CA1133806A - Detergent phosphatizer composition and method of using same - Google Patents
Detergent phosphatizer composition and method of using sameInfo
- Publication number
- CA1133806A CA1133806A CA326,560A CA326560A CA1133806A CA 1133806 A CA1133806 A CA 1133806A CA 326560 A CA326560 A CA 326560A CA 1133806 A CA1133806 A CA 1133806A
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- phosphatizing
- composition
- oxidizer
- iron
- 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
Links
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
- C23C22/05—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
Abstract
ABSTRACT OF THE DISCLOSURE
Room temperature detergent a liquid iron phosphatizer composition for use in industrial metal cleaning and spray washing applications, which also can be heated to clean and phosphatize under heavy-soil load conditions. The composition consists essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum compounds and from about 1 weight percent to about 20 weight percent of at least one oxidizer.
Room temperature detergent a liquid iron phosphatizer composition for use in industrial metal cleaning and spray washing applications, which also can be heated to clean and phosphatize under heavy-soil load conditions. The composition consists essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum compounds and from about 1 weight percent to about 20 weight percent of at least one oxidizer.
Description
~3380~
-1- C-11~4Y
" ~ETERGE~T I~ON PHOSPHRTIZER COMPOSI~O~
AND METHOD OF USING SAME"
This invention relates to a composition and process for cleaning and phosphatizing metals prior to painting.
More particularly, this invention relates to a composition and process for cleaning and phospha-tizing metals which substantially reduces the energy requirements of the cleaning and phosphatizing pro-cess.
Both iron and zinc phosphatizing processes are utilized to impart a crystalline phosphate layer to metal surfaces in order to improve paint adhesion and corrosion resistance. While phosphatizing pro-cesses nave been wid~ly used in the past, their use has been accompanied by a number of ~actors such as 1~ the requirements for high operating temperatures, high energy costs and o~er-phosphatizing due to over-activation by heat.
~?
-- 11338~6
-1- C-11~4Y
" ~ETERGE~T I~ON PHOSPHRTIZER COMPOSI~O~
AND METHOD OF USING SAME"
This invention relates to a composition and process for cleaning and phosphatizing metals prior to painting.
More particularly, this invention relates to a composition and process for cleaning and phospha-tizing metals which substantially reduces the energy requirements of the cleaning and phosphatizing pro-cess.
Both iron and zinc phosphatizing processes are utilized to impart a crystalline phosphate layer to metal surfaces in order to improve paint adhesion and corrosion resistance. While phosphatizing pro-cesses nave been wid~ly used in the past, their use has been accompanied by a number of ~actors such as 1~ the requirements for high operating temperatures, high energy costs and o~er-phosphatizing due to over-activation by heat.
~?
-- 11338~6
-2- C-1194IA
These disadvantages are overcome by the compo-sition and process of the instant invention, in which a heavy metal accelerator and an oxidizing agent are added to an iron phosphatizing composition to permit improved coating ability at reducea operating temper-atures. Suitable oxidizing agents include bromates, chlorates, iodates, sulfites, nitrates, nitrites, hydrogen peroxide, chlorites and organic nitro com-pounds. The compounds used most frequently are the chlorates.
As used herein, an iron phosphatizing composi-tion and process is distinguished from a zinc phos-phatizing composition and process in several ways.
Iron phosphatizing compositions contain no zinc, when applied have a thin amorphous structure and are applied at coatweights oflO to 90 mg~ft. while zinc phosphate coatin~ compositions contain zinc ~s an essential ingredient, when applied have a relatively heavy, definite crystal structure and are applied at coatweights of 100 to 1000 mg/ft.2.
~ eavy metal accelerators useful in the composi-tions of the instant invention include compounds of such metals as vanadium, titanium, zirconium, tungs-ten and molybdenum. The compounds utilized most frequently are the molybdates.
The molybdenum compounds promote the phosphate action on the surface of metals by seeding or plating out on the surface, and then incorporating themselves as l~wer oxides of molybdenum with the iron phosphate
These disadvantages are overcome by the compo-sition and process of the instant invention, in which a heavy metal accelerator and an oxidizing agent are added to an iron phosphatizing composition to permit improved coating ability at reducea operating temper-atures. Suitable oxidizing agents include bromates, chlorates, iodates, sulfites, nitrates, nitrites, hydrogen peroxide, chlorites and organic nitro com-pounds. The compounds used most frequently are the chlorates.
As used herein, an iron phosphatizing composi-tion and process is distinguished from a zinc phos-phatizing composition and process in several ways.
Iron phosphatizing compositions contain no zinc, when applied have a thin amorphous structure and are applied at coatweights oflO to 90 mg~ft. while zinc phosphate coatin~ compositions contain zinc ~s an essential ingredient, when applied have a relatively heavy, definite crystal structure and are applied at coatweights of 100 to 1000 mg/ft.2.
~ eavy metal accelerators useful in the composi-tions of the instant invention include compounds of such metals as vanadium, titanium, zirconium, tungs-ten and molybdenum. The compounds utilized most frequently are the molybdates.
The molybdenum compounds promote the phosphate action on the surface of metals by seeding or plating out on the surface, and then incorporating themselves as l~wer oxides of molybdenum with the iron phosphate
3~ which ~orms in the reaction. ~owever, the mo~y~denum 113380~
comes out in the form of oxides rather than the metal, and leads to a supplementary protective non- -corrosive coating. Although applicant does not wish to be bound by theory, it is believed that the chem-ical plating, precipitating or coating reaction inthe absence of heat is as follows:
I. 2Fe + 4H -~ 2Fe + + 2H2~
II 2~ + 4MoO~ + ~H~ oxidizer~ 2Mo205~+ 2H20 +
III 2Fe + 2MoO4 + 6H ~ Mo20~ + 2Fe + 3~2 IV. 2Fe + 2PO4--~2FePo4~
2FePO4 + 3M2s V 2Fe + 6MoO4 ~ 18H + 2PO4 ~ Coating The detergent iron phosphatizer composiitons of the present invention may be applied by ccnventional immersion or spray processes. Typical processes which may be used include a three-stage process which com-prises a cleaning and phosphatizing step, a water rinse step and a chromic acid or non-chromic acid rinse step. Non-chromic acid containing rinse for-mulations such as sodium nitri~e or organic chelating agents may be used where it is ecologica~ly desirable to eliminate chromium from a~ueous discharges. Better phosphate coatings may be obtained by using a ~ive-stage process which comprises an alkaline cleaningstep, a rinse step, a phosphatizing step, an addi-tional rinse step and a chromic acid or non-chromic
comes out in the form of oxides rather than the metal, and leads to a supplementary protective non- -corrosive coating. Although applicant does not wish to be bound by theory, it is believed that the chem-ical plating, precipitating or coating reaction inthe absence of heat is as follows:
I. 2Fe + 4H -~ 2Fe + + 2H2~
II 2~ + 4MoO~ + ~H~ oxidizer~ 2Mo205~+ 2H20 +
III 2Fe + 2MoO4 + 6H ~ Mo20~ + 2Fe + 3~2 IV. 2Fe + 2PO4--~2FePo4~
2FePO4 + 3M2s V 2Fe + 6MoO4 ~ 18H + 2PO4 ~ Coating The detergent iron phosphatizer composiitons of the present invention may be applied by ccnventional immersion or spray processes. Typical processes which may be used include a three-stage process which com-prises a cleaning and phosphatizing step, a water rinse step and a chromic acid or non-chromic acid rinse step. Non-chromic acid containing rinse for-mulations such as sodium nitri~e or organic chelating agents may be used where it is ecologica~ly desirable to eliminate chromium from a~ueous discharges. Better phosphate coatings may be obtained by using a ~ive-stage process which comprises an alkaline cleaningstep, a rinse step, a phosphatizing step, an addi-tional rinse step and a chromic acid or non-chromic
-4- C-1194IA
acid rinse step. The five-stage process permits the application of a more uniform phosphate coating. As previously stated, an advantage of the composition and p~ocess of this invention is the ability to oper-ate efficiently at reduced temperatures. Best re-sults are obtained at temperatures of 60 to 130~. as opposed to conventional operating temperatures of 140 to 160~F.
