29th September 1990

Gems and chemistry of Heat Treatment of

Geuda

Programme Leaders:

Professor O.A. Illeperuma,

Senior Research Associate, Institute of Fundamental Studies
and
Dr. M.S. Rupasinghe,
Research Associate, Institute of Fundamental Studies
 WHAT ARE GEMS?

Gems may be described as those specimens of minerals or organic materials used for

personal adornment that possess beauty, rarity, and durability. Organic materials used as

gems include pearl, coral, amber, and jet. Gems are devided into two classifications:

i) diamonds and

ii) colored stones.

In its broadcast sense, the term "colored stones" is used in the jewelry trade to

refer to all gem minerals and organic gem materials, but not diamonds. In a narrower

sense, pearls are. also eliminated from this classification and treated separately; Diamond

is considered separately for several reasons:

i) In its finer qualities it is usually nearly colorless, whereas the finer qualities in

the major varieties of the other gem minerals are coloures;

ii) its physical and optical properties are sufficiently different from other gems to

make its beauty and use totally distinctive;

iii) unlike good-quality coloured stones, diamonds have been consistently available in

both quantity and quality to permit standardization in general marketing proce­

dures and pricing.

The subsequent competition in sales has demanded a specialization that has not been

required of individual coloured-stone speices. In other words, competitive diamond market­

ing is a fultime occupation. The sources of rough, the cutting techniques and marketing

are totally foreign to those of coloured stones, and thus it has rarely been practical to

attempt to combine the two other than at the retail sales level.

FACTORS THAT A F F E C T T H E VALUE OF GEMSTONES.

The basic factors that contribute to the value of a gemstone are;

a) BEAUTY (color, luster, perfection of cutting, etc.),

b) DURABILITY,

c) RARITY,
 It is interesting to note that a gem material or potential gem material may sometimes

be too rate to be in demand. Unless it is common enough to be known to consumers, too

little demand exists for it to achieve sufficient status to bring high prices.

d) D e m a n d

The fourth factor having a bearing on the value of gemstones is DEMAND, or VOGUE.

There are times when some of the less important gemstones enjoy great demand and other

times when they are in ralative eclipse.

From time to time, fashion dictates the use of very large stones or numerous small

stones massed in settings. Factors such as these have a bearing on value at that time.

e) Tradition

One of the important factors affecting the demand and value of gemstones is TRA­

DITION. It might be said that tradition, as applied to gems, is the sum of all the efforts

throughout the centuries to interest and educate the public in the use of gems for ornamen­

tation, symbolism, and as a medium of exchange. Such efforts include promotions on the

part of jewellers, publicized purchases and use of gems by royalty and wealthy individuals,

the symbolic use of gems in various churches and other developments in which gems play

a part. All of these activities have, over a period of time, created an acknowledgement by

the public of the importance of gems.

f) Portability

. Another factor contributing to the importance of gems is PORTABILITY. This applies

to any fine gemstone because it represents a high concentration of value in a small object,

permitting the owner to transport great wealth on his person. This is what gives gemstones

a universal security value, perhaps greater than any other commodity. This is the factor

that has influenced royalty and many wealthy families to invest a certain amount of their

funds in jewels. When everything else fails, even their government, they can take or send

their gems out of the country and realize a return on them quickly.
 d) DEMAND (or V O G U E ) ,

e) TRADITION, and

f) PORTABILITY.

a) B e a u t y

Unless a gem material possesses BEAUTY, it can be considered a gemstone.

A transparent coloured stone, such as ruby,, depends for its beauty on several factors;

namely, the quality and depth of colour, the degree of transparency, and fashioning. The

beauty of an opaque stone depends mainly on colour and, to a lesser extent, on fashioning.

It is not necessary that a specimen display its maximum beauty in order to be valuable.

For example, a fine-quality rough specimen of ruby with highly abraded surfaces might be

very unattractive to the layman but have great potential beauty that could be revealed

by proper fashioning. Thus, to qualify as a gem or gem mineral, a specimen must display

beauty or posses potential beauty that can be revealed by fashioning.

b) Durability

Another essential quality for a gem is DURABILITY. To be of use as a personal

ornament, however, a stone must withstand ordinary wear well enough to retain its beauty

for a reasonable period.

One outstanding characteristic of gems is chemical and structural STABILITY. Un­

like some metals that oxidize and slowly disintegrate, or some fabrics and woods that

decompose, gems will withstand for centuries conditions that .quickly destroy most other

materials. In this sense thay are exceptionally durable.

c) Rarity

The third factor contributing to the value of a gemstone is RARITY. Rarity frequently

plays a very important role in determining the value of a gemstone, since, obviously, the

rather the material in great demand as a gemstone, the higher its value. In sizes over 2

carats, the finest qualities of ruby and emerald are more valuable per carat than colourless

diamonds of comparable quality.

 T H E CLASSIFICATION OF G E M S T O N E S

Of approximately two thousand minerals that have been identified, only about ninety

have varieties that produce specimens possessing the requisite beauty and durability to be

considered gemstones. Of this ninety, only about twenty are particularly important to the

jeweller.

Since most gemstones are minerals, the classification method used in gemology is the

same one applied by mineralogists to the various minerals, with minor adjustments. Each

mineral that produces gemstones is considered a gem SPECIES. A gem species is charac­

terized by a definite chemical composition and usually a characteristic crystal structure;

therefore, each species possesses characteristic properties. Most species, however, include

a number of different types of material with variations that are usually based on color,

transparency or phenomena; each of these is called a VARIETY. For example, ruby and

sapphire are both varieties of the gem species corundum. Ruby is the red variety and sap­

phire is the name applied to blue and all other colors. Since both are corundum, ruby and

sapphire have the same basic chemical composition, the same crystal structure, and the

same properties. They differ only in color. Rubies and sapphires also occur in "asteriated"

or "star" varieties.

Sri Lanka in relation to its surface area, is the most dense gem-bearing country in the

world. No other country in the world exept perhaps Bras., has such a wide variety of gem

stones as Sri Lanka (Table 1 and Figure l ) .

In addition to the commonly found gem stones, one also finds associated with the gem

gravels, minerals such as taaffeite, Sinhalite, Olivine, Ekanite etc. which may be useful as

index minerals. These are the potential of valuable elements generally found in the gem

gravels such as gold, thorium, uranium, inobium, tantalum, have rarely been considered.

Corrundum is one of the fairly common minerals in Sri Lanka and also in the earth's

crust. It is found in many different kinds of rocks and in many places on the earth's sur­

face, but only under the rare occurrence of nearly ideal conditions is transparent material
 formed. With the exception of black star sapphire, only the transparent to translucent

varieties are classed as gems tones.

Corrundum was formed under a wide variety of geological conditions. In almost any

mineral, crystals suitable for gem use occur only under usually good conditions.

Conditions conducive to ideal crystal growth seem even more rare during the for­

mation of corrundum than of most other gem minerals, for it is among the most widely

occurring but least commonly transparent minerals. The right conditions seem to occur

most frequently in the contact metamorphism of certain limestones that recrystallize into

marble. In the process, the necessary impurities in the limestone, mainly aluminium oxide,

are concentrated under conditions that permit them to crystallize as corrundum.

Corrundum also occurs in a variety of aluminium rich igneous rocks. There are some

pegmatite dikes (Fig.2) bearing a higher than ordinary percentage of aluminium in which

gem quality material was formed. Also it is occasionally found in very basic igneous rocks.

Corrundum is next to Diamond, in the grade of hardness. Many gems obtained from

Illama show round or oval shapes due to rolling in river beds and streams. But often

corundum gives a crystal form due to its hardness.

 Some Characteristics of Corundum

Corundum

Ruby Sapphire

— blue sapphire

— yellow sapphire

Star stones -.golden sapphire

—white sapphire

_ padmaraja

Star blue sapphire —white blue

—yellow blue

Star red Ruby — Geuda

Chemical Composition : AL2O3

The colour caused by chromium oxide in the red; titanium and iron oxide

in the blue, iron oxide in the yellow, clrromium and iron oxide in the

orange, iron and titanium oxide in the green and chromium, titanium

and iron oxide in the purple.

Crystallographic Character :

Hexagonee system - usually occurs in a double pyramid with

twelve inclined faces

Hardness : (Diamond has 10)

Specific Gravity : Ruby : 3,95 to 4,05 Normal 4,00

Sapphire : 3,95 to 4,03 Normal 3,99

Characteristic Inclusions

Needlelike rutile crystals

- zircon crystals

- spinel crystals
 - mica crystals

- hematite slabs

- garnet grains

- liquid and gas filled inclusions

Degree of Transparency : Transparent to opaque

Retractive Index : 1,762- 1,770

 Table 1 : Gems in Sri Lanka

Mineral Chemical formula Variety

Silicates
Feldspar Orthoclase
Moonstone
Olivine (Mg, Fe ) [Sio ] 2 4

Garnet Mg Al (Si0 ] 3 2 4 3 Pyrope

Fe Al [Si0 ]
3 2 4 3 Almandine
Ca Al [Si0 ]
3 2 4 3 Grossularite
Mn Al [Si0 ] 3 2 4 3 Spessartite
Zircon Zr[Si0 ] 4

Titanite CaTi[0/Si0 ] ' 4

(sphene)
Andalusite Al [0/Si0 ]
2 4

Sillimanite Al [Si0 ]
2 6

(Fibrolite)
Topaz A1 [F /Si0 ]
2 2 4

Kornerupine Mg Al6[(0,OH) /B0 /(Si0 ) ]

4 2 4 4 4

Danburite CaB (Si0 ) 2 4 2

Epidote Ca (Fe,Al)Al [0/OH/Si0 [Si 0 l

2 2 4 2 7

Ekanite K (Ca,Na) ThfSisOzo] 2

Beryl A^BesfSieOig] Aquamarine

Cordierite Mg Al3[Al SU0 ]
2 18

(Iolite)
Tourmaline (Na,Ca) (Li Mg,Fe Al) B Si6(0,OH) i ) ) 9 3 3 Schrol
Axinite Ca (Mn,Fe) Al Al [B0 OH/Si40 ]
2 3 12 Uwait
Pyroxene LiAl[Si 0 ] 2 6 Spodumene
Mg [Si 0 ]
2 2 6 Enstatite
(Fe, Mg) [Si 0 l 2 2 5 Hypersthens
CaMg (Si0 ) 3 2 Diopside
Scapolite

Haloids (Na,Ca) [(Cl ,S0 C0 ) _ 8 2 4> 3 1 2 (ALi_ Si _ 0 ) ] 2 3 2 8 6

Fluorite
CaF 2
 Sulphides
Chalcopyrite Cu Fe S 2

Marcasite FeS 2

Pyrites Fe S 2

Oxides
Quartz Si0 2 Rock crystal, Amethyst
Rose-quartz, Smoky-quartz,
Brown-quartz, Citrine
Quartz with inclusions Quartz - Cat's eye
Quartz - Tiger's eye
Quartz Chalcedony, Jasper,
(Cryptocrystalline) Agate
Chrysoberyl BeAl 0 2 4 Chrysoberyl Cat's eye
Spinel MgAl 0 2 4 Ceylonite
Taaffeote AUMgBeOs
Corundum A1 0
2 3 Ruby, Star-ruby,
Sapphire, Star sapphire,
Yellow sapphire, Pink sapphire,
Padmaraga
Rutile Ti0 2

Carbonates
Calcite CaC0 3

Phosphates
Apatite Ca(F,Cl)Ca4(P0 )3 4

Monazite Ce(P0 ) 4

Borates
Sinhalite Mg A1(B0 ) 4

Tungsten
Scheelite CaW0 4
 • 80°00' 81°00*

o 10°00'
io ocr
I
WVC-Western Vijayon Complex
EVC-Eastern Vijoyan Complex
H6-Highlond Group
SWG-Soulhwest Group

main gemming areas

study areas

Scale 1:500.000
0 10 20 30 Mis
10 30 50Kms

B0°00 81°00*

Figure 1
LEGEND
 Chemistry of colour of blue sapphires and

heat treatment

A characteristic feature of the transition elements is-the wide variety of colours ex­

hibited by these compounds. The colour of a compound is due to its absorption of visible

light. As you know the visible light (white light) which the human eye can see is composed

of several types of colours. A common demonstration of this is the rainbow where sun­

light gets dispersed by tiny droplets of water giving the characteristic colours from violet

to red. Transtion metals have d orbitals and transitions between different d orbitals can

occur with absorption of light in the visible region. The colour of a compound that is

absorbing light in the visible region is the complement of the absorbed light. For example
3 +
an aqueous solution containing T i is violet in colour which is due to the absorption of

most of the green and yellow light and the transmission of blue and some red. In simple

terms, coloured compounds absorb some colours of visible light and the transmitted colour

is what the human eye sees as the colour of a particular compound.

The beautiful colours of gems are due to the presence of traces of transition elements

in them. Most gems are mixed oxide crystals (silicates, aluminosilicates, borosilicates,

alumina, silica). These aluminosilicates and pure oxides like corundum (aluminium oxide)

are white. However in the presence of traces of transition elements such as iron, titanium,

and chronium, these compounds exhibit brilliant colours. Some examples are given in table

1.

Blue sapphires contain small amounts of iron and titanium as impurity ions. Their

combined percentage concentration is generally less than 1%. It has been found that both

iron and titanium are necessary for a sapphire to exhibit the blue colour. However some
3 +
synthetic corrundum samples with T i incorporated into it also show the characteristic

blue colour. The oxidation states of iron and titanium in blue sapphire are not well
2 + 3 +
established. It is quite possible that all four possible oxidation states, i.e. F e , F e ,
4 + 3 +
Ti , Ti may be present and their relative concentrations are important factors in

determining colour.
 Scientists have explained the origin of blue colour as due to the absorption of visible
2 + 4 +
light by the ion-pair F e /Ti . An electron transfer arising from this light absorption
3 + 3 +
results in F e /Ti . The question of the origin of colour of blue sapphire is not fully

established.

Chemistry of geuda heat treatment

The white sapphire popularly known as geuda has the same basic structure of corun­

dum as the blue sapphire. However these stones appear as white, pale blue or colourless

stones with silkiness. The stone is not clear and various non-uniform inclusions are gener­

ally present.

The geuda stones until 1970 were generally discarded as valueless stones. Then the

Thai gem merchants started buying the geuda stones oh a large scale. The Thai gem

traders having masterminded the technique of geuda heat treatment to convert them to

valuable blue sapphire, were buying these geuda to be exported to Thailand. The Thais

used empty tar barrels lined with bricks to heat geuda stones. A burner using LP gas

and oxygen was generally employed for heating geuda placed in an alumina crucible. The

exact details of the heat treatment remained a close secret among the Thai gem traders.

However, since then several Sri Lankans have mastered this technique and heat treatment

is done fairly extensively in Sri Lanka. The furnaces used in Sri Lanka are made in Sri

Lanka. There are many varieties available. Out of these the Lakmini furnace manufactured

by Ceylon Ceramics Limited is most popular.

The geuda heat treatment requires heating geuda stones placed in an alumina crucible

to a temperature of around 1850°c initially. The stones are next maintained at a tempera­

ture of about 1700 - 1800°c for several hours. The exact temperature and the duration of

heating depends on the type of geuda to be heated. Another important requirement is that

the stones should be heated in a reducing atmosphere. The carbon monoxide formed in

the combustion of LP gas with oxygen provides the reducing atmosphere necessary. How­

ever higher temperatures generally jequire more oxidizing conditions and this can cause

the appearance of white colour again. Thus carefully controlled conditions are absolutely
 essential for a successful heat treatment.

What happens during heat treatment? Several things may happen.

3 +
Since the geuda stones are normally heated in a reducing atmosphere some F e can
2 + 2 + 4 + 2 + 4 +
be converted to F e . Now with both F e and T i present, F e - Ti interaction

becomes possible. This is called a charge-transfer transition which results in blue colour
3 + 4 +
(Note that the presence of F e can impart only a pale yellow colour while T i does not

give any colour). If the iron concentration is high relative to titanium, after reduction, a
2 +
yellow or a green (due to F e ) sapphire may result. If the titanium content is higher,

then asterism or the formation of a white star like appearance may result. This may also
3 + 4 +
cause silkiness to reappear. In this process atmospheric oxygen converts T i to T i

which appears as T i 0 . 2

2Ti 0 2 3 + 0 2 — • 4Ti0 2

Ti0 2 separates as needles, silkiness or star like structures. These features are not

desirable in the geuda heat treatment since a clear blue coloured stone is the ultimate

goal. Such features can be removed by reheating the stones above 1600°c and cooling

rapidly so as to prevent entry of oxygen.

Another possibility regarding the chemical reactions which occur during heat treat­
3
ment is as follows. Under reducing condition T i + is produced by the following reactions.

2
O - —• l/20 2 +2e
3 2 +
Fe + + e — * F e
4 + 3
Ti + e — • Ti +
2 4 3 + 3 +
Fe + + T i + — • T i + Fe

The last reaction usually goes in the opposite direction. However at elevated temper­

atures and strongly reducing conditions, it may well be possible. Thus basic research into

what exactly takes place during heat treatment is quite important.

The Institute of Fundamental Studies has initiated a research programme to study

such scientific aspects such as original of the colour of blue sapphire and the chemistry of

the heat treatment process.

Heat treatment of other gems

Heat treatments of most gems have been practiced for a very long time Red agate and

carnelian that have been heat treated to enhance colour are reported to have been found in

Tutankhamen's tomb (about 1300 BC). During this century Wild made a scientific study

on the effect of heat on a variety of gems in 1932. Heat treatment is widely practiced by

gem producing countries and exporting countries in order to enhance colour and improve

clarity. The deep blue (almost black) Australian sapphires can be lightened by heating

under oxidizing conditions. Table 2 gives some examples for such processes.
Table 1. Colouring ions in gems

Gem Basic Structure Transition

Metal ions

Emerald Beryllium alumino 3

Cr +

silicate

Blue sapphire Corundum (aluminium 3 + 4

F e , Ti +

oxide)

Ruby Corrundum 3
Cr +

Alexandrite, cats eye Beryl (Beo A 1 0 )

2 3
3 +
Fe , Cr 3 +

Table 2 - Major changes on heating gemstones

Type of gem Change upon heating

Beryl, agnamarine green to blue, yellow to colourless,

orange to pink

Corrundum, ruby purple to brown to red

pink to orange

Quartz, amethyst colourless, yellow-brown, green

or milky

Carnelian Yellow, brown or red

Topaz Yellow, brown, blue

to colourless

Tourmaline Blue or blue green green,

red to pale red or colourless

Zircon Brown to reddish, green

to blue or yellow