US3390988A - Method of manufacturing metallic images on aluminum and aluminum alloys - Google Patents

Method of manufacturing metallic images on aluminum and aluminum alloys Download PDF

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US3390988A
US3390988A US308695A US30869563A US3390988A US 3390988 A US3390988 A US 3390988A US 308695 A US308695 A US 308695A US 30869563 A US30869563 A US 30869563A US 3390988 A US3390988 A US 3390988A
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molar
image
aluminum
acid
nuclear
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Dippel Cornelis Johannes
Jonker Hendrik
Kinderen Antonius Johannes Der
Helfferich Johannes
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/62—Metal compounds reducible to metal
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/77—Photosensitive materials characterised by the base or auxiliary layers the base being of metal
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development

Definitions

  • This invention relates to a method of producing internal and external metallic images by photographic means aluminum and aluminum alloy carriers. 1 a
  • the nuclear-introduction method This method is referred to as the nuclear-introduction method.
  • the solution containing -mercurous-ions with which the carrier is brought into contact after exposure is referred to as the nucleareintroduction bath.
  • An improvement in the photographic sensitivity is possible by adding also silver ions to the nuclear-introduction bath. In this case the treatment with the nuclear-introduction bath may give rise to the formation of alatent silver amalgam nuclear image.
  • the photosensitive compounds which, after exposure, can liberate metallic mercury in the form of a physicallydevelopable nuclear image from mercurous compounds by means of disproportionating according to the equation 2 Hs s include the aromatic diazosulphonates, which are preferably used in combination with a so-called:anti-regression agent, that is a compound which, when added to the layer, prevents the reformation of diazosulphonate from its light-reaction product by binding either the sulphite, or'the diazonium-radical, or. both of them so that it re- 3,390,988 latented July 2, 1963 "ice mains possible for the sulphite to react with the mercurous compound while forming mercury nuclei.
  • a so-called:anti-regression agent that is a compound which, when added to the layer, prevents the reformation of diazosulphonate from its light-reaction product by binding either the sulphite, or'the diazonium-radical, or. both of them so
  • the impregnation with silver halide is effected by submerging the hydrophilic oxide-layer successively into a solution of a halide and into a solution of silver nitrate whereby the silver halide deposits in the layer.
  • silver images of a brown color are obtained which gradually become black by treatment with a dilute solution of gold chloride.
  • due to the precipitation reaction occurring in the pores it is diflicult to provide a sufficient amount of photosensitive material in the layer.
  • anodized aluminum has a number of properties which render its use as a photographic carrier material extremely attractivefIt is a dimensionally stable material which, if correctly after-treated, is also resistent to the action of acids and salt solutions. Also it can resist comparatively high temperatures and endures a temperature up to 600 C. without objection. In addition, it has reasonable resistivity against scratches and shocks because of the hard oxide layer.
  • This aluminum amalgam is also known to be a strong reducing agent which is capable of depositing metallic mercury and/or silver from solutions containing soluble mercury and/ or silver compounds, such as nuclear introduction baths and physical developers.
  • This aluminum amalgam is also known to be a strong reducing agent which is capable of depositing metallic mercury and/or silver from solutions containing soluble mercury and/ or silver compounds, such as nuclear introduction baths and physical developers.
  • a principal object of the invention is furthermore to provide a solution of this fog problem and thus render possible the use of the nuclear-introduction method in a general sense with the use of a carrier of aluminum or an aluminum alloy made superficially hydrophilic by the provision of a porous layer of aluminum.
  • aluminum or aluminum alloy may be chosen for the carrier if the surface is oxidized so that an outer porous oxide is formed which is separated from the metal by an intermediate non-porous layer and by preventing or suppressing the adsorption of mercury ions by the aluminum metal carrier.
  • This mercuric adsorption effect may be prevented by carrying out one or more of the following steps: adjusting the concentration of the mercuric ions in the nuclear introduction bath being adjusted to be at least about molar, treating the outer porous oxide layer before sensitization with the solution of a mercuric compound and treating the latent image prior to development with a solution of an organic hydroxy acid which acid does not form a permanent precipitate with mercury and silver 1ons.
  • the fog which usually occurs may have at least two causes:
  • the porous oxide layer in order to carry out the method of the invention it is essential for the porous oxide layer to be separate from the metal by an intermediate layer which is substantially not porous.
  • the porous oxide layer is provided chemically, for example by treatment in a hot solution of soda in chromate, the separation from the basic metal is insufiicient and a non-porous intermediate layer must be provided in a separate treatment by anodically after oxidizing the carrier with its oxide layer in a suitable electrolyte.
  • a borax-boric acid electrolyte is extremely suitable for providing or strengthening a substantially non-porous intermediate layer.
  • the range of concentrations of the mercurous compound in the nuclear-introduction bath in which the method according to the invention is applicable extends from about 5X 10* molar to about 2 l0 molar. However, for reasons of homogeneity in density and photographic sensitivity, the range of concentration from about 5 X lO molar to about 5 x l0 molar is preferred. With several layers which are otherwise separate from the carrier metal by means of a non-porous intermediate layer of sufficient thickness, the mercuric-adsorption effect does not give rise to fog formation when using mercurous concentrations located at the upper limit of, or just above, the aforementioned preferred range of concentrations.
  • the mercuric-adsorption effect will be prevented if, before or during the nuclear introduction, the oxide layer is able to become saturated sufficiently with mercuricions without resulting in a decrease of the concentration of mercuric-ions on the nuclear introduction bath below the equilibrium value.
  • This may be achieved by adding the mercuric-ions to be adsorbed in addition to those present in the equilibrium to the nuclear-introduction bath, or by subjecting the oxide layer, prior to sensitization, to a short separate treatment in a dilute solution of a mercuric salt, followed by carefully rinsing in distilled water.
  • the adjustment of the concentration of mercuric-ions in the nuclear-introduction bath to a value of at least about 10* molar is preferred.
  • the adsorptive properties of the relevant oxide layer are determinative of how far the adjustment of the concentration of mercuric-ions must exceed the said limit. One will preferably not exceed that concentration which is precisely capable of completely suppressing the fog, since a further increase results in a rapid decline in photographic sensitivity for reasons readily understood.
  • the maximum mercuri-concentration to be used is, for example, 2 10 molar when using an oxide layer obtained with the aid of an oxalicacid electrolyte' The foregoing is, of course, also dependent upon the thickness of the relevant oxide layer.
  • the mercuric-adsorption elfect may also be prevented or neutralized by adding an organic hydroxy-acid to the nuclear-introduction bath, or by treating the latent nuclear image before its intensification into an image having the desired optical density or the desired amount of image metal with a solution of such an acid.
  • organic hydroxy-acid examples include citric acid, glycolic acid, tartaric acid, glyceric acid and malic acid. Especially when added to the nuclear introduction bath, these acids should be employed in a concentration such as to prevent a permanent deposit in the bath.
  • a concentration of the mercurous compound of 5 X mola-r to 5 1O molar and for the acid preferably a concentration of 10 molar to 3 l0- molar is used in the bath.
  • Citric acid and glycolic acid are the preferred acids to be employed in these baths as they result in images which are completely free from fog.
  • the use of these baths is also favorable for the formation of an external nuclear image.
  • the fog formation may also be prevented by the treatment of a latent nuclear image with a solution of the lastrnentioned acids, especially in the case of oxide layers manufactured with the use of sulphuric acid electrolyte.
  • concentration of the acids in the after-treating bath is preferably about 0.3 mols/litre.
  • the duration of the treatment may then be about 1 minute.
  • the aluminum and the aluminum alloys suitable for the method according to the invention are unalloyed aluminum having a purity preferably higher than 99.5% of Al, Al-Si-Mg alloys, Al-Mn-Mg alloys or Al-Mg alloys containing at the most 5% of Mg.
  • the aluminum Before carrying out the superficial oxidizing process, the aluminum may have to be subjected to one or more pretreatments, according to the quality of the initial product of the desired structure of the oxide layer. A large number of such pretreatments are described in the handbooks.
  • the aluminum surface must be carefully degreased and, if necessary, etched in order to remove the natural oxide film. Irregularities in the surface such as occur, for example, due to drawing, rolling or pressing and which also become visible in the oxide layer must be removed, for example by chemical or electrolytic polishing.
