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Ionic Radius
Angstroms
Ionic Potential
Lithium
0.60
1.67
Sodium
0.95
1.05
Potassium
1.33
0.75
The melting point of pure lithium is 180.5 C but of course pure lithium is only available in
metallic form which is highly reactive and must be packed in oil. Lithium carbonate has
a melting point of 720 C and spodumenes melting point is 1420 C which means it must
be used in combination with other fluxes to achieve lower firing temperatures. Phase
diagrams available from the ACS demonstrate the eutectics achieved with spodumene.
The temperature composition projection of lithium and sodium oxides demonstrates how
the eutectic of lithium and sodium works to lower melting temperatures. It is important
to note that these diagrams do not indicate what form of lithium was used and this can
affect the result. In some cases, only lithium carbonate might be suitable due to limits
on alumina or iron for example.
Lithium makes up just 0.002% or 20 ppm of the earths crust but there are many viable
reserves identified by the US Geological Survey at almost 13 million tonnes contained
lithium in the world.
Lithium is currently extracted from both mineral and brine
resources. Many minerals contain traces of lithium but the primary ones used
commercially are amblygonite, spodumene, lepidolite, petalite, and montebrasite.
Lepidolite also contains fluorine. The lithia to alumina ratio in these minerals is
consistent and lower lithia levels are compensated by more silica.
At present,
spodumene is the dominant mineral supplied in North America supplemented by some
petalite from Zimbabwe and Brazil. Lithium brines have become the major source for
lithium carbonate production due to the lower conversion costs compared to hard rock.
In both glass and ceramic applications, it has been said that lithium carbonate can
cause outgassing problems as the CO2 is released. In glass this impacts fining, in
ceramics it may show up as pinholes in the glaze or body.
Comparative Analysis of Lithium Minerals
Mineral
Formula
Lithium Content
Spodumene LiAlSiO6
Petalite
LiAlSi4O10
Lepidolite
K(LiAl)3(SiAl)4O10(OHF)2
Amblygonite LiAlPO4(FOH)
Montebrasite LiAlPO4(F9)H)
4-8%
3.5 - 4.9%
3-6
8-10
7
Figures for current demand for lithium in North America show about 50% is used in
glass, ceramics and aluminum smelting primarily for its fluxing capabilities. The
balance is made into downstream chemicals, metal or pharmaceutical uses. The US
Geological Survey estimated 2001 consumption in the USA at 1400 tons of contained
lithium, half of what it was in each of the previous four years, reflecting the economic
slowdown and particularly the drastic decline in aluminum production, where lithium
carbonate is used as a flux to improve throughput.
On its own, spodumene converts to its beta phase when heated to 1080C at which point
it undergoes a volume expansion of about 30% and a decrease in specific gravity from
3.2 to 2.4 but reaches a stage of extreme thermal stability only compromised when it
melts at 1420C. This aspect of expansion during firing with high loadings of spodumene
to create a thermally stable ceramic was exploited by S.D. Stookeys famous patents for
2
Pyro Ceram products such as Corningware and Visions cookware and also enables the
open flame cooking pots used throughout Asia. Comments on the development of
these body formulas emphasize the critical nature of getting the correct addition ranges
of each component and proper firing cycle to assure the finished properties are as
desired which often is only reached after a long series of tests. Were he still alive, it
would be interesting to ask Mr. Stookey how many formulas and firing cycles he tried!
While the application list for lithium is growing longer and longer with much current
enthusiasm focused on the lithium ion battery, the important thing is lithiums use in
ceramics which has been researched since before the 20 th century. It is important to
maintain consumer confidentiality which means full exploitation of lithiums potential
requires individual experimentation. One caution however, with lithium more may not be
better and instead the key is identifying the range where the maximum benefits can be
found depending on the desired characteristics. In all cases however the benefits go
beyond lower firing times and temperatures summarized as follows based on the
application starting with
Lithiums Benefits To Glaze and Enamel:
As both glaze and enamel are glassy materials, they will be addressed under one
heading. Specifics of the application may limit alumina or iron in turn dictating use of
lithium carbonate instead of spodumene which may cause other issues. Some of the
benefits overlap and are extensions of the new body properties.
Viscosity Lithia lowers the viscosity of glass giving better flow characteristics and
permitting a thinner and more even glaze or enamel coating which has benefits in
limiting thermal expansion and controlling crazing. A thinner coating will be less
affected by changes in temperature.
Lustre/Brilliance Lithia increases the luster and brilliance of glass and in glaze will
enhance the colour significantly.
Lower Maturation Times/Temperatures The high fluxing capability of lithium enables
glazes or enamels to mature faster or at lower temperatures or a combination of the
two.
Low expansion glazes Fast fire low expansion ceramics require low expansion
glazes which can be produced with lithium additions. Some glaze formulas show lithia
contents from .5% to 25%.
Lower Thermal Expansion Equal weights of lithium and other fluxes will provide
many more molecules of lithium so less can be used. Combined with lithiums
inherently better thermal expansion characteristics means there is less potential for
thermal expansion in a lithia based glaze which contains a smaller total flux content.
Improved Thermal Shock Resistance Similar to the comments on thermal
expansion, contraction and expansion rates are based on the oxide weights in a glaze.
Using lithium as the flux means the flux makes up a smaller proportion of the glaze
3
In summary, benefits in both glass and ceramic applications are quite similar and are
usually achieved with very low levels of lithium or spodumene additions. Replacement
of soda by lithium can be done on a mol or weight basis and while the debate on which
is correct is unresolved, although the mol basis may be better. 7% spodumene or
0.5% lithia added to a glaze has been shown to increase the brightness, gloss, stability,
wear and acid resistance while improving uniformity and fluidity allowing more even
coverage and reducing firing temperatures and maturing times. In glass containing
lithium increased tensile strength is reported and in ceramics another benefit may be
improved chip resistance although more work needs to be done to verify this.
A key aspect to economic supply of any mineral is the transportation cost which nature
sometimes overlooked. For example there is a large lithium mineral deposit in
Canadas far north which may be inexpensive to mine and concentrate but the transport
costs to market mean it can only be developed if consumers move north.
The TANCO Mine in Canada
While TANCOs mine is in southeastern Manitoba, north of Minnesota, the economics
of transportation and production from this site are workable thanks in part to mother
nature which left a most interesting pegmatite orebody containing over 80 different
minerals, some of which were found there first, and which has been the subject of
numerous P.H.D. theses and lots of study since its first documented exploration in 1914
by a survey crew. During the late 1920s a shaft still used for fresh air supply to todays
mine was dug to extract tin. The pegmatite was explored further and in the late 1930s
spodumene was mined but the records suggest little was shipped and the claim was
abandoned. In 1955 a 300 foot deep incline was put in with intent to capitalize on the
new demand for lithium grease. In 1967, the mine reopened as the Tantalum Mining
Corporation of Canada to recover tantalum from the pegmatite. In the 1970s Corning
approached the mines owners about spodumene production to supply their Martinsburg
facility and helped establish the flow sheet and circuit controls leading to Manitoba
spodumene being a popular gift when transformed into Corningware.
Today the deposit is mined about 60 meters under Bernic Lake, accessed by both a 20
degree incline and a shaft for hoisting the ore to surface. Mining is done by the room
and pillar method and the rooms average 22 square meters with a 20 meter roof
although in some areas it is as high as 50 meters. Ore is moved by train from the mine
face to the hoist. TANCOs geologists carefully study the ore underground to make sure
it is suitable before being moved for surface beneficiation. The mill has six levels which
crush, grind, float, concentrate, magnetically remove iron, dry and classify the ore
before it is packed or shipped in bulk. TANCO has a fully equipped lab on site to
analyze samples from each shipment by XRF, AA or UV spectrophotometry with
metallurgical balances computed on an IBM microcomputer system. Every shipment is
tested and a split is kept for future reference, and the lab results specific to each
shipment are supplied to the customer. The minesite also has fully equipped machine
and diesel repair shops and they keep a large inventory of spare parts. TANCO is
working towards ISO approval and follows the Total Quality Concepts reflected in their
mission statement, better every day. Today TANCO processes over 700 tons of ore
per day and the product list has expanded to include not only spodumene and tantalum
concentrates but also montebrasite and pollucite, a source of cesium. The pollucite is
6
converted on site to cesium formate, a biodegradable high density solution used in oil
well drilling which allows extraction of reserves not otherwise recoverable. Cesium
formate is the next generation of drilling and completion fluids and the market is still
growing as users have found the performance substantially exceeded expectations.
TANCOs pegmatite holds the worlds largest proven reserve of cesium and an
expansion of the chemical plant is now underway.
TANCO is a wholly owned
subsidiary of the Cabot Corporation who purchase all their tantalum concentrates and
through Cabot Specialty Fluids Division sell the cesium formate to the oil well drilling
industry.
Tanco Lithium Minerals
Li2O
Fe2O3
Al2O3
P2O5
Na2O
K2O
MnO2
Concentrate -
200 mesh
Montebrasite
7.25
0.07
26.0
0.30
0.30
0.20
0.04
7.1
0.12
25.0
0.35
0.30
0.35
0.06
7.0
0.13
26.5
8.0
0.3
0.6
0.3
Acknowledgements
American Ceramic Society Phase Diagrams for
Ceramicists; 1956 ACS
Anonymous 1980- present
Fishwick, John H., Applications of Lithium in
Ceramics; 1974(?) Cahners Books, Boston, Mass
Harben, Peter; Mineral Handybook, 1995,
Industrial Minerals Books
Lawrence, W. G., Ceramic Science for the Potter,
1972, Chilton Book Company
Stookey, S.D., Low Expansion Glass-Ceramic and
Method of Making It, US Patent 3157522,
November 17, 1964
U.S. Geological Survey, Lithium 2001 Annual
Review, USGS 2001