THE IDENTIFICATION OF BLUE DIFFUSION-TREATED SAPPHIRES By Robert E. IZane, Robert C. IZammerling, John I. Koivula, lames E. Shigley, and Emmanuel Fritsch Blue diffusion-treated sapphires are be- he heat treatment of pale, colorless, or milky white coming more prevalent than ever before. T"geuda" sapphires to produce attractive blue stones The diffusion technique, which involves has been practiced for a number of decades. These stones the addition of color-causing chemicnls have become a staple in today's international gem markets. during heat trentment, results in a thin layer of color at the surface of colorless or A different but related color-enhancement technique that light-colored sapphire. The color was emerged in the late 1970s and early 1980s is now also found to be stable to routine cleaning pro- becoming prevalent in the trade: diffusion treatment (see cedures; however, it may be partially or figure 1).This process involves the diffusion at very high completely-removed if the stone is re- temperatures (1700° and higher) of color-causing transi- polished pf, recut. Recently, significant tion elen~entssuch as iron, titanium, chromium, or nickel quantities of so-called "deep" diffusion- (depending on the color desired) into a region that extends treated sapphires have entered the market. just below the surface of the otherwise colorless or very This article documents the properties of light colored corundum (Carr and Nisevich, 1975). The these and other blue diffusion-treated sap- result is a thin color layer at and just below the surface of phires, and presents means of identifying the gemstone (see figure 2). This layer may be partially or this method using simple gemological tests. completely removed if the stone is repolished or recut. It is commonly used on corundum that does not respond to standard heat treatment. Unlike some treatment methods, ABOUT THE AUTHORS the diffusion treatment of sapphires does not have any Mr. Kane is supervisor of identification at the GIA parallel in nature. As Nassau (1981)stated, "the results of Gem Trade Laboratory, Inc. Santa Monica. Mr. Kam- merling is director of technical development, Mr. diffusion treatment . remind one more of Lechleitner Koivula is chief gemologisl, Dr. Shigley is director synthetic emerald overgrowth on a natural beryl than of of research, and Dr. Fritsch is research scientist at the Gemological Institute of America, Santa heated aquamarine." Monica, California. Since 1979, numerous brief reports of diffusion-treated Acknowledgments: The authors are graleful to the corundum have been published (Crowningshield, 1979a following for providing information, gem materials, and b, 1980; Brauner, 198 1; Crowningshield and Nassau, and research assistance: Karla and Bob Brom, 1981, 1982; Fryer et al., 1981, 1982a and b; Graziani et al., The Rainbow Collection; Jeffery Bergman, Gem Source; Robert K. Stevenson, Long Gems Ltd.; 1981; Leone and Cumo, 1981; Mat, 1981; Nassau, 1981, Edward Boehm, formerly 01 Overland Gems, now 1982; Herzberg, 198 1; Scarratt, 1981, 1983; Hinni, 1982; 01 the Gubelin Gemmolog~calLaboratory; Barry Read, 1982; "New CIBJO guidelines given to sapphire Hodgin. Dino DeGhionno, Lorri Dee Rascoe, J. Michael Allbr~tton,Terry Payne, Loretta Loeb, Sam description," 1983; Hughes, 1987; Ohguchi, 1983a and b; Muhlmeisler, Mike Moon, and Maha Smith, all of Kammerling et al., 1990a; Koivula and Kammerling, 1990). GIA; and Shane McClure and Karin Hurwit, of the Although relatively little corundum treated in this GIA Gem Trade Laboratory. John Armstrong and Paul Carpenter, of the California Institute of Tech- manner was seen in the mid- to late 1980s, it appears to nology, provided the electron microprobe analyses. have become quite prevalent in the international gem Gems & Gemology, Vol. 26, No. 2, pp. 115-133 markets in recent months. In late 1989, several blue 0 1990 Gemological Institute of Anierica diffusion-treated sapphires (and samples of starting mate- Diffusion-Treated Sapphires GEMS & GEMOLOGY Summer 1990 115 Figure 1. These blue sapphires (0.67-2.85 ct) have all been diffu- sion treated, reportedly by a process that produces an unusually deep layer of color at and just under the surface of the stone. Courtesy of Gem Source; photo by Shane F. McClure. rial) were donated to GIA by Karla and Bob Brom, loss of over lo%, yet they retain a fine color." of The Rainbow Collection, Honolulu, Hawaii According to a report in Jewellery News Asia (figure 3).They report (pers.comm., 1990)that they ("New colour diffusion for sapphires," 1990))the have received 500 ct of faceted and cabochon-cut vendor claims that about 25,000 ct of this material material from a scientist in Bangkok, Thailand, have been treated and repolished, with 12,500 ct who purports to use a complex treatment process currently in the world market. Trade sources and involving eight to 10 separate heating periods of 40 our own observations at Tucson indicate that a hours each. number of vendors are now