Uncategorized – Coconino Lapidary Club

USE OF COLOR IN MINERAL IDENTIFICATION

Mineral Man Mel — Thu, 03 Jun 2021 18:48:41 +0000

In some minerals color is directly related to a metallic element, is characteristic, and can be useful in identification. As examples, azurite as shown in Figure 1A, is always blue due to the presence of copper, and rhodochrosite, shown in Figure 1B, is always pink to red due to the presence of manganese,. However minerals such as fluorite, colorless in it self, can be yellow, blue, purple, or green due to low concentrations of metal impurities.

Accordingly color alone, generally is insufficient for identification, but when linked with knowledge of other properties of a mineral can be useful in its identification.

Understanding of the roles of metals as sources of colors in a mineral, particularly when augmented with knowledge of its location where found, can be useful in identification. In this Blog I’ll describe how the presence of a transition metal element, present intrinsically or as an impurity, and certain structural features within the mineral are sources of colors or when present, can modify the appearance of the mineral.

Figure 1A. Azurite, Czar Mine, Copper Queen Mine, Queen Hill, Bisbee. Cochise County, Arizona[Ref1]

Figure 1B. Rhodochrosite, N’Chwaning Mines, Kuruman. Kalahari Manganese
Field, Northern Cape, South Africa[Ref2]

CAUSES 0F COLORS AND COLOR EFFECTS IN MINERALS

The color of a mineral that we see arises from transmission of light over the visible wavelengths of light within the visible light spectrum which are framed by one or more regions of wavelengths that are absorbed as shown in Figure 1C.

Figure 1C. With absorption of specific wavelength{s) of white light spanning wavelengths of red to purple results in transmission of light over a wavelength range imparting color[Ref3]

Extensive studies have shown that light absorption by a number of processes are among the causes of the colors in minerals as summarized in TABLE I[Ref4].

Absorption of light by electrons in transition metals present intrinsically or as impurities are involved in light absorption processes and the excitation of electrons within their intrinsic energy distribution within conductors and semiconductors upon light absorption also imparts colors in other minerals which are conductors and semiconductors. Excitation of an electrons or a hole (hole = absence of a negatively charged ion or electron) associated with color centers which reside in defects within the crystal lattice imparts colors in some minerals

Structural features in minerals with sizes of the order of the wavelengths cause physical optical effects: light scattering, interference, and diffraction of light. These can either introduces colors or add optical features to the appearance of the mineral.

TABLE I. CAUSES OF COLORS AND COLOR EFFECTS IN MINERALS[Ref4].

Light Absorption by Transition Metals[Ref4,5,6]

Among the causes of color in minerals listed in TABLE I[Ref4] are the ions of transition metals that contribute to the color of many minerals through selective light absorption over the visible light spectrum. They can be present as a major constituent such as manganese (Mn) in rhodochrosite(MnCO₃) giving it its pink-red color, present as a low concentration impurity in a mineral such as chromium (Cr)substituting for aluminum (Al) in Ruby giving its red color and the formula {Al,Cr_minor)₂O₃, and as ions of iron, chromium , manganese, titanium(Ti) participating in intervalence charge (electron) transfer between two of their ions and with the oxygen ion[Ref5].

Transition metals are present as a formulaic constituent and some as an impurity are shown along with their associated colors in TABLES II and III.

In a transition metal ion with a partially filled d-shell the electrons in the outer region of the d-shell are unpaired. The surrounding oxygen ions of the crystal lattice exert forces on the outer d-shell electrons dermining their occupied and empty energy levels[Ref5]. The forces and energy levels depend on the strength and nature of the bonding as well as the valence of the transition metal ion. These energy levels are quantized so that a absorption of a specific amount energy is required to to increase an electrons energy to another level. Absorption of light of that energy at the corresponding wavelength provides the energy required for excitation of the unpaired electron to a higher level.

As an example consider absorption and transmission of light in the ruby. The sumation of surrounding forces on the chromium ion Cr³⁺ result in two energy levels, C and D, avialable for an excited electron as shown in Figure 2[Ref3]. Symmetry conditions deny occupancy of level B by an excited electron [Ref].

As shown in Figure 3 light of 414 and 561 nm wavelengths is absorbed . With abosrbtion of these wavelengths light in the regions of 480 nm and greater than 620 nm are transmitted imparting the red color of the ruby.

Figure 2. Excitation of d-elecrons in Cr³⁺ in a ruby crystal upon absorption of 414 nm (2.99 eV) ultraviolight light and of 561 nm (2.21 eV) yellow- green light[Ref]. The peak abosorption and transmission of light within the ruby at these wavelengths are shown in the two spectra shown in Figure [Ref3]

Figure 3. Transmittance spectrum (Right) of a 1-cm thick ruby crysta[Ref4]. Absorptioon of light is greatest at 414 nm and 561 nm and transmittance in the blue at 480 nm and in the red at wavelengths greater than 620 nm in the red.

TABLE II. TRANSITION METALS PRESENT AS AN INTRINSIC CONSTITIUENT IN A MINERAL AND ASSOCIATED COLORS[Ref5,6]

TABLE III. TRANSITION METALS PRESENT AS AN IMPURITY IN A MINERAL AND ASSOCIATED COLORS[Ref5,6].

Light Absorption By Charge Transfer Between Transition Metal Ions and Between oxygen ions and Transition Metal Ions[Ref7,8].

