Seeking Low-Cost Perfection: Synthetic Gems Robert E. Kane* 1811-5209/09/0005-0169$2.50 DOI: 10.2113/gselements.5.3.169 S ynthetic gems are superlative examples of crystal growth. Today, industrial and scientific crystal growth is a highly sophisticated endeavor employing a wide range of methods. Many of these have been adapted to grow gems for jewelry use. Most major gemstones have been synthesized, and these products are commercially available around the world, often at a fraction of the cost of a natural gem of comparable size and quality. Distinguishing them from their natural equivalents involves a number of interesting challenges. Inclusions (internal features) observed by microscopy often provide conclusive proof of synthetic origin. When routine testing procedures (refractive index, specific gravity, fluorescence, and internal inclusions) do not provide sufficient evidence, laboratories must employ more advanced analytical instrumentation. Keywords : gemstone, synthetic gem, man-made gem, laboratory-grown gem, gem testing, gemology Why Synthetic Gemstones? Synthetic gemstones are produced in a laboratory—they are gems made by man (Fig. 1). They have essentially the same chemical composition and crystal structure as their natural counterparts. Thus synthetic gems closely duplicate the physical and optical properties of natural stones. Gemological guidelines dictate that the name of a man-made gem be preceded by the word synthetic (e.g. synthetic ruby), though many manufacturers use the terms created or cultured (e.g. created emerald). Scientists often ask why synthetic gems are considered in such a different light from natural gems, since they are chemically and crystallographically analogous to the natural gems. In fact, the physical and optical properties of synthetics are often “better” than those of natural gems: larger dimensions, better and more homogeneous color, and fewer inclusions. But since the creation of the first modern synthetic gem circa 1885, the “Geneva ruby” (see Fritsch and Rondeau 2009 this issue), manufactured gems have always sold at significantly lower prices than natural gems of equal size and quality. A rather dramatic example was provided in 2006 by an 8.62-carat untreated Burmese ruby that sold at Christie’s for a world-record price of $3.6 million, a staggering $420,000 per carat. A comparable Verneuil (see Table 1) synthetic ruby retails for around $6 per carat, and a similar flux-grown synthetic ruby commands approximately $650 per carat. The vast majority of buyers value the authenticity of a natural gem over the “perfection” of its synthetic counterpart. It is often a question of affordability—when given the choice, most of us would choose a natural product, * Fine Gems International P.O. Box 1710, Helena, Montana 59624, USA E-mail: [email protected] E lements , V ol . 5, pp. 169–174 whether it is a natural granite countertop over a man-made Formica one, or a natural emerald over a synthetic one. Rarity is also a factor—fine-quality natural gem stones are rare, whereas their man-made analogues can be massproduced. Hundreds of minerals have been synthesized for experimental and industrial applications—often as crystals too small to be faceted or not of gem quality, or as species not typically used as gemstones. Table 2 lists the major gem materials and when they were first synthesized. Historically, many of the breakthroughs in gem synthesis have been a direct result of the synthetic-gemstone manufacturer’s own investigations and pioneering research. For example, Carroll Chatham, founder of Chatham Created Gems, brought to market the first commercially available, faceted, flux-grown, synthetic emeralds in the 1940s. However, many synthetic minerals were originally developed through experimental petrology; for example, tourmaline was synthesized to study the origin of color in tourmaline (Barnes 1950; Taran et al. 1990, 1993, 1996). These man-made tourmalines were overgrowths on the order of 1 mm or less in thickness, and thus synthetic tourmaline has not yet reached the size and quality required for the gem market. Also, the initial synthesis of opal helped in the in-depth understanding of the unique structure of natural opal (Jones et al. 1964) and led to further development of