US3007817A - Cold cleaning and cold phosphate coating process - Google Patents
Cold cleaning and cold phosphate coating process Download PDFInfo
- Publication number
- US3007817A US3007817A US699469A US69946957A US3007817A US 3007817 A US3007817 A US 3007817A US 699469 A US699469 A US 699469A US 69946957 A US69946957 A US 69946957A US 3007817 A US3007817 A US 3007817A
- Authority
- US
- United States
- Prior art keywords
- solution
- cleaning
- cold
- phosphate coating
- phosphate
- 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
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the present invention relates to a process of phosphate coating which enables the surface preparation of the metal and the phosphate coating steps to be accomplished at temperatures below about 100 F.
- one or more cleaning operations are normally employed and these cleaning operations may comprise the use of molten alkali cleaners, vapor degreasers, aqueous acidic pickling solutions, aqueous alkaline cleaners, etc.
- these cleaners have usually been used under raised temperature conditions, that is at temperatures above about 140 F. and extending to the boiling point of the particular solution involved. Maintaining such cleaners at elevated conditions involves considerable expense and it has long been recognized that it would be desirable to precondition and clean metallic surfaces under lower temperatures.
- conventional cleaning compositions applied by conventional methods of application have not been found to be satisfactory when operated at such lower temperatures.
- a further object of this invention is to provide a cold cleaning composition which functions both to clean the metallic surface and precondition that surface so that it is in a condition to receive a fine-grained adherent phosphate coating, which phosphate coating is characterized by fine grain size, good adherence and is particularly useful as a base for paint, as a lubrication aid in deformation operations, as a coating in wear-resistant applications, etc.
- a still further object of this invention is to provide a cold cleaning and cold phosphate coating process which is adapted to operate on a continuous line basis at speeds which are conventional in high production operations such as those encountered in automobile parts and hard goods manufacturing lines, etc.
- the method of this invention comprises the steps of forcefully spraying an aqueous alkaline cleaning solution on the surface to baleaned and thereafter contacting that cleaned surface with an aqueous acidic hos hate coatm solution where the tem erature of both the cleaning and coating solution is below about i00 F.
- cold cleaning is intended to mean the cleaning of a metallic surface with an aqueous alkaline cleaning solution having a temperature between about 60 F. and 100 F.
- the expression cold phosphate coating as used in this specification and in the appended claims, is intended to mean the application to a metallic surface of an aqueous acidic phosphate coating solution having a temperature between about 50 F. and 110 F.
- the basic aqueous alkaline cleaning solution is not particularly critical in so far as the ingredients which can be employed in its formulation are concerned. Any of the alkali metal ortho phosphates and borates can be used satisfactorily, the sodium ortho phosphates and sodium borates being particularly desirable because of their pre-conditioner for fineained zinc hos hat a. u:
- the polyphosphates should be avoided. For example is undesirable to replace the ortho pitTosphates with polyphosphates, metaphosphates, or pyrophosphates as illustrated specifically by tetrasodium pyrophosphate, sodium tetrameta phosphate, etc.
- the important aspects of the alkaline cleaning solution, per se, are its alkalinity and the type and amount of surface active agent incorporated therein.
- the aqueous alkaline cleaning solution functions satisfactorily when the total alkalinity is in the range of about 2 to about 36 points, and the free alkalinity is in the range of about 1.0 to about 18 points when the ratio of free alkalinity to total alkalinity is in the range of about 0.05 to about 0.5, and preferably in the range of about 0.25 to about 0.5.
- the term point, as used in this specification and in the appended claims refers to the number of ml. of N/ 10 sulfuric acid which is required to titrate a 10 ml. sample of the aqueous solution to a phenolphthalein endpoint to thus determine the points of free alkalinity, and to a brom-cresol green end-point to thus determine the points of total alkalinity.
- alkyl-aryl polyether alcohols containing not more than eight oxyethylene groups have been found to be particularly effective in the above described aqueous alkaline cleaning compositions, as discussed in detail hereinafter.
- the surface of the metal to be pre-conditioned for receiving a zinc phosphate coating is forcefully sprayed with a solution of the above described type, the solution having a temperature between about 60 -F. and about 100 F., preferably between about 70 F. and F., for a time of contact between the surface and the cleaning solution in the range of about /z to about 1% minutes.
- the pressure with which the cleaning solution is applied and the distance of the spray nozzle from the surface being cleaned is important to the attainment of uniformly good cleaning results, from piece to piece and batch to batch, particularly where the surfaces are covered with varying quantities of oil, grease, drawing lubricants and the like.
- the cleaning solution should be forcefully applied to the work as a spray.
- the expression forcefully sprayed (ing) is intended to mean that the sprayed solution has a velocity at the moment of impact with the surface being sprayed equivalent to that which is obtained from spraying water through a V-nozzle under a pressure of between about 15 p.s.i. and 50 p.s.i. gauge, when the nozzle is about 12 inches to about 30 inches from the surface being sprayed, and the orifice in the nozzle is about ,6 of an inch in diameter.
- the degree of grain refinement in the subsequently applied zinc phosphate coating is enhanced by the modification of the alkaline cleanlnc solution to include a small amount of the titanium ion when added in the form specified below.
- concentration of the titanium ion in the operating cleaning solution should be in the range of about 0.0004% to about 0.05% weight/ volume.
- the preferred form of the titanium material for incorporation in the cleaning solutions of this invention is the titanium-containing compound produced by the method of United States Patent 2,874,081, issued Februmy 17, 1959, since this material has been found to give the best over-all results.
- this titanium-containing aqueous phosphate solution as a separate treatment step or as a modification of the water rinse step following the forceful spray cleaning step by either spray or immersion application and for this purpose other conventional titanium-containing compositions may also be employed, such as, for example, the composition and method of US. Patent No. 2,310,239.
- the treating solution would be an aqueous solution containing 0.1% to 2% disodium phosphate and 0.005% to 0.05% titanium ions therein.
- the titanium-containing material is typically prepared by admixing disodium ortho-phosphate or sodium tripolyphosphate and titanyl sulfate for about -60 minutes to form an aqueous slurry having a pH in the range of 5.7 to 7.8 at a temperature not exceeding 75 F., with the quantity of titanium sulfate being selected so as to produce a titanium concentration in the dried final product between about 1% and about 4%.
- the slurry is then aged at a temperature of 160 F.-l90 F. for about 30 minutes or more and after this aging treatment is dried to a powder.
- This dried powder can be added as such to the cleaning composition of this invention either in its concentrated or dilute form to produce the above given concentrations of titanium in the operating solutions.
- a typical composition, so formed, that is satisfactorily added is a slurry containing 3.2 grams titanyl sulfate, 16 grams sodium tripolyphosphate and 60 ml. water.
- alkyl-aryl polyether alcohol surface-active agents which have been found to be unusually satisfactory are prepared by reacting t-octylphenol with ethylene oxide to produce octylphenoxy ethanols having controlled numbers of polyoxyethylene groups. These materials have the general formula:
- a concentrated make-up material suitable for use in making up the aqueous cleaning solutions of this invention may contain the following ingredients in the range of relative proportions shown:
- Trisodium phosphate Na PO -12H O 15-30 Borax (Na B O -l0H O) 25-40 Sodium nitrite 0-12 Octylphenoxy ethanol (5-8 OCH CH 1-5 groups) 1-5 Pine oil 0-25 OPERATING SOLUTION Percent weight/ volume Trisodium phosphate (Na PO -12H O) 0.0l-4 Borax (Na B O -10H O) 0.02-5.35 Sodium nitri 01.7 Octylphenoxy ethanol (5-8 0CH2CHg groups) .007-0.83 Pine nil 0-2.84
- the phosphate coating solution is preferably an aqueous acidic zinc phosphate solution of the type which 15 formed from zinc dihydrogen phosphate or its chemical equivalent, and which operates at a pH range between about 1.5 and 3.5.
- Sgch solutions may be conventional in all respects except that they should contain an oxidizing agent vfliich is capable of accelerating the rate of metal attack s5 that a uniform phosphate coating can be obtained in a relatively short period of tim for example, about one to about two minutes.
- Nitrite is the preferred accelerating agent for use in these zinc dihydrogen phosphate solutions when they are applied after the above cleaning step.
- oxidizing agents such as bromates, sulfites and nitroorganic compounds including m-nitrobenzene sulfonate and picric acid, particularly where low coating weights are satisfactory.
- oxidizing agents other than nitrite may even be employed where heavier coating weights are desired by including in the solution a small proportion of an acetic amino acid such as sodium ethylene diamine tetra-acetate.
- the phosphate coating solutions may satisfactorily have a total acid of about 10-50 points and contain about 0.5% to 2.5% P0 sutficient zinc to form the dihydrogen phosphate, .002%-.15% nitrite, or .03 %-0.5% bromate, or .02%-.15% sulfite, or .03%0.5% sodium meta nitrobenzene sulfonate, or .01%-.3% picric acid or nitrate in combination with one of these agents, particularly nitrite. Where sodium ethylene diamine tetra-acetate is used it should be present in an amount of at least about 0.01%. These solutions are preferably applied by spraying, but may be applied in other conventional ways, at temperatures between about 70 F.
- the method of this invention represents the first time in this art that it has been considered feasible to obtain cold clean and cold phosphate coat metallic surfaces on a production line basis. lifter the phosphate coating has been formed on the metal surface, additional resi ance to corrosion 1s obtained by rinsing the coating in a conventional dilute agueous chronuc acid solution, e.g., an aqueous solution containing about 2 to about 4 ounces of CrO, per 100 gallons of water.
- a conventional dilute agueous chronuc acid solution e.g., an aqueous solution containing about 2 to about 4 ounces of CrO, per 100 gallons of water.
- Example I A plurality of aqueous alkaline cleaners were prepared containing specific quantities of ingredients within the small range of variation shown, in percent by weight:
- aqueous operating baths were made by using 1 to 1% ounces of the above materials per gallon of water. These solutions were sprayed on mild steel automobile body parts at a temperature of about 90 F. from diameter V nozzles located 12"-14" from the parts at a line pressure of 20 p.s.i. so that the contact time between the solution and the surface being preconditioned was between 1 to 1% minutes. These solutions were used as the preconditioner and cleaning solution for commercial scale quantities of parts prior to the phosphate coating of those parts with a variety of phosphate coating solutions.
- One phosphate coating solution which was used for treating such preconditioned parts contained in percent by weight: 0.18% N 0.22% zinc, 0.66% P0 0.007% nitrite, 0.047% sodium, balance water. This solution had a total acidity of about points and a free acidity of 0.3-0.9.
- Another phosphate coating solution used after preconditioning with the above solution contained 0.18% NO,, 0.23% Zn, 0.59% P0 0.03% Ni, 0.018% sodium and 0.007% N0 balance water. This solution had a total acidity of about 9.5-l2.5 points and a free acid of 0.3- 1.0 points. Both of these phosphate solutions were spray applied, at a temperature of 100 F.-ll0 F., and an inspection of the coatings obtained showed that the surfaces were uniformly coated with a fine grain, adherent, typically appearing zinc phosphate coating.
- Example IV A commercial installation was provided with the cold cleaner composition set forth above in Example I and used for spraying mild steel automobile body parts including bumper guards, body trim and the like under the same conditions of application with respect to temperature of the solution, nozzle type and location and line pressure as set forth in Example I.
- the cleaned parts after water rinse were then spray coated with an aqueous acidic zinc phosphate solution containing 0.26% zinc, 0.78% P0 1.07% N0 balance water.
- An analysis of this solution showed that it had a free acid of 0.3 point and a total acid of 11.5 points.
- the phosphate solution was maintained at a temperature between F. and F. and was sprayed on the cleaned part surfaces so that the contact time of the solution and the surface was an average of about 1% minutes.
- Example V The cold cleaner composition of Example I was reformulated except that the octylphenoxy ethanol containing an average of 7-8 oxyethylene groups was replaced with an octylphenoxy ethanol, in the same relative proportions, having an average of 5 oxyethylene groups.
- Another cleaning solution was prepared similar in every respect to the composition of Example I except that an octylphenoxy ethanol having an average of 3 oxyeth-' ylene groups was employed in the same concentration as that used for the same ingredient in Example I.
- a still further composition was prepared in all respects similar to the composition of Example I except that the octylphenoxy ethanol contained an average of 9-10 oxyethylene groups.
- Each of these cleaners was operated in the same manner described in Example I, and satisfactory cleaning and surface conditioning was obtained with the octylphenoxy ethanols containing an average of 5 oxyethylene groups, whereas the operation of the solution containing an average of 3 oxyethylene groups was unsatisfactory and the operation of the solution containing an average of 9-10 oxyethylene groups in the octyl phenoxy ethanol was found to produce an excessive quantity of foam so that re-circulation of the cleaner was inelfectual and operation on a continuous basis was unsatisfactory.
- a method for cold cleaning and cold coating metallic surfaces which comprises the steps of forcefully spraying against said surface an aqueous alkaline solution consisting essentially of water, hydrated ortho phosphates and borates and having a total alkalinity between about 2 and about 36 points and a ratio of free alkalinity to total alkalinity in the range of about 0.05 to 0.5 and about 0.007% to about 0.83% of an octyl phenoxyethanol having 5-8 oxyethylene groups, and thereafter contacting said surface with an aqueous acidic zinc phosphate coating solution and maintaining said surface in contact with said phosphate solution until a phosphate coating is formed thereon, said cleaning solution having a temperature between about 60 F. and 100 F. and said phosphate coating solution having a temperature between about 50 F. and 110 F.
- said aquwus alkaline cleaning solution consists essentially of the solution resulting from incorporating ,4 oz. to 10 ozs./gallon of water of a material consisting of, in parts by weight, up to 12 parts sodium nitrite, 15-30 parts trisodium phosphate, 25-40 parts borax, and 1-5 parts octyl phenoxyethanol having an average of -8 oxyethylene groups.
- said zinc phosphate coating solution contains the nitrite ion as an accelerator.
- An aqueous cold cleaning solution for metallic surfaces comprising an aqueous alkaline solution consisting essentially of water, hydrated ortho phosphates and borates and having a total alkalinity in the range of about 2 to about 36 points and a ratio of free alkalinity to total alkalinity in the range of about 0.05 to about 0.5 and having incorporated therein about 0.007% to about 0.83% octyl phenoxyethanol having 5-8 -OCH CH groups.
- a concentrated make-up material for a cold alkaline cleaner for metals consisting of, in parts by weight, 15-30 parts trisodium phosphate, 25-40 parts borax, up to 12 parts sodium nitrite, 1-5 parts octyl phenoxyethanol having 5-8 oxyethylene groups and up to 25 parts pine oil.
- a concentrated make-up material for a cold alkaline cleaner for metals consisting of, in parts by weight, 15-30 parts trisodium phosphate, 25-40 parts borax, up to 12 parts sodium nitrite, and 1-5 parts octyl phenoxyethanol having 5-8 oxyethylene groups.
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- 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)
- Detergent Compositions (AREA)
- Chemical Treatment Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE567592D BE567592A (et) | 1957-11-29 | ||
NL233553D NL233553A (et) | 1957-11-29 | ||
US699469A US3007817A (en) | 1957-11-29 | 1957-11-29 | Cold cleaning and cold phosphate coating process |
CH5940258A CH393871A (fr) | 1957-11-29 | 1958-05-12 | Procédé de nettoyage à froid et de phosphatation à froid de surfaces métalliques |
DK199858AA DK103221C (da) | 1957-11-29 | 1958-05-30 | Fremgangsmåde til rensning og forbehandling af metalliske overflader til kold phosphatovertrækning, samt hertil anvendelig vandig opløsning og en blanding til fremstilling af denne. |
FR1207826D FR1207826A (fr) | 1957-11-29 | 1958-07-18 | Procédé de nettoyage à froid et de phosphatation à froid et produits pour sa mise en oeuvre |
DEM38799A DE1151708B (de) | 1957-11-29 | 1958-09-02 | Verfahren zur Spritzkaltreinigung von Metallen von der Phosphatierung |
GB38488/58A GB871606A (en) | 1957-11-29 | 1958-11-28 | Improvements relating to the production of phosphate coatings on metallic surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US699469A US3007817A (en) | 1957-11-29 | 1957-11-29 | Cold cleaning and cold phosphate coating process |
Publications (1)
Publication Number | Publication Date |
---|---|
US3007817A true US3007817A (en) | 1961-11-07 |
Family
ID=24809471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US699469A Expired - Lifetime US3007817A (en) | 1957-11-29 | 1957-11-29 | Cold cleaning and cold phosphate coating process |
Country Status (8)
Country | Link |
---|---|
US (1) | US3007817A (et) |
BE (1) | BE567592A (et) |
CH (1) | CH393871A (et) |
DE (1) | DE1151708B (et) |
DK (1) | DK103221C (et) |
FR (1) | FR1207826A (et) |
GB (1) | GB871606A (et) |
NL (1) | NL233553A (et) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3288655A (en) * | 1963-12-18 | 1966-11-29 | Lubrizol Corp | Phosphating a steel strip prior to anealing and temper rolling |
US3294593A (en) * | 1961-12-07 | 1966-12-27 | Hoechst Ag | Solution and process for producing a phosphate coating on a metal body |
US3331710A (en) * | 1963-08-23 | 1967-07-18 | Hooker Chemical Corp | Method for coating aluminum |
US3397093A (en) * | 1964-05-19 | 1968-08-13 | Hooker Chemical Corp | Treatment of metal surfaces |
US4717497A (en) * | 1984-03-10 | 1988-01-05 | Amchem Products, Inc. | Tin-plate degreasing detergent |
EP0264151A1 (de) * | 1986-10-17 | 1988-04-20 | Metallgesellschaft Ag | Verfahren zur Erzeugung von Phosphatüberzügen |
EP0271069A2 (en) * | 1986-12-09 | 1988-06-15 | Nippondenso Co., Ltd. | Process for the phosphate chemical conversion treatment of a steel material |
CZ297641B6 (cs) * | 2005-02-08 | 2007-02-21 | Hauser@Ladislav | Zarízení pro odmaštování a fosfátování |
US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4121217B2 (ja) | 1999-06-30 | 2008-07-23 | 株式会社スーパーブラストシステムズ | 人工緑青発生法 |
CN110983313A (zh) * | 2019-12-26 | 2020-04-10 | 南京派诺金属表面处理技术有限公司 | 用于pc线磷化后载盐及其使用工艺 |
Citations (12)
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CH48594A (de) * | 1909-08-17 | 1910-11-01 | Chemische Werke Vorm Dr Heinri | Verfahren zur Darstellung eines Natriumperborat enthaltenden Bleichmittels |
US2034361A (en) * | 1929-03-23 | 1936-03-17 | Roy C Sutton | Alkaline detergent powder and method of making the same |
GB515100A (en) * | 1937-06-14 | 1939-11-27 | Griffith Laboratories | Improvements in or relating to alkaline detergent products |
US2293716A (en) * | 1941-02-03 | 1942-08-25 | Parker Rust Proof Co | Metal treating solution |
US2310239A (en) * | 1941-10-25 | 1943-02-09 | Westinghouse Electric & Mfg Co | Corrosion resistant coating for metal surfaces |
US2322349A (en) * | 1941-10-25 | 1943-06-22 | Westinghouse Electric & Mfg Co | Corrosion resistant coating for metal surfaces |
US2407589A (en) * | 1944-02-03 | 1946-09-10 | Wyandotte Chemical Corp | Aqueous alkaline reacting cleaning bath having reduced foaming characteristics |
US2603605A (en) * | 1948-03-15 | 1952-07-15 | Ici Ltd | Process for production of washing powder from a normally oily liquid synthetic soapless detergent |
US2614992A (en) * | 1950-11-30 | 1952-10-21 | Mankowich Abraham | Paint stripping compositions |
US2623856A (en) * | 1952-12-30 | Tetraborate detergent compositionx | ||
GB716517A (en) * | 1951-04-02 | 1954-10-06 | Rohm & Haas | Improvements in or relating to detergent materials |
US2874081A (en) * | 1956-08-02 | 1959-02-17 | Parker Rust Proof Co | Pretreatment solution for phosphate coating, method of preparing the same and process of treating metal surfaces |
-
0
- BE BE567592D patent/BE567592A/xx unknown
- NL NL233553D patent/NL233553A/xx unknown
