Professional Documents
Culture Documents
LIBRO Metalurgia de Metales Raros A.n.zelikman
LIBRO Metalurgia de Metales Raros A.n.zelikman
T!r
1
C.1
i
A.N. Eelikman, O.E. Krein, and G.V. Samsonov
I . , ..
" *
r
r-.
-I
1lllllllllll1
IlI1
1l1ll1Il11110068748 l
A. N. Zelikman, 0. E. Krein, and G. V. Samsonov
METALLURGY
OF RARE METALS
Izdatel'stvo Metallurgiya
Moskva 1964
Copyright 01966
Israel Program for Scientific Translations Ltd.
IPST Cat. No. 1455
P r i c e : $ 8.12
VI/18/3.5
~ - - .. -- -. . _. ._. ..... ..
TABLE OF CONTENTS
Page
. REFRACTORY METALS
Part One
Chapter I. TUNGSTEN ................................................ 1
.
2 MINERALS. ORES. A N D ORE CONCENTRATES .................... 9
.
3 PROCESSING OF TUNGSTEN CONCENTRATES ...................1 2
.
5 PROCESSING OF SODIUM TUNGSTATE SOLUTIONS ............... 19
.
6 PROCESSING OF SCHEELITE CONCENTRATES .................... 24
...
lll
Page
7 .
PURIFICATION OF TUNGSTIC ACID ............................ 30
.
8 PRODUCTION OF TUNGSTEN TRIOXIDE AND QUALITY
CONTROL ..................................................... 33
.
9 COSTS OF PRODUCTION OF TUNGSTIC ANHYDRIDE .............. 34
.
10 PRODUCTION OF METALLIC TUNGSTEN ........................ 35
.
11 REDUCTION OF TUNGSTEN TRIOXIDE BY HYDROGEN ............. 36
.
12 REDUCTION OF TUNGSTEN TRIOXIDE BY CARBON ............... 44
.
13 PRODUCTION OF SOLID TUNGSTEN ............................ 46
Pressing ................................................... 47
Sintering .................................................. 49
C h e m i c a l Methods ......................................... 81
Leaching ............................................. 81
iv
Page
Isolation of molybdenum from t h e ammoniacal
..........................................
solutions 84
........................................... 86
residues
Extraction of molybdenum into the final product and
............................................ 89
costing
19 . PROCESSING OF LOW-GRADE CONCENTRATES .................. 90
.
Chapter I11 TANTALUM AND NIOBIUM ................................ 99
.
22 GENERAL DATA ON TANTALUM AND NIOBIUM ................ 99
.
25 PROCESSING OF TANTALITE-COLUMBITE BY FUSION WITH
.
26 PROCESSING OF TANTALITE-COLUMBITE BY FUSION WITH
.
27 DECOMPOSITION OF TANTALITE-COLUMBITE WITH HYDRO-
.
29 SEPARATION OF TANTALUM AND NIOBIUM AND PURIFICATION
OF THEIR COMPOUNDS ....................................... 117
.
30 METHODS FOR THE PRODUCTION OF METALLIC TANTALUM
.
31 FUNDAMENTAL PRINCIPLES OF METALLOTHERMY .............. 131
.
32 PRODUCTION OF TANTALUM AND NIOBIUM POWDERS BY
.
33 PRODUCTION OF TANTALUM AND NIOBIUM BY ELECTROLYSIS . 137
Page
Electrolytic Production of Tantalum ......................... 137
.
34 PRODUCTION OF NIOBIUM BY THE CARBIDE REDUCTION
.
35 PRODUCTION OF TANTALUM AND NIOBIUM BY REDUCTION
. .
36 PRODUCTION OF SCLID DUCTILE TANTALUM AND NIOBIUM ... 145
.
37 RECOVERY OF METALLIC TANTALUM AND NIOBIUM WASTES ..... 154
44 .
PURIFICATION OF TECHNICAL GRADE TITANIUM CHLORIDE .... 176
45 .
PRODUCTION OF TITANIUM DIOXIDE ........................ 180
.
46 PRODUCTION OF METALLIC TITANIUM ....................... 185
.
47 REDUCTION OF TITANIUM TETRACHLORIDE WITH MAGNESIUhl
(THE K ROLL PROCESS) ........................................ 186
.
48 REDUCTION OF TITANIUM TETRACHLORIDE BY SODIUM ........ 194
vi
Pages
Processing of the Reaction Mixture ....................... 197
.
50 ELECTROLYTIC REFINING OF TITANIUM AND TITANIUM-
.
51 REFINING OF TITANIUM BY THE IODIDE PROCESS ............ 204
.
52 PRODUCTION OF SOLID TITANIUM ....................... 208
..........................
T h e Melting of Titanium Alloys 210
.
Chapter V ZIRCONIUM .......................................... 213
.
53 GENERAL DATA ON ZIRCONIUM ........................... 213
.
54 MINERALS. ORES. AND ORE CONCENTRATES ................ 220
.
55 PRODUCTS FORMED IN THE PROCESSING OF ZIRCON
.
56 METHODS FOR THE DECOMPOSITION OF ZIRCON
.
57 DECOMPOSITION OF ZIRCON BY FUSION WITH SODIUM
.
58 DECOMPOSITION OF ZIRCON BY FUSION WITH LIME ........ 226
.
59 ISOLATION OF ZIRCONIUM FROM HYDROCHLORIC AND
SULFURIC ACID SOLUTIONS ............................... 227
.
60 PROCESSING OF ZIRCON BY SINTERING WITH POTASSIUM
.
61 DECOMPOSITION OF ZIRCON BY REDUCTION WITH CARBON
.
62 PRODUCTION OF ZIRCONIUM TETRACHLORIDE .............. 234
Page
63 .
METHODS FOR THE SEPARATION OF HAFNIUM AND
ZIRCONIUM ............................................... 238
.
64 MANUFACTURE OF ZIRCONIUM ........................... 245
.
65 THERMAL REDUCTION OF ZIRCONIUM CHLORIDE WITH
.
66 REDUCTION OF POTASSIUM FLUOZIRCONATE BY SODIUM ... 252
.
67 REDUCTION OF ZIRCONIUM DIOXIDE BY CALCIUM AND
.
68 PRODUCTION OF ZIRCONIUM BY ELECTROLYSIS ............ 253
.
69 THE THERMAL DISSOCIATION (IODIDE) METHOD ............ 255
.
70 PRODUCTION OF SOLID ZIRCONIUM ...................... 256
Part Two . T H E R A R E - E A R T H M E T A L S
Viii
Page
Extraction ........................................... 288
.
75 CONTROL OF SEPARATION AND PURITY OF LANTHANIDE
.
76 MANUFACTURE OF RARE-EARTH METALS ................ 292
.......................................
the m e t a l 300
306
Uses of Germanium ....................................
307
.
78 OCCURRENCE ...........................................
309
Behavior of Germanium During Processing of Sulfide
312
.
79 EXTRACTION OF GERMANIUM FROM VARIOUS RAW MATERIALS
312
Primary Processing of Germanium-Containing Products ......
312
Production of Technical Grade Germanium Tetrachloride
314
Extraction of Germanium from the Copper Concentrates of
Tsumeb .............................................
314
Extraction of Germanium from the Dusts Formed in the Shaft
318
Extraction of Germanium from the Dust of Gas- Producing
Plants ..............................................
319
.
81 PURIFICATION OF GERMANIUM TETRACHLORIDE AND
PRODUCTION OF GERMANIUM DIOXIDE ......................
321
.............................
322
Production of Germanium Dioxide .......................
323
ix
Page
Precautions Used t o Obtain High-Purity Germanium
.
82 PRODUCTION OF GERMANIUM ........................... 324
.
83 PURIFICATION OF GERMANIUM AND PREPARATION OF
GERMANIUM MONOCRYSTALS ............................ 325
.
88 EXTRACTION OF GALLIUM FROM THE WASTES OF THE
ELECTROLYTIC REFINING OF ALUMINUM .................... 345
.
89 PRODUCTION OF GALLIUM .............................. 347
Crude Indium
9 4. REFINING OF CRUDE INDIUM.............................. 364
.................................. 364
Selective Cementation
................................ 364
Electrochemical Methods
..................................... 366
C h e m i c a l Methods
..................................... 367
Vacuum Distillation
.................. 368
.......................
Examples of Technological Processes 375
101 .
EXTRACTION OF RHENIUM FROM THE VARIOUS WASTES
FORMED IN THE PROCESSING OF MOLYBDENITE CONCENTRATES . 390
.
102 PRODUCTION OF RHENIUM ................................. 396
xi
Page
Reduction of Potassium Perrhenate i n a Solution by
Hydrogen Under Pressure ................................ 399
......................
T h e r m a l Dissociation of the Halides 400
-. ......................... .............................'I
Page
........
460
Production of Lithium by Electrolysis of Molten Salts
Production of Lithium by Thermal Reduction With Metals ....
463
119. PURIFICATION OF LITHIUM ............................... 465
Izv.
Izvest iy a Bulletin
Kirg SSR
Kirgizskaya SSR Kirgiz SSR
LGU
Leningradskii Gosudarst Leningrad State University
vennyi Universitet
XiV
__
. .-. .- . -. .. - ..... I I I .....
I... .." I . . . 1 . # . . # , 1 1 , , , I, I I I I I
I
Abbreviation Full n a m e (transliterated) Translation
xv
FOREWORD
xvi
INTRODUCTION
xvii
TABLE I
I I I I I I I I f 4.0026 I
I
e
132.905
LANTHANIDESIRME-EMTH ELEMENTS)
the E a r t h ' s c r u s t is v e r y nonuniform. The nine most abundant elements
account for 98.13 7'0' of the total amount of m a t t e r in the E a r t h ' s crust, i. e.,
the remaining 83 elements account f o r only 1.8770 of it.
TABLE 2
T h e increasing use of chemical elements (both in the free state and as compounds)
'oral number
Period Elements
,f elements
~
T h e 18th century
I, I, I, I*
" H. Pt, Ir, J 30
T h e 19th century
I, ,, I, .I " m, w,
Ba. Br. Cd, Mn. I,62
lanthanides ( 1 5 elements)
Rh 69
U p to 1957
N o t e : the metals used since ancient times are underlined; the rare metals are boxed in.
TABLE 3
Metals produced today* ( t h e rare metals are underlined)
- --
V, Nb. Ta. As. Sb. B i 6 3
VI
-----
Cr. Mo. W . Se, T e . Po 6 5
VI1
-
Mn. R e 2 1
Actinides
---
Th. U, Pu 3 3
Total. 70 41
XiX
TABLE 4
Abundance
Decade Chemical el em en t s and their occurrence in wt%
limits, wt?
- - - -
I 10-50 0 Si
47.2 27.6
1-10
A1 Fe Ca Na K Mg
8.80 5.10-~
3.60 2.64 2.60 2.10
Ill 1-10-1 Ti H C
0.60 (0.15) 0.10 __-- -
1v
Mn P S Ba CI Sr Rb F
0.09 0.08 0.05 0.05 0.045 0.04 0.031 0.027
Zr Cr V Cu N
0.020 0.02 O.Oj5 0.01 0.01
~
V lo-*- 10-3 Ni Li Zn ce Sn Co
8.10 6.5.10d3 5.10-3 4.5.10-3 4.10-3 3.10-3
Y Nd La Pb Cia
2.8.1(r3 2.5.10-3 1.8.10-3 1.6.10-3 1.5.10-3
Nb Gd
1.10-~ 1.1073
VI 10-3-10-4 Th Cs Pr Sm Ge Be
8.1Oy 7.10-4 7.10-4 6.10-'7.10-4 7.10-'
Sc As Dy Er Yb U
6 . 1 ~ - ~5.11)-~ 4.5.10-4 4.10-' 3.10-4 3.10-'
TI Mo Hf B Br Ho
3.10-4 3.10-4 3.2.10-4 3.10-4 1.6.10-4 1.3.10-'
Eu w Lu
1.2.10-4 1.10-4 1.10-~ -
VI I 0-4-10-5 Tu Se Cd Sb I Bi
8.10-5 6.10-5 (5.lOP5) (4.10-5)(3.10-5) (2.10-')
Ag In
--- (1.10-~)(1.10-5)
~~
VI11
IX
xx
Classification of r a r e metals
TABLE 5
Refractory
V Vanadium, niobium, tantalum
rare
VI Molybdenum, tungsten
metals
VI1 (Rhenium)*
Dispersed
IV Germanium
rare
VI Selenium, tellurium
metals
VI1 Rhenium
I1 Radium
I11 Actinium and actinides (thorium. protactinii Radioactive
uranium and transuranium elements) rare metals
V
Polonium
* Rhenium is a typical dispersed e l e m e n t but because of its properties i t may also he classified
as a refractory metal.
the extracted metal from the bulk of the accompanying elements, and to
concentrate it in solution o r in the precipitate. This is accomplished
either by pyrometallurgical process e s (roasting, smelting, distillation,
etc. ) or by hydrometallurgical methods (processing with acids, alkali
solutions, etc. ).
The second stage consists of the isolation and purification of chemical
compounds and is characterized by the major p a r t played by chemical
processes in aqueous solutions (precipitation, crystallization, extraction,
ion exchange, etc. ). Pyrometallurgical processes (distillation of chlorides
or oxides, fractionation) a r e occasionally used for the production of pure
compounds.
The third stage - preparation of pure r a r e metals - m a k e s use of
various (mainly pyrometallurgical) processes for the reduction of the
chemical compounds. In accordance with the reduction methods used,
r a r e metals may be classified into three groups (Table 6 ) .
TABLE 6
Methods for the production of the rare metals
Method of reduction
I Metal
xxiv
Development of the r a r e - m e t a l industry in the USSR
No rare-metal industry existed in Russia before the 1911 Revolution. Nevertheless, leading Russian
scientists forecast the great potentialities of various rare-metal ore deposits in the enormous area of Russia.
Important studies on the occurrence of scattered rare metals (indium. thallium, rubidium, and cesium)
in Russia were conducted by V. I. Vernadskii in the years 1909-1915; they were a valuable contribution
to the geochemistry of those elements. V. I. Vernadskii announced in 1916 that Russia had raw materials
for t h e production of vanadium, lithium, lanthanum, cerium. thorium, boron. bismuth, cadmium.
molybdenum, titanium, tin, radium, selenium, uranium. cesium, and zirconium. None of these metals
was produced in Russia a t that time.
Mendeleev's periodic table of elements played a most important part in the development of the
chemistry of the rare metals. T h e periodic table m a d e i t possible to predict undiscovered elements and
their properties and thus facilitated the prospecting work. T h e properties of gallium. germanium and
scandium were brilliantly predicted by Mendeleev in 1811, before their discovery.
A number of new metallurgical processes which were subsequenrly applied to in the production of
rare metals were developed by Russian scientists before the revolution. These include the powder.metallurgy
(sintering) methodused in the production of refractory metals (tungsten, molybdenum. tantalum. and
niobium). T h e method was developed in 1826 by the Russian metallurgist P. G. Sobolevskii who used it in
the manufacture of platinum products.
In 1860-1865 Beketov laid the scientific foundations for a very important method of metal production -
thermal reduction. He discovered the aluminothermal method and was the first to use if in the production
of barium, potassium, rubidium and cesium. Thermal reduction is used today i n the production of many
rare metals and their alloys.
Some attempts were made by Russian engineers and workers to organize small-scale production of certain
rare metals and their compounds and alloys even before the Revolution. For example. molybdenum and
tungsten steels w e r e produced in 1896 in the Putilov plant under the guidance of Prof. Lipin. and their
properties were investigated,
Further steps in the organization of the production of rare metals and their alloys were taken in Russia
in the war years 1914-1918. During that period. a beginning was m a d e in the small-scale exploitation of
tungsten ores from the Urals and the Transbaikalia and of molybdenum ores from the Chikoi deposits, and
the production of ferrotungsten was organized a t the Obukhov plant in Petrograd and at the Motovilikha
plant in Perm. T h e Izhora plant began the production of special molybdenum steels.
The producrion of small amounts of selenium and tellurium compounds from the wastes of sulfuric
acid plants was begun in 1916. T h e production technology of lithium compounds from lepidolite from
Russian deposits was developed under the guidance of V . G. Khlopin. At the same t i m e , the "Elektrosila"
plant in Petrograd began pilot-plant producrion of ferrotitanium and titanium carbide, and the conversion
of the latter into titanium tetrachloride. However, these attempts were not continued.
Geological surveys of rare metals were started as early as 1922. These surveys which became very
intensive during the first f e w five-year planning periods resulted in a sufficient supply of local raw materials
being made available to the Soviet rare-metals industry.
In 1938 A. E. Fersman analyzed the surveys of raw materials in the USSR and noted that the occurrence
of the following elements had not been reported: scandium, gallium. germanium. rhenium, and thallium.
By now, deposits of these elements have also been discovered and investigated.
Following the successful research work of the geologists, great advances were made in mining. ore dressing.
chemistry and metallurgy.
A rare-element office was set up in 1922. forthe investigation and development of new technological
processes for the manufacture of rare metals and their compounds. T h e State Institute of Rare Metals was
founded in 1931. In the same year the first chairs of technology and metallurgy of rare metals were created
in higher schools of engineering in the Soviet Union.
There was a rapid development in the production of rare metals in the USSR. Production of the following
metals was organized: tungsten in 1927, molybdenum in 1928. hard alloys in 1929. alloys of iron with
tungsten and molybdenum in 1931, beryllium in 1932, tantalum and lithium in 1933, and ferrovanadium in
1932-1935.
A very rapid development in the production of rare metals has taken place in the last 15 years (the
postwar period). This was caused by the need for materials with very different physicochemical properties in
modem industries: high-speed and high-flying aircraft production, electro-vacuum technology, semi
conductor electronics, and production of atomic power. Thus, the need of aviation for light and refractory
alloys led t o the large-scale production of titanium -a m e t a l which was a laboratory curiosity only 15years
ago. T h e production of germanium was organized as a result of the rapid development of semiconductor
electronics. The birth of nuclear power industry necessitated the production of uranium and thorium -the
xxv
main nuclear fuels, as well as of other nuclear reactor materials, especially zirconium, beryllium, and
lithium. T h e rare metals are of primary importance for the further increase in the production of special
steels and of ultrahard, refractory and corrosion-resistant materials, electrical illumination lamps, radio
valves, X-ray apparatus. radar sets, photoelectric devices, and various parts for cars, tractors, etc.
At present, the Soviet Union produces on an industrial scale a l l techmlogically important rare metals.
A continuously increasing consumption of the rare metals is due to the rapid development of the production
of special steels, hard and refractory alloys, of the electrical and electronic industries and other branches
of technology. As a result, i t is planned to increase t h e production of rare metals in order to satisfy the
requirements of the national economy.
xxvi
P a r t One
Chapter Z
TUNGSTEN
P r o p e r t i e s of tungsten
1
The mechanical properties of tungsten depend to a g r e a t extent on its
.
mechanical and thermal history Tungsten cannot be worked mechanically
i n the cold; its forging. rolling. and drawing a r e c a r r i e d out when hot .
The physical and mechanical properties of tungsten a r e shown below .
Atomic number . . . . . . . . . . . . . . 14
Atomic weight . . . . . . . . . . . . . . 183.92
Density. g/cm3 . . . . . . . . . . . . . . 19.3
. . . . . .
Crystalline l a t t i c e type and parameter body-centered Fube
a = 3.1641 A
Melting point . 'C . . . . . . . . . . . . . . 3395 1 1 5
Boiling point. " C . . . . . . . . . . . . . 5930
Heat of fusion. c a V g . . . . . . . . . . . . 61
Heat of vaporization. c a l / g . . . . . . . . . . 1183
Heat capacity . c a l / g . " C at:
18' . . . . . . . . . . . . . . 0.031
1000" . . . . . . . . . . . . . . 0.0365
1400" . . . . . . . . . . . . . . 0.043
2100" . . . . . . . . . . . . . . 0.048
.
Thermal conductivity c a l / c m . sec "C. at:
20" . . . . . . . . . . . . . . 0.31
821" . . . . . . . . . . . . . . 0.28
1121' . . . . . . . . . . . . . . 0.24
Linear expansion coefficient ( 0 t o 500") of forged rods . 4.98 X
.
Electrical resistivity ohm c m . l o 6 at:
20" . . . . . . . . . . . . . . 5.5
300' . . . . . . . . . . . . . . 27.14
1200' . . . . . . . . . . . . . . 40.0
2000" . . . . . . . . . . . . . . 66.0
2430' . . . . . . . . . . . . . . 81.1
3030" . . . . . . . . . . . . . . 103.3
Electron work function eV . . . . . . . . . . . 4.55
Energy radiated by the surface. w a t t / c m 2 . at:
800" . . . . . . . . . . . . . . 0.9
1600" . . . . . . . . . . . . . . 18.0
2200' . . . . . . . . . . . . . . 64.0
2700" . . . . . . . . . . . . . . 153.0
3030" . . . . . . . . . . . . . . 255.0
Thermal neutron capture cross section. barn* . . . . 19.2
Brinell hardness. kg/mmz:
of a sintered rod . . . . . . . . . . . 200 -.230
of a forged rod . . . . . . . . . . . 350 .400
Tensile strength. kg/mmz:
of a sintered rod . . . . . . . . . . . 13
of a forged rod . . . . . . . . . . . 35 .150
of a nonannealed wire . . . . . . . . 180 .415
of an annealed wire . . . . . . . . . . 110
Young's modulus (of a wire). kg/mmz . . . . . . . 35000 .38000
-____---------
* One barn = lo-" c m 2 .
. . . . ~ . . . . . .
Tungsten at t e m p e r a t u r e s below i t s melting point does not r e a c t with
hydrogen. Reaction between tungsten and nitrogen, with formation of
tungsten nitride WN2, takes place only above 2000".
Tungsten is rapidly oxidized by water vapor at red heat (600 to 700")
with formation of W Q :
W + 3H,O 2 WO, + 3H,.
Solid carbon and carbon-containing g a s e s (CO, C H I , C2H2,etc.) r e a c t with
tungsten at 800 to 1000" with formation of tungsten carbides (WC and W2C).
The presence of even s m a l l amounts of carbide in the metal makes it
brittle and strongly reduces i t s electrical conductivity.
At ambient temperatures, tungsten is not attacked by hydrochloric,
sulfuric, nitric, and hydrofluoric acids a t any concentration, o r by aqua
regia. At 80 to 100" the m e t a l is not attacked by hydrofluoric acid; it
is attacked v e r y slowly by hydrochloric and sulfuric acids, and m o r e
noticeably s o by n i t r i c acid and aqua regia. Tungsten dissolves rapidly
in a mixture of hydrofluoric and nitric acids.
Tungsten is not affected by alkali solutions a t room temperature, but
is oxidized by molten alkalies (in the presence of a i r ) with the formation
of tungstates. This p r o c e s s is very rapid in the presence of oxidizing
agents (NaNQ, NaN02, KClQ, PbO,).
3
l1l11ll11llIll l l I1 Il1
4
The solubility of sodium tungstate in water is:
Temperature."C . . . . -5 0 5 6 10 20 40 80 100
Solubility of the anhydrous
salt.% . . . . . . 30.6
-- 35.4
Na2W0,. 10H,O
41.0 41.8 41.9 42.2
Na,WO,
43.8
' 2H,O
41.4 49.2
S o d i u m p a r a t u n g s t a t e 5 N a 2 0 . 12W03.rtH10 crystallizes f r o m
solutions of normal tungstates as a result of careful neutralization to a
pH of 5.5 to 6. This is accompanied by hydrolysis:
I2Na,WO, + 7H20 --f 5Na,O. 12W0, + 14NaOH.
The alkali hydroxide formed in the reaction is neutralized by the acid.
The salt hydrates contain 28 and 25 water molecules after crystalliza
tion in the cold and a t 60 to 80" respectively.
The solubility of the paratungstate in water is strongly affected by the
temperature :
Temperarure,'C . , . . , . . 12.4 39.6 101.8
Solubility of the anhydrous s a l t , % . 5.52 17.94 70 6
n = llHZ0 n = SH,O
5
Calcium tungstate may b e prepared by precipitation on the addition of
calcium chloride or lime to solutions of the alkali tungstate, or by d i r e c t
solid-state interaction of calcium oxide with tungstic anhydride a t 600 to
800". Calcium tungstate is decomposed by acids, with formation of
tungstic acid.
Heteropolyacids and their salts. Tungsten has a number of known
heteropolyacids which form s a l t s with phosphoric, arsenic, silicic and
other acids. Those acids a r e formed through the substitution 'of (WOd2
and ( W ~ 0 7 ) ~ions
for oxygen ions in silicic, phosphoric, a r s e n i c and other
acids.
For instance, there a r e potassium and sodium s a l t s of silicotungstic
acid H~[Si(W20~)6].nH~0, an acid which does not exist in the free state. The
composition of the potassium s a l t is Ks[Si(W207)6].xHp0 ( where x is 12 o r 20)
(where x is 10 o r 18). Salts
and of the sodium s a l t - Na4 H4[Si( W Z Oti]~ )~ H z O
e
T u n g s t e n c h 1o r i d e s .
Tungsten forms a s e r i e s of chlorides:
WCl,, WC15, WCl,, WCl2, and oxychlorides: WOCl, and W02C12.
T h e h e x a c h 1o r i d e WCl, is formed when a s t r e a m of d r y chlorine
i s passed over tungsten powder at 750 to 800" a s dark-violet crystals. The
hexachloride melts at 2 7 2 and boils at 337". It exists in two crystalline
modifications: a- WC16 and 6-WCl,. The transition from the a- to the
@-modificationoccurs a t about 230" and i s accompanied by a large change
in volume.
The hexachloride i s decomposed by water, with the formation of tunstic
acid:
+
WCI, 4H20 = H,WO, 6HCI. +
The tunsten o x y c h l o r i d e s WOzClzand WOCl4 a r e formed as a result
of the action of chlorine on tungstic anhydride or on a mixture of WO, and
carbon. W0,Cl2 is pale yellow and melts at 266"; WOC1, is red-brown,
melts at 209 and boils at 232".
The lower tungsten chlorides a r e formed by the reduction or thermal
dissociation of the higher chlorides. The pentachloride WC15 is a black
crystalline substance which melts at 2 4 8 and boils at 276"; WCZ4 i s a gray-
brown nonvolatile substance.
1455
I
Tungsten sulfides. Tungsten forms two sulfides: WS2 which occurs in
nature as the m i n e r a l tungstenite, and W%. The disulfide may be prepared
by the interaction of sulfur vapor with powdered tungsten o r W Q a t 800 to
900". Its s t r u c t u r e and properties resemble those of molybdenum disulfide
(see p. 105).
The trisulfide WS, is formed by bubbling hydrogen sulfide through hot
acidified solutions of tungstates. WS, dissolves in alkali sulfides with
formation of sulfur-containing salts. The dark-brown tungsten trisulfide
is precipitated when a solution of the sulfur-containing s a l t is acidified:
Na,WS, + H,SO, = WS, + Na,SO, + H,S.
Tungsten carbides. Tungsten f o r m s two carbides: W C and W2C. Those
carbides a r e hard, refractory substances. The melting points of W2C
and W C a r e 2750 and 2900" respectively. The microhardness of WC is
1 7 6 0 kg/mm2. The m o s t common method for the production of the carbides
is ignition of a mixture of powdered tungsten and carbon (carbon black) at
1000 to 1500".
U s e s of tungsten
Tungsten m i n e r a l s
9
Tungsten o r e s and deposits
10
successfully achieved by electromagnetic separation in a high-intensity
magnetic field (wolframite is slightly magnetic while c a s s i t e r i t e is non
magnetic). The magnetic separation is occasionally preceded by
calcination, which converts the pyrite into the magnetic oxide Fe304 this
being subsequently separated from the wolframite in a low-intensity
magnetic field.
TABLE 7
Technological requirements for some types of tungsten concentrates (GOST 213-56)
Chemical composition,qo
KVG Wolframite
hubnerite 0.04 0.5 0.2 0.2 0.2 - 'roduction of
ferrorungsten
KVGT Wolframite
KShT,
KShT,
hubnerire
Scheelite
0.10
0.20
0.20
0.8
0.8
0.8
0.10
0.10
0.10
1.00
0.20
0.20
0.15
0.20
0.20
SiO,
+ 3Na,C03 = Na3P0, + 3CaC0,;
Ca, (POJ,
As,S, + 6NazC0, + 70, = 2Na3As0, 3Na,SO, + 6C0,;
A
13
I Wolframite concentrate
I Scheelite concentrate
1 1
Comminution Comminution
Fusion Fusion
1 1
Filtration
s. &
Tailings Solution (Na2W0,,
1 Na2Si03 and other
T o waste impurities)
1
Purification from Si,
P. As and Mo
1 1
-1
CaC12
I
Precipitation of sodium tungstate
4
J.
Precipitate CaWO, Mother liquor
HC1\+ 1 1
Decomposition To storage container
1 (trap)
Filtration and washing of
the tungstic acid
1 1
Wash liquor
To calcination or
ammoniacal purification
14
Continuous p r o c e s s e s a r e preferably used for l a r g e - s c a l e production.
Tubular rotating furnaces lined with chamotte b r i c k s a r e employed in the
continuous p r o c e s s .
In a method developed in the USSR (by Bogomoltskaya, Semenovykh,
Matusevich, e t al.), the composition of the charge is designed f o r it not to
melt but to remain in the f o r m of particles that can be caked / 3 / . This
protects the lining from corrosion by the melt and prevents deposit forma
tion in various p a r t s of the furnace. In o r d e r to prevent melting of the
charge the solid tailings from the leaching of the cake are added to i t in
an amount calculated to reduce the W Q content to about 20 to 22%.
The extent of decomposition of the concentrate in this c a s e is fairly
high - 9 8 to 99 70. The disadvantage of the p r o c e s s l i e s in the fact that the
concentrates a r e diluted with the tailings, which leads to a d e c r e a s e in the
output of the furnace. However, this disadvantage is offset by the fact that
standard rotating furances can be used and by the long s e r v i c e life of the
furnace.
I I I
c, I I
15
,!I .I I II .
I I II I. 111 111 II .. I 111. 111
. II 1111 1111 I I 1.1 I 1.11. 11.11
located in the lower furnace head. The temperature is controlled by
adjusting the r a t e of supply of the fuel or a i r to the b u r n e r or jet. The
furnaces a r e rotated at 0.5 to 2 rpm.
A furnace 20 m long and with an external d i a m e t e r of 2.2 m rotating
a t a speed of 2.5 r p m and placed at a slope angle of 3", has a n output
of 2 5 tonslday (for a charge containing 20 to 22'70 W Q ) .
When a rotating furnace is used the charge must be fed in continously.
The comminution of the concentrate is usually c a r r i e d out in ball mills
with a peripheral discharge (through screening cloths), which operate
in a closed cycle with an a i r separator.
The charge components (concentrate, soda, and saltpeter) a r e fed
from the s t o r a g e bins to the mixer-conveyor with the aid of dosing devices
(automatic balance) and a conveyor system. When prepared, the charge
is fed into the hopper of the furnace. At the exit of the furnace, the fused
p a r t i c l e s a r e passed through a r o l l e r c r u s h e r (the crushed particle s i z e
is 2 to 5 cm) into a continuous wet mill and the resulting pulp is fed into
a leaching apparatus fitted with a s t i r r e r (Figure 5).
Leaching. The following components of the cake a r e dissolved when
i t is leached with water: sodium tungstate, soluble s a l t s of impurities such
a s sodium silicate NazSiQ, sodium monohydrogen phosphate, and mono-
hydrogen arsenate, NazHP04and NazHAsO,t:, sodium molybdate NazMo04,
sodium sulfate NaZSO4, and unreacted sodium carbonate. The solid residue
contains the oxides and hydroxides of iron and manganese, undecomposed
concentrate, and other insoluble compounds.
The leaching i s c a r r i e d out at 80 to 90" in batch or continuous equipment
( r e a c t o r s with s t i r r e r s or drum leachers) made of iron. As a rule, two-
or three-stage leaching is c a r r i e d out in o r d e r to ensure quantitative
extraction of tungsten. Regular or superheated steam is used for heating.
The use of superheated steam is l e s s convenient, since this leads to
dilution of the solution by the condensate.
In the continuous process, the leaching is c a r r i e d out in rotary drum
l e a c h e r s ; each leacher consists of a s t e e l drum (Figure 4) with s t e e l
lids (fitted with hollow pivots fastened to the bearings) bolted to i t s ends.
The inner p a r t of the casing and the marginal walls of the lids a r e
protected by removable a r m o r plates. The drum is rotated by a motor,
through a reduction g e a r which t r a n s m i t s the motion to a toothed wheel
fastened on the end lids. The leacher i s held in a horizontal position on
two supports. In o r d e r to accelerate leaching and, at the s a m e time, to
c r u s h the cake particles, the leaching apparatus is filled with crushing
rods 40 to 80 m m in diameter. The hot fused m a s s is continuously charged
through the hollow pivot together with hot water (or a weak solution of
sodium tungstate). The pulp is continuously discharged through the
second hollow pivot.
A f a i r l y high degree of extraction of the tungsten (about 98 to 99%)
is obtained during the leaching. The concentrated sodium tungstate
solutions have a density of 1.26 to 1.40 (depending on the p r o c e s s
conditions.), i. e . , contain 190 to 270g W Q in one l i t e r of solution. The
dry residues f r o m leaching and filtration amount to about 30 to 407' by
weight of the starting concentrate (without taking into account the residues
* Inweakly a l ka l i ne solutions, most of the phosphorus a n d arsenic is present as the HP0:- and HASO:
ions rather than a s the PO:- a n d As0:- ions.
FIGURE 4. Drum-type leacher.
1 -end lid; 2-steel casing; 3-armor plates; 4-hOllOw pivots; 5-bearings; 6-reduction gear.
FIGURE 5 . Diagram of installation for the continuous fusion and leaching process
1 -elevator; 2-ball mill; 3-conveyor (screw); 4-elevator; J - a i r separator; 6-auromatic
dosing devices; I-conveyor; 8-mixing conveyor; 9-charge bin; 10-feeder; 1 1 -furnace;
12-roller crusher; 13-drum leacher; 14-reactor with stirrer; 15-filter.
18
FeWO, + 2NaOH Na,W04 + Fe (OH),,
MnWO, + 2NaOH Z Na,W04 + Mn (OH),.
As compared with fusion with sodium carbonate, the method has the
economic advantage of not requiring the use of a furnace. It h a s the
drawback that only very finely divided concentrate may be used (i. e . ,
investment in comminution equipment) and that it requires a l a r g e e x c e s s
of sodium hydroxide, which is much m o r e expensive than sodium carbonate.
If the particle s i z e employed is 0.03 -0.04mm, the temperature i s 1 0 0
110", and the excess of sodium hydroxide is 50% o r m o r e above the
theoretical amount, a high extent of decomposition (98 - 9 9 % ) is obtained.
The oxidation of the f e r r o u s and manganous hydroxides to f e r r i c and
manganic kiydroxides is accelerated by bubbling a i r through the solution.
The decomposition is c a r r i e d out in s t e e l vats fitted with s t i r r e r s and
heated with regular steam.
Soviet workers (Meerson and Nadoltskii 1 5 1 ) have shown that the
consumption of alkali may be reduced and the decomposition may be
accelerated by conducting the alkali processing in heated ball mills. The
increase in the reaction r a t e is attributed to the abrasive action of the
balls, which remove the iron and manganese hydroxide l a y e r s from the
surface of the concentrate particles.
19
I 1l11l1l111111l1l1llIll l l I I1 Il 1 Il lIllIllIl1
+
NHJI + H,O NH.,OH HCI,
+ +
NaOH HCI 2 NaCl H,O.
+
Mg (NHJ PO, H 2 0 MgHPO, + NH4OH.
As i s evident from the above equation, a certain excess of ammonia
must be present in solution in o r d e r to prevent hydrolysis. The presence
of ammonium chloride is also n e c e s s a r y since i t prevents precipitation
of magnesium hydroxide by reducing the OH--ion concentration to the
extent where the solubility product of Mg(OH), is not reached.
The precipitation of magnesium ammonium phosphates and arsenates
i s c a r r i e d out in the cold. The required concentration of ammonia and
ammonium chloride in the solution is established and an excess of a
magnesium chloride solution is added.
At a certain reagent r a t i o a crystalline precipitate consisting of the
magnesium ammonium s a l t s is formed in the solution, on prolonged (up
to 48 hours) standing. The gelatinous normal phosphate and arsenate
(Mg,(P04), and Mg3(As04)z)a r e partially precipitated together with the
ammonium salts.
20
Removal of molybdenum. Molybdenum must be eliminated from the
sodium tungstate solution if i t s concentration exceeds 0.3 g/l*.
I
Sedimentation and decantation
4 . 1
MgCIz
7
I
Solution
soEton
r
Separation of arsenic and
phosphorus
H,SiO, precipitate
(contaminated with W)
Reprocessing (in
the fusion
section)
1
Sedimentation and
decantation
. 1 7
1
T o waste disposal
blolybdenum ;eparation
1
Filtration
. 1 - .1
Pure solution of sodium bios,
tungstate Precipitate
1
T o tungsten separation
from solution
21
Na,MoO, + 4Na,S+4H,O = Na,MoS, +
8NaOH,
+
Na,MoS, + 2HC1= MoS, 2NaCl+ H,S.
22
I
which may be washed with relative ease, are formed when a hot concentrat
ed solution of sodium tungstate is poured into boiling hydrochloric acid.
The r a t e of introduction of the solution into the hydrochloric acid affects
the particle s i z e of the precipitate. This may be due to the fact that
different r a t e s of pouring bring about formation of different numbers of
crystallization c e n t e r s which, a t a given r a t e of growth of the crystals,
determine the particle s i z e of the precipitate.
The tungstic acid is precipitated in earthenware r e a c t o r s o r in i r o n
r e a c t o r s lined with rubber o r with acid-resistant material.
A sodium tungstate scilution containing 110 to 120 g W 0 3 / l is heated to
80 to 90" and added at a predetermined r a t e to a boiling 25 t o 30% solution
of hydrochloric acid. The r a t e of addition is determined empirically,
depending on the required particle s i z e of the acid. The purity and the
particle s i z e of the acid also depend on the final acidity of the solution,
which is maintained in the range between 7 and 12 70.
The precipitated tungstic acid must be thoroughly rinsed to remove
sodium chloride and other soluble contaminants. The multiple washing
is c a r r i e d out f i r s t by decantation with hot distilled water and then in
suction-filters which a r e lined with rubber o r some other acid-resistant
material. The washing is repeated 6 to 8 times; HC1 o r NH4Cl is added
to the water used in the third rinsing to a concentration of 1%in o r d e r
to p e r m i t better sedimentation of the tungstic acid. Glass or chlorinated
PVC cloth is used a s the filter material. F u r t h e r amounts of water a r e
removed from the filtered acid by centrifuging.
The total yield at the precipitation stage is 98 to 9970, and the l o s s e s
during washing amount to 0.3 to 0.4%.
Precipitation of calcium tungstate. The most widely used method for
the isolation of tungsten compounds from solution is the precipitation of
calcium tungstate (artificial scheelite). A fairly complete precipitation
may be obtained because of the low solubility of calcium tungstate, which
d e c r e a s e s a s the temperature is increased ( s e e p. 5). At the s a m e time,
sodium ions remain in the mother liquor, and the acid obtained has a low
content of sodium-containing contaminants.
To effect the precipitation, an aqueous solution of calcium chloride is
usually added to the sodium tungstate solution. A crystalline precipitate,
which s e t t l e s readily, is formed:
Na,WO, + CaCI, = CaWO, + 2NaCI.
The completeness of the precipitation of calcium tungstate depends on
the alkalinity and concentration of the sodium tungstate solution. It is
recommended that the precipitation be c a r r i e d out f r o m solutions heated
to boiling, and having a density of 1.14 to 1.16 (120 to 130 g WO3/l) and an
alkali hydroxide content of 0.3 to 0.70/0. Incomplete precipitation is
observed if the hydroxide concentration is below 0.3 70, while the precipitate
formed in the presence of m o r e than 0.770 hydroxide is voluminous, settles
slowly, and entrains impurities.
Other sparingly soluble calcium s a l t s , CaS04, C a C Q , CaSiQ, Ca3(P0.),,
and CaMo04, a r e coprecipitated with calcium tungstate. The concentrations
of silicon, phosphorus, and molybdenum in the CaW04 precipitate a r e
considerably reduced by the preliminary purification. The calcium sulfate
concentration in the precipitate depends on the initial concentration of
23
sulfate ions in the solution and on the excess of the calcium chloride
precipitant used. The l a r g e r the excess taken, the higher the concentration
of CaS0, in the precipitate. The considerable solubility of CaSO, (2g/l
a t 20") p e r m i t s its removal by washing with hot water.
Calcium hydroxide a s slaked l i m e may a l s o be used to precipitate
calcium tungstate; however, the precipitate then contains m o r e impurities.
The precipitati,on of calcium tungstate is c a r r i e d out in iron or wooden
vats fitted with stirrers.
The extent of precipitation of tungsten from solution is 99 to 99.5%.
The concentration of W Q in the mother liquor should not exceed 0.05 to
0.07 g/l.
The washed precipitate, as a s l u r r y or a paste, is decomposed by
heating with hydrochloric acid:
CaWO., + 2HC1 S,WO, + CaCI,.
A high final acidity of the s l u r r y (90 to 1 0 0 g HCl/1) is maintained
during the decomposition stage; this e n s u r e s that the phosphorus, a r s e n i c
and p a r t of the molybdenum a r e separated from the tungstic acid
precipitate (molybdenic acid dissolves in hydrochloric acid).
The acid decomposition of calcium tungstate is c a r r i e d out in i r o n
r e a c t o r s lined with rubber o r some other acid-resistant coating and fitted
with rubber-lined mechanical s t i r r e r s .
Hydrochloric acid is heated to 60 to 65" and the aqueous s l u r r y o r paste
containing the calcium tungstate is added with constant s t i r r i n g . The
spent acid usually contains 0.3 to 0.5 g W Q / 1 , which is recovered a s
calcium tungstate by precipitation with lime.
The tungstic acid is washed by the method described above. The total
degree of extraction is 98 to 9 9 % . The filtered and dried acid usually
contains 0.2 to 0.370 of impurities.
24
The value of the equilibrium constant may be used to calculate the
minimum amount of sodium carbonate (over the stoichiometric amount)
which must be taken in o r d e r to bring about quantitative dissolution of
the tungsten.
The amount of Na2CQ required f o r the formation of 294g of Na2W04is
1 0 6 g. In o r d e r to retain the sodium tungstate in solution, it is n e c e s s a r y
that the solution contain a certain amount of sodium carbonate, which may
be calculated from the equilibrium constant:
* A soda leaching process of wolframite concentrates with sodium carbonate solutions in autoclaves has been
recently developed / 2 0 / . In order to obtain an effective decomposition it is necessary that the CO,
formed in the reaction
FeWO, + Na,CO. + H,O - Fe(0H). + Ne.WO, + COB
be continuously removed from the system.
25
The studies of Maslenitskii have shown that a t 1 8 0 - - 2 0 0 " the reaction
proceeds a t a satisfactory r a t e and to a satisfactory degree of completion.
If the solution temperature must be increased above the normal boiling
point, the heating is done in autoclaves (hermetically sealed containers)
and not i n open vessels. When an aqueous solution is heated to 200" in a n
autoclave, its vapor p r e s s u r e reaches 1 5 atm.
Syrokomskii and Maslenitskii / 4 / w e r e the f i r s t to develop a method for
the decomposition of scheelite concentrates with sodium carbonate solutions
in an autoclave. This method gives good r e s u l t s i n the processing of both
lean (containing up to 2 0 % W03) scheelite Concentrates and r i c h tailings
(containing up to 5 70 W03) from enrichment plants, as well as ordinary
concentrates. As compared with the fusion of scheelite concentrate with
sodium carbonate and sand, the decomposition with sodium carbonate
solution has the advantage of not requiring a furnace or the associated
preparatory stages. The disadvantage of the autoclave p r o c e s s is that
the consumption of sodium carbonate is high. The amount of sodium
carbonate required for the quantitative decomposition of the scheelite
concentrate depends on its W 0 3 concentration. An amount 2 . 5 to 3 t i m e s
the stoichiometric is required f o r the decomposition of rich concentrates.
An amount 4 to 4.5 t i m e s the stoichiometric is required f o r the decomposi
tion of lean concentrates (15 to 2 0 F WO3). The processing of the con
centrates with sodium carbonate solutions is c a r r i e d out in autoclaves of
various types :
a) fitted with a mechanical s t i r r e r and heated by means of spent s t e a m ;
b) heated and s t i r r e d by means of live steam; the mixing is accom
plished by bubbling the s t e a m through the s l u r r y ;
c) horizontal autoclaves, containing balls rotating with the charge.
Heating is c a r r i e d out by means of live steam (Figure 7).
Recent investigations have shown that the use of autoclaves containing
milling equipment r e s u l t s in an i n c r e a s e in the r a t e of decomposition and
a reduction in the sodium carbonate consumption (to 1.75 to 2 . 0 equivalents)
in the processing of standard scheelite concentrates. This can be
attributed to the abrasive action of the balls, which remove the CaC03
l a y e r f r o m the surface of the scheelite particles. However, the design
of ball autoclaves is m o r e complicated than that of other types.
The autoclaves a r e built of special nickel steel and ordinary carbon
steels. Batch p r o c e s s is generally used in autoclave operation. An
aqueous s l u r r y containing the sodium carbonate a n d the scheelite concen
t r a t e (particle s i z e 0 . 5 to 0.6") is run from the mixer to the autoclave
through a gravity-flow line ( s e e Figure 7). When leaching is complete,
the s l u r r y is discharged from the autocalve into the evaporator, in which
the p r e s s u r e is lower than in the autoclave (i. e . , about 1 . 5 to 2 atm) and
in which the s l u r r y boils vigorously and is thus rapidly cooled. The
evaporator (Figure 7) consists of a cylindrical s t e e l vessel with conical
upper and lower ends. The s l u r r y is fed from the autoclave into the
center of the evaporator through a pipe. The steam formed passed through
a splash-head and is discharged through a nozzle. The s l u r r y is run-off
through the lower nozzle. The lower end of the evaporator is protected
against the thrust of the inflowing s l u r r y s t r e a m by means of a guard made
of armor-plated steel. The s l u r r y from the evaporator p a s s e s into a
collector and, from there, to the filtering and washing stages.
26
Auxiliary steam
- 1 .. I I
Acid decomposition
21
Scheelite concentrate
(contaminated with molybdenum)
Sodium carbonate
Preparation of slurry
.1
Leaching in autoclave
1
Filtration
$ -
Residue Solution
Wash water
4
Washing
To waste
I 7
Separation of silica
HCl
Filtration
4
Silica-containing
residue
Precipitation of MoS,
.1
Filtration and washing
3. -1
Evaporation Conversion into pulp
CaCb \ .1 and filtration
Precipitation .I4
1
Precipitate Solution
Filtration and washing
b
A
CaWO,
Solution
Drying and partial Second precipitation
calcining
precipitate
HCl
I
I
Decomposition
1
To waste
disposal.
1
Molybdenum concentrate
Washing and I
To waste disposal
filtration
7 . 1
Solution to H,WO,
waste precipitate
disposal J.
Drying
J.
Calcination
28
Scheelite concentrate
Size reduction
1
Decomposition
Hydrochloric acid
+ O.Z%niuic
I-- ---
Ammonium tungstate
-
Residues (SiOz and
solution undecomposed
Hydrochloric acid
_____I
I
Neutralization
mi nera 1)
(or evaporation)
Crystallization
Filtration
$--- -7
Mother liquor Ammonium paratungstate
I crystals
HC1
J. 1
Calcination
>ation of tungstic I
acid
1
Filtration
.L .L
Precipitate Solution
(containing
impurities)
1
To collecting
2 I
vessel
29
The p r o c e s s is c a r r i e d out in an iron r e a c t o r lined with rubber o r some
other acid-resistant m a t e r i a l ; the v e s s e l is filled with concentrated
hydrochloric acid (- 250% of the stoichiometric amount) and n i t r i c acid
is added. The concentrate is then fed into the reactor. The p r o c e s s is
c a r r i e d out f o r 6 t o 8 hours at 70 to 80" with stirring. The residue (which
c o n s i s t s of tungstic acid, silica, and undecomposed mineral) is rinsed
s e v e r a l t i m e s with hot water (as described on p. 23). The washed technical
grade tungstic acid precipitate containing 2 to 3 % impurities is forwarded
to the purification s t a t e (see Figure 9).
One of the drawbacks of the acid decomposition method is the l a r g e
consumption of.hydrochloric acid. This may be counteracted by working
in heated ball mills, in which the decomposition and the milling a r e
conducted simultaneously, while the tungstic acid layer is removed from
the surface of the scheelite p a r t i c l e s f 51. This r e s u l t s in an increased
r a t e of decomposition and a reduction of the acid consumption to 15070 of
the stoichiometric amount.
The technical grade tungstic acid produced by one of the above methods
may contain 0.2 to 3 70 impurities in the f o r m of calcium and sodium s a l t s ,
silica, molybdic acid, adsorbed iron, manganese and aluminum salts,
phosphorus, a r s e n i c and other compounds, and undecomposed scheelite
(in the case of tungstic acid produced by the decomposition of scheelite
concentrate).
The total concentration of SiO, and alkali and alkaline-earth metal
s a l t s (which together account for the bulk of the impurities) is expressed
as the "chlorination residue". This is the residue obtained on chlorinating
an accurately weighed amount of tungstic acid ( o r tungstic anhydride) with
d r y chlorine o r HCI a t 800". The chlorination l i b e r a t e s the volatile
chlorides of tungsten, iron, manganese, aluminum, phosphorus, etc. The
residue contains Si& and the alkali and alkaline-earth metal chlorides.
The maximum permissible "chlorination residue'' in tungstic acid o r
anhydride used for the production of tungsten wire is 0.1 70; in the anhydride
usedfortheproduction of tungsten carbide i t is 0.1 to 0.15% (seeTable 10).
Tungstic acid i s usually purified by the ammonia process. Tungstic
acid dissolves readily in ammonium hydroxide solutions with formation of
a solution of ammonium tungstate. Most of the impurities, silica,
iron and manganesd hydroxides, and calcium in the form of CaW04 remain
in the residue. The tungsten is precipitated from the ammoniacal solution
a s tungstic acid o r ammonium paratungstate.
30
water and becomes l e s s readily soluble in ammonium hydroxide. Ignition
of HzW04at 500" c a u s e s a complete l o s s of water andleads to the formation of
tungstic anhydride, which is only sparingly soluble in ammonium hydroxide.
Tungstic acid is s e n t to the dissolution stage in the f o r m of a suspension
(1kg of WO, p e r 1.5 l i t e r of water) preheated to 80 to 85". The suspension
is poured into a r e a c t o r containing a 25 To solution of ammonium hydroxide
(the consumption of ammonium hydroxide ( d = 0 . 9 1 ) is 115 l i t e r s p e r lOOkg
of WO,). The ammoniacal solution is left to settle f o r 8 to 1 2 h r s and is
separated f r o m the residue (SiOz, CaO, etc. ) by decantation. The density
of the solution is 1 . 2 9 to 1.30, which corresponds to a W q content of
320 to 330 g / l .
The ammoniacal solution is f r e e of the bulk of the impurities originally
present in the technical grade tungstic acid. However, it may contain
molybdenum, sodium, magnesium and iron salts.
31
If the s t a r t i n g solution of ammonium tungstate contains molybdenum,
ammonium paramolybdate crystallizes out together with ammonium
paratungstate. The paratungstate is l e s s soluble than the paramolybdate;
hence, molybdenum may be separated from tungsten by fractional
crystallization.
TABLE 8
Efficiency of the ammoniacal purification of tungstic acid
(according to Smithells j 1/)
32
8. PRODUCTION OF TUNGSTEN TRIOXIDE AND
QUALITY CONTROL
33
f o r c e s between the particles is stronger than in c o a r s e powders, and
prevents the powder from becoming m o r e densely packed.
A new and m o r e accurate method f o r controlling the physical s t r u c t u r e
of the powder has been recently introduced; it is based on the m e a s u r e
ment of the amount of adsorbed methaxiol vapors (the larger the specific
s u r f a c e of the powder, the higher the degree of adsorption). The device
shown in Figure 1 7 h a s been developed in the USSR f o r this purpose.
As is evident from Table 9, the methanol adsorption method is m o r e
sensitive than the bulk density method.
TABLE 9
Variation of the physical properties of tungstic anhydride powder with the temperature
of ignition of tunstic acid
_. _ _
Methanol ad- Bulk density,
sorbed, mg/g sorbed, m g g g/cm3
TABLE 1 0
Approximate specification for technical grade tungsten trioxide
Concentration, To
Component ~~ ~
Tungsten trioxide. . . . .
. 2 99.8 2 99.95
Molybdenum.. . . . . . . c 0.1 5 0.02
..........
Arsenic 5 0.015 5 0.02
. . . . . . . .
Phosphorus 5 0.025 5 0.01
Sulfur........... 5 0.015 5 0.02
. . . .
Chlorination residue 0.10 - 0.15 0.10
......
Calcium o x i d e . - 5 0.01
. . . . . . . .
Sesquioxides 5 0.04 5 0.01
Weight losses upon ignition . 0.5 0.05
34
..............
Raw material -scheelite concentrate 83.0
Reagents-sodium carbonate, quartz sand, hydrochloric
..................
acid. calcium chloride, etc. 9.1
..............
Auxiliary materials -filter cloth, etc. 0.2
....
Energy consumption -electrical, fuel. steam, water 1.7
Wages with benefits.......................... 2.0
Overheads ................................ 3.4
Total ... 100.0
~
The main item in the cost price (83.0%) is the raw material. Hence,
the cost of tungstic anhydride will be reduced in the first place by reducing
the consumption of scheelite concentrate required to produce one ton of
tungstic anhydride by reducing the l o s s e s occurring in individual processing
stages.
The total degree of extraction of WO, from the concentrate into the
finished product (tungstic anhydride) is now 93 to 9570. The approximate
l o s s e s a t each stage a r e shown below in %:
35
lg KD,= - -
3266.9
T
~ + 4.0667;
4508
Ig Kpl = - -
T
+ 5.1086;
36
-
Ig KP, = - 904
T
+ 0.9054;
2325
lg K,,, - -
T
+ 1.650.
1
The log Kp-- relationship is l i n e a r a s shown graphically in Figure 12.
T
The graph showing the variation of K, with temperature indicates the
optimum conditions f o r the reduction of tungsten oxides.
Each value of log K Pon the ordinate corresponds to a fixed water-vapor
to-hydrogen ratio in the gas mixture. Let u s assume that a given tem
p e r a t u r e (e. g . , 850") the g a s composition corresponds to point A . No
reduction of WO, takes place a t this composition a s the water vapor
concentration in the gas is above the equilibrium value. In o r d e r to effect
the reduction, i t is necessary to reduce the concentration of water vapor
by drying the hydrogen. At 850' the reduction of W Q to tungsten could
proceed only if the humidity of the hydrogen (i. e . , the -)
PH*
ratio is
below the value corresponding to point B .
-041
37
I;
b
R 2
W
m
Reduction furnaces
1
I
FIGURE 14. Rotary-tube furnace for t h e reduction of tungstic anhydride with hydrogen.
1 -furnace casing; 2-lining; 3-shaped cer am i c lining; 4-steel tube; 5-diaphragms; 6
longitudinal shelves; I-motor; 8-pulley; 9-reduction gear; 10-chain: 11-charging hopper;
12-loosening device; 13-screw feeder; 14-discharge hopper; 15-discharging device: 16
e l e c t r i c motor; 11-coupling Joint; 18-reduction gear; 19-base.
39
In addition to the multitube furnaces described above, continuous r o t a r y d r u m
electrical furnaces are beginning to be used in the USSR 1 3 1 . Such
furnaces have some advantages -. high productivity, the elimination of
manual labor, and lower electrical energy consumption p e r unit weight
of product.
The electrical furnace designed by Babich (Figure 14) consists of a
stainless s t e e l tube (400" in diameter and 4 m long) supported by two
r o l l e r s and rotated by means of e l e c t r i c motor and a transmission system.
The tube is placed in a heating chamber.
The tube contains diaphragms 5 with an opening in their center and
longitudinal fins 6 made of angle iron and welded to the tube. The
diaphragms prevent the material, which is of a r a t h e r high density from
slipping along the tube. The m a t e r i a l is thus kept in a reducing atmos
phere in the heated zone for a longer time. The longitudinal fins d i s p e r s e
the m a t e r i a l and thus promote better contact between the solid p a r t i c l e s
and the hydrogen. The forward p a r t of the furnace accommodates the
charging hopper 11 with a loosening device 1 2 and a s c r e w feeder 13. The
end of the furnace is connected to the discharge hopper 14 with a s c r e w -
type discharging device 15. The furnace casing i s mounted on a base 1 9
made of angle iron, sloping a t 2 to 4" in the discharge direction.
The length of the furnace is divided into four thermal zones; the
temperature of each zone is regulated automatically.
Hydrogen e n t e r s the tube through the discharge hopper of the furnace
and the direction of i t s flow through the furnace is opposite to that of the
material; the hydrogen leaves the furnace a t the upper end and is sub
sequently regenerated.
The furnace t u r n s a t about 2 r p m . The hydrogen s t r e a m moves a t
a r a t e of 18 to 20 m3/hr.
Supply of hydrogen to the furnace. The hydrogen fed to the furnace must
be thoroughly dried and purified to remove oxygen and water vapor.
The use of electrolytic hydrogen (i. e . , hydrogen prepared by electrolyz
ing water) is preferable when pure tungsten powder is required. A little
sodium hydroxide is added to the water in o r d e r to increase i t s conductivity.
The hydrogen produced in electrolytic cells is collected in gas holders
from which it is fed into the furnace through a system of pipes after
passing through a purification system.
The oxygen is removed by passing the gas through a vertical furnace
packed with a catalyst (copper turnings or a special Fe-Cu-Ni catalyst)
heated to 600 to 650". On the surface of the catalyst the oxygen combines
with hydrogen, yieIding water. The water vapor is removed when the
hydrogen is passed through a drying system consisting of columns packed
with a moisture-absorbing substance (NaOH, CaC12, silica gel, PzO5).
The drying is c a r r i e d out most conveniently with the aid of s i l i c a gel
(dried and granulated silicic acid) which has a high sorption capacity.
The silica g e l is regenerated by heating to 180". There is usually a
heater on the column containing the s i l i c a gel. After a certain period,
the column i s closed off and the s i l i c a gel i s regenerated.
Dried hydrogen is supplied to all tubes of the furnace from the
hydrogen delivery line through nozzles cut in the discharge ends of the
tubes.
In o r d e r to reduce the hydrogen l o s s e s during reduction, the spent
hydrogen leaving the furnace is regenerated in a special regeneration
40
setup (Figure 15). At the exit from the furnace 1 the spent hydrogen e n t e r s
the collector 2 , and p a s s e s through the t r a p 3 into condenser 4 . The trap
is partially filled with water and the hydrogen delivery tube from the
collector i s i m m e r s e d in the water. A fraction of the water vapor condenses
in the trap. The condensation is completed in the water-cooled condenser
tube 4 . The condensate is discarded. The hydrogen leaving the condenser
is mixed with f r e s h oxygen-free hydrogen from the supply line and the
mixture is passed through the drying tower 5 which contains one of the
desiccants mentioned above. The moisture-absorbing particles entrained
with the g a s s t r e a m a r e trapped in the bag filter 6 .
41
The f i r s t stage consisting of the reduction to W 0 2 is c a r r i e d out in one
group of furnaces while the second stage (the reduction from W O , to W)
in another.
In the production of a special type of tungsten, which is used to
manufacture non-sagging wire for lamp filaments, the two-stage reduction
p r o c e s s may be used f o r the preparation of tungsten powder with a m o r e
diversified particle s i z e . For this purpose, the boats entering the second
reduction stage a r e loaded with a mixture of tungsten dioxide and tungstic
anhydride a t various ratios (25 to 50% W q ) . The reduction conditions
selected in accordance with the required particle s i z e of the tungsten
powder. Some two-stage reduction conditions a r e listed in Table 11.
TABLE 11
I Conditions I
rate of
Reduction hydrogen
motion of Purpose
stage consumption
the boat,
mrj hr
cm/hr
The fine tungsten powder (brand VCh) prepared under these conditions
has the following granular composition: 56 to 60% below 0.6 1 ; 3 8 to '$070
in the 0.6 to 1 . 2 1 range; 3 to 5% in the 1. 2 to 1.81 range. The bulk
density i s 2.2 to 2.5g/cm3'
The particle size of tungsten powder depends on a number of factors: the most important of them are
the reduction temperature. t h e particle size of the starting oxides, and the rate of flow of hydrogen.
The effects of the temperature and the particle size of the starting oxides are interdependent. Coarse
tungstic anhydride cannot be used for the production of fine powder, but fine powder m a y he used for the
production of coarse tungsten powder /28/. This is due t o the growth of oxide particles, whose rate increases
with the temperature. The stronger such growth is exhibited by WO, particles, and the weakest by WO,
particles. Moreover, the finely divided oxides grow more rapidly than the coarse ones. For instance.
WO, particles with a size below 1 p show a noticeable growth rate a t 400", and grow rapidly a t 850. When
the particle size is increased from 1 to 5 p, the growth of the WO, particles only starts a t 600 to 800".
42
The vapor p r e s s u r e over fine particles is higher than over c o a r s e
particles; this can b e attributed to the accumulation of surface energy
in fine particles. Hence, at high temperatures (- 800") the W Q particles
grow because of the vaporization of fine particles and the condensation of
the vapors on the l a r g e r particles.
The tungstic anhydride not reduced in the low-temperature zone e n t e r s
the high-temperature zone of the furnace. At temperatures above 600 to
700" the WO, is partially vaporized and reduced to W Q on the surface of
the previously formed c o a r s e W Q crystals, thus assisting the further
growth of those crystals.
The f i r s t three factors favor the entry of unreduced W Q into the high-
temperature zone. The remaining three factors (the increased height
of the layer, the low flow r a t e of hydrogen, and the increase in i t s
moisture content) have the s a m e effect since they diminish the reduction
rate and thus favor the entry of a l a r g e fraction of the W Q into the high-
temperature zone.
By varying the factors mentioned above, it is possible to vary both the
average particle size of the tungsten powder and the size distribution of
the particles.
-vacuum
Pump
Particle size, p
FIGURE 16. Curves showing the size FIGUW 11. Apparatus for the measurement of the
distribution of tungsten powder. adsorption of methanol.
1-flask, "generator" of methanol vapor; 2-mano
meter for measurement of the methanol vapor pressure;
3-manometer for accurate measurement of the pressure
within the system; 4-test tubes containing the powder;
S-glass container -receiver.
43
Direct determination of the particle s i z e is c a r r i e d out by means of a
statistical microscopic method, a s follows: a sample of the powder is
mixed and triturated with a solution of turpentine in turpentine oil and a
drop of the mixture is placed on a slide on a microscope fitted with an
eyepiece s c a l e (or an eyepiece hairline). The r e s u l t s of several
measurements (the total number of measured p a r t i c l e s must be not l e s s
than 2 0 0 to 300) a r e used to calculate the distribution (in percent) of the
p a r t i c l e s by s i z e (in microns) (Figure 16).
The indirect methods for determining the granule s i z e composition of
the powder include the determination of the bulk density and the determina
tion of the relative specific surface of the powder. The bulk density is
the weight of a unit volume of the loose (uncompressed) powder. It
depends not only on the particle s i z e and the s i z e distribution of the
particles, but also on their shape and the degree of roughness of their
surface. Nevertheless, the particle s i z e remains the most important
factor a s a rule, the l a r g e r the particles, the higher the bulk density of
the powder.
Another method which is used in the Soviet Union f o r the quality control
of tungsten powder is the measurement of the relative specific surface of
the powder. The relative specific surface i s obtained from measurements
of the adsorption of methanol vapor (CH,OH) or the gas permeability.
The apparatus used f o r measuring the adsorption of methanol is shown
in Figure 17. The amount of adsorbed methanol i s calculated from the
difference in the methanol vapor p r e s s u r e before and after adsorption.
The amount of adsorbed methanol (in m g / g powder) is used a s a m e a s u r e
of the relative specific surface of the powder. The finer the powder, the,
l a r g e r i s i t s specific surface and the higher the amount of the adsorbed
methanol vapor.
The method of g a s permeability, developed by Deryagin, is based on
the measurement of the r a t e of passage of a i r through a powder l a y e r
of a given thickness.
Tungstic anhydride may be reduced by carbon where the presence of carbon in tungsten is permissible,
e. g . , in the production of hard alloys.
T h e overall reaction of the reduction of tungstic anhydride by carbon is given by the equation:
W03+X= W+3CO.
In reality, the reduction proceeds through intermediate stages in which lower oxides are formed (as
in the reduction with hydrogen). The main reducing agent is carbon monoxide (CO) rather than carbon; it
reduces tungsten oxide as follows*:
4W03 + CO 2 W,OI~+ COZB (1)
__--__--------
* It is probable that there are actually four reduction stages, as in the reduction with hydrogen.
44
T h e carbon dioxide formed in the reaction reacts ( a t the reaction temperature) with the carbon in
the charge as follows:
co, + c 2 2co. (4)
The equilibrium constant of these four reactions is the ratio of the partial pressures of CO and CO, :
321.6
log K, = __ - 0.0647.
Figure 18 shows the equilibrium composition of the gaseous phase ( t h e CO content is in percent) as a
function of the temperature, for the four reactions written above. The CO equilibrium pressure curve for
the reaction W0,-W intersects the curve of CO equilibrium pressure over carbon a t about 750'. At that
temperature. the CO has the s a m e equilibrium pressure in both reactions.
0"
V
+
0
V
e,
Temperature. ' C
Below 750" the W 0 2 cannot be reduced to W since the equilibrium pressure of CO over C is lower
rhan the equilibrium pressure in the reduction of WO,. In order to create a high concentration of CO in the
gaseous phase and to accelerate the reduction process it is desirable t o carry out the process a t high
temperatures (above 1000") where the gaseous phase consists almost exclusively of carbon monoxide.
In contrast to the reduction of W 0 3 by hydrogen. the reduction by carbon produces a fine tungsten
powder even when high temperatures are employed (1400 to 1500') and the charge is introduced rapidly
into the high-temperature zone of the furnace. T h e charge must not remain in the high-temperature zone for
a longer t i m e than that required for a quantitative reduction, or sintering of the powder particles will occur.
T h e growth of tungsten particles during the reduction with carbon is inhibited by the presence of a thin
layer of carbon black on the surface of the oxide particles. Because of the adsorption capacity of the carbon
black, the W 0 3 and lower oxide vapors which are formed a t high temperatures in the pores of the charge are
reduced mainly on the surface of the carbon black particles rather than on the surface of the primarily
formed crystals of reduced tungsten. Such reduction is favored by the fact that even if the average con
centration o f CO, in the reaction space a t high temperatures is quite low, it is still lower on the surface
of the carbon black particles and the concentration of the reducing agent (gaseous CO) is a t maximum.
45
Industrial reduction of W 0 3 by carbon
T h e tungstic anhydride used for the production of hard alloys must contain 99.85 to 99.9% WO,.
T h e reduction of WO, is carried out by using pure brands of carbon black, such as l a m p black, or gas
,a Asbestos 1
81 I .-s!
r
4 8 1 I
9
FIGURE 19. Carbon tube furnace.
1 -casing; 2-graphite (or carbon) heating tube; 3-tubular screen; 4-carbon-black packing;
5-cooler; 6-contact cones; 7-current leads; 8-hatch for carbon black; 9- bus bars.
T h e WO, and the l a m p black are mixed in ball mills, pug mills, or some other type of mixers for
granulated substances. T h e mixture is swaged in carbon dies or compressed into cylindrical bricks.
T h e reduction is carried ouf in carbon tube furnaces (Figure 19). A graphite or carbon tube serves
both as the heater and as the furnace space. The tube is 1000 to 1 5 0 0 m m long and I S to 100" in diamerer.
As a result of the low mechanical strength of graphite, i t is necessary t o use thick-walled tubes; hence,
the electrical resistance of the heater is quite low. For this reason. the furnace requires a high current
at a low voltage (15 t o 25V). T h e current is supplied through copper busbars to water-cooled contacts with
conical openings in the center. Intimate contact between the carbon tube of the furnace and the current
input is produced with the aid of graphite. copper, or cast-iron c l a m p cones of various types. Either
carbon black or crushed c o a l is used as the thermal insulator.
T h e furnace is contained within a n iron casing fitted with openings for the introduction and discharge
of the thermal insulation packing. In order to facilitate the replacement of a burnt-out heater, some
types of furnaces have the heater tube installed within a carbon tube screen (Figure 19). A cooler is
connected directly to the graphite tube.
Using a furnace of the above type. a temperature of more than 2000" m a y be obtained with a 20 to 50 kw
heater. The reduction is carried out a t 1450 to 1550'. T h e molds containing the charge or the pressed
briquettes move continuously along the furnace tube and remain in the hot zone for 30 minutes or one hour.
T h e reduction yields friable gray blocks which a r e crushed and sifted.
T h e tungsten contains 0.1 to 0.5%carbon and 0.1 t o 0.157aoxygen. The total concentration of other
impurities (Si, Ca. Fe) does not exceed 0.1 to 0.2%.
46
1) pressing of powder (into bricks, b a r s ) ;
2) sintering (heating to a given temperature) ;
3) working into the final product (by forging, drawing o r rolling).
Pressing
FIGURE 20. Dies for pressing tungsten powder into bars. FIGURE 21. The distribution
of powder layers in a pressed
1 -face plates; 2 -joint pins.
briquette.
47
The p r e s s u r e exerted upon the powder during p r e s s i n g is not uniformly
distributed within the compact. This is due to the friction between the
powder p a r t i c l e s and the walls of the die. As a result, in any vertical
section through the compact, the upper l a y e r s (i. e . , the l a y e r s lying n e a r e r
to the r a m ) a r e d e n s e r than the lower l a y e r s ; in the upper l a y e r s the
density i n c r e a s e s from the center t o the periphery, while in the lower
l a y e r s it i n c r e a s e s from the periphery to the center (Figure 21). The
nonuniform p r e s s i n g is exhibited especially strongly in the c a s e of
compacts of considerable height. Hence, the shape of the dies used in
the p r e s s i n g of tungsten powder m u s t be such that the compression takes
place along the s m a l l e s t dimension.
A lubricating substance - a solution of glycerol in alcohol (in a ratio
of 1.5 : 1) o r of paraffin in gasoline (4 to 570 paraffin) - is a l s o added to the
powder before the pressing, in o r d e r to prevent stratification and to obtain
a compact of uniform thickness. During p r e s s i n g the lubricating solution
is squeezed out onto the walls of the die and reduces the friction between
the wall and the powder particles.
48
the s i z e of the bar*. The density of the b a r s produced under those
conditions is 1 2 to 13g/cm3, corresponding to a porosity of 3 0 to 40%.
The porosity of the pressed tungsten b a r cannot be reduced since the
tungsten c r y s t a l s have a very high strength in the cold and a r e not deformed
during pressing. When the tungsten particles have been compacted to a
degree such that their displacement ceases, any further increase in the
p r e s s u r e causes chipping o r lamination of the bar, which under these
conditions behaves as a compact body.
The limiting p r e s s u r e (above which lamination takes place) i s known
as the critical p r e s s u r e and i t s value f o r tungsten is 4 to 6 tons/cm2.
Sintering
_-_--_----___
f Hence, t h e m i n i m u m :ated power of a press for the smallest hars would he:
49
from the casing into the furnace space and mixes with the main s t r e a m of
hydrogen which e n t e r s the furnace f r o m the discharge end through the
cooler of the furnace.