photonic crystals, which currently have widespread technological applications. Interestingly, although patents for a technique to grow opal were filed by the Australian organization CSIRO in 1964, it was not until 10 years later that the French synthetic emerald maker Pierre Gilson finally learned how to produce man-made opals that were stable, beautiful, and large enough for use in jewelry. In contrast, synthetic sodalite was grown hydrothermally by the Chinese for gemological applications (which apparently never came to be), but may ultimately be of interest to materials scientists (see, for example, Trill et al. 1999). For the past several decades, many of the advances in gem synthesis have been by-products of technological research, particularly in the field of lasers. Indeed, ruby and emerald make excellent solid-state lasers when the crystals are large and homogeneous. Contributions also came from the semiconductor industry (most recently with moissanite, SiC), and work on integrated circuits, microelectronics, computer memory devices, and the like. In many instances, these 169 J une 2009 16 17 1 13 2 3 18 15 21 14 6 19 7 5 22 20 4 10 23 9 8 11 12 25 Primary Methods of Gem Crystal Growth Different laboratory gem-manufacturing techniques often employ specific growth methods, which produce synthetic gems with predictable features: characteristic crystal habits and most notably typical inclusions. Understanding these often enables the gemologist to identify the growth method and the specific manufacturer. Shown here are synthetic flux-grown emeralds produced by Gilson (3, 6, 7), Seiko (5), Lennix (8), Inamori (9), and Chatham (10, 11, 12), as well as Russian hydrothermal (1, 2) and Russian flux (4) synthetic emeralds. The blue synthetic sapphire crystals (13, 15) were grown by Chatham in a flux environment, and the faceted blue sapphire (14) by a melt method. The synthetic rubies were made by several methods: Russian hydrothermal (16, 17), Chatham flux (19, 22), Douros flux (18, 21), Ramaura flux (20, 23), and Kashan flux (24, 25). The faceted synthetic stones range in weight from 1.21 to 6.57 cts, and the synthetic crystals range from 10.21 to 482.51 cts. Synthetics courtesy of Thomas Chatham ; photo © Tino H ammid and Robert E. K ane Figure 1 Today, industrial and scientific crystal growth around the world is a highly sophisticated endeavor employing many different methods. Many of these have been adapted to grow gems. The groupings in Table 1 (adapted from Nassau 1980) illustrate some of the major techniques utilized by professional crystal growers. developments originated from billion-dollar corporations investing hundreds of millions of dollars in crystal-growth research. In contrast to the very small number of jewelryquality synthetic gem manufacturers, many thousands of researchers worldwide are involved in industrial crystal growth. The general public is unaware that man-made crystals influence virtually every aspect of modern living, either directly or indirectly. More than 400 tons of synthetic diamonds are produced each year for industrial use, such as in machining and cutting tools. Man-made crystals help to regulate our cities’ power supplies. They play an integral part in the systems used to manage our financial centers and credit card purchases; enable operation of our cell phones, digital cameras, televisions, and (synthetic) quartz watches; supervise communications; direct airline traffic; and help diagnose and cure diseases. As some of these synthesis technologies make their way into gem and jewelry applications, the gemologist is faced with increasingly difficult challenges when it comes to differentiating between synthetic and natural gems. In gem synthesis, there have been more developments in the last two decades than in the previous 50 years. E lements 24 Melt techniques are among the oldest and simplest—they require that the gem species melts congruently. Melt techniques are commonly employed to grow ruby, sapphire, chrysoberyl (alexandrite), and many crystals with a garnet structure (e.g. yttrium aluminum garnet, YAG). For those gems that melt incongruently—for example beryl—solution growth (in particular, under hydrothermal conditions) comes close to their natural conditions of formation. Some