Transition metals can exist in different valence states. These ions can form covalent bonds with oxygen in which electrons in outer shells can travel between the ions upon being supplied sufficient energy. This can result in charge transfer in the form of an electron upon absorption of light with wavelengths in the Ultraviolet through Visible into Near Infrared light ranges. Charge transfer from an adjacent oxygen to a transition metal ion and charge transfer between neighboring transition metal ions connected by an oxygen atom can occur. The direction of transfer charge is from the ion of least positive valence number to the neighbor of higher valence. For example the deep violet-blue color of cordierite var. Iolite as shown in Figure 4 results from the neighboring absorption peak centered at 600 nm due to charge transfer from a ferrous ion Fe²⁺ to a neighboring ferric ion Fe³⁺, and extending through the blue range of the spectrum as shown in Figure 5[Ref10]. Other examples of the processes of charge transfer in minerals with their associated colors are given in TABLE IV.

Figure 4. Cordierite var. Iolite, Mogok, Pyin-Oo-Lwin District, Mandalay Region, Myanmar[Ref9].

Figure 5. Absorption spectrum of cordierite var. Iolite from Tamil Nadu, India[Ref10].
Note that the wide absorption peak in the 400 to 600 nm range results in a transmission window in the violet.

TABLE IV. CHARGE TRANSFER PROCESSES IN SOME MINERALS WITH THEIR COLORS

Charge Transfer	Color and Mineral*	Reference
Oxygen to Metal Transfer
O^2-  Fe³⁺	Yellow to Brown: beryl/heliodor, quartz/citrine	11
O^2–  Fe⁴⁺	Purple: quartz/amethyst	11
O^2-  Cr⁶⁺	Yellow to red: Crocoite	11
O^2- U⁶⁺	Yellow: uranophane	11
Intervalence Charge Transfer
Fe²⁺–O—Fe³⁺	Violet: jadeite Blue: lazulite, vivianite,	11,12
Fe²⁺–O—Ti⁴⁺	Blue: berlaquamarine, corundum/sapphire, cordierite, amphibole,	11
Mn²⁺–O—Ti⁴⁺	Greenish-yellow: tourmaline	11
Others
Fe²⁺Ti⁴⁺ and both Fe³⁺ and Cr³⁺	Orange, sapphire	13

*For information on any mineral Google “Mindat.org + Mineral name”

Light Absorption By Color Centers[Ref4]

Unpaired electrons can be located on a non-transition metal ion or on a defect in the crystal lattice form color centers as shown in the Fluorite structure and quartz structure shown in Figures 5 and -6. An electron present at a lattice vacancy forms an electron color center and absence of an electron from where an electron pair is normally present forms a hole (lack of a negatively charged ion) center.

In fluorite the absence of a fluorine ion F^-1 from its normal position forms an F-center occupied by an electron as shown in Figure 6. Absorption at longer wavelengths by the F-center is responsible for a purple color in fluorite[Ref5].

In smoky quartz the presence of an aluminum ion Al³⁺as a low level impurity substituting for a silicon ion Si⁴⁺is required[Ref5]. Removal of an electron from an oxygen ion O^2- adjacent to aluminum ions by radiation results in the formation of a singly negative oxygen forming an electron-hole. To preserve charge neutrality a positive hydrogen ion H+ is present. Aluminum not substituting for silicon does not form smoky quartz. The same mechanism accounts for the yellow color of citrine[Ref11].

Figure 6. Schematic of normal fluorite structure (A) and fluorite with an
F-center occupied with an electron (B)[Ref5].

Figure 7. Schematic of the normal quartz structure (A) and containing impurity aluminum ions Al³⁺ replacing silica ions Si⁴⁺in the lattice (B)[Ref5]. Radiation has removed an electron from oxygen leaving a hole center of smoky quartz. To preserve charge neutrality a positive hydrogen ion H+ is present. Aluminum not substituting for silicon does not form smoky Quartz.

Light Absorption in Metals and Semiconductors: Band Theory[Ref5]

The band theory treats electrons as belonging to the crystal as a whole and capable of occupying bands or ranges of energies as shown for metals and semiconductors in Figures 8 and 9.[Ref5]. Colors of representative minerals described by band theory are shown in TABLE IV.

TABLE IV. COLORS OF METALS AND SEMICONDUCTORS DESCRIBED BY BAND THEORY[Ref5].

The Band Theory of Metals[Ref5]

In a metal such as copper or iron each metal atom contributes its outer electrons to a common pool in which they are free to move freely through the crystal accounting for the large electrical conductivity of metals as well as the metallic luster and specular reflection of metals. In a typical metal which contains 10²³ electrons per cm^-3 all essentially equivalent to each other, such that quantum mechanically

the energy levels are broadened into bands as shown in Figure 8A. The density of electrons each energy level is limited and states are filled to the maximum Fermi surface (level). Upon absorption of light electrons are excited to empty bands of higher energy with density of states varying with as shown in Figure 8B.

If the efficiency of absorption decreases with increasing energy in the blue-green spectrum as in gold and copper the spectrum features the yellow and reddish colors of gold and copper upon reemission of the electrons as shown by the reflectance spectra shown in Figure 9[Ref18]. The spectra of silver and aluminum in the figure show that light across the visible spectrum is absorbed and re-emitted leading to their white color.

Figure 8. Energy band of a typical metal (A) and showing energy transitions upon light absorption (B)[Ref5]. The Fermi Surface is the maximum energy of an electron in the valence band.

Figure 9. Reflectance (or fraction of light reflected) spectra of aluminum (Al), Silver (Ag), gold(Au), and copper(Cu)[Ref14] as also shown in the specimens in Figures 10-12.

Figure 10. Native silver on native arsenic, Pohla-Tellerhauser mine, Pohla, Saxony, Germany[Ref15].

Figure 11. Group of twinned native gold crystals, Round Mountain Mine, Round Mountain, Round Mountain Mining District, Toquima Range, Nye County, Nevada[Ref16].

Figure 12. Twinned crystals of native copper, Chino Mine, Santa Rita, Santa Rita mining district, Grant County, New Mexico[Ref17].

Figure 13. Energy bands in a typical semiconductor (A), energy transitions upon light absorption in (B), the dependence of color on energy(C), and the color stemming from a band gap of that energy (D)[Ref5].

The Band Theory of Semiconductors[Ref5]

Many sulfide minerals are semiconductors that exhibit substantial electrical conductivity, high refractive indices, and often a metallic luster[Ref4]. In minerals where bonding is predominantly covalent or ionic the sulfur electrons occupy a valence band as shown in Figures 13A and 13B. A band comprised of empty metal electron orbitals exists at higher energies separated from the valence band by an energy gap as shown in Figure 13. Absorption of light by electrons of energy greater that the gap energy excites them into the conduction band as shown in the Figures 13C and 13-D. If the band gap is smaller that the energy of the visible light range all of the light is absorbed and the mineral behaves like a metal and appears black or grey as shown in Figures 13–C and13 -D and by tetrahedrite with a band gap of 0.000 eV[Ref21] and galena with a band gap of 0.993 eV[Ref 22] and shown in Figures 14 and 15. As the band gap energy increases the wavelengths excited in the spectrum become shorter and colors shift through red to yellow. The band gaps of those semiconductors such as diamond and sphalerite with band gaps of about 5.5 and 3.5 eV are greater than available energy at the lowest wavelength (highest energy) of the visible spectrum and the light is absorbed. With an intermediate band gaps of 1.99 eV and 2.197eV, respectively cinnabar appears red and orpiment yellow-orange as shown in Figures 16 and 17[Ref23].

Figure 14. Hopper crystal of tetrahedrite, Romania[Ref26]. The crystal is black because with a band gap of 0.000 eV tetrahedrite absorbs all visible wavelengths[Ref18,19].

Figure 15. Galena, Sweetwater mine, Ellington, Reynolds County, Missouri[Ref20].

Figure 16. Cinnabar, Almade’n mine, Almade’n, Almade’n Mining District, Ciudad Real, Castle-La Manch, spin[Ref21].

Figure 17. Orpiment, Twin Creeks Mine, Potosi Mining District, Osgood Mountains,
Humboldt County, Nevada[Ref22].

Light Absorption and Colors in Impurity and Defect Semiconductors[Ref5]

Certain impurities can cause light absorption in large band gap minerals. Absorption of light nitrogen and boron impurity centers as shown in Figure A and –B results, respectively in yellow and blue colored diamonds.

Yellow Diamonds

Figure 18. Light absorption in the blue-violet spectral range by a
nitrogen impurity results in the yellow color of a diamond[Ref23].

Figure 19. Yellow diamond of 32.77 carats[Ref27].

Blue Diamond

Figure 20. The boron acceptor atom accepts electrons with energies corresponding to the green to red region of the visible spectrum resulting in transmission of the blue color[Ref23].

Figure 21. The blue Hope diamond[Ref28].

Green Diamond

A green color in a diamond arises from absorption of light in the yellow to red wavelength region by electrons associated with defects in the periodicity of the diamond crystal lattice as shown in Figure [Ref24].

Figure 22. The defects in the diamond lattice that are responsible for a green color in a diamond: In Figure 2.A, absorption by unbonded electrons surrounding a lattice vacancy (missing carbon atom); in 2.B light absorption by unbound electrons surrounding a lattice vacancty associated by a pair of neighboring nitrogen atom impurities; in 2.C light absorption by electrons associated with a hydrogen atom with a neighboring nitrogen atom impurity; in 2.D absorption of light by a defect comprised of two neighboring carbon lattice vacancies with an associated nickel atom[Ref24].

Pink Diamond

Color defect centers developed along deformation planes in the diamond crystal lattice diamond are responsible for the coloration in pink diamonds as shown in Figure23[Ref25,26].

Figure 23. Pink Diamonds, Argyle Mine, East Kimberly region, Australia[Ref39].

Colors and Features Caused by Physical Optics

Play of color due to structural characteristics of the gemstone can be useful in mineral identification. Iridescence, opalescence and labradorescence, chatoyancy, and asterism are characteristics of a limited number of minerals.

Opalescence

Opalescence is an opal-like play of light producing flashes of different colors as in an opal as shown in Figure 24[Ref40]. The various colors are produced by diffraction from regions with layers of different thickness of formed by silica spheres of different uniform diameters[Ref41]

Figure 24. Structure of precious opal showing uniform layers of silica spheres[Ref30].

Figure 25. The “Virgin Rainbow” opal, Coober Pedy, Australia[Ref31]

Labradorescence

Labradorite is a feldspar mineral comprised having striations of exsolved lamellae of nanometer of albite in the 10s to 100sof nanometers size range in anorthite with both having different calcium and sodium concentrations. Accordingly their refractive indices are unequal[Ref39,40] and the striations diffract light giving the colors according to the thicknesses of the lamellae giving the labradorescence as shown in Figure 25[Ref44].

Figure 26. Labradorite cabochon showing striations with alternating lamellae of albite and anorthite of different thicknesses, hence different colors[Ref32].

Iridescence

Iridescence is the play of colors produced in a thin film of different refractive index than in the surroundings and varying thickness such as the wall of a soap bubble or layer of oil on water[Ref45]. Like diffraction the colors depend on thickness and angle at which viewed. The iridescence of some specimens of the copper mineral chalcopyrite as shown in Figure is a classic example of iridescence on a mineral surface where the colors range from blue to red with increasing thicknesses of the film.

Figure 27. Iridescent chalcopyrite, Greystone Quarry, Lezant, Cornwall,
England[Ref34].

Chatoyancy

Chatoyancy is an effect of preferential light scattering by parallel aligned rod like mineral inclusions like the fibers of crocidolite (asbestos) cemented in quartz of the gemstone tigers eye as shown in Figure 28[Ref35,36]. Aligned needle-like microcrystals crystals of rutile are responsible for the chatoyancy of chrysoberyl as shown in Figure .[Ref37]

Figure 28. Chatoyant tigers eye showing aligned structure of crocidolite[Re38].

REFERENCES

Ref 1. https://www.mindat.org/photo-257370.html

Ref 2. https://www.mindat.org/photo-83179.html

Ref 3. http://gemologyproject.com/wiki/index.php?title=Causes_of_color

Ref 4. . https://en.wikipedia.org/wiki/File:Ruby_transmittance.svg

Ref 5. http://www.minsocam.org/msa/collectors_corner/arc/color.htm

Ref 6 https://en.wikipedia.org/wiki/Transition_metal

Ref 7. https://www.higp.hawaii.edu/~gillis/GG671b/Week02/Readings/Deep%20Reading/Burns_CrystalFieldTheory_Ch2and3.pdf

Ref 8. https://www.gia.edu/doc/SP88A1.pdf

Ref 9. https://www.mindat.org/photo-650677.html

Ref 10. http://minerals.gps.caltech.edu/files/Visible/cordierite/Cordierite2016_India.gif

Ref 11. https://www.gia.edu/doc/SP88A1.pdf

Ref 12. http://minerals.gps.caltech.edu/color_causes/ivct/index.htm

Ref 13. file:///Users/millardjudy/Downloads/[20834799%20-%20Advances%20in%20Materials%20Science]%20Heat%20treatment%20enhancement%20of%20natural%20orange-red%20sapphires.pdf

Ref 14. https://eng.libretexts.org/Bookshelves/Materials_Science/Supplemental_Modules_(Materials_Science)/Optical_Properties/Metallic_Reflection

Ref 15. https://www.mindat.org/photo-109627.html

Ref 16. https://www.mindat.org/photo-112379.html

Ref 17. https://www.mindat.org/photo-78563.html

Ref 19. https://materialsproject.org/materials/mp-647164/

Ref 20. https://materialsproject.org/materials/mp-21276/

Ref 21. https://i.pinimg.com/originals/72/26/67/7226674458e6dd34ba15b72f4034130f.jpg

Ref 22. https://en.wikipedia.org/wiki/Hopper_crystal

Ref 23. https://materialsproject.org/materials/mp-641/

Ref 24. https://www.mindat.org/photo-85601.html

Ref 25. https://www.mindat.org/photo-83818.html

Ref 26 https://www.mindat.org/photo-56538.html

Ref 27. http://www.webexhibits.org/causesofcolor/11A0.html

Ref 28. https://www.gia.edu/gems-gemology/spring-2018-natural-color-green-diamonds-beautiful-conundrum

Ref 29. https://www.gia.edu/doc/Characterization-and-Grading-of-Natural-Color-Pink-Diamonds.pdf

Ref 30. https://br.pinterest.com/pin/27092035231593578/

Ref 31. https://www.smithsonianmag.com/travel/the-hope-diamond-102556385/

Ref 32. https://www.pinterest.com/pin/AaGzMFSFFrs9vFLxcvJNl4g6FGLK1W2_i5FGc6i82BuZSmK7fjG7pJ0

Ref 33. http://www.uniqueopals.ch/opal-play-of-colour.htm

Ref 34. http://www.uniqueopals.ch/opal-play-of-colour.htm

Ref 35. https://www.geologyin.com/2016/07/worlds-most-expensive-opal-literally.html

Ref 36. https://www.mindat.org/min-2308.html

Ref 37. https://www.britannica.com/science/exsolution

Ref 38. https://www.google.com/search?client=firefox-b-1-d&q=refractive+index+of+albite

Ref 39. https://www.google.com/search?client=firefox-b-1-d&q=refractive+index+of+anorthite

Ref 40. https://www.sciencedirect.com/topics/medicine-and-dentistry/diffraction-grating

Ref 41. https://austinbeadgallery.com/what-to-look-for-in-labradorite-cabochons/

Ref 42.

https://www.asu.edu/courses/phs208/patternsbb/PiN/rdg/interfere/interfere.shtml

Ref 43. https://www.crystalclassics.co.uk/product/chalcopyrite-(irridescent)/

Ref 44. https://en.wikipedia.org/wiki/Chatoyancy

Ref 45. https://www.asbestos.com/blog/2020/04/20/asbestos-jewelry-mesothelioma/

Ref 46. https://blogs.scientificamerican.com/rosetta-stones/tiger-s-eye-a-deceptive-delight/

Ref 47. https://en.wikipedia.org/wiki/Chrysoberyl#Cymophane

Meteorites

Mineral Man Mel — Sat, 27 Jun 2020 18:18:06 +0000

Meteorites are stuff from outer space; each is a solid piece of debris which formed from dust within the protoplanetary disc or from object such as an asteroid, planetesimal, or planet, and which travels through space and falls through the atmosphere to the surface of earth. As alien objects which fall dramatically they have evoked interest and wonder among many people. I remember vividly at the age of ten watching with my dad the meteorites fall during a Perseid Meteor Shower such as shown in time lapse photography in Figure 1. We both were greatly excited by the sights of the darting meteor trails and the awe felt by both of us felt was almost palpable. This fond memory has prompted me to write about meteorites in hopes of further acquainting my readers with them.

I will write three blogs about meteorites; in the first I’ll consider both iron and stony-iron meteorites, and the following blogs will be about chondrites and achondrites, both classes of stony meteorites, and lastly about chondrules, which are constituents of chondrites and are sub-millimeter to millimeter-sized spherules containing silicates and another minerals and are often quite beautiful.

The three major classifications of meteorites based on their mineral compositions are: stony meteorites which are comprised of silicate minerals, iron meteorites which primarily are comprised of an alloy of iron and nickel, and stony-iron meteorites which are comprised of a mixture of iron-nickel alloy and silicate minerals. Iron-nickel meteorites can also contain sulfide, carbide, phosphide minerals of iron, nickel, cobalt, and chromium, as well as native carbon. The class of stony-iron meteorites are comprised of two subclasses, pallasites and mesosiderites[. The distribution of classes of meteorites found world-wide are shown in TABLE 1 and examples of them are Figures 2-5.

Figure 1. Time-lapse photograph showing meteors falling during a Perseid Meteor Shower[

TABLE 1. DISTRIBUTION OF CLASSES OF METEORITES BY FALLS FOUND THROUGHOUT THE WORLD

METEORITE CLASSIFICATION	PERCENTAGE
Stony	97.4
Iron-Nickel	2.0
Pallasite	0.2
Mesosiderite	0.4

IRON AND STONY-IRON METEORITES

Meteorites containing an iron-nickel alloy are classified as the iron meteorites, and the stony iron meteorites, the latter including the pallasites and the mesosiderites.

In the iron meteorites the iron-nickel alloy is present as two minerals: kamacite which contains up to 7.5% dissolved nickel in solution with iron and taenite with more than 25% nickel in solution. Other minerals which contain iron, nickel, cobalt, phosphorous, oxygen, sulfur, and carbon in lesser abundance may be present in iron meteorites. These minerals with their compositions are summarized in Table 2. Each minda.org reference contains representative photographs of the mineral.

TABLE 2. MAJOR MINERALS FOUND IN IRON AND STONY IRON METEORITES

MINERAL	CHEMICAL FORMULA	MINDAT.ORG REFERENCE
Kamacite	(Fe,Ni)	8
Taenite	(Fe,Ni)	9
Troilite	FeS	10
Daubre’elite	Fe²⁺Cr³⁺₂S₄	11
Cohenite	(Fe,Ni,Co)₂₃C₆	12
Schreibersite	(Fe,Ni)₃P	13
Chromite	Fe²⁺Cr³⁺O₄	14
Magnetite	Fe₃O₄	15
Corundum	Al₂O₃	16
Graphite	C	17
Diamond	C	18
Lonsdaleite	C	19

Figure 2. Canyon Diablo meteorite, Barringer Meteor Crater region, Coconino County, Arizona. Note the sculpting of its form by ablation and loss of the molten surface layer of iron alloy formed by frictional forces during its fall through the air.

Figure 3. Etched slice of a Canyon Diablo meteorite, Barringer Meteor Crater Region, Coconino county, Arizona[Ref28]. Note both the brown crystal of troilite with a grey rim of cohenite and the The angular Widmenstatten are comprised of angular interleaving bands of the iron-nickel alloys kamacite and taenite referenced in TABLE 1.

The Structure and Metallurgy of Iron-Nickel Meteorites

Iron-nickel meteorites are thought to be remnants of the cores of planetesimals following collision between them . With slow cooling during solidificaiton of the core the liquid alloy mixture of iron and nickel results in a mixture of the two minerals kamacite and taenite. With sufficiently slow cooling to 912 deg C and below discrete visible crystals of each mineral form separately as shown in the iron-nickel phase diagram. The interleafed arrangement of the crystals results in the arrangement called Widmanstatten Figures as shown in Figure 3 which become visible upon etching with an acid. The different grey-tones of the crystals develop from different etching susceptibilities which arise from the different atomic arrangements within face-centered cubic kamacite and body-centered cubic taenite.

Structure, Mineral Composition, and Formation of Stony-iron Meteorites

Stony-iron meteorites consist of approximately equal parts of iron-nickel alloy and silicate minerals as opposed to stony meteorites which primarily are made up of silicate minerals. Stony-iron meteorites are divided into two groups, the pallasites and the mesosiderites Pallasites have silicate minerals, mostly olivine embedded in the meteoric iron. Mesosiderites are breccias comprised of fragments of meteoric iron interspersed with fragments of silicate minerals.

Pallasites

Results of a recent study suggest that pallasite meteorites may have formed in a glancing impact between a body with a largely solidified core surrounded by a molten layer and a larger body. It is assumed that loss of the solid core and formation a body comprised of aggregates of fragments of olivine surrounded by molten iron-nickel alloy ensued. Solidification of the molten alloy results in cementation of the olivine fragments which results in the structure shown in Figure 4

Figure 4. The olivine usually is present in a 2/1 volume ratio with the iron-nickel matrix. The boundary regions between an olivine crystal and metal may contain thin layers of a mineral such as troilite, schreibersite, or chromite.

Mesosiderites

Mesosiderites are considered to have formed from fragments of iron-nickel alloy and silicate minerals which resulted from collision of metal-rich and silica-rich asteroids. The fragments may be of the igneous rocks, basalts, gabbros, and pyroxenites of igneous rocks as well as fragments of the minerals orthopyroxene, olivine, and plagioclase. The Iron-nickel metal is mostly in the form of millimenter or sub-millimeter grains admixed with grains of silicate minerals in the same size range surrounding the larger fragments of rocks and minerals. These structural features are shown in Figure 5.

Figure 5 . Mesosiderite, found at Gillio, Libya in 1985. Metal nodules, pyroxene, on Ca-pyroxene fragments, plagioclase, pyrrhotite, chromite, and both kamacite and taenite are present.

Art Deco Rubies

Mineral Man Mel — Sun, 05 Apr 2020 16:14:00 +0000

Art Deco is my favorite style of jewelry, with its flair of design and the use of unusual combinations of gemstones. Art Deco is a style of architecture and design which first appeared in France just before World War I, reached its high point during the 1925 Paris Exposition of Decorative Arts, and extended into the 1940’s. Today, authentic Art Deco period jewelry and art objects, as well as reproductions, remain esteemed by wearers of jewelry and collectors. In the following gallery I’ve included ruby jewelry and art objects which greatly appeal to me.

RUBY JEWELRY AND ART WORKS GALLERY

Figure 1. Art Deco brooch with carved ruby and surrounding diamonds [Ref 1].

Figure 2. Art Deco diamond and ruby floral cluster setting in a platinum ring [Ref 2].

Figure 3. Art Deco ruby and diamond decorated onyx compact [Ref 3].

Figure 4. Art Deco carved ruby and emerald, diamond, onyx, and enamel
pendant brooch [Ref 4].

Figure 5. Art Deco carved jade, diamond, ruby, and platinum card case [Ref 5].

Figure 6. Art Deco ruby and diamond necklace and brooch [Ref 6].

Figure 7. Art Deco ruby, onyx, and diamond set platinum brooch [Ref 7].

Figure 8. Art deco carved ruby, sapphire, emerald, and diamond “Tutti Frutti” bracelet [Ref 8].

Figure 9. Art Deco ruby and diamond yellow gold watch [Ref 9].

Figure 10. Art Deco carved jade, ruby, and onyx
Pendant brooch [Ref 10].

REFERENCES

Ref 1. http://www.gemscene.com/art-deco.html

Ref 2. https://www.carters.com.au/index.cfm/item/387782-an-art-deco-style-diamond-and-ruby-ring-of-floral-cluster-design/

Ref 3. https://www.pinterest.com/pin/509751251551385459/

Ref 4. https://www.pinterest.com/pin/509751251547056346/

Ref 5. https://www.pinterest.com/pin/94716398384257546/?lp=true

Ref 6. https://www.flickr.com/photos/clivekandel/6839720818

Ref 7. https://www.1stdibs.com/jewelry/brooches/brooches/1920s-art-deco-ruby-onyx-diamond-platinum-canvas-brooch/id-j_1323593/

Ref 8. https://www.christies.com/features/Cartier-jewels-collecting-guide-9582-1.aspx

Ref 9. https://www.1stdibs.com/jewelry/watches/wrist-watches/1940s-art-deco-112-carat-ruby-101-carat-diamond-yellow-gold-watch/id-j_4725961/

Ref 10. https://www.pinterest.com/pin/354799276872845520/

Largest Star Sapphire/Ruby

Mineral Man Mel — Sun, 26 Jan 2020 17:16:52 +0000

We usually think of star sapphires and rubies as stones in the few carat range, not in hundreds and thousands of carats. But some are an amazing size. At the top, are the World’s Largest which are truly awesome. In this blog I’ll describe the worlds largest blue star sapphire, star ruby, and black star sapphire, as well as gems ranking near their size but just below the record. I’ll also include a short history of each gem.

Worlds Largest Blue Star Sapphire: The Star of Adam [Ref 1, Ref 2]

The world’s largest star sapphire weighs an amazing 1,4O4 carats, and when held, largely occupies the palm of a hand, as shown in Figure 1.

Figure 1. Star of Adam

The stone was found in the fall of 2015 at mine in the famed alluvial gem deposits near Ratnapura, Sri Lanka [Ref 1 Ref 2]. At first sight, the owner estimated the value of the gem at $175 million. As of January 2016, the owner was pondering whether to auction the gem or to display it. A diligent trip over the internet disclosed no further information about any attempt to auction the gem. However, the gem may have been sold in a private transaction.

World’s Largest Black Star Sapphire: The Black Star of Queensland [Ref 3, Ref 4, Ref 5]

The Black Star of Queensland, as shown in Figure 2, weighs 733 carats, and was the world’s largest sapphire until being displaced by the Star of Adam. This gem is also seen to fill the palm of a hand but does not have the cabochon height of the Star of Adam.

Reportedly, the rough stone was found by a twelve-year old boy, Roy Spencer, in the mid-1930s, in the Reward Claim near Anakie, Queensland, Australia [Ref 3]. The boy’s father, Harry Spencer, assumed it was merely a black crystal and the family used it as a doorstop for over a decade. A second look disclosed the gem.

The stone was sold by Spencer in 1947 to the jeweler Harry Kazanjian for $18,000AU which funded a new house for the family. The subsequent history of the stone has been shared by owners and institutions. The gem was loaned to the Natural History Museum of the Smithsonian Institution in 1969. In 1971 it was seen around Cher’s on television show. To fulfill a childhood dream, the artist and jeweler, Jack Armstrong, and his wealthy girlfriend, Gabrielle Grohe, convinced the Kazanjian family to sell the gem in 2003 [Ref 4]. In 2010 [Ref 5], the pair squabbled over the stone and Armstrong agreed to pay $500,000 for Grohe’s share, but failed to pay, and due to a judge’s ruling he lost all right to the gemstone.

Figure 2. Worlds largest black star sapphire [Ref 6].

World’ Largest Star Ruby: the Appalachian Ruby Star [Ref 7]

The Appalachian Ruby Star weighs 139.43 carats and barely edges out the Rosser Reeves Star ruby, that weighs in at 138.72 carats, as shown in Figure 3. The Appalachian Star ruby was cut from a rough ruby, which also yielded three additional stones. The weight of the group of four star rubies became known as the Mountain Star Ruby Collection and is shown in Figure 4. The aggregate weight of the rubies totals 342 carats.

The rough ruby was found in 1990 by Wayne Messer, a fishing guide in Western North Carolina. He had noted traces of corundum in a stream bed and traced the alluvial stones back to their source. Upon digging some eight feet, found the rough ruby. The quartet of star rubies was cut by Sam Fore from the rough stone which weighed 377 carats.

The Appalachian Star ruby was exhibited in 1992 at the Natural history Museum in London, drawing an estimated 150,000 people. Several attempts were made over the years to sell the collection, appraised at a value close to $100 million. Only recently, following the death of Messer, was the collection offered for sale.

Figure 3. The Appalachian Star, World’s Largest Star ruby [Ref 7].

Figure 4. The four star rubies, cut from the large rough ruby which gave the Appalachian Star [Ref 7].

The Rosser Reeves Ruby [Ref 8, Ref 9]

At a weight of 138.7 carats, the Rosser Reeve Ruby is the world’s second heaviest star ruby, and was found in Sri Lanka. The gem is named after Rosser Reeves a pioneer in the advertising industry. Rosser donated the gem to the Smithsonian Institute in 1965. Despite his attractive tale of buying the gem at an auction in Istanbul, he actually bought the gem from Robert C. Nelson Jr. At purchase, the stone weighed just over 140 carats, but was scratched and so was re-polished, which also helped to re-center the star on the Cabochon. Fortunately for museum goers, this beautiful gem still can be seen at the Smithsonian institute. As a note, the Wikipedia article used as the reference for this segment of the blog was written by Brendan Reeves, great grandson of Rosser.

Figure 5. The Rosser Reeves star ruby [Ref 9].

REFERENCES

Ref 1. https://www.forbes.com/sites/trevornace/2016/01/10/worlds-largest-blue-star-sapphire-found-worth-300-million/#6a06d4f075d1

Ref 2. https://www.mindat.org/loc-3147.html

Ref 3. https://en.wikipedia.org/wiki/Black_Star_of_Queensland#cite_note-5

Ref 4. https://www.upi.com/Feature-Legendary-sapphire-for-sale/10481044491153/

Ref 5. http://articles.latimes.com/2010/jan/05/local/la-me-blacksapphire5-2010jan05/2

Ref 6. https://www.pinterest.com/pin/863987509737025682/

Ref 7. https://www.mnn.com/earth-matters/wilderness-resources/blogs/extremely-rare-star-rubies-found-fishing-guide-could-fetch-millions

Ref 8. https://en.wikipedia.org/wiki/Rosser_Reeves_Ruby

Ref 9. https://geogallery.si.edu/10002811/rosser-reeves-star-ruby

Corundum – From Sapphires to Rubies

Mineral Man Mel — Sun, 10 Nov 2019 17:08:54 +0000

Gemstones of the mineral corundum [Ref 1] offer a rainbow of colors for the lapidarist and jewelry maker as displayed in Figure 1.

Traditionally, of these, the ruby and blue sapphire, along with diamond and emerald, are considered to be the four-membered family of precious gems. Corundum gemstones, other than the ruby and blue sapphire, are also considered sapphires, having colors ranging from green to pink.

In this blog, I’ll describe the crystallography of corundum, and the physical and optical properties of corundum, including the sources of the colors in its gemstones. I will also present a gallery of ruby and sapphire mineral specimens.

Figure 1. A rainbow of the gemstones from corundum: ruby, blue sapphire, and green to pink sapphires.

CRYSTALLOGRAPHY OF CORUNDUM [Ref 1]

Crystal System of Corundum

Corundum crystallizes in the Trigonal System, which has three axes in a plane and are arranged at 120 degrees to each other, with an axis perpendicular to the plane, as shown in Figure 2. Of the typical forms of crystals shown in the figure, corundum frequently crystallizes as a hexagonal prism, terminated by the basal pinacoid; as a bipyramid, the hexagonal prism is terminated by a bipyramid; the rhombehedron and the hexagonal prism are terminated by the rhombehedron, and the schalenohedron. Examples of corundum crystals taking these forms are shown in Figures 5-11. Figure 7 shows a diagram of a crystal exhibiting all of these forms except the rhombohedron and schalenohedron. The latter form is shown by the sapphire crystal in Figure 10.

Figure 2. The four axes of the trigonal crystal system

Figure 3. Properties of the Trigonal Crystal System

Figure 4. Crystal of corundum with typical forms; only the schalenohedron is not shown.

Twinning in Corundum [Ref 1].

Multiple twinning on the rhombohedral plane with laminar structure with striations on both the basal pinacoid perpendicular to the c-axis and the hexagonal prism or on bipyramid faces, as shown by the terminated bipyrimidal sapphire crystal, shown in Figure 10 [Ref 12]. Corundum is also twinned on the hexagonal prism faces of tabular crystals exhibiting an arrowhead shape, as shown by the sapphire specimen in Figure 11[Ref 13]. The view is at the base of the arrowhead shape and pointing towards the tip. Less frequent twinning in corundum occurs on the basal pinacoid, perpendicular to the long axis of the crystal, as showing repetitive twinning along its length in Figure 12.

The view is at the base of the arrowhead shape and pointing towards the tip. Less frequent twinning in corundum occurs on the basal pinacoid, perpendicular to the long axis of the crystal, as showing repetitive twinning along its length in Figure 12.

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MECHANICAL PROPERTIES OF CORUNDUM [Ref 2]

The high values of hardness and ultimate strength and its resistance to cleavage, underlie the toughness of corundum gemstones and their wide usage in rings and bracelets, both susceptible to impact while worn. Values of the strength factors of corundum are summarized in TABLE I.

TABLE I. STRENGTH FACTORS OF CORUNDUM GEMSTONES

PROPERTY	VALUE/OBSERVATION	REFERENCE
Mohs Hardness SCALE	9 (Member of scale)	11
Ultimate Compressive Strength	435,000 psi	13
Ultimate Tensile Strength	43,500 psi	13
Flexural Strength	58, 000	13
Tenacity	Brittle	11
Fracture	Irregular/Uneven, Conchoidal	11
Cleavage	None Observed	11

OPTICAL PROPERTIES OF CORUNDUM [Ref 1]

The Refractive Index values of corundum lie in the ranges 1.759-1.772 depending on direction of light polarization. These values are considerably below the value of 2.418 for diamond [Ref 3], and underlies the beauty of corundum gemstones being in their vivid colors and not in brilliance or fire.

The light reflected from the surface, without penetration into gemstones is colorless, as often seen in photographs of gemstones, as in Figure 14.

Light scattering from oriented needle-like crystals of rutile, or to colloidal or other material in oriented tubules is observed in the star sapphire and star ruby as described in another blog on star rubies and sapphires [Ref 4].

Figure 14. Reflections from the surface of the ruby gemstone are colorless, while those reflected from the back of the stone are colored.

SOURCES OF COLOR IN CORUNDUM GEMSTONES

Corundum is aluminum oxide, with the formula Al₂O_3. Each trivalent aluminum Al³⁺ion is surrounded by six oxygen ions, located at the tips of an octahedron in the crystal lattice of corundum, shown in Figure 15. Defects in the forms of ions of metal impurities substituting for the aluminum ion, are responsible for the colors of corundum [Ref 5 ]. The impurity metal ions and the associated colors are summarized in Table I, shown in Figure 4. The divalent and trivalent ions substitute for the aluminum ion in the lattice of the corundum lattice.

Figure 15. Crystal lattice of corundum.

Figure 4. Sources of colors in corundum gemstones. See legend for terms below.

Legend for Figure 4
Cr³⁺ = Trivalent chromium ion
Fe³⁺ = Trivalent iron ion
Fe²⁺ = Divalent iron ion
Ti⁴⁺ = Tetravalent titanium ion
O¹-V = neighboring monovalent oxygen ion O^1- and lattice vacancy V in lattice
taking the place of an Al³⁺ ion.
Al³⁺ = Trivalent aluminum ion

COLOR CHANGES IN HEAT TREATED SAPPHIRES

Consideration of the various colors in natural sapphires, having different combinations and concentrations of the ions and ion pairs, before and after their heat treatment, serves to demonstrate their effects on color in corundum gemstones. The results of heat treatments are shown in Figures 16-18.

Some sapphires are heat treated to improve the attractiveness of their colors. Studies were carried out to identify changes in concentrations of ions that led to improvements in the aesthetics of the gem stone. The studies showed two major effects in the brown-toned sapphires and in the optical absorption spectrum of sample rO 4/5, red orange. The red trace of the absorption spectrum shows increased absorption due to the chromium ion, a decreased absorption due to trivalent iron ion pairs contributed from paired divalent and trivalent iron ions and single trivalent iron ions. The heat treatment resulted in an increased number of paired divalent iron ions and tetravalent titanium ions. The lessened absorption by iron ions resulted in smaller contributions to the color of the gemstone in the yellow to orange spectral range. Increased trivalent chromium ion concentration resulted in increased absorption of the blue and yellow spectral range and increased transmission in the red spectral range. Increased absorption in the yellow-orange range, due to increased absorption by paired divalent iron and tetravalent titanium ions resulted in increased transmission in the blue spectral range. The lessened transmission in the yellow-orange and increase transmission in the red and blue color ranges resulted in the cherry-pink color of the gemstone.

Figure 16. Ranges of colors in sapphires obtained with heat treatment under reducing conditions, within two temperature ranges.

Figure 17. Samples of sapphires before and after heat treatments at 1100-1700
Degrees C. Samples before treatment are shown in the top row and after treatment shown in the following rows.

Figure 18. Changes in light absorption and transmission in a sapphire with a red-orange color before treatment and a cherry-pink color achieved after treatment.

GALLERY OF SAPPHIRE AND RUBY SPECIMENS

Many specimens on display are from alluvial deposits where erosion of the edges and faces arose from wear against surrounding gravel and sand.

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Ref 1. https://www.mindat.org/min-1136.html

Ref 2. http://www.matweb.com/search/datasheet_print.aspx?matguid=c8c56ad547ae4cfabad15977bfb537f1

Ref 3.

https://refractiveindex.info/?shelf=3d&book=crystals&page=diamond

Ref 4. https://en.wikipedia.org/wiki/Asterism_(gemology)

Ref 5.

https://www.researchgate.net/publication/273531857_The_Color_Change_of_Natural_Green_Sapphires_by_Heat_Treatment/download

Ref 6.

https://www.degruyter.com/downloadpdf/j/adms.2012.12.issue-2/v10077-012-0006-3/v10077-012-0006-3.pdf