WO2006126234A2 - Process for production of jewels - Google Patents

Process for production of jewels Download PDF

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Publication number
WO2006126234A2
WO2006126234A2 PCT/IT2006/000387 IT2006000387W WO2006126234A2 WO 2006126234 A2 WO2006126234 A2 WO 2006126234A2 IT 2006000387 W IT2006000387 W IT 2006000387W WO 2006126234 A2 WO2006126234 A2 WO 2006126234A2
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WO
WIPO (PCT)
Prior art keywords
substrate
process according
gold
film
deposited
Prior art date
Application number
PCT/IT2006/000387
Other languages
French (fr)
Other versions
WO2006126234A3 (en
Inventor
Vincenzo Palmieri
Paolo Favaron
Original Assignee
Istituto Nazionale Di Fisica Nucleare
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Istituto Nazionale Di Fisica Nucleare filed Critical Istituto Nazionale Di Fisica Nucleare
Priority to EP06756295A priority Critical patent/EP1888809A2/en
Publication of WO2006126234A2 publication Critical patent/WO2006126234A2/en
Publication of WO2006126234A3 publication Critical patent/WO2006126234A3/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/005—Coating layers for jewellery
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks

Definitions

  • the present invention concerns a process for production of jewels, utilising PVD deposition techniques and metallic or mineral film masking techniques on metallic, plastic and self-stick substrates.
  • the invention concerns a process that utilises Physical Vapour Deposition (PVD) techniques for the production of coatings on substrates which can be mineral and/or metallic and/or plastic.
  • PVD Physical Vapour Deposition
  • Masking or lithographic techniques are utilised in order to create coatings according to a predefined design.
  • a PVD technique in particular a technique selected in the group consisting of: sputtering, ion plating, cathodic arc.
  • a mask preferably with thickness of 0,1-0,5 mm, that partially covers the same substrate, in order to produce a predetermined design on the substrate.
  • said mask is metallic, preferably in steel.
  • said mask is in plastic and self-sticking.
  • said mask is obtained by gluing a self-sticking film to the substrate, carving with laser the film according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser, the self-sticking film being subsequently removed.
  • said mask is obtained by disposing on the substrate a fotoresist film, carving with laser the film or by photolithography according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser.
  • the film is removed and the precious metal deposited on it is recovered.
  • a predefined design of the substrate by means a lithographic technique.
  • said support or housing is comprised in a vibrating or rotating samples holder.
  • said substrate is housed inside of a rotating cage or sifter, the deposition being made from different directions.
  • said substrate is in microlapped silicon, said at least a material layer being a metal layer, in particular gold, the system metal-silicon being subjected to an annealing, so as to promote the diffusion of the metal in the silicon in order to improve the adhesion thereof.
  • the annealing temperatures are comprised between 150 and 400 0 C, and the times intervals are comprised between 5 and 300 minutes.
  • temperatures are comprised between 180 and 260 0 C 1 and the times intervals are comprised between 10 and 60 minutes.
  • the substrate are deposited at least two layers of material, chosen so that they assure a better adhesion of the layers deposited on the support.
  • the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 90 and 900 nm.
  • the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 200 and 700 nm.
  • the layer in contact with the substrate is of carbon.
  • the layer in contact with the substrate is of a material with high affinity to oxygen.
  • the layer in contact with the substrate is of a material selected in the group consisting of Titanium, Vanadium, Hafnium, Tantalum, Niobium, Zirconium e Chromium.
  • the thickness of said at least a deposited layer is such that it assures a chromatic interaction between this and the substrate.
  • the layer deposited most faraway from the substrate has a thickness comprised between 100 nm and 2,5 micron.
  • the layer deposited most far- away from the substrate has a thickness comprised between 100 nm and 1 ⁇ m.
  • the substrate is of a material selected in the group consisting of gold, silver, platinum, gold and precious metals alloys.
  • on the substrate are subsequently deposited, by means of different masks, layers of red gold, white gold and other metals that yield different chromatic shades.
  • the substrate is mirror-like on at least a side.
  • said substrate is coated with a transparent protective material.
  • said transparent protective material is a polyurethanic paint or other hardening lake.
  • a film of gold that will be fully mirror-like, subsequently on it a fotoresist film is deposited and let dry, then the whole is plunged in the acid solution, in order to reveal the grain of the crystalline structure, the solution acting everywhere, except under the polymeric film, which is then removed with jerk or solubilised in solvents.
  • one deposits on the substrate, for example sapphire, yellow gold according to a predetermined design by means of masking, one then deposits on this a layer of a material selected from the group consisting of white gold, carbon, chromium, niobium and ruthenium, according to the sandwich composed as follows: white gold along all the surface - yellow gold according to a predetermined design and deposited by means of masking - sapphire.
  • the substrate is a slice of silicon microlapped with optical finishing and mirror appearance on the surface of at least a side.
  • the advantage of this last solution is the three-dimensional effect of depth of the design through the sapphire and the protection of the design inside the sandwich.
  • the weight of the material deposited on the substrate is increased by means of electroforming with gold on the face of the silicon slice opposite to that interested by the deposition, so as to hardening the jewel and make it of 750 thousandths.
  • said silicon slice is mounted or stuck in a cage of noble metallic material, so as to harden the jewel.
  • said substrate is constituted by a sheet of plastic material, in particular Kapton, metallised on at least a side.
  • At least a layer is of one or more materials selected from the group consisting of: onyx, black onyx, mother-of-pearl, glass.
  • step A the substrate is at first subjected to ultrasounds in a bath containing alkaline soap dissolved in demineralised water, and subsequently is washed by means of ultrasounds in only demineralised water, or subjected to ultrasounds in an alcohol bath or in subsequent baths of each of the three substances: percloroethylene, acetone and alcohol.
  • step C the substrate is bombarded with argon or nitrogen ions by means of ionic gun, in particular a gridless ion gun, scanning with the ions the surface to be coated, by bending the beam or by moving the substrates.
  • step C one triggers a low- pressure and low-power radiofrequency glow discharge, confined on the substrates, which cleans the substrate by desorbing as a function of power at least a part of the adsorbates on the surface, or by disintegrating the dust.
  • step C the support is electrically connected to ground or at negative potential with respect to the vacuum chamber.
  • step C the material one intends to deposit is negatively polarised, and gas noble is injected, in particular argon, in the deposition chamber.
  • gas noble is injected, in particular argon, in the deposition chamber.
  • filtered or not filtered arc deposition technique is used.
  • sputtering deposition technique is used with control of induced stresses on said at least a layer in the deposition phase.
  • control of stresses is effectuated by means of a common d iff radiometric characterisation with Eulerian cradles, correlating the textures of the same film of said at least a layer of material to the deposition parametres.
  • control of stresses is effectuated according to the following steps: C.1 depositing a film of said at least of material on a substrate, in particular sapphire, of thickness comprised between 70 and 130 micron;
  • step B the vacuum level is comprised between 1e '6 and 1e "3 Pascal.
  • said vacuum level is comprised between 1e ⁇ 5 e 1e "4 Pascal.
  • the energy of the particles impinging on the substrate that supports the growing film of said at least a material layer is e modulated and controlled by applying a negative polarisation voltage on the substrate, determining in such a way the quantity of impurities englobed in said film and the adhesion of said at least a material layer.
  • a jewel characterised in that it is produced utilising the process according to the invention.
  • the substrate is of black onyx, on which a layer of 24 or 18-carat gold is deposited.
  • the substrate is mirror-like on the side interested by the deposition of gold or even on the opposite side.
  • said substrate is a transparent material coated with a material selected from the group consisting of: Titanium, Vanadium, Hafnium, Tantalum, Niobium,
  • said substrate is of microiapped silicon, on which it is deposited an intermediate layer of a material selected from the group consisting of: Titanium, Vanadium,
  • said substrate is a metal turned at high speed using diamond tools, and is such not to interact with the carbon of the tool, and on this is deposited said gold.
  • said metal is copper or aluminium.
  • the substrate is self-sticking on a side not interested to the deposition of material, so as to obtain a self- sticking jewel that adheres directly to the skin every time one wishes to wear it.
  • the substrate is of stone, in particular pink quartz, on which a layer of gold is deposited.
  • the substrate is of yellow or white gold, whereon is respectively deposited a layer of white or yellow gold.
  • the substrate is coloured with paint.
  • the jewel is protected by an external protective layer of a material selected from the group consisting of silica, amorphous diamond, polyurethanic paints or other polymeric paints.
  • a material selected from the group consisting of silica, amorphous diamond, polyurethanic paints or other polymeric paints.
  • Examples of these different techniques are: - The deposition of thin film of controlled-thickness materials; - The deposition of material on a substrate by direct-current or radiofrequency "sputtering"; - The design of configurations of the process of sputtering at high frequency and high confinement of plasma;
  • the deposition parameters of the coating for example: discharge current and voltage, form and amplitude of the confinement magnetic fields, vacuum degree, i.e. degree of the residual pressure before the deposition process, operating gas pressure, configuration of the deposition source and type of chosen PVD process;
  • composition of the coating (stoichiometric ratio, lattice vacancies and interstitial impurities);
  • the morphological properties of the coating for example: porosity, dimensions and coupling of the crystalline grains
  • micro-structural properties for example: phases, crystalline structure, stress and study of the crystalline lattice
  • the Carbon depending on the deposition condition and on the percentage of micro-drops can assume either the graphitic status or the diamond status, and therefore different colours and different transparency, and therefore can be used both for decorative aims and for anti-scratch aims.
  • the Kapton used as substrate and subsequently coated with a thin film of carbon and then gold, or inversely at first with gold and then with carbon, or even with different layers of both materials, or still with white gold and subsequently with yellow gold or vice versa, provided that it is done using suitable masks in order to create designs of different form and different colour, can lead to flexible jewels, adaptable to the body and even self-sticking.
  • the configuration of the apparatus used with the method of the present invention is illustrated in the figure and is that relevant to the process of vacuum metal deposition or sputtering and of ion plating; the concept does not change for the chatodic arc configuration, it is only necessary to substitute in the figure the source of sputtering with a arc source.
  • the substrates are cleaned by means of ultrasonic cleansing in baths containing alkaline soaps dissolved in demineralised water, and then e rinsed with ultrasounds in only demineralised water.
  • the samples are then disposed on a substrates-holder electrically connected to ground or to a voltage tat is negative with respect to the chamber, if one wants to improve the adhesion.
  • a thin steel mask preferably having thickness of 0,1-0,5 mm, whereon a design, an inscription or an ideogram is carved.
  • the deposition chamber is closed and then vacuum is made.
  • Cleaning out the system of contamination is an operation of fundamental importance, in general valid for all typologies of jewel made using the method according to the invention.
  • the degree of vacuum needed to have the best properties of adhesion of the substrate coating is of the order of 1 e "8 -1 e "7 mbar (1 e- 6 -1 e "5 Pascal).
  • the deposition process could start.
  • the material one intends to deposit is polarised negatively, and noble gas, usually Argon, is injected in the deposition chamber.
  • noble gas usually Argon
  • N 1 is the density of the i-th impurity that is present in the vacuum system
  • a is the adhesion or "sticking" coefficient of the impurities to the film
  • R is the sputtering speed.
  • the impurities to which one refers here are essentially gaseous (and therefore usually oxygen, water vapour, hydrocarbons, nitrogen, CO 2 ).
  • the amount of impurity in the film decreases and consequently at the interface as well.
  • the impurities stick less and less to the growing film, owing to the decrease of the sticking coefficient with increasing temperature.
  • the above-mentioned negative voltage acts so that the electrons do not lick the growing film. Indeed, the electron bombarding of the film promotes the typical columnar growing and therefore the high- porosity growing of the film.
  • a high bias voltage contributes to decrease the impurities fraction (it is however to be considered that a excessive bias voltage can damage the growing film since the deposed material undergoes a sputtering phenomenon).
  • the polarisation voltage of the substrate can far exceed 120 Volts, and reach even the 1000 Volts. Such values enable to avoid the electron bombarding (and consequently the abnormal heating up of the substrate) and therefore to be reasonably close to the deposition source, exploiting at best the high deposition speed that is typical of the chatodic arc source.
  • the speeds usually to be used in the sputtering and ion plating are of some nanometres per second.
  • the deposition speeds can even exceed tens of nanometres per second, owing to the fact that for the present application it is convenient to use the non-filtered arc, since there is no need to eliminate the macro-particles that are typical of the arc deposition.
  • the deposition occurs therefore by lighting a plasma on the chatodic surface (which will be covered beforehand with the material one intends to deposit).
  • Atoms of the species one intends to deposit are therefore expulsed from the cathode and arrives on the substrate in the region not covered by the mask.
  • the polichromaticity of the substrate for example mother-of-pearl
  • a particularly preferred thickness range is from 100 to 2 micron, taking anyway into account that thin thicknesses are preferable from the point of view of the polichromaticity and stress, and instead high thicknesses are preferable for the resistance to abrasion.
  • the precious metal films have stresses induced during the growing phase. Also such stresses play a role with respect to the problem of adhesion.
  • the pressure of the process gas for example Argon, is an important parameter for the stress, since by varying the pressure one can pass from a compressive stress condition to tension stress condition, passing through minimum stress points. At the end of the process, one waits for the cooling of the pieces that, because of the involved powers and as a function of the non-perfect plasma confinement, can reach high temperatures. Once broken the vacuum and opened the chamber, the sample is taken away by removing the mask.
  • the process can be used for coating planar substrates either masked or not masked, in order to produce small medals, but can be used also in order to coat crude hard stones, as for example pink quartz, or cut- worked hard stones, as for example faceted black onyx.
  • the minerals are disposed inside a suitable vibrating sample-holder in the form of a bowl, while a source deposits from above precious metal on moving substrates so as to have coating uniformity, or disposed inside a rotating cage (such as sifter), while the lateral sources deposit on the moving stones, through the meshes of the cage.
  • the substrate is well cleaned, by the sputtering deposition one obtains a good adhesion, whilst using the chatodic arc deposition one obtains a coating with even larger adhesion to the substrate.
  • This enables to have deposition of gold and other precious metals on stones with irregular forms, which can be used both for necklaces and for other ornamental uses, such as for example paperweights and buckles.
  • the process according to the invention applies to any type of jewel or valuables, including for example mosaic plugs or other non-wearable product.
  • the deposition for example on pink quartz crystal is particularly pleasant to the sight, since the impression one receives therefrom is that of a massive gold nugget. If the dimension of the substrates are not excessive, by suitably dimensioning the chamber, the vacuum pumping system and the deposition sources, and with substrates to be coated of the order of the centimetre, one can produce without difficulty even amounts of thousands of pieces per day.
  • the substrates usable with this process there are mother- of-pearl and black onyx, as well as minerals like: Aquamarine, Agate, Alabaster, Amber, Amethyst, Andalusite, Aragonite, Avventurine, Azurrite, Bazzite, Benitoite, Beryl, Brasilianite, Chalcedony, Celestine, Cianyte, Citrine, Coral, Cordierite, Corundum, Cornelian, Chrysoberyl, Danburite, Jasper, Dioptase, Eliolite, Heliodor, Hematite, Epidote, Epsomite, Euclase, Fluorapatite, Fluorite, Forsterite, Galena, Gypsum, Jade, Graphite, Garnet, Howleyite, Idocrase, Labradorite, Lapislazuli, petrified Wood, Lepidolite, Leucite, Ludlamite, Magnetite, Malachite, Minium
  • Silicon, Glass of the Cathedral or Tiffany type in the versions: transparent, opalescent and translucent; Gold of different colour with respect to deposed film; plastic, metallic or vitreous substrates coated with the above-mentioned materials and with carbon films in the various allotropic states including those of diamond and graphite type and subsequently coated with film of gold and precious metals alloys.
  • the above-described method is valid in general, however in some cases a serious problem can appear, that is the problem of a bad adhesion between the coating metal film and the substrate.
  • the adhesion indeed has to be not only absolutely high, but even constant along time.
  • Vanadium, Hafnium, Tantalum, Niobium, Zirconium e Chromium Such materials have also the advantage of constituting a barrier of diffusion between substrate and coating, in the same way as the Palladium in the galvanic technique is deposited as barrier between Gold and Argent or between Gold and Copper.
  • the thickness of Titanium or Chromium or any other buffer layer is anyway extremely thin, around the hundreds of nanometres.
  • the type of jewel is constituted by a gold film on mother-of-pearl.
  • the technical concept underlying such a jewel is to transfer the polichromaticity of the substrate of mother-of-pearl to the gold deposited on the surface. If the film is sufficiently thin, the polychromatic properties of the mother-of-pearl are still visible through the layer of gold and in fact show up and change of colour upon varying the observation angle. In other words, the gold assumes the polichromaticity of the mother-of-pearl.
  • the specific technique of realisation is the deposition of gold on substrate of mother-of-pearl by sputtering, ion plating or chatodic arc, using of course also masking technique.
  • the type of jewel is constituted by a film of gold on black onyx.
  • the technical concept underlying such a jewel is to heighten the reflectivity of the gold by exploiting the black body absorption that is peculiar black onyx.
  • a gold leaf is deposited mechanically on a substrate
  • 18-carat gold 750 thousandths
  • the deposition on black onyx shows up the yellow of the gold in contrast with the black of the onyx, hence all the obtainable colorations of the 18-carat gold, and even more those of the 24-carat gold, assume a peculiar coloration, heighten by the deepness of the surrounding black.
  • the specific technique of realisation is the deposition of gold on black onyx substrate by sputtering, ion plating or chatodic arc, using masking techniques.
  • the type of jewel of this example is constituted by a film of gold on mirrors (obtainable in micro-lapped silicon, glass, quartz or sapphire (AI 2 O 3 ) or other material metallised by sputtering or chatodic arc, metal turned by diamond tools, or metal lapped with submicrometric grain abrasives).
  • the technical effect obtained with such a jewel is that the film of gold becomes more or less visible depending on the observation angle.
  • the substrate is preliminarily deposited with a metallic film of cheap materials, such as for example Titanium or Chromium or Niobium, or even with precious metal such as white gold, platinum or palladium.
  • a metallic film of cheap materials such as for example Titanium or Chromium or Niobium, or even with precious metal such as white gold, platinum or palladium.
  • precious metal such as white gold, platinum or palladium.
  • An equivalent situation is that of glass fully mirror coated by gold and subsequently masked and then coated with for example white gold or platinum, according to chosen design.
  • metal that has been high-speed turned using diamond tools, one can use for example Copper, Aluminium or others metals that do not interact with the carbon of the tool.
  • mirror lapping it is instead usable a wider range of materials.
  • mirrors it is possible to deposit directly the gold, but in order to avoid an immediate damaging of the mirror part it is possible to protect the mirror surface with transparent hardening lakes, for example polyurhetanic varnishes, and subsequently execute maskings and gold deposition.
  • transparent hardening lakes for example polyurhetanic varnishes
  • the type of jewel of this example is constituted by a film of gold on thin substrates of glass, quartz, sapphire or other material of different nature as long as it has a mirror finishing (for example microlapped silicon), coated on both sides with a metallic film of Chromium, Steel, Titanium, Niobium, Zirconium, Aluminium, Magnesium, Copper or other metal; and subsequently strengthen in the back by means of electro- moulding, increasing the thickness of back gold so that its weight be at least 3 times the substrate's weight.
  • a mirror finishing for example microlapped silicon
  • the steps are the following ones: the thin glass is coated by a metallic film for example chrome, in order to obtain the mirror surface.
  • the metallised glass is coated then with a thick film of gold on the back side by electroforming, in order to increase the thickness to a value such that the jewel can be considered 750 thousandths.
  • the chromed front face is masked and coated with a thin film of gold, according to the design of the mask thus producing a pleasant mirror effect.
  • the specific realisation technique is the metallisation of the substrate with metal such that Titanium o Chromium by sputtering, ion plating or cathodic arc, subsequent electromoulding for increasing thickness so as to bring the jewel to 750 thousandths fineness, and subsequent deposition of precious metal on the opposite face using masking techniques.
  • the type of jewel of this example is constituted by a film of gold on cathedral glass, blown or opalescent.
  • the technical concept underlying such an example is to exploit the chromaticities and the transparency or opalescence of glass combined with those of low-thickness gold.
  • the specific realisation technique is the deposition of gold on blown or opalescent cathedral glass substrate, by sputtering, ion plating or cathodic arc, utilising masking techniques.
  • the type of jewel of this example is constituted by a film of gold on plastic substrate even self-sticking.
  • the specific realisation technique consists in that the plastic substrate is at first metallised and then coated with a precious metal by sputtering, ion plating or cathodic arc, utilising masking techniques.
  • the type of jewel of this example is constituted by a film of gold on minerals (for example pink quartz, amethyst).
  • the technical concept underlying such a jewel is to exploit for example the sputtering effectuated on row pink quartz, used in the preparation of necklaces. By depositing gold on pink quartz, the impression one obtains is that of a necklace constituted of nuggets.
  • the rough surface of the raw not-dressed quartz show up the reflectivity of the deposited gold, producing a pleasant visual effect.
  • the specific realisation technique consists in the fact that the minerals are washed with suitable soaps, dried in alcohol and subsequently placed in vacuum, or even with the help of heating-up lamps, afterwards they are coated by cathodic arc or sputtering.
  • the substrates In the case of stones to be strung in a necklace, it is advised to insert the substrates inside a little cage with large mesh, but of course smaller than the stones to be coated.
  • the cage is disposed over the deposition source and is rotated during the process. The stones are then coated in a substantially uniform manner.
  • Example 8 The type of jewel of this example is constituted by a film of white gold on yellow gold; film of yellow gold on white gold and film of non- precious metals on yellow gold.
  • the specific realisation technique consists in the deposition of a film of precious metal on substrates of different colour precious metal by sputtering, ion plating or cathodic arc, utilising masking techniques.
  • the type of jewel of this example is constituted by a film of gold on a substrate that is corroded or electrocorroded with acid treatment both before and after the gold deposition.
  • the specific realisation technique consists in that, after the chemical etching for revealing the crystalline grains, the substrate has to be masked and on it the film of gold has to be deposited. It is also possible a change: on the mirror lapped substrate, a film of gold is deposited that will be fully mirror-like, then on it is deposited and let dry a fotoresist film. Then the whole is plunged in the acid solution, that produces the desired effect of revealing the grains. The solution acts everywhere except under the polymeric film, that is then removed with a jerk, or solubilised in solvents, e.g. acetone.
  • the process according the present invention allow to save material of coating and therefore to make cheaper and accessible a great amount of jewel.

Abstract

Process for the production of jewels, constituted by a substrate, that is mineral, metallic, glassy or plastic and high-resistant to temperature, whereon is deposited at least a layer of mineral or metallic material, characterised in that it comprises the following subsequent steps: A. degreasing of the substrate by means of ultrasounds; B. positioning the substrate on a support or housing inside a vacuum chamber; C. depositing said at least a material layer, the deposition being made with a PVD technique, in particular a technique selected in the group consisting of: sputtering, ion plating, cathodic arc. The invention also concerns a jewel, characterised in that it is produced utilising the process according to the invention.

Description

PROCESS FOR PRODUCTION OF JEWELS, UTILISING PVD DEPOSITION TECHNIQUES AND METALLIC OR MINERAL FILM MASKING TECHNIQUES ON METALLIC, PLASTIC AND SELF-STICK SUBSTRATES
The present invention concerns a process for production of jewels, utilising PVD deposition techniques and metallic or mineral film masking techniques on metallic, plastic and self-stick substrates.
More in detail, the invention concerns a process that utilises Physical Vapour Deposition (PVD) techniques for the production of coatings on substrates which can be mineral and/or metallic and/or plastic. Masking or lithographic techniques are utilised in order to create coatings according to a predefined design.
It is known the mechanical deposition utilised for producing gold or other precious material coatings on stone, as for example gold on onyx for producing jewels of various form.
The fundamental limit of such a technique, also known in other fields and applied to the goldsmith field, is the fact that the thickness of the coating is such that it hidden the chromatic characteristics of the substrate. The chromatic interactions between the substrate and the coating are therefore prevented. The type of jewel which can be produced is therefore limited as well.
Moreover, the thin layers needed in order to obtain the above- mentioned interactions are difficult to realise owing to the fact that the adhesion of the applied layer to the substrate needs to be assured. It is object of he present invention to provide with a process for the production of jewels that overcomes the drawbacks of the relevant prior art. Further specific object of the present invention is to provide with a jewel produced using the process object of the invention. It is subject matter of the present invention a process for the production of jewels, constituted by a substrate, that is mineral, metallic, glassy or plastic and high-resistant to temperature, whereon is deposited at least a layer of mineral or metallic material, characterised in that it comprises the following subsequent steps: A. degreasing of the substrate by means of ultrasounds;
B. positioning the substrate on a support or housing inside a vacuum chamber; C. depositing said at least a material layer, the deposition being made with a PVD technique, in particular a technique selected in the group consisting of: sputtering, ion plating, cathodic arc.
Preferably according to the invention, during the deposition, on the substrate is positioned a mask, preferably with thickness of 0,1-0,5 mm, that partially covers the same substrate, in order to produce a predetermined design on the substrate.
Preferably according to the invention, said mask is metallic, preferably in steel. Preferably according to the invention, said mask is in plastic and self-sticking.
Preferably according to the invention, said mask is obtained by gluing a self-sticking film to the substrate, carving with laser the film according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser, the self-sticking film being subsequently removed.
Preferably according to the invention, said mask is obtained by disposing on the substrate a fotoresist film, carving with laser the film or by photolithography according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser.
After the deposition in both last cases, the film is removed and the precious metal deposited on it is recovered.
Preferably according to the invention, after the deposition, is realised a predefined design of the substrate by means a lithographic technique.
Preferably according to the invention, said support or housing is comprised in a vibrating or rotating samples holder.
Preferably according to the invention, said substrate is housed inside of a rotating cage or sifter, the deposition being made from different directions.
Preferably according to the invention, said substrate is in microlapped silicon, said at least a material layer being a metal layer, in particular gold, the system metal-silicon being subjected to an annealing, so as to promote the diffusion of the metal in the silicon in order to improve the adhesion thereof. Preferably according to the invention, the annealing temperatures are comprised between 150 and 400 0C, and the times intervals are comprised between 5 and 300 minutes.
Preferably according to the invention, temperatures are comprised between 180 and 260 0C1 and the times intervals are comprised between 10 and 60 minutes.
Preferably according to the invention, on the substrate are deposited at least two layers of material, chosen so that they assure a better adhesion of the layers deposited on the support. Preferably according to the invention, the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 90 and 900 nm.
Preferably according to the invention, the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 200 and 700 nm.
Preferably according to the invention, the layer in contact with the substrate is of carbon.
Preferably according to the invention, the layer in contact with the substrate is of a material with high affinity to oxygen. Preferably according to the invention, the layer in contact with the substrate is of a material selected in the group consisting of Titanium, Vanadium, Hafnium, Tantalum, Niobium, Zirconium e Chromium.
Preferably according to the invention, the thickness of said at least a deposited layer is such that it assures a chromatic interaction between this and the substrate.
Preferably according to the invention, the layer deposited most faraway from the substrate has a thickness comprised between 100 nm and 2,5 micron.
Preferably according to the invention, the layer deposited most far- away from the substrate has a thickness comprised between 100 nm and 1 μm.
Preferably according to the invention, the substrate is of a material selected in the group consisting of gold, silver, platinum, gold and precious metals alloys. Preferably according to the invention, on the substrate are subsequently deposited, by means of different masks, layers of red gold, white gold and other metals that yield different chromatic shades. Preferably according to the invention, the substrate is mirror-like on at least a side.
Preferably according to the invention, said substrate is coated with a transparent protective material. Preferably according to the invention, said transparent protective material is a polyurethanic paint or other hardening lake.
Preferably according to the invention, on said substrate is deposited a film of gold, that will be fully mirror-like, subsequently on it a fotoresist film is deposited and let dry, then the whole is plunged in the acid solution, in order to reveal the grain of the crystalline structure, the solution acting everywhere, except under the polymeric film, which is then removed with jerk or solubilised in solvents.
Preferably according to the invention, one coats the substrate, for example sapphire, on a side with a metallic film, in particular a material selected in a group consisting of white gold, carbon, chromium, niobium and ruthenium, in order to make it mirror-like, and subsequently one coats it on the opposite side with a film of yellow gold by means of masking, in order to have a sandwich constituted as follows: white gold along all the surface - substrate - yellow gold. Preferably according to the invention, one deposits on the substrate, for example sapphire, yellow gold according to a predetermined design by means of masking, one then deposits on this a layer of a material selected from the group consisting of white gold, carbon, chromium, niobium and ruthenium, according to the sandwich composed as follows: white gold along all the surface - yellow gold according to a predetermined design and deposited by means of masking - sapphire.
Preferably according to the invention, the substrate is a slice of silicon microlapped with optical finishing and mirror appearance on the surface of at least a side. The advantage of this last solution is the three-dimensional effect of depth of the design through the sapphire and the protection of the design inside the sandwich.
Preferably according to the invention, the weight of the material deposited on the substrate is increased by means of electroforming with gold on the face of the silicon slice opposite to that interested by the deposition, so as to hardening the jewel and make it of 750 thousandths. Preferably according to the invention, said silicon slice is mounted or stuck in a cage of noble metallic material, so as to harden the jewel.
Preferably according to the invention, said substrate is constituted by a sheet of plastic material, in particular Kapton, metallised on at least a side.
Preferably according to the invention, at least a layer is of one or more materials selected from the group consisting of: onyx, black onyx, mother-of-pearl, glass.
Preferably according to the invention, in step A the substrate is at first subjected to ultrasounds in a bath containing alkaline soap dissolved in demineralised water, and subsequently is washed by means of ultrasounds in only demineralised water, or subjected to ultrasounds in an alcohol bath or in subsequent baths of each of the three substances: percloroethylene, acetone and alcohol. Preferably according to the invention, in step C the substrate is bombarded with argon or nitrogen ions by means of ionic gun, in particular a gridless ion gun, scanning with the ions the surface to be coated, by bending the beam or by moving the substrates.
Preferably according to the invention, in step C one triggers a low- pressure and low-power radiofrequency glow discharge, confined on the substrates, which cleans the substrate by desorbing as a function of power at least a part of the adsorbates on the surface, or by disintegrating the dust.
Preferably according to the invention, in step C the support is electrically connected to ground or at negative potential with respect to the vacuum chamber.
Preferably according to the invention, in step C, the material one intends to deposit is negatively polarised, and gas noble is injected, in particular argon, in the deposition chamber. Preferably according to the invention, filtered or not filtered arc deposition technique is used.
Preferably according to the invention, sputtering deposition technique is used with control of induced stresses on said at least a layer in the deposition phase. Preferably according to the invention, the control of stresses is effectuated by means of a common d iff radiometric characterisation with Eulerian cradles, correlating the textures of the same film of said at least a layer of material to the deposition parametres.
Preferably according to the invention, the control of stresses is effectuated according to the following steps: C.1 depositing a film of said at least of material on a substrate, in particular sapphire, of thickness comprised between 70 and 130 micron;
C.2 if the film turns out to be stressed after the deposition, bending the coated substrate in a concave or convex way on the side of the film, depending on whether the stress induced in the film is compressive or tensive, the bending of the substrate being proportional to the stress in the film.
The control of stresses is effectuated in an original way, just depositing films on such substrates and correlating the bending of the substrate to the deposition parameters. Preferably according to the invention, in step B the vacuum level is comprised between 1e'6 and 1e"3 Pascal.
Preferably according to the invention, said vacuum level is comprised between 1e~5 e 1e"4 Pascal.
Preferably according to the invention, the energy of the particles impinging on the substrate that supports the growing film of said at least a material layer is e modulated and controlled by applying a negative polarisation voltage on the substrate, determining in such a way the quantity of impurities englobed in said film and the adhesion of said at least a material layer. It is further specific subject matter of the present invention a jewel, characterised in that it is produced utilising the process according to the invention.
Preferably according to the invention, the substrate is of black onyx, on which a layer of 24 or 18-carat gold is deposited. Preferably according to the invention, the substrate is mirror-like on the side interested by the deposition of gold or even on the opposite side.
Preferably according to the invention, said substrate is a transparent material coated with a material selected from the group consisting of: Titanium, Vanadium, Hafnium, Tantalum, Niobium,
Zirconium, Chromium, white gold, Platinum, Palladium, and mirror treated before step C. Preferably according to the invention, said substrate is of microiapped silicon, on which it is deposited an intermediate layer of a material selected from the group consisting of: Titanium, Vanadium,
Hafnium, Tantalum, Niobium, Zirconium, Chromium, on which said gold is deposited.
Preferably according to the invention, said substrate is a metal turned at high speed using diamond tools, and is such not to interact with the carbon of the tool, and on this is deposited said gold.
Preferably according to the invention, said metal is copper or aluminium.
Preferably according to the invention, the substrate is self-sticking on a side not interested to the deposition of material, so as to obtain a self- sticking jewel that adheres directly to the skin every time one wishes to wear it. Preferably according to the invention, the substrate is of stone, in particular pink quartz, on which a layer of gold is deposited.
Preferably according to the invention, the substrate is of yellow or white gold, whereon is respectively deposited a layer of white or yellow gold. Preferably according to the invention, the substrate is coloured with paint.
Preferably according to the invention, the jewel is protected by an external protective layer of a material selected from the group consisting of silica, amorphous diamond, polyurethanic paints or other polymeric paints. The invention will be now described, by way of illustration and not by way of limitation, by particularly referring to the drawing of the enclosed Figure.
In the goldsmith field, several sophisticated technologies have not been applied, all referable and/or usable to the PVD technique, which belong to the field of microelectronics and to the field of the particle accelerator construction, in particular the technology of thin film deposition.
Examples of these different techniques are: - The deposition of thin film of controlled-thickness materials; - The deposition of material on a substrate by direct-current or radiofrequency "sputtering"; - The design of configurations of the process of sputtering at high frequency and high confinement of plasma;
- The control of the adhesion of the film to the substrate by controlling the stresses induced in the film during the growing phase;
- The modulation and the control of the energy of the particles incident on the substrate which supports the growing film;
- The control of the ratio between the number of ions bombarding the growing film and the number of neutral atoms which is deposited; - The deposition of cushion layers that increase the adhesion of the final layer;
- The use of the filter for the reduction of micro-drops (also called micro-particles) in the chatodic arc deposition;
- Annealing of the system constituted by a silicon substrate and a metal substrate, in particular gold, so as to promote the diffusion of gold or other metal in he silicon in order to improve the adherence. The production process according to the present invention uses such technologically advanced knowledges in order to produce jewels, by combining them in an inventive and innovative way. Such a process is based on the correlation of four variables:
1. the deposition parameters of the coating (for example: discharge current and voltage, form and amplitude of the confinement magnetic fields, vacuum degree, i.e. degree of the residual pressure before the deposition process, operating gas pressure, configuration of the deposition source and type of chosen PVD process);
2. The composition of the coating (stoichiometric ratio, lattice vacancies and interstitial impurities);
3. The morphological properties of the coating (for example: porosity, dimensions and coupling of the crystalline grains) and micro-structural properties (for example: phases, crystalline structure, stress and study of the crystalline lattice);
4. The adaptation of the crystalline lattice properties of the film with those of the substrate by means of a cushion layer of a third suitable material. With the process according to the invention, one allows the introduction, in the today's goldsmith market, of sophisticated materials that are at present not known in the field but that are known to those working in the field of microelectronics and of particle accelerator construction, in particular in the thin film deposition technology. Examples of such materials are:
- The Silicon used both in massive form and in wafer form, or even in thin film form;
- The carbon in the form so-called diamond-like as a thin film;
- The Kempton, plastic high flexibility material that can stand high temperatures of deposition.
The Carbon, depending on the deposition condition and on the percentage of micro-drops can assume either the graphitic status or the diamond status, and therefore different colours and different transparency, and therefore can be used both for decorative aims and for anti-scratch aims.
The Kapton, used as substrate and subsequently coated with a thin film of carbon and then gold, or inversely at first with gold and then with carbon, or even with different layers of both materials, or still with white gold and subsequently with yellow gold or vice versa, provided that it is done using suitable masks in order to create designs of different form and different colour, can lead to flexible jewels, adaptable to the body and even self-sticking.
The fabrication technique of jewels having a base constituted by a substrate in a material different from that of the coating is described in the following in its typical configuration and according to the simplest process. Using the information in the following description, handmade articles of sufficient quality and good finishing are obtained, even if it is evident that the addition of more sophisticated substrate cleaning techniques (such as a plasma cleaning treatment of the type "glow discharge" or a ion beam cleaning), the addition of further apparatuses for diagnostics and in situ characterisation, although not necessary, are surely useful with respect to quality of the coating.
The configuration of the apparatus used with the method of the present invention is illustrated in the figure and is that relevant to the process of vacuum metal deposition or sputtering and of ion plating; the concept does not change for the chatodic arc configuration, it is only necessary to substitute in the figure the source of sputtering with a arc source. Before the PVD deposition, for example of gold on onyx, the substrates are cleaned by means of ultrasonic cleansing in baths containing alkaline soaps dissolved in demineralised water, and then e rinsed with ultrasounds in only demineralised water. Indeed, even paying the maximum attention, if the operations for the assemblage of substrate to be coated are not carried out with extreme care, it can happen that on the substrates to be coated there can be contamination, that is in general: 1) dust, 2) dust coming from walls of the vacuum bell, due to former depositions, 3) residuals of washing or even: 4) print of grease released in the possible contact with the finger of the operator. In such a case, it is extremely efficient to effectuate one of the following two operations: i) bombarding the substrates, before the deposition, with ions of Argon or Nitrogen or Oxygen by means of a gridless ion gun, scanning with the ions the surface to be coated, by bending the beam or by moving the substrates; ii) triggering of a low-pressure and low-power radiofrequency glow discharge, confined on the substrates, which cleans the substrate by desorbing all the adsorbates on the surface, or by disintegrating the dust, which however, unlike the sputtering, does not modify the surface morphology of the substrate.
Once the surface cleaning is done, by one of the two methods, one can possibly start with the deposition of suitable cushion layers, whose need will be explained in the following, and subsequently the deposition of the precious metals.
Once dried, the samples are then disposed on a substrates-holder electrically connected to ground or to a voltage tat is negative with respect to the chamber, if one wants to improve the adhesion. On the samples is disposed a thin steel mask, preferably having thickness of 0,1-0,5 mm, whereon a design, an inscription or an ideogram is carved.
The deposition chamber is closed and then vacuum is made. The more the vacuum is high, the better will be the obtained result, since a good starting vacuum reduces the quantity of possible impurity included in the films, and increases the adhesion of the substrate as well. Cleaning out the system of contamination is an operation of fundamental importance, in general valid for all typologies of jewel made using the method according to the invention. The degree of vacuum needed to have the best properties of adhesion of the substrate coating is of the order of 1 e"8-1 e"7 mbar (1 e-6-1 e"5 Pascal).
In order to increase the amounts of production, industrially it is of customary use a degree of "dirty vacuum" in the range between 1e~5 e 1e'6 mbar, quickly obtained with rapid times of pumping. Although with such a degree of vacuum it is in any case possible to produce the handmade article, the level of adhesion of the film to the substrate is compromised and in such a case it is necessary to make resort to other parameters, such as the speed of deposition or the voltage of polarisation or bias of the substrate, or the presence of cushion layers at the interface between coating and substrate. Briefly, it is possible to use an inferior degree of vacuum, however the reliability and repeatability of the process are compromised.
At this point, the deposition process could start. For better precaution it is possible, but not strictly needed, to carry out a further cleaning of the substrates, or by means of ionic by means of irradiation (a flux of ions of argon or in general noble gas is separated on the substrate), or by means of glow discharge.
The material one intends to deposit is polarised negatively, and noble gas, usually Argon, is injected in the deposition chamber.
In the sputtering and ion plating techniques, polarising negatively the substrate (on average between 0 and 120 Volts) promotes the ionic bombarding of the film, thus increasing the pureness thereof. Further, it is possible to obtain an analogous effect by a suitable magnetic confinement of the plasma and a suitable localisation of the substrates to be coated, i.e. it is possible to make the plasma bombarding the growing film. The plasma desorbs impurities weakly linked to the surface, besides cleaning the surface. Where there is plasma-substrate interaction, the adhesion is much better than elsewhere. A disadvantage is however given by the fact that the plasma, where it licks the substrate, heats it up as well. This means that this method is applicable on non-low-melting materials, but it is not on common plastic substrates, which would polymerise or even melt after few seconds. The fraction f, of the i-th impurity englobed inside a film normally follows the progression described by the following formula:
N,a,
N,a, + R where N1 is the density of the i-th impurity that is present in the vacuum system, a, is the adhesion or "sticking" coefficient of the impurities to the film, and R is the sputtering speed. The impurities to which one refers here are essentially gaseous (and therefore usually oxygen, water vapour, hydrocarbons, nitrogen, CO2). Hence, by increasing the sputtering speed, the amount of impurity in the film decreases and consequently at the interface as well. Likewise, in the heating of the substrate, the impurities stick less and less to the growing film, owing to the decrease of the sticking coefficient with increasing temperature.
Moreover, the above-mentioned negative voltage acts so that the electrons do not lick the growing film. Indeed, the electron bombarding of the film promotes the typical columnar growing and therefore the high- porosity growing of the film.
If one applies a negative polarisation voltage (bias) to the substrate, the formula describing the fraction / of the z-th impurity englobed in the film is practically the same as before, where however the product N, a, is to be reduced of a quantity b(f) that is function of the bias current:
[N1CX1 -S(J)] 1 [N1(X1 -bG)]+ R
In other words, a high bias voltage contributes to decrease the impurities fraction (it is however to be considered that a excessive bias voltage can damage the growing film since the deposed material undergoes a sputtering phenomenon).
In the case of chatodic arc, the polarisation voltage of the substrate can far exceed 120 Volts, and reach even the 1000 Volts. Such values enable to avoid the electron bombarding (and consequently the abnormal heating up of the substrate) and therefore to be reasonably close to the deposition source, exploiting at best the high deposition speed that is typical of the chatodic arc source. The speeds usually to be used in the sputtering and ion plating are of some nanometres per second. With the chatodic arc, the deposition speeds can even exceed tens of nanometres per second, owing to the fact that for the present application it is convenient to use the non-filtered arc, since there is no need to eliminate the macro-particles that are typical of the arc deposition. The deposition occurs therefore by lighting a plasma on the chatodic surface (which will be covered beforehand with the material one intends to deposit).
Atoms of the species one intends to deposit are therefore expulsed from the cathode and arrives on the substrate in the region not covered by the mask.
Concerning the dimension of the deposed films, although with thickness lager than 10 micron the effect is still visible, the polichromaticity of the substrate, for example mother-of-pearl, show up at most on thin thicknesses less than a micron. A particularly preferred thickness range is from 100 to 2 micron, taking anyway into account that thin thicknesses are preferable from the point of view of the polichromaticity and stress, and instead high thicknesses are preferable for the resistance to abrasion.
It is to be observed that in the sputtering it is possible that the precious metal films have stresses induced during the growing phase. Also such stresses play a role with respect to the problem of adhesion. The pressure of the process gas, for example Argon, is an important parameter for the stress, since by varying the pressure one can pass from a compressive stress condition to tension stress condition, passing through minimum stress points. At the end of the process, one waits for the cooling of the pieces that, because of the involved powers and as a function of the non-perfect plasma confinement, can reach high temperatures. Once broken the vacuum and opened the chamber, the sample is taken away by removing the mask. The process can be used for coating planar substrates either masked or not masked, in order to produce small medals, but can be used also in order to coat crude hard stones, as for example pink quartz, or cut- worked hard stones, as for example faceted black onyx.
In such a case, the minerals are disposed inside a suitable vibrating sample-holder in the form of a bowl, while a source deposits from above precious metal on moving substrates so as to have coating uniformity, or disposed inside a rotating cage (such as sifter), while the lateral sources deposit on the moving stones, through the meshes of the cage.
If the substrate is well cleaned, by the sputtering deposition one obtains a good adhesion, whilst using the chatodic arc deposition one obtains a coating with even larger adhesion to the substrate. This enables to have deposition of gold and other precious metals on stones with irregular forms, which can be used both for necklaces and for other ornamental uses, such as for example paperweights and buckles.
In general, the process according to the invention applies to any type of jewel or valuables, including for example mosaic plugs or other non-wearable product.
The deposition for example on pink quartz crystal is particularly pleasant to the sight, since the impression one receives therefrom is that of a massive gold nugget. If the dimension of the substrates are not excessive, by suitably dimensioning the chamber, the vacuum pumping system and the deposition sources, and with substrates to be coated of the order of the centimetre, one can produce without difficulty even amounts of thousands of pieces per day. Among the substrates usable with this process there are mother- of-pearl and black onyx, as well as minerals like: Aquamarine, Agate, Alabaster, Amber, Amethyst, Andalusite, Aragonite, Avventurine, Azurrite, Bazzite, Benitoite, Beryl, Brasilianite, Chalcedony, Celestine, Cianyte, Citrine, Coral, Cordierite, Corundum, Cornelian, Chrysoberyl, Danburite, Jasper, Dioptase, Eliolite, Heliodor, Hematite, Epidote, Epsomite, Euclase, Fluorapatite, Fluorite, Forsterite, Galena, Gypsum, Jade, Graphite, Garnet, Howleyite, Idocrase, Labradorite, Lapislazuli, petrified Wood, Lepidolite, Leucite, Ludlamite, Magnetite, Malachite, Minium, Mica, Neptunite, Niningerite, Onyx, Olivine, Opale, Orthoclase, Obsidian, Pyrite, Proustite, Quartz in all varieties, Rhodocrosite, Rhodonite, Rutile, Rock salt, Smithsonite, Sodalite, Stilbite, Uklexite, Vesuvianite, Wavellite, Zircon, Zincite, either as stone or as pastry, with surface either raw or finished by diamond cut or of sifter.
Also usable with the process according to the invention are Silicon, Glass of the Cathedral or Tiffany type, in the versions: transparent, opalescent and translucent; Gold of different colour with respect to deposed film; plastic, metallic or vitreous substrates coated with the above-mentioned materials and with carbon films in the various allotropic states including those of diamond and graphite type and subsequently coated with film of gold and precious metals alloys.
The above-described method is valid in general, however in some cases a serious problem can appear, that is the problem of a bad adhesion between the coating metal film and the substrate. The adhesion indeed has to be not only absolutely high, but even constant along time.
An example is the bad adhesion of the Gold on Silicon. In order to solve this problem, one makes resort to, as above mentioned, the adoption of buffer layers of materials with high affinity to the oxygen, such as Titanium,
Vanadium, Hafnium, Tantalum, Niobium, Zirconium e Chromium. Such materials have also the advantage of constituting a barrier of diffusion between substrate and coating, in the same way as the Palladium in the galvanic technique is deposited as barrier between Gold and Argent or between Gold and Copper. The thickness of Titanium or Chromium or any other buffer layer is anyway extremely thin, around the hundreds of nanometres.