~oth the three- and fi~e-stage process may be controlled manually or automatically. Automatic con-trol is, however, preferred because it permits more accurate control of the concentration of the coating compositions, thereby resulting in a more uniform coating on the metal surfaces being treated.
The compositions of the present invention may be prepared by conventional liquid or powder blending techni~ues.
The liquid iron phosphatizing compositions of the present invention do not contain zinc and con-sist essentially of:
_ mponentAmount (Wei~ht Percent) Water 94 to 50 Phosp~oric Acid 5 to 40 ~eavy Metal Accelerator0.1 to 5 25 Oxidizing Agent 1 to 20 These compositions may also contain ca~stic to con-trol p~ and from about ~.5 to about 15 weight percent of a nonionic detergent if it is desired to use a detergent phosphatizer composition in a three-step process which combines the cleaning and phosphatiæing 1~338(~6
acid rinse step. The five-stage process permits the application of a more uniform phosphate coating. As previously stated, an advantage of the composition and p~ocess of this invention is the ability to oper-ate efficiently at reduced temperatures. Best re-sults are obtained at temperatures of 60 to 130~. as opposed to conventional operating temperatures of 140 to 160~F.
~oth the three- and fi~e-stage process may be controlled manually or automatically. Automatic con-trol is, however, preferred because it permits more accurate control of the concentration of the coating compositions, thereby resulting in a more uniform coating on the metal surfaces being treated.
The compositions of the present invention may be prepared by conventional liquid or powder blending techni~ues.
The liquid iron phosphatizing compositions of the present invention do not contain zinc and con-sist essentially of:
_ mponentAmount (Wei~ht Percent) Water 94 to 50 Phosp~oric Acid 5 to 40 ~eavy Metal Accelerator0.1 to 5 25 Oxidizing Agent 1 to 20 These compositions may also contain ca~stic to con-trol p~ and from about ~.5 to about 15 weight percent of a nonionic detergent if it is desired to use a detergent phosphatizer composition in a three-step process which combines the cleaning and phosphatiæing 1~338(~6
-5- C-1194IA
steps, The preferre~ compositions consist essentially of fro~ about 45 to about 85 weight percent water, from about 10 to about 40 weight percent phosphoric acid, from about 0.5 to about 2 weight percent of at least one heavy metal accelerator, and from about 3 to about 10 weight percent of at least one oxidizer.
The solid powder phosphatizing compositions of the present invention consist essentially of:
_ mponent Amount (Weight Percent) Mono Sodium Phosphate 25 to 85 ~eavy Metal Accelerator 0,1 to Oxidizing ~gent 1 to 50 The preferred oxidizing agent is a blend of a 1~ chlorate and a nitrate and these compositions may also contain from about 0.5 to about 15 weight per-cent of a nonionic detergent. The preferred powder coating compositions consist essentially of from about 40 to about ~0 weight percent mono sodium 2~ phosphate, from about 0.5 to about 2 wei~ht percent of at least one heavy metal accelerator an~ from about 30 to about 50 weight per~ent of at least one oxidizer.
~he compositions of the present invention may be use~ in spray or immersion processes in concen-trations of at least 1 oz./gallon of water and pre-ferably at least 3 oz./gal10n of watex.
T~e following examples are representative of - 113;~8~6
steps, The preferre~ compositions consist essentially of fro~ about 45 to about 85 weight percent water, from about 10 to about 40 weight percent phosphoric acid, from about 0.5 to about 2 weight percent of at least one heavy metal accelerator, and from about 3 to about 10 weight percent of at least one oxidizer.
The solid powder phosphatizing compositions of the present invention consist essentially of:
_ mponent Amount (Weight Percent) Mono Sodium Phosphate 25 to 85 ~eavy Metal Accelerator 0,1 to Oxidizing ~gent 1 to 50 The preferred oxidizing agent is a blend of a 1~ chlorate and a nitrate and these compositions may also contain from about 0.5 to about 15 weight per-cent of a nonionic detergent. The preferred powder coating compositions consist essentially of from about 40 to about ~0 weight percent mono sodium 2~ phosphate, from about 0.5 to about 2 wei~ht percent of at least one heavy metal accelerator an~ from about 30 to about 50 weight per~ent of at least one oxidizer.
~he compositions of the present invention may be use~ in spray or immersion processes in concen-trations of at least 1 oz./gallon of water and pre-ferably at least 3 oz./gal10n of watex.
T~e following examples are representative of - 113;~8~6
-6- C-1194IA
the compositions of the present invention:
ComponentAmount (Weight Percent) Water 73 5 75% Phosphoric Acid15 Sodium Chlorate 3 Sodium Molybdate Nonionic Detergent 8 ComponentAmount (Weight Percent) Water 41.5 75~ Phosphoric Acid 35 Sodium Chlorate 10 Sodium Molybdate 15 Sodium Nitrate 5 Sodium Hydroxide 7.5 ComponentAmount (Weight Percent) Water 50 20 75% Phosphoric Acid35 Sodium Molybdate 2 Sodium Nitrate 5 Sodium Nitrite 0.5 Sodium Hydroxide 7.S
-ComponentAmount (Weight Percent) Water 40 75% Phosphoric Acid 35 Sodium Chlorate 10 30 Sodium Nitrate Sodium ~ydroxide 7.5 Sodi~m Meta~anadate 2.5 113380~
the compositions of the present invention:
ComponentAmount (Weight Percent) Water 73 5 75% Phosphoric Acid15 Sodium Chlorate 3 Sodium Molybdate Nonionic Detergent 8 ComponentAmount (Weight Percent) Water 41.5 75~ Phosphoric Acid 35 Sodium Chlorate 10 Sodium Molybdate 15 Sodium Nitrate 5 Sodium Hydroxide 7.5 ComponentAmount (Weight Percent) Water 50 20 75% Phosphoric Acid35 Sodium Molybdate 2 Sodium Nitrate 5 Sodium Nitrite 0.5 Sodium Hydroxide 7.S
-ComponentAmount (Weight Percent) Water 40 75% Phosphoric Acid 35 Sodium Chlorate 10 30 Sodium Nitrate Sodium ~ydroxide 7.5 Sodi~m Meta~anadate 2.5 113380~
-7- C-1194IA
Component Amount (Weight Percent) Sodium Chlorate 5.0 Sodium Molybdate 0.5 5 Nonionic Detergent 4.5 Sodium Nitrate 45 Mono Sodium Phosphate 45 EXA~LE 6 This example demonstrates the synergistic ef-fects of the use of sodium molybdate (heavy metal accelerator) in combination with sodium chlorate (oxidizer~, which improves the phosphate coating ability of the formulation at reduced operating tem-peratures.
Formulation Data:
Formula Material A B C D
Water 58% 61% 59% 62%
Sodium Chlorate 3~ --- 3~
Sodium Molybdate 1~ 1% --- ---75% Phosphoric Acid15% 15% 15~ 15%
50~ NaOH 5% 5% 5~ 5 ~onionic Detergent12% 12% 12% 12 Hydrotrope 6% 6~ 6~ 6 Procedure:
Formulations containing the above combination as well as each indi~idual component and a control were prepared in the la~oratory as given in the for-mula description abo~. Four hundred fifty (4~0~
grams of each material (A, B, C and D) was added to five gallons of hot water (3 oz./gallon) which was 11338(~6
Component Amount (Weight Percent) Sodium Chlorate 5.0 Sodium Molybdate 0.5 5 Nonionic Detergent 4.5 Sodium Nitrate 45 Mono Sodium Phosphate 45 EXA~LE 6 This example demonstrates the synergistic ef-fects of the use of sodium molybdate (heavy metal accelerator) in combination with sodium chlorate (oxidizer~, which improves the phosphate coating ability of the formulation at reduced operating tem-peratures.
