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EP0032306B1 - Bad, Verfahren und Konzentrat zur Beschichtung von Aluminium - Google Patents

Bad, Verfahren und Konzentrat zur Beschichtung von Aluminium Download PDF

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Publication number
EP0032306B1
EP0032306B1 EP80304673A EP80304673A EP0032306B1 EP 0032306 B1 EP0032306 B1 EP 0032306B1 EP 80304673 A EP80304673 A EP 80304673A EP 80304673 A EP80304673 A EP 80304673A EP 0032306 B1 EP0032306 B1 EP 0032306B1
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EP
European Patent Office
Prior art keywords
litre
aluminium
coating solution
conversion
coating
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
Application number
EP80304673A
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English (en)
French (fr)
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EP0032306A1 (de
Inventor
Timm Lee Kelly
Frank Jeffrey Frelin
Anthony Joseph Malloy
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Henkel Corp
Original Assignee
Amchem Products Inc
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Publication date
Priority claimed from US06/107,017 external-priority patent/US4273592A/en
Priority claimed from US06/165,734 external-priority patent/US4313769A/en
Application filed by Amchem Products Inc filed Critical Amchem Products Inc
Priority to AT80304673T priority Critical patent/ATE13077T1/de
Publication of EP0032306A1 publication Critical patent/EP0032306A1/de
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Publication of EP0032306B1 publication Critical patent/EP0032306B1/de
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Definitions

  • This invention relates to an aluminium-coating solution, process and concentrate, as well as aluminium articles coated thereby.
  • aluminium is here used to embrace not only pure aluminium but also alloys of aluminium, for example those aluminium alloys which contain minor amounts of metals such as magnesium, manganese, copper and silicon.
  • the coatings should be clear and colourless when applied to the cans, it is also necessary that they should afterwards so remain. Specifically the coating must be able to resist discolouration when the coated can is subjected to moderately hot water, for example at water temperatures within the range of from about 60°C (140°F) to about 77°C (170°F), during operations usually called “Pasteurization” of the cans. Such a “Pasteurization” treatment has a tendency to cause an uncoated or an inadequately-coated aluminium surface to blacken or otherwise discolour, thereby giving the can an unattractive appearance.
  • coated aluminium cans should be able to undergo discolouration, since this can be the basis for a simple test designed to confirm the presence of the desired coating.
  • One such test conventionally employed in the can industry is known as the "muffle test". By means of such a test a can manufacturer is able to sample cans randomly from the production line and to confirm that the desired clear and colourless coating although invisible is actually present on the cans.
  • phosphate in the solution is said to contribute to the corrosion-resistance and paint-receptive properties of the coating, and moreover to render the coating susceptible to the so-called "muffle test" should that wish to be used in order to confirm the presence of the coating on an aluminium surface.
  • Phosphate however is not altogether a welcome ingredient, since it has been found to cause a decrease in the adhesion of certain water-borne siccative coatings and thus it would be desirable to produce a coating in which phosphate is not an essential ingredient.
  • alkaline aqueous solutions for aluminium surfaces which include either titanium or zirconium ions and a complexing agent.
  • the recommended pH is at least 10.
  • the solution generally contains an alkali metal, for example, in the form of a salt with as anions hydroxides, carbonates, phosphates or borates.
  • a surfactant is also an optional ingredient.
  • the treated surface is generally rinsed with water, and in a particularly preferred embodiment, the rinsed surface is then contacted with an aqueous acidic solution containing tannin or tannic acid.
  • a chromate-free, acidic, aqueous coating solution of pH from 1.5 to 5, capable of forming a clear, colourless and corrosion-resistant coating upon an aluminium surface which contains:-
  • the acidic, aqueous coating solution of this invention can be used to treat a bright shiny aluminium surface in such a manner that its bright shiny appearance is not impaired, yet there is formed upon the surface a uniformly colourless and clear coating, which exhibits excellent corrosion-resistance and to which overlying siccative coatings will tightly adhere.
  • the coating solutions of the present invention are able to form this desirable type of coating upon aluminium even in the absence of materials which either are toxic or create waste disposal problems; thus the coating solutions of this invention can be and are free from not only hexavalent chromium but also elements such as manganese, iron, cobalt, nickel, molybdenum and tungsten, as well as toxic materials such as ferricyanide and ferrocyanide.
  • the absence of such materials from the coating solution makes it unnecessary to subject the effluent to any special treatment before it is discharged to the environment or to a sewage-disposal plant.
  • the coatings formed by the coating solutions of this invention are especially valuable if they are to serve as the foundation for overlying siccative coatings applied in the form of water-based compositions.
  • siccative coatings formed from water-based compositions do not adhere to conversion coatings of the prior art Zr, Ti, or Hf type as well as siccative coatings formed from compositions based upon organic solvents.
  • the siccative coatings formed from water-based compositions tend not to adhere so well to underlying conversion coatings formed from the phosphate-containing solutions of United States Patent No.
  • component (c) is the polyhydroxy compound we have observed that the corrosion resistance of the coatings formed by the coating solutions may tend to vary, dependent on the type of water used in preparing such compositions. Generally speaking, it seems that the corrosion-resistance properties of the coatings are better when they are formed from solutions made up in hard water than when they are formed from solutions made up in soft water. The relatively low calcium concentration in soft water appears to be detrimental to the corrosion resistance of the resultant coatings; or perhaps one should instead say that the relatively high concentration of calcium in hard water is beneficial to the corrosion-resistance of the resultant coatings. There is however no variation in corrosion-resistance of the coating dependent upon water-hardness in the solution when component (c) is either surfactant alone or a mixture of surfactant with polyhydroxy compound.
  • surfactant is used herein to mean any material which when present in a small amount will markedly reduce the surface tension of water.
  • surfactant is used herein to mean any material which when present in a small amount will markedly reduce the surface tension of water.
  • the term thus embraces all the various conventional classes of surfactants, namely anionic, cationic, non-ionic and amphoteric surfactants. It should however be noted that the use of a non-ionic surfactant is preferred in accordance with the present invention.
  • the acidic aqueous coating solution must as stated contain one or more of the Group IVa metals titanium, zirconium and hafnium in conjunction with fluoride and with a polyhydroxy compound and/or a surfactant. Any convenient sources of these components may be employed which are soluble in the solution
  • the sources of the zirconium, titanium or hafnium one can for instance use soluble fluozirconate, fluotitanate or fluohafnate compounds, such as fluozirconic, fluotitanic and fluohafnic acids and the corresponding salts such as ammonium and alkali metal fluozirconates, fluotitanates and fluohafnates.
  • suitable sources include metallic fluorides such as zirconium fluoride (ZrF 4 ), titanium fluoride (TiF 3 , TiF 4 ), and hafnium fluoride (HfF 4 ).
  • the coating solutions can moreover be prepared from mixtures of soluble compounds, one of which contains the Group IVa metal(s) and the other of which contains the fluoride.
  • soluble compounds one of which contains the Group IVa metal(s) and the other of which contains the fluoride.
  • water-soluble salts comprising nitrates and sulphates of Zr, Ti or Hf (for example zirconium nitrate, zirconium sulphate, titanium (iv) sulphate and hafnium nitrate) the hydrofluoric acid and its water-soluble salts such as ammonium and alkali metal salts thereof.
  • the minimum fluoride concentration is that required to combine with all of the zirconium, titanium and/or hafnium to form a soluble complex therewith, for example a fluozirconate, fluotitanate or fluohafnate.
  • the minimum amount of fluoride is thus dependent on the amount of zirconium, titanium and/or hafnium in the solution.
  • the coating solution when operating on an industrial scale, should contain an excess of fluoride beyond that amount complexed with aluminium and any other constituents in the solution that form complexes with the fluoride.
  • excess fluoride is referred to herein as "available fluoride"; and the manner in which one calculates the amount of "available fluoride” is well-understood in the art.
  • a coating solution which contains available fluoride is one in which fluoride is available to complex with aluminium.
  • the available fluoride concentration should be no greater than 26.3x 10- 3 mole/litre (or no greater than 500 parts per million) in order to avoid undue etching of the aluminium surface, which tends to give a dull and frosty appearance to the surface, and so as also to avoid adverse affects on the corrosion resistance and paint-receptive properties of the coating, as well as to avoid precipitation of calcium or other such ions present in the solution.
  • the source of fluoride for use in the coating solution can be any material which is soluble therein and provides a source of fluoride capable of complexing aluminium, provided that it does not contain anything else which adversely affects the-coating process. Supposing however that fluoride is added as a complex fluoride of titanium, zirconium or hafnium, then another source of fluoride should also be added to the solution so as to serve as a source of fluoride for complexing the aluminium that builds up during continuous operation.
  • Alternative sources of fluoride for this purpose include materials such as HF, salts thereof, NH4F . HF, alkali metal bifluorides, H 2 SiF 6 or HBF 4 .
  • the particularly preferred sources of fluoride are HF and HBF 4 .
  • a surfactant when present in the solutions of the present invention it will preferably be a non-ionic surfactant. Although as little as 10 parts per million (equivalent to 0.01 g/litre) of surfactant can suffice it is preferred to use the surfactant in a concentration of from 20 to 100 parts per million. Still higher amounts, for example up to about 500 parts per million, can be used without detriment, but we have found that in general little or no additional improvements are achieved at such higher concentrations.
  • a polyhydroxy compound When a polyhydroxy compound is to be present it may be any water-soluble polyhydroxy compound which has no more than seven carbon atoms.
  • the source may obviously be the polyhydroxy compound itself, but it may also be any compound soluble in the coating solution which when dissolved therein yields the desired polyhydroxy compound and is not otherwise detrimental to the coating-ability of the solution or the corrosion-resistance and paint-adherence of the coatings.
  • examples of such compounds include gluconic acid and its salts, sodium glucoheptonate, sorbitol, mannitol, dextrose, ethylene glycol, and glycerine.
  • Particularly preferred polyhydroxy compounds are gluconic acid and its alkali metal and ammonium salts.
  • the source of polyhydroxy compound may also be any compound soluble in the coating solution which there yields gluconate and/or gluconic acid; and examples of such compounds are stable gluconolactones such as glucono-de/ta-lactone and glucono-gamma-lactone.
  • the presence of the polyhydroxy compound in the coating solution allows the operator of the manufacturing process to conduct a simple test so as to check whether the coating has been formed on the aluminium surface. Because the coating is not visible to the eye it is very helpful to have some simple test to confirm that the coating solution is forming a coating, especially in industrial operations which can involve the treatment of vast quantities of aluminium in a relatively short time. Without some check it would be easy for some change in the operating parameters of a bath of the coating solution, occurring as a result of mechanical or human failure and which renders it ineffective, to go unnoticed and lead to much defective output before it is discovered. Improper replenishment of the coating solution can for instance easily go undetected for quite some time unless a careful check upon the quality of the product is maintained.
  • an aluminium surface coated with the solution of the present invention containing the specified polyhydroxy compound but no phosphate, will undergo a colour change when subjected to a relatively high temperature for a relatively short period of time, for example about 482°C (900°F) for 5 minutes, changing from colourless and invisible to a visible coating coloured from light golden brown to darker shades of brown or purple.
