US3743777A - Process for hardening coatings with lasers emitting infra-red radiation - Google Patents

Process for hardening coatings with lasers emitting infra-red radiation Download PDF

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Publication number
US3743777A
US3743777A US00053976A US3743777DA US3743777A US 3743777 A US3743777 A US 3743777A US 00053976 A US00053976 A US 00053976A US 3743777D A US3743777D A US 3743777DA US 3743777 A US3743777 A US 3743777A
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United States
Prior art keywords
scanning
laser beam
infra
laser
radiation
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Expired - Lifetime
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US00053976A
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English (en)
Inventor
H Hanus
F Aussenegg
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Allnex Austria GmbH
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Vianova Resins AG
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Priority claimed from AT691469A external-priority patent/AT295000B/de
Priority claimed from AT338770A external-priority patent/AT303927B/de
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • ABSTRACT This invention is directed to a process for hardening or curing conventional protective coatings applied to :1 suitable substrate utilizing lasers emitting infra-red ra diation with a wave length of from 1-1 00,11 and preferably 3-25 The coatings are hardened within a few minutes of treatment without discoloration normally associated with short curing durations.
  • the present invention is concerned with the curing of protective coatings. More particularly, it is concerned with a process for hardening coatings with lasers emitting infra-red radiation. Hardening or curing as used herein embraces the physical and/or chemical formation of films of protective coatings on substrates from a solution or dispersion of a paint, varnish or the like. Laser (light amplification by stimulated emission of radiation) is a source of light or radiation emitting monofrequency radiation (monocolored light) in optimally parallel form.
  • the heat sources utilized in hardening coatings can be convection ovens or thermical infra-red radiators.
  • the heat transport by convection is effected in most cases by the air which is heated with heating rods or the like, and which will transfer the heat to the object by natural or artificial flow.
  • lnfra-red radiators are advantageous over convection ovens in that a part of the heat energy is directly absorbed by the coating and not by the air. From the start of the curing,the coating will harden not only on the surface as is the case in convection ovens but throughout the coating. Solvents and/or eventual decomposition products are released completely, i.e. evaporate or volatilize. Deficiencies of the surface of the cured film are,therefore,minimized.
  • the light infra-red radiators emit radiation of a wave length of from 0.5-4.0p with a maximum emission at a wave length of l-Zg.
  • Such radiators have disadvantages in that the solvents and decomposition products released during the hardening are highly absorptive of the short infra-red wave lengths of the spectrum, and thus the major portion of theenergy is lost in the heating of the ambient, and the advantages of hardening by infra-red radiation uniform hardening of the entire coat without deficiencies of the surface, etc., are realized only to a minor extent.
  • the absorption of the coating in the near infra-red region is dependent upon the binding agent and the pigments, so that different color shades will not harden uniformly.
  • the darlt infrared radiators emit infra-red radiation of longer wave length with maximum wave lengths between 3-5 Solvents and decomposition products absorb these longer waves to a minor extent.
  • the absorption of the longer waves by the coating is substantially independent from the type of the binding agent and the pigments.
  • the power per surface unit of the dark radiator is much lower on account of the lower temperature and thus radiators with greater surfaces are required. Since the radiation power emitted by a plane radiator cannot be concentrated at random, the radiation flux density obtainable with darlc infrared radiators is relatively small. The hardening times are therefore considerably longer than with light infra-red radiators.
  • the hardening time required with dark infra-red radiators can be shortened considerably.
  • the essence of the invention is the fact that coatings are hardened with laser emitting infra-red monofrequency and parallel radiation with a small beam diameter.
  • irradiation with great density and high local temperatures in the irradiated coating and the substrate, respectively, are possible, which results in very short hardening times.
  • the hardened films have no deficiencies. Despite the high temperatures the films are not discolored due to the short hardening times.
  • the invention is characterized in that coatings based on condensation resins or polymerization resins are hardened with lasers emitting infra-red radiation with a wave length of from 1400p, preferably 3"25/L-
  • the radiation emitted by lasers within the range selected according to this invention will be absorbed by the coating, independent from the type of binding agent, or pigments, etc.
  • laser hardening combines the advantage of high density (higher than that of light infra-red radiators) with the advantage of an infrared emission frequency which is, in comparison to dark infra-red radiators, still more distant from the visible range.
  • the hardening times required with this source of infra-red radiation lie between 30 seconds and a few minutes.
  • All chemical and/or physical film-forming coating materials can be hardened with lasers, e.g. polycondensation resins, polymerization resins, sinterable synthetic resin powders, polymers, etc., which are optionally present as solutions and can form films by releasing the solvents.
  • the coatings can be hardened on metals, stone materials, glass, wood, rubber, synthetic materials, etc.
  • the hardening process of the invention is particularly suitable for painting or coating small parts, e.g. parts of precision instruments, and also for the refinishing of coatings, since the heating by radiation can be localized very exactly.
  • the laser beam can be diverged by optical elements such as mirrors, lenses, etc.
  • optical elements such as mirrors, lenses, etc.
  • relatively simple means e.g. a motile mirror
  • coatings on large objects can be hardened.
  • the high power CO2 lasers available up to now, however, have a far field pattern with multimode structure, i.e. the distribution of the radiation intensity is not uniform within the beam diameter. Furthermore, the distribution varies during the action.
  • optical measures alone such as beam diversion, beam division, combination, etc., it is not possible to obtain an optimal uniformity of the irradiation of an area.
  • the laser beam is diverged in two dimensions with a concave mirror or with a focusing lens.
  • the direction of the beam is deflected by suitable movement of the optical elements.
  • the movement can be an eccentric rotation or a periodic swinging. In the latter case, in order to cause a uniform irradiation, the periodic swinging must be carried out with constant velocity (with the exception of the turning points) and the deflection angle should be a linear function of time.
  • the deflection of the beam can also be effected by a moving plane mirror.
  • the laser beam is diverged in one dimension by a cylindrical concave mirror or by a cylindrical focusing or cylindrical diverging lens (diversion to a strip).
  • a swinging movement linear function of time as above
  • the beam is periodically deflected vertically. Also in this case the deflection may be effected with an additional plane mirror.
  • the laser beam is not diverged but is periodically deflected in two dimensions by means of one or two plane mirrors.
  • the duration of the periods may be equal or different.
  • the movement in one of the two dimensions can be without return, i.e. the area is scanned periodically only in one direction, and only once in the other direction (linear scanning).
  • Method (a) With method (a) the inhomogeneous intensity of the laser beam is compensated in restricted areas only. The decreasing intensity towards the edges of the beam cannot be compensated and will result in a relatively broad marginal area getting reduced irradiation intensity.
  • Methods (b) and (e) have an advantage over (a) in that the exposure of the area is dependent with method (b) partly and with method (c) exclusively upon the relative movement between laser beam and object and can thus be controlled better. It is evident that in all cases the movements of beam and/or object can be combined. For hardening coatings on objects of complicated shape and/or with other than plane surfaces, the elements and movements are varied in known manner so that a uniform irradiation is obtained.
  • the following Examples are being set forth to illustrate the invention. However, they are not to be construed as limiting its scope.
  • EXAMPLE 1 a A paint is applied to a steel panel 0.9 mm thick with a film applying blade to give a wet film thickness of 0.150 mm. The film is allowed to dry for 5 minutes at room temperature and is then hardened with a C0, laser at a wave length of 10.6 a maximum power of 100 watt, and a beam diameter of 1,5 cm.
  • the Paint Composition is as follows:
  • EXAMPLES 2-6 Analogous to Example 1 five different paints were applied to a steel panel and hardened. The results are shown in Table II and are compared with the stoving schedules required in convection ovens to obtain equal film hardness.
  • Paint (a) comprises:
  • Paint (0) comprises:
  • the laser beam is diverged by means of a convex mirror of 1 1.8 cm radius.
  • the diverged beam is deflected to the predried film over a periodically swinging plane mirror. If the plane mirror is not moved, the beam will reach the panel such that an elliptic area with only the semi-axis of 2 cm and 4 cm being hardened. lBy swinging the plane mirror an area of 8 X 10 cm is hardened. In this arrangement this means a deflection of the axis of the diverged beam by about 6.
  • the deflection angle should be a linear function of time.
  • the swinging has a frequency of about 1 lHlertz.
  • the pigmented paint consists of 80 parts by weight of a commonly available stoving alkyd resin based on dehydrated castor oil fatty acid, about 34 percent fatty acid content, 60 percent in xylol/butanol, and 20 p.b.w. of an available non-plasticized melamineformaldehyde-resin, partially etherified with butanol, as binding agent.
  • Pigmentation total binding agent (solid resin) Ti (Rutile type) 1 1.
  • Laser C0 laser, type LG 1106, Siemens A.G., Kunststoff, power 100 watt, beam diameter 1.5 cm.
  • Laser Powermeter Model 201 Broad Band CW Laser Powermeter of Coherent Radiation Laboratories, Palo Alto, Calif., USA. a
  • EXAMPLE 8 A paint coating according to Example 1 is hardened with the following laser arrangement: The laser beam is diverged by means of a cylindrical mirror with a radius of 14.7 cm. The beam is directed to the paint tilm. The cylindrical mirror is swung periodically. 1f the mirror is not moved, the beam will harden an area of X 1 cm. This area is increased to 5 X 9.5 cm by swinging the mirror. The axis of the beam in this arrangement is deflected by about 12. The swinging has a frequency of about 0.25 ll-lertz. The deflection angle should be a linear function of time. The results are as follows:
  • the pigmented paint of Example 1 is hardened with the following laser arrangement.
  • the coherent laser beam is directed to the dried film over a periodically swinging plane mirror.
  • the coated object is moved forward vertically to the plane of the scanning laser beam.
  • the scanning breadth is 9 cm, which corresponds to a deflection of the axis of the laser beam of about 16.
  • the deflection angle should be a linear function of time.
  • the swinging mirror has a frequency of about 0.25 l-lertz.
  • the feed to the scanning beam is 0.3 0.5 mm/sec.
  • the method of forming a protective coating on a substrate comprising the steps of 1. providing a substrate coated with a coating composition in the unhardened state but which is capable of hardening to a thermoset state when exposed to infra-red radiation;
  • the infra-red laser radiation has a wavelength of from about 3 to 25 10.
  • the coating being hardened is a member of a group consisting of polycondensation resins, polymerization resins, sinterable synthetic resin powders,

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
US00053976A 1969-07-17 1970-07-10 Process for hardening coatings with lasers emitting infra-red radiation Expired - Lifetime US3743777A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT691469A AT295000B (de) 1969-07-17 1969-07-17 Verfahren zur Härtung von Anstrichstoffen und Überzügen auf Basis von Kondensations- und Polymerisationsharzen mit Infrarot-Strahlen
AT338770A AT303927B (de) 1970-04-14 1970-04-14 Verfahren zur Härtung von Anstichstoffen und Überzügen mittels von einem Laser emittierter Infrarot-Strahlung

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US3743777A true US3743777A (en) 1973-07-03

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US (1) US3743777A (xx)
BE (1) BE752919A (xx)
CA (1) CA928170A (xx)
CH (1) CH519999A (xx)
CS (1) CS151556B2 (xx)
DE (1) DE2025122C3 (xx)
ES (1) ES381303A1 (xx)
FR (1) FR2055282A5 (xx)
GB (1) GB1264723A (xx)
NL (1) NL7010550A (xx)
RO (1) RO56296A (xx)
SE (1) SE364906B (xx)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3848104A (en) * 1973-04-09 1974-11-12 Avco Everett Res Lab Inc Apparatus for heat treating a surface
US4009364A (en) * 1973-03-28 1977-02-22 Vianova-Kunstharz, A.G. Curing of protective coatings with IRASER beams
US4015100A (en) * 1974-01-07 1977-03-29 Avco Everett Research Laboratory, Inc. Surface modification
US4081572A (en) * 1977-02-16 1978-03-28 Xerox Corporation Preparation of hydrophilic lithographic printing masters
US4135077A (en) * 1976-09-16 1979-01-16 Wills Kendall S Laser bread browning apparatus
US4167669A (en) * 1971-09-09 1979-09-11 Xenon Corporation Apparatus for rapid curing of resinous materials and method
DE3037168A1 (de) 1979-10-02 1981-04-23 Nippon Electric Co., Ltd., Tokyo Magnetischer aufzeichnungstraeger mit einer schutzschicht, sowie verfahren zu dessen herstellung mittels laserstrahlen
DE3050791C2 (de) * 1979-10-02 1984-10-31 Nippon Electric Co., Ltd., Tokio/Tokyo Verfahren zum gleichzeitigen Herstellen von zwei magnetischen Aufzeichnungstr{gern
US4960611A (en) * 1987-09-30 1990-10-02 Kansai Paint Company, Limited Method of remedying coating
US4987044A (en) * 1989-05-31 1991-01-22 E. I. Du Pont De Nemours And Company Method and apparatus for maintaining desired exposure levels
US5014207A (en) * 1989-04-21 1991-05-07 E. I. Du Pont De Nemours And Company Solid imaging system
US5484980A (en) * 1993-02-26 1996-01-16 General Electric Company Apparatus and method for smoothing and densifying a coating on a workpiece
DE4443129A1 (de) * 1994-12-03 1996-06-05 Jet Laser Systeme Ges Fuer Obe Verfahren zum Beschichten eines Trägermaterials
US5607730A (en) * 1995-09-11 1997-03-04 Clover Industries, Inc. Method and apparatus for laser coating
US6025037A (en) * 1994-04-25 2000-02-15 U.S. Philips Corporation Method of curing a film
WO2012114038A1 (fr) * 2011-02-25 2012-08-30 Saint-Gobain Glass France Traitement thermique de revêtement par laser
WO2016003301A1 (en) * 2014-07-04 2016-01-07 Politechnika Wrocławska Method for preparing of thin and ultrathin polymer films on solid substrates
WO2020099729A1 (fr) * 2018-11-14 2020-05-22 Saint-Gobain Glass France Procede de gravure selective d'une couche ou d'un empilement de couches sur substrat verrier
EP3799964A1 (fr) * 2019-10-02 2021-04-07 ETA SA Manufacture Horlogère Suisse Procdede de fabrication d'une piece mecanique epilamee
US12099330B2 (en) * 2019-10-02 2024-09-24 Eta Sa Manufacture Horlogère Suisse Method for manufacturing an epilame mechanical part

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4271347A (en) * 1978-10-18 1981-06-02 The United States Of America As Represented By The Secretary Of The Treasury Method and apparatus for accelerating chemical reactions using a spread beam deflector with single or multiple reflectors
LU84911A1 (fr) * 1983-07-14 1985-04-17 Cockerill Sambre Sa Procede et installation de cuisson d'un revetement organique applique sur un support
DE4323654C2 (de) * 1993-07-15 1995-04-20 Ver Glaswerke Gmbh Verfahren zur Herstellung einer wenigstens eine Schicht aus einem Metalloxid vom n-Halbleitertyp aufweisenden beschichteten Glasscheibe
DE19831781A1 (de) * 1998-07-15 2000-01-27 Industrieservis Ges Fuer Innov Verfahren zur Pulverlackierung
GB2452545A (en) * 2007-09-07 2009-03-11 Fira Internat Ltd Lignocellulose coated with laser fused powder

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Publication number Priority date Publication date Assignee Title
US2498339A (en) * 1947-09-11 1950-02-21 William J Miskella Combination paint booth and baking oven
US2820131A (en) * 1951-08-01 1958-01-14 Sprague Electric Co Curing oven
US3305666A (en) * 1963-08-28 1967-02-21 Zaromb Solomon Methods and apparatus for treating conductive surfaces
US3364087A (en) * 1964-04-27 1968-01-16 Varian Associates Method of using laser to coat or etch substrate
US3392045A (en) * 1966-01-17 1968-07-09 Gen Electric Epoxidized polyolefin-ethylene polymer compositions and laminates therefrom
US3396401A (en) * 1966-10-20 1968-08-06 Kenneth K. Nonomura Apparatus and method for the marking of intelligence on a record medium
US3398016A (en) * 1964-07-10 1968-08-20 Du Pont Coating and drying thermally sensitive thermoplastic film
US3409460A (en) * 1966-04-08 1968-11-05 Itt Rayonier Inc Emulsion coating of cellulosic films
US3410203A (en) * 1967-02-01 1968-11-12 Rca Corp Non-impact printer employing laser beam and holographic images
US3506779A (en) * 1967-04-03 1970-04-14 Bell Telephone Labor Inc Laser beam typesetter

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Publication number Priority date Publication date Assignee Title
US2498339A (en) * 1947-09-11 1950-02-21 William J Miskella Combination paint booth and baking oven
US2820131A (en) * 1951-08-01 1958-01-14 Sprague Electric Co Curing oven
US3305666A (en) * 1963-08-28 1967-02-21 Zaromb Solomon Methods and apparatus for treating conductive surfaces
US3364087A (en) * 1964-04-27 1968-01-16 Varian Associates Method of using laser to coat or etch substrate
US3398016A (en) * 1964-07-10 1968-08-20 Du Pont Coating and drying thermally sensitive thermoplastic film
US3392045A (en) * 1966-01-17 1968-07-09 Gen Electric Epoxidized polyolefin-ethylene polymer compositions and laminates therefrom
US3409460A (en) * 1966-04-08 1968-11-05 Itt Rayonier Inc Emulsion coating of cellulosic films
US3396401A (en) * 1966-10-20 1968-08-06 Kenneth K. Nonomura Apparatus and method for the marking of intelligence on a record medium
US3410203A (en) * 1967-02-01 1968-11-12 Rca Corp Non-impact printer employing laser beam and holographic images
US3506779A (en) * 1967-04-03 1970-04-14 Bell Telephone Labor Inc Laser beam typesetter

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* Cited by examiner, † Cited by third party
Title
AGA Laboratories Research Bulletin 92, November 1962, pp. 32 47 *
Laser Application, IEEE Spectrum, May 1968, pp. 82 92 *
Practical Uses of Lasers Science Journal, June 1966, pp. 32 43 *

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167669A (en) * 1971-09-09 1979-09-11 Xenon Corporation Apparatus for rapid curing of resinous materials and method
US4009364A (en) * 1973-03-28 1977-02-22 Vianova-Kunstharz, A.G. Curing of protective coatings with IRASER beams
US3848104A (en) * 1973-04-09 1974-11-12 Avco Everett Res Lab Inc Apparatus for heat treating a surface
US4015100A (en) * 1974-01-07 1977-03-29 Avco Everett Research Laboratory, Inc. Surface modification
US4135077A (en) * 1976-09-16 1979-01-16 Wills Kendall S Laser bread browning apparatus
US4081572A (en) * 1977-02-16 1978-03-28 Xerox Corporation Preparation of hydrophilic lithographic printing masters
DE3037168A1 (de) 1979-10-02 1981-04-23 Nippon Electric Co., Ltd., Tokyo Magnetischer aufzeichnungstraeger mit einer schutzschicht, sowie verfahren zu dessen herstellung mittels laserstrahlen
US4380558A (en) * 1979-10-02 1983-04-19 Nippon Electric Co., Ltd. Process for manufacturing a protective polysilicate layer of a record member by a laser beam and a magnetic record member suitably manufactured thereby
DE3050791C2 (de) * 1979-10-02 1984-10-31 Nippon Electric Co., Ltd., Tokio/Tokyo Verfahren zum gleichzeitigen Herstellen von zwei magnetischen Aufzeichnungstr{gern
US4960611A (en) * 1987-09-30 1990-10-02 Kansai Paint Company, Limited Method of remedying coating
US5014207A (en) * 1989-04-21 1991-05-07 E. I. Du Pont De Nemours And Company Solid imaging system
US4987044A (en) * 1989-05-31 1991-01-22 E. I. Du Pont De Nemours And Company Method and apparatus for maintaining desired exposure levels
US5484980A (en) * 1993-02-26 1996-01-16 General Electric Company Apparatus and method for smoothing and densifying a coating on a workpiece
US6025037A (en) * 1994-04-25 2000-02-15 U.S. Philips Corporation Method of curing a film
DE4443129C2 (de) * 1994-12-03 2000-05-18 Jet Laser Systeme Ges Fuer Obe Verfahren zum Beschichten eines Trägermaterials
DE4443129A1 (de) * 1994-12-03 1996-06-05 Jet Laser Systeme Ges Fuer Obe Verfahren zum Beschichten eines Trägermaterials
US5607730A (en) * 1995-09-11 1997-03-04 Clover Industries, Inc. Method and apparatus for laser coating
EA027409B1 (ru) * 2011-02-25 2017-07-31 Сэн-Гобэн Гласс Франс Термическая обработка покрытия лазером
FR2971960A1 (fr) * 2011-02-25 2012-08-31 Saint Gobain Traitement thermique de revetement par laser
CN103379980A (zh) * 2011-02-25 2013-10-30 法国圣戈班玻璃厂 激光涂层的热处理
US20140059878A1 (en) * 2011-02-25 2014-03-06 Saint-Gobain Glass France Heat treatment of a laser coating
JP2014511268A (ja) * 2011-02-25 2014-05-15 サン−ゴバン グラス フランス レーザーコーティングの熱処理
AU2012220431B2 (en) * 2011-02-25 2015-11-26 Saint-Gobain Glass France Heat treatment of a laser coating
CN103379980B (zh) * 2011-02-25 2016-08-10 法国圣戈班玻璃厂 激光涂层的热处理
WO2012114038A1 (fr) * 2011-02-25 2012-08-30 Saint-Gobain Glass France Traitement thermique de revêtement par laser
WO2016003301A1 (en) * 2014-07-04 2016-01-07 Politechnika Wrocławska Method for preparing of thin and ultrathin polymer films on solid substrates
WO2020099729A1 (fr) * 2018-11-14 2020-05-22 Saint-Gobain Glass France Procede de gravure selective d'une couche ou d'un empilement de couches sur substrat verrier
CN112969671A (zh) * 2018-11-14 2021-06-15 法国圣戈班玻璃厂 在玻璃基材上选择性蚀刻层或叠层的方法
JP2022510109A (ja) * 2018-11-14 2022-01-26 サン-ゴバン グラス フランス ガラス基材の層又は層の積層物の選択的エッチングのための方法
JP7234358B2 (ja) 2018-11-14 2023-03-07 サン-ゴバン グラス フランス ガラス基材の層又は層の積層物の選択的エッチングのための方法
EP3799964A1 (fr) * 2019-10-02 2021-04-07 ETA SA Manufacture Horlogère Suisse Procdede de fabrication d'une piece mecanique epilamee
WO2021063534A1 (fr) * 2019-10-02 2021-04-08 Eta Sa Manufacture Horlogère Suisse Procede de fabrication d'une piece mecanique epilamee
CN114631065A (zh) * 2019-10-02 2022-06-14 伊塔瑞士钟表制造股份有限公司 用于制造经防油处理的机械部件的方法
US20220334538A1 (en) * 2019-10-02 2022-10-20 Eta Sa Manufacture Horllgère Suisse Method for manufacturing an epilame mechanical part
US12099330B2 (en) * 2019-10-02 2024-09-24 Eta Sa Manufacture Horlogère Suisse Method for manufacturing an epilame mechanical part

Also Published As

Publication number Publication date
CH519999A (de) 1972-03-15
ES381303A1 (es) 1972-12-01
NL7010550A (xx) 1971-01-19
DE2025122C3 (de) 1974-07-25
CS151556B2 (xx) 1973-10-19
BE752919A (fr) 1971-01-04
CA928170A (en) 1973-06-12
DE2025122A1 (de) 1971-01-28
FR2055282A5 (xx) 1971-05-07
SE364906B (xx) 1974-03-11
RO56296A (xx) 1974-04-29
DE2025122B2 (de) 1973-12-06
GB1264723A (xx) 1972-02-23

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