EP0725844B1 - A process for activating a metal surface for conversion coating - Google Patents

A process for activating a metal surface for conversion coating Download PDF

Info

Publication number
EP0725844B1
EP0725844B1 EP94900395A EP94900395A EP0725844B1 EP 0725844 B1 EP0725844 B1 EP 0725844B1 EP 94900395 A EP94900395 A EP 94900395A EP 94900395 A EP94900395 A EP 94900395A EP 0725844 B1 EP0725844 B1 EP 0725844B1
Authority
EP
European Patent Office
Prior art keywords
activating
bath
aqueous
metal substrate
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
Application number
EP94900395A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0725844A1 (en
EP0725844A4 (sv
Inventor
Linda S. Kramer
Robin M. Dunn
Terrence R. Giles
Robert W. Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
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 Henkel Corp filed Critical Henkel Corp
Publication of EP0725844A1 publication Critical patent/EP0725844A1/en
Publication of EP0725844A4 publication Critical patent/EP0725844A4/xx
Application granted granted Critical
Publication of EP0725844B1 publication Critical patent/EP0725844B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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

Definitions

  • the invention is an improved method for providing a phosphate conversion coating on a metal substrate.
  • compositions and processes have been used to provide an adherent, uniform phosphate coating on a metal surface.
  • the phosphate coating is applied to enhance the adhesion of subsequently applied coatings and to provide for improved corrosion resistance of the coated metal substrate.
  • Phosphate coating processes (known as phosphating or phosphate conversion coating processes) are well known in the art.
  • the phosphating process comprises contacting the metal surface with a acidic phosphate solution.
  • the phosphating solution generally contains ions of metals such as zinc, nickel, manganese, copper, chromium and other metals which are known to provide conversion coatings on metal substrates in an acidic phosphate solution.
  • the metal substrate can be contacted with the acidic phosphate solution by immersion, spraying, roller coating, flowing and other means known for contacting a metal with an aqueous solution.
  • Acidic phosphate conversion coating solutions are well known in the art and have been found very useful for providing a base for application of a protective coating to the metal substrate.
  • conversion coatings can be improved if, prior to contacting the metal to be phosphate coated with the acidic phosphate solution, the metal surface is first activated by contact with an aqueous activating composition.
  • the aqueous activating compositions are generally mixtures comprising water with a reaction product of a titanium compound and a phosphate.
  • the aqueous activating compositions are at an alkaline pH, generally in the range of about 7 to about 11 and preferably in the range of from about 8 to about 10.
  • Titanium compound-phosphate compound reaction products generally contain from about 0.005 to about 25% by weight titanium.
  • a cleaned metal substrate is contacted with an aqueous activating composition to assist in providing an even coating with low coating weight and small crystal morphology in the phosphate conversion coating step.
  • the aqueous activating composition loses its activating ability as time passes and the aqueous composition ages.
  • the activating ability of the aqueous activating composition declines with time even if the composition has not been exhausted by contact with metal substrates. It would be useful to be able to extend the useful life of the aqueous activating compositions.
  • the time period since preparation of the aqueous activating composition is known as the aging period or aging.
  • a phosphate conversion coating which has a small crystal size, optimal coating weight and a more even coating than substrates which have been contacted with acidic phosphate solutions without prior contact with the aqueous activating composition.
  • the metal substrate Before the metal substrate is contacted with the aqueous activating composition and conversion coated, it is important that the metal substrate be clean. Cleaning of the metal substrate is generally accomplished by contacting the metal substrate with an acidic or an alkaline cleaning composition. Generally, the alkaline compositions are preferred since the activating composition is at an alkaline pH. However, as long as the metal substrate is rinsed of the cleaning solution, an acidic cleaning solution can be utilized.
  • United States Patent No. 4,529,451 describes a method for forming conversion coatings on metallic surfaces using an aqueous zinc phosphate immersion bath while exposing the immersed metallic surface to ultrasonic energy. Whatever the merits of this procedure, it will however appear subsequently that the present invention is not concerned with this kind of phosphate conversion coating operation in an acidic bath but with an earlier stage of surface preparation carried out in an alkaline medium.
  • processes for forming a phosphate conversion coating on a metal substrate by the successive steps of first cleaning the metal surface, then activating the thus-cleaned metal surface by contact with an aqueous, alkaline dispersion of an activating composition, and thereafter coating the thus-activated metal surface by contact with an aqueous acidic phosphate coating solution, characterized in that the aqueous, alkaline activating composition employed in the activating step is subjected to ultrasonic vibration energy so as to extend its useful life.
  • the process of the invention is most advantageous when the ultrasonic vibration energy is applied to aqueous, alkaline dispersions of activating compositions having an average age greater than five days.
  • the aqueous, alkaline dispersion of activating composition employed in the activating step and which is subjected to the vibration energy is very preferably one of those based upon titanium and phosphorus, and it is indeed desirably one which contains a reaction product formed between a titanium compound and a phosphorus compound.
  • the composition employed in the activating step and which is subjected to the ultrasonic vibration energy will preferably also contain a condensed phosphate.
  • the process of this invention advantageously comprises the steps of:
  • the metal substrate is preferably contacted with the aqueous, alkaline dispersion of activating composition at a temperature within the range of from ambient up to 66°C (150°F).
  • the metal substrate will usually comprise one or more of the following metals, namely iron, zinc, zinc alloys, aluminium and aluminium alloys.
  • the metal substrate can be contacted with the aqueous, alkaline activating composition in an activating zone, while the ultrasonic vibration energy is applied to the aqueous alkaline activating composition in an ultrasonic zone outside of the activating zone.
  • Figures 1 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 1 before and after ageing for 12 days.
  • Figures 2 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 2 before and after ageing for 12 days.
  • Figures 3 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 3 before and after aging for 12 days.
  • Figure 4 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 4 before and after aging for 12 days.
  • Figure 5 (a) and (b) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 5 before and after aging for 12 days.
  • Figure 6 (a), (b) and (c) are scanning electron photomicrographs of 1,000 magnification of phosphated cold rolled steel panels prepared by the process using a fresh control bath each day without ultrasonic energy applied.
  • Figure 7 (a), (b), (c), and (d) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 6, after aging for 1, 2, 5 and 6 days.
  • Figure 8 (a), (b), (c), and (d) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 7, after aging for 1, 2, 5 and 6 days.
  • Figure 9 are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 8, after aging for 1, 2, 5 and 6 days.
  • Figure 10 (a), (b), (c), and (d) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 9, after ageing for 1, 2, 5 and 6 days.
  • Figure 11 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 10, after ageing for 1, 2, 5 and 6 days.
  • Figure 12 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of phosphated cold rolled steel panels prepared by the process using Bath 11 after ageing for 1, 2, 5 and 6 days.
  • Figure 13 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of cold rolled steel panels phosphated on days 1, 2, 5 and 6 by the process using a freshly prepared FIXODINE® brand activating control bath each day without ultrasonic energy applied.
  • Figure 14 is a scanning electron photomicrograph at 1,000 magnification of a phosphated cold rolled steel panel, prepared without contact with an activating bath in the process.
  • Figure 15 (a), (b), (c), (d) and (e) are scanning electron photomicrographs at 1,000 magnification of the outer surface of phosphated panels of cold rolled steel (CRS), electrogralvanized steel (EG) and aluminum alloy 6061(6061) prepared using activating Bath 11 under various conditions in the process.
  • CRS cold rolled steel
  • EG electrogralvanized steel
  • Al alloy 6061(6061) prepared using activating Bath 11 under various conditions in the process.
  • Figure 16 (a), (b), (c), (d) and (e) are scanning electron photomicrographs at 1,000 magnification of the inner surface of phosphated panels of CRS, EG and 6061 prepared using activating Bath 11 under various conditions in the process.
  • Figure 17 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of the outer surface of phosphated panels of CRS, EG and 6061 prepared using activating Bath 12 under various conditions in the process.
  • Figure 18 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of the inner surface of phosphated panels of CRS, EG and 6061 prepared using activating Bath 12 under various conditions in the process.
  • Figure 19(a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of the outer surface of phosphated panels of CRS, EG and 6061 prepared using activating Bath 13 under various conditions in the process.
  • Figure 20 (a), (b), (c) and (d) are scanning electron photomicrographs at 1,000 magnification of the inner surface of phosphated panels of CRS, EG and 6061 prepared using activating Bath 13 under various conditions in the process.
  • Figure 21 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of the outer phosphated surface of metal panels prepared using a freshly prepared control bath in the process.
  • Figure 22 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of the inner phosphated surface of metal panels prepared using a freshly prepared control bath in the process.
  • Figure 23 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels (a) CRS, (b) EG and (c) 6061 prepared using stirred Bath 14 (for comparison) in the process.
  • Figure 24 are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels (a) CRS, (b) EG and (c) 6061 prepared by the process by applying ultrasonic energy to Bath 15 while the metal panels were immersed in the bath.
  • Figure 25 are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels (a) CRS, (b) EG and (c) 6061 prepared using Bath 15 five minutes after stopping application of ultrasonic energy to the bath in the process.
  • Figure 26 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared using stirred Bath 16 in the process (for comparison).
  • Figure 27 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared by the process by applying ultrasonic energy to Bath 17 while the metal panels were immersed in the bath.
  • Figure 28 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared by the process wherein the metal panels are immersed in Bath 17 five minutes after the ultrasonic vibrations were discontinued.
  • Figure 29 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared using stirred Bath 18 in the process (for comparison).
  • Figure 30 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared by the process by immersing the panels in Bath 19 while ultrasonic energy was applied to Bath 19.
  • Figure 31 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of phosphated metal panels prepared by the process by immersing the panels in Bath 19 five minutes after the application of ultrasonic energy to the bath was stopped.
  • Figure 32 (a), (b), and (c) are scanning electron photomicrographs of phosphated metal panels prepared by the process using a freshly prepared control bath.
  • Metal substrates which can be advantageously treated by the process of the present invention include iron, zinc, zinc alloys, aluminum and aluminum alloys containing at least about 60%-70% aluminum.
  • the substrate to be treated by the process of the present invention need not be made of the metal alone. That is, zinc plated and aluminum composite materials may be advantageously treated by the process of the invention.
  • the metal must be clean to permit an adherent phosphate coating to be formed.
  • the metal substrates are generally cleaned by contact with an alkaline or an acid cleaning solution to remove any grease, dirt, scale, oxidized coating and the like from the surface of the metal substrate.
  • Acid cleaners generally contain sulfuric and/or phosphoric acid.
  • the metal substrate is aluminum, a small amount of fluoride ion is generally included in the cleaning composition.
  • Alkaline cleaners can be utilized to prepare the metal substrate for accepting the phosphate coating.
  • Alkaline cleaners are generally composed of alkali materials such as caustic, soda ash, trisodium phosphate, sodium polyphosphate, sodium silicate, and surfactants.
  • the metal substrate to be cleaned is contacted with a dilute solution of the alkaline cleaner.
  • the metal to be cleaned is generally contacted with the aqueous cleaning solution at a temperature in the range of from about ambient to about 71.1°C (160°F) and preferably from about 37.8°C (100°F) to about 65.6°C (150°F).
  • Metal can be cleaned by contacting the metal with the aqueous cleaning composition by immersion, spraying, flowing, and other means for contacting a metal with an aqueous cleaning solution.
  • the metal substrate is immersed in the aqueous solution or the aqueous cleaning solution is sprayed onto the metal substrate.
  • the metal is contacted with the cleaning solution for from about 30 seconds to about 10 minutes and preferably from about 1 to about 3 minutes.
  • the cleaning solution is rinsed from the surface of the metal substrate with water.
  • the metal substrate is contacted with a aqueous, alkaline dispersion of an activating composition.
  • a preferred activating composition is a reaction product of a titanium compound with a phosphate compound.
  • the activating compositions are mixed with the water to form an aqueous activating composition (activating bath) and contacted with the metal substrates.
  • the aqueous activating composition contains from about 0.05 to about 25 grams per liter of the activating composition.
  • the activating composition is not soluble in water and a dispersion of the activating composition in an aqueous phase (activating bath) is obtained.
  • the activating composition is a reaction product of a titanium containing composition with a phosphate. This reaction product can be combined with an additional phosphate material such as sodium tripolyphosphate, sodium pyrophosphate, disodium phosphate and the like.
  • the activating composition is a dry material containing at least 0.005% titanium and is mixed with water to form the aqueous activating composition.
  • the activating composition may contain an alkaline material such as sodium carbonate or caustic to help provide an aqueous activating composition with an alkaline pH. The pH is generally between about 8 and 10.
  • the cleaned metal substrate is then contacted with the activating bath for from about 5 seconds to about 10 minutes, preferably from about 20 seconds to about 5 minutes.
  • the activating bath is contacted with the metal substrate at a temperature of from about ambient to about 65.6°C (150°F), preferably from about 23.9 to 43.3°C (75 to about 110°F).
  • a phosphate conversion coating which is later formed on the substrate, has a smaller crystal size, an optimum coating weight and is more uniform. That is, the surface of the metal substrate is more uniformly coated with a phosphate coating.
  • the ultrasonic power can be applied to the aqueous, alkaline activating dispersion alone or it can be applied to the aqueous, alkaline activating dispersion when in contact with a metal surface which is to be activated. The most dramatic results are provided when the ultrasonic power is applied to the aqueous, alkaline activating dispersion when in contact with the metal substrate to be activated.
  • Ultrasonic power can be applied to the aqueous, alkaline activating dispersion in the metal contacting zone in the presence or absence of a metal substrate or can be applied to the aqueous, alkaline activating dispersion in a separate ultrasonic treating zone outside of the contacting zone.
  • the ultrasonic power can be applied to the aqueous, alkaline activating dispersion continuously, only when the aqueous activating composition is being used to activate a metal substrate, only when the aqueous activating composition is not being used to contact metal substrate, in a predetermined discontinuous manner or in a discontinuous random manner.
  • the metal substrate is contacted with the aqueous activating composition at the same time as ultrasonic power is applied to the composition.
  • the metal substrate can be contacted with the aqueous activating composition by immersion, spraying, flowing or any other method used for contacting a metal substrate with an aqueous composition.
  • the aqueous activating composition has a lesser improvement on the final phosphate coating when the ultrasonic power is applied to the aqueous activating composition in the absence of the metal substrate or applied to the aqueous activating composition externally to the contact zone.
  • Excellent phosphate coatings are formed on the metal substrate when the ultrasonic power is applied to the aqueous activating composition in a contacting zone during contact with the metal substrate to be activated.
  • the metal substrate After the metal substrate has been removed from contact with the activating bath, the metal substrate is then passed to a phosphate conversion coating zone.
  • the activated metal substrate In the phosphate conversion coating zone, the activated metal substrate is contacted with an acidic phosphate containing conversion coating solution to provide an adherent metal phosphate coating on the metal substrate.
  • Phosphate conversion coating compositions are well known to one skilled in the art. Phosphate conversion coating compositions have been used for more than 40 years. The acidic phosphate compositions are well known; however, new additives to increase the rate at which the coating is formed, alter the size and shape of the crystals of the coating and the like can be included in the composition to provide a more useful coating.
  • the goal of a phosphate conversion coating process is to provide an adherent coating with a crystal structure optimized for the intended use, with maximum coverage for the weight of phosphate coating.
  • the phosphate coating is desirably as even as possible and of the lowest weight per unit area. Uniform coatings of small crystal size and excellent coverage can be provided by the process of the present invention.
  • contact with the activating bath is required to provide a uniform coating having crystals with a small size.
  • the substrate is then rinsed to remove the acid phosphate solution.
  • the phosphate coating can be further improved by contacting the phosphate coated metal with a sealing and adhesion promoting composition.
  • a sealing and adhesion promoting composition is an acidic chromate containing solution.
  • other post treatment solutions can be utilized.
  • the phosphated metal can be coated by additional coating materials known in the art.
  • Metal test panels were processed using a standard phosphating process cycle. In the tests, the metal test panels were treated according to the following process. The metal test panels were cleaned by contact with PARCO® CLEANER 1500C at 2 ounces per gallon at 43.3°C (110°F) by spraying for 2 minutes; rinsing with warm water with a 45 second spray; contact with an aqueous activating composition of water and FIXODINE® ZN at 26.7°C (80°F) by immersion for 30 seconds; contact with BONDERITE® 3080 phosphating solution according to the manufacturers' recommendations, by immersion in the aqueous phosphating solution at 44.4°C (112°F) for 2 minutes. After immersion in the phosphate coating composition, the panels were rinsed with cold water for 30 seconds and oven dried.
  • PARCO® CLEANER 1500C is an alkali cleaner (product of Parker+Amchem).
  • FIXODINE® ZN activating composition is a composition containing a reaction product of a titanium containing compound with phosphates, subsequently mixed with sodium phosphates and sodium carbonate (product of Parker+Amchem).
  • BONDERITE® 3080 phosphating composition is an aqueous acidic zinc-manganese-nickel-phosphate conversion coating composition (product of Parker+Amchem).
  • a standard water solution was prepared by diluting 79 ml CaCl 2 solution (10 g/l) 53 ml MgSO 4 solution (10 g/l) 26 ml NaHCO 3 solution (10 g/l) to 9 liters with deionized water. This solution is noted as standard water and was utilized to prepare the FIXODINE® ZN brand activating baths. The standard water was analyzed and found to contain: 21 ppm Ca, 10 ppm Mg, 7 ppm Na and hardness (as CaCO 3 ) of 120 ppm.
  • Activating Baths 1-4 were prepared by mixing 1.5 grams of FIXODINE® ZN brand activating composition and 0.22 grams of soda ash (for adjustment of pH 9,0 ⁇ 0.3) per liter of standard water.
  • Bath 5 was prepared by mixing 1.5 grams of FIXODINE® ZN brand activating composition and 0.22 grams of soda ash (pH adjustment to 9.0 ⁇ 0.3) per liter of deionized water.
  • Total titanium is the total amount of titanium in the activating bath in parts per million.
  • Filterable titanium is the amount of titanium, in parts per million, in the activating bath which passes through a filter medium with 2.5 micron openings.
  • Total alkalinity is determined as the number of ml of 0.1N H 2 SO 4 required to titrate a 10 ml sample to a bromphenol blue end point.
  • test panels were prepared after ultrasonic vibrations had been applied to the activating baths in accordance with the experimental design.
  • the ultrasonic vibrations were applied to the activating baths in the ultrasonic power zone of a BRANSONIC® Model PC620 at 40 kilohertz in all experiments reported in this application.
  • Test panels were prepared by the process on day 1 after ultrasonic treatment of the activating bath (if applicable) and on day 12 before and after ultrasonic treatment of the activating bath.
  • the ultrasonic treatment of the activating Baths 1 through 4 was in the treating zones in the absence of the metal substrate.
  • Tables 1 through 5 disclose the properties of the bath and in addition provide coating weight, crystal size and crystal number.
  • the crystal number is the number of crystals in one square inch of the scanning electron photomicrograph at 1,000 magnification of the surface of the coated substrate.
  • the maximum crystal number reported is 100. This includes metal substrates wherein there are more than 100+ crystals per square inch in the scanning electron photomicrograph at 1,000 magnification of the coated metal surface.
  • the preferred coatings have an optimum coating weight, small crystal size and a large crystal number.
  • Tables 1-5 show that ultrasonic energy treatment of aged activating baths, when not in contact with the metal substrate, provides a lower coating weight with a smaller crystal size and a larger crystal number than aged aqueous activating baths which have not been ultrasonically treated.
  • the best phosphate coatings after 12 days aging of the bath were obtained by using activating baths which had been treated with ultrasonic vibrations every day during the 12 days of aging.
  • the coating weight after 12 days aging was the same as the coating weight of phosphate coating obtained by using the fresh activating bath in the process, with the same crystal size and nearly the same crystal number.
  • Activating Bath 5 was prepared with deionized water. It is generally known that the activating effect of the activating bath made with deionized water deteriorates during aging. Bath 5 was included in this study to show that the effect of the application of ultrasonic energy to the Baths 1 through 4 was different than the effect seen with deionized water. With the application of ultrasonic energy to the activating bath, excellent coatings were obtained, even after aging of the baths.
  • Figures 1 through 6 are scanning electron photomicrographs, at a magnification of 1,000, of phosphate coated cold rolled steel panels.
  • the phosphate coating was applied to cold rolled steel panels which had been activated with activating baths according to the experimental design. It is clear from an examination of the figures, and in particular, a comparison of Figures 5 and 1 with Figures 2 through 4 that the ultrasonic treatment of the activating bath substantially improves the phosphate coating which is formed on the metal substrate by the process.
  • test panels were coated according to the following procedure.
  • STEP MATERIAL TEMPERATURE TIME APPLICATION METHOD Clean PARCO® CLEANER 1500C 12.47 g/l (2 oz per gal) 48.9°C (120°F) 120 seconds spray Rinse water 37.8°C (100°F) 60 seconds spray Activation PARCOLENE® ZR or FIXODINE® Z8 32.2-37.8°C (90-100°F) 30 seconds immersion or spray Conversion Coating BONDERITE® 958 according to manuf. recommend-ations 48.9-54.4°C (120-130°F) 120 seconds immersion Rinse cold water 60 seconds spray Rinse deionized water 30 seconds spray Oven Dry 107.2°C (225°F) 5 minutes
  • Table 6 shows the parameters of the activating baths.
  • the content of titanium was adjusted to be approximately the same in all the baths.
  • the amount of magnesium and calcium in the aqueous activating bath is shown in Table 6.
  • application of ultrasonic energy to the activating bath is also shown in Table 6.
  • the ultrasonic energy was applied to the baths in the absence of the metal substrate.
  • Table 7 sets forth the coating weight, the crystal size and the coverage of the phosphate coating on the activated metal substrate provided by the process.
  • the Coating Ratings 1 through 6 utilized in Table 7 and other tables in the specification are as follows: Ratings of 1-3 were given to panels which showed a continuous coating at 1,000 times magnification. A rating of 1 indicates small crystal size morphology, a rating of 3 indicates poor (large) crystal size morphology.
  • Ratings of 4-6 were given if any discontinuinties were observed in the coating at 1,000 times magnification. A rating of 4 indicates a coating with low coating weight and small crystal size, but with surface areas void of phosphate coating. A rating 6 indicates poor surface coverage and large crystal size.
  • Bath 7 is a sonicated bath with the same composition as Bath 6. As shown in Table 7, use of Bath 6 as an activating bath in the process provided a good coating when fresh, but did not provide suitable coatings on days 5 and 6. The crystal size substantially increased with a concurrent increase in coating weight. The coating weight, crystal size and coverage of the phosphate coating when prepared by the process which utilizes the sonicated activating Bath 7 was equivalent, even after aging, to that provided by the control, which was a fresh activating bath prepared every day and applied by spraying onto the cold rolled steel panel.
  • Table 7 also shows that the magnesium and calcium hardness in the water used to prepare the activating bath affected the ability of the bath to promote an optimal coating on the cold rolled steel panel.
  • the loss of coating quality can be seen by the results reported as Baths 8, 9, 10 and 11.
  • the ultrasonically treated Baths 9 and 11 promoted slightly better phosphate coatings than Baths 8 and 10 which were not ultrasonically treated. After one day aging the coatings were not satisfactory.
  • Scanning electron photomicrographs at 1,000 times magnification of the phosphate coatings produced by use of activating Baths 6 through 11 and the Control Bath are shown in Figures 7 through 13 respectively.
  • Figure 14 is a scanning electron photomicrograph at 1,000 magnification of a phosphate coating produced on a non-activated cold rolled steel surface.
  • Table 7 also shows the characteristics of phosphate coatings produced by the process using activating Baths 10 and 11 after aging for 13 days; using the same procedure as for the previous examples (Bath 11, sonicated in the absence of the metal substrate). The phosphate coatings produced by the process using the activating Baths 10 and 11 aged for 13 days were not satisfactory.
  • the parts to be coated are irregularly shaped with recessed or boxed areas. These recessed areas are more difficult to coat with a high quality phosphate coating.
  • a series of experiments were carried out to determine the effect of ultrasonic energy application during the phosphate coating process, when the surface of the substrate is not directly exposed to the ultrasonic vibrations.
  • Four inch by six inch metal panels were inserted into a plastic frame to form a box in which the internal surfaces of the box were not directly exposed to the ultrasonic vibrations.
  • the two panels inserted in the plastic frame were separated by 5/8th of an inch between the panels.
  • the top and bottom of the box contained holes which allowed the activating bath to fill the box while hindering the circulation of the activating solution in the box.
  • the coatings formed on the panels were rated according to the method set forth (1-6).
  • compositions of the baths are set forth in Table 8.
  • Figures 15 and 16 are scanning electron photomicrographs, at a 1,000 times magnification, of the phosphated side of the panel which was the the outer surface of the box and the side of the phosphated panel which formed the inner surface of the box which were treated by aqueous activiting Bath 11.
  • the various treatments are noted as a, b, c, d, and e in Figure 15 and Figure 16.
  • Figures 15 and 16 clearly show the improvement in the phosphate coating on both the inner and outer surfaces when ultrasonic vibrations are applied to the activating bath when it is in contact with the metal substrate in the process of the invention.
  • Table 9 presents the crystal size and coverage of the phosphate coating when applied to cold rolled steel, galvanized steel and aluminum alloy 6061 by the process of the invention when ultrasonic energy is applied to the activating baths, as set forth in Table 8, when the baths are in contact with the box formed from the metal panels.
  • the phosphate coatings formed by the process are improved.
  • the surfaces of the metal panels which faced the interior of the box also showed improvement in the phosphate conversion coating.
  • coating coverage and crystal size on an electrogalvanized steel on both the inner and outer panel surfaces was excellent.
  • the effect of the 150 day old activating Bath 11 without application of ultrasonic vibrations (stirred) is shown for comparison.
  • the inner and outer panel surfaces of aluminum phosphated after treatment with activating Bath 11 showed a significant improvement due to application of ultrasonic vibration when in contact with the metal substrate.
  • the inner surface is almost completely covered with a phosphate coating with application of ultrasonic energy while it is almost completely bare when treated with the activating bath without application of ultrasonic energy.
  • the outer surfaces of the CRS were completely phosphate coated when activated by the 150 day old Bath 11 with application of ultrasonic energy.
  • the inner surfaces of the CRS showed incomplete coating but the coating is significantly better than the coating formed when processed with Bath 10 after only 1 day aging ( Figure 11(b)).
  • Baths 12 and 13 which contained a reduced amount of the activating composition also showed improved phosphated coating when ultrasonic energy was applied to the activating bath when the bath was in contact with the metal substrates.
  • Figures 17 and 18 are scanning electron photomicrographs at 1,000 magnification of the outer surface and the inner surface of the metal panels prepared by the process of the invention utilizing Bath 12 with the reduced content of activating composition.
  • a comparison of Figure 17 and 18 (a) and (b) clearly shows the improvement when ultrasonic energy is applied to the activating bath when the bath is in contact with the metal substrate.
  • the inner and outer surfaces of the panels show improved phosphate coating.
  • Figures 17 and 18 (c) and (d) show the effect of application of ultrasonic energy to the activiting bath on the coating of electrogalvanized steel and aluminum alloy 6061.
  • Figures 19 and 20 are scanning electron photomicrographs at 1,000 magnification of the outer and inner surfaces of metal panels treated with activating Bath 13. It is clear from a comparison of Figure 19 and Figure 20 (a) and (b) that application of ultrasonic energy to the bath while the metal substrate is immersed in the bath substantially improves the crystal size and coverage obtained in the phosphate coating formed by the process of the invention.
  • Figures 21 and 22 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of the outer and the inner surfaces of panels formed from cold rolled steel, galvanized steel and aluminum alloy 6061 using a freshly prepared control bath for activation.
  • Figures 15, 16, 17, 18, 19 and 20 illustrate that the application of ultrasonic energy to the aqueous activating bath in the presence of the metal substrate to be activated comprises a significant improvement in the activation of both the exposed and recessed surfaces.
  • the figures also indicate that the concentration of the activating composition in the activating bath can be reduced if ultrasonic energy is applied to the activating bath while the metal substrate is in contact with the activating bath.
  • Tests were run to determine the effect of application of ultrasonic energy to FIXODINE® Z8 aqueous activating baths.
  • Treatment Baths 14, 15, 16, 17, 18 and 19 were prepared.
  • Baths 14, 15, 16, and 17 utilized various concentrations of FIXODINE® Z8 and were prepared utilizing tap water.
  • Baths 18 and 19 were prepared with PARCOLENE® Z at a low concentration utilizing tap water.
  • compositions of the baths and the treatments are set out in Table 10.
  • BATH CONDITIONER CONCENTRATION WATER SONICATED TOTAL Ti PPM 14 FIXODINE® Z8 1.5 g/L Tap NO 16 15 FIXODINE® Z8 1.5 g/L Tap YES 17 16 FIXODINE® Z8 0.5 g/L Tap NO 5 17 FIXODINE® Z8 0.5 g/L Tap YES 4 18 PARCOLENE® Z 0.4 g/L Tap NO 6 19 PARCOLENE® Z 0.4 g/L Tap YES 6 CONTROL FIXODINE® Z8 1.5 g/L Tap NO 16
  • the activating Baths 14-19 were then aged for 90 days and used to treat cold rolled steel, electrogalvanized steel, and aluminum alloy 6061. In all cases when ultrasonic vibration energy was applied to the activating baths (Baths 14-19) while the baths were in contact with the metal substrate, the phosphated coatings were good. The results of the tests are shown in Table 12.
  • Table 12 presents the characteristics of the phosphate coatings formed on the metal substrates according to the process of the invention utilizing the activating Baths 14, 15, 16, 17, 18 and 19. The results shown in Table 12 were obtained utilizing the baths which had been aged for 90 days. It is clear that the 90 day old FIXODINE® Z8 bath (Bath 14) does not provide an acceptable phosphate coating on the surface of cold rolled steel, electrogalvanized steel or aluminum alloy 6061. However, application of ultrasonic energy to the aged bath (Bath 15), when in contact with the metal substrate produces excellent phosphate coatings on cold rolled steel, electrogalvanized steel and aluminum treated by the process of the invention.
  • Figures 23 (a), (b) and (c) are scanning electron photomicrographs at 1,000 magnification of panels phosphated utilizing the process of the invention and utilizing Bath 14 as the activating bath.
  • Figure 24 is a scanning electron photomicrograph at 1,000 magnification of the crystal structure of the phosphate coating formed by the process of the invention on various metal substrates when ultrasonic energy is applied to Bath 15 while Bath 15 is in contact with the metal substrate.
  • Figure 24 (a), (b) and (c) shows that cold rolled steel, electrogalvanized steel and aluminum alloy 6061 are provided with excellent phosphate coatings by the process of the invention.
  • Figure 25 is a scanning electron photomicrograph at 1,000 magnification of the phosphate coating provided on panels which were contacted with activating bath 15 five minutes after application of ultrasonic energy to the activating bath was discontinued. Figure 25 shows that the phosphate coating is acceptable even when the metal substrate is contacted with activating Bath 15 five minutes after the application of ultrasonic energy to the bath has been stopped.
  • Baths 14 and 15 produced coatings identical to the control bath after aging for one day. After aging for 90 days, the difference in the phosphate coating produced by the process due to application of ultrasonic energy to the activating bath can be clearly seen.
  • Figures 23 through 25 show the effects of application of ultrasonic energy to the activating bath on the phosphate coating produced by the process of the invention. The coatings formed after the ultrasonic energy application had been discontinued 5 minutes before the panels were entered in the solution were satisfactory (see Figure 25).
  • Baths 16 and 17 contained a concentration of the activating composition only 1/3 of the concentration in Baths 11 and 12. Baths 16 and 17 showed a reduced activating ability after aging only one day. Bath 16, with stirring only, and contacted with the metal panel, produced a coating with larger crystal size and higher coating weights than Bath 14.
  • Figures 26, 27 and 28 show the coatings formed after aging the baths for 90 days. Panels treated with activating Bath 16 produced poor coatings when phosphated; however Bath 17 produced excellent phosphate coatings on cold rolled steel, electrogalvanized steel and aluminum alloy 6061 when ultrasonic energy was applied to the Bath 17 while activating Bath 17 was in contact with the metal substrate or within 5 minutes of stopping the application of the ultrasonic energy to the bath.
  • Phosphate coatings produced on cold rolled steel, aluminum alloy 6061 and electrogalvanized steel by the process using activating Bath 17 with application of ultrasonic energy to the activating bath when in contact with the metal panel were identical with phosphate coatings prepared by the process utilizing the control bath ( Figure 32).
  • the aluminum panel appeared to have several small voids in the coating where the metal surface could be seen in the scanning electron photomicrograph. After the application of ultrasonic energy to activating Bath 17 had been discontinued for 5 minutes, a slight loss of activating ability can be noted.
  • the phosphated coatings produced by the process using activating Bath 17 with application of ultrasonic energy to the bath when in contact with the metal substrate were comparable to coatings produced from the fresh control bath containing 3 times the concentration of the FIXODINE® Z8 activating composition.
  • the PARCOLENE® Z bath which does not contain condensed phosphates, (Bath 18), produces poor coatings when the activating bath is prepared with tap water containing calcium and magnesium ion. After aging for only one day, the bath produced coatings similar to panels processed without contact with an aqueous activating bath.
  • Activating Bath 19 to which ultrasonic energy was applied while in contact with the metal substrate, when phosphated, provided a coating comparable to the FIXODINE® Z8 Bath 14 on cold rolled steel and electrogalvanized steel.
  • the coating produced by using activating Bath 19 on aluminum in the process was slightly more porous than that produced by using Bath 14.
  • phosphate coatings can be improved by the process of the present invention if ultrasonic energy is applied to the aqueous activating composition (activating bath) when not in contact with a metal substrate or when the aqueous activating bath is in contact with the metal substrate which is subsequently to be coated with a phosphate conversion coating.
  • the process of the present invention with the improvement of applying ultrasonic energy to the aqueous activating bath in the process improves the phosphate coating produced by the process and extends the life of the aqueous activating composition.
  • Aged baths retain their activating ability over extended periods.
  • the activating bath can contain lower concentrations of the activating composition and still be useful in activating the metal substrate in a phosphate coating processes.
  • the lower concentrations of the activating composition which can be used in the activating bath along with the longer useful life of the activating bath, provides a less expensive and more environmentally friendly process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Materials For Medical Uses (AREA)
EP94900395A 1993-10-26 1993-10-26 A process for activating a metal surface for conversion coating Expired - Lifetime EP0725844B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1993/010243 WO1995012011A1 (en) 1993-10-26 1993-10-26 A process for activating a metal surface for conversion coating

Publications (3)

Publication Number Publication Date
EP0725844A1 EP0725844A1 (en) 1996-08-14
EP0725844A4 EP0725844A4 (sv) 1996-09-11
EP0725844B1 true EP0725844B1 (en) 1999-08-18

Family

ID=22237103

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94900395A Expired - Lifetime EP0725844B1 (en) 1993-10-26 1993-10-26 A process for activating a metal surface for conversion coating

Country Status (10)

Country Link
EP (1) EP0725844B1 (sv)
JP (1) JPH09504052A (sv)
CN (1) CN1106072A (sv)
AT (1) ATE183554T1 (sv)
AU (1) AU679472B2 (sv)
BR (1) BR9307897A (sv)
DE (1) DE69326085T2 (sv)
ES (1) ES2137348T3 (sv)
WO (1) WO1995012011A1 (sv)
ZA (1) ZA948135B (sv)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111474092B (zh) * 2020-04-27 2023-04-07 安徽工业大学 一种研究蒸气在细颗粒表面核化特性的实验方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2456947A (en) * 1944-12-21 1948-12-21 Westinghouse Electric Corp Corrosion resistant coating for metal surfaces
US4311157A (en) * 1980-02-26 1982-01-19 Rock Oil Corporation Sonic treating apparatus
SU1036680A1 (ru) * 1982-04-28 1983-08-23 Предприятие П/Я Г-4855 Способ получени фосфата титана
US4529451A (en) * 1983-01-03 1985-07-16 Detrex Chemical Industries, Inc. Zinc phosphate coated metal and process of producing same
AU2448684A (en) * 1983-03-02 1984-09-06 Parker Chemical Company Metal treatment before phosphate coating
US4531978A (en) * 1983-04-11 1985-07-30 Detrex Chemical Industries, Inc. Method of forming chromate conversion coatings on aluminum surfaces and the coating formed thereby
JPS61170576A (ja) * 1985-01-23 1986-08-01 Kawasaki Steel Corp 耐食性および色調外観の優れた亜鉛めつき系クロメ−ト処理鋼板の製造法
JPH0394075A (ja) * 1989-09-04 1991-04-18 Nippon Parkerizing Co Ltd 表面調整処理方法
US5176755A (en) * 1990-02-14 1993-01-05 Armco Inc. Plastic powder coated metal strip

Also Published As

Publication number Publication date
CN1106072A (zh) 1995-08-02
DE69326085T2 (de) 2000-04-13
JPH09504052A (ja) 1997-04-22
AU679472B2 (en) 1997-07-03
ES2137348T3 (es) 1999-12-16
BR9307897A (pt) 1996-09-10
EP0725844A1 (en) 1996-08-14
AU5540194A (en) 1995-05-22
ZA948135B (en) 1995-06-26
ATE183554T1 (de) 1999-09-15
EP0725844A4 (sv) 1996-09-11
WO1995012011A1 (en) 1995-05-04
DE69326085D1 (de) 1999-09-23

Similar Documents

Publication Publication Date Title
CA2175065A1 (en) A process for activating a metal surface for conversion coating
EP0977908B1 (en) Conditioning metal surfaces prior to phosphate conversion coating
RU2109845C1 (ru) Состав концентрата для получения водного раствора для нанесения покрытия для обработки металлических поверхностей, водный раствор для нанесения фосфатного покрытия кристаллической структуры на металлическую поверхность, способ фосфатирования металлической поверхности и пополняющий состав для добавления к раствору для нанесения покрытия
US4838957A (en) Phosphate coatings for metal surfaces
JP2806531B2 (ja) 鉄又は鉄合金材料の表面処理用リン酸亜鉛系水溶液及び処理方法
US5976272A (en) No-rinse phosphating process
US6197126B1 (en) Nickel-free phosphating process
JP2680618B2 (ja) 金属のりん酸塩処理方法
EP0866886B1 (en) Zinc phosphate conversion coating compositions and process
US6214132B1 (en) Conditioning metal surfaces prior to phosphate conversion coating
JPH04228579A (ja) リン酸塩で金属表面を処理する方法
JP2004521187A (ja) 多金属物品を処理する方法
US6551417B1 (en) Tri-cation zinc phosphate conversion coating and process of making the same
KR0171219B1 (ko) 망간 및 마그네슘 함유 아연 포스페이트 코팅의 형성방법
US3741747A (en) Highly alkaline titanated cleaner
US4622078A (en) Process for the zinc/calcium phosphatizing of metal surfaces at low treatment temperatures
JP3137535B2 (ja) 塗装性に優れた亜鉛含有金属めっき鋼板複合体、およびその製造方法
EP0653502A2 (en) Zinc-containing metal-plated composite steel article and method of producing the same
JPH01277A (ja) 電着塗装前処理りん酸塩処理方法
EP0544650A1 (en) A process for phosphate-coating metal surfaces
CA1224121A (en) Process for phosphating metals
JP2003155578A (ja) 鉄及び／又は亜鉛系基材用化成処理剤
US5776265A (en) Process for activating a metal surface for conversion coating
US5383982A (en) Process of producing phosphate coatings
EP0725844B1 (en) A process for activating a metal surface for conversion coating

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960515

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 19960726

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE DE ES FR GB NL PT SE

17Q First examination report despatched

Effective date: 19961106

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990818

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990818

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990818

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990818

REF Corresponds to:

Ref document number: 183554

Country of ref document: AT

Date of ref document: 19990915

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69326085

Country of ref document: DE

Date of ref document: 19990923

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19991118

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2137348

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20001002

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20001003

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20001107

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20011004

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011027

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020702

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021026

GBPC Gb: european patent ceased through non-payment of renewal fee
REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021113