US3522021A - Process for metalliding aluminum surfaces - Google Patents

Process for metalliding aluminum surfaces Download PDF

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Publication number
US3522021A
US3522021A US741332A US3522021DA US3522021A US 3522021 A US3522021 A US 3522021A US 741332 A US741332 A US 741332A US 3522021D A US3522021D A US 3522021DA US 3522021 A US3522021 A US 3522021A
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United States
Prior art keywords
aluminum
metalliding
salt
coating
metal
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Expired - Lifetime
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US741332A
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English (en)
Inventor
Newell C Cook
William J Hayes
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GANNON UNIVERSITY ERIE
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General Electric Co
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Assigned to GANNON UNIVERSITY ERIE, PA reassignment GANNON UNIVERSITY ERIE, PA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GENERAL ELECTRIC COMPANY
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/007—Electroplating using magnetic fields, e.g. magnets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/38—Systems for generation, homogenisation or stabilisation of the main or gradient magnetic field
    • G01R33/389—Field stabilisation, e.g. by field measurements and control means or indirectly by current stabilisation
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/939—Molten or fused coating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/941—Solid state alloying, e.g. diffusion, to disappearance of an original layer
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/12743—Next to refractory [Group IVB, VB, or VIB] metal-base component
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories

Definitions

  • This invention relates to a method for forming diffusion coatings on aluminum and aluminum alloy surfaces. More particularly this invention is concerned with an electrolytic process for alloying the surface of aluminum in molten salt baths.
  • diffusion coatings can be formed on metal surfaces by several high temperature processes evaporative, gaseous, pack cementation, immersion in molten metals and electrolysis in molten salts. These methods, however, have been used almost exclusively to coat metals that melt above 1000 C. in which operating temperatures were usually above 800 C. and frequently at 1000-1200" C. The low melting point of aluminum (660 C.) and the high temperatures generally required for operating most of the coating processes had made it appear unlikely that diffusion coatings could be formed on aluminum and aluminum alloys.
  • hard, adherent, tough, corrosion resistant coatings can be formed on aluminum and aluminum alloys by electrolytically depositing certain metals onto the aluminum surface from fused halide salt mixtures operating at temperatures below the melting point of aluminum and using anodes of the material being deposited, current densities which match the diffusion rates, and atmospheres that are inert to the coating system.
  • a metalliding metal is employed as the anode and is immersed in a fused mixed halide bath composed essentially of a mixture of the chlorides, bromides, with or without the fluorides of members from the alkali, alkaline earth metals and from 0.01 to 100 mole percent of a halide of the metalliding metal.
  • the cathode employed is aluminum or an aluminum alloy upon which deposit is to be made. It has been found that such a combination is an electric cell in which an electric current is generated when an electrical connection, which is external to the fused bath, is made between the aluminum cathode and the metalliding anode.
  • the metalliding metal dissolves in the fused salt bath and metalliding ions are discharged at the surface of the aluminum cathode where they form a deposit of the metalliding metal which immediately diffuses into and reacts with the aluminum to form a metallide coating.
  • metallide is 3,522,021 Patented July 28, 1970 employed to designate any solid solution or alloy of the metalliding metal and the aluminum metal substrate regardless of whether the aluminum does or does not form an intermetallic compound with the metalliding reagents in definite stoichiometric proportions which can be represented by a chemical formula.
  • the rate of dissolution and deposition of the metalliding agent is self-regulating in that the rate of deposition is equal to the rate of diffusion of the metalliding metal into the aluminum cathode.
  • the deposition rate can be decreased by inserting some resistance in the circuit. A faster rate can be obtained by impressing a limited amount of voltage into the circuit to supply additional direct current.
  • the molten salts that can be employed in the process of this invention are the mixtures of chlorides, and/or bromides, with or without the fluorides, of Group I-A, II-A metals and/or the halides of the metalliding metal being employed, that melt below the melting point of aluminum or the aluminum alloy coating being formed thereon, and which mixtures do not contain metal ions that interfere with the desired coating process.
