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WO1990012485A2 - Fabrication d'alliages par evaporation a partir de sources de vapeur multiples - Google Patents

Fabrication d'alliages par evaporation a partir de sources de vapeur multiples Download PDF

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Publication number
WO1990012485A2
WO1990012485A2 PCT/GB1990/000610 GB9000610W WO9012485A2 WO 1990012485 A2 WO1990012485 A2 WO 1990012485A2 GB 9000610 W GB9000610 W GB 9000610W WO 9012485 A2 WO9012485 A2 WO 9012485A2
Authority
WO
WIPO (PCT)
Prior art keywords
evaporation
crudble
vapour
conduit
temperature
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/GB1990/000610
Other languages
English (en)
Other versions
WO1990012485A3 (fr
Inventor
Robert Lewis Bickerdike
Alan William Bishop
David John Bray
Robert William Gardiner
Brian William Viney
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UK Secretary of State for Defence
Original Assignee
UK Secretary of State for Defence
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 UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Publication of WO1990012485A2 publication Critical patent/WO1990012485A2/fr
Publication of WO1990012485A3 publication Critical patent/WO1990012485A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/243—Crucibles for source material

Definitions

  • This invention relates to improved apparatus and a method for the preparation of alloys by a physical vapour deposition process of the type described in our earlier British Patents GB 1206586 and GB 1265965.
  • the alloy constituents are evaporated from one or more evaporation baths to be condensed upon a temperature controlled collector and the apparatus is operated under vacuum within a vacuum chamber.
  • the apparatus and method described here are particularly adapted to produce substantial quantities of the desired alloy for engineering purposes.
  • the deposit is of such a thickness and has sufficient structural integrity that it can be removed from the collector for working into sheet, strip or other wrought form and heat-treated before, during or after working to achieve the desired mechanical properties.
  • the deposited alloy may be removed and pulverised for subsequent processing by powder metallurgical techniques, for example when it is desired to obtain articles close in form to the finished product.
  • magnesium alloys have not found widespread use in aerospace applications, partly because of certain shortcomings in mechanical properties, but principally because of their poor corrosion resistance.
  • RSR rapid solidification rate
  • the addition of elements such as aluminium, chromium or silicon which are known to form protective surface films in other alloy systems is ineffective because of their insufficient solubilities in the magnesium matrix. Under normal equilibrium conditions, the concentration of such additives in solid solution is too low to provide an effective barrier to corrosion.
  • the additives For the purpose of improving corrosion resistance it is very important that the additives should be assimilated into a solid solution with a uniform electrode potential. If they are allowed to segregate and form precipitates, and if the precipitates and matrix have different electrode potentials, then they effectively behave as tiny Galvanic cells and corrosion resistance is worsened rather than improved.
  • Rapid solidification and physical vapour deposition techniques provide the means to overcome thermodynamic constraints and achieve compositions which are beyond the scope of the ingot metallurgist by 'freezing' constituent atoms in position before they have the opportunity to migrate and segregate as they would in conventional melt chill processes. These techniques therefore offer a potential solution for improving corrosion resistance in magnesium alloys by increasing the population of corrosion - inhibiting species in the magnesium matrix without forming harmful precipitates.
  • Physical vapour deposition has several advantages over RSR processing. Firstly, the cooling rate is higher, thereby improving the opportunity for forming solid solutions. Secondly, the choice of potential alloying constituents is considerably widened because whilst certain elements may not be miscible in the molten state, perhaps because of phase differences, their vapours can be mixed intimately. This is particularly true in the case of magnesium because, at the melting temperature of many potentially interesting alloying additions, magnesium has a very high vapour pressure and will quickly evaporate away.
  • the composition of the deposit is non-uniform across the substrate due to imperfect mixing of the vapour streams.
  • Better mixing can be achieved by increasing the separation of the collector from the sources but this has the effect of lowering the deposition rate.
  • Hitherto vapour deposition from multiple sources has either been a compromise between homogeneity in the deposit and the rate of deposition or has required special equipment to effect movement of the substrate relative to the position of the sources. This latter option is complicated by the need to maintain the apparatus under vacuum.
  • the invention is an apparatus for the production of an alloy by a process of evaporating the alloy constituents under vacuum and condensing the constituent vapours upon a collector, said apparatus comprising: a conduit defining a rising flue which has a discharge opening at its upper end; a collector positioned so as to collect vapours issuing from the discharge opening of the rising flue; a first evaporation crucible located and configured so as to discharge into the rising flue at a position remote from the discharge opening thereof; a second evaporation crucible located within the rising flue at a position intermediate the discharge opening thereof and the first evaporation crucible said second evaporation crucible being configured and disposed such that there is an unobstructed flue passage therearound; a first heating means which heats a charge in the first
  • the invention provides a method for the production of an alloy by a process of evaporating the alloy constituents under vacuum and condensing the constituent vapours upon a collector, said method comprising: evaporating a charge of a first alloy constituent or first alloy constituents of relatively high volatility from a first evaporation crucible by heating this charge to a sufficient temperature to generate an appreciable vapour pressure; evaporating a charge of a further alloy consitituent or futher alloy constituents of relatively low volatility from a second evaporation crucible by heating this charge to a sufficient temperature to generate an appreciable vapour pressure; maintaining a stream of constituent vapours from the respective evaporation crucibles by continued heating of the charges; directing the constituent vapour streams into a rising flue defined by a conduit which houses at least the second evaporation crucible; heating the walls of the conduit in at least that portion thereof above the second evaporation crucible to a temperature at least as high as that of the second e
  • the walls of the vessel must be formed from a material inert to the metal vapours with which they come into contact.
  • the choice of material will therefore be determined by the nature of the metals to be evaporated.
  • the dimensions of the conduit must be such that sufficient scattering occurs by reflection of vapour atoms from its hot walls to promote thorough mixing. If the conduit is too large in relation to the sizes of the respective sources and the flow rates of vapour therefrom, efficient mixing may not take place because the separation distance between the conduit walls and the sources is too great for sufficient scattering to occur.
  • the constituent evaporated from the lowermost evaporation crucible is the most volatile and is also the principal alloy constituent. Difficulties arising from unwanted condensation of vapour in undesired parts of the apparatus and reverse flow of vapour streams in the cooler regions are thus minimised.
  • the flue is constructed in a number of longitudinal sections. This not only simplifies assembly of the apparatus between each operation by allowing easier access to the or each evaporation crucible within the flue passage, but also facilitates use of different materials in the different sections.
  • the lowermost section can be formed from a thermally insulating material to minimize conduction of heat downwards from the hottest regions of the
  • the equipment has the capability to produce homogenous alloys at a deposition rate of several millimetres per hour or even higher.
  • the drawback of using very high rates of deposition is the occurrence of an unacceptable degree of porosity in the product so in practice the rate is optimised to achieve a sensible
  • Figure 1 is a schematic diagram of the apparatus
  • Figure 2 is a vertical section through a preferred form of the apparatus with some detail omitted from the right hand side for clarity.
  • reference numeral 1 denotes a lower evaporation source positioned at the bottom of a chimney 4 within which there is disposed a second evaporation source 2. Facing the mouth of chimney 4 is a collector 5 which receives the mixed vapours emanating therefrom.
  • Sources 1 and 2 each have an associated heater 6, 7.
  • the lower heater 6 operates directly to heat the walls of a crucible which houses the lower evaporation source 1 whilst the second heater 7 operates to heat up the walls of the chimney which in turn radiates heat to the second evaporation source 2.
  • vapour is generated from the second source whilst satisfying the condition that the chimney walls should be at least as hot as the hottest source.
  • Vapour from source 1 is supplied to the chimney 4 and flows past source 2 into a mixing zone 8 where it mixes with vapour from source 2.
  • the mixing zone is simply that portion of the chimney above source 2 where both species of vapour coexist. Collisions between vapour stream 1 and the walls of the chimney or the second source 2 act so as to randomize movement of the vapour atoms and this assists thorough mixing with the vapour from source 2. Similarly, collisions between the vapour stream from source 2 and the walls of the chimney encourage intimate mixing by imparting random movement to the vapour atoms.
  • the mixed vapour stream emerging from the mouth of the chimney is therefore substantially homogeneous and a deposit with uniform microstructure is formed on the collector 5.
  • Figure 2 shows a preferred form of the apparatus in vertical section with detail omitted from the right hand side for clarity.
  • the arrangement depicted here has been developed particularly for the deposition of magnesium alloyed with lower vapour pressure constituents such as aluminium, chromium or silicon.
  • the lower evaporator comprises a mild steel crucible 10 standing on an alumina support ring 11 which acts so as to minimize conduction of heat away from the crucible to support table 12.
  • the crucible is sealed with a gasket 30 and screw-top lid 31, both made from mild steel.
  • Disposed in the centre of the lid and gasket assembly is a graphite nozzle 32 the purpose of which is to control the flow of magnesium vapour from the crudble.
  • the nozzle, gasket and crucible lid are optional features which may be required for evaporating certain elements from the lower crudble.
  • the evaporation rate was unacceptably low. Increasing the temperature had little effect until a point was reached when the oxide was dispersed to the periphery of the crucible, leaving a clean pool of molten metal in the centre. At this temperature the evaporation rate was too high. This difficulty was eventually overcome by operating the lower evaporator at a temperature suffidentiy high that the magnesium surface was dear of oxide and by interposing a nozzle at the mouth of the source to reduce the flow rate to the desired level.
  • the required evaporation temperature for magnesium is in the range 700-800°C.
  • Support table 12 is recessed at 13 and 14 to provide positive engagement for the support ring 11 and lower heater support 15, respectively.
  • Lower heater support 15 is an alumina tube having slots 16 therein through which are threaded heater element 17.
  • the heater element 17 comprises a single strip of tantalum metal wound in the form of a helix around lower crudble 10. To reduce radiation losses the heater is surrounded by three stainless steel screens 18. Molybdenum disc 19 is then placed over the crudble and screens to reduce the amount of heat radiated from top heater 27 down to the mild steel crudble 10.
  • the vapour After passing through the nozzle 32 the vapour enters vertical chimney 40 which, in practice, is formed in three sections.
  • Lower section 41 is made from alumina which has a poor thermal conductivity and therefore helps to insulate the first evaporation source from the higher temperatures prevailing at the second evaporation source.
  • the middle section-42 and top section 43 are formed of graphite for reasons which will become apparent below.
  • Crudble 20 holding the second evaporation source is located at the junction between the middle section 42 and the top section 43 of the chimney. It rests on a graphite support ring 21 which contains a number of holes to f adlitate passage of magnesium vapour from the lower source past the ⁇ udble 20 into the top section of the chimney.
  • the top section of the chimney defines a mixing zone 44.
  • vapour from the lower source mixes with vapour from the second source before flowing out of the chimney and condensing on a temperature controlled collector 50.
  • Different materials may be employed for the crudble 20 depending on the material to be evaporated.
  • An alumina crucible is suitable for the evaporation of aluminium or chromium, whereas a vitreous carbon crudble is used for the evaporation of silicon.
  • a second radiant heater 27 is used to heat the chimney in the ' vidnity of the second evaporation source. Heat radiated from the chimney is then used in turn to heat the second evaporation source to generate vapour therefrom.
  • Successful operation of the invention depends on maintaining the temperature of the chimney at least as high as that of the second evaporator otherwise vapour condenses on the chimney walls.
  • graphite has a high thermal conductivity and a high emissivity which allows rapid transfer of heat to the inside wall of the chimney and thence to the crucible 20 by radiation.
  • graphite is physically and chemically stable up to 3000°C in vacuum and can be easily machined to shape.
  • the upper heater 27 is also a single tantalum strip wound in a helix through slots 26 in tubular alumina heater supports 25. These upper heater supports are coupled to their lower counterparts 15 through the agency of spigots 24 which protrude through the molybdenum disc 19.
  • the spigots 24 are dimensioned to be a loose fit in the bores of the alumina tubes.
  • the operating temperature of the second evaporator will obviously depend on the material being evaporated. For example, aluminium and chromium require a temperature of 1300°C to achieve a satisfactory evaporation rate whilst silicon requires a temperature of about 1550°C. This figure represents the maximum feasible operating temperature of the apparatus as described because at higher temperatures the tantalum was susceptible to chemical interaction with the support material. By using a different combination of heater and support material the operating temperature range may be extended.

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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)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

Appareil et procédé améliorés pour la fabrication d'alliages par l'évaporation et la condensation de vapeurs comprenant l'utilisation d'au moins deux sources d'évaporation qui communiquent avec un conduit muni d'une seule sortie de décharge orientée vers un récipient. On prévoit des moyens pour chauffer les parois dudit conduit à une température qui est au moins aussi élevée que celle de la source la plus chaude de manière à supprimer la condensation et à provoquer le mélange des divers écoulements de vapeurs par leur diffusion sur les parois chaudes. Dans une réalisation préférée, les sources (1, 2) sont montées verticalement, l'une au-dessus de l'autre sur une gaine (4) chauffée par un radiateur chauffant (7). Ladite gaine envoie de la chaleur, par radiation, à la deuxième source (2). On évapore le constituant le plus volatil de la source inférieure (1) au moyen du radiateur (6) et ladite vapeur en montant passe devant la deuxième source (2) pour aboutir à la zone de mélange (8). Dans ladite zone, la vapeur se mélange avec la vapeur de la source (2), et le mélange ainsi obtenu passe de la gaine au récipient (5).
PCT/GB1990/000610 1989-04-21 1990-04-20 Fabrication d'alliages par evaporation a partir de sources de vapeur multiples Ceased WO1990012485A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8909088A GB2230792A (en) 1989-04-21 1989-04-21 Multiple source physical vapour deposition.
GB8909088.0 1989-04-21

Publications (2)

Publication Number Publication Date
WO1990012485A2 true WO1990012485A2 (fr) 1990-11-01
WO1990012485A3 WO1990012485A3 (fr) 1990-11-29

Family

ID=10655463

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Application Number Title Priority Date Filing Date
PCT/GB1990/000610 Ceased WO1990012485A2 (fr) 1989-04-21 1990-04-20 Fabrication d'alliages par evaporation a partir de sources de vapeur multiples

Country Status (4)

Country Link
EP (1) EP0469050A1 (fr)
JP (1) JPH04505478A (fr)
GB (2) GB2230792A (fr)
WO (1) WO1990012485A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993012262A1 (fr) * 1991-12-16 1993-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Alliage de magnesium contenant du titane obtenu par refroidissement brusque de vapeur
GB2267913A (en) * 1991-12-16 1993-12-22 Secr Defence Titanium containing magnesium alloy produced by vapour quenching
GB2290309B (en) * 1993-02-15 1996-10-30 Secr Defence Diffusion barrier layers
BE1010720A3 (fr) * 1996-10-30 1998-12-01 Centre Rech Metallurgique Procede et dispositif pour revetir en continu un substrat en mouvement au moyen d'un alliage metallique en phase vapeur.
WO2018059019A1 (fr) * 2016-09-27 2018-04-05 京东方科技集团股份有限公司 Creuset, dispositif et système de dépôt par évaporation

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2230792A (en) * 1989-04-21 1990-10-31 Secr Defence Multiple source physical vapour deposition.
GB2248852A (en) * 1990-10-16 1992-04-22 Secr Defence Vapour deposition
US5253266A (en) * 1992-07-20 1993-10-12 Intevac, Inc. MBE effusion source with asymmetrical heaters
US6830626B1 (en) * 1999-10-22 2004-12-14 Kurt J. Lesker Company Method and apparatus for coating a substrate in a vacuum
DE10256038A1 (de) * 2002-11-30 2004-06-17 Applied Films Gmbh & Co. Kg Bedampfungsvorrichtung
JP2009149916A (ja) * 2006-09-14 2009-07-09 Ulvac Japan Ltd 真空蒸気処理装置
WO2011085109A1 (fr) * 2010-01-06 2011-07-14 Directed Vapor Technologies International, Inc. Procédé de co-évaporation et de dépôt de matériaux à des pressions de vapeur différentes
DE102014109196A1 (de) * 2014-07-01 2016-01-07 Aixtron Se Vorrichtung zum Erzeugen eines Dampfes aus einem festen oder flüssigen Ausgangsstoff für eine CVD- oder PVD-Einrichtung
DE102014109195A1 (de) * 2014-07-01 2016-01-07 Aixtron Se Vorrichtung und Verfahren zum Erzeugen eines Dampfes aus mehreren flüssigen oder festen Ausgangsstoffen für eine CVD- oder PVD-Einrichtung
JP7465761B2 (ja) * 2020-08-25 2024-04-11 キヤノントッキ株式会社 坩堝，蒸発源及び蒸着装置
EP4053303A1 (fr) 2021-03-01 2022-09-07 Carl Zeiss Vision International GmbH Procédé de dépôt de vapeur de revêtement d'un verre de lunette, système de dépôt physique en phase vapeur et creuset pour dépôt physique en phase vapeur

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GB990288A (en) * 1961-09-05 1965-04-28 Ibm Improved method of depositing silicon monoxide films
DE1266607B (de) * 1961-09-29 1968-04-18 Philips Nv Verfahren zur Herstellung lichtabsorbierender, farbiger, durchsichtiger Schichten auf einen Traeger durch Aufdampfen im Vakuum
US3361591A (en) * 1964-04-15 1968-01-02 Hughes Aircraft Co Production of thin films of cadmium sulfide, cadmium telluride or cadmium selenide
NL6504932A (fr) * 1965-04-17 1966-10-18
FR1534681A (fr) * 1966-06-15 1968-08-02 Michel A Braguier Procédé de métallisation au zinc en continu d'une bande en matière diélectrique
GB1206586A (en) * 1966-09-07 1970-09-23 Mini Of Technology Vacuum deposition process of forming alloys
GB1292544A (en) * 1970-02-04 1972-10-11 Gen Electric Co Ltd Improvements in or relating to the manufacture of electroluminescent devices
US3751310A (en) * 1971-03-25 1973-08-07 Bell Telephone Labor Inc Germanium doped epitaxial films by the molecular beam method
GB2084197B (en) * 1980-09-23 1984-02-22 Univ Delaware Deposition material by vacuum evaporation
GB2230792A (en) * 1989-04-21 1990-10-31 Secr Defence Multiple source physical vapour deposition.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993012262A1 (fr) * 1991-12-16 1993-06-24 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Alliage de magnesium contenant du titane obtenu par refroidissement brusque de vapeur
GB2267913A (en) * 1991-12-16 1993-12-22 Secr Defence Titanium containing magnesium alloy produced by vapour quenching
GB2290309B (en) * 1993-02-15 1996-10-30 Secr Defence Diffusion barrier layers
BE1010720A3 (fr) * 1996-10-30 1998-12-01 Centre Rech Metallurgique Procede et dispositif pour revetir en continu un substrat en mouvement au moyen d'un alliage metallique en phase vapeur.
WO2018059019A1 (fr) * 2016-09-27 2018-04-05 京东方科技集团股份有限公司 Creuset, dispositif et système de dépôt par évaporation

Also Published As

Publication number Publication date
GB2248457B (en) 1993-05-05
GB9121008D0 (en) 1991-12-11
EP0469050A1 (fr) 1992-02-05
GB8909088D0 (en) 1989-06-07
GB2248457A (en) 1992-04-08
GB2230792A (en) 1990-10-31
WO1990012485A3 (fr) 1990-11-29
JPH04505478A (ja) 1992-09-24

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