(via Gemmology Queensland, Vol 3, No.1, Jan 2002/IGC Conference Madrid 2001) George Bosshart writes:
The Gubelin Gem Lab engaged in a new study of HPHT-annealed specimens in order to elaborate criteria for the separation of the fancy diamond colors produced by the General Electric Company from the natural pink and blue colors. The key characteristics of the natural colors are briefly outlined and first indicators for HPHT treatment detection are given below.
Natural pink colors exist in both type Ia and type IIa diamond but exhibit a wider color variety in the first group. Type Ia diamond is found in pure pink to red to purple hues but pink and red are more frequently combined with orange and brown color modifiers. Type IIa diamond is limited to light pink to pink hues which may be modified by secondary orange or brown colors. Red hues do not occur in this group but purple does, as a rare and subordinate modifier at least.
In our natural pink study group of over 100 gem quality diamonds, 75% belonged to type Ia, 2% to the mixed type IbIaA, and 22% to type IIa (of which 15% revealed nitrogen-free infrared survey spectra, whereas 7% showed trace amounts of nitrogen as A or B aggregates or as single nitrogen).
In pink type Ia diamond in particular, an irregular color lamination and patchiness can frequently be observed under magnification. These obvious disturbances are plausibly interpreted as being caused by internal plastic deformation which itself is a reaction of the diamond structure to the impact of geotectonic shear stress (active during orogenetic phases), thus avoiding breakage. However, the cause for the pink color center, a wideband absorption centered at 560nm (2.2 eV), is not known in detail.
The strength of the 560nm absorption band determines the intensity of the type Ia pink color. Pink changes to red or purple when this band reaches higher amplitudes (with absorption coefficients in the order of 0.6 cm¯¹ and above). Nitrogen contents in the form of A and/or B aggregates vary in natural pink diamond from extremely small (in type IIa) to extremely large. In type Ia diamond, hydrogen may be present as well, however, in minor to moderate amounts only. Type IIa diamond features the same 560 nm absorption system and an identical but limited intensity relationship (mentioned above). It follows that neither nitrogen nor hydrogen impurities cause the pink color.
In pink diamond, a slight increase of the general absorption in the blue to violet regions of the spectrum results in an orange color modifier which in turn may alter to a brown modifier when the underlying absorption rises more strongly. This absorption is caused by another, equally unknown type of structural defect in the diamond crystal lattice.
In addition to the above color centers, N3 and H3 absorption in type Ia diamond may add a yellowish to orangy modifier component when present in some strength. This combination is typically encountered in Argyle and Brazilian brownish to purplish pink and red diamond. A rarely occurring 480nm absorption band adds a pure orange component to pink diamond colors.
Natural blue diamond varies less than in hue than pink color group. The only modifier of importance is gray. Natural blue occurs in type IIb diamond exclusively (rare specimens being gray violet rather than blue and belonging to hydrogen-rich type IaB). Type IIb diamond is an electric semiconductor due to the substitution of carbon atoms by ppb amounts of boron on the lattice sites of diamond.
The absorption diagram of blue diamond is characterized by a unique mid-infrared absorption superimposed n the inherent diamond absorption in the two-phonon region, with lesser absorption in the adjacent one and three phonon areas. The strongest absorption band is situated at 2802 wavenumbers. It is also typical for blue diamond that the absorption level steadily decreases from the mid-infrared through the near-infrared and visible regions into the ultraviolet part of the electromagnetic spectrum without showing any absorption bands. The absorption minima of blue diamonds fluctuate from 240nm at the base of the fundamental absorption edge to about 500nm. This variation does have an influence on the exact hue of the blue colors which may range from violetish to slightly greenish blue. The dominant wavelengths, as determined by colorimetric measurement, lie in the 465 to 495nm region and confirm that the primary hue is blue. Only one specimen was encountered so far with a dominant wavelength of 435nm corresponding to a violet-blue hue.
The hues of type IIb diamonds frequently are not easy to determine visually due to their weak color saturations and relatively high tones. The type IIb infrared absorption, e.g. the 2802 wn band, could serve as an indicator for the saturation of blue since it is related to the boron content. However, the absorption coefficient of this and other MIR absorption bands for some reason does not appear to be straightforward measure of the blue saturation of type IIb diamond. When the general absorption in type IIb diamond rises to higher levels, and this is particularly important in the visible part of the spectrum, the color impression shifts to bluish gray and even to neutral gray colors (44% of the blue group of 75 specimens grade blue, 40% mixed blue to gray, 8% neutral gray and 1% violet blue).
