UNITED STATES PATENT OFFICE.

THEODCRE. W. FRECEI, J.R., OF CLEVELAND, OHIO, ASSIGNOR TO GENERAL ELECTRIC

- COMPANY, A CORPORATION OF NEW YORK,
TUNGSTEN MANUFACTURE.
1,089,757.
NoDrawing.
Specification of Letters Patent. Patented Mar. 10, 1914.
Application filed October 9, 1912. Serial No. 724,825.
To all whom it may concern: lilade by swaging, rolling, drawing or other
Be it known that I, THEODoRE. W. FRECH, methods of mechanical working, as described
Jr., a citizen of the United States, residing in great detail in British Patents 23,499 of
at Cleveland, in the county of Cuyahoga, 1999. and 8031 of 1910 and in the patent to
State of Ohio, have invented certain new William D. Coolidge, No. 1,082,933, Decem 60
and useful Improvements in Tungsten Man ber 30, 1913, under the title of tungsten and
ufacture,
cation.
of which the following- is a specifi methods of making the same for use as fila
My invention relates to the manufacture ments of iricandescent lamps and for other
O of tungsten for use in the filaments of in
purposes, and assigned to the assignee of
candescent electric lamps and for other pur this application. As set forth in these Brit 65
poses. Encandescent lamp filaments made of ish patents and in the U. S. patent above
tungsten such as can be produced by my mentioned, the offsetting of tungsten fila
process can be operated on alternating cur ments can be prevented by the addition of .
5. rent for an indefinite time without the trans foreign material to the metal; and in par
ticular, coherent tungsten possessing some
verse “faulting' or displacement of adja 70
or all of the
cent sections of filament known as “offset been produced re above set forth has
from tungstic oxid (WO)
ting', and give very uniform and good re-- which has been fired in a Hessian or Bat
sults as regards length of life, maintenance tersea crucible, and also from powdered ma
20 of candie-power, and strength after burn terial to which have been added one or more 75
ing. By this process, also, can be produced of various refractory oxids such as those of
tungsten which possesses a greater or less thorium, zirconium, yttrium, erbium, di
degree of ductility and pliability even after dymium, or ytterbium, or substances which
prolonged exposure to high temperature, as when decomposed by heating give such ox
25 in the incandescence of electric lamp fila ids, particularly thorium nitrate. The cru 88)
ments and of electric furnace resistors, etc. cible firing, indeed, owes its efficacy in part
By my process, furthermore, can be pro to substances such as these (consisting
duced coherent tungsten capable of mechani largely of alumina and silica) found in the
cal working while hot and which if such oxid after the firing and probably vola
30 hot working is sufficiently prolonged becomes
freely capable of mechanical working and tilized into it from the crucible, and in part 85
to a coarsening of the tungstic oxid which
shaping, when cold by reason of properties results from the firing. While thoroughly
of ductility, maleability, pliability, etc. - efficacious and more reliable than the other
or, in general, of undergoing permanent de modes of “addition' as heretofore em
85 formation in any way under the application ployed, this firing treatment is expensive,
90
of force below the ultimate breaking strength because for the best results a crucible can
of the material-acquired during the hot be used only once and because when car
working or (if the material, possessed any ried out at the most effective temperatures
such properties before) greatly increased by it generally involves the loss of a substan
40 a change in the material which occurs dur tial amount of tungstic oxid by volatiliza 95
ing the hot working. Different lots of such tion, and does not always produce a defi
metal, also, exhibit great uniformity and nite quantitative effect as to the amount of
reliability as regards their capacity for the “addition' thus made to the oxid.
45 drawing down to the very finest sizes-as
for example, that required for a 10 watt My process possesses all the efficacy and
reliability of the crucible firing above men 100
110 volt sign lamp. Tungsten produced in tioned without any of its disadvantages, be
accordance with my invention and thus hot ing simple, economical, easy to carry out
worked also tends when subjected to high and control, and perfectly definite in its ef
temperature to retain the ductility, etc., ac fects. In this process, suitable substances or
50 quired during the hot working-or, at least. “addition' material whose introduction 105
loses the same but gradually.. makes the metal filaments finally produced
I have hereinafter described my process capable of incandescence on alternating cur
with particular reference to its employment rent without offsetting (such as: the oxids
for the production of cdherent tungsten out and compounds above referred to) are em
55 of which electric lamp filaments are to be ployed. This “addition' material is in 110
 1,089,757
2.
troduced into the material from which the with thorium nitrate solution. Though the
filaments are eventually to be produced at a proportions can be varied, good results are
suitable stage and the whole is then heated, obtained by using, with a kilogram of tung
especially good results being obtained when stic oxid, 75 cubic centimeters of thorium
this heating is carried out under oxidizing nitrate solution of such strength that 10 70
conditions. By this mode of procedure the cubic centimeters of it contain 1 gram of
effect of such substances in giving to the thorium oxid (ThC). The weight of a
metal eventually obtained the property of thorium nitrate solution of this strength is
1.1484 times that of an equal volume of wa
not offsetting and of retaining its ductility ter, which fact affords a convenient test. 75
0 even when highly heated is improved; and The mixture obtained by the addition of the
the degree of coarseness or fineness of the thorium nitrate solution to the tungstic oxid
tungsten-hitherto found to be a matter of
considerable moment as regards the facility as just described contains approximately
with which material to which such additions three-fourths of one per cent. of thorium
oxid by weight. To this mixture sufficient 80
5. as above mentioned have been made can be water is added to make a thick solution or
hot worked-ceases to be of prime impor paste, which is thoroughly stirred over a
tance. The treatment can advantageously water bath, so that the materials are thor
be carried out with the compounds from oughly, intimately, and uniformly incorpo
which tungsten is produced, preparatory to rated together. According to one mode of 85
20 their reduction, though it can also be car procedure, this stirring over the water bath
ried out in other ways. Superior results are is continued until the material becomes a
obtained by employing thorium nitrate and thick mud that can be molded like clay, and
introducing it into the material when the this mud is packed with a ram-rod into a
latter is in the form of tungstic oxid, and tubular mold of about 1' internal diameter 90
25 afterward heating the oxid with, this addi
tion in an oxidizing atmosphere. This mode and about 10' long. The material is then
pushed from the mold and the slug or rod
of procedure greatly intensifies and improves thus obtained is dried in an ordinary gas
the final effects of the thorium nitrate addi
tion as regards the non-offsetting properties to oven until it will hold together sufficiently
30 of the filament and its retention of ductility
bear handling. Alternatively, the heat 95
ing
after high heating. The good results may be continued of the material over the water bath may
possibly be due to some sort of chemical re ness and the tungsfic until it is evaporated to dry
action between the tungstic oxid and the tained may be pressedoxid powder thus ob
thorium nitrate, or to elimination of impuri rectangular slug or briquet aabout dry in mold into a
1' or 00
35 ties E. in the tungstic oxid; or it may 3' square and 97' long, the mold being Sufi
be that the thorium nitrate or the thoria
under these conditions in some way facili ciently reinforced to withstand high pres
tates some molecular or intermolecular sure and a hydraulic press being employed.
change in the tungstic oxid; or the action It will be understood that the formation of 05
40 may be of some still different character, or a the oxid into a slug in either of these ways
combination of various effects. is merely to put it in a convenient form for
I will now describe in detail how my in the subsequent heating operation and to ob
viate the necessity of employing boats to
vention can be successfully quality
carried outcom
of tung contain the loose powder, since most of the
45
mercially.
stic oxid canAbe E.
produced by dissolving tung materials which would be convenient for 110
stic oxid (WO) as pure as commercially ob or would bewould
such boats be liable to contaminate it
rapidly deteriorated by it, or
tainable in ammonia water, purifying the are unduly expensive.
ammonium tungstate thus formed by crys The firing of the slug may conveniently
tallization over a steam bath, and then; after be carried out in a porcelain tube furnace 115
50 washing with distilled water and drying,
decomposing the ammonium tungstate by about 24' long and of 1 internal diam
the application of moderate heat, say 400 eter electrically heated by a suitable ex
to, 500° C., which drives off the ammonia ternal through
winding, the slug being pushed
this furnace at the rate of about 1'
and leaves tungstic oxid. Alternatively,
55 and with very good results, the ammonium every nace
four
being
minutes.
open to
Theatmosphere,
the
ends of thisoxidiz
fur 2.
tungstate solution may be precipitated with
concentrated hydrochloric acid-care being ing conditions will exist within it without
any special steps being taken to introduce
taken in the addition of the hydrochloric oxidizing
acid to the solution not to pass the neutral advantagegas be
into it. The furnace may to
maintained at such a temper 12
60 point-the resulting crystals of ammonium ature that its interior matches in color with
tungstate filtered off, washed with distilled the carbon filament of an ordinary
water, and heated as before to convert to filament lamp operated at 45% of thecarbon, volt
tungstic oxid. -
The tungstic oxid purified as just de age for which it would operate at the stand
65 scribed or in any adequate manner is mixed ard efficiency of 3.1 watts per candle. The
 1,089,757
slugs shrink slightly during this firing op 2. The process of preparing a compound 45
eration, and when they come from the containing tungsten for subsequent reduc
furnace they are green in color. This
change in color may possibly be due to the tion to tungsten and the drawing of the said
tungsten down to wire which consists in
formation of a low thorium tungstate or heating said compound under oxidizing con
tungsten thoriate by reaction between the
tungsten trioxid and the thorium- nitrate, or ditions
to other causes.
with a compound of thorium.
3. The process of preparing an oxid of 50
The fired slug may be pulverized in an ore tungsten for subsequent reduction to tung
10 crusher and the oxid powder then reduced sten and the drawing of the said tungsten
in a porcelain tube furnace electrically oxid down to wire which consists in heating said
heated by an external platinum winding, under oxidizing conditions with a com 55
hydrogen being passed over the surface of pound of thorium.
the oxid in the tube and the temperature 4. The process of preparing an oxid of
15 gradually raised until the interior of the tungsten for subsequent reduction to tung
furnace matches in color with the carbon down sten and the drawing of the said tungsten
filament of an ordinary carbon filament oxid to wire which consists in heating said 60
under
lamp burning at 45% of its voltage for a pound of thorium oxidizing conditions with a com
3.1 watt per candle efficiency-though a which is broken up upon
20 temperature at which the interior of the heating to produce an oxid of thorium.
tube will match with such a filament burn for5. subsequent
The process of preparing tungstic oxid
ing at 30%. of the rated voltage as just the drawing of reduction to tungsten and 65.
the said tungsten down to
stated will suffice. Alternatively, the slug wire which consists in heating said oxid
may be reduced with hydrogen in the same
25 way without crushing; this will give a mass under oxidizing conditions with a compound
of tungsten particles so soft and friable that of6.thorium.
The process of preparing tungstic oxid 70
it can be pulverized between the fingers. for subsequent
This mass may be reduced to powder in any the drawing of reduction to tungsten and
the said tungsten down to
suitable
mortar.
way, as by grinding in a porcelain wire which consists in heating said oxid
30
The tungstenpowder obtained in any of under oxidizing conditions with a com
pound of thorium
the ways above indicated may be pressed up heating producewhich
into a rod and worked into filament form or 7. Thetomethod an oxidis broken up upon 75
of thorium.
which consists in heating
35 into any other desired shape as described in to a suitable temperature in an oxidizing
the above mentioned British patents and the atmosphere tungstic oxid with which is in
above patent of William D. Coolidge. timately incorporated a comparatively small 80
What I claim as new, and desire to secure proportion
by Letters Patent of the United States, is:- In witnessofwhereof,
thorium nitrate.
1. The step in the manufacture oftung my hand this 28th day Iofhave
40 sten
hereunto set
September, 1912,
for use in incandescent lamp filameats
which consists in adding to a tungsten bear THEODORE. W. FRECH, Jr.
ing material a relatively small amount of . Witnesses:
a compound of thorium and heating the JoHN M. STRON?,
mixture under oxidizing conditions. RALPH. B. HunTER.