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1、,材料学院C168 tele：67792908 mobile：13162567728,GEMSTONE ENHANCEMENT AND ITS DETECTION IN THE 2000S Shane F. McClure, Robert E. Kane, and Nicholas Sturman,ABOUT THE AUTHORSMr.McClure is director of West Coast Identification Services at the GIA Laboratory in Carlsbad California Mr. Kane is president and C

2、EO of Fine lnternational in Helena Montana. Mr. sturman is supervisor of Pearl Identification at the GIA Laboratory in Bangkok,GEMSTONE ENHANCEMENT1.THERMAL ENHANCEMENT2.DIFFUSION TREATMENT3.CLARITY ENHANCEMENT4.IRRADIATION AND COMBINED TREATMENTS5.SURFACE COATING6.DYEING7.BLEACHING8.IMPREGNATION9.L

3、USTER ENHANCEMENThttp:/,Advances in technology and increased demand for lower-priced gem materials contributed to the proliferation of new treatments throughout the first decade of the 2000s. The developments that made the most difference were the diffusion treatment of corundum with beryllium, diff

4、usion of copper into feldspar, clarity enhancement of ruby and diamond, and heat treatment of diamond, ruby, and sapphire. Gemological laboratories and researchers have done their best to keep up with these treatments, and the jewelry trade has struggled with how to disclose them. This article summa

5、rizes these developments and the methods used to identify the various enhancements.,Another decade has passed since we reviewed the events of the 1990s as they pertained to gemstone enhancements and their detection (McClure and Smith, 20001. At that time, we observed that the issue of disclosure (an

6、d, especially, the failure to disclose) had caused major upheaval in all areas of the jewelry industry. We ended that retrospective article by stating there would be no end to fresh challenges in treatment identification and disclosure as we entered the new millennium .,The 2000s certainly lived up

7、to our expectations. There were treatments discovered that no one suspected were possible. There were crises of disclosure that resulted in televised exposes and unfavorable publicity for the industry. There were improvements in treatments developed in the 90s that made them more efficient and often

8、 harder to detect.,Detection methods have also become more and more complex. Gemological laboratories have had to invest in more sophisticated instrumentation, sometimes at great expense. For the frontline laboratories, being a good gemologist is no longer good enough. You must also have training in

9、 the earth sciences and analytical instrumentation to function effectively in such an environment. Now more than ever, the gemologist in the trade must be able to recognize when a stone requires more advanced testing.,It is important to emphasize that many of these treatments can still be detected w

10、ith standard gemological equipment, but staying current on the latest developments is absolutely essential. The knowledge base concerning treatments is constantly changing.,Nearly every gem material (e.g., figure 1) is subject to treatments of one form or another. Building on previous reviews, the a

11、im of this article is to provide an overview of the treatments and identification challenges associated with them that were common during the first decade of the 2000s. The authors strongly recommend that readers familiarize themselves with the original references, as all the pertinent information c

12、annot be presented in a review article.,Figure 1. The 2000s continued to see the widespread use of treatments on a wide variety of gemstones. The gems shown here were enhanced during the 2000s by heat (unless otherwise noted, or other methods known prior to the decade: (1) 8.43 ct aquamarine; (2) 16

13、.86 ct tanzanite: (3)10.08 ct tourmaline; (4) 4.65 ct Paraiba tourmaline; (5) 3.36 ct red beryl (clarity enhanced); (6) 3.07 ct ruby; (7) 53.54 ct Cu-bearing tourmaline, Mozambique; (8) 13.97 ct zircon; (9) 2.60 ct emerald (clarity enhanced); (10) 6.43 ct zircon; (11) 8.04 ct blue sapphire; (12) 12.

14、15 ct pink sapphire (13) 13.67 ct yellow sapphire; and (14) 9.07 ct blue topaz (irradiated and heated). Nos. 1, 3, 6, 8,9,11, 12, and 13 are courtesy of Evan Caplan (Omi Gems, Los Angeles); 2, 4, 5, 7, and 10 are from Fine Gems International; and 14 is from Tino Hammid. Photo by Tino Hammid, Robert

15、E. Kane.,NOMENCLATURE AND DISCLOSURE,In the early 2000s, a group that came to be known as the Laboratory Manual Harmonisation Committee (LMHC) was formed at the request of leaders of the colored stone industry. Its purpose was to bring together representatives of many of the major gem laboratories a

16、nd attempt to standardize wording on their reports (International labs. . . ,2000).,THERMAL ENHANCEMENT,For a wide variety of gem materials, heat treatment is still the most common enhancement. In some cases, heat treatment can still be identified by routine methods, In others, conclusive identifica

17、tion is possible only with advanced instrumentation and techniques.,In still other gems (e.g., aquamarine, citrine, amethyst, and tourmaline), heat treatment remains virtually unidentifiable by any currently known methods. For this last group of stones, which are heated to induce permanent changes t

18、o their color, this enhancement may be the rule rather than the exception. One should assume that most of those gem materials have been heated.,High-pressure, high-temperature (HPHT) treatment of diamonds was only introduced commercially in 1999, and much of the first decade of the 2000s was devoted

19、 to expanding this high-tech treatment to colored diamonds on the one handand detecting it on the other. Research efforts thus far have provided methods to identify not only the lightening of off-color diamonds, but also the production of a wide variety of fancy colors.,Diamond. The last decade bore

20、 witness to the greater presence of color-treated diamonds, with the global trade reportedly approaching 25,000 carats permonth in the latter half of the decade (3-5% of the total diamond trade; Krawitz, 2007). Although not specifically noted, this figure probably refers mostly to irradiated and ann

21、ealed diamonds of many different colors. Irradiation, heating, HPHT, or a combination of these treatments can create virtually every hue (figure 2), including black and colorless.,Figure 2. This group of diamonds (0.30-0.74 ct) illustrates the wide array of colors that can be produced by artificial

22、irradiation with subsequent annealing. Courtesy of Lotus Color; photo by Robert and Orasa Weldon.,HPHT Treatment to Remove Color. HPHT treatment of diamonds to remove or induce color was a central topic of the diamond community throughout the 2000s. In 1999, General Electric Co. and Lazare Kaplan In

23、ternational announced the commercial application of an HPHT process for faceted diamonds (Pegasus Overseas Limited, 1999) that removed color from brown type a stones (by annealing out vacancy clusters associated with the brown color in plastically deformed diamonds; Fisher, 2009).,Even though scient

24、ists had recognized these and other possibilities 30 years earlier (see, e.g., Overton and Shigley, 2008),the results came as a surprise to many in the diamond worlda type a brown diamond of any size could be transformed into a colorless stone (see, e.g ,Smith et al., 2000). After HPHT treatment, th

25、e majority of these diamonds received D through G color grades, and the results were permanent (Moses et al., 1999). Gemological researchers globally mobilized to understand and identify the process (e g. Chalain et al., 1999, 2000; Schmetzer, 1999; Collins et al., 2000; Fisher and Spits, 2000; Smit

26、h et al 2000).,By late 2000, more than 2,000 decolorized type a HPHT-treated diamonds had been seen at the GIA Laboratory (McClure and Smith, 2000). Today, with several treaters in various countries removing color from diamonds with HPHT annealing, this treatment has become almost commonplace.,Deter

27、mining diamond type is central to the detection of colorless to near-colorless HPHT-treated diamonds. For a thorough review of how diamond type is determined, see Breeding and Shigley (2009). Nearly 99% of all natural gem diamonds are typea. Thus far, all colorless to near-colorless HPHT-treated dia

28、monds reported in the literature have been type a.,Fortunately, it is easy to determine if a diamond is not a type a by using the DiamondSure (Welbourn et al., 1996), SSEF Type II Diamond Spotter (Boehm, 2002; Hanni, 2002), or other simple gemological methods (Breeding and Shigley, 2009). At the pre

29、sent time, if a colorless to near-colorless diamond is not type IIa, then it is not HPHT treated.,Visual features related to damage caused by the extreme conditions of the treatment may be seen in some colorless to near-colorless HPHT-treated diamonds. These include a frosted appearance caused by et

30、ching or pitting, as well as gray or black graphitization, on naturals or fractures where they come to the surface.,Such features are not commonly observed in untreated colorless type IIa diamonds, although lightly pitted surfaces and graphitized or graphite inclusions have been seen on rare occasio

31、ns. Therefore, such features are a good indication of treatment, but they are not proof by themselves (Moses et al., 1999;McClure and Smith, 2000; Gelb and Hall, 2002).,Because these heat damage-related features are not always present in a faceted diamond or may be difficult to discern, detection of

32、 HPHT treatment in a type IIa diamond generally requires measurement of the absorption and/or photoluminescence (PL) spectra taken with the diamond cooled to a low temperature (see Chalain et al., 1999, 2000; Collins et al.,2000; De Weerdt and Van Royen, 2000; Fisher and Spits, 2000; Hanni et al., 2

33、000; Smith et al., 2000;Collins, 2001, 2003; Novikov et al., 2003; and Newton, 2006).,HPHT Treatment to Produce Color. Refinements to HPHT processing have yielded commercial production of a variety of colors in both type I (orangy yellow, yellow, to yellow green) and type (pink or blue) diamonds (Sh

