RU2761391C1 - Methods for applying metal coatings made of titanium nitride to glass products - Google Patents

Abstract

FIELD: glass industry.

SUBSTANCE: group of inventions relates to the field of decoration of glass and products made from it, namely to methods of applying titanium nitride to glass products, and can be used in the glass industry. Air is pumped out of the spraying chamber to a vacuum of 0.02 Pa and the rotation of the basket with glass products is started at a basket rotation speed of 2 rpm. Then argon gas is supplied at a pressure of 0.06 Pa and a source of ion cleaning of the surface of glass products is turned on at the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes, while cleaning the surface layer of glass products is carried out by bombarding in high vacuum with argon ions with an energy of 100-100000 eV. Then, magnetron sputtering sources with installed targets made of titanium VT1-0 are turned on and an opaque reflective layer of titanium is applied to glass products at a pressure of 0.05 Pa of argon gas. After that, an arc evaporator with an installed target made of titanium VT1-0 is turned on, reactive nitrogen gas is injected into the chamber with a pressure from 0.12 to 0.2 Pa and at a current of inverter sources of 130-150A, titanium nitride is applied to glass products for 15-20 minutes. In another embodiment of the method, a magnetron sputtering source with installed targets made of titanium VT1-0 is included and a transparent reflective layer of titanium is applied to glass products at a pressure of 0.05 Pa of argon gas. Then an arc evaporator is turned on with a VT1-0 titanium target installed, reactive nitrogen gas is injected into the chamber with a pressure of 0.1 Pa and at an inverter source current of 130-150, a layer of titanium nitride is applied to glass products for 2 minutes.

EFFECT: increase in the strength of the decorative coating is provided.

2 cl

Description

The group of inventions relates to the field of decorating glass and glass products and can be used in the glass industry at the technological stage of applying decorative coatings to glass household goods (glasses, wine glasses, glasses, glasses, vases, mugs, plates, etc.) [IPC C23C14 / 00, C23C16 / 00, C23C18 / 18].

From the prior art there is known a METHOD FOR PREPARING TITANIUM COATINGS [WO 0022187 (A1), 2000-04-20] containing at least one layer selected from layers consisting of titanium nitride TiN, layers consisting of titanium carbonitride TiCN, layers consisting titanium nitride and another metal M (Ti, M) N or Til-xMxN and layers consisting of titanium carbonitride and another metal M (Ti, M) NC or Til-xMxNC /, in which the specified coating is applied continuously and in one one operation by plasma chemical vapor deposition (PACVD) from a gas mixture containing a reducing gas, hydrogen, titanium chloride.

The disadvantage of the analogue is the insufficient strength of the coating

Also known from the prior art is a METHOD FOR OBTAINING A NANOFILM OF TITANIUM NITRIDE ON THE SURFACE OF A SUBSTRATE, A SUBSTRATE WITH A FILM AND THEIR APPLICATION [CN108546929 (A), 2018-09-18], comprising the steps of: transporting the substrate into the reaction chamber through the loading lock chamber, the reaction the chamber is evacuated to vacuum; an inert gas is passed into the reaction chamber and a coating is applied using ammonia plasma and a gaseous source of titanium, after which several cycles of flushing the reaction chamber with gas are carried out, the temperature of the reaction chamber is maintained at 150-220 ° C, and the reaction of deposition of an atomic layer of titanium nitride with plasma amplification is performed to obtain a substrate with a titanium nitride nanofilm on the surface.

The disadvantage of this analogue is the need to maintain a high temperature for the deposition of the atomic layer of titanium.

The closest in technical essence is the METHOD FOR APPLICATION OF PROTECTIVE-DECORATIVE COATINGS [RU2039844C1, publ. 07/20/1995], mainly coatings based on oxides of titanium, chromium, tungsten, zirconium, hafnium or vanadium, as well as interstitial phases selected from a number of carbides, nitrides and carbonitrides of these metals, including coating the surface of a metallic or non-metallic material by sputtering targets from active metals, their alloys or composite materials by ion bombardment in a glow discharge in a mixture of inert and reaction gases with their separate supply to the reaction volume, previously filled with an inert gas to a pressure of (3.0-3.5) · 10-3 mm Hg. followed by deposition of sprayed particles on the surface of the product, characterized in that the reaction gas is supplied to the near-surface zone of the product, heated to 300 360 ° C until the pressure in the reaction volume is (6.0-10) · 10-3 mm Hg. the spraying time is controlled within the limits necessary to obtain a decorative effect of a given intensity and gamut of color shades, and water vapor, carbon dioxide, air or a mixture of oxygen-containing gases are used as the reaction gas.

The main technical problem of the prototype is the need to heat products to a temperature of 300-360 ° C before applying coatings on them, which complicates the coating technology, limits the use of materials for applying coatings on them with no melting point, and also increases the time required for the technological operation on application for the time of heating and cooling of the product.

The objective of the invention is to eliminate the disadvantages of the prototype.

The technical result of the invention is to increase the strength of the decorative coating.

The specified technical result is achieved due to the fact that the method of applying titanium nitride to glass products, characterized in that air is pumped out of the spraying chamber to a vacuum of 0.02 Pa and the basket with glass products is rotated at a basket rotation speed of 2 rpm, then argon gas at a pressure of 0.06 Pa and include a source of ionic cleaning of the surface of glass products with the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes, while cleaning the surface layer of glass products by bombardment in high vacuum with argon ions with an energy of 100 - 100000 eV, which sputter the surface layer with the removal of adsorbed atoms and oxides, then turn on magnetron sputtering sources with VT1-0 titanium targets installed and at an argon gas pressure of 0.05 Pa, an opaque reflective layer is applied to glass products for 20 -25 minutes with the following parameters: current sources 9-10 A, voltage e 380-400 V, after which the arc evaporator with an installed VT1-0 titanium target is turned on, a reactive nitrogen gas with a pressure of 0.12 to 0.2 Pa is admitted into the chamber, and at a current of inverter sources of 130-150 A, glass products are applied titanium nitride for 15-20 minutes.

The specified technical result is achieved due to the fact that the method of applying titanium nitride to glass products, characterized in that air is pumped out of the spraying chamber to a vacuum of 0.02 Pa and the basket with glass products is rotated at a basket rotation speed of 2 rpm, then argon gas at a pressure of 0.06 Pa and include a source of ionic cleaning of the surface of glass products with the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes, while cleaning the surface layer of glass products by bombardment in high vacuum with argon ions with an energy of 100 - 100000 eV, which sputter the surface layer with the removal of adsorbed atoms and oxides, then turn on the magnetron sputtering source with VT1-0 titanium targets installed and at an argon gas pressure of 0.05 Pa, a transparent reflective layer is applied to glass products for 4 minutes with the following parameters: current sources 9-10 A, nap voltage 380-400 V, then turn on the arc evaporator with an installed VT1-0 titanium target, a reactive nitrogen gas with a pressure of 0.1 Pa is admitted into the chamber, and at a current of inverter sources of 130-150 A, a layer of titanium nitride is applied to glass products for 2 minutes.

Implementation of the invention.

Initially, the incoming inspection of high-quality utensils is carried out for rejection of products due to chips, violation of geometry, and battle. Further, the products go to the engraving workshop, where the engraving pattern is applied in an automated way on programmed machines. The engraved utensils are delivered to the washing workshop, where the products go through the stages of washing, rinsing and drying in a sectional tunnel-type machine, for example, MPS-1600, for which water is prepared using the installed OSMOS purification system.

The utensils that have passed the surface cleaning go to the masking section, where on the outer surface of each product is applied in manual mode, using winding machines, a masked layer, 2-3 cm wide, made of polyethylene tape, which provides a clear boundary between the surface areas of the product subject to and not subject to decorating by spraying. The rest of the outer surface of the products, which is not subject to decorating by spraying, is masked with plastic molds made individually for each product range. The prepared dishes are delivered to the spraying shop, where they are installed in cylindrical stainless steel baskets made according to the planetary rotation scheme, while the baskets can be made in various versions and contain from one to eight carriers in each, depending on the size of the products. The assembled baskets, in the amount of 10 pieces inclusive, are installed in the seats of the carousel of the spray chamber of the vacuum installation.

For spraying, a VTT-1200-V2-IS1_ARC1 vacuum spraying unit is used, which includes: a pumping station, a sputtering chamber, a control rack, a rack of inverter power supplies for an ion cleaning source and two magnetrons, a control unit for three inverters of an arc evaporator.

The pumping station includes: oil rotary vane pump HENA 300 from Pfeiffer, Roots OKTA 500 rotary pump from Pfeiffer, steam-oil diffusion pump NVDM-630. Working fluids: for the HENA 300 pump, vacuum oil Pfeiffer 3, for НВДМ-630 vacuum oil VM-1С.

The spraying chamber contains: a carousel with planetary rotation of the substrate, with the ability to control the rotation speed of the carousel, a slot-type ion cleaning source, two planar-type magnetrons, and a planar-type arc evaporator. The unit provides control of the technological process by means of a graphical user interface, both in automatic and manual modes.

Consider the technology of sputtering titanium nitride.

The purpose of titanium nitride sputtering is to obtain a decorative gold-colored coating with a gradation: light gold, gold, dark gold, as well as to obtain a "shining graphite" coating, which is a translucent mirror layer with a black gloss.

Spraying technology of titanium nitride for the formation of a coating of the "Gold" type.

The baskets loaded with masked dishes are loaded into the spraying chamber. The chamber is evacuated to a vacuum of 0.02 Pa, the rotation of the carousel is started at a speed of 2 rpm, the argon gas supply is turned on in the pressure stabilization mode of 0.06 Pa, and the source of ion cleaning of the substrate surface is turned on with the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes. The bombardment of the glass surface in high vacuum with argon ions with an energy of 10e2-10e5 eV sprays the surface layer, thereby removing the adsorbed atoms and oxides of the film and creating conditions for increasing the adhesion of the sprayed coating. Then, the sources of magnetron sputtering with installed VT1-0 titanium targets are switched on and, when the pressure of the admitted argon gas is stabilized, 0.05 Pa, the most opaque reflective metal layer is applied for 20-25 minutes with the parameters: current of sources 9-10 A, voltage 380- 400 V. Then the arc evaporator is turned on with an installed VT1-0 titanium target, a reactive nitrogen gas is admitted into the chamber with pressure stabilization from 0.12 to 0.2 Pa, and at a current of 130-150 A inverter sources, a titanium nitride layer is applied for 15-20 minutes. The thickness of the applied titanium nitride film depends on the ratio of the currents of the inverter power supplies of the evaporator and the deposition time. When the spraying time is less than the specified, the layer thickness decreases, which does not provide the required decorative quality, with an increase in the spraying time, the layer thickness increases, which can worsen the adhesion of titanium nitride. The shades of gold are dependent on the pressure of the nitrogen reactive gas supplied, and range from light gold to dark gold at the pressures indicated above. At the end of the spraying process, atmospheric pressure is admitted to the spraying chamber, the chamber is opened and the baskets are unloaded, the carriers with dishes are disassembled, the masking forms and plastic tape are removed. Finished products are sent to the packaging area.

Spraying technology of titanium nitride for the formation of a "shiny graphite" coating.

The baskets loaded with masked dishes are loaded into the spraying chamber. Air is pumped out of the chamber to a vacuum of 0.02 Pa, the rotation of the carousel is started at a speed of 2 rpm, the argon gas supply is turned on in the pressure stabilization mode of 0.06 Pa, and the source of ionic cleaning of the substrate surface is turned on with the following parameters: anode voltage 3 kV, current anode 200 mA, cleaning time 20 minutes. Then, magnetron sputtering sources with VT1-0 titanium targets installed are turned on and, when the pressure of the admitted argon gas is stabilized at 0.05 Pa, a transparent reflective metal layer is applied for 4 minutes with the following parameters: source current 9-10 A, voltage 380-400 V. Then the arc evaporator is turned on with the VT1-0 titanium target installed, the reactive nitrogen gas is admitted into the chamber with stabilization at a pressure of 0.1 Pa, and at a current of 130-150A inverter sources, a titanium nitride layer is applied for 2 minutes. This results in a transparent mirror finish with a black tint. By changing the time of applying a metal layer by magnetrons, the transparency of the coating can be changed. The time for applying a titanium nitride layer with an arc evaporator is limited to the given value. Increasing the spray time results in a golden hue.

The specified technical result of the invention is achieved due to uniform ionic cleaning of the substrate surface of the glass product from adsorbed atoms and oxides of the film by rotating the carousel at a speed of 2 rpm and bombarding the glass surface in high vacuum with argon ions with an energy of 100-100000 eV in a single vacuum cycle with application coating layers, in addition, the technical result is achieved by intensifying the process by applying metal with an arc evaporator at the maximum possible speed; by simplifying the technology, in contrast to magnetron sputtering, by eliminating the need to control and maintain at a certain level the percentage of argon and nitrogen (oxygen) in the gas mixture during the formation of the coating.

Claims (2)

1. A method of applying titanium nitride to glass products, characterized in that air is pumped out of the spraying chamber to a vacuum of 0.02 Pa and a basket with glass products is rotated at a basket rotation speed of 2 rpm, then argon gas is supplied at a pressure of 0.06 Pa and include a source of ionic cleaning of the surface of glass products with the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes, while cleaning the surface layer of glass products by bombardment in high vacuum with argon ions with an energy of 100-100000 eV, which spray the surface layer with the removal of adsorbed atoms and oxides, then turn on magnetron sputtering sources with VT1-0 titanium targets installed and at an argon gas pressure of 0.05 Pa an opaque reflective layer is applied to glass products for 20-25 minutes with the following parameters: current sources 9-10 A, voltage 380-400 V, after which they turn on the arc evaporator with the installation With a VT1-0 titanium target, a reactive nitrogen gas with a pressure of 0.12 to 0.2 Pa is admitted into the chamber, and titanium nitride is applied to glass products for 15-20 minutes at a current of inverter sources of 130-150 A. 2. A method of applying titanium nitride to glass products, characterized in that air is pumped out of the spraying chamber to a vacuum of 0.02 Pa and the basket with glass products is rotated at a basket rotation speed of 2 rpm, then argon gas is supplied at a pressure of 0.06 Pa and include a source of ionic cleaning of the surface of glass products with the following parameters: anode voltage 3 kV, anode current 200 mA, cleaning time 20 minutes, while cleaning the surface layer of glass products by bombardment in high vacuum with argon ions with an energy of 100-100000 eV, which spray the surface layer with the removal of adsorbed atoms and oxides, then turn on the magnetron sputtering source with VT1-0 titanium targets installed and at a pressure of an admitted argon gas of 0.05 Pa, a transparent reflective layer is applied to glass products for 4 minutes with the following parameters: current sources 9-10 A, voltage 380-400 V, then turn on the arc evaporator with With a VT1-0 titanium target, a reactive nitrogen gas with a pressure of 0.1 Pa is admitted into the chamber, and at a current of inverter sources of 130-150 A, a layer of titanium nitride is applied to glass products for 2 minutes.