CN1680623A - Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles - Google Patents
Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles Download PDFInfo
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- CN1680623A CN1680623A CNA200410023096XA CN200410023096A CN1680623A CN 1680623 A CN1680623 A CN 1680623A CN A200410023096X A CNA200410023096X A CN A200410023096XA CN 200410023096 A CN200410023096 A CN 200410023096A CN 1680623 A CN1680623 A CN 1680623A
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
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Abstract
A phosphate solution of Zn Zn-Ca and Fe series. Contents of it are H3PO4, nitrate and their Zn2+,Ca2+,Mn2+,Ni2+ salts, ammonium molybdate, ammonium wolframate, phytic acid, H2O2 and non-ionic surface active agent. pH is 2.0-5.8.
Description
Technical Field
The invention belongs to the technical field of phosphating treatment before steel surface spraying, and relates to a multi-mode and quick room-temperature zinc-series or zinc-calcium-series or iron-series clean phosphating solution.
Background
Phosphating, which has been known for over 100 years, is a process in which a metal workpiece is treated in a solution containing a metal or ammonium dihydrogen phosphate and an accelerator as main components, and a phosphate film is formed on the surface of the treated metal. The phosphating film has the functions of increasing the adhesive force, corrosion resistance, protection, friction reduction, lubrication and the like of the coating. The phosphating solutions can be classified into zinc series, manganese series, iron series, etc. according to the cation of the film.
And (2) phosphorizing, wherein the following reaction occurs when the steel surface is contacted with a phosphorizing liquid:
Thereafter, [ OH]formed-]Raising the pH value of the steel surface to react:
meanwhile, when metal ions M exist in the phosphating solution2+(e.g., Zn)2+、Mn2+、Ca2+、Ni2+Etc.) in time:
in the drying process of the phosphating film:
therefore, in the iron-based phosphating, the main component of the phosphating film is FePO4、2Fe2O3(ii) a In zinc-based phosphating, the main component of the phosphating film is FePO4、Zn3(PO4)2And 2Fe2O3。
Any steel surface to be sprayed needs to be phosphated. Phosphating is a process necessary for the production of automobiles, household appliances and most machinery. At present, domestic phosphating technologies generally exist: the cost is high, the phosphating temperature is high, the service life of the phosphating solution is short (some phosphating solutions are scrapped after being used for more than 100 hours at high frequency), the eutrophicated wastewater and waste residues of the water body are more (the waste residues belong to dangerous waste), and most room-temperature phosphating solutions contain toxic substances such as nitrite, chromium and the like. Therefore, the phosphating solution is required to be updated. The phosphated wastewater is a very important pollution source for causing water eutrophication. The eutrophication of water body, namely the environmental problem caused by the over-bearing capacity of phosphorus and nitrogen discharged in the water body in the natural environment, is one of the most serious environmental problems in China at present. More than 2 million phosphorization production lines exist in China, and some enterprises generate dozens of tons or even hundreds of tons of phosphorization wastewater which needs to be discharged and exceeds the standard of phosphorus by more than tens of times every day. The degreasing agent can be a phosphorus-free degreasing agent to radically eliminate nitrogen and phosphorus pollution, and the phosphatization can not be used by the current technological level.
Phosphorization can be divided into high-temperature phosphorization and medium-temperature phosphorization according to the treatment temperature, and normal (low and room) temperature phosphorization (15-45 ℃); the cation for forming the film can be classified into zinc, manganese, iron, etc. The phosphating solution for the prior spraying pretreatment generally needs to be washed by water after phosphating, otherwise, the phosphating film is coated with ash, and decomposition products of an accelerator in the phosphating solution (such as Cl after sodium chlorate reaction)-、Na+Ions, auxiliaries (e.g. F)-Ions or fluorides) significantly affect the quality of the phosphating film; the phosphating temperature is basically above 15 ℃, and the material is generally heated in winter; the room-temperature phosphating solution accelerator generally contains toxic Ni (nickel) and Cr (chromium) and is carcinogenic and decomposed to generate toxic gas Nitric Oxide (NO)x) Nitrite, poor phosphating quality, etc.; the sediment is more in the phosphorization process, and the phosphorization is 1m2Several grams or even more of sludge are produced.