Formulation Data:
Formula Material A B C D
Water 58% 61% 59% 62%
Sodium Chlorate 3~ --- 3~
Sodium Molybdate 1~ 1% --- ---75% Phosphoric Acid15% 15% 15~ 15%
50~ NaOH 5% 5% 5~ 5 ~onionic Detergent12% 12% 12% 12 Hydrotrope 6% 6~ 6~ 6 Procedure:
Formulations containing the above combination as well as each indi~idual component and a control were prepared in the la~oratory as given in the for-mula description abo~. Four hundred fifty (4~0~
grams of each material (A, B, C and D) was added to five gallons of hot water (3 oz./gallon) which was 11338(~6
-8- C-1194IA
allowed to spray continuously at 15 PSI without addi-tional heat, during which time Triplicate R-35 "Q"
panels were placed in the spray for two minute inter-vals at various temperatures as the solution cooled.
The panels were spray water rinsed and immediately dryed and wrapped in foil for coating weight evalu-ation, The spray washer was thoroughly rinsed be-tween each process. The operating temperature was measured immediately after processing each series of panels.
Results:
TABLE I
Temperature Average Coating Weight Form. Series (C.)(mgs/ft.~) A A4 23.0 17.44 A 1 25.0 16.80 A 2 28.0 19.20 A 3 30.0 24.32 A 4 34.5 24.48 A 5 40.5 25.g2 A Al 48.0 32.32 B 4 24.0 14.40 B 3 30.0 14.72 B 2 36.0 22.56 B 1 41.0 26.24 2~ C 4 23.0 7.84 C 3 29.0 14.88 C 2 35.0 15.~2 C 1 49,0 17.92 D 6 26.0 10.50 ~ 5 27.0 14,00 ~ 4 30.5 13.20 D 3 35.0 14.70 ~ 2 37.5 14.20 D 1 43.0 15.50 11338~6
allowed to spray continuously at 15 PSI without addi-tional heat, during which time Triplicate R-35 "Q"
panels were placed in the spray for two minute inter-vals at various temperatures as the solution cooled.
The panels were spray water rinsed and immediately dryed and wrapped in foil for coating weight evalu-ation, The spray washer was thoroughly rinsed be-tween each process. The operating temperature was measured immediately after processing each series of panels.
Results:
TABLE I
Temperature Average Coating Weight Form. Series (C.)(mgs/ft.~) A A4 23.0 17.44 A 1 25.0 16.80 A 2 28.0 19.20 A 3 30.0 24.32 A 4 34.5 24.48 A 5 40.5 25.g2 A Al 48.0 32.32 B 4 24.0 14.40 B 3 30.0 14.72 B 2 36.0 22.56 B 1 41.0 26.24 2~ C 4 23.0 7.84 C 3 29.0 14.88 C 2 35.0 15.~2 C 1 49,0 17.92 D 6 26.0 10.50 ~ 5 27.0 14,00 ~ 4 30.5 13.20 D 3 35.0 14.70 ~ 2 37.5 14.20 D 1 43.0 15.50 11338~6
-9- C-1194IA
Table I clearly demonstrates the improved coating weights obtained with the compositions of the present invention.
Table I clearly demonstrates the improved coating weights obtained with the compositions of the present invention.
Claims (9)
1. A liquid iron phosphatizing composition which consists essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum compounds and from about l weight percent to about 20 weight percent of at least one oxidizer.
2. An iron phosphatizing composition as in Claim l, wherein the oxidizer is at least one member selected from the group consisting of chlorates, bromates, iodates, nitrates, sulfites, nitrites, hydro-gen peroxide, chlorites and organic nitro compounds.
