Cubic zirconia

Cubic zirconia (CZ) is the cubic crystalline form of zirconium dioxide (ZrO₂). The synthesized material is hard, optically flawless and usually colorless, but may be made in a variety of different colors. It should not be confused with zircon, which is a zirconium silicate (ZrSiO₄). It is sometimes erroneously called cubic zirconium.

Because of its low cost, durability, and close visual likeness to diamond, synthetic cubic zirconia has remained the most gemologically and economically important competitor for diamonds since commercial production began in 1976. Its main competitor as a synthetic gemstone is a more recently cultivated material, synthetic moissanite.

Technical aspects

Cubic zirconia is crystallographically isometric, an important attribute of a would-be diamond simulant. During synthesis zirconium oxide would naturally form monoclinic crystals, its stable form under normal atmospheric conditions. A stabilizer is required for cubic crystals to form, and remain stable at ordinary temperatures; this may be typically either yttrium or calcium oxide, the amount of stabilizer used depending on the many recipes of individual manufacturers. Therefore, the physical and optical properties of synthesized CZ vary, all values being ranges.

It is a dense substance, with a specific gravity between 5.6 and 6.0 — at least 1.6 times that of diamond. Cubic zirconia is relatively hard, 8–8.5 on the Mohs scale— slightly harder than most semi-precious natural gems.^[1] Its refractive index is high at 2.15–2.18 (compared to 2.42 for diamonds) and its luster is adamantine. Its dispersion is very high at 0.058–0.066, exceeding that of diamond (0.044). Cubic zirconia has no cleavage and exhibits a conchoidal fracture. Because of its high hardness, it is generally considered brittle.

Under shortwave UV cubic zirconia typically fluoresces a yellow, greenish yellow or "beige". Under longwave UV the effect is greatly diminished, with a whitish glow sometimes being seen. Colored stones may show a strong, complex rare earth absorption spectrum.

History

Discovered in 1892, the yellowish monoclinic mineral baddeleyite is a natural form of zirconium oxide.^[2]

The high melting point of zirconia (2750 °C or 4976 °F) hinders controlled growth of single crystals. However, stabilization of cubic zirconium oxide had been realized early on, with the synthetic product stabilized zirconia introduced in 1929. Although cubic, it was in the form of a polycrystalline ceramic: it was used as a refractory material, highly resistant to chemical and thermal attack (up to 2540 °C or 4604 °F).^[3]

In 1937, German mineralogists M. V. Stackelberg and K. Chudoba discovered naturally occurring cubic zirconia in the form of microscopic grains included in metamict zircon. This was thought to be a byproduct of the metamictization process, but the two scientists did not think the mineral important enough to give it a formal name. The discovery was confirmed through X-ray diffraction, proving the existence of a natural counterpart to the synthetic product.^[4]^[5]

As with the majority of grown diamond substitutes, the idea of producing single-crystal cubic zirconia arose in the minds of scientists seeking a new and versatile material for use in lasers and other optical applications. Its production eventually exceeded that of earlier synthetics, such as synthetic strontium titanate, synthetic rutile, YAG (yttrium aluminium garnet) and GGG (gadolinium gallium garnet).

Some of the earliest research into controlled single-crystal growth of cubic zirconia occurred in 1960s France, much work being done by Y. Roulin and R. Collongues. This technique involved molten zirconia being contained within a thin shell of still-solid zirconia, with crystal growth from the melt. The process was named cold crucible, an allusion to the system of water cooling used. Though promising, these attempts yielded only small crystals.

Later, Soviet scientists under V. V. Osiko at the Lebedev Physical Institute in Moscow perfected the technique, which was then named skull crucible (an allusion either to the shape of the water-cooled container or to the form of crystals sometimes grown). They named the jewel Fianit after the institute's name FIAN (Physical Institute of the Academy of Science), but the name was not used outside of the USSR. Their breakthrough was published in 1973, and commercial production began in 1976.^[6] In 1977 cubic zirconia begun to be mass-produced in the jewelry marketplace by the Ceres Corporation with crystals stabilized with 94% yttria. Other major producers include Taiwan Crystal Company Ltd, Swarovsi and ICT inc.^[7]^[5] By 1980 annual global production had reached 60 million carats (12 tonnes)and continued to increase with production reaching around 400 tpa in 1998.^[7]

Because the natural form of cubic zirconia is so rare, all cubic zirconia used in jewelry has been synthesized, or created by humans.