The research and development direction of phosphorization is nontoxic and environment-friendly at present, low temperature, low cost and high performance, and with the daily rise of environmental protection and the progress of science and technology, the phosphorization is clean (finally) soon.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multi-mode and quick room-temperature zinc-series or zinc-calcium-series or iron-series clean phosphating solution aiming at the defects in the prior art. Such that: (1) the phosphating solution has long service life and no wastewater. Each component of the phosphating solution enters the phosphating film to become a component of the phosphating film and the sediment or volatilizes in the drying process of the phosphating filmThe phosphating process does not generate by-products or certain components which affect the regulation of the phosphating solution, so that the service life of the phosphating solution is long, and the film after phosphating can be recycled and added into the phosphating solution without washing or rinsingAnd (4) waste water. (2) The quality is good. The proportion of the passivation film in the phosphating film is controlled by the synergistic action of a proper amount of ammonium molybdate, nitrate and the like, the concentration and the pH value of phosphating solution are controlled, so that the film after phosphating is not washed and the defects of hanging ash and the like are not generated, the phosphating film has excellent corrosion resistance, the coating has ideal adhesive force, and the quality indexes of the corrosion resistance and the like of the phosphating film exceed the quality indexes of the phosphating of the zinc system and the iron system at normal temperature. (3) And energy is saved. And the phosphorization is carried out at the room temperature of 10-40 ℃ (the lowest temperature is 1 ℃), so that the energy is saved to the greatest extent. (4) And the material is saved. Suitable membranes have a weight (1 g/m)2Left and right), the sediment is few, really accomplish the bonderizing and needn't heat, and the molecule or the ion that constitute the bonderizing liquid all get into the phosphating coat or volatilize in the phosphating coat drying process and phosphating solution long-lived, the phosphating solution that the work piece was taken away or the washing water of phosphating coat can be retrieved and add to the phosphating solution and use, and consumption obviously reduces. (5) Is environment-friendly and safe to use. The phosphating solution does not contain toxic Cr and nitrite, phosphating is carried out at room temperature, surface adjustment is not needed, and water washing can be avoided after phosphating; no waste water, less waste slag and recoverable raw material for producing phosphorized liquid, iron oxide red, etc. (6) The operation is simple. The phosphating process has wide control parameters and multiple modes: the phosphating solution is stable and simple to operate, the phosphating time can be 30 seconds to dozens of hours (although the quality of a phosphating film of a workpiece is not influenced by the long phosphating time, the service life of the phosphating solution is influenced and sediment is generated), and the phosphating solution is directly dried or air-dried without water washing. All phosphating modes can be used: brushing, dipping, spraying or a combination thereof.
The technical scheme adopted for solving the technical problems of the invention is that the components of the phosphating solution of the multi-mode quick room-temperature cleaning zinc-based or zinc-calcium-based or iron-based phosphating solution are all composed of molecules or ions which can become the components of a phosphating film or sediment components or can be volatilized in the drying process of the phosphating film, so that the accumulation of byproducts and certain components which influence the adjustment of the phosphating solution is not generated in the phosphating process. The phosphating solution contains phosphoric acid, nitric acid or salts of ammonium, zinc, calcium, nickel and manganese (except alkali metals) of phosphoric acid and nitric acid, ammonium molybdate, ammonium tungstate, phytic acid, hydrogen peroxide, nonionic surfactant and the like, does not contain carcinogenic substances and toxic gas NO generated by decompositionxThe nitrite does not contain toxic Cr salt, and also does not contain Zn, Mn and Ni salt, and each componentThe content ranges are as follows:
phosphates and phosphoric acid (with PO)4 3-Meter): 6.8 to 32.0 g.L-1；
Nitrate (in NO)3 -Meter): 0.1 to 10.0 g.L-1；
Molybdate (in MoO)4 2-Meter): 1.0 to 8.1 g.L-1；
Tungstate (WO)4 2-Meter): 0.0 to 4.1 g.L-1；
Zn2+：0.0～12.5g·L-1；
Ca2+：0.0～6.5g·L-1；
Mn2+：0.0～4.5g·L-1；
Ni2+：0.0～3.5g·L-1；
Phytic acid: 0.0 to 5.1 g.L-1；
H2O2：0.0～5.0g·L-1
Nonionic surfactant: 0.0 to 1.0 g.L-1；
pH value: 2.0 to 5.8;
control parameters when the phosphating solution is applied are as follows: and (3) phosphating time: 30-900 s (the phosphating time is prolonged to 72h, and the quality of a phosphating film is good); and (3) phosphorization temperature: 1-50 ℃; and (3) a phosphorization mode: dipping, spraying, brushing, or a combination thereof.
