Manataka American Indian Council
Synthetic and Simulant
Synthetic and simulant are terminology used by the USBM for laboratory grown gemstones. Others in the gemstones industry may use different terms to refer to laboratory grown gemstones. Laboratory grown synthetic gemstones have essentially the same appearance and optical, physical, and chemical properties as the natural material that they represent. Synthetic gemstones produced in the United States include alexandrite, coral, diamond, emerald, garnet, lapis lazuli, quartz, ruby, sapphire, spinel, and turquoise. Laboratory grown simulants have an appearance similar to that of a natural gemstone but have different optical, physical, and chemical properties. The gemstone simulants produced in the United States include coral, cubic zirconia, lapis lazuli, malachite, and turquoise. Additionally, certain colors of synthetic sapphire and spinel, used to represent other gemstones, would be classed as simulants. Colored and colorless varieties of cubic zirconia are the major simulants produced.
In the past few years, the use and consumer acceptance of synthetic and simulant gemstones have grown. Much of this growth is the direct result of the recognition of these gemstones for their own merits, not just as inexpensive substitutes for natural gemstones. In 1993, the reported value of production of U.S. synthetic and simulant materials was $17.9 million, about a 5% decrease from that of 1992, according to the USBM. Since the USBM began collecting data on the value of production of synthetic and simulant gemstones in 1986, the U.S. production has averaged about $17.0 million per year, with a low of $10.3 million in 1986 and a high of $20.5 million in 1990. During the past 5 years, the annual value of production has averaged $18.8 million with annual increases or decreases from 5% to 13%.
Figure 10. -- Synthetic ruby.
(Photo is courtesy of J.O. Crystals.)
Synthetic and simulant gemstone producers use many different production methods, but they can be grouped into one of three types of processes: melt growth, solution growth, or extremely high-temperature, high-pressure growth.
The year 1902 saw the first production of synthetic ruby using the Verneuil flame-fusion process. Later, sapphire, spinel, rutile, and strontium titanate were grown with this technique. In this process, a single crystal, called a boule, forms in the flame of a simple, downward-impinging oxygen-hydrogen blowtorch. Pure oxides of aluminum (in the cases of ruby, sapphire, and spinel) or titanium (rutile and strontium titanate) are poured into the top of a small furnace and melted. Other oxides are added as needed for process control and to obtain the specific color desired. The melted material solidifies as a boule on a rotating fire-clay peg as the peg is slowly withdrawn. A boule has a very characteristic shape, with a rounded end, a long cylindrical body, and a tapering end. It is usually about 13 to 25 millimeters in diameter, 50 to 100 millimeters long, and weighs 75 to 250 carats.
Another melt technique is the Bridgman-Stockbarge solidification method, named for an American, P.W. Bridgman, and a German, D.C. Stockbarge, who, aided by three Russians, J. Obreimov, G. Tammann, and L. Shubnikov, discovered and perfected the process between 1924 and 1936. Currently, the method is used primarily for growing nongem halide, sulfide, and various metallic oxide crystals, one of the metallic oxides being aluminum oxide or sapphire.
The Bridgman-Stockbarge process uses a specially shaped crucible, which is a cylindrical tube open at one end and capped at the other by a small, pointed cone. The crucible is filled with the powdered chemicals necessary to grow a specific crystal and is lowered slowly through a furnace. The small, pointed end of the cone cools first because it is the first part of the crucible that moves from the hottest part of the furnace into cooler regions and it is the first part to emerge from the furnace. As the crucible cools, the molten materials solidify, hopefully in a single crystal, in the point of the crucible. The crystal then acts as a seed around which the remainder of the molten material solidifies until the entire melt has frozen, filling the container with a single crystal.
This process is simple, and crystals of various sizes can be grown. The crystals are typically about 50 millimeters in diameter and 15 millimeters in length, but large ones exceeding 890 millimeters in diameter and weighing more than 1,000 kilograms have been grown. The crystals have the same shape as the crucible.
The Czochralski pulled-growth method is used for ruby, sapphire, spinel, yttrium-aluminum-garnet (YAG), gadolinium-gallium-garnet (GGG), and alexandrite. Czochralski developed his method in about 1917.
In the Czochralski method, ingredient powders--nutrients--are melted in a platinum, iridium, graphite, or ceramic crucible. A seed crystal is attached to one end of a rotating rod, the rod is lowered into the crucible until the seed just touches the melt, and then the rod is slowly withdrawn. The crystal grows as the seed pulls materials from the melt, and the material cools and solidifies. Yet, because of surface tension of the melt, the growing crystal stays in contact with the molten material and continues to grow until the melt is depleted.
Typically, the seed is pulled from the melt at a rate of 1 to 100 millimeters per hour. Crystals grown using this method can be very large, more than 50 millimeters in diameter and 1 meter in length, and of very high purity. Each year producers using this method grow millions of carats of crystals.
Certain gemstones pose unique problems when attempts are made to grow them. The problems arise because certain materials are either so reactive that they cannot be melted even in unreactive platinum and iridium crucibles or they melt at higher temperatures than the crucible materials can endure. Therefore, another melting system must be used, called the skull melting system. Cubic zirconia, because of its high melting point must be grown using the skull melting method.
The "skull" is a hollow-walled copper cup. Water is circulated through the hollow walls to cool the inside wall of the skull. The cup is filled with powdered ingredients and heated by radio frequency induction until the powders melt. Because the water cools the walls of the skull, the powdered materials next to the walls do not melt, and the molten material is contained within a shell of unmelted material. Therefore, the reactive or high-temperature melt is contained within itself. When the heat source is removed and the system is allowed to cool, crystals form by nucleation and grow until the entire melt solidifies. Crystals grown using this system vary in size, depending on the number of nucleations. In growing cubic zirconia, a single skull yields about 1 kg of material per cycle.
Solution techniques for making synthetic gems include flux methods for emerald, ruby, sapphire, spinel, YAG, GGG, and alexandrite. The other solution method is the hydrothermal method, often used for growing beryl (emerald, aquamarine, and morganite) and quartz.
Quartz crystals are grown in a hydrothermal solution in large pressure vessels known as autoclaves. Careful control of temperature and pressure in the different areas of the autoclave result in the feed material, known as lascas, dissolving in the hotter portion. The material redeposits on seed crystals, located in the cooler portion, forming synthetic quartz crystals. The process usually takes 30 to 60 days for the crystals to reach the desired size. The process can produce rock crystal, amethyst, and citrine, or in some cases blue or green quartz with no natural counterpart The same system is used to grow beryl crystals.
Other techniques involve solid- or liquid-state reactions and phase transformations for jade and lapis lazuli; vapor phase deposition for ruby and sapphire; ceramics for turquoise, lapis lazuli, and coral; and others for opal, or glass and plastics simulants or imitations.
The Verneuil, Czochralski, and skull melting processes are the melt techniques most often used for gem materials.
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