US3729346A - High-pressure spray process for phosphating iron or steel surfaces - Google Patents
High-pressure spray process for phosphating iron or steel surfaces Download PDFInfo
- Publication number
- US3729346A US3729346A US00145931A US3729346DA US3729346A US 3729346 A US3729346 A US 3729346A US 00145931 A US00145931 A US 00145931A US 3729346D A US3729346D A US 3729346DA US 3729346 A US3729346 A US 3729346A
- Authority
- US
- United States
- Prior art keywords
- spray
- phosphating
- pressure
- iron
- rust
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title abstract description 31
- 230000008569 process Effects 0.000 title abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 22
- 229910052742 iron Inorganic materials 0.000 title abstract description 11
- 239000007921 spray Substances 0.000 title description 25
- 229910000831 Steel Inorganic materials 0.000 title description 13
- 239000010959 steel Substances 0.000 title description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 229910019142 PO4 Inorganic materials 0.000 abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 12
- 239000010452 phosphate Substances 0.000 abstract description 9
- 238000005507 spraying Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 7
- 235000021317 phosphate Nutrition 0.000 description 14
- 238000000576 coating method Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 7
- 229910000165 zinc phosphate Inorganic materials 0.000 description 7
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/76—Applying the liquid by spraying
Definitions
- the application of the treatment solutions is carried out at a spray-pressure of about 0.5-1.5 atmospheres gauge.
- Another object of the present invention is to provide a spray-process for phosphating surfaces of objects made of iron or steel which obviates a subsequent passivation treatment of the phosphated surfaces with solutions containing chromic acid or chromates.
- the high-pressure spray process according to the present invention produces satisfactory phosphate coatings over the entire indicated pressure range. Particularly favorable results with respect to stability against fly-rust and coating structure are obtained if the acid solutions of phosphates of film forming metals are sprayed upon the metal surfaces at a spray pressure in the range of 30 to 50 atmospheres gauge.
- the temperature at which the phosphating solution is applied to the metal surface lies advantageously in the range between 40 and C.
- the high-pressure spray process is caried out with the same layer-forming coating solutions which have heretofore been conventionally used for spray-phosphating at low pressure.
- the acid solutions contain phosphate ions and cations of polyvalent metals, such as magnesium, manganese, cadmium, cobalt, nickel and lead, individually or in admixture with each other. Because of the particularly favorable properties of the phosphate layers prepared therewith in regard to corrosion stability and improved lacquer adhesion, those solutions are preferably used which contain zinc or calcium as layer-forming cations, but also those solutions are suitable which contain zinc and calcium ions together in various atomic weight ratios. For acceleration of the coating formation, customary accelerators are added to the phosphating solutions.
- oxidizing agents such as nitrites, nitrates, chlorates, perborates or hydrogen peroxide, or with the combination nitrite/ nitrate, nitrite/chlorate or nitrate/perborate.
- the phosphating solutions used in the high-pressure spray process according to the present invention contain phosphate ions, polyvalent metal ions and accelerators in the customary concentrations. Also, the ratio of free acid to bound acid, as well as the Working pH, lie within the conventional limits.
- cleaning and phosphating may be carried out in one working step.
- non-ionic wetting agents such as reaction products of the ethylene oxide with fatty alcohols, alkylphenols, fatty amines or polyoxypropyleneglycols, are added to the acid phosphating solution.
- concentration of the wetting agents in the phosphating solution lies within the customary limits of 0.1 to 5 gm./
- the phosphating of iron and steel surfaces by the highpressnre spray process can be carried out in automatic installations as well as with the aid of manual spraying equipment.
- the iron and steel surfaces phosphated by the process pursuant to the present invention are resistant against fly-rust, so that a subsequent treatment with chromic acid or chromate solutions is unnecessary.
- the phosphate layers produced thereby are more closed and have a finer crystals structure than phosphate coatings produced with the same phosphating solution, but at a low spraying pressure by known processes; with respect to corrosion protection and lacquer adhesion they are at least equivalent to the latter.
- the high-pressure spray process according to the present invention has the additional advantage relative to the known low-pressure spray processes that it does not require a subsequent passivation of the phosphatized metal surfaces. Consequently not only the chromic acid passivation step, but also the required work-physiological protective measures and the detoxification of the waste liquids are obviated. This is particularly advantageous in cases where ferrous metal surfaces are to be phosphated by manual spraying; thus, the layer-forming phosphating treatment can now also be applied where its application was heretofore not feasible with regard to Work-physiology and waste liquid detoxification, as well as to fixed metal structures, such as overhead eelctrical transmission line towers, bridges, etc.
- the phosphated bodies were rinsed with tap water, then with completely desalted water and finally dried in a hot air stream.
- This treatment provided the steel bodies with a homogeously formed, dense zinc phosphate layer.
- the treated surface showed no deposit of fiy-rust.