The p r e s s e d b a r s a r e mounted in nickel boats whose bottoms a r e covered
with a thin layer of tungsten powder. Each boat contains from 3 to 3 0 b a r s ,
(depending on t h e i r size).
B
C
50
where E is the radiation intensity (watt/cm2), and c is the Stefan-Boltzmani?
constant.
51
These r e s u l t s a r e somewhat low since the energy radiated by the end s u r
f a c e s of the b a r and the tungsten plates holding the b a r ends has been neglected.
Moreover, a p a r t of the heat is l o s t b y convection through the hydrogen atmos
phere. The various heat l o s s e s a r e tabulated in Table 12.
TABLE 12
Distribution of heat in the "fusion" of tungsten bars,%
Bar size, m m
Item (heat losses) ~
32x32~450
I I
Heat lost through radiation from the bar surface . 76.0 76.0
Heat lost through radiation ...
from the bar ends 0.5 5.5
Heat lost through radiation ....
from the holding
clamps ................................. 13.0 8.0
Heat lost through hydrogen convection ......... 0.5 0.5
Other losses ............................... 10.0 10.0
52
I
* Inthe case of some brands of tungsten sintering is carried out in two stages. In the first stage the ciirrent
is increased to 40 t o 507oof the fusion current and is maintained a t that level for 5 t o I minutes. This
produces vaporization of most of the additives (see p. 56) which are then deposited on the inner parts of
the apparatus. T h e second stage of sintering is carried out in another vessel.
53
FIGURE 27. Tungsten bars.
a-compressed; b-sintered.
Sintering mechanism / 7/
The sintered tungsten has the polyhedral s t r u c t u r e characteristic of compact
metals (Figure 28). However, in contrast to the metal prepared by melting,
the tungsten prepared by sintering still p o s s e s s e s some porosity which i s
eliminated only through mechanical working of the b a r (forging, drawing).
54
The contraction i s caused by surface tension which tends to reduce
the total f r e e surface in the sintered b a r . The p a r t i c l e s a r e deformed
and "flow" into the pores. Such deformation i s made possible by the fact
that when the temperature i s increased, the strength of the c r y s t a l s
d e c r e a s e s m o r e rapidly than does the surface tension.
a b
Structure of the b a r s
55
111 I I I,
The b e s t workability during the subsequent hot-forging operation is
obtained in the case of sintered tungsten b a r s with a uniform s t r u c t u r e
and an average grain s i z e of about 2 2 p (i. e . , 2000 g r a i n s p e r mm').
The typical s t r u c t u r e of a b a r sintered a t a high temperature is shown
i n F i g u r e 28.
In o r d e r to control the recrystallization taking place in incandescent
tungsten w i r e s used in e l e c t r i c lamps and electronic devices, and in o r d e r
to obtain w i r e s with a predetermined s t r u c t u r e , a s m a l l amount of an
additive, thorium oxide, aluminum oxide, o r a silica- containing mixture
(SiOz+Na20+Kz0) is added t o the tungsten intended for use in wire
manufacturing; The additives are usually added as a solution of the
respective s a l t s to a suspension of tungstic acid in water. The components
are thoroughly mixed, the mixture is evaporated, dried, and forwarded
to the reduction stage. The composition of the additive and the amount
of i t introduced into the tungsten determine the brand of the finished
product.
Most of the silica and the alkali metal oxides a r e vaporized during
sintering and entrain with them other admixtures (CaO, MgO, e t c . ) . This
cleanses the surfaces of the s e p a r a t e c r y s t a l s (the admixtures a r e present
as films on the intercrystalline boundaries) and thus promote the rapid
sintering and i n c r e a s e in density of the b a r s .
The thorium and aluminum oxides a r e not expelled during sintering and
affect the s t r u c t u r e of the sintered b a r , depending on the amount added.
As a rule, thorium oxide at concentrations of 0.75 to 1.1 qo i n t e r f e r e s with
c r y s t a l growth during sintering.
56
111 I I I I I, I I I 1 I111 I I I
In addition, the quality of a tungsten b a r is determined by i t s workability;
to test this, 7 or 1 0 sample b a r s a r e taken out of each batch and subjected
t o all stages of mechanical working.
57
temperature i s reduced from 1350 to 1200". In forging from a diameter
of 9 to a diameter of 5 m m , the b a r s a r e manually fed to the forging
machine. When the diameter i s reduced the b a r s a r e fed to the next
machine in which the dies have a s m a l l e r diameter. In the next forging
stage (reduction of the diameter from 5 to 2 ")the rods a r e fed
mechanically to the forging machine by means of a special conveyor.
The rod f i r s t p a s s e s through a gas-heated furnace in which i t s temperature
is increased to 1300" (Figure 3 3 ) . In o r d e r to prevent oxidation and to
reduce wear of the dies, the rod is preliminarily coated with a layer of
aquadag ( a mixture of fine graphite and ammonia water containing s u g a r ) .
58
I
59
Chupter II
MOLYBDENUM
P r o p e r t i e s of molybdenum
Atomic n u m b e r . . .................................... 42
Atomic weight ...................................... 95.95
Density. gl c m 3 ...................................... 10.2
60
Lattice type and parameter ........................... Body-cen!ered cubic
a = 3.14 A
Melting point, " C .......
2620 + 10
Boiling point, ' C ........... ..........
- 4800
Superconductivity transition
0.9 to 0.98
61
111 1111 1111 111.11111111111 111111111111III1111111111111111111111 I 1111III I I 11111111 11111 1.11111l11 Ill IIII I II
solution, when the metal is heated in a hydrogen atmosphere. At 1000°
the solubility of hydrogen is 0.5 cm3 p e r 100 g of the metal.
Molybdenum r e a c t s with nitrogen at temperatures above 1500" with
formation of the nitride. At low nitrogen p r e s s u r e s ( - 0.01 m m Hg) no
such reaction is observed up to 2400".
The metal i n t e r a c t s with solid carbon, hydrocarbons, and carbon
monoxide at 1100 to 1200" with the formation of the carbide MozC.
Fluorine attacks the metal at ambient temperatures, while chlorine
attacks i t above 250" when the volatile halides, MoF, and MoC15
respectively, a r e formed, Iodine vapor does not r e a c t with molybdenum.
Molybdenum r e a c t s with bromine at high temperatures.
Molybdenum disulfide, MoSz, is formed in the reaction of molybdenum
with s u l f u r vapor above 440" or with hydrogen sulfide above 800". Sulfur
dioxide oxidizes the metal at 700 to 800".
Silicon r e a c t s with molybdenum above 1200". The disilicide MoSO,
formed is very stable in the a i r up to 1500".
Molybdenum is resistant t o hydrochloric and sulfuric acids at room
temperature, but dissolves to a certain extent in these acids at 80 to 100".
Molybdenum is dissolved slowly by nitric acid or aqua r e g i a in the
cold, and rapidly at elevated temperatures.
Molybdenum is not attacked by hydrofluoric acid, but dissolves rapidly
in a mixture of nitric and hydrofluoric acids. A mixture of five volumes
of nitric acid, three volumes of sulfuric acid, and two volumes of water
is a useful solvent for molybdenum.
Molybdenum is not attacked by cold solutions of alkali hydroxides.
Some etching takes place in hot solutions. The metal i s rapidly oxidized
by fused alkalies, especially in the presence of oxidants, with formation
of molybdates.
62
Molybdenum trioxide dissolves in hydrochloric and sulfuric acids.
M o Q dissolves in aqueous alkalies and ammonia, with formation of
molybdates.
M o l y b d e n u m d i o x i d e M o o z is a dark-brown powder produced
by reducing M o Q with hydrogen a t 450 to 470". Its density is 6.34 and
i t s heat of formation is 141 kcal/mole.
Molybdenum dioxide is virtually insoluble in water, aqueous solutions
of alkali hydroxides and non-oxidizing acids. Nitric acid oxidizes Moo2
to MOO,.
T h e i n t e r m e d i a t e o x i d e Mo4Oll is formed by reduction of M o Q
with hydrogen, by careful oxidation of M o Q , and by heating a mixture of
MoQ and M o Q or M o Q and molybdenum powder in an i n e r t atmosphere
( e . g. , in nitrogen). Mo4Oll has a blue-violet color.
The oxide is sparingly soluble in water, sulfuric and hydrochloric acids
and dilute solutions of alkali hydroxides.
Molybdic acid and molybdates. White voluminous precipitates of
hydrated molybdenum trioxide a r e formed when molybdate solutions a r e
treated with acids. The dihydrate MoQ-ZHzO ( o r HzMoO4.H20) is stable up
to 61°; the monohydrate MoQ.Hz0 ( o r HzMoO,) is stable between 6 1 and
120". Elimination of water, with formation of MOO,, takes place above
120". Molybdic acid i s sparingly soluble in water, i t s solubility at 15
and 80" being 2 . 1 2 6 and 5.185 g/1 respectively. It is, however, readily
soluble in strong inorganic acids.
Molybdic acid s a l t s a r e known as normal molybdates. Their composition
corresponds to the formula Me2O.MoQ o r MezMoO,, where Me20 is a
monovalent metal oxide.
Molybdic acid can add on various numbers of M o Q molecules with
formation of polyacids whose composition corresponds to the general
formula x H p O . yMoO,, where y > x . The s a l t s of these acids are known
a s polymolybdates. In contrast with the normal molybdates, the MezO:
M o Q ratio in the polymolybdates is s m a l l e r than unity and v a r i e s over a
wide range. Thus, f o r instance, the following types of molybdates are
known:
Me,O. 2Mo0,- dimolybdates
-paramolybdates
5Me20. 12Mo0,
Me20'3M003) -metamolybdates
Me2,0.4M00,
Me,O. lOMo0,- decamolybdates and many others.
63
The properties of some molybdates and polymolybdates a r e reviewed
below.
N o r m a l s o d i u m m o l y b d a t e NazMo04. This s a l t c r y s t a l i z e s
f r o m solutions in which the NazO:M o Q r a t i o is higher than unity. The
dihydrate, NazMo0,.2Hz0, is formed between 10 and IOO", while the
decahydrate is formed below 10". The melting point of anhydrous
Na2Mo04 is 627", i t s density is 3.28.
The solubility of sodium molybdate in water at 15.5 and 100" is 39.27
and 45.57'70 respectively.
S o d i u m p a r a m o l y b d a t e , 5Naz0.12MoQ.38Hz0, crystallizes from
solutions of the normal sodium molybdate when these a r e neutralized
to pH = 5. The solubility of the crystalline hydrate a t 30" is 1 5 7 g p e r
1 0 0 g water. The anhydrous salt is sparingly soluble in water.
-
A m m o n i u m p a r a m o 1y b d a t e 3 ( NH4)zO 7M o a 4 Hz 0 crystallizes
out from ammoniacal solutions in which the molecular r a t i o NH, : Moo3
is 6 : 7 or slightly higher. This r a t i o is produced by evaporation of the
solution, the ammonia being expelled, o r by neutralizing p a r t of the
ammonia.
Ammonium paramolybdate is stable in a i r . Its aqueous solutions a r e
slightly acid. Its solubility in water a t 20" is about 300 and a t 80 to 90"
about 500 g / l .
Ammonium paramolybdate begins to decompose a t 150" with evoIution
of ammonia and formation of the tetramolybdate (N&)zO. 4MoQ. T h e ,
ammonia i s expelled quantitatively a t 350" and molybdenum trioxide
remains behind.
Ammonium paramolybdate is a common commercial product and an
intermediate in the production of pure molybdenum trioxide.
C a 1c i u m m o 1y b d a t e , CaMoO,, occurs in nature a s the mineral
powellite. The s a l t i s white. It i s prepared from aqueous solutions of
molybdates by the addition of calcium chloride. Calcium molybdate may be
prepared by d i r e c t interaction of calcium oxide and molybdic anhydride
a t t e m p e r a t u r e s above 450". The density of the s a l t i s 4.28. Its melting
point is 1520".
The solubility of calcium molybdate in water a t 20 and 100" is 0.0058
and 0.0235 g/lOOg solution respectively 1 2 5 1 .
Calcium molybdate is an important technological product, used a s an
additive in steel. It is also used in the smelting of ferromolybdenum.
.
I r o n m o 1y b d a t e s The normal ferrimolybdate, Fe2(Mo0,)3. n H 2 0
s e p a r a t e s out a s a yellow precipitate when f e r r i c chloride o r sulfate is
added to a solution of sodium molybdate. Precipitates, whose composition
corresponds to the above formula, a r e formed only within a certain pH
range (pH =: 3.5). The precipitate formed at higher pH contains iron
hydroxide and has a brown color, while the precipitate formed at lower
pH contains molybdic acid. When heated above 600°, the ferrimolybdate
decomposes to yield Fez03 and MoQ.
F e r r o u s molybdate, FeMo04, i s not precipitated from molybdate
solutions, since Fez+ions reduce (Moo4)'- ions. However, FeMoO, is
formed when a mixture of FeO and M o Q is heated at 500 to 600" in the
absence of a i r .
L e a d m o l y b d a t e , PbMo04, is a white, sparingly soluble salt.
It o c c u r s in nature as the mineral wulfenite. The s a l t may be prepared
64
by precipitation from solutions of alkali metal molybdates, o r by heating
a mixture of PbO and MOO, at 500 to 600". The density of lead molybdate
is 6.92. Its melting point is 1065".
C o p p e r m o 1y b d a t e . The anhydrous copper molybdate, C u M o 0 4 ,
is a green-yellow powder which is prepared by heating a mixture of CuO
and M o 4 at 500 to 700". The s a l t m e l t s with decomposition a t 820". The
basic, bright-green copper molybdates a r e precipitated from aqueous
solutions of sodium molybdate by the addition of copper salts. Depending
on the conditions of precipitation, the composition of the precipitate either
corresponds to the formula C u O . 3 C u M o 0 4 - 5 H 2 0 o r r e s e m b l e s the
composition of the mineral lindgrenite, ZCuMo04 C u ( o J 3 ) ~ .
Heteropolyacids and their salts. Molybdenum, like tungsten, has a
tendency to form complex compounds with phosphoric, arsenic, silicic,
and boric acids ( s e e p. 6).
Ammonium phosphomolybdate - (NH4)3P04. 1 2 M o Q 6HzO o r
( N H 4 ) 3 H 4 [ P ( M ~ 2 ( & ) 64H20-is
. one of the well known s a l t s belonging to this
type of compounds. It is a sparingly soluble s a l t which is precipitated
when a solution of ammonium molybdate in nitric acid is poured into a
phosphate solution containing HN03. This reaction is used extensively
for the detection and determination of phosphoric acid.
Molybdenum blue. When a solution of molybdic acid o r an acid
molybdate solution i s treated with a reducing agent such a s SQ, HzS, Zn,
glucose, e t c . , the solution a s s u m e s a deep-blue color which is associated
with the formation of the so-called molybdenum blue. Molybdenum blue
i s a compound whose composition corresponds approximately to the
formula Mo5014. x H 2 0 ( o r according to other data - M0~023. x H 2 0 ). The
composition i s variable.
In solution molybdenum blue exists in a colloidal state and is readily
adsorbed by surface-active substances, e. g . , by plant o r animal tissues,
to which it i m p a r t s a blue color.
The formation of molybdenum blue is a widely used analytical reaction.
Molybdenum sulfides. Molybdenum f o r m s four sulfides: MoS,, Mo2S5,
MoS2, and Mo2S3. Only MoSz and MoS, a r e of industrial importance.
MoSz exists in nature a s the mineral molybdenite, the main source of
molybdenum ( s e e p. 6 9 ) . Synthetic molybdenum disulfide i s produced by
heating a higher sulfide in the absence of a i r , by the action of sulfur vapor
on molybdenum powder o r by fusing molybdenum trioxide with soda and
sulfur.
The higher sulfide, MOSS, is precipitated when H2S i s passed through
hot acidified solutions of molybdates. Molybdenum trisulfide dissolves
in ammonium and sodium sulfide solutions, with the formation of
thiomolybdates:
+ MoS, (NH,),S = (NH4),MoS4.
The thiomolybdates a r e readily soluble in water. When their solution
i s acidified, they decompose with separation.of molybdenum trisulfide:
65
TABLE 1 3
Some properties of molybdenum chlorides and oxychlorides / 19/
<eat of formation.
Compound Color Behavior at various temperatures
kcal/ mole
~ ~~
MoOCI, Green
-
1 aim.
Melts a t 104, boils a t
- .- -..-
- 180'
173.0
153.5
Uses of molybdenum
molybdenum in iron is -
Molybdenum forms a solid solution in steel. The solubility of
8%. A fraction of the molybdenum exists a s
complex iron-molybdenum carbide.
Usually, molybdenum is introduced into the s t e e l together with other
alloying additives such a s chromium, nickel, and vanadium; the
molybdenum concentration in s t r u c t u r a l s t e e l s does not exceed 0.57'0,
while in high-speed s t e e l in which i t replaces tungsten i t s concentration
reaches 7.5 to 8.5%.
Molybdenum noticeably improves the properties of steel by producing
a uniform and fine-grained structure. By reducing the eutectoid
decomposition temperature of steel, molybdenum widens the temperature
range of hardening and tempering and affects the hardenability of steel.
Molybdenum improves the following mechanical properties of steel: the
elastic limit, the wear resistance, and the impact strength. Alloying
66
of molybdenum with chromium-nickel s t e e l s eliminates tempering
brittleness. This is one of the most valuable properties of molybdenum.
Molybdenum is usually added to s t e e l s in the form of ferromolybdenum
(50 to 7 0 % Mo). Calcium molybdate, which is cheaper than f e r r o
molybdenum, is the form used when it is only n e c e s s a r y to introduce
s m a l l amounts of molybdenum. During smelting the calcium molybdate
is reduced by the iron. The molybdenum formed dissolves i n the s t e e l
while the calcium oxide remains in the slag.
Molybdenum is a l s o used in alloys of c a s t iron. Molybdenum reduces
the grain s i z e of g r a y i r o n and improves i t s high-temperature properties
and wear resistance. C a s t i r o n containing silicon and molybdenum
is used f o r the production of acid-resistant equipment.
Heat- and acid-resistant alloys. Molybdenum is a component of many
acid-resistant and heat-resistant alloys, the other components being
mainly nickel, cobalt, and chromium.
The m a j o r components of heat-resistant alloys a r e nickel and cobalt,
their concentration being a s high a s 50 to 6 0 % . Most of the heat-
r e s i s t a n t alloys, which a r e also acid-resistant, contain 20 to 30% Clr
and 1 t o 7 % Mo. Alloys having maximum resistance to acids (i. e . , which
r e s i s t the effect of all mineral acids except hydrofluoric) contain up to
15 to 2 0 % molybdenum. The other components a r e nickel, cobalt,
chromium, and iron.
Molybdenum and molybdenum-base alloys. The high melting point,
high-temperature strength, and high electrical conductivity of molybdenum
a r e the reasons f o r i t s extensive use in the electrical bulb and radio
industries. Molybdenum wire i s used in the manufacture of filament
supports in electrical bulbs and g r i d s for electronic tubes. Molybdenum
rods sealed into special g l a s s a r e used a s c u r r e n t terminals in electrical
vacuum equipment.
Molybdenum is readily rolled into thin foils (0.1 to 0.2" thick) which
a r e used in the manufacture of anodes for oscillator tubes and kenotrons.
Molybdenum foil is also used in the manufacture of X-ray tubes.
Molybdenum wire and bands a r e used a s h e a t e r s for high-temperature
e l e c t r i c furnaces.
Molybdenum and tungsten w i r e s a r e joined in thermocouples used for
measuring temperatures from 1 2 0 0 to 2000" in i n e r t or reducing
atmospheres,
The recently achieved production of l a r g e molybdenum ingots, weighing
lOOOkg or m o r e , has extended the possible u s e s of molybdenum. Molyb
denum is now used either pure or a s an alloy to ensure the maintenance
of high-temperature strength, e. g . , in the manufacture of turbine blades and
other p a r t s of jet engines and rockets.
In o r d e r to prevent high- temperature oxidation of molybdenum p a r t s ,
they a r e coated with molybdenum silicide, a nickel-chromium alloy, o r
some other protective coating.
Molybdenum may be used a s a s t r u c t u r a l m a t e r i a l in nuclear power
plants since it combines high- temperature strength with relatively s m a l l
thermal-neutron capture c r o s s section.
Large molybdenum rods (1m long and 30 to 40" in diameter) have
been lately used a s heating elements in glass-melting furnaces. Molyb
denum is virtually unaffected by molten glass. Molybdenum is also used
in the manufacture of s t i r r e r s and other p a r t s f o r glass-producing
equipment.
67
1, I, ,I .. .
,
I 111 .I I. ..I 1
. I I. I
.
, I I I. I. I., .
I .I* I,. I. I I
Uses of molybdenum compounds. Molybdenum disulfide (either pure
molybdenite or synthetic MoS,) may be used as a lubricant. Molybdenite
lubricants are superior to graphite and may be used between - 4 5 and -1400".
Sodium molybdate is extensively used in the manufacture of pigments
and lacquers. Molybdenum compounds a r e used f o r dyeing silk, wool,
cotton fabrics, and f u r s ; advantage is taken of the fact that molybdates
a r e readily reduced with formation of molybdenum blue.
The molybdenum oxides M o Q and M o a a r e used a s catalysts in the
chemical industry.
The fact that microamounts of molybdenum in the soil stimulate
growth in vegetables, especially the leguminous species, h a s been
recently discovered. This h a s resulted in an extended u s e of molybdenum
compounds (mainly ammonium molybdate) a s fertilizers.
Molybdenum minerals
68
P Ow e 11i t e , CaMo04, a product of oxidation of molybdenite, is
frequently found a s a secondary m i n e r a l in the form of a thin coating on
molybdenite; it is r a r e l y found as a p r i m a r y mineral. The color of
powellite ranges f r o m white to gray, i t s density is 4.35 t o 4.52; and its
Mohs hardness is 3.5. The m i n e r a l often contains some tungsten since
powellite and scheelite a r e isomorphous.
-
M o l y b d i t e Fez( MOO^)^ 7 i H 2 0 is formed in the weathering of
molybdenite and is frequently found together with the l a t t e r in molybdenite
oxidation zones. Molybdite h a s a variable composition, which is some
times described by the general formula nFepOs-yMoOs.zH20.Molybdite may
be an important s o u r c e of molybdenum. F o r instance, about 25% of the
molybdenum in the upper zones of the l a r g e s t deposits outside the Soviet
Union (in Climax, Colorado) is in the form of molybdite.
W u 1f e n i t e , PbMo04, is found in the oxidation zones of lead o r e
deposits. Depending on the concentration of impurities, the color of the
m i n e r a l may be yellow, bright-red, olive-green, o r grayish. Its density
is 6.7 to 7.0, i t s Mohs hardness is 2.5 to 3.
This m i n e r a l is not of industrial importance at present.
69
Concentration of molybdenum o r e s
Molybdenum con-
I Maximum impurity conrents.70
Brand
~
centration,
minimum,% P As cu I sio, Sn
1455
70
16. PROCESSING OF STANDARD MOLYBDFNITE
CONCENTRATES
71
The high exothermic effect accompanying the oxidation of molybdenite
p e r m i t s the roasting of molybdenite concentrates to be accomplished at
the expense of the heat of reaction.
It is well known that sulfides undergo spontaneous oxidation at tempera
t u r e s above their flash point. The data in Table 1 5 show that molybdenite
has a relatively low flash point, close to the flash points of pyrite and
chalcopyrite.
TABLE 1 5
MoS,
2Cu2S
- MOO,
-+ 4CuO
266.3
253.8
365-465*
465**
-
ZNiS + 2 N i 0
2ZnS 2Zn0
189.2
665
615
360
* T h e first figure is for a particle size < 0.063 m m . the second for particle sizes between 0.09 and
0.127 m m
** For particle sizes of 0.09 to 0.127mm.
72
I
I
/U 20 30 40 W
T i m e, minutes MOO3 CUO, w t %
FIGURE 31. Rate of interaction of MoS, FIGURE 38. Phase diagram
with MOO, a t various temperatures. M o Q -CuO.
1-700'; 2-600"; 3-500".
In addition to copper, iron, and zinc sulfates, calcium sulfate may also
be formed during roasting if the concentrate contains calcium carbonate:
+
CaCO, MOO, + CaMOO,, CO,;
+
CuO + MOO, + CuMoO,;
CUSO, + MOO3 + +
CuMoO, so3(SO,,0 2 ) ;
73
with an increased copper content 1181. Of the above molybdates, those
of calcium and lead are sparingly soluble in ammonia water. T h e i r
presence in the calcines c a u s e s a s h a r p d e c r e a s e in the degree of
extraction of molybdenum. Copper and zinc molybdates are readily
soluble in ammonia solutions, while iron molybdate is slowly decomposed
by ammonia water.
Molybdenite concentrates always contain silica. However, t h e r e is
virtually no interaction between s i l i c a and M o q .
Roasting procedure
Such furnaces have been used for a long time for the roasting of
pyrites and of copper and zinc sulfide concentrates. These furnaces
ensure good mixing, countercurrent flow of solid and gas, and rapid
oxidation of the suspended m a t e r i a l passing f r o m one hearth to another.
A vertical c r o s s section through an eight-hearth furnace, of which
seven hearths a r e for roasting and the eighth, upper hearth is for drying,
is shown in Figure 39. The furnace consists of a vertical cylinder made
of s t e e l sheets and lined with r e f r a c t o r y (chamotte) bricks. The inner
diameter of the furnace is 5.4m. The cylinder is divided into seven
s t o r i e s by refractory brick crowns, which also s e r v e a s the eight hearths
The distance between the c e n t e r s of the hearths is 0.894m. A rotating
s t e e l shaft, 1.29 to 1.52m in diameter and lined on the outside with
refractory bricks p a s s e s through the c e n t e r of the furnace. The center
shaft c a r r i e s two r a k e s a t each hearth, which a r e fastened to special
74
sockets within the shaft. The rake is fitted with paddles, made of
chromium-containing cast iron or a special alloy, to move the material.
The center shaft and the r a k e s a r e air-cooled on the inside.
Sulfide concentrate
1-crowns; 2-central shaft; 3-raker; 4-paddles; 5-openings in the crowns, for the
passage of material; 6-storage bin for the concentrate; I-feeder; 8-feed tray.
75
e n s u r e s that the m a t e r i a l p a s s e s through the entire surface of the hearths.
Since the paddles over each hearth a r e placed at opposite angles with
respect to the shaft, the materia1 moves f i r s t from the periphery to the
center and then from the center to the periphery and thus drops from
hearth to hearth.
16
..... .. .-. ..
hearth to a common g a s vent. This p e r m i t s the maintenance of the required
temperature a t each hearth. The resulting temperature distribution in the
hearths is shown in Figure 40. The dust entrainment is a s high a s 1870,
the dust being mostly unroasted concentrate. The dust is trapped and
returned for roasting in the furnace.
Fluidized-bed roasting
77
The fluidized-bed roasting of molybdenite concentrates was f i r s t
studied in the USSR. It is now used on an industrial s c a l e 1121.
The design of one industrial furnace and of the whole installation a r e
shown in Figure 42. The furnace consists of a refractory chamber with
a rectangular c r o s s section, whose lower p a r t is fitted with an a i r -
distributing screen. The s c r e e n consists of a s e r i e s of s t e e l nozzles
with mushroom-shaped removable caps ( F i g u r e 4 3 ) . The space
between the nozzles is filled with heat-resistant concrete. The a i r inlet
holes a r e beneath the mushroom-shaped caps. This prevents leakage of
the solid m a t e r i a l below the screen.
7 8 9 M
78
The bed temperature is regulated automatically. The temperature
control s y s t e m is based on variations in the concentrate supply rate.
When the temperature becomes too
high o r too low, a s compared with the
required temperature, there is an
automatic d e c r e a s e or i n c r e a s e of the
r a t e of feed of the concentrate. This is
accomplished by varying the r a t e of
rotation of the feeder trays. P r a c t i c e
has shown that the system p e r m i t s a
reliable temperature control to within
f 2 . 5 O of the average p r e s e t temperature
79
Distillation method
80
TABLE 16
Vapor pressure of MOO,
Leaching
81
concentrate
I,
Leaching
NH,OH solution
-
I
Residues Solution
1
Second
extraction of
molybdenum
J Purification <
("3,S
Sulfide c a k e
Purified
solution/------
1 To waste
HC1 ------+ A
Method I
Neutralization
Method I1
Evaporation
4- .1
P
Acidic moiher
Polymolybdate Crystallization
liquor
precipitate
.1 -I
Molybdenum
Recr~srallization
regeneration Mother 1iqu or
3.
I
Ammonium paramolybdate
liquor
crystals
i
Periodically drain off 1
Calcination
in order to
remove 1
impurities
82
.
.. -. - . . ,
The calcines are leached with an 8 to 10% solution of ammonium
hydroxide in the cold o r at 70"; the leaching is c a r r i e d out in i r o n vessels.
Rotating-drum e x t r a c t o r s o r vats fitted with mechanical s t i r r e r s a r e used.
The d r u m e x t r a c t o r s have the advantages of being hermetically sealed
and of ensuring good mixing as well a s the possibility, when filled with
balls, of effecting additional grinding.
The s t i r r e r - f i t t e d e x t r a c t o r s a r e not hermetically sealed. As a result,
a p a r t of the ammonia evaporates and the consumption of ammonia is
increased. Depending on the type of apparatus used, the consumption of
ammonia is 115 to 140% of the stoichiometric amount.
T h r e e or four successive processing stages are used in o r d e r t o
provide a higher degree of leaching of molybdenum from the calcines.
The solutions f r o m the first two processing stages a r e collected together
and are treated to remove impurities. The weak solutions from sub
sequent leachings a r e returned to the initial leaching stage. The s l u r r i e s
from each leaching stage a r e filtered on f i l t e r p r e s s e s or suction filters.
The residues a r e rinsed with hot water and the wash waters a r e recycled t o
the f i r s t leaching stage. The residue is subjected to a second molybdenum
leaching stage (see p. 87).
The strong ammonia solutions from the leaching contain 140 to 19Og
M o Q / I . Their density i s 1.10 to 1 . 1 6 .
83
ammonium sulfide, while a white precipitate (lead molybdate) f o r m s in
the absence of such an excess.
The e x c e s s ammonium sulfide is bound by the addition of a certain
amount of f r e s h ammoniacal solution from the calcine-leaching operation.
The sulfides a r e precipitated in wood o r rubber-lined i r o n vats with
stirring.
84
permissible concentration, so that i t is n e c e s s a r y to c a r r y out additional
recrystallizations. For these reasons, the polymolybdate separation
method is now extensively used in the Soviet Union.
Separation of polymolybdate by neutralization J 141 Polymolybdates
of various compositions a r e precipitated during the neutralization of
ammonium molybdate solutions by hydrochloric acid ; thzir composition
depends on the ultimate pH of the solution and the temperature.
In manufacturing practice, the precipitation is c a r r i e d out from
solutions containing 280 to 300 g M o Q / l . When necessary, the solutions
are preliminarily concentrated by evaporation.
Up to 9 6 to 9 7 % of the molybdenum is contained in the precipitate in the
form of tetramolybdate dihydrate if the hot (55 to 65") solution is carefully
neutralized with hydrochloric acid (to a pH between 2 and 3 ) . The
hydrolysis reaction is given by the equation:
4 (NHJ,MoO, + 5HtO -+ (NH,,&O.4Mo03.2HzO + 6NH40H.
The crystalline precipitate formed must be rapidly separated by
filtration, since the dihydrate is converted into the anhydrous t e t r a
molybdate (NH,J2O. 4MoOj on prolonged contact with the mother liquor.
The conversion i s accompanied by a d e c r e a s e in c r y s t a l size. A highly
dispersed precipitate which i s difficult to f i l t e r is formed a s a result.
After centrifuging and washing with water, the polymolybdate
precipitates s t i l l contain a s m a l l amount of contaminants. Most of the
contaminants (Zn, Cu, Ni, Sb, As, Mg, P, and S ions) remain in the
slightly acidic mother liquor. Tungsten, however, i s an exception, a s
most of i t is coprecipitated with the polymolybdate. The precipitates also
contain an increased amount of chloride ions (0.2 to 0.4%) which a r e
difficult to remove by washing with water.
Recrystallization of the polymolybdate is c a r r i e d out in o r d e r to remove
the chloride ions. The s a l t is dissolved in a 3 to 57' solution of ammonia,
at 7 0 to 80°, in an amount such that a saturated solution i s formed
(density 1.41 to 1.42). The solution is cooled to 15 to 20" and 50 to 6 0 %
of the molybdenum is precipitated a s crystalline ammonium paramolybdate
3 ( N ~ ) 2 0 . 7 M O4Hz0.
~.
The mother liquor i s used f o r the successive recrystallization of about
ten portions of polymolybdate precipitates. Impurities gradually
accumulate in the mother liquor and it has to be purified.
The combined precipitation of polymolybdates through neutralization
and subsequent recrystallization from an ammoniacal solution yields
ammonium paramolybdate of a higher degree of purity than that obtained
by evaporation and crystallization of the p a r a - s a l t . The ammonium
paramolybdate prepared by the method contains the following impurities
(in% of Mo) :
85
s t i r r e r s . The r e a c t o r s a r e fitted with steam jackets. The addition of acid
to the required pH between 2 and 3 is controlled with the aid of a g l a s s
electrode pH-meter. The pH is approximately determined by the
appearance of a violet color on Congo Red indicator paper.
The acidic mother solution which remains after separation of the
c r y s t a l s s t i l l contains 3 to 4% of the initial molybdenum content. This
corresponds to a Mo concentration of 6 to 10 g/l. The solution is
allowed to stand f o r a prolonged time, the pH is adjusted to 2, and
amorphous polymolybdate precipitates of variable composition a r e
separated and returned to the purification stage. The residual mother
liquors contain about 1g Moil. Molybdenum may be isolated from them
by sorption on ion-exchange r e s i n s (see p. 92).
. 86
I
Roasted concentrate
(calcines)
I
Ammonia water
F I
Leaching
3 . 7 1 '
Cake Solution
1
1 Removal of impurities
Drying
m
Soda ash
P I
Mixing
Cake Solution
1
I
.L
To separation
of ammonium
Sinrering
paramolybdate
1
Leaching
+ .L
Residues Solution
Precipitation
To waste of iron
molybdate
*
Solution Precipitate
.I
NHdOH
To trap
Leaching
I J.
Precipitate
I
.
I
I
HC1 (Fe(OH), Solution
\ J .
1
Dissolution
1
FeC1, solution
I 4
FIGURE 46. Processing of molybdenum calcines including sintering of leaching
residues with soda ash.
Leaching with soda ash solutions in autoclaves. Calcines in which molybdenum occurs as CaMoO,
and other molybdates (and which have a very low MOO, and MoS, content) may be leached directly with
soda-ash solutions instead o f being fused with soda; the leaching is carried out in autoclaves at 180 to
200' which corresponds t o a pressure of about 12 to 15 a t m .
Digestion of the cinders with acids f 27 f Fusion with soda ash i s not a
convenient method for processing calcines with an increased tungsten
content ( 3 to 5% W) since all the tungsten p a s s e s into solution in the form
87
-
Drying and roasting
30% HC1
Y
-
I
NHS solution
Residues
1
Decomposition
Calcines
Leaching
Ammonium
molybdate solution
N Hs
Y
:Neutralization
1
Washing and filtration
;
Wash waters
Residues
t o waste
1
Roasting
1 /
Ammonia water
Leaching
Filtration
.1 .1
Residues to Ammonium
(NH&
waste molybdate solution
, -b *
I 1
Solution
.1
Sulfide waste
l--
I HCl
P 1
Precipitation
Ammonium polymolybdate
solution precipitate
1
Recrystallization
Centrifuging
88
of sodium tungstate. No methods f o r the separation of tungsten from
molybdenum have a s yet been developed. In such a c a s e , the calcines a r e
digested with hydrochloric acid (Figure 47). When the calcines a r e digested
with hot 20 to 30% acid, the molybdates a r e decomposed quantitatively with
formation of molybdic acid which readily dissolves in hydrochloric acid.
Iron, calcium, copper, and other impurities a r e also dissolved. The
tungsten minerals present in the calcines (scheelite, wolframite) a r e
decomposed only partially by the acid. In addition to these minerals, the
residue contains silica, M o a and MoS,. Neutralization of the acid pulp
with ammonia water to pH 2.5 to 3 r e s u l t s in the precipitation of i r o n
molybdate in a mixture with molybdic acid and polymolybdates. Calcium,
p a r t of the iron, the copper, and other impurities remain in solution.
The precipitate is separated by filtration. It is then ignited at 580 to
600" in o r d e r to oxidize M o Q and MoS, and is le?ched with ammonia water.
The degree of extraction of molybdenum from the calcines by this method
is 80 to 8 5 % .
89
19. PROCESSING OF LOW-GRADE CONCENTRATES
- -
The molybdenum concentration in the low-grade concentrates ranges
from 5 to 20% i n the presence of l a r g e amounts of copper, iron and
other impurities. For instance, the low-grade molybdenite concentrates
obtained in the concentration of copper-molybdenum o r e s from a certain
deposit had the following approximate composition: 1 5 to 20% Mo, 3 to 5 %
Cu, 1 2 to 1 5 % S i Q , 1 0 to 1 5 % Fe, and 2 0 to 2 5 % S. Low-grade con
centrates containing 5 to 6 % molybdenum a r e obtained by concentration
of oxidized o r e s containing powellite.
Roasting
Trapping of dust < ‘.1
-
Calcine
Gases t o the
solutions
atmosphere
First leaching
Filrration
I _
Returned
Dust t o the ex
&\ cake
traction of R e CaC1, Filtrate
Soda ash
7 . - 1
Precipitation Decantate
Water
7
7I
Soda ash
Soda ash
Washing
Fifth leaching
Water ‘7
Calcium
1
molybdate
to the
exrrac
ion of hlo.
Re
Wash
- 5 Filtration Filtration
.1
Waste residues
Calcium
1 \ Filtrate
to waste;
molybdate
I
Drying
5
Packing
90
includes roasting of sulfide concentrates, leaching with soda a s h solutions
and precipitation of technical grade calcium molybdate from solution / 15/.
In o r d e r to ensure a high degree of extraction of the molybdenum, the
calcines from the roasting of low-grade sulfide concentrates and powellite
concentrates a r e leached with soda solutions which differ from ammonia
water in that they readily decompose all molybdates.
Leaching. The following reactions take place during leaching with
soda solutions:
+
MoO, Na,COs = Na,Mo04 CO,;
+
+ + +
PCuMoO, 2Na,COs H20= 2Na,Mo04 CuCO,.Cu (OH), CO,;
+
+ + +
FeMoO, Na,COs H,O = Na,MoO., Fe (OH), CO,;
+
CaMoO, + Na,CO, Na,MoO, CaCOs.
+
A p a r t of the siltca, phosphorus, arsenic, and a fraction of the copper
in the concentrates a r e dissolved together with the molybdenum. Copper
is probably dissolved in the form of r a t h e r unstable complexes of the
type xCuC03-yNa2CO3. However, if the solution a t the end of the leaching
is neutral or slightly alkaline, copper carbonate complexes a r e de
composed and the copper is precipitated a s basic carbonates. Most of
the silica i s also precipiated under the s a m e conditions (hydrolysis of
NazSiO, with precipitation of HzSiQ).
An 8 to 1 0 % soda solution is used for leaching, which is c a r r i e d out in
4 to 5 countercurrent stages ( s e e Figure 48). This r e s u l t s in a b e t t e r
utilization of the soda and p e r m i t s the removal of solutions which a r e
neutralized to a pH of 8 to 8.7 by f r e s h portions of the m a t e r i a l to be
leached. The leaching i s c a r r i e d out in i r o n r e a c t o r s fitted with s t i r r e r s
and heated by dry steam which p a s s e s through a steam jacket or coil.
The filtered solutions containing 50 to 70 g of molybdenum p e r l i t e r a r e
sent to precipitation of calcium molybdate.
Precipitation of calcium molybdate. The addition of calcium chloride
to the sodium molybdate solution precipitates calcium molybdate. The
precipitation is c a r r i e d out in wood or rubber-lined iron vats at 80 to 90".
The degree of precipitation depends on the pH of the solution, the amount
of precipitant added and the initial molybdenum concentration. In o r d e r
to precipitate at l e a s t 97 to 98% of the molybdenum, the p r o c e s s must be
c a r r i e d out in neutral or weakly-alkaline solution, using a small (10 to 1 5 % )
excess of calcium chloride which prevents contamination of the precipitate
by calcium sulfate. The white, fine crystalline calcium molybdate
precipitate is washed with water t o remove sulfates and is then separated
by filtration and ignited at 600 to 700" in muffle furnaces.
TABLE 1 7
MDKl
MDKz 44.0
91
The approximate chemical composition of calcium molybdate used in
f e r r o u s metallurgy for the introduction of molybdenum into s t e e l and in
the smelting of ferromolybdenum is shown in Table 17.
The concentration of molybdenum in the mother liquor from the
precipitation of the calcium molybdate is about 1 g/l. Molybdenum is
extracted f r o m these solutions by sorption on ion-exchange resins. The
sorption is c a r r i e d out from weakly-acidic solutions (pH 2 to 3), using
the anionic r e s i n of AN-1 brand. The sorption capacity of this r e s i n for
molybdenum is 20 to 22%. The molybdenum is eluted with a solution of
ammonium hydroxide, and the elution yields a solution containing 50 to 7 0 g
of molybdenum p e r liter.
92
TABLE 18
Equilibrium constants of t h e reduction of MOO, and WO, by hydrogen
Temperature. ' C
-
oxide and M o Q form a eutectic which melts at 550 to 600".
In the second reduction stage ( M o a Mo) the temperature along the
furnace tube changes from 6 5 0 to 950". The molybdenum powder from
the second reduction usually contains 0.7 to 2 % oxygen. To eliminate
this oxygen a third reduction is c a r r i e d out at 1000 to 1 1 0 0 ~
The capacity of the boats during the second reduction is about twice
and in the third reduction about five times that of the f i r s t reduction.
This is due to the difference between the bulk density of M o Q (0.4 to
0.5 g/cm3), Mooz (1 to 1 . 5 g / c m 3 ) , and Mo ( - 2.5g/cm3).
The f i r s t and second reductions a r e c a r r i e d out in furnaces with
9 to 11 chromium-nickel steel tubes. These furnaces have been described
in the chapter on tungsten ( s e e Figure 13).
At 1000 to 1100" the resistance of the chromium-nickel s t e e l tubes
and the nichrome h e a t e r s to the effect of a i r is noticeably lower than at
lower temperatures. The third reduction is therefore c a r r i e d out in
tube furnaces with a hermetically-sealed jacket which is filled with
hydrogen in o r d e r to protect the tubes and h e a t e r s from oxidation.
The molybdenum powder obtained after the third reduction contains
about 0.25 to 0.370 oxygen. Its approximate granulometric composition
is a s follows:
Particle size, p ...... > 0.6 0.6 -1.2 1.2 -1.8 1.8-2.4
Fraction. % .... . .... . 40-60 20 -30 10 -20 1-3
93
I 11111111111 I l l I I
The nature of the powder metallurgy method has been described in the
chapter on tungsten. We shall deal h e r e only with some special features
of this p r o c e s s a s applied to the production of ductile molybdenum.
In the production of relatively s m a l l b a r s , with a c r o s s section between
2 and 1 6 cm2 and a length of 4 5 0 to 600 mm, the molybdenum powder is
p r e s s e d in s t e e l dies a t 3 tons/cm2. The p r e s s e d molybdenum b a r s a r e
s t r o n g e r than s i m i l a r tungsten b a r s , owing to the finer particle s i z e of the
molybdenum powders and also to the fact that they p o s s e s s some plasticity.
The presintering and high-temperature sintering of the b a r s is c a r r i e d
out in the s a m e equipment a s that used in the production of tungsten.
After a presintering in hydrogen at 1100 to 1200", the b a r s a r e
sintered at high temperatures, the maximum temperature being 2200 to
2400".
In the c a s e of b a r s with a c r o s s section of 1 8 X 18 mm the maximum
c u r r e n t applied ( - 90% of the fusion current) is about 4500 amp. As a
result of the fine particle s i z e , the b a r s contract rapidly. Contraction
i s complete within 1 0 to 15 minutes a t the maximum temperature. The
porosity of the b a r is reduced from 4 0 % f o r the p r e s s e d b a r to 10 to 15%.
The sintered b a r s have a g r a i n s i z e corresponding to 2500 to 5000 grains/
mm2.
Large b a r s with a c r o s s section of 4 0 X 4 0 and 60x60" a r e sintered
in installations operating under m o r e d r a s t i c conditions, viz., at c u r r e n t s
of 8000 to 12,000 amp. The temperature is increased gradually, over
6 0 to 80 minutes, to the maximum temperature. The sintering time at
this temperature is 50 to 70 minutes. The method cannot be used f o r the
production of l a r g e r b a r s since direct heating of l a r g e r b a r s by the
passage of a c u r r e n t is accompanied by a l a r g e temperature drop from
the center to the surface of the bar, resulting in nonuniform properties
of the b a r a c r o s s i t s section. It is difficult, moreover, to obtain a
uniform density on p r e s s i n g l a r g e b a r s in s t e e l dies.
Uniform l a r g e b a r s , weighing 3 0 to IOOkg, a r e produced by hydrostatic
p r e s s i n g and such b a r s a r e sintered by indirect radiation heating.
In hydrostatic p r e s s i n g the metal powder is contained in an elastic
( e . g . , rubber) shell which is placed in a hermetically-sealed compression
-
chamber and water (or some other liquid) under p r e s s u r e is applied
( F i g u r e 49). A p r e s s u r e of 1500kg/cm2 is created in the hydrostatic
chamber and the powder is subjected to uniform compression in all
directions.
94
In contrast to conventional p r e s s i n g in a s t e e l die, hydrostatic compres
sion is distinguished by the absence of friction between the powder and the
die walls. It thus eliminates nonuniformity in the p r e s s e d b a r .
In o r d e r to obtain regular-shaped b a r s , e. g . , a cylindrical o r
rectangular c r o s s section, the rubber shell filled with the powder is
placed in a perforated s t e e l c a s e in the shape of a tube or a rectangular
c r o s s section, the rubber shell filled with the powder is placed in a
perforated s t e e l c a s e in the shape of a tube or a rectangular box 1161.
Large b a r s a r e sintered in muffle furnaces with molybdenum h e a t e r s
( s e e Figure 50).
95
the upper electrode (consumable molybdenum electrode) and the lower
electrode which consists of the molten metal in the copper mold. A direct
c u r r e n t is used for melting, the consumable electrode being used a s the
cathode and the melt a s the anode.
The c u r r e n t is rectified with the aid of g e n e r a t o r s or l a r g e selenium
or germanium r e c t i f i e r s (8000 a m p e r e s o r more).
96
I
plate of the crystallizer descends together with the ingot a s the melting
proceeds (Figure 52) / 8 / .
A constant a r c voltage of 30 to 40 V is maintained by means of
automatic control of the distance between the electrodes (i. e., a r c length),
which ranges from 1 0 to 25" depending on the melting conditions.
97
98
Chapter III
TANTALUM AND NIOBIUM
99
are heated to 200 to 300". Rapid oxidation with the formation of Nb205
and Ta& takes place above 500".
TABLE 1 9
__ .
5300
50 2470 1 1 0
-4930
100
Tantalum and niobium absorb nitrogen a t temperatures a s low a s 600".
At higher temperatures the nitrides NbN and TaN, with melting points of
2300 and 3087" respectively, a r e formed.
Carbon and carbon-containing g a s e s interact with the metals a t high
temperatures (1200 to 1400") with the formation of the hard, refractory
carbides, TaC, melting at 3880°, and NbC, melting at 3500"
Tantalum and niobium combine with boron and silicon yielding the
hard, refractory borides and silicides, NbBz (mp 2900"), T a & (mp 3000")
and TaSiz (mp 2400").
Tantalum and niobium a r e not attacked by hydrochloric, sulfuric,
nitric, phosphoric o r organic acids a t any concentration at temperatures
below 100 to 150". The resistance of tantalum to hot hydrochloric and
sulfuric acids is higher than that of niobium.
The metals a r e soluble in
hydrofluoric acid, and dissolve very rapidly in a mixture of hydrofluoric
Nb2.05 TazO5
Density ............................ 4.55 8.71
Melting point, ' C .................... - 1 5 1 0 - 1620
Heat of formation, kcal/mole ......... 455.2 488.8
0 .
1455 I02
The anhydrous tantalum and niobium fluorides NbF5and TaF5a r e very hy
groscopic, deliquescent substances which fume in a i r . They a r e formed when
metallic tantalum o r niobium o r their pentoxides a r e treated with fluorine o r
hydrogen fluoride; the fluorides have low melting points.
NbF, TaFS
................... 80
.
Melting point, 'C
Boiling point, C ................... 234.9
95
229.2
103
lemon-yellow tantalum complex is precipitated after boiling in a weakly
acid solution at pH 3 to 4. The orange-colored niobium complex is
precipitated from neutral o r very weakly acid solutions in the presence
of an e x c e s s of tannin. The difference in the conditions of precipitation
of the tantalum and niobium complexes p e r m i t s the separation of tantalum
f r o m niobium, a fact which finds use in quantitative chemical analysis.
The complexes of fluoroniobic or fluorotantalic acid with some organic
solvents, e. g . , tributyl phosphate and methyl isobutyl ketone, a r e of
technological importance (for their composition s e e p. 125).
constant i s 1 1 . 6 .
Solid-electrolyte condensers made of tantalum and niobium a r e
characterized by a high capacitance and s m a l l size, by a high insulation
resistance, 2 to 3 times higher than that of aluminum condensers, and
by the stability of the oxide film. They can be used over a wide
temperature range from -80 to +200". Miniature tantalum condensers a r e
extensively used in radio transmitters, r a d a r setups, and other types
of equipment.
The tantalum o r niobium components of the condensers a r e prepared
f r o m thin foils o r porous plates which a r e produced by p r e s s i n g the
metallic powder.
Construction of chemical apparatus. The corrosion resistance of
niobium and especially of tantalum in acids and other media, together
with their high electrical conductivity and ductility, make these metals
valuable s t r u c t u r a l m a t e r i a l s for chemical and metallurgical equipment.
I04
Tantalum and niobium a r e used f o r the production of condensers, heaters,
lining of vessels, s t i r r e r s , and other parts. Tantalum s e r v e s instead of
platinum in the production of spinnerets f o r the drawing of synthetic silk
threads.
Atomic energy. Niobium i s characterized by a combination of
properties that satisfy the requirements of atomic energy with respect
to s t r u c t u r a l materials: high melting point, good workability, corrosion
resistance, and a relatively low thermal neutron capture c r o s s section of
about 1.15 barn.
Below 900" t h e r e is almost no interaction between niobium and uranium,
so that niobium is used to make the protective shells of uranium fuel
elements for nuclear reactors. This p e r m i t s the use of liquid-metal
coolants - sodium o r sodium-potassium alloys with which niobium does
not r e a c t below 600". In o r d e r to i n c r e a s e the s e r v i c e life of uranium
fuel elements, the uranium is alloyed with about 7% niobium. The
addition of niobium stabilizes the protective oxide film on the uranium
and thus i n c r e a s e s i t s resistance to water vapor.
The production of refractory and hard alloys. Niobium and tantalum
a r e components of various refractory alloys used in the turbines of jet
engines. The properties of molybdenum, titanium, zirconium, aluminum,
copper and their alloys a r e markedly improved by the addition of
niobium o r tantalum. Niobium-based refractory alloys have been
proposed a s a structural material for various p a r t s of jet engines and
rockets, specifically for the production of turbine blades, the leading
edges of wings, the foreparts of planes and rockets, and the lining of
rockets. Niobium and niobium-based alloys may be used a t service
temperatures of 1 0 0 0 to 1200".
Niobium and tantalum carbides a r e components of some types of
tungsten carbide hard c e r m e t s for metal cutting.
The production of steels. Tantalum and especially niobium a r e
extensively used a s alloying additives in steels. Niobium became of
i n t e r e s t in 1933 to 1 9 3 4 in connection with the discovery of i t s effect on
chromium-nickel stainless steels. The addition of niobium i n an amount
6 to 1 0 times higher than that of carbon in the steel eliminates inter-
crystalline corrosion of stainless steel and prevents damage to welded
joints.
In addition, niobium and tantalum a r e added to various refractory
s t e e l s (especially those used for gas turbines) a s well a s to tool and
magnetic steels.
Niobium i s added to s t e e l s a s an alloy with iron (ferroniobium)
containing up to 6 0 % Nb. Ferrotantaloniobium with various tantalum :
niobium ratios in the alloy i s also used.
Other uses. Tantalum wire and sheets a r e used in bone and plastic
surgery, notably in the setting of bones, "patching" s k u l l damage,
application of sutures, etc. The metal has no irritating effect on live
tissues and does not impede the vitaL activity of the organism.
Some tantalum and niobium compounds such a s fluoride complexes and
oxides a r e used a s catalysts in organic synthesis.
I05
106
M i c r o 1i t e is a mineral whose composition is analogous to that of
pyrochlore, but with tantalum in place of niobium.
Niobium and tantalum usually occur together in these m i n e r a l s since
pyrochlore and microlite f o r m a s e r i e s of isomorphous mixtures. The
composition of minerals in the pyrochlore-microlite s e r i e s is v e r y
complex and variable:
107
not m o r e than 10% NbzO5, while second-grade concentrates m u s t contain
a t l e a s t 4 0 % Taz05; f i r s t - g r a d e columbite concentrates must contain at
l e a s t 60% NbzQ and second-grade concentrates at l e a s t 50% Nb205 1 2 2 , 2 3 1 .
1 2 -30 50-58
53-59.6 12-18
2.09-15.7 10.5-19.0
I08
..I I
. 11.11 .,M. 111 1111.1 1111.1111111 I,. .... .....,,...,,
I.,
titanium, and lanthanides. The concentrates of these m i n e r a l s are
decomposed by digestion with acids (H2S04, HF) o r by chlorination.
I Tantalite-columbite
(concentrate)
.1
1
Size-reduction
.1
Fusion with NaOH
1
Aqueous processing of the m e l t
.1 .1
Precipitate: sodium Solution: Na2SiOs, Na,SnOs,
tantalate and niobate, Na,WO,, NaA10, and
Fe,Os, Mn,O,. NazTiO, other impurities, and
and other impurities excess hydroxide
.1
-1
HC1
Decomposition
.1
1
To waste or to the
precipitation stage in
the regeneration of wastes
Solution: FeCl,, MnCl, Precipitate:
(Ta. Nb),Os x H,O.
and impurities (Si, T i ,
Fe. etc. )
1
Washing of precipitate and
filtration
Mixture of oxides
( T a , Nb),O,. x H,O
FIGURE 53. Production of a mixture of tantalum and niobium oxides by fusion of the concentrate
with sodium hydroxide.
_-_____________
* A recently developed method for the decomposition of tantalite concentrates involves treatment with
NaOH solutions a t 200' in autoclaves; this provides a high degree of decomposition and reduces the
hydroxide consumption by a factor of three as compared with the fusion method 1241.
109
Fusion and aqueous processing of the melt, Assuming that ortho s a l t s
are the only s a l t s formed, the p r o c e s s e s qccurring during the fusion
may be approximately described by the following equations:
+ +
Na3TaOl 3OH,O = 4Na20.3Ta20,.25H20 1ONaOH;
+
12Na3Nb0, + 43H20 = 7Na20~6Nb20,~32H,0 22NaOH.
It must be taken into account that in addition to FeO and MnO, F e z 0 3and
a r e a l s o formed during fusion, since the oxygen present in the
It'hI304
melt causes partial oxidation of the divalent i r o n and manganese to higher
valency compounds. The f e r r i c i r o n is present in the melt a s f e r r i t e ,
NazO. FezQ. F e r r i t e decomposes during aqueous treatment according to
the equation:
Na,0.Fe20, + +
H20 = 2NaOH F%OP
110
portions of the concentrate a r e added, the temperature of the furnace is
gradually increased to 800'. This is necessary in o r d e r to keep the m e l t
liquid. The melt is held f o r 20 t o 30 minutes a t the maximum temperature
and is then poured directly into water; safety m e a s u r e s must be taken,
as contact of the alkali with the skin may cause s e r i o u s burns.
The aqueous processing is c a r r i e d out at a solid :liquid r a t i o of 1 : 3
o r somewhat higher. A concentrated alkaline solution is formed in the
f i r s t stage of the processing; this solution contains the bulk of the
impurities - silicon, tin, tungsten, aluminum, sulfur, and phosphorus -
in the form of water-soluble sodium salts. The dark-brown precipitate
contains sodium niobates and tantalates as well as i r o n and manganese
oxides and hydroxides and sodium titanate.
The precipitate is allowed to settle, the solution is separated by
decantation, and the precipitate is washed s e v e r a l times with hot water
containing about 5% NaOH, which is added in o r d e r to prevent the
dissolution of niobium and tantalum.
Digestion of the precipitbte with acid. The precipitate is decomposed
by heating with hydrochloric acid. Sodium niobate and tantalate a r e
converted into the hydrated oxides:
Iron and manganese oxides dissolve in the acid, yielding the respective
chlorides. Chlorine is evolved a s a result of the reduction of manganese
from higher valency s t a t e s to manganous compounds:
Mn,O, + 8HC1= 3MnCI, + C1, + 4H,O.
When the cake is treated with hydrochloric acid, sodium titanate is
converted to titanic acid HzTiQ, which is partially dissolved. The bulk
of the titanium remains in the precipitate together with niobium and
tantalum oxides.
Digestion with -20% hydrochloric acid is c a r r i e d out in rubber-lined
iron vessels o r earthenware tanks heated by superheated steam. When
the decomposition i s completed, the color of the dark-brown precipitate
turns white, which i s the color of the niobium and tantalum oxides, while
the color of the solution turns dark-yellow as a result of the presence
of iron and manganese chlorides. The finely dispersed precipitate of
hydrated pentoxides i s difficult to separate by filtration. The precipitate
is rinsed with hot water, acidified with hydrochloric acid, in o r d e r to
remove the iron and manganese salts, and the solution is separated by
decantation. The rinsed precipitate is separated by filtration while s t i l l
hot. The precipitate, consisting of the hydrated pentoxides, is dried at
100 to 120". The powder obtained after drying still contains 2 0 to 25% HzO.
The approximate composition of the oxide mixture obtained by the above
method i s : 96 to 99% (Ta, IW I)~ O ~ , to 0.5% SnO2, up to 0.570 SiQ, 0.5
0.1
to 1.070 Ti&, up to 1% FeO+MnO, on the dry, water-free product.
The oxide mixture is subsequently converted into pure compounds.
2 6 . PROCESSING OF TANTALITE-COLUMBITE B Y
FUSION WITH POTASSIUM HYDROXIDE i 4 /
Fusion with potassium hydroxide is expedient if i t is desired t o produce a purer mixture of tantalum
and niobium oxides. When the concentrate is fused with potassium hydroxide (in the same way as the
fusion with sodium hydroxide described above). the minerals tantalite and columbite a r e decomposed, and
water-soluble potassium tantalate and niobate, as well as iron and manganese oxides, are formed. T h e
main impurities (silica, cassiterite, wolframite. and titanium minerals) react to yield the potassium salts
of silicic, stannic, tungstic, and titanic acids.
When t h e m e l t is leached wirb water. K2Si03, KzWO,, KzSn03, and KA102 are dissolved together
with niobium and tantalum. Although K2Ti0, is a sparingly soluble salt, a fraction of the titanium
dissolves in the presence of tantalum and especially niobium; this is attributed t o the formation of complex
titanium-tantalum or titanium-niobium compounds. T h e alkaline solution is then treated with sodium
chloride or sodium hydroxide, and the sparingly soluble sodium tantalate and niobate are precipitated.
The silicon, tungsten, tin, and aluminum present as impurities remain in the solution. T h e precipitate,
consisting of sodium tantalate and niobate is digested with acids, and a mixture of tantalum and niobium
oxides with a very low impurity content is obtained.
When t h e above method was used a concentrate containing 44%Ta20,, 16.1% Nb,Os, 6.5% TiO,,
9.9% SiO,. 6.1% FeO, 5.3% MnO, 4.4% SnO,, 3.7% A1,0, and 0.2% WO, yielded a mixture of tantalum
and niobium pentoxides containing 99.22% Ta2O5+Nb2O5. 0.36% TiO,, 0 . 0 1 6 Fe203 and traces of SnO,.
The compounds SiO, and MnO were not found in the mixture.
A pentoxide mixture of the above composition c a n be used for the production of tantalum-niobium
alloys by thermal reduction with carbon or by electrolysis (see below).
+
Fe (RO,), 16HF + 2H,R%, + FeF, + 6H,O;
+
Mn (R0J2 16HF 2H,RF, -f + MnF, + 6H,O.
All elements (tin, titanium, silicon, tungsten, etc. ) originally p r e s e n t
in the associated minerals a r e dissolved, together with niobium, tantalum,
iron, and manganese.
Thus, the decomposition of concentrates by hydrofluoric acid yields
solutions which a r e contaminated with l a r g e amounts of impurity elements,
which hamper the separation of pure tantalum and niobium compounds.
This is the main reason for the limited use of the above method in
industrial practice. However, recently developed methods for the
separation of tantalum from niobium and their isolation from other
elements have shown that the decomposition of tantalite (columbite) with
hydrofluoric acid as a technological p r o c e s s has the advantage of being
much s h o r t e r ( t h e r e a r e fewer stages) than the fusion of concentrates with
alkalies.
The digestion of concentrates with hydrofluoric acid is c a r r i e d out in
s t e e l tanks covered with lead and lined with graphite blocks. The s t i r r e r s
may be prepared from monel metal, an alloy of nickel containing 27 to
29% copper.
I12
The o r e concentrate, which is crushed to a particle s i z e of about
0.074mm, is decomposed with hot 70 to 72% HF. The acid consumption
depends on the composition of the concentrate and the original mineral
(the NbzO5: T a 2 a and F e O : MnO ratios), and on the processing conditions.
The consumption of 70% H F is 1.2 t o 2.5 toniton concentrate.
In s o m e industries, a mixture of hydrofluoric and sulfuric acids is used
in o r d e r to i n c r e a s e the degree of decomposition of the concentrate. In
most c a s e s the pulp is heated with superheated steam, which is injected
through a rubber hose. The pulp may be heated by means of electric
graphite heaters.
P a r t of the hydrofluoric acid evaporates during the decomposition
process. This r e q u i r e s that the apparatus be fitted with good exhausts
and that the H F be absorbed in a s c r u b b e r irrigated with l i m e water.
Twofold processing of the concentrate is occasionally required in o r d e r
to provide quantitative decomposition. When the decomposition is
completed, the pulp is diluted with water. The solutions a r e filtered
using cotton or polyvinylchloride filter t i s s u e s in rubber-lined filter-
presses.
Until recently, tantalum and niobium were isolated from the hydrofluoric
acid solutions in the form of the fluoride complexes, K2TaF7and KzNbOF5.
HzO, by a method which is described below. At present tantalum and
niobium a r e extracted from these solutions by selective extraction with
organic solvents. The nature of the extraction p r o c e s s is discussed in
Section 29.
113
TABLE 21
Chloride
Temperature, 'C
bo i1ing
1 Chloride
Temperature, 'C
melting boiling
Crushed concentrate
1
Briquetting
I
4
Drying and coking of
briquettes
1
Chlorination
1
Distillate Residue: Ce, La
I chlorides, CaCI2. NaCl
1
Solid chlorides: NbOCls ,
I
Liquid chlorides:
To the extraction Of
NbC15, TaC1, , FeClS TiCl, contaminated by
lanthanides
and others SiCl,. and others
~ ~.
J J
To t he production of To purification
pure tantalum and ni-
obium compounds
114
The C O : C 0 2 ratio in the g a s e s depends on the temperature and the
chlorination conditions. Carbon monoxide is the main component of the
gaseous phase a t temperatures between 750 and 850". The chlorination
is c a r r i e d out in shaft furnaces, and the charge is briquetted.
Mixing, briquetting, and coking. Petroleum coke is used a s the
reducing agent; the amount taken is determined experimentally, and
fluctuates between 20 and 300/0.
The crushed concentrate and coke (particle s i z e 0.177 to 0.15") are
mixed in the required ratio in screw-type, paddle o r other type blenders.
A binder is added to the mixture before briquetting; petroleum o r coal
pitch, resins, and some other m a t e r i a l s a r e used as binders,
Roller p r e s s e s a r e the most convenient briquetting equipment. They
consist of two r o l l e r s rotating in opposite directions and fitted with belt-
type f o r m e r s with egg-shaped o r pillow-like cavities (Figure 55).
Chl ori
3
4
The charge on the rotating r o l l e r s is fed from the top and fills the
f o r m e r cavities. P r e s s i n g i s done at about 150 to 300kg/cm2. When
pitch o r resin a r e used a s binders the mixture is heated by means of
steam fed to the steam jacket of the blender, to 80 to 1 2 0 " before pressing
in o r d e r to soften the binder. The approximate s i z e of the pellet-shaped
briquetts is 50X40X35mm.
The briquettes a r e coked, i. e . , heated to 700 to 800" in the absence of air
in o r d e r to i n c r e a s e their strength, to expel1 the volatile components and
to i n c r e a s e their porosity (gas permeability).
I15
The coking is c a r r i e d out in batch or continuous r e t o r t furnaces.
Chlorination. The chlorination of the briquettes is usually c a r r i e d out in
electrical shaft furnaces (Figure 56) with an internal diameter of the shaft
of about 4.5 to 6 m and a height of up to 8 m. The furnace is lined with
dense chamotte o r Dinas bricks. The lower p a r t of the furnace contains
two rows of carbon electrodes. There a r e t h r e e electrodes in each row,
a t an angle of 120". The space between the electrodes is packed with
carbon rods, which s e r v e a s an electrical r e s i s t o r which maintains the
required temperature in the furnance. A voltage of 6 0 to 100 V is applied
to the electodes, the voltage being reduced a s the packing heats up.
The briquettes a r e charged into the furnace through a hermetically-
sealed charging device. They f i l l a p a r t of the furnace space over the
packing. By controlling the level of the raw m a t e r i a l in the furnace and
the r a t e of supply of chlorine, the process may be c a r r i e d out at the
expense of the heat of the chlorination and the supply of heat may be shut
off o r considerably reduced.
The chlorine coming from storage tanks, which a r e usually located
in a special basement, p a s s e s through a chlorine-supply line and i s fed
to the furnace through tuyeres placed below the upper row of electrodes.
The variables which must be controlled during the operation of the
furnace a r e : the r a t e of supply of chlorine, the g a s p r e s s u r e in the
furnace, the temperature, and composition of the exhaust gases.
The vapor-gas mixture containing volatile niobium, tantalum, titanium,
iron, silicon and aluminum chlorides p a s s e s through a tube a t the top
of the furnace into a s e r i e s of condensers (Figure 57). Solid niobium and
tantalum chlorides (NbOC13, NbC15, TaC15) condense together with iron
and aluminum chlorides in the f i r s t condenser which i s maintained at
1 6 0 to 180". The second condenser s e r v e s for the condensation of liquid
titanium chloride. Spray condensers containing precooled l i q u i d TiC14
a r e most often used f o r this purpose. A fraction of the niobium, tantalum
and iron chlorides, entrained with the gas s t r e a m , may condense in the
second condenser, Moreover, SiC14, which is soluble in liquid titanium
chloride, condenses together with TiC14 (for m o r e details s e e chapter on
titanium). The g a s e s from the second condenser, which may occasionally
contain some chlorine and HC1 vapors, a r e passed through a sanitary
scrubber which is irrigated with l i m e water in o r d e r to bind the chlorine.
The nonvolatile lanthanide, calcium and sodium chlorides formed in
the chlorination a r e fused a t the p r o c e s s temperature (800 to 900") and
flow through the p o r e s in the carbon packing onto the furnace bottom,
from which they a r e periodically discharged.
Thus, the chlorination of loparite yields t h r e e products: a melt
containing lanthanide chlorides, a condensate consisting of tantalum and
niobium chlorides contaminated by iron, and technical titanium t e t r a
chloride.
The purification of titanium tetrachloride will be described in the
chapter I ' Titanium". However, we must note h e r e that tantalum and
niobium chlorides a r e sparingly soluble in TiC14. At 18" the solubility
of TaC15 and NbC15 in Tic14 is 0.4 and 0.4570by weight respectively, and
i t i n c r e a s e s in the presence of aluminum chloride. The solubility of
Nb0Cl3 and TiC14 does not exceed a few hundredths of one percent 1 2 5 1 .
In o r d e r to obtain a mixture of tantalum and niobium oxides, the
chloride condensate is subjected to hydrolytic decomposition in a hydro
chloric acid solution:
1 I6
+ +
2 N W 1 3 ( X 3) HZO + N ~ , O ~ . X H ~ 6HC1;
O +
+ +
2TaC1, (x 5) HzO + TazO,. xHsO IOHCI. +
Under certain conditions, which must be determined in each case, the
hydrolysis can be c a r r i e d out so a s to ensure that the concentration of
iron in the tantalum and niobium hydroxides is reduced to a negligible
value. The hydrolysis also c a u s e s partial separation of titanium, which
is p r e s e n t a s an impurity. The resulting mixture of hydroxides (up to
80% (Nb,Ta)z05, 1.5 to 370 Ti&, 3 to 7% Fez% and 0.5 to 2% S i Q ) is then
forwarded to the purification stage and the separation of tantalum and
niobium i s then c a r r i e d out.
- To the sanitary
--
scrubber
U
FIGURE SI. Installation for the chlorination of ritanium-tantalum
niobium concentrates.
1 -furnace (chlorinator); 2-condenser for trapping niobium and
tantalum chlorides; 3-container for solid chlorides; 4-spray
condenser; 5-cooler for the titanium’ chloride which is returned
for spraying; 6-condenser; 7 - ~ o n t a i n e r for titanium chloride;
8 - p u m p ; 3-thickener; 10-conveyer for the supply of slurries;
I I -filter; 12-container for technical grade titanium chloride.
I I7
2) extraction with organic solvents.
Of m a j o r i n t e r e s t from the industrial point of view a r e also separation
methods based on differences in the volatilities of the chlorides (rectifica
tion methods) and the selective reduction of niobium pentachloride to
lower chlorides.
Ion-exchange methods for the separation of tantalum from niobium have
been developed, but t h e i r output is low and they may be used only for
relatively s m a l l - s c a l e production of pure tantalum and niobium compounds.
Removal of accompanying elements and contaminants from pure
compounds usually takes place during the separation of niobium from
tantalum.
FIGURE 58. Solubility of potassium FIGURE 59. Solubility of the complex tantalum and
niobium oxyfluoride and potassium niobium fluorides in hydrofluoric acid at 25' as a
fluotantalate in 1% HF. function of the acid concentration.
I18
Curves based on the data of Savchenko and Tananaev 1111 on the
solubilities of the complex tantalum and niobium fluorides a t 25" as a
function of the H F concentration a r e presented i n Figure 59.
The solubility isotherm of the complex niobium salts is composed of
two sections. The f i r s t region of increasing solubility corresponds to
the equilibrium between the solution and K2NbOF5.H20 in the solid,
concentration, t o a maximum at -
crystalline phase. The solubility of the s a l t i n c r e a s e s with increasing H F
770HF. This i n c r e a s e in solubility is
attributed to the increased stability of [NbF7I2- ions with increasing HF
concentration. As a result, p a r t of the potassium niobium oxyfluoride
is converted into potassium fluoniobate:
KZNbOF, + 2HF Z KzNbF7 + HZO
-
The solution becomes unsaturated with r e s p e c t to K2NbOF5 HzO and this
c a u s e s dissolution of an additional amount of the crystals. When the HF
concentration reaches 7 % , the solution becomes saturated with respect
to both salts. This "transition point'' corresponds to the common solubility
of K2NbOF5.H 2 0 and K2NbF7.