  • the metal halide mixture which can be em ployed in the process of this invention, includes the alkali and alkaline earth metal chlorides; mixtures of the above chlorides with the alkali and alkaline earth metal fluorides; mixtures of the alkali and alkaline earth metal bromides and chlorides; and mixtures of these bromides and fluorides providing the salt mixtures melt below the melting point of aluminum and the alloy coating being formed thereon.
  • a mixture containing substantial concentrations of fluoride it is preferred to avoid the use of the fluorides of potassium, rubidium and cesium because of the displacement of these metals by aluminum and the 'volatilization of these metals with obvious disadvantages.
  • the temperature at which the process of this invention is operated is critical but can readily be determined by one skilled in the art from such melting points.
  • the particular halide mixtures employed in the process of this invention must melt below the melting point of aluminum or the alloy coating.
  • chloride systems or mixed chloride-fluoride systems which melt low enough to permit their use.
  • Many of these halide eutectic systems can be found in and in Phase Diagrams for Ceramists by Levin, Robbins, and McMurdie published by American Ceramic Society (1964) and in Phase Diagrams for Nuclear Reactor Materials by R. E. Thoma of Oak Ridge National Laboratory, ONRL-2548.
  • the process of this invention In order to produce diffusion coatings rapidly, it is preferred to operate the process of this invention at temperatures as high as possible; e.g., 500 C. to about 650 C. Inasmuch as the diffusion coatings of some metals form compounds that lower the melting point of aluminum, the process in those instances has to be run considerably below the melting point of aluminum; e.g., at 400 to 500 C. for magnesiding, etc. Other diffusion coatings form compounds that have very high melting pointsthat is, the rare earth aluminidesand in such instances it is preferable to operate as close as possible to the melting point of aluminum; i.e., 600650 C. It has been found that the density of the salts, about 2 to 3, will give sufficient bouyancy to the light weight aluminum that it is possible to operate very near to the melting point of aluminum without causing distortion of the parts being coated.
  • the metalliding reagents which can be diffused into aluminum in accordance with the process of this invention include the metals lithium, magnesium, scandium, yttrium, lanthanum and the natural rare earths of the lanthanide series, actinium and the natural rare earths of the actinide series, hafnium and zirconium. Combinations of these metalliding reagents can also be diffused into the aluminum surfacesimultaneously, when proper adjustments of molar concentrations of the metalliding ions are made in the salt, and/or sequentially, by selecting the correct sequence as dictated by reactivities of the metalliding agents.
  • the amount of metalliding halide in the fused salt bath can be from 0.01 to 100 mole percent. It is preferred in most instances for ecenomy that the amount of metallidinghalide in the fused salt bath be maintained at about 0.1 to 50 mole percent, and even more preferred from 0.1 to 5 mole percent.
  • the chemical composition of the fused salt bath is critical if good metallide coatings on aluminum are to be obtained.
  • the starting salt should be as anhydrous and as free of all impurities as is possible, or should be easily dried or purified by simply heating during the fusion step. Because most of the metalliding reagents which can be diffused into aluminum react With oxygen, nitrogen and hydrogen, the process must be carried out in an inert atmosphere and especially in the substantial absence of oxygen. Thus, for example, the process can be carried out in an argon gas atmosphere. By the term substantial absence of oxygen, it is meant that neither atmospheric oxygen nor oxides of metals are present in the fused salt bath.
  • an electric current will flow through the circuit without any applied electromotive force.
  • the anode acts by dissolving in the fused salt bath to produce electrons and the metalliding ions.
  • the electrons flow through the external circuit formed by the conductor and the metal ions migrate through the fused salt bath to the aluminum metal cathode to be metallided, where the electrons discharge the metalliding ions and form a metallide coating on the aluminum.
  • the amount of current can be measured with an ammeter which enables one to readily calculate the amount of metal being deposited on the aluminum cathode and being converted to the metallide layer. Knowing the area of the article being plated, it is possible to calculate the thickness of the metallide coating formed, thereby permitting accurate control of the process to obtain any desired thickness of the metallide layer.
  • the process operates very satisfactorily without impressing any additional electromotive force on the electrical circuit, it has been found that it is possible to apply a small voltage to obtain constant current densities during the reaction, and to increase the deposition rate of the metalliding agent being deposited.
  • the additional should be adjusted so that the diffusion rate of the metalliding reagent into the aluminum cathode is not exceeded.
  • the additional (when external resistance is negligible) should not exceed 1.0 volt and preferably should fall between 0.1 and 0.5 volt.
  • the deposition rate of the iding agent must always be adjusted so as not to exceed the diffusion rate of the iding agent into the substrate material if high efficiency and high quality diffusion coatings are to be obtained.
  • the maximum current density for good metalliding will generally not exceed 10 amperes per dm. Higher current densities can sometimes be used to form coatings but in addition to the formation of a metallide coating, plating of the iding agent occurs over the diffusion layer.
  • Very low current densities (0.0l0.1 amp/rim?) are often employed when diffusion rates are correspondingly low, and when very dilute surface solutions or very thin coatings are desired.
  • the composition of the diffusion coating can be changed by varying the current density, producing under one condition a composition suitable for one application and under another condition a composition suitable for another application.
  • current densities to form good quality metallide coatings on aluminum fall between 0.1 and 5 amperes/ dm. for the preferred temperature ranges of this disclosure.
  • the source for example, a battery or other source of direct current
  • the source should be connected in series with the external circuit so that the negative terminal is connected to the external circuit, terminating at the aluminum cathode being metallided and the positive terminal is connected to the external circuit terminating at the metal anode. In this way, the voltages of both sources are algebraically additive.
  • measuring instruments such as voltmeters, ammeters, resistances, timers, etc., may be included in the external circuit to aid in the control of the process.
  • the metallided aluminum compositions prepared by the process of this invention have a Wide variety of uses. They can be used to fabricate vessels for chemical reactions, to make gears, bearings and other articles requiring hard wear and corrosion resistant surfaces, and other articles where close tolerances are needed. Other uses will be readily apparent to those skilled in the art as well as other modifications and variations of the present invention in light of the above teachings.
  • EXAMPLE 1 A mixture of barium chloride 1070 g., 5.2 moles), potassium chloride (555 g., 7.4 moles) and sodium chloride (342 g., 5.9 moles) was charged into a Monel pot (3%" ID. x 3 /2" OD. x 12" deep, with a top flange 6 /2" x /2: thick) which was then sealed with a water-cooled nickel plated steel cover plate (6%" diam. x 1" thick) fitted with two glass electrode towers (1%" diameter), a bubbler for introducing inert gas beneath the salt and a thermocouple well for measuring and controlling the temperature of the molten salt. The cell was alternately evacuated to 0.5 mm.
  • Cerium chloride (37.1 g., 0.15 mole) was added to bring total molar concentration of CeCl in the fused salt to -0.9% and after one-half hour of electrolytic cleanup at 0.1 ampere against a nickel screen, an aluminum strip (8 X 1.2 x 0.1) was cerided at 600 C. as follows:
  • KHN Knoop Hardness Number EXAMPLE 3
  • the sample could be bent in a two inch radius before cracking on the compression side and in a one inch radius before cracking on the tension side.
  • the surface of the sample was readily polished by emery paper into a smooth shiny surface that has retained its luster for three months in air; also the surface of the coating is resistant to both concentrated and dilute nitric acid. Pure cerium is very reactive with nitric acid and tarnishes rapidly in air.
  • CeCl 103 g., 0.42 molebringing total molar concentration of CeCl in salt to 3.1 mOle percent
  • the coating was very flexible, maintained its bright finish for several months exposure in air and X-ray examination showed it to be an alloy of aluminum and magnesium.
  • a method for forming metallide coatings on aluthickness can be made it the current densities are low minum and aluminum alloys with a metalliding metal (-0.125 amp/dm?) so that magnesium concentration in selected from the group consisting of lithium, magnesium, the coating remains low.
  • salts selected from the group consisting of the chlo- WaS llfanlded at as follows: rides, and bromides of sodium, potassium, rubidium,
  • the method of claim 1 wherein the salt composition scribed in Table III. is a mixture of chlorides and bromides.
  • the fused salt consists essentially of barium chloride, potassium, sodium chloride and cerium chloride.
  • the fused salt is composed essentially of barium chloride, lithium chloride and yttrium chloride.
  • the fused salt consists essentially of barium chloride, potassium chloride, sodium chloride and uranium chloride.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electrolytic Production Of Metals (AREA)
US741332A 1968-07-01 1968-07-01 Process for metalliding aluminum surfaces Expired - Lifetime US3522021A (en)

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US74133268A 1968-07-01 1968-07-01
US74149668A 1968-07-01 1968-07-01

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US741496A Expired - Lifetime US3530371A (en) 1968-07-01 1968-07-01 Internal field-frequency control for impulse gyromagnetic resonance spectrometers

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US741496A Expired - Lifetime US3530371A (en) 1968-07-01 1968-07-01 Internal field-frequency control for impulse gyromagnetic resonance spectrometers

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US (2) US3522021A (enrdf_load_stackoverflow)
DE (2) DE1928454C3 (enrdf_load_stackoverflow)
FR (2) FR2012109A1 (enrdf_load_stackoverflow)
GB (2) GB1243877A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037608A (en) * 1988-12-29 1991-08-06 Aluminum Company Of America Method for making a light metal-rare earth metal alloy
US6045631A (en) * 1997-10-02 2000-04-04 Aluminum Company Of America Method for making a light metal-rare earth metal alloy
WO2009106269A1 (de) * 2008-02-26 2009-09-03 Ewald Dörken Ag Beschichtungsverfahren für ein werkstück
US20090321404A1 (en) * 2008-06-27 2009-12-31 Lincoln Global, Inc. Addition of rare earth elements to improve the performance of self shielded electrodes
US20110132769A1 (en) * 2008-09-29 2011-06-09 Hurst William D Alloy Coating Apparatus and Metalliding Method

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CH521582A (de) * 1969-11-08 1972-04-15 Spectrospin Ag Verfahren und Vorrichtung zur Fourieranalyse von Interferenzsignalen
DE2126744C3 (de) * 1971-05-28 1975-09-04 Spectrospin Ag, Faellanden, Zuerich (Schweiz) Verfahren zur Aufnahme von Spinresonanzspektren und Vorrichtung zu dessen Durchführung
JPS4832586A (enrdf_load_stackoverflow) * 1971-08-30 1973-04-28
US3789832A (en) * 1972-03-17 1974-02-05 R Damadian Apparatus and method for detecting cancer in tissue
US4015196A (en) * 1974-04-05 1977-03-29 National Research Development Corporation Analysis of materials
US4110681A (en) * 1977-02-16 1978-08-29 International Business Machines Corporation NMR field frequency lock system
GB1601816A (en) * 1977-05-27 1981-11-04 Nat Res Dev Investigation of samples by nmr techniques
US4166972A (en) * 1977-10-05 1979-09-04 Southwest Research Institute NMR discrimination apparatus and method therefor
JPS5485093A (en) * 1977-12-20 1979-07-06 Hitachi Ltd Magnetic field stabilizing apparatus in nuclear magnetic resonator
GB1578910A (en) * 1978-05-25 1980-11-12 Emi Ltd Imaging systems
US4543529A (en) * 1983-01-04 1985-09-24 Nmr Imaging, Inc. Method of tuning an NMR apparatus
US4959543A (en) * 1988-06-03 1990-09-25 Ionspec Corporation Method and apparatus for acceleration and detection of ions in an ion cyclotron resonance cell
DE69131447T2 (de) * 1990-11-19 2000-01-27 Nikkiso Co., Ltd. Fouriertransformation-massenspektrometer
US7777485B2 (en) * 2006-08-15 2010-08-17 General Electric Company Method for multiplexed MR tracking
WO2013046337A1 (ja) * 2011-09-27 2013-04-04 株式会社エム・アール・テクノロジー 画像撮像装置及び画像撮像方法
CN104746114B (zh) * 2015-04-20 2017-10-20 华北理工大学 一种Fe‑Mo复合材料及其制备方法

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US2786809A (en) * 1953-09-30 1957-03-26 Horizons Titanium Corp Electrolytic cladding
US2828251A (en) * 1953-09-30 1958-03-25 Horizons Titanium Corp Electrolytic cladding process
US3024175A (en) * 1959-08-04 1962-03-06 Gen Electric Corrosion resistant coating
US3024176A (en) * 1959-08-04 1962-03-06 Gen Electric Corrosion resistant coating
USRE25630E (en) * 1964-08-04 Corrosion resistant coating
US3232853A (en) * 1962-03-05 1966-02-01 Gen Electric Corrosion resistant chromide coating

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US3358222A (en) * 1964-06-05 1967-12-12 Varian Associates Gyromagnetic resonance apparatus utilizing pulsed rf excitation
US3461381A (en) * 1968-06-14 1969-08-12 Varian Associates Phase sensitive analog fourier analyzer readout for stored impulse resonance spectral data

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USRE25630E (en) * 1964-08-04 Corrosion resistant coating
US2786809A (en) * 1953-09-30 1957-03-26 Horizons Titanium Corp Electrolytic cladding
US2828251A (en) * 1953-09-30 1958-03-25 Horizons Titanium Corp Electrolytic cladding process
US3024175A (en) * 1959-08-04 1962-03-06 Gen Electric Corrosion resistant coating
US3024176A (en) * 1959-08-04 1962-03-06 Gen Electric Corrosion resistant coating
US3232853A (en) * 1962-03-05 1966-02-01 Gen Electric Corrosion resistant chromide coating

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037608A (en) * 1988-12-29 1991-08-06 Aluminum Company Of America Method for making a light metal-rare earth metal alloy
US6045631A (en) * 1997-10-02 2000-04-04 Aluminum Company Of America Method for making a light metal-rare earth metal alloy
WO2009106269A1 (de) * 2008-02-26 2009-09-03 Ewald Dörken Ag Beschichtungsverfahren für ein werkstück
US20110000793A1 (en) * 2008-02-26 2011-01-06 Ewald Doerken Ag Coating method for a workpiece
US20090321404A1 (en) * 2008-06-27 2009-12-31 Lincoln Global, Inc. Addition of rare earth elements to improve the performance of self shielded electrodes
US9138831B2 (en) * 2008-06-27 2015-09-22 Lincoln Global, Inc. Addition of rare earth elements to improve the performance of self shielded electrodes
US20110132769A1 (en) * 2008-09-29 2011-06-09 Hurst William D Alloy Coating Apparatus and Metalliding Method

Also Published As

Publication number Publication date
FR2012109A1 (enrdf_load_stackoverflow) 1970-03-13
DE1928454B2 (de) 1977-09-22
GB1243877A (en) 1971-08-25
US3530371A (en) 1970-09-22
DE1928454A1 (de) 1970-07-30
DE1933010A1 (de) 1970-01-08
GB1266236A (enrdf_load_stackoverflow) 1972-03-08
FR2012104A1 (enrdf_load_stackoverflow) 1970-03-13
DE1928454C3 (de) 1978-09-21

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