Difference between revisions of "Sapphirine"

From The Gemology Project
Jump to: navigation, search
Line 1: Line 1:
Sapphrine
+
{{Sapphirine}}
[[Image:Large-Sapphirine.jpg]]
+
[[Image:Large-Sapphirine.jpg|left|framed| From Kolonne,Sri lanka]] <br clear="left" />
 +
{{images}}
 +
 
 +
Sapphirine is a mineral group.  For many centuries, most gem spinels were misidentified as [[sapphire]] or [[ruby]] because they have similar properties and occur in the same geological deposits. The historically significant 5.08 centimeter "Black Prince Ruby" in the center of the British Imperial Crown was only recently identified as a spinel. This stone is irregular in shape and has a somewhat squareish outline. Additionally, it was not faceted, merely polished. Spinels also occur in a vast array of colors. They are slightly softer than sapphires but still very durable.<br>The earliest known use of spinels was as ornaments found in Buddhist tombs in Afghanistan. Blue spinels have been found in England, dating back to the Roman occupation (51 BC to 400 AD).
 +
 
 +
<!-- [[Image:DSC_7858_d.jpg|left|thumb|250px|Cobalt Blue Spinel, 3.96 ct <br /> Photo by Jeff Scovil<br />Courtesy of R.W. Wise Goldsmiths]] -->
 +
<br clear="all" />
 +
 
 +
==Chemical composition==
 +
 
 +
Common spinel belongs to the "spinel series", which belongs to the "spinel group".<br />
 +
The general formula for the spinel group is A<sup>2+</sup>B<sup>3+</sup><sub>2</sub>O<sub>4</sub>. The 3 series of the spinel group are defined by the B<sup>3+</sup> cation.<br />
 +
The spinel group is made up of 3 [[isomorphous replacement|isomorphous]] series.
 +
 
 +
The  isomorphous series:
 +
* Spinel series (aluminum)
 +
** Spinel - MgAl<sub>2</sub>O<sub>4</sub> (n = 1.719, sg ~ 3.60)
 +
** Hercynite - FeAl<sub>2</sub>O<sub>4</sub>
 +
** Gahnite - ZnAl<sub>2</sub>O<sub>4</sub> (n = 1.805, sg = 4.62)
 +
** Galaxite - MnAl<sub>2</sub>O<sub>4</sub>
 +
 
 +
* Magnetite series (ferric iron)
 +
** Magnetite - FeFe<sub>2</sub>O<sub>4</sub>
 +
** Magnesioferrite - MgFe<sub>2</sub>O<sub>4</sub>
 +
** Ulvöspinel - FeFeTiO<sub>4</sub>
 +
** Franklinite - ZnFe<sub>2</sub>O<sub>4</sub>
 +
** Jacobsite - MnFe<sub>2</sub>O<sub>4</sub>
 +
** Trevorite - NiFe<sub>2</sub>O<sub>4</sub>
 +
 
 +
* Chromite series (chrome)
 +
** Chromite - FeCr<sub>2</sub>O<sub>4</sub>
 +
** Magnesiochromite - MgCr<sub>2</sub>O<sub>4</sub>
 +
 
 +
Most of the above series members are rare in nature with the exception of the members of the spinel series, magnetite and chromite. To gemologists common spinel and gahnite are of most interest.
 +
 
 +
When gemologist refer to "spinel", we usually imply common spinel, that is the spinel that belongs to the spinel series of the spinel group.
 +
 
 +
==Diagnostics==
 +
 
 +
Spinel can be confused with many stones by appearance alone, yet optical properties usually rule out most of them.<br />
 +
As spinel belongs to an isomorhous series, the optical and physical properties may vary.
 +
 
 +
===Color===
 +
 
 +
Spinel: colorless, green, blue, red, black.<br />
 +
Gahnite: blue-green, yellow, brown.
 +
 
