close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3028243

код для вставки
United States Patent O?ice
1
3,028,236
Patented Apr. 3, 1962
2
the remainder being columbium in a minimum amoun‘
3,028,236
Stanley T. Wlodek, Niagara Falls, Edward D. Weisert,
of at least 45 weight percent is particularly outstanding
for use under oxidizing conditions and particularly high
temperature oxidizing conditions since the alloy strongly
COLUMBIUM BASE ALLOY
Tonawanda, and Peter M. Moanfeldt, Niagara Falls,
5 resists reaction with oxygen attemperatures in excess 01
N.Y., assignors to Union Carbide Corporation, a cor
poration of New York
1100“ C.
No Drawing. Filed Dec. 22, 1958, Ser. No. 781,836
9 Claims. (Cl. 75-174)
The maximum bene?tsof the present alloy are obtained
when the alloy consists essentially of from 5 to 20 weight
titanium, 3 to‘ 12 weight percent chromium, 2 to
This invention relates to a columbium base alloy con 10 percent
6 weight percent. aluminum, 1 to; 5lweight percent vana
taining aluminum and vanadium as the major alloying
dium, up to 30 weight percent in the aggregate of at least
ingredients.
one metal selected from the group consisting of tungsten
The development. of rockets and missiles and advances
and tantalum, up to 5 weight percent in the aggregate
in nuclear reactors and gas turbines necessitate the use of
materials of construction capable of withstanding ex- ’15 of at least one metal selected from the group consisting
of manganese, nickel, iron, cobalt, zirconium, and haf
treme operating conditions. It is necesassary under these
nium, up to 3 weight percent in the aggregate of at least
conditions to have superior alloys which combine work
one alloying element selected from the group consisting of
ability, high-temperature strength and high-temperature
barium, silicon, beryllium, yttrium, boron and the rare
oxidation resistance.
metals, and the remainder being columbium in a
Accordingly, it is an object of the present invention to 20 earth
minimum amount of at least 50 weight percent.
provide an alloy which is characterized by resistance to
Within the compositional ranges set forth above, cer
hightemperature oxidation at temperatures in excess of
tain speci?c compositions have been found to have excep
1000° C.
'
tional properties. These compositions are shown in Table
It is another object of the pt esent invention to provide
I which follows: '
an alloy which is amenable to heat treatment by conven-_
tional means.
'
TABLE I
Still another object of the present invention is to pro—
Alloy
Composition
vide an alloy which, when subjected to an oxidizing at
mosphcre at elevated temperatures, forms a pellicular
metal oxide which adheres ?rmly to the alloy and is not
63
substantially volatilized therefrom.
Other objects will be apparent from the subsequent
20
9
5
disclosure and appended claims.
The alloy which satis?es the objects of the present in- '
vention consists essentially of 0.5 to 10 weight percent 35
aluminum, 0.5 to 10 weight percent vanadium, up to 40
weight percent titanium, up to 30 weight percent chro
mium, up to 30 weight percent in the aggregate of at least
one metal selected from the group consisting of tungsten
and tantalum, up to 10 weight percent in the aggregate of 40
at least one metal selected from the group consisting of
manganese, nickel, iron, cobalt, zirconium and hafnium,
up to 5 weight percent in the aggregate of at least one
eusmc§
...
zormpEi!
The alloys of the. present invention may be prepared
by any number of methods such as the conventional meth
ods using inert operating conditions, e.g., by the con
sumable arc-melting technique described in US. Patent
No. 2,640,860, by non-consumable arc welding, by press
ing and sintering of metallic powders or by other powder
metallurgical processes. Great caution should be exer
cised to protect the metals from the atmosphere since con
tamination of the alloying mass by nitrogen and oxygen,
alloying element selected from the group consisting of
barium, silicon, beryllium, yttrium, boron and the rare 45 etc. destroys many of the valuable properties of the alloy.