34、igley, 2008; see, e.g., figure 3).,Figure 3. This 0.34 ct Fancy Light gray-blue diamond was successfully turned Fancy blue by HPHT treatment. Photos by Elizabeth Schrader.,Identifying HPHT-treated type la diamonds requires both IR and low-temperature visible-range spectroscopy, but several gemologic

35、al properties offer evidence (see Reinitz et al., 2000). The pink and blue HPHT-treated diamonds initially examined by Hall and Moses (2000, 2001b) ranged from Faint and Very Light to Fancy Intense and Fancy Deep. Low-temperature PL spectra identified these products.,As discussed below, combining tr

36、eatments (e.g., HPHT annealing, irradiation, then low-temperature heating) can produce interesting results, such as intense pink-to-red diamonds (Wang et al., 2005b). Smith et al. (2008a,b) contributed useful charts for identifying the natural or treated origin of color in pink and blue diamonds.,He

37、at-Treated Black Diamond. In the late 1990s, it became popular to pave-set small natural-color black diamonds alongside colorless diamonds in jewelry (Federman, 1999; Gruosi, 1999; Misiorowski, 2000).This design trend continued into the 2000s. As is often the case with successful jewelry lines, less

38、- expensive approaches soon followed.,Harris and Vance (1972) had experimented with the production of artificial graphitization in diamond, which Hall and Moses (2001 a) confirmed by heating a sample under vacuum for a few minutes to several hours and turning it black; Raman spectra showed a pattern

39、 that matched graphite. Notari (2002) discussed several different commercially practiced methods of heating to produce graphitization and black coloration in diamonds.,In many cases, microscopic examination with fiber-optic illumination can provide proof of heat treatment in black diamondsthe black

40、(graphitized) areas are largely confined to surface-reaching cleavages and fractures (Hall and Moses, 2001a). In natural-color black diamonds, the graphitization is randomly dispersed throughout, referred to as a salt and pepper effect (Kammerling et al., 1990b).,This random orientation is also seen

41、 in other color-causing inclusions in natural-color black diamonds, such as magnetite, hematite, and native iron (Titkov et al., 2003). This determination, however, requires a gemologist experienced in examining known samples of both natural-color and heat-treated black diamonds (see, e.g. Smith et

42、al., 2008c).,Ruby and Sapphire. As in the preceding two decades, the heat treatment of corundum to substantially change its color remained a troublesome issue. Heating was applied to the vast majority of rubies and all colors of sapphires during the 2000s.,In some cases, clarity was also affected, a

43、s with the flux-assisted healing of fractures (in combination with high-temperature heat treatment) that began in the early 1990s with the discovery of huge quantities of ruby at Mong Hsu, Myanmar (see Peretti et al., 1995; figure 4).,Figure 4. Heat treatment with the stone placed in a flux has larg

44、ely healed this fracture in a Mong Hsu ruby. However, it has left behind a fingerprint that looks similar to those found in synthetic rubies, another challenge for the gemologist. Photomicrograph by S. F. McClure; magnified 40 x.,There were also new areas of concern, such as beryllium diffusion with

45、 high heat (see Diffusion Treatment below) and the Punsirihigh-temperature treatment for blue sapphires. With regard to the latter, concerns arose in late 2003 when some laboratories first observed unusual color concentrations in larger heat-treated blue sapphires (figure 5) immersed in methylene io

46、dide (Scarratt, 2004; Smith et al., 2004). All had one consistent characteristic: a colorless or near-colorless outer rim and a deep blue (or, if color change, purple) interior (figure 6).,Figure 5. This matched pair of blue sapphires (3.07 and 3.10 ct) were heat treated by the Punsiri method. Photo

47、 by Maha Taanous.,Figure 6. The unusual color zoning in this color-change sapphire is typical of stones treated by the Punsiri method. Photomicrograph by S. F. McClure; magnified 10 x.,After comprehensive analytical research (and GIA and AGTA observation of the technique as performed by treater Tenn

48、akoon Punsiri in Sri Lanka), the SSEF,AGTA, and GIA laboratories all came to the same conclusion: These stones were not diffused with beryllium or any other element (McClure, 2003b; Hanni et al., 2004; ICA issues its first lab report. ., 2004). The major gem labs continue to identify sapphires treat

49、ed by the Punsiri method as natural sapphires that show evidence of heat treatment.,Beginning mid-decade, demand and scarcity significantly drove up prices for colorless or white sapphire. As a result, dealers in Sri Lanka reported that lightly colored sapphires had been heated to render them colorl

50、ess (Robertson, 2008). Ironically, the scarcity of natural white sapphire was caused in part by the large quantities that were being used for Ti blue diffusion and, to a lesser extent, Cr red diffusion.,Since the two previous G McClure and Smith, 2000), heat-treatment technologyin the form of electr