 +
Varieties:
 +
*Pleonaste (also named ceylonite) - (Mg,Fe)Al<sub>2</sub>0<sub>4</sub> - dark green to blue-green; black
 +
*Gahnospinel - (Mg,Zn)Al<sub>2</sub>0<sub>4</sub> - pale to dark blue, black.
 +
 
 +
Spinel is allochromatic and variety colors are produced by transition metals:
 +
* Cr<sup>3+</sup> - red, pink
 +
* Fe<sup>2+</sup> - blue, violet
 +
* Fe<sup>2+</sup> + Co<sup>2+</sup> - darkblue
 +
* Fe<sup>3+</sup> - green
 +
 
 +
===Diaphaneity===
 +
 
 +
Transparent to opaque.
 +
 
 +
===Refractometer===
 +
 
 +
Spinel is isotropic and the refractive index of common spinel is generally around 1.712 to 1.720. Red spinel can have a refractive index up to 1.74.<br />
 +
The only other isotropic gemstone that falls within this range is grossular garnet, but it will usually be higher and the color is also different.<br />
 +
Other members of the spinel series, such as gahnite will have higher refractive indices.
 +
 
 +
All other gemstones can easily be seperated from spinel by their optic nature.
 +
 
 +
Synthetic spinel has a usual refractive index of 1.727.<br />
 +
Gahnospinels have a refractive index between 1.725 and 1.753, while pleonaste (ceylonite) has an R.I. range of 1.77 to 1.80.<br />
 +
Black spinel-hercynite (pleonaste) stones from Thailand may have an RI upto 1.789 with an average SG of 3.86 (Seriwat, 2008)
 +
 
 +
===Specific gravity===
 +
 
 +
As with the refractive indices, the specif gravity of spinel can vary due to isomorphous replacement.<br />
 +
The values for most gem grade material lies between 3.58 and 3.61. Pleonaste has a S.G. between 3.63 and 3.90.<br />
 +
Gahnospinels may have a specific gravity up to 4.06.
 +
 
 +
===Polariscope===
 +
 
 +
Common spinel is isotrope and will remain dark under crossed polars.<br />
 +
Verneuil type synthetic spinel will always (maybe with the exception of red) show strong anomalous birefringence due to excess Al<sub>2</sub>O<sub>3</sub> (see [[spinel#synthetics|synthetics]]). This anomalous extinction (as it is currently named)  can be seen as "tabby" extinction, resembling the color distribution of a cat's fur, or/and as an Andreas cross caused by pseudo-birefringence.
 +
 
 +
Natural and flux-melt synthetic spinel may show weak anomalous extinction.
 +
 
 +
===Spectra===
 +
 
 +
[[Image:Spectrum natural blue spinel iron.jpg|thumb|left|240px]]<br />Spectrum of a natural blue spinel, colored by iron and minor traces of cobalt.<br clear="all" />
 +
 
 +
==Phenomena==
 +
 
 +
* Asterism (4 and 6-pointed stars)
 +
* Color change (rare)
 +
 
 +
==Occurrence==
 +
 
 +
Myanmar; Vietnam; Thailand; Sri Lanka; Pakistan; Afghanistan; Tadshikistan; Kenia; Tanzania; South-Africa; Brazil.
 +
 
 +
==Synthetics==
 +
 
 +
Spinel is synthesized by the [[flame fusion|Verneuil (flame-fusion) process]] and the flux-melt method, although the first process does not render a true synthetic in most cases.
 +
 
 +
===Flame fusion===
 +
 
 +
Flame fusion synthetic spinels are produced since 1908 (by accident while creating synthetic corundum), but were not commercially available until 1930.
 +
 
 +
It was found that while trying to synthesize spinel through the Verneuil process, the resulting boules would easily fracture and no reasonably sized gemstones could be cut from them.<br />
 +
The ratio MgO to Al<sub>2</sub>O<sub>3</sub> is 1:1 for common spinel and by changing that ratio (adding Al<sub>2</sub>O<sub>3</sub>) the boules became stable. Because that alters the chemical formula of the synthetic, it is not a true synthetic (but accepted as such). Sometimes these are named "beta-corundum" due to the excess of alumnia.
 +
 