-
1957
- 1957-11-29 US US699469A patent/US3007817A/en not_active Expired - Lifetime
-
1958
- 1958-05-12 CH CH5940258A patent/CH393871A/fr unknown
- 1958-05-30 DK DK199858AA patent/DK103221C/da active
- 1958-07-18 FR FR1207826D patent/FR1207826A/fr not_active Expired
- 1958-09-02 DE DEM38799A patent/DE1151708B/de active Pending
- 1958-11-28 GB GB38488/58A patent/GB871606A/en not_active Expired
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US2623856A (en) * | 1952-12-30 | Tetraborate detergent compositionx | ||
CH48594A (de) * | 1909-08-17 | 1910-11-01 | Chemische Werke Vorm Dr Heinri | Verfahren zur Darstellung eines Natriumperborat enthaltenden Bleichmittels |
US2034361A (en) * | 1929-03-23 | 1936-03-17 | Roy C Sutton | Alkaline detergent powder and method of making the same |
GB515100A (en) * | 1937-06-14 | 1939-11-27 | Griffith Laboratories | Improvements in or relating to alkaline detergent products |
US2293716A (en) * | 1941-02-03 | 1942-08-25 | Parker Rust Proof Co | Metal treating solution |
US2310239A (en) * | 1941-10-25 | 1943-02-09 | Westinghouse Electric & Mfg Co | Corrosion resistant coating for metal surfaces |
US2322349A (en) * | 1941-10-25 | 1943-06-22 | Westinghouse Electric & Mfg Co | Corrosion resistant coating for metal surfaces |
US2407589A (en) * | 1944-02-03 | 1946-09-10 | Wyandotte Chemical Corp | Aqueous alkaline reacting cleaning bath having reduced foaming characteristics |
US2603605A (en) * | 1948-03-15 | 1952-07-15 | Ici Ltd | Process for production of washing powder from a normally oily liquid synthetic soapless detergent |
US2614992A (en) * | 1950-11-30 | 1952-10-21 | Mankowich Abraham | Paint stripping compositions |
GB716517A (en) * | 1951-04-02 | 1954-10-06 | Rohm & Haas | Improvements in or relating to detergent materials |
US2874081A (en) * | 1956-08-02 | 1959-02-17 | Parker Rust Proof Co | Pretreatment solution for phosphate coating, method of preparing the same and process of treating metal surfaces |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3294593A (en) * | 1961-12-07 | 1966-12-27 | Hoechst Ag | Solution and process for producing a phosphate coating on a metal body |
US3331710A (en) * | 1963-08-23 | 1967-07-18 | Hooker Chemical Corp | Method for coating aluminum |
US3288655A (en) * | 1963-12-18 | 1966-11-29 | Lubrizol Corp | Phosphating a steel strip prior to anealing and temper rolling |
US3397093A (en) * | 1964-05-19 | 1968-08-13 | Hooker Chemical Corp | Treatment of metal surfaces |
US4717497A (en) * | 1984-03-10 | 1988-01-05 | Amchem Products, Inc. | Tin-plate degreasing detergent |
EP0264151A1 (de) * | 1986-10-17 | 1988-04-20 | Metallgesellschaft Ag | Verfahren zur Erzeugung von Phosphatüberzügen |
US4867853A (en) * | 1986-10-17 | 1989-09-19 | Metallgesellschaft Aktiengesellschaft | Process of producing phosphate coatings |
EP0271069A2 (en) * | 1986-12-09 | 1988-06-15 | Nippondenso Co., Ltd. | Process for the phosphate chemical conversion treatment of a steel material |
EP0271069B1 (en) * | 1986-12-09 | 1994-08-31 | Nippondenso Co., Ltd. | Process for the phosphate chemical conversion treatment of a steel material |
CZ297641B6 (cs) * | 2005-02-08 | 2007-02-21 | Hauser@Ladislav | Zarízení pro odmaštování a fosfátování |
US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
Also Published As
Publication number | Publication date |
---|---|
DK103221C (da) | 1965-11-29 |
GB871606A (en) | 1961-06-28 |
CH393871A (fr) | 1965-06-15 |
FR1207826A (fr) | 1960-02-18 |
BE567592A (et) | |
NL233553A (et) | |
DE1151708B (de) | 1963-07-18 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP 32100 STEPHENSON Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:003942/0016 Effective date: 19810317 |
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Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |