US3746536A - Sealing alloy - Google Patents

Sealing alloy Download PDF

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Publication number
US3746536A
US3746536A US00168824A US3746536DA US3746536A US 3746536 A US3746536 A US 3746536A US 00168824 A US00168824 A US 00168824A US 3746536D A US3746536D A US 3746536DA US 3746536 A US3746536 A US 3746536A
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US
United States
Prior art keywords
alloy
weight
content
rare earth
oxide film
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.)
Expired - Lifetime
Application number
US00168824A
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English (en)
Inventor
T Kuse
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.)
Toshiba Corp
Original Assignee
Tokyo Shibaura Electric Co Ltd
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
Priority claimed from JP6864370A external-priority patent/JPS493723B1/ja
Priority claimed from JP6864470A external-priority patent/JPS493724B1/ja
Priority claimed from JP11908870A external-priority patent/JPS493890B1/ja
Application filed by Tokyo Shibaura Electric Co Ltd filed Critical Tokyo Shibaura Electric Co Ltd
Application granted granted Critical
Publication of US3746536A publication Critical patent/US3746536A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C03C27/02—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing by fusing glass directly to metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel

Definitions

  • This invention relates to an alloy scalable to soft glass and especially suitable for sealing cathode ray tubes.
  • a 18Cr-Fe alloy having a thermal expansion coefficient of 113x10 cm./ cm./ C., which approximates the thermal expansion coefiicient of soft glass is known.
  • This alloy is well known as an or type stainless steel, which is designated as SUS 24 in the Japanese Industrial Standard (JIS).
  • SUS 24 approximately corresponds to AISI-430 in the American Standard of Testing Material (ASTM).
  • the composition thereof is: 16-18% Cr, not more than 0.12% C, not more than 0.75% Si, not more than 1.00% Mn, not more than 0.04% P, not more than 0.03% S (all by weight) and balance Fe.
  • the SUS 24 alloy is, after being formed into a desired shape, subjected to wet hydrogen furnace treatment for 10-90 minutes under the conditions of 900-1200 C. of furnace temperature and -40 C. of hydrogen dew point for the purpose of forming oxide film on the surface thereof.
  • the alloy piece thus having the oxide film on the surface thereof is scalable to soft glass.
  • the oxide film is firmly bonded to soft glass.
  • the 18Cr-Fe alloy is disadvantageous in that it is inferior in corrosion resistance.
  • the 18Cr-Fe alloy sealed to soft glass is susceptible to intergranular corrosion when the sealed alloy piece is pickled.
  • the following problems are left to be solved with respect tothe 18Cr-Fe alloy: Bonding strength between the oxide film and the substrate alloy is weak; the electric resistance of the oxide film is so high that establishment of an electric contact through the oxide film is impossible; and the alloy is liable to undergo precipitation of 7 phase from the or phase; when it is heat-treated etc.
  • an alloy comprising 15- 30% by weight of Cr, 0.001-2.0% by Weight of at least one element selected from a rare earth metal group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and balance of Fe is provided.
  • the alloy of this invention having a composition within the scope of the above-mentioned range possesses very excellent corrosion resistance. Further, the alloy of this invention may contain 0.1-0.9% by weight of Ti, 0.l5-1.5% by weight of Al and 0-0.5% by weight of M0 in addition to the rare earth element or elements. Addition of Ti, Al or Mo increases bonding strength between the oxide film and the substrate alloy, decreases electric resistance of the formed oxide film and prevents precipitation of 7 phase out of or phase.
  • FIG. 1 represents a phase diagram of the Cr-Fe binary system
  • FIG. 2 is a graph showing the relation between the Cr content and the thermal expansion coeflicient of Cr- Fe alloy.
  • FIG. 3 is a graph showing the relation between the Cr content and the mechanical properties of Cr-Fe alloy.
  • the Cr-Fe alloy becomes brittle as the Cr content thereof increases, since 7 phase is precipitated with increase in the Cr content as shown in FIG. 1. So the Cr-Fe alloy the Cr content of which is too high is not suitable as a glass sealable alloy.
  • the relation between the mechanical properties and the Cr content is shown in FIG. 3. As learned from FIG. 3, increase in the Cr content enhances hardness and tensile strength, but abates ductility and thus the alloy becomes brittle.
  • the Cr content which gives satisfactory mechanical properties to the alloy was experimentally searched for and the results showed that Cr alloys the Cr content of which is in the range of 15-30% by weight are most suitable in this respect.
  • the Cr-Fe alloys containing 15-30% by weight Cr have a thermal expansion coefiicient approximately the same as that of soft glass (70 10-' -l10; 10" cm./cm./ C.) as shown in FIG. 2.
  • the rare earth elements include the lanthanum series elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) and Se and Y.
  • the soft glass-sealable alloy of this invention comprises 15-30% by weight Cr, at least one of the above-mentioned rare earth elements in an amount of 0.00l-2.0% by weight and balance Fe.
  • Tables 1 and 2 An example showing the effect of addition of the rare earth is given in Tables 1 and 2.
  • Misch Metal is a mixture of rare earth elements mainly comprising Ce. 2. Numerals stand for content in percent by weight.
  • the SUS 24 alloy is liable to undergo precipitation of 7 phase from on phase, that is to say, is susceptible to metallographic transformation when it is heat-treated, when such a metallographic transformation occurs, the thermal expansion coefficient of the alloy is lowered. If the thermal expansion coeflicient of the alloy which is sealed to glass decreases, the difference in the coefficient between the alloy and the glass increases, which will result in cracking of the glass.
  • Aluminum does not exhibit the above-mentioned effect thereof until the content thereof reaches 0.15% by weight, over which the effect is remarkably manifested. Increase of the Al content has tendencies to lower the transformation temperature and to increase expansion coefficient. If 1.5% by weight or more A1 is incorporated, the alloy will give greater strain to glass to which the alloy is sealed, which constitutes a reason for possible cracking of the glass.
  • No'rE.-Numerals stand for content in percent by weight.
  • the alloy of this invention may contain Mn and Si. As to the content thereof, it is desirable to follow the SUS 24 alloy, that is, Mn should preferably be not more than 1.0% by Weight and Si should preferably be not more than 0.75% by weight. As to P and S, the SUS 24 alloy should preferably be followed, too.
  • An alloy for use in sealing to soft glass which consists essentially of the following ingredients in the percentages by weight specified:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Soft Magnetic Materials (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
US00168824A 1970-08-07 1971-08-04 Sealing alloy Expired - Lifetime US3746536A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP6864370A JPS493723B1 (fr) 1970-08-07 1970-08-07
JP6864470A JPS493724B1 (fr) 1970-08-07 1970-08-07
JP11908870A JPS493890B1 (fr) 1970-12-26 1970-12-26

Publications (1)

Publication Number Publication Date
US3746536A true US3746536A (en) 1973-07-17

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US00168824A Expired - Lifetime US3746536A (en) 1970-08-07 1971-08-04 Sealing alloy

Country Status (5)

Country Link
US (1) US3746536A (fr)
DE (1) DE2139145B2 (fr)
FR (1) FR2105849A5 (fr)
GB (1) GB1320609A (fr)
NL (1) NL170160C (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926622A (en) * 1973-10-03 1975-12-16 Hitachi Metals Ltd Pitting resisting alloy steels
US4296178A (en) * 1979-05-18 1981-10-20 Varian Associates, Inc. Article comprising a substrate and chromium alloy coating
US4414023A (en) * 1982-04-12 1983-11-08 Allegheny Ludlum Steel Corporation Iron-chromium-aluminum alloy and article and method therefor
US4494987A (en) * 1982-04-21 1985-01-22 The United States Of America As Represented By The United States Department Of Energy Precipitation hardening austenitic superalloys
US4661169A (en) * 1982-04-12 1987-04-28 Allegheny Ludlum Corporation Producing an iron-chromium-aluminum alloy with an adherent textured aluminum oxide surface
US5578265A (en) * 1992-09-08 1996-11-26 Sandvik Ab Ferritic stainless steel alloy for use as catalytic converter material
US20140182932A1 (en) * 2011-05-10 2014-07-03 Saint-Gobain Glass France Disk having an electric connecting element
US10305239B2 (en) 2011-05-10 2019-05-28 Saint-Gobain Glass France Pane comprising an electrical connection element
US10355378B2 (en) 2011-05-10 2019-07-16 Saint-Gobain Glass France Pane having an electrical connection element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60227336A (ja) * 1984-04-25 1985-11-12 Toshiba Corp 表示管用リ−ドフレ−ム材
JPH0665737B2 (ja) * 1986-05-13 1994-08-24 日新製鋼株式会社 ガラス封着用金属板

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926622A (en) * 1973-10-03 1975-12-16 Hitachi Metals Ltd Pitting resisting alloy steels
US4296178A (en) * 1979-05-18 1981-10-20 Varian Associates, Inc. Article comprising a substrate and chromium alloy coating
US4414023A (en) * 1982-04-12 1983-11-08 Allegheny Ludlum Steel Corporation Iron-chromium-aluminum alloy and article and method therefor
US4661169A (en) * 1982-04-12 1987-04-28 Allegheny Ludlum Corporation Producing an iron-chromium-aluminum alloy with an adherent textured aluminum oxide surface
US4494987A (en) * 1982-04-21 1985-01-22 The United States Of America As Represented By The United States Department Of Energy Precipitation hardening austenitic superalloys
US5578265A (en) * 1992-09-08 1996-11-26 Sandvik Ab Ferritic stainless steel alloy for use as catalytic converter material
US20140182932A1 (en) * 2011-05-10 2014-07-03 Saint-Gobain Glass France Disk having an electric connecting element
US10305239B2 (en) 2011-05-10 2019-05-28 Saint-Gobain Glass France Pane comprising an electrical connection element
US10355378B2 (en) 2011-05-10 2019-07-16 Saint-Gobain Glass France Pane having an electrical connection element
US11217907B2 (en) 2011-05-10 2022-01-04 Saint-Gobain Glass France Disk having an electric connecting element
US11456546B2 (en) 2011-05-10 2022-09-27 Saint-Gobain Glass France Pane having an electrical connection element

Also Published As

Publication number Publication date
NL7110847A (fr) 1972-02-09
NL170160C (nl) 1982-10-01
NL170160B (nl) 1982-05-03
GB1320609A (en) 1973-06-20
DE2139145A1 (de) 1972-02-10
FR2105849A5 (fr) 1972-04-28
DE2139145B2 (de) 1973-10-25

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