There is a small proportion (7%) of type IIb diamonds which possesses an increased absorption in the entire ultraviolet region. Accordingly their absorption minimum is more pronounced than in the pure blue colors and shifts into the center of the visible region, with dominant wavelengths ranging from about 500 to slightly over 600nm. Such diamonds essentially appear gray with a greenish to yellowish color modifier. It is interesting to note that greenish gray and yellowish gray colors also occur in type Ia diamond, showing high B nitrogen aggregate and high hydrogen contents, respectively high A aggregate and H contents.
The presence of gray color modifier in type IIb blue diamond may be interpreted as a color generated by the combination of boron with single nitrogen or other chemical impurities and/or by structural defects. However, gray color may also be independent of boron traces at all. A very weak 270 nm band was encountered in several natural blue diamonds and is allocated to single nitrogen.
HPHT Pink and Blue
Prior to 1999, it may have appeared inconceivable that natural off-color diamonds could be improved to obtain the best colors known (D to H color grades), i.e. colorlessness. However, the General Electric Company successfully achieved this breakthrough by applying a modified version of the high pressure/high temperature technology used to grow synthetic diamonds. Since the turn of the millennium, GE has been marketing these virtually colorless diamonds predominantly on the American market and under the brand name, Bellataire (formerly GE POL).
Fancy pink and blue diamond colors are described ad desirable as the white ones. As a consequence, the production of pink and blue became the second great challenge and in 2000. GE managed to add convincing pink and blue color replicas to the wide range of already existing treated diamond colors. In contrast to those irradiated and annealed pink to purple and irradiated blue to green diamond colors, General Electric’s latest products look entirely natural. The exact starting material and its abundance will not be made public by GE. However, experience gained in our study of GE POL diamonds before and after HPHT-annealing (Smith et. al 2000) tells us that the potentially improvable diamond rough must be restricted to type IIa brown respectively type IIB gray to brown specimens of fairly high clarity grades. This implies that the number of diamonds HPHT-annealable to pink and blue colors is considerably inferior to that of the colorless type IIa specimens and that most of the enhanced fancy colors may be low in intensity. A preliminary sampling consisted of six (0.14 to 8.55 ct) pink and two (0.21 and 0.27 ct) blue diamonds HPHT-annealed by GE. The pink stones investigated evidenced that only type IIa and near-type IIa diamonds had been selected. Colorimetric data showed that the resulting pink and blue hues are well within the range of their natural type IIa resp. IIb counterparts. Red or strong blue colors were not observed in this batch, but it included light to intense pink to purple pink colors plus one faint blue and one medium blue specimen each. Brown resp. gray modifiers were subordinate. At this moment, it is safe to state that, comparable to colorless Bellataire diamonds, gemological standard methods (microscopy, UV fluorescence etc.) will not permit a safe separation of natural and HPHT-annealed type IIa pink and semi-conductive blue diamonds. The mid-infrared and UV/VIS spectra of five (out of six) pink samples revealed nitrogen (A or B aggregates, N3 and N9 centers), however, in trace amounts only. The spectra of the blue specimens were very similar to those of the natural colors as well.
Among the optical techniques, Raman photo-luminescence with He/Cd and an Arion laser offer the most promising results. The color enhanced diamonds showed a smaller number of PL bands than recorded for natural colors and the intensities of the bands also differed noticeably. As an example, the 575nm and 637nm bands of the Nº and N centers respectively were definitely stronger than in natural pink diamonds. More and improved criteria are to be expected for both color groups from a larger data base. Advanced testing methods such as X-ray topography or cathodoluminescence applied during our former investigation of eleven colorless diamonds before and after HPHT processing by GE were not used for reasons of limited time and absence of diamonds selected to be processed.
What can be expected as the ultimate achievements in color enhancement by HPHT-annealing?
Cape series diamond becoming colorless and brown resp. gray diamond adopting other colors than colorless, pink or blue.
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