(1982) Henry A Hanni writes:
For the past two years blue sapphires with good color and pleasing size have become more abundant in the trade. Surprisingly, these stones are offered in lots in which the individual stones are uniformly colored. This is not common with larger gems of high value. Initially, we dealt with such sapphires very carefully and objectively due to a vague suspicion.
During the course of our investigation (Bosshart 1981) the subject of heat treatment of corundum has been brought up at various international meetings of gemologists. Finally, Nassau, Crowningshield and Liddicoat went public with some presentations, which if not quite complete are fairly comprehensive. This report is supplementary state of the author to a recent publication (Hanni 1982).
Heat treatment of corundum has long been practiced, on the one hand after indigenous methods in the countries of origin (i.e. Sri Lanka), on the other hand after an industrial method employed since 1973. With local methods, controlling of temperature and environment is not satisfactorily possible. Because of this, the results are unreliable. Application of the industrial method, carried out in the USA and Thailand, guarantees constant, controlled conditions and leads to the desired results. Let us consider the patents of Union Carbide in 1973 as a starting point. In these patents, techniques are described which allow (at first applied to synthetics only) a homogenization or improvement of the color or the development of asterism. Over the last years, these processes have been tried and improved on natural corundum. Presently, masters of such techniques reside in Thailand. Their latest surprising creations are yellow to orange corundums produced by heat treating raw material corundum of an as yet undescribed type.
The aim of heat treatment is to reach a uniform distribution of color, to clarify or to increase the color, or to attain better purity by dissolving certain inclusions. Critical is whether these stones have absorbed foreign matter during the process of heat treatment, or the required improvement was achieved with those components already present in the stone. Recently, Dr Nassau has reviewed the different processes (Nassau 1981, tab 1). These nine types of treatment may be divided into two groups: With Nos. 1-6, a simple heating occurs; with Nos. 7-9, color producing chemicals are added during the process. Case No.6 may be regarded separately, since with this treatment, natural-looking fingerprint inclusions are generated in synthetic stones.
Heat treatment
This represents a normal annealing (but an extremely high temperature), a process which is well-known and applied to amethyst, zircon, topaz, tourmaline, etc. The new color is considered to be stable. Corundum treated after the processes Nos. 1-5 may be traded without complementary designation according to the regulations of CIBJO colored stones commission (CIBJO 1981).
For example, process No. 3 can be demonstrated with blue sapphire as follows: iron and titanium in the form of Fe/Ti-pairs in the corundum crystal lattice are responsible for the blue color in sapphires (Schmetzer & Bank, 1981). If one of the two partners is less abundant, its deficiency cannot be compensated by addition of the other partner. The solubility of iron and titanium is higher at high temperatures than at low temperatures. If a corundum saturated in Fe and Ti cools slowly, TiO2 is able to unmix from the corundum lattice as rutile (or silk). In this way, Ti is eliminated as a color producing component. On the other hand, by reductive heating a light blue rutile containing corundum to 1600°C and cooling it rapidly, one may obtain stones with intense blue color and a better transparency. The rutile has dissolved and joined with the possibly present iron to form the color yielding Fe/Ti pairs (Fe²+ / Ti4+ charge transfer).
Heat treatment processes used on sapphires and rubies (after K Nassau, 1981)
1. Treatment: Heating only
Specific process: Moderate temperature (1300°C)
Result: Develops potential asterism
2. Treatment: Heating only
Specific process: High temperature (1600°C) / rapid cooling
Result: Removes silk and asterism
3. Treatment: Heating only
Specific process: Reductive heating (1600°C)
Result: Develops potential blue color
4. Treatment: Heating only
Specific process: Oxidative heating (1600°C)
Result: Diminishes blue color
5. Treatment: Heating only
Specific process: Extended heating (1800°C)
Result: Diminishes Verneuil banding and strain
6. Treatment: Heating under unknown conditions (this process is used on synthetic material to generate inclusions with a natural appearance)
Specific process: ?
Result: Introduces fingerprint inclusions
7. Treatment: Diffusion of impurities into the material (extended heating at 1800°C)
Specific process: Add TiO2
Result: Produces asterism
8. Treatment: Diffusion of impurities into the material (extended heating at 1800°C)
Specific process: Add TiO2 and / or Fe2 O3
Result: Produces blue color
9. Treatment: Diffusion of impurities into the material (extended heating at 1800°C)
Specific process: Add Cr2 O3, NiO, etc
Result: Produces other colors
Diffusion treatment
Method Nos. 7-9 are completely different from the above because minute quantities of ‘trace elements’ are added during the process. Proof of such a treatment is important for more than commercial reasons, since these products must be labeled ‘treated corundum’ according to the rules of CIBJO. The introduction of the ‘traces’ is diffusion induced. At the high temperature of 1700°C, the crystal lattice of corundum is somewhat expanded. The atoms are more mobile and interatomic distances enlarged relative to the cold state. Under conditions near the melting point, the iron or titanium present in higher concentrations outside the crystal is able to travel a short distance into the crystal. The depth of this diffusion process is dependant on the temperature and the duration of the treatment. Partial melting at the surface is frequently brought about by the strong heating, as well as by the reduction in melting point temperature caused by ‘trace elements’. The polished faces of a stone are dotted with tiny pits and droplets and must be repolished.
However, the diffusion treatment only reaches superficial areas. By replolishing a diffusion-treated corundum, its former colorlessness may be brought out again.
Occasionally, diffusion-treated corundums are incorrectly termed ‘coated sapphires’. In contrast to beryl with an overgrowth of synthetic emerald (after Lechleitner), diffusion-treated corundum does not display a ‘cultivated’ layer, but a barely measurable quantity of color has been soaked by the surface.
The diffusion method is not only used for producing blue corundum but is also employed with other elements to produce red (chromium), padparadscha and other colors.
Features of heat treated corundums
The raw material from which the following features are described are sapphires from Sri Lanka. They form the bulk of treatable material which reaches a high quality. Initially, these sapphires were weak in color, partially interspersed with silk, colored in narrow bands only, or of a yellowish cloudiness. With the sudden and intense heating which usually last one to two days, tension fractures may develop. Endangered regions are located at material inhomogenities. Therefore, tension cracks will most probably develop around inclusions and at the surface. The differential dilations of mineral, gas, and fluid inclusions contribute additionally to the formation of fissures. This mechanism occurs in nature during the metamorphism of rocks. But due to the rapid rates of artificial heating, these inclusions differ from those seen in natural stones. This is evident when comparing pictures of untreated corundums (Gubelin, 1973) with those presented in this paper.
In addition to the change of the original inclusions, we recognize the development of new forms of inclusions, for example, altered zonal structures of possibly former rutile; white spheric aggregates with a thorny surface. These ‘ping-pong balls’ frequently are surrounded by disc-shaped tension fissures. They resemble the natural, structured healing fissures in untreated Sri Lankan sapphires. Normally, the subtle healing fissures similar to insect wings transform to more bulky forms as hoses or rows of droplets; may show a type of tension crack for corundum, but similar to those seen in peridot. These fissures are again disc-shaped, iridescent and resemble atolls. Frequently, the center contains a tiny grain. The fissures are smooth and structured at the periphery only. A further feature of heat treated corundums is the grainy, pockmarked surface.
Normally, all facets or parts of the girdle are overlooked. The repolished girdle frequently is composed of several steps.
Features of diffusion treated corundums
A dark ring rimming the stone near the girdle is the first recognizable characteristic in diffusion treated stones. This sign is visible with the naked eye. In this zone, the stone is thin and the effect of the diffusion-layer is more prominent. In the center, we find in many cases a ‘hole’ of color. Here the effect of the diffusion layer is weakest. The girdle may appear colorless if the diffusion layer has been removed totally when repolished. Damaged spots and small pits in the surface of a pre-cut stone ready for treatment facilitate reinforced absorption of the coloring elements. A crack, i.e contact of two surfaces leads to a double diffusion layer, and therefore to a stronger color reception. Also concentrations of color in depressions are frequently encountered.
The recognition of corundum colored by a diffusion process should not present great difficulties. In most cases it will suffice to look at the stones in front of a diffusely bright background when they are immersed in a liquid with a high refractive index. At low magnification, the stronger colored facet edges are easily visible. Also, due to unequal forces applied during the repolishing, the differences in saturation of the individual facets are visible in immersion.
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