US3526550A - Surface preparation of iron-chromium alloy parts for metal-to- glass seals - Google Patents

Surface preparation of iron-chromium alloy parts for metal-to- glass seals Download PDF

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Publication number
US3526550A
US3526550A US679810A US3526550DA US3526550A US 3526550 A US3526550 A US 3526550A US 679810 A US679810 A US 679810A US 3526550D A US3526550D A US 3526550DA US 3526550 A US3526550 A US 3526550A
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Prior art keywords
iron
oven
oxide
coating
alloy
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US679810A
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English (en)
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Eugene P Larson
Edward C Slick
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GTE Sylvania Inc
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Sylvania Electric Products Inc
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/04—Joining glass to metal by means of an interlayer
    • C03C27/042—Joining glass to metal by means of an interlayer consisting of a combination of materials selected from glass, glass-ceramic or ceramic material with metals, metal oxides or metal salts
    • C03C27/046—Joining glass to metal by means of an interlayer consisting of a combination of materials selected from glass, glass-ceramic or ceramic material with metals, metal oxides or metal salts of metals, metal oxides or metal salts only

Definitions

  • the invention relates to an oxide coated stainless steel alloy and to the method of its production and more particularly to the oxide coating on stainless steel alloys containing a small percentage of nickel and to the method of producing the coating.
  • oxidized alloy articles are bonded with or embedded in glass in applications where hermetic seals need not be a consideration.
  • An example of such usage is the embedding of oxidized studs into the rim or wall portion of the face panel of a color cathode ray tube wherein the studs support the foraminous mask associated with the face panel.
  • Another object of the invention is to provide an oxide coating on the alloy article to provide a seal to glass which does not occlude gases in the form of bubbles, nor diffuse suflicient siliceous material through the oxide to the base metal to impair the adherence of the oxide to the metal.
  • a further object of the invention is to provide a method which is less complicated and less expensive than conventionally utilized procedures for forming the desired oxide coating on a chrome-iron alloy.
  • FIG. 1 is a diagrammatic representation of one embodiment of the invention illustrating an apparatus for carrying out a batch oxidation process
  • FIG. 2 is a representation of another embodiment utilizing a continuous oxidation process
  • FIG. 3 is an enlarged view of an oxidized stainless steel stud, the thickness of the coating being exaggerated to provide clarity of illustration.
  • the chrome-iron alloy or stainless steel utilized in these parts preferably has the composition consisting of at least 5% chromium, less than 0.15% carbon, 1.0% maximum each of manganese and silicon, no more than .5% of nickel and the balance iron except for minor traces of elements such as sulfur, phosphorous and aluminum.
  • other stainless steel alloys may be used in the carrying out of this invention since the essential elements of the alloy necessary to form the oxides are the iron and chromium therein.
  • the articles being oxidized as an example may be lead-in wires for electronic tubes, to be fused into a glass header, high voltage anode buttons for electronic picture tubes, or support studs to be embedded in the flange of a face plate of a tri-color dot picture tube for supporting the perforated mask associated with the plate.
  • the parts to be oxidized if small, and here illustrated as support studs 22, may be spacedly placed in a tray or boat 24 so that oxidizing gases may fully reach all parts intended to be oxidized, the boat being pushed along the chute by a rod or other means to desired locations in the chute.
  • the ends of the chute are closed by gravity operated doors 25 and 26, pivoted adjacent their upper ends, as at 28.
  • the natural gas is that normally fed from the gas mains to domestic and commercial users and consists of a mixture of gases containing essentially the following combustible gases: methane (CH ethane (C H carbon monoxide (CO) and propane (C H having a B.t.u. of approximately 1040.
  • methane CH ethane
  • propane C H having a B.t.u. of approximately 1040.
  • This gas is burned in atmospheric air under controlled conditions to form the cracked gas utilized in the invention, the cracked gas having the following percentage composition:
  • the carbon dioxide and Water vapor of the mixture dissociate into the monoxide of carbon and nascent oxygen according to the reaction (1) and hydrogen and nascent oxygen according to the reaction (2).
  • the iron and chromium in the alloy at the surface of the parts and because of the existence of the nascent oxygen are oxidized to ferrous oxide and chromium oxide according to the reactions:
  • the cracked gas is fed into the chute and oven at the rate per hour of 1.5 to 4 cu. ft. per square inch of cross section of the duct (and at a preferred flow of 2.5 cu. ft. per hr. per square inch of cross section of the chute).
  • the gas is initially fed into and through the chute to thoroughly purge the unit of air.
  • a loaded boat 24, or a plurality of aligned loaded boats are placed into the purging chamber 16 of the chute and allowed to remain there from one to three minutes, the time depending on the mass of the boat and of the parts 22 in the boats; the more mass, the longer the time.
  • the furnace door 25 should be in the closed position after insertion of the boat and during this initial period.
  • the door 25 is again momentarily opened to admit a push rod to engage the nearby boat, and thrust it (or the aligned plurality of them) into the open proper and into the center of the hot zone in the oven which is maintained at a temperature of between 2050 F. and 2150 F., preferably 2100 F.
  • the boats are allowed to remain in the hot oven area for a period of 5 to 15 minutes, according to the mass of parts 22 and that of the boat so as to permit the parts to reach the temperature of the ambient atmosphere within the oven. This period can be determined by the time necessary for the furnace controller, and which measures the temperature of the atmosphere within the oven, to return to the optimum predetermined interior temperature position. A period of an additional 20 to 30 minutes, preferably 25 minutes is allowed at the optimum temperature in order to develop the hitherto described oxide coating on the parts 22.
  • the door 25 is momentarily opened to allow for the repositioning, by the use of the push rod or the like, of the boat into the cooling area 18 of the chute and to enable the placing of a second boat into the purging chamber 16 of the chute.
  • the boat in the cooling chamber is permitted to remain therein for a period of fifteen to twenty minutes depending on the mass of the boat and articles and then removed through the door 26.
  • FIG. 2 A preferred continuous process of handling the articles or the articles on boats is disclosed in FIG. 2.
  • articles such as lead-in wires 50
  • wire feed apparatus such as is shown in the patent to Englert 2,979,228 from a hopper 52 onto a horizontal metallic wire mesh belt 54 trained over an idler roll 56 and a drive roll 58, the latter 'being coupled to a motor (not shown) in a well known manner.
  • the upper run off of the belt is surrounded intermediate its length by a heat insulated oven 60, heated by suitable means, as electric resistance wires 62 embedded in the walls of the oven and connected to a suitable source of supply.
  • the belt extends through openings 64 and 66 in the end walls of the oven.
  • a takeoif belt 78 may be provided to move the articles to the next processing station.
  • a cracked gas containing carbon dioxide, carbon monoxide, hydrogen and water vapor in the proportions hitherto defined is fed at the rate defined to the space beneath the shroud 70 by means of pipe 80. In this case, it is the cross-sectional area of the shroud which is a factor of the gas flow rate rather than the cross-sectional area of the chute.
  • the shroud 70 and upper run of the belt adjacent thereto are surrounded by a jacket 82 cooled by a refrigerant, as water, as in the previous form of invention.
  • FIG. 2 there is shown at 50 a representation of a lead-in wire in the process of being oxidized while in FIG. 3 there is shown a stud utilized for associating a face plate of a color television tube with its perforated mask, the stud being oxidized, the oxide coating being exaggerated in size for the sake of clarity of illustration.
  • an improved oxide coating on stainless steel alloy material and an advantageous method for forming the same.
  • the oxide coated article exhibits improved sealing with compatible glass having substantially matching thermal expansion and provides a resultant bonding joint of superior quality.
  • the method of forming the oxide on the alloy material is accomplished with standard equipment obviating the necessity of building expensive specialized machinery.
  • the new process utilizes less hazardous gases than those normally used by the prior art for oxidizing subject type of alloys.
  • a process for oxidizing articles made of ironchromium alloys to promote glass-to-metal bonding comprising the steps of:
  • a stainless steel article having a coating thereon, said coating being an oxide coating including a rhombohedral solid solution of oxides of iron and chromium in the form of Fe O Cr O 9.
  • An article as defined in claim 9 having an exposed surface coating of ferrosoferric oxide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
US679810A 1967-11-01 1967-11-01 Surface preparation of iron-chromium alloy parts for metal-to- glass seals Expired - Lifetime US3526550A (en)

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US67981067A 1967-11-01 1967-11-01

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US (1) US3526550A (enrdf_load_stackoverflow)
BE (1) BE723184A (enrdf_load_stackoverflow)
GB (1) GB1253059A (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715244A (en) * 1971-08-26 1973-02-06 Corning Glass Works Chromium film microcircuit mask
US3775999A (en) * 1972-06-08 1973-12-04 Ibm Method of sealing electrodes to glass with a glass frit
US3804609A (en) * 1971-12-30 1974-04-16 Ibm Method of gas panel construction
US3837724A (en) * 1971-12-30 1974-09-24 Ibm Gas panel fabrication
US4149910A (en) * 1975-05-27 1979-04-17 Olin Corporation Glass or ceramic-to-metal composites or seals involving iron base alloys
US4348241A (en) * 1981-02-12 1982-09-07 Shinhokoku Steel Corporation Heat-treatment of semifinished product-sliding surface of shaping members in plastic metal-working apparatus
US20070131022A1 (en) * 2005-12-14 2007-06-14 Denso Corporation Gas sensor
US20100119740A1 (en) * 2008-10-17 2010-05-13 Electronics Packaging Solutions, Inc. Glass-to-metal bond structure
US9328512B2 (en) 2011-05-05 2016-05-03 Eversealed Windows, Inc. Method and apparatus for an insulating glazing unit and compliant seal for an insulating glazing unit
US9540863B2 (en) 2010-06-02 2017-01-10 Eversealed Windows, Inc. Multi-pane glass unit having seal with adhesive and gas-restrictive coating layer
US9546513B2 (en) 2013-10-18 2017-01-17 Eversealed Windows, Inc. Edge seal assemblies for hermetic insulating glass units and vacuum insulating glass units

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1787977A (en) * 1928-06-25 1931-01-06 Frank A Fahrenwald Process of heat-treating steel
US2502855A (en) * 1944-10-18 1950-04-04 Sylvania Electric Prod Preoxidation of stainless steel
US2519127A (en) * 1945-04-23 1950-08-15 American Steel & Wire Co Method of drawing stainless steel wire
US2680085A (en) * 1949-10-26 1954-06-01 Smith Corp A O Method of maintaining dimensional tolerances in partially enameled metal objects
US2933423A (en) * 1958-03-03 1960-04-19 Kimble Glass Co Preoxidation of stainless steel for glass-to-metal sealing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1787977A (en) * 1928-06-25 1931-01-06 Frank A Fahrenwald Process of heat-treating steel
US2502855A (en) * 1944-10-18 1950-04-04 Sylvania Electric Prod Preoxidation of stainless steel
US2519127A (en) * 1945-04-23 1950-08-15 American Steel & Wire Co Method of drawing stainless steel wire
US2680085A (en) * 1949-10-26 1954-06-01 Smith Corp A O Method of maintaining dimensional tolerances in partially enameled metal objects
US2933423A (en) * 1958-03-03 1960-04-19 Kimble Glass Co Preoxidation of stainless steel for glass-to-metal sealing

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715244A (en) * 1971-08-26 1973-02-06 Corning Glass Works Chromium film microcircuit mask
US3804609A (en) * 1971-12-30 1974-04-16 Ibm Method of gas panel construction
US3837724A (en) * 1971-12-30 1974-09-24 Ibm Gas panel fabrication
US3775999A (en) * 1972-06-08 1973-12-04 Ibm Method of sealing electrodes to glass with a glass frit
US4149910A (en) * 1975-05-27 1979-04-17 Olin Corporation Glass or ceramic-to-metal composites or seals involving iron base alloys
US4348241A (en) * 1981-02-12 1982-09-07 Shinhokoku Steel Corporation Heat-treatment of semifinished product-sliding surface of shaping members in plastic metal-working apparatus
US20070131022A1 (en) * 2005-12-14 2007-06-14 Denso Corporation Gas sensor
US7484402B2 (en) * 2005-12-14 2009-02-03 Denso Corporation Gas sensor
US20100119740A1 (en) * 2008-10-17 2010-05-13 Electronics Packaging Solutions, Inc. Glass-to-metal bond structure
US9540863B2 (en) 2010-06-02 2017-01-10 Eversealed Windows, Inc. Multi-pane glass unit having seal with adhesive and gas-restrictive coating layer
US9328512B2 (en) 2011-05-05 2016-05-03 Eversealed Windows, Inc. Method and apparatus for an insulating glazing unit and compliant seal for an insulating glazing unit
US10119327B2 (en) 2011-05-05 2018-11-06 Astravac Glass, Inc. Method and apparatus for an insulating glazing unit and compliant seal for an insulating glazing unit
US11035168B2 (en) 2011-05-05 2021-06-15 Astravac Glass, Inc. Method and apparatus for an insulating glazing unit and compliant seal for an insulating glazing unit
US9546513B2 (en) 2013-10-18 2017-01-17 Eversealed Windows, Inc. Edge seal assemblies for hermetic insulating glass units and vacuum insulating glass units

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BE723184A (enrdf_load_stackoverflow) 1969-04-01
GB1253059A (enrdf_load_stackoverflow) 1971-11-10

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