Synthesis

Worker monitoring melting zirconium oxide and yttrium oxide in an induction heated "cold crucible" to create cubic zirconia.

Currently the primary method of cubic zirconia synthesis employed by producers remains to be through the skull-melting method. This method was patented by Josep F. Wenckus and coworkers (1997). This is largely due to the process allowing for temperatures of over 3000 degrees to be achieved, lack of contact between crucible and material as well as the freedom to choose any gas atmosphere. Primary downsides to this method include the inability to predict the size of the crystals produced and it is impossible to control the crystallization process through temperature changes.^[3]^[8]

The apparatus used in this process consists of a cup-shaped crucible surrounded by radio-frequency (RF) activated copper coils and a water-cooling system.^[3]^[9]

Zirconium dioxide thoroughly mixed with a stabilizer (normally 10% yttrium oxide) is fed into a cold crucible. Metallic chips of either zirconium or the stabilizer are introduced into the powder mix in a compact pile manner. The RF generator is switched on and the metallic chips quickly start heating up and readily oxidize into more zirconia. Consequently, the surrounding powder heats up by thermal conduction and begins melting, which in turn becomes electroconductive and thus it begins to heat up via the RF generator as well. This continues until the entire product is molten. Due to the cooling system surrounding the crucible, a thin shell of sintered solid material is formed. This causes for the molten zirconia to remain contained within its own powder which prevents it from contamination from the crucible and reduces heat loss. The melt is left at high temperatures for some hours to ensure homogeneity and ensure all impurities have evaporated. Finally, the entire crucible is slowly removed from the RF coils to reduce the heating and let it slowly cool down (from bottom to top). The rate at which the crucible is removed from the RF coils is chosen as a function of the stability of crystallization dictated by the phase transition diagram. This provokes the crystallization process to begin and useful crystals begin to form. Once the crucible has been completely cooled to room temperature, the resulting crystals are multiple elongated-crystalline blocks.^[8]^[9]

The reason behind this shape is dictated by a concept known as crystal degeneration according to Tiller. The size and diameter of the obtained crystals is a function of the cross-sectional area of the crucible, volume of the melt and composition of the melt.^[3] The diameter of the crystals is heavily influenced by the concentration of ${\ce {Y2O3}}$ stabilizer.

Phase relations in zirconia solids solutions

When observing the phase diagram the cubic phase will crystallize first as the solution is cooled down no matter the concentration of ${\ce {Y2O3}}$ . If the concentration of ${\ce {Y2O3}}$ isn’t high enough the cubic structure will start to break down into the tetragonal state which will then break down into a monoclinic phase. If the concentration of ${\ce {Y2O3}}$ is between 2.5-5% the resulting product will be PSZ (partially stabilized zirconia) while monophasic cubic crystals will form from around 8-40%. It should be noted that below 14% at low growth rates tend to be opaque indicating partial phase separation in the solid solution (likely due to diffusion in the crystals remaining in the high temperature region for a longer time). Above this threshold crystals tend to remain clear at reasonable growth rates and maintains good annealing conditions.^[8]

Doping

Because of cubic zirconia's isomorphic capacity it can be doped with several elements to change the color of the crystal. A list of specific dopants and colors produced by their addition can be seen below.

Dopant^[8]^[9]	Symbol	Color(s)
Cerium	Ce	yellow-orange-red
Chromium	Cr	green
Cobalt	Co	lilac-violet-blue
Copper	Cu	yellow-aqua
Erbium	Er	pink
Europium	Eu	pink
Iron	Fe	yellow
Holmium	Ho	Champagne
Manganese	Mn	brown-violet
Neodymium	Nd	purple
Nickel	Ni	yellow-brown
Praseodymium	Pr	amber
Thulium	Tