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GB1602838A - Treating surfaces of inorganic materials - Google Patents

Treating surfaces of inorganic materials Download PDF

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Publication number
GB1602838A
GB1602838A GB2369877A GB2369877A GB1602838A GB 1602838 A GB1602838 A GB 1602838A GB 2369877 A GB2369877 A GB 2369877A GB 2369877 A GB2369877 A GB 2369877A GB 1602838 A GB1602838 A GB 1602838A
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United Kingdom
Prior art keywords
solution
paint
complexing agent
ammonium thioglycolate
coating
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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
Application number
GB2369877A
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Al Hajry M N
Original Assignee
Al Hajry M N
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Al Hajry M N filed Critical Al Hajry M N
Priority to GB2369877A priority Critical patent/GB1602838A/en
Publication of GB1602838A publication Critical patent/GB1602838A/en
Expired legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102Pretreatment of metallic substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C23C22/02Chemical 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 non-aqueous solutions
    • 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
    • C23C22/60Chemical 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 alkaline aqueous solutions with pH greater than 8

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Description

(54) IMPROVEMENTS RELATING TO METHODS OF TREATING SURFACES OF INORGANIC MATERIALS (71) 1, MOHAMMED NASSER AL-SRY of PO Box 881, King Abdul Aziz Street, Al-Khobar, Saudi Arabia, of Saudi Arabian nationality, do hereby declare the invention for which I pray that a patent may be granted to me and the method by which it is to be performed to be particularly described in and by the following state menu : This invention relates to methods of treating surfaces of inorganic materials, such as metals, and more particularly to the surface treatment of materials which are liable to oxidisation. It is also, however, applicable to the treatment of surfaces of other materials such as tile, concrete, stone, terrazzo and similar inorganic materials.
It is the object of the invention to provide a method of treating surfaces of inorganic materials which will ensure strong adhesion of a coating of another material, such as paint, applied to the surface.
According to the present invention, a method of treating a surface of an inorganic material comprises the steps of applying to a surface of the material a composition containing a complexing agent comprising obth a sulph-hydro and a carboxylic acid group and applying over the complexing agent a film-forming coating which also contains a complexing agent comprising both a sulph-hydro and a carboxylic acid group and/or an anti-oxidant.
The composition applied in the first step may be an alkaline solution of the complexing agent. A preferred example of such a complexing agent is an ammonium salt of thioglycolic acid, which is preferably applied in the form of a mildly alkaline aqueous solution with a pH value between 7.5 and 10, though it is also possible to apply it as an alcoholic solution. Another example which has proved effective is obtained by neutralising thioglycolic acid with triethanolamine. The surface of the inorganic material before treatment should be free from excessive loose particles, e.g.
of rust or scale, but a certain degree of oxidation of the surface is desirable.
An ammoniacal solution of thioglycolic acid is known to react with iron to form a complex ferrous thioglycolate ion. The complexing agent used in the first step of the method of the present invention is believed to form a complex with metallic or semi-metallic substances (e.g. Fe or Si) in the surface being treated. In the case of oxidisable metals the complexing action is valuable in blocking access of oxygen to the surface. The complexing agent may also, or alternatively, act as an anti-oxidant or oxygen scavenger which reacts with any oxygen that may be present. In the case of a metal surface, e.g. iron, the surface is thus "passivised" and protected from oxidisation. The applied complexing agent, however, appears to decompose after a time, say 48 hours, so that the protection resulting from the first step of the method would be only temporary.The major advantage of this invention lies in the fact that the complexing agent applied in the first step enables the coating applied in the second step to have a very high degree of adhesion to the surface.
The film-forming coating applied in the second step may be a paint, e.g. a primer paint; for example a paint based on a resin which will react with carboxylic acid groups such as those present in the complexing agent. Thus a paint based on a polyurethane resin, or an alkyd resin or an epoxy resin may be employed.
Tests have proven that a very high degree of adhesion of the paint to the surface of the material can be achieved by a suitable choice of conditions. It is believed that the adhesion is caused by reaction between the paint and the carboxylic acid groups of the complexing anent applied in the first step in the process. This high degree of adhesion is dependent on the inclusion of a complexing agent of the & ove-specified kind and/or an antioxidant in the paint or other film-forming coating. The reason for this is believed to be due to the action of the complexing agent and/or the anti-oxidant in preventing diffusion of oxygen through the film forming coating to the underlying surface of the material.The best results are obtained where the same complexing agent is present in the film-forming coating as in the composition applied in the first step and is also included in any further coatings, such as finish coats of paint, but the use of another type of anti-oxidant in such subsequent coatings is also effective. Adequate results, though without the very high degree of adhesion, can also be obtained by incorporating the complexing agent only in the first primer paint coating applied to the treated surface.
As mentioned above, the composition containing the complexing agent should be applied to a surface of the material which is free from excessive loose particles. In most cases, this will necessitate a preliminary step of cleaning the surface to remove any loose material, such as scale, and to degrease it, leaving the surface neutral or slightly alkaline for the subsequent application of the alkaline solution of the complexing agent. Where a degreasing treatment is effected by means of an alkaline detergent which does not decompose the complexing agent, the complexing agent may be incorporated in the detergent so that the degreasing and the application of the complexing agent to the clean surface are combined in a single step.
The method of the invention has been employed to produce highly adherent coatings on the surfaces of iron, steel, galvanised iron, stainless steel, aluminium, tile, terrazzo, concrete and stone.
A particularly useful application is for the application of non-slip coatings, for example on galvanised iron stair treads, or on flooring of tile ar terrazzo material.
Specific embodiments of this invention will now be described in more detail by way of example.
When the method af the invention is to be applied to a surface of iron or steel it is first essential to remove excess scale or other loose material, such as heavy rust, by mechanical means, such as wire brushing or where the material is in the form of a sheet or strip issuing from a mill be descaling rollers. In the latter case, no further cleaning may be necessary, but in general it will be necessary to carry out a degreasing step by conventional means, e.g., application of a strong alkaline clean ing agent such as caustic soda.The effect of these preliminary cleaning steps should be to ensure that the surface is firm and does not carry any loose material, and that the surface is neutral or mildly alkaline (e.g., pH 7 to 10). The presence of iron oxide does not have a deteriorating effect and can be beneficial.
The cleaned surface is then treated with the complexing agent in the form of an aqueous ammoniacal solution of thioglycolic acid, i.e., an aqueous solution of ammonium thioglycolate.
The solution is formed by diluting thioglycolic acid at a ratio of one part thioglycolic acid to six parts distilled water and adding .880 ammonia solution until a pH of 9/9.5 is achieved, thus producing an approximately 70% w/w solution of ammonium thioglycolate in water. In many cases, provided that the surface is free from loose material, the solution of ammonium thioglycolate can be mixed with a degreasing agent so as to carry out the degreasing step simultaneously with the application of the complexing agent. For these two steps to be combined, however, it is important that the degreasing agent should not be too strongly alkaline. The combined solution of the degreasing agent and ammonium thioglycolate should have a pH value between 7.5 and 10.For this purpose the degreasing agent may be chosen from among the many known alkaline detergents of appropriate pH value which are commercially available. The iron or steel surface which has thus been treated is found to be temporarily protected from oxidisation or passivised for a period of up to 48 hours. It is believed that the ammonium thioglycolate (HS.CH2.COO.NH4) forms a complex or a chelate with the Fe through the SH group and thereby blocks access of atmospheric oxygen to the iron or steel surface.
While the surface is in this condition the chosen coating (e.g. a primer paint) is applied to the treated or passivised surface before the initial coating of thioglycolate has had time to decompose. In order to obtain improved adhesion of the chosen coating as compared with that obtainable by conventional methods it is necessary to incorporate in the coating 5 to 25 millilitres of ammonium thioglycolate 70% w/w solution to 5 litres of the chosen coating.
After addition of the thioglycolate to the coating the latter is stirred for up to 15 minutes before application to the treated or passivised surface of the iron or steel. On drying the coating is found to adhere very strongly indeed to the surface.
A further coating or coatings may be applied to the primer coated surface, these further coatings all desirably also containing similar additions of ammonium thioglycolate, to ensure that a strong bond is produced between each coating and the preceding coating as well as between the surface of the metal and the coatings.
Specific treatments according to the invention for various metal articles are described in the following examples.
EXAMPLE I On mild steel up to 26 gauge, a combined degreasing and passivising treatment was effected with an aqueous solution con taining one part of the 70% ammonium hioglycolate solution to 25 parts of a com -'siercially available alkaline detergent.
excess detergent was removed from the c:urface, which was dried, and a primer ; > ating was applied of a polyurethane based paint containing 25 ml of the ammonium thioglycolate solution to 5 litres of paint, mixed for 15 minutes before application.
EXAMPLE 2 On mild steel of 26 gauge to i inch plate, the process of example 1 was repeated except that the degreasing and passivising step was carried out with 1 part of the ammonium thioglycolate solution to 5 parts of the detergent, and in the primer coating only 15 ml of the ammonium thioglycolate solution was used in 5 litres of the polyurethane paint.
EXAMPLE 3 On mild steel thicker than 1 inch plate, a preliminary degreasing step was effected with a strong aqueous solution of caustic soda, which was then rinsed off and the surface dried but not neutralised. The surface was then treated with the 70% solution of ammonium thioglycolate referred to above. After this had been dried, a primer coat of the polyurethane paint containing 5 ml of the ammonium thioglycolate solution to 5 litres of paint was applied.
EXAMPLE 4 In the case of articles of stainless steel, a preliminary cleaning step was effected with an aqueous solution of hydrochloric acid. This was followed by a combined degreasing and passivising treatment using 10 parts of the alkaline detergent mentioned above to 1 part of the ammonium thioglycolate solution. After this had been dried, a primer coating was applied of the polyurethane paint containin 5 ml of the ammonium thioglycolate solution to 5 litres of the paint.
EXAMPLE 5 For treatment of articles of aluminium or aluminium alloy, the surface was first cleaned; with a conventional acid descaler, followed by a degreasing and passivising treatment with 10 parts of the abovementioned alkaline detergent to 1 part of the ammonium thioglycolate solution.
After this had been dried, a primer coating was applied of the polyurethane paint containing 5 ml of the ammonium thioglycolate to 5 litres of the paint.
In all of these examples, the primer coating was found to have exceptionally good adhesion to the underlying metal.
EXAMPLE 6 To apply a non-slip coating to clip-on stair treads of 21 mm galvanised steel, a combined degreasing and passivising treatment was effected as in Example 1 with an aqueous solution of 1 part of the ammonium thioglycolate solution to 25 parts of the alkaline detergent. Excess detergent was removed and the surface dried. A primer coating of a two-pot polyurethane paint containing ammonium thioglycolate was then applied; 25 ml of the ammonium thioglycolate solution was mixed into 5 litres of the polyurethan base for 15 minutes, the hardener was mixed in, and the primer coating was applied to the stair treads.Two finish coats of a two-pot polyurethane paint containing ammonium thioglycolate and an inert non-slip synthetic resin filler were then applied; these coats were made up as for the primer coat, except that 1 kg of finely powdered synthetic resin was mixed in with the hardener. The polyurethane paint was found to harden before the powdered resin filler could dissolve in it to any substantial extent. The non-slip coatings thus produced on the stair treads were found to have improved wear characteristics as compared with such coatings produced by conventional painting processes.
EXAMPLE 7 To apply a non-slip coating to a terrazzo floor, the clean floor was treated with the 70% solution of ammonium thioglycolate described above.
A two-pot polyurethane varnish-type seal was then applied, with 15 ml of the ammonium thioglycolate solution mixed into 5 litres of the polyurethane base for 15 minutes before addition of the hardener and application of the seal to the floor.
The seal was allowed to dry for 2 hours.
Two further coatings of the seal were applied, each 5 litres of the seal containing, in addition to 15 ml of the ammonium thioglycolate solution, 1 kg of a finely powdered synthetic resin non-slip filler and a red pigment, which were mixed in with the hardener immediately before application to the floor. The coated floor had a smooth matt non-slip finish which was resistant to wear and soiling and which could easily be cleaned by conventional methods.
WHAT WE CLAIM IS: 1. A method of treating a surface of an inorganic material comprising the steps of applying to a surface of the material a composition containing a complexing agent comprising both a sulph-hydro and a carboxylic acid group and applying over the complexing agent a film-forming coating which also contains a complexing agent comprising both a sulph-hydro and a carboxylic acid group andlor an anti-oxidant.
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (16)

**WARNING** start of CLMS field may overlap end of DESC **. On mild steel up to 26 gauge, a combined degreasing and passivising treatment was effected with an aqueous solution con taining one part of the 70% ammonium hioglycolate solution to 25 parts of a com -'siercially available alkaline detergent. excess detergent was removed from the c:urface, which was dried, and a primer ; > ating was applied of a polyurethane based paint containing 25 ml of the ammonium thioglycolate solution to 5 litres of paint, mixed for 15 minutes before application. EXAMPLE 2 On mild steel of 26 gauge to i inch plate, the process of example 1 was repeated except that the degreasing and passivising step was carried out with 1 part of the ammonium thioglycolate solution to 5 parts of the detergent, and in the primer coating only 15 ml of the ammonium thioglycolate solution was used in 5 litres of the polyurethane paint. EXAMPLE 3 On mild steel thicker than 1 inch plate, a preliminary degreasing step was effected with a strong aqueous solution of caustic soda, which was then rinsed off and the surface dried but not neutralised. The surface was then treated with the 70% solution of ammonium thioglycolate referred to above. After this had been dried, a primer coat of the polyurethane paint containing 5 ml of the ammonium thioglycolate solution to 5 litres of paint was applied. EXAMPLE 4 In the case of articles of stainless steel, a preliminary cleaning step was effected with an aqueous solution of hydrochloric acid. This was followed by a combined degreasing and passivising treatment using 10 parts of the alkaline detergent mentioned above to 1 part of the ammonium thioglycolate solution. After this had been dried, a primer coating was applied of the polyurethane paint containin 5 ml of the ammonium thioglycolate solution to 5 litres of the paint. EXAMPLE 5 For treatment of articles of aluminium or aluminium alloy, the surface was first cleaned; with a conventional acid descaler, followed by a degreasing and passivising treatment with 10 parts of the abovementioned alkaline detergent to 1 part of the ammonium thioglycolate solution. After this had been dried, a primer coating was applied of the polyurethane paint containing 5 ml of the ammonium thioglycolate to 5 litres of the paint. In all of these examples, the primer coating was found to have exceptionally good adhesion to the underlying metal. EXAMPLE 6 To apply a non-slip coating to clip-on stair treads of 21 mm galvanised steel, a combined degreasing and passivising treatment was effected as in Example 1 with an aqueous solution of 1 part of the ammonium thioglycolate solution to 25 parts of the alkaline detergent. Excess detergent was removed and the surface dried. A primer coating of a two-pot polyurethane paint containing ammonium thioglycolate was then applied; 25 ml of the ammonium thioglycolate solution was mixed into 5 litres of the polyurethan base for 15 minutes, the hardener was mixed in, and the primer coating was applied to the stair treads.Two finish coats of a two-pot polyurethane paint containing ammonium thioglycolate and an inert non-slip synthetic resin filler were then applied; these coats were made up as for the primer coat, except that 1 kg of finely powdered synthetic resin was mixed in with the hardener. The polyurethane paint was found to harden before the powdered resin filler could dissolve in it to any substantial extent. The non-slip coatings thus produced on the stair treads were found to have improved wear characteristics as compared with such coatings produced by conventional painting processes. EXAMPLE 7 To apply a non-slip coating to a terrazzo floor, the clean floor was treated with the 70% solution of ammonium thioglycolate described above. A two-pot polyurethane varnish-type seal was then applied, with 15 ml of the ammonium thioglycolate solution mixed into 5 litres of the polyurethane base for 15 minutes before addition of the hardener and application of the seal to the floor. The seal was allowed to dry for 2 hours. Two further coatings of the seal were applied, each 5 litres of the seal containing, in addition to 15 ml of the ammonium thioglycolate solution, 1 kg of a finely powdered synthetic resin non-slip filler and a red pigment, which were mixed in with the hardener immediately before application to the floor. The coated floor had a smooth matt non-slip finish which was resistant to wear and soiling and which could easily be cleaned by conventional methods. WHAT WE CLAIM IS:
1. A method of treating a surface of an inorganic material comprising the steps of applying to a surface of the material a composition containing a complexing agent comprising both a sulph-hydro and a carboxylic acid group and applying over the complexing agent a film-forming coating which also contains a complexing agent comprising both a sulph-hydro and a carboxylic acid group andlor an anti-oxidant.
2. A method according to Claim 1,
wherein the composition applied in the first step is an alkaline solution of the complexing agent.
3. A method according to Claim 1 or 2, wherein the complexing agent used in the first step is an ammonium salt of thioglycolic acid.
4. A method according to Claim 3, wherein the ammonium salt of thioglycolic acid is applied to the surface in the form of a mildly alkaline aqueous solution with a pH value between 7.5 and 10.
5. A method according to Claim 3, wherein the ammonium salt of thioglycolic acid is applied to the surface in the form of an alcoholic solution.
6. A method according to any one of the preceding claims, wherein the filmforming coating is a paint.
7. A method according to Claim 6, wherein the paint is based on a resin which will react with carboxylic acid groups such as those present in the complexing agent.
8. A method according to Claim 7, wherein the paint is based on a polyurethane resin.
9. A method according to Claim 7, wherein the paint is based on an alkyd resin.
10. A method according to Claim 7, wherein the paint is based on an epoxy resm.
11. A method according to any one of the preceding claims, wherein the same complexing agent is present in the filmforming coating as in the composition applied in the first step.
12. A method according to Claim 11, wherein a further coating or coatings of film-forming material is or are applied, the or each said further coating also including the same complexing agent.
13. A method according to any one of the preceding claims, wherein the surface of the material is subjected to a preliminary cleaning step to remove any loose material and to degrease it, before application of the composition containing the complexing agent.
14. A method according to Claim 13, wherein the preliminary cleaning step leaves the surface neutral or slightly alkaline, with a pH value of 7 to 10.
15. A method according to Claim 14, wherein an alkaline detergent which does not decompose the complexing agent is used, and the complexing agent is incorporated in the detergent so that the degreasing and the application of the complexing agent to the surface of the material are combined in a single step.
16. A method according to any one of the preceding claims, substantially as hereinbefore described in any one of the foregoing Examples.
GB2369877A 1978-05-30 1978-05-30 Treating surfaces of inorganic materials Expired GB1602838A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2123442A (en) * 1982-06-18 1984-02-01 Western Electric Co Chemical surface modification of metals coating with metals
WO1997049756A1 (en) * 1996-06-26 1997-12-31 Elf Atochem S.A. Method of bonding high molecular resins to metals
EP1538135A1 (en) * 2003-11-19 2005-06-08 Bio Services Belgium bvba Composition and working method to remove oxides of metals (rust) from surfaces
WO2005068402A1 (en) * 2004-01-06 2005-07-28 Bioservices Belgium Bvba A method and composition to easily remove metal oxides from substrates
EP1568800A1 (en) * 2004-02-25 2005-08-31 Posco Method of protecting metals from corrosion using thiol compounds

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2123442A (en) * 1982-06-18 1984-02-01 Western Electric Co Chemical surface modification of metals coating with metals
WO1997049756A1 (en) * 1996-06-26 1997-12-31 Elf Atochem S.A. Method of bonding high molecular resins to metals
EP1538135A1 (en) * 2003-11-19 2005-06-08 Bio Services Belgium bvba Composition and working method to remove oxides of metals (rust) from surfaces
WO2005068402A1 (en) * 2004-01-06 2005-07-28 Bioservices Belgium Bvba A method and composition to easily remove metal oxides from substrates
EP1568800A1 (en) * 2004-02-25 2005-08-31 Posco Method of protecting metals from corrosion using thiol compounds

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Effective date: 19920530