  • This test referred to herein as the "muffle” test, can be used upon randomly selected samples of the treated aluminium articles to check whether or not the desired invisible coating has been formed upon the aluminium surface. If not, the uncoated aluminium surface will have a dull greyish appearance after the muffle test.
  • Both the polyhydroxy compound and also the surfactant have the further advantage that their presence in the coating solution improves the ability of coatings formed therefrom to withstand blackening (or other discolouration) for a period of at least 5 minutes, and often indeed up to as long as 15 minutes, when subjected to Pasteurization-type procedures in water having a temperature within the range of from say 60°C to 77°C (140°F-170°F).
  • siccative coatings particularly water-borne siccative coatings
  • water-borne siccative coatings will adhere especially well to coatings which have been formed from solutions which contain polyhydroxy compounds but are free from phosphate. This may be contrasted with the fact that although organic-borne siccative coatings do adhere well to coatings containing phosphates, certain water-borne coatings do not adhere thereto nearly as well.
  • coated aluminium cans which have a high level of water-stain resistance and are capable of discolouring when subjected to the aforementioned muffle test can be produced from coating solutions containing as little as 0.025x10- 3 mole/litre of the polyhydroxy compound; but the coating solutions will preferably contain from 0.3x10- 3 mole/litre to 1.75x10- 3 mole/litre of the polyhydroxy compound. It is indeed possible to use higher amounts, for example up to 2.5x10- 3 mole/litre, but generally we have found that little or no additional improvements are achieved at such higher concentrations.
  • the solutions of the present invention contain not only the polyhydroxy compound but also surfactant, it is recommended that at least 40 parts per million of the polyhydroxy compound should be present, but that although higher amounts can be used it is also recommended that no more than 1,000 parts per million of the polyhydroxy compound should be present.
  • the coating solution will besides surfactant also contain preferably from 40 to 400 parts per million of the polyhydroxy compound.
  • the pH of the acidic aqueous coating solution can vary over the wide range from 1.5 to 5.
  • surfactant is present in the solutions of the present invention improvements in corrosion resistance attributable thereto are observed particularly within the pH range of from 3.5 to 4.5.
  • polyhydroxy compound is present in the solutions of the present invention, improvements in corrosion resistance attributable thereto are observed, particularly within the pH range of from 3.0 to 5.0, and especially within the range of from 3.0 to 4.0.
  • the pH of the coating solution may conveniently be adjusted to any desired value by using appropriate amounts of any acid or base which will not interfere with the coating process.
  • the acid employed can for example be perchloric acid or sulphuric acid, but will preferably be nitric acid; and the base employed for pH adjustment will preferably be ammonium hydroxide.
  • the coating solutions of the present invention should very desirably be kept free from chromium, from iron cyanides, and from any materials which in the solution will tend to form solids which precipitate.
  • the coating solutions can be free from phosphate it is not in all circumstances necessary that they should be phosphate-free. Specifically, when the conversion coating is to serve as the foundation for siccative coating compositions based upon organic solvents it is permissible for the coating solution of the present invention except when it contains the polyhydroxy compound and is surfactant-free, optionally to include phosphate in concentrations of from 10 parts per million to 1,000 parts per million, as described in United States of America Patent No. 4,148,670.
  • Still other materials which optionally can be included in the coating solutions of the present invention are various other acids, such as for example glutaric, ascorbic, maleic or salicylic acids, which if present in concentrations of at least 5 parts per million and preferably within the range of from 100 to 500 parts per million may serve to improve the adhesive properties of the resultant coatings, or achieve other advantages.
  • acids such as for example glutaric, ascorbic, maleic or salicylic acids, which if present in concentrations of at least 5 parts per million and preferably within the range of from 100 to 500 parts per million may serve to improve the adhesive properties of the resultant coatings, or achieve other advantages.
  • the choice of any particular concentration will depend on various considerations.
  • the solution is to operate at a relatively high pH, then relatively smaller amounts of zirconium, titanium and/or hafnium should be present, in order to deter precipitation.
  • relatively higher amounts of the aforementioned metals should be used; and similarly, when the temperature at which the coating solution is to be contacted with the aluminium surface will be relatively low, then again relatively higher amounts of all the ingredients should be used.
  • Solution A one preferred coating solution in accordance with the present invention
  • the zirconium source in Solution A is preferably ammonium fluorzirconate, and the polyhydroxy compound is preferably gluconic acid.
  • the source of available fluoride is preferably hydrofluoric acid, and nitric acid is preferably used if needed to adjust the pH to a value in the desired range.
  • hafnium When hafnium is added to Solution A, it is preferably added in a concentration in the range of from 0 : 5x10- 3 mole/litre to 1.75x10- 3 moles/litre.
  • the preferred source of hafnium is HfF 4 .
  • Solution A may also contain any of the other previously-discussed optional ingredients.
  • Solution B Another preferred coating solution in accordance with the present invention (hereinafter identified as "Solution B") can be formulated as follows:
  • Solution 1 3 will preferably contain:
  • the zirconium source in Solution B will preferably be fluozirconic acid, at least in the make-up composition, since this will provide not only the Zr but also the necessary fluoride.
  • Nitric acid is preferably used if needed to adjust the pH to a value in the desired range.
  • the coating solution of the present invention will most conveniently be prepared from an aqueous concentrate of the ingredients by diluting it with an appropriate amount of water.
  • a concentrate suitable for making up Solution A should thus for example be such that when it has been diluted down to form only from 0.5 to 10 weight percent of the resultant coating solution, the concentrations of the various ingredients in the coating solution will be:
  • the concentrate will preferably be such that when diluted down to form no more than from 0.5 to 10 weight percent of the resultant coating solution the latter will contain:
  • a concentrate suitable for making up Solution B should, by way of further example, be such that when it has been diluted down to form only from 0.5 to 10 weight percent of the resultant coating solution, the concentrations of the various ingredients in the coating solution will be:
  • Replenishment may naturally be effected by monitoring the amount still present of each individual ingredient, and then adding an additional amount thereof to replace whatever has been lost; but it is obviously more convenient and therefore preferable to replenish the coating solution by adding thereto enough of an aqueous concentrate which has been formulated to contain the ingredients to be replenished in relative amounts which will be effective to maintain all said ingredients in the solution within their effective operating concentrations.
  • the replenishing composition will preferably contain a relatively high proportion of available fluoride when substantial aluminium build-up in the coating solution is encountered.
  • Preferred sources of available fluoride for use in replenishment are hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ) or a mixture thereof or fluoboric acid (HBF 4 ).
  • Constant A one preferred replenishment concentrate (hereinafter identified as "Concentrate A”), which is recommended for replenishing the aforesaid Solution A, can be formulated as follows:-Concentrate A:
  • the available fluoride in Concentrate A will preferably be hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ) or a mixture of these two sources.
  • HF hydrofluoric acid
  • NH 4 HF 2 ammonium bifluoride
  • Constant B another preferred replenishment concentrate (hereinafter identified as "Concentrate B"), which is recommended for replenishing the aforesaid Solution B, can be formulated as follows:-Concentrate B:
  • the coating process of the present invention can be used to coat surfaces of pure aluminium or of aluminium alloys in which aluminium is the predominant ingredient.
  • aluminium is the predominant ingredient.
  • aluminium alloys containing minor amounts of alloying elements such as, for example, magnesium, manganese, copper and silicon. It is our belief that one of the widest uses of the coating process of the present invention will be in the coating of aluminium surfaces which have a bright, shiny appearance; and aluminium cans and aluminium strip are examples of such articles, which can be effectively coated by means of the process of this invention.
  • the most popular alloy used in the manufacture of aluminium cans is that known as Aluminium Alloy 3004.
  • the nominal chemical composition of Aluminium Alloy 3004 is 1.2% manganese, 1.0% magnesium and the balance aluminium and normal impurities. Certainly the process of the present invention is well able to form the desired coatings upon this important Aluminium Alloy 3004.
  • the coating process of the present invention should be carried out upon a clean aluminium surface.
  • the process may therefore include the preliminary step of cleaning the aluminium surface by means of existing aluminium cleaning compositions such as alkaline or acidic cleaning solutions, which may be applied thereto by conventional techniques.
  • the preliminary cleaning step will preferably be carried out using a cleaning solution which consists of an acidic aqueous solution of a mixture of hydrofluoric acid (HF), sulphuric acid (H 2 S0 4 ) and surfactant.
  • a cleaning solution which consists of an acidic aqueous solution of a mixture of hydrofluoric acid (HF), sulphuric acid (H 2 S0 4 ) and surfactant.
  • HF hydrofluoric acid
  • H 2 S0 4 sulphuric acid
  • the coating solution can be brought into contact with the aluminium surface by any convenient method.
  • the solution can for example be applied to the aluminium surface by spraying it thereon, or the aluminium article can be dipped into the solution so that its surface is-immersed therein, or the solution can be applied to the surface by roll- or flow-coating techniques or by misting techniques.
  • the solution can be contacted with discrete articles, such as for example cans; or it can be contacted with continuous forms of aluminium blank, such as aluminium strip, which will subsequently be fabricated into discrete articles.
  • the temperature of the coating solution when it is brought into contact with the surface is not very critical, and can vary within wide limits, just so long as the chosen temperature permits the reactive ingredients of the solution to react with the aluminium surface and form a conversion coating thereon.
  • a coating solution such for instance as the aforesaid Solution A
  • a coating solution such for instance as the aforesaid Solution B
  • the temperature of the coating solution is too high, problems may be encountered, such as a dull and frosty appearance imparted to the aluminium surface.
  • the temperature at which this may occur will depend on various parameters of the coating process, including for instance the period of contact between the solution and the aluminium surface and the reactivity of the solution, the latter being in turn dependent on the pH of the coating solution and the concentration of ingredients therein.
  • there may be other temperature-related problems-with coating solutions such as Solution A if the pH value rises above 4.5 then precipitation of zirconium and/or hafnium oxides may become a problem at operating temperatures in excess of 71°C (160°F). With coating solutions such as Solution B it is preferred to avoid operating temperatures in excess of 60°C (140°F).
  • the operating temperature of Solution A will preferably be in the range of from 54°C (130°F) to 66°C (150°F).
  • the operating temperature of Solution B will preferably be in the range of from 43°C (110°F) up to 54°C (130°F).
  • the period of contact between the coating solution and the aluminium surface will usually need to be at least 5 seconds, and preferably should be not less than 15 seconds.
  • the rinsing procedure should very desirably include a final rinse with deionized water, since rinsing with water that contains even a small amount of dissolved solids may result in a coating to which a subsequently applied siccative coating does not adhere well.
  • aqueous solution of chromium for example one containing hexavalent chromium solution
  • no such chromium-after-rinse is needed in the process of this invention.
  • the coated surface has been water-rinsed, or otherwise treated as described above, it should normally be dried, subject only to the comments made below. Drying can be carried out in any convenient manner, for instance by oven drying or forced circulation of hot air.
  • the conversion coating After the conversion coating has been applied, it can be provided with a further sanitary or decorative coating, for example by applying some kind of siccative coating material to the conversion coated surface. While such siccative coating materials will usually be applied after the conversion-coated aluminium surface has been water-rinsed and dried, it should be noted that sometimes the sanitary siccative coating material will be applied after the water-rinse but before drying, so that both the conversion coating of the present invention and the sanitary siccative coating will be dried simultaneously.
  • siccative coating materials which may be employed for their functional and/or aesthetic value over the conversion coatings formed by the process of the present invention, for such siccative coating materials (both the water-based and the solvent-based compositions) are of course in themselves well-known.
  • the process of the present invention may well form part of a still larger manufacturing procedure.
  • the cans will be cleaned and conversion coated by means of the coating process employing the coating solution of the present invention, then sanitary and/or decorative siccative coatings will be applied to the conversion-coated cans, thereafter these doubly-coated cans will be filled with beer and sealed, and finally, the beer-filled cans will be subjected to pasteurization.
  • This invention of course extends to aluminium articles whose surfaces have been provided with a conversion coating thereupon, and if desired otherwise treated, in accordance with the process of this invention. It extends also to the concentrates employed in making-up and/or replenishing the solutions used in such processes.
  • the zirconium, titanium and/or hafnium present in the coating solutions of the present invention is believed to be present in a complexed form which is both soluble in the solution and reactive with the aluminium surface to form thereon a coating which contains such metal(s) without affecting the bright shiny appearance of the aluminium surface.
  • the coating solution should be kept free from constituents which might combine with the aforementioned metals to form undesirable compounds and/or complexes, that is to say compounds and/or complexes which either will precipitate from the solution and/or will not react with the aluminium surface and/or will indeed react but in such a manner than the bright shiny appearance of the underlying aluminium surface is altered.
  • the aluminium surfaces treated with the solutions identified in the examples were drawn-and-ironed aluminium cans, which were first degreased, as necessary, in an acidic aqueous cleaner containing sulphuric acid, hydrofluoric acid and detergent. Unless stated otherwise, the coating solutions were applied by spraying for about 20 seconds at the appropriate temperatures. After treatment with the solutions described in the examples, the aluminium surfaces were rinsed firstly with tap water and then with deionized water, and thereafter dried in an oven for 3.5 minutes at about 204.4°C (400°F).
  • the aluminium cans were tested for corrosion resistance by subjecting them to a water stain resistance test designed to simulate can exposure during commercial pasteurization processes.
  • the test consisted of immersing the cans for a period of 30 minutes in a hot solution of distilled or deionized water containing 0.22 g/I of sodium bicarbonate, 0.082 g/I of sodium chloride, and 2.18 g/I of a water-conditioner ( * Dubois 915, which exhibits a total alkalinity of 5.8% Na 2 0 and on analysis contains sodium nitrate, carbonate, triethanolamine and dodecylphenyl polyethylene glycol). The solution was maintained at 65.6 ⁇ 2.8°C (150° ⁇ 5°F) during the test.
  • the aluminium cans after treatment with the indicated solutions, were also tested for paint adhesion.
  • a portion of the surface was painted with a water-based white base coat (No. CE3179-2 white polyester sold by PPG Industries Inc.) and the other portion of the surface was painted with a water based varnish (Purair * S145-121 sold by Inmont Corporation) to be referred to in the examples as CE3179-2 and S145-121 respectively.
  • the painted surface was immersed in boiling water for 15 minutes. After removing the painted surface from the aforementioned, it was cross-hatched, using a sharp metal object to expose lines of aluminium which showed through the paint or lacquer, and tested for paint adhesion.
  • This test included applying transparent adhesive tape (Scotch ** transparent tape No. 610) firmly over the cross-hatched area and then drawing the tape back against itself with a rapid pulling motion such that the tape was pulled away from the cross-hatched area.
  • the results of the test were rated as follows:
  • the following acidic aqueous concentrate was prepared for use in connection with the first group of examples:
  • the above composition was prepared by combining an aqueous solution of 23.4 grams of 45 wt.% fluozirconic acid with a portion of the water, and then the aqueous ammonia was added to the resulting solution. A white precipitate was formed, but it dissolved upon addition of nitric acid.
  • the resulting clear solution was diluted to 1 litre with deionized water resulting in a concentrate that was used to prepare treatment solutions at 2.5% by volume in water comprising 2 parts deionized water and 1 part hard water.
  • hard water refers to tap water from the township of Ambler, Pennzylvania, United States of America, which includes about 80 to about 100 ppm of calcium and has a conductivity of about 400 to about 600 ohms-1).
  • a non-ionic surfactant Surfonic * LF-17
  • Solutions of varying acidity were prepared by adjusting the pH of the aforementioned composition with appropriate amounts of an aqueous solution of 15% (w/v) ammonium carbonate or dilute nitric acid.
  • Said other surfactant was a modified low-foaming polyethoxylated straight-chain alcohol (Triton DF-16 * ).
  • Triton DF-16 * modified low-foaming polyethoxylated straight-chain alcohol
  • Table III shows the effect of gluconic acid concentration on water-stain resistance of coatings applied at varying temperatures from 32.2°C to 65.6°C (90°F to 150°F).
  • Zirconium was present in each solution in the form of ammonium fluozirconate ((NH 4 ) 2 ZrF 6 ) at a concentration of 1.25 ⁇ 10 -3 * M/l, and each solution was adjusted to a pH of 3.8 by the addition of concentrated nitric acid. Two cans were employed in determining the water-stain resistance rating of each solution.
  • Table IV below also shows the effect of gluconic acid concentration on water-stain resistance, as well as on the adhesion of water-based siccative coatings, at two different pH and temperature levels.
  • Zirconium was again present in each solution in the form of ammonium fluozirconate ((NH 4 ) 2 ZrF 6 ) at a concentration of 1.25x10 -3 mole/litre, and the pH of each solution was adjusted by the addition of concentrated nitric acid.
  • Two cans were employed in determining each paint adhesion rating (“Adhesion") while each water-stain resistance rating (“Resistance”) represents the average rating of six cans.
  • aqueous concentrate of the type used to formulate the compositions of Examples 1-15 was diluted with a sufficient amount of water (two parts deionized water and one part hard water) to yield a coating solution containing 2.5% by volume of the concentrate, to which was added 20 ppm of Surfonic LF-17.
  • Four solutions were thus prepared, to each of which was added 0.1 g/I of one of the following ingredients: glutaric acid, ascorbic acid, maleic acid or salicylic acid.
  • the pH of each of the compositions was 3.5 and each was used in treating aluminium cans in the manner described above in connection with the preceding Examples.
  • compositions were formulated by including 0.5 ⁇ 10 -3 M/l of gluconic acid in each of the compositions of Examples 42-45 above. Coatings formed from such compositions exhibited improved adhesion with respect to top coats formed from various water-based resin coating compositions.
  • Table V below shows the effect of ammonium fluozirconate concentration on water-stain resistance of coatings applied at varying temperatures from 32.2°C to 65.6°C (90°F to 150°F).
  • Gluconic acid was present in each solution at a concentration of 0.5x 10- 3 mole/litre, and each solution was adjusted to a pH of 3.8 by the addition of concentrated nitric acid. Two cans were employed in determining the water-stain resistance rating of each solution.
  • Table VI shows the effect of ammonium fluozirconate concentration on water-stain resistance, as well as on the adhesion of water-based siccative coatings, at three different pH and two different temperature levels.
  • gluconic acid was present in each solution at a concentration of 0.5 ⁇ 10 -3 mole/litre, and the pH of each solution was adjusted by the addition of concentrated nitric acid.
  • Two cans were employed in determining each paint adhesion rating while each water-stain resistance rating represents the average of six cans.
  • Table VII below illustrates the water-stain resistance of coatings formed from a solution of hafnium tetrafluoride, hydrofluoric acid and gluconic acid at varying temperatures from 32.2° to 65.6°C (90°F to 150°F).
  • the solution contained 1.25 ⁇ 10 -3 mole/litre of hafnium tetrafluoride, 2.5 ⁇ 10 -3 mole/litre of hydrofluoric acid and 0.5 ⁇ 10 -3 mole/litre of gluconic acid.
  • coatings were also formed from a similar solution free of gluconic acid. The pH of both solutions was adjusted to 3.8 by the addition of concentrated nitric acid. Two cans were employed in determining the water-stain resistance rating of the solutions.
  • Tables VIII, IX, X and XI illustrate the effect of pH and temperature on the water-stain resistance of coatings formed from a solution of ammonium fluozirconate and gluconic acid, as well as on the adhesion of further water-based siccative coatings to such coatings.
  • the solution employed contained 1.25 ⁇ 10 -3 mole/litre of the ammonium fluorzirconate and 0.5 ⁇ 10 -3 mole/litre of the gluconic acid.
  • coatings were also formed from a similar solution free of gluconic acid. The pH of both solutions was adjusted to the values shown in the tables by the addition of concentrated nitric acid.
  • Table XII shows how the addition of phosphate to an ammonium fluozirconate solution adversely affects the adhesion of water-based siccative coatings to coatings formed from such solutions.
  • concentration of phosphate and ammonium fluozirconate in each of the solutions prepared is shown in the table.
  • the phosphate was added as phosphoric acid.
  • the pH of the solutions was varied as shown in the table, and again concentrated nitric acid was employed to adjust the pH.
  • the solutions were applied as a temperature of 54.4°C (130°F). Two cans were employed in determining each paint adhesion rating of each solution.
  • Table XIII below shows how the addition of phosphate and gluconic acid to ammonium fluozirconate solutions affects the adhesion of water-based siccative coatings to coatings formed from such solutions.
  • concentration of each of these materials in each of the solutions prepared is shown in the Table.
  • the phosphate was added as phosphoric acid.
  • the pH of the solutions was varied as shown in the Table and concentrated nitric acid was employed to adjust the pH. The solutions were applied at the temperatures indicated. Two cans were employed in determining each paint adhesion rating of each solution.
  • the present invention provides the means for forming on an aluminium surface a non-chromate coating which is colourless and clear without modifying the appearance of the aluminium surface.
  • the coated surface exhibits improved corrosion resistance, as exemplified by the test results reported above, and exhibits excellent adhesion to overlying siccative coatings formed from either water-based or organic-solvent based coating compositions.

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Claims (22)

1. Chromatfreie, saure, wässrige Überzugslösung mit einem pH-Wert von 1,5 bis 5, die fähig ist einen klaren, farblosen und korrosionsbeständigen Umwandlungsüberzug auf einer Aluminiumoberfläche zu bilden, enthaltend:
(a) eines oder mehrere der Gruppe lVa Metalle Zirkonium, Hafnium und Titanium in einer Gesamtkonzentration von mindestens 0,5×10-3 Mol/Liter;
(b) Fluorid in einer Menge von zumindest ausreichend zur Umsetzung und Bildung eines löslichen Komplexes mit allen anwesenden Gruppe IVa Metallen; und
(c) einen Zusatz in Form von:
(i) einem oberflächenaktiven Stoff anwesend in einer Konzentration von mindestens 0,01 g/I; und/oder
(ii) einer organischen Polyhydroxyverbindung mit bis zu 7 Kohlenstoffatomen, anwesend in einer Konzentration von mindestens 0,025×10-3 Mol/Liter, wenn der Zusatz diese organische Polyhydroxyverbindung allein ist, wobei die Lösung frei von Phosphat und Bor ist.
2. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 1, in welcher Fluorid anwesend ist in einer Menge entsprechend mindestens 4 Molen je Mol der genannten Gruppe Vla Metalle.
3. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 1 oder 2, worin das Gruppe IVa Metall Zirkonium ist oder enthält.
4. Umwandlungsüberzugslösung für Aluminium gemäß einem der vorgehenden Ansprüche, in welcher der (c) Zusatz ein oberflächenaktiver Stoff ist oder einen solchen enthält und der pH-Wert der Lösung im Bereich von 3,5 bis 4,5 liegt.
5. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 4, in welcher Zirkon anwesend ist in einer Konzentration von 0,75×10-3 bis 2×10-3 Mol/Liter und eine oberflächenaktive Substanz anwesend ist in einer Konzentration von 0,01 bis 0,5 g/I.
6. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 5, in welcher Zirkon anwesend ist in einer Konzentration von 1×10-3 bis 1,75×10-3 Mol/Liter, ein oberflächenaktiver Stoff anwesend ist in einer Konzentration von 0,02 bis 0,1 g/I und die Lösung einen pH-Wert im Bereich von 3,7 bis 4,3 aufweist.
7. Umwandlungsüberzugslösung für Aluminium gemäß einem der vorgehenden Ansprüche, welche einen oberflächenaktiven Stoff enthält in Form eines nichtionischen oberflächenaktiven Stoffes.
8. Umwandlungsüberzugslösung für Aluminium gemäß einem der vorgehenden Ansprüche, welche, wenn der Zusatz nicht die organische Polyhydroxyverbindung allein ist, auch mindestens 10 ppm einer Borverbindung enthält.
9. Umwandlungsüberzugslösung für Aluminium gemäß einem der vorgehenden Ansprüche, die neben mindestens 0,01 g/l eines oberflächenaktiven Stoffes auch mindestens 0,025×10-3 Mol/Liter der genannten Polyhydroxyverbindung enthält.
10. Umwandlungsüberzugslösung für Aluminium gemäß einem der Ansprüche 1 bis 3, in welcher der (c) Zusatz die Polyhydroxyverbindung ist oder diese enthält.
11. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 10, deren pH-Wert im Bereich von 3 bis 5 liegt.
12. Umwandlungsüberzugslösung für Aluminium gemäß Anspruch 11, die 0,5x10-3 bis 1,75x10-3 Mol/Liter Zirkonium und 0,3×10-3 bis 1,75×10-3 Mol/Liter der Polyhydroxyverbindung enthält.
13. Umwandlungsüberzugslösung für Aluminium gemäß einem der Ansprüche 1 bis 8, in welcher der (c) Zusatz der oberflächenaktive Stoff allein ist.
14. Umwandlungsüberzugslösung für Aluminium gemäß einem der vorgehenden Ansprüche, die auch Tannin enthält.
15. Verfahren zur Bildung eines klaren, farblosen, korrosionsbeständigen Überzuges auf einer Aluminiumoberfläche, wobei die Oberfläche mit einer chromatfreien, sauren, wässrigen Überzugslösung gemäß einem der vorgehenden Ansprüche während einer ausreichenden Zeitdauer bei der Arbeitstemperatur in Berührung gebracht wird zur Ausbildung des gewünschten Überzuges.
16. Verfahren gemäß Anspruch 15, in welchem eines Folge von Aluminiumoberflächen behandelt werden mit einer Umwandlungsüberzugslösung, in welcher der (c) Zusatz ein oberflächenaktiver Stoff ist und die Überzugslösung gelegentlich oder kontinuierlich nach Bedarf aufgefrischt wird mit einem wässrigen Auffrischungs-Konzentrat, so daß die Konzentration der Zusätze in der Überzugslösung innerhalb der angegebenen Bereiche bleiben, unter Verwendung eines Auffrischungs-Konzentrates enthaltend 0,05 bis 0,5 Mol/Liter Zirkonium, 0,2 bis 10 Mol/Liter Fluorid und 1 bis 100 g/I eines oberflächenaktiven Stoffes.
17. Verfahren gemäß Anspruch 15, in welchem eine Folge von Aluminiumoberflächen behandelt wird mit einer Umwandlungsüberzugslösung, in welcher der (c) Zusatz eine Polyhydroxyverbindung ist und die Überzugslösung gelegentlich oder kontinuierlich aufgefrischt wird nach Bedarf mit einem wässrigen Auffrischungs-Konzentrat um die Konzentrationen der Zusätze in der Überzugslösung innerhalb der angegebenen Bereiche zu halten, unter Verwendung eines Auffrischungs-Konzentrates enthaltend 31×10-3 bis 251×10-3 Mole/Liter Zirkonium, ein Ausgangsmaterial, welches 90x10-3 bis 695x10-3 Mole/Liter eines nichtkomplexierten verfügbaren Fluorids liefert und 19×10-3 bis 148×10-3 Mole/Liter einer Polyhydroxyverbindung.
18. Verfahren gemäß einem der Ansprüche 15 bis 17, bei welchem nach der Bildung des Umwandlungsüberzuges auf der Aluminiumoberfläche in einer nachfolgenden Stufe ein darüberliegender Sikkativüberzug aus Wasser aufgebracht wird.
19. Wässriges Konzentrat zur Verdünnung mit Wasser unter Bildung einer Umwandlungsüberzugslösung zur Verwendung in dem Verfahren gemäß Anspruch 16, derart, daß eine wässrige Lösung enthaltend 0,5 bis 10 Gew.-% dieses Konzentrates ausreichend sauer ist zur Bildung eines Umwandlungsüberzuges auf Aluminium und die (A) mindestens 0,5×10-3 Mol/Litre eines oder mehrere der Gruppe IVa Metalle Zirkonium, Titanium und Hafnium enthält; (B) Fluorid in einer Menge zumindest ausreichend zur Verbindung und Ausbildung eines löslichen Komplexes mit im wesentlichen dem gesamten Zr, Ti und/oder Hf; und auch (C) mindestens 0,01 g/I eines oberflächenaktiven Stoffes.
20. Wässriges Konzentrat zur Verwendung bei der Auffrischung einer Umwandlungsüberzugslögung in dem Verfahren gemäß Anspruch 16, enthaltend 0,05 bis 0,5 Mol/Liter Zirkonium, 0,2 bis 10 Mol/Liter Fluorid und 1 bis 100 g/I eines oberflächenaktiven Stoffes.
21. Wässriges Konzentrat zur Verdünnung mit Wasser zur Bildung einer Umwandlungsüberzugslösung zwecks Verwendung in dem Verfahren gemäß Anspruch 17, derart, daß eine wässrige Lösung enthaltend 0,5 bis 10 Gew.-% des Konzentrates frei von Phosphat und Bor ist, einen pH-Wert im Bereich von 3 bis 5 aufweist und (A) mindestens 0,5x10-3 Mol/Liter Zirkonium oder Hafnium oder eine Mischung der beiden, (B) mindestens 0,025x10-3 Mol/Liter einer wasserlöslichen Polyhydroxyverbindung mit nicht mehr also 7 Kohlenstoffatomen und (C) zumindest genügend Fluorid zur Verbindung mit allem Zirkonium und/oder Hafnium, welches in der Lösung anwesend ist, und Ausbildung eines löslichen Komplexes, enthält.
22. Wässriges Konzentrat zur Verwendung bei der Auffrischung einer Umwandlungsüberzugslösung in dem Verfahren gemäß Anspruch 17 enthaltend 31×10-3 bis 251×10-3 Mole/Liter Zirkonium, ein Ausgangsmaterial, welches 90×10-3 bis 695×10-3 Mole/Liter eines nichtkomplexierten verfügbaren Fluorids liefert und 19×10-3 bis 148×10-3 Mole/Liter einer Polyhydroxyverbindung.
EP80304673A 1979-12-26 1980-12-22 Bad, Verfahren und Konzentrat zur Beschichtung von Aluminium Expired EP0032306B1 (de)

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US06/107,017 US4273592A (en) 1979-12-26 1979-12-26 Coating solution for metal surfaces
US107017 1979-12-26
US06/165,734 US4313769A (en) 1980-07-03 1980-07-03 Coating solution for metal surfaces
US165734 1980-07-03

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EP0032306B1 true EP0032306B1 (de) 1985-05-02

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DE (1) DE3070603D1 (de)
DK (1) DK553280A (de)
ES (1) ES8300142A1 (de)
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NO (1) NO803937L (de)
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US8123967B2 (en) 2005-08-01 2012-02-28 Vapor Technologies Inc. Method of producing an article having patterned decorative coating
WO2022072857A1 (en) * 2020-10-02 2022-04-07 Solugen, Inc. Compositions for corrosion inhibition

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DE3236247A1 (de) * 1982-09-30 1984-04-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur oberflaechenbehandlung von aluminium
US5064500A (en) * 1987-06-01 1991-11-12 Henkel Corporation Surface conditioner for formed metal surfaces
DE4317217A1 (de) * 1993-05-24 1994-12-01 Henkel Kgaa Chromfreie Konversionsbehandlung von Aluminium
US5397390A (en) * 1993-08-13 1995-03-14 Ardrox, Inc. Composition and method for treatment of phosphated metal surfaces
US5531820A (en) * 1993-08-13 1996-07-02 Brent America, Inc. Composition and method for treatment of phosphated metal surfaces
USRE35688E (en) * 1993-08-13 1997-12-16 Brent America, Inc. Composition and method for treatment of phosphated metal surfaces
US8951362B2 (en) * 2009-10-08 2015-02-10 Ppg Industries Ohio, Inc. Replenishing compositions and methods of replenishing pretreatment compositions

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JPS5290433A (en) * 1976-01-26 1977-07-29 Nippon Packaging Kk Surface treatment of aluminum and its alloy
DE2704261A1 (de) * 1977-02-02 1978-08-03 Metallgesellschaft Ag Verfahren zur oberflaechenbehandlung von aluminium oder aluminiumlegierungen

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8123967B2 (en) 2005-08-01 2012-02-28 Vapor Technologies Inc. Method of producing an article having patterned decorative coating
WO2022072857A1 (en) * 2020-10-02 2022-04-07 Solugen, Inc. Compositions for corrosion inhibition

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DE3070603D1 (en) 1985-06-05
AU543720B2 (en) 1985-05-02
EP0032306A1 (de) 1981-07-22
CA1174945A (en) 1984-09-25
NZ195810A (en) 1983-07-15
MX157394A (es) 1988-11-22
PL228759A1 (de) 1981-09-04
NO803937L (no) 1981-06-29
AU6584780A (en) 1981-07-02
ES498079A0 (es) 1982-11-01
PL131953B1 (en) 1985-01-31
ES8300142A1 (es) 1982-11-01
DK553280A (da) 1981-06-27
BR8008489A (pt) 1981-07-14

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