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US3196536A - Method of connecting graphite articles to one another or to articles of different materials - Google Patents

Method of connecting graphite articles to one another or to articles of different materials Download PDF

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Publication number
US3196536A
US3196536A US211872A US21187262A US3196536A US 3196536 A US3196536 A US 3196536A US 211872 A US211872 A US 211872A US 21187262 A US21187262 A US 21187262A US 3196536 A US3196536 A US 3196536A
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US
United States
Prior art keywords
articles
weight
graphite
alloy
gold
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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.)
Expired - Lifetime
Application number
US211872A
Inventor
Knippenberg Wilhelm Franciscus
Huizing Albert
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B7/00—Heating by electric discharge
    • H05B7/02—Details
    • H05B7/14—Arrangements or methods for connecting successive electrode sections
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3013—Au as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/006—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of metals or metal salts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of metals or metal salts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/125—Metallic interlayers based on noble metals, e.g. silver
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/126—Metallic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/126—Metallic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • C04B2237/127—The active component for bonding being a refractory metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/704—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the ceramic layers or articles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/708—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the interlayers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/76—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc
    • C04B2237/765—Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc at least one member being a tube
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • graphite is to be understood herein to mean not only carbon crystallized in the form of graphite, but also a material consisting in part of non-crystallized carbon, as may be the case, for example, with commercial products referred to as electrographite.
  • connections between graphite and certain metals may be established with the use of molten metal.
  • Such connections usually have the above-mentioned disadvantages not at all or to a reduced extent only.
  • connections may be obtained with the use of indium or an indium alloy. It is also known, for example, that graphite bodies may be connected to aluminum with the use of tin. Such connections have the disadvantage, however, that indium, in dium alloys and tin have comparatively low melting points.
  • connection between graphite and metals with the use of oxides.
  • a connection between iron and graphite may be obtained by heating in an oxidizing atmosphere, the connection being established by ferric oxide produced.
  • ferric oxide produced Such a connection has a comparatively low mechanical strength.
  • An object of the invention is to overcome the abovementioned disadvantages.
  • articles of graphite are connected together or to articles of other materials by soldering with an alloy of gold having a content of tantalum and/or columbium of at least 1% by weight in vacuo or in an atmosphere of inert rare gas.
  • Alloys having a lower content of tantalum and/or columbium provide insufficient wetting of the surfaces to be connected.
  • Alloys having a tantalum content up to by weight and those having a columbium content up to 10% by weight have melting points lower than 1,300 C. and are 3,195,536 Patented July 27, 1965 ductile.
  • the alloys may therefore readily be formed into wire or foil, which may be advantageous in soldering.
  • alloys having a tantalum content from 5% to 10% by weight.
  • the content of columbium is preferably chosen not higher than about 5% by weight.
  • Alloys of gold with tantalum and/or columbium provide very good wetting of surfaces of graphite articles in soldering.
  • other materials of the most widely varying kinds such as quartz, ceramics and metals, more particularly molybdenum and tungsten, are properly wetted.
  • a graphite rod of 6 mms. in diameter is soldered, at one end, to a tungsten plate with an alloy consisting of 97% by weight of gold and 3% by weight of columbium.
  • the solder in the form of a circular piece of foil of 10 mms. in diameter and microns thick is brought between the rod and the plate.
  • heating takes place to about 1,300 C. in an atmosphere of argon.
  • a graphite tube and a ceramic tube of alumina having the same dimensions as specified in Example 1, are connected together with the use of an alloy consisting of 97% by weight of gold and 3% by weight of tantalum.
  • the tubes are ground at one of their ends to have a conical shape so as to fit into each other over a length of a few mms.
  • a strip of foil 150. microns thick of the said alloy is provided between the ends of the tubes, whereupon heating takes place in vacuo to about l,300 C.
  • a method of joining graphite articles to other articles selected from the group consisting of graphite, quartz, ceramics and metals comprising applying an alloy consisting essentially of gold and a member selected from the group consisting of tantalum in an amount of from 1% to 25% by weight and columbium in an amount of from 1% to 10% by weight in contact with opposing surfaces of said articles and melting said alloy in an inert atmosphere.
  • the alloy is an alloy of gold and from 1% to 25 by weight of tantalum.
  • the alloy is an alloy of gold and from 1% to 10% by weight of columbium.
  • the alloy is an alloy of gold and from 1% to 5% by weight of columbium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Ceramic Products (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)

Description

United States Patent MEN-19D {BF CUNNECTTNG ARTECLES Tl) GNE ANQTHER 0?; T9 ARTICLES 0F DIF- FERENT MATERIALS Wilhelrnus Franciscns Knippenherg and Albert Huizing, Emmasingel, Eindhoven, Netherlands, assignors to North American Philips Company, Hue, New York, N.Y., a corporation of Delaware N0 Drawing. Filed July 23, 1962, Ser. No. 211,872
Claims priority, application Netherlands, Aug. 29, 1961,
268,735 Claims. (Cl. 29-47237) This invention relates to connecting graphite articles to one another or to articles made of different materials.
The term graphite is to be understood herein to mean not only carbon crystallized in the form of graphite, but also a material consisting in part of non-crystallized carbon, as may be the case, for example, with commercial products referred to as electrographite.
Connections to graphite articles obtained with the use of a glue on a basis of organic materials are not suitable for many uses since such connections can resist only comparatively low temperatures. Since gas-tight and liquidtight graphites are now available, tight connections are desired. Mechanical connections, for example screwed or clamped connections, are not serviceable in this case.
It is also known that connections between graphite and certain metals may be established with the use of molten metal. Such connections usually have the above-mentioned disadvantages not at all or to a reduced extent only.
Thus, it is known that such connections may be obtained with the use of indium or an indium alloy. It is also known, for example, that graphite bodies may be connected to aluminum with the use of tin. Such connections have the disadvantage, however, that indium, in dium alloys and tin have comparatively low melting points.
Known also is the use of higher melting metals or alloys, for example solder on a bases of one or more of the metals copper, silver and gold, for connecting graphite articles to other articles consisting wholly or at least at one surface of titanium, zirconium or alloys thereof. A comparatively high-melting connection is thus obtained, it is true, but the use is limited to making connections of graphite to the metals titanium and zirconium.
Finally, it is known to establish connections between graphite and metals with the use of oxides. Thus, for example, a connection between iron and graphite may be obtained by heating in an oxidizing atmosphere, the connection being established by ferric oxide produced. Such a connection has a comparatively low mechanical strength.
An object of the invention is to overcome the abovementioned disadvantages.
According to the invention, articles of graphite are connected together or to articles of other materials by soldering with an alloy of gold having a content of tantalum and/or columbium of at least 1% by weight in vacuo or in an atmosphere of inert rare gas.
Alloys having a lower content of tantalum and/or columbium provide insufficient wetting of the surfaces to be connected.
The use of a tantalum content higher than about 25% by weight, or of a columbium content higher than about 10% by weight involves the disadvantage that the alloys have melting points which are too high for easy working up, or are brittle.
Alloys having a tantalum content up to by weight and those having a columbium content up to 10% by weight have melting points lower than 1,300 C. and are 3,195,536 Patented July 27, 1965 ductile. The alloys may therefore readily be formed into wire or foil, which may be advantageous in soldering.
Very satisfactory results are obtained with alloys having a tantalum content from 5% to 10% by weight. The content of columbium is preferably chosen not higher than about 5% by weight.
Alloys of gold with tantalum and/or columbium provide very good wetting of surfaces of graphite articles in soldering. Besides, other materials of the most widely varying kinds, such as quartz, ceramics and metals, more particularly molybdenum and tungsten, are properly wetted.
In all these cases a very rigid connection is obtained which is little sensitive or not sensitive at all to variations in temperature. This is possibly due to the particular duc tility of the alloys concerned, so that stresses resulting from the different coefficients of expansion of the materials to be connected and of the alloy may readily be absorbed.
Examples (1) Two graphite tubes having an internal diameter of 8 mms. and an external diameter of 10 mms. are soldered together with an alloy consisting of by weight of gold and 5% by weight of tantalum. To this end, an annular piece of wire 200 microns thick of the alloy is brought between the ends of the tubes. Then the solder is melted in vacuo by high-frequency heating to about 1,300 C.
(2) A graphite rod of 6 mms. in diameter is soldered, at one end, to a tungsten plate with an alloy consisting of 97% by weight of gold and 3% by weight of columbium. The solder in the form of a circular piece of foil of 10 mms. in diameter and microns thick is brought between the rod and the plate. Next, heating takes place to about 1,300 C. in an atmosphere of argon.
(3) A graphite tube and a ceramic tube of alumina having the same dimensions as specified in Example 1, are connected together with the use of an alloy consisting of 97% by weight of gold and 3% by weight of tantalum. To this end, the tubes are ground at one of their ends to have a conical shape so as to fit into each other over a length of a few mms. A strip of foil 150. microns thick of the said alloy is provided between the ends of the tubes, whereupon heating takes place in vacuo to about l,300 C.
What is claimed is:
1. A method of joining graphite articles to other articles selected from the group consisting of graphite, quartz, ceramics and metals comprising applying an alloy consisting essentially of gold and a member selected from the group consisting of tantalum in an amount of from 1% to 25% by weight and columbium in an amount of from 1% to 10% by weight in contact with opposing surfaces of said articles and melting said alloy in an inert atmosphere.
2. The method of claim 1 wherein the alloy is an alloy of gold and from 1% to 25 by weight of tantalum.
3. The method of claim 1 wherein the alloy is an alloy of gold and from 5% to 10% by weight of tantalum.
4. The method of claim 1 wherein the alloy is an alloy of gold and from 1% to 10% by weight of columbium.
5. The method of claim 1 wherein the alloy is an alloy of gold and from 1% to 5% by weight of columbium.
References Cited by the Examiner UNITED STATES PATENTS 2,739,375 3/56 Coxe 29-473.1 X 2,979,813 4/61 Steinberg 29472.7 X
JOHN F. CAMPBELL, Primary Examiner.

Claims (1)

1. A METHOD OF JOINING GRAPHITE ARTICLES TO OTHER ARTICLES SELECTED FROM THE GROUP CONSISTING OF GRAPHITE, QUARTZ, CERAMICS AND METALS COMPRISING APPLYING AN ALLOY CONSISTING ESSENTAILLY OF GOLD AND A MEMBER SELECTED FROM THE GROUP CONSISTING OF TANTALUM IN AN AMOUNT OF FROM 1% TO 25% BY WEIGHT AND COLUMBIUM IN AN AMOUNT OF FROM 1% TO 10% BY WEIGHT IN CONTACT WITH OPPOSING SURFACES OF SAID ARTICLES AND MELTING SAID ALLOY IN AN INERT ATMOSPHERE.
US211872A 1961-08-29 1962-07-23 Method of connecting graphite articles to one another or to articles of different materials Expired - Lifetime US3196536A (en)

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NL268735 1961-08-29

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US3196536A true US3196536A (en) 1965-07-27

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US (1) US3196536A (en)
AT (1) AT248834B (en)
BE (2) BE621795A (en)
CH (2) CH445267A (en)
GB (1) GB937947A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425116A (en) * 1966-08-10 1969-02-04 Us Navy Brazing method
US3442006A (en) * 1962-12-17 1969-05-06 Snecma Process for welding or brazing two members of which at least one is made of graphite
DE1671658B1 (en) * 1966-03-25 1971-05-13 Siemens Ag Application of the process for the production of a firmly adhering coating consisting essentially of metal carbide of at least one of the metals from group IVa, Va and VIa on the surface of carbon bodies for the production of solderable coatings for the production of vacuum-tight metal-carbon-
US3725719A (en) * 1970-11-30 1973-04-03 Varian Associates Method and aritcle for inhibiting gaseous permeation and corrosion of material
US3813759A (en) * 1971-09-09 1974-06-04 English Electric Co Ltd Method of brazing
US4000026A (en) * 1973-03-12 1976-12-28 Union Carbide Corporation Method and cement for bonding carbon articles
US5853661A (en) * 1994-07-05 1998-12-29 Cendres Et Metaux Sa High gold content bio--compatible dental alloy
US5972157A (en) * 1995-11-20 1999-10-26 Alliedsignal Inc. Joining of rough carbon-carbon composites with high joint strength

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA775521B (en) * 1977-09-14 1979-01-31 De Beers Ind Diamond Wire drawing die composites
US4180700A (en) * 1978-03-13 1979-12-25 Medtronic, Inc. Alloy composition and brazing therewith, particularly for _ceramic-metal seals in electrical feedthroughs
FR2751640B1 (en) * 1996-07-23 1998-08-28 Commissariat Energie Atomique COMPOSITION AND METHOD FOR REACTIVE BRAZING OF CERAMIC MATERIALS CONTAINING ALUMINUM

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739375A (en) * 1952-09-12 1956-03-27 Handy & Harman Joining of non-metallic materials and brazing filler rods therefor
US2979813A (en) * 1956-09-28 1961-04-18 Horizons Inc Joining of graphite members

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739375A (en) * 1952-09-12 1956-03-27 Handy & Harman Joining of non-metallic materials and brazing filler rods therefor
US2979813A (en) * 1956-09-28 1961-04-18 Horizons Inc Joining of graphite members

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442006A (en) * 1962-12-17 1969-05-06 Snecma Process for welding or brazing two members of which at least one is made of graphite
DE1671658B1 (en) * 1966-03-25 1971-05-13 Siemens Ag Application of the process for the production of a firmly adhering coating consisting essentially of metal carbide of at least one of the metals from group IVa, Va and VIa on the surface of carbon bodies for the production of solderable coatings for the production of vacuum-tight metal-carbon-
US3425116A (en) * 1966-08-10 1969-02-04 Us Navy Brazing method
US3725719A (en) * 1970-11-30 1973-04-03 Varian Associates Method and aritcle for inhibiting gaseous permeation and corrosion of material
US3813759A (en) * 1971-09-09 1974-06-04 English Electric Co Ltd Method of brazing
US4000026A (en) * 1973-03-12 1976-12-28 Union Carbide Corporation Method and cement for bonding carbon articles
US5853661A (en) * 1994-07-05 1998-12-29 Cendres Et Metaux Sa High gold content bio--compatible dental alloy
US5972157A (en) * 1995-11-20 1999-10-26 Alliedsignal Inc. Joining of rough carbon-carbon composites with high joint strength

Also Published As

Publication number Publication date
BE621795A (en) 1900-01-01
GB937947A (en) 1963-09-25
CH427308A (en) 1966-12-31
AT248834B (en) 1966-08-25
CH445267A (en) 1967-10-15
BE621794A (en) 1900-01-01

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