Properties of Low-Viscosity

Nitrocelluloses of Varied
Nitrogen Content
Viscosity changes the solubility of nitro-
cellulose of a given nitration, very low-
viscosity material being more soluble than
regular grades. It is indicated that the
film properties of these very low-viscosity
types are the result of degradation of the
cellulosic residues involved. Film proper-
ties vary with nitrogen content, viscosity,
formulation, and kind of plasticizer.
Changing the nitrogen content does not
alter the resistance of cellulose nitrates
to the action of heat or light.
In lacquers, drying time and hardness
are not affected by changes in viscosity or
nitrogen of the base material. Fence life
is dependent on both of these factors, while
resistance to temperature change is de-
pendent on viscosity alone; the difference
is ascribed to the poorer water resistance
of lower nitration materials.
W. E. GLOOR
Hercules Powder Company,
Filmington, Del.
tioiis in the characteristics of the nitrocellulose. However, in
alcohol there is a definite effect of viscosity, nitrogen content,
and alcohol strength on the solubility of the nitrocelluloses.
This is indicated in Figure 1 which gives the limits of practical
solutions of nitrocelluloses in benzene (0.5 per cent) denatured
alcohol of anhydrous and 95 per cent grades. For the first
time me have definite evidence that viscosity as well as nitro-
gen content has an effect on the solubility of nitrocellulose, as
is shown b y the increasing distance between the upper and
lower solubility limits with both alcohols. This effect of
viscosity on the solubility of nitrocellulose would be expected
from the studies of Staudinger, X a r k , Carothers, and others
on the relations between
chain length and solubility
in synthetic polymers, but
had not been found previ-
ously because the dope types
then used were of too high
a degree of polymerization.
Sitrocelluloses in the ranges

T HE purpose of this paper is to present the

results of an investigation of the properties
of a number of nitrocelluloses of viscosity
ranging from 10 to 100 centipoises (l/3? to 1;’2 second by the
falling ball method) and nitrogen contents ranging from 9.5
tested a r e believed t o
have a molecular weight of
10,000 to 20,000 as meas-
ured by osmotic methods (1)
to 12.5 per cent. These data not only serve to indicate par- which is in the range where
ticular fields of application for the different, materials but’ s o l u b i l i t y of polymers is
also serve to shorn the possibilities for varying the present known to change. Figure 1
products, and give on a broad basis the effects of the variables shows that, while substitu-
in nitrocellulose on the results that can be obtained with it. FIGURE 1. EFFECT OF SITRO-
tion does play an important
When the demand for low-viscosity nitrocellulose arose GEN ~ X D VISCOSITY ON SOLU-
part in determining the dis-
about fifteen years ago, producers developed it from nitro- BILITY OF NITROCELLULOSE IN persion of cellulose nitrate,
celluloses then available. As a result the use of the material 2B ALCOHOL molecular qize as eupre\.ed
was limited by the solvent and compatibility properties of the i n v i s c o s i t y a1.o enters.
12 per cent nit’rogen grade. Continued demand for more The latter probably is more influential in the solubility of
soluble materials has led to the introduction of 11.5 per cent other cellulose esters made by soluble processes. Practi-
nitrogen and, more recently, 10.8 per cent nitrogen grades cally, these data show that, while a 1,14-second nitrocotton
which, while not completely soluble in the commercial grades of 10.8 per cent nitrogen content is soluble in absolute alcohol,
of alcohol, require the addition of only a small percentage of ayj-second material of equal nitrogen content is not.
acetate or coal-tar solvent to give a sparkling solution. This
paper, it is hoped, will extend the available data on the prop- Dependence of Dilution Ratio on Viscosity
erties of low-viscosity cellulose nitrates as influenced by the I n a general way it has been assumed that nitrogen content
degree of nitration. is the only major variable influencing dilution ratio tests,
once agreement has been reached on a method. Dilution
Solubilit p tests were run on all the materials tested by the following
From the data obtained, it wac found that the dispersing method: Thirty grams of nitrocellulose were dissolved in a
properties of the usual solvents are not affected by the varia- mixture of 120 grams of butyl acetate and 50 grams of cello-
1162
OCTOBER, 1933 INDUSTRIAL AND EN \TEERING CHEMISTRY 1163

solve. It was necessary to use this mixed solvent to obtain

clear solutions in all cases. To 20-gram portions in a 125-cc.
