US3870573A - Scale modifier for phosphate solutions - Google Patents

Scale modifier for phosphate solutions Download PDF

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Publication number
US3870573A
US3870573A US439671A US43967174A US3870573A US 3870573 A US3870573 A US 3870573A US 439671 A US439671 A US 439671A US 43967174 A US43967174 A US 43967174A US 3870573 A US3870573 A US 3870573A
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Prior art keywords
scale
phosphate
solution
sulfonic acid
naphthalene sulfonic
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US439671A
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Colin Smith
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Henkel Corp
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Oxy Metal Industries Corp
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Assigned to HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY reassignment HOOKER CHEMICALS & PLASTICS CORP, A CORP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to PARKER CHEMICAL COMPANY, A DE CORP. reassignment PARKER CHEMICAL COMPANY, A DE CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations

Definitions

  • Scale formation originates from various causes. One is that the surface of the metal being treated with the composition is attacked by the composition to result in dissolution of the base metal which then reacts with phosphate to form scale. Another is that the phosphate compositions themselves may tend to dissociate to form scale.
  • n is a number from 2 to 8 inclusive, and salts thereof.
  • a particularly preferred material is that sold by Ciba- Geigy (U.K.) Limited under the trademark Belloid, for example Belloid SFD.
  • the dispersing agent may be used in any amount that is effective to give improved results.
  • the improvement that is obtained in the invention vmost usually is a change in the nature of the deposit that is formed.
  • this'cleaning can very easily be effected, for example, by merely rinsing the surfaces carrying the deposit.
  • the high molecular weight dispersing agent may be included in any aqueous acidic phosphating solution comprising scale forming metal ions and phosphate ions employed in the phosphate coating of metals.
  • the solution may be, for example, a zinc phosphate solution or other coating phosphate solution (e.g., containing Mg, Mn or Fe ions). It may also be a non-coating phosphate solution, e.g., a sodium phosphatesolution. Initially, such non-coating solutions are generally free of scale forming metal ions and scale formation is not then a problem. However, during use iron or other metal ions are generated from the surface being treated to yield an acidic solution containing iron or other scale forming ions such as those of aluminum or zinc. Accordingly, scale formation again becomes a problem, even though the amount of iron may be less than the amount of heavy metal in a coating phosphate solution. Thus, scale formation in both coating and non-coating solutions can be reduced or eliminated by the invention.
  • the dispersing agent may be included in concentrates, either aqueous or non-aqueous, that are diluted before use to form a working solution or it may be added directly to a working solution.
  • the solution may contain any of the various additives known in the art.
  • concentration of the various components of the solution will be selected having regard to the end use. For example lighter coatings, and therefore lower concentrations, are required when the coating is to serve as a paint base than when it is only to provide corrosion resistance.
  • Typical concentrations and components for a zinc phosphate solution include the following:
  • the metal surface to be treated is washed, rinsed and then has the zinc phosphate solution applied to it, normally by spray or immersion. Conventional further treatment, such as rinsing and drying, may be conducted. Application of the treatment solution is normally carried out at elevated temperatures, for ex- 3 ample 100 to 200F and preferably 130 to 170F.
  • the metal surface treated may be zinc, aluminum, iron (or alloys containing predominant amounts of these).
  • an aqueous acidic phosphating composition containing scale forming metal ions comprising including at least 0.0005% of'a naphthalene sulfonic acid/formaldehyde condensation product or a salt thereof.
  • composition of claim 1 wherein the naphthalene sulfonic acid/formaldehyde product has the general formula:
  • composition of claim 2 wherein said scale forming metal is selected from the group consisting of zinc, manganese, magnesium, iron, aluminum and cal-

Abstract

Disclosed is a composition suitable for phosphatizing metal surfaces wherein an additive is included to modify the properties of the scale which is unavoidably formed on processing equipment. The scale is rendered relatively non-adherent to process equipment surfaces through inclusion of a small quantity of a naphthalene sulfonic acid/formaldehyde condensation product in the treating solution.

Description

United States Patent Smith SCALE MODIFIER FOR PHOSPHATE SOLUTIONS Colin Smith, Brentford, England Oxy Metal Finishing Corporation, Warren, Mich.
Filed: Feb. 4, 1974 Appl. No.: 439,671
Inventor:
Assignee:
Foreign Application Priority Data Feb. 9, 1973 Great Britain 6551/73 US. Cl. 148/22, 148/615 R, 148/615 Z, 252/80 Int. Cl. B23k 35/22, C23f 7/08 Field of Search 148/615 R, 6.15 Z, 6.17, 148/624, 22, 28; 117/161 L; 252/80, 81, 86, 381, 382, 383, 178
References Cited UNlTED STATES PATENTS 3/1968 Trugcsser ct al 106/90 1 Mar. 11, 1975 3,582,376 9/1968 Ames 106/89 Primary ExaminerLeon D. Rosdol Assistant E.raminerCharles R. Wolfe Attorney, Agent, or Firm-Arthur E. Kluegel; Richard P. Mueller; B. F. Claeboe [57] ABSTRACT 3 Claims, N0 Drawings 1 SCALE MODIFIER FOR PHOSPHATE SOLUTIONS BACKGROUND OF THE INVENTION It is well known to form phosphate coatings on metal surfaces by treatment with an acid heavy metal phosphate solution, that is to say by applying to the surfaces an aqueous composition containing heavy metal ions (e.g., Zn, Mn, Mg or Fe) and phosphate ions. One of the chronic problems of such phosphate processes is the buildup of a tightly adherent scale on the apparatus used for storing, heating and applying the phosphate solution, for example on the tank and, especially, on the headers, nozzles and heating elements used. The scale build-up may be so serious as to reduce flow rates and, when application is by spray, may result in changes in the spray pattern, making it difficult to obtain uniform application rate. Scale build-up on heating elements causes insufficient heat exchange and problems in maintaining temperature.
Scale formation originates from various causes. One is that the surface of the metal being treated with the composition is attacked by the composition to result in dissolution of the base metal which then reacts with phosphate to form scale. Another is that the phosphate compositions themselves may tend to dissociate to form scale.
DESCRIPTION OF THE INVENTION where n is a number from 2 to 8 inclusive, and salts thereof.
A particularly preferred material is that sold by Ciba- Geigy (U.K.) Limited under the trademark Belloid, for example Belloid SFD.
The dispersing agent may be used in any amount that is effective to give improved results. The improvement that is obtained in the invention vmost usually is a change in the nature of the deposit that is formed. Thus instead of the deposit being formed as scale which is move the sludge this'cleaning can very easily be effected, for example, by merely rinsing the surfaces carrying the deposit.
Little improvement is obtained if the amount of dispersing agent in the working phosphating solution is less than 0.00055 and it is generally of no further advantage to include more than 0.1%. Best results are usually obtained with amounts of from 0.001 to 0.01% by weight.
The high molecular weight dispersing agent may be included in any aqueous acidic phosphating solution comprising scale forming metal ions and phosphate ions employed in the phosphate coating of metals. The solution may be, for example, a zinc phosphate solution or other coating phosphate solution (e.g., containing Mg, Mn or Fe ions). It may also be a non-coating phosphate solution, e.g., a sodium phosphatesolution. Initially, such non-coating solutions are generally free of scale forming metal ions and scale formation is not then a problem. However, during use iron or other metal ions are generated from the surface being treated to yield an acidic solution containing iron or other scale forming ions such as those of aluminum or zinc. Accordingly, scale formation again becomes a problem, even though the amount of iron may be less than the amount of heavy metal in a coating phosphate solution. Thus, scale formation in both coating and non-coating solutions can be reduced or eliminated by the invention.
The dispersing agent may be included in concentrates, either aqueous or non-aqueous, that are diluted before use to form a working solution or it may be added directly to a working solution.
In addition to including zinc or other metal, e.g., alkali metal ions and phosphate ions, the solution may contain any of the various additives known in the art. The concentration of the various components of the solution will be selected having regard to the end use. For example lighter coatings, and therefore lower concentrations, are required when the coating is to serve as a paint base than when it is only to provide corrosion resistance. Typical concentrations and components for a zinc phosphate solution include the following:
Component Concentration Range Calcium 0 to 100 g/l Zinc l to 50 g/l Nitrate 0 to 250 g/l Phosphate 1 to 100 g/l Sodium 0 to 50 g/l Iron (Fe") 0 to 10 g/l standard methods, for example as described in British tightly adherent, the deposit is formed as an easily re- I movable precipitate or sludge. Thus although the equipment has to be cleaned from time to time to re- Pat. Specifications No. 1296883 or 1297715 and in standard references such as the Metal Finishing Guide Book.
Typically, the metal surface to be treated is washed, rinsed and then has the zinc phosphate solution applied to it, normally by spray or immersion. Conventional further treatment, such as rinsing and drying, may be conducted. Application of the treatment solution is normally carried out at elevated temperatures, for ex- 3 ample 100 to 200F and preferably 130 to 170F. The metal surface treated may be zinc, aluminum, iron (or alloys containing predominant amounts of these).
EXAMPLE A phosphating solution was prepared having the following analysis:
Pointage* 20 Free Acid** 4 P 0.8% N0 0.95% Zn 0.63% Ni 0.00271 Pointage ml of M naOH added to a 10 ml sample to reach the phenolphthalein end point.
"ml of N/IO naOH added to a 10 ml sample to reach the bromo-cresol green end point.
It was applied to steel articles by spray at 65C. It was observed that during use sludge and scale was formed, the scale being tightly adherent and the sludge being difficult to remove.
The process was repeated except that 0.004% of Belloid SFD was included in the solution. It was found that after the same duration of processing substantially the same amount of scale and sludge has been formed but that it was very easy to remove this merely by hosing the apparatus.
What is claimed is:
1. In an aqueous acidic phosphating composition containing scale forming metal ions the improvement 4 4 comprising including at least 0.0005% of'a naphthalene sulfonic acid/formaldehyde condensation product or a salt thereof.
2. The composition of claim 1 wherein the naphthalene sulfonic acid/formaldehyde product has the general formula:
3. The composition of claim 2 wherein said scale forming metal is selected from the group consisting of zinc, manganese, magnesium, iron, aluminum and cal-

Claims (3)

1. IN AN AQUEOUS ACIDIC PHOSPHATING COMPOSITION CONTAINING SCALE FORMING METAL IONS THE IMPROVEMENT COMPRISING INCLUDING AT LEAST 0.0005% OF A NAPHTHALENE SULFONIC ACID/FORMALDEHYDE CONDENSATION PRODUCT OR A SALT THEREOF.
1. In an aqueous acidic pHosphating composition containing scale forming metal ions the improvement comprising including at least 0.0005% of a naphthalene sulfonic acid/formaldehyde condensation product or a salt thereof.
2. The composition of claim 1 wherein the naphthalene sulfonic acid/formaldehyde product has the general formula:
US439671A 1973-02-09 1974-02-04 Scale modifier for phosphate solutions Expired - Lifetime US3870573A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB655173A GB1408702A (en) 1973-02-09 1973-02-09 Phosphate coating compositions and processes

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US3870573A true US3870573A (en) 1975-03-11

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US (1) US3870573A (en)
JP (1) JPS5320257B2 (en)
BR (1) BR7400898D0 (en)
CA (1) CA1020850A (en)
DE (1) DE2402702A1 (en)
FR (1) FR2217438B1 (en)
GB (1) GB1408702A (en)
ZA (1) ZA74440B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147567A (en) * 1976-11-24 1979-04-03 Imperial Chemical Industries Limited Phosphating process
WO2001096627A1 (en) * 2000-06-16 2001-12-20 Henkel Kommanditgesellschaft Auf Aktien Improved phosphating operation
US20040011430A1 (en) * 2001-06-18 2004-01-22 Cuyler Brian B Phosphating operation
US20050154358A1 (en) * 2004-01-14 2005-07-14 Dunn Steven B. Styptic applicator with file

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377487A (en) * 1978-10-31 1983-03-22 Occidental Chemical Corporation Metal coating process and compositions
DE3571562D1 (en) * 1984-05-21 1989-08-24 Sumitomo Metal Ind Method for continuous drawing of wire rod
JPS61257481A (en) * 1985-05-10 1986-11-14 Nippon Parkerizing Co Ltd Aqueous solution for surface conditioning for forming phosphate film by chemical conversion treatment
DE3712339A1 (en) * 1987-04-11 1988-10-20 Metallgesellschaft Ag METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3582376A (en) * 1968-09-09 1971-06-01 Western Co Of North America Quick-setting cement composition containing portland cement,alpha gypsum and a dispersant
US3582375A (en) * 1968-03-21 1971-06-01 Western Co Of North America Well cementing composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3582375A (en) * 1968-03-21 1971-06-01 Western Co Of North America Well cementing composition
US3582376A (en) * 1968-09-09 1971-06-01 Western Co Of North America Quick-setting cement composition containing portland cement,alpha gypsum and a dispersant

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147567A (en) * 1976-11-24 1979-04-03 Imperial Chemical Industries Limited Phosphating process
WO2001096627A1 (en) * 2000-06-16 2001-12-20 Henkel Kommanditgesellschaft Auf Aktien Improved phosphating operation
US20040011430A1 (en) * 2001-06-18 2004-01-22 Cuyler Brian B Phosphating operation
US8062435B2 (en) 2001-06-18 2011-11-22 Henkel Kommanditgesellschaft Auf Aktien Phosphating operation
US20050154358A1 (en) * 2004-01-14 2005-07-14 Dunn Steven B. Styptic applicator with file

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ZA74440B (en) 1974-11-27
CA1020850A (en) 1977-11-15
JPS5320257B2 (en) 1978-06-26
BR7400898D0 (en) 1974-09-10
GB1408702A (en) 1975-10-01
JPS49125237A (en) 1974-11-30
DE2402702A1 (en) 1974-08-22
AU6478174A (en) 1975-07-24
FR2217438B1 (en) 1978-10-13
FR2217438A1 (en) 1974-09-06

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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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Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084

Effective date: 19741220

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004194/0047

Effective date: 19830928