The phosphating solution does not contain alkali metal salts.
The main drying treatment modes after the phosphating of the workpiece include the following steps:
① drying or naturally drying without washing;
② and washing with water, oven drying, and naturally drying or washing with hot water and naturally drying.
The manufacturing method of the product of the invention is as follows: dissolving the industrial salt such as phosphate, nitrate and molybdate or acid in a certain amount of tap water, adjusting the pH value to the required value by using industrial phosphoric acid or ammonia water after dissolving, and adding the nonionic surfactant. Phosphates, nitrates and molybdates refer to ammonium, zinc, calcium, manganese and nickel salts. A non-ionic surfactant such as TX-10.
Any molecule or ion of the phosphating solution in the invention enters the phosphating film to become a component of the phosphating film and the sediment, or volatilizes in the drying process of the phosphating film, so that no byproduct accumulation of film forming reaction and certain phosphating solution component accumulation exist in the phosphating process. Thus, the addition of certain substances to the phosphating solution changes the actual composition of the phosphating solution after a long period of use to the appropriate composition or design requirement of the phosphating solution because neither new irreversible substances nor certain components are added in the phosphating process at higher concentrations than when formulated.
Typical molecules or ions included in the phosphating solution are:
(1) the film can be formed into sediment (the sediment is all substances forming the phosphating film): phosphate radical anion (as PO)4 3-Meter) metal cation M2+(e.g., zinc Zn)2+Mn of Mn2+Calcium, Ca2+Ni-Ni2+Molybdenum ions, etc.) that bind to the phosphate that becomes insoluble (the unwashed phosphating film is not allowed to contain soluble salts, which affects the quality of the phosphating film, and the clean phosphated phosphating film is free of soluble salts).
The iron-based phosphating solution generally does not contain zinc, manganese and other ions. The zinc phosphating solution necessarily contains Zn2+. All phosphating solutions must have some of these ions (phosphate ions are essential) and no exception is made with clean phosphating solutions.
(2) Non-phosphating film forming part of four types: the first one is that the phosphating solution is forced to be scrapped and byproducts appear in the film-forming reaction, for example, when sodium chlorate is used as an accelerator, sodium chlorate becomes sodium chloride (NaCl) after the film-forming reaction, the sodium chlorate is continuously supplemented along with the continuous phosphating, the concentration of the sodium chloride is continuously increased, and after the concentration reaches a certain concentration, the sodium chloride is generated due to chloride ions (Cl)-) The phosphating film is influenced to force the phosphating solution to be scrapped; the second type is alkali metal ion (sodium Na)+Potassium, K+) Only the pH value of the phosphating solution is influenced, and the influence can be eliminated by adding phosphoric acid; however, if the phosphated films are not washed with water, they will adsorb in the form of alkali or saltsThe additive is attached to the phosphating film and can affect the performance of the phosphating film; the third kind is that the additive for improving the performance of the phosphate film is added artificially, such as sodium fluoride (NaF), EDTA, citric acid, etc. which are usually added, most of which do not take part in the film forming reaction and are used for complexing and eliminating harmful aluminum plasma and iron ion (Fe) which is dissolved too fast to exceed the film forming requirement2+、Fe3+) The influence of (1) is continuously supplemented along with the continuous progress of the phosphorization, the phosphorization liquid is scrapped after reaching a certain concentration, and the phosphorized film is washed by water, otherwise the phosphorized filmis dusted and even rusted; the fourth type is ammonia (NH)3) Or ammonium (NH)4 +) The pH value of the phosphating solution can be influenced, the influence can be eliminated by adding phosphoric acid, and if the phosphating film after phosphating is not washed, the phosphating film can be volatilized in the drying process of the phosphating film, so that the influence is not generated.
The cleaning phosphating solution is characterized in that any molecule or ion of the phosphating solution is volatilized in the drying process of the phosphating film, no by-product influencing the adjustment of the phosphating solution and accumulation of a certain component are generated in the phosphating process, namely, the first type, the second type and the third type of ions cannot exist, only the fourth type of ions exist, and of course, the second type of ions are allowed if the phosphating process allows the phosphating film after phosphating to be washed by water. The general phosphating solution has two or three types of ions in the first type, the second type and the third type. Therefore, theoretically, the service life of the phosphating solution is 'infinite', and the general phosphating solution is scrapped in the using process.
The reason why the cleaning phosphating solution provided by the invention does not need to be washed by water for phosphating film after phosphating
One is as follows: the phosphating solution does not contain the first type, the second type and the third type of ions, only contains the fourth type of ions in the four types, and the composition substances of the phosphating film which is not washed and is washed are consistent.
The second step is as follows: the residual phosphating solution on the surface of the phosphating film continues to form the film in the drying process of the phosphating film. For the above reasons, the kind of the constituent material of the phosphating film thereof is not increased by the residual phosphating solution on the surface of the phosphating film.
And thirdly: the composition (or concentration) of the phosphating solution remained on the surface of the phosphating film is just suitable for the drying speed, so that the surface of the phosphating film is not coated with ash (the ash is soluble or insoluble phosphate or oxide).
The quality of the phosphating film on the product treated by the phosphating solution is as follows:
① the phosphating film is continuous, uniform and compact, has no quality defect, and has a slightly gray or colored appearance;
② the corrosion resistance time (copper sulfate dripping resistance time, liquid preparation and detection according to GB 6807-86 appendix D) of the phosphating film is 50-600 s(s).
③ testing the film weight of the phosphating film to be 0.5-2.1 g.m according to the specification of GB/T9792--2。
④, the matching performance of the paint film is measured according to the regulation of GB 1720-79 paint film adhesion measuring method, and the matching performance reaches grade 1.
The design idea of the formula of the phosphating solution is embodied as follows: any molecules or ions of the phosphating solution become components of the phosphating film and the sediments or are volatilized in the drying process of the phosphating film; low consumption, convenient operation, fast phosphorization, high quality and environmental protection, and can replace the phosphorization of zinc series, iron series and the like used before the surface of steel is sprayed.
The product of the invention refers to the process flow for treating the surface of steel: degreasing and washing the surface of the steel, (degreasing and derusting in case of rust, washing), phosphorizing and drying.
The product of the invention has the following technical effects:
(1) the phosphating solution has long service life and no wastewater.
(2) The phosphating quality is greatly improved, and the phosphating modes are multiple: the corrosion resistance and the film weight of the phosphate film at room temperature are broken through and exceed the quality requirement of the phosphate before spraying specified by GB/T6807-2001. All phosphating modes of brushing, dipping and spraying can be adopted for phosphating.
(3) And energy is saved. And the phosphorization is carried out at the room temperature of 10-40 ℃ (the lowest temperature is 1 ℃), so that energy sources and preparation time are saved to the greatest extent.
(4) And the material is saved.
(5) Is environment-friendly and safe to use.
(6) The operation is simple. The phosphating process has wide control parameters and multiple modes, the phosphating solution is stable, the phosphating time can be 30 seconds to dozens of hours (the phosphating time is long, although the quality of a phosphating film of a workpiece is not influenced, the service life of the phosphating solution is influenced, sediment is generated), and the direct drying or self-drying is carried out without water washing after the phosphating. All phosphating modes can be used: brushing, dipping, spraying or a combination thereof.
Detailed Description
In the following non-limiting examples of the present invention, the test pieces were cold-rolled sheets of 70X80X 2.0mm, and after removing oil and rust by the recommended procedures using strong acid and strong alkali and washing with tap water, they were immediately phosphated to obtain a phosphate film having uniform gray-color and no quality defects. The corrosion resistance time was checked according to the provisions of GB 6807-86 appendix D, taking the average of three times. The adhesion was measured by spraying according to the regulations of GB 1720-79 "determination of adhesion of paint film".