- a non-ionic wetting agent (addition product of 1 mol of nonylphenol to 9 mols of ethylene oxide) 1.6
- the phosphate-coated iron sheets were electrophoret- 4 ically lacquered and subjected to the salt-spray test according to ASTM B 117-64 with cross-cut. After 350 hours the following values were obtained:
- a rust-protective phosphate coating to a ferric metal surface, which comprises spraying an aqueous phosphoric acid solution of phosphates of layer-forming metals selected from the group consisting of zinc phosphate, calcium phosphate and mixtures thereof, in the presence of oxidizing agent accelerators under pressure onto said surface, the improvement which consists in that the spray pressure is from 10 to 100 atmospheres gauge.
- aqueous phosphoric acid solution of phosphates is an aqueous phosphoric acid solution of zinc phosphate.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Paper (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT487270 | 1970-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3729346A true US3729346A (en) | 1973-04-24 |
Family
ID=3569322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00145931A Expired - Lifetime US3729346A (en) | 1970-06-01 | 1971-05-21 | High-pressure spray process for phosphating iron or steel surfaces |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3729346A (fr) |
| DE (1) | DE2123966C3 (fr) |
| FR (1) | FR2093957B1 (fr) |
| GB (1) | GB1321003A (fr) |
| SE (1) | SE366347B (fr) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017335A (en) * | 1975-10-30 | 1977-04-12 | Economics Laboratory, Inc. | Liquid phosphatizing composition and use thereof |
| US4060433A (en) * | 1976-03-05 | 1977-11-29 | Economics Laboratory, Inc. | Foam phosphatizing method and composition |
| US4108690A (en) * | 1976-04-05 | 1978-08-22 | Amchem Products, Inc. | Method for producing an amorphous, light weight calcium phosphate coating on ferrous metal surfaces |
| US4384900A (en) * | 1979-12-21 | 1983-05-24 | Gerhard Collardin Gmbh | Method of treating metal surfaces prior to phosphatization |
| CN103451638B (zh) * | 2013-09-02 | 2015-10-28 | 东南大学 | 一种增强钢铁材料表面抗氧化能力的压力磷化法 |
| EP4249635A1 (fr) * | 2022-03-25 | 2023-09-27 | Hamilton Sundstrand Corporation | Application de revêtements de conversion chimique de type ii (ccc) à l'aide d'agents moussants |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5811514B2 (ja) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | 金属表面の保護方法 |
| IT1302593B1 (it) * | 1998-10-02 | 2000-09-29 | Abb Ricerca Spa | Procedimento di pretrattamento di lamierati metallici destinati allaverniciatura |
| CN116356269A (zh) * | 2021-12-28 | 2023-06-30 | 无锡互盛智能科技有限公司 | 一种超高寿命金属制品的涂装工艺 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1042545A (fr) * | 1951-10-03 | 1953-11-02 | Procédé de phosphatation, desoxydation et passivation des surfaces métalliques par la vapeur |
-
1971
- 1971-05-04 SE SE05782/71A patent/SE366347B/xx unknown
- 1971-05-07 GB GB1379271*[A patent/GB1321003A/en not_active Expired
- 1971-05-14 DE DE2123966A patent/DE2123966C3/de not_active Expired
- 1971-05-21 US US00145931A patent/US3729346A/en not_active Expired - Lifetime
- 1971-06-01 FR FR7119712A patent/FR2093957B1/fr not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4017335A (en) * | 1975-10-30 | 1977-04-12 | Economics Laboratory, Inc. | Liquid phosphatizing composition and use thereof |
| US4060433A (en) * | 1976-03-05 | 1977-11-29 | Economics Laboratory, Inc. | Foam phosphatizing method and composition |
| US4108690A (en) * | 1976-04-05 | 1978-08-22 | Amchem Products, Inc. | Method for producing an amorphous, light weight calcium phosphate coating on ferrous metal surfaces |
| US4384900A (en) * | 1979-12-21 | 1983-05-24 | Gerhard Collardin Gmbh | Method of treating metal surfaces prior to phosphatization |
| CN103451638B (zh) * | 2013-09-02 | 2015-10-28 | 东南大学 | 一种增强钢铁材料表面抗氧化能力的压力磷化法 |
| EP4249635A1 (fr) * | 2022-03-25 | 2023-09-27 | Hamilton Sundstrand Corporation | Application de revêtements de conversion chimique de type ii (ccc) à l'aide d'agents moussants |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2123966B2 (de) | 1979-06-21 |
| DE2123966A1 (de) | 1971-12-16 |
| SE366347B (fr) | 1974-04-22 |
| GB1321003A (en) | 1973-06-20 |
| DE2123966C3 (de) | 1980-03-13 |
| FR2093957B1 (fr) | 1973-11-23 |
| FR2093957A1 (fr) | 1972-02-04 |
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