 +
For the creation of red stones, this alteration was no option and, usually, no red synthetic spinel boules created by the flame-fusion process result in large stones (but are known to excist). The larger sized red synthetic spinels are mostly created with the flux-melt method. The few red synthetics that are created through the Verneuil process will show curved striae like their synthetic corundum cousins.
 +
 
 +
As a result in the changing of the MgO:Al<sub>2</sub>O<sub>3</sub> ratio, the flame fusion synthetics have higher refractive indices (usually stable at 1.727) and a higher specific gravity (3.64).
 +
 
 +
{| {{table}} width="70%" style="margin-left:0;"
 +
|-
 +
|colspan="5" align="center"|Properties of flame fusion synthetic spinel
 +
|-
 +
!color
 +
!coloring agent
 +
!RI
 +
!SG
 +
!other diagnostics
 +
|-
 +
|colorless||none||1.728-1.740||3.65-3.80||LWUV: green; SWUV: white/blue
 +
|-
 +
|red||Cr<sup>3+</sup>||1.722-1.725*||3.58-3.60||curved striae; spectrum; fluorescence
 +
|-
 +
|pink||Cu||1.727-1.740||3.65-3.80
 +
|-
 +
|yellow||Mn||do.||do.||LW/SWUV: green
 +
|-
 +
|emerald green||Mn + Co<sup>3+</sup>||do.||do.
 +
|-
 +
|tourmaline green||Cr<sup>3+</sup>||do.||do.||spectrum
 +
|-
 +
|beryl green||Cr<sup>3+</sup> + Mn||do.||do.||spectrum
 +
|-
 +
|zircon blue||Co<sup>3+</sup> + Cr<sup>3+</sup> + Ti||do.||do.||spectrum
 +
|-
 +
|sapphire blue||Co<sup>3+</sup>||do.||do.||spectrum; fluorescence; CCF
 +
|-
 +
|amethyst violet||Co<sup>3+</sup> + Mn||do.||do.
 +
|-
 +
|alexandrite color change||Cr<sup>3+</sup> + V||do.||do.||spectrum
 +
|-
 +
|lapis lazuli||Co<sup>3+</sup>||1.725||3.52||spectrum; CCF
 +
|-
 +
|colspan="5"|
 +
Strong "tabby" extinction can be seen in all<br />
 +
<nowiki>*</nowiki> Henn, 1995 metions a low value of 1.720.
 +
|}
 +
 
 +
===Flux-melt===
 +
 
 +
First commercial production of flux-melt synthetic spinel started around 1980, although successful experiments date back to 1848 (by the French chemist Ebelmen). As of 1989 larger volumes of this synthetic appeared on the market, produced in Novosibirsk, Russia.
 +
 
 +
Apart from red, blue synthetics have also been produced by the flux-melt process.<br />
 +
These are true synthetics.
 +
 
 +
{| {{table}} width="70%" style="margin-left:0;"
 +
|-
 +
|colspan="5" align="center"|Properties of flux-melt synthetic spinel
 +
|-
 +
!color
 +
!coloring agent
 +
!RI
 +
!SG
 +
!other diagnostics
 +
|-
 +
|red||Cr<sup>3+</sup>||1.716-1.719||3.58-3.62||LW/SWUV: distinct red-orange/red<br />flux residu inclusions
 +
|-
 +
|blue||Co<sup>2+</sup> + Fe<sup>2+</sup>||1.719||3.58||spectrum; SWUV: inert; LWUV: weak read<br />flux residu inclusions
 +
|}
 +
Tabby extinction is also seen in these synthetics. Careful observation of inclusions is the main means of separation for red stones. Blue flux-melt synthetics can also be distinguished by the spectrum.
 +
 
 +
===Czochralski pulling method===
 +
A recent development (2007) is the procuction of red to pink synthetic spinels by the Czochralski pulling method.
 +
 