  • the chemical process may be carried out, for example, by submerging in hot concentrated phosphoric acid with additions of nitric acid, sulphuric acid and salts of heavy metals. A thin irridescent film is thus formed which can be removed by treatment in cold chromic acid or by treatment with nitric acid.
  • a matted surface is obtained, for example, by treatment with a hot concentrated solution of phosphoric acid and hydrofluoric acid or fluorides.
  • Oxide layers which are best usable may be obtained by anodic oxidation with electrolytes such as oxalic acid, sulphuric acid, chromic acid, phosphoric acid and mixtures of sulphuric acid and oxalic acid or chromic acid.
  • the treatment in oxalic-acid electrolyte is carried out best at a temperature from about 20 to 40 C., and a current density of 1 to 2 amp/cm. in a 5 to 8% solution of oxalic acid.
  • the voltage of the bath adjusts itself to about 40 volts.
  • the oxide layers obtained therewith have a very light yellowish color. These layers yield a sensitive photographic material on which deep black images may be obtained.
  • Usable porous oxide layers may also be obtained by chemical oxidation, for example by treatment in a hot solution of soda and chromate. However, as previously mentioned, these layers have to be anodically afteranodized, though for a comparatively short period, in order to provide a non-porous intermediate layer.
  • the oxide layer may be sealed in known manner in order to make the image resistant to atmospheric attack and prevent the formation of spots due to dust or fat.
  • the material is treated with boiling distilled water or with hot solutions of electrolyte.
  • a very suitable sealing bath contains cobalt acetate, nickel acetate and boric acid.
  • the nuclear-introduction bath containing citric acid or glycolic acid may be combined with the developer by adding one or more silver salts, a photographic reducing agent and, if necessary, a development stabilizer. This results in the simplification of the method.
  • the total concentration of the silver salts in such a developer is preferably about 10 times as high as that of the mercurous salts.
  • an internal nuclear image such as is desirable for normal photographic uses
  • start is made from a predominantly internal nuclear image which is intensified by means of a stabilized purely-physical development into an image having the desired optical density.
  • Factors enhancing the formation of an internal image are for example: the use of a hydrophilic layer having a concentration of the photo-sensitive substance such that light absorption also takes place in portions of the layer situated at a greater depth, the avoidance of over-exposure, the use of nuclear-introduction baths containing silver-ions and having a comparatively high concentration of mercurous-ions, and the avoidance of over-development.
  • an external, electrically-conductive image may be manufacture by starting from a predominantly external nuclear image or from a nuclear image situated predominantly closely beneath the surface of the carrier.
  • a non-stabilized purelyphysical developer can be used for the intensification
  • the nuclear image beneath the surface can be caused to grow rapidly out of the carrier also by the use of a stabilized developer.
  • a special feaure of the method according to the invention is that it permits the manufacture of external, electrically-conductive images which are short-circuited to the aluminum carrier as well as those which are not shortcircuited.
  • External, electrically-conductive images excellently isolated from the aluminum substratum may be obtained by the procedure of first causing anodic oxidation in an electrolyte known for obtaining porous oxide-layers such as for example, an electrolyte of oxalic acid or sulphuric acid and the strengthening of the non-porous intermediate layer by anodization in an electrolyte as usually employed for providing a non-porous oxide layer, such as the known electrolyte of borax-boric acid.
  • the plate was anodically oxidized at 20 C., in a solution of of oxalic acid in water at a DC-voltageof 40 to 45 volts and a current density of 1 amp/cm. for 60 minutes, rinsed in distilled water for 2 minutes, in 5% chromic acid of 60 C. for 1 minute, again rinsed in distilled water and dried.
  • the plate thus sensitized was exposed behind a linenegative to a 125 watt high-pressure mercury-vapor lamp placed at a distance of 30 cms. for seconds, then submerged for 2 seconds in a nuclear-introduction bath consisting of a solution of 0.05 molar mercurous-nitrate and 0.03 molar silver nitrate and 0.1 molar nitric acid in distilled water and then rinsed in distilled water for 5 seconds. Next the plate was developed for 3 minutes in a solution of the following composition.
  • Ultravon W is a moistening agent containing sodium neptadecylbenzimideazolemonosulphate as an active component.
