US3791852A - High rate deposition of carbides by activated reactive evaporation - Google Patents

High rate deposition of carbides by activated reactive evaporation Download PDF

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US3791852A
US3791852A US00263708A US3791852DA US3791852A US 3791852 A US3791852 A US 3791852A US 00263708 A US00263708 A US 00263708A US 3791852D A US3791852D A US 3791852DA US 3791852 A US3791852 A US 3791852A
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metal
substrate
gas
atoms
deposition
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R Bunshah
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University of California
University of California Berkeley
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University of California Berkeley
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    • 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
    • C23C14/0635—Carbides

Definitions

  • Tinsley [5 7 ABSTRACT Process and apparatus for the production of carbide films at high rates by physical vapor deposition.
  • the metal is evaporated in a vacuum chamber by an electron beam, the hydrocarbon gas is introduced into the chamber, and the metal vapor atoms and gas atoms are activated by electrons deflected from the electron beam to the reaction zone by a low voltage electrode at the reaction zone.
  • the reaction takes place primarily in the vapor phase in the reaction zone, rather than on the substrate.
  • a high reaction efficiency is obtained with the activated atoms and a deposition rate in the range of 1 to 12 micrometers per minute and higher is achieved.
  • This invention relates to process and apparatus for the formation of carbide films on substrates, such as cutting tools and wear and abrasion resistant surfaces, and for use as superconductors and for the synthesis of carbide powders.
  • the films are produced by physical vapor deposition of the carbide compound by reactive evaporation in a zone away from the substrate.
  • Carbide films have been prepared by chemical vapor deposition in the production of tool bits and the like; however, the rate of deposition has been relatively slow.
  • Oxide and nitride films have been produced by reactive evaporation, normally at a relatively low rate of deposition. It is an object of the present invention to provide process and apparatus for the production of carbide films by reactive evaporation, and in particular, to produce the carbide film at a high rate of deposition, typically in the range of l to 12 micrometers per minute.
  • a number of processes are available for depositing compounds from the vapor phase onto a substrate: chemical vapor deposition; sputtering of the compound from a target of the same composition; direct evaporation of the compound from an evaporation source of the same composition; and reactive evaporation in which metal vapor atoms from an evaporation source containing the appropriate metal react with reactive gas atoms present in the vapor phase to form compounds.
  • a typical example of reactive evaporation formation of compounds is 2Al (vapor) 3/2 (gas) Al O (solid).
  • the choice of process depends on the ability to deposit compounds of desired composition and structure, and the rate of deposition.
  • the sputtering process suffers from a low deposition rate, typically in the order of 0.1 micrometers per minute, and sometimes the breakup of the compound into fractions which may not recombine to yield the desired composition in the deposited film.
  • Direct evaporation of compounds is often possible but some compounds of particular interest have very high melting points which require the use of a high intensity heat source to produce appreciable evaporation rate, and also the possible breakup of the compound into fractions during evaporation.
  • the evaporant is a metal whose melting point is lower than the metal compound, and higher metal atom densities in the vapor phase are easier to produce and high deposition rates are possible.
  • metal vapor atoms react with gas atoms to form compounds.
  • gas atoms In the example set out above, vaporized aluminum metal atoms combine with oxygen to form aluminum oxide.
  • vaporized titanium metal atoms should react with a hydrocarbon gas such as acetylene to form titanium carbide, but titanium carbide has not been produced by the prior art reactive evaporation process.
  • the deposition rate in a reactive evaporation process depends upon the supply of metal vapor atoms, the supply of gas atoms, collision between metal and gas atoms, and the probability of a subsequent reaction to form a compound when such collisions occur.
  • the overall yield of the reaction would be determined by all of the above mentioned factors, any one of which can be the rate limiting step.
  • the mean free path exceeds the source to substrate distance and collision between the reactants can occur only on the substrate.
  • the mean free path decreases, eventually becoming smaller than the source to substrate distance, so that collisions between the reactants now occur in the vapor phase.
  • the supply of vaporized metal atoms and gas atoms, i.e., their partial pressures, must be large and hence collision between the reactants takes place primarily in the vapor phase.