 +
==Inclusion images: Click on Image for Full Size==
 +
 
 +
[[image:SP713Fzm1brE2U.jpg|thumb|left|200px|Apatite inclusions and their star-like outgrowths along the 60 degree hexagonal plane - looking much like stellate dislocation systems, in a cobalt blue spinel.<br />Photo courtesy of John Huff, gemcollections.com]]
 +
[[image:SP820AO2-16.jpg|thumb|left|200px|Octahedral spinel inclusions with "Saturn-ring" stress fractures in a Burma red spinel.<br />Photo courtesy of John Huff, gemcollections.com]]
 +
[[image:SP820A02colW.jpg|thumb|left|200px|Octahedral inclusions in a Burma red spinel.<br />Photo courtesy of John Huff, gemcollections.com]]
 +
[[image:Spinel_test_00.jpg|thumb|left|200px|Euhedral inclusions in spinel.<br />Photo courtesy of Conny Forsberg]]
 +
<br clear="all" />
 +
{{inclusions}}
 +
 
 +
==Sources==
 +
* [http://www.amazon.com/gp/product/0195149106?ie=UTF8&tag=gemsandwhywelove&link_code=as3&camp=211189&creative=373489&creativeASIN=0195149106 Introduction to Optical Mineralogy'' 3rd edition (2003), Prof. W.D. Nesse]
 +
 
 +
* [http://www.amazon.com/gp/product/0750658568?ie=UTF8&tag=gemsandwhywelove&link_code=as3&camp=211189&creative=373489&creativeASIN=0750658568 Gems Their Sources, Descriptions and Identification'' 4th Edition (1990) - Robert Webster (6th ed.)]
 +
* ''Edelsteinkuntliches Praktikum'' - Ulrich Henn, Gemmologie Jahrgang 44 / Heft 4 / Dezember 1995, Spinell pp.54-62
 +
* ''Diploma course notes'' 1987 - Gem-A
 +
* ''Über die Eigenshaften von im Flussmittelverfahren hergestellten synthetischen roten und blauen Spinellen aus Russland'' - U. Henn/H. Bank, Gemmologie Jahrgang 41 / Heft 1 / April 1992, pp1-7
 +
* ''Black Opaque Gem Minerals Associated with Corundum in the Alluvial Deposits of Thailand''. Australian Gemmologist, 2008, Vol. 23, No. 6, pp. 242-253. Dr. Seriwat Saminpanya<br />
 +
 
 +
* [http://www.amazon.com/gp/product/B000WDQF18?ie=UTF8&tag=gemsandwhywelove&link_code=as3&camp=211189&creative=373489&creativeASIN=B000WDQF18 Gemmology 3rd edition (2005) - Peter Read ]

Revision as of 18:17, 1 November 2009

Template:Sapphirine

From Kolonne,Sri lanka

Sapphirine image gallery

Sapphirine is a mineral group. For many centuries, most gem spinels were misidentified as sapphire or ruby because they have similar properties and occur in the same geological deposits. The historically significant 5.08 centimeter "Black Prince Ruby" in the center of the British Imperial Crown was only recently identified as a spinel. This stone is irregular in shape and has a somewhat squareish outline. Additionally, it was not faceted, merely polished. Spinels also occur in a vast array of colors. They are slightly softer than sapphires but still very durable.
The earliest known use of spinels was as ornaments found in Buddhist tombs in Afghanistan. Blue spinels have been found in England, dating back to the Roman occupation (51 BC to 400 AD).


Chemical composition

Common spinel belongs to the "spinel series", which belongs to the "spinel group".
The general formula for the spinel group is A2+B3+2O4. The 3 series of the spinel group are defined by the B3+ cation.
The spinel group is made up of 3 isomorphous series.

