agent+priming paint of the present invention | 300 hours | No change | |
| Comparative Examples | Acid etching+priming paint+finish paint | 300 hours | The part rustization |
| Hand washing+priming paint+finish paint | 300 hours | Whole rustization |
Claims (11)
1, a kind of converting agent of iron rust, this transforming agent is a kind of based on phosphoric acid, with water is solvent, and contains the treatment solution that organic acid, catalyzer, rust-preventive agent, inhibiter, promoting agent, permeate agent and iron alloy powder are formed, and it is characterized in that concrete Chemical Composition is (weight %): phosphoric acid (H
3PO
4, 85%) and be 35-50%, organic acid is 8-10%, and tap water is 35-45%, and catalyzer is 1.0-2.0%, and rust-preventive agent is 0.2-0.8%, and inhibiter is 0.05-0.5%, and promoting agent is 0.01-1.0%, and permeate agent is 0.05-2.0%, iron alloy powder is 4-9%.
2,, it is characterized in that catalyzer should be MnCO according to the described transforming agent of claim 1
3, ZnCO
3, any one component among the ZnO.
3,, it is characterized in that inhibiter is any one component in Sodium Benzoate, tartrate and the citric acid according to the described transforming agent of claim 1.
4,, it is characterized in that rust-preventive agent should be MoO according to the described transforming agent of claim 1
3And KNO
2In any one component.
5,, it is characterized in that permeate agent should be any one component in glycerol, Sorbitol Powder and the polyoxyethylene glycol according to the described transforming agent of claim 1.
6,, it is characterized in that promoting agent should be any one component in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, dodecanol sodium sulfate, dodecyl alcohol phosphoric acid ester and the alkyl polyoxyethylene phosphoric acid fat according to the described transforming agent of claim 1.
7,, it is characterized in that organic acid should be any one acid in formic acid, acetate, propionic acid, butyric acid, the valeric acid according to the described transforming agent of claim 1.
8,, it is characterized in that content should be MnCO at the catalyzer of 1.0-2.0% according to claim 1,2 described transforming agents
3, ZnCO
3, any two kinds and two or more sum are formed among the ZnO.
9,, it is characterized in that content should be that any two kinds and two or more sum are formed in Sodium Benzoate, tartrate and the citric acid at the inhibiter of 0.05-0.5% according to claim 1 and 3 described transforming agents.
10,, it is characterized in that content should be that any two kinds and two or more sum are formed in glycerol, Sorbitol Powder and the polyoxyethylene glycol at the permeate agent of 0.05-2.0% according to claim 1 and 5 described transforming agents.
11,, it is characterized in that content should be that any two or more sum in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate, dodecanol sodium sulfate, dodecyl alcohol phosphoric acid ester, the alkyl polyoxyethylene phosphoric acid fat is formed at the activator of 0.01-1.0% according to claim 1 and 6 described transforming agents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125516A CN1074062C (en) | 1999-12-03 | 1999-12-03 | Converting agent of iron rust |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99125516A CN1074062C (en) | 1999-12-03 | 1999-12-03 | Converting agent of iron rust |
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| Publication Number | Publication Date |
|---|---|
| CN1264754A CN1264754A (en) | 2000-08-30 |
| CN1074062C true CN1074062C (en) | 2001-10-31 |
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ID=5283982
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99125516A Expired - Fee Related CN1074062C (en) | 1999-12-03 | 1999-12-03 | Converting agent of iron rust |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696498B (en) * | 2009-09-27 | 2012-02-22 | 大连三达奥克化学股份有限公司 | Compound type rust solvent for pretreatment of spraying and coating of bin body of mortar shell for machine and preparation method thereof |
| CN101982564B (en) * | 2010-09-25 | 2015-04-29 | 湖南立发釉彩科技有限公司 | Rust-removing and anti-rusting agent for iron and steel |
| CN102153920B (en) * | 2011-05-12 | 2012-12-12 | 安徽工业大学 | Aqueous rusted anti-corrosive coating and preparation method thereof |
| CN102337529A (en) * | 2011-11-07 | 2012-02-01 | 大连三达奥克化学股份有限公司 | Building deformed steel bar passivation antirusting agent and preparation method thereof |
| CN103276383B (en) * | 2013-06-07 | 2015-08-05 | 合肥华清金属表面处理有限责任公司 | A kind of Environmental protection type thread steel surface antirust treatment agent |
| CN104651847A (en) * | 2013-11-25 | 2015-05-27 | 陈克华 | Steel surface rust conversion emulsion |
| CN103882440B (en) * | 2014-03-05 | 2017-02-08 | 山东科技大学 | Preparation methods of organic oxime rust transforming agent and aqueous iron rust transforming undercoat |
| CN105482712A (en) * | 2016-01-27 | 2016-04-13 | 程大彪 | Iron rust transforming agent coating |
| CN106010159A (en) * | 2016-05-20 | 2016-10-12 | 黄健 | Rust removal and prevention agent for metal surfaces |
| CN105885568A (en) * | 2016-06-22 | 2016-08-24 | 安徽汇利涂料科技有限公司 | Water-based rust converting primer and preparation method thereof |
| CN106835105A (en) * | 2016-12-23 | 2017-06-13 | 句容亿格纳米材料厂 | Organic converting agent of iron rust and preparation method thereof and application method |
| CN107142484A (en) * | 2017-06-04 | 2017-09-08 | 深圳朝伟达科技有限公司 | A kind of metal rust-removing anti-rust sealer and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049871A (en) * | 1989-08-30 | 1991-03-13 | 克雷默斯公司 | A kind of converting agent of iron rust and using method thereof |
| CN1197824A (en) * | 1997-04-28 | 1998-11-04 | 中国船舶工业总公司第十二研究所 | Alcohol-base rust transfering transparent paint |
-
1999
- 1999-12-03 CN CN99125516A patent/CN1074062C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049871A (en) * | 1989-08-30 | 1991-03-13 | 克雷默斯公司 | A kind of converting agent of iron rust and using method thereof |
| CN1197824A (en) * | 1997-04-28 | 1998-11-04 | 中国船舶工业总公司第十二研究所 | Alcohol-base rust transfering transparent paint |
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| Publication number | Publication date |
|---|---|
| CN1264754A (en) | 2000-08-30 |
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