(1) Example 1
The formula of the phosphating solution is as follows: ammonium dihydrogen phosphate [ NH]4H2PO4]：33.5g·L-1(ii) a Ammonium heptamolybdate [ (NH)4)6Mo7O24·4H2O]：8.5g·L-1(ii) a Phytic acid (C)6H18O24P6)：3.0g·L-1(ii) a Nickel nitrate [ Ni (NO)3)2·6H2O]：13.50g·L-1(ii) a With ammonia (NH)3·H2O) adjusting the pH value to 5.0.
Phosphating conditions and results: brushing the working solution on the test piece once at 10 ℃, then drying at 120 ℃ for 10min, checking the corrosion resistance time to be 220s after 30min, and checking the corrosion resistance time to be 320s after 12h (h); the adhesive force reaches 1 grade.
(2) Example 2
The formula of the phosphating solution is as follows: zinc dihydrogen phosphate [ Zn (H)2PO4)2]：27.8g·L-1(ii) a Ammonium heptamolybdate: 8.1 g.L-1(ii) a Phytic acid: 1.0 g.L-1(ii) a Calcium nitrate [ Ca (NO)3)2]：5.8g·L-1(ii) a Ammonium nitrate [ NH]4NO3]：2.1g·L-1(ii) a The pH was adjusted to 2.4 with ammonia.
Phosphating conditions and results: soaking the test piece in phosphating solution at 15 deg.C for 5min, oven drying at 120 deg.C for 8min, detecting corrosion resistance time of 120s after 30min, and measuring film weight of 1.25 g.m-2The adhesive force reaches 1 grade.
(3) Example 3
The formula of the phosphating solution is as follows: diammonium hydrogen phosphate [ (NH)4)2HPO4]：16.0g·L-1(ii) a Ammonium nitrate: 4.5 g.L-1(ii) a Ammonium heptamolybdate: 8.0 g.L-1(ii) a With phosphoric acid (85% H)3PO4) The pH was adjusted to 3.5.
Phosphating conditions and results: soaking the test piece in phosphating solution at 10 deg.C for 5min, taking out, oven drying at 120 deg.C for 10min, detecting corrosion resistance time of 138s after 30min, and film weight of 0.81 g.m-2The adhesive force reaches 1 grade.
The invention is suitable for phosphating treatment before spraying the surfaces of steel and iron such as cold-rolled plates, hot-rolled plates, angle steel and the like. The phosphorizing liquid is composed of phosphoric acid, nitric acid or its ammonium, zinc, calcium, nickel, manganese salts, ammonium molybdate, ammonium tungstate, phytic acid, hydrogen peroxide, etc., and does not contain carcinogenicity and toxic gas NO generated by decompositionxThe nitrite salt of (1) does not contain toxic Cr salt, and can not contain harmful Zn, Mn and Ni salt. The phosphorization speed is high, and phosphorization can be carried out by dipping, spraying, brushing or a combination mode of the dipping, the spraying and the brushing at the temperature of 1-50 ℃. The phosphating solution is stable and is simple to operate. The phosphating film is continuous, uniform and compact, has no quality defect, is gray or colored in appearance,can resist copper sulfate dripping for 50-600 s, and has the film weight of 0.3-2.1 g.m-2The adhesive force reaches 1 grade after painting. Less sediment and no wastewater discharge after phosphorization.
Claims (4)
1. The clean zinc or zinc-calcium or iron phosphating liquid features that its components are composed of molecules or ions capable of being used as the components of phosphating film or the components of deposited slag or volatilizing during the drying of phosphating film, and this can prevent the accumulation of by-product and certain component affecting the regulation of phosphating liquid.
2. The multimode, rapid room-temperature zinc-based or zinc-calcium-based or iron-based cleaning phosphating solution according to claim 1, which is characterized by comprising salts of ammonium, zinc, calcium, nickel and manganese except alkali metals of phosphoric acid, nitric acid or phosphoric acid and nitric acid, wherein the content ranges of the components are as follows:
phosphoric acid and phosphoric acid salts (with PO)4 3-Meter): 6.8 to 32.0 g.L-1；
Nitric acid and nitrate (with NO)3 -Meter): 0.1 to 10.0 g.L-1；
Molybdate (in MoO)4 2-Meter): 1.0 to 8.1 g.L-1；
3. The multi-mode, rapid room-temperature zinc-based or zinc-calcium-based or iron-based clean phosphating solution according to claim 2, which is characterized by containing ammonium tungstate, phytic acid, hydrogen peroxide and a nonionic surfactant:
tungstate (WO)4 2-Meter): 0.0 to 4.1 g.L-1；
Zn2+：0.0～12.5g·L-1；
Ca2+：0.0～6.5g·L-1；
Mn2+：0.0～4.5g·L-1；
Ni2+：0.0～3.5g·L-1；
Phytic acid: 0.0 to 5.1 g.L-1；
H2O2：0.0～5.0g·L-1
Nonionic surfactant: 0.0 to 1.0 g.L-1；
4. The multi-way, rapid room temperature cleaning zinc-based and iron-based phosphating solution according to claim 1, 2 or 3, characterized by a pH value of 2.0-5.8.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410023096XA CN100383281C (en) | 2004-04-09 | 2004-04-09 | Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles |
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| CNB200410023096XA CN100383281C (en) | 2004-04-09 | 2004-04-09 | Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles |
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| CN100383281C CN100383281C (en) | 2008-04-23 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840B (en) * | 2007-11-28 | 2010-06-16 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
| CN102121103B (en) * | 2010-01-11 | 2012-07-04 | 张华斌 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
| CN102747356A (en) * | 2012-07-30 | 2012-10-24 | 长沙学院 | Normal temperature calcium-manganese phosphorizing liquid |
| CN102899651A (en) * | 2011-07-29 | 2013-01-30 | 史学斌 | Multi-function metal surface treatment agent |
| CN103769432A (en) * | 2014-01-28 | 2014-05-07 | 威海银兴预应力线材有限公司 | Steel strand production device and electrolysis phosphating technology |
| CN104313620A (en) * | 2014-10-14 | 2015-01-28 | 熊荣鑫 | Method for cleaning rust on surfaces of iron and iron alloy |
| CN106756926A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of environment-friendly phosphating solution and its application for steel |
| CN108998787A (en) * | 2018-06-13 | 2018-12-14 | 河南北方红阳机电有限公司 | A kind of novel spraying phosphorus is at film liquid and its spray phosphorus technique |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | Phosphating solution, phosphate coating, preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238557C (en) * | 2003-07-11 | 2006-01-25 | 余取民 | Environmental protection type multi mode, fast and enery saving iron series phosphatizing solution |
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- 2004-04-09 CN CNB200410023096XA patent/CN100383281C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840B (en) * | 2007-11-28 | 2010-06-16 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
| CN102121103B (en) * | 2010-01-11 | 2012-07-04 | 张华斌 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
| CN102899651A (en) * | 2011-07-29 | 2013-01-30 | 史学斌 | Multi-function metal surface treatment agent |
| CN102747356A (en) * | 2012-07-30 | 2012-10-24 | 长沙学院 | Normal temperature calcium-manganese phosphorizing liquid |
| CN102747356B (en) * | 2012-07-30 | 2014-08-20 | 长沙学院 | Normal temperature calcium-manganese phosphorizing liquid |
| CN103769432A (en) * | 2014-01-28 | 2014-05-07 | 威海银兴预应力线材有限公司 | Steel strand production device and electrolysis phosphating technology |
| CN104313620A (en) * | 2014-10-14 | 2015-01-28 | 熊荣鑫 | Method for cleaning rust on surfaces of iron and iron alloy |
| CN106756926A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of environment-friendly phosphating solution and its application for steel |
| CN108998787A (en) * | 2018-06-13 | 2018-12-14 | 河南北方红阳机电有限公司 | A kind of novel spraying phosphorus is at film liquid and its spray phosphorus technique |
| CN108998787B (en) * | 2018-06-13 | 2021-01-26 | 河南北方红阳机电有限公司 | Phosphorus spraying film forming solution and phosphorus spraying process thereof |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | Phosphating solution, phosphate coating, preparation method and application thereof |
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