  • an adequate supply of metal atoms in the vapor phase can be obtained by using a high rate evaporation source and an adequate supply of gas atoms is provided by having a sufficiently high partial pressure of gas atoms in the gas phase, resulting in a high collision rate between the metal and gas atoms in the vapor phase.
  • One of the rate limiting steps mentioned above affecting the overall yield of the reaction is the probability of a reaction when the two reacting species collide. This reaction probability can be increased by activating one or both of the reactants.
  • the invention provides for physical vapor deposition of carbide films by reactive evaporation with activated metal vapor and hydrocarbon gas atoms in the vapor phase in a reaction zone, i.e., in the space between the substrate and the metal source.
  • the source metal is heated and vaporized in a vacuum chamber by an electron beam to provide the metal vapor atoms in the reaction zone.
  • the hydrocarbon gas is introduced into the reaction zone and the metal vapor and gas atoms are activated by some of the electrons of the metal heating electron beam which are deflected into the reaction zone by a low voltage field produced by a deflection electrode positioned at the reaction zone.
  • the activation of the reactants increases the probability of a reaction between them, and the metal vaporhydrocarbon gas reaction is achieved with a high efficiency producing the desired metal carbide film on the substrate.
  • deposition rates substantially higher than those previously obtained are achieved and substrate temperature is not a limiting factor as in chemical vapor deposition.
  • the acts of compound synthesis and film growth are separated.
  • the microstructure of the deposit and hence its physical and mechanical properties, are dependent on the substrate temperature which can be varied at will. Hence the properties of the deposit can be controlled, which is an important advantage.
  • the stoichiometry of the compound i.e. the ratio of cations to anions
  • Deposition rates of l to 12 micrometers per minute and higher are obtained.
  • FIGURE of the drawing is a schematic vertical sectional view of a vacuum chamber and associated equipment suitable for performing the process of the invention and incorporating the presently preferred embodiment of the apparatus of the invention.
  • the apparatus includes a vacuum chamber which may comprise a conventional cover or dome 10 resting on a base 11 with a sealing gasket 12 at the lower rim of the cover 10.
  • a support and feed unit 13 for a source metal rod 14 may be mounted in the base 11.
  • the unit 13 includes a mechanism (not shown) for moving the metal rod 14 upward at a controlled rate.
  • Cooling coils 15 may be mounted in the unit 13 and supplied with cooling water from a cooling water source 16.
  • An electron gun 20 is mounted in unit 13 and provides an electron beam along the path 21 to the upper surface of the metal rod 14, with the electron gun being energized from a power supply 22.
  • a substrate 24 on which the carbide film is to be deposited is supported in a frame 25 on a rod 26 projecting upward from the base 11.
  • the substrate 24 may be heated by an electric resistance heater 27 supported on a bracket 28.
  • Energy for the heater 27 is provided from a power supply 29 via a cable 30.
  • the temperature of the substrate 24 is maintained at a desired value by means of a thermocouple 32 in contact with the upper surface of the substrate 24, with the thermocouple connected to a controller 33 by line 34, with the controller output signal regulating the power from the supply 29 to the heater 27.
  • the desired low pressure is maintained within the vacuum chamber by a vacuum pump 36 connected to the interior of the chamber via a line 37.
  • Gas from a gas supply 39 is introduced into the zone between the metal rod 14 and substrate 24 via a line 40 and nozzle 41.
  • a shutter 43 is mounted on a rod 44 which is manually rotatable to move the shutter into and out of position between the metal rod 14 and substrate 24.
  • a deflection electrode typically a tungsten rod 46
  • An electric potential is provided for the rod 46 from a voltage supply 47 via line 48.
  • An electric insulating sleeve 49 typically of glass, is provided for the rod 46 within the vacuum chamber, with the metal surface of the rod exposed only in the zone between the source and substrate.
  • the evaporation chamber may be a 24 inch diameter and 36 inch high water cooled stainless steel bell jar.
  • the vacuum pump may be a 10 inch diameter fractionating diffusion pump, with an anti migration type liquid nitrogen trap.
  • the source metal unit 13 may be a 1 inch diameter rod fed electron beam gun, self-accelerated 270 deflection type, such as Airco Temescal Model RlH-270.
  • the power supply 22 may be an Airco Temescal Model CV30 30 kw unit which may be operated at a constant voltage such as 10 kilovolts, with a variable emission current.
  • a typical substrate is a 6 inch by 6 inch metal sheet in the order of 5 mils thick.
  • Various metals have been used including stainless steel, copper, titanium and zirconium.
  • the substrate is based about eight inches above the surface of the metal source 14.
  • the heater 27 may be a 4 kilowatt tungsten resistance heater providing for heating the substrate to 700 C. and higher.
  • the reaction takes place primarily in the vapor phase in the reaction zone away from the substrate, and the reaction is independent of substrate temperature-As discussed below, the density of the deposit is a function of the substrate temperature and when a carbide powder is desired, the substrate may be left at ambient temperature or heated to a relatively low temperature, resulting in a powdery deposit.
  • the source metal may be a solid rod or billet and for the feed unit mentioned above, the rod is 0.975 inches diameter and 6 inchesin length. Titanium, zirconium,
  • hafnium, vanadium, niobium and tantalum have been utilized in making carbide films. Alloys and mixtures of metals may be used to produce mixed carbides and alloy carbides.
  • a hydrocarbon gas which readily disassociates is desired for the process.
  • the hydrocarbon gas for the reaction is introduced into the vacuum chamber through a series of needle valves and the preferred range for gas pressure is 2 X torr to 8 X 10" torr.
  • Acetylene is the preferred gas for the synthesis of carbides and ethylene may also be utilized.
  • the supply 47 provides a low voltage to the deflection electrode 46 and preferably is a DC. supply with a variable output voltage.
  • the usual potential for the deflection electrode is in the range of about 50 to about 200 volts, and preferably in the range of 60 to 100 volts. Higher voltages may be used if desired.
  • a Lambda Model 71 continuously variable voltage DC. power supply has been utilized.
  • A.C. potential also has been used on the deflection electrode, with voltages in the same range.
  • titanium carbide was formed by activated reactive evaporation deposition utilizing titanium metal and acetylene gas, with the following reaction:
  • the vacuum chamber was initially pumped down to 10 torr pressure and was then purged with the gas to 10* torr for a few minutes. The chamber was again pumped down to 10' torr. This procedure was used to minimize the presence of extraneous gases.
  • the electron gun When the pressure in the chamber was again down to 10' torr, the electron gun was turned on and a molten pool of metal was formed by the electron beam at the upper end of the rod 14.
  • the shutter 43 was in position blocking the substrate 24.
  • the reaction gas was then introduced into the vacuum chamber at a controlled rate to obtain the desired chamber pressure.
  • the power supply for the deflection electrode 46 was turned on and the potential increased until the reaction began, as indicated by a substantial increase in current in the electrode 46.
  • steady state conditions were ob tained the shutter 43 was moved to one side and the carbide film was deposited on the substrate. The process was continued until the desired thickness of film was obtained, after which the shutter was moved to the blocking position and the various supplies were turned off.
  • the gas partial pressure within the chamber, the deflection electrode potential, and the electron beam current required to produce the carbide film are somewhat interrelated and may be varied over a substantial range. With higher electron beam currents, the deflection electrode potential required for initiating the reaction decreases. Similarly, with higher gas partial pressures, the required electrode potential decreases.
  • successful formation of carbide films was achieved with electron gun power in the range of one kilowatt to three kilowatts, with gas partial pressure in the range of 1 X l0" to 3 X 10 torr, and electrode potential in the range of 60 to volts.
  • Acetylene (C H is a preferred hydrocarbon gas for the process because it is a highly unsaturated hydrocarbon.
  • Methane (CH is not a suitable gas due to the saturated carbon-hydrogen bond.
  • Ethylene (C l-l is an unsaturated hydrocarbon gas which may be used in some instances.
  • the acts of compound formation and deposit growth are separate steps in this process.
  • the character of the deposit changes with substrate temperature. In the range from 0C to about 0.3 Tm (Tm being the melting point of the compound in degrees Kelvin) the deposit is of less than full density, the density increasing with deposition temperature.
  • the morphology exhibited by the deposit is of tapered crystallites with porosity in between the crystallites. Such deposits show microhardness values of about 3,000 kg/mm at a 50 gram load for TiC and unit stoichiometry and these microhardness values are comparable to those reported for TiC synthesized by other methods.
  • substrate temperatures greater than 0.3 Tm approximately the deposit becomes fully dense and its morphology now shows columnar grains across the thickness of the deposit.
  • Such a structure contains fewer imperfections (i.e. porosity, cracks etc.) and hence exhibits much higher microhardness values, 4,000 to 5,000 kg/mm at 50 gram load. This is to be expected since the properties of brittle materials such as ceramics are primarily governed by the imperfection content.
  • the stoichiometry of the carbide deposit can be controlled by changing the relative amounts of the reactants.
  • the carbon to metal ratio is increased by increasing the partial pressure of the carbon containing gas at a constant evaporation rate of titanium.
  • a titanium carbide deposit of unit stoichiometry TiC can be produced at a deposition rate of 4 micrometers per minute at a source-tosubstrate distance of 8 inches.
  • Typical film thicknesses are in the range of 25 to micrometersDepo sition rates of 1 to 12 micrometers per minute have been achieved. Higher and lower rates may be had by varying the parameters of the system.
  • the metal evaporation rate may be controlled by varying the output of the electron gun and the gas pressure may be controlled by adjusting a valve 41 in the gas line 40.
  • evaporating a metal by an electron beam directed to the metal producing a metal vapor in a zone between the metal and the substrate; introducing a hydrocarbon gas into said zone; and generating. a low voltage electric field in said zone and deflecting electronsto said zone ionizing the metal vapor and gas atoms in said zone, so that the metal vapor atoms and gas atoms react in said zone to form a metal carbide which then deposits on said substrate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)
US00263708A 1972-06-16 1972-06-16 High rate deposition of carbides by activated reactive evaporation Expired - Lifetime US3791852A (en)

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Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3916052A (en) * 1973-05-16 1975-10-28 Airco Inc Coating of carbon-containing substrates with titanium carbide
US4297387A (en) * 1980-06-04 1981-10-27 Battelle Development Corporation Cubic boron nitride preparation
US4336277A (en) * 1980-09-29 1982-06-22 The Regents Of The University Of California Transparent electrical conducting films by activated reactive evaporation
US4416912A (en) * 1979-10-13 1983-11-22 The Gillette Company Formation of coatings on cutting edges
US4656052A (en) * 1984-02-13 1987-04-07 Kyocera Corporation Process for production of high-hardness boron nitride film
US4698235A (en) * 1982-09-29 1987-10-06 National Research Development Corporation Siting a film onto a substrate including electron-beam evaporation
DE3627151A1 (de) * 1986-08-11 1988-02-18 Leybold Heraeus Gmbh & Co Kg Verfahren und vorrichtung zum reaktiven aufdampfen von metallverbindungen
US4748027A (en) * 1984-02-29 1988-05-31 Nexus Aps Powder product and a method for its preparation
US4781989A (en) * 1986-03-07 1988-11-01 Mitsubishi Kinzoku Kabushiki Kaisha Surface-coated cutting member
US4816291A (en) * 1987-08-19 1989-03-28 The Regents Of The University Of California Process for making diamond, doped diamond, diamond-cubic boron nitride composite films
US4957773A (en) * 1989-02-13 1990-09-18 Syracuse University Deposition of boron-containing films from decaborane
US4980021A (en) * 1989-04-03 1990-12-25 Shin-Etsu Chemical Co. Ltd. Method for preparation of edged medical tool
DE4006457C1 (en) * 1990-03-01 1991-02-07 Balzers Ag, Balzers, Li Appts. for vapour deposition of material under high vacuum - has incandescent cathode and electrode to maintain arc discharge
DE4336680A1 (de) * 1993-10-27 1995-05-04 Fraunhofer Ges Forschung Verfahren und Einrichtung zum Elektronenstrahlverdampfen
US5434008A (en) * 1990-08-07 1995-07-18 The Boc Group, Inc. Thin gas barrier films
US5436035A (en) * 1991-12-05 1995-07-25 Alusuisse-Lonza Services Ltd. Coating a substrate surface with a permeation barrier
US5614273A (en) * 1993-10-27 1997-03-25 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung, E.V. Process and apparatus for plasma-activated electron beam vaporization
DE19724996C1 (de) * 1997-06-13 1998-09-03 Fraunhofer Ges Forschung Verfahren zum plasmaaktivierten Elektronenstrahlverdampfen und Einrichtung zur Durchführung des Verfahrens
US5804258A (en) * 1996-01-10 1998-09-08 Alusuisse Technology & Management Ltd. Process and device for coating a substrate surface with vaporized inorganic material
US20020139667A1 (en) * 2001-03-29 2002-10-03 Guangxin Wang Methods for electrically forming materials; and mixed metal materials
WO2003080890A1 (en) * 2002-03-26 2003-10-02 Matsushita Electric Industrial Co., Ltd. Production metod and production device for thin film
WO2003082482A1 (en) * 2002-03-25 2003-10-09 Penn State Research Foundation Method for producing boride thin films
US20040172827A1 (en) * 2003-03-03 2004-09-09 Kinstler Monika D. Fan and compressor blade dovetail restoration process
US20040207074A1 (en) * 2003-04-16 2004-10-21 The Regents Of The University Of California Metal MEMS devices and methods of making same
US20040234785A1 (en) * 2003-02-28 2004-11-25 Zi-Kui Liu Boride thin films on silicon
US20070028841A1 (en) * 2003-04-03 2007-02-08 Microemissive Displays Limited Method and apparatus for depositing material on a substrate
US20090041935A1 (en) * 2007-08-10 2009-02-12 Mutsuki Yamazaki Method for causing particulate base material to carry alloy particle
US8526137B2 (en) 2010-04-16 2013-09-03 International Business Machines Corporation Head comprising a crystalline alumina layer
US9023422B1 (en) * 2011-08-31 2015-05-05 Maxim Integrated Products, Inc. High rate deposition method of magnetic nanocomposites
CN106676480A (zh) * 2017-03-10 2017-05-17 南京大学 一种蒸发速率可控的电子束蒸发源
US10167555B2 (en) 2014-08-18 2019-01-01 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US11499230B2 (en) 2014-08-18 2022-11-15 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
RU232765U1 (ru) * 2024-12-23 2025-03-19 Федеральное государственное автономное образовательное учреждение высшего образования "Томский государственный университет систем управления и радиоэлектроники" Устройство реактивного электронно-лучевого осаждения нитридных покрытий

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5318184B2 (enrdf_load_stackoverflow) * 1973-08-04 1978-06-13
JPS51107287A (ja) * 1975-03-18 1976-09-22 Fujikoshi Kk Koshitsuhimakukeiseisochi
JPS5841351B2 (ja) * 1975-08-19 1983-09-12 ニホンシンクウギジユツ カブシキガイシヤ カツセイカハンノウジヨウチヤクソウチ
GB1579999A (en) * 1977-09-12 1980-11-26 Gen Electric Annular metal cutting die of titanium carbide coating tool steel and method of shaving metal rods
ES8103780A1 (es) * 1979-08-09 1981-03-16 Mitsubishi Metal Corp Procedimiento para la fabricacion de cuchillas dotadas de recubrimiento,para herramientas de corte
US4609564C2 (en) * 1981-02-24 2001-10-09 Masco Vt Inc Method of and apparatus for the coating of a substrate with material electrically transformed into a vapor phase
US4537794A (en) * 1981-02-24 1985-08-27 Wedtech Corp. Method of coating ceramics
US4596719A (en) * 1981-02-24 1986-06-24 Wedtech Corp. Multilayer coating method and apparatus
JPS5928629B2 (ja) * 1981-03-30 1984-07-14 工業技術院長 硬質被膜の製造方法
JPS60234965A (ja) * 1984-05-04 1985-11-21 Diesel Kiki Co Ltd 薄膜製造方法
GB8508699D0 (en) * 1985-04-03 1985-05-09 Barr & Stroud Ltd Chemical vapour deposition of products
JPS6222314A (ja) * 1985-07-22 1987-01-30 株式会社ボッシュオートモーティブ　システム 薄膜製造方法
US4816293A (en) * 1986-03-27 1989-03-28 Mitsubishi Denki Kabushiki Kaisha Process for coating a workpiece with a ceramic material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230110A (en) * 1962-01-22 1966-01-18 Temescal Metallurgical Corp Method of forming carbon vapor barrier
US3373050A (en) * 1964-12-30 1968-03-12 Sperry Rand Corp Deflecting particles in vacuum coating process
US3419487A (en) * 1966-01-24 1968-12-31 Dow Corning Method of growing thin film semiconductors using an electron beam
US3677795A (en) * 1969-05-01 1972-07-18 Gulf Oil Corp Method of making a prosthetic device
US3695910A (en) * 1969-01-21 1972-10-03 Anthony W Louderback Method of applying a multilayer antireflection coating to a substrate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3230110A (en) * 1962-01-22 1966-01-18 Temescal Metallurgical Corp Method of forming carbon vapor barrier
US3373050A (en) * 1964-12-30 1968-03-12 Sperry Rand Corp Deflecting particles in vacuum coating process
US3419487A (en) * 1966-01-24 1968-12-31 Dow Corning Method of growing thin film semiconductors using an electron beam
US3695910A (en) * 1969-01-21 1972-10-03 Anthony W Louderback Method of applying a multilayer antireflection coating to a substrate
US3677795A (en) * 1969-05-01 1972-07-18 Gulf Oil Corp Method of making a prosthetic device

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3916052A (en) * 1973-05-16 1975-10-28 Airco Inc Coating of carbon-containing substrates with titanium carbide
US4416912A (en) * 1979-10-13 1983-11-22 The Gillette Company Formation of coatings on cutting edges
US4297387A (en) * 1980-06-04 1981-10-27 Battelle Development Corporation Cubic boron nitride preparation
US4336277A (en) * 1980-09-29 1982-06-22 The Regents Of The University Of California Transparent electrical conducting films by activated reactive evaporation
US4698235A (en) * 1982-09-29 1987-10-06 National Research Development Corporation Siting a film onto a substrate including electron-beam evaporation
US4656052A (en) * 1984-02-13 1987-04-07 Kyocera Corporation Process for production of high-hardness boron nitride film
US4748027A (en) * 1984-02-29 1988-05-31 Nexus Aps Powder product and a method for its preparation
US4781989A (en) * 1986-03-07 1988-11-01 Mitsubishi Kinzoku Kabushiki Kaisha Surface-coated cutting member
DE3627151A1 (de) * 1986-08-11 1988-02-18 Leybold Heraeus Gmbh & Co Kg Verfahren und vorrichtung zum reaktiven aufdampfen von metallverbindungen
US4816291A (en) * 1987-08-19 1989-03-28 The Regents Of The University Of California Process for making diamond, doped diamond, diamond-cubic boron nitride composite films
US4957773A (en) * 1989-02-13 1990-09-18 Syracuse University Deposition of boron-containing films from decaborane
US4980021A (en) * 1989-04-03 1990-12-25 Shin-Etsu Chemical Co. Ltd. Method for preparation of edged medical tool
DE4006457C1 (en) * 1990-03-01 1991-02-07 Balzers Ag, Balzers, Li Appts. for vapour deposition of material under high vacuum - has incandescent cathode and electrode to maintain arc discharge
US5434008A (en) * 1990-08-07 1995-07-18 The Boc Group, Inc. Thin gas barrier films
US5516555A (en) * 1990-08-07 1996-05-14 The Boc Group, Inc. Evaporation method for forming a gas barrier film having an organosilicon dispersed discontinuously in an inorganic matrix
US5436035A (en) * 1991-12-05 1995-07-25 Alusuisse-Lonza Services Ltd. Coating a substrate surface with a permeation barrier
US5614273A (en) * 1993-10-27 1997-03-25 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung, E.V. Process and apparatus for plasma-activated electron beam vaporization
DE4336680C2 (de) * 1993-10-27 1998-05-14 Fraunhofer Ges Forschung Verfahren zum Elektronenstrahlverdampfen
DE4336680A1 (de) * 1993-10-27 1995-05-04 Fraunhofer Ges Forschung Verfahren und Einrichtung zum Elektronenstrahlverdampfen
US5804258A (en) * 1996-01-10 1998-09-08 Alusuisse Technology & Management Ltd. Process and device for coating a substrate surface with vaporized inorganic material
DE19724996C1 (de) * 1997-06-13 1998-09-03 Fraunhofer Ges Forschung Verfahren zum plasmaaktivierten Elektronenstrahlverdampfen und Einrichtung zur Durchführung des Verfahrens
US20020139667A1 (en) * 2001-03-29 2002-10-03 Guangxin Wang Methods for electrically forming materials; and mixed metal materials
WO2002079546A1 (en) * 2001-03-29 2002-10-10 Honeywell International Inc. Methods for electrolytically forming materials; and mixed metal materials
US7252751B2 (en) 2001-03-29 2007-08-07 Honeywell International Inc. Methods for electrically forming materials
US6827828B2 (en) * 2001-03-29 2004-12-07 Honeywell International Inc. Mixed metal materials
US20040168932A1 (en) * 2001-03-29 2004-09-02 Guangxin Wang Methods for electrically forming materials
US20030219911A1 (en) * 2002-03-25 2003-11-27 Xianghui Zeng Method for producing boride thin films
US6797341B2 (en) * 2002-03-25 2004-09-28 Penn State Research Foundation Method for producing boride thin films
WO2003082482A1 (en) * 2002-03-25 2003-10-09 Penn State Research Foundation Method for producing boride thin films
WO2003080890A1 (en) * 2002-03-26 2003-10-02 Matsushita Electric Industrial Co., Ltd. Production metod and production device for thin film
US20050087141A1 (en) * 2002-03-26 2005-04-28 Kazuyoshi Honda Production method and production device for thin film
US20040234785A1 (en) * 2003-02-28 2004-11-25 Zi-Kui Liu Boride thin films on silicon
US7090889B2 (en) 2003-02-28 2006-08-15 The Penn State Research Foundation Boride thin films on silicon
US8122600B2 (en) * 2003-03-03 2012-02-28 United Technologies Corporation Fan and compressor blade dovetail restoration process
US20040172827A1 (en) * 2003-03-03 2004-09-09 Kinstler Monika D. Fan and compressor blade dovetail restoration process
US7595098B2 (en) 2003-04-03 2009-09-29 Microemissive Displays Limited Method and apparatus for depositing material on a substrate
US20070028841A1 (en) * 2003-04-03 2007-02-08 Microemissive Displays Limited Method and apparatus for depositing material on a substrate
US7569411B2 (en) 2003-04-16 2009-08-04 The Regents Of The University Of California Metal MEMS devices and methods of making same
US7166488B2 (en) * 2003-04-16 2007-01-23 The Regents Of The University Of California Metal MEMS devices and methods of making same
US20040207074A1 (en) * 2003-04-16 2004-10-21 The Regents Of The University Of California Metal MEMS devices and methods of making same
US20090041935A1 (en) * 2007-08-10 2009-02-12 Mutsuki Yamazaki Method for causing particulate base material to carry alloy particle
CN101364647B (zh) * 2007-08-10 2010-12-22 株式会社东芝 微粒负载方法和微粒负载装置
US8526137B2 (en) 2010-04-16 2013-09-03 International Business Machines Corporation Head comprising a crystalline alumina layer
US9023422B1 (en) * 2011-08-31 2015-05-05 Maxim Integrated Products, Inc. High rate deposition method of magnetic nanocomposites
US10167555B2 (en) 2014-08-18 2019-01-01 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US10683574B2 (en) 2014-08-18 2020-06-16 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US10947622B2 (en) 2014-08-18 2021-03-16 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
US11499230B2 (en) 2014-08-18 2022-11-15 Dynetics, Inc. Method and apparatus for fabricating fibers and microstructures from disparate molar mass precursors
CN106676480A (zh) * 2017-03-10 2017-05-17 南京大学 一种蒸发速率可控的电子束蒸发源
CN106676480B (zh) * 2017-03-10 2019-11-08 南京大学 一种蒸发速率可控的电子束蒸发源
RU232765U1 (ru) * 2024-12-23 2025-03-19 Федеральное государственное автономное образовательное учреждение высшего образования "Томский государственный университет систем управления и радиоэлектроники" Устройство реактивного электронно-лучевого осаждения нитридных покрытий

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JPS5148463B2 (enrdf_load_stackoverflow) 1976-12-21
DE2330545A1 (de) 1974-01-03
JPS4952186A (enrdf_load_stackoverflow) 1974-05-21
DE2330545B2 (de) 1977-06-08
GB1392583A (en) 1975-04-30

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