gem materials can be synthesized only by a single method; synthetic moissanite, for example, requires sublimation (Table 1), and cubic zirconia requires skull melting (Table 1; Fig. 2). Others, in particular synthetic ruby, are grown by a variety of methods—for example, melt crystallization (flame fusion or Verneuil), hydrothermal solution, and flux growth (Fig. 3). In general, melt-crystallization techniques are low-cost and high-volume, yielding very inexpensive synthetic rubies and sapphires. Synthetic rubies and sapphires grown by hydrothermal solution or flux solution, on the other hand, are high-cost and low-volume. The synthetic stones produced by these methods can cost as much as a hundred times more than a melt-grown ruby or sapphire. Also, the synthesis of diamond by high-pressure and hightemperature solution growth (Fig. 4) requires very expensive equipment. 170 J une 2009 Table 1 General Categories of Gem and Mineral Crystal-Growth Techniques A Melt growth Solidification in a container Czochralski growth (pulling from a seed in contact with the corresponding melt) Verneuil or flame-fusion growth (projecting molten oxides from a flame on a seed) Zone growth (crystallizing from a seed in a corresponding powder, locally molten) Skull melting (mass crystallization from a molten volume using the same unmelted powder as the crucible) Solution growth Growth from water or other solvents Gel reaction growth Hydrothermal growth (growth in a fluid under an appropriate pressure and temperature) Flux and flux zone growth (growth in an anhydrous molten salt) Growth by electrolysis High-pressure flux growth Vapor phase growth Sublimation growth Growth by reaction in a vapor phase Chemical vapor phase transport growth A dapted from Nassau (1980) Variations Unique to Gem Synthesis Reagent-grade chemicals and controlled conditions enable the gem crystal growers not only to perfect a natural process, but in some cases “improve” upon it by creating unique gems. Exceptionally bright, vivid colors not found in nature can be created in synthetic gems. For example, Co2+ in sufficient quantity can produce an unnaturally bright blue color in hydrothermally grown synthetic quartz. In the hydrothermal beryl crystals grown in Russia, a rich “turquoise” blue has been achieved by adding copper. B While naturally yellow sapphires can be colored by Fe3+, heated dark yellow sapphires owe their color to the O - ion that accompanies Mg2+ in a charge-compensation mechanism (Emmett et al. 2003). The O- ion is also referred to as a trapped hole center. Ni is responsible for the bright lemon yellow of Verneuil-grown (or flame-fusion) synthetic sapphires. The use of alternative color-causing elements might lead a purist to wonder if these are imitations rather than true synthetics, since there are no naturally occurring equivalents. Identification of Synthetic Gemstones Identification of gems is one of the core activities of gemologists (Fritsch and Rondeau 2009 this issue). For much of the twentieth century, the modestly equipped expert gemologist could successfully identify most synthetic gem materials. As the technological sophistication of gem synthesis has increased—exponentially in the case of diamonds—the challenge facing the jeweler-gemologist has also increased. Colorless synthetic cubic zirconia (CZ) is produced annually by the ton for use as a faceted imitation of diamond (A). Numerous colors can be produced to imitate other gem species and varieties. For example, the addition of cobalt produces purple cubic zirconia, and the color becomes a deep blue with increased stabilizer concentration. (B) The irregular shape of the rough CZ crystals is typical of the skull melting method used to grow them. Photo A by Shane F. McClure, courtesy of GIA, and photo B by Tino Hammid Most physical and optical properties of synthetic gems overlap with those of their natural counterparts (with the exception of the presence and nature of internal inclusions). However, a few other differences in properties between natural and synthetic gems also exist. Some hydrothermal synthetic emeralds, such as those made by the Biron Corporation, possess lower refractive indices and birefringence than typical natural emeralds (Kane and Liddicoat 1985). This is also the case with flux-grown synthetic emeralds. These differences in properties can be explained in part by the lesser number of molecules or ions occupying channel positions. E lements Figure 2 Inclusions can often provide conclusive proof of synthetic origin. The first “Geneva rubies” caused panic in the mid1880s among European jewelry dealers because they were initially sold as genuine natural gems. Since then, detailed observation under the microscope and the interpretation of internal features have continued to provide conclusive 171 J une 2009 After decades of anticipation, synthetic diamonds grown under high pressure and high temperature (HP–HT) conditions are now a commercial reality in the international market, both as loose stones and set in jewelry. Shown here are examples of 1.00–1.25 carat synthetic yellow diamond jewelry produced by Gemesis Corp (the colorless diamonds are natural). The unset synthetic diamonds (weighing less than 1.00 carat each) are from Chatham Created Gems and Lucent Diamonds. Composite photo jewelry images courtesy of G emesis Corp. Loose diamond photos by H arold and Erica Van Pelt; courtesy of GIA Figure 4 Hand-painted illustration from Edmond Frémy’s 1891 book on the synthesis of ruby. In 1887, Frémy and Feil were the first to synthesize ruby by the flux method. This rare plate shows tiny flux-grown synthetic rubies filling a crucible, as well as beautiful examples of 19th century French-made jewelry set with Frémy’s faceted flux-grown synthetic rubies. Courtesy of GIA Figure 3 proof of synthesis in many types of man-made gems (Fig. 5). The appearance and nature of healed fractures, as well as the presence of minute amounts of flux or crucible material, are particularly helpful in the identification of synthetic gems. The inclusions present in a synthetic gemstone are often characteristic of a particular laboratory growth method (see, for example, Sunagawa 2005). Rubies and blue sapphires grown by the flame-fusion melt method often show curved growth layers and spherical, elongated, or distorted gas bubbles. Those produced by flux melt techniques frequently reveal residual unmelted flux, or inclusions of flux with a retraction bubble (due to volume loss during cooling to room temperature). Hydrothermally grown crystals often display “chevron-like,” “mosaic,” or “zigzag” growth structures. These are phantom features of fast-growing faces that are not smooth but covered by growth hillocks centered on spiral dislocations. When routine, standard testing procedures—refractive index, specific gravity, fluorescence, internal inclusions observed by microscopy—do not provide sufficient evidence to determine the synthetic or natural origin of a gemstone, E lements laboratories must employ more advanced analytical instrumentation. For example, separating natural and synthetic rubies on the basis of trace element chemical composition, as determined by energy-dispersive X-ray fluorescence (ED-XRF) spectrometry (Muhlmeister et al. 1998; Devouard and Notari 2009 this issue; Rossman 2009 this issue). Natural alexandrite contains water, whereas most synthetic alexandrite results from melt growth and is therefore anhydrous. The difference is clearly seen using infrared spectroscopy (Stockton and Kane 1988). The same technique can be applied to synthetic emeralds. Hydrothermally grown emeralds, although they contain water, always show small differences compared to their natural counterparts in the presence, speciation, and topological orientation of water (see, for example, Schmetzer 1989; Bellatreccia et al. 2008), as revealed by the presence or absence of certain infrared absorption spectral features. Nondestructive, rapid identification of mineral inclusions within faceted gemstones by Raman microspectroscopy (Fritsch and Rossman 1990) can indicate whether the stone was grown in nature or the laboratory. Chemical fingerprinting by laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) can help to distinguish a natural from a synthetic origin for various gem species and varieties (Günther and Kane 1999). The identification of synthetic diamonds is aided by methods such as visible light, infrared, and photoluminescence spectroscopy (Shigley 2005). Conclusions Man-made gemstones have a legitimate place in the market. The concern is not the manufacture of these scientific marvels, but the unscrupulous selling of them as natural stones. As technological innovation continues to produce extraordinary synthetic diamonds and synthetic colored gemstones, research facilities around the world will continue meeting the identification challenges they present with practical and advanced analytical testing methods. By doing so, public trust in the authenticity of gemstones and jewelry will be maintained. 172 J une 2009 Table 2 A B Chronology of the Synthesis of Major Gemstones Approximate year of Synthetica availability gemstone in quantity Chemical formula Manufacturing technique 1885 1887 1905 1910 1910 1935c 1947 1948 1950 Ruby (Geneva) Rubyb (Frémy and Feil) Ruby Sapphire Spinel Emerald Star ruby and sapphire Rutiled Quartz Strontium titanate (not sphene) a,d Rubyd,e,f (Remeika U.S. patent) Emerald YAGa (yttrium aluminum “garnet”) Al2O3 Al2O3 Al2O3 Al2O3 MgAl2O 4 Be3Al2Si6O18 Al2O3 TiO2 SiO2 Crucible (melt) Flux (solution) Verneuil (melt) Verneuil (melt) Verneuil (melt) Flux (solution) Verneuil (melt) Verneuil (melt) Hydrothermal (solution) SrTiO3 Verneuil (melt) Al2O3 Flux (solution) Be3Al2Si6O18 1970 Diamondd,e,g C 1972 1973 1974 1974 1975 Cu2+ Al6 (PO4) 4 (OH) 8.4H2O BeAl2O 4 SiO2.nH2O SiO2 SiO2 1976 1976 Turquoise Alexandrite Opalh Citrine (quartz) Amethyst (quartz) GGGa (gadolinium gallium “garnet”) Lapis lazulia,i Cubic zirconiad 1976 Alexandrited BeAl2O 4 1978 1981 Corala CaCO3 Be3Al2Si6O18 Hydrothermal (solution) Czochralski pulling (melt) High Pressure and high temperature (solution) Ceramic Flux (solution) Aqueous solution Hydrothermal (solution) Hydrothermal (solution) Czochralski pulling (melt) Ceramic Skull Melting (melt) Czochralski pulling (melt) Ceramic Hydrothermal (solution) Al2O3 Flux (solution) Cu2CO3 (OH) 2 BeAl2O 4 Aqueous Solution Zone (melt) Be3Al2Si6O18 Hydrothermal (solution) MgAl2O 4 Al2O3 SiO2 Flux (solution) Hydrothermal (solution) Hydrothermal (solution) SiO2 Hydrothermal (solution) Al2O3 Hydrothermal (solution) SiC (6H polytype) Sublimation (vapor) C CVD (chemical vapor deposition) 1955 1963 1965 1968 C 1975 D Aquamarine e Orange and blue sapphire Malachite Cat’s-eye alexandrite Red beryl (and various other colors) Spinel Ruby Pink quartz Ametrine (citrine and amethyst quartz) Sapphire (various colors) Moissanite j (silicon carbide) 1982 1983 1987 1988 1989 1993 1994 1994 (A) This large “nail-head spicule” in a Biron hydrothermal synthetic emerald consists of a cone-shaped void that is filled with fluid and a gas bubble. Although not visible at this viewing angle, the spicule is capped by a poorly developed, ghost-like phenakite crystal. Dark-field illumination, magnified 50x. (B) This Ramaura flux-grown synthetic ruby displays characteristic, nearly straight, parallel growth bands, which at some viewing angles exhibit unusual iridescence. In this view, the very slight differences in angle between facets cause the growth features to be iridescent in one and not in the others. Dark-field illumination, magnified 50x. (C) The shiny, metallic appearance of platinum is very evident in this large, thick, angular platinum inclusion in a Chatham flux-grown synthetic blue sapphire. Dark-field and fiber-optic illumination, magnified 35x. (D) The finger print appearance of this healed fracture in a flux-grown synthetic sapphire is due to the capture of some flux during crystal growth. Dark-field illumination, magnified 30x. Photomicrographs by Robert E. K ane Figure 5 E lements 1995 1997 2003 Diamond Y3Al5O12 Gd3Ga5O12 (Na,Ca) 8 (Al,Si)12O24 (S,SO 4) ZrO2 + stabilizer The majority of the 1885–1978 data were adapted from Nassau (1980). a Gemologists use the term “imitation” for man-made materials that do not have a naturally occurring equivalent in large crystals (e.g cubic zirconia) or do not share chemistry and crystallographic structure with a natural counterpart (e.g. strontium titanate, YAG, GGG, lapis lazuli, and coral). b Only small flux-grown ruby crystals (>3 mm) c Nassau (1980) reported 1950; however, several gemologists published work on IG-Farben (“Igmerald”) synthetic emeralds in 1935. In 1848 J.J. Ebelman reported success in growing flux synthetic emeralds. However, it was Hautefeuille and Perrey’s 1888 and 1890 published reports that forged the path for all later flux emerald growth. d Process developed for potential technological use e Experimental production only f Modern flux-growth of large ruby crystals g In 1954 General Electric succeeded in synthesizing very tiny (150-micron) diamonds, which were not of gem quality. Although only experimental and not commercially available, 1970 marked the first time that “sizable” faceted synthetic diamonds had been synthesized by General Electric. In 1985, Sumitomo Electric Industries (Japan) began marketing for industrial uses yellow synthetic diamond crystals in sizes up to 2 carats. By 2008, faceted HP–HT synthetic diamonds were available for sale around the world in many colors, including colorless, yellow, brown, blue, pink, red, purple, and green. h The chemical formula listed is for natural opal. Some man-made opals do not contain H O (or as much as natural 2 opals do) and contain ZrO2. Thus they are considered imitations (not synthetics) by some gemologists. i The chemical formula listed is for natural lapis lazuli, which is an aggregate of several minerals, predominantely polycrystalline lazurite. j Synthetic silicon carbide has been produced for technological uses for many decades. However, 1997 marked the first time large, near-colorless crystals were grown for use as faceted imitation diamonds. 173 J une 2009 REFERENCES Barnes WH (1950) An electron microscopic examination of synthetic tourmaline crystals. American Mineralogist 35: 407-411 Bellatreccia F, Della Ventura G, Piccinini M, Grubessi O (2008) Single-crystal polarised-light FTIR study of an historical synthetic water-poor emerald. Neues Jahrbuch für Mineralogie, Abhandlugen 185: 11-16 Devouard B, Notari F (2009) The identification of faceted gemstones: From the naked eye to laboratory techniques. 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Gems & Gemology 34: 80-101 Nassau K (1980) Gems Made by Man. Chilton Book Company, Radnor, PA, 364 pp Rossman GR (2009) The geochemistry of gems and its relevance to gemology: Different traces, different prices. Elements 5: 159-162 Schmetzer K (1989) Types of water in natural and synthetic emerald. Neues Jahrbuch für Mineralogie Mh, pp 15-26 Shigley JE (ed) (2005) Gems & Gemology in Review: Synthetic Diamonds. Gemological Institute of America, Carlsbad, CA, 294 pp NanoGeoScience, University of Stockton CM, Kane RE (1988) The distinction of natural from synthetic alexandrite by infrared spectroscopy. Gems & Gemology 24: 44-46 Sunagawa I (2005) Crystals: Growth, Morphology, Perfection. Cambridge University Press, Cambridge, UK, 295 pp Taran MN. Lebedev AS, Platonov AN (1990) An optical-spectroscopic study of synthetic iron-containing tourmalines. Izvestiya Akademii Nauk SSSR, Neorganicheskie Materialy 26: 1025-1030 Taran MN, Lebedev AS, Platonov AN (1993) Optical absorption spectroscopy of synthetic tourmalines. Physics and Chemistry of Minerals 20: 209-220 Taran MN, Langer K, Platonov AN (1996) Pressure- and temperature-effects on exchange-coupled-pair bands in electronic spectra of some oxygen-based iron-bearing minerals. Physics and Chemistry of Minerals 23: 230-236 Trill H, Eckert H, Srdanov V, Stucky GD (1999) Magnetic iron clusters in sodalites. In: Materials Research Society Symposium Proceedings Series 577, San Francisco, April 5–9, 1999 Copenhagen O ur group is international, with researchers from chemistry, physics, geology, mineralogy, engineering and biology. We work together in a dynamic team to solve questions of relevance to energy and the environment. We combine a unique set of nano-techniques with classical methods to understand the fundamental processes that take place at the fluid (water, gas, oil) interface with Earth materials. Total of 6 to 8 new positions as: Associate Professor, Assistant Professor, Post-Doctoral Fellow, and PhD Student In the following topics: aqueous geochemistry (surface complexation), physics or applied X-ray physics, biochemistry or molecular biology Full details: http://nano.ku.dk/english/nanogeojobs only complete applications will be considered. For questions: Group Leader, Prof. Susan Stipp, [email protected]; +45 35 32 02 02 E lements 174 J une 2009
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