The isomorphous series:

  • Spinel series (aluminum)
    • Spinel - MgAl2O4 (n = 1.719, sg ~ 3.60)
    • Hercynite - FeAl2O4
    • Gahnite - ZnAl2O4 (n = 1.805, sg = 4.62)
    • Galaxite - MnAl2O4
  • Magnetite series (ferric iron)
    • Magnetite - FeFe2O4
    • Magnesioferrite - MgFe2O4
    • Ulvöspinel - FeFeTiO4
    • Franklinite - ZnFe2O4
    • Jacobsite - MnFe2O4
    • Trevorite - NiFe2O4
  • Chromite series (chrome)
    • Chromite - FeCr2O4
    • Magnesiochromite - MgCr2O4

Most of the above series members are rare in nature with the exception of the members of the spinel series, magnetite and chromite. To gemologists common spinel and gahnite are of most interest.

When gemologist refer to "spinel", we usually imply common spinel, that is the spinel that belongs to the spinel series of the spinel group.

Diagnostics

Spinel can be confused with many stones by appearance alone, yet optical properties usually rule out most of them.
As spinel belongs to an isomorhous series, the optical and physical properties may vary.

Color

Spinel: colorless, green, blue, red, black.
Gahnite: blue-green, yellow, brown.

Varieties:

  • Pleonaste (also named ceylonite) - (Mg,Fe)Al204 - dark green to blue-green; black
  • Gahnospinel - (Mg,Zn)Al204 - pale to dark blue, black.

Spinel is allochromatic and variety colors are produced by transition metals:

  • Cr3+ - red, pink
  • Fe2+ - blue, violet
  • Fe2+ + Co2+ - darkblue
  • Fe3+ - green

Diaphaneity

Transparent to opaque.

Refractometer

Spinel is isotropic and the refractive index of common spinel is generally around 1.712 to 1.720. Red spinel can have a refractive index up to 1.74.
The only other isotropic gemstone that falls within this range is grossular garnet, but it will usually be higher and the color is also different.
Other members of the spinel series, such as gahnite will have higher refractive indices.

All other gemstones can easily be seperated from spinel by their optic nature.

Synthetic spinel has a usual refractive index of 1.727.
Gahnospinels have a refractive index between 1.725 and 1.753, while pleonaste (ceylonite) has an R.I. range of 1.77 to 1.80.
Black spinel-hercynite (pleonaste) stones from Thailand may have an RI upto 1.789 with an average SG of 3.86 (Seriwat, 2008)

Specific gravity

As with the refractive indices, the specif gravity of spinel can vary due to isomorphous replacement.
The values for most gem grade material lies between 3.58 and 3.61. Pleonaste has a S.G. between 3.63 and 3.90.
Gahnospinels may have a specific gravity up to 4.06.

Polariscope

Common spinel is isotrope and will remain dark under crossed polars.
Verneuil type synthetic spinel will always (maybe with the exception of red) show strong anomalous birefringence due to excess Al2O3 (see synthetics). This anomalous extinction (as it is currently named) can be seen as "tabby" extinction, resembling the color distribution of a cat's fur, or/and as an Andreas cross caused by pseudo-birefringence.

Natural and flux-melt synthetic spinel may show weak anomalous extinction.

Spectra

Spectrum natural blue spinel iron.jpg

Spectrum of a natural blue spinel, colored by iron and minor traces of cobalt.

Phenomena

  • Asterism (4 and 6-pointed stars)
  • Color change (rare)

Occurrence

Myanmar; Vietnam; Thailand; Sri Lanka; Pakistan; Afghanistan; Tadshikistan; Kenia; Tanzania; South-Africa; Brazil.

Synthetics

Spinel is synthesized by the Verneuil (flame-fusion) process and the flux-melt method, although the first process does not render a true synthetic in most cases.

Flame fusion

Flame fusion synthetic spinels are produced since 1908 (by accident while creating synthetic corundum), but were not commercially available until 1930.

It was found that while trying to synthesize spinel through the Verneuil process, the resulting boules would easily fracture and no reasonably sized gemstones could be cut from them.
The ratio MgO to Al2O3 is 1:1 for common spinel and by changing that ratio (adding Al2O3) the boules became stable. Because that alters the chemical formula of the synthetic, it is not a true synthetic (but accepted as such). Sometimes these are named "beta-corundum" due to the excess of alumnia.