The second region in the isotherm corresponds to the equilibrium be
tween the solution and KzNbF7 crystals. The solubility of the s a l t f i r s t
d e c r e a s e s ( t o 26 to 27% HF) and then increases. The d e c r e a s e in solubility
is attributed to the suppression of the hydrolysis of K2NbF7with increasing
H F concentration. The subsequent increase in solubility at higher H F
concentrations is attributed to the formation of a new ionic species
[NbF,]- according to the equation:
119
KzNbOFSconcentrarion, 70
HF.
120
-
3 0 4 0 % HF
I
Dissolution
1
Settling, decantation,
I
filtration
.1 5.
Solution of Insoluble residue
-
H2TaFl and
HzNbOF5
7--
I
To waste
-
KCl
Dilution of the
solution and heating
Precipitation of the
tantalum salt
I
Filtration and washing
1 -1
Precipitate Mother solution containing
KZTaFl K,NbOF, and impurities
( T a . Ti, Fe)
-
7
Recrystallization from
1-270 HF
Evaporation
- 1 I
Mother
Crystallization
solution
I
KZNbOF5. HZO
1
Mother solution
Drying a t
I
I 120-150' I
crystals
.1
I
1 Recrysta 11i za cion
Mother solution is from 1-270 HF
discarded after 6-10
recrysrallizations 3
Mother solution
5.
I
Drying
J.
FIGURE 62. Flow sheet of the separation of tantalum and niobium by fractional crystallization
of their complex fluoride salts.
The hydrochloric acid formed in the reaction has little effect on the
ratio of the solubilities of potassium fluotantalate and potassium niobium
oxyfluoride. Potassium fluoride i s not commonly used in practice since
it is expensive and difficult to handle (very hygroscopic).
121
The tantalum s a l t s e p a r a t e s out of solution in the form of needle-shaped
crystals, which are separated by filtration after allowing the solution to
cool. Silicon in the form of KzSiF, is precipitated quantitatively with the
tantalum salt. The precipitate a l s o contains up to 50% of the titanium and
a s m a l l fraction of the niobium (5 to 6 % of the amount initially present in
the solution) in the f o r m of complex fluoride s a l t s .
An additional purification stage involves the recrystallization of KzTaF,
122
'I
When a solution contains simultaneously the compounds of two elements,
the distribution of each element between the aqueous and organic phase
will correspond to the values of their distribution coefficients.
The r a t i o of the distribution coefficients of two elements is known as the
s e p a r a t i o n c o e f f i c i e n t : /3 = % . This coefficient determines the
5%
Aqueous
ohase 4
3
FIGURE 63. Diagram of a packed FIGURE 64. Diagram of a pulsating
extraction column. tray column for extraction processes.
123
1
lIl l l l l Il1
3 ; outlet
c
0 O .v
.- m
u z-!- , Aqueous
2 02 1
t I 1 phase
- In ,; Organic
Starting phase
solution
-- Mixer
!-Settler
O
C Q 4 I
'2 v I
;g -#
&.io
..
current extraction in a cascade of mixer-settler
1-mixing chamber; 8-turbine; 3- hollow
cells (view from the top).
shaft; 4-partition; 5-settling chamber.
124
A cell of a well-known m i x e r - s e t t l e r extractor with a mixing pump is
shown in Figure 6 5 . The cell consists of mixing and a settling chambers
separated by a partition. The cells a r e connected together forming a
cascade of m i x e r - s e t t l e r s (Figure 6 6 ) . The mixing chamber is fitted with
a s m a l l turbine rotating on a shaft, which e n s u r e s a rapid mixing of the
aqueous and organic phases, the t r a n s f e r of phases between adjacent cells,
and level control of the liquid phases.
The mixer is separated into two sections by a horizontal partition. The
hollow shaft of the turbine p a s s e s through an opening in the horizontal
partition. The turbine pumps the aqueous solution (i. e . , the heavy phase)
through the hollow shaft from the lower to the upper section, dispersing
the liquid through openings between the blades, where it is mixed with
the organic solvent (the light phase) which is fed to the upper section of the
mixing chamber.
A constant level between the aqueous (heavy) phase and the phase
mixture in the lower section is maintained automatically. This is explained
by the fact that the liquid i s aspired by the turbine at a certain level.
Thus, when the output of the turbine exceeds the r a t e of flowof liquid, the
phase mixture is pumped from the upper to the lower chamber until a
regular flow of the liquid is established.
The level of the phase mixture in the upper chamber (i. e . , the level of
the interface between the phase mixture and the a i r ) gradually d e c r e a s e s
from cell to cell in the cascade, in the streaming direction of the light
phase. The phase mixture flows by gravity through the partition and into
the settling chamber in which the phases separate. The light phase p a s s e s
through an opening in the upper p a r t of the settling chamber into the
mixing chamber of the preceding cell while the heavy phase p a s s e s through
an opening n e a r the bottom of the chamber into the lower section of the
mixing chamber of the following cell.
Thus, the flow of the heavy phase in one direction of the cascade i s
forced by the turbine, while the flow of the light phase in the opposite
direction is caused by the gradual d e c r e a s e in the liquid level in the upper
section of the m i x e r s .
In continuous countercurrenf extraction the starting aqueous solution i s
fed to the middle of a system of e x t r a c t o r s of the m i x e r - s e t t l e r type, a s
shown in Figure 6 6 . In this c a s e the system has extraction and washing
sections. The organic solution entering the wash sections comes in contact
with the aqueous washing solution which extracts the impurities previously
removed by the solvent in the extraction section.
The extractive separation of tantalum and niobium, with simultaneous
removal of other (impurity) elements i s mostly c a r r i e d out from solutions
of tantalum and niobium fluorides, containing hydrofluoric and sulfuric
acids, The solutions a r e obtained a s a r e s u l t of the decomposition of o r e
concentrates by hydrofluoric acid, a s described above, o r by dissolution
of the oxides in HF.
The best extractants of those tried out a r e methyl isobutyl ketone and
tributyl phosphate (Table 2 2 ) .
Tributyl phosphate (TBP) is superior to methyl isobutyl ketone because
of i t s relatively high boiling and flash points. It has the disadvantages Of
high density and viscosity. For this reason T B P is often diluted with some
light i n e r t diluent, e. g. , kerosene o r xylene [C,H4(CH,)2 1. Tributyl
I25
phosphate f o r m s stoichiometric complexes with the extracted compounds.
.
Thus, the complex T B P HF is formed with hydrofluoric acid.
Depending on the hydrofluoric acid concentration, tantalum and
niobium are present in solution i n the f o r m of various complex acids:
HzTaF7, HzNbF,, HTaF6, HNbF6, and HzNbOF5.
1.7 -2.2
- 3.45
145
0.6
126
2) re-extraction of niobium f r o m the organic solvent by water;
3) re-extraction of tantalum f r o m the solvent by water of by aqueous
solutions of s a l t s such a s ammonium fluoride.
0 2 4 C I 10 12 14 16
HF concentration. N
FIGURE 61. Degree of extraction by methyl
isobutyl ketone of tantalum and niobium from
solutions with different HF concentrations.
TABLE 23
Distribution coefficients of the ions of some elements between TBP and an
aqueous solution containing 10 moles HF and 12 moles H,SO, per liter
I
Concentration in the
Ion and its valence
starting solution, gt 1 a=
Corg
caq
2 183
2 119
10 0.001
2 0.017
10 0.02
2 0.05
127
' I /
Methyl isobutyl ketone AqJeous I4 15 I,?
solution
FIGURE 68. Flow sheet of the processing of columbite concentrate, including the ex
tractive separation of tantalum and niobium:
1-teactor for the decomposition of the concentrate; 2-tank for the dilution of the
pulp; 3-filter press; 4 -container for the filtrate; 5-column for the joint extraction
of tantalum and niobium; 6-column for the reextraction of niobium; I-column for
reextraction of tanralum; 8 and 9-apparatus for the steam distillation of rhe solvent;
10 -collector for the tantalum solution; 11-vessel for the precipitation of T a 2 0 s ;
12 -filters; 13 -ignition furnaces; 14-collector for the niobium solution; 15
vessel for the precipitation of Nb,05.
TABLE 24
Concentration, 70
Element
Nb205 ta205
Zr < 0.05 < 0.05
Ta < 0.03 -
Nh - < 0.03
F 0.06 0.06
Fe < 0.03 < 0.01
Ti < 0.015 < 0.015
Si 0.01 0.01
w < 0.01 < 0.01
Ni 0.005 0.005
cu < 0.004 < 0.004
A1 0.002 0.002
Mg, Co, Zn, < 0.002 < 0.002
Cr. Mn, Sn,
V , Mo
Cd < 0.0005 < 0.0005
B < 0.0001 < 0.0001
-
The organic solvent containing the niobium and the tantalum is fed to
the middle of a pulsating column serving for the reextraction of niobium
with water which is fed into the upper section of the pulsating column.
128
Rectification may be successfully employed in the separation of the mixture of tantalum and niobium
pentachlorides. as the boiling points of the chlorides differ by 14.3' (the boiling points of TaC15 and NbC1, are
234.0 and 248.3' respectively).
T h e use of the rectification process for the separation of tantalum and niobium is expedient when the
ore concentrates are processed by the chlorination method, yielding a condensare of tanralum and niobium
chlorides, e. g., in the processing of loparite concentrates. The chlorination of the concentrate usually
yields a condensate in which a large fraction of the niobium is present as the oxychloride NbOCI,. Thus.
additional chlorination is required in order to convert the oxychloride to the chloride.
T h e Soviet scientific literature contains descriptions of laboratory experiments on the rectification of
tantalum and niobium chlorides in sieve-tray glass columns with a diameter of 32 t o 34" and 25 trays, as
well as larger-scale experiments in stainless-steel columns /15/.
The starting mixture of chlorides contained 80.2% Nb. 12.3% T a , 0.3% T i , 7.2% Fe. and 0.22% W;
after rectification the yield of niobium chloride was about 6 0 % . and it contained 0.008% Ta (on the Nb),
- 0.005% T i , 0.00270 W . and < 0.001% Fe. About 80% T a was obtained in the form of a concentrate
containing 8070Ta (on the total amount of T a + N b ) . This concentrate, as well as other intermediate fractions.
m a y be subjected to a second rectification in order to obtain the pure compounds.
The rectification method is characterized by a high output and a high degree of separation. It may
b e carried out in continuous operation columns. T h e pure tantalum and niobium chlorides produced may be
used as the starting material for the production of tantalum and niobium (see Section 35).
As compared with tantalum pentachloride. niobium pentachloride is more readily reduced by hydrogen
(or by metals such as aluminum) t o the lower chlorides. This is used as the basis of a process for the
separation of tantalum and niobium. NbC1, is reduced by hydrogen at 450 -550" t o the nonvolatile
trichloride:
NbCl, + +
H2+ NbCI, ZHCI.
TaC15 is not reduced under those conditions.
_______-----__
* The nature of the rectification process will b e discussed in Chapter IV.
129
In one variation of the method. tantalum and niobium are separated by volatilizing the NbCI, + TaCI,
mixture a t 180-200’ and passing the gaseous chlorides together with hydrogen through a long tube heated
to 500-550’. T h e NbCI, formed condenses on the walls of the tube, while the TaCI, remains in the
gaseous phase and is collected in the condenser. T h e yield of pure NbCl3 from the pentachloride has been
reported to be about 1 0 % / 1 / .
T h e difficulty of effecting the reaction as a continuous process and the necessity for repeating the
process on the condensate in order to obtain pure tantalum pentachloride are among the disadvantages of
the process.
Metallic niobium can be produced from rhe trichloride by reducrion wirh hydrogen.
L
0
v,
C
.*
Y
2
C
u -
Volume of solution passed through
-_ _ _ _ _ _ _ _ - - _ _ - _ -
T h e fundamentals of ion-exchange chromatography method of separation of elements with similar
properties will be discussed in Chapter VI.
I30
second fraction contains the r e s t of the niobium and all the titanium, and
the third fraction contains pure tantalum (see Figure 69).
131
Me'is the reducing agent;
Q is the heat of reaction.
The r a t e and the extent of the reduction depend on the affinity of the
metal acting a s reducing agent and the metal in the compound to be reduced
for oxygen, chlorine, fluorine, and other elements.
-158
coo
-14d
-130
- 120
g -??0
.
Y
m
M
2-" -I00
9
\-
c- -90
.-
I
m
E
L
-80
2 -70
L;I
-60
-50
-40
-30
-20
I32
Temperature, ' K
a
a-chlorine: b -fluorine.
The dependence of the f r e e energy of formation of oxides and halides on
the temperature is shown in F i g u r e s 70 and 71. To facilitate comparison,
the values of AF a r e related to one g-atom of oxygen, chlorine, and fluorine.
A comparison of those values shows that the most active reducing
agent f o r the r a r e metal oxides is calcium, followed by magnesium and
aluminum; for the chlorides - sodium, calcium, magnesium; and f o r the
fluorides - calcium, sodium, magnesium.
If one of the participants in the t h e r m a l reduction reaction displays
a high vapor p r e s s u r e a t the temperature of the reaction, the changes
in p r e s s u r e may have an appreciable effect on the course of the reaction
and may even r e v e r s e its direction. Thus f o r instance, the standard
affinity of calcium for oxygen (144.3 kcal) is much higher than that of
aluminum (123.8 kcal) and aluminum oxide should, therefore be reduced
by calcium. However, the reduction reaction is reversible:
A1,0, + 3Ca 3Ca0 + 2A1.
Depending on the external p r e s s u r e , it may proceed in the direction of the
formation of aluminum or the reduction of calcium oxide by the aluminum.
The boiling points of calcium and aluminum a r e 1480 and 2330" respectively.
When the reaction is c a r r i e d out under reduced p r e s s u r e , calcium (which
has a lower boiling point) is expelled from the reaction zone. Under such
conditions, calcium oxide is reduced by aluminum (this p r o c e s s is used in
the production of metallic calcium). In a sealed reactor, in which vapor
p r e s s u r e of calcium may build up, the reaction would r e s u l t in the forma
tion of elementary aluminum.
The heat evolved in the t h e r m a l reduction by metals is often sufficient
to support a spontaneous p r o c e s s a t a high r a t e (the reaction must first
be initiated somewhere in the mixture). In other c a s e s the heat evolved
is not sufficient to support the p r o c e s s and unless external heating is
supplied, the reaction c e a s e s before i t can spread over the entire mixture.
In o r d e r to find out if the reduction i s spontaneous o r must be supported
by external heating, we must know the specific heat effect q, i. e . , the
amount of heat required p e r g of the charge.
The specific heat effect of the reaction M e X + Me' = M e + Me'X + Q i s :
where MMcx i s the molecular weight of the compound and AMe is the atomic
weight of the reducing agent.
The maximum heat effect of the reaction is obtained a t a stoichiometric
ratio of the components in the charge. An excess or deficiency of the
reducing agent diminishes the specific heat effect since a p a r t of the
m a t e r i a l absorbs heat (heating-up, melting) without taking p a r t in the
reaction. Nevertheless, in most c a s e s an excess of the reducing agent
i s required in o r d e r to obtain a higher degree of completion of the
reduction.
A heating additive (activator) is added to the charge if the specific heat
effect of the reaction is not sufficient to support the reaction. The
activator r e a c t s with the reducing agent with the evolution of a l a r g e amount
of heat, which i n c r e a s e s the specific heat effect.
1455 134
In other c a s e s the heat of reaction is s o high that the reaction is
extremely vigorous and partial ejection of the charge (caused by the
rapid expansion of g a s e s entrapped in the p o r e s of the charge) a s well a s
evaporation of the reducing agent and the compounds participating in the
reaction take place. In such c a s e s the reaction i s slowed down by the
addition to the charge of fluxes which absorb a p a r t of the heat, (this
being consumed in the heating and melting of the flux). Fluxes a r e also
added when a lower-melting, lower-viscosity s l a g is required.
The reducing agents used in thermal reduction by m e t a l s must satisfy
the following requirements :
1) the reducing agent (metal) must provide for the highest possible
degree of completion of the reduction a t the lowest possible supply of
external heat;
2) the slags formed and the excess reducing agent must be readily
separated from the metallic product (by rinsing, vacuum distillation,
removal of slag);
3) the reducing agent must be of high purity, in o r d e r to prevent
contamination of the metal product;
4) the reducing agent must have a low solubility in the metal product
and must not form chemical compounds with i t ;
5) the reducing agent must be readily available and reasonably cheap.
The melting and boiling points of the most common metal reducing
agents and the products of thermal reduction reactions a r e listed in
Table 25.
TABLE 25
Melting and boiling points of metallic reducing agents and their compounds
-1- - -
-_ 1 I I
Element
Na 97.7 1704
Ca 851 1480 2510 182 2021 1418 2501
Mg 650 1126 2800 714 1418 1262 2221
A1 659 2330 2045 192.4 180 1270 1272
. . _ _ _ ~
136
33. PRODUCTION O F TANTALUM AND NIOBIUM
BY ELECTROLYSIS
137
4Ta5+ + 20e + 4Ta;
loo*-- 20e 50,. --f
Of the electrolyzer designs which have been tried out best r e s u l t s were
obtained when a nickel (or nickel-chromium alloy) crucible was used a s the
cathode, with a graphite anode placed a t the center of the crucible 1141.
A diagram of such an electrolyzer is shown in Figure 72. It consists
of a nichrome crucible, appliances f o r supporting and lifting the anode,
a feeder and a heat-insulating jacket. The lower, cone-shaped p a r t of the
crucible has an opening which is closed by a stopper with a rod serving
a s c u r r e n t terminal. A hollow perforated graphite anode is placed a t the
center of the crucible. Tantalum pentoxide is fed into the bath through
the hollow anode by means of an automatic batch feeder. This method of
feeding prevents contamination of the cathodic deposit with the undissolved
138
pentoxide. A flange exhauster s e r v e s to evacuate the gaseous products.
The electrolyzer is supplied with a controlled d i r e c t c u r r e n t .
I39
residual Ta205 concentration in the electrolyte, at which the anodic effect
t a k e s place, depends on the anodic c u r r e n t density. As the anodic density
is increased, the anodic effect is observed at higher Ta2O5 concentrations
i n the electrolyte. The temperature of the electrolyte is maintained at
6 8 0 - '720'.
The average bath potential is determined by means of the equation:
* [InRussian: "total electrical energy", but this would be in contradiction with the statement in the last
paragraph of the section (80% current efficiency). I
140
I
141
(where M e - Na or K). Coarsely crystalline deposits of niobium and
tantalum a r e formed on the cathode in the electrolytic decomposition of
these complexes, while chlorine is evolved a t the graphite anode.
3 4 . PRODUCTION O F NIOBIUM BY T H E C A R B I D E
R E D U C T I O N METHOD / 13/
I42
I
To the'pump "
FIGURE 14. Diagram of a vacuum furnace with a
graphite heating element.
1-water-cooled cover; 2-water-cooled base
plate: 3- tubular graphite heating element:
4 -current terminals; 5-screens; 6-support;
I -pelletized charge; 8-sleeve connector to
the pump; 9 -rubber seals; 10-washer (elec
trical insulator); 11-window.
143
The product consists of sintered porous niobium pellets, which retain
the initial shape of the compacts but with a certain reduction in size.
The pellets a r e forwarded to electron-beam melting. They may a l s o
be sintered in vacuo a t 2300 to 2350°, yielding a ductile metal. In another
technological p r o c e s s , the pellets a r e pulverized and the powder is
p r e s s e d into b a r s and sintered in vacuo. To facilitate the comminution
the pellets a r e hydrogenated (heated in hydrogen a t 360"). The metal
absorbs hydrogen and becomes brittle.
The carbide reduction method h a s the advantage of a high d i r e c t yield
of the useful metal (at l e a s t 9670) and the use of a cheap reducing agent.
The method may also be used f o r the production of tantalum and tantalum-
niobium alloys. It has the disadvantage of requiring the use of high-
temperature vacuum furnaces of complex design.
T h e production of tantalum and niobium from their chlorides has recently attracted attention: this
method is especially suitable when the processing of concentrates results in chlorides a s the end product.
Niobium and tantalum pentachlorides m a y b e reduced by metals (sodium, magnesium) or hydrogen.
These methods are not industrially used as yet, and they will be described only briefly on the basis of
laboratory data / l / .
Reduction of chlorides by magnesium is an exothermic reaction:
2TaC1, + 5Mg + 2Ta + 5MgCI5 + 38 kcal.
T h e heat of reaction is sufficient for a sklf-sustained reaction. T h e reduction is carried out in a steel
crucible containing a charge consisting of T a C l S , magnesium turnings and potassium and sodium chlorides
which act as flux (reducing the reaction rate by decreasing the specific heat effect of the process). T h e
crucible is slowly lowered into a furnace heated t o about 750'. The reaction is rapid. T h e tantalum
particles formed are protected against oxidation by the molten salt mixture consisting of MgCl,, NaCl and KCl.
T h e powder is freed from chlorides by washing with water and dilute hydrochloric a c i d , and is then
rinsed with alcohol and dried in vacuum. T h e yield of tantalum powder is high (about 98%). T h e particle
size of the powder is between 1 and l o p . T h e powder contains 0.1-0.5% Mg, - 0.3% Fe. and -0.1% Ti.
T h e same method may b e used to produce niobium or niobium-tantalum alloys, by simultaneous reduction
of their chlorides.
In order to produce tantalum and niobium powders of higher purity, it is preferable t o reduce the
gaseous chlorides by liquid magnesium, as in the production of zirconium.
Reduction of tantalum and niobium chlorides t o the m e t a l by hydrogen is carried out at temperatures
above 600'. T h e production of niobium has been studied more thoroughly, and the process may be effected
with simultaneous removal of iron chloride from niobium chloride and the separation of tantalum and
niobium. According to one method which has been described, niobium pentachloride is produced by
chlorination of ferroniobium, containing 70% Nb*Ta, 24.7%Fe, 1 . 7 % Mn, 1.5% Al. 1% Ti, 0.3% W ,
0.2% Sn. and 0.2% Cr. A mixture of NbCI,, TaCI,, and FeCIa was condensed after chlorination a t about
1000". In order to separate the iron, the chlorides were distilled in hydrogen at 350". Under these
conditions ferric chloride was reduced to the nonvolatile FeCI,. T h e tungsten present as an impurity was
separated at the same t i m e .
Tantalum was separated from niobium by passing a mixture of the gaseous chlorides and hydrogen through
a rube heated to 500-551)". Under these conditions niobium pentachloride was reduced t o the nonvolatile
NbC1, , while TaCI, was not reduced and was collected by condensation a t low temperatures.
Niobium trichloride is stable in air. It is reduced t o the metal by hydrogen a t 800-1000"; the reduction
144
3 6 . PRODUCTION OF SOLID, DUCTILE TANTALUM
AND NIOBIUM
145
II I I I
resistivity up to 1600". The resistivity increases somewhat between
1600 and 1900" and drops to a minimum a s the temperature is further
increased.
The d e c r e a s e in resistivity at llC0 to 1600" is associated with
incipient sintering and further removal (evaporation) of certain impurities
(alkali metals - sodium and potassium, and their s a l t s ) , a s well as with
incipient elimination of carbon as carbon monoxide, formed by the inter
action of carbon with the oxide film.
A slight i n c r e a s e in the electrical resistivity between 1600 and 1900",
which is accompanied by an increase in the weight of the bar, is probably
caused by some slight absorption of gases (nitrogen, oxygen) which a r e
present in the interior of the vacuum vessel used for the sintering.
Temperature, ' C
I46
I
TABLE 26
Sintering parameters of tantalum bars ( 2 0 X 2 0 x 600 mm) pressed from electrolytic powder
147
b a r s + ; the only difference being that the space under the cover, which
contains the bar, is connected to a vacuum pump. In addition, graphite
and molybdenum sheet s c r e e n s are placed around the b a r in o r d e r to
reduce heat l o s s e s and to provide a m o r e uniform heating of the b a r .
148
FIGURE 11. Diagram of induction vacuum
furnace.
1-window; 2-water-cooled lid: 3-tungsten
cylinder heated by induction current; 4-molyb
denum screens; 5 -quartz tube; 6-inductor
(water-cooled copper tube); I -water-cooled
cylinder: 8 -bar t o b e sintered; 9-molyb
denum screens; 10-graphite support; 11
waler-cooled plate; 12-bus bars (current leads
to the inductor); 13-vacuum seals and elec
trical insulation; 14-rubber rings.
149
insufficient, This is especially true in the case of niobium, whose melting
point is about 500" lower than that of tantalum. Because of the higher
melting point of tantalum, a r c melting of this metal results in a m o r e
complete removal of impurities.
Electron-beam melting, This p r o c e s s , which was developed only
recently, p e r m i t s v e r y high-purity niobium and tantalum ingots to be
produced.
Electron-beam heating of metals i s based on the conversion of most of
the kinetic energy of the electrons into heat upon impact against the metal
surface. A s m a l l e r proportion of the kinetic energy i s converted into
X-ray energy.
The impact of an electron moving with a velocity D, with the body to be
heated r e s u l t s in an energy distribution obeying the equation:
151
Niobium :
ingot diameter, m m 50 75 100
power, kw 30 60 120
Tantalum :
ingot diameter, m m 35 50 75 100
power, kw 30 60 120 240
.
)
152
pump consists of a steel cylinder 1 with an
excentric rotor 2 inside it. The r o t o r c a r r i e s
blades 3 s e t within grooves; the blades p r e s s
(with the aid of springs) against the inner
s u r f a c e of the cylinder. When the r o t o r is
s e t in motion, the blades act as pistons. When
the r o t o r is rotated in a counterclockwise
direction, the a i r is pumped through sleeve
connection 5 and expelled through the escape
valve 4 into the space above the oil. The
cylinder is i m m e r s e d in oil which s e r v e s
a s a lubricant and provides a hermetic s e a l
on the pump.
One- and two-stage pumps of this type
a r e manufactured. The two-stage pump
consists of two pumps connected in s e r i e s
and mounted on a common shaft.
Diffusion pumps. Diffusion pumps
operating on m e r c u r y o r oil vapor, but
based on the s a m e principle, a r e used in
industry. A diagram of a diffusion pump
is shown in Figure 81. The pump consists
of a water-cooled cylindrical s t e e l vessel 1
containing m e r c u r y or oil (which have a low
vapor p r e s s u r e a t ambient temperatures) on
the bottom. A funnel-shaped tube 2 with a
cap 3 suspended over it (thus creating a
FIGURE 82. Two-stage oil diffusion ring-shaped nozzle 4 in the upper p a r t of the
Pump.
I53
FIGURE 83. A typical high-vacuum system.
1-volume to b e evacuated; 2-diffusion pump; 3-vacuum
valve; 4 -vacuum faucets; 5-preliminary vacuum cylinder;
6-mechanical (rotary) pump.
154
-. . . . .. I I,
Chapter IV
TITANIUM
Properties of titanium
Atomic n u m b e r . . ............................. 22
Atomic weight ............................... 41.90
Density, g/cmS .............................. 4.51 (a-titanium)
Melting point, 'C ............................ 1668i 4
Boiling point, " C ............................ - 3300
Superconductance transition temperature. K ...... 0.53
I55
TABLE 27
T h e mechanical properties of titanium
Method of producti6n M
c
and processing g
*" 6
.e
U E Y
IE 00
823 6
�-,A Gi
156
Titanium r e a c t s with nitrogen at temperatures above 600" with the
formation of nitride (TiN) films and solid solutions of nitrogen in titanium.
Titanium nitride is very hard and m e l t s at 2950". Titanium absorbs
hydrogen with the formation of solid solutions and hydrides (TiH and TiHz).
The solubility of hydrogen in a-titanium is about 1%by weight ( o r 3 3 %
(atomic)). Unlike oxygen and nitrogen, the absorbed hydrogen may be
expelled almost quantitatively from titanium by heating in a vacuum at
1000 to 1200".
Titanium r e a c t s with carbon and carbon-containing g a s e s (CO, CHd at
high temperatures (above lOOO"), yielding a hard, refractory carbide
( T i c , mp 3140"). The presence of carbon (as an impurity) has a strong
effect on the mechanical properties of titanium (see Figure 84).
.
"E
"
E
M
3
f?
B
w
#+
z 2
DG
D ai az ~3 LV ~6
-m
$ 0
om5 a010 a m m o
Concentration, % Hydrogen content.%
FIGURE 84. Effect of nitrogen. FIGURE 85. Effect of
oxygen, and carbon on the hardness hydrogen on the impact
of titanium after melting. strength of titanium.
1 --metal containing nitrogen; 2
metal containing oxygen; 3-metal
containing carbon.
157
Titanium dissolves readily in hydrofluoric acid. Titanium is resistant to
cold and hot solutions of alkali hydroxides (at concentrations of up to 20%).
1
TiOl.3,.
The l a t t i c e parameter fluctuates from
a=4.182 ton=4.152 A
158
I
159
which has an extremely high dielectric constant and which is used for the
production of high-capacity electrical condensers.
.
T i t a n i u m s u 1f a t e s Solutions containing mainly titanyl sulfate
TiOSOI a r e formed when titanium dioxide or metatitanic acid a r e dissolved
in sulfuric acid. The normal sulfate Ti(S0J2 has not been isolated from
aqueous solutions, although i t is possible that in strongly acid solutions
p a r t of the titanium is present as Ti& ions. Titanyl sulfate, which
crystallizes from solutions as the dihydrate TiOSO4. 2Hz0, is the only
stable sulfate known.
The stability of titanium sulfate solutions v a r i e s depending on the
concentrations of the titanium and the sulfuric acid. When the solutions
a r e diluted and heated, the sulfates hydrolyze with the precipitation of the
sparingly soluble metatitanic acid:
TiOSO, + 2H,O -f H,TiO, + H,W4.
This reaction is used in the manufacture of titanium dioxide.
The sulfates of tetravalent titanium a r e readily reduced in solution
(for instance, by zinc o r iron) to the trivalent titanium sulfate Ti2(S0J3
o r the acid salt Ti3H(S04),. Ti3+ions a r e violet.
Halides. Titanium combines with halogens yielding volatile higher
halides of the type TiR4 (where R is F, C1, Br, o r I). In addition, there
a r e halides in which titanium is trivalent o r divalent. The properties of
some of the halides a r e listed in Table 29.
TABLE 29
Heat of
Melting
Halide Color
point, " C
Boiling point, 'c 'ormation,
kcallmole
T i t a n i u m c h 1o r i d e s .
Titanium tetrachloride TiCld is the main
starting compound for the production of titanium metal. It is a colorless
liquid with a density of 1.727. The chloride is produced by the effect
of chlorine on titanium dioxide (usually in the presence of carbon) at
700 to 900'.
Titanium chloride hydrolyzes in water o r in moist air, with the
precipitation of metatitanic acid:
TiCI, + 3H,O + H,TiO, + 4HCI.
This explains the appearance of a dense white smoke when titanium
chloride is brought into contact with humid air. Titanium chloride is a
160
volatile substance which boils without decomposing at 136". The heat of
evaporation of TiC1, is - 9 kcal/mole.
Two lower chlorides a r e known: TiC13 and TiC12. They a r e produced
by reduction of TiC1, with hydrogen, titanium, sodium, and other metals,
a t 600 to 800".
The lower chlorides tend to disproportionate, i. e . , to decompose into
compounds in which the valency of titanium is lower and higher than i t s
valency in the starting compound:
above c
+ Tic!,,
4600
2TiCI, 2 TiClz
above 4 7 6 0 ~
2TiC12ZTiCI, + Ti.
TABLE 30
The properties of titanium carbide and nitride
Co111 pou n d
20''
loo'<
162
The use of titanium in shipbuilding and the automobile and r a i l r o a d - c a r
industries is very promising.
In addition to t h e i r high strength, titanium and titanium-based alloys
p o s s e s s an increased resistance to corrosion. A s a result, they find
increasing use in the manufacture of chemical equipment, medical
instruments, etc.
P u r e titanium (in the f o r m of forged p a r t s , ribbons, and wire), is used
in the vacuum-tube industry for the production of anodes, grids, anti-
cathodes, X-ray tubes, and other p a r t s . Titanium powder is used in the
s a m e field a s a g e t t e r (gas absorber).
At present, the leading countries in the production of titanium and
titanium-basedalloys a r e the USA and the USSR. Titanium is aloo
commercially produced in Canada, United Kingdom, Japan, and other
countries. The titanium production in the USA in 1960 to 1 9 6 2 amounted
to about 7000 to 8000 tons p e r year. A s the c o s t of titanium d e c r e a s e s ,
there will be an i n c r e a s e in the demand and production volume of this
metal.
Titanium in s t e e l s . Because of i t s g r e a t affinity f o r oxygen and
nitrogen, titanium is used to deoxidize steel and to f r e e i t from dissolved
nitrogen (titanium f o r m s with nitrogen a nitride insoluble in the steel).
The removal of oxygen and nitrogen from the steel leads to the creation
of a fine, dense s t r u c t u r e of improved mechanical properties. In addition
to the oxygen and nitrogen, titanium also binds sulfur with the formation of
a stable sulfide. This prevents the formation of l a y e r s of the low-melting
eutectic F e - F e S on the grain boundaries of the steel, which causes hot-
brittleness of the steel.
Common brands of s t e e l a r e deoxidized and freed from nitrogen by the
addition of 0.03 to 0,2%titanium, in the form of ferrotitanium (an iron-
titanium alloy containing 18 to 2570 Ti).
Titanium is used a s an additive to manganese, chromium, chromium-
molybdenum, and chromium-nickel steels. The addition of titanium to
chromium-nickel stainless s t e e l s prevents intercrystalline corrosion,
which is caused by the precipitation of chromium carbides on the grain
boundaries (during welding or tempering of the steel).
Titanium in nonferrous alloys. The addition of titanium to copper or
to copper- or aluminum-based alloys improves their physical and
mechanical properties and their resistance to corrosion. Cuprotitanium
( a copper-titanium alloy containing 6 to 1270 Ti) is usdd for the deoxidation
of copper. The strength of aluminum bronze ( a copper-aluminum alloy)
is increased by the addi+:?n of 0.5 to 1.5570 Ti. The titanium i s added in
the form of "alutite">I:, containing 40% Al, 22 to 5070 Ti, 40% Cu.
Titanium in r e f r a c t o r y alloys. Titanium carbide, which is distinguished
by i t s high hardness and refractoriness, is a component of hard titanium-
tungsten tool steels. These alloys contain 1 0 to 40% T i c , 50 to 85% WC,
while the remainder is cobalt.
These alloys a r e effectively employed in the production of steel-cutting
tools, and a r e of g r e a t economic importance.
Titanium carbide is also a component of s c a l e - r e s i s t a n t refractory
alloys which a r e used f o r the production of gas-turbine p a r t s f o r jet
engines .
Titanium dioxide. The most important use of titanium dioxide is the
production of a white pigment - titanium white. Titanium white has good
_______________
* [Russian trade name for a titanium master alloy. 1
163
covering power and is nonpoisonous, which makes it superior to lead
whites. Titanium dioxide is used in painting machine p a r t s and ships,
is added to the rubber compositions which it is d e s i r e d to color white,
is used f o r imparting a dull finish to silk, is added a s an opacifier to
paper pulp, and is used in the production of glazes and enamels.
The total production of titanium pigments in the Western countries was
400,000 and about 1,000,000 tons in 1955 and 1960 respectively.
The high dielectric constants of the various crystalline f o r m s of
titanium dioxide (anatase 78, rutile 173 to 180) and of barium titanate is
the reason f o r the use of these compounds in the production of solid di
e l e c t r i c s for condensers, radio p a r t s , and high-frequency furnaces.
Natural titanium dioxide (rutile) or the technical grade dioxide a r e
used a s components of the coating of electrical welding electrodes.
'0
Se tt %J - - + V
In the E a r t h ' s c r u s t titanium is present
as the dioxide or a s titanates - s a l t s of titanic
acid. The element tends to form complex
anions, comprising niobium, silicon, and
Y p
zirconium. Thus, in addition to the simple
titanates, there a r e complex titanoniobates,
m I \ "
f! TO silicotitanates, etc.
T h e r e a r e about 70 known titanium
I 77,
minerals. The ones of g r e a t e s t commercial
importance a r e rutile, ilmenite, perovskite,
and sphene, which a r e true titanium minerals.
FIGURE 88. The "geochemical R u t i l e , a n a t a s e a n d b r o o k i t e are
star" of titanium, according t o
allotropic modifications of titanium dioxide.
Fersm an.
F e r r o u s iron is present a s an impurity. Ofthe
three minerals, rutile is of com.mercia1 i m
portance. Rutile has adiamond-metallic luster, is transparent, and its color is
red-brown or, occasionally, yellowish, bluish, violet, or black. Its
density is 4.18 t o 4.28.
Large rutile deposits a r e r a r e . Rutile deposits have been found in
Canada, Brazil, and Australia. The l a r g e s t amounts of rutile (up to
164
70 to 80% of the total o r about 70,000 tons) is mined in Australia. Rutile
concentrates contain 90 to 95% Ti%.
I l m e n i t e (iron metatitanate F e T i Q ) is the most common titanium
mineral. It was first found in the Ural mountains, in the llmenskie mountains.
The mineral is brown o r black-brown, its density is 4.56 to 5.21. Its
chemical formula indicates a T i 4 content of 52.6670. However, some
ilmenites contain 60 to 6570TiG. This is attributed to the oxidation of
divalent to the trivalent iron as a result of prolonged weathering.
TABLE 3 1
Approximate composition of some ilmenite concentrates. in 70
165
and magnesium as impurities. Its color is black, red-brown, red, or
yellow. Its density is 3.95 to 4.04. Large deposits of perovskite o r e s
have been found in the USSR. The beneficiation of these o r e s is simple.
With increasing consumption of titanium raw materials, perovskite o r e s
will become one of the most important s o u r c e s of titanium.
-
Sp h e n e o r t i t a n i t e (calcium titanosilicate CaO. Ti@ S i Q ) contains
38.870 Ti&. A fraction of the CaO may be replaced by F e O and MnO. The
m i n e r a l has a yellow color, its density is 3.4 to 3.56. Sphene deposits
have been found in the USA, Canada, Madagascar, and in many regions in
the USSR. The titanium content in sphene is lower than in ilmenite,
rutile o r pervoskite. However, i t s utilization may be profitable under
certain conditions (combined utilization with other o r e s - apatite and
nepheline).
In addition to the raw m a t e r i a l s listed above, complex minerals may
also be used a s a source of titanium. Loparite and some other titanium-
niobium minerals belong to this class.
The T i 4 content in the o r e s processed v a r i e s within wide limits - from
6 to 357'0.
In the beneficiation of ilmenite sands, the heavy minerals, the so-called
schlichs (magnetite, ilmenite, rutile, zircon, and others), a r e extracted
f i r s t , by gravity methods (wet jigging, screw-type separators, tables).
The main methods used for the separation of the schlichs a r e electrostatic
and electromagnetic. If the magnetic permeability of iron i s assigned a
value of 100, that of magnetite would be 40.2, of ilmenite 24.7, of rutile
0.4, and of silicates l e s s than 0.2. Magnetic separation is used to separate
magnetite from ilmenite, and ilmenite f r o m rutile and nonmagnetic heavy
minerals.
In the case of the collective concentrate of heavy minerals obtained from the
sands of the Samotkanskii deposit, electrostatic separationin conjunction with
magnetic separation is successfully employed to produce rutile concentrates
(containingup to 957'0 TiO,), ilmenite concentrates (containing60 to 6270 TiO,)
and zircon concentrates (up to 67.5% ZrG) /27/.
Flotation methods have been recently developed f o r the extraction of
ilmenite.
Magnetic separation is used with success for the beneficiation of
titanomagnetite o r e s impregnated with c o a r s e ilmenite particles (in the
form of c r y s t a l s with a size of 0.1 to 0.2"). By using weak magnetic
fields an iron concentrate (magnetite), an ilmenite concentrate (the weakly:
magnetic fraction), and tailings (the nonmagnetic fraction) a r e obtained.
The approximate composition of ilmenite concentrations is shown in Table 3 1.
Some titanomagnetites cannot be enriched by mechanical processes, a s
they consist of a solid solution of TiO, in Fe304. Metallurgical beneficiation
- smelting in electrical furnaces with the production of pig iron and Ti-
rich slags - may be used in such cases.
1455 166
.. .
this purpose. Hence, the technical grade titanium chloride obtained in
the chlorination of titanium raw m a t e r i a l s is subjected t o further purifica
tion. The purified titanium chloride is a transparent, c o l o r l e s s o r light
y e l l o q liquid.
T i t a n i u m d i o x i d e is produced in different g r a d e s of purity and
s t r u c t u r e , depending on its intended use.
1 n m e n i t e concentrate I
.I J-
Sulfuric acid method for Reductive smelting
Pig iron
By-product
Chlorine
FeSO, * IHZO
7
Chlorination
1
Technical
TiC1,
1
Purification
Hydrolysis or
"burning"
T o the production of
titanium
FIGURE 89. General flow sheet of the production of titanium tetiachloride and titanium
dioxide from ilmenite concentrates.
167
F e r r o t i t a n i u m is produced from ilmenite concentrates by thermal
reduction with aluminum in electrical furnaces. The alloys contain
25 to 30% Ti, 5 to 870Al, 3 to 4.570 Si; the remainder is iron.
v
The industrial methods f o r the production of titanium tetrachlor' e and
titanium dioxide from the main raw material, ilmenite concentrates, are
described below.
A flow sheet of the processing of ilmenite concentrates is shown in
Figure 89. It will be seen that titanium chloride is produced by chlorination
of titanium slags (75 to 8570Ti%) formed in the smelting of ilmenite
concentrates. Two methods a r e used f o r the production of titanium
dioxide: a) direct decomposition of ilmenite concentrates (or titanium
slags) with sulfuric acid followed by precipitation of metatitanic acid from
the sulfate solution; b) hydrolytic decomposition (or "burning") of
titanium tetrachloride.
+ +
3Ti0, C = Ti30, CO
+
FeTi03+ C = Fe + TiO, CO
1
up to - 1240"
The intermediate oxide Ti305and the oxide Ti2% may dissolve the
f e r r o u s oxide and the ilmenite, and form solutions with Ti02 and the
monoxide TiO. These reactions lead to the formation of complex compounds
which crystallize when the slags solidify. The most important of these
substances is a n o s o v i t e , whose composition can be expressed by the
general formula m[(Mg, Fe, Ti)O 2TiO&z[(Al,Fe, Ti)203.Ti02]. The formula
shows that titanium exists in anosovite in various valencies - Tik, Ti3+,
and Ti2+.
168
In addition to anosovite, the lower titanium oxides and the solid solution
of ilmenite in Ti203, the slags may also contain titanium oxycarbonitride
Ti(C, 0, N). This is a solid solution of titanium carbide, nitride, and
monoxide (Tic-TiN-TiO). The
oxycarbonitride i s formed a t tempera
t u r e s above 1600" in the presence of
an e x c e s s of carbon. The lower
oxides, and especially titanium oxy
carbonitride, cause an i n c r e a s e in
the melting point and the viscosity of
the slags. The melting point and
viscosity of the slags may be reduced
by the addition of fluxes such a s
calcium, magnesium, and aluminum
oxides. However, this r e s u l t s in a
.~ _- ." d e c r e a s e of the TiOz content of the
FIGURE 90. Diagram of an electric ar c furnace s l a g s and causes increased consump
for the smelting of slags. tion of chlorine, because of the
1 - electrodes ( t he third electrode fs not shown): formation of calcium, magnesium,
2 -charge; 3-steel jacket: 4-asbestos-cement and aluminum chlorides. Hence, the
sheet: 5 --magnesite grit; 6 --magnesite re tendency i s to c a r r y out the smelting
fractory bricks; I -tapping hole; 8-pig iron; with the addition of a s little flux a s
9 -slag hardened on the walls: 10-slag.
possible, o r altogether without it.
-
The reductive smelting i s c a r r i e d
out in three-phase electric a r c furnaces (5000 to 10,000 kVa), s i m i l a r to
the ones used in the production of ferroalloys such a s ferrochromium.
A diagram of a 5000 kVa furnace is shown in Figure 90 / 251. The bath
is a cylindrical jacket lined with magnesite r e f r a c t o r i e s . The bath walls
have descending steps. The tapping hole is a t a height of 310" above
the lower point of the hearth. In the working zone of the furnace the walls
have a thickness of 690" and the hearth 1380 mm. Above the bath there
a r e three graphitized electrodes (500" in diameter) which a r e held in
cooled clamps and a r e connected to a displacing device.
A l a y e r of slag (about 0.5m thick) is allowed to harden preliminarily on
the lining of the furnace in o r d e r to protect i t against rapid attack by the
corrosive titanium slags. A thick l a y e r of pig iron ( 0 . 5 m o r more) i s
always left on the hearth in o r d e r to prevent attack by the slag.
The smelting i s c a r r i e d out with a covered charge hole, i. e . , with the
a r c covered by the charge (the electrodes a r e immersed deep inside the
charge). Coke or anthracite, crushed to a particle s i z e of 3 to 4 m m , is
used a s the reducing agent. The components of the charge (concentrate,
coal) p a s s from the storage bins through metering trolleys into three
furnace bins which a r e positioned above the furnace. F r o m the bins the
charge on moving trays i s charged into the space between the electrodes
and along the furnace walls.
For the best utilization of the reducing agent and in o r d e r to reduce
dust formation and the consumption of electrical energy, it is most
convenient to use a pelletized charge. However, this causes difficulties
because of the sintering of the pellets and their cementation by the boiling
melt, which reduces the gas-permeability of the charge. A s a result, in
industrial practice the smelting is c a r r i e d out on a mixed charge, i. e . , a
169
When a mixture of ilmenite concentrate and carbon is heated t o 1900-2000' the ilmenite is reduced
yielding titanium carbide and iron (pig iron):
+ + +
FeTiO, 4C -+ Tic Fe XO.
As the pores of the charge contain some nitrogen, the product is, in fact, not the pure carbide but the
carbonitride Ti(C,N) (a solid solution of titanium carbide and nitride) or the oxycarbonitride Ti(Ci,N,O).
T h e formation of such products is associated with the fact that the carbide T i c , the nitride TiN, and the
monoxide T i 0 have crystal lattices of the same type with close values of lattice parameters. These
compounds form a continuous series of solid solutions.
After the cake has been ground, most of the iron is extracted from titanium carbide by electromagnetic
separation. Titanium carbide (or, more accurately, titanium oxycarbonitride) obtained is forwarded to
chlorination.
170
I
T h e reaction of the carbide (or oxycarbonitride) with chlorine is a rapid reaction taking place a t a
relatively low temperature (300-400") and is accompanied by the evolution of a considerable amount of
heat. which is sufficient t o support the Chlorination process. This is the main advantage of the chlorination
of titanium carbide over t h e chlorination of rutile or titanium slags.
/4 /3 /'
a b
FIGURE 91. Diagram of a core furnace:
a-longitudinal section; b -cross section: 1-refractory brick lining;
2 -graphite electrodes; supplying the current to the core: 3-granulated
coke core; 4 -charge positioned around the core; 5-reacted part of the
charge.
It has been reported that in some plants the carbidization of ilmenite is a stage preliminary to the
chlorination. According to o n e report, the carbidization is carried out i n resistance furnaces resembling
the ones used for the production of silicon carbide (carborundum). Such furnace is shown schematically
in Figure 91. It is pan-shaped, and its end walls are connected to current terminal electrodes. A core
consisting of coke particles, which serves as the heating e l e m e n t , is positioned between the electrodes.
T h e charge is poured around the core. T h e charge layers adjacent to the core are heated to the required
temperature (1900 to 2000"). T h e temperature decreases with increasing distance from the core, and no
carbidization rakes place in the outer layers of the charge adjacent to the walls. These layers serve as
thermal insulation, and are returned to be mixed with the fresh charge.
T h e consumption of electrical energy is about 5000 kwh per ton of cake.
After grinding to a particle size of -0.30 m m and magnetic separation, oxycarbonitride of the following
composition is obtained: 68.1% T i , 2% Fe, 9.3'70 C . and 0.470 N.
171
conditions) should proceed mainly according to reaction (2), i. e . , with the
formation of carbon monoxide. Since reaction (2) yields two molecules of
CO while reaction (1) yields one molecule of CQ, increasing the chlorina
tion temperature i n c r e a s e s the consumption of carbon p e r mole of TiC1,
and increases the total volume of the gaseous phase (and thus reduces the
TiC1, concentration in the g a s mixture).
TABLE 32
Equilibrium composition of the gaseous phase i n t h e chlorination of titanium dioxide
by chlorine in t h e presence of carbon
(According to t o d n e v and Pamfilov)
0.370
0.600 0.047 4.9.10-7
172
I
that the active titanium dioxide formed in the reaction is rapidly chlorinated
in the presence of carbon. It is probable that the formation of active
titanium dioxide is the f i r s t stage in the chlorination of T i 2 Q and Ti305
as well.
In addition to titanium oxides, the m a t e r i a l to be chlorinated contains
various amounts of the oxides of iron, manganese, calcium, magnesium,
aluminum, silicon, vanadium, and some other elements. Of these
elements, Fe, Al,Si, V, Cr, Ta, and Nb form volatile chlorides ( s e e p. 177).
F r e e silicon r e a c t s slowly with chlorine in the presence of carbon a t
800 to goOD, but the s i l i c a t e s a r e chlorinated rapidly.
Procedures
* These a r e t h e waste liquors of cellulose pulping. They contain organic substances. T h e concentrated
lyes have binder propertes.
173
The specific output of chlorinators with a stationary layer of pelletized
charge (in the chlorination of titanium slags) is about 7 0 to 100 kg TiC14
p e r s q u a r e m e t e r of furnace c r o s s section p e r hour. The degree of
extraction of titanium f r o m the slags to form the technical grade TiCll is
about 83 to 85%.
The CO : C Q weight r a t i o in the vapor-gas mixture at the exit from
the shaft furnace ranges from 5 : 1 t o 8 : 1 depending on the temperature
conditions and theheight of the charge
layer. In the presence of an inflow of
a i r , the gas mixture becomes explosive.
To prevent the inflow of a i r , an over
p r e s s u r e of 3 to 5 m m H g i s maintained
a t the outlet of the shaft furnace.
In shaft furnaces with a productivity
of 25 tons TiCI4 p e r day, most of the heat
(62.070) comes from the chlorination
reaction. The heat furnished by the
electrical elements amounts to 38% ,
corresponding to a consumption of 7.84 kwh
p e r ton TiC14. The vapor-gas mixture
entrains 66.2% of the heat from the
furnace. Heat l o s s e s through the lining
and the jacket of the furnace account f o r
33.8% of the heat, which i s nearly equal
to the amount supplied by electrical
heating / 3 2 1 .
Chlorination in the melt 1301. This
method f o r the chlorination of titanium
s l a g s was proposed in the USSR by an
engineer, Solyakov. The chlorination i s
c a r r i e d out in a bath of molten potassium
and sodium chlorides, in which the charge
( a mixture of ground slag and coke) is
introduced. The charge may be introduced
through a charging tube in the roof of the
chlorinator, with the aid of dry compressed
a i r o r nitrogen. The chlorine i s fed to
FIGURE 93. Diagram of a three-chamber the lower p a r t of the chlorinator and is
fluidized-bed chlorinator. dispersed through a grid fitted in the
1-stack: 2-overflow, for the passage of interior, or by means of special nozzles.
material from higher t o lower chamber; At 700 to 800" the chlorination in the
3 -dispersing grating; 4-fluidized bed; melt proceeds rapidly. The titanium
5 -storage bin; 6 -collector for residues chloride together with the volatile chloride
(nonchlorinated material and nonvolatile
impurities (SiC14,AlC13, FeCl3) p a s s e s
chlorides).
into a condensation system, while the
0
nonvolatile chlorides (MgC12,CaC12,etc.
. - -. -. )
remain in the melt. After considerable amounts of the nonvolatile
chlorides have accumulated, there i s a change in the properties of the
, melt, and especially in i t s viscosity, which i n t e r f e r e s with its saturation
by chlorine. For this reason, the melt is periodically tapped out of the
chlorinator and a f r e s h batch of the molten s a l t s is added.
174
In the chlorination, the required melt temperature is maintained by
the heat evolved in the exothermic reactions. The excess heat is removed
by means of cooled ducts (made of graphite plates) mounted on the walls
of the chlorinator.
A s compared with the chlorination of pelletized charges in electrical
shaft furnaces, chlorination in m e l t s has the advantages of not requiring
a pelletizing operation, of a higher output of the chlorination apparatus, and
of a lower dust content in the vapor-gas mixture.
175
for the TiC14, and s a n i t a t i o n s c r u b b e r s , f o r the absorption of
the excess chlorine.
A d i a g r a m of the condensation system was shown in Chapter I11
(Figure 57).
The bulk of the dust and the iron chloride a r e trapped in a dust chamber,
with walls cooled by a s t r e a m of a i r passed through the jacket. The gas
temperature at the exit of the dust chamber is maintained a t 160 to 180".
The vapor-gas mixture coming out of the dust chamber s t i l l contains a
substantial amount of dust. A.ccordingly, the condensation of titanium
chloride i s c a r r i e d out m o s t conveniently in s p r a y condensers, in which
cooled titanium tetrachloride is used a s the s p r a y liquid ( s e e Figure 57).
The s l u r r y from the irrigated condenser p a s s e s through an intermediate
collector into a thickener f o r the separation of s l i m e s . P a r t of the
chloride is withdrawn from the intermediate collector and is used for
irrigation. The clarified chloride from the thickener flows into collector
tank f o r technical grade chloride. The thickened pulp is sent to an
evaporator, to remove titanium tetrachloride / 3 0 1 .
The g a s e s issuing from the s p r a y condenser s t i l l contain s o m e titanium
chloride. It may be trapped in tubular condensers cooled by brine (CaC12
solution) a t -10 to 15'. F r o m there the g a s e s p a s s through a sanitation
scrubber sprayed with l i m e water (for the absorption of chlorine and
hydrochloric acid vapors) and a r e vented to the atmosphere.
The pipelines of the condensation system may be occasionally clogged
by a mixture of iron chloride, titanium oxychloride and dioxide. The
l a s t two compounds a r e formed in the reaction of TiC14 with water vapor:
176
Gases (N, C1) and s e v e r a l chlorides S i c 4 , SnC14, VOCIs, CrQC12, AICI3,
titanium oxychloride TiOC12,NbC15, and TaC15 are present in a dissolved
state. The main impurities suspended in titanium chloride are iron
chloride, titanium dioxide, and fine carbon particles. The solubility of
FeC13 in TiCll is very low: 0.04370 at 110" and 0.00370 at 40". The
solubility of A1C13, TaC15, and NbC15 is substantial, as is evident from
Table 33.
TABLE 33
Solubility i n titanium tetrachloride,%/ 19/
f i l l , 10 20 30 40 SO W 70 W W I N
SiC1, , mol. 70
FIGURE 94. Phase diagram of the system FIGURE 95. Solubility of titanium
TiCl,-SiCl,. oxychloride TiOC1, in TiC1,. as a
function of the temperature.
177
178
between the vapors and the descending
phlegm. This is achieved by packing the
column, or by mounting a number of
bubble-cap, sieve, or meshed t r a y s along
i t s height. Each t r a y is covered by a
layer of liquid; the vapors bubble through
the opening in the column and through the
liquid on it. P a r t of the liquid flows down
--
Jrl
column is shown in Figure 96. Continuous
rectification columns have two sections -
a lower (stripping) and an upper (rectify
ing) section. The starting mixture is
U fed to the upper p a r t of the stripping
section. T h e r e it comes into contact with
FIGURE 96. Diagra'm of a continuous the vapors whose initial composition is
rectific.i:ion installation. s i m i l a r to that of the pot residue (HB).
1 -pressure tank with TiCI,; 2-heater; A s a result the L B is extracted (stripped)
3 -stripping section of the rectification from the mixture. In the upper section
column: 4-rectifying section of the the vapors coming from the stripping
column; 5-dephlegmator; 6-boiler; section of the column come into contact
I-condenser; 8-pot residue with the descending liquid (the phlegm)
collector; 9 -distillate collector;
whose initial composition is the same
10-flow-rate adjustment valve for the
distillate.
a s that of the distillate (pure LB). A s a
result the vapors a r e enriched (rectified)
with LB. The vapors used to feed the
column a r e produced by - repeated
evapora
tion of the pot residue (HB) in the evaporator, while the phlegm is produced
by condensation of the vapors in the reflux condenser.
The ratio of the amount of phlegm (the distillate returned to i r r i g a t e the
column) to that of the distillate taken out of the column is known a s the
reflux ratio. It indicates how many kg-moles of distillate m u s t be returned
to the column in o r d e r to collect one kg-mole of distillate.
The purification of titanium tetrachloride by rectification is c a r r i e d
out in stainless s t e e l columns with perforated t r a y s (or t r a y s with slit-
shaped perforations) in two stages. In the f i r s t stage silicon tetrachloride
is removed by maintaining a temperature of 58" in the upper p a r t of the
column (the boiling point of SiC14). The pot residue (Tic14 containing the
high-boiling chlorides and oxychlorides as impurities) e n t e r s the second
column in the top section of which a temperature of 136" (the boiling point
of TiC14) is maintained. The distillate consists of pure titanium chloride.
Impurities such a s chlorides with a higher boiling point (AlOCl, FeC13,
NbC15, e t c . , a s well a s titanium oxychloride TiOC12) a r e separated out.
Purified titanium chloride is a transparent, c o l o r l e s s or slightly
yellowish liquid in which the impurity content is close to the sensitivity
limit of spectroscopic analysis. The concentrations of the most common
impurities such as Al, V, C r , Cu, Si, Mn, Ta, N b , and Zr range from lo-' to
10-37~ (of each impurity).
179
The degree of extraction of titanium (yield of purified chloride from
the technical tetrachloride) purified chloride is 9570.
* T h e active H,SO, is the total amount of che free acid and the acid bound to the titanium sulfates.
180
The bulk of the iron must be removed froin the solution prior to the
hydrolytic precipitation of the titanic acid, in order to prevent contamina
tion of the precipitate.
In o r d e r to remove the iron from the solution, the trivalent iron i s
reduced to the divalent state, and f e r r o u s sulfate i s crystallized ( a s
FeSO4- 7Hz0) by utilizing the considerable d e c r e a s e in the solubility of
FeS04 accompanying the cooling of the solution. The solubility of FeSO,
7 H z 0 in a solution containing 1 2 0 to 1 4 0 g/1 TiOz and 240 g / l i-IzSO, i s
(the values a r e converted to F e concentration in the solution):
Temperature.'C. ........ 30 20 14 10 5 0 -6
...........
Fe content,g/l 88 70 48.5 43 35 25 14
181
Hydrolysis. Metatitanic acid is precipitated from titanium sulfate
solutions by hydrolytic decomposition. The main hydrolysis reaction i s :
TiOSO, f H,O .+ H2Ti03 + H2S0,.
The composition of the solution and the method of hydrolysis used
influence strongly the composition and s t r u c t u r e of the resulting
precipitates. F o r instance, the production of fine titanium dioxide (used
a s a pigment) r e q u i r e s that the hydrolysis be c a r r i e d out in solutions
containing 180 to 2OOgJl Ti& and having an "acid factor" not higher than
2%. F r o m solutions containing up to 1 2 0 to 1 5 0 g / l Ti& metatitanic acid
is obtained which upon ignition yields c o a r s e titanium dioxide.
The specifications with regard to the physical properties of titanium
dioxide used in metallurgy (for the production of hard alloys, nonferrous
metal alloys and titanium metal) are not very s t r i c t , and the main
requirement is that the product be of the required degree of purity.
However, h e r e too (and especially f o r the production of hard alloys) the
product must be of a standard particle size.
Because of i t s l a r g e specific surface, the precipitated metatitanic acid
usually contains adsorbed SO:- ions which a r e strongly bound to the precipitate.
The sulfate groups a r e removed completely only by igniting the precipitate
to 850 to 900".
T h e r e a r e two commercial methods f o r the hydrolysis - the dilution
method, and the nucleation method.
T h e d i l u t i o n m e t h o d . The starting solution is concentrated by
evaporation to a TiO, content of 240 to 260 g / l and an active H2S04content
of 480 to 520 g / l . The concentrated solution i s then diluted under s t r i c t l y
controlled conditions, by the addition of water to an active H2S04content
of 3 8 0 to 400 g/l. Crystallization nuclei a r e formed in the solution during
dilution, and metatitanic acid then precipitates out.
In o r d e r to prevent the premature s t a r t of the hydrolysis the evaporation
is c a r r i e d out at 70 to 75" under reduced p r e s s u r e (60mmHg) in vacuum
evaporators.
The dilution conditions must be s t r i c t l y controlled in o r d e r to obtain
a precipitate with the required structure.
T h e n u c l e a t i o n m e t h o d . In o r d e r to effect the hydrolysis, nuclei,
which a r e prepared in advance in the form of a colloidal solution of
hydrated titanium oxide, a r e introduced into the titanium sulfate solution.
The colloidal solution is obtained by partial neutralization of the titanium
sulfate solution with a sodium hydroxide solution (about 1 0 0 g j l ) to pH = 3 .
The Ti@ content of the solution containing the nuclei i s about 5 0 g j l . The
nuclei a r e added in an amount equal to 1 %of the T i 4 content, the solution
is s t i r r e d , heated to boiling, and allowed to stay at that temperature for
2 to 4 hours. The precipitate contains 95 to 9 6 % of TiO,.
Metallurgical titanium dioxide is usually produced by the nuclei in
troduction method, which is less expensive since it p e r m i t s the use of the
sulfate solutions directly after the filtration (without advance concentration
by evaporation).
The metatitanic acid precipitate produced by one of the above methods i s
separated by filtration, and washed on drum or sheet vacuum filters.
_---------_---
* The "acid factor" is the ratio ofthe concentration of active H,SO, to the concentration of TiO, in
the solution (see footnote. p. 180).
182
The ignition of metatitanic acid. The ignition of the metatitanic acid
precipitate r e s u l t s in the removal of S Q and water and in the formation of
crystalline titanium dioxide. The water is removed at 200 to 300", the
SO, at 500 to 950".
Depending on the temperature, the ignition yields T i Q with the
s t r u c t u r e of anatase ( a t temperatures up to 950") or rutile (above 950").
In the production of metallurgical titanium dioxide the ignition is c a r r i e d
out at 1000 to llOOo, which e n s u r e s complete removal of SQ. The product
is a c o a r s e dioxide with the s t r u c t u r e of rutile.
When using the above technique, the m a t e r i a l s consumed in the
production of one ton of titanium dioxide a r e :
The sulfuric acid method f o r the production of titanium dioxide has the
disadvantage of being expensive, because of the consumption of l a r g e
amounts of sulfuric acid to dissolve the iron in the ilmenite (1.76 kg of
H2S04 is theoretically needed to dissolve one kg of iron).
183
The chloride solutions are hydrolyzed by nucleation (seeding) o r by
the dilution method. The hydrolysis reaction i s :
TiCl, f 3H202 H,TiOs + 4HC1.
When using the seeding method f o r the hydrolysis, the nuclei a r e
pH 2 to 3 and heating to -
precipitated from a p a r t of the solution by neutralization with NaOH to
80". The precipitate is then added to the main
solution which is heated to 100". The hydrolysis is rapid and is completed
within 1 0 minutes with the precipitation of 95 to 96% of the titanium from
the solution.
The hydrolysis may be successfully c a r r i e d out without seeding by
pouring the concentrated solution of titanium chloride into boiling water
and boiling the mixture.
The precipitates formed in the hydrolysis are washed and ignited at
850 to 900" yielding titanium dioxide having the c r y s t a l lattice of rutile.
High-purity titanium dioxide is obtained by using purified titanium chloride.
Hydrolysis in the gaseous phase. The interaction of water vapor and
gaseous TiC14 a t 300 to 400" yields titanium dioxide:
TiCI, + 2H20 + Ti02 + 4HCI.
The hydrolysis is c a r r i e d out a s a continuous p r o c e s s by feeding a
s t r e a m of a i r saturated with water vapor and a s t r e a m of a i r saturated
with titanium tetrachloride vapor into a reaction chamber preheated to
300 to 400". Before entering the chamber each s t r e a m is preheated to
300 to 400", The g a s e s from the hydrolysis chamber a r e fed to a dust-
separation chamber (which is heated to 2 0 0 to 400" in o r d e r to prevent
condensation of the HCl), f o r the separation of the T i Q . The T i 4 may
be entrapped in porous c e r a m i c filters. The main difficulty in the p r o c e s s
l i e s in the selection of a m a t e r i a l resisting the effect of hydrogen chloride
in the presence of water vapor.
Combustion of Tiel4. F r o m the standpoint of chlorine regeneration,
the most expedient method f o r the production of TiOz is by the action of
oxygen on Tiel4:
+
TiCI, 0, + TiOz + X I , .
The reaction takes place a t 900 to 1100" and may be c a r r i e d out a s a
continuous process.
In one variant of the method, the a i r s t r e a m and the T i e l 4 vapors
(which a r e usually diluted with nitrogen) a r e preheated to 1000 to 1100" and
fed to reaction chambers in which the temperature is maintained at 750".
The titanium tetrachloride r e a c t s with the air a t the exit of the g a s -
feeding tubes, with the formation of a yellow-green flame. The gas s t r e a m
entrains the titanium dioxide particles (as smoke) to the dust- separation
chamber. The amounts of g a s introduced p e r l i t e r of reaction-chamber
volume a r e : 0.5 1 TiC14, 0.5 1 nitrogen, and 1 1 air. The selection of
[structural] m a t e r i a l s f o r the above p r o c e s s is e a s i e r than in the c a s e of
gaseous-phase hydrolysis.
184
..... .... .. _ .. _. .
46. PRODUCTION OF METALLIC TITANIUM
The high chemical activity of titanium makes the production of the pure
metal from i t s compounds difficult. At the s a m e time, the modern
specifications f o r titanium require a high-purity metal.
A s mentioned above, oxygen, nitrogen, and carbon present a s i m
purities increase the strength of titanium and reduce i t s ductility. The
presence of hydrogen has little effect on the hardness and strength of
titanium, but causes a s h a r p d e c r e a s e in impact strength. This is
attributed to the precipitation of titanium hydrides on the grain boundaries.
TABLE 34
Free energy changes in the interaction of titanium with
various gases
Reaction
’ 250 c 8000 c
++
Ti 0, = TiO, . . . . .
2Ti CO, = TiO. +
Tic
.........
. . . . . . . . .
-212
-i75
-186.5
-152
i
Ti + -=L
Ne = TiN . . . . . . . . . . . . -73.4 -69
3Ti + 2CO = TiO, + 2TiC . . . . . . . . . -258.2 -217
Ti + 2H.O = TiO, + 2Hz . . . . . . . . . -51 .5 -48.2
Ti + 2C0, TiO, + 2CO . . . . . . . . . -44.7 -48.2
Ti + C = TIC. . . . . . . . . . . . . . -57.2
-
-60
185
of heat, and the reaction is explosive and difficult t o control. Moreover,
the high chemical activity of sodium necessitates special preventive
m e a s u r e s when dealing with it. Investigations have shown, however, that
the difficulties accompanying the reduction of titanium chloride by
sodium have been exaggerated to a g r e a t extent. A l s o , thermal reduction
with sodium has some advantages over the thermal reduction with
magnesium ( s e e below, Section 48).
1I 1
Vacuum distillation
3 . 1 r
Condensate
MgC12, Mg
Electrolysis electrodes
Chlorine Magnesium
Arc melting
1
To the chlorinator,
I
4
Pressure working
for the production
F _.^.
I J
Wastes
Electrolytic refining
FIGURE 91. Flow sheet of commercial methods for the production of titanium from
titanium tetrachloride.
186
helium). A pool of molten magnesium lies at the bottom of the reactor,
and titanium tetrachloride is fed to the apparatus (from a p r e s s u r e tank)
at a controlled r a t e ; the T i C b vapor r e a c t s with the magnesium as
follows:,
TiC14 (gas) + 2Mg (liquid) -+ Ti (solid) + 2MgC12 (liquid).
The reaction is exothermic. The heat evolved (122 kcal p e r mole of
T i c 4 o r 2545 kcal p e r kilo of titanium) suffices to maintain the reaction
without a supply of heat from the outside.
It would seem a t f i r s t sight that the reduction with magnesium should
proceed without difficulties up to the quantitative utilization of the
magnesium, since a t the p r o c e s s temperature (800 to 900O) the p h a s e s should
be separated into l a y e r s : the upper l a y e r consisting of liquid magnesium
(density 1.47g/cm3), the lower of MgC1, (density 1.67g/cm3), and on the
bottom heavier p a r t i c l e s consisting of titanium sponge agglomerates
(density 4.5g/cms). Thus, the liquid magnesium upper l a y e r should be
accessible f o r reaction with the TiC14 vapors throughout the reduction
process.
The true mechanism of the reduction is m o r e complex and has not been
adequately studied. Since this is a batch process, i t s r a t e v a r i e s with the
amount of titanium chloride added into the r e a c t o r and consequently, with
the amount of magnesium consumed and the accumulated reaction products
- titanium sponge and magnesium chloride (slag).
At the s t a r t , when l e s s than 6070 of the TiC1, have been introduced into
the apparatus, the reduction takes place very rapidly. After about 50%
of the magnesium have been consumed the remaining magnesium disappears
a s a one-phase melt, since i t is completely absorbed in the p o r e s of the
sponge; this leads to a d e c r e a s e in the reduction rate. The accumulating
slag (liquid magnesium chloride) also reduces the p r o c e s s rate. One l i t e r
of magnesium yields 0.354 1 of titanium and 3 . 6 8 1 of magnesium chloride.
The level of the magnesium chloride gradually r i s e s , above the sponge
level, when the reaction practically ceases. This is shown by a d e c r e a s e
in the temperature and an i n c r e a s e in the p r e s s u r e in the r e a c t o r (since
the titanium tetrachloride supplied to the r e a c t o r is not consumed).
Magnesium chloride is discharged periodically to b a r e the surface of
the sponge and to utilize m o r e fully the working volume of the reactor.
This results in an i n c r e a s e in the reaction rate.
Rather than charging the apparatus with the whole amount of magnesium
a t the s t a r t , i t is b e t t e r to add the magnesium periodically in o r d e r to
have a uniform-rate process. The periodic addition of magnesium r e s u l t s
in a higher degree of utilization of the magnesium and in the production
of titanium sponge of m o r e uniform composition.
The lower temperature l i m i t of the reduction is the melting point of
MgCl, (714") while the upper limit is 975". Above that temperature the
titanium is fused together with the iron (the melting point of the titanium-
iron eutectic i s 1085"). Moreover, the iron r e a c t s with the Tic14 yielding
lower titanium chlorides and iron titanide (FeTi):
+
Fe + PFiCI, = FeCl, 2TiC&;
+ +
Fe TiCI, = FeCI, TiCI,;
+ +
3Ti 2FeC1, = 2FeTi TiCI,;
187
Fe + PTiCl, = FeTi + TiCI,;
Fe + 4TiC1, = FeTi + BTiCl,.
This may r e s u l t in the contamination of titanium with iron, and to a
rapid failure of the equipment, The temperature range in which the
reduction may be c a r r i e d out is fairly wide (720 to 975'). In practice the
p r o c e s s is c a r r i e d out a t 800 to 900".
The temperature may be maintained by controlling the rate of supply
of titanium tetrachloride. In o r d e r to i n c r e a s e the output of the apparatus,
a p a r t of the excess heat is removed by cooling the outer walls of the
r e a c t o r with cold air.
Lower titanium chlorides a r e formed towards the end of the reduction
when most of the magnesium has been consilmed; some of the reactions
involved a r e :
PTiCI, + Mg = PTiCI, + MgCI,;
TiCI, + Mg = TiCI, + MgCI,;
3TiC1, + Ti = 4TiC1,;
TiCl, +Ti = PTiCI,.
188
Of the total amount of magnesium chloride formed, 75 to 85% is drained
during the reduction and forwarded to electrolysis.
1w3
of the p r o c e s s the liquid magnesium level i s
slightly above the perforated bottom of the pot.
The titanium sponge gradually grows and fills the
pot. The liquid magnesium is absorbed into the
sponge p o r e s from below. Magnesium chloride
FIGURE 99. Diagram of an
insert pot reactor with a
flows through the perforations into the r e t o r t space
perforated bottom. below the pot, and i s discharged.
Reactors with an i n s e r t pot have the following
1-body; 2 -insert pot with
disadvantages: a low coefficient of utilization of
perforated bottom; 3-device
for discharging slag; 4 -
the working volume of the r e t o r t (0.4 to 0.45); a
lid with sleeves for the in ring-shaped gap between the pot and the r e t o r t
troduction of magnesium, which i n t e r f e r e s with heat t r a n s f e r and reduces
chloride, and protective gas. the r a t e of the p r o c e s s ; the complex design of
slag discharge mechanism. A.s a r e s u l t extensive
use is made of r e a c t o r s without an i n s e r t pot, in
which the reaction products (the reaction m a s s ) accumulates inside the
retort. In these r e a c t o r s the slag is discharged by a simple technique
(through a sleeve fitted to the bottom of the r e t o r t ) ; the volume of the
* T h e lid is occasionally welded to the flange of the retorr. At the end of the operation the welded joinr
is cut on a l a t h e and the lid is removed.
189
r e t o r t is utilized m o r e fully (the utilization coefficient is 0.5 to 0.6); the
heat is led off m o r e efficiently through the r e t o r t walls which a r e cooled
by a s t r e a m of a i r , s o that the p r o c e s s r a t e can be increased. The
temperature in r e a c t o r s of this type may be controlled by simply taking
the temperature of the e x t e r i o r of the walls at s e v e r a l height levels of
the retort, without the need f o r inserting thermocouples into the reactor,
The r e a c t o r s a r e heated in electrical or gas-fired furnaces. It must,
however, be borne in mind that heating is required only a t the beginning
of the reaction (heating the installation fusion of the f i r s t batch of
magnesium charged) and a t its end.
190
191
As a result, a new au t o m at i c control system has been recently developed; i t consists in t h e o p t i m u m
p r o g r a m m i n g of t h e supply of TiC1, t6 t h e installation. T h e temperature and pressure are used only as
check, but they do not determine t h e r at e of supply of TiCI, t o t h e installation. T h e reduction t i m e be
comes shorter and enables t h e process t o b e carried out under standard conditions /26/
192
2) the reaction mixture is extracted from the r e t o r t (or the i n s e r t
pot) with the aid of a pneumatic chisel or by drilling - on a lathe and is
charged in a granulated form into a perforated
s t e e l basket which is fitted into the distillation
retort.
The second method p e r m i t s a n i n c r e a s e in
the output of the distillation unit, because of
the m o r e complete filling of the retort. How
ever, the removal of the reaction m a s s and
i t s t r a n s f e r to the basket is accompanied by
the absorption of moisture (by magnesium
chloride), and formation of the nonvolatile
hydroxychloride MgOHCI, which r e s u l t s in an
i n c r e a s e in the oxygen content of the sponge.
For this reason i t is recommended that the
removal and charging of the m a s s be c a r r i e d
out in special d r y rooms, with an atmospheric
moisture content not higher than 0.5% (dew
point -40"). The need for dry rooms i n c r e a s e s
the capital investment. Moreover, the working
conditions in such rooms a r e unfavorable to
the health of the presonnel.
In o r d e r to prevent the r e t o r t walls (which
a r e heated to 900 to 1000") f r o m caving in
FIGURE 102. Thermal purification under the effect of the atmospheric p r e s s u r e ,
of titanium sponge in vacuo, with the furnace jacket i s hermetically sealed and a
out transfer from the reduction "countervacuum" of about 0.2 mm Hg is main
vessel.
tained in it. A vacuum of the o r d e r of
1 -reduction vessel (retort); 2 - Hg i s created inside the r e t o r t with the aid of a
titanium sponge; 3-electrical vacuum system consisting of a r o t a r y and
furnace with a sealed jacket; a diffusion pump ( s e e Figure 83).
4 -sleeve connection t o vacuum
A water-cooled condenser i s fitted to the
system (to produce counter-
vacuum in the furnace); 5 -
flange of the r e t o r t i f the distillation i s c a r r i e d
rubber gaskets; 6-screens; 1 out in the r e t o r t used for the reduction, with
water-cooled condenser; 8 - out transferring the reaction mixture 1 3 3 1 .
condensate - Mg and MgC1,; The r e t o r t is then t r a n s f e r r e d to the distillation
9-sleeve connection to the furnace (Figure 1 0 2 ) . The r e t o r t is allowed
vacuum system. to remain in the furnace for a prolonged time
( 2 0 to 25 hours) a t 900 to 925', and i s then
withdrawn, cooled, t r a n s f e r r e d to a special
room, dismaitled, and the sponge is excavated with pneumatic chisels.
Depending on the degree of adhesion of the bulk of the titanium sponge
(the bloom) i t is withdrawn either in one piece or in a granulated f o r m .
The fraction of the sponge removed from the walls i s collected separately
since it contains l a r g e r amounts of impurities. The sponge particles a r e
crushed to the required particle s i z e f i r s t with a h a m m e r or in a p r e s s ,
and then in a mill.
The refined sponge is characterized by the following approximate
impurity contents: 0.0016% Hz, 0.05% Q, 0.002% Nz, 0.07% C1, 0.08% Mg,
0.13% Fe, 0.03% Si, 0.1% C.
After fusion in an a r c furnace, the hardness of the titanium i s 1 0 0 to
150 kg/mm2.
193
The condensate produced contains magnesium and magnesium chloride,
and is returned to the magnesium production plant.
The vacuum distillation method has the disadvantages of low output, high
consumption of electrical energy (18 to 22 kwh/kg sponge), and the need
f o r a complex equipment to c r e a t e the high vacuum.
194
Sodium Titanium terrachloride
1
1
Fusion
I
Filtration
I
Metering TLI-
Argon
Reduction
1
Metering
-1
Removal of the reaction mass
-
Crushing
Water I
Leaching :
Hydrochloric acid
I
Solution to waste
Fractionation by screening
-.
1
Pelletizing
I
Ingot casting
195
However, i t was found in practice that these disadvantages and difficul
ties can be overcome.
The overall flow sheet of thermal reduction with sodium is shown in
Figure 103.
Reduction
196
The reduction is c a r r i e d out in stainless-steel r e a c t o r s , into which
measured amounts of T i Q and liquid N a are charged simultaneously a t
a ratio close to the stoichiometric (i. e . , 2.06 kgTiCI4 p e r kg Na).
The apparatus is f i r s t evacuated, then filled with argon and heated in a
furnace to about 650 to 700". The reaction is allowed to proceed for a
certain time, during which a liquid melt accumulates in the r e t o r t ; the
furnace is then shut off and the p r o c e s s continues at the expense of the
heat of reaction, which maintains the temperature a t 850 to 880". The
e x c e s s heat is removed by blowing air round the retort.
In the first stage of the reaction, the reduction takes place to a con
siderable extent in the gaseous phase, with the formation of finely-
dispersed titanium and the lower chlorides. The lower chlorides dissolve
in the sodium chloride, and a r e reduced by the sodium present in the
melt, yielding titanium c r y s t a l s which a r e heavier and thus settle to the
bottom. At the end of the p r o c e s s the furnace is turned on and the r e t o r t
is maintained a t 950 to 970" in o r d e r to effect quantitative reduction of
the lower chlorides and to cause consolidation of the metal particles.
In one plant in the USA (in the city of Ashtabula) the p r o c e s s i s c a r r i e d
out in r e a c t o r s made of two steel l a y e r s (the inner l a y e r i s high-carbon
steel, the outer is stainless steel). The r e t o r t h a s a diameter of 1.5 m,
a height of 4.2 m, and a wall thickness of 2 5 mm. Electrolytic sodium i s
used a s the reducing agent. It is supplied in metallic drums, under a
protective layer of paraffin, o r in tank c a r s in an argon atmosphere. In
o r d e r to pump the sodium out of the tank c a r i t is melted with the aid of
oil (heated to 120") circulating within a coil fitted in the tank c a r . The
sodium i s purified by filtration through 2 0 l a y e r s of a 0.044" nickel gauze
and a porous metallic f i l t e r with 2 0 b holes. The purified sodium contains
not m o r e than 0.0570 impurities. The sodium and titanium chlorides a r e
continuously metered into the r e a c t o r for 5 to 7 hours. In o r d e r to
complete the reaction the furnace is turned on and the r e a c t o r is allowed
to remain at about 1000" for 4 to 6 hours, the r e a c t o r i s then cooled f o r
2 to 4 hours and transferred to a "nest" in which it i s cooled by a forced
flow of a i r .
The r a t e of supply of TiC1, to the r e a c t o r is on the average 400 kg/m2. h r ,
which is twice that used in the thermal reduction by magnesium. Each
reduction cycle yields about one ton of titanium.
I97
1455
198
49. R E D U C T I O N O F TITANIUM DIOXIDE
TABLE 35
Free energy of formation of some m e t a l l i c oxides
A F , kca' [-atom 0
Oxide
25'C 1000°C
1
- AlZOs ............ -125 -100
3
Reduction by calcium
199
I!. .................................
...
.I._ ..........................-.-,...,. .....
111...1..--...1 I I I , ................
The reduction is c a r r i e d out in argon atmosphere at 1000 t o 1100". At
that temperature the calcium is liquid, and a fraction of it is in the gaseous
stage (the vapor p r e s s u r e of calcium at 1000" is l l m m H g ) , which e n s u r e s
good contact between the calcium and the titanium dioxide. The calcium
used in the reduction must be preliminarily purified by distillation and
f r e e f r o m nitrogen and carbon (in o r d e r to prevent contamination of
titanium by t h e s e elements).
The reduction yields fine grained titanium (particle s i z e 2 to 3 ~ since )
the presence of s t r a t a of r e f r a c t o r y calcium oxide i n t e r f e r e s with the
growth of titanium particles. The growth of the p a r t i c l e s is favored by
the addition of CaClz (about one mole of CaClz p e r 2 moles of CaO), which
f o r m s a liquid phase.
calcium.
200
The reduction product is crushed, treated f i r s t with a l a r g e volume of
water and then with dilute acids (acetic, nitric, or hydrochloric), washed
with water, and vacuum-dried a t 40 to 50".
In o r d e r to reduce the oxygen concentration in the powder to about 0.270
it is n e c e s s a r y to c a r r y out a second reduction of the powder by calcium.
Even after the second reduction the metal is characterized by g r e a t e r
h a r d n e s s and lower ductility a s compared with titanium produced by the
reduction of TiC1,; this is a result of i t s higher oxygen and nitrogen
contents.
Titanium produced by t h e r m a l reduction with calcium has the following
composition: 98.5 to 99.070 Ti, 0.03 to 0.1570 N, 0.2 to 0.4% 0, 0.01 to
0.03% H, 0.1 to 0.270 Si, 0.01 to 0.0570 C, 0.10 to 0.2570 Fe, 0.05 to 0.1570
Al, 0.1 t o 0.370Ca, < 0.0370 Mg, 0.01 t o 0.1%. Cu.
Titanium powders produced by the reduction of T i Q with calcium a r e
used f o r the manufacturing of solid titanium b a r s and products by
powder metallurgy methods and for the production of alloys of titanium
and other metals. Moreover, they may be used a s the starting m a t e r i a l
for the production of high-purity titanium by t h e r m a l dissociation of
titanium iodide or by electrolytic refining ( s e e below).
20 1
The reduction p r o c e s s is c a r r i e d out in equipment made of refractory
steel, which is charged with the pelletized titanium dioxide - calcium
hydride mixture. The air in the r e a c t o r is evacuated and the reactor is
filled with dried hydrogen and heated to 900 to 1100". The powder
produced is washed with water and dilute acids (hydrochloric or acetic)
to remove the excess calcium and calcium oxide.
Powdered titanium hydride is mainly used in the powder metallurgy
of titanium.
Ti - 2e-+Tiz+,
Ti2+ -e --f Ti3+.
+
Ti3+ e + Tizf,
Tiz+ + 2e + Ti.
202
dissolution of titanium the oxygen present a s impurity remains in the anodic
slag a s titanium oxides (Ti@, TiZQ). The carbon in a f r e e state remains
on the surface of the electrolyte o r in the form of carbide in the anodic
residue; the nitrogen remains in the anodic residue a s nitride, or is
evolved as gas at the anode; silicon is evolved with the g a s e s a s SiCI,;
the iron and the nobler metals (Ni, Cu, Sn) accumulate in the anodic residue.
The anodic dissolution potentials of s e v e r a l alloying additives (AI, Cr, Mn,
V) are close to that of titanium. Thus, they p a s s into the molten chloride
and, when their concentration reaches a certain level, they may be
deposited on the cathode together with the titanium.
The refining conditions depend on the content of impurities. When
various elements a r e present together, they have a combined effect on the
anodic dissolution. The removal of impurities such a s 0, N, C, Fe, and Si
and of the alloying additives Mo and Sn is easiest. It is m o r e difficult to
remove V, Al, and Mn present a s impurities. These elements may be
removed by twice-repeated refining.
Electrolyzers with packed anodes a r e the ones most often used in
electrolytic refining. A diagram of such electrolyzer is shown in
Figure 105. The metal to be refined (in the form of turnings or granules,
2 to 3 m m in size) is placed in a perforated steel basket which s e r v e s as
the anode. When a deposit of titanium accumulates on the cathode, the
cathode is raised into the upper chamber, a discharge pallet is placed
underneath and the deposit i s cut out with a special knife.
203
The electrolysis is c a r r i e d out a t 850" in an argon atmosphere, a t an
anodic c u r r e n t density of 0.1 to 0.5 amp/cm2 (depending on the composition
of the titanium to be refined) and a starting cathodic c u r r e n t density of 0.5
to 1.5 amp/cm2. A c o a r s e crystalline deposit of titanium f o r m s on the
cathode. The c u r r e n t efficiency is 90% and higher.
The use of electrolytic refining for the purification of crude titanium
produced by d i r e c t reduction of titanium slags (e. g., by aluminum o r
magnesium) is of g r e a t interest. Research on the subject is now in
progress .
Equipment
204
Titanium wire 3 to 4 m m in diameter (in the form of U-shaped loops)
is stretched with the aid of tungsten hooks fastened to steatite insulators.
The total length of the filament is about 11 meters. The ends of the
filament a r e fastened t o molybdenum terminals.
The airtight lid is fitted with a socket holder f o r the g l a s s ampoule
containing the iodine, and with sleeve connections to the vacuum pump.
The r e t o r t is placed in a thermostat which maintains the temperature of
the titanium undergoing purification a t the desired level (between 1 0 0 and
200"). The r e a c t o r is first evacuated to a residual p r e s s u r e of 2 -
5- Hg. The r e a c t o r is then disconnected from the evacuation
system and the iodine is introduced. In o r d e r to introduce the iodine, a
special device is used to break the drawn-out tip of the ampoule.
205
Electric c u r r e n t is then applied to the filament. The amount of iodine
introduced into the r e a c t o r is determined by the optimum p r e s s u r e of the
iodine vapor. In practice, the amount of iodine added is 7 to 10% of the
amount of titanium to be refined.
The installation is designed to produce 24 kg of refined titanium p e r
working cycle, or 1 0 kg p e r day.
Procedure
24
22
20
18
16
-> I4
a
l
M
u
0 It
IO
8
6
0 IW ZW 3m 4cM 5110
T i 4 pressure, m m Hg Current. a m p
FIGURE 107. Rateof deposition of titanium a t a FIGURE 108. Voltage-current curves for the de
filament temperature of 1500", as a function of position of iodide titanium a t various deposition
the vapor pressure of Tire temperatures.
206
vaporization of titanium is observed at higher temperatures. The filament
temperature is usually maintained at 1300 to 1400O in o r d e r to prevent the
fusion of the filament.
One s e r i o u s difficulty is to maintain a constant temperature on the
filament surface during the accumulation of the deposit. Neglecting the
heat l o s s e s by heat conductance through the electrodes and by convection
(which are relatively small), we may assume that the electrical energy
supplied s e r v e s to compensate f o r the heat lost by radiation emitted by
the surface of the filament on which the titanium is deposited. In o r d e r to
maintain the temperature of the filament constant a s its diameter grows,
i t is necessary that the c u r r e n t intensity and the voltage be s o adjusted
that the power radiating from unit incandescent surface remains constant.
The following equation must then be satisfied:
I.!? = Y = const,
where
I is the c u r r e n t intensity;
E is the voltage,
W
---C=const.
207
l1ll1l1Il l l
Titanium Titanium
Iodide sponge (reduced Iodide ,ponge (reduced
Element Element
titanium with titanium with
magnesium) magnesium)
Carbon -
0.01 0.03 0.01-0.03 Magnesium 0.0015- 0.002 0.04- 0.12
Oxygen 0.005-0.01 0.05-0.15 Manganese 0.005-0.013 0.03-0.06
Nitrogen 0.001 -0.004 0.01 -0.05 Molybdenum 0.0015 -
Aluminum 0.013- 0.05 < 0.005 Nickel 0.003
Copper 0.0015- 0.002 < 0.03 Silicon 0.03 < 0.01
Iron 0.0035- 0.025 0.03-0.2 Tin 0.001-0.01 < 0.03
208
Various types of furnaces with consumable electrodes a r e used f o r the
melting of titanium. In the most widely used @pes of furnaces the
consumable electrode of the desired length is
prepared outside the furnace and is then
inserted in the furnace which contains a long,
water-cooled copper mold (Figure 109). The
consumable electrode is welded to the electrode
holder ( a r m ) which s e r v e s to supply the
c u r r e n t to the electrode and to move it during
the melting.
As a safety precaution, a r c furnaces a r e
mounted in a chamber with thick reinforced
concrete walls and ceilings. The control
panel is located behind a concrete wall.
The consumable electrodes a r e prepared
by p r e s s i n g titanium sponge (particle s i z e
5 to 30") o r powder in hydraulic p r e s s e s
fitted with s t e e l dies, under p r e s s u r e s of
2 to 4 tons/cm2. In most c a s e s the titanium
i s p r e s s e d into cylindrical pellets of s m a l l
height (diameter 500") which a r e then
welded together in an argon a r c into electrodes
of the desired length. In some c a s e s the
pellets a r e joined together to form the
FIGURE 109. Diagram of electric-
arc furnace with consumable elec
consumable electrode by sintering with the
trodes. aid of contact heating in the melting furnace
itself. To accomplish this, the pellets a r e
1-current leads t o the mold: 2
put in the furnace one over the other. The
sleeve connection to vacuum: 3
flexible bus bar supplying the
furnace is evacuated, the electrode holder
current to the electrode: 4-de is welded to the upper pellet and a p r e s s u r e
vice for lifting the electrode: of about one ton i s applied to the pellet column
5-electrode holder (arm): 6 by means of the feed mechanism. The current
vacuum seals: I-lid: 8-furnace from the generators used f o r the melting i s
body: +water inlet and outlet then turned on. The contact s i t e s between the
tubes: 10-rubber seals: l l - c o n
pellets, which have a high resistance, a r e
sumable titanium electrode: 12
cooled copper mold: 13-water
rapidly heated to about 800". At this tempera
jacket: 14-ingot: 15-cooled ture and p r e s s u r e the pellets rapidly s i n t e r
bottom of the mold. and cohere. The sintering i s accompanied
by partial degassing of the pellets (i. e . ,
elimination of dissolved hydrogen, magnesium, and other volatile i m
purities).
In a vacuum of about 0.1 to 0.01 m m Eg, an a r c may be formed because
of the presence (in the narrow gap between the consumable electrode and
the melt) of ionized vapors of titanium and gaseous impurities and metals
evolved during the melting (sodium, magnesium).
It is recommended that the melting be c a r r i e d at a residual p r e s s u r e
(in the furnace chamber, i. e . , in the space above the melting crucible)
of 0.01 m m Hg. Under these conditions the actual p r e s s u r e in the crucible
( a t the molten metal level) is always higher and attains about 0.1 mmHg.
The selection of vacuum pumps for the a r c furnace will be determined
by the necessity for evacuating the g a s e s evolved and f o r maintaining a
certain vacuum. The magnitude of the gas flow created during the melting
209
depends on the concentration of volatile substances in the sponge and on
the melting rate. Thus, at a melting r a t e of 5 kg/min the gas flow i s :
... .... 0.25
Concentration of gases in the sponge, I/kg 1 2
Gas flow*. mm Hg l/sec.. ..................... 15.9 63.4 126.8
210
Since only a s m a l l amount of the metal is in the molten s t a t e during
a r c melting, i t is difficult to e n s u r e the uniformity of the alloy. It is
advisable to mix the alloying additive with the sponge before p r e s s i n g the
consumable electrode. A less satisfactory method consists in a uniform
distribution over the melting zone of pellets made of the alloying additives.
In all these methods, the production of a uniform alloy r e q u i r e s a
second melting, in which the ingot produced by the first melting is used
a s the consumable electrode.
21 1
The final porosity of articles made of titanium hydride does not exceed
270, the linear contraction being 1 2 to 14%. Thus, the density of a r t i c l e s
made of p r e s s e d titanium hydride (density when p r e s s e d 3.2 to 3.8 g/cm3)
sintered f o r 8 hours a t 1300O i n c r e a s e s to 4.45g/cm3. Because of the
l a r g e contraction during the sintering, hydride powders cannot be used f o r
the production of standard s i z e a r t i c l e s ,
The l i n e a r contraction during sintering (for 15 hours a t 1000" and
4 hours a t 1200O) of c o a r s e titanium powders produced by the grinding of
titanium sponge is only 4 to 570. The production of solid m e t a l involves
intermediate forging (compression) of the m e t a l followed .by a second
sintering.
One of the advantages of powder metallurgy is that the resulting alloys
a r e uniform. The pulverized alloying constituents must be throughly
mixed before p r e s s i n g with titanium or titanium hydride powder.
Large b a r s weighing 50 to 6 0 kg may be sintered in vacuum induction
furnaces.
In addition to the conventional powder metallurgy method, another method
used in titanium metallurgy consists of combined pressing, sintering, and
mechanical treatment under p r e s s u r e . A description of the method is
given below. The titanium powder i s tightly packed in a steel tube, the
tube ends a r e sealed by welding, and the tube with the powder is hot-rolled
at 900". The s t e e l shell protects the metal against oxidation. After the
rolling the s t e e l shell is cut and is readily separated from the titanium
sheet a s a result of the formation of a thin intermediate l a y e r of a titanium-
i r o n alloy.
The mechanical properties of titanium produced by powder metallurgy
techniques a r e virtually the s a m e a s those of arc-melted titanium. How
ever, powder metallurgy cannot supersede the melting method because of
the limited dimensions of the bars. The powder metallurgy method is m o r e
suited to m a s s production of s m a l l sized titanium and titanium-alloy
a r t i c l e s . Its advantages a r e : the economical utilization of the metal
(finishing operations a r e few), production of a r t i c l e s of any desired density,
and the production of uniform alloys.
212
Chapter V
ZIRCONIUM
213
TABLE 37
Physical properties of zirconium and hafnium
Atomic number 40 72
Atomic weight 91.22 178.6
Density, g/cmS 6.52 13.3
(for Q zr) (for a - H D
Melting point, "C 1852 i 10" 2130 i 15:
Boiling point. " C - 3600 - 5400
Transition temperature to superconducting state, 'K 0.7 0.35
Specific heat, cal/g, ' C
25 -100' 0.066 0.035
1000-1500' 0.113 -
Linear expansion coefficient 8 9 - lo-' 5 9 . 10-1
at 20-7OO'C) (at 0-10OO'C)
Total radiation (watt/cm2) at various temperatures,
"C
927 2.03
1127 5.40
1227 7.20
1327 10.0
Electrical resistivity, o h m . cm, at 'C:
20 41 *
800 143.
Thermal neutron capture cross section, barns 0.18* 0.02
_ _ . -
Zirconium i s stable in air. When the solid metal is heated to 400 to 600",
it i s coated with an oxide film, but above 800" i t becomes rapidly oxidized
with the formation of the higher oxide Zr02. Zirconium powder i s oxidized
in the a i r with spontaneous ignition a t 180 to 285" (depending on the particle
size).
Zirconium actively absorbs hydrogen at temperatures a s low a s 300 to
400°, with the formation of a solid solution of hydrogen in zirconium and of
zirconium hydrides (ZrzH, ZrH, and ZrHz). The hydrogen can be expelled
from the metal by heating to 1200 to 1300" in a high vacuum.
Above 900" zirconium rapidly absorbs nitrogen and r e a c t s vigorously
with carbon monoxide. Zirconium forms very hard and r e f r a c t o r y
compounds with nitrogen and carbon - the nitride ZrN (mp 2930") and the
carbide Z r C (mp 3530").
In contrast to hydrogen, oxygen and nitrogen cannot be removed from
zirconium by heating in vacuo,
The corrosion resistance of zirconium is superior to that of titanium
and approaches that of tantalum and niobium. Thus, below 100" zirconium
r e s i s t s hydrochloric and n i t r i c acids of all concentrations and of sulfuric
acid of concentrations up to 50%.
Zirconium is r e s i s t a n t to aqua r e g i a a t room temperature, dissolves
in hydrofluoric acid and in concentrated sulfuric acid a t loo", but is not
dissolved by aqueous solutions of alkali hydroxides.
214
Chemical properties / 171
Compounds of tetravalent zirconium a r e the only ones of practical
importance; lower valency compounds a r e unstable and have been in
adequately studied.
Zirconium dioxide. Zirconium dioxide Z r Q is produced by ignition of
zirconium hydroxide o r other zirconium s a l t s - sulfates, nitrates.
The pure dioxide is white. After the ignition, Z r Q is virtually insoluble
in hydrochloric, nitric and dilute sulfuric acids. The dioxide dissolves in
hydrofluoric and in hot concentrated sulfuric acids.
Zirconium dioxide is very stable and has refractory properties. The
heat of formation of Z r Q is 259.5 kcallmole, its melting point is 2700 to
2900". Z r Q exists in s e v e r a l crystalline modifications. The monoclinic
form is stable up to 1000 to llOOo, the tetragonal at 1100 to 1900", and
the trigonal above 1900°.
Zirconium dioxide is amphoteric. The fusion of ZrOz with alkalies
yields zirconates ( s a l t s of zirconic acid), while the dissolution of the di
oxide in acids r e s u l t s in the formation of the respective s a l t s - zirconium
sulfates, chlorides and nitrates. In aqueous solution these s a l t s hydrolyze
with the formation of zirconyl (ZrO") s a l t s , e. g. :
ZrC1, + H,O = ZrOCI, + 2HC1
Zirconates. Salts of metazirconic ( H 2 Z r Q )and orthozirconic ( H 2 Z r 0 4 )
acids a r e known. Most zirconates a r e insoluble in water.
S o d i u m a n d p o t a s s i u m z i r c o n a t e s a r e produced by the fusion
of Z r Q with alkali hydroxides, sodium carbonate or potassium carbonate.
They a r e sparingly soluble in water, but undergo hydrolytic decomposition
by reactions of the type:
+
Na, ZrOs $- 2H,O 2 ZrO (OH), 2NaOH.
C a l c i u m a n d m a g n e s t u m z i r c o n a t e s (CaZr-03 and MgZr03)
a r e produced by heating a mixture of Z r Q with CaO or MgO powders to
1400 to 1600". The melting points of calcium and magnesium zirconates
a r e 2 3 5 0 and 2150" respectively.
Sulfates. The anhydrous zirconium sulfate Z r (Sod2 ( a white crystalline
substance) is formed when ZrOz i s heated with concentrated sulfuric acid.
Its dissolution in water is accompanied by hydrolysis and complex-forma
tion:
+ +
Zr (So,), HzO 2 (ZrO) SO4 H,S04,
+
ZrO (SO,) HzS04ZH, [ZrO (SO,),] - zirconylsulfuric acid.
Upon evaporation of the sulfuric acid solution, zirconylsulfuric acid
crystallizes out a s the trihydrate H,[Zro(SO~,]* 3&0.
The formula of the normal zirconium sulfate Zr( S04)2 4Hzo is -
occasionally incorrectly ascribed to the trihydrate; from the standpoint
of chemical composition both formulas a r e identical.
When a weakly acid solution containing zirconyl sulfate is boiled,
hydrolysis takes place with the formation of sparingly soluble basic
zirconium sulfates whose composition can be expressed by the general
formula xZrOp. ySOs zHnO.
In the basic sulfates the m o l a r r a t i o Z r Q : SO, > 1.
Halides. Z i r c o n i u m c h l o r i d e a n d o x y c h l o r i d e . Zirconium
tetrachloride ZrCI, is one of the starting m a t e r i a l s for the production of
zirconium metal. The chloride is formed a s a r e s u l t of the high-tempera
t u r e interaction of chlorine with a mixture of zirconium dioxide and carbon
or zirconium carbide:
+ +
210, 2C 2C1, = ZrCI, +
2CO;
+
ZrC 2C1, = ZrC1, + C.
The chloride is a white crystalline powder which sublimes a t low
temperatures. The vapor p r e s s u r e over the solid s a l t is 1 atm at 330".
The s a l t m e l t s a t 437" under a p r e s s u r e of 18.7 atm. The heat of
formation of solid Z r C , is 2 3 1 . 9 kcal/mole, the heat of sublimation i s
28.5 kcal/mole. Zirconium chloride is very hygroscopic and is hydrolyzed
in aqueous solutions (and in humid a i r ) with the formation of zirconium
oxychloride ZrOCla (zirconyl chloride).
Zirconium oxychloride is stable in aqueous solutions. It crystallizes
out a s the crystalline hydrate ZrOClz' 8 H z 0 . The c r y s t a l s a r e in the
shape of tetragonal p r i s m s with well-defined cleavage. The s a l t i s readily
soluble in water and sparingly soluble in concentrated hydrochloric acid
( s e e Figure 1 1 3 ) .
ZrOC12. 8 H 2 0 may be dried in a i r without decomposition. In dry a i r
the hydrate l o s e s some water and is converted into the dihydrate ZrOClz
2 H z 0 . Quantitative dehydration takes place at 180 to ZOO". The heat
of formation of anhydrous ZrOCl2 i s 246 kcal/mole.
Z i r c o n i u m b r o m i d e a n d i o d i d e . F r o m the standpoint of their
properties Z r Br, and ZrI, resemble zirconium chloride. Like the chloride
they a r e readily sublimed. The vapor p r e s s u r e over the solid s a l t s
attains one atmosphere a t 3 5 7 " for ZrBr, and a t 4 3 0 " for ZrI,. At elevated
p r e s s u r e s these s a l t s melt a t 450 and 499" respectively. Zirconium iodide
is used to p r e p a r e high-purity zirconium metal by the thermal dissociation
method.
Z i r c o n i u m f l u o r i d e s a n d c o m p l e x f l u o r i d e s . Zirconium
fluoride ZrF, i s formed by the interaction between gaseous hydrogen
fluoride and zirconium dioxide at 500 to 600°, or when zirconium dioxide
is heated with acid ammonium fluoride.
210, + 4HF ZrF, + 2H20;
=
ZrO, + 2NH,HF, = ZrF, + 2NH, + 2H,O.
Zirconium fluoride is a white substance, which boils at 908". The heat
of formation of ZrFl is 456 kcal/mole.
The crystalline hydrate Z r F 4 . H 2 0 is precipitated on the addition of
hydrofluoric acid to a solution of zirconium chloride or sulfate. The
fluoride dissolves in the presence of excess hydrofluoric acid; this is
due to the formation of the complex acid:
ZrF, + 2HF H, [ZrF,].
Similarly, the dissolution of zirconium dioxide (or hydroxide) in
hydrofluoric acid is accompanied by the reaction
+
210, 6HF Z H,[ZrF,] + 2H,0.
Complex s a l t s - fluozirconates K2ZrF, and Na2ZrF6- a r e formed in
solutions containing potassium and sodium ions.
216
Potassium' fluozirconate is of importance in technology. This s a l t
readily crystallizes out of solutions a s colorless rhombic prisms. The
solubility of this s a l t is strongly affected by the temperature ( s e e Table40),
so that i t can be purified by recrystallization. The fluozirconate is stable
in the a i r and i s not hygroscopic. The s a l t is used a s starting m a t e r i a l
f o r the production of metallic zirconium.
Nitrates. Zirconium hydroxide dissolves in n i t r i c acid. Depending on
the concentration of the nitric acid, the s a l t crystallizing out of solution
i s either the normal nitrate Z r ( N Q ) 4 5H20 o r zirconyl nitrate ZrO(N03),.
.
2Hz0 and dizirconyl nitrate Zr,Q(NQ), 2H20. In manufacturing
p r o c e s s e s zirconium is occasionally isolated a s zirconyl nitrate.
Phosphates. On the addition of orthophosphoric acid or sodium phos
phate t o an acid solution of a zirconium compound, a white precipitate
of the phosphate ZrHz(P04), s e p a r a t e s out; it is converted upon ignition
into the pyrophosphate ZrP20,. Zirconium phosphate is insoluble in
water and in sulfuric and hydrochloric acids of concentrations up to 20%.
This makes it possible to s e p a r a t e zirconium f r o m almost all other
elements.
Zirconium carbide and nitride. The carbide Z r C and nitride ZrN a r e
very hard, refractory substances wit'n metallic properties (metallic
l u s t e r , electrical conductivity). The melting point of the carbide i s
3530", that of the nitride i s 2930". The two compounds have the s a m e
c r y s t a l lattice (f. c. c. ) and form a continuous s e r i e s of solid solutions.
The heat of formation of ZrC i s 48.2 kcal/mole, that of ZrN is 82.2 kcal/
mole.
The carbide is produced by heating a mixture of zirconium dioxide and
carbon at 1900 to 2000", through the reaction:
ZrOz + 3C = ZrC + 2CO.
If the process is c a r r i e d out in the presence of nitrogen, the carbide
produced always contains some nitrogen. Zirconium nitride is formed by
the reaction of nitrogen with zirconium powder a t 800 to 1000" o r between
gaseous ammonia and zirconium tetrachloride.
Uses of zirconium / I S /
217
zirconium a s a s t r u c t u r a l m a t e r i a l in nuclear technology is explained by
its low t h e r m a l neutron capture c r o s s section (about 0.2 barn), i t s high
r e s i s t a n c e to corrosion and favorable mechanical properties.
The low t h e r m a l neutron capture c r o s s section of zirconium was not
at f i r s t evident, since zirconium usually contains 0.5 t o 370 of hafnium
which h a s a much higher capture c r o s s section (about 115 barns).
Accordingly, before zirconium could be used in nuclear technology it
was n e c e s s a r y to solve the difficult problem of the separation of zirconium
f r o m i t s chemical analog - hafnium,
Zirconium and i t s alloys a r e used in nuclear power r e a c t o r s which
operate a t temperatures which a r e too high for the use of aluminum to
be possible. Zirconium is used to make protective shells for uranium
fuel elements, coolant circulation tubes, and other s t r u c t u r a l p a r t s .
The heat resistance of zirconium and i t s resistance to the effect of water
and s t e a m may be improved by the addition of tin (1.4 to 1.670) a s well a s
of s m a l l amounts of iron (0.1 to 0.1570), chromium (0.08 to 0.127’0)~and
nickel (0.04 to 0.0670). The alloy containing these additives is known a s
“Zircalloy-2” /1, 2, 1 6 / .
Like molybdenum, zirconium is used f o r alloying uranium used a s
nuclear fuel; the addition of zirconium improves the mechanical strength
and corrosion resistance of the uranium.
Electronics. The use of zirconium in vacuum tubes i s due to i t s ability
to absorb gases, and s o to maintain a high vacuum in electronic
instruments. F o r this purpose zirconium powder of ductile zirconium
is applied to the surfaces of anodes, grids, and other heated p a r t s of
vacuum tubes. The application of zirconium to the surface of g r i d s in
radio tubes s u p p r e s s e s grid emission.
Zirconium foil is used in X-ray tubes with molybdenum anticathodes.
The foil s e r v e s a s f i l t e r which r e n d e r s the radiation m o r e monochromatic.
Pyrotechnics and manufacture of munitions. Zirconium powder, which
h a s a low ignition temperature and a high burning rate, is used in this
branch of technology.
Zirconium powder is used a s the ignitor in mixtures f o r detonator caps,
and in mixtures for photographic flash bulbs. Mixtures of zirconium
powder with oxidants (barium nitrate or potassium chlorate) a r e used a s
smokeless powder.
Machine building. Until recently ductile zirconium and i t s alloys were
used mainly in nuclear technology. However, with the further i n c r e a s e in
i t s production volume and decrease in p r i c e zirconium may be effectively
used as m a t e r i a l for chemical plant equipment; it is employed a s acid-
r e s i s t a n t m a t e r i a l f o r the production of centrifuge p a r t s , pumps,
condensers, and evaporators; general purpose machine p a r t s (pistons,
rods, shafts, etc.) - in turbine building (turbine blades and other p a r t s ) -
and in the production of medical instruments.
Production of steels and nonferrous m e t a l alloys. Zirconium is
extensively used as an additive to steel, serving to deoxidize the steel, to
remove nitrogen, and to bind sulfur. In addition, zirconium is a valuable
alloying element which is added to certain brands of a r m o r steel, s t e e l s
f o r forged gun p a r t s , stainless steels, and high-temperature steels.
Zirconium is added to s t e e l s in the form of ferrosilicozirconium (40 to
4570 Zr, 20 t o 2470 Si; remainder iron).
218
Zirconium is a component of a s e r i e s of nonferrous alloys (copper,
magnesium, lead, nickel base alloys).
Copper alloys containing 0.1 to 570 Z r can be hardened by thermal
treatment (quenching and tempering). The tensile strength reaches
50 kg/mm2, which is 5070 higher than that of nonannealed copper. When
a r t i c l e s made of pure copper ( w i r e s , sheets, tubes) are heated up to
200" their strength d e c r e a s e s considerably because of the r e l e a s e of
cold-hardening. The addition of zirconium i n c r e a s e s the annealing
temperature of copper to 500". The addition of s m a l l amounts of
zirconium to copper i n c r e a s e s i t s strength with only an insignificant
d e c r e a s e in the electrical conductivity of the copper. Zirconium is added
to copper in the f o r m of a hardening copper-zirconium alloy containing
1 2 to 14% Zr. Copper-zirconium alloys a r e used f o r the production of
electrodes for spot welding and f o r electrical bus b a r s when a high
strength is required.
Mangesium alloys containing zirconium a r e now increasingly used. The
addition of s m a l l amounts of zirconium favors the formation of fine-grained
magnesium castings and thus i n c r e a s e s the strength of the metal.
Magnesium alloys with zinc and zirconium a r e very strong. Magnesium
alloy with 4 to 570Zn and 0.6 to 0.770 Z r does not display c r e e p below 200"
and i t s use a s a s t r u c t u r a l m a t e r i a l for jet engines has been recommended.
Zirconium is added (in the form of a silicon-zirconium alloy) to lead
bronzes. It promotes the dispersion of lead and completely prevents the
segregation of lead in the alloy. Copper-cadmium alloys containing up
to 0.3570 Z r a r e characterized by their high strength and electrical
conductance.
Zirconium is a component of a number of corrosion-resistant alloys.
Thus, an alloy containing 5470Nb, 4070Ta and 6 to 770 Z r has been proposed
a s a substitute for platinum.
Manufacture of refractories, porcelain, enamels, glazes and glass.
These branches of industry at present account for m o r e than 5070Of the total
consumption of zirconium; zirconium is used in the form of i t s minerals
(zircon and baddeleyite) and chemical compounds (zirconium dioxide,
zirconates, zirconium diboride).
Zirconium dioxide (mp 2700 to 2900") and the mineral zircon (ZrSi04)
a r e used a s r e f r a c t o r i e s .
P u r e zirconium dioxide is unsatisfactory a s a refractory m a t e r i a l
because of i t s t h e r m a l instability which causes a r t i c l e s heated to high
temperatures to crack upon cooling. This is associated with phase t r a n s
formations in the dioxide; such transformations a r e accompanied by
volume changes which cause the cracking. The cracking is prevented by the
addition of s t a b i l i z e r s - magnesium or calcium oxides. The stabilizers
dissolve in the zirconium dioixde forming a solid solution with a cubic
c r y s t a l lattice, which is stable a t both high and low temperatures.
Zirconium dioxide o r the minerals zircon and baddeleyite are used in
the production of r e f r a c t o r y bricks for metallurgical furnaces, crucibles
f o r melting m e t a l s and alloys, refractory tubes, and other articles.
Zirconium m i n e r a l s o r zirconium dioxide a r e added to certain brands
of porcelain used f o r the production of insulators for high-voltage lines,
f o r high-frequency circuits, and f o r the spark plugs in internal-combustion
engines. Zirconium-containing porcelain has a high dielectric constant
and a low expansion coefficient.
219
220
,, ..
2400 of a baddeleyite- zircon mixture containing
1 \ approximately 7 5 to 82% ZrOz, 2 to 5%
2300 \
1
j , ZrU, Fe&, 6 to 1770 si%, 1.3 to 1.770 A l z q
2fw (ss) \ and 0.2 to 0.8% Ti&.
21UU -1 I The major impurities in the concentrates
2wo \.+
-I a r e silica, iron, aluminum, and titanium.
1900 IPSl4 + 1 I; High-quality concentrates a r e produced by
/sou I1 17?5*lU 1:1 1 3 gravitational beneficiation on concentration
1700
1600
-
- '
ZrQi+(ss)
t sto4
1675*5*"A
zrsi04
tables (resuiting in the removal of the lighter
Al- containing minerals) and electromagnetic
22 1
Zircon-containing o r e s a r e enriched by gravitational methods in
conjunction with magnetic and electrostatic separation. The separation
of zircon f r o m quartz is c a r r i e d out by concentration on tables. nmenite
and garnet (a silicate of aluminum, iron, calcium, and other elements) are
separated by magnetic methods with the use of weak fields (zircon is non
magnetic). Monazite is separated by magnetic separation in strong fields.
The rutile and the zircon are separated by electrostatic methods or by
flotation.
A m o r e complete removal of the iron (which is of importance when the
zircon is to be used as a component of enamels) is attained by treating
the concentrate with hot sulfuric acid.
The approximate composition of zircon concentrates is shown in
Table 38.
TABLE 38
Approximate composition of zircon concentrates,%
TiO,
31.20 5.5
66.42 33.0 Traces
61.31 34.8 1.7
66.3 31.0 2.3
222
Ferrosilicozirconium is produced directly by smelting zircon
concentrates. Technical zirconium dioxide s e r v e s as raw m a t e r i a l f o r
the smelting of ferrozirconium and is used for the production of re
fractories. The high-purity dioxide is used f o r the production of high-
quality refractory a r t i c l e s (crucibles, tubes, etc. ).
Potassium fluozirconate and zirconium tetrachloride a r e used mainly
for the production of metallic zirconium.
The main methods f o r the production of zirconium dioxide, potassium
fluozirconate and zirconium chloride f r o m zircon concentrates a r e
reviewed below.
223
Titanium present a s an impurity (in the form of rutile and ilmenite)
r e a c t s with sodium hydroxide to yield sodium titanates.
Iron and aluminum a r e present in the melt as f e r r i t e (NazO*Fez%)
and aluminate ( N a 2 0 .Al&).
The fusion with sodium hydroxide is c a r r i e d out in iron crucibles o r
c a s t i r o n v e s s e l s a t 600 to 650".
The sodium hydroxide is added in a 50% e x c e s s (over the stoichiometric
amount needed) in o r d e r to ensure quantitative decomposition of the zircon,
The melt is granulated by pouring into water a thin jet.
I Zircon concentrate
Crushing
NaOH 7 Fusion
Water
*)Leaching
7
4
Solution Residue
-
Na,SiO, , Na AlO,, NazZrOs, ZrO(OH), ,
NaOH and other FeZOs,Na, TiOs ,
-
HSiOs
7I
-
HC1
F
5 1 H2S04
Leaching Leachin;
FIGUW 111. Flow sheet of the processing of zircon by fusion with sodium hydroxide.
224
Leaching the melt with water. The leaching of the alkaline melt with
water is c a r r i e d out in iron tanks fitted with s t i r r e r s or in drum-type
leaching equipment of the ball type, in two stages with intermediate
decantation.
During the leaching with water most of the silicon p a s s e s into solution
in the form of sodium silicate Na2Si03. At the s a m e time there i s a
partial hydrolysis of sodium zirconate with the formation of zirconium
hydroxide :
+ +
NazZr03 3HzO = Zr (OH), 2NaOH.
In the second stage leaching of the residue with water, partial hydrolysis
of sodium silicate also takes place a s the alkalinity of the solution
decreases:
+
Na,SiO,+ 2H,O = H,Si03 2NaOH.
Sodium titanate remains in the residue together with the zirconium
while sodium aluminate p a s s e s into solution. The f e r r i t e is decomposed
a s 'follows :
+ +
Na,O . FezO, HBO= Fe,O, 2NaOH.
Thus, the residue from the leaching of the melt with water contains
sodium zirconate, zirconium hydroxide, residual sodium silicate, silicic
acid, sodium titanate, iron oxides, and a certain amount of sodium
zirconosilicate. The approximate composition of the residue i s : 80 to
84% ZrOz, 8 to 1 2 % SO2, 4 to 670Na20. The residue is forwarded to acid
leaching.
Acid leaching. Either hydrochloric or sulfuric acid is used f o r the
leaching. Zirconyl chloride solutions a r e formed in the f o r m e r c a s e ,
while solutions containing zirconyl sulfate and zirconylsulfuric acid a r e
formed in the l a t t e r case:
+
Na,ZrO, + 4HCl = ZrOC1, 2NaCl+ 2H20,
Na,ZrO,+ + +
2HzS04 = ZrOSO, Na,S04 2H,O,
+
ZrOSOa HzSO, Hz [ Z f l (m4)zl.
225
58. DECOMPOSITION OF ZIRCON B Y FUSION WITH LIME
I Zircon concentrate I
Sintering
7
LeachinE with acids
.1 1
First variant Second variant
1
6-10'70
I
HC1
I
First leaching in
the cold
Leaching
l -
c/ H2S04
Recidue
CaSO,. HzSi03
1 J
Solution Residue
CaC1, ,colloidal
HC1 25-3070
H z S i Q . Fe. etc. P
Second leaching
with heating
7 7
Residue Solution Solution
HZSiO, ZrOCIZ HdZrO( SOd21
1
F Z i r { ? G j
ZrOS04
1
frnmralution
i- -
Isolation of Isolation of the Isolation of
ZrOClZ. BHZO basic sulfate H2[Zr4S04)z
by hydrolysis 3 HzO
FIGURE 112. Flow sheet of the processing of zircon by sintering with lime.
226
I
oxide. In addition, i t is possible that the reaction is catalytically
accelerated because of the chlorinating action of calcium chloride:
221
2. Hydrolytic precipitation of basic zirconium sulfates; this may be
c a r r i e d out from both hydrochloric and sulfuric acid solutions.
3. Isolation of the crystalline zirconylsulfuric acid hydrate
-
Hz[ZrO(SO,),] 3 H z 0 f r o m sulfuric acid or zirconium oxychloride solutions.
isolated a s crystals,
MCl concentration, g/l The method yields zirconium compounds
FIGURE 113. Solubility of ZrOC1,- of a very high degree of purity since most
8 H Z 0 in hydrochloric acid a t 20". of the impurities (Fe, Al,a p a r t of titanium,
and some others) remain in the hydrochloric
mother liquor. Also the s a l t may be
purified by recrystallization. Zirconium oxychloride can be readily
converted to other pure zirconium compounds : zirconium hydroxide,
dioxide, fluorides, nitrate o r sulfate. To do this zirconium oxychloride
is dissolved in water, zirconium hydroxide precipitated by the addition of
ammonia and the hydroxide is then dissolved in the respective acid.
Zirconium dioxide prepared by this method contains 99.6 to 99.8% Z r Q .
---------------
* Azeotropic solutions are solutions which
distill without a change in composition (i. e., the liquid and
vapor phases have the same composition).
228
I
229
The method yields technical grade zirconium dioxide containing 97 t o
98% Z r q . The main impurities are: 0.5 to 1.5% Ti(&, 0.2 to 0.8% Si(&,
0.1 to 0.15% Fez@, 0.2 t o 0.5% CaO, 0.2 to 0.4% PzO, , and up to 0.3% S@.
Additional purification of the basic sulfate is required to obtain a product
of a Bigher degree of purity.
TABLE 39
____
Y
H2SO4 210, g/ 100 g Zr02 g/lOO g
concentration, '70 solution concentration, % solution
31.2
33.1
35.6 16.20 0.14
39.6 9.60 0.15
42.5 5.30 70.5 0.50
44.1 3.51 72.9 2.0
46.1 1.03
... ~.
1455
230
6 0 . PROCESSING OF ZIRCON BY SINTERING WITH
POTASSIUM FLUOSILICATE
I Zircon concentrate I
.1
Crushing
KzSiF6. KCl
Sintering
,
-
SiO,, undecomposed
4
Crystzllization
mineral
I+
Washing KzZrF6 ( HO Mother liquor
crystals
I 7
NHPH
2
Wash watet Solid residue
1
To waste
I
Removal of Hf
by fractional
crystallization
Precipitation of
zirconium
hydroxide
1
7
Mother liqlmr
Precipitation of To isolation
Zr(OH)r of Hf
1
Sintering
1$
FIGURE 114. Flow sheet of the processing of zircon by fusion with potassium fluosilicate.
23 1
The potassium fluosilicate required for the p r o c e s s is readily prepared
f r o m a relatively cheap substance - sodium fluosilicate, which is a by-
product of the manufacture of hydrofluoric acid and cryolite. The inter
action of a saturated solution of Na2SiF6with a saturated solution of KC1
c a u s e s precipitation of K2SiF6:
Na,SiF, + 2KC1 &SiF, + 2NaCI.
-
--f
This can be explained by the fact that the solubility of K2SiF6 ( 1.13 g / l )
is much lower than the solubility of Na2SiF6 ( 6.7g/l).
A flow sheet of the processing of zircon by sintering with potassium
-
fluosilicate is shown in Figure 114. The zircon concentrate is crushed to
a particle s i z e of l e s s than 0.074" and mixed with potassium fluosilicate
and potassium chloride. The potassium chloride intensifies the degree
of decomposition of the mineral. The K2SiF6is taken in 50% e x c e s s over
the stoichiometric amount.
The degree of decomposition of zircon is strongly affected by the
sintering temperature of the charge. When the p r o c e s s is c a r r i e d out
a t 650 to 700" the degree of decomposition reaches 97 to 9870 *e. The
sintering is c a r r i e d out in r o t a r y furnaces. The sintered m a s s consists
of burnished and slightly fused grains with a particle s i z e of 0.5 to 10".
It is crushed to a particle s i z e of l e s s than 0.15 m m and leached with 1%
HC1 (at a solid :liquid ratio of 1 : 7) at 85". The leaching time is 1.5 to
2 hours.
TABLE 40
Solubility of K2ZrF6 in wateI
Solubility,
1. "C
g/lOOg. H2O
10 1.22 60 3.81
20 1.55 IO 5.06
30 1.92 80 6.90
40 2.31 90 11.11
50 2.94 100 23.53
---------------
* Because of the difficulties involved inmaintaining a constant temperature in rotary furnaces, there a r e
wide fluctuations i n the degree of decomposition of the concentrate and it is usually lower than this value.
232
c r y s t a l s prepared by this method f r o m zircon concentrates from the Azov
region of the USSR have the following composition: 31.9 to 3270 Z r +Hf,
27.2 to 27.670 K, 39.9 t o 40.0570 F, 0.044 to 0.04570 F e , 0.041 to 0.04270
Ti, 0.06 to 0.0770 Si, 0.006 to 0.008% C1, 1.5 t o 2.570 Hf (on the zirconium).
Hafnium is separated f r o m zirconium by fractional crystallization.
All leaching and crystallization operations may be c a r r i e d out in
s t a i n l e s s s t e e l equipment; the corrosion of such equipment is negligible
because the inner walls a r e coated with a film of insoluble fluorides.
In o r d e r to convert i t into zirconium dioxide, potassium fluozirconate
is dissolved in water (25 to 3 0 g K,ZrF6 in one l i t e r of water a t 50 to 60")
and the resulting solution is poured into a solution of ammonium hydroxide;
the N H 4 0 H is taken in 15070 e x c e s s over the stoichiometric amount r e
quired f o r the reaction:
K2ZrF, + 4NKOI-I = Zr (OH), + 4NH$ + 2KF.
The fluoride s a l t s a r e removed f r o m the zirconium hydroxide by
washing with water containing 0.570 NHS, the hydroxide is separated by
filtration, dried and ignited a t 900" to zirconium dioxide.
The precipitation with ammonia f r e e s the zirconium f r o m the iron and
titanium which a r e bound in ammoniacal fluoride complexes and thus
only a s m a l l fraction i s precipitated. Thus, zirconium dioxide containing
0.005% F e and 0.00570 T i was prepared f r o m fluozirconate containing
0.03270 F e and 0.012 Ti.
This p r o c e s s is characterized by i t s s m a l l number of operations and i t s
simplicity. A s w i l l be shown below, hafnium can be readily separated
from zirconium by this p r o c e s s , and zirconium dioxide of a high degree
of purity can be produced.
6 1 . D E C O M P O S I T I O N O F Z I R C O N BY R E D U C T I O N WITH
CARBON TO C A R B I D E O R C A R B O N I T R I D E / 1 , 2 /
Zirconium carbide or carbonitride are produced by reducing the zircon with carbon; during the reduction
most of the silicon is removed as S i 0 whose vapor pressure at 2000 to 2200" is close to one atmosphere.
The main reactions occurring during the reduction of zircon with carbon are:
ZrSiOl + +
6C = ZrC S i c + 4CO;
ZrSiO, + 5C = ZrC + S i + 4CO;
+
ZrSi0, 4-4C = ZrC S i 0 + 3CO;
ZrSiOl + 3C = Zr +
Si0 + 3CO.
In the presence of a suitable amount of carbon in the charge, the reduction occurs mainly in
accordance with reaction (3). Silicon monoxide is also formed by a side reaction involving the reduction
of zircon by silicon:
ZrSiO, +Si = ZrO, +
2.50.
Moreover. the reduction involves a number of other side reactions, one of which is the formation of
the easily melted zirconium silicide ZrSi,.
When using a charge containing 18 to 20% carbon (in the form of powdered coke), 95 10 96%of the
silicon is removed as S i 0 by carrying out the reduction in an electric-arc furnace.
A diagram of one type of one-phase a r e furnace used for the reductive melting of zircon a t one
plant in the USA is shown in Figure 115. T h e furnace bath consists of a steel cylinder 2.14111 in diameter.
The pressed carbon a t the bottom setves as one of the electrodes. The second carbon electrode. which
is about 6 0 0 m m in diameter. is placed in the center of t h e furnace. A part of the charge adjacent t o the
walls does not take part in the reaction and serves as a protective thermal insulation layer. Low-voltage
233
(- 50V) current is supplied to the electrodes and this necessitates the use of a short arc. In such a c a s e the
losses of heat through marginal radiation on the walls ar e minimal. T h e radiation losses through t h e cover
of the furnace a r e also very small since t h e electrode serves as a shield. T h e total furnace power is 750kw.
The furnace is allowed to cool, the mass is discharged by rotating the furnace, and the carbide particles
are separated from the fraction of the charge which has not reacted. T h e consumption of electrical energy
is 8000 to 11,000 kwhlton zirconium carbide.
One of the disadvantages of the process is t h e fact that the losses caused by dust formation during the
charging and discharging of t h e furnace ar e high. To reduce dust formation the charge is fed into paper
bags. However. even in this case the mechanical losses reach 8%.
Since the pores of the charge contain nitrogen. t h e product formed.in the fusion is usually the
carbonitride ( a solid solution of zirconium nitride in zirconium carbide). The carbonitride formed has the
following approximate composition: 75 to 85% Zr, 3 to 5 % C, 2 to 4 % Si, up to 2% N , 1 to 2 % F e .
up to 2 % T i , and 1 to 1 0 % 0.
234
reaction involved is:
ZrSiO, + 4CI1+ 4C = ZrC1, + SiCI, + 4 0 .
A mixture of the pulverized concentrate, carbon and a binder (either coal
t a r o r sulfite-pulping liquors a r e used a s the binder) is pelletized. The
pellets a r e coked a t 700 to 800". The chlorination of the pellets is c a r r i e d
out in shaft furnaces lined with Dinas [silica r e f r a c t o r y ] bricks. Since the
chlorination reaction is endothermic, constant inflow of heat is required
to maintain the furnace temperature at 800 to 1000". The p r o c e s s may
be c a r r i e d out without external supply of heat if a certain amount of a i r is
introduced into the furnace together with the chlorine; the heat evolved
in the combustion of a p a r t of the coal in the charge is sufficient to maintain
the temperature.
The difference between the volatilization temperature of ZrCll (330O)
and the boiling point of SiC14 (58")p e r m i t s the condensation of the zirconium
chloride in the p r i m a r y condensers which a r e maintained a t 150 to 180°,
and the condensation of liquid silicon chloride in the secondary condensers
in which the temperature is maintained a t -loo by cooling with water o r with
a s a l t solution. The silicon chloride finds use in the production of various
organosilicon compounds and may be used a s the starting m a t e r i a l for the
production of semiconductor grade silicon.
Zirconium chloride produced by the above p r o c e s s is contaminated with
silica, which is formed a s a r e s u l t of the interaction of a p a r t of the
SiC14with moisture and oxygen which may be present in the furnace. F o r
the s a m e reason zirconium chloride contains the oxychloride ZrOC12.
The d i r e c t chlorination of zircon in mixture with carbon h a s recently
found increasing industrial use. The disadvantages of the p r o c e s s (the
high temperature) a r e compensated by the elimination of the expenses
involved in the pretreatment of the concentrate in o r d e r to separate the
bulk of the silicon (e. g . , by carbidization) and by the production of a
valuable by-product - silicon tetrachloride.
T h e carbide and carbonitride a r e chlorinated a t a low temperature (350 to 450") and the heat evolved
i n the reaction is sufficient to maintain the process even in small chlorinators. T h e chlorination reactions
are: + + +
ZrC 2C1, + ZrCl4 C 202 kcal
ZrN + XI,+ ZrCl4 + N, + 160 kcal
A diagram of a furnace used for the chlorination of zirconium carbonitride in a plant in the USA
is shown in Figure 116. T h e chlorination is carried out in a shaft furnace about o n e meter in diameter
and about 2.5 m high. T h e chlorine enters the furnace through a perforated graphite plate over which there
is a layer of coke particles. T h e process is started by heating the coke layer with hot air. T h e carbo
nitride is then passed over the heated layer and the chlorine is fed to the furnace. Intensive chlorination
of the carbonitride starts a t 400" and is maintained by the reaction heat evolved.
T h e condenser is a nickel cylinder 1250 mm in diameter and 2 4 5 0 m m high. T h e temperature in the
condenser is maintained a t 150'. At the exit from the condenser zirconium chloride is screened on a sieve.
T h e screened fraction is degassed in a low vacuum i n order to separate SiC14 and TiC1,. T h e zirconium
tetrachloride produced is contaminated with oxygen and with dust particles entrained from the furnace.
T h e product is bright-yellow.
235
The cost of zirconium chloride produced by chlorination of zirconium carbonitride is higher than that
of the chloride produced by direct chlorination of zircon. T h e process has the advantages o f a low
chlorination temperature, simplicity of operation, and the production of technical chloride of a higher
degree of purity.
-ZzrO,
1
2
+ 1 C + Cl, = -ZrCI,
1
2
+-COCO,.
1
2 (3)
236
At temperatures above 700" the chlorination preferentially takes place
in accordance with equation (l), which involves the g r e a t e s t d e c r e a s e in
free energy.
The chlorination is c a r r i e d out in shaft furnaces charged with the
pelletized raw materials. A diagram of one of the furnaces used and the
chlorination apparatus is shown in Figure 117. The furnace consists of
a s t e e l shell lined with Dinas bricks. The internal dimensions of the shaft
a r e : diameter 650 to 700mm, height about 2000". The current is
supplied to t h r e e graphite plates mounted in the furnace lining.
FIGURE 117. Apparatus for the chlorination of a pelletized mixture of zirconium dioxide and
carbon.
1-charging bin: 2-feeder; 3-quartz bricks: 4-manholes (for cleaning); 5-steel shell;
6-insulation bricks; 7-cooled copper electrode for the supply of the current; 8-graphite
electrode with a sleeve; 9-chlorine supply tubes; 10-gas exhaust (nickel tube); 11- first
condenser; 12-air jacket; 13-partition; 14-discharge hole; 15-air heater; 16-fan;
17-cyclone-type condenser; 18-water scrubber; 19-scrubber irrigated with an alkali
solution; 20-exhaust tube for the gas (to the cooler); 21-circulation pump; 22-tube for
the entry of the wash water.
The charge contains 81% zirconium dioxide, 14.5% g a s black and 4.570
dextrin (which a c t s a s a binder). The mixture is moistened with water
and pelletized with a r o l l e r p r e s s (the s i z e of the pellets is 3 5 X 25 X
20"). The pellets a r e dried a t 140".
When starting the furnace, the pellets a r e charged t o a level somewhat
above the middle of the electrodes. Carbon plates a r e laid o v e r the l a y e r
of pellets (from the center to each electrode); the plates a r e in contact
237
with the electrodes and s e r v e f o r the initial heating of the pellets. An
additional amount of the pellets is then fed to the furnace, until the pellets
r e a c h the required level. The electrical conductivity of the hot pellets
is high enough to p e r m i t heating the charge by a d i r e c t passage of e l e c t r i c
current. The furnace temperature in the vicinity of the h e a t e r s is main
tained a t about goo", and in the upper zone of the furnace a t 250 to 500".
Under normal operating conditions the voltage applied to the electrodes is
15 V and the c u r r e n t is 250 amperes.
The chlorine pipelines, the charging tubes, the g a s exhaust lines, and
the condensers a r e made of nickel sheets.
The condensers a r e fitted with jackets within which t h e r e is a circulation
of heated air. The temperature of the f i r s t condenser is maintained a t
150 to 200" and of the second condenser a t 100 to 150". The excess
chlorine is absorbed in s c r u b b e r s (irrigated with alkaline water) which
a r e fitted after the condensers.
The consumption of electrical energy is 3 kwh/kg of zirconium chloride.
The degree of extraction of zirconium into the chloride is 92 to 93%.
Zirconium chloride prepared by one of the above methods contains a
number of impurities. The chloride is purified by sublimation ( s e e
Section 65).
238
Number of crystallizations
FIGURE 118. Change in the hafnium content
of K2ZrF, as a function of t h e number of
successive crystallizations.
239
is dissolved in the mother liquor of the preceding crystallization. The
solid :liquid r a t i o during the dissolution is 1 : 7, which corresponds to a
K2ZrF6concentration of 0.5 m o l e s / l (or about 140 g/l). The solutions a r e
cooled to 1 7 t o 19". The solubility of KzZrF6 at that temperature is
16.3 g/l. The c r y s t a l s formed a r e allowed to settle, the mother liquor
is decanted, the mother liquor from the preceding stage is poured on the
c r y s t a l s and the next crystallization stage performed.
TABLE 41
Solubilities of zirconium- and hafnium-potassium hexafluorides
Solubility ratio
K2HfF6/ K2ZrF6
0.1942 1.5
0.1008 1.51
-
Separation by extraction
240
I
The equilibrium constant of the reaction is
Y= .
[Zr (NO,), 2TBP ]
[Zr02+] [H+]*[NOT]‘ [TBP]‘ *
The r a t i o
24 1
zirconium and hafnium sulfates or oxychlorides containing ammonium
thiocyanate NH&NS. The composition of zirconium compounds in such
solutions has not been thoroughly studied. It can be expected that in
addition to the simple thiocyanates Me(SCN)d the solutions also contain
complex anions such as [Me(SCN)6]2-, (where Me=Zr o r Hf).
The organic solvent is preliminarily saturated with thiocyanic acid
HCNS. The hafnium is preferentially extracted into the organic phase,
and the separation coefficient may he as high as 80.
Feed solution
( 1 2 5 g / l ZrO, + 5MHNOs; Hf/Zr = 2.5%)
40% TBP i n
11
Extraction with methyl
isobutyl ketone
containing HCNS
J.= -1
Aqueous phase Zr
Organic phase
2
ketone
I
.I
1 Recycled
FIGURE 122. Flow sheet of the separation of zirconium and hafnium by extraction with methyl
isobutyl ketone from solutions containing thiocyanates.
242
The organic phase (extract) containing hafnium and some zirconium is
washed with hydrochloric acid to extract the zirconium. The hafnium is
then reextracted with a sulfuric acid solution and hafnium compounds a r e
isolated from the solution. A flow sheet of the p r o c e s s is shown in
Figure 122.
Zirconium and hafnium may b e separated by ion exchange on cation exchange (when the zirconium and
hafnium are present in the solution as cations) or anion exchange resins. T h e cation exchange separation
from nitric acid solutions / l o / will b e described as an example.
ZrOZf and HfOz+ are first sorbed on the cation exchange resin a t the top of t h e column or in a separate
column until i t becomes saturated. They are then eluted with 0.5 M HzS04. Zirconium is eluted first and
moves to the bottom of the c o l u m n a h e a d o f thehafnium. With a column of sufficient length this method
may be used t o extract 95 -98% zirconium with a hafnium content of less than 0.01%
I
FIGURE 123. Flow sheet of the separation of zirconium and hafnium
by ion exchange.
1-saturation column; 2-column for separation by elution; 3
pump; 4-storage tank for the starting solution containing
Zr(Hf)(iSO& + 2 MHNOS; 5-storage tank containing 0.5M H,SO,
used for elution of zirconium; 6-storage tank for 1 . 5 M H2S04
used for elution of hafnium; I-collector for solution of pure
zirconium in H z S 0 4 ; 8-collector for the hafnium-containing
sulfuric acid solution.
During the elution use is m a d e of the different tendencies of ZrO2+ and Hf02+ ions to form CZrO(S04)zJz~
and [HfO(S0,),12- complex ions.
T h e flow sheet of the process is shown in Figure 123. T h e solution (17 g/l Zr and 2 M HN03) is
circulated for a while through the saturation column. A 0.51 M solution of HzS04 is then passed first through
the saturation column and then through the separatory column (which is packed with cation-exchange resin
in the H-form) until hafnium appears in the solution a t the exit of the column. The filtrate, which is
collected. contains zirconium.
___-----___---
* T h e principle of the ion exchange methods for the separation of elements with similar properties
has been discussed in Chapter VI.
243
T h e elution is then continued with 1.5 M H,SO, t o extract the fraction containing the hafnium and the
remaining fraction of the zirconium. This method may be used to recover 93% of the zirconium with a Hf
content of 0.035%.
The drawback of the ion exchange method is its low output (about 0 . 0 5 g Zr/hr per c m z of column
cross section). It gives, however, a sharp separation and may b e used as a continuous method.
Rectification
244
- +
3ZrC1, 2POC1, 6NaCI-
300-400' C
SNa,ZrCI, + 2POC1,t;
Na2ZrC16% 2NaCI + ZrC1.t.
In this c a s e zirconium chloride is obtained directly.
In another method, the complex chloride vapor is passed through a
layer of coke heated to 800". The following reaction takes-place:
- +
3zrc14 ~ P O C I ~2 ~~ Z ~ C + +
5 I ,2 ~ ~ 1 2, ~ 0 t .
Phosphorus trichloride (bp 75") can be easily separated from ZrCll / 2 1 / .
245
Like titanium, zirconium actively absorbs oxygen, nitrogen, and
hydrogen. The solubility of oxygen in zirconium reaches 40 at.% (10.6%
by weight). Zirconium contairring m o r e than 0.2% oxygen cannot be
mechanically worked. The solubility of nitrogen in zirconium is about
20 at.%. The mechanical properties and corrosion resistance of pure
zirconium a r e strongly affected by i t s nitrogen content. The solubility
of hydrogen in a-zirconium is up to 5 at.%, and in p-zirconium i t is higher.
The presence of hydrogen in zirconium (even at concentrations of 0.003 70)
markedly reduces the impact strength of the metal. Carbon, CO, and C 0 2
r e a c t with zirconium at high temperatures, yielding the refractory
carbide Z r C (mp 3530"). The presence of carbon has little effect on the .
mechanical properties of zirconium but reduces its corrosion resistance
to water at high temperatures.
In parallel with the similarity of their properties, there is a noticeable
similarity in the methods of production of zirconium and titanium. These
methods shall accordingly b e discussed m o r e briefly. They may be
classified into three groups!:
1. Thermal reduction with metals:
a) reduction of zirconium tetrachloride by magnesium;
b) reduction of potassium fluozirconate KzZrFBby sodium and of
zirconium fluoride by calcium;
c) reduction of zirconium dioxide by calcium o r calcium hydride.
2. Electrolysis of molten salts.
3. Thermal dissociation of zirconium iodide.
The main commercial method f o r the production of ductile zirconium
is based on the reduction of ZrC14 with magnesium. Zirconium powder
(which is used a s such) is produced by reduction of K2ZrF6by sodium and
by reduction of Z r Q by calcium or calcium hydride. Electrolytic
methods f o r the production of zirconium have been increasingly used.
Thermal dissociation of zirconium iodide is used for the production of
zirconium of the utmost purity. When necessary, the method is used f o r
the refining of zirconium sponge o r powder.
The strength of pure zirconium is not high enough and i t s corrosion
resistance is markedly affected by the presence of very s m a l l amounts
of certain contaminants (e. g . , nitrogen). The mechanical properties and
the corrosion resistance a r e improved by the addition of alloying elements.
246
The s e p a r a t e p r o c e s s
247
is placed on the floor of the vessel. The converter with sublimed zirconium
chloride is placed i n the upper p a r t of the vessel. The lid is sealed in the s a m e
way a s in the sublimation apparatus. A drip pan and shields a r e fitted over
the crucible to prevent radiation heat transfer and the penetration of solid
zirconium chloride particles into the crucible.
248
t o a temperature above the melting point of MgClz which is formed in the
reduction process. At the s a m e time the intermediate zone of the r e t o r t
is heated to 450 to 500°, i. e . , to the temperature required f o r the
volatilization of zirconium chloride. At the end of the reduction the
temperature of the intermediate zone is increased to 650". The reaction
of the gaseous ZrC14 with the liquid magnesium r e s u l t s in a continuous
removal of chloride f r o m the gaseous phase and thus in the volatilization
of f u r t h e r amounts of chloride from the coil.
The presence of an i n e r t gas in the r e t o r t reduces the volatilization
r a t e of the chloride and thus reduces the reduction rate. Rapid volatiliza
tion takes place in ;he absence 'of'an i n e r t gas, and the reaction is SO f a s t
that the reaction m a s s may be o w h & a t e dand the crucible melted. This
is due to the fact that the reduction is exothermic. The p r e s s u r e , which
may i n c r e a s e a s a result of the overheating of the reaction m a s s during
the reduction is automatically decreased by maintaining the Pb-Sb alloy
in a molten s t a t e ( a t 250 to 300").
Two hundred kg of ZrC1, a r e reduced in one operation in a v e s s e l
700" in diameter and 1750 m m high, yielding about 75 kg of zirconium.
The duration of the p r o c e s s is 2 4 to 30 hours. The zirconium yield is
- 93%.
The container i s cooled to room temperature and the crucible is taken
out. The zirconium is at the bottom of the crucible in the form of a sponge.
It is protected against oxidation by a dense layer of magnesium chloride.
The combined p r o c e s s
The vessel used for the combined sublimation of the chloride and i t s
subsequent reduction with magnesium is shown in Figure 126. Its use
eliminates the t r a n s f e r of the sublimed ZrC1, from one vessel to another,
which brings the chloride into contact with a i r and causes i t s partial
hydrolysis. Moreover, carrying out both p r o c e s s e s in a single vessel
reduces the total p r o c e s s time by about 3 5 70.
In the combined vessel (Figure 126) a container with zirconium chloride
is fitted over the crucible containing the magnesium b a r s .
The vessel is covered with a lid fitted with a coil. It is sealed with the
aid of a Pb-Sb alloy seal, a s described above. At f i r s t the vessel i s
evacuated, filled with hydrogen and the iron and chromium chlorides a r e
reduced at 300". It is evacuated to remove the HC1 vapors, then filled
with argon and the reduction is c a r r i e d out. The lower zone of the
apparatus is heated to 825", which also causes an i n c r e a s e in the
temperature of the intermediate zone (to about 400 to 450'). The ZrC1,
is volatilized and r e a c t s with the molten magnesium.
When the apparatus is charged with 250 kg of ZrCl,, the reduction
time is about 15 hours. The temperature of the intermediate zone is
thenincreased to 650" in o r d e r to volatilize the remaining ZrC1, which
condenses on the water-cooled coil. The total p r o c e s s cycle has a
duration of 44 hours, a s compared with about 64 hours in the s e p a r a t e
process.
249
250
the vacuum furnace is raised when the temperature of the upper p a r t
drops to 400'.
Various types of sponge a r e formed in the crucible after the distillation.
The bulk (70%) consists of a dense metal containing almost no magnesium
o r magnesium chloride.
25 1
A1 . . 0.003
. . <Z.IO-'
cu .. .. .0.003
. 0.065
Ni . . <0.0002
B
C
.. .. (0.002
0.0095
Fe
Hf . . . 0.0085
. , 0.01
0
Pb
Si
... ... 0 . 00.007
64.1
cd
co . . 4 0 0002
Cr . . -0:0015
2
N
. . 0.002
. . . 0.004
Ti
v
.. .. ~0.005 0.002
<0.001
252
of the calcium. The powders produced a r e suitable f o r use in vacuum
technology, pyrotechnics, photographic flash powders and for military
uses.
The reduction may be c a r r i e d out in hermetically sealed r e a c t o r s ; when
using s m a l l s i z e r e a c t o r s , the lid is welded before each reduction. The
reaction is conducted at 950 to 1100". The calcium oxide is leached with
dilute hydrochloric acid. The oxygen content is reduced by holding the
zirconium powder in a molten calcium bath o r in calcium vapor; the use
of calcium vapor is m o r e effective.
The difficulties experienced in freeing the zirconium f r o m oxygen a r e
due to the fact that the oxygen is in the form of a solid solution.
The reduction by calcium hydride is c a r r i e d out at approximately the
s a m e temperatures a s those used in the reduction with calcium (900 to
1100") ; the product is zirconium hydride, which is used f o r the production
of zirconium a r t i c l e s by powder metallurgy techniques.
253
anode. A s t e e l o r molybdenum rod may be used as the cathode. A carbon-
black packing is used a s t h e r m a l insulation.
I t is very important t o d r y in advance the crucible, the whole electrol
y z e r and the initial s a l t s used in the process. The electrolyte i s purified by
preliminary electrolysis a t a reduced potential (1.5 to 2V) using graphite
cathode. This causes the deposition of metallic contaminants m o r e
noble than zirconium. The cathode is then replaced and the electrolysis
is c a r r i e d out at 7 5 0 to 860' at a potential of 3.5 t o 4V and a c u r r e n t
density of 2.5 to 4 amp/cm2. The metal is deposited on the cathode in the
form of c o a r s e c r y s t a l s 0.3 to 0.5 mm in size. The rate of deposition
is 0.5 g / a m p . h r , the c u r r e n t efficiency is 6 0 to 65%.
254
When graphite crucibles a r e used for the electrolysis, the duration of
the electrolysis is limited by the gradual saturation of the graphite crucible
with the melt. This drawback is eliminated in an electrolyzer developed
by Soviet scientists. The bath is made of s t a i n l e s s s t e e l and is cooled with
water. The electrolyte in contact with the walls solidifies, creating a
c r u s t which protects the walls against corrosion 1 2 2 1 .
After remelting in vacuum the electrolytic zirconium h a s mechanical
properties s i m i l a r to those of zirconium produced by t h e r m a l reduction of
zirconium chloride with magnesium.
If proper equipment f o r continuous o r semicontinuous electrolysis is
developed, the electrolytic production of zirconium will b e able to compete
with the method based on t h e r m a l reduction with magnesium.
3Zr14 + Z r + 421-13
with the result that the concentration of Z r b in the gaseous phase decreases.
The vapor p r e s s u r e of ZrI, i n c r e a s e s above 450" because of the
disproportionation of the lower chlorides:
255
In o r d e r to maintain the required temperature of the walls adjacent to
the crude zirconium, the apparatus is i m m e r s e d in a molten-salt thermo
stat. The filament temperature is controlled by the method described
in the chapter on titanium.
Zirconium sponge (prepared by t h e r m a l reduction of the chloride with
magnesium) o r powder (prepared by reducing zirconium dioxide with
calcium o r by electrolysis) may be used a s the starting material. About
5 0 g of iodine a r e introduced into the v e s s e l f o r each kg of crude
zirconium taken. A number of V-shaped zirconium filaments is usually
mounted inside the vessel; the filament diameter is about 2 mm.
Zirconium rods, 25 to 3 0 mm in diameter and up to 2 m long, a r e obtained
at the end of the process. Up to 50 kg of purified zirconium is produced
in one vessel. Depending on the conditions, a rod 25" in diameter
can be grown within 3 0 to 40 hours.
The iodide purification p r o c e s s removes oxygen and nitrogen (since
zirconium nitrides and oxides do not r e a c t with iodine) and metallic
contaminants which do not form volatile iodides.
The concentration of impurities in zirconium produced by the iodide
p r o c e s s i s , 70:
. . . 2.10-' N . . . 1.10-3
Fe
Ai . . . 3.10-3
Cu . . .<5.10-5
3 .. . .. < 1 - 1 0 - 3
.<1.10-3
Mo . . .<l.10-3
o ...
H
1.10-2
. . . l.10-3
Ti . . . Ni ... C . . . 1.10-2
256
may also be produced by powder metallurgy. The metal produced by
powder metallurgy usually has higher oxygen and nitrogen contents than
the metal produced by vacuum melting of the sponge. It has a lower
corrosion resistance.
The mechanical properties of solid zirconium prepared by various
methods a r e compared in Table 42.
TABLE 42
Elongation of a
Tensile strength Vickers hardness.
sample, %
257
Part Two
Chapter VI
THE RARE -EARTH METALS (LANTHANIDES)
258
filled 4f-orbital. Hence, gadolinium and lutecium have the most stable
f-orbital configurations. A valency of 4+ is exhibited by cerium and
praseodymium (the f i r s t f-electrons a r e easily t r a n s f e r r e d to the W-orbital)
and terbium and dysprosium, which follow gadolinium in the s e r i e s . A
valency of 2+ is exhibited by samarium, europium, and ytterbium, i. e.,
in elements in which the number of electrons in the f-orbital is either
equal o r close to 7 o r 14.
TABLE 4 3
Electron structure, valency, ionic radii and ionization potentials of
the lanthanides -
.0
~ ~
n
E
F
U #
m
m N-shell (n=4) o-shell ( n = 5 ) x I
.d
L
ol
2
E
0
2 -C
m>
C
k%
- - ..
5
8 .-EO + .
u -*
'g
~ ~
E m 4
2
4s 4P 4d 41 5s 5P 5 :. t
? L U 9&
~
259
lutecium and is the cause of the different solubilities of the Ianthanides and
the stability of their complex compounds.
TABLE 44
Color of the trivalent lanthanide ions
~~ _- - ~ __ . - . -
57 La
colorles
58 Ce
colorles
59 Pr green-
yellow
60 Nd red-
violet
61 Pm
pink
62 Sm
yellow
63 Eu
)ale-pink
64 Gd
olorless
65 Tb
pale-pink
66 Dy pale-
green-
yellow
67 Ho dark
tellow
68 Er
pink
69 Tu pale-
green
70 Yb
olorless
71 Lu
:olorless
__ - .. . -~ -
260
Atomic number
FIGURE 130. Magnetic moments of the trivalent
lanthanide ions.
261
P
TABLE 45
cn
Cn
a-La
'
57
I
, 6.162 920t5 3470 99.5
-.
6.27 56.8 E l - : a z 3.710
--
1.871 3.33 -2.4 3915 11.2
N
Q:
I
n = 3.6725 1.828 2.7 -2.2 / 3592 8.9
genal (Mg type) c = 11.8354
a-Nd 60 7.001 1024t5 3210 75.6 6.52 64.3 1 44 The same a = 3.6579 1.821 3.3 : -2.246 3860 13.9
c = 11.7992
a-Sm 62 , 7.536 1072+ 5 1670 SO. 6 a = 8.996 1.802 3.2 -2.2 3480
I 23"13'
Eu
a-Gd
a-Tb
~
I
1
63
64
65
' 5.245
7.886
1 8.253
826t 10
1312.h 15
1 3 6 8 t 10
1430
2830
2480
42.2
80.9
72.0
9.633
7.136i
I
140.5
- '
,
44,000
44
Close-packed hexa-
gonal (Mg type)
The same
a = 4.5820
(I
c =
a =
= 3.6360
5.7826
3.6010
2.042
1.802
1.182
2.54
3.07
3.09
I
,
I
-2.2
-2.2
-2.2
-
5730
5864
15.9
c = 5.6936
1 2330 I
'
1380 i 20 69.8 6.72 56 1100 '
a = 1 j
'
~
1
3.5903 1.773 3.09 -2.2 6433 24.4
I
1 1 I
HO 67 8.179 1 5 0 0 t 25 2380 ' 69.0 6.45 87
c = 5.6475 ;
I 64 a = 3.5773 1.716
~
1
I
I c = 5.6158 I
Er 1 68 '
I
9.062 1 5 2 5 t 25
i 2390 ' 78.6 6.66 ' 107 166 a =
c =
3.5588
5.5874
1.157 3.12 -2.1
I
74-74 119.5
S o m e of the physical properties of the
lanthanides a r e shown in Table 45. The
melting points of the elements belonging
O
“
m
1 %
those of the elements of the yttrium sub
group. It is noteworthy that the boiling
points of S m , Eu, and Yb, which may have
a valency of 2+, a r e much lower than those
of the other lanthanides. Mention must b e
made of the large thermal neutron capture
c r o s s sections of gadolinium, samarium,
and europium.
The p u r e lanthanides are ductile and
a r e worked without difficulty (by forging,
rolling). The mechanical properties a r e
strongly affected by the concentration of
impurities, and especially of oxygen, sulfur,
nitrogen, and carbon. The tensile strengths
and moduli of elasticity of the metals in
the yttrium subgroup (except ytterbium)
a r e higher than those of the metals of the
cerium subgroup (Table 45).
All the lanthanides a r e paramagnetic,
except Gd, Dy, and Ho, which have f e r r o
magnetic properties. cy -Lanthanum be
comes superconducting at 4.9”K and ,B-La
m
m m m 3
(0
0
3
3 not become superconducting even i f the
temperature is reduced to a fraction of 1°K.
c-
N
Chemical properties / 1, 2/
m
N m o m
“ 0 3
cd m c d w The lanthanides a r e characterized by
their high chemical activity. They form
m o m o
very stable oxides, halides, and sulfides,
d
3 G
c
o
m
d
m
and r e a c t with hydrogen, carbon, carbon-
containing gases, nitrogen, phosphorus,
0 o o m and a number of other elements.
N
m
3 $N Z N : 8m The metals a r e decomposedby water
m o m
(slowly in the cold, and m o r e rapidly in hot
m
u
N N N
water) and readily dissolve in hydrochloric,
+ sulfuric, and nitric acids. The lanthanides
2
a r e not attacked by hydrofluoric and phos
phoric acids because of the formation of
m
0
? protective films of sparingly soluble salts.
263
lanthanides in having an oxide C e 2 4 which is easily oxidized to the dioxide
C e Q ; a s a r e s u l t cerium and cerium-rich alloys a r e pyrophoric. All
lanthanides are rapidly oxidized in a i r a t temperatures above 180 to 200°
with the formation of oxides of the type I n z Q (except cerium, praseodymi
um, and terbium which form C e Q , Pr60il, and Tb4@).
TABLE 46
The melting and boiling points of lanthanide fluorides and chlorides of the
LnxS type, in 'C /21
Fluorides Chlorides
Element
melting boiling melting boiling
264
The halides (except the fluorides) a r e hygroscopic and readily
hydrolyze with the formation of oxyhalides LnOX. Lower halides (LnX2)
a r e known to exist only in the c a s e s of samarium, europium, and
ytterbium.
The l a n t h a n i d e h y d r o x i d e s LXI(OH)~
a r e basic and are sparingly
soluble in water and alkalies. Because of the decreasing basicity i n the
transition from cerium to lutecium, t h e r e is a d e c r e a s e in the pH a t which
the hydroxides s t a r t to precipitate and in their solubility products
(Table 47).
TABLE 47
T h e pH of precipitation and the solubility product of hydroxides of the Ln(OH)s type
~~
Q4 r
I
I
I
( a Ce Pr Nd Pm Sm Eu Ed Tb Py fio Er Tm Yb Lu
Temperature, ' C
FIGURE 131. Solubilities of some FIGURE 132. Solubility of lanthanide oxalates in water a t 25'C.
tures.
265
FIGURE 133. Absorption spectra of solutions of chlorides of trivalent lanthanides,
266
The c h l o r i d e s , s u l f a t e s , a n d n i t r a t e s of the trivalentlanthanides
a r e soluble i n water and in most c a s e s crystallize as crystalline hydrates
of variabie composition. The solubility of the sulfates Lnz(SO43. 8Hz0
d e c r e a s e s sharply a s the temperature is increased from 0 to looo
(Figure 131).
The f l u o r i d e s and o x a l a t e s a r e sparingly soluble in water and
dilute inorganic acids. The fluorides a r e precipitated either a s the
crystalline hydrates LnF, -0.5HzO (La, Ce, etc. ) o r anhydrous s a l t s (e. g.,
of Pr and Nd). The most common composition of the oxalates is
-
Lnz(CZO,), 1OHzO. The oxalates of the lanthanides of the yttrium subgroup
a r e m o r e soluble in water than a r e the oxalates of the cerium subgroup
(Figure 132). When heated to 500 to 600" the oxalates decompose yielding
oxides of the LnzQ type.
The lanthanide p h o s p h a t e s , c a r b o n a t e s , and f e r r i c y a n i d e s
a r e also sparingly soluble i n water.
Most of the simple lanthanide s a l t s have a tendency towards the forma
tion of double o r complex s a l t s with ammonium and alkali metal s a l t s and
with a number of s a l t s of bivalent elements. The most important of these
a r e : the d o u b 1e n i t r a t e s of the lanthanides with ammonium nitrate
Ln(N03),. 2NH4N03*4Hzo and magnesium nitrate 3Mg(N03)z.
24H20, whose solubilities increase in the transition from lanthanum to
gadolinium; the double lanthanide potassium ( o r sodium) sulfates
(e. g., Lnz(S04)3.MeS04.nH20w here n is 1 o r 2). F r o m the standpoint
of their solubility in water, double lanthanide sulfates can be subdivided
into three groups: sparingly soluble (La, Ce, P r , Nd, Sm), of medium
solubility (Eu, Gd, Tb, Dy) and readily soluble (Ho, E r , Tu, Yb, Lu, u). This
is extensively used f o r the advance separation of the lanthanides into the
cerium and yttrium subgroups.
The lanthanides f o r m complex compounds with many organic substances.
The most important a r e the complexes with citric acid and with a number
of aminopolyacetic acids: n i t r i l o t r i a c e t i c acid (NTA), e t h y l e n e
d i a m i n e t e t r a a c e t i c acid (EDTA) and some other so-called
"complexones" ( s e e p. 356). In most cases the stability of the organic
acid complexes of the lanthanides increases from La to Lu, which is the
principle of some methods of separation of the lanthanides. The lanthanide
compounds a r e characterized by the fact that their absorption s p e c t r a a r e
composed of s h a r p bands and lines. The rslative intensities of the bands
in the wavelength range f5om 2000 to 7000 A a r e shown in Figure 133. In
the visible (3900 to 7700 A ), the Ce3+, Gd", La3', Lu3+, and Yb3+ ions a r e
colorless. The remaining lanthanide ions display characteristic colors.
Uses of r a r e - e a r t h metals f 4f
267
F e r r o u s and nonferrous metallurgy. The lanthanides find extensive use
a s additives in the production of steel, pig iron, and nonferrous metal
alloys. They a r e used mainly as f e r r o c e r i u m o r mischmetall ( a lanthanide
alloy in which the main components a r e cerium or c e r i u m and lanthanum).
Lanthanide oxides a r e also used a s additiviesl51.
The addition of lanthanides improves the quality of s t a i n l e s s and high-
speed steels, high-silicon s t e e l s used in electrical technology, and re
f r a c t o r y s t e e l s ; they i n c r e a s e the mechanical strength (and especially the
impact strength), corrosion resistance, and r e f r a c t o r i n e s s , improve the
workability of the steels, the surface of castings, and i n c r e a s e the re-
crystallization (grain growth) temperature of steel. F r o m 0.9 to 2.25 kg
of mischmetall is usually added p e r ton of steel. The addition of cerium
or mischmetall causes deoxidation, desulfurization, and probably denitridi
zation of the steel.
The lanthanide m e t a l s also improve the quality of pig iron (casting
properties, hot ductility, resistance to oxidation, and strength).
The addition of 0.3570 mischmetall to nichrome prolongs i t s s e r v i c e
life a t 1000" by a factor of 10.
F e r r o u s alloys with a high concentration of cerium group metals (70 to
7570lanthanides and 25 to 3070Fe) a r e pyrophoric and find extensive use
in the production of flints ( f o r lighters) and a r e used in a r t i l l e r y for t r a c e r
compositions. Mischmetalls or a mischmetall alloy with tin and magnesium
may also be used for s i m i l a r purposes.
The addition of lanthanide metals to various aluminum and magnesium
alloys i n c r e a s e s their high-temperature strength. Aluminum-copper and
aluminum-copper-silicon alloys containing 0.05 to 0.3570 cerium a r e used
for the production of various a i r c r a f t engine parts. The introduction of
mischmetall i n c r e a s e s the c r e e p strength of the high-strength fine-grained
magnesium alloys (with zinc and zirconium) used in aviation. These
magnesium alloys contain 0.5 to 4 % Zn, 0.6 to 0.770 Zr, and 1.25 to 2.7570
lanthanides.
The production of glass and ceramics. The g l a s s industry is one of
the m a j o r consumers of lanthanides.
The introduction of lanthanides in the composition of glass produces
g l a s s e s which absorb ultraviolet and infrared light. Glass containing
2 to 4% C e 2 Q is used for the production of protective goggles for g l a s s
blowing and welding works. Praseodymium and neodymium h a v e a s i m i l a r
effect.
Cerium-containing g l a s s is r e s i s t a n t (does not fog) under the effect of
radioactive radiation. It is' used in nuclear technology.
Some lanthanide oxides a r e used in the production of optical glass.
Thus, La203is one of the components of silicon-free g l a s s f o r photo
graphic l e n s e s and periscopes. NdzO3together with V20, a r e added to
optical g l a s s for photometers, Nicol p r i s m s and other instruments.
Lanthanide oxides have been used for a long time a s decolorizers and
colorants of glass. Thus, the addition of a small amount of C e Q de
colorizes g l a s s while the addition of up to 1% of cerium oxide makes the
g l a s s yellow while the addition of l a r g e r amounts makes it brown.
Neodymium oxide colors the glass bright red, praseodymium oxide green,
and a mixture of both produces a blue color.
268
Lanthanide oxides a r e extensively used in the optical industry a s
abrasives in the polishing of glass. Cerium dioxide is used preferentially
f o r this purpose (it is known a s "Polirit") in the f o r m of powders of
various particle s i z e s which a r e obtained by varying ignition temperature.
As polishing m a t e r i a l C e q is s u p e r i o r to the conventional polishing
m a t e r i a l ("rouge") from the standpoints of polishing speed and quality.
In c e r a m i c industry lanthanide oxides a r e used a s colorants and
opacifiers f o r porcelain, glazes, and enamels, The u s e of lanthanide
sulfides and oxysulfides a s r e f r a c t o r y and i n e r t substances f o r the
production of metal-melting crucibles is contemplated.
Nuclear technology. Lanthanides with a l a r g e thermal neutron capture
c r o s s section - gadolinium, samarium, and europium (see Table 45) -
a r e of utmost importance f o r nuclear technology. The oxides of these
m e t a l s a r e components of c e r a m i c shields used in atomic r e a c t o r s and
nuclear engines.
Lanthanum s a l t s are used a s coprecipitants ("carriers") f o r the p r e
cipitation and separation of the transuranium elements formed in atomic
r e a c t o r s (e. g . , f o r the separation of plutonium f r o m uranium, and isolation
of neptunium).
Electronics, X-ray and radio technology. In electronics lanthanides
a r e used a s components of nonsputtering gas a b s o r b e r s (getters). Thus,
one of the widely-used gas a b s o r b e r s of the T s E T O type consists of a
finely-divided and sintered mixture of mischmetall with aluminum and
thorium ( 8 0 % Th, 14.570mischmetall and 5.570 Al). Thorium actively
absorbs hydrogen, but a s an absorber of nitrogen it is l e s s active than
cerium and lanthanum.
Neodymium oxide is used in electronic devices as a dielectric with a
low linear expansion coefficient.
Thulium has recently found a very important use; upon irradiation with
r e a c t o r neutrons it becomes a source of y-radiation. The radioactive
isotope (TmI7') formed a s a result of the irradiation is used for the
production of portable s o u r c e s of soft X-rays for medical use and defecto
scopy to replace the bulky X-ray equipment. Such instruments consume
only 0.1 to 0.2 g of thulium oxide over a s e r v i c e life of one y e a r (the half-
life of Tm17' i s 129days). The activity of thulium preparations may be
regenerated by repeating the irradiation.
The promethium isotope Pm14' (half-life 2.7years) i s used for the
production of nuclear "microcells" in which the soft 0-radiation of the
promethium is converted into electrical energy. Such microcells may
be used in miniature receivers, hearing aids, and devices for rockets,
artificial satellites, etc.
E l e c t r i c illumination technology. In this industry lanthanide fluorides
have been in use f o r a long time f o r the production of carbon electrodes
f o r searchlights and movie p r o j e c t o r s ; the lanthanides i n c r e a s e the
illumination intensity. The fluorides (mainly CeF3) a r e introduced a s
components of the central p a r t of the electrode (the "core").
Chemical and light industry. Lanthanide compounds a r e used in the
production of lacquers, paints, and phosphorescent compositions (phos
phors) a s catalysts for the synthesis of ammonia and oxidation p r o c e s s e s
in organic chemistry and a s chemical reagents in analytical chemistry
and photochemistry.
269
Various lanthanide compounds a r e used f o r coloring and tanning of
leather, and in the textile industry as mordants and water-proofing agents.
Agriculture. Lanthanide compounds have been recently used in
agriculture a s insectofungicides (pest control agents) and as microferti
l i z e r s to accelerate plant growth.
72. OCCURRENCE / 1 4 /
270
TABLE 48
T h e composition of some lanthanide minerals
-
Mineral Formula Approximate composition Density. g/ c m 3
~~ .
Monazite ( C e, L a . . . )PO4 5 0 -60% (Ce, La.. .),Os,22-31.5% 4.9 -5.5
P205, 4- 12% Tho,. 0.1 - 0.5% U,
occasionally ZrO, (up to 7%) and
SiO, (up to 6 % )
Xenotime YP04 5 2 - 6 2 . 6 9 YzOs contaminated with 4.45-4.59
C e, Er, and other lanthanides,
occasionally Tho,. UO, (up t o 5 % ).
ZrO, (up to 3%). SnO,. SiO, (up t o
9%1
Bastnasite (Ce, La.. .)FC03 7 3 - 7 7 k ( C e. La, Pr),03, 6.2-8.5PF. 4.8 - 5.2
19.8- 20.2% co,
Gadolinite YZFeBe2SizOlo 10-13.770 FeO, 30.7-46.5% Y z 0 3 , 4.1-4.5
5--23%(Ce, La.. . ) , 0 3 2, 3-24.5%
SO,. 0 . 3 - 0. 4 ~0 Th 0 , . 9-10.2%
BeO, impurities: C a , Mg
Orthite (allanite Ca. Ce.. .),.(Al, Fe), X Up to 6 % C e2 0 s , up to 7 % (La, Ce),03, 1.1
Si3O,,(O, OH) occasionally Be0 (up to 3.8%). up
to 8% Y,03 (yttroorthite), impurity:
Tho,
Loparite (Na, C a s C e. . . ), X 39.2-40%Ti02. 32-3470 t.5-4.89
( T i , Nb. Ta),Os .
( C e, La.. ),03,8-107’0 (Nb, Ta),O,
4.2-5.270 CaO, 7.8-9%Na20,
impurities: Sr. K.Si, Th (0.5-0.6%)
ite- poly-
Eu xen (Y. C e . C a. . . ) x 18.2-27.7%(Y. Er.. .),Os, 0.2-4.370 k.78-5.37
crase* ( T i . Nb. Ta),Os ( C e , La.. . ) , 0 3 1, 6 -3 0 % Ti 0 , ,
4.3-41.470 Nb,Os, 1.3- 23%
TaZO,, 1-570 Tho,. 0.4- 12% UOt
Fergusonite ( Y. E r . C e, U) X $6 -57.5%(Nb. Ta ), 0 5 , 31.42% 5.58-6.23
(Nb. T a . Ti)O, Yz03. 0.9-6%(Ce. La.. .),03,up to
14%Erz03, 1-3.4% T h o , . 1.2
6% UO,, up to 670 TiO, , impurities:
ZrO, , SnO,, W 0 3
Samarskite f , Er.. .),.(Nb, Ta)60, 6.4-14.570 Y2 0 s , 2.7-13.470 Er,O3, 5.6-5.8
up t o 8 % ( C e , L a . . . ) , 0 3 , 21.1
46.8% Nb,O,, 1.8-27.0%Ta,0s,
0 . 4 - 2 % T h 0 2 , 4-167oUOz, i m
purities: T i , Zr, Sn. and others
~~
* T h e mineral is known as polycrase when the (Nb, Ta),05 : TiO, ratio is 1 : (4-6) or lower, and as
euxenite when the ratio is higher than 1 : 3.
271
The lanthanides accumulate in various types of magmatogenic, sedimen
t a r y and metamorphogenic deposits*. Until the present the lanthanide
industry has been based mainly on the exploitation of monazite p l a c e r s and
deposits containing the mineral b a s t n a s i t e (bastnasite-calcite veins).
One of the main s o u r c e s of elements of the cerium subgroup is
m o n a z i t e , which is usually found in pegmatites, and occasionally in
granites and gneisses. A s the bedrock is decomposed, the monazite
p a s s e s into r i v e r and submarine p l a c e r s together with ilmenite, zircon,
magnetite, and other minerals.
The lowest monazite concentration in the worked p l a c e r s is about 1%.
The l a r g e s t deposits have been found in India, Brazil, the USA, Australia,
Madagascar, and Ceylon. Monazite concentrates containing 58 to 65%
Ln203 a r e prepared by gravitational and magnetic beneficiation methods.
F r o m these, the lanthanides a r e isolated a s by-products in the extraction
of thorium.
The approximate composition of monazite concentrates i s shown below
(in 70) :
~(Ln)z03+Y,0s . . . . 58-65 Other (Ln),03+Y,03 . 1-2
c+03 . . . . . . . . .21-30 poz . . . . . . . . . 3.5-6.5
La,03 . . . . . . . . . 1 6 18 " - . . . . . . . . .0.154.3
U9Ua
PrzOs . . . ...... 3-4 PZOS . . . . . . . . . 26-30
Ndz03 . . .
. . . . . . 10-12 Fe,03 . . . . . . . . 0.5-0.8
Sm,03 . . . . . . . . . 1-1.5 TiO, . . . . . . . . . 0.2-1.7
SiO,' ......... 1-2
---------------
* Meramorphogenic deposits are deposits which have undergone changes (outside the wearhering zone)
after their formation; these changes cause, in particular. a partial or total recyrstallization of the rocks
with the formation of new structures and minerals.
2 72
The sulfuric acid method 110, 151
+
2 W-4 PO, 3H2S04 (Lnh (SO,), 2H3P0,, +
+ +
-+
273
Dilute NH40\ 7
Sulfate solution
1
Settling, decantation, filtration,
and rinsing
Precipitate:
ThP,O,, a fraction
of the lanthanides
-Filtrate
(thorium concentrate)
Neutralization t o
1
To the production
pH 2.3
of pure thorium
Setrling, decantarion, filtration
compounds
s
Precipitate:
.
~-
.i
Filtrate
the major fraction
lanthanides
of the T / N H 4 0 H
I
T o the production of
Neutralization to
pH 6.0
pure lanthanide
compounds Precipitate : Solution
uranium. the
residual lanthanides
(uranium concentrate -
1%
1
Discarded
1
To the extraction
of uranium
FIGURE 135. Flow sheet of the processing of sulfate solutions by the stepwise neutralization
method.
274
I
TABLE 49
Composition of precipitates and distribution of thorium. lanthanides, and uranium in
the fractions from the stepwise neutralization of sulfate solutions / 1 6 1
275
a 4570 solution of NaOH at a ratio of 1.5 kg of NaOH p e r kg of monazite
-
(i. e., 30070 e x c e s s over the stoichiometric amount) and by carrying out
the decomposition f o r 3 hours a t 140". Increasing the processing tempera
ture to 200" r e s u l t s in virtually quantitative decomposition but the hydroxide
precipitates formed are sparingly soluble in acids, probably because of
t h e i r partial dehydration. The main disadvantage of the u s e of sodium
hydroxide f o r the decomposition of monazite is associated with the
consumption of l a r g e amounts of the reagent.
Soviet scientists were able to effect a considerable reduction in the
consumption of sodium hydroxide (to 15070of the stoichiometric amount)
and to accelerate the p r o c e s s by using a ball m i l l heated to 130" as the
reactor. The abrasive effect of the balls a c c e l e r a t e s the reaction since
i t destroys the hydroxide layer formed on the g r a i n s of the mineral. Since
the p r o c e s s combines decomposition with grinding, i t does not require the
u s e of a finely divided concentrate.
Grinding
1-
Decomposition
I
Wash waters
I
Dilution and mixing
.1
Filtration and washing
Precipitate Filtrate
Lanthanide and Th Na3P04,NaOH
hydroxides
1
HCI
Y
Dissolution
I I
J-
Evaporation and
crvstallization
I
J.
7
Solution
Na3P0, 1 2 H 2 0 Solution
crystals NaOH
NaOH
--r- (Na,PO, )
7 By-product
L
Dilution and neutralization,
pH 5.8
1 .1
Precipitate
Solujion NaOH
Th(OH),(U, lanthanides)
(thorium concentrate) 7
Precipitation
J
Lanthanide hy
droxides
FIGURE 196. Flow sheet of the alkaline method for the processing of monazite
276
The flow sheet of the alkaline method for the processing of monazite
is shown in Figure 136. The concentrate is decomposed with alkali in
steel reactors. The resulting s l u r r y is discharged into a tank in which it
is diluted with the wash waters from subsequent stages (to a NaOH
concentration of 300/0). In o r d e r to prevent the crystallization of sodium
phosphate, the s l u r r y is heated to 100 to llOo, allowed to stand f o r one hour
at that temperature (to obtain precipitates which are easy to separate
by filtration), and is filtered while still hot. The hydrated cake is washed
with water until the PzQ content is reduced to 0.470 o r less. The filtrate
containing the Na3P04 and the e x c e s s NaOH is evaporated in an evaporator
and the residue is taken f o r the crystallization of trisodium phosphate
(Na3P04-12H20)which is a valuable by-product*.
Since the solubility of Na3P04 in NaOH solutions is v e r y low ( a t 20" the
solubility of Na3P04 in 36% NaOH is only 1.3%), the m a j o r fraction of the
sodium phosphate may be separated from the solution. The NaOH solution
remaining from this stage is returned f o r the decomposition of the
concentrate.
The hydroxide precipitate is dissolved in concentrated hydrochloric
acid, which is taken in about 125%excess with respect to the stoichiometric
amount needed for the reactions:
Jh(OH), + 3HC1 + h C 1 3 + 3Hzo;
Th(OH)4 + 4HCl -+ ThC14 + 4HzO.
After heating f o r one hour to 80" the solution is diluted with water. The
insoluble residue (quartz, zircon, etc. ) is separated by filtration. The
resulting chloride solution is diluted and neutralized with sodium hydroxide
to pH 5.8. This leads to the virtually quantitative precipitation of the
thorium a s thorium hydroxide. Most (99.3% ) of the uranium and about 370
of the lanthanides in the solution a r e coprecipitated with the thorium.
The thorium concentrate is used f o r the preparation of pure thorium
compounds and f o r the extraction of the uranium in it. The approximate
composition of the thorium concentrate is shown below inyo :
211
As compared with the decomposition of monazite by sulfuric acid, the
alkaline method has the advantage of resulting in the separation of
phosphorus from the thorium and the lanthanides in the f i r s t stage of the
process, and yielding a useful by-product - sodium phosphate. The
disadvantages of the alkaline method include a lower degree of decomposi
tion (even if the concentrate is very finely divided) and the consumption
of large amounts of sodium hydroxide.
Fractional crystallization
278
The c r y s t a l s a r e dissolved in a f r e s h portion of the solvent, the solution
is evaporated and the crystallization is repeated. The mother liquor
from the f i r s t crystallization is subjected to a second evaporation and
crystallization. The mother liquor from the second crystallization is then
combined with the c r y s t a l s formed after the second evaporation of the
starting solution. This yields three fractions, each of which is then
subjected to crystallization in a similar manner and the mother liquors
and crystals from successive crystallizations a r e combined.
I Starting solution ]
I
so1
Intermediate fractions
TABLE 50
Relative solubilties of the double lanthanide ammonium and lanthanide magnesium nitrates
(the solubility of the lanthanum salt is taken as unity)
-~
Salt
Ln(NOs)~*2N~NO~.4HzO
2Ln(NC&. 3Mg(NOs),. 2 4 H z 0 1.2 1.2 1.5 3.8
_ _ ~ - - .._____._ .- ___
279
The fractional crystallization of bromates of the elements of the
yttrium group is c a r r i e d out in a s i m i l a r manner.
Fractional precTpitation
The f r a c t i o n a l p r e c i p i t a t i o n o f t h e d o u b l e s u l f a t e s
and hydroxides is m o s t frequently used.
-
The precipitation of the double sulfates (Ln)2(S0J3 Na2S04-nHz0is
extensively used f o r the separation of the lanthanides into cerium and
yttrium groups and occasionally into t h r e e groups:
1) c e r i u m group (La, Ce, Pr, Nd, Sm) - sparingly soluble double
sulfates;
2) terbium g.roup (Eu, Gd, Tb, Dy) - double sulfates of intermediate
solubility;
3) yttrium group (Ho, E r , Tu, Yb, Lu, Y) - soluble double sulfates.
In most c a s e s the u s e of the method is confined t o a rough separation
into the c e r i u m and yttrium (including terbium) groups. The precipitation
is c a r r i e d out from cold sulfuric o r nitric acid solutions containing
sodium sulfate which is added either a s a solid or a s a saturated solution
until the disappearance of the neodymium lines from the absorption
spectrum of the sample.
The separation of lanthanides by fractional precipitation of their hydrox
ides is based on the different pH a t which the precipitation o c c u r s ( i t
d e c r e a s e s f r o m lanthanum to lutecium, s e e Table 47). The solution
containing the lanthanides is gradually neutralized by the addition of a
dilute solution of ammonium hydroxide or by passing through the solution
a s t r e a m of ammonia mixed with a i r (the Trombe method).
The fractions precipitated at the different pH values a r e separated;
a fraction enriched with samarium, europium, and the yttrium e a r t h s is
obtained a t a low pH, followed by the intermediate fractions (Nc? + Pr
contaminated with La), and finally a r i c h lanthanum concentrate (98 to 99%
La) is produced at higher ( > 8.6) pH values.
The fractional precipitations of oxalates (for the cerium group elements)
and ferrocyanides (for the yttrium group) a r e also used for separation.
Selective oxidation
280
isolated from the solution by crystallization a s c e r i u m ammonium hexa
n i t r a t e (NHJ2Ce(NO& o r by precipitation as the basic c e r i u m nitrate
which is formed when the solution is diluted and neutralized
to pH z 0.7 to 1.
Another method which is extensively used f o r the purification of cerium
is the selective extraction of Ce(NO.Jr f r o m 6 t o 8 N n i t r i c acid by diethyl
e t h e r o r tributyl phosphate (see below).
Selective reduction
La = La3f + 3; . . . . . . . . . . -2.37
Y = Y3f +3 9 . . . . . . . . . . . -2. I
Pr = Pr3f +3 e . . . . . . . . . . . -2.0
~ m ~ f = ~ m ~ + .+ .e .
...... -1.72
Yb2f= Yb3++2 .......... -I. 15
Eu2f = Eu3+ +e . . . . . . . . . . -0.43
Pr3f = PI'+ +e . . . . . . . . . . +1.60
~ e 3 f= ~ e ' f +e . . . . . . . . . . + I .61
28 1
water (to remove potassium, a p a r t of which is also separated) and
europium is then extracted with hydrochloric acid.
Another variant of the separation of samarium f r o m europium consists
in the selective oxidation of a mixture of the divalent sulfates of these
elements with n i t r i c acid: samarium is m o r e readily oxidized and is
extracted into solution.
282
Cation and anion exchange r e s i n s a r e produced commercially in the
f o r m of granulated m a t e r i a l s of various particle sizes.
Like the conventional chemical reactions, the ion exchange process,
obeys the Law of Mass Action and is characterized by the ion exchange
constant. Thus, the reaction on cation exchange r e s i n s can be expressed
by the equation:
RMi + Ma Z R 4 + M i ,
where MI and M Z a r e the cations to be exchanged, and R is the insoluble
anion in the cation exchange resin.
F o r a reaction involving exchange of cations of the s a m e valency, the
ion exchange equilibrium may be expressed a s follows, in accordance with
the Law of Mass Action:
283
takes place. The r e s i n capacity is usually determined f r o m the efflux
c u r v e s which show the dependence of the concentration of the exchanged
ion in the filtrate a s a function of the volume
of the solution passed ( F i g u r e 139). The
volume of f i l t r a t e p r i o r to the "breakthrough"
(section 'la") is a m e a s u r e of the working
sorpti'on capacity of the resin. The a r e a
SIcorresponds to the total amount of the ion
absorbed in the r e s i n p r i o r t o the "break
through", while the total area bounded by the
discharge curve is a m e a s u r e of the total
capacity of the resin. The ion exchange in
cludes the following stages:
Volume of solution passed through
1) sorption of ion f r o m solution; the
the column filtration of the solution through the r e s i n
bed is continued either to "breakthrough"
FIGURE 139. Efflux curve for or to complete saturation of the r e s i n ;
sorption on resin under dynamic
conditions.
2) washing the r e s i n with water;
3) elution of the sorbed ion and regenera
a-volume of solution passed prior tion of resin.
to the "breakthrough"; s,-area
In most c a s e s the elution is c a r r i e d out
numerically equal t o the working
sorption capacity of the resin (prior
with solutions containing ions with which the
to the "breakthrough"); C/Cp - r e s i n must be "charged" f o r the sorption
ratio of the ion concentration in cycle. The elution curve has the shape
the filtrate to its initial concentra shown in Figure 140. During the elution
tion. the concentration of the ion in the filtrate
f i r s t i n c r e a s e s rapidly
- " and then d e c r e a s e s
just a s rapidly. When the sorption is c a r r i e d out f r o m solutions with a low
concentration of the ion to be extracted, the sorption-elution cycle yields
solutions in which the concentration of the ion is 1 0 to 100 times higher
than in the starting solution.
FIGURE 140. Typical elution FIGURE 141. Elution curves for two
curve. ions ( M I and M 2 )sorbed on a resin.
The different ions differ in their affinity f o r the resin, which depends
mainly on the ionic charge and the s i z e of the hydrated ion. This is the
principle of the separation of ions by the ion exchange method.
The separation of ions of elements with s i m i l a r properties (e. g . ,
zirconium and hafnium, tantalum and niobium, lanthanide elements) is
284
best c a r r i e d out by the so-called ion exchange chromatography*. The
mixture of ions to be separated is f i r s t sorbed in the upper p a r t of the
r e s i n charge in a column. The ions a r e then eluted from the saturated
layer. Depending on their affinity f o r the resin, the ions in the mixtulre
a r e separated during the elution into individual zones which move along
the column at definite r a t e s . The zone containing the ions with the lowest
affinity for the r e s i n will have the highest r a t e of motion.
The separation of ions MI and M2 (if the affinity of M Ifor the r e s i n is
higher than that of M2)would yield an elution curve such a s that shown in
Figure 141, in which each of the two curves
corresponds to a sorption band containing one
of the ions. At the exit of the column the
filtrate fractions containing MI and M2ions a r e
collected separately. Theoretically, each
zone should contain the ions of only one of the
elements to be separated. In practice, how
ever, the zones a r e superimposed (the
extremities of the elution curves often spread
out) which makes quantitative separation
difficult.
The separation of ions with s i m i l a r proper
ties may be made m o r e efficient by using eluent
solutions containing some complex-forming
agent which binds the ions to be separated into
complex compounds of various degrees of
stability.
ron exchange p r o c e s s e s a r e c a r r i e d out in
cylindrical columns charged with the granulated
resin. A draining system (grid) which allows
the solution which has passed through the r e s i n
bed to be tapped without entrainment of resin
particles is fitted to the lower p a r t of the
FIGURE 142. Diagram of an
installation for the separation filter (see Figure 142).
of elements by ion exchange. Various types of cation exchange r e s i n s a r e used
f o r the separation of lanthanides by ion exchange
1-column; 2-grid; 3-ion
exchange resin; 4-upper
(the resin used in the USSR is KU-2, in the
layer of the resin, with the USA Dowex 50 and others). These r e s i n s a r e
mixture of elements to be strongly acid cation exchange r e s i n s produced
separated sorbed on it; 5 by copolymerization of styrene and divinyl
pressurized vessel with the benzene and containing S03H as the active
solution containing the elements
group.
to be separated; 6-vessel with
The affinity of the lanthanides f o r the resin
the eluent; I-collection vessel
for the filtrate.
decreases from La3+ to Lu3+,i. e . , a s the size
of the hydrated ions is reduced. However, the
affinities of the various lanthanides f o r the
r e s i n differ only very slightly and the separation is not entirely satisfac
tory. Better separation is obtained by eluting with solutions containing
* T h e chromatographic method was developed by the Russian botanist Tsvet in 1903, who intended t o use
i t for the separation of plant pigments. T h e term "chromatographic adsorption" was proposed by Tsvet
on account of the colored adsorption bands which were produced on the adsorbent during the separation.
285
organic compounds which form complexes of different degrees of stability
with the lanthanides.
The o r d e r of the elution corresponds to the relative strength of the
anionic lanthanide complexes. As the eluent moves along the column (or
a number of columns connected in s e r i e s ) the mixture of cations is
separated into sorption zones (bands) which move at certain definite
velocities. Various organic compounds which form lanthanide complexes
a r e used f o r the elution: c i t r i c acid, nitrilotriacetic acid (NTA), and
ethylenediaminetetraacetic acid (EDTA). EDTA is the eluent most widely
used in the chromatographic separation of the lanthanides. It is an
a-amino acid. EDTA is a tetrabasic acid with two nitrogen atoms:
CH2COOH
\
CH2COO- I
The stability constant of these complexes is given by the equation:
286
which improve the separation. The copper complex with EDTA is m o r e
stable than the complexes of most of the lanthanides with EDTA ( s e e
Figure 143). Thus, when the eluent containing the complex lanthanide-
EDTA ions is passed through the separatory column, the copper ions p a s s into
solution and d i s p I a c e the lanthanide ions from the soIution into the resin,
thus retarding their motion. The lanthanide ions a r e displaced from the
solution on to the r e s i n in an o r d e r corresponding to the strength of their
complexes with EDTA, which r e s u l t s in the formation of better defined
sorption zones.
Usually the pH of the eluent is adjusted to 4 to 8.5 (depending on the
operating conditions) by neutralization with ammonium hydroxide. Thus,
the eluent contains the ammonium salt of EDTA. A dilute solution of EDTA
(0.5 to 1%) is used a s the eluent since the ammonium s a l t s of the
lanthanide-EDTA complex acid (NH4( LnEDTA) nHzO) and the copper complex
-
Cuz(EDTA) 5Hz0 a r e not very soluble. The use of m o r e concentrated
solutions causes the precipitation of s a l t s which clog the p o r e s between
the r e s i n grains and thus interfer with the normal operation. The low
EDTA concentration in the eluent limits the output of the separation
p r o c e s s since the lanthanide concentration in the filtrate is low.
la&hMn&EuMn&2b&+fin4
Elements T i m e , hours
FIGURE 143. Dependence of log K FIGURE 144. Elution curves of terbium. europium,
on the atomic number of t h e lantha and samarium sorbed on the resin by a 0.26 M so
nides ( K is the stability constant of lution of EDTA, a t pH = 3.62.
the lanthanide-EDTA complex).
287
stability of their EDTA complexes. Figure 144 gives the elution curves
(with EDTA solutions) for the separation of three elements. The f i r s t
wave corresponds to the elution of terbium, the second to europium, and
the third to samarium, in accordance with the decreasing complex strength
in sequence Tb-Eu-Sm.
The EDTA solutions a r e regenerated by acidification to pH 0.5 to 1.
This causes the decomposition of the lanthanide complexes and the p r e
cipitation of the sparingly soluble EDTA.
If the initial specific charge on the column* with the lanthanide mixture
is small ( l e s s than 5% on the weight of the resin) and the total length of
the separatory columns is l a r g e enough, each filtrate fraction at the
i s s u e from the l a s t column contains only one of the elements to be separated.
The chromatographic method may be used to prepare individual
lanthanides of a high degree of purity, but the yields a r e low. Accordingly,
in most cases the elements a r e preliminarily separated by some other
method and the ion exchange method is used only for the separation and
purification of like elements.
Extraction
Atomic number
_________-----
* T h e specific charge is the ratio of the weight of the ions sorbed on the resin to the total weight of the
resin.
288
When lanthanide n i t r a t e s a r e extracted by T B P from solutions in which
the HN03 concentration is above 5 M the distribution coefficients steadily
i n c r e a s e with the atomic number of the element (Figure 145). The
separation coefficients 0 = f o r two adjacent elements depend on the
=Z
nitric acid concentration*. Thus, f o r Z-values between 57 (lanthanum)
and 6 4 (gadolinium) the separation coefficients a r e 1.9 and 1.6 f o r solutions
with nitric acid concentrations of 15.6 and 1 2 M respectively. The n i t r i c
acid concentration may be reduced without decreasing the value of 0 by
adding t o the solution certain n i t r a t e s (Al(NQ)s, LiNQ) which a c t a s
salting-out agents, i. e., which displace the lanthanide n i t r a t e s into the
organic phase. The separation coefficients for adjacent elements in the
yttrium group ( Z = 64-71) a r e lower than in the cerium group. Hence,
their separation by extraction is m o r e difficult than the separation of
elements in the cerium group.
The distribution coefficients i n c r e a s e with increasing concentration of
the lanthanide in the solution; this makes i t advantageous to p r o c e s s l a r g e
amounts of lanthanides.
Two extraction methods a r e used for separation purposes:
1) in countercurrent in column extractors o r a s e r i e s of m i x e r - s e t t l e r
extractors, with the aqueous and organic phases moving continuously in
countercurrent ( s e e Figure 66) ;
2) in semi-countercurrent in which the aqueous phase is stationary
while the organic phase is in motion and the mixture to be separated is
added at the beginning to the f i r s t extractor (Figure 146).
Extractant
cP
FIGURE 146. Diagram of semi-countercurrent extraction.
1 -mixing chamber: 2-settler; I, 11,111, IV, V -aqueous fractions.
When using the first method the starting mixture of the lanthanides is
separated into two fractions. Since the separation involves not two, but
a l a r g e number of elements, the p r o c e s s must be repeated many times
(i. e . , multistage extraction is required) and the number of separations
must be at l e a s t n- 1, where n is the number of elements to be separated.
However, the p r o c e s s has the advantage of being completely continuous,
which is to be p r e f e r r e d for the separation of l a r g e quantities.
--------------
* a Z + l and a Z are the distribution coefficients for elements with atomic numbers Z + l and Z respectively.
289
In semi-countercurrent extraction the starting mixture of elements to
be separated is introduced into the f i r s t extractor and the remaining
extractors a r e filled with a solution of nitric acid ( o r a solution containing
nitric acid and the salting-out agent). The organic phase (TBP) is then
fed into the system and p a s s e s successively through all the extractors.
The contact between the aqueous and organic phases in each extractar
r e s u l t s in the establishment of an equilibrium distribution of the elements
between the two phases. Elements with lower atomic numbers concentrate
in the f i r s t extractors while elements with higher atomic numbers con
centrate in the l a s t extractors. Thus, a single passage of the extractant
leads to the separation of the lanthanide mixture into a number of
fractions. The technique is convenient when separation of small
quantities is involved. Both undiluted TBP and solutions with a high
concentrationof lanthanidenitrates (100-20Og/lof Ln203) areviscous. Thus,
it is recommended that extractors of the mizer-settler type be used.
The extractive separation method has a high output and i t s use is
increasingly frequent.
Separation scheme
~
0:idation Af C e
ce4+ arfd separation
concentrate-
&
To purification Fractional precipitation of th
hydroxides or crystallization!
of the double nitrates
La concentrate 1-1
b
Fractional crystallization of the double nitrates
(repeated a few :imes)
chromatography
Reduction with Zn
290
The mixture taken for the separation usually contains hydroxides and
is f r e e of contaminants. The cerium is separated f i r s t , by oxidation
( s e e p. 281). After the separation of the cerium, lanthanum concentrate
is isolated from the nitrate (occasionally chloride) solution by fractional
concentration of the hydroxides o r fractional crystallization of the double
ammonium nitrates. The remaining elements a r e subjected to a rough
separation into s e v e r a l fractions by fractional crystallization of the double
nitrates. Neodymium and praseodymium a r e then separated by extraction
and by the chromatographic method.
Samarium and europium a r e isolated and separated from the inter
mediate samarium-europium fraction by the reduction method (,see p. 281).
The elements of the third fraction a r e separated by reduction, extraction
and ion exchange.
The above scheme still includes fractional crystallization as a means
of rough separation. In m o r e modern schemes extractive methods a r e
used for the separation into fractions.
+
2(Ln),03 6S,CI, + 4(Ln)CI, + 3 S 0 , + 9s;
--f
(Ln),O, +
6NH4CI 2 ( Ln)CI, + 6NH3 + 3H,O.
--f
(in -
chloride. In this p r o c e s s a mixture of the lanthanide oxides and NH&1
1000Jexcess over the stoichiometric amount needed) is heated
a t 200 to 300" until a sample withdrawn from the reaction mixture proves
- - -- -- - -- --- - --
* Carbon tetrachloride is a nonflammable liquid boiling a t 18".
292
to be fully soluble in water. The e x c e s s NH&l is then expelled by heating
the chloride to 300 to 320° in vacuo (0.5 to 2 mmHg). The elimination of
ammonium chloride must be quantitative to prevent contamination of the
lanthanides by nitrogen.
Since the anhydrous lanthanide chlorides a r e very hygroscopic, they
m u s t be t r a n s f e r r e d rapidly f r o m one container to another when hot and
out of contact with humid air. It is best to s t o r e the chlorides in an i n e r t
gas.
Anhydrous lanthanide fluorides may be prepared by dehydration of the
hydrates precipitated from solution o r by the action of hydrogen fluoride
o r ammonium bifluoride on lanthanide oxides.
D e h y d r a t i o n o f f l u o r i d e h y d r a t e s . Lanthanide fluorides a r e
sparingly soluble and a r e precipitated quantitatively from chloride, sulfate
and nitrate solutions by the addition of hydrofluoric acid. They are
precipitated either as the hydrated fluorides of the LnF3 0.5HzO type -
(La, Ce, and other fluorides) or a s the anhydrous fluorides (Pr and Nd).
When a solution containing the fluoride precipitates is heated under an
infrared lamp, the hydrated fluorides a r e converted into the anhydrous
form. The precipitates a r e then separated by filtration, washed with
alcohol, and dehydrated further by heating to 400" in a d r y i n e r t gas
atmosphere (argon) under reduced p r e s s u r e (about 100" Hg). The
fluorides prepared by the above method a r e still contaminated with the
oxyfluorides LnOF. The formation of the oxyfluorides may be prevented
by drying in a s t r e a m of hydrogen fluoride.
F l u o r i n a t i o n o f o x i d e s . Fluorides of a higher degree of purity,
which a r e not contaminated with oxyfluorides, a r e produced by the action
of gaseous hydrogen fluoride on the oxides:
(Ln),O, + 6HF + + 3H,O.
2( Ln)F3
A rapid reaction takes place at 550 to 575". The p r o c e s s may be c a r r i e d
out in nickel or nickel-copper ( 7 0 % Ni, 30% Cu) tubes inwhichthe boats with
the oxides move in a direction opposite to the direction of the gas flow.
At 500 to 600" the r a t e of attack of d r y hydrogen fluoride on nickel is very
low (about 0.9 "/year) because of the formation of a protective film of
nickel fluoride. Graphite boats may be used. Hydrogen fluoride i s fed
into the tube from s t e e l tanks. The unreacted gas a t the i s s u e from the
tube may be absorbed either in a sodium carbonate solution or in con
d e n s e r s cooled with dry i c e (solid C Q ) and returned to the fluorination
process.
Ammonium bifluoride NH,HFz may be used a s the fluorinating agent
instead of hydrogen fluoride. Lanthanide oxides a r e fused with ammonium
bifluoride a t 200":
( Ln),OS + 6NH,HF, + a( Ln)F, + 3H,O + 6NH4F.
The excess ammonium bifluoride and ammonium fluoride a r e then
expelled by distillation at 450". The p r o c e s s yields a fluoride with a
composition s i m i l a r to that of the fluoride produced by fluorination with
gaseous HF. However, ammonium fluoride must be quantitatively r e
moved in o r d e r to prevent contamination of the m e t a l s with nitrogen.
Since this is r a t h e r difficult, it is best to p r e p a r e lanthanide fluorides by
fluorination with hydrogen fluoride.
293
In contrast with lanthanide chlorides, lanthanide fluorides a r e not very
hygroscopic. However, they can absorb gases from air. Hence, it is
recommended that they be stored in an i n e r t gas atmosphere.
The purity of the metals thus produced depends on the impurity content
of the starting m a t e r i a l s and of the crucible material used f o r the
smelting of the metals and of the electrodes (when electrolytic methods
a r e used).
The data in Table 51 show the resistance of various refractory materials
and metals to the action of molten lanthanides. Of the oxides, electrically
fused magnesium oxide and beryllium oxide possess a satisfactory
resistance up to 1200". Tantalum is the most resistant of the refractory
metals, and may be used for melting lanthanides at temperatures up to
1700". Molybdenum is also quite resistant, and is frequently used a s the
cathode in the electrolytic production of r a r e - e a r t h metals.
TABLE 51
Interaction of lanthanides with various electrode and crucible materials
Material I
Behavior
1455
294
electrolysis of anhydrous lanthanide chlorides dissolved in molten alkali
or alkaline-earthchlorides. This method is used f o r the production of
commercial quantities of mischmetall, cerium, lanthanum, neodymium,
and other metals of the cerium group. During the electrolysis the molten
metals a r e deposited on the cathode since their melting points a r e
relatively low.
The electrolytic production of metals of the yttrium group (with the
exception of ytterbium) which have high melting points (1350 to 1700") is
m o r e difficult. Electrolysis which would deposit the molten metals on the
cathode is virtually impossible a t s u c h temperatures, because of the
vaporization of the halides and the difficulties associated with the selection
of bath and electrode materials. In o r d e r to obtain these metals in a liquid
state without raising the bath temperature above 1100" the electrolysis is
c a r r i e d out with liquid cadmium or zinc cathodes and the larithanides a r e
obtained as an alloy with the cathodic metal. The r a r e - e a r t h metals a r e
then separated from zinc or cadmium by vacuum distillation of the latter.
This method has been used on a laboratory scale for the production of
lanthanum, samarium, gadolinium, europium, and dysprosium.
295
molten mixtures. The bath contains about 58 to 6 0 % LnCls and the r e s t
consists of the alkali and alkaline-earth chlorides. The addition of small
amounts of calcium fluoride is r e
commended.
A n electrolyzer used in Germany for
the production of technical grade misch
metal1 / l o / is shown in Figure 148. It
consists of a graphite crucible (serving
a s the cathode) on a grapliite bottom
plate placed in a cast-iron body. The
body is fitted with pivots which permit
the bath to be rotated. The electrical
current is supplied to the body, which
is in electrical contact with the graphite
plate, by means of a packed layer of
graphite and pitch. The graphite
crucible is fastened to the bottom plate
with the aid of a cast-iron ring. The
cast-iron body together with the crucible
FIGURE 149. Diagram of an electrolyzer for a r e mounted within an iron jacket. The
the production of pure rare-earth metals.
space between the jacket and the crucible
1-furnace; 9-graphite crucible (anode); is packed with crushed chamotte and the
3-beryllium oxide crucible; 4-molten bottom is lined with chamotte bricks.
cerium; 5-molybdenum cathode; 6
The bath volume is 30 l i t e r s . A lifting
electrolyte; I -nickel crucible; 8-tubular
quartz shield; 9-asbestos gasket; 10-water graphite anode 100" in diameter is
cooled copper tube connecting t h e anode to the fitted in the center of the bath.
current; 1 1 --graphite cover. At f i r s t the electrolyte is fused by
passing current through the graphite rod
placed between the electrodes. The
rod is then removed and the bathismaintained in a molten state by the heat
evolved in the passage of the current through the melt. Additional batches
of the charge a r e periodically fed into the electrolyte and the process is
continued until the crucible has been filled. The concentration of oxy
chlorides LnOCl (which a r e formed by the interaction of lanthanide
chlorides with moisture from the air) in the lanthanide chlorides taken for
electrolysis must be a s low a s possible. The oxychlorides a r e not de
composed by the current, but their presence in the melt causes partial
precipitation of the metal on the cathode in a finely dispersed state ( a s a
I' mist"). The fine metallic particles float to the surface of the bath and
a r e oxidized if the electrolysis is c a r r i e d out in the presence of air. When
the finely dispersed metal particles reach the anode they a r e chlorinated,
yielding chlorides which dissolve in the melt. The appearance of these
finely dispersed particles r e s u l t s in a sharp decrease in the current
efficiency. The deposition of the metal in a finely dispersed state is also
observed a t very high o r very low current densities.
The electrolysis is c a r r i e d out at a potential of 12 to 15 V and a current
296
contents a r e poured into s t e e l pans preheated to 500 to 550’. During the
pouring the metal is protected against oxidation by the molten salt.
The mischmetall or cerium produced by the electrolysis contains 94 to
99% lanthanide elements and a s e r i e s of impurities: carbon, calcium,
aluminum, up to 1% silicon, 1 t o 2.5% iron, etc. A metal of a higher
degree of purity may be produced by using electrodes made of metals which
do not r e a c t with lanthanides (molybdenum and especially tantalum), by
using pure mangesium and beryllium oxides f o r the lining of the crucible,
and by conducting the electrolysis in an i n e r t gas atmosphere.
Cerium of a higher degree of purity has been produced on a laboratory
s c a l e by the electrolysis of its chloride using a molybdenum cathode, by
keeping the metal out of d i r e c t contact with the graphite. A diagram of
the electrolyzer used is shown in Figure 149.
A graphite crucible serving a s the anode is protected against oxidation
by placing it inside a nickel crucible, and a molybdenum rod is used a s
the cathode. To prevent oxidation, the upper p a r t of the rod (i. e . , the p a r t
outside the melt) is enclosed in a quartz tube. The molten metal is
collected in a beryllium oxide crucible placed beneath the cathode on the
bottom of the graphite crucible, The cerium produced under these
conditions is - 99.770 pure. The main contaminants a r e : F e 0.02 to
0.04”/0, Si 0.06 to 0.670, Mo < O.Ol”/o, Mg O.Ol%, Ni 0.4 to 0.670, A1 0.1 to
0 . 6 0 / , Be 0.2 to 0.970, Ca 0.05 to 0.2570.
Electrolyzers of this type have been used f o r the production of relatively
pure m e t a l s of the cerium group, a s well a s the higher-melting metals of
the yttrium group. In the case of the yttrium group metals, molten zinc
or cadmium (contained in a c e r a m i c crucible on the bottom of the graphite
crucible) s e r v e s a s the cathode. The c u r r e n t is supplied to the liquid
cathode by means of a molybdenum rod insulated with a porcelain tube
(to prevent contact with the electrolyte). Zinc o r cadmium a r e easily
removed from the cathodic alloy by vacuum distillation a t 900”.
297
samarium, europium, and ytterbium, whose compounds a r e reduced only
to the lower halides. A method was accordingly developed f o r the produc
tion of these three lanthanides by reduction of their oxides with lanthanum
and a simultaneous vacuum sublimation of the products.
TABLE 52
Heats and free energies of formation of lanthanide halides,
k cal / g - at o m of chlorine and fluorine
I Chlorides Fluorides
Pr
..
Nd
-86
24.7
-82.3
-81
-80.3
-74
I - 69.7
- 68.7
- 68.3
- 87
-140.3
-138.7
-134.3
-136.7
-134
-132.3
-131.3
-130.3
-120
-118.3
-117.7
-116.3
Pm -84 -136 -129.7 -115.7
Sm -82.7 -13.5 -128.7 -114.7
EU -77.7 -130.3 -124.3 -110.3
Gd -81.7 -134.7 -128.7 -114.7
Tb -70.3 -133.3 -127.3 -113.3
-78.7 -126.7 -112.7
2
Er
-77.7
-77.3
-132.7
-131.7
-130.7
-125.7
-124.7
-112
-111
TU -76.3 -130.3 -124.3 -111
Yb -71.3 -125.3 -119.3 -106
LU -76 -130.7 -124.7 -111.3
Na -98.3 -136 -129 -112.6
ca -95.3 -145.1 -139.1 -124.8
-131.5 -126 -112.8
-107.7 -102 - 89.7
298
__ .. -.. . .... - , I . , ..
The calcium is added to the mixture in a -
15 to 2070 excess over the
stoichiometric amount needed f o r the reaction: 2LnC13+3Ca = 2Ln +
3CaC12. When the process is c a r r i e d out
on a s m a l l scale, the reaction heat does
C a O packing not suffice to m e l t the produced metal
and the slags. To increase the heat of
reaction, iodine is added to the charge
Fired refractory ( 0 . 3 to 0.7 moles iodine/mole chloride)
lining
together with an additional amount of
calcium needed to form Car2*.
Moreover, the introduction of iodine
reduces the melting. point of the slag by
the formation of a eutectic mixture of
CaClz and CaI2. The hermetically
sealed vessel containing the charge is
heated to 700" in o r d e r to initiate the
reaction. The metals a r e produced in
C a O packing
an average yield of 95'3'0, in the form of
FIGURE 150. Reaction vessel (bomb) used dense ingots which a r e easily separated
for the thermal reduction of lanthanide from the slag. The metals contain
chlorides by calcium.
about 270 calcium which is separated by
remelting of the metals in vacuo, in
magnesium oxide or beryllium oxide crucibles.
Magnesium oxide crucibles cannot be used if the reduction is to be
effected at temperatures above 1200" (e. g . , in the case of gadolinium).
Tantalum is the most suitable reactor m a t e r i a l since i t does not r e a c t
with most of the lanthanides below 1500 to 1600".
The reduction is c a r r i e d out in a welded tantalum crucible covered
with a perforated lid, in an argon atmosphere. High-frequency heating
is employed (no heating additives a r e added to the charge). The
lanthanides adhere strongly to the tantalum and the tantalum shell must
be removed by mechanical means. In o r d e r to save tantalum, the
crucibles a r e made of thin (0.02 to 0.06") foil.
Reduction of the fluorides. Lanthanides with high melting points (Tb,
Dy, Ho, Er, Tu, Lu, Y) cannot be produced by the reduction of their
chlorides. The main difficulty i s the high vapor p r e s s u r e s of the lanthanide
chlorides a t the temperatures (1500 to 1600') required for the production
of ingots. The boiling points of lanthanide fluorides a r e higher than those
of the chlorides (see Table 46). Moreover, a s compared with the chlorides,
the fluorides have the advantage of being nonhygroscopic. Thus, their
handling is m o r e convenient.
According to American literature, the reduction of the fluorides by
calcium is c a r r i e d out in tantalum crucibles in an argon atmosphere.
When mixing calcium with lanthanide fluorides, c a r e is taken to reduce
a s much a s possible the contact with the atmosphere. Calcium is added
to the charge in a 10% excess over the stoichiometric amount needed f o r
the reaction:
+
3Ca = Z n + 3CaF,.
The charge is packed in a tantalum crucible (which is degassed in
advance by heating in vacuo), covered with a perforated lid and placed in
_______-_____-
* T h e heat of formation of CaII is 128.5 kcal/mole.
299
the quartz tube of a vacuum induction furnace. In o r d e r t o degas the charge
the crucible is heated slowly in vacuo to 600". At that temperature, pure
argon is fed into the apparatus until the p r e s s u r e reaches 500mmHg and
heating i s continued to the temperature a t which an active reaction begins
between the fluoride and the calcium. Depending on the m e t a l to be
produced, that temperature lies between 800 to 1000". The reaction is
exothermic but the heat evolved is not sufficient t o r e a c h the required final
temperature and the heating must be continued. In o r d e r to obtain a high
yield of the m e t a l (in the ingot) the temperature a t the end of the process
must be highar than the melting points of the m e t a l and the slag (the
melting point of CaFz is 1418"). A temperature of 1450" is sufficient in
the c a s e of the low-melting lanthanides and Gd,Tb, and Dy, while tem
p e r a t u r e s 50° above the melting point are required f o r lanthanides with
higher melting points.
After the temperature of vigorous reaction has been reached, the
reaction is completed within a few minutes; the maximum temperature is
then maintained f o r another 15 minutes in o r d e r to obtain satisfactory
separation of the metal from the slag. Under these conditions, the yield
of the m e t a l (in the ingot) reaches 97 to 99%. The mixture is cooled and
the b r i t t l e s l a g is easily separated from the metal. The main contaminant
in the ingot is calcium (0.1 to 2%). To remove the calcium, the ingot is
remelted in vacuo, in the s a m e crucible. Using this method, 300g of the
metal may be produced in a crucible 50" in diameter and 200" high.
The tantalum concentration in the light lanthanides (from La to Nd) is
0.02 to 0.0370, and in the heavy lanthanides 0.1 to 0 . 5 % . The concentra
tions of other impurities a r e : Ca 0.0170, N 0 . 0 0 5 ~ 0 ,0 0.03 to O.l%, C
0.0075%, and F 0.005%.
* To prevent rontamination with copper. the surface of the condenser is coated with a thin layer of the
oxide of the m e t a l t o be produced.
A suspension of the oxide i n alcohol is used for the coating.
300
301
Part Three
Chapter VII
GERMANIUM
Properties of germanium
Germanium is a light-gray e l e y e n t , with a diamond-type cubic lattice
and a lattice p a r a m e t e r a = 5.657 A (Figure 151). Each germanium atom
is surrounded by four equidistant atoms positioned on the vertexes of a
tetrahedron; the atoms a r e bonded through paired valency electrons.
Some physical proDerties of germanium a r e listed below:
302
. . . . . . . . ..._.... .............
_______-_-_____
[or "band" theory.]
** It must be noted that the location of an electron at a certain energy level designates its potential energy
rather than its geometrical (physical) position.
303
Two types of conductivity may be distinguished in semiconductors
e 1e c t r o n and h o 1e t y p e conductivity*. Both types of conductivity a r e
the result of the disturbance (caused by heat, illumination, e t c . ) of the
separate valency bonds between the paired electrons and the transfer of
electrons into the conductivity zone (Figure 153). When an electrical field
is acting on the body, the f r e e electrons move in a certain direction
creating an electrical current. Such conductivity is known as n - t y p e
conductivity.
........
. ....
. . ......
a
..........
.......
. . . . . . .1
b
1 %..*
C
'***.**-*'
d
h-q: mu-h
FIGURE 152. Energy zones.
_______-------
* [Or "n-type" and "p-type" conductivity, respectively. ]
304
h the ideal c a s e (i. e., semiconductor c r y s t a l s not containing impurities)
the number of f r e e electrons equals the number of holes, and the contribu
tions of electrons and positive charges (holes) to the conductivity a r e equal.
Such conductivity is known a s i n h e r e n t conductivity. The addition of
s m a l l amounts of other elements may c r e a t e conditions such that the
numbers of electrons and holes a r e not equal. In such a c a s e (depending on the
nature of the additive) the conductivity is created preferentially through
the motion of either electrons (n-type semiconductors) o r holes (p-type
semiconductors) .
Some of the additives which c r e a t e an n-type conductivity in germanium
(the so-called donor additives) are elements whose valency is higher than
four, e. g. , arsenic, antimony, and phosphorus. This is because when
a pentavalent element replaces a germanium atom in the lattice, the fifth
electron is weakly bound to the atom and readily p a s s e s into the
conductivity zone (see Figure 153). The additives producing p-type
conductivity (acceptor additives) comprise elements with a valency below
four - indium, gallium, aluminum, copper, zinc, etc. One unfilled lattice
point remains when the atom of a trivalent element replaces an atom of
tetravalent germanium. In such a case the number of holes is g r e a t e r than
the number of electrons.
The conductivity of semiconductors is strongly affected by external
factors such a s illumination, heat, and electric field. The effect of a light
beam on the conductivity is known a s the p h o t o e 1e c t r i c effect.
One of the important properties of semiconductors is that a thin film
which conducts the c u r r e n t only in one direction is created on the boundary
when semiconductors of different types (n- and p-type) a r e brought into
contact. This film is known a s the b a r r i e r layer. Accordingly, semi
conductors may be used a s rectifiers.
Some of the electrical properties of germanium, which a r e of value f o r
i t s characterization a s a semiconductor, a r e listed below:
--------------
* T h e mobility of the current carriers (p) is a measure of the
drift (motion) rate of electrons or holes in an electric field
with an applied voltage of one volt.
305
The action of ammonia on germanium o r germanium dioxide a t 700 to
800" r e s u l t s in the formation of germanium nitride Ge3N2. The nitride is
not decomposed by water, dilute alkalies, o r acids. It dissociates a t
about 1000".
A vigorous reaction between germanium and chlorine is observed a t
room temperature, with the formation of GeC14 (bp 83"). Germanium
r e a c t s with bromine and iodine on heating. Sulfur vapor r e a c t s with
germanium, yielding GeS.
Germanium is not attacked by hydrochloric o r dilute sulfuric acids.
The metal is slowly dissolved by hot concentrated sulfuric acid, with the
evolution of S Q . Nitric acid r e a c t s with germanium, yielding the hydrated
-
dioxide GeOn nH20. The metal is readily dissolved by aqua regia. Alkali
solutions have little effect on germanium, but i t is rapidly dissolved by
molten alkalies in the presence of air.
Germanium dissolves in dilute hydrogen peroxide solutions, yielding
pe rge r m anic acid.
Germanium f o r m s no carbides. It can be fused in a graphite crucible
without significant contamination with carbon.
306
GeS, + + 2) H,O zGeO,- n H,O + 2H&
(rt
Uses of germanium / 5 /
307
a r e m o r e stable to mechanical vibration and impact, and a r e much s m a l l e r
in size. Since no energy is used to heat the emitter ( a s in vacuum tubes),
the efficiency of crystal amplifiers attains 40 to 50%. All these advantages
favor the use of c r y s t a l rectifiers and amplifiers, especially so in complex
computers, remote control, and r a d a r setups.
Rectifying contacts (known as p-n o r n-p junctions) a r e produced in
germanium monocrystals through the diffusion of impurities to the surface
layer of a germanium plate. One commonly used method for the formation
of a rectifying contact is the application of molten indium to the surface
of a plate of n-type germanium. As a r e s u l t of the diffusion of indium
atoms into the germanium, a thin layer with p-type conductivity is created
at the contact s i t e .
In addition to i t s use a s rectifiers in radio receivers, germanium has
been recently used a s high-power rectifiers. of standard frequency AC, for
currents of 6000 to 10,000 amp o r more. These r e c t i f i e r s a r e characterized
by their high efficiency (the direct current produced is 95% of the
alternating current used). Germanium rectifiers operate a t current
densities which exceed several times the maximum permissible current
density in selenium and other rectifiers. They a r e s m a l l in size and a r e
especially convenient to move from place to place.
Germanium triodes a r e extensively used for the amplification,
generation, o r transformation of electrical oscillations. There a r e two
types of triodes: n-p-nandp--n-p. In n - p - n triodes two l a y e r s
of n-type germanium a r e separated by a thin layer with a p-type
conductivity, while in p - n- p triodes the center layer has n-type
conductivity while the external l a y e r s a r e of p-type ( s e e Figure 154).
a b
1-germanium; 2-indium.
308
vessels, and various mechanisms, s o that automatic signalization and
control a r e readily effected, Thermistors a r e a l s o used in time relays
and in instruments ensuring a gradual (at any desired rate) increase of
the current in a circuit.
Germanium is used f o r the production of p h o t o c e 11s with a b a r r i e r
layer and of t h e r m o e l e m e n t s .
Germanium f i 1m r e s i s t o r s a r e used in radio technology. A thin
film deposited on glass by thermal dissociation of the gaseous mono-
germane Ge�& o r germanium halide (GeC14, G I 4 ) has a resistance between
1000 o h m s and several megohms.
Other uses of germanium a r e of secondary importance. Thus, for
instance, uses have been proposed for some germanium alloys. An
aluminum-germanium alloy (7470Al, 2170 Ge, 270 Fe, and 370Si) has been
recommended for the production of vacuum tube cathodes. The use of the
low-melting eutectic Au-Ge alloy (12% Ge, mp 356") has been proposed
to obtain hard coatings on gold and for improving the quality of the gold
solders. The presence of small amounts of germanium improves the
fatigue and corrosion resistance of magnesium castings and increases
their creep strength.
The production of germanium in the Western countries in 1 9 6 0 to
1962 is estimated at 6 0 to 70 tons. The production volume at the present
time is very probably higher.
78. OCCURRENCE
309
Behavior of germanium during processing of sulfide
raw m a t e r i a l s
310
I
TABLE 53
Approximate composition of the dust formed in the smelting of copper
concentrates in water-jacketed furnaces
Ge 0.36 0.007-0.008
Zn 28 23.6-31.36
Pb 25 16.35-19.5
Cd 3 i' 0.10-0.13
0.66-1.06
cu 1.5
As 1.3 Not determined
Bitumen 6.34-7.10
31 1
by the fuming process. It must be noted that the l a r g e s t fraction of the
germanium (of i t s total content in the raw material) passes into the slags,
although i t s concentration in the dusts is higher than in the slags.
In slags ......................
In ash ......................
.51.1
.19.0
) 70.7
When the same coal was burned in a deficient supply of oxygen (e. g. , in
gas generators), the distribution of germanium was different. About 75%
of the germanium passed into the dust from the flues and 2 5 % of the
germanium passed into the ash and slags. This is attributed to the fact
that the volatile germanium monoxide GeO is formed in reducing medium.
The concentration of germanium in the dust and carbon black from gas
producingplants sometimes attains 1%. Thus, the germanium concentration
in the dust from gas-producing plants in England is 0.29 to 1.24%. The
dust also contains 0.38 to 0.7570 Ga203.
In coke-chemical plants, germanium occurs at higher concentrations
in the ammoniacal (tar-supernatant) waters and the t a r products, which
may be used as sources of germanium 1 1 3 1 .
312
By adding a controlled amount of the dust, germanium may be precipitated
together with copper and arsenic, leaving the l e s s noble cadmium and
other elements in solution. In some processes germanium is precipitated
from the acid solutions by hydkogen sulfide a s germanium disulfide GeS2.
Sublimation of germanium sulfide GeS or monoxide GeO in a reducing
medium. This method of concentration of germanium may be used f o r the
extraction of germanium from o r e concentrates, dusts, coal, and other
types of raw materials. Either s u l f u r o r pyrite may be used a s the
sulfurizing agents .
Sulfatizing roasting of the material. In o r d e r to convert germanium
and other components of the raw material into their respective sulfates,
the material is heated with sulfuric acid to 450 to 500" and the product i s
leached with dilute sulfuric acid. During the sulfatizing roasting, most
of the arsenic is evolved with the gases a s As&. The germanium is
isolated from the solution.
Fusion of the m a t e r i a l with sodium hydroxide. The fusion of the
material with sodium hydroxide yields soluble sodium germanate which is
leached with water together with other soluble s a l t s (sodium silicate,
aluminate, and arsenate). The hydrated germanium dioxide is then
precipitated from the solution in a certain pH range.
The reductive smelting of the material in the presence of copper o r
iron is based on the concentration of the germanium in the copper o r iron
alloy, from which it i s then extracted by treating with hydrochloric acid.
F
d
tures up to the boiling point of the acid. A s a result GeC14 i s distilled
together with a fraction of the hydrochloric
acid and is condensed. Germanium can
;i I20
K 100
be separated from most other elements
(Fe, Cu, Cd, Zn, Pb, Si, e t c . ) in this way.
Arsenic chloride is volatilized to
gether with GeC14. The boiling point of
AsC13 is 130". However, i t has an
e 800 appreciable vapor p r e s s u r e at the boiling
50
GeCl,, m o l e% point of GeC14 (83"). - * T h i s , and the fact
that AsC13 and G e C 4 form a continuous
FIGURE 156. Phase diagram of the
s e r i e s of liquid solutions (Figure 156),
system GeC1,- ASCIS.
explain the fact that the AsC13 d i s t i l s
over together with the germanium chloride.
In o r d e r to separate the bulk.of the arsenic, the As3+ is oxidized to As5+
with the aid of chlorine. This leads to the formation of arsenic acid which
remains in the solution:
313
The condensed technical grade germanium chloride is then purified by
m e of the methods described below (Section 81).
The m a t e r i a l is treated with HCl in distillation vats, consisting of
enameled steel boilers with steam jackets and bottom discharge. The
boilers a r e fitted with s t i r r e r s and lids, through which p a s s tubes f o r the
introduction of chlorine and the removal of the GeC14 vapors into the
condensers. The germanium-containing m a t e r i a l and hydrochloric acid
are charged into the boilers and chlorine is bubbled through the solution
(in o r d e r to oxidize the arsenic) to saturation, or e l s e pyrolusite M n q
(which r e a c t s with the HC1, with evolution of Clz) is added to the solution. The
pulp is then heated and GeC14 is distilled by passing a slow s t r e a m of
chlorine. The GeC14 vapors are fed to a refractory-glass condenser
cooled with brine to -10".
314
-,
Zinc
SO, Roasting
Agglomytion
Agglomerate (to t h e
production of zinc)
I
Dust
I /H2s04
I Precipiale Filtration
PbSO4
1
Cementation
Zinc dust
(i Cadmium solution I
Filtration
I
1
Dissolution
Second cementation
zinc dust
Filtration
.1
Germanium concentrate
Solution t o
1
t--Distillation
AHC1
waste
I
Crude GeCl4
Purification
315
Beneficiation of these o r e s (by flotation) yields copper concentrates
containing 0.2 to 0.470 Ge. The average composition of the concentrates
i s : 0.2570 Ge, 25.070 Pb, 27.870 Cu, 7.92% Zn, 7.5% As, 22.2% S, and
2.370 Fe.
Germanium is extracted by a method based on the sublimation of
germanium monosulfide, a s a result of the heating of the concentrate in
a neutral o r a reducing atmosphere. In a Hz o r CO atmosphere, 90 to
93 70 of the germanium is sublimed a t 800". In a neutral atmosphere (e. g. ,
in flue gas, containing mainly Nz and CQ) the same extent of sublimation
is obtained only at 1000". In a CO atmosphere, the volatilization of lead
at 800 to 900" is insignificant. The arsenic is sublimed, together with
the germanium. In a CO atmosphere arsenic sulfide is reduced a s
follows:
AS& +
3CO + 2As 3COS. +
The metallic a r s e n i c is readily volatilized and condensed. Carbonyl
sulfide COS is ignited a t the point of issue of the g a s e s from the condenser,
yielding C O , and S O , . The GeS sublimate is subjected to oxidative roasting,
with the simultaneous volatilization of the arsenic in the form of AszQ.
The oxide residue is enriched in germanium. It is treated with hydro
chloric acid and the GeC14 is distilled. The distribution of the germanium,
the composition of the products, and their yield in each operation a r e
shown in Table 54.
TABLE 54
Distribution of germanium between the products of processing of germanium concentrates
(from Tsumeb) by the sulfide sublimation method
Concentration, 70 Distribution, 70
Yield,
Product
% Ge As Pb Ge As Pb
The flow sheet of the process i s shown in Figure 158. The sublimation
is c a r r i e d out in vertical r e t o r t furnaces. The r e t o r t is made of carbo
f r a x * and is externally heated with the flue gases. The pelletized charge
is introduced into the r e t o r t through a special hermetically sealed device.
Before pelletizing, the powdered concentrate is mixed with 1 0 % of
petroleum pitch, in o r d e r to prevent softening of the pellets (due to the
formation of low-melting eutectic mixtures of copper and lead sulfides).
The addition of the petroleum pitch separates the sulfide particles. Coal,
coke or peat powders, o r even sawdust may be used instead of the pitch.
In o r d e r to prevent sintering of the pellets, the pellets (dried in advance
to a moisture content of 2 % ) a r e mixed with crushed charcoal o r coke
before being fed into the furnace.
The maximum temperature in the r e t o r t is 870 to 980". Producer gas
( 2 8 to 3070 CO, 2% Hz, remainder nitrogen) is introduced into the bottom
____________--_
* A refractory material based on carborundum (silicon carbide).
316
and top of the retort. The effluent gases, at 700°, a r e withdrawn at the
maximum temperature point (i. e., from the center of the furnace shaft) in
order to prevent premature condensation of the sulfide and arsenic vapors.
The sublimates, consisting of germanium sulfide, arsenic, lead, and a
small fraction of zinc, a r e trapped in water-cooled condensers, dust
chambers, and bag filters. About 80% of the germanium is trapped in the
condensers, and 2070 in the bag filters. Since the arsenic-containing dust
is explosive, provision must be made for protective devices (explosion
valves) against air leaks into the system during discharge. The collected
sublimates a r e subjected to oxidative roasting in the form of a thin l a y e r on
trays, in an electrical muffle furnace at 550". Arsenic oxide is trapped in
bag f i l t e r s and the residual oxide mixture is used for the extraction of
germanium by distillation.
I Flotation concentrate I
1
Crushing in a h a m m e r m i l l
1,
Mixing in a horizontal
mixer
Petroleum pitch
Drying t o a moisture
content of 2 %
1
Pelletizing Crushed charcoal
or coke
I/
Mixing
Gas generator
I
Sulfide cinders - 1
Distillation in a retort
furnace
Condensat ion
1
Trapping in bag filters
Sulfide sublimates
1
Oxidizing roasting
.
I
I
Material enriched with
Dust
AS203
germanium
1
To the distillation of
GeC1,
FIGURE 158. Flow sheet of the extraction of germanium from the Tsumeb
concentrates by the suifide sublimation method.
317
Extraction of germanium from the dusts formed in the shaft smelting
of copper concentrates from Katanga 1161
The dust serving a s raw m a t e r i a l contains 0.3670 Ge, 28% Zn, 370 Cd,
2570 Pb, 1.5% Cu, and 7 . 3 % As. The flow sheet f o r the processing of this
dust is shown in Figure 159. The processing comprises the following
main operations : sulfatizing roasting, leaching of the sulfatized dust with
sulfuric acid, oxidation of the arsenic and its subsequent precipitation, and
the isolation of a product enriched in germanium.
The dust discharged from the bag f i l t e r s is moistened to a moisture
content of 20% and is stored in pits. The caked material is crushed in a
percussive-disc m i l l (disintegrator) and is mixed with water and sulfuric
acid in a screw-type mixer. The paste-like m a s s is fed into a rotary
kiln (1m in diameter and 2 2 m long). It is fired f o r 4 hours at 450 to 500".
The productivity of the furnace is 700 to 820 kg of d r y dust p e r hour.
About 90% of the arsenic is removed with the g a s e s during the firing.
C a C 0 3 ; KMnO,
Dust from bag filters
I Precipitation of As
Moistening
Storing in piles
E
I
H 22
-:. 7 Filtration
H2s04\ I
1- '
To the atmosphere
c.r-r
1,
1
Gas purification
Wash
waters
1 1
Oxidation
.-
Spent electrolyte,
Slurry. to the
slurry field
Fi 1tia tion
Supplementary precipi
tation of Ge a t pH
Filtrate
Solution I
Lead c a k e I
To Cd cementation
t.
Germanium
unit cake
FIGURE 159. Flow sheet of the processing of germanium-containing dusts a t the Kolvezi plant
i n Katanga.
318
. . .. ..
In o r d e r to separate the arsenic, i t is oxidized in advance by adding
M ~ I Qto the clarified solution, and the oxidation is completed by adding
KMn04. The arsenic is precipitated at pH 2.2 to 2.4 (produced by the
addition of limestone), in the form of iron arsenate FeAsO, and, possibly,
arsenates of other elements. The l o s s e s of germanium with the
precipitate are 3 to 570. The residual As and Fe concentrations in the
solution are only 0.4 and 0.1 g / l respectively.
Germanium is isolated from the arsenic-free solution by a two-stage
p r o c e s s with the aid of magnesium oxide. A precipitate r i c h e r in
germanium (containing magnesium germanate Mg2Ge04) is precipitated,
first at pH 4.9. It is separated by filtration and the remaining germanium
is precipitated at pH 5.5 to 5.7; the precipitate formed is returned to the
preceding precipitation. The solutions a r e neutralized with magnesium
oxide. The quantitative precipitation of germanium i n the second stage is
caused by the precipitation of copper hydroxide, which adsorbs the
germanium hydroxide.
The germanium cake taken out of the p r e s s filters contains 8 to 10% Ge,
10 to 18% Cu, 1 5 to 20% Zn, 1 to 1.5% Cd, and 0.7 to 270 As.
The product is treated with hydrochloric acid in o r d e r to obtain
germanium tetrachloride.
319
Dust from gas-producing
I-
]
Reductive fusion
Slags C---
-1 Dust
-
Copper alloy
(Ge.Ga)
LI
hS04 FeCl,. C1,
7
Dissolution
7
Distillation
1
To the extraction o f
I
To purification
gallium
320
Purification by rectification
I
Purification by extraction with hydrochloric acid 151
The removal of a r s e n i c f r o m germanium chloride by extraction with
hydrochloric acid is based on the difference in the solubilities of &C14
and AsC13 i n concentrated HC1 (Table 55).
TABLE 55
Solubilities of GeCl, and AsCl, in hydrochloric acid a t 25°C
322
with a starting As concentration of -
out at a low temperature (Oo o r below). In the case of germanium chloride
0.01 mole YO, two extractions with
-
atoms As p e r cm3 Ge ( o r - -
37.470 HC1 (saturated with chlorine) reduce the As concentration to 8.3 l O I 5
2.4
reduce the As concentration to 6 . 1 . 1015 atoms As p e r cm3 Ge (or -
mole 70 As) while four extractions
1.7
moleyo As).
The extraction may be c a r r i e d out a s a continuous process in a packed
column of the type shown in Figure 162. The g l a s s column is packed with
g l a s s s p i r a l s . The lighter phase (HCI + Cl2) is fed from the bottom while
the heavier phase (the germanium chloride to be purified) is fed from the
top. The purified GeC14 is discharged continuously through a sleeve in
the lower p a r t of the column.
323
I 1l 1l11l 1l1111l11l 1l11l 1l 1l11l 11l1l 1l11l11l 1l 11l1l I1 I I I I I I1 II1 I
FIGURE 163. Diagram of a furnace used in the reduction of GeO, with hydrogen.
324
program and p a s s f i r s t through the reduction zone, then through the
germanium melting zone and a r e finally withdrawn f r o m the furnace.
0 1
I 3l 4l
2 5
End of the withdrawal
6 7 6
, I
8
Time, hours
325
1ll11l1l1l1lll I
I
- ~
Concentration of impurities
a b
1455
326
I
TABLE 56
Approximate values of the distribution coefficients of some impuritier in
germanium
P 0.12 TI 4.
AS 0.04 cu 1.5
Sb 0.003 Ag lo-'
Bi 4. lo-' Au 3.
B 10 Ni 5 *lo-'
A1 0.10 Zn 0.01
Ga 0.10 co 10-6
In 0.001 si >1
Sn 0.02
327
coefficients. The curves show that for effective purification the distribu
tion coefficients must differ markedly from unity ( K Q 1 or K > 1). P u r i
fication by fractional crystaIIization is impossible if = 1.
C
4
3
2
1.0
u a8
$ a6
._
2 a4
a3
p: Q2
8
::PO80.1
,Z
0.06
,E PO4
0.03
0102
'Ole Fraction
ai oz 0.3 a4 as a6 ai ae 0:
of bar solidified XlA
FIGURE 167. Impurity distribution in t h e
bar as a function of the solidified fraction
of the bar %/A, at different distribution co
efficients. T h e initial impurity concen
tration Go = 1.
328
to directional crystallization, the volume of the melt r e m a i n s constant
until the molten zone reaches the end of the bar.
"'0 1 2 3 4 5 6 7 8 9
XiL
FIGURE 169. Changes in the impurity con
centration during the zone melting process,
as a function of the xlL ratio at different
values of K. Initial concentration C o = l .
Impurities which reduce the melting point of the metal ( K < 1) move from
the starting p a r t (head) of the sample in the direction of movement of the
molten zone. If K > 1 the dissolved substances (impurities) move in a
direction contrary to the direction of the molten zone. The impurity
distribution over the length of the b a r undergoing purification by zone
melting may b e approximately calculated by the equation:
c = C,[1 -(I -KIe-Kx3,
329
passages through one zone. In this way a single operation r e s u l t s i n
s e v e r a l purification cycles without the need for periodic removal of p a r t s
of the b a r (which is required in directional crystallization).
As is evident from Figure 169, zone melting is not an effective method
f o r the removal of impurities which raise the melting point of germanium
(K > 1). The best method f o r the removal of such impurities (e. g., B, Si,
see Table 57) is the directional crystallization method.
330
germanium upon melting. The decrease in the volume of the melt ( a s is
the case with germanium) causes transfer of m a t t e r in the direction of
movement of the zone. In o r d e r to obtain a b a r with a uniform c r o s s
section, the quartz tube with the boat is positioned at a certain slope whose
angle depends on the ratio of the densities of the solid and liquid phases.
In the case of germanium, the slope angle is 2" (the b a r end towards which
the zone moves is placed slightly higher than the other end).
The effectiveness of zone melting is shown in Figure 171, The specific
resistance of germanium b a r before zone melting is from 0.3 to 7 o h m . cm.
After the zone melting most of the b a r has a specific resistance close to
the resistance of the pure germanium.
* The use of DC motors makesitipossible to control the pulling rate by varying the voltage applied to the
motors.
331
seed-pulling and rotating mechanism is then turned on. At the same time,
observations a r e made through the window in o r d e r to ensure that the
contact between the crystal and the melt is not broken. Because of the
effect of surface tension, the liquid level a t the contact s i t e would be higher
than the level of the melt. The b a r diameter i n c r e a s e s as the drawing
proceeds. Upon reaching the required diameter, the diameter is kept
constant by controlling the supply of heat to the melt and the drawing rate.
In the case of a stationary seed in equilibrium with the melt, the amount
of heat supplied to the melt Qi equals the amount of the heat lost Qo ( a s a
result of heat conducted through the seed, and the lifting rod, l o s s e s
through radiation, etc. ). An increase in Qi must cause an upward shift
(i. e., to increase the distance from the melt) of the boundary between
332
I"
333
The concentration of admixtures after a single passage of the molten
zone along the rod can be expressed by the equation:
KX
c, = KCF- T,
where C. is the admixture concentration at a distance x from the point
at which solidification started; Ci is the initial concentration of the
admixture in the molten zone; is the distribution coefficient; L is the
width of the molten zone; and x is the length of the solidified section.
Quality control
In t h e purification of germanium by fiactional crystallization and the production of monocrystals, the
quality of the product is controlled by physical methods. T h e properties usually controlled are*: the
conductivity type, specific resistance, and lifetime of minority carriers (which depends on t h e recombina
tion of electrons and holes i n t h e volume of the semiconductor). In addition the mobility of the charge
carriers i s determined by measuring the Hall coefficient.
T h e electrical resistance of the rod is measured over its length without cutting. Rod sections with a
specific resistance below 30 ohm. c m a r e usually retumed to additional purification.
contaminants.
Germanium wastes
+
GeC1,
+
Purification by rectification
+
GeCl,
J.
Hydrolysis
J.
pG-1
FIGURE 174. Flow sheet of the processing of germanium wastes.
-_-------------
* A discussion of the nature of these parameters and the methods o f their determination is outside the scope
of this book. T h e reader is referred to special textbooks /2-4/.
334
The production of these plates is accompanied by the formation of l a r g e
amounts of waste material: fine dust from the cutting and polishing
operations, broken particles, solutions. In practice, not more than 20%
of the germanium is obtained a s plates which can be used in semiconductor
devices, while the remaining 80% is waste.
The dusts and fine particles may be processed a s shown in Figure 174.
The germanium in the etching solutions and wash liquors is precipitated
as mangnesium germanate o r a s some other compound.
335
Chapter VIII
GALLIUM
85. G E N E R A L D A T A ON G A L L I U M
P r o p e r t i e s of gallium
TABLE 57
Properties of gallium as predicted by Mendeleev* and as determined after discovery
Property
As determined after its
As predicted by Mendeleev
discovery
Atomic weight
68
69.72
Melting point, 'C
Low melting point
29.8
Density, g/ cms
5.9
5.9
Atomic volume
11.5
11.7
Oxidation i n air
Not oxidized
Slight oxidation a t red heat
Decomposition by water vapor
At red heat
At a high temperature
Compound formulas
B c I , , hpos, b p ( S o &
I G a C h G a A , Ga2(SO& I
24H20
Boiling point of the chloride.
'C Volatile 200
;
a = 4.5167 A . = 4.5107 d ,
c = 7.6448 A
_____----____-_
* Two natural isotopes of gallium are known: Ga" (60.5% i n the mixture found in
nature) and Gal1 (39.570).
336
Density :
solid (20'C) .......................... 5.904
liquid (29.8'C) ....................... 6.095
liquid (11OO'C) ....................... 5.445
Melting point, 'C ............................ 29.8
Boiling point, 'C ............................ 2230
Heat capacity, c a l / g 'C of:
solid Ga (0-24'C) ..................... 0.090
liquid Ga (29-127'C). .................. 0.098
Heat conductivity a t 30"C, c a l / c m * sec. 'C 0.01 -0.09
Linear expansion coefficient:
solid Ga (O'C) ......................... 1.8.
liquid Ga (100°C) ...................... 12.
Viscosity (in centipoises) at 98°C .............. 1.612
at 11OO'C ............ 0.578
Surface tension a t 30°C in H2 ot CO,
atmosphere. d y n e s l c m ................... I35
Specific electrical resistance, ohm* c m :
solid Ga (O'C) ......................... 53.4. lo-'
liquid Ga (30°C) ....................... 21.2.
Transition temperature to superconducting
state, " K .............................. 1.1
............. -0.52
Normal electrode p t e n t i a l , volts
Thermal neutron capture cross section, barns ... 2.11
Gallium is a liquid with an extended temperature range (30 to 2230").
The vapor p r e s s u r e s of gallium at 1349 and 1974" a r e 1 and 400mmHg
r espectively.
Upon rapid cooling, liquid gallium may be maintained in a supercooled
state down to -40". On solidification its volume i n c r e a s e s by 3 . 2 % .
Gallium is not attacked by a i r at room temperature. It i s oxidized by
d r y oxygen above 260", but the oxidation is very slow since the oxide film
protects the metal.
Gallium dissolves slowly in sulfuric and hydrochloric acids, with the
evolution of hydrogen. Gallium i s not dissolved by nitric acid (of any
concentration) at room temperature, but dissolves slowly in the hot acid,
through the reaction:
Ga + 6HN03 = Ga (NO,), +
3H20 + 3N0,.
Gallium belongs to Group I11 of the periodic system. The most stable
compounds a r e those of trivalent gallium, which in many respects resemble
337
the aluminum compounds. In addition, compounds of mono- and divalent
gallium a r e a l s o known.
Gallium oxides. T h e r e a r e two known gallium oxides - G a z Q and GazO.
The dehydration of gallium hydroxide yields the higher oxide GazO3-a white
substance, insoluble in water. Its density is 6.44; GazQ melts at 1740"
without decomposition. The heat of formation of G a z Q is 256 kcal/mole.
Ga20 is prepared by reduction of GazQ with hydrogen a t 700 to 800" o r
by heating G a z Q with gallium in an i n e r t medium. GazO is dark brown.
It undergoes sublimation a t 650 to 700".
Gallium hydroxide Ga(OH), is precipitated f r o m solutions of gallium
s a l t s a s a white gelatinous precipitate. It exhibits distinct amphoteric
properties, and, like A1(OH)3, dissolves in both acids and alkalies. On
dissolving in alkalies i t yields sodium gallate, and on dissolving in acids
i t yields the respective s a l t s : the sulfate Gaz(S04),, the chloride GaC13, etc.
The acidic properties of gallium hydroxide a r e somewhat stronger than
those of aluminum hydroxide. As a consequence, LU(OH)~,is precipitated
from solution a t pH 10.6 to 4.1 while Ga(OH), is precipitated a t pH 9.7 to
3.4.
In contrast to Al(OH)3, Ga(OH)3dissolves not only in strong alkalies
but also in ammonium hydroxide. The hydroxide is reprecipitated from
the ammoniacal solution upon boiling.
Gallium chloride. Gallium trichloride is a colorless, hygroscopic
substance which fumes in a i r . This is due to the hydrolysis of the chloride
upon contact with atmospheric moisture.
2GaCf, + 3H80 = Ga,O, + 6HCI.
The chloride m e l t s a t 7 8 and boils at 200". The heat of formation of the
chloride i s 125 kcal/mole.
Gallium chloride is readily extracted by e t h e r s from hydrochloric acid
solutions; this property is used f o r the separation of gallium from other
elements ( s e e Section 88). The reaction of GaC13 with Ga yields GaClZ- a
colorless crystalline substance melting a t 170.5'. The boiling point of
GaClz is 535".
Gallium sulfate. A solution of gallium sulfate is formed when gallium
hydroxide i s dissolved in sulfuric acid. The sulfate crystallizes a s the
.
hydrate Ga2(SO4), 18H20. It is dehydrated on heating and the anhydrous
s a l t decomposes above 520". Gallium sulfate forms double s a l t s (of the
alum type) with alkali metal sulfates, e. g. , KGa(S04)z 12 HzO.
Gallium ferrocyanide. Ga,[Fe( CN),I3 is a white, crystalline, sparingly
soluble substance. It is precipitated on the addition of potassium f e r r o
cyanide to a solution containing a gallium salt. The precipitation of gallium
a s the ferrocyanide is used in industry for the separation of gallium from
a number of elements : aluminum, chromium, manganese, cadmium,
lead, bismuth, and thallium.
Uses of gallium / 3 /
Gallium i s one of the r a r e metals which have not yet found extensive
use in industry. The known r e s e r v e s of gallium make i t possible to
produce this metal in amounts much l a r g e r than the amounts required
today.
338
Some of the intended uses of gallium / 1 to 3 / a r e listed below
Semiconductor electronics is one of the m o r e promising uses of gallium.
In this branch, gallium is used a s a doper for germanium (gallium imparts
to germanium conductivity of the p-type). In addition, some attention has
been recently given to the use of intermetallic compounds of gallium (with
antimony, arsenic, and phosphorus) which p o s s e s s semiconductor p r o p e r
t i e s f o r the preparation of new types of semiconductor devices. The use
of gallium antimonide GaSb has been recommended for the preparation of
thermocouples (emf = 400 V) and phototriodes which a r e sensitive to the
infrared region of the spectrum.
Nuclear technology. Gallium and i t s alloys can be used a s the liquid
medium for the removal of heat in nuclear power r e a c t o r s . The existence
of a liquid phase of galIium metal within a wide range of temperature, i t s
low vapor p r e s s u r e , and low neutron capture c r o s s section make gallium
a valuable heat-transfer material. However, the use of gallium in this
field is hindered by the fact that i t interacts with most s t r u c t u r a l m a t e r i a l s
a t the working temperatures used, The m a t e r i a l s most r e s i s t a n t to the
action of gallium a r e niobium (up to 400°), tantalum (up to 450") and
tungsten (up to 800"). A s compared with gallium, the eutectic alloy Ga -
Zn- Sn has a l e s s corrosive effect on metals.
Optical instruments, luminiferous compositions, ultraviolet lamps.
Gallium may be used for the production of m i r r o r s with a high reflecting
power. Gallium is used a s an activator (for the excitation of the fluores
cence) in luminescent compositions f o r lamps and luminescent paints; the
amounts used for these purposes is insignificant.
It h a s been recommended that an aluminum-gallium alloy be used
instead of m e r c u r y a s the cathode in the ultraviolet lamps used in physio
therapy. In that c a s e the radiation emitted by the lamp is enriched with
blue and red components, which improves i t s therapeutic action.
The production of alloys. Gallium f o r m s low-melting alloys with a
number of metals: Bi, Pb, Sn, Cd, Zn, In, and T1. For instance, gallium
containing 2 4 % indium melts at 15.7", gallium containing 1 2 % tin melts at
17", and the Ga-Tl eutectic mixture melts at 27.V. These alloys may be
used in thermoregulators, sprinkler devices ( f i r e signals) and as substitu
ents for m e r c u r y (in rectifiers, current switches, hydraulic s e a l s ) . They
have been recommended a s coatings for the working (friction) s u r f a c e s of
bronze bearings, and may also be used in dentistry (for the preparation
of teeth fillings).
It has been recommended that gallium and i t s low-melting alloys ( e . g . ,
the alloy containing 6 0 % Sn, 3 0 % Ga, 1 0 % In) be used a s the liquid in
high-temperature thermometers (600 to 1300') and manometers.
86. OCCURRENCE
339
gallite (CuGaSz), is known (it was discovered in 1958). The m i n e r a l
germanite has a relatively high gallium content ( s e e Section 78).
The association of gailium and aluminum is based on the similarity of
the chemical progerties of these elements and o,n the similarity of their
ionic radii (0.57 A in the c a s e of A13+ and 0.63 A in the case of Ga3+). As
a result, gallium ions may be substituted f o r aluminum ions in the
crystal1in.e lattices of the main commercial aluminum m i n e r a l s - bauxite
and nepheline. The gallium concentration in these m i n e r a l s ranges f r o m
0.001 to 0.0470.
The association of gallium with zinc is based on the fact that zinc
blende ZnS and gallium sulfide GaS a r e isomorphous, i. e . , they have the
a.
s a m e crystalline lattice with a p a r a m e t e r as= 5.5 The gallium
concentration in zinc blende is r a r e l y above 0 . 0 0 2 ~ 0 . However, in some
c a s e s zinc blende contains 0.170 Ga. In addition to gallium, zinc blende
often contains some other scattered metals : indium, thallium, and
germanium.
The presence of gallium in 2ome iron o r e s is attributed to the similarity
of the ionic radii of Fe3+(0.67 A ) and gallium.
Gallium o c c u r s in coals together with germanium. Coal ash often
contains from 0.01 to 0.1% gallium. In the coal gasification process, the
gallium and germanium accumulate in the dusts (the entrained soot). The
gallium concentration in the dusts from gas-producing plants i s occasionally
0.3 to 0.570. The accumulation of gallium in the volatile fractions of the
ash and the soot i s attributed to the volatility of the lower gallium oxide
GazO which is vaporized a t 650 to 700".
At present, the wastes of aluminum manufacturing a r e the main raw
m a t e r i a l for the production of gallium. In some c a s e s gallium is
extracted from the wastes of zinc manufacturing and of gas-producing
plants (together with germanium). Gallium is not a s yet extracted from
iron o r e s .
340
the charge components. When nepheline o r e s (nepheline is (Na, K)zO. A1203.
2SiOz) a r e used a s the raw material, they are also processed by the soda-
l i m e method.
In the Baier method, which was developed i n Russia, bauxite o r e is
processed with sodium hydroxide solutions in autoclaves at 200 to 225".
Aluminum hydroxide is precipitated from the solutions a s a result of the
hydrolysis (decomposition) of sodium aluminate, and the p r o c e s s is
accelerated by the introduction of s e e d s of freshly-precipitated aluminum
hydroxide to the solution:
NaAlO, + 2H,O = AI (OH), + NaOH.
The mother liquor is evaporated i n o r d e r to increase the sodium
hydroxide concentration and is returned to the leaching of f r e s h amounts
of bauxite.
Both in the f i r s t and the second methods, most of the gallium (70 to 803'0)
accompanies the aluminum into the solution in the form of sodium gallate.
When aluminum hydroxide is precipitated from the solution by the
carbonation o r the decomposition methods, gallium hydroxide is precipitated
after the aluminum hydroxide. This is attributed to the different pH at
which the precipitations of Al(OH)3 and Ga(OW3from alkali solution begin.
As a result the mother liquor from the decomposition p r o c e s s and the
l a s t fraction of the precipitate formed in the carbonation p r o c e s s a r e
enriched with gallium.
Thus, in the processing of bauxite containing 0.002570 Ga by the Baier
method, the content of GazO3 in A1203in the recycled mother liquors
(after the decomposition) is 0.15 to 0.370 i. e . , it is 3 0 to 50 times higher
than in the raw material. In the soda-lime method of processing of the
bauxites, the solutions takenfor carbonation contain about 100 to 1 2 0 g / l
MZO3and 0.03 to 0.04 g / l GazO3. The precipitate formed in the f i r s t stage
of the p r o c e s s contains 85 to 90% of the A1 and at most 2 0 % of the Ga
initially present in the solution, i. e . , the mother liquor is enriched in
gallium. A gallium concentrate is isolated from the mother liquor.
Aluminate solutions a r e the main raw material f o r the production of
gallium. In addition, gallium may be extracted from the wastes of the
electrolytic production of aluminum.
In the electrolytic production of aluminum, gallium is deposited on the
cathode together with the aluminum. The gallium concentration in the
aluminum is 0.01 to 0.02%/o. In the refining of alcminum by the three-layer
electrolysis method, gallium accumulates in the residual anodic alloy. Its
concentration in the anodic alloy may be a s high a s 0.2%.
341
Solutions obtained by the soda-lime method / 8/
The carbonation is a two-stage p r o c e s s (Figure 175). About 90% of
the aluminum is precipitated in the f i r s t stage, while most of the gallium
remains in the solution. In the second carbonation, the remaining
aluminum is precipitated together with the gallium. The Ga2Q concen
tration in the precipitates (the primary gallium concentrate) is s e v e r a l
tenths of one percent.
The precipitates consist of sodium alumocarbonate Nap0 .A1pO3.2C02.nHzO
contaminated with gallium. In o r d e r to separate the bulk of the aluminum
from the gallium, the precipitate is treated with lime water a t 90" ( o r at
140" in an autoclave) a t a molar CaO: Al& ratio of 4 : 1 . As a result,
6 0 to 7 0 % of the aluminum is precipitated a s tricalcium aluminate while
85 to 90% of the gallium p a s s e s into solution from which i t is precipitated
(by carbonation) as a gallium concentrate containing 2 to 5% Ga&. The
decomposition with lime water is roughly described by the equation:
.
Na,O A l p , .2CO, + 5Ca(OHJS+ 2H,O = 3CaO - Also3.6H,O + 2CaC0, + 2NaOH.
The formation of sodium hydroxide ensures the retention of the gallium
in the solution, provided that the precipitation of aluminum a s calcium
aluminate is not quantitative. Thus, the amount of CaO taken f o r the
reaction must be s m a l l e r than the stoichiometric amount needed.
The simplest method involves the isolation of gallium from the recycled
solutions of the Baier process by electrolysis on a m e r c u r y cathode / l o / .
This causes no substantial change in the composition of the aluminate
solution, which may be returned to the production cycle (Figure 176).
A diagram of the electrolyzer is shown in Figure 1 7 7 . A hollow'
rotating iron drum, p a r t of which is immersed in mercury, s e r v e s as
the cathode. A thin layer of mercury coats both surfaces of the drum.
A nickel sieve shaped a s a half-cylinder s e r v e s a s the anode. The anode
surface a r e a is 1 / 2 0 the a r e a of the cathode.
In aluminate solutions gallium is present a s the GaOi anion. Its
electrolytic reduction may involve two different mechanisms :
1. The GaG- anions a r e discharged on the anode with the formation of
GaO+ cations :
GaOT -2e -+ Gao+ 0. +
The GaO+cations a r e discharged on the cathode with the deposition of
gallium and the formation of the anion:
2Ga0+ + 3e -+ Ga + GaOF.
2. Hydrogen is evolved on the cathode, reducing the GaG- anions and
the G a o cations:
GaOT + 2H + e -+ Ga + 2(OH)-.
GaO++ H + 2e -P Cia + O K .
342
Aluminate solution
First carbonation
1
Filtration
- I
.1 4.
Solution Precipitate
(85-90% of t h e initial
F
COZ
I
Second carbonation
amount of Al)
Filtration
Solution
-pitate
(NazCOd (A1 and Ga)
Treatment with l i m e
-
co2
- 4
Solution.
- - I
Carbonation
I
Filtration
Filtration
Precipitate
( cal ci u m aluminate)
I
T o preparation of
charge for sintering
(gallium con-
NazCOs solution
I
.L
Evaporation
1
Na,CO,
1
To preparation of charge for
sintering of bauxite
FIGURE 175. Flow sheet o f processing the al u m i n a t e solution obtained by the sintering
T e t hod. with gallium as a by-product.
343
Continuous electrolysis of
the alkali solution
7 1
Slimes Recycled
electrolyte
Amalgam (Ga, Na, and
others) -1
To the Baier
1
Extraction with water
process
at 9O'C
1 Neutralization to p H = 6
3
"II-
FIGURE 117. Diagram of an electrolyzer for the extraction of gallium from
solutions from the Baier process.
1 -rotating iron cathode; 2-nickel anode; 3-container with mercury;
4-bakelite support for the axis of the drum cathode; 5-tube for the
discharge of the spent electrolyte.
344
The optimum conditions for the electrolysis of solutions containing
0.2 to 0 . 3 g G a l l a r e a s follows: temperature 40 to 50°, cathodic c u r r e n t
density 0 . 4 5 amp/dm2. Under these conditions, the c u r r e n t efficiency
is 2.7 to 2 . 8 7 0 . The consumption of electrical energy is about 1 5 5 kwh/kg
Ga. The electrolysis is continued until the Ga concentration in the m e r c u r y
reaches 0 . 3 to 0.470. Sodium is also deposited on the m e r c u r y cathode;
under the electrolysis conditions used i t s concentration in the m e r c u r y
is 0.1 to 0 . 2 % .
The electrolyte may contain impurities (Mo, Zn, V, Ni, F e , Mg, Ca). The
molybdenum and vanadium a r e present in the electrolyte a s sodium
molybdate and vanadate. These two s a l t s a r e reduced by the hydrogen
evolved in the electrolysis, and yield the lower oxides V O n .n H20, Moop which
a r e insoluble in alkalies and a r e precipitated with the slimes. A fraction
of the silicon, a s well a s the zinc, p a s s into the m e r c u r y together with
the gallium. Iron, which is present in the alkali electrolyte a s a colloidal
divalent hydrate, p a s s e s quantitatively into the mercury.
The amalgam containing 0 . 3 to 0.4% Ga is leached with water in a
s t a i n l e s s s t e e l r e a c t o r heated to 100". Sodium, being m o r e electro
negative, is dissolved f i r s t and c r e a t e s an alkaline solution of a concentra
tion sufficient for the extraction of the gallium. In a boiling alkaline
solution the iron is precipitated a s the hydrate and is separated by
filtration. The resulting gallium solution is not concentrated enough, and
thus the gallium is precipitated a s the hydroxide by neutralizing the
solution with sulfuric acid to pH = 6 . The hydroxide precipitate is again
treated with sodium hydroxide solution, yielding a sodium gallate solution
containing 6 0 to 8 0 g Ga/l. F r o m this solution the gallium is isolated
by electrolysis ( s e e below).
345
I
while copper and iron remain in the insoluble residue. The gallium may
be isolated from the aluminate solution by one of the methods described
above. The method based on the use of alkalies has the disadvantages of
a low decomposition r a t e and a low degree of extraction of the gallium into
the solution.
The methods based on the use of acids involve the dissolution of the
anodic alloy in sulfuric o r hydrochIoric acids. The gallium, aluminum,
and i r o n a r e dissolved while the copper remains in the insoluble residue.
The gallium may be extracted from the sulfuric acid solutions byprecipita
tion with potassium ferrocyanide o r some organic precipitant. The
extraction of gallium by e t h e r s from hydrochloric acid solutions is an
effective method for freeing the gallium from most impurities.
346
Purification of gallium compounds by extraction
347
treatments with hydrochloric and nitric acids a r e occasionally used, The
washed metal usually contains 99.9 to 99.9570 gallium.
The gallium dissolved by the acid solutions is recovered.
348
conveniently c a r r i e d out in an instrument (Figure 179) with a rotating drum
having a poly(viny1 chloride) tube (filled with gallium) coiled over it. A
p a r t of the drum is immersed in water. The r a t e of rotation of the drum
may be regulated between 118 and 1 revolution p e r hour, which corresponds
to a zone moving r a t e of 1.3 to 1 0 cmlhour. The zones a r e melted with the
aid of a heater placed over the drum, and running water is used as the
coolant. The end opposite the direction of movement of the zones is fitted
with a shield of aluminum sheet, which accelerates the solidification of
the gallium. Gallium of a degree of purity of 99.9999% was produced by
using a tube 5 m m in diameter and 100 m m long, the zone moving a t a r a t e
of 2 to 4 cm/hour. 99.999% pure gallium was used a s the starting material.
The yield of the pure metal was about 50"/0.
Gallium monocrystals a r e easily produced by drawing from melt. F o r
this purpose the gallium is fused in a quartz crucible heated to 38" in a
water thermostat; the sharp edge of a g l a s s tube filled with liquid nitrogen
is then immersed in the molten gallium and is withdrawn slowly from the
melt. In the drawing process, the bulk of the impurities remains in the
residual melt.
349
Chapter IX
INDIUM
Properties of indium
. ..................
Transition temperature t o the super-
conducting state, K
--------------
3.37
* Natural indium consists of two isotopes: In"' (4.33%) and In115 (95.67%).
350
-
sulfate, chloride and nitrate a r e hydrolyzed in solutions a t pH above
3.5 to 3.7, with the precipitation of indium hydroxide o r basic indium
salts.
Indium chloride InC13 is a colorless volatile substance. The vapor
p r e s s u r e of InC13 over the solid s a l t is one atm a t 498". Under p r e s s u r e
the chloride m e l t s at 586". The s a l t is readily soluble i n water and i t s
solubility a t 22" is 33.5 g/l. Solutions of InCl3 a r e formed upon the
dissolution of In2% o r metallic indium in hydrochloric acid.
Indium sulfate Ing(SO4)3 is a water-soluble s a l t (62.1% a t 25"). F r o m
neutral solution it c r y s t a l l i z e s a s the pentahydrate IXI~(SO~)~
5Hz0. It
slowly l o s e s water a t 100 to 120" and is converted to the anhydrous salt.
Depending on the sulfuric acid concentration and the temperature, i t is
precipitated from acid solutions a s Inz(so4)3. 10Hz0, In2(sOd3 6H20, o r -
-
the acid s a l t In2(S04)3H2S04. which may be regarded a s a complex
s a l t with the formula H[In(S04)2]-3 1 H20 ( s e e Table 58).
The solubility of indium sulfate is strongly affected by the sulfuric acid
concentration. At H2S0, concentrations above 5570 the solubility of indium
351
sulfate is only 0.570 and the acid salt is precipitated f r o m the solution. The
precipitation of indium f r o m sulfuric acid solutions by "salting-out" with
sulfuric acid may be used as a means for the purification of indium.
TABLE 58
Solubility of Inr(SO,), as a function of the sulfuric acid concentration
I
fi
I
A t 20'
! C
I
Ac 60'
s CI
e
g? Composition of
the solid phase
O
$ 93 3,
Composition of
the solid phase
d .E
m - g .s 2 3
5 6 3?2 fzz
4
~- ! -
3.6 54.80
10.3 44.56
20.2 39.24
25.3 28.86 In, . 6H10
~ _ _ _ _ - -
1-
28.2 21.58 36.7 12.65
49.7
53.4
54.9
i:;:
0.55
I~,(so,),x
X HzS04 . 7Hz0
-
:::: 1;
68.0
In,;&, x-
x H2S04. 7H10
-.
Uses of indium
352
of indium. This causes the diffusion of indium into the s u r f a c e l a y e r and
makes the coating adherent. Indium coatings have a high reflectance. In
contrast to s i l v e r coatings they do not darken and retain their reflectance
coefficient. Hence, indium is used in the manufacturing of reflectors.
The production of alloys. Some indium alloys with lead, tin, silver,
cadmium and bismuth a r e of importance f o r technology. The In- Sn-Cd-
Bi, In- Pb- Sn, and In- Pb alloys a r e used a s s o l d e r s f o r joining metals,
glass, quartz, and ceramics. Indium-tin alloy (50% In, 5070 Sn) s o l d e r s
a r e used in vacuum technology f o r making glass-to-glass o r glass-to-metal
joints. These solders produce vacuum-tight joints. Low-melting alloys
containing indium a r e used in f i r e a l a r m s . One of these alloys contains
18.4% In, 40.770 Bi, 22% Pb, 10.6%Sn, and 8.1670Cd. It melts a t 46.5".
An alloy containing 19% In, 71 7'0 Ag, and 10% Cd is cheaper than
hafnium and is being used recently in the USA for the production of control
rods f o r nuclear r e a c t o r s . This alloy is characterized by its high thermal
conductivity, corrosion resistance, and strength, and i t s thermal neutron
capture c r o s s section is sufficiently high. An alloy containing 54 to 6 2 % In,
8 to 1 8 %Cd, and the balance bismuth has also been proposed a s a neutron-
absorbing material.
Semiconductor electronics. A l a r g e fraction of the indium produced is
used a t present in semiconductor electronics. Both pure indium and
indium compounds a r e used in this field.
Very pure indium i s used in the production of high-power germanium
rectifiers. The presence of indium i m p a r t s to germanium a p-type
conductivity. The indium i s fused on the surface of germanium plates.
The indium atoms diffuse into the germanium surface and c r e a t e a zone
with p-type conductivity.
A number of indium compounds (oxide, sulfide, selenide, telluride,
antimonide, arsenide, etc. ) have semiconducting properties. They may
be used in thermocouple materials. F o r instance, thermocouples made
of indium arsenide o r phosphide may operate at high temperatures.
The indium and indium compounds used in semiconductor electronics
must be of a very high degree of purity. Thus, attention has been recently
given to the development of indium- refining methods.
91. OCCURRENCE
ffQ
r-7*'
il
CuFeSnS, (up to 0.1 $' 6 In).
The indium concentration in sphalerites
(zinc blendes) fluctuates between 0.1 and
0.0001 '7'0. The higher indium concentrations
FIGURE 180. T h e ge och em i cal a r e found in zinc deposits of increased iron
"star" of indium. and tin contents.
353
The position of indium in the periodic table (Figure 180) explains to a
certain extent its geochemical association with a number of elements. The
association with cadmium and tin is caused by the s i m i l a r values of the
atomic r a d i i of indium and these elements; the association with zinc and
lead is attributed to the known similarity in the properties of elements
positioned diagonally in the periodic table; the association with gallium
and aluminum is due to the fact that indium and these elements belong to
the s a m e group.
The various waste m a t e r i a l s and intermediate products of zinc and lead
manufacturing are the main s o u r c e s of indium. In addition to indium,
these products often contain cadmium and some rare scattered metals :
gallium, thallium, 2nd germanium.
Attention has been recently given to the extraction of indium from the
wastes of production of tin.
The behavior of indium in the various stages of zinc and lead manu
facturing processes, and the methods of extracting indium from the waste
m a t e r i a l s of these p r o c e s s e s a r e discussed below.
354
Thus, in pyrometallurgical production of zinc, indium is extracted from
the dusts of pellet coking furnaces and from the lead produced in the
rectification of crude zinc.
-
in two stages: neutral leaching and acid leaching (Figure 181).
Neutral leaching
-
Solution Cake from the
neutral leaching
Pure solution
m
Removal of impurities
Cu-Cd
Spent electrolyte
(-100g
cakes
H,S04/1)
Solution ( 5 g H,S04/1)
(ZnS04) acid leaching
-1
1
To the electrolysis To processing
for the extraction of
Pb, Zn. I n , etc.
During the leaching most of the indium remains in the insoluble residue -
the zinc cake. This is attributed to the fact that in the neutral leaching
the leaching is continued until the solution reaches a pH of 5.2 (which
corresponds to the beginning of zinc hydroxide precipitation). Quantitative
precipitation of indium hydroxide takes place a t pH 4.67 to 4.85.
The hydrated oxides of iron, gallium, germanium, and other elements
also concentrate in the cakes from the neutral leaching. In the acid
leaching, the zinc is the first to be extractedinto the solution since it is
the main component of the precipitate. As a result the bulk of the indium,
gallium, germanium, and other components remain in the cake together with
the lead sulfate.
F o r some unknown reason, a fraction of the indium always remains in
the sulfate solutions from the neutral leaching, which explains the presence
of indium in the copper-cadmium cakes produced a s a result of the removal
of copper and cadmium from the solution by cementation on zinc dust.
355
I, .......
I
..I". I.I.. 1111......1.......111......,,...~,,.11~..1.......111.1 ,,...,,...
I. ..I, ....
I
Zinc concen
+ TO purification
Production of lead
356
TABLE 59
Smelting product
I In concentration.%
Fraction of the total
amount of In,%
scrapings........... 0.0015-0.002 5
357
out f i r s t (pH of -
the leaching is usually a two-stage p r o c e s s . Neutral leaching is c a r r i e d
5.2 is reached a t the end of the dissolution); it r e s u l t s
in the extraction of the bulk of the zinc while the indium r e m a i n s in the
insoluble residue.
Acid leaching is then c a r r i e d out and the indium i s dissolved. The bulk
of the lead remains in the insoluble residue, a s PbS04.
TABLE 60
Valency of the
Element pH of precipitation
ion
. ~ . - - -.
1455
358
roo
80
60
40
20
0
0.88 264 4.63 6.20 208
_-------------
* It is of interest to mention a recently developed method for the extraction and purification of indium
by extraction with alkylphosphoric acids /21/.
359
~1/~13+ ........... -1.53
Zn/Zn2+ . . . . . . . . . . . -0.76
Ga/Ga3 . . . . . . . . . . . -0.52
Fe/Fe2+ . . . . . . . . . . . -0.44
Cd/Cd2+ . . . . . . . . . . . -0.40
hm3+ . . . . . . . . . . . -0.34
TI/TI+ . . . . . . . . . . . -0.336
GeIGe'+ . . . . . . . . . . . -0.15
Sn/Sn2+ . . . . . . . . . . . -0.136
AslAs3+ . . . . . . . . . . . +0.247
cu/cu2+ . . . . . . . . . . . $0.34
in mercury (In - -
The amalgam method i s based on the marked solubility of some metals
-
7570, T1 457'0, Ga 27'0) and the s t r i c t sequence of
transport of the metals from the solution into the amalgam and from the
amalgam into the solution, on the stability of the amalgams in aqueous
solutions and the absence of chemical interaction between the metals and
the mercury, on the l a r g e density of mercury and the amalgams, which
makes i t possible to concentrate large amounts of the metal (indium) in a
s m a l l volume of the amalgam (about lOkg of indium may be concentrated
in one l i t e r of mercury).
360
of 1 N), c is the ion concentration in the solution, n is the valency of the
ion, and F i s the Faraday number.
This causes a d e c r e a s e in the difference between the absolute values
of the potentials of the metal to be deposited by cementation and the metal
on which cementation takes place and leads to a slow-down of the cement
ation process.
Increasing the concentration of excess sulfuric acid also causes a shift
of the cathode potential of indium in the direction of m o r e negative values.
This is attributed to the binding of indium ions a s complex salts, which
reduces the concentration of indium ions in solution
In3+ +- 2 ~ 0 f 2 [In (SOJJ.
The cementation on aluminum is favored by the presence of chloride
ions (10 to 2 0 m l of hydrochloric acid is added to one l i t e r of the solution).
This may probably be attributed to the p a r t i a l decomposition of the sulfate
complex in the presence of chloride ions:
[In (S04)J + 3C1- InCI, + 2SO:-.
Moreover, the hydrochloric acid dissolves the passivating oxide l a y e r s
formed on the aluminum surface.
The cementation of indium on aluminum yields a precipitate which can
be readily removed from the surface, a fact which makes this process
advantageous a s compared with the cementation on zinc.
The presence of appreciable amounts of a r s e n i c in the solution leads to
incomplete precipitation of indium; this is attributed to the formation of
indium orthoarsenite InAsO, which has a low degree of dissociation.
Hence, in the c a s e of solutions with a high a r s e n i c concentration the
a r s e n i c must be separated from the solution (e. g . , by cementation on
iron in the presence of copper).
The indium sponge produced by the cementation i s washed with water,
p r e s s e d into pellets and fused under a protective layer of sodium hydroxide.
The crude product contains 96 to 9 9 % indium, depending on the impurity
concentration in the starting solution.
361
sometimes repeated two or three times). The hydrated precipitate is
treated with an alkali solution with intensive heating. A s a result of the
alkaline treatment, sodium stannate, aluminate, and gallate pass into the
solution while the indium remains in the precipitate since the sodium
indates a r e unstable in a boiling solution.
I Rotary-kiln oxides I
J.
Solution
.L
Solution
1
Neutralization
- Acid leaching
4.
Precipitate
Precipitate
3
Iron
turnings
:Dissolution
T J.
Solution
17
ZnO
Preci pi ta I e
To the extraction
of lead
Neutralization
(pH 4.8-4.9)
J.
I Btion
To the electrolytic
Precipitate
I
I
-Y
NaOH solution
Dissolution
J.
Precipitate Solution
*
solution
-7
NaC1 I
Cementation <
Aluminum
sheets
-
Indium sponge Solution
+
Pelletizing I
A
Additional cementation
dust
NaOH 3. 1 1
Fusion Solution Precipitate
.1 1
To waste Dissolution
J.
Solution
J.
FIGURE 184. A typical flow sheet of the extraction of indium from the rotary-kiln
oxides.
362
I
Oxidative refining
.1 .
I
Oxides (drosses) Purified lead
2-570 In
Neutral leaching
. 1 ~ 3 .
Solution Residue
4
To the isolation
1- H2SO4
Acid leaching
of zinc
J.1
Solution Residue
I .
I
Zinc sheets
Y 1
Cementation
To the smelting
of lead
I I
+ .
I
Solution Indium sponge
.I 1
To the leaching of Pelletizing
zinc cinders 1
Fusion of the pellets
1
F l
FIGURE 185. Extraction of indium from the lead produced in the refining
of crude zinc.
363
The total degree of extraction of the indium from the lead into the crude
m e t a l is about 90% 1191.
The crude indium contains a number of impurities: Cd, Pb, Al, Zn, Sn,
Cu, Fe, T1, etc.
Since indium is used in semiconductor electronics, the refining is
c a r r i e d out with special c a r e .
The following refining methods a r e used in practice:
1) selective cementation,
2) electrochemical methods,
3) chemical methods,
4) vacuum distillation,
5) zone melting and rod drawing from melt.
In actual practice, u s e is made of a combination of s e v e r a l of those
methods.
Selective cementation
The crude indium is dissolved in sulfuric .acid and some of the impurities
a r e then separated by cementation, using the differences in the normal
potentials of the elements ( s e e p. 460). For instance, the tin present a s
an impurity is separated by cementation on crude indium plates. After
prolonged contact (7 0 to 100 hours) between the solution of indium in
sulfuric acid and the cementation-base metal, the tin concentration in the
solution is reduced to 0.003 g / l .
- 1 %In
0.37'0 Cd. Cadmium and thallium a r e deposited on the zinc together
with a very s m a l l fraction of the indium. The mechanism of this p r o c e s s
has not been elucidated. In o r d e r to have a satisfactory deposition it i s
required that the zinc plates have a f r e s h active s u r f a c e ; hence, they a r e
remelted every day. It must be noted that the above purification method
is complicated and h a s been recently replaced by simpler methods.
364
The addition of glue makes it possible to obtain compact cathodic
deposits. The crude indium anodes a r e enclosed in cotton bags in o r d e r
to prevent the t r a n s f e r of fine lead, tin, and copper p a r t i c l e s to the cathode.
The cathode may be made of high-purity indium o r aluminum sheets. The
electrolysis is c a r r i e d out a t a cathodic c u r r e n t density of about 100 amp/ m2
and a t a voltage of about 2 V.
Second electrolysis
r-- ~ --7
Purified Inz(SOJ,
soh tion
1
Third electrolysis
J.--
Spent electrolyte
FIGURE 186. Flow sheet of the el ect r o ch em i c a l separation of indium and thallium.
365
Chemical methods
366
FIGURE 187. Flow sheet of the refining of indium by dissolution in molten salts and disproportionation.
Vacuum distillation
This method may be used to f r e e the indium from metals with a low
boiling point. Thus, cadmium (bp 765") may be separated by melting
indium in a vacuum at 900". The cadmium concentration in the indium
may be reduced to 1 O - 5 % .
367
Zone melting and rod drawing from melt
_____________----
* T h e nature of the Lone melting and rod drawing from m e l t methods has been described in the chapter on
germanium.
368
Chapter X
THALLIUM
P r o p e r t i e s of thallium
369
TABLE 61
Physical constants of thallium and lead
3 70
Thallium carbonate TlzC03 is hydrolyzed in solution.
In a neutral medium o r an acetic acid solution thallium is quantitatively
precipitated ( a s the sulfide) by ammonium sulfide or hydrogen sulfide.
The sulfide dissolves in inorganic acids.
TABLE 62
Uses of thallium / 3 , 3 3 /
311
A radioactive isotope TlZ4O(half-life = 2.7 y e a r s ) is used a s a p - r a d i a
t i o n s o u r c e i n m a t e r i a l - t e s t i n g i n s t r u m e n t s (defectoscopes)
and in p r o c e s s control, in particular for the measurement of the thickness
of products and coatings.
A t h a l l i u m g a s - d i s c h a r g e t u b e (i,e., a g l a s s tubefilledwith
argon arc thallium vapor) e m i t s monochromatic light with a wavelength
of 5350 A(green). This tube is used for the calibration of spectroscopic
instruments, for the control of photographic paper and films, and for
the evaluation of X-ray pictures in medicine.
M o n o c r y s t a l s of a s o l i d s o l u t i o n of t h a l l i u m b r o m i d e
a n d i o d i n e (about 4270 TlBr and 587'0 TU) a r e u s e d f o r t h e p r o d
u c t i o n of w i n d o w s , l e n s e s , p r i s m s , a n d c e l l s f o r o p t i c a l
i n s t r u m e n t s o p e r a t i n g i n t h e i n f r a r e d r e g i o n of t h e
s p e c t r u m . They a r e used in infrared military devices and in spectro
scopes and microscope objectives for work in the infrared region of the
spectrum.
The addition of thallium carbonate to the initial m a t e r i a l s in g l a s s
manufacturing i m p a r t s to the g l a s s a high refractive power.
T h a l l i u m i s a c o m p o n e n t of a n u m b e r of b e a r i n g a l l o y s
to which it i m p a r t s a high anti-friction coefficient. Thus, the alloy con
taining 7291, Pb, 15% Sb, 5 % Sn, and 870 T1 is superior to the best tin-based
bearing alloys.
The introduction of thallium to lead alloys improves their corrosion
resistance. F o r instance, the alloy containhg 7 0 % Pb, 2070 Sn, and 10%
T1 is not attacked by hydrochloric and nitric acids. This and some other
lead-thallium alloys may be used a s insoluble anodes in the electrodeposi
tion of metals.
Thallium sulfate was used in agriculture as a poison (against rodents),
but has been displaced by cheaper poisons.
Thallium s a l t s may be used a s anti-knock additives to fuels �or internal
combustion engines, a s catalysts for organic synthesis, etc.
96. OCCURRENCE
372
The vapor p r e s s u r e of TlzO at 900" is 1 2 0 m m Hg, while the vapor p r e s s u r e
of TlCl reaches 1 atm at 806". In the agglomeration roasting of lead
concentrates m o r e than 50% of the thallium is entrained with the gases.
The dust from the electrostatic f i l t e r s usually contains a few tenths of
one percent of thallium 1 3 5 1 .
In the shaft furnace smelting of lead, also, a fraction of the thallium
is entrained with the g a s e s and concentrates in the dust.
In the roasting of zinc concentrates a fraction of the thallium concen
t r a t e s in the dust together with the cadmium. The thallium remaining in
the cinders i s dissolved during the leaching. When the cadmium and copper
a r e removed from the solution by cementation on zinc dust, the thallium
p a s s e s into the copper-cadmium cake.
The dusts from the processing of copper concentrates in roasting and
smelting furnaces a r e enriched with thallium.
Thallium may also be produced from the dusts collected in the installa
tion for the purification of the roasting g a s e s in sulfuric acid plants.
Thallium may thus be extracted from the d u s t s of lead, zinc, copper,
and sulfuric acid manufacturing and from the copper-cadmium cake
produced in the hydrometallurgical processing of zinc cinders.
373
If the m a t e r i a l s to be processed have been produced by cementation (e. g . ,
copper-cadmium cakes), and in which the components a r e in a metallic
form, the m a t e r i a l s a r e subjected to preliminary oxidative roasting in
o r d e r t o facilitate the leaching.
The thallium in the dusts is mainly in the form of T120 and thallium
chloride.
The leaching may be c a r r i e d out either with water (thallous oxide is
readily soluble in water) or with dilute sulfuric acid.
Thallium is separated from the solution a s the hydroxide, chloride or
chromate, or by cementation. The selection of the method to be used
depends on the thallium concentration in the solution and on the concentra
tions of other elements accompanying the thallium.
Precipitation of thallium hydroxide. This method i s used for the
isolation of thallium f r o m dilute solutions (0.05 to 1g T l / l ) . Thallium
hydroxide Tl(OH)3is precipitated a t pH E 4, which makes it possible to
s e p a r a t e the thallium from the bulk of the cadmium and zinc (Cd(OH)2i s
precipitated a t pH = 8, while Zn(OH)2 is precipitated a t pH >, 5 . 2 ) . The
thallium in the leach liquors is p r e s e n t a s the monovalent ion. The T1+
is oxidized to T13+by means of potassium permanganate or ammonium
persulfate. The oxidation with potassium permanganate involves the
reaction:
3T1,S04 + 4KMn0, + 8H,SO, = 3T12(SO,), + 4Mn0, + 2K2S0, + 8H,O,
whose main product is tetravalent manganese since the Mn- ions a r e
oxidized by excess permanganate to MnOz.
After the oxidation the solution i s neutralized with sodium hydroxide to
pH 4 to 5, and heated to 7 0 to 80" with hydrolysis of the thallium sulfate:
TI, (SO,), f 6H20 --f T1 (OH), + 3H,S04.
The hydrated manganese dioxide formed during the oxidation s o r b s the
thallium hydroxide and thus facilitates the m o r e quantitative precipitation
of the thallium.
Precipitation of thallium chloride. The precipitation of the sparingly
soluble chloride is used in s e v e r a l technological p r o c e s s e s . This method
should be employed for solutions with relatively high thallium concentra
tions (above 5 g/l).
The solubility of TlCl in water at 20" i s about 0.3270 ( s e e Table 63).
The presence of an excess of the precipitating agent (usually NaCl) reduces
the solubility and thus leads to a fairly quantitative precipitation. The
effect of the NaCl concentration on the solubility of the TlCl is a s follows:
NaCl concentration, 70 0 0.146 0.293 0.858 1.17
TlCl solubility.% 0.32 0.208 0.142 0.095 0.065.
314
The thallium amalgam formed .is then subjected to electrolysis and the
thallium is deposited on the cathode. This is accompanied by further
purification of the thallium.
Examples of technologic a1 p r o c e s s e s
375
composition: 0.4 to 0.670 Tl, 20 to 2570 As,
6 to 1470 Zn, 0.02 to 0.0670 Cu, 4.5 to 870 Fe.
2070 Mn, 0.9 to 1.470 Cd, -
KMn04
NaOH-
- -
-
Solution
1
Oxidation
TLeaching
Dilute H2S0,
Precipitate PbSO,
.1
T o lead smelting
Neutralization
(pH 4.5-5)
- - ---i
Solution Precipitate
J- 4.
To wastes Drying and crushing
- 7 1 -
C o al H2SO4
Sulfating (300-350")
.1
Roasting t500-600")
1
LeachinE
- Distillate (As203)
3. J.
Solution Precipitate
Zn dust- I 1
To wastes
Cementation
7 4.
Solution Precipitate
& -Air
Oxidation
Leaching
1
Evaporation to a TI concentration
of l o g 1
I
Na2COs .1
-
Removal of Cd, Zn, Cu
~~ . . .
1 .1
Solution Precipitate (Zn, Cd
and Cu carbonates)
Zn sheets 1
Cementation
1
FIGURE 188. Flow sheet for the extraction of thallium from dust, including a
TI(OH)S precipitation stage.
3 76
I
J.
Residue
1 ~
Additional leaching
Water
-
Leaching
Solution
1
5
Solution
- J . Cake
Filtration
5 - 7
-
.1
To agglo
Residue Solution
mera tion 1
To waste
Zn+Hg
First cementation
J.
Amalgam Solution
(Zn, Cd. Pb. TI)
5.
Electrodeposition Second cementa tion
5 . 7
Solution Amalgam
Amalgam Zinc 1 Zn. Cd, Pb.T1
(Cd. Pb. T1) met L Sludge L.
1
Electrodeposition
collection
r---l
Sludge Solution
of Cd
: & .1 5
Amalgam ( P b , TI) Cd metal Purification To
I
Thallium
solution
I I
Mercury
I
Residue
5
Solution
-
Separation of lead
7
Thallium
I
To leaching a t
1 amalgam a t start of the
To the extraction
of lead
1
Electrodeposition ll process
5 -
of thallium
1 II
Electrolyric
thallium Mercuryl
5. J'
Preparation of Zn
Melting
1 amalgam
FIGURE 189. Flow sheet of the production of thallium from lead plant dusts by the a m a l g a m method.
311
volatilized a s AszQ. The sulfatized m a t e r i a l is leached with water at a
solid : liquid r a t i o of 1 : 1 0 at 80". The thallium is separated from the
filtered solution by cementation on zinc powder. The cementation i s
c a r r i e d out a t pH 2, at 40". This c a u s e s precipitation of up to 99.5%
of the thallium; the cementation precipitate contains 4 to 67'0 T1. It is
regarded as a thallium concentrate. In o r d e r to facilitate i t s dissolution,
the precipitate is preliminarily oxidized in a s t r e a m of a i r a t 200". The
oxidized m a t e r i a l is leached with water, with heating. The solution is
evaporated to a thallium concentration of about 1 0 g / l , and the copper,
zinc, and cadmium present in the solution a s contaminants a r e precipitated
a s the carbonates upon the addition of sodium carbonate. The thallium
is then separated f r o m the purified solution by precipitation on zinc plates
( a t pH 1). The thallium sponge formed is p r e s s e d into pellets and fused
under a l a y e r of sodium hydroxide. The metal produced in the above
p r o c e s s contains about 96 % thallium.
The amalgam method for the extraction of thallium (Figure 189) was
developed in the USSR and is used f o r the extraction of thallium from the
agglomerated dusts of a lead plant 1341. The dusts taken for processing
contain 0.2 to 1.5'7'0 T1.
The dust is leached with water in t h r e e stages at a solid :liquid ratio
of 1 : 5 a t 80 to 90". The leaching is c a r r i e d out in rubber-lined steel
r e a c t o r s fitted with s t i r r e r s (the rubber lining is n e c e s s a r y in o r d e r t o
prevent cementation of the thallium on the iron). The solution from the
f i r s t leaching stage is taken f o r cementation while the solutions from the
second and third leachings a r e returned to the preceding leaching stage.
The extraction of thallium into the solution is 72 to 79%.
Solution from
the filter
378
controlled by measuring the amalgam potential. When all the zinc has
been consumed, the amalgam potential drops sharply to 0.66 to 0.68 V
(the potential of the zinc amalgam is 1.0 to 1.04 v)*. Zinc is added to the
r e a c t o r to replace the zinc which has been consumed. After passing through
the two r e a c t o r s the solution is forwarded to a bath f o r the separation of
the sludge (entrained m e r c u r y particles) and is collected in a receiver.
The total degree of extraction of thallium into the amalgam is 93 to 98%.
The bulk of the cadmium and lead from the solution a r e precipitated to
gether with the thallium during the cementation.
In o r d e r to separate the m e t a l s composing the amalgam, i t i s electro
lytically decomposed in t h r e e stages. Each stage is c a r r i e d out in an
electrolyte of a certain composition. The f i r s t stage involves the s e p a r a
tion of the zinc. The electrolyte is a 2 N solution of (NH4)2S04in 1 N NH40H.
The second stage involves the separation of the cadmium. It is c a r r i e d
out in the s a m e electrolyte. The third stage consists in the separation of
the thallium. The electrolyte used is a 2 N solution of H2SO4.
The lead is separated by making use of the ability of thallium to displace
lead from the amalgam. F o r this purpose the amalgam ( a f t e r the electro-
deposition of the cadmium) i s treated with
an alkaline solution containing thallium.
The amalgam is decomposed in electro
l y z e r s made of a vinyl polymer ( F i g u r e 191).
Five rotating copper d i s c s i m m e r s e d in
the amalgam s e r v e a s the anodes. Their
surface i s rapidly coated with a l a y e r of
amalgam. The d i s c s rotate at about
30 rpm. Aluminum plates, which a r e
placed in the upper p a r t of the bath in
gaps between the discs, s e r v e a s the
cathodes.
Zinc i s deposited at an amalgam poten
tial between -0.85 and -0.74 V, cadmium
is deposited between -0.56 and -0.40 V,
FIGURE 191. Diagram of an electrolyzer and thallium between - 0 . 2 2 and -0.013 V
for the decomposition of the amalgam.
( a l l the potentials given a r e with respect
1-bath made of a vinyl polymer; 2 to the hydrogen electrode).
shaft: 3-copper discs -anodes; 4 The thallium i s deposited on the cathode
aluminum plates -cathodes; 5-copper a s a sponge which is easily removed. The
bus bar connected to the cathodes; 6
sealing; 7-pulley: 8-amalgam.
sponge is washed, p r e s s e d , and remelted.
Technological p r o c e s s involving a
chloride precipitation stage 136,371
(Figure 192). The agglomeration dust containing 0.1570 T1 is leached with
hot water. The leach liquor contains 100 to 120mg T1/1. The degree of
extraction of the thallium into the solution is 65 to 75%.
The thallium is precipitated from the solution with sodium sulfide.
Cadmium, arsenic, antimony, and other elements a r e coprecipitated with
the thallium a s the sulfides. When the sulfide precipitate is dissolved in
H2S04 ( a t a solid :liquid ratio of 1 : 1 at 80 to 90") the bulk of the impurities
remains in the insoluble residue. Thallium i s precipitated from the
solution a s thallium chloride upon the addition of common salt. The
* These values of the potential are with respect to the normal calomel electrode.
379
thallium chloride is decomposed with concentrated H2S04 a t 350 t o 400".
The sulfate product is dissolved in water. At the s a m e time soda ash is
added i n o r d e r to remove the cadmium f r o m the solution. Thallium is
separated f r o m the solution by cementation on zinc sheets. The thallium
sponge is pelletized and fused under a l a y e r of sodium hydroxide.
T-
-
Lead cak e
1
To lead
manufacturing
Leaching
Water
and filtration
Solution
1-
Precipitation
Na,S
Thallium
7 Solution
HZSO4 1 1
concentrate (T1,S)
T o waste
7
Dissolution
.L .
J-
\r
NaCl I
Solution
Precipitation of T l C l
Sulfide residue
(Cd. As, Sb)
Solution
T-=pci ta t e
.1
T o waste
Sulfatizing
Na2S0,
I/--- I
.1 .1
Solution Carbonate residue
Zn sheets
To cadmium production
Cementation
.L .L
Mother liquor T1 sponge
.1 17 NaOH
T o waste
Melting
1 -
Metallic thallium
380
38 1
Chapter X I
RHENIUM
382
Linear expansion coefficient:
along the C axis ................... 12.45.
perpendicular to the C axis ........... 4.67.
238
226
2ro
196
182
168 C.Rby weight
& 154
i 140
% 126
E 112
-'5 8498
&' 70
56
42
28
14
eo
8 6
.d
54
2 2
Gi
0 400 800 1200 lwO2OoO
Temperature, " C C, at. 5
FIGURE 193. Tensile strength and elonga FIGURE 194. Phase diagram of t h e system
tion of forged rhenium (15% reduction i n rhenium- carbon.
a r e a ) , tungsten and molybdenum.
384
The trioxide disproportionates in vacuo at t e m p e r a t u r e s above 4 0 0 " by
the reaction:
3Re0, -+ Re02 Re20,. +
Rhenium trioxide is sparingly soluble in water and in dilute sulfuric
and hydrochloric acids. It h a s an appreciable volatility above 400". The
vapor p r e s s u r e of Reo3 a t 3 5 0 , 420, and 614" is 0.005, 0.288, and
0 . 7 6 m m Hg respectively /25/.
R h e n i u m d i o x i d e Re@ is a dark-brown solid which is prepared by
reduction of RezO, with hydrogen at 300" or by decomposition of ammonium
perrhenate NH4Re04a t 400° in an i n e r t atmosphere (argon, nitrogen).
Rhenium dioxide decomposes upon heating (above 750") in vacuum, yielding
rhenium and Re2@:
7Re0, + 2Re20, 3Re. +
The vapor p r e s s u r e of R e o z at 650 and 750" is 1.3 - and 4 . 3 - lo-'
m m Hg respectively / 25/.
TABLE 63
Salt
I I8 I 19
Solubility, @ l , at temveratures (
I 20 (21.6124.1 28 I
. " .0
30 I 80 189.51 93
. . . . . . . 9.52 - - 10.7
....... - - 53.2
- -
....... - - 623-
.......
.......
.......
.......
- ,. "I I . 1 J 1
385
I
There a r e two known rhenium oxychlorides: ReOC14 (mp 30°, bp 2.28")
and Re03C1 ( m p 4.5", bp 130"). The oxychlorides a r e formed by heating
ReC15 or Reel3 t o 150 to 400' in the p r e s e n c e of oxygen /1, 2,21/.
Rhenium sulfides. Rhenium f o r m s two sulfides - the heptasulfide
Re2S7and the disulfide Res2.
R h e n i u m h e p t a s u l f i d e is a dark-brown substance which is p r e
cipitated by hydrogen sulfide f r o m both acid and alkaline solutions. F r o m
acid solutions, a satisfactorily quantitative precipitation is obtained a t
r a t h e r high acidities (4 NHC1 o r 6 NHzSOd. The precipitation of Re2S7
from alkaline solutions is slow; in o r d e r to obtain a quantitative precipita
tion, the solution is saturated with hydrogen sulfide and allowed to stand
f o r s e v e r a l hours. Rhenium heptasulfide is sparingly soluble in solutions
of the alkali m e t a l sulfides.
R h e n i u m d i s u 1f i d e Resz is prepared by t h e r m a l decomposition of
Re2S7 (above 300") o r by d i r e c t interaction between rhenium and sulfur at
850 to 1000". The crystalline lattice of the disulfide is hexagonal, like the
lattice of molybdenite. The sulfide is black and has a density of 7.5. It is
oxidized in a i r above 300°, yielding Re207. Rhenium disulfide is oxidized
by n i t r i c acid and hydrogen peroxide, yielding HReO, solution.
Uses of rhenium / 3 , 4 , 6 J
Rhenium and its alloys have already found some valuable uses. The
most important of these a r e described below.
Production of electrical lamps and vacuum-tube devices, In this field,
tungsten has been replaced by rhenium or rhenium-tungsten and rhenium-
molybdenum alloys in s o m e important uses. As compared with tungsten,
rhenium has the advantages of a higher strength, retention of ductility in the
recrystallized state, lower tendency to vaporization in the presence of
t r a c e s of moisture ( i t is r e s i s t a n t to the so-called hydrogen-water cycle),
a higher electrical resistance, and not having stable carbides.
These advantages of rhenium a r e of special importance in c a s e s in which
a long s e r v i c e life of the lamps and electronic devices is required,
especially s o under dynamic load conditions (e. g . , in electronic tubes f o r
r a d a r in aviation, in photographic projection lamps, in lamps for r a i l
ways, etc.). Rhenium and rhenium-tungsten alloys a r e used for the
production of filaments, of cathode and heater c o r e s , and the grid windings
in radio tubes.
In contrast to tungsten, the recrystallized W + 30% Re alloy is fairly
ductile a t room temperature. The alloy Mo + 50% Re is also used in
electronic devices. This alloy combines a high ductility (it can be cold
worked) with a high strength. Since it h a s a l e s s e r tendency ( a s compared
with tungsten) to vaporize in the presence of t r a c e s of moisture, rhenium
is used in discharge tubes filled with hydrogen containing water vapor.
The use of rhenium and i t s alloys in vacuum tube technology started only
recently and i t s potential uses in this branch a r e by no means exhausted.
Thermocouples for high temperatures, made of rhenium and rhenium-
tungsten o r rhenium-molybdenum alloys, have a high, stable thermo
electromotive force.
386
Thermocouples of (W+570 Re)-(W + 2 0 % Re) have been developed and
a r e used in the USSR. Over the range 0-2500" the thermoelectromotive
force of this thermocouple is a linear function of the temperature ( s e e
F i g u r e 195). The thermoelectromotive force is 3 0 m V a t 2000". This
thermocouple has the advantage of being made of electrodes whichmaintain
their ductility after prolonged heating to high t e m p e r a t u r e s .
Temperature. " C
387
Or b
2500
Pow
o 20 w 60 BO im
Nb Re,% by weight Re
"0 C'
0 20 00 60 80 100 0 20 10 60 80 I00
To Re,Yo by weight Re W Re,% by weight Re
FIGURE 196. Phase diagrams of the systems rhenium -refractory
metals.
a-Nb-Re; b-Ta-Re; c-Mo-Re; d-W-Re.
100. OCCURRENCE
388
The rhenium concentration in molybdenites from various deposits is
within l o - ' - 1 0 - 5 q ~ . Molybdenites f r o m copper-molybdenum deposits have
the higher rhenium contents. Thus, molybdenite from the copper s l a t e
deposits of Mansfeld (German Democratic Republic) contains 0.01% rhenium.
The molybdenite concentrates f r o m copper-molybdenum deposits in the
USSR contain 0 . 0 2 5 to 0 . 0 4 7 0 rhenium. In addition to molybdenite concen
t r a t e s , some copper sulfide concentrates also s e r v e a s a source of
rhenium J 3 J .
389
When using wet dust-collecting methods, most of the rhenium is
collected in the acid solutions. To i n c r e a s e the rhenium concentration,
the solution is returned s e v e r a l t i m e s to the wet dust-collector (i. e . , the
solution is recycled). The solutions withdrawn f r o m the wet dust-
collecting s y s t e m contain 0.2 to 0.8g R e / l and 30 to 60gH2S04/1.
In the c a s e of a nonquantitative volatilization of the rhenium during the
roasting of molybdenite concentrates, the rhenium remaining in the
cinders p a s s e s together with the molybdenum into the sodium carbonate
or ammonium hydroxide solutions (during the leaching of the cinders),
but r e m a i n s in the mother liquor a f t e r precipitation of the molybdenum
compounds.
Thus, in the processing of molybdenite concentrates, rhenium may be
produced f r o m the dusts obtained in the roasting of the concentrates, from
the acid solutions of the wet dust-collectors, and f r o m the mother liquor
(waste solution) after the hydrometallurgical processing of molybdenite
cinders.
Se . . . . . . 0.06 CI . . . . . . 0.92
1465
390
In the dusts from the roasting of molybdenite concentrates the rhenium
is present mainly a s Rez07, which makes i t possible to extract i t by
leaching with water. Since a fraction of the rhenium in the dusts may be
present as a component of the lower oxides (which a r e sparingly soluble
in water), the leaching is c a r r i e d out in the presence of oxidizing agents,
e. g., pyrolusite. The leaching of the dusts is occasionally preceded by
certain pyrometallurgical operations: roasting with sublimation (in
o r d e r to i n c r e a s e the rhenium concentration in the dust) or roasting with
the addition of l i m e (to bind the M o Q a s calcium molybdate CaMoO,).
During the subsequent leaching with water, the sparingly soluble calcium
molybdate is separated from the calcium perrhenate Ca(Re04)2which is
extracted into the solution.
The following methods may be used to e x t r a c t the rhenium from the
solutions obtained in the leaching of the dusts, the solutions from the wet
dust-collecting systems, and the mother liquors remaining after the
precipitation of molybdenum compounds:
1) precipitation a s a sparingly soluble compound (potassium perrhenate
KRe04, rhenium sulfide ResS,) ;
2) sorption on ion exchange r e s i n s or activated carbon;
3) extraction with organic solvents.
The l a s t two methods a r e used to p r e p a r e m o r e concentrated solutions,
from which the rhenium is then precipitated a s potassium or ammonium
perrhenates, which a r e the main starting m a t e r i a l s for the production
of rhenium. Some technological p r o c e s s e s which make use of the various
methods f o r the extraction of rhenium from manufacturing wastes a r e
described below.
39 1
The degree of precipitation of the rhenium is 98 to 99%. The mother
liquor contains 0.02 to 0.5g Re/l. The rhenium may be extracted f r o m
the mother liquor by sorption on resins. The technical potassium
perrhenate is purified by s e v e r a l successive recrystallizations.
Water
I 7
'7'
Leaching
Pyrolusite
-
Filtration
1 3-
Residue Solution
.1
To molybdenum
production Neutralization
Solution Residue:
.1 CaMoO,, CaSO,,
Evaporation Fe(OH), Cu(OH),
I
I
To molybdenum
production
Precipitation of potassium
Derrhenate
I I
Precipitate KReO, S o h rion
I
Purification by recrystallization
.1
To the regeneration
of rhenium
FIGURE 197. Flow sheet of the extraction of rhenium from the dust collected
in the electrostatic filters in the manufacture of molybdenum.
392
I
Technical KReO,
Water
\I/.
Firstrystallization
4 7
II
KReO, crystals Water
/ .
2 c o n d recrystallization
.
m me04crystais
J
Third recrystallization- Water
Mother
I
KReO, crystals
Water
liquors J. . -
Fourth recrvstallization
7-
Evaporation tc
dryness
KReO, crystals
/ .
Fifth recrystallization
Water
Asf r I
processing
$-----i
KRiO,
Jlution
_i
Solid
residue-
t o waste
+, KReO,
393
Dust 6UX
\
Slaked lime 40% -f Preparation of the charge -Roasting 570-67O’C
t
1
Water
75 1\
Water
12.5 1\
W Evaporation
rg Water Water
P to 20g/l
Filtration
0.5 g/ 1
Filtration 90 1 KReO,
Water Water
f c 60 1
FIGURE 199. Flow sheet of the extraction of rhenium from the dust, including roasting with lime.
Re . . . . . . 0.015-0.04 c q - .. . . . 0.7-1.3
MO . . . . . . 0.4-0.9 N~ ...... 28-35
SO:-
-
"- * . . . '-%
. . . . 15-35 pH of t h e
solution
. 8.5-8.7
The molybdenum and the rhenium a r e extracted from the above solution
by selective sorption of the molybdenum ions on an anion exchange resin
followed by the sorption of rhenium on activated carbon (Figure 200) / 3 / .
The solution is acidified to pH = 3 and heated to expel the carbon dioxide
(the starting solution contains sodium carbonate). The cold filtered
solution is then passed through an ion exchange column filled with the
anion exchange r e s i n "Espatite AN-1" in the sulfate form. The grain s i z e
of the r e s i n is 0.15 to 0.6 mm. In the weakly acid solution the molybdenum
is present a s the anion of isopolyacids (e. g . , [ M O , O ~ ~ ]anions)
~ which a r e
sorbed on the resin. The capacity of the resin f o r molybdenum is about
20%. The filtration r a t e is about 5 volumes of solution p e r one volume of
r e s i n p e r hour. After the saturation of the resin the molybdenum is eluted
with a solution of ammonium hydroxide. The r e s i n is then charged again
with SO:- ions, which is accomplished by passing s u l f u r i c acid (18 g / l )
through the column.
Wash waters
Distillate. ammonia
J
at 100" Molybdenum
Air 1 Rhenium solution solution
.1
\
Cooling t o
1
< 30°C
1y
Adsorption filter
Activated
carbon
To CaMo04
manufacturing
Filtration
/\
Cake to be
Solution
& with\ Re
Carbon enriched
discarded
.1
To KReO, manufacturing
Solution to the waste
FIGURE 200. Flow sheet of the extraction of rhenium from the mother liquors in manufacture
of calcium molybdare.
395
followed by the rhenium (which is desorbed with a sodium carbonate solution
heated to 90"). The rhenium concentration in the solution is 200 to 400mgJl.
More concentrated solutions a r e obtained by repeating the sorption on the
carbon. The final solutions a r e treated to precipitate the rhenium a s
potassium perrhenate.
More effective ion exchange methods f o r the extraction of rhenium
f r o m the solutions coming f r o m the dust-collecting s y s t e m s have been
recently developed. Strongly basic anion exchange r e s i n s a r e used f o r
the sorption. The ReOi and Moo:-ions a r e adsorbed together on the r e s i n
--
f r o m nearly neutral solutions. The molybdenum is then eluted with a
10% alkaline solution, followed by the rhenium which is eluted with a
7 N solution of hydrochloric or perchloric acid 1191.
396
I
Reduction of ammonium perrhenate with hydrogen
+
+ - +
1Cat.l H KReO, [Cat.]K HReO,;
+
[Cat.]NH, KReO, [Cat.]K NH,ReO,.
--t
397
The sulfide method. Potassium perrhenate is dissolved i n hot 10% HC1.
Hydrogen sulfide is bubbled through the solution, resulting in the precipita
tion of rhenium sulfide RezS,. The sulfide is suspended in a 10% solution of
ammonium hydroxide and is oxidized with hydrogen peroxide. This yields a
solution containing ammonium perrhenate and ammonium sulfate :
Re$, + 16NH40H+ 28H,O, + 2NH,ReO, + 7(NH,),SO, f 36H,O
The solution is evaporated and ammonium perrhenate is crystallized.
The presence of ammonium sulfate c a u s e s a s h a r p drop in the solubility of
ammonium perrhenate ( t o about 5 g/l), which makes it possible to isolate
the bulk of the rhenium f r o m the solution.
Reduct i on
TABLE 64
398
Reduction of rhenium dioxide by hydrogen 1 11 /
The method was developed a t the Battelle Institute in the USA and i s
known a s the ' I chloride method" since the pure rhenium dioxide i s
produced f r o m the chloride. Technical grade rhenium produced by the
reduction of potassium perrhenate with hydrogen, or rhenium s c r a p f r o m
mechanical working, o r precipitates formed in the regeneration of rhenium f r o m
mother liquors may s e r v e a s the starting material. The starting m a t e r i a l
is f i r s t heated f o r one hour in a c u r r e n t of hydrogen at 1000" (in o r d e r to
reduce the oxides) and is then chlorinated with chlorine at 750" to produce
ReC15 which is then distilled (its bp is 330"). The resulting chloride i s
decomposed with cold water ( a t a temperature not exceeding 10"). Hydrated
rhenium dioxide is the main reaction product (about 7 0 % Re):
3ReC1, + (8+ x)H,O + 2Re0,. xH,O + HReO, + 15HCI.
As is evident from the above reaction, a fraction of the rhenium remains
in the solution a s rhenic acid. In addition, the solution contains a v e r y
s m a l l amount of chlororhenic acid H2ReOC15.
In o r d e r to facilitate the separation of the hydrated dioxide precipitate
by filtration, carbon dioxide is bubbled through the suspension f o r thirty
minutes p r i o r to the filtration. The precipitate (Re20 .xHaO) i s separated by
filtration in a centrifuge and is dried in a vacuum. In o r d e r to extract the
rhenium remaining in the filtrate, i t s lower f o r m s a r e oxidized with
hydrogen peroxide to HReO,, the solution is neutralized with ammonium
hydroxide, and ammonium perrhenate is isolated and returned to the
20" -
reduction cycle. The rhenium dioxide is reduced with hydrogen in
molybdenum boats (in a l a y e r thick) by holding f i r s t for one
hour at 400", then for one hour at 600". The slightly sintered powder is
crushed and subjected to further reduction for 2 hours at 800". The total
yield of rhenium by the above method is 957'0. The use of the above method
yields rhenium virtually f r e e of alkali metals and most other elements
except iron and silicon ( s e e Table 64).
The increased potassium content of rhenium produced by the reduction of solid potassium perrhenate
with hydrogen is attributed to the fact that at the high reduction temperatures a small fraction of the
potassium enters the crystal lattice of the rhenium. Hence, it could be expected that a more thorough
removal of the potassium could b e achieved by reducing the KReO, in an aqueous solution by hydrogen
under pressure.
Soviet workers found that a t a partial hydrogen pressure of 60 a t m and a temperature of 200'. the
rhenium c a n b e precipitated quantitatively (as a mixture of the metal and the lower oxides) from solutions
containing up to lOOg KReOJliter:
KRPO, (solution) + 31/2H, - Re + KOH + 3H20.
T h e precipitates a r e washed with dilute hydrochloric acid and water and are reduced with hydrogen
a t 850 to 900".
T h e rhenium powder produced by this method contains 0.004 to 0.006% potassium. i. e. , its potassium
content is the s a m e as that of the p~ /der produced from ammonium perrhenate. The main advantage of
the autoclave process is that it involves a small number of stages since the conversion of potassium perrhenate
into ammonium perrhenate need not be carried out.
399
Production of rhenium powder by electrolysis 14, 241
First Second
Ammonium sulfate 40 60
+ 7H Re + OH- + 3H20;
i?.eO,
Re07 -+
-
+ 7H+ + 7e Re + OH- + 3H80.
The cathodes are periodically withdrawn and the rhenium deposit removed. T h e deposit is washed
with water, with dilute hydrochloric a c i d , then again with water and is dried.
The yield of rhenium when using potassium perrhenate is 9 0 to 95%. and when using ammonium
perrhenate it is 9 3 t o 98%. T h e current efficiency is 25 to 27 and -3 5 % respectively.
T h e approximate concentrations of impurities in electrolytic rhenium are as follows: 0.00270 Cu.
0.002% Fe, 0. 003% Mo. 0.005% C a , < 0.003%AI. 0.0015% Na, and O.O05%K when using ammonium
perrhenate or 0.03% K when using potassium perrhenate.
As compared with the powder produced by reduction of perrhenates with hydrogen, electrolytic
rhenium has a coarser particle size. Its conversion into a dense, ductile metal by powder metallurgy
techniques is difficult.
400
Rhenium coatings o n tungsten. which are produced by this method, adhere strongly t o the base metal.
Soviet workers /20/ developed a method for the coating of tungsten and molybdenum with rhenium by thermal
decomposition of rhenium oxyrhloride ReOC1,. Rhenium oxychloride has t h e following advantages over
rhenium pentachloride: in contrast t o ReC15 (which dissociates a t 200" from the solid state to chlorine and
the nonvolatile rhenium trichloride ReCls 1, rhenium oxychloride is not decomposed upon heating up to
600'. This makes it possible to maintain a high concentration of ReOC1, in the vapor phase (ReOCl, boils
a t 228'). T h e rate of deposition of rhsriium o n a m e t a l l i c s u r f a c e heated to 1200 t o 1300' is -160mg/cme.
hour. i. e. , 16 rimes higher than the rate of deposition from ReC1,. Rhenium oxychloride is decomposed
with the production of rhenium by the reaction
3Re33, %
,-.e
1200--1300~c + R~O,CI+ 3'/2~~,.*
T h e volatile Re03C1 is expelled together with the chlorine. The theoretical yield of rhenium in the
above reaction is 66% but the actual yield is 50 to 60%.
T h e oxychloride is produced through the oxidation of ReCIS at 150 t o 180' in a current of oxygen.
Rhenium oxychloride is readily purified by rectification.
A diagram of a n apparatus for the continuous coating of tungsten wire with rhenium is shown in
Figure 201.
40 1
M
402
I
403
Part Four
Chapter XII
BERYLLIUM
P r o p e r t i e s of beryllium
404
Thermal expansion coefficient (25--1000°C) ..........18.77 .
Specific electrical resistance (ohm. c m 10') at:
0°C ........................................ 4.0
1OO'C ...................................... 6.5
500'C ....................................... 18.0
800°C ...................................... 31.0
Electron work function, eV ......................... 3.92
Thermal neutron capture cross section, barns. .......... 0.0090
405
the modulus of rigidity is -
The modulus of elasticity of technical beryllium is 28,000 kg/mm2,
13,800 kg/mm2. Depending on the degree of
-
deformation and the holding time, the recrystallization temperature of
beryllium ranges from 700 to 900". The Brinell hardness of technical
beryllium produced by different methods is 100 to 150kg/mm2.
The most important problem in the metallurgy of beryllium is the
development of techniques f o r the production of a ductile metal. One of
the ways in which this can be accomplished is by increasing the purity of
the metal. While the elongation (under a tensile load) of technical beryllium
is only 0 . 3 to 770, the elongation of pure monocrystal beryllium reaches
70 to 80 and occasionally 140% (in c r e e p deformation along the base plane
of the hexagonal crystalline cell of beryllium i t may be as high a s 220%).
Beryllium has five known isotopes, of which only Be: i s stable (the
unstable isotopes a r e Be6, Be', Be*, Be" and Bel'). Beryllium has a very
low t h e r m a l neutron capture c r o s s section - 0.009 barn.
TABLE 65
i
~
406
The corrosion resistance of beryllium in water is strongly affected by
the methods used f o r i t s preparation and processing and i t s chemical
407
This property may be used for the separation of beryllium hydroxide
f r o m l a r g e amounts of aluminum.
The complex carbonate is hydrolyzed upon boiling, with the precipitation
of a sparingly soluble basic s a l t of beryllium:
+
2(NH,), [Be (CO&] H,O = Be (OH), . BeCO,,+ 2 (NHJ,C03 + CO,.
There a r e three known modifications of beryllium hydroxide: an
amorphous form, a metastable (e-)crystalline form, and a stable 8-form.
The amorphous f o r m consists of the above-mentioned hydrate Be(OH)z.xHzO
(up to 95% water) precipitated from a cold solution. When stored in a i r or
in water the hydroxide is aged and is converted into the metastable
0-form; the @ - f o r mis precipitated f r o m boiling solutions of the beryllates.
Upon aging, beryllium hydroxide becomes insoluble in alkalies and even
in acids.
Beryllium hydroxide l o s e s most of i t s water when heated t o 200 to 300°,
but f o r quantitative dehydration heating to a high temperature (700 to 800")
is required.
Halides. Beryllium fluoride is produced by the reaction between fluorine
and beryllium oxide, oxyfluoride or carbide, o r by the decomposition of
the complex ammonium fluoberyllate:
(NH4),BeF, --f BeF, + 2NH,F.
Beryllium fluoride is a colorless, very hygroscopic crystalline sub
stance, with a m p of 787 and a bp of 1327". Its density i s 1.986 g/cm3.
Upon heating in oxygen or in a i r it is converted into the oxyfluoride
5BeFz. 2BeO; beryllium fluoride r e a c t s with the alkali metal fluorides
and ammonium fluoride yielding complex fluoberyllates ( Na2BeF4, NaBeF3),
In contrast to AlF,, BeF3 dissolves readily in water (its maximum
concentration in the solution is 18 m o l e s j l ) , a fact which may be used for
the separation of aluminum and beryllium in the hydrometallurgical pro
cessing of raw materials.
S o d i u m t e t r a f l u o b e r y l l a t e Na2BeF4 is the most stable of the
sodium beryllates; it is known to exist in three crystalline "forms. The
y - f o r m has a rhombohedral structure, i t is stable at room temperature,
and is the l e a s t water soluble f o r m of NazBeF4 (at 20" i t s solubility is
1.37g/100 g solution). The p-form (which has a monoclinic structure)
is very unstable and is readily converted into the y-form. Its solubility
in water at 20" is 1.7g/lOOg solution. The @-form(with a hexagonal
structure) is formed above 300" and is converted into the y-form upon
cooling,
A m m o n i u m t e t r a f l u o b e r y l l a t e (NH4)zBeF4is the most
important of the ammonium fluoberyllates; i t s solubility a t 0 and 25" is
27.1 and 32.3 g/ l O O g of solution respectively. Ammonium fluoberyllate
f o r m s mixed c r y s t a l s with sulfates; upon heating to 900" i t decomposes
t o ammonium fluoride and beryllium fluoride.
B e r y l 1 i u m c h 1o r i d e BeClz is produced by heating the metal to
600" in a c u r r e n t of chlorine or by chlorination of a BeO+C mixture a t
700 to 800"; it is a white crystalline substance with a mp of 405". The
chloride is volatilized at 477" and boils at 487". The density of BeClz
is 1.9. It is readily soluble in water and crystallizes from aqueous
solutions a s the crystalline hydrate BeC12- 2HzO. BeClz hydrolyzes in
humid a i r or in water with the evolution of hydrogen chloride:
408
BeCI, + 2H,O = Be (OH), + 2HC1.
BeC12 readily dissolves in organic solvents (alcohol, e t h e r , pyridine,
acetone) and f o r m s organometallic compounds.
Beryllium sulfate BeS04 is produced by dissolving beryllium oxide in
hot concentrated sulfuric acid. BeS04 undergoes a polymorphic t r a n s
formation at 580 to 635", i t s thermal dissociation s t a r t s a t 760 to 830"
(with the evolution of SO3), and total decomposition o c c u r s at 1 2 0 0 to 1300".
Beryllium sulfate readily dissolves in water, and i t s solubility i n c r e a s e s
markedly with increasing temperature:
409
of t he rare refractory metals); great hardness. T h e beryllides of 40 elements a re known a t present. and
the existence has been established of 90 binary beryllide phases and a large number of ternary and multi
component phases containing beryllium. T h e physical properties of some of t h e beryllides with the highest
melting points a r e listed in T a b l e 66.
There a r e several methods for the preparation of the beryllides: synthesis from t h e components, either
by fusing together or by sintering the powders (powder metallurgy method) which is often carried out in
vacuo and after which the sintered pellets are crushed and t h e resulting beryllide powders a re converted
into dense, solid products by hot pressing; metallothermic methods which involve the reduction of
beryllium oxide with t h e m e t a l whose beryllide is to b e produced and which a t the s a m e t i m e produces a
volatile or low-melting oxide. It should be mentioned that because of the high vapor pressure of beryllium
at elevated temperatures. beryllides of a predetermined composition may b e produced mainly by powder
metallurgy methods (which do not require a high temperature) while fusion and metallothermic methods
are only seldom used.
TABLE 66
Properties of the beryllides of some metals
-
x
.-
.o N Y
U m
E ol
S E SN
2 $ E
$5
u
C
.3
0
n
-2 23
0 -
c " Y
M
::"E 2"o F
.-
I
#
$ E 2%- .3 0
v o
c(9
5
-
.-
> %
____
;;b
~
5: o mi
m
The beryllides are metal-like compounds which ar ttractive as refractory materials. components
of refractory alloys, and as materials with special nuclear-physical properties. Some beryllides have
semiconductor properties and are of interest for high-temperature semiconductor technology and also in
industrial c a t a l yt i c processes. Many refractory metals can be effectively protected against corrosion at
high temperatures by creating on their surface a refractory coating composed of the beryllide of the
respective metal.
410
Nuclear technology; The s m a l l m a s s of the beryllium atom* together
with the s m a l l t h e r m a l neutron capture c r o s s section combine to make
beryllium an effective m a t e r i a l for the moderation of neutrons t o the
velocities at which a chain reaction in a nuclear r e a c t o r h a s the highest
productivity. As a neutron-moderating material, beryllium is s u p e r i o r
to hydrogen, deuterium, graphite, and oxygen. Moreover, beryllium
reflects neutrons and may be used f o r the manufacturing of r e f l e c t o r s f o r
nuclear r e a c t o r s (the .use of such reflectors f o r the shielding of the active
zone, i. e . , the zone containing the nuclear fuel, makes it possible to reduce
the dimensions of that zone). The use of beryllium a s a moderator,
reflector and s t r u c t u r a l m a t e r i a l in r e a c t o r s is also favored by the fact
that it r e s i s t s the effect of neutron bombardment (does not change its
dimensions and properties), by the absence of noticeable induced radiation,
and by its high t h e r m a l conductivity. The u s e of beryllium a s a light metal
is especially convenient for the nuclear r e a c t o r s of transportation v e s s e l s
(boats, including submarines, airplanes, etc. ).
The use of beryllium a s a shell for r e a c t o r fuel elements makes i t
possible to i n c r e a s e the shell temperature to 500 to 600". The fact that
beryllium e m i t s neutrons upon bombardment with 0-particles is used f o r
the production of radium-beryllium and polonium-beryllium neutron
sources. Beryllium foil is used a s the window in Geiger counters,
scintillation counters, etc.
In addition to beryllium, the l e s s expensive beryllium oxide and
beryllium carbide also find use in nuclear technology.
J e t a i r c r a f t and m i s s i l e technology. Beryllium has a high specific
modulus of elasticity up to 6 0 0 to 700" ( s e e Figure 202). A s a result,
beryllium has a promising use a s a lining for the fairings in supersonic
jet aircraft, the nose cones of rockets and guided m i s s i l e s , etc.
The high heat of combustion of beryllium and some beryllium compounds
favor their use a s components of solid m i s s i l e fuels. Thus, the heat of
combustion of beryllium borohydride Be(BH4)2is 1 6 1 0 0 kcal/kg, i. e . , the
highest of all boron and beryllium compounds. The heat of combustion of
beryllium metal is also high, i. e . , 15,00Okcal/kg.
Production of alloys. The most important industrial use of beryllium
a s yet i s the production of dispersion-hardening alloys, mainly copper-
based ones (beryllium bronzes, containing 0.5 to 3.070 Be).
The capacity for aging (dispersion hardening) is associated with the
formation of hard and sufficiently high-melting solid compounds
(beryllides) between beryllium and almost all other metals; during the
aging, the beryllides a r e precipitated in a finely-divided form on the
grain boundaries of the main alloy.
The addition of beryllium to copper improves its mechanical properties
(hardness to 400kg/mm2, the tensile strength to 120 to 130kg/mm2, the
fatigue limit upon bending to 30 to 32 kg/mm2, and the fatigue limit upon
torsion to 1 7 to 1 9 k g / m m ). The high strength c h a r a c t e r i s t i c s of
beryllium bronzes a r e the reason �or their extensive use in the production
of critical machine p a r t s (springs, valve seats, valves, bearings, various
- In the case of neutrons the loss of energy ( i . e . , the decrease in velocity) upon collision with a nucleus
increases as the mass of the nucleus approaches that of the neutron, by analogy with the case of two
colliding billiard balls, in which the loss of energy is greatest when the two balls have the s a m e masses.
41 I
instrument p a r t s , watch mechanisms, telephone and telegraph parts). The
absence of s p a r k upon impact makes i t possible t o use beryllium bronzes
f o r the production of s p a r k l e s s work tools (chisels, hammers, etc. ) f o r use
in mines, in handling flammable m a t e r i a l s , and in plants with incendiary
hazards. In addition, beryllium bronzes have a high corrosion r e s i s t a n c e
t o heating in air and to s e a water. Beryllium is added to copper a s a
copper-beryllium m a s t e r alloy containing - 4q0Be.
Beryllium finds an extensive use a s an alloying component in s t e e l s
and aluminum, magnesium, nickel, and chromium alloys. Of the m o r e
important beryllium-containing aluminum alloys we rnay mention the
brands AMg6 (an AI-Mg alloy containing 0.0001 to 0.005% Be), and AL8U
(0.05 to 0.1570 Be) which retain t h e i r strength and ductility up to 250 to
300" and at the s a m e time have an improved corrosion resistance.
Beryllium is a good deoxidant in the smelting of various alloys, in
cluding light alloys, bronzes, and aluminum alloys.
The addition of beryllium to magnesium and magnesium-based alloys
makes i t possible to reduce the waste of m a t e r i a l during the smelting
and casting, to reduce the hydrogen consumption and at the s a m e time to
eliminate the porosity of c a s t products.
The addition of beryllium to i r o n i n c r e a s e s i t s coercive force.
The addition of beryllium to iron-nickel and iron- chromium alloys
makes the s t r u c t u r e of the alloy finer and, in addition to being very hard,
the alloys also become fairly ductile and corrosion-resistant. Chromium-
nickel s t e e l s containing beryllium a r e of improved refractoriness.
Beryllium is usually added to iron and s t e e l in the form of ferroberyllium
(up to 8 0 % Be).
Great prospects for the use of beryllium alloys a r e offered by the
existence of the high-temperature 8-modification of beryllium, which has
a body-centered cubic lattice and thus i s m o r e ductile than the hexagonal
a-form. It i s of importance to stabilize the /3-modification by alloying
the beryllium with other metals and especially with nickel, chromium,
cobalt, copper, manganese, and iron. Nickel is a good s t a b i l i z e r of the
/3-modification; the addition of nickel ( 8 % ) . to beryllium makes the
beryllium ductile up to 1070" while technical beryllium containing no nickel
is destroyed at that temperature.
The manufacturing of r e f r a c t o r i e s . Because of i t s high melting point,
strength, high thermal conductivity, high electrical resistivity, and
resistance to heating, beryllium oxide has become an important component
of high-quality refractories. Beryllium oxide is used for the manufacturing
of crucibles, tubes, linings f o r c o r e l e s s induction furnaces, and shielding
f o r graphite crucibles (to reduce l o s s e s through radiation).
Missile bodies may be coated with a l a y e r of beryllium oxide. This
coating is vaporized during the passage of the m i s s i l e through the dense
l a y e r s of the atmosphere, and the vaporization consumes a l a r g e amount
of heat. Of the other fields in which beryllium and beryllium compounds
a r e used, we should mention X-ray technology (windows in X-ray tubes),
electronics, and catalysis.
412
common a r e beryl, chrysoberyl, phenacite, helvite, danalite, and b e r
trandite. Beryl is the main commercial beryllium mineral, but phenacite
and helvite a r e also of commercial value.
B e r y l 3 B e 0 . A1203. 6SiOz [or Be3Alz(Si601z)]contains 14.1% BeO,
19.0% AlzO3, and 66.9% Si&. It is often contaminated with NazO, LizO,
KZO, RbsO and CszO. Depending on the nature of the impurities they
contain, beryls a r e classified a s alkali-free (total alkali content below
0.570) and alkaline beryls (total alkali content above 0.5%). The alkali-free
group c o m p r i s e s the previous-stone b e r y l s - the blue aquamarine, the
wine-yellow heliodor (colored by iron), and the green emerald (colored by
chromium).
The Mohs hardness of beryl is 7.5 to 8, i t s density is 2.63 to 2.91.
P h e n a c i t e o r beryllium silicate 2 B e 0 . S i Q [or Bez(Si04)]contains
45.570 BeO, 54.570 SiOz, and very s m a l l amounts of MgO, CaO, Al&,
and NazO. Phenacite is either colorless o r light yellow. Its Mohs hard
n e s s is 7.5, i t s density is 2.96 to 3.0. It is often associated with beryl,
chrysoberyl, and f e l s p a r s ; it i s very often found in emeralds. Phenacite
f o r m s no concentrated deposits,
H e l v i t e MnB(BeSi04)6S2 contains 13.670 B e 0 and (in the form of i m
purities) up to 1570 Fe, Zn, etc. Its color i s most often yeliow and more
r a r e l y green; i t s Mohs hardness is 6 to 6.5, and i t s density is 3.16 to 3.36.
Outside the USSR, the main beryllium o r e deposits a r e found in Brazil,
krgentina, Congo (Leopoldville), India, Southern Rhodesia, Australia,
and the USA (South Dakota and California). A l l these deposits contain
mostly beryl. The l a r g e s t phenacite and helvite deposits a r e in Norway.
The production of beryllium concentrates in the Western countries
increased continuously after the Second World War, up to 1956. The
maximum production level - 11,700 tons of concentrate (11 to 13% BeO) -
was reached in 1956.
According to approximate data, the world production of beryllium
concentrates was 8100 tons in 1960.
41 3
regulators in acid flotation, while sodium sulfide, sodium hydroxide or
sodium carbonate a r e used in alkaline flotation. The flotation of b e r y l
with cationic collectors is also possible.
The approximate chemical composition of b e r y l concentrates is as
follows :
...... 10-13
...... 62-65
...... 17-23
...... 0.4-2.0
...... 0.3-3.0
...... 0-0.7
...... 0-0.8
...... 0-0.2
0-1.5
414
(NH4)*S04 concentration. g/1
415
Beryl
\ ye
Fusion (sintering)
X
BeS04 solution
9 ET
A I
Se?ond evaporation
L l"i"i""
'"""""
1
i
.* 1
mO
r L u) BeSO, -250
Granulation in water
g% Crystallization
3- al
v1 1 ( NHdzSO,
60 g/l
Drying
tCentrifuging
1 I
Crushing
-HZSO4
1 NH4A1(SOS2 -
-
Sulfatizing
Centrifuging crysta1s
1 I Wash water
-
H,O Leaching (I
Third evaporation
I
HzO Filtration I
7
Crystallization
Cake (SiO,+
CaSOS
.1
To waste
I
Centrifuging
Mother liquor
Solution I
Roasting -SO,+H,O
Cooling
I
Be0
NHhA1(SOSz
Wash waters
crystals
FIGURE 204. Flow sheet of the production of beryllium oxide by the sulfate process with
preliminary sintering of the concentrate with lime.
416
solution and crystallization. The i r o n sulfate is separated from the mother
liquor from the second crystallization (which contains ammonium and iron
sulfates and some BeS04) and the solution is combined with the solution
used f o r the second crystallization.
The concentration of calcium sulfate in the solution containing aluminum
and beryllium sulfates is determined by i t s solubility, which at 20" is
2 g / l ; the solubility d e c r e a s e s during the evaporation and the Cas04 almost
quantitatively p a s s e s into the solid phase during the precipitation of the
alum.
Drying and roasting. The BeS04. 4 H z 0 c r y s t a l s a r e separated by
centrifuging and roasted to yield beryllium oxide:
BeSO, . 4H,O = Be0 + SO3 + 4H,O.
The roasting is c a r r i e d out in a tubular r o t a r y furnace at 1000 to 1150";
the product is beryllium oxide containing up to 0.1% FezQ+Alz03, 0.08%
CaO, and 0.27'0 Si-.
One of the widely used sulfate methods is based on the decomposition
w i t h s u l f u r i c a c i d w i t h o u t a p r e l i m i n a r y u s e of a n
a l k a l i n e f l u x d u r i n g t h e f u s i o n , which reduces the consumption
of sulfuric acid. The beryl concentrate i s fused without a flux and
granulated in cold water, yielding a vitreous m a s s that i s soluble in
sulfuric acid.
In this case the fusion is c a r r i e d out in an a r c furnace at 1 7 0 0 " , the
fused m a s s i s granulated in rapidly running water, and the granulated
m a s s is heated in a r o t a r y gas furnace to 900" (in o r d e r to increase the
degree of decomposition of the concentrate by the sulfuric acid). This
makes it possible to convert 90% of the beryllium to a soluble form. The
heat-treated fused m a s s is crushed in a ball mill to a particle s i z e of
-0.074mm, subjected to a i r classification, and the further processing i s
in principle the s a m e a s that used in the f i r s t variant described above
(Figure 205). There is a difference in that after the separation of the
aluminum in the form of alum, beryllium hydroxide i s precipitated from
the sulfate solution by hydrolysis. F o r this purpose, sodium hydroxide i s
added to the solution (to a NaOH concentration of 1.5 N) and the solution i s
boiled. This causes hydrolysis of the sodium beryllate:
417
Fusing in a r c furnace
Granulation in water
Heating to 900-950'
Grinding in a ball m i l l
- Air classification
-I
Sulfa t izing
I
4
H20 Leaching
Cake & waste
Solution
.1
Crystallization of A1 alum
-
1
Centrifuging
NaOH %
-I chnc)ail
Solution
.1
Be(OH)2
> Dissolution
H7.S04
1
(NHdzSO, A as alum
Evaporation of solution
Crystallization
Roasting a t 1150"
I
FIGURE 205. Flow sheet of the production of beryllium oxide by the sulfate method.
41 8
Mixing 2
1
Charge
.1
Sintering
.1
Crushing
I
Leaching c HzO
I
Filtration$ -
NaOH solution
I I Cake t o waste
(silica and cryolith)
Precipitation of beryllium
hydroxide
.1
Settling
l.
-I Filtration - -
I
Blowing with air
BeSO, solution
Precipitatg (Fe(OH)$)
to waste
J.
Crystallization
4
BeSO,. 4 H z 0
.1
Roasting
FIGURE 206. Flow sheet of the processing of beryl concentrate by sintering with
sodium fluosilicate.
419
conductivity of the charge is low and the thickness of the l a y e r in a muffle
furnace must not exceed 25"). The sintered m a s s is crushed and
leached with water, while heating with superheated s t e a m ; a s a result the
Na2BeF, and a fraction of the aluminum, silicon and i r o n p a s s into the
solution while the bulk of the aluminum and the silicon remain in the solid
phase. The solid and liquid phases a r e separated in a f i l t e r - p r e s s and the
,
cake is discarded. The composition of the s a l t s dissolved in the solutior,
is (converted to the oxides) 8 2 to 88% BeO, 67'0 A1203, 6 to 10% Si@ and
a s m a l l amount of iron. The solution is heated with steam t o 40 to 50"
and beryllium hydroxide is precipitated by the addition of a 207'0 solution of
sodium hydroxide :
Na,BeF, + 2NaOH = Be (OH), 4NaF. +
The addition of an excess of sodium hydroxide is to be avoided in o r d e r
to prevent the conversion of the beryllium to soluble beryllates.
The hydroxide precipitate is allowed to settle for 2 to 3 hours, and is
then separated by filtration in vacuum f i l t e r s and washed with heating
(with spent steam) to 70 to 80". After the washing, the beryllium
hydroxide precipitate is dissolved in sulfuric acid. Iron is removed
f r o m the solution by precipitation a s the hydroxide or a s a basic salt. The
sulfate (BeSO,. 4&0) is crystallized f r o m the purified solution, and is
then roasted to convert it into the oxide ( a s described above).
-
Starting materials Apparatus Intermediate products Wastes
-
(2 hours a t 760") Sinter
-
Water + Leaching tank e------ .- -_ j "Red mud"
NaOH solution
------+
Filter press
Fez(S04)s - \
Cryolite Precipitation
tank
'
NaF solution
FIGURE 207. Flow sheet for the processing of beryl concentrate by sintering with sodium fluosilicate
and iron cryolite.
420
- -
The decomposition of b e r y l with the aid of sodium fluosilicate h a s
s e v e r a l variants. A variant extensively used in industrial practice
involves the substitution of sodium carbonate and "iron cryolite" Na,FeFs
f o r p a r t of the sodium fluosilicate in the charge:
+
3Be0. A1,OS . 6Si0, 2Na,SiF, +
Na,CO, 3Na,BeF, -. +
8Si0, Alsos CO, + +
3Be0 . AI,Os 6Si0, + 2NasFeF, + 3Na,BeF, +
A1,0, Fe,Os + 6Si0,. +
This causes a s h a r p reduction in the consumption of the costly fluo
silicate, since the sodium fluoride solution is returned to the formation
of i r o n cryolite:
+
12NaF Fez (SO,), = 2NasFeF, + 3Na,SO,.
The first to study the chlorination of beryllium oxide was Avdeev, in the
middle of the nineteenth century. Many studies of the p r o c e s s were
c a r r i e d out by Soviet scientists - Spitsin, Belyaev, and Novoselova.
The chlorination of beryllium oxide with gaseous chlorine is usually
c a r r i e d out in the presence of carbon:
Be0 + C + C1, -+ BeCI, + CO.
The reaction begins at 600" but the industrially favorable chlorination
temperature is 900 to 950". The chlorination temperature may be reduced
sharply by using carbon tetrachloride a s the chlorination agent:
2Be0 + CCI, -+ ZBeCI, + CO,.
42 1
This eliminates one operation - mixing of beryllium oxide with the
carbon-and markedly simplifies the technological process. When CCl,
i s used, the chlorination of B e 0 may be c a r r i e d out to a high degree of
completion ( 9 2 to 94%) at 650 to 700". A fraction of the CC14 is converted
to C&16 through thermal dissociation.
The chlorination r a t e of B e 0 is affected by the conditions of roasting
(of beryllium hydroxide to BeO) before the chlorination, since the activity
of beryllium oxide is reduced by high roasting temperatures.
The iron, aluminum, and silicon oxides present i n the beryllium oxide
a s impurities a r e also chlorinated at the Be0 chlorination temperature
( 9 0 0 to 950") and p a s s ( a s the chlorides) into the gaseous phase together
with BeClz.
Coal Binder
1Mixing :
1
Pelletizing
J.
Coking (roasting)
1
Chlorination with chlorine
.1
Condensation
5
Rectification
1
Solid residue I
L
Beryllium chloride vapor
(iron chloride)
I
A1 and Si chloride vapors
.1 1
Condensation Condensation
1
To waste
1455
422
Chlorination of beryllium oxide by chlorine in the presence of carbon
(Figure 208). Dry beryllium hydroxide (5070BeO) is mixed with charcoal
and a binder and is pelletized in a p r e s s under a p r e s s u r e of 150kg/cm2
( s e e Figure 55). The pellets a r e coked at 1000" and then chlorinated in an
electrical shaft furnace. Beryllium chloride is condensed in a bin- shaped
nickel condenser. The beryllium chloride obtained by condensation is
contaminated with iron, aluminum, and silicon chlorides and is purified
by distillation in a c u r r e n t of Hz in a s t e e l muffle at 500 to 550". A s a
result f e r r i c chloride is converted to f e r r o u s chloride which is not volatile
at that temperature; the remaining chlorides e n t e r two nickel collectors
(placed one over the other) and beryllium chloride (9770 of the total amount
of BeC12) condenses in the f i r s t collector (which is heated to 350") while
the aluminum and silicon chlorides a s well a s 35% of the beryllium chloride
condense in the second, unheated collector.
To tt
423
Chlorination of beryllium oxide by carbon tetrachloride is c a r r i e d out
i n a furnace (Figure 209) consisting of a graphite heater in a shaft lined
with fused quartz bricks. The carbon tetrachloride p a s s e s f r o m a
measuring v e s s e l into the ring-shaped space between the h e a t e r and the
furnace lining. The furnace lid is fitted with a cap with a tube connection
and a charging bin made of s t a i n l e s s s t e e l and lined with graphite. A
nichrome h e a t e r protected by a quartz casing is fitted within the cap, to
prevent condensation of the beryllium chloride.
The furnace is preheated in a current of nitrogen to the required
temperature, and the feed of C C 4 begun (the CC14 consumption is 2.4 kg/
minute p e r square m e t e r of furnace c r o s s section). A new batch of
beryllium oxide pellets is fed to the furnace every 6 hours; the pellets
a r e prepared by p r e s s i n g a mixture of B e 0 and a binder ( a s t a r c h paste
of dextrine), followed by drying at 200" and roasting in s t a i n l e s s - s t e e l
v e s s e l s at 600". The total duration of a furnace run is determined by
the s e r v i c e life of the graphite heater and ranges from 25 to 30 days.
The chlorination products p a s s into a condenser s y s t e m : f i r s t into a
nickel condenser heated t o 300 to 320", then into a second nickel condenser
heated to 200 to 250" and then into a third unheated condenser made of
IX18H9T stainless steel, which s e r v e s to condense the excess CC14,
hexachloroethane (which distills off a t 185.6"), the contaminant chlorides
(FeC13, AlCla), and a s m a l l amount of entrained BeClz. The condensation
product from the third condenser is treated on a f i l t e r with C C 4 , the
resulting solution of hexachloroethane in CC14 i s returned to the
chlorination p r o c e s s , and the chlorides residue is returned to the hydro-
metallurgical processing in o r d e r to extract the beryllium.
The main technological and economical p a r a m e t e r s of the p r o c e s s
a r e a s follows: CC14 consumption is 1.6 kg/kg BeCla, degree of condensa
tion of BeClz is 97.870, the direct yield of beryllium is 85 to 8670, and the
total yield (including the processing of wastes) is 96%.
424
I ,111 111 I
(Approximate
425
out at 1400" i n a c u r r e n t of hydrogen, and is repeated in a vacuum furnace
at a vacuum of mmHg. The purity of beryllium obtained after two
successive meltings was 99.8% (the balance is oxygen).
T h e high-temperature variant of t h e above process, which is used a t a plant i n t h e USA, employs a n
electrolyte consisting of 13 t o 15% BeC1, and a n equimolar mixture of sodium chloride and potassium
chloride. T h e melting p i n t of t h e electrolyte is 760 to 790", but as the BeC1, concentration decreases
during t h e electrolysis t h e melting point increases and finally reaches 900 to 925'. At t h e end of t h e
electrolysis the c e l l contents ar e transferred into another vessel; t h e electrodeposited beryllium accumulates
in t he bottom layer of t h e melt. T h e upper layer. which contains only a s m a l l amount of beryllium entrapped
in t he salts, is removed and returned t o the preparation of fresh portions of electrolyte, while the bottom
laye r , which contains t h e bulk of t h e beryllium, is crushed to a particle s i z e of 100 to 150 mm. T h e m e t a l ,
remaining after t h e salts a r e washed out. contains 99.4 t o 99.5% Be.
The selection of the starting halide and reducing agent for the production
of beryllium is based on the facts that the melting and boiling points of
beryllium fluoride a r e higher than those of beryllium chloride (which makes
it possible to increase the process temperature to the melting point of
beryllium without the need for elevated p r e s s u r e s and f o r the more
426
complicated equipment) and that magnesium whose affinity for fluorine is
g r e a t e r than that of beryllium does not f o r m an alloy with beryllium.
The reduction of beryllium fluoride by magnesium involves the reaction
BeF,+Mg =Be+MgF,+-36 kcal.
A flow sheet f o r the production of beryllium by t h e r m a l reduction with
magnesium, including the production of beryllium fluoride from the oxide,
is shown in Figure 211.
Dissoluti? T;;sl
m
7- 1
Precipitation of impurities c
Water
1 I
Cake to waste
Wash waters
Pure filtrate
T
J. I (NHS, BeF4 solution
Evaporation :
1
Centrifuging
s.
- I
Mothe: liquor
T
+ Dissolution
T
'
( N HSzBeF4 N b F vapor
Decomposition 2 Condisation
BeF, solution
&
I
BeFz
1
Ammonium fluoride
- I
I
Thermal reduction with
MgF, to waste
HF - Centrifuging
t
Leaching
Mg B magnesium
I
.L
MgF, + BeF, T
1 Metallic beryllium I
FIGURE 211. Flow sheet for t h e thermal reduction of beryllium fluoride by magnesium.
427
Be0 + 2NH,HF, = (NH4),BeF4 + 2H,O
is t r a n s f e r r e d by decantation t o a second r e a c t o r in which it is treated
with ammonium sulfide in o r d e r t o precipitate the heavy metals. The
precipitate is separated by filtration; the filtrate (with a Be content of
- 20 g/l) is evaporated and allowed to crystallize in rubber-lined
evaporators. Since the crystallization takes place during the evaporation,
the amount of mother liquor returned to the p r o c e s s does not exceed
57'0 of the total volume of the liquid phase. The c r y s t a l s a r e separated
f r o m the mother liquor in continuously operating stainless s t e e l centri
is s m a l l ( - 0.02% A1 and -
fuges. The concentration of contaminants in the fluoberyllate c r y s t a l s
0.02% Fe). The silicon content is not of
importance since the silicon is separated during the subsequent
decomposition stage.
The fluoberyllate c r y s t a l s a r e decomposed by heating t o 950" in graphite
crucibles placed ininduction or gas furnaces. The decomposition reaction
is :
(NH,),BeF, BeF, NH4F.* +
F r e s h portions of fluoberyllate a r e added to the crucible during the course
of the decomposition p r o c e s s (which begins at 125"). The ammonium
fluoride vapors formed in the decomposition a r e evacuated through the top
of the crucible into a cooled i r o n condenser. The condensed ammonium
fluoride*;: is returned to the dissolution of the beryllium oxide. During
the decomposition the silicon is volatilized a s SiF,. The molten beryllium
fluoride is poured into graphite molds in which it solidifies a s a vitreous
substance containing up to 0.02'7'' Al, 0.02% Fe, and 0.01% Si.
Reduction. Beryllium fluoride is reduced with magnesium a t the
lowest possible temperature (800 to 1000") a t which the reaction products
a r e still i n the solid s t a t e (the melting point of BeFz is about 800", of
magnesium 650", and of beryllium and magnesium fluoride 1 2 5 0 to 1300").
When the reduction is completed, the temperature is raised to 1300"
causing the whole reaction to melt. The melting point is reduced and the
fluidity of the s l a g is increased by using excess beryllium fluoride, which
f o r m s with the magnesium fluoride a s l a g whose melting point is n e a r the
melting point of beryllium. The presence of an excess of beryllium fluoride
also causes a slow-down in the reaction r a t e (the reaction is strongly
exothermic). The introduction of beryllium fluoride causes no contamina
tion of the metal and favors the formation of l a r g e beryllium buttons.
After melting the charge in a graphite crucible at 1300", the beryllium
buttons a r e collected in a compact ingot which floats on the surface of
the slag. Beryllium solidifies f i r s t when the crucible contents a r e cooled.
Thus, solid beryllium may be withdrawn f r o m the molten s l a g bath. The
residual liquid s l a g is poured into a pan. The slag is crushed and treated
with ammonium fluoride o r hydrofluoric acid. As a result of this t r e a t
ment, BeFz is dissolved while the magnesium fluoride r e m a i n s a s an
insoluble residue. The BeFz solution is filtered and taken for the
dissolution of the ammonium fluoride.
_------------
* [sic. 1
**
-
Actually, the volatile product of the fluoberyllate decomposition -ammonium fluoride -decomposes
in accordance with the equation NH4F NHS+HF and a t low temperatures the equilibrium shifts to the
-
right-hand side. Thus, further condensation results in the precipitation not of NH4F but of a NH3 HF
compound having the approximate formula NH3F. 0.5 HF and melting a t 83".
428
A diagram of the furnace used f o r the reduction is shown in Figure 212.
12
Fe . . . . . . . 0.08-0.10
AI . ...... 0.02-0.03
Si . . . . . . . 0.01-0.03
Mn . . . . . . . 0.01-0.02
109. VACUUM M E L T I N G OF B E R Y L L I U M
429
-Water
Water
430
Because of the high reactivity of molten beryllium, difficulties a r e
encountered in the selection of m a t e r i a l s f o r crucibles, pans, stopping
l e v e r s , and other p a r t s which come in contact with the molten metal.
The most suitable m a t e r i a l s a r e beryllium oxide (although it is expensive
and c a u s e s some contamination of the metal with oxygen) and graphite,
in spite of the fact that graphite and beryllium f o r m a carbide and that
graphite absorbs a noticeable amount of molten beryllium. Pans a r e made
of graphite, and a l a y e r of beryllium carbide powder f o r m s a t the graphite-
beryllium boundary during the casting. In o r d e r to prevent interaction
between beryllium carbide and moisture (which leads to the formation of
g a s e s which may dissolve in the beryllium), the carbide is removed
completely by brushing and when not used the pans a r e stored in a furnace
at ZOOo.
Because of the high affinity of beryllium f o r oxygen, it is impossible
to use any g a s (including i n e r t gases, from which the thorough removal of
oxygen is v e r y difficult) a s a protective atmosphere, and high-quality metal
is produced only by melting in vacuum. The melting and casting of
beryllium a r e usually combined (Figure 213).
43 1
b
3 . production of semiproducts which a r e worked to the final dimension
by p r e s s u r e working (extrusion, forging, rolling) :
a) any method mentioned in paragraphs 1 and 2 ;
b) hydrostatic or pneumatic hot p r e s s i n g in a vacuum.
H o t p r e s s i n g i n v a c u o is c a r r i e d out under a p r e s s u r e of
10 to 20 kg/cm2 a t 1050" using --powder with a particle s i z e below 0.074".
The pressing is c a r r i e d out in s t e e l dies
and p r e s s u r e is produced by the punch
weight.
Hot p r e s s i n g i n a i r resemblesin
principle the p r e s s i n g in vacuum but is
c a r r i e d out in graphite dies which burn and
thus prevent oxidation of the powder; an
advance pressing of the beryllium powder
also prevents oxidation. Since appreciable
interaction between the powder and the die
walls may take place at 1100 to 1200",
leading to the formation of beryllium carbide,
the reaction between the graphite and the
beryllium walls is prevented by coating the
graphite walls of the die with a protective
layer (beryllium oxide coating or low-
carbon s t e e l lining).
The c r o s s section of a die used in the
production of l a r g e p a r t s is shown in
FIGURE 214. Die used for the hot
Figure 214. The graphite body has two
pressing of beryllium blocks 152.4 linings: an external graphite lining which
and 304.8" in diameter. facilitates dismantling, and an inner s t e e l
lining with a longitudinal cut which
1-boiler-iron plate: 2-intermediate
plate; 3-steel lining of the punch: facilitates the removal of the punch. The
4-steel insert; 5-thermocouple in inner and outer s u r f a c e s of the steel lining
sertion point, for measuring the die- a r e chromium plated to protect the s t e e l
body temperature ; 6-intermediate against interaction with the graphite and
plate; I-device for measuring the the beryllium. The punches and base
temperature of the upper punch; blocks a r e made of low-carbon steel. The
E-induction coils; 9-graphite tube;
die is placed within a quartz tube which
10-quartz tube; 11-die body; 12
lower punch; 13-special refractory prevents arcing between the graphite and
rings; 14-press base. the induction coil and s e r v e s a s thermal
insulation.
During the hot pressing, the temperature
is measured with the aid of a thermocouple. The wall thicknesses of dies
used f o r the p r e s s i n g of blocks 152.4 and 304.8 m m in diameter were
50.8 and 76.2 mm, respectively. The blocks made in these dies weighed
1.8 to 13.6 kg. The die was heated by means of a high-frequency
generator; the power required to heat blocks 152.4 and 304.8" in
diameter was about 30 and about 50kwh respectively. An 80-ton p r e s s w a s
used f o r pressing.
The p r e s s i n g involves the following operations. The die is mounted on
the p r e s s and beryllium powder is fed into the die cavity. The die i s then
heated slowly (over 1.5 to 2 hours) to 1100"; a p r e s s u r e of 50 kg/cm2 is
applied at 1000" and is increased to 70kg/cm2 a s the temperature reaches
1100". This p r e s s u r e is maintained f o r 30 to 40 minutes at 1100".
432
The density of hot-pressed blocks made a t 1100" under a p r e s s u r e of
50 t o 70 kg/cm2 is close to the theoretical.
W a r m p r e s s i n g is c a r r i e d out in a vacuum a t 550 to 600'. under a
p r e s s u r e o f 4 to 14 to&/cm2. This method makes it possible to produce
a metal of theoretical density, with a
fine-grained structure, g r e a t h a r d n e s s
and strength. The b a r s made by warm
p r e s s i n g a r e cold-hardened to a noticeable
extent, and their properties resemble those
those of cold-worked metal. The warm
p r e s s i n g is c a r r i e d out in dies made of
high-speed s t e e l s (1870W, 4070 Cr, 1% V)
or r e f r a c t o r y steels.
Beryllium powder is also p r e s s e d at
800" (i. e . , a t a temperature intermediate
between warm and hot pressing) and
p r e s s u r e s up to 3 tons/cm2.
H o t s t a m p i n g involves the
compaction (at 400 to 600") of s e m i -
finished b a r s made by cold pressing, with
subsequent sintering and hot or warm
p r e s s i n g to p a r t s of the required shape.
F o r g i n g i s used to convert
beryllium powder into p a r t s by pressing
in shaped s t e e l dies. The die with the
powder is heated in an inert atmosphere to
1000 to 1150", and i s then transferred to
the die support (which is preheated to
400 to 800" and p r e s s e d under 150 to
FIGURE 215. Diagram of installation
for the hot hydrostatic pressing of
.
700 k g / c m This method may be used
beryllium powder. to produce p a r t s weighing up to 7 kg, and
having a shape and dimensions close to
1-vacuum line; 2-high-pressure line; the required.
?-graphite filter; 4-steel plate; 5
steel envelope: 6-pressure chamber:
H o t h y d r o s t a t i c pressing is a
7-beryllium powder; 8-silicon carbide promising method for the production of
packing; S-gas burner heads; 1 0 p a r t s of a complicated shape. The nature
refractory bricks. of this p r o c e s s was described in the
chapter on molybdenum.
In one variant, the hot hydrostatic
pressing of beryllium powder is c a r r i e d out at 1000 to llOO', under a
p r e s s u r e of 7 to 2 0 atm, using argon or some other i n e r t gas a s a
protective atmosphere. The beryllium powder is fed into a steel die whose
inner surface has the s a m e shape a s the p a r t to be produced. The die is
then placed in a tube in the heating zone (Figure 215). The space between
the tube and the outer surface of the s t e e l die is packed with a nonsinterable
m a t e r i a l impermeable to gases (e. g., silicon carbide). Argon is then
pumped into this space until the above-mentioned p r e s s u r e is reached,
while the inner space of the die containing the beryllium powder is
evacuated (by connecting t o a vacuum system) t o a residual p r e s s u r e of
0.05 m m Hg.
In addition to the above method use is made of "warm" hydrostatic
p r e s s i n g in molten lead a t lower temperatures but higher p r e s s u r e s .
433
The various powder metallurgy methods produce beryllium powders
of markedly differing mechanical properties. Beryllium with the best
p r o p e r t i e s is prepared by hot pressing in vacuum.
As a rule, beryllium alloys a r e not prepared by direct alloying of the components ( e . g. , copper with
beryllium. nickel with beryllium, aluminum with beryllium. e t c . ) but by thermal reduction with metals
or reduction with carbon in the presence of the second alloy component. This produces beryllium mister
alloys (alloys which are used to introduce the alloying components into the alloy composition).
Beryllium alloys are occasionally m a d e by powder metallurgy techniques, i. e . , by mixing the
powdered beryllium and second component, pressing the mixture and sintering. For instance. such
techniques have been recently used for the production of a nickel-beryllium master alloy containing
10 to 20% Be, and beryllium alloys with rhenium, tungsten, and other refractory metals.
Master alloys of beryllium with aluminum and copper have been prepared by thermal reduction of
beryllium chloride or fluoride with magnesium-aluminum or magnesium-copper alloys.
For this use, beryllium is taken in the form of sodium fluoberyllate:
434
NarBeFI + Mg-AI -t - +
Be A1 MgF, + 2NaF.
alloy master alloy
Beryllium chloride is reduced in a molten salt medium (molten sodium and potassium chlorides). T h e
reduction of beryllium chloride by a copper-magnesium alloy (20% Mg) a t 950" in the presence of a 200%
excess of beryllium chloride (above the stoichiometric amount) produces a copper-beryllium alloy containing
1.7 to 1.6%Be and 13 to 1470Mg.
T h e reduction involves the reaction:
BeCI, + Mg-Cu + Be-Cu + MgClt.
alloy master alloy
centration is increased to -
In order to remove the magnesium the alloys are remelted in vacuo; as a result. the beryllium con
2%.
Master alloys containing up to 3% Be a r e produced in the reduction of BeCl, by aluminum alloys.
Copper-beryllium and nickel-beryllium master alloys are also produced by thermal reduction ( i n a n
electric furnace) of beryllium oxide by carbon in the presence of the m e t a l forming the alloy with beryllium.
T h e direct reduction of beryllium oxide with carbon yields beryllium carbide BezC rather than beryllium.
In the presence of a m e t a l with a high boiling point (e. g. , copper) the reduction of beryllium oxide takes
place as follows:
BeO(so1id) + C(so1id) + xCu(1iquid) -+ BeCu,jliquid) + CO(gas); (1)
ZBeO(so1id) + 3C(solid) + xCu(1iquid) + Be,C, xCu(1iquid) + 2CO(gas): (2)
BBeCu,(liquid) + C(so1id) -+ Be&, xCu(1iquid); (3)
BeO(so1id) + Be,C, xCu(1iquid) + 3BeCu,(liquid) + CO(gas). (4)
Reaction ( 1 ) takes place at low beryllium concentrations in the alloy, reactions (2) and (3). as well
as reaction (1). take place as the beryllium concentration is increased, and reaction (4) takes place only
in the presence of large amounts of beryllium carbide.
Carbon Copper
1 '
Rich Be,Cu residue
Smelting - I
Dust
from the bucket
7
t1
Crushing
Removal of rich
beryllium carbide
T
Pou!ing
Be-Cu
1 alloy
.1
Purification by
cooling
/ \
.L Pouring
The optimum process temperature (at which the formation of beryllium carbide is still slow while the
losses through vaporization of copper and beryllium a r e small) ranges from 1800 to 2100'; the best results
are obtained at 19.50'.
During the smelting beryllium oxide and the graphite form a fine suspension in the molten alloy while
the carbide Be,C dissolves in considerable amounts in the melt a t the reduction temperature. However,
the solubility of BezC in the alloy decreases as the temperature is reduced to 900 to 1000" and almost
435
I I I l l II
complete removal of the carbide may b e achieved by cooling and mixing the alloy before it is discharged
from the furnace. T h e Be0 and C flow on the surface together with the carbide.
A flow sheet for the smelting of copper-beryllium alloys in an electrical arc furnace is shown in
Figure 216, and a diagram of the furnace is shown in Figure 217. T h e charge is composed of beryllium
oxide, copper, recycled slags, and coal of low ash content. For e x a m p l e , 100 kg of Be0 is mixed
the amount of Be0 taken is calculated t o bring the Be content of the alloy to
in a 107oexcess above the stoichiometric amount needed for the reduction of the BeO.
-
with 835 kg of copper, 1 8 5 kg of slag, 150 kg of scrap, and 67 kg of coal. When compounding the charge,
5% and the coal is taken
After the mixing the charge is fed t o a three-phase electrical furnace with three short electrodes
fastened with the aid of adapters t o water-cooled copper sockets. T h e sockets a r e fastened o n hollow steel
electrode holders which are connected to the copper bus bars supplying the current. At the end of the
smelting, the current is turned off, the electrodes are withdrawn, and the melt is discharged (by tilting
the furnace) through the tap hole into a carbon-lined steel bucket; the temperature of the m e l t during
the pouring is 1300 to 1500’.
T h e beryllium carbide, beryllium oxide and carbon float on the surface and remain in the bucket during
the pouring. T h e m e l t is cast into a c e r a m i c crucible in which i t is cooled t o 900 to 950” with continuous
stirring. When the temperature drops to 900 to 950”. the impurities are removed from the surface and the
m e l t is cast in graphite molds. T h e slag is ground in a ball mill, which is lined with copper-beryllium
alloy plates.
T h e coarse fraction from the grinding (scraps) contains 6.570Be. 9O%Cu. 2’7.C. and 1.5700, while
the fine fraction (slag) contains 8% Be, 65%Cu, and 20% 0. T h e scraps and slags are returned to the
smelting.
T h e productivity of the furnace is 2.6 tons of copper-beryllium alloy per day, the consumption of
electrical energy is 2.75 kwh/kg. T h e alloy obtained by thermal reduction in a n electric furnace contains
4 to4.57oBe. 0 . l k F e . O.O8%Si, and 0.0670Al.
Nickel-beryllium and some other master alloys are prepared by similar methods.
436
113. TOXIC PROPERTIES AND 'SAFETY MEASURES
437
5. Filtration of g a s e s and vapors discharged during the technological
process, collection of beryllium-containing substances, and provision
of special storage rooms for the solid wastes. Stores should also be
constructed in accordance with these safety principles.
6. Use of personal safety equipment (goggles, r e s p i r a t o r s , g a s masks,
p n c z x d i c helmets, pneumatic suits) and working suits of special cloths
("lavsan", coarse wool cloths, and polyvinyl chloride tissues) which a r e
removed in a special chamber before the personnel leaves the plant.
7. Apreliminary (for new personnel) and subsequent regular periodic
medical inspections.
8. Regular control of the beryllium content in working rooms and in the
vicinity of the plant.
The personnel health hazards in beryllium plants may be completely
eliminated by proper manufacturing procedures and by the observance of
all safety precautions (of both personal and general nature) in the
processing of beryllium and i t s compounds.
438
Chapter XIII
LITHIUM
P r o p e r t i e s of lithium
439
1002 ...................................... 41.0
230' C ................................... 45
440
Lithium burns in oxygen above 200°, yielding the oxide. Lithium causes
vigorous decomposition of water, with the evolution of hydrogen and the
formation of lithium hydroxide, a s follows:
2Li + 2H20 = 2LiOH + H,.
Lithium hydride LiH ( with a melting point of 680O) is formed when
lithium is heated in nitrogen to 350 to 400".
Heating a mixture of lithium and carbon leads to the formation of
lithium carbide Li2C2, which decomposes water, with the evolution of
acetylene.
Lithium and gaseous ammonia form the amide:
2Li + 2NH, = 2LiNH2 + H,.
At elevated temperatures lithium r e a c t s with chlorine and with bromine,
iodine, and sulfur vapors yielding the respective halides and the sulfide;
lithium ignites a s a result of i t s reaction with nitric acid, and forms an
amalgam with mercury. The reaction of lithium with carbon dioxide leads
to the formation of lithium oxide or carbonate. This eliminates the
possibility of using carbon dioxide f i r e extinguishers for extinguishing
burning lithium.
Most metals and alloys a r e attacked by molten lithium.
Among the steels, chromium s t e e l s a r e the most resistant to lithium.
Of all s t e e l s tested, the best r e s u l t s were obtained with s t e e l lKh12MV4B
(the corrosion r a t e at 800" was 0.7mm/year). Pure nickel and the alloy
Inconel (11 to 15% Cr, 7 0 % Ni, 10% Fe) have a satisfactory resistance to
molten lithium up to 225" but a r e attacked rapidly above 600".
Niobium, tantalum, and molybdenum a r e most resistant to the effect of
lithium at up to 1000" (their solubility in lithium at 1000" is
Zirconium and titanium have a limited resistance to lithium at 1000".
Quartz, glass, and porcelain a r e rapidly dissolved by lithium at
temperatures above 200".
Oxides. Lithium and oxygen form the oxide Liz0 and the peroxide
Liz%.
L i t h i u m o x i d e is a colorless crystalline substance formed when
lithium is oxidized in a current of oxygen above 200" or when lithium
hydroxide, carbonate, or nitrate a r e decomposed at 750 to 880". The
heat of formation of Liz0 is 143.2 kcal/mole. Lithium oxide has a :ace
centered cubic lattice (CaF2 type) with a lattice parameter of 4.62 A ;
i t h a s a high thermal stability, a high melting point (above 1400"), and
s t a r t s to volatilize at 1000 to 1040" ( a s h a r p increase in the volatility of
lithium oxide is observed in the presence of water vapor, due to partial
conversion of the oxide to the more volatile lithium hydroxide). Liz0
dissolves slowly ( a s compared with the other alkali oxides) in water, with
the evolution of large amounts of heat and the formation of lithium
hydroxide. LizO absorbs Cc>,from the air, with the formation of lithium
carbonate. Metals (even noble metals) a r e attacked rapidly by lithium
441
oxides. At temperatures above 1000" aluminum, magnesium, and silicon
reduce the oxide to lithium metal.
L i t h i u m p e r o x i d e Li2Q cannot be produced by direct combination
of lithium metal and oxygen, but can be produced indirectly. F o r instance,
it is formed in the interaction of an alcoholic solution of lithium hydroxide
with hydrogen peroxide. The peroxyhydrate - -
Li20z H24 3H20 - a white, -
crystalline, sparingly-soluble substance is formed in the presence of an
excess of the alcohol; the peroxyhydrate is converted to lithium peroxide
by drying over phosphorus pentoxide. The heat of formation of lithium
peroxide is 151.8 kcal/mole. L i 2 Q is thermally unstable, and completely
decomposes (to lithium oxide and oxygen) upon heating to 195".
Lithium hydroxide is a white substance with a density of 1.46. It can be
prepared by dissolving LizO in water, o r through a substitution reaction
between lithium sulfate and potassium hydroxide ( o r barium or calcium
hydroxides), and through a substitution reaction involving the decomposition
of lithium carbonate by calcium hydroxide:
Li,cO, + Ca (OH),= 2LiOH + CaCQ.
The evaporation of a LiOH solution in a C Q - f r e e gas atmosphere causes
-
the precipitation of the crystalline hydrate LiOH HzO which upon heating
to 600" is readily converted f i r s t to LiOH and subsequently (at 780") to
LizO. The solubility of lithium hydroxide in water is much lower than that
of the other alkali hydroxides. The solubility of the hydroxide LiOH and the
crystalline hydrate LiOH. H20 i n c r e a s e s with increasing temperature; thus
the solubility of LiOHin water at 0 and 100" is 12.7 and 17.5g/lOOg water,
while the solubility of LiOH. HzO at 10 and 80' is 22.3 and 26,8g/lOOg water
respectively. The melting point of LiOH is 450". At about 1000" lithium
hydroxide is completely decomposed yielding lithium oxide and water;
the vapor p r e s s u r e of water over lithium hydroxide at various temperatures
is listed below:
Temperature. " C ................ 520 610 610 124 812 924
Vapor pressure. of H,O, mm Hg .... 2 23 61 121 322 160
442
443
I IIIII
444
Uses of lithium
445
aviation, military technique, as lubricants in equipment f o r a r c t i c uses,
a s impregnation lubricants for porous bearings (prepared by powder
metallurgy) intended for low or high temperature uses, etc.
Ceramics and g l a s s industry. The addition of lithium compounds
(carbonate, oxide, titanate, and zirconate) or concentrates (lepidolite,
petalite) to the ceramic mixtures used in 'the production of faience,
porcelain, heat-resistant ceramics, and refractories makes it possible
to reduce markedly the firing temperature, and to produce denser and
mechanically stronger ceramic products with a lower thermal expansion
coefficient (i.e . , with increased resistance to thermal shock).
The introduction of lithium oxide a s a component in g l a s s e s improves
the quality of the glass, simplifies the production technology, and
facilitates subsequent glass-working. Lithium g l a s s e s a r e extensively
used in the production of g l a s s articles for television and radio industries,
light-sensitive glasses, g l a s s e s which transmit ultraviolet light and absorb
infrared light, lithium-borate g l a s s e s f o r X-ray tubes, optical glasses,
and electrical insulation glasses.
An important type of lithium-containing vitreous material is the so-called Pyroceram -a vitreous-
crystalline material formed in the crystallization of light-sensitive glass (containing 60 to 85% S O , ,
5.5 t o 15% Li,O, and 2 Io 25% A1,0,) under shortwave irradiation and after heat treatment. T h e tensile
strength of Pyroceram ranges from 25.3 (for nonpolished) to 14 kg/mmz (for polished Pyroceram), its Mohs
hardness is 1.5 and its density is 2.5 t o 2.6. The thermal expansion coefficient of Pyroceram may be varied
within very wide limits and may assume both negative and positive values (up to 20.10-6). T h e hear
conductivity of Pyroceram is three times that of Pyrex glass; it has a high thermal stability and a high
softening point ( u p t o 1350").
446
i
can be removed f r o m high-carbon-chromium and austenitic s t e e l s and
f r o m alloys based on copper, copper-silicon, zinc, lead, tin, magnesium,
and aluminum. At the same time, the lithium added a c t s a s a modifier
which i m p a r t s to the metal a fine-grained s t r u c t u r e , while the addition of
lithium to c a s t i r o n removes gaseous inclusions, i n c r e a s e s the fluidity
and favors the ordered distribution of graphite p a r t i c l e s (in particular, it
leads to the formation of c a s t i r o n with spheroidal graphite).
Lithium is used in antifriction bearing alloys, because of i t s ability to
f o r m (with a number of metals) chemical compounds of relatively high
meltingpoints, which a r e precipitated by suitable heat treatment in the
form of very fine particles. These particles wedge the slip planes of the
crystallites of the base metal o r alloy and improve i t s hardness, wear-
resistance and thermal stability. Lead-lithium alloys p o s s e s s especially
valuable antifriction properties.
The use of lithium s a l t s a s components of molten-salt baths for the
electrolytic production of metals is of g r e a t importance for the manufactur
ing of some light and r a r e metals.
Lithium vapors a r e used for the creation of a reducing and protective
atmosphere in furnaces. At the s a m e time the lithium removes moisture,
oxygen and nitrogen from the furnace volume and prevents the carbonizing
o r decarbonizing of the surface layer of metals and alloys during t h e i r
heat- treatment (annealing).
Other uses. Lithium compounds a r e used in the chemical industry
(hydride, alumohydride, amide) in the synthesis of various organic
compounds and a s catalysts in the production of polymers (lithium
s t e a r a t e and carbonate) ; in gas-purification techniques ( a i r conditioning),
and in the pharmaceutical, textile and food industries. Lithium hydride
and alumohydride a r e used a s sources of hydrogen.
447
There a r e up to 150 known lithium-containing minerals, but only two
types - s i l i c a t e s and phosphates - a r e of commercial value. The silicate
group c o m p r i s e s the minerals spodumene, lepidolite, zinnwaldite and
petalite, and the phosphate group - the double phosphates with aluminum,
i r o n and manganese (lithiophilite and amblygonite).
S p o d u m e n e Lip0.A1203-4Si0, contains 2.9 t o 7.60/0Li20, 20 to 3070
A12Q, and 6 0 to 6570S O z a s well a s s m a l l amounts of Na20, CaO, MgO
and occasionally CrpO3 (in some c a s e s i t contains 0.03 to 0.1% gallium).
The m i n e r a l has a white-gray color with a greenish o r yellowish tinge, a
hardness of 6.5 to 7, a density of 3.13 t o 3.20, and a melting point of
1380'. It is associated with quartz, felspar, micas, and other components
of the granitic pegmatites.
L e p i d o l i t e is lithium mica [(Li, K)(F, O�I)].3siOp. Alz03 containing
4.8 to 13.90/0/020, 1.2 to 4.9% Li20, 11.3 to 28.8% &03, 46.9 to 6 0 . 0 %
Si%, 0.6 to 3.2% H 2 0 , 1.4 to 8.7% F, and s m a l l amounts of MgO, FeO,
CszO, and RbpO (up to 4 % ) . The m i n e r a l is white but it is often colored
by contaminants (which impart to i t a pink, violet o r orange color). Its
hardness is 2 t o 3, i t s density is 2.8 to 2.9.
Z i n n w a l d i t e (Li, K),A13Fe(F, O�I)zSi15016is a lepidolite modification
enriched with iron. The mineral has a gray or brown color and a vitreous
l u s t e r (the cleavage planes have a mother-of-pearl l u s t e r ) . It has a
density of 2.9 to 3.2, a hardness of 2 to 3, and a melting point of 945 to
997". It is encountered together with lepidolite or under the s a m e conditions
of occurrence a s lepidolite, and is often associated with wolframite,
scheelite, cassiterite, fluorite, and quartz.
P e t a 1i t e is an alumosilicate Li(AISi,Olo) with a lithium oxide content of
3 to 470. The mineral is gray and occasionally yellowish or pinkish, and
has a hardness of 6 to 6.5 and a density of 2.3 to 2.5. I t i s usually found
together with lepidolite, amblygonite, beryl, and pollucite.
A m b l y g o n i t e LiAI(P0,)F contains 7 to 1 0 % LizO. Its color i s white
with a yellow, blue o r green tinge and it has a hardness of 6 and a density
of 2.98 to 3.15.
Spodumene and lepidolite (and to some extent amblygonite and petalite)
have a commercial use.
Large r e s e r v e s of lithium have accumulated in sedimentary deposits.
These include some mineral deposits and salt-water lakes in which the
lithium accumulates together with sodium, potassium and boron.
Commercial lithium deposits a r e found in the USSR, Canada, Africa,
Brazil, Australia, Spain, Sweden, The German Democratic Republic,
and Czechoslovakia. The lithium o r e production outside the e a s t e r n bloc
in 1957 to 1960 was of the o r d e r of -250,000 tons ( a s a 5 %spodumene
concentrate).
448
Lithium o r e s a r e enriched by hand-picking, thermal enrichment (de
crepitation), magnetic enrichment, flotation and enrichment i n heavy
suspensions. In most c a s e s modern enrichment methods employ a
combination of s e v e r a l of the above techniques.
Thermal enrichment (decrepitation) is based on the fact that spodumene
undergoes a phase transformation (from the a-form with a density of
3.15 t o 3.20 t o the f - f o r m with a density of 2.44) upon heating t o 1000 to
1100". The 2 4 % increase in volume causes cracking and marked crushing
of the mineral.
The o r e s a r e crushed to a particle s i z e of - 2 0 to -50" and
roasted f o r 1 t o 2 hours in a r o t a r y kiln a t 1050 t o 1100". The roasting
product is then subjected to a i r - s e p a r a t i o n or sieving in which the fine
spodumene powder is separated f r o m the c o a r s e r quartz grains. The
enrichment is m o r e difficult in the c a s e of o r e s containing a l a r g e amount
of other minerals that also undergo decrepitation ( e . g . , micas, fluorite,
calcite). Moreover, the presence of a l a r g e amount of micas causes
fusion of the o r e at the decrepitation temperature. The decrepitation-
enrichment product containing P-spodumene i s especially suitable for
subsequent processing with sulfuric acid since P-spodumene i s readily
decomposed by the sulfuric acid.
The flotation of spodumene i s c a r r i e d out with the aid of anionic
collectors (fatty acids and their soaps, e. g., oleic acid, aluminum and
sodium oleates) in which case the lithium minerals a r e separated with the
foamy product (direct flotation) or with the aid of cationic collectors, in
which c a s e the b a r r e n rock minerals a r e separated with the foam product
while the lithium minerals remain in the tailings ( r e v e r s e flotation).
The flotation of 1e p i d o 1i t e i s c a r r i e d out mainly with cationic collectors
since flotation with fatty acids o r their s a l t s requires the advance t r e a t
ment of the o r e with hydrofluoric acid. The cationic collector used i s
IM-11, which extracts quantitatively the muscovite and s e p a r a t e s it from
the lepidolite.
T A B L E 67
Concentrate Concentrate
Components :om PO nents
ipodumene amblygonite epidolite lepidolite
449
ammoniacal collector (the so-called "kateksol" [sic], a higher fatty acid
product) or with technical soap, with the simultaneous use of water g l a s s
for the depression of the quartz.
Enrichment in heavy suspensions. The difference between the densities
of the lithium minerals and the minerals of the bare rock (quartz, felspar)
is only 0.2 to 0.5, i. e., it is not large enough to permit separation by
sedimentation or on concentration tables, but i t makes i t possible to effect
separation in heavy suspensions. In the last process, the ground o r e is
immersed in a suspension of a given density; the o r e particles of lower
density flow to the surface while the particles of g r e a t e r density settle on
the bottom. Either ferrosilicon or magnetite a r e commonly used a s the
suspensoid in the enrichment of spodumene o r e s by the above method.
Magnetic Separation is used as a finishing operation f o r the separation
of magnetic minerals, and also in the enrichment of zinnwaldite o r e s
(zinnwaldite is weakly magnetic).
The approximate composition of lithium concentrates is shown in
Table 67.
450
T
Enriched ore (3-5%Liz0)
Decrepitation a t 1100'
1
Cooling to 120'
1
Crushing
-.5
93% HzSO, \
CaCOS - 1
Sulfatizing a t 250"
Ld
Leaching
1
Filtration --
Ca(OH),
\ I/ Na,CO, 1 c,Water
Washing
Precipitation of Mg and
Ca I .1 I Filtration
.1
Slimes Wash waters
I
Precipitate ( M g 1 (to waste)
5
and Ca hydroxides) Li,S04 as 10%
1 solution
To leaching (as the
precipitate accumulates)
Carbon
black\
1 /
Evaporation
.1
H2S04
1 5
Precipitate 20% solution of Li,S04
(A1 and Fe
hydroxides)
1 4
Precipitation of Li,CO,
S a u r a t e d Na,CO, solution
.1
11
Mother liquor
Li,CO, crystals
L
Washing
3.
Hot water
-J
. Filtration --
I Li,CO,
FIGURE 218. Flow sheet for the processing of spodumene by the sulfuric acid method (USA),
solution by precipitation, respectively, a s magnesium hydroxide (by
neutralizing the solution with lime, to pH 1 2 to 14) and calcium carbonate
(bytreating the solution with sodium carbonate). The remaining solution con
tains up to 100 g LizS04perl i t e r and is contaminated with aluminum (from the
ore) andiron(disso1ved out of the s t e e l piping). The i r o n and aluminum
a r e precipitated a s the hydroxides by adding sulfuric acid t o the solution
(to pH 7) together with a s m a l l amount of carbon black (which absorbs
contaminants present in t r a c e amounts). The solution is then evaporated
to a Li2S04content of 200 g / l i t e r , and the iron and aluminum hydroxides
a r e precipitated simultaneously. The solution is filtered (using a plate
and frame-filter p r e s s ) and lithium carbonate is precipitated by the
addition of a saturated solution of sodium carbonate. The lithium carbonate is
washed twice with deionized water yielding a product with a carbonate
content of 96 to 97%. The precipitate is separated by centrifuging, and
dried a t a reduced p r e s s u r e (510 to 635 m m Hg). The d r y lithium
carbonate i s contaminated with sulfate ions, chloride ions, the oxides
of sodium, potassium, iron, calcium, and the heavy metals, and contains
0.01 % moisture.
Lepidolite is also decomposed with sulfuric acid. In one of the methods,
the lepidolite is crushed to a particle s i z e of -0.1 mm, mixed in a s t e e l
r e a c t o r with concentrated acid a t a weight ratio of 1 : 1.1, and the mixture
is heated as follows: f o r 3 hours at 120", f o r 1 hour a t 136", f o r 1.5 hours
a t 156", for 1.5 hours at 194", f o r 1 hour at 200" and f o r 0.5 hour at 340".
The sulfatizing leads to the production of silica and of lithium, aluminum,
potassium, sodium, rubidium, and cesium sulfates. The overall p r o c e s s
is expressed by the equation:
3Si0, . A1,0, . 2 [(Li, Y) (F, OH)] H,SO, + +
+ + +
LizS04 AI, (SO,), KzSO, H,SiO, + SiF, + + H,O.
The reaction m a s s is allowed to cool, treated with water, the solution
(containing the sulfates) is filtered and the bulk of the aluminum is
removed a s alums. The alums a r e formed by adding potassium sulfate
to the solution:
+
AI, (SO,), KzSO, = 2Y [AI (SOJzl.
The solubility of alum i n c r e a s e s sharply with increasing temperature:
452
The lime method
u
.d
4d
respective hydroxides .
453
process a r e precipitated by carbonation (passing a stream of CO, or furnace gases) of t h e LiOH-containing
filtrate; this causes neutralization of t h e alkali.
T h e a l umi na t e is hydrolyzed as a result of the sharp decrease in t h e alkalinity of t h e solution, and
aluminum hydroxide is precipitated:
NaAIOz + 2H10= A1 (OH), + NaOH.
T h e hydroxide formed reacts with CO, yielding sodium carbonate and causing almost quantitative
hydrolysis of the a l um i n at e and precipitation of t h e aluminum. T h e c a l c i u m is precipitated as CaCO,.
Lithium carbonate is obtained by evaporation and a second carbonation.
IJ
Spodumene -6% L i p
1
Wet milling
CaCO,
Wet milling
J. 1
.
1 7
Mixing
J.
Pulp (65% solids)
1
Roasting a t
1000-1200'
J.
> Wet milling
J.
- Overflow
1
Fourth thickening <
\
Sands
1
Fifth thickening
3
-
-l.
LiOH HzO
crystals
1
Centrifuging
1 1
Mo the rJ
liquor
Sands Overflow. 1
Drying
L Overflow
Sixth thickening
7
Sands
( t o waste)
FIGURE 220. Flow sheet for t h e processing of spodumene by roasting with l i m e (USA).
1455
454
The sulfate method
0-Li
/
0-Li
The position of the lithium atoms explains the relative ease with which
they a r e replaced by the atoms of other alkali metals and especially
potassium. However, potassium atoms a r e l a r g e r than lithium atoms,
hence the substitution of potassium for lithium is possible only if the
atomic bonds in the spodumene crystal lattice a r e weakened, i. e . , at
elevated temperatures.
According to Plyushchev, the reaction between spodumene and
potassium sulfate and the liberation of lithium a s a water-soluble substance
s t a r t s even before the fusion of the reaction mixture, i. e . , at 700°, and
involves a solid-phase reaction which p a s s e s through the stage of formation
-
of a potassium-sodium leucite (K, Na)A1[Si206], sodium-potassium alumo
silicate which i s sparingly soluble in water.
In practice, the sintering is c a r r i e d out at 9 2 0 to 1150". During the
sintering a-spodumene is converted into 0-spodumene which e n t e r s a
substitution reaction with the &SO4:
1455
455
Thermal enrichment
3.
Sieving
3. 1
Coarse fraction (quartz) Fine fraction (spodumene)
Mixing +
3.
Sintering
e
Sinter Water
--J
Leaching 4
Settling, filtration,
washing
.
.
.1
~
1
Solution (LizS04, Cake
KzSO4, Na2S04, 1
A1dSOds FeZ(SO&) Washing and filrration
$. .L
K2C4
o-itn
1 of Fe and A1
Cake to Wash
waters
.
1 =
-- 1
L
Solution Precipitate
1 (Fe, Al)
Evaporation and
crystallization
I
To waste
3.
Centrituging
7 . 1
1
Centrifuging
.
3. -.1
LizC03 precipitate NaZSO4solution
1 1
D q ing To waste, o r to
r”l
t h e isolation of
LizCOs NazS04. 10HzO
FIGURE 221. Flow sheet for the processing of spodumene by sintering with potassium sulfate,
456
sintered by heating for 2 hours a t 1100 to 1150°, usually in a r o t a r y kiln.
The s i n t e r is leached with cold water, since the solubility of LizSO,
d e c r e a s e s with increasing temperature. The solution i s separated f r o m
the solid residue by decantation or by settling and filtration, the cake
(consisting almost exclusively of sodium-potassium alumosilicate) is
discarded, and the solution containing LiZSO, a s well a s KzS04 and s m a l l
amounts of NaZSO4, Alz(S04)3and Fez(S04)3is treated with a solution of
potassium carbonate, which cause.s precipitation of the aluminum and iron
a s the hydroxides. After filtration, the solution contains lithium, potassium
and sodium sulfates; the solution is evaporated, causing the precipitation
of most of the potassium sulfate (together with the Na2S04), which i s
separated by centrifuging. The potassium sulfate i s returned to the
p r o c e s s , while the solution is heated to 80 to 90" and the sparingly soluble
lithium carbonate is precipitated by the addition of a sodium carbonate
solution.
30,
451
potassium sulfate, at a weight-ratio of 10 :3.5 is sintered at 900". The
s i n t e r is leached with water and the lithium (up to 90 to 95% of the amount
initially present) and all the soluble sulfates a r e extracted. In o r d e r to
precipitate the iron and alumonium hydroxides, potassium permanganate
is added to the solution (to oxidize Fez+to FeS+)and the solution is made
alkaline by the addition of KOH. The excess oxidizing agent is reduced
with methanol to MnOz, which is separated together with the insoluble
residue, The mixture is separated by filtration and the filtrate is
concentrated to a lithium content of 10 g/l. Potassium sulfate is p r e
cipitated during the concentration; this precipitation is aided by the
addition of KCl a s a salting-out agent. The potassium sulfate is
separated and the solution is treated with a saturated solution of potassium
carbonate, causing the precipitation of lithium carbonate, which is
separated by centrifuging; the mother liquor contains up to 40% of the
initial amount of lithium. The evaporation of the mother liquor is re
peated, causing crystallization of a mixture of potassium and lithium
sulfates which is dried, crushed, and returned to the sintering stage.
The mother liquor is returned to the evaporation of the basic solutions.
The total degree of extraction of lithium in the final product is 9070, and
the final product contains 9770 lithium carbonate.
Chlorination roasting
458
end, a current of d r y hydrogen chloride is passed through the solution.
All the chlorides a r e precipitated, while the lithium chloride which
remains in the solution is crystallized (by evaporation) a s LiCl HzO. -
The Iithium chloride is dehydrated and taken f o r eIectrolysis, for the
preparation of lithium metal.
Q Spodumene
Sintering
1
Leaching c
1
-l. Filtration .-
( N H d 2 C 0 3 7 1
Precipitation of Li,CO,
1
-I Filtrarion 1-
Li,CO, crystals Mother liquor I
1 Water
7Washing 1
Li,CO, crystals Wash b a r e r /
1
Causricizing
Ca(OH),
J.
-I Filtration ~r,
CaCO, precipitate LiOH solution
( t o sintering) 1
Evaporation
.1
Crystallization
.1
Centrifuging
I
Mother liquor
Another variant involves t h e sintering of spodumene with CaCOS and CaClz a t 1150 to 1200': the
lithium chloride formed is volatilized ( i t volatilizes a t about 1000') and is collected i n dry or wet condensers
together with the dust. In t h e wet process, t h e lithium chloride vapor coming from the reactor as a
mixture with t he dust-containing gases is separated from t h e dust, washed with a large amount of water,
459
and the dilute solution formed is filtered. T h e filter residue is returned to t h e roasting kiln. The solution
is evaporated to a LiCl concentration of 40%, the NaCl precipitate is removed, t h e solution is cooled,
and the crystallized KCl is separated. The lithium is then precipitated from the solution as t h e carbonate.
In the dry method, the lithium chloride is extracted from the dust with the a i d of organic reagents.
460
The USSR specifications for the maximum impurity content of LiCl a r e
a s follows: 0 . 1 2 % Na, 0.03% Ca, 0 , 0 5 7 0 Al, 0.005%Fe, 0 . 1 % SO:-,
0 . 0 5 7 0 S i Q , 0 . 0 0 5 % PG-.
A diagram of a bath used in the electrolytic production of lithium is
shown in Figure 2 2 5 . The bath consists of a s t e e l jacket (wall thickness
4 to 5 mm) lined with talcum stone o r magnesite; the anodic space is
separated from the cathodic space by an alundum ( A l 2 4 ) partition that does
not reach the bottom of the electrolyzer. The r a t i o of the anodic to
cathodic space volumes is 1 : 2 . A graphite anode and an iron rod cathode
a r e used. The cathodic current density is 5 amp/cm2. The chlorine gas is
removed by means of an exhaust fitted in the anodic space. F r e s h lithium
chloride is added periodically to the anodic space to replace the lithium
chloride consumed during the electrolysis. The lithium metal formed in
the electrolysis flows to the surface of the molten electrolyte and collects
under the cover of the cathodic space. The lithium is scooped from
the cathodic space and cast into ingots. The electrolysis is carried out
at 400 to 430". The current efficiency is about 7570, and the consumption
of electrical energy is 5 5 to 6 0 kwh/kg lithium. The metal produced
contains at l e a s t 9870 lithium, the main impurities being sodium,
magnesium (up to l % ) , iron (up to 0.0470), potassium (0.01 to O.o5q0), and
silicon ( 0 . 0 2 to 0.057'0). The magnesium, silicon, and sodium e n t e r the
metal from the talcum-stone lining; the sodium content depends on the
purity of the lithium chloride while the potassium content depends on the
conditions of the electrolysis. Increasing the potassium chloride
concentration in the electrolyte leads to an increase in the potassium
concentration in the lithium, to 2 to 3'70. It should be mentioned that the
decomposition potentials of the potassium and lithium chlorides have
s i m i l a r values (i. e . , at 405" the difference between them is only 0.112 V),
hence, it is not possible to prepare potassium-free lithium by electrolysis
of a eutectic mixture of the chlorides.
f -)
FIGURE 226. Diagram of a bath for t h e electrolytic
production of lithium (West Germany).
I - b a t h lining; 2-anode: 3-opening for t h e in
troduction of the salts: 4-liquid lithium: 5
cathode; 6-diaphragm: I-body of electrolyzer.
46 1
An electrolyzer used for the production of lithium at the Degussa-
Rheinfelden plant ( W e s t Germany) is shown in Figure 226. On the exterior
the bath is lined with refractory bricks, and the internal lining consists of
a dense l a y e r of talcum or alundum about 50" thick. The top of the bath
is made of the s a m e material, of the s a m e thickness, and has a round
opening at its center (100" in diameter, serving f o r the collection of the
metal), and openings f o r the charging of the r a w m a t e r i a l s and f o r the
evacuation of the chlorine. The lithium-collecting device h a s a cylindrical
shape with a cupola-shaped tip, which facilitates the collection of the fine
lithium particles as they float on the surface of the melt. The tip of the
collecting device is fitted with an iron-wire partition f o r the separation
of the f r e e chlorine from the metallic lithium.
The anode consists of 3 graphite plates (150 X 6 0 0 X 70") and six
graphite rods with a screw thread f o r the connection of the anodes to the
electrical bus bars. A vertical s t e e l rod 50 mm in diameter, which is
connected to a tubular refractory-steel casting 102 m m in diameter,
s e r v e s as the cathode. The rod p a s s e s through the hollow of the s t e e l
casting, which is fastened to the bottom of the bath; the electrical contact
to the cathode is accomplished by means of copper clamps and a cable
which is connected to a bus b a r passing beneath the floor.
The lithium chloride taken for the electrolysis (containing 94 to 98%
LiC1, 2.5 70 KC1, 1.5% NaC1, 0.5% FezOs) is melted i n advance and ground.
The mixture taken f o r electrolysis contains 5270 lithium chloride and 4870
potassium chloride. The electrolyte is molten in advance in a 500 kg
crucible, maintained f o r 6 to 7 hours at 390", analyzed, and then kept f o r
another 5 hours under these conditions. The molten electrolyte i s poured
into the preheated electrolysis bath, and the c u r r e n t is switched on. F r e s h
2.5 kg portions of lithium chloride a r e added to the bath each - 2 hours.
The lithium formed in the electrolysis flows to the upper p a r t of the
collecting device, where it is stored under a layer of oil (of high boiling
point). The metal is periodically withdrawn with the aid of a perforated
ladle (made of thin iron wire); the metal remains i n the ladle while the
oil p a s s e s through the openings, except f o r a s m a l l amount that remains
in the ladle and protects the lithium during the t r a n s f e r to the collecting
vessel.
The daily production of each bath is 4 to 5 kg of lithium, containing
(after remelting) 9770 lithium and s m a l l amounts of potassium and sodium.
The c u r r e n t efficiency is 83 70, the specific consumption of electrical
energy is 144 kwh/kg.
Lithium of a higher degree of purity is prepared in baths lined with
graphite. Very pure lithium (containing 0.4 to 0.7% Na, 0.0170 K, 0 . 0 2 %
Ca, 0.001% Fe, and 0.06% N) may be prepared in these baths by using
pure lithium chloride. The current efficiency with such baths reaches
up to 90% and the yield of lithium is 95'70.
In o r d e r to remove occluded electrolyte and oxides from the electrolytic
lithium it is remelted under a layer of vaseline oil o r paraffin, in steel
or zirconia crucibles lined with lithium fluoride (which r e s i s t s the effect
of molten lithium up to 800").
In o r d e r to prevent oxidation, lithium metal is stored (in the shape of
rods, wire, or ingots) in a hermetically sealed vessel under an i n e r t
liquid (e. g., mineral oils, paraffin, kerosene). Lithium products may
also be coated with a layer of paraffin, for instance by passing lithium
462
rods through a molten paraffin bath. Recently, lithium products have been
stored by pressing in thin aluminum o r copper shells; this simplifies the
handling of lithium since fragments of the required length may be cut
before use.
KC1
&I
Dissolution H20
41
Filtratiom
1;
Evaporation
Drying :
1
1 Electro1ysis 7
1
Chlorine
Metallic lithium
1
Purification by
Spent electrolyte
.1
Dissolution
.I
Filtratioj
- H,O
remelting
J. wastes Filtrate (LiC1. KC1)
Inert liquid or
paraffin
I
--+ Packing
.1
Final product I I
k . 1
HC1
Neutralization
.I
Filtration
J
Evaporation
.1
LiCl + KC1
T h e spent electrolyte consists of a mixture of KCI and LiCl contaminated with graphite dust (formed
as a result of the decomposition of the anode and the bath lining if this is m a d e of graphite). This mixture
is processed for the recovery of t h e lithium chloride, which is returned to the electrolysis as shown in
Figure 227. T h e salt mixture is leached with wateriniron reactor. T h e solution is strongly alkaline, owing
to the interaction between the metallic lithium occluded in the electrolyte and the water; it is neutralized
with hydrochloric a c i d to a weakly acid reaction and is evaporated to crystallize t h e LiCl +KC1 mixture.
In practice, this mixture contains up to SO%LiCl. T h e composition is adjusted and the mixture is returned
t o the electrolysis.
In spite of the fact that the commercial production of lithium by electrolysis of molten salts is a
successful process. considerable difficulties a r e involved in the design of equipment for the production of
pure lithium chloride (because of its high chemical rear:ivity), and because of the unavoidable contamina
tion of the lithium with sodium and some other Plements.
463
I l11ll11l I Il1I Ill Il
In order to eliminate these difficulties, a study was m a d e of methods for the production 3f lithium by
thermal reduction with metals, and such methods a r e used occasionally. They are based on the reduction
of lithium oxide, carbonate, or fluoride or the direct reduction of spodumene with aluminum, silicon, or
magnesium (in a vacuum).
Reduction of lithium oxide. T h e reduction of lithium oxide m a y be represented by means of the
following equations:
3Li,O+ 2AI = 6Li f AI,O, -
33.6 kcal,
2Li,O + +
S i = 4Li SiOz - 76.3 kcal;
Li,O + + +
Mg = 2Li MgO 3.8 kcal.
Thus, the reduction of lithium oxide is either endothermic or slightly exothermic. Thus, it can be
carried out only in a vacuum, where the high evaporation pressure of the metallic lithium shifts the
reaction t o the right-hand side and ensures its completion. In addition, lithium produced in a vacuum is
purified and protected against oxidation during the process.
Oxides of t h e reducing agents used a r e formed during the reduction, and they combine with the lithium
oxide yielding aluminates, silicates. etc. In order t o prevent this reaction. the charge taken contains
calcium oxide which combines with the A1,Os or S O , t o yield the monoaluminate o r silicate respectively:
2Li,O + +
2Ca0 Si = 4Li (vapor) Ca,SiO,;+
3Li,O + + +
CaO 2A1= Li (vapor) CaO AI,O,. .
T h e lithium oxide used in thermal reduction with metals is produced by roasting lithium hydroxide or
carbpnate at 800'.
T h e thermal reduction process is carried out as follows. T h e LiO, is mixed with the CaO. the mixture
which is taken in a -
is roasted, crushed. and mixed with the ground (to -0.15mm) reducing agent -silicon or aluminum powder,
10% excess above the stoichiometric amount needed: the mixture is pelletized and
transferred t o a vacuum furnace which is diagrammatically shown in Figure 228. T h e working space of the
furnace is connected t o a condenser, a diffusion pump and a rotary (oil) vacuum pump. The furnace is
heated with the aid of heaters positioned in a tubular muffle, and the temperature is controlled by means
of a thermocouple and a galvanometer. T h e residual pressure in ihe system prior t o the beginning of the
reduction process is lO-'mm Hg. Thedegreeofextraction of lithium during the reduction with silicon
( a t 1300') is 92 to 9374, while in the reduction with aluminum ( a t 900') it is of the order of 80%.
T h e reduction of lithium oxide with magnesium is not satisfactory because of the high vapor pressure
of magnesium (the melting points of magnesium and lithium a r e 1100 and 1327" respectively) which
accompanies the lithium in the distillate: the degree of extraction of the lithium with the lithium-
magnesium distillate formed at 950" does not exceed 73%.
464
F
Reduction of lithium halides. Because of its great volatility, LiCl cannot b e reduced to lithium by a
vacuum-thermal method; hence, lithium fluoride LiF (which a t 1390' has a vapor pressure of about
81 m m Hg) is taken for the reduction. T h e lithium fluoride is mixed with aluminum o r silicon and calcium
oxide. In this case the calcium oxide is added not only in order t o bind the A1,Os or SiO, formed in the
process (to calcium aluminate or silicate respectively) but also in order to bind the fluorine as c a l c i u m
fluoride. T h e formation of calcium fluoride prevents volatilization of the aluminum and silicon (as AlF,
and SiF,) together with the lithium vapor.
T h e following reactions occur when the charge is heated in a vacuum:
+
6LiF 4Ca0 +
2AI = 6Li + Ai,O, . CaO + XaF,.
+ +
4LiF X a O Si = 4Li + CaO . SiO, + ZCaF,.
T h e condensate from the thermal reduction with aluminum (which is carried out a t 1000') contains
about 90% metallic lithium, the rest being lithium fluoride: the yield of lithium passing into the condensate
is 4 4 to 45%; the lithium yield in thermal reduction with silicon (which is carried out a t 1100') is only
22 t o 23%.
Reduction of lithium aluminate. T h e research of Kiselev has shown that high-purity lithium may be
prepared by reduction of lithium aluminate with aluminum: a lithium yield of over 90% is obtained by
reducing the monoaluminate Li,0'A1,03 in a vacuum (0.1 to 0.5" Hg) a t 1150 to 1200'.
T h e direct reduction of spodumene is based on the fact that when spodumene is roasted with l i m e (CaO)
the l i m e replaces and liberates the lithium oxide: when this process occurs in the presence of a reducing
agent, the lithium oxide is reduced to the metal.
T h e spodumene conceiitrate is crushed to a particle size of -0.014mm. mixed with CaO and aluminum
or ferrosilicium, and heated to 1050 to 1150" in a special retort in vacuo (lo-'" Hg). T h e yield of
lithium reaches 85%, the degree of purity of the metal is 90%. Because of their high vapor pressure, the
potassium and sodium present as impurities are volatilized together with the lithium and collect mainly o n the
coolest parts of the condenser.
In spite of some advantages of the lithium-manufacturing methods based on thermal reduction with
metals ( t h e use of cheap reducing agents, the possibility of producing lithium of a high degree of purity,
the possibility of using directly the products of lithium ore dressing or even the ore itself). these methods
do not have extensive commercial use; this is due to a certain extent t o the complexity of the equipment
used for the thermal reduction in a vacuum (as compared with the simpler equipment needed for molten
salt electrolysis) and t o the extensive use of the molten-salt electrolysis processes.
decomposed at -
hydride (decomposition of KH and NaH occurs a t 425 to 500" while LiH is
1000" in vacuo). To effect the hydrogenation, the
lithium is hydrogenated in a c u r r e n t of hydrogen a t 700 to 800", the
lithium hydride formed is melted (the melting point of LiH is 690"), and
the sodium and potassium (formed in the decomposition of the KH and NaH,
which a r e formed during the hydrogenation) a r e easily volatilized.
The refining by distillation at reduced p r e s s u r e s (vacuum distillation)
is based on the different vapor p r e s s u r e s of lithium, sodium, magnesium
and potassium (Figure 229).
465
IllIllIlIl I
466
BIBLIOGRAPHY
467
5. M e e r s o n , G . A . , N.N. K h a v s k i i , K. Y a . S h a p i r o , and A . P .
.
N a d 01 ' s k i i Issledovaniya PO pererabotke vol'framovykh kontsentratov,
Metallurgiya i tekhnologiya tsvetnykh metallov (Studies on t h e Processing of
Tungsten Concentrates, Metallurgy and Technology of the Nonferrous Metals). -
Sbornik nauchnykh trudov Instituta tsvetnykh metallov im. M. I. Kalinina,
No. 33, Metallurgizdat. 1960.
6. V a s i l ' e v a , A. I., Ya. I. G e r a s i m o v , and Yu. P. S i m a n o v . Konstanty
ravnovesiya reaktsii vosstanovleniya okislov vol'frama vodorodom (Equilibrium
Constants of t h e Reactions in the Reduction of Tungsten Oxides by Hydrogen). -
ZhFKh, 31 (3):682. 1957.
7. M e e rs o n , G. A. Sovremennoe sostoyanie teorii osnovnykh protsessov porosh
kovoi metallurgii (Current State of t h e Theory of the Main Processes in Powder
Metallurgy). -In: "Voprosy poroshkovoi metallurgii", Kiev. 1955.
8. N o r t h c o t t , L. Molybdenum [Russian translation. 19591.
9. N a t a n s o n , A. K. ( Editor). Molybdenum. Collection of Papers [Russian
translation. 1962.3
10. Z e 1 i k m a n , A. N. and L. V. B e 1y a e v s k a y a . Issledovanie reaktsii okisleniya
molibdenita (Studies of Molybdenite Oxidation Reactions). - ZhNKh, Vol. 1 ,
No. 10. 1956.
11. Z e 1 i k m a n , A. N. Reaktsii v tverdoi faze s uchastiem trekhokisi molibdena
(Solid State Reactions with Molybdenum Trioxide). -ZhNKh, Vol. 1 , No. 12.
1956.
12. Z e l i k m a n , A . N., L . M . B e l y a e v s k a y a , O.E. K r e i n , and V . M . P e t r o v .
Obzhig molibdenitovykh kontsentratov v kipyashchem sloe (Roasting of
Molybdenite Concentrates in a Fluidized Bed). -In: Sbornik "Primenenie v SSSR
protsessov obzhiga v kipyashchem sloe", NTO TsM, p. 251. 1960. (see also
Tsvetnye Metally, No. 8.1956).
13. B u r o v o i , L A. and I. M. Be r n s h t e i n . Polnaya avtomatizatsiya pechi dlya
obzhiga molibdenitovykh kontsentratov v kipyashchem sloe (Complete
Automation of Kilns for t h e Fluidized Bed Roasting of Molybdenite Concentrates). -
Byulleten' TsIIN TsM, Nos. 11 -12 : 12-20. 1956.
14. Z o l o t a r e v , L. L. Opyt ochistki ot zagryaznyayushchikh primesei v proizvodstve
paramolibdata ammoniya (Experience in the Purification of Ammonium
Paramolybdate). -Tsvetnye Metally, No. 1 : 51. 1958.
15. L e b e d e v , K. B. Proizvodstvo molibdata kal'tsiya Alma- Ata (Production of
Calcium Molybdate Alma-Ata). -1zd. A N KazSSR. 1962.
.
16. B o r o k , B A . Gidrostaticheskoe pressovanie metallicheskikh poroshkov,
Poroshkovaya metallurgiya (Hydrostatic Pressing of Metallic Powders). - Sbornik
trudov konferentsii, Yaroslavl'. 1956.
17. S t r o e v , A . S . , A . M . I v a n o v , and E . S . O v s e p y a n . Dugovaya plavka
molibdena v vakuume (Arc Melting of Molybdenum in Vacuo). -In: Sbornik:
"Primenenie vakuuma v metallurgii", Izd. A N SSSR 1958.
18. Z e 1 i k m a n , A. N. and L. V. B e 1y a e v s k a y a . Issledovanie nekotorykh
protsessov, protekayushchikh pri obzhige molibdenitovykh kontsentratov
468
(Studies of Some Processes Occurring in t h e Roasting of Molybdenite
Concentrates). -In: Sbornik trudov Moskovskogo instituta tsvetnykh metallov,
No. 25, Metallurgizdat. 1955.
19. S h a r u p i n , B. N. Termokhimicheskie svoistva khloridov i oksikhloridov
molibdena (Thermochemical Properties of Molybdenium Chlorides and Oxy
chlorides). Author's Summary of Thesis for t h e Degree of Candidate of Technical
Sciences. -LGU. 1960.
20. M a s 1e n i t s k i i , N. N. Avtoklavno-sodovyi protsess pererabotki produktov
obogashcheniya vol'framovykh rud ( T h e Autoclave- Soda Ash Processing of En
riched Tungsten Ores). - In: Sbornik "Primenenie avtoklavnykh protsessov v
metallurgii tsvetnykh i blagorodnykh metallov", TsIIN TsM, 1960 (In t h e s a m e
.
collection, see the paper by V. A. Boiko, V. M Poprukailo, and D. A.
Malakhov).
21. S p i r i d o n o v a , V. I. , S . I. S o b o 1 ' , e t al. Pererabotka sul'fidnogo molibdenovo
go syr'ya s primeneniem okislirel'nogo avtoklavnogo vyshchelachivaniya
(Processing of Molybdenum Sulfide Ores by Oxidative Autoclave Leaching). -
Bid.
22. I o r d a n o v , Khr. 0 primenenii gipokhloritnogo metoda dlya pererabotki
molibdenovogo kontsentrata (Processing of Molybdenum Concentrates by the
Hypochlorite Method). -Minnoe Delo i Metallurgiya (Bulgaria), No. 9 : 25 -27.
1961.
23. Z e l i k m a n , A.N., N . N . G o r o v i t s , and T . E . P r o s e n k o v a . Davlenie
para trekhokisi molibdena ( T h e Vapor Pressure of Molybdenum Trioxide). -
ZhNKh, No.4. 1956.
24. N o y , J. M. and D. C. S m i t h . A Molybdenum Trioxide Sublimation Furnace.
US Patent 2,958,588 November [Russian translation. 1960. ]
25. S p i t s y n , V. L and I. A. S a v i c h . Rastvorimost' molibdata kal'tsiya v vode
( T h e Solubility of Calcium Molybdate in Water). -ZhOKh, Vol. 22 : 1278. 1952.
26. Z e 1i k m a n , A. N. and T. E. P r o s e n k o v a . 0 rastvorimosti molibdatov
kal'tsiya, medi, tsinka, zheleza i svintsa v vode i razbavlennykh rastvorakh
a m m i a k a (On the Solubility of Calcium, Copper, Zinc, Iron and Lead
Molybdates in Water and Dilute Ammonium Hydroxide Solutions). - ZhNKh,
Vol. 6, No. 1. 1961.
27. A i r a p e t y a n , G. M. Kislotnyi sposob pererabotki molibdensoderzhashchikh
otvalov poluchaemykh v proizvodstve paramolibdata ammoniya ( T h e Acid
Processing of Molybdenum-Containing Wastes from the Production of Ammonium
Paramolybdate). -Promyshlennost' Armenii, No. 3. 1958.
28. T r e t ' y a k o v , V. I. Metallokeramicheskie tverdye splavy (Hard Alloys Made
by Powder Metallurgy). - Metallurgizdat. 1962.
29. P e r 1 o v , P. M. Primenenie avtoklavno-sodovogo protsessa pererabotki
volframo-molibdenovykh produktov, Obogashchenie rud ( T h e Use of the
Autoclave -Soda- Ash Method in t h e Processing of Tungsten-Molybdenum
Products, Ore Enrichment). -Mekhanobr, No. 4 (28). 1960.
30. E s p e , W. T h e Technology of Metals for Vacuum Tubes [Russian translation.
1962.1
469
Chapter 111. Tantalum and Niobium
470
(Production of Electrolytic Tantalum, Niobium and Their Alloys). - Poroshkovaya
Metallurgiya, No. 4 : 47. 1961; No. 5 : 43. 1961.
15. N i s e 1 ' s o n , L. A. Razdelenie i ochistka tantala i niobiya rektifikatsiei ikh
khloridov (Separation and Purification of Tantalum and Niobium by Rectifica
tion of Their Chlorides). -ZhNKh, No. 12. 1958 (see also Byulleten' TsIIN
TsM, N0..12 :2603. 1963).
16. G r u b e r , H. Melting of Metals with Electron Beams [Russian Translation.
1963. ]
17. Z a k h a r o v a , G.V., I. A . P o p o v , L.P. Z h o r o v a , and 8 . V . F e d i n .
Niobii i ego splavy (Niobium and Its Alloys). -Metallurgizdat. 1961.
18. B e r e n g a r t , A . S . , I . E . V i l ' k o m i r s k i i , V.A. K o z h e m y a k i n , T.S.
S e d y k h , and 0. I. Er o k h i n a . Issledovanie protsessa khlorirovaniya
loparitovykh kontsentratov (Investigations of t h e Chlorination of Loparite
Concentrates). -Tsvetnye Metally, No. 4 : 56-61. 1962.
19. G a g a n o v , T . P . , V. D . P o n o m a r e v , and 0. A. K h a n . Ob usloviyakh
ekstraktsionnogo razdeleniya i sostave kompleksov tantala i niobiya (On t h e
Conditions for the Extractive Separation and the Composition of Tantalum
and Niobium Complexes). -In: Sbornik "Razdeleniya blizkikh PO svoistvam
redkikh metallov, p. 79. Metallurgizdat. 1962.
.
20. 0 r e k h o v , M. A. and A. N. Z e I i k m a n 0 vzaimodeistvii pyatiokisi tantala i
niobiya s rastvorami KOH pri povyshennykh temperaturakh ( T h e Interaction of
Tantalum and Niobium with KOH Solutions a t Elevated Temperatures). -1zv.
Vuz. , Tsvetnaya Metallurgiya, No. 5. 1963.
21. La p i t s k i i , A. V. 0 produktakh vzaimodeistviya pyatiokisi niobiya i
pyatiokisi tantala s e d k i m i shchelochami ( T h e Products of the Interaction of
Niobium and Tantalum Pentoxides with Alkali Hydroxides). - Vestnik MGU,
NO. 6 : 121. 1958.
22. P o l ' k i n , S. I . , Yu. F. G l a d k i k h , and Yu. A. B y k o v . Obogashchenie rud
tantala i niobiya ( T h e Enrichment of Tantalum and Niobium Ores). -
Gosgortekhizdat. 1963.
.
23. Z i v , E. F. and A. I. V a i s e n b e r g Trebovaniya promyshlennosti k kachestvu
mineral'nogo syr'ya (Industrial Requirements with Respect to the Quality of
Mineral Raw Materials). - Spravochnik dlya Geologov, No. 49, "Niobii i
Tantal". Gosgeolizdat. 1960.
.
24. 2 e 1 i k m a n , A. N. and M. A. 0 r e k h o v Razlozhenie tantalitovogo
kontsentrata rastvorami edkogo natra pri povyshennykh temperaturakh i
davleniyakh (Decomposition of Tantalite Concentrate by Sodium Hydroxide
Solutions a t Elevated Temperatures and Pressures). - Izv. A N SSSR, Metallurgiya
i Gornoe Del0 (in print).
1 25. M o r o z o v , I . S. and D . Y a . T a p t y g i n . - 2 h N W . No. 8:1915. 1957.
26. S m e l y a n s k i i , M . Y a . , V. A . B o y a r s h i n o v , G u t t e r m a n , L. G . T k a c h e v ,
.
and V. P. T s i s h e v s k i i Dugovye vakuumnye pechi i elektronnye plavil'nye
ustanovki (Vacuum Arc Furnaces and Electron Melting Devices). - Energoizdat.
1962.
47 1
I I I 1l111l1l1l1lI l
472
'I
473
474
Chapter V. Zirconium
475
13. E m e l ' y a n o v , V . S . and A . I , E v s t y u k o v (Editors) Metody polucheniya
chistykh metallov (Methods for t h e Production of Pure Metals). Collection of
translated papers. -IL. 1957 (This is a series of papers i n the production of
zirconium and titanium by the iodide method).
14. E v s t y u k o v , A. I., I. P. B a r i n o v , and D. D. A b a n i n . Issledovanie
iodidnogo protsessa polucheniya tsirkoniya s ispol'zovaniem karbida tsirkoniya
v kachestve syr'ya (Investigation of t h e Production of Zirconium from Zirconium
Carbide by the Iodide Method). -In: Sbornik "Metallurgiya i metallovedenie
chistykh metallov", Atomizdat. 1959.
15. Metody razdeleniya blizkikh po svoistvam redkikh metallov (Methods of
Separation of Rare Metals with Similar Properties). - Metallurgizdat. 1962.
(A series of papers on t h e separation of zirconium and hafnium).
16. K a g a n o v i c h , S. Ya. Tsirkonii i gafnii (Zirconium and Hafnium). -1zd.
AN SSSR. 1962.
17. B 1u m e n t h a 1 , W. B. T h e Chemical Behavior of Zirconium [Russian
translation. 1963.3
18. C h u k h l a n t s e v , V . G . and A. K . S h t o l ' t s . 0 tsirkonosilikatakh natriya
(On the Sodium Zirconosilicates). -ZhNKh, No. 6 : 1332. 1961.
19. C a x , R . P., H . C . P e t e r s o n , and G . H . B e y e r . -Ind.Eng.Chem., 59 ( 2 ) :
141. 1958 (Separation of Hf from Zr by extraction with TBP).
20. S h e l t o n , S . M . , E.D. D i l l i n g , and J.H.Mc C l a i n . Proizvodstvo
metallicheskogo tsirkoniya (Zirconium Metal Production). -Paper Presented
t o t h e First International (Geneva) Conference on the Peaceful Uses of Atomic
Energy, Vol. 8 : 585-637. Metallurgizdat. 1958.
21. N i s e 1 ' s o n , L. A. Wzdelenie i ochistka galogenidov tsirkoniya i gafniya,
niobiya i tantala metodami, osnovannymi na razlichii v letuchestyakh
(Separation and Purification of t h e Halides of Zirconium and Hafnium, and
Niobium and Tantalum by Methods Based on Differences in Their Volatilities). -
In: Sbornik "Razdelenie blizkikh PO svoistvam redkikh metallov" p. 168,
Metallurgizdat. 1962.
22. 0 g a r e v , A. N. e t al. Poluchenie plastichnogo tsirkoniya elektrolizom
rasplavlennykh solei (Production of Ductile Zirconium by Electrolysis of Molten
Salts). -Paper Presented t o the Second International (Geneva) Conference on the
Peaceful Uses of Atomic Energy, Vol. 3 : 414, Atomizdat. 1959.
23. K a p I a n , G. E., G. F. S i 1 i n a , and Y-u.I. O s t r o u s h k o . Elektroliz v
metallurgii redkikh metallov (Electrolysis in the Metallurgy of the Rare Metals). -
Metallurgizdat. 1 963.
476
2. V i c k e r y ,R. C. Chemistry of t h e Lanthanides. -London. 1953.
3. T r i f o n o v , D. N. Redkozemel'nye elementy ( T h e Lanthanide Elements). -
Izd. A N SSSR. 1960.
4. K o g a n , B. I. Ekonomicheskie ocherki po redkim zemlyam (Economic Survey
o n t h e Rare Earths). -1zd. A N SSSR. 1961.
5. Redkozemel'nye elementy v stalyakh i splavakh ( T h e Lanthanides in Steels
and Alloys). -Trudy Soveshchaniya, Metallurgizdat. 1959.
6. S a v i t s k i i , E. M. (Editor). Properties and Uses of the Lanthanide Metals.
[Russian translation. 1960. 3
7. K o m i s s a r o v a , L. N. and V. E. P 1y u s h c h e v (Editors). Redkozemel'nye
metally ( T h e Lanthanide Metals). Collection of translated papers. -E. 1957.
8. K o m i s s a r o v a , L. N. and V.E. P l y u s h c h e v (Editors). Metody razdeleniya
redkozemel'nykh metallov (Methods for t h e Separation of the Lanthanide Metals).
Collection of translated papers. -1L. 1961.
9. K o m i s s a r o v a , L . N. and V . E . P l y i i s h c h e v (Editors). Metallurgiya
redkozemel'nykh metallov ( T h e Metallurgy of t h e Lanthanide Metals). Collection
of translated papers. -IL. 1962.
10. Z e 1 i k m a n , A. N. Metallurgiya redkozemel'nykh metallov, toriya i urana
( T h e Metallurgy of the Lanthanides, Thorium, and Uranium). - Metallurgizdat.
1961.
11. Redkozemel'nye elementy (poluchenie, analiz, primenenie) (The Lanthanides ;
Preparation, Analysis and Uses). Collection of papers of Soviet authors. -
Izd. A N SSSR. 1958.
12. S p e d d i n g , F . H . and A . H . D a a n e . TheRareEarths. -New York. 1961.
13. R y a b c h i k o v , D. I. (Editor). Redkozemel'nye elementy ( T h e Lanthanides),
Collection of papers of Soviet authors. -1zd. A N SSSR 1963.
14. G i n z b u r g , A. I. and V. P. F a g u t o v (Editors). Geologiya mestorozhdenii
redkikh elementov, vyp. 3. Redkozemel'nye elementy i ikh mestorozhdeniya
( T h e Geology of Rare-Element Deposits, No. 3. T h e Lanthanides and Their
Deposits). -Gosgeolizdat. 1959.
15. K a p l a n , G . E . , T . A . U s p e n s k a y a , Y u . I . Z a r e m b o , and 1 . V . C h i r k o v .
Torii, ego syr'evye resursy, khimiya i tekhnologia (Thorium, Its Raw Materials,
Chemistry and Technology). -Atomizdat., 1960.
16. G u r h b e r r , F. L. Thorium Production Technology. -USA. 1958.
477
4. S h a s h k o v , Yu. M. Metallurgiya poluprovodnikov ( T h e Metallurgy of Semi
conductors). - Metallurgizdat. 1960.
5. S a z h i n , N. P. Germanii i e g o primenenie (Germanium and Its Uses). -
Khimicheskaya Nauka i Promyshlennost' No. 5 :487. 1956.
6. Voprosy metallurgii i fiziki poluprovodnikov (Problems of the Metallurgy and
Physics of Semiconductors). -Trudy Soveshchanii PO Poluprovodnikovym
Materialam, Izd. AN SSSR. 1957. (Second conference); 1961 (Fourth conference)
7. P f a n n , W. G. Zone Melting. [Russian translation. 1960. ]
8. P a r r , N. Zonnaya ochistka i ee tekhnika, 1960. (Zone Refining and Its
Techniques, 1960). -Metallurgizdat. 1963.
9. P o w e 1 1 , A. R. , F. M. L e v e r , and R. E. W o 1 p o 1e . Izvlechenie i rafinirovanie
germaniya i galliya (Iz pyli gazogeneratorov i germanite v Anglii) (Extraction
and Refining of Germanium and Gallium (from Gasgenerator Dusts and Germanite
i n England)). - "Germanii" A collection of translated papers. Institut metallurgii
im. Baikova. 1955.
10. 0 k u n e v , A. I. and Yu. F. R y a b o v . Povedenie germaniya pri pirometallurgi
cheskoi pererabotke mednykh rud i kontsentratov ( T h e Behavior of Germanium in
t h e Pyrometallurgical Processing of Copper Ores and Concentrates). - Tsvetnye
Metally, No. 7 3 8 . 1958.
11. I o f f e , A. F. Poluprovodniki v sovremennoi fizike (Semiconductors in Modern
Physics). -Izd. A N SSSR. 1957.
12. F r i t s c h e , K. T h e Preparation of Semiconductors. [Russian translation. 1964. ]
.
13. Lo m a s h o v , I. P. and B. I. L o s e v Germanii v iskopaemykh uglyakh
(Germanium in Mined Coals). -Izd. AN SSSR. 1962.
24. R o s n e r , 0. Recovery and Purification of Germanium. Dussian translation.1957. 3
15. T h e u e r e r , H. C. Purification of Germanium Chloride by Extraction with
Hydrochloric Acid and Chlorine. [Russian translation. 1957. ]
16. The Production of Germanium. [Russian translation. 1957. ]
17. T h o m p s o n , A.R., and J.R. M u s g r a v e . Germanii, izvlekaemyi kak pobochnyi
produkt, stanovitsya materialom pervostepennogo znacheniya (Germanium
Extracted as a By-product, Becomes a Material of Primary Importance).
"Germanii", a collection of translated papers. -1L. 1955.
478
I
4. E i n e c k e , E. Das Gallium. -Leipzig. 1937.
5. B e n e s 1a v s k i i , S. I. Perspektivy kompleksnogo ispol'zovaniya boksitov
(Prospects for the Combined Utilization of Bauxites). -Tsvetnye Metally, No. 1:93.
1957.
6. .
W a g n e r , G. and V. G i t z e n Gallium [Russian translation. 1953. ]
7. K O v a 1e n k o , P. N. Znacheniya pH osazhdeniya gidrookisi galliya i ee
9. .
V i 1 ' f e 1 ' d t , K. and M. L a i p e i r e s Production of Gallium as a By-product of
2 0. M i l l s , J . F . , B. G . H u n t , and G . H . T u r n e r . -J.Electrochem.Soc.,
21. .
L e v i n , I. S. and T. V. Z a b o 1 o t s k i i Otdelenie indiya o t tsinka i
Z. 132-157. 1957.
479
*
480
0
.
39. P a p p , E. and K. S h o i m a r Poluchenie galliya chistotoi 99.9999% metodom
drobnoi kristallizatsii i zonnoi plavki (Production of 99.999970 Pure Gallium by
Fractional Crystallization and Zone Melting Methods). - Izv. Vuzov. Tsvetnaya
Metallurgiya, No. 5 : 108. 1963.
40. S h e k a , I. A., I. S. C h a u s , and T. T. M i t y u r e v a . Gallii (Gallium). -
Gostekhizdat, UkrSSR. 1963.
48 1
16. P a v 1o v a , E. I. Poluchenie reniya i ego splavov s vol'framom (Preparation of
Rhenium and Rhenium-Tungsten Alloys). --bid, p. 159.
17. Z e 1 i k m a n , A. N. and V. F. P r i t u 10. Issledovanie avtoklavnogo sposoba
polucheniya reniya iz perrenata kaliya (Investigation of t h e Autoclave Method
For t h e Preparation of Rhenium from Potassium Perrhenate). -Izv. Vuzov,
Tsvetnaya Metallurgiya, No. 4 : l l l . 1961.
18. P o r t ,John. Rhenium. -Amsterdam-New York. 1962.
.
19. M a l o u f , E. E., J. D. P r a t e r , and S. R. Z i m m e r 1 e y Rhenium. -Amsterdam-
New York. 1962.
20. Z e l i k m a n , A . N . , N . V . B a r y s h n i k o v , and M . V . T e s l i t s k a y a . Poluchenie
renievykh pokrytii metodom termicheskoi dissotsiatsii oksikhlorida (Preparation of
Rhenium Coatings by Thermal Dissociation of t h e Oxychloride). - Izv. AN SSSR,
Metallurgiya i Gornoe Delo, No.4:161. 1963.
21. B a r y s h n i k o v , N. V. and A. N. Z e 1 i k in a n . Termodinamicheskie svoistva
khloridov i oksikhloridov reniya ( T h e Thermodynamic Properties of Rhenium
Chlorides and Oxychlorides). - Izv. Vuzov, Tsvetnaya Metallurgiya, No. 6.1962.
22. Z e l i k m a n , A . N . , V . M . P e t r o v , and K . N . E g o r y c h e v . Povedenie reniya
pri obzhige molibdenovykh kontsentratov ( T h e Behavior of Rhenium During the
Roasting of Molybdenum Concentrates). - Izv. A N SSSR, Metallurgiya i Gornoe
Delo, No. 6: 103. 1963.
23. D e e v , V. I. and V. I. S m i r n o v . 0 povedenii reniya pri okislitel'nom obzhige
molibdenovykh kontsentratov ( T h e Behavior of Rhenium During t h e Oxidative
Roasting of Molybdenum Concentrates). -Tsvetnye Metally, No. 3. 1964.
24. Renii (Rhenium). -Trudy 2- i Vsesoyuznoi konferentsii PO probleme reniya,
Izd. A N SSSR. 1964.
25. D e e v , V. I. and V. I. S m i r n o v . Davlenie para disul'fida, dvuokisi, i
trekhokisi reniya ( T h e Vapor Pressures of Rhenium Disulfide, Dioxide, and
Trioxide). -DAN SSSR, No.4: 822. 1961.
26. Z e 1 i k m a n , A. N. and N. V. B a r y s h n i k o v . Poluchenie renievykh pokrytii
metodom termicheskoi dissotsiatsii ego khloridov (Preparation of Rhenium
Coatings by Thermal Dissociation of Its Chlorides). - Izv. Vuzov, Tsvetnaya
Metallurgiya, No. 2: 120. 1963.
.... I
6. Be 1 y a e v , R. A. Okis' berilliya, svoistva i primenenie (Beryllium Oxide -
Properties and Uses). - Atomizdat. 1962.
7. S c h r e i t e r , W. , Seltene Metalle, Bd. 1. -Leipzig. 1960.
8. S h m i d t , R. Novye priemy uluchsheniya plastichnosti berilliya (New Methods
for Improving the Ductility of Beryllium). - Atomnaya Tekhnika z a Rubezhom,
No. 12. 1960.
9. Redkie elementy i titan v splavakh tsvetnykh metallov (Rare Elements and
Titanium in Nonferrous Alloys). -Informatsiya Giredmeta, No. 15 (26). 1962.
10. V o 1 , A. E. Stroenie i svoistva dvoinykh metallicheskikh sistem ( T h e Structure
and Properties of Binary Metallic Systems). - Fizmatgiz. Vol. 1. 1959.
11. P a u s h k i n , Ya. M. Khimiya reaktivnykh topliv (topliva dlya vozdushno
reaktivnykh i raketnykh dvigatelei) ( T h e Chemistry of Jet Fuels (Fuels for Jet
and Rocket Engines)). -Izd. A N SSSR. 1962.
12. B e u s , A. A. Trebovaniya promyshlennosti k kachestvu mineral'nogo syr'ya
( T h e Requirements of Industry with Respect t o the Quality of Mineral Raw
Materials). -Spravochnik dlya geologov, No. 36, "Berillii", Gosgeolizdat. 1959.
13. B e u s , A. A. , A. I. G i n z b u r g , e t al. Geologiya mestorozhdenii redkikh
elementov. vyp. 4. Nekotorye tipy pnevmatolitogidrotermal'nykh mestorozhdenii
berilliya ( T h e Geology of Rare-Element Deposits, No. 4, Some Types of
Pneumatolithohydrothermal Beryllium Deposits). - Gosgeolizdat. 1959.
14. E i g e 1 L. E. Rudy chernykh, tsvetnykh i redkikh metallov i ikh promyshlennoe
I,
znachenie ( T h e Ores of Ferrous, Nonferrous and Rare Metals, and Their Industrial
Importance). -Gosgortekhizdat. 1962.
15. P o 1 ' k i n , S. I. Flotatsiya rud redkikh metallov i olova (Flotation of the Ores
of Rare Metals and Tin). -Gosgortekhizdat. 1960.
16. Izvlechenie i ochistka redkikh metallov (Extraction and Refining of t h e Rare
Metals), pp. 376 -427. -Atomizdat. 1960.
17. B e r e n g a r t , A. S. and M. T. G 1 u s h k o v a . Issledovanie reaktsii khlorirovaniya
okisi berillya chetyrekhkhloristym uglerodom (Investigation of the Chlorination
of Beryllium Oxide with Carbon Tetrachloride). -Sbornik nauchnykh trudov
Giredmeta, Vol. 1 : 60. Tekhnologiya, Metallurgizdat. 1959.
18. N o v o s e 1 o v a , A. V. and K. N. S e m e n e n k 0 . Khlorirovanie Be0 chetyrekh
khloristym uglerodom ( T h e Chlorination of Be0 with Carbon Tetrachloride). -
ZhNKh, No. 9: 2213. 1958.
19. V i l ' k o m i r s k i i , I. E., G. F. S i l i n a , A. S . B e r e n g a r t , and V. L S e m a k i n .
Poluchenie berilliya vysokoi chistoty khloridnym metodom (Preparation of High-
Purity Beryllium by the Chloride Method). -Atomnaya Energiya, Vol. 2, No. 3.
1961.
20. M e e r s o n , G . A . , G.E. K a p l a n , G . F . S i l i n a , and D . D . S o k o l o v .
Tekhnologiya polucheniya izdelii iz chistykh berilliya i okisi berilliya dlya ikh
primeneniya v yadernykh reaktorakh (Technology of t h e Production of Articles
of Pure Beryllium and Beryllium Oxide, for Use in Atomic Reactors). -Sbornik
dokladov sovetskoi delegatsii na mezhdunarodnoi konferentsii PO ispol'zovaniyu
atomnoi energii, Geneva. 1955. "Issledovaniya v oblasti geologii, khimii i
metallurgii', Izd. A N SSSR. 1955.
483
21. S a m s o n o v , G . V . and M.S. K o v a l ' c h e n k o . Goryachee pressovanie
(Hot Pressing). - Gostekhizdat UkrSSR, p. 140. 1962.
22. L ' y u i s . Berillidy (Beryllides). -Problemy Sovremennoi Metallurgii. No. 6:98.
1961.
23. E m e l ' y a n o v , V . S . and A . I . E v s t y u k h i n a (Editors). Methods for the
Production of Pure Metals. Collection of translated papers. -1L. 1957.
24. M i l l e r , A. Plavka berilliya vo vzveshennom sostoyanii (The Fluidized-Bed
Melting of Beryllium). -Atomnaya tekhnika z a rubezhom, No. 12. 1962.
25. K Oz I o v , V. M. and V. D. T u r o v s k i i. BeriIIii. Toksikologya, klinika
porazhenii, gigiena truda (Beryllium, Toxicoloy, Treatment and Industrial
Hygiene). -Atomizdat. 1962.
26. S i n e l ' n i k o v , I . D . , V . E . I v a n o v , V . M . A m o n e n k o , and V . D . B u r l a k o v .
Rafinirovanie berilliya i drugikh metallov kondensatsiei na nagretykh poverkh
nostyakh (Refining of Beryllium and Other Metals by Condensation on Heated
Surfaces). Reports of Soviet Scientists to the Second International Conference on the
Peaceful Uses of Atomic Energy. - Sbornik "Yadernoe goryuchee i reaktornye
materialy" (Report No. 2051). Atomizdar. 1959.
27. I v a n o v , E . S . and V. M . S h m e l e v . Plavka i l i t ' e berilliya ( T h e Melting and
Casting of Beryllium). Report No. 2048. - b i d .
28. F i s h m a n , M. A. and P. S. S o b o 1 e v . Praktika obogashcheniya rud tsvetnykh i
redkikh metallov (The Enrichment of Nonferrous and Rare Metal Ores), Vol. 4. -
Gosgortekhizdat. 1963.
1. O s t r o u s h k o , Y u . I . , P . I . B u c h i k h i n , V . V . A l e k s e e v a , ' T . F . N a b o i s h
c h i k o v a , G.A. K o n d a , S . A . S h e l k o v a , R . N . A I e k s e e v a , and M.A.
M a k o v e t s k a y a . Litii, ego khimiya i tekhnologiya (Lithium, Its Chemistry
and Technology). -Atomizdat. 1960.
2. P 1y u s h c t e v , V. E. (Editor). Lithium. Collection of translated papers. - IL.
1959.
3. Sbornik nauchnykh trudov Giredmeta (1931-1956), Vol. 1. Tekhnologiya. -
Metallurgizdat. 1959.
4. K o g a n , B. I. Litii, oblasti ego osvoennogo i vozmozhnogo primeneniya
(Lithium -Its Known and Possible Uses). -VINITI. 1960.
5. K O g a n , B. I. Trebovaniya promyshlennosti k kachestvu mineral'nogo syr'ya.
Spravochnik dlya geologov, vyp. 41, Litii, 2-e izd. ( T h e Requirements of
Industry with Respect t o t h e Quality of Mineral Raw Materials. A Handbook for
Geologists, No. 41. Lithium, Second Edition). - Gosgeolizdat. 1959.
6. Primenenie redkikh elemenrov v stekol'noi promyshlennosti ( T h e Use of Rare
Elements in t h e Glass Industry). -1nformatsiya Giredmeta, No. 20 (31). 1962.
7. Kratkii spravochnik inzhenera-fizika (Yadernaya fizika, atomnaya fizika
(Short Manual for Engineers-Physicists (Nuclear and Atomic Physics)). -
Atomizdat. 1961.
484
8. Issledovanie splavov tsvetnykh metallov (Investigation of Nonferrous Alloys). -
Sbornik statei, No. 3 , Izd. AN SSSR. 1962.
9. Geokhimiya redkikh elementov ( T h e Geochemistry of the Rare Elements).
Collection of translated papers. -1L. 1959.
10. P 01 ' k i n , S. I. Flotatsiya iud redkikh metallov i olova (Flotation of the
Ores of Rare Metals and Tin). -Gosgortekhizdat. 1960.
11. S e r g e e v a , 0. S. (Editor). Lithium. Collection of translated papers. - IL. 1954.
12. Sbornik "Redkie shchelochnye elementy" (The Rare- Alkali Elements). A collec
tion. - Khimikometallurgicheskii institut SO AN SSSR, Novosibirsk. 1960.
13. Poluchenie khloristogo litiya iz spodumena (Preparation of Lithium Chloride from
Spodumene). -US patent No. 26274452. 1953; RZh, No. 2, 2156P. 1953.
14. K o l c h i n , 0. P. (Editor). Extraction and Refining of the Rare Metals. [Russian
translation. 1960.1
15. L e a v e n w o r t h , H . and R . C h e a r y . -Acta Metallurgica, 9 ( 5 ) : 5 1 9 . 1961.
16. S h a m r a i , F. I. Litii i ego splavy (Lithium and Its Alloys). - Izd. A N SSSR.
1952.
17. E g e 1 L. E. Rudy chernykh, tsvetnykh i redkikh metallov i ikh promyshlennoe
I,
znachenie ( T h e Ores of Ferrous, Nonferrous, and Rare Metals and Their Industrial
Importance). -Gosgortekhizdat. 1962.
18. G r i s h i n , V . K., M. G . G l a z u n o v , A . G . A r a k e l o v , A . V . V o l ' d e i t , and
G . S . M a k e d o n s k a y a . Svoktva litiya ( T h e Properties of Lithium). -
Metallurgizdat. 1963.
485
$8.12
NASA TT F-359