selling diffusion- More recently, at the 1990 Tucson Show, signifi- treated blue sapphires. cant quantities of faceted blue diffusion-treated Another point of interest not previously men- sapphires were offered for sale by Gem Source, of tioned in the literature is the experimentation in Las Vegas, Nevada, and Bangkok, Thailand (again, Bangkok, Thailand, with diffusion treatment that see figure 1). According to a promotional flier involves not only iron and titanium, but also other provided by the vendor, these blue sapphires had color-causing impurities such as cobalt. We had an been subjected to "new techniques resulting in opportunity to examine a number of these stones much deeper penetration of the metal ions. The as well. penetration is so deep that many stones treated To better understand the different types of with this method are entirely recut, with a weight diffusion-treated stones on the market, the pro- 116 Diffusion-Treated Sapphires GEMS & GEMOLOGY Summer 1990 persons involved in the heat treatment of cor- undum in Thailand. Five of the heat treaters returned the treated sapphires with very little or no apparent improvement in color. The sixth person, however, presented the Bangkok dealer with the intensely colored blue sapphire rough shown on either side of the untreated material in figure 4. Elated over the apparently successful heat treatment, the Bangkok dealer began organizing the purchase of large quantities of Montana sap- phire rough. When he cut a portion of the treated rough, however, he discovered that the blue color was confined to a very thin area near the surface (R. K. Stevenson, pers. comm., 1984). In June of 1990, Bob Crowningshield of the East Coast GIA Gem Trade Laboratory reported seeing an- other lot of diffusion-treated Montana sapphire rough that was being marketed as heat-treated material. Disclosure Practices. Although there is no world- wide agreement concerning disclosure practices Figure 4. In the early 1980s, a gem dealer in Bangkok supplied six different heat-treating for the heat treatment of blue sapphire, there is operations with light-colored Montana sapphire general consensus in the trade that disclosure of rough (as seen in the center of this photo). diffusion-treated corundum is essential because Five lots of the heat-treated sapphires were the added color is confined to a surface layer. returned with little or no improvement in Consequently, while the terminology may vary, color. The sixth operation, however, returned corundum treated in this manner is nearly always intensely colored blue sapphires to the dealer described as synthetically or artificially colored. (as seen here. on either side of the original For example, the GIA Gem Trade Laboratory light-colored rough). Subsequent cutting re- issues the following conclusion on identification vealed that the blue color was confined to reports: a thin superficial layer: The sapphires had been diffusion treated. The largest piece DIFFUSION-TREATED NATURAL SAPPHIRE weighs 0.75 ct. Photo by Shane F. McClure. Note: The color of this stone is confined to a shallow surface layer that has been produced by Carbide). Carr and Nisevich later described this diffusing chemicals into the surface by heat treatment procedure as a separate process (1976 treatment. and 1977). When the Linde division of Union Carbide ceased production of synthetic star cor- THE DIFFUSION MECHANISM undum, all four of these patents were assigned to The color in blue sapphire is due to Fez+-0-Ti4+ Astrid Corp. of Hong Kong, which had acquired charge transfer, influenced by Fez+ 3Fe3 + charge Linde's stock of synthetic star rubies and star transfer and Fe3+ absorptions (Smith and Strens, sapphires (Nassau, 1981). Astrid Corp., a member 1976; Schmetzer, 1987). Diffusion treatment first of the Golay Buchel group, produced diffusion- brings the necessary iron and titanium coloring treated sapphires in Bangkok until the early 1980s agents into contact with the stone's surface. The (D. Biddle, pers. comm., 1990). stone is then heated, sometimes to just below its However, it appears that diffusion treatment is melting point, causing the corundum lattice to being practiced by other firms. In late 1984, a expand and allowing the thermally energized tran- Bangkok gem dealer reported to one of the authors sition metal ions to migrate into a layer at the (R. Kane) that he had given very light colored surface, resulting in a near-surface concentration sapphire rough from Montana to six different of color. 118 Diffusion-Treated Sapphires GEMS & GEMOLOGY Summer 1990 Generally spealzing, tlie higher the temperature n~aintainedand the longer the time used for the heating step, the greater the depth of color penetra- tion will be. In this regard, the possible difference between so-called "deep" diffusion treatment and earlier diffusion-treated stones may be in a higher temperature being reached and/or maintained. It may also be in the use of more than one heating stage in the treatment procedure.