For the creation of red stones, this alteration was no option and, usually, no red synthetic spinel boules created by the flame-fusion process result in large stones (but are known to excist). The larger sized red synthetic spinels are mostly created with the flux-melt method. The few red synthetics that are created through the Verneuil process will show curved striae like their synthetic corundum cousins.

As a result in the changing of the MgO:Al2O3 ratio, the flame fusion synthetics have higher refractive indices (usually stable at 1.727) and a higher specific gravity (3.64).

Properties of flame fusion synthetic spinel
color coloring agent RI SG other diagnostics
colorless none 1.728-1.740 3.65-3.80 LWUV: green; SWUV: white/blue
red Cr3+ 1.722-1.725* 3.58-3.60 curved striae; spectrum; fluorescence
pink Cu 1.727-1.740 3.65-3.80
yellow Mn do. do. LW/SWUV: green
emerald green Mn + Co3+ do. do.
tourmaline green Cr3+ do. do. spectrum
beryl green Cr3+ + Mn do. do. spectrum
zircon blue Co3+ + Cr3+ + Ti do. do. spectrum
sapphire blue Co3+ do. do. spectrum; fluorescence; CCF
amethyst violet Co3+ + Mn do. do.
alexandrite color change Cr3+ + V do. do. spectrum
lapis lazuli Co3+ 1.725 3.52 spectrum; CCF

Strong "tabby" extinction can be seen in all
* Henn, 1995 metions a low value of 1.720.

Flux-melt

First commercial production of flux-melt synthetic spinel started around 1980, although successful experiments date back to 1848 (by the French chemist Ebelmen). As of 1989 larger volumes of this synthetic appeared on the market, produced in Novosibirsk, Russia.

Apart from red, blue synthetics have also been produced by the flux-melt process.
These are true synthetics.

Properties of flux-melt synthetic spinel
color coloring agent RI SG other diagnostics
red Cr3+ 1.716-1.719 3.58-3.62 LW/SWUV: distinct red-orange/red
flux residu inclusions
blue Co2+ + Fe2+ 1.719 3.58 spectrum; SWUV: inert; LWUV: weak read
flux residu inclusions

Tabby extinction is also seen in these synthetics. Careful observation of inclusions is the main means of separation for red stones. Blue flux-melt synthetics can also be distinguished by the spectrum.

Czochralski pulling method

A recent development (2007) is the procuction of red to pink synthetic spinels by the Czochralski pulling method.

Inclusion images: Click on Image for Full Size

Apatite inclusions and their star-like outgrowths along the 60 degree hexagonal plane - looking much like stellate dislocation systems, in a cobalt blue spinel.
Photo courtesy of John Huff, gemcollections.com
Octahedral spinel inclusions with "Saturn-ring" stress fractures in a Burma red spinel.
Photo courtesy of John Huff, gemcollections.com
Octahedral inclusions in a Burma red spinel.
Photo courtesy of John Huff, gemcollections.com
Euhedral inclusions in spinel.
Photo courtesy of Conny Forsberg


Sapphirine inclusions gallery

Sources

  • Gems Their Sources, Descriptions and Identification 4th Edition (1990) - Robert Webster (6th ed.)
  • Edelsteinkuntliches Praktikum - Ulrich Henn, Gemmologie Jahrgang 44 / Heft 4 / Dezember 1995, Spinell pp.54-62
  • Diploma course notes 1987 - Gem-A
  • Über die Eigenshaften von im Flussmittelverfahren hergestellten synthetischen roten und blauen Spinellen aus Russland - U. Henn/H. Bank, Gemmologie Jahrgang 41 / Heft 1 / April 1992, pp1-7
  • Black Opaque Gem Minerals Associated with Corundum in the Alluvial Deposits of Thailand. Australian Gemmologist, 2008, Vol. 23, No. 6, pp. 242-253. Dr. Seriwat Saminpanya