A PROCESS FOR THE PREPARATION OF A DARK-COLOURED,WAVE-LENGTH SELECTIVE OXIDE FILM ON ALUMINIUM

Abstract: A dark-coloured, wave-length selective oxide film on aluminium is prepared thereby that the metal subsequent to a cleaning treatment is submerged into a bath consisting of an aqueous solution having pH 8.9 - 10.9 and at a temperature of from 20 to 100`C under conditions which result in an electrode potential of between -1.1 and -0.6 volt relative to a saturated calomel electrode. The said potential can advantageously be maintained by either addition of H<u2>uO<s2>s to the bath or by electric polarization. In a more specific embodiment of the process there is used an aqueous solution of 1-100 g NH<u4>uCl or (NH<u4>u)<u2>uSO<s4>S per liter solution with or without addition of aluminate ions Al0<u2>u<s->s or Ca<s++>s, the pH of the solution, if necessary, being adjusted to pH 9 by addition of NH<u3>u, NaOH, KOH, Ca(OH)<u2>u and that the content of silicon, chromium and phosphorus each is maintained under 10 ppm.

Description: "A process for the preparation of a dark-coloured, wave-length selective oxide film on aluminium" . The present invention pertains to a process for the preparation of a dark-coloured, wave-length selective oxide film on aluminium, and the characteristic feature of the process according to the invention is that the metal subsequent to cleaning is submerged into a bath consisting of an aqueous solution having pH 8,9 - 10,9 and at a temperature of from 20 C to 100 C under conditions which result in an electrode potential of between -1,1 and -0.6 volts relative to a saturated calomel electrode. These and other features of the process according to the invention appear from the patent claims. The dark-coloured, wave-length selective oxide film on aluminium results in that products achieved by the process according to the invention are suitable for use inter alia for thermal solar panels and because of the characteristic appearance also for decorative purposes. The term "spectral selectivity" is to begin with to be described in connection therewith that aluminium, obtained by the process according to the present invention, to the eye will essentially be perceived as having a black colour. Thereafter processes for the black-colouring of aluminium will be described to the end of showing that the invention is founded on other principles than those previously known. Finally, the results from optical measurements which have been carried out, as well as some illustrative Examples, will be presented. As known, an absolutely black surface will absorb most radiation, but it will according to Kirchhoff' s equation also have the highest loss of heat through radiation. Collectors for solar heat should have a high absorption coefficient for the frequencies which the main portion of the energy of the sun rays have, at the same time as the radiation of heat should be as low as possible. The heat radiation has a much lower frequency than the main portion of the solar radiation. Thus, it is desirable that the absorption coefficient varies with the frequency of the radiation, so that the absorption coefficient is high for high frequency and low for low frequency, i.e. a spectral selectivety which is suitable for thermal solar panels. In addition to the classic division in black, grey, white, reflecting and bright surfaces, there exist also surfaces having a spectrally selective film. The appearance of a surface having a spectrally selective film will vary with the wave-length for the change from low to high reflection, and for solar panels it is desired that the change is to occur at a higher wave-length than perceived by the eye. A surface of a spectrally selective film for solar panels will usually by the eye be conceived as nearly black. The reduced radiation of long-wave infrared radiation is important for a solar panel, as it thereby is possible to obtain a higher temperature than for an absolutely black surface. Whereas an absolutely black surface will attain equilibrium between incoming and emitted radiation at about 80 C at about 60 latitude, it is not unrealistic to expect temperatures of over 200 C for equilibrium for radiation equilibrium for aluminium treated with the process according to the present application. The in¬ creased temperature is of decisive importance for the possibilities of economical storage of solar heat. The "classic" example of a surface having a spectrally selective absorbing film is so-called "black chromium" (chromium black) reported some years ago by G.E. McDonald (Sol. Energy 17, 119 (1975)) . The correct explanation of the phenomenon was found by Fan et Spura (Appl. Phys. Lett. 30, 511 (1977)) who stated that these layers consisted of polycrystalline Cr ? 0 admixed with extremely fine-grained chromium metal. As aluminium treated by the process according to the present invention is given a nearly black appearance, the main features of known processes for black-colouring of aluminium will be described. A series of mutually related processes is based on the precipitation of black salts on the surface and another series of processes is to apply a porous oxide film on aluminium by anodization and fill dyestuff into the pores. To illustrate the first group of processes, it is to begin with referred to an example where also the thermal characteristics is commented. According to Dutch Patent 21 066 76 copper-containing aluminium alloys can be black-coloured by means of a two-stage chemical process wherein the first bath consists of water to which NiCl~, NH.C1 and KCNS have been added, and the next bath consists of water to which HNO_ has been added. This process aims at giving a material having a high emission of thermal long-wave radiation, which is important for cooling surfaces, but undesired for solar heat collectors, for which it as previously mentioned is desired to have low emission for radiation having long wave-lengths. Industrial anodizing of aluminium, for instance in sulphu¬ ric acid, chromic acid, oxalic acid or mixtures thereof, gives oxide films having thicknesses which usually are from 5 to 30 micrometers thick. Only an inner layer of up to 700 Angstrom is porefree, whereas the essential portions of the layer has tunnel-shaped pores being open to the surface . These films can be inked up and blackened by filling the pores with organic or inorganic dyestuff after or under the very anodizing. For instance French Patent 22 149.10 describes a colouring process based on an anodic treatment in a bath consisting of water to which CuSO., NiSO., (NH.) 2 S0 4 and H 3 B0 3 have been added. Thus, a black compound is used and the result is there¬ fore black also in a physical sense and not in the sense of spectral selectivity. A further type of anodizing is the preparation of so-called barrier layers. These are impervious and transparent and up to 7000 Angstrom thick. There exist further hard anodizing processes which give " dark and sometimes nearly black oxide films. The more usual process uses a sulphuric acid bath at a temperature of about 0°C, about 70 volts and 5-20 A/dm . The dark colour is in the various hard-anodizing processes only achieved with relatively thick films, usually only at about 50 micrometers. It has for comparison been effected a series with hard-anodizing and these showed that super-pure aluminium was never coloured dark. Dark colour requires either contaminated or alloyed aluminium grades. It was shown that certain phases of contamination and alloying elements were transferred to the film in unoxidized form. As far as it is known, no satisfactory explanation has been published re the dark colouring which can occur in hard-anodizing. It is possible that the dark colour which is achieved in such hard-anodizing for the formation of black films on aluminium basis also shows some degree of wave-length selective characteristics, but the develop¬ ment work in this field was not continued because of the fact that according to the theories and equations of Maxwell and Garnett, the films must be too thick to have optimum characteristics as solar collectors. Anyway hard- anodizing is a rather expensive process. With the more simple and cheap process according to the pre¬ sent invention, spectrally selective surfaces on aluminium is formed thereby that it is submerged for a relatively short period of time into an aqueous solution at a controlled electrode potential. The surface will then be nearly black with a shimmer of violet, blue or green, and by varying the conditions, also brown or yellow appearance can be obtained. The invention is in the following to be explained by means of the following description and with reference to the attached drawings, wherein: Figure 1 shows reflectivity as a function of the wave-length of light for aluminium surfaces which have been oxidized by the process of the present invention. Figure 2 shows a graphic illustration of the area of poten¬ tial versus pH for the blackening of aluminium in basic ammonium chloride solutions included in a so-called Pourbaix-diagram, and Figure 3 shows the importance of a series of different ions which are necessary or desirable for blackening, ions which are without importance for the blackening, as well as ions which positively prevent blackening, respectivel . Figure 3 does also indicate insolubility in the actual pH-range for a series of ions. Figure 1 shows optical reflectivity as a function of the wave-length for a couple of typical films prepared by means of the process according to the present invention. The meaning of the terms A and B is given in Example 1. An "absolutely black" body will in such diagram have a reflectivity of zero for all wave-lengths and an "absolutely bright" body will have a reflect- ivity of 1.0. It is seen that the reflectivity of aluminium treated by the process according to the present invention has the quite specific characteristic that it shows a change from low reflectivity to high reflectivity over a wave-length range of about 1 micrometer. In spite of the fact that samples have been examined under electron microscope up to 100.000 x magnification, the structure and composition of the film is not known. However, it is supposed that its optical characteristics are due to a film of aluminium oxide particles in an isolating matrix of aluminium oxide, as ..no- other possible explanation has been found. It is known that transparent films with electrically conductive particles are wave-length selective, and this can also be derived from the equations of Maxwell Garnett for the wave character of light (J.C. Maxwell Garnett, Phil. Trans, R.Soc, London, 205, 237 (1906)) . The absorbing film achieved by the process according to the invention is in this way based on other chemical and physi¬ cal principles than the methods for black-colouring of aluminium described above. The absorbing characteristics achieved by the process according to the present invention are supposed to be caused by the electromagnetic interference phenomenon occurring in a film of particles in an isolating matrix as treated by Fan et Spura (cf. the foregoing) and which can be calcu- kated from the said equations of Maxwell Garnett. The black appearance has no connection with black dyestuff or dark inorganic salts. The background for this statement is that according to accepted inorganic chemistry there exists no black or strongly coloured compounds in the system of aluminium, chlorine, nitrogen, oxygen, hydrogen which is a system typical for an essential portion of the invention. In spite of this films formed by submerging aluminium under the more detailedly specified conditions will result in a nearly black, brown or yellow appearance with strong wave-length selective characteristics. Figures 2 and 3 sum up the results from an extensive research program. Figure 2 shows the pH-potential dia¬ gram for aluminium with the area included which accord¬ ing to experiments givesfil s suitable for solar panels. This area is at the right side of the diagram restricted by dissolution of the film under formation of aluminate ions. A too high potential will result in pit corrosion. A too low potential or a too low pH will result in normal¬ ly transparent oxide films. These limits appear to be dependent of the exposure conditions. A higher potential can be used in solutions having a low chlorine content, and the pH-limits can be somewhat shifted by changing the temperature, and the limits can also be somewhat shifted by addition of certain substances to the bath. A series of experiments was effected to find the effect of the various substances in the bath. The experiments seem to indicate that the formation of a wave-length selective film is not depending on the chemical composition of the solution as long as a small group of substances which have a harmful effect on the film formation is not used. The essential point is that the aluminium is treated within the correct area of potential and pH. It is advantageous to use a salt solution which contains ammon¬ ium-, alkali metal- or earth alkali metal-hydroxides. Figure 3 shows the ions which can be used and the ions which prevent the formation of films suitable for solar panels. According to the •experiments which have been carried out silicate-, chromate- and phosphate-ions will result in transparent films, even in small amounts. Borate-, tetraborate- and carbonate-ions in large amounts (some % ) are also disadvantageous. These circumstances presuppose that is must be operated within the correct pH-potential area. If the pH and potential are not under control, it can also be found that for instance addition of soda .(Na-CO.,) and borax of soda (Na O will have a favourable effect thereby that they shift pH and potential into a more favourable area without the specific harmful effects of these ions being brought to expression. As ions which are necessary for the carrying out of the process according to the present invention appear then OH- and + - ++ NH. , optionally with addition of AIO ^ or Ca The electrode potential of aluminium in an aqueous air- saturated solution is normally a number of hundreds mV too low for optimum formation of spectrally selective films even if the bath contains the correct mixture of ions. The corrosion potential can be adjusted by addition of oxidant (advantageously H ^ O,,) or by electric polariza¬ tion with very low current density and effect. The process according to the invention is thereby basically different from" normal anodizing. In normal anodizing cell voltages of usually between 15 and 30 volts and current 2 densities of 0,5 to 3 A/dm and acid baths are used. The invention described herein uses slightly alkaline baths, cell voltages of a number of hundreds mV and current densi- 2 ties of a number of mA/dm . Measured in electric effect are only used effects of order of size 1/1000 of those used in ordinary anodizing. The process is to some extent sensitive to temperature, and the the best temperature for super-pure aluminium will be 25 - 55 C, as it over 55 C often will not be obtained satisfactory films. Below 20 C the formation of films is unadvantageously slow. For alloyed aluminium there are no such strongly restricted temperature limits, but no advan--, tage has been shown by passing beyond 100 C. Different aluminium alloys are behaving differently. Experi¬ ments have so far comprised super-pure aluminium 99,5% Al and NACO 57 S. For these aluminium grades equally valuable films have been obtained, but the conditions must be adapted to the alloy. It is prerequisited that the more usual types of aluminium can be treated, and it is to be supposed that alloys which are particularly well suited can be found. The fact the super-pure aluminium can be used shows that the formation of the wave-length selective, film is not dependent on cathodic phases from the aluminium (from con¬ taminations or alloying elements) . Example I A sheet of commercial pure aluminium (99,5% aluminium) was pickled in a bath consisting of 5% NaOH in water at 40 C for 3 minutes. Thereupon the sheet was flushed with water and passivated in 1 minute in 2 % HNO_ in aqueous solution. After repeated flushing in water the sheet was placed in a bath at 40°C consisting of: 2% NH.C1 in water to which NH-. had been added to pH 9,5. The sheet was provided with an electric connection made from aluminium and was anodically polarized to a potential of -0.8 volts relative to a saturated calomel electrode. The tank for the bath was prepared from polyethylene and was provided with an electrode of 18/8 stainless steel serving as counter-electrode. A current of about 3,5 A 2 per dm aluminium passed at the beginning of the exposure. This current .decreased., gradually. Already after 10 minutes the aluminium sheet ' had been given a black-v/iolet-shimmering appearance. The optical characteristics are shown by the curve A in Figure 1. For sheets treated in 20 minutes the appearance was blue-black-shimmering, and the optical characteristics were as shown by the curve B in Figure 1. Prolonged exposure beyond 30 minutes resulted in a slow brightening and is normally not recommended. After com¬ pleted exposure the sheet was taken up, flushed in water and dried. Example II A series of sheets of 57S aluminium was pickled as in Example I. After flushing in water, this aluminium grade must be passivated in at least 5 minutes in 2% aqueous HNO at room temperature. After having been flushed, the sheets were placed in a bath consisting of 2 % NH.C1 in water plus 1,0% H„0 to which NaOH had been added to pH 9,5. The bath was at 40 C. The tank for the bath was prepared from polyethylene. The great majority of types of plastic materials can be used, whereas glass or porcelain has drawbacks because of the possibility that silicate ions may be given off. H 2 ° 2 will gradually be decomposed and consumed. Correct concentra¬ tion of H„0„ was controlled by measuring the electrode potential on one of the sheets. The sheet was raised so that one of the clips of a vacuum tube voltmeter, could be placed thereon without letting the " clip dip " into the water * . The " other connection of the vacuum tube voltmeter was connected to a saturated calomel electrode situated in the' bath. A potential of preferably between -0.9 and -0.7 volts is to be measured on the aluminium sheet. If the potential is lower, H„0 is added. In this particular case the potential was -0,8 volt to begin with and decreased to -0,95 volt after 10 minutes. One of the sheets was then taken up but found to need further treatment. 0.03% aqueous H„0„ was added. After further 10 minutes the sheets were taken up, flushed and dried. They were then dark brown. Example III The following 12 baths were prepared: 1. 3 ml 30% H 2 0 2 /1 + NaOH to pH 10,3 2. + KOH to pH 10, 3 3. + Ca(OH) 2 to pH 10, 3 4. + 0,1 mole NaOH + HCl to pH 10,3 5. + 1 mole NaOH + HCl to pH 10,3 6 : + 1 mole KOH + HCl to pH 10,3 (continued from the table on the preceding page) 7. 3 ml 30% H 2 0 2 /1 + 0,5 mole Ca (OH) + HCl to pH 10,3 8. " " " + 1 mole NaOH + 0,01 mole NaAlO + HCl ' to pH 10, 3 9. " i . n + i mo ι e KOH + 0,01 mole NaAlO + HCl to pH 10, 3 10. " " " + 1 mole ( H^SO + H 3 to pH 10,3 11. " .. .. + 2 moles NH 4 N0 3 + H 3 to pH 10,3 12. " ιι ιι + ι m ole (NH. SO + 0,01 mole NaAl0 2 + NH to pH .10,.3 Samples of super pure aluminium were first electropolished at about 20 volts in a bath consisting of 5% HC10. in absolute alcohol at 15 C and flushed in water. They were then placed in the above described baths which thermostati¬ cally were maintained at 40 C. A set of samples was taken up after 15 minutes. All samples gave a satisfactory result, They were all rather alike, having a dark appearance, shim¬ mering in green or violet. The samples from the baths con¬ taining Ca(OH)„ and those from the baths to which NaA10„ had been added, had the darkest appearance. Another set of samples were removed after 45 minutes. The baths had then been given an addition of 1 ml 30% perhydrol (H 2 0 ) 20 minutes after the starting up. They were all brown. The samples from the baths without any addition of HCl were clearly brighter than the other ones, which is ascribed to the fact that pH had fallen to 9,7 whereas pH was about 10 for the other baths. As mentioned under the summing up, tests were also conducted with baths containing silicate-, chromate-, bichromate-, phosphate- and borate ions. These tests did not give: satisfactory results.

Claims: CLAIMS . 1. A process for the preparation of a dark-coloured, wave-length selective oxide film on aluminium, characterized in that the metal subsequent to cleaning is submerged in a bath consisting of an aqueous solution at pH 8,9 to 10,9 at a temperature of from 20 to 100°C under conditions which result in an electrode potential of between -1,1 and -0,6 volt relative to a saturated calomel electrode . 2. A process according to claim 1, characterized in that the electrode potential is maintained within the said range by addition of H„0„ to the bath. 3. A process according- to claim 1, characterized in that the electrode potential is maintained within -the said range by electric polarization. 4. A process according to any of claims 1-3, characterize in that it as aqueous solution is used a solution of 1-100 NH.C1 or (NH.)„S0 4 per liter with or without addition of aluminate ions A10~~ ~ or Ca , and that the pH of the solut if necessary, is adjusted to pH 9 by means of addition of NH-., NaOH, KOH, Ca(OH) 2 and that the content of silicon, chromium and phosphorus is each maintained under 10 parts per million.

Inventors: VIDEM K
Applicants: INST ENERGITEKNIK, VIDEM K, ENERGITEKNIKK INST
Application year: 1980
Main classification: C25D11
IPC codes: C23C22, C25D11, F24J2