In the following some example of jewels realisable with the invention process are given.
Example 1
The type of jewel is constituted by a gold film on mother-of-pearl. The technical concept underlying such a jewel is to transfer the polichromaticity of the substrate of mother-of-pearl to the gold deposited on the surface. If the film is sufficiently thin, the polychromatic properties of the mother-of-pearl are still visible through the layer of gold and in fact show up and change of colour upon varying the observation angle. In other words, the gold assumes the polichromaticity of the mother-of-pearl. The specific technique of realisation is the deposition of gold on substrate of mother-of-pearl by sputtering, ion plating or chatodic arc, using of course also masking technique.
Example 2
The type of jewel is constituted by a film of gold on black onyx. The technical concept underlying such a jewel is to heighten the reflectivity of the gold by exploiting the black body absorption that is peculiar black onyx. Usually in the production of jewels, where a gold leaf is deposited mechanically on a substrate, one tries to deposit 18-carat gold (750 thousandths) since fine 24-carat gold has a colour even too intense and not always accepted by the market. The deposition on black onyx, on the contrary, shows up the yellow of the gold in contrast with the black of the onyx, hence all the obtainable colorations of the 18-carat gold, and even more those of the 24-carat gold, assume a peculiar coloration, heighten by the deepness of the surrounding black.
The specific technique of realisation is the deposition of gold on black onyx substrate by sputtering, ion plating or chatodic arc, using masking techniques.
Example 3
The type of jewel of this example is constituted by a film of gold on mirrors (obtainable in micro-lapped silicon, glass, quartz or sapphire (AI2O3) or other material metallised by sputtering or chatodic arc, metal turned by diamond tools, or metal lapped with submicrometric grain abrasives).
The technical effect obtained with such a jewel is that the film of gold becomes more or less visible depending on the observation angle.
When one deposits a film of gold on a mirror, because of the low roughness, gold acts as mirror too. Upon varying the angle of observation of the jewel, the gold appears clearly visible or it blends with the substrates, conferring to gold on the surface a sort of "see-not see" effect. The specific technique of realisation is the deposition of gold on mirror substrate by sputtering, ion plating or chatodic arc, using masking techniques. In the case of micro-lapped silicon, it is compulsory to use cushion layers, for example Chromium or Titanium. Hence, the substrate is masked and is subjected to the two subsequent metallisations. In the case of glass, quartz, sapphire or other transparent substrate, the substrate is preliminarily deposited with a metallic film of cheap materials, such as for example Titanium or Chromium or Niobium, or even with precious metal such as white gold, platinum or palladium. One makes then the mirror and subsequently one masks and deposits gold according to the chosen design. An equivalent situation is that of glass fully mirror coated by gold and subsequently masked and then coated with for example white gold or platinum, according to chosen design. In the case of metal, that has been high-speed turned using diamond tools, one can use for example Copper, Aluminium or others metals that do not interact with the carbon of the tool. In the case of mirror lapping, it is instead usable a wider range of materials. For such "mirrors", it is possible to deposit directly the gold, but in order to avoid an immediate damaging of the mirror part it is possible to protect the mirror surface with transparent hardening lakes, for example polyurhetanic varnishes, and subsequently execute maskings and gold deposition.
Example 4
The type of jewel of this example is constituted by a film of gold on thin substrates of glass, quartz, sapphire or other material of different nature as long as it has a mirror finishing (for example microlapped silicon), coated on both sides with a metallic film of Chromium, Steel, Titanium, Niobium, Zirconium, Aluminium, Magnesium, Copper or other metal; and subsequently strengthen in the back by means of electro- moulding, increasing the thickness of back gold so that its weight be at least 3 times the substrate's weight.
The technical concept underlying such a jewel is to exploit the optical and mirror finishing of the glass, increasing the thickness of the gold in the back part until the jewel is 750 thousandths.
Briefly the steps are the following ones: the thin glass is coated by a metallic film for example chrome, in order to obtain the mirror surface. The metallised glass is coated then with a thick film of gold on the back side by electroforming, in order to increase the thickness to a value such that the jewel can be considered 750 thousandths. Finally the chromed front face is masked and coated with a thin film of gold, according to the design of the mask thus producing a pleasant mirror effect.
One can also deposit on the substrate for example sapphire, yellow gold according to a chosen design by means of masking, then one deposits on this a layer of material selected in the group comprising white gold, carbon, chromium, niobium e ruthenium, in order to create the mirror effect, thus obtaining the following sandwich: white gold along all the surface - yellow gold according to a chosen design deposited using the mask - sapphire. This allows to observe the yellow gold behind glass and have at the same time the mirror effect. The specific realisation technique is the metallisation of the substrate with metal such that Titanium o Chromium by sputtering, ion plating or cathodic arc, subsequent electromoulding for increasing thickness so as to bring the jewel to 750 thousandths fineness, and subsequent deposition of precious metal on the opposite face using masking techniques.
Example 5
The type of jewel of this example is constituted by a film of gold on cathedral glass, blown or opalescent.
The technical concept underlying such an example is to exploit the chromaticities and the transparency or opalescence of glass combined with those of low-thickness gold.
The specific realisation technique is the deposition of gold on blown or opalescent cathedral glass substrate, by sputtering, ion plating or cathodic arc, utilising masking techniques.
Example 6
The type of jewel of this example is constituted by a film of gold on plastic substrate even self-sticking.
The technical effect one obtains in this case is that of a flexible end also self-sticking jewel.
The specific realisation technique consists in that the plastic substrate is at first metallised and then coated with a precious metal by sputtering, ion plating or cathodic arc, utilising masking techniques.
Example 7
The type of jewel of this example is constituted by a film of gold on minerals (for example pink quartz, amethyst). The technical concept underlying such a jewel is to exploit for example the sputtering effectuated on row pink quartz, used in the preparation of necklaces. By depositing gold on pink quartz, the impression one obtains is that of a necklace constituted of nuggets.
Moreover, the rough surface of the raw not-dressed quartz show up the reflectivity of the deposited gold, producing a pleasant visual effect.
The specific realisation technique consists in the fact that the minerals are washed with suitable soaps, dried in alcohol and subsequently placed in vacuum, or even with the help of heating-up lamps, afterwards they are coated by cathodic arc or sputtering. In the case of stones to be strung in a necklace, it is advised to insert the substrates inside a little cage with large mesh, but of course smaller than the stones to be coated. The cage is disposed over the deposition source and is rotated during the process. The stones are then coated in a substantially uniform manner.
Example 8 The type of jewel of this example is constituted by a film of white gold on yellow gold; film of yellow gold on white gold and film of non- precious metals on yellow gold.
At present this type of jewel is made by mechanical coating. The technical concept underlying such a jewel realised according to the invention is to apply a film that is extremely sticking to the substrate, obtaining the same effect of the prior art, but with a saving of material and better quality of the product (adhesion of the two layers).
The specific realisation technique consists in the deposition of a film of precious metal on substrates of different colour precious metal by sputtering, ion plating or cathodic arc, utilising masking techniques.
Example 9
The type of jewel of this example is constituted by a film of gold on a substrate that is corroded or electrocorroded with acid treatment both before and after the gold deposition.
The technical concept underlying such a jewel is to exploit the fact that some metals, if treated with suitable chemical etchings used in metallography (for example Tin in HCI, Copper in FeCI3), reveal the grains of their crystalline structure, obtaining a pleasant chromatic effect. This structure can also be coloured with subsequent paint and then on this is deposited gold according to the chosen design.
The specific realisation technique consists in that, after the chemical etching for revealing the crystalline grains, the substrate has to be masked and on it the film of gold has to be deposited. It is also possible a change: on the mirror lapped substrate, a film of gold is deposited that will be fully mirror-like, then on it is deposited and let dry a fotoresist film. Then the whole is plunged in the acid solution, that produces the desired effect of revealing the grains. The solution acts everywhere except under the polymeric film, that is then removed with a jerk, or solubilised in solvents, e.g. acetone.
With the innovative process according to the invention it is therefore possible to produce a great quantity of new jewels having chromatic properties so far unknown in the field, and whose quality is definitely superior to the quality obtained with the traditional technique.
Further, the process according the present invention allow to save material of coating and therefore to make cheaper and accessible a great amount of jewel.
The preferred embodiments have been above described and some modifications of this invention have been suggested, but it should be understood that those skilled in the art can make variations and changes, without so departing from the related scope of protection, as defined by the following claims.

Claims

1. Process for the production of jewels, constituted by a substrate, that is mineral, metallic, glassy or plastic and high-resistant to temperature, whereon is deposited at least a layer of mineral or metallic material, characterised in that it comprises the following subsequent steps:
A. degreasing of the substrate by means of ultrasounds;
B. positioning the substrate on a support or housing inside a vacuum chamber;
C. depositing said at least a material layer, the deposition being made with a PVD technique, in particular a technique selected in the group consisting of: sputtering, ion plating, cathodic arc.
2. Process according to claim 1 , characterised in that, during the deposition, on the substrate is positioned a mask, preferably with thickness of 0,1-0,5 mm, that partially covers the same substrate, in order to produce a predetermined design on the substrate.
3. Process according to claim 2, characterised in that said mask is metallic, preferably in steel.
4. Process according to claim 2, characterised in that said mask is in plastic and self-sticking.
5. Process according to claim 2, characterised in that said mask is obtained by gluing a self-sticking film to the substrate, carving with laser the film according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser, the self-sticking film being subsequently removed.
6. Process according to claim 2, characterised in that said mask is obtained by disposing on the substrate a fotoresist film, carving with laser the film or by photolithography according to a predetermined design, without damaging the substrate, the deposition coating the substrate only in the region eroded by the laser.
7. Process according to claim 1 , characterised in that, after the deposition, is realised a predefined design of the substrate by means a lithographic technique.
8. Process according to claim 1 , characterised in that said support or housing is comprised in a vibrating or rotating samples holder.
9. Process according to any claim 1 to 8, characterised in that said substrate is housed inside of a rotating cage or sifter, the deposition being made from different directions.
10. Process according to any claim 1 to 9, characterised in that said substrate is in microlapped silicon, said at least a material layer being a metal layer, in particular gold, the system metal-silicon being subjected to an annealing, so as to promote the diffusion of the metal in the silicon in order to improve the adhesion thereof.
11. Process according to claim 10, characterised in that the annealing temperatures are comprised between 150 and 400 0C, and the times intervals are comprised between 5 and 300 minutes.
12. Process according to claim 11, characterised in that temperatures are comprised between 180 and 260 0C, and the times intervals are comprised between 10 and 60 minutes.
13. Process according to any claim 1 to 9, characterised in that on the substrate are deposited at least two layers of material, chosen so that they assure a better adhesion of the layers deposited on the support.
14. Process according to claim 13, characterised in that the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 90 and 900 nm.
15. Process according to claim 14, characterised in that the overall thickness of the deposited layers comprised between the substrate and the layer deposited most far-away from this is comprised between 200 and 700 nm.
16. Process according to any claim 13 to 15, characterised in that the layer in contact with the substrate is of carbon.
17. Process according to any claim 13 to 15, characterised in that the layer in contact with the substrate is of a material with high affinity to oxygen.
18. Process according to claim 17, characterised in that the layer in contact with the substrate is of a material selected in the group consisting of Titanium, Vanadium, Hafnium, Tantalum, Niobium, Zirconium e Chromium.
19. Process according to any claim 1 to 18, characterised in that the thickness of said at least a deposited layer is such that it assures a chromatic interaction between this and the substrate.
20. Process according to any claim 1 to 19, characterised in that the layer deposited most far-away from the substrate has a thickness comprised between 100 nm and 2,5 micron.
21. Process according to claim 20, when dependant on claim 19, characterised in that the layer deposited most far-away from the substrate has a thickness comprised between 100 nm and 1 μm.
22. Process according to any claim 1 to 9 and 13 to 21 , characterised in that the substrate is of a material selected in the group consisting of gold, silver, platinum, gold and precious metals alloys.
23. Process according to any claim 13 to 22, when dependent on claim 2, characterised in that on the substrate are subsequently deposited, by means of different masks, layers of red gold, white gold and other metals that yield different chromatic shades.
24. Process according to any claim 1 to 23, characterised in that the substrate is mirror-like on at least a side.
25. Process according to claim 24, characterised in that said substrate is coated with a transparent protective material.
26. Process according to claim 25, characterised in that said transparent protective material is a polyurethanic paint or other hardening lake.
27. Process according to any claim 24 to 26, characterised in that on said substrate is deposited a film of gold, that will be fully mirror-like, subsequently on it a fotoresist film is deposited and let dry, then the whole is plunged in the acid solution, in order to reveal or highlight the grain of the crystalline structure, the solution acting everywhere, except under the polymeric film, which is then removed with jerk or solubilised in solvents.
28. Process according to any claim 24 to 26, when dependent on claim 2, characterised in that one coats the substrate, for example sapphire, on a side with a metallic film, in particular a material selected in a group consisting of white gold, carbon, chromium, niobium and ruthenium, in order to make it mirror-like, and subsequently one coats it on the opposite side with a film of yellow gold by means of masking, in order to have a sandwich constituted as follows: white gold along all the surface - substrate - yellow gold.
29. Process according to any claim 24 to 26, when dependent on claim 2, characterised in that one deposits on the substrate, for example sapphire, yellow gold according to a predetermined design by means of masking, one then deposits on this a layer of a material selected from the group consisting of white gold, carbon, chromium, niobium and ruthenium, according to the sandwich composed as follows: white gold along all the surface - yellow gold according to a predetermined design and deposited by means of masking - sapphire.
30. Process according to claim 24, characterised in that the substrate is a slice of silicon microlapped with optical finishing and mirror appearance on the surface of at least a side.
31. Process according to claim 30, characterised in that the weight of the material deposited on the substrate is increased by means of electroforming with gold on the face of the silicon slice opposite to that interested by the deposition, so as to hardening the jewel and make it of 750 thousandths.
32. Process according to claim 30 or 31 , characterised in that said silicon slice is mounted or stuck in a cage of noble metallic material, so as to harden the jewel.
33. Process according to any claim 1 to 32, characterised in that said substrate is constituted by a sheet of plastic material, in particular
Kapton, metallised on at least a side.
34. Process according to any claim 1 to 32, characterised in that said at least a layer is of one or more materials selected from the group consisting of: onyx, black onyx, mother-of-pearl, glass.
35. Process according to any claim 1 to 34, characterised in that in step A the substrate is at first subjected to ultrasounds in a bath containing alkaline soap dissolved in demineralised water, and subsequently is washed by means of ultrasounds in only demineralised water, or subjected to ultrasounds in an alcohol bath or in subsequent baths of each of the three substances: percloroethylene, acetone and alcohol.
36. Process according to any claim 1 to 35, characterised in that in step C the substrate is bombarded with argon or nitrogen ions by means of ionic gun, in particular a gridless ion gun, scanning with the ions the surface to be coated, by bending the beam or by moving the substrates.
37. Process according to any claim 1 to 35, characterised in that in step C one triggers a low-pressure and low-power radiofrequency glow discharge, confined on the substrates, which cleans the substrate by desorbing as a function of power at least a part of the adsorbates on the surface, or by disintegrating the dust.
38. Process according to any claim 1 to 37, characterised in that in step C the support is electrically connected to ground or at negative potential with respect to the vacuum chamber.
39. Process according to any claim 1 to 38, characterised in that, in step C, the material one intends to deposit is negatively polarised, and gas noble is injected, in particular argon, in the deposition chamber.
40. Process according to any claim 1 to 39, characterised in that filtered or not filtered arc deposition technique is used.
41. Process according to any claim 1 to 39, characterised in that sputtering deposition technique is used with control of induced stresses on said at least a layer in the deposition phase.
42. Process according to claim 41 , characterised in that the control of stresses is effectuated by means of a common d iff radiometric characterisation with Eulerian cradles, correlating the textures of the same film of said at least a layer of material to the deposition parametres.
43. Process according to claim 42, characterised in that the control of stresses is effectuated according to the following steps: C.1 depositing a film of said at least of material on a substrate, in particular sapphire, of thickness comprised between 70 and 130 micron; C.2 if the film turns out to be stressed after the deposition, bending the coated substrate in a concave or convex way on the side of the film, depending on whether the stress induced in the film is compressive or tensive, the bending of the substrate being proportional to the stress in the film.
44. Process according to any claim 1 to 43, characterised in that in step B the vacuum level is comprised between 1e"6 and 1e"3 Pascal.
45. Process according to claim 44, characterised in that said vacuum level is comprised between 1e"5 e Ie"4 Pascal.
46. Process according to any claim 1 to 45, characterised in that the energy of the particles impinging on the substrate that supports the growing film of said at least a material layer is e modulated and controlled by applying a negative polarisation voltage on the substrate, determining in such a way the quantity of impurities englobed in said film and the adhesion of said at least a material layer.
47. Jewel, characterised in that it is produced utilising the process according to any claim 1 to 46.
48. Jewel according to claim 47, characterised in that the substrate is of black onyx, on which a layer of 24 or 18-carat gold is deposited.
49. Jewel according to claim 48, characterised in that the substrate is mirror-like on the side interested by the deposition of gold or even on the opposite side.
50. Jewel according to claim 49, characterised in that said substrate is a transparent material coated with a material selected from the group consisting of: Titanium, Vanadium, Hafnium, Tantalum, Niobium, Zirconium, Chromium, white gold, Platinum, Palladium, and mirror treated before step C.
51. Jewel according to claim 49 or 50, characterised in that said substrate is of microlapped silicon, on which it is deposited an intermediate layer of a material selected from the group consisting of: Titanium, Vanadium, Hafnium, Tantalum, Niobium, Zirconium, Chromium, on which said gold is deposited.
52. Jewel according to claim 51 , characterised in that said substrate is a metal turned at high speed using diamond tools, and is such not to interact with the carbon of the tool, and on this is deposited said gold.
53. Jewel according to claim 52, characterised in that said metal is copper or aluminium.
54. Jewel according to any claim 47 to 53, characterised in that the substrate is self-sticking on a side not interested to the deposition of material, so as to obtain a self-sticking jewel that adheres directly to the skin every time one wishes to wear it.
55. Jewel according to claim 47, characterised in that the substrate is of stone, in particular pink quartz, on which a layer of gold is deposited.
56. Jewel according to claim 47, characterised in that the substrate is of yellow or white gold, whereon is respectively deposited a layer of white or yellow gold.
57. Jewel according to any claim 47 to 56, characterised in that the substrate is coloured with paint.
58. Jewel according to any claim 47 to 57, characterised in that the jewel is protected by an external protective layer of a material selected from the group consisting of silica, amorphous diamond, polyurethanic paints or other polymeric paints.
PCT/IT2006/000387 2005-05-25 2006-05-22 Process for production of jewels WO2006126234A2 (en)

Priority Applications (1)

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EP06756295A EP1888809A2 (en) 2005-05-25 2006-05-22 Process for production of jewels

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM2005A000258 2005-05-25
IT000258A ITRM20050258A1 (en) 2005-05-25 2005-05-25 JEWELERY PRODUCTION PROCEDURE, USING PVD DEPOSITION TECHNIQUES AND METAL OR MINERAL FILM MASKING ON METALLIC, MINERAL, PLASTIC AND SELF-STICK SUBSTRATES.

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WO2006126234A2 true WO2006126234A2 (en) 2006-11-30
WO2006126234A3 WO2006126234A3 (en) 2007-09-20

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CN109881168A (en) * 2019-04-17 2019-06-14 深圳市森泰金属技术有限公司 A kind of preparation method of transparent Anti- tarnishing ceramic membrane

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DE102011002077A1 (en) * 2011-04-15 2012-10-18 Kunststoff-Institut für mittelständische Wirtschaft NRW GmbH (KIMW NRW GmbH) Producing plastic workpiece with metallic coating, by coating surface of workpiece with coating withstanding subsequent coating process, and removing coat in those regions of workpiece surface
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CN103978207B (en) * 2014-05-14 2015-10-28 陕西科技大学 A kind of increasing material manufacture method of selective applying glue
WO2016058593A1 (en) * 2014-10-13 2016-04-21 Lpkf Laser & Electronics Ag Method for producing a molded item and a covering layer for use with the method
CN108249741A (en) * 2018-03-16 2018-07-06 郭言光 Full-automatic glass product blows tire machine and blows tire method
CN108249741B (en) * 2018-03-16 2023-11-10 济南晶焱自动化科技有限公司 Full-automatic glass product blowing machine and blowing method
CN109881168A (en) * 2019-04-17 2019-06-14 深圳市森泰金属技术有限公司 A kind of preparation method of transparent Anti- tarnishing ceramic membrane

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