3. An iron phosphatizing composition as in Claim 1 which further contains caustic.
4. An iron phosphatizing composition as in Claim 1 which further contains at least one nonionic detergent of 0.5 to 15 weight percent.
5. A process for phosphatizing metallic surfaces at solution temperatures of 60° to 130°F. which comprises coating said metallic surfaces with an iron phosphatizing composition consisting essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum and from about 1 weight percent to about 20 weight percent of at least one oxidizer.
6. A process for treating metallic surfaces at a solution temperature of 60° to 130°F. which com-prises the steps of cleaning and phosphatizing the metallic surface with an iron phosphatizing composition consisting essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum and from about 1 weight percent to about 20 weight percent of at least one oxidizer, rinsing the cleaned and phosphatized metallic surfaces with water and applying a chromic acid rinse.
7. A process as in Claim 6, wherein the cleaning and phosphatizing step and the chromic acid rinse step are automatically monitored to insure the maintenance of uniform concentrations of the active ingredient in the coating solutions being used.
8. A metal treating process comprising an alkaline cleaning step, a rinse step, a phosphatizing step at a solution temperature of 60° to 130°F. which utilizes an iron phosphatizing composition which consists essentially of from about 50 weight percent to about 94 weight percent water, from about 5 weight percent to about 40 weight percent phosphoric acid, from about 0.1 weight percent to about 5 weight percent of at least one heavy metal accelerator selected from the group consisting of vanadium, titanium, zirconium, tungsten and molybdenum and from about l weight percent to about 20 weight percent of at least one oxidizer, a further rinse step and a chromic acid rinse step.
9 A process as in Claim 6, wherein the cleaning, phosphatizing and chromic acid rinse step are automatically monitored to insure the maintenance of uniform concentrations of the active ingredient in the coating solutions being used.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US90416178A | 1978-05-08 | 1978-05-08 | |
| US904,161 | 1978-05-08 | ||
| US96500178A | 1978-11-30 | 1978-11-30 | |
| US965,001 | 1978-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133806A true CA1133806A (en) | 1982-10-19 |
Family
ID=27129389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA326,560A Expired CA1133806A (en) | 1978-05-08 | 1979-04-27 | Detergent phosphatizer composition and method of using same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1133806A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039363A (en) * | 1987-12-18 | 1991-08-13 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| WO2002079539A2 (en) * | 2001-03-29 | 2002-10-10 | Macdermid Plc | Treatment of zinc and zinc alloy surfaces |
| EP1394288A2 (en) * | 1996-10-30 | 2004-03-03 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| EP1483429A1 (en) * | 2002-02-14 | 2004-12-08 | MacDermid, Incorporated | Magnesium conversion coating composition and method of using same |
-
1979
- 1979-04-27 CA CA326,560A patent/CA1133806A/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039363A (en) * | 1987-12-18 | 1991-08-13 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
| EP1394288A2 (en) * | 1996-10-30 | 2004-03-03 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| EP1394288A3 (en) * | 1996-10-30 | 2004-04-21 | Nihon Hyomen Kagaku Kabushiki Kaisha | Treating solution and treating method for forming protective coating films on metals |
| WO2002079539A2 (en) * | 2001-03-29 | 2002-10-10 | Macdermid Plc | Treatment of zinc and zinc alloy surfaces |
| WO2002079539A3 (en) * | 2001-03-29 | 2003-06-05 | Macdermid Plc | Treatment of zinc and zinc alloy surfaces |
| EP1483429A1 (en) * | 2002-02-14 | 2004-12-08 | MacDermid, Incorporated | Magnesium conversion coating composition and method of using same |
| EP1483429A4 (en) * | 2002-02-14 | 2005-04-20 | Macdermid Inc | Magnesium conversion coating composition and method of using same |
| CN100339506C (en) * | 2002-02-14 | 2007-09-26 | 麦克德米德有限公司 | Magnesium conversion coating composition and method of using same |
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