  • EXAMPLE 3 A cylinder manufactured of an aluminum alloy containing 0.5% to 2% of Mg, 0.5% to 1.5% of Si and 0.2% to 1.5% of Mn and in which the impurities of Fe and Cu were less than 0.4% and 0.05% respectively and the total of the other impurities was less than 0.1%, was submerged in dilute sulphuric acid (180 to 200 g./litre) of to C. for 1 minute and then in nitric acid (1:1) of room temperature. Next it was rinsed in distilled water for 3 minutes and etched in a solution of ammonium bifiuoride gs./litre) of about 20 C. for 5 minutes. After rinsing thoroughly, the cylinder was treated at 100 C.
  • a dull oxide-layer was formed on the aluminum by this treatment.
  • EXAMPLE 4 An aluminum plate having a purity of at least 99.7% in which the impurity of Si-l-Fe together with at the most 0.3% and that of Cu-l-Zn together at the most 0.08%, was degreased with carbon tetrachloride, immerged successively in ethanol and in concentrated nitric acid, rinsed with water and treated at 100 C. for 5 minutes in a bath of the following composition:
  • the plate was anodically oxidized further for 30 minutes in the electrolyte bath used in Example 3.
  • the voltage of the bath was from 30 to 38 volts, the current density 1.5 ampsJdm. and the temperature 50 C.
  • After anodization there was rinsed in water, in 2% NaOH for a few seconds, again in water, then in chromic acid at 60 C. for a few seconds, again in water and dried.
  • the plate was sensitized in the manner described in Example 1 and exposed behind a. negative to a 125-watt high pressure mercury-vapor lamp at a distance of 30 cms. for 20 seconds.
  • the exposed plate was submerged in the nuclear-introduction bath from Example 1 and then developed for 4 minutes by means of a physical developer of the following composition:
  • EXAMPLE 5 An aluminum plate anodized as in Example 1, after drying, was submerged in a bath containing 5 molar mercuric nitrate and 10 molar nitric acid for 5 seconds, rinsed in distilled water for 3 minutes and dried.
  • the plate was sensitized in the same manner as in Example 1 and then exposed behind a sensitometer wedge to a 125-watt high-pressure mercury vapor lamp at a distance of 30 cms. for 10 seconds, then submerged for 3 seconds in an aqueous solution containing:
  • Example 1 0.005 molar mercurous nitrate 0.003 molar silver nitrate 0.01 molar nitric acid and then rinsed in distilled water for 5 seconds. The plate was subsequently physically developed for 3 minutes and treated further as described in Example 1.
  • a fog-free print of the wedge was obtained which varied from black to blank. If the pre-treatment with mercuric-ions was omitted, a copy with a heavy fog resulted.
  • EXAMPLE 6 An aluminum plate pre-treated, anodized and sensitized as described in Example 1 was exposed behind a sensitometer wedge to a high-pressure mercury-vapor lamp placed at a distance of 60 cms. for seconds and then treated for 3 seconds in a nuclear-introduction bath consisting of an aqueous solution of:
  • EXAMPLE 7 An aluminum plate pre-treated, anodized and sensitized in the manner described in Example 1 was exposed behind a sensitometer wedge to a high-pressure mercuryvapor lamp placed at a distance of 60 cms. for 10 seconds and then treated for 3 seconds in a nuclear-introduction bath of the composition:
  • EXAMPLE 8 An aluminum plate pre-treated in the manner described in Example 1 was anodized at 20 C. in a 18% by weight solution of sulphuric acid at a voltage of 14 to 15 volts and a current density of 1 amp./dm. for 60 minutes. Next this plate was rinsed in distilled water for 2 minutes, treated in a 5% solution of chromic acid at 60 C. for 1 minute, again rinsed in distilled water and dried. The plate was sensitized in the manner of Example 1, streaked off between rubber strips, dried, exposed to a high-pressure mercury-vapor lamp at a distance of 60 cms. for 1 minute and treated in the nuclear-introduction bath from Example 5. After rinsing in distilled water for 10 seconds, the plate was held submerged in an aqueous solution of 0.3 molar glycolic acid for 1 minute, again rinsed and physically developed for 5 minutes in a developer of the composition:
  • EXAMPLE 9 An aluminum plate pre-treated, anodized and sensitized in the manner described in Example 1 was exposed behind a sensitometer wedge to a high-pressure mercuryvapor lamp placed at a distance of 30 cms. for 5 minutes, submerged for 3 seconds in the following nuclear introduction bath:
  • a fog-free print of the wedge was obtained. If no additional mercuric salt was added to the nuclear introduction bath and if the treatment with citric acid after the nuclear introduction was omitted, a heavy fog occurred.
  • a print of the wedge was obtained which varied from black to blank with considerably deeper blackenings than in the case where after-anodization in oxalic acid did not take place. Besides, the photographic sensitivity had increased due to this after-anodization.
  • EXAMPLE 11 In an aluminum plate polished by anodization in the manner of Example 1, after sensitization, exposure be hind .a line-negative (radio scale) to a 125-.watt highpressure mercury-vapor lamp at a distance of 30 cms. for 1 minute, and treatment in the nuclear introduction bath from Example 1, photographic color images were obtained in the following manner.
  • the plate provided with the latent nuclear image was rinsed in a freshly prepared solution of 0.3, molar citricacid for 1 minute, rinsed with distilled water for 10 seconds, and developedin an ammoniacal, stabilized, coloring physical developer at 20 C. for 6 minutes.
  • an aqueous 10% by weight solution of potassium ferric cyanide was used.
  • the dye-image was fixed with the aid of an aqueous solution containing 20% by weight of sodium thiosulphateand 0.8% by weight of potassium metabisulphite.
  • the plate was rinsed in tap water for 20 min: utes and treated with the cobalt-nickel sealing bath from Example 1 for 40 minutes.
  • the ammoniacal, stabilized coloring physical developer was of the following composition:
  • Solution A 1% by weight of sodium thiosulphate 0.45 molar ammonia and 0.8 by weight of silver nitrate.
  • Solution B Color-component solution B magenta color component2% by weight of 1- phenyl-3-methyl-5-pyrazolon in ethanol.
  • Solution C --% by weight solution of Genochrorn in water 25 mls. of solution A were mixed with 20 mls. of a 1% by weight solution of Lissapol N, 2 mls. of a 1% by weight solution of Armac 12D, 0.2 mls. of solution C and to this mixture the following amounts of one or more of the solutions B were added:
  • Color images may also be manufactured on an aluminum plate matted by etching and subsequently anodized.
  • EXAMPLE 12 An aluminum plate polished by anodization in the'manner as in Example 1 was sensitized by impregnating in a 0.3 molar solution of o-methoxybenzenediazosulphonicacid sodium in methylglycol for 2 minutes, then streaking otf and drying. The plate was subsequently exposed behind a negative of a printed circuit to a 125-watt highpressure mercury-vapor lamp placed at a distance of 30 cms. for seconds, submerged for 2 seconds in a nuclearintroduction bath containing 5 10 molar mercurous nitrate 0.01 molar silver nitrate 0.001 molar nitric acid 0.1 molar citric acid and rinsed in distilled water for 5 seconds.
  • the plate was developed at 20 C. in the physical developer from Example 3 until an external, electricallyconductive silver image was obtained the resistance of which was less than 1 ohm per square. During this process the developer was refreshed several times. After rinsing, drying and scaling in the manner described in Example 1, an acrylonitrile-butadiene copolymer glue on the basis of acrylonitri-lbutadienes was smeared on the image side of the plate, followed by drying of the plate in an oven at 160 for 10 minutes. Then the silver image was transferred to hard paper by pressing the aluminum plate into the paper at 160 C. at a pressure of 60 kgsjom. for 20 minutes. After cooling, the aluminum plate and the hard paper were separated. The external silver image was thus passed into the hard paper.
  • EXAMPLE 13 An aluminum plate anodized in the manner of Example 8, after rinsing, was anodized further in a bath containing 10 g. of borax and 40 g. of boric acid per litre at 20 ,C., for 1 hour. The voltage of the bath in the first minute was slowly raised from O to volts and then maintained at 100 volts. The current density was carefully maintained below 0.2 amp./dm. After rinsing in distilled water for 5 minutes and drying, the plate was sensitized in the manner of Example 1, exposed behind a negative to a high-pressure mercury-vapor lamp at a distance of 30 cms. for 60 seconds and then developed at 20 C. for 10 minutes in a disproportionating developer consisting of:
  • EXAMPLE 14 An aluminum plate anodized and sensitized in the manner described in Example 1 was exposed behind a grid, used as a negative, to a 125-watt high-pressure mercuryvapor lamp placed at a distance of 30 cms. for seconds, treated in a nuclear-introduction bath of the composition:
  • EXAMPLE 0.01 molar p-methylaminophenol sulphate 0.08 molar citric acid and 0.05 molar silver nitrate until a visible, external silver image was produced, rinsed in distilled Water and sealed in the manner described in Example 1 After rinsing, there was submerged for 1 minute in an aqueous solution of 0.01 molar palladium chloride, 0.01 molar hydrochloric acid and 1 molar potassium chloride rinsed in distilled water, submerged in a 1 molar solution of potassium chloride for 10 minutes, again rinsed in distilled water and, at last, treated for 6 minutes in a solution heated to 95 to 99 C., which contained per litre:
  • the pH value of said bath was adjusted from 4.5 to 5 with the aid of The deposition of nickel took place selectively.
  • the aluminum plate was held submerged in an aqueous solution of ferric-ammonium oxalate (2 gs. per litre) at 65 C. for 20 minutes.
  • the pH value of said bath was adjusted from 5.5 to 6.3.
  • the color could be intensified by subsequently submerging the plate in a 0.1% by weight aqueous solution of gallic acid for 1 minute. This color is light-resistant; after this treatment the material was treated further in the manner described in Example 1.
  • a method of producing a photographic contrast on a base consisting essentially of aluminum comprising the steps, oxidizing the surface of a base consisting essentially of aluminum in a manner so as to provide a porous aluminum oxide outer layer separated from the metal by a substantially non-porous intermediate layer, sensitizing said porous outer layer with an organic material the light decomposition product of which reacts with mercurous ions in the presence of water to form a latent mercury image, exposing desired portions of said sensitized layer to light of desired intensity, treating said exposed layer with an aqueous solution containing mercurous ions in a concentration of at least about 10- molar to form a mercury latent image and then physically developing said mercury image by applying to said layer an aqueous solution of a salt of a metal selected from the group consisting of mercury, siliver, gold, platinum and palladium and a water soluble organic reducing compound for said salt said reducing compound capable of reducing said salt to metal on said latent mercury image.
  • organic hydroxy acid is selected from the group consisting of citric acid and glycolic acid.
  • a method of producing a photographic contrast on a base consisting essentially of aluminum comprising the steps oxidizing the surface of a base consisting essentially of aluminum in a manner so as to provide a porous aluminum oxide outer layer separated from the metal by a substantially non-porous intermediate layer, treating said aluminum oxide outer layer with an aqueous solution containing mercuric ions, sensitizing said porous outer layer with an organic material the light decomposition product of which reacts with mercurous ions in the presence of water to form a latent mercury image, exposing desired portions of said sensitized layer to light of desired intensity, treat-ing said exposed layer with an aqueous solution containing mercurous ions in a concentration of at least about 10- molar to form a mercurous latent image and then physically developing said mercurous image by applying to said layer an aqueous solution of a salt of a metal selected from the group consisting of mercury, silver, gold, platinum and palladium and a water soluble organic reducing compound for said salt

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3731622A (en) * 1970-03-18 1973-05-08 California Electro Scient Intermittent type drum advancing means in a high speed printer
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JP2006507206A (ja) * 2002-11-21 2006-03-02 コミツサリア タ レネルジー アトミーク アルミニウムまたはアルミニウム合金を酸化することによるモノリシック水和アルミナ、非晶質または結晶アルミナ、アルミン酸、及び複合材料の調整法
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ES291595A1 (es) 1963-12-01
DK109586C (da) 1968-05-13
DE1213239B (de) 1966-03-24
CH446882A (de) 1967-11-15
GB1064726A (en) 1967-04-05
NL283265A (da)
BE637400A (da)
AT243614B (de) 1965-11-25
SE330127B (da) 1970-11-02

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