U.S. patent number 3,594,895 [Application Number 04/748,227] was granted by the patent office on 1971-07-27 for ceramic to metal seal.
Invention is credited to Rowland M. Cannon, Jr., Russell J. Hill.
United States Patent |
3,594,895 |
Hill , et al. |
July 27, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
CERAMIC TO METAL SEAL
Abstract
This disclosure is directed to metal to refractory seals wherein
a ductile 50 atomic percent alloy of a group IVb metal with a group
VIII metal of the same period is used to braze ceramic to metal. A
preferred example is sealing Tantalum or Niobium to alumina with a
50 a/o Ti-Ni alloy braze.
Inventors: |
Hill; Russell J. (Wilmington,
MA), Cannon, Jr.; Rowland M. (Arlington, MA) |
Family
ID: |
25008543 |
Appl.
No.: |
04/748,227 |
Filed: |
July 29, 1968 |
Current U.S.
Class: |
228/124.6;
428/633; 428/661; 428/662; 228/249; 428/660; 428/670;
228/262.9 |
Current CPC
Class: |
B23K
35/3033 (20130101); C04B 37/026 (20130101); C04B
2235/667 (20130101); Y10T 428/12618 (20150115); Y10T
428/12806 (20150115); C04B 2237/348 (20130101); Y10T
428/12875 (20150115); C04B 2237/126 (20130101); C04B
2237/30 (20130101); C04B 2237/34 (20130101); Y10T
428/12812 (20150115); B23K 35/3093 (20130101); C04B
2237/122 (20130101); C04B 2237/403 (20130101); C04B
2237/76 (20130101); C04B 2237/127 (20130101); C04B
2237/765 (20130101); C04B 2237/343 (20130101); B23K
35/3046 (20130101); C04B 2235/6567 (20130101); B23K
35/32 (20130101); Y10T 428/12819 (20150115) |
Current International
Class: |
B23K
35/30 (20060101); C04B 37/02 (20060101); B23K
35/32 (20060101); B23K 35/24 (20060101); B23k
031/02 () |
Field of
Search: |
;29/473.1,472.7,504,195 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Campbell; John F.
Assistant Examiner: Shore; Ronald J.
Claims
What we claim is:
1. A metal to ceramic seal which consists essentially of a ductile
brazing alloy interposed between the metal and ceramic, said alloy
consisting essentially of a single phase ductile alloy within the
range of 48 a/o--52 a/o of titanium with a member selected from the
group consisting of Fe, and Co and mixtures thereof.
2. A seal as in claim 1 wherein said ceramic is alumina, said metal
is selected from the group consisting of Tantalum and Niobium and
said 50 a/o brazing alloy is a Ti-Fe or Ti-Co alloy having a
composition range of 50 a/o .+-. 2 a/o.
3. A metal to ceramic seal which consists essentially of a ductile
brazing alloy interposed between the metal and ceramic, said alloy
consisting essentially of a single phase ductile alloy within the
range of 48 a/o--52 a/o of zirconium with a member selected from
the group consisting of Ru, Rh and Pd and mixtures thereof.
4. A metal to ceramic seal which consists essentially of a ductile
brazing alloy interposed between the metal and ceramic, said alloy
consisting essentially of a single phase ductile alloy within the
range of 48 a/o--52 a/o of hafnium with a member selected from the
group consisting of Os, Ir, Pt and mixtures thereof.
5. A method of bonding a metal member and a nonmetallic refractory
body which consists essentially of interposing therebetween a
preform of a single phase ductile alloy within the range of 48
a/o--52 a/o of titanium with a member selected from the group
consisting of Fe and Co, and mixtures thereof, then melting only
said alloy under nonoxidizing conditions, and thereafter cooling
the assembly whereby said alloy forms a tight high temperature
resistant bond between the metal member and the refractory
body.
6. The method of claim 5 wherein said ceramic is alumina, said
metal is selected from the group consisting of Tantalum and Niobium
and said 50 a/o brazing alloy is a Ti-Fe or Ti-Co alloy having a
composition range of 50 a/o .+-. 2 a/o.
7. A method of bonding metal member and a nonmetallic refractory
body which consists essentially of interposing therebetween a
preform of a single phase ductile alloy within the range of 48
a/o--52 a/o of zirconium with a member selected from the group
consisting of Ru, Rh, Pd and mixtures thereof, then melting only
said alloy under nonoxidizing conditions, and thereafter cooling
the assembly whereby said alloy forms a tight high temperature
resistant bond between the metal member and refractory body.
8. A method of bonding a metal member and a nonmetallic refractory
body which consists essentially of interposing therebetween a
preform of a single phase ductile alloy within the range of 48
a/o--52 a/o of hafnium with a member selected from the group
consisting of Os, Ir, Pt and mixtures thereof, then melting only
said alloy under nonoxidizing conditions, and thereafter cooling
the assembly whereby said alloy forms a tight high temperature
resistant bond between the metal member and the refractory body.
Description
The present invention relates to the bonding of nonmetallic
refractory members to metal members, and more particularly to a
temperature resistant, oxidation resistant metal to ceramic seal
capable of use in cesium environments.
The problems involved in obtaining satisfactory ceramic to metal
seals are well known, and various brazing alloys have been
suggested by workers in the art, as in, for example, U.S. Pats.
Nos. 3,091,028 and 2,857,663. Such seals are important to
satisfactory operation of high power electron tube devices and are
notably so in devices employing metal vapors or liquid therein such
as arc devices and thermionic converters.
A common prior art method of making such seals involves first
placing a layer of metal on the surface of the ceramic body or
member then brazing the metal body or member to the metallized
ceramic with the aid of a fusible metallic shim therebetween. Any
of the several diverse metal to metal interfaces present in the so
sealed structure may have a brittle intermetallic phase in the
metal junction due to interaction between metal, braze, and
metallized ceramic. Besides the high failure rate, the joint or
seal as a whole may be weak due to the various intermetallic phases
present. Eliminating the metallizing step and brazing directly to
the ceramic body offers promise for more facile sealing techniques,
even better seals. The braze metal must then be some material which
reacts strongly with the ceramic in order to achieve the desired
bond. Yet, the high chemical reactivity of such a braze metal may
cause the braze also to react strongly with the metal member. Thus,
if a pure metal braze is employed, the solution resulting from
dissolution of the metal body and the braze metal has a
progressively lower melting point than the pure braze metal and
substantial, even complete, dissolution of the metal body can
result if the completed seal is subjected to high operating
temperatures. On the other hand, if a eutectic braze is employed,
the metal from the metal body which dissolves therein often forms a
brittle intermetallic phase between itself and one or both of the
braze constituents.
In any event, an upper operating limit of about 500.degree. C. is
commonly set for the ultimate equipment sealed by conventional
brazing alloys and the heretofore employed ceramic to metal sealing
techniques.
An object of the present invention is to provide an improved bond
for joining nonmetallic refractory bodies to metallic members.
A further object of the invention is to provide a ceramic to metal
seal having good compatibility with a cesium environment and
operation at elevated temperatures.
Still another object of the invention is to provide a high quality
ceramic to metal seal employing a ductile metal braze.
Further objects and the advantages of the present invention will be
apparent from the description thereof which follows.
Briefly stated, the practice of the present invention comprises
forming the seal with a 50 atomic percent alloy of one member
selected from the group IVb metals and the other member selected
from the group VIII metals of the same period. More specifically,
the alloys contemplated for the braze material are the 50 a/o
alloys of: titanium with iron, cobalt, nickel or mixtures thereof;
hafnium with osmium, iridium, platinum, or mixtures thereof;
zirconium with rhodium, ruthenium, palladium, or mixtures
thereof.
Most significant in terms of the ceramic to metal seal is that this
group of 50 atomic percent alloys or intermetallic compounds are
ductile and have a significant homogeneity range on either side of
the 50 a/o. They remain ductile within this range of homogeneity.
Thus, the Ti-Ni system has a homogeneity range of 46--53 a/o Ti.
The other systems have similar, but not necessarily identical
homogeneity ranges. For further description of the alloys per se
reference is made to a series of articles by F. E. Wang or F. E.
Wang et al. in Journal of Applied Physics, Vol. 36, p. 3232 (1965);
Vol. 38, p. 822 (1967); and Vol. 29, p. 2192 (1968). Attention is
directed also to U.S. Pat. No. 3,174,851 for description of the 50
a/o Ti-Ni alloy.
While reference has been made above to 50 a/o, the ductile alloy
brazes contemplated for practice of this invention may be of any
specific composition within their homogeneity range. Therefore,
within the context of this invention a general reference to these
alloy brazes as 50 a/o ductile alloys should be taken as a
reference to include the entire range of homogeneity. As a
practical matter the braze alloy composition should be held within
somewhat narrower limits than the entire homogeneity range, 50 a/o
.+-. 2 a/o being preferred.
When the IVb--VIII ductile 50 a/o alloys are used as brazes to join
ceramic bodies to metal members, they perform in a beneficial and
perhaps unique manner. The molten alloy reacts with the ceramic to
form a hermetic joint, eliminating need for preliminary metallizing
of the ceramic. Moreover, the braze reacts only slightly with the
metal member in the seal assembly. Any intermetallic reaction
products between the braze alloy and the metal member are not
precipitated as a brittle intermetallic phase. After the seal has
been formed no subsequent conditioning steps are needed. These
ductile 50 a/o alloy brazes have general applicability to the many
refractory ceramics usually joined to metal members, including for
example, alumina, zirconia, magnesia yttria, sapphire. They have,
also, general applicability to the metals usually joined to
ceramics for electronic uses, including for example, tantalum,
niobium, the group VIII metals. Importantly, they can be used at
elevated temperatures, e.g. to 800.degree. C.
One exemplary instance of a preferred embodiment of practice
according to the invention is formation of a seal between a niobium
member or a tantalum member and a high purity alumina body with a
ductile 50 a/o alloy of titanium-nickel.
Use of these ductile 50 a/o alloy brazes permits seal fabrication
by relatively uncomplicated techniques. According to one method,
the ceramic body and the metal member to be joined are juxtaposed
with a shim or wire of the chosen intermetallic alloy placed
between them. This assembly is then heated, e.g. in a vacuum
furnace or by radio frequency induction heating in an argon
atmosphere to the melting point of the chosen alloy, at which point
the molten alloy reacts with and wets the ceramic body and also
brazes to the metal member. The braze material remains as a single
phase ductile intermetallic alloy. Thereafter the assembly is
cooled as rapidly as the ceramic will allow. The joint is ready for
use without further conditioning. It is airtight, heat and
oxidation resistant and stable for use over extended periods of
time; it may be employed in a cesium environment,
For further understanding of the invention more detailed specific
examples of the practice thereof is now presented.
A nickel titanium alloy of exactly 50 a/o employed as the braze
alloy had the following properties:
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Density 6.45 g./cc. Melting point 1250.degree. C. Electrical
resistivity 80 .mu..OMEGA.cm. (room temperature) Expansion
coefficient 10.4 .times. 10.sup.-.sup.6 .degree. C..sup.-.sup.1
Ultimate tensile strength 140,000 p.s.i. Yield strength 81,000
p.s.i. Young's Modulus 11 .times. 10.sup. 6 p.s.i. Tensile
elongation up to 15 percent
__________________________________________________________________________
A washer (0.005 inches thick) of the alloy was placed at the bottom
of a tantalum cup and a high purity alumina tube was placed on top
the washer. The so assembled cup, washer and tube was heated
inductively in a stream of commercial grade argon to a temperature
just above 1250.degree. C. to melt the washer. The assembly was
then cooled in the argon stream and removed, with the whole
heating, melting and cooling process taking about 5 minutes.
Examination of the cooled assembly showed that very little
dissolution of the tantalum had taken place during the brief period
the braze was molten and that an airtight satisfactory seal was
formed.
In the same fashion a 50 a/o hafnium-iridium braze alloy washer
formed a good seal between a tantalum cup and an alumina tube.
Sealed assemblies, sealed by the 50 a/o Ti-Ni, braze alloy in the
manner described above were fully fabricated and tested for
temperature resistance in the presence of cesium. They proved
satisfactory at elevated temperatures up to 800.degree. C.
In the same fashion a tantalum tube was brazed to magnesia with the
above 50 a/o Ti-Ni alloy. In this instance the differential
expansion between magnesia and tantalum caused the magnesia to
crack upon cooling, but the seal itself appears satisfactory.
* * * * *