Erlenmeyer flaqk, with room temperature between 24 and O

26' C., diluent was added Ti-ith shaking unt'il the familiar
precipitation end point occurred. Dilution ratio was calcu-
lated as cubic centimeters of diluent divided by cubic centi-
meters of solvent a t the precipitation point.
The data are plotted in Figure 2 ; in both cases viscosity
(as expressed in relative molecular weights) is found t,o hare a n /PO 40 /1: 0 /a0 /LO /!O
appreciable effect, particularly in the lower nitrogen ranges. %Np/N N/TRoc~LLwos€S $4 /ff NirlXOCELLULQTE5
In fact', using petroleum diluent, the viscosity becomes the FIGURE
2. LINESOF EQ~-.IL
DILUTION
RATIO
deciding factor in this test. A. I n toluene
An idea of the relative molecular sizes of the different B. I n varnish makers' and painters' n a p h t h a
materials used in this work can be obtained by measuring
viscosity in different' solvents. One per cent solutions were t 11 e 11i t r o c e 1l u 1o s e s
used in acetone, a ketone type, and cellosolve, a "two-type" which would give good
solvent, measuring viscosities in an Ostn-ald viscometer a t films, as against that
25" C. Relative molecular weights (R. S. second = 1.00), of t h e b r i t t l e types.
calculated on the basis of Ptaudinger's equation ( d ) ,
AVap = KMCM
Two e x a m p l e s f r o n i
Table I were selected s t
for this comparison-
are conipared 011 the relation I l l , = X,B,, S O B o ,assuming materials of 10.6 $&'
and
that the different nitrogen t,ypes are equally solvated. Data 12.0 per cent' nitrogen
are presented in Table I. The decrease in size of t'he niacro- using a K,nvalue of 13.4
X ( 5 ) in Staud-
9 9
molecules is about fourfold, going from 100 to 10 centipoises,
for all the material.: tested in both solvents. inger's equation (Table u
11). P
TABLEI. VISCOSITY ASD RELATIVEM O L E C C L ~TEIGHTS R
Here it is assumed
that each celluloae unit 8 q
(RMW) O F NITROCELLULOSES has an oeffective length
,--.icetone-- ---Cellosolve--
of 5.15 A., half the well- m.0 /LO 120
SP. SSl. k n o w n l e n g t h of the SN2 & NImCAULLAWS
TTt. per virconity viscosity
Cs Unit, of 1% of 1% cellulose x-ray crystal-
T-iscoeity X? B soln. RMiT soln. RlITT
Centipoise8 % lite. Sitrogen content
22 9.47 0.142 0.19 0.211 0.18
p l a y s s o m e part, but FLEXIBILITYOF x;NPL.4STICIZED
6 10 05 0.109 0.15 0.167 0.14 the limit of chain length 3-ITROCELLC-LOSE FII,MS
32 9.72 0.225 0.31 0,330 0.28 below which good films
46 10.18 0.313 0 44 0.500 0.43
90 10.01 0.367 0.51 0.567 0.49 cannot be obtained is about
11 10.69 0.173 0.25 0.231 0.22
26 10.66 0.269 0.39 0.381 0.34 150 to 200 A. for a 12 per 40
50 10 66 0.392 0.56 0.589 0.52 c e n t n i t r o g e n material.
98 10.33 0.416 0.59 0.611 0.53
i 10.98 0 . I41 0.21 0.260 0.23 This is noticeably below the 2.
28 11.34 0.288 0.43 0,4.55 0.42
45 10.80 0.352 0.51 0 . 537 0.48 limit ofo chain length (700
1Oi 10.95 0.500 0.73 0.760 0.68 t'o 1300 A.) given by Caroth-
8 11.47 0.160 0.24 0.223 0.20
25 11.45 0.327 0.49 0.469 0.43 ers and Van Xatta ( 2 ) as
39 11.43 0.407 0.61 0.537 0 49
A.5. '/P sec. 11.5 0.456 0.68 0.701 0.64 the lower limit for a polymer
10 11.84 0.228 0.35 0.291 0 27
intended for fiber spinning,
45 12.0 0.418 0.64 0,687 0.65
R.S.1/2 see. 1 2 . 0 0.650 1.00 1.060 1.00 as might be expected. t
18 12.28 0.324 0.50 0.380 0.37
107 12.51 0,596 0.95 0.822 0.81 Tensile strength and flexi- f/o
bility tests were made on
all the l/r-.;econd and t$
TABLE 11. BRITTLENESS OF NITROCELLULOSE F I L m is AFFECTED
BY C H A I S L E N G T H O F xITROCELLTTLOSE
second samples, unplasti-
cized and plasticized with
Viscosity
Sitro- From 1% From 1% both dibutyl phthalate (a
cellulose Acetone Celiosoive &
ni:;
Used N> l f o l . wt. Length Mol. wt. Length Length Film
d v e n t ) and ;actor oil (a FIGURE 4. EFFECT OF SITRO-
GES CONTEVT O Y FLEXIBILITY
n o n s o 1v e n t ) T e n s i l e
OF PL~STICIZED NITHOCELLU-
26 10.66 6440 134 7560 160 147 Brittle
strength d e t e r i n i n a t i o n s LOSE F [ L \ l S
50 10.66 9380 165 11600 242 203 O.K. w e r e m a d e o n the Xew 3 . 10 Darts '/,-second nitr11c~I111-
18 12.28 8350 160 8100 155 158 Brittle
R.S. l/isec. 1 2 . 0 10600 206 14600 283 244 O.K. J e r s e y Zinc machine (S),
R.6. I/? sec. 1 2 . 0 16400 320 22500 438 379 O.K. and the S c h o p p e r f o l d B
te-ter TTas u-ed for flexi- C.
bility nork. T1ie.e teztq D.
Physical Properties Dependent o n Chain Length mere made on film. dried E
a t 25" C. and 00 ner cent
I n casting films of these nitrocelluloses on glass to a thick- r e l a t i v e liurniditiT for 8
ness of 0.0035 inch for film testing, it m-as noticed that ma- days; flexibility n a- alao determined 011 identical film:, dried
terials of visconity helow 39 centipoises did not give good, 8 day- inore a t 65" C.
flexible sheets; rather, on drying out, the sheets cracked when With unplasticized film- the higher nitrogen materials
on the glass in many ca.ses a i d when stripped from the glass gave the better tensile qtrengtli and elongation curve*, but
in all cases. I t is of interest to calculate the chain length of the heqt flexibilities come, for both ll4-second, and 2-becond
1164 IYDL-STRIAL AND EUGINEERING CHEhlISTRl- T'OL. 27, NO. 10

types, 111the 10 5 to 11 5 per cent nitrogen range>. A i Figure Formula A [Hard) B !Soft) P (Pigmented)
3 shows, the best flexibilities and ten5ile strength> with the Nitrocellulose 10 10 10
D a m m a r (den ayed 4 4
1 ?-second unplasticized film were obtained a t a >omenhat Dibutyl phthalate 3 6 6
Ti02 pigment .. 10
higher nitrogen content than with the .-second film.
Addition of plasticizer 111 casting films changes their char- These were dissoli-ed to a nitrvcellulose concentration of
acter in era1 important way.. With dibutrl phthalate a. 10 per cent for ?-second types, 12.5 per cent for 1/4-second
the plastifierj the \,est flexi-
types, 15 per cent for second (18 to 25 centipoises) types,
bilities are obtained in the
and 20 per cent for 1 issecond (under 15 cent'ipoisej) mate-
11 to 12 per cent nitrogen
rials in a solvent of the following composition: 6.9 S.D. 10 1.
range, except with the
alcohol, 6.8 butyl alcohol, 6.8 ethyl acetate, 34.5 butyl acetate,
second film. containing 3 45.0 toluene. Their properties, as affected by the variable.
parts plasticizer to 10 part- of the nitrocellulosea will be discussed in the ensuing para-
nitrocellulose, which show>
graph;;.
bezt flexibility with the 10.8
Drying time and Pfund hardness do not vary consistently
p e r cent nitrogen material. m-ith the nitrogen concentration or the yisco5ity. Apparently
Using castor oil, a maximuin
the solvent mixture used had about the same smelling effect
appears a t this n i t r o g e ii on all the materials and thus evaporated a t the same rate
content with all ,-second from all of them. While the Pfund hardneqs test might seem
films, while with ?-second
to depend on the brittleness, etc., of the film, it must be re-
materials the maximum lies
/oo //.e 11.0 menibered that the stresses applied are compressive and are
in the 11 to 12 per cent ni- shearing rather than tensile; thus the differences in flexibility
$$ % /M U / m & . . L W OJC5
t , r o g e n r a n g e . These re-
FIGURE3 . NITROGEX Cov-
and distensibility do not apply here nearly t o the extent that
sults are presented in Fig- they do in the film tests.
TENT Z'S. FILM R E T E N T I O X OF
ure 4. The shape of the
FLEXIBILITY OK HEATING
4-second curyes mentioned
,4. 10 , p a r t s plasticized 1/2-second
is characteristic, showing a ViscositF- and Nitrogen Affect Film Life
nitrocellulose, 5 parts dibutyl
phthalate
B. 10 parte plasticized l/i-second
distinct maximum a t 10.8 These lacquers were exposed in the suniiner of 1933 a t
nitrocellulose, 5 parts dibutyl per cent nitrogen and also Wilniington on fences a t an angle of 45' to the horizontal,
phthalate
C. Unplasticized '/vsecond ni- a marked lack of flexibility facing south. In Figure 6 are plotted the lines of equal fence
trocellulose
D. 10 p a r t s plasticized '/,-second
in films of h i g h e r n i t r o - life (isovitals) using data taken on the clear lacquers made
nitrocellulose, 3 p a r t s d i b u t y l gen and low p l a s t i c i z e r from nitrocellulose of viscosity and nitrogen concentration
phthalate
E . Unplasticised '/esecond nitro- c o n t e n t ' . I n the tensile corresponding to the values on the coordinate axes. These
cellulose tests with both viscosity clear lacquers mere sprayed in three coats on bare steel, fail-
tvses and ulasticizers. the ures being noted a t t'he first appearance of cracking or check-
11 to 12 per cent nitrogen materiaiq-gave the keqt value.. ing.
The t,no formulas show the same general kind of diagram,
Heat Resistance as Measured by Flexibility the film life increasing along a line bisecting the axes. Also,
with both formulas these contours of equal film life show a
On the samples whose flexibility was measured after lieat- ridge or ,shoulder around which they seem to bend, indicating
ing for 8 days, the data show that, the films plasticized wit11 that abore about 11 per cent nitrogen and 40 centipoises vis-
castor oil were very much more embrittled than were tlioae cosity there i i little difference in tmhesuitability of nitrocellu-
plasticized with dibutyl phthalate. The effect of nitrogen loses for lacquer clears, as far as summer fence life is concerned.
content on retention of flexibility after heating was quite This is most evident Tvith the softer B types; JTitli the harder
marked, the relations being plotted in Figure 5 . Result+ A forniulas there is an indication of still greater fence life
with V,-second nitrocellulose show that, unless well plasti- above 12 per cent nitrogen and 80 to 100 centipoises viscosity.
cized, heated films made with it do not retain their flexibility Belov t1ie.e limits fence life decreaies Tvith both decreasing
as well as '2-second films. The effect, of increasing nitrogen nitrogen content and viscojity. The softer B forinula Yeem.
content is not at' all definite but seems t'o depend on the inore affected by variations in nitrocellulose cDnceiitration
amount and kind of plasticizer as well as the viscosity of the than the -1forniula. Tlii.: ix probably caused by the coni-
nitrocellulose. The castor oil films kept their flexibility much
less than those plasticized with dibutyl phthalate, eqpecially
in the lower nitrogen ranges. Below 10.5 per cent nitrogen
none of the films plasticized with castor oil was flexible enough
to withstand one Schopper double fold after 8 days of heating.
"Sweating out" did not seem any more pronounced on t1ie.e
samples than on those of higher nitrogen content, although
no quantitative tests were made on this point.
The effect of heat on the color of clear and ziiic oxide pig-
mented films of these materials seemed to be the same for all.
Also, no difference in color waq noticed on espozure of a
series of these films to ultraviolet light, either clear or pig-
mented. This would be expected from the fact that light'
transmission of nitrocellulose films is almost indepeiideiit of
the nitration of the material.
I I I I I I I
so /a
I
Formulation of Lacquers 40 80 /Po
,~~~~OCCELLIULOJE rwos/ry
40
- cp.
From the data given a few typical lacquer formula- were 6 . FESCELIFE I N REL.ITIO\TO VISCOSITI. I \ D
FICLRE
made up with every nitrocellulose; the solids content n-a. : COYTE\TOF \ I T R X L L L C L O S E
A-ITROGEV
OCTOBER. 1935 INDUSTRIAL hZD EXGIYEERING CHEZZISTRY
binatiun 01 knov n longer life of softer lacquer formulas,
nhich would enable the difference in the nitrocelluloses to
exert a n effect, and the fact that the high gum content of the
harder lacquers masks the differences in flexibility of the ni-
trocelluloses used.
Effect of Viscosity on Resistance to Temperature
Change
Temperature change testa were made on a n endless belt
which carried the coated metal panels through a 40" C.
chamber for one hour and a 0" to 2" C. chamber for 2 hours
continuously over the period of test. Data are plotted in
Figure 7 and show conclusively that the viscosity of the
nitrocellulose is the major factor in determining resistance to
this agency of breakdown. The B formulas made from 20 to
40 centipoise nitrocelluloses have nearly three times the tem-
perature change resistance of the A formulas made from the
same nitrocelluloses, although the '/2-second lacquers do not
show nearly as much difference between formulas. The
value of softer formulas in Tvorking with materials below '/z
.econd in viscosity is obvious. The data on pigmented
lacquers showed that their fence failure is also a function of
viqcoqity.
Correlation of Physical Tests and Exposure Data
While i t was not possible to obtain any degree of corre-
cpondence between results of tensile or flexibility tests of the
unplasticized nitrocelluloses and weathering or temperature
change resistance with the hard A formulas, nor of flexibility
and these agents with the soft B formula, a fair correlation
was obtained between tensile strength and fence life in the
73 beries. This is shown for ',/4-second and 'lrsecond samples
i n Figure 8. These data co\'er the range of nitrogen contents
uqed in this work and show that in the softer durable finishes
there is some relation between film-weathering resistance
and the tensile propertie- of the nitrocellulose used.
Special Formulation for Quarter-Second Films
Throughout all these data one finds that while l/r-second
material compares rather favorably with '/n-second in the
wfter formulations, in the harder films, containing less plas-
ticizer and more gum, it gives much more brittle structures.
This is evident on comparing flexibilities (Figure 4) where a
critical point in the flexibility-nitrogen concentration curve
almost ditappears on adding more plasticizer, or in compar-
iiig retention of flevibility on heating (Figure 5) where the
\ \
LACQUERS
E'lCL H L 7 . T E M P E R 4 T U R E C I I 4 T G E R E S I S T . I T C E OF
I\ I t F L I T I O \ r O \-ISCOSITY 4 \ D \ITROGE\ COYCEYTR4TIOY OF
NITROLELLLLOSE
116.5
addition of pla*ticizer alters the shape of the curve completely.
I n these two comparisons nitrogen content has some effect,
but the 1/4-second materials all behave alike. Comparing
fence lives, lacquers made from ?-second filrns have nearly
the same life in both hard and soft formulas in the lom-nitro-
gen range, and the soft B compositions have twice the life of
the A. formulas in the commonly used nitrogen range; the
same relations are true of weathering tests of '/*-second lac-
quers. However, in the temperature change tester, the hard
'/,-second lacquers gave uniformly only half the life of the
s o f t e r formulas u-itig
this viscosity, w l i e r e a -
r e s i b t a n c e was nearly
the same for hard and
soft 2-sc>condcoating-.
Since this iq more nearly
a function of embrittle-
300 ment unromplicated by
s Jo 70
o t h e r agencies, the in-
M Y 5 FENcz L/*
d i c a t i o n is that where
FIGURE8. CoRREL.4TION BE-
T\VEEY TEssrLESTRENGTH .4so satisfactory results are
FENCE LIFE OF NITROCELLU-obtained when using a
LOSES IN LACQUER FORMULA B hard 1/2-second formula.
e q u a l l y acceptable re-
sults are not probable if '/?-second nitrocellulose is suh-
stituted in the formula. -4reformulation towards greater
softness is indicated in such cases.
Role of Moisture and Light i n Lacquer Failures
By comparing the results of weathering tests, where the
lacquers are exposed to naturally varying light, tempera-
tures, and moisture, with the results of the temperature
change test, where the panels are subjected t o a fixed arbi-
trary cycle of temperature, a n indication of the re4stance of
these materials to the influences peculiar to weathering alone
may be obtained. Since for all practical purposes and cer-
tainly within the limits of accuracy imposed by the te,t con-
ditions, all the nitrocelluloses are equally resistant to light,
the differences between the two tests must be chiefly attribut-
able to the influence of moisture on the film decomposition.
Comparison of the data for the two tests shows that the low-
nitrogen materials give shorter fence lives for a given nitro-
cellulose viscosity; this is most evident with the soft forrnu-
las, while temperature-change data show viscosity to be the
controlling factor in this test. It is known that the more
highly substituted cellulose products are more water-re-
sistant, and these are the ones which give the best fence
life, where moisture is one of the agents to be combated. For
instance, where a film made from nitrocellulose of 12 per cent
nitrogen content and 45 centipoises viscosity has a permea-
bility constant of 1.6 (grams of water per sq. em. per em. per
hour) a t 23" C., a film made from material of 10.7 per cent
nitrogen content and similar viscosity has a constant of 3.1,
passing almost twice as much water vapor. Aleo resins,
notably dammar, are known to decrease the water vapor
permeability of filins greatly, and here we find the high-resin
formula X giving fence results more in accordance with the
temperature-change lives, minimizing the effect of mois-
ture as would be expected. Lastly, the lacquers made with
the lowest nitrogen materials ,.how the most rusting upon
failure,
Since it is known that light has a denitrating and depoly-
merizing effect, it seems that the 10.0 to 10.5 per cent nitrogen
materials are farther along the road to ultimate decomposition
and thus are not as well suited for outside exposure as the
higher nitrogen types. HoweTrer, it is evident from these
data that an 11.5 to 12.0 per cent nitrogen nitrocellulose would
gii e a more witable finish for outside work than, for example,
 1166 INDUSTRIAL AND ENGINEERING CHEMISTRY
a 10.8 per cent nitrogen material of the same viscosity, while
the latter might have advantages of solubility and miscibility.
These data also show that the well-known brittleness of
very lorn-viscosity types extend over the whole range of nitro-
gen content, and that it is not probable that this charac-
teristic can be altered by a mere change in nitrogen of the
material.
Acknowledgment
The writer wishes to thank R. L. Stern of Union Plant for
many of the materials tested, and H . M. Spurlin for the tem-
perature-change tester used. The interest of D. R. Wiggam
Columbium
and
Tantalum
CLARENCE W. BALKE
Fansteel Products Company, Inc.,
North Chicago, Ill.
T
HE present state of the columbium and
tantalum industry in the United States is
the result of nearly twenty years of re-
search, investigation, and technological effort. As a result
of this activity and many practical tests of the metals con-
tinued over a long period of time, there is a constantly in-
creasing interest in the metals, particularly in tantalum, and
numerous unforeseen applications are constantly being made.
Tantalum was first developed in Germany for lamp filaments,
and when this use of the metal was discontinued, because of
its replacement by tungsten, there seems t o have been no
tantalum industry of consequence anywhere in the world.
However, a t the present time the wide variety of application..
of this metal insures the permanency of an industry devoted
to the manufacture of tantalum and columbium and the fab-
rication of these metals into useful forms.
Treatment of Ore
Tantalum and columbium are always found associated with
each other in their minerals. There are but two minerals of
consequence from the commercial standpoint as sources for
these metals-namely, tantalite and columbite. While
these minerals are found in limited quantities in many locali-
ties, they are, for the most part, accessory minerals and can be
VOL. 27, NO. 10
and W. M. Billing in this subject led to permission to publish
the results.
Literature Cited
(1) Buchner and Samwell, Trans. Faraday Soc., 29, 40 (1933).
( 2 ) Carothers and Van Natta, J . Am. Chem. Soc., 5 5 , 4717 (1933).
(3) Nelson and Rundle, Proc. Am. Soc. Testing .Ifateriala, 21, 1111
(1921).
( 4 ) Staudinger, ‘:Die hochmolekularen organischen Verbindungen,”
p. 5 6 , Berlin, Julius Springer, 1932.
( 5 ) Ibid.: pp. 506-7.
RECEIYED April 19, 1935. Presented before the Division of P a i n t and
Varnish Chemistry a t t h e 8 9 t h Meeting of t h e American Chemical Society,
New York, X. Y.,April 22 t o 26, 1935.
Tantalum and columbium, from the min-
erals tantalite and columbite, are separated
from each other by the recrystallization of
their double fluorides with potassium.
The electrolysis of the fused double fiuo-
rides yields the respective metals in the form
of finely crystalline powder. These powders
are hydraulically pressed into bars which
are heat-treated in vacuum furnaces to pro-
duce ingots of the metals which are then
capable of being rolled into sheet or drawn
into wire a t room temperature.
The sheet may be spun, drawn, or con-
verted into seamless tubing. Improved
processes for the fabrication of apparatus
and equipment of tantalum have greatly
increased the range of its usefulness and
application in the chemical and rayon in-
dustries. Methods of hardening have re-
cently been developed by w-hich the degree
of hardness and depth of penetration can
he varied through wide ranges and dupli-
cated with fidelity. Both columbium and
tantalum are finding increased use in the
construction of powTer and other vacuum
tubes. Their carbides have been incorpo-
rated into a series of hard carbide composi-
tions for use as tools, dies, and abrasion-
resisting surfaces.
extracted a t a profit only in connection with mining for other
minerals. Only in western Australia has tantalite been found
in sufficient concentration t o warrant mining operations for
this mineral alone. Australian tantalite contains more than
60 per cent of tantalum oxide with about one-fourth that per-
centage of columbium oxide. This mineral is also unusually
free from objectionable impurities such as titanium, tin, and
tungsten, and is relatively free from gangue material which is
u.ually mica, silica, or feldspar. While ferrotantalum or so-
called ferrocolumbium can be produced directly from the ore,
the preparation of these metals in the pure condition involves
a somewhat elaborate chemical and metallurgical process.
The pulverized ore is fused with caustic soda which con-
verts the tantalum and columbium content of the mineral