To protect the alloying materials from these atmospheric
earth metals, and the remainder being columbium in a
contaminants the alloying operation should be performed
minimum amount of at least 30 weight percent.
under vacuum or in an inert atmosphere, such as argon
In the foregoing alloys, the colubium contentis ad
or
helium, or under a protective slag or under a combina
vantageously in excess of 45 percent and preferably in
tion of protective slag and controlled atmosphere. The
excess of 70 percent.
50 ?nal shaping of the alloy metal may be accomplished after
Even where the alloy has a very high columbium con
cooling by any of several procedures, such as, extrusion,
tent, the addition thereto of small amounts of the alumi
swaging, rolling or grinding the cast or sintered shape.
num and vanadium greatly enhances the alloy’s proper—
The examples provided below are prepared in a non
ties. For example, an alloy containing about 4 weight
percent each of aluminum and vanadium, the balance 55 consumable arc furnace such as that described by W. Kroll
in Transactions of the Electra-Chemical Society, volume
~- being columbium and incidental impurities exhibits su
78, 1940, pages 35 through 47. The procedure consists
perior properties. If, in addition to the aluminum and
of placing the component metals on a water cooled, copper
vanadium, about 7 weight percent of titanium is added,
crucible shaped to retain the charge in a hearthlike de
the properties of the alloy are still further enhanced.
pression and incorporated in a gas tight container sup
While the foregoing alloy satis?es all of the objects set
forth above it has been found that an alloy consisting 60 plied with a tungsten electrode capable of impressing an
arc onto the charge. After careful evacuation of the sys
essentially of l to 25 weight percent titanium, 1 to 15
tem
the charge was melted four times under an argon
weight percent chromium, l to 6 weight percent alumi
atmosphere until a homogeneous alloy of the desired com
num, 0.5 to 6 weight percent vanadium, up to 30 weight
percent in the aggregate of at least one metal selected
position was obtained.
to 5 weight percent in the aggregate of at least one metal
by exposing highly polished specimens measuring approxi
from the group consisting of tungsten and tantalum, up 65
The oxidation resistance of the alloy was determined
mately 1.60 x 0.85 x 0.65 centimeters to a stream of
selected from the group consisting of manganese, nickel,
pure, dry oxygen within an air tight container. The
iron, cobalt, zirconium and hafnium. up to 3 weight per
specimens were suspended and heated in this atmosphere
cent in the aggregate of at least one alloying element
70 at 800° C., 1000“ C., or,l200° C. and the amount of
selected from the group consisting of barium, silicon,
pellicular metal oxide formed on the surfaces during the
beryllium, yttrium, boron and the rare earth metals, and
exposure was continuously measured and recorded auto
8,028,286
'
3
4
per square centimeter was found to be 3.8 at 800° C., 23.8
maticaily by means of balances of the Mauer type. By
at 1000° C. and 65.5 at 1200° C.
this method an accurate rate of oxidation weight gain
could be obtained for the alloys tested. The weight gain
is expressed in milligrams of weight gained per square
EXAMPLE VIII
Adopting the procedures described above, an alloy
was prepared containing 90 percent columbium, 5 percent
aluminum and 5 percent vanadium. Upon testing for its
oxidation resistance, the 100 hour weight gain, expressed
centimeter of surface exposed for at least 100 hours at
the different temperatures.
EXAMPLE I
in milligrams per square centimeter, was found to be 98.8
Adopting the procedures described above, an alloy was
prepared containing 57 percent columbium, 20 percent 10 at 1000° C.
EXAMPLE IX
titanium, 5 percent iron, 10 percent chromium, 4 percent
Adopting
the
procedures
described above, an alloy was
aluminum, and 4 percent vanadium. Upon testing for its
prepared containing 94 percent columbium, 3 percent
oxidation resistance, the 100 hour weight gain, expressed
aluminum and 3 percent vanadium. Upon testing for its
in milligrams per square centimeter, was‘ found to be
9.68 at 800° C., 48.1 at 1000° C., and 132.0 at 1200° C. 15 oxidation resistance, the 100 hour weight gain, expressed
in milligrams per square centimeter, was found to be 46
Unalloyed columbium showed weight gains of 3630
at 800° C. and 92.2 at 1000° C.
milligrams per square centimeter at 800° C., 6670 milli
grams per square centimeter at 1000° C., and 24,000
EXAMPLE X
milligrams per square centimeter at 1200° C. under
; Adopting the procedures described above, an alloy was
identical testing conditions.
20
EXAMPLE II
prepared containing 90 percent columbium, 7 percent
aluminum and 3 percent vanadium. Upon testing for its
oxidation resistance, the 100 hour weight gain, expressed
Adopting the procedures described above, an alloy
in milligrams per square centimeter, was found to be
was prepared containing 57 percent columbium, 20 per
18.9 at 800° C. and 140 at 1000° C.
cent titanium, 5 percent nickel, 10 percent chromium, 4 25
EXAMPLE XI
percent aluminum, and 4 percent vanadium. Upon test
ing for its oxidation resistance, the 100 hour weight gain,
Adopting the procedures described above, an alloy was
expressed in milligrams per square centimeter, was found
prepared containing 70 percent columbium, 5 percent
to be 5.85 at 800' C., 32.4 at 1000° C., and 189.4 at
aluminum, 5 percent vanadium and 2.0 percent tantalum.
30 Upon testing for its oxidation resistance, the 100 hour
1200' C.
EXAMPLE III
weight gain, expressed in milligrams per square centi
meter, was found to be 24.2 at 800° C. and 122 at 1000° C.
Adopting the procedures described above, an alloy
was prepared containing 60.2 percent columbium, 18.3
EXAMPLE XII
percent titanium, 3.3 percent nickel, 3.3 percent iron, 8.3 35 Adopting the procedures described above, an alloy
percent chromium, 3.3 percent aluminum, and 3.3 percent
was prepared containing 72 percent columbium, 5 percent
vanadium. Upon testing for its oxidation resistance, the
aluminum, 5 percent vanadium and 20 percent titanium.
100 hour weight gain expressed in milligrams per square
Upon testing for its oxidation resistance, the 100 hour
centimeter, was found to be 14.7 at 800° C., 30.5 at
weight gain, expressed in milligrams per square centi
1000° C. and 193 at 1200° C.
EXAMPLE IV
40 meter, was found to be 13.6 at 800° C. and 105 at
1000° C.
Although it is preferable to use high-purity metals in
Adopting the procedures described above, an alloy
the preparation of the alloys of the present invention, a
was prepared containing 63 percent columbium, 20 per
small amount of variance in purity can be tolerated be
cent titanium, 9 percent chromium, 5 percent vanadium
fore product quality suffers appreciably. The alloys of
45
and 3 percent aluminum. Upon testing for its oxidation
the working examples are prepared from commercially
resistance, the 100 hour weight gain, expressed in milli
available metals which contain a small percentage of inci
grams per square centimeter, was found to be 12.5 at
dental impurities.
'
800° C., 61.6 at 1000' C. and 184 at 1200° C.
What is claimed is:
EXAMPLEV
1. An alloy consisting essentially of from 1 to 25
50
Adopting the procedures described above, an alloy was
prepared containing 63.5 percent columbium, 20 percent
weight percent titanium, 1 to 15 weight percent chromium,
1 to 6 weight percent aluminum, 0.5 to 6 weight percent
vanadium, up to 30 weight percent in the aggregate of at
titanium, 9 percent chromium, 4 percent vanadium, 3 per
least one metal selected from the group consisting of
cent aluminum, and 0.5 percent zirconium. Upon testing
for its oxidation resistance, the 100 hour weight gain, ex 55 tungsten and tantalum, up to 5 weight percent in the ag
gregate of at least one metal selected from the group
pressed in milligrams per square centimeter, was found to
consisting of manganese, nickel, cobalt, iron, zirconium,
be 8.71 at 800' C., 69.7 at 1000° C. and 315 at 1200° C.
EXAMPLE VI
and hafnium, up to 3 weight percent in the aggregate of at
least one alloying element selected from the group con
Adopting the procedures described above, an alloy was 60 sisting of barium, silicon, beryllium, yttrium, boron and
the rare earth metals, the remainder being columbium in
a minimum amount of at least 45 weight percent.
titanium, 8 percent chromium, 4 percent vanadium, 3 per
2. An alloy consisting essentially of from 5 to 20
cent aluminum, and 4 percent manganese. Upon testing
weight percent titanium, 3 to 12 weight percent chromium,
for its oxidation resistance, the 100 'hour weight gain,
expressed in milligrams per square centimeter, was found 65 2 to 6 weight percent aluminum, 1 to 5 weight percent
vanadium, up to 30 weight percent in the aggregate of at
to be 12.5 at 800° C., 134 at 1000'‘ C. and 342 at 1200° C.
least one metal selected from the group consisting of
tungsten and tantalum, up to 5 weight percent in the ag
EXAMPLE VII
gregate of at least one metal selected from the group con
Adopting the procedures described above, an alloy was
of manganese, nickel, iron, cobalt, zirconium, and
prepared containing 53 percent columbium, 20 percent 70 sisting
hafnium, up to 3 weight percent in the aggregate of at
titanium, 3 percent vanadium, 3 percent aluminum, 3
least one alloying element selected from the group con
percent chromium, 3 percent cobalt, 3 percent iron, 3
sisting of barium, silicon, beryllium, yttrium, boron and
percent nickel, 3 percent silicon, 3 percent tantalum and
the rare earth metals, and the ‘remainder being columbium
3 percent tungsten. Upon testing for its oxidation resist
ance, the 100 hour weight gain, expressed in milligrams 75 in a minimum amount of at least 50 weight percent.
prepared containing 46 percent columbium, 35 percent
3,028,286
6
3. 'An alloy consisting-essentially of about 20. weight
percent titanium, about 9 weight percent chromium,
7. An alloy consisting essentially of about 4 weight
percent
aluminum, about 4 weight percent vanadium, the
about 5 weight percent vanadium, about 3 weightpercent
balance being columbium and incidental vimpurities.
aluminum, ‘the‘balancecbeing columbium and incidental
8. An. alloy consisting essentially of about 7 :weight
4. Analloy consisting essentially of about ‘10 weight 5 percent titanium, about 4 weight percent aluminum, about
4 weight percent vanadium, the balance being columbium
percent titanium,- about8 weight-percent chromium, about
and incidental impurities.
,
'
'
4fweight percent vanadium, about 3 weight percent alumi
9. An‘ alloy consisting essentially of - from .5 to 10
num, the :balance :being- columbium and incidental‘ im
weight percent aluminum, from .5 to lO-wveight vpercent
impurities. "
purities.
‘
‘
-
'
_
>
-
_
vanadium, .the balance being columbium-and incidental
.5. An alloy consistingsessentiallytoi about 20 vweight 10 impurities.
percent titanium, about 9- weight percent chromium,
about 5:,weighti-percentlvanadium,=about '4-1weightpercent '
References‘ Cited in the ?le-of this patent
iron, about 3.-weight~per_cent aluminum, the balance-‘be
' UNITED STATES PATENTS
.-ing- columbium and incidental impurities. '
r 6.
- alloy-lconsisting'tessentially .of - about 7 10 weight
15
percent ititanium,-about>-9é'vveight-percent chromium, about
4 weight percentvanadium, about 3-Weightapercent alumi
num, about"2-=weight-»percent iron, the balancebeing co
lumbium and .-incidentaleimpurities. .
‘
20
2,822,268
__, ______________ __l-Feb. 4, 1958
2,838,395
- "Rhodin _______ __' _____ __ June 10, 1958
2,838,396
Rhodin _________ __'____ June 10,1958
. 2,860,970
Thielemann __________ __ Nov. 18, 1958
2,882,146
'Rhodin ____________ -_ Apr. 14, 1959
2,883,282 '
Wainer __'_ __________ __ Apr. 21, 1959
Документ
Категория
Без категории
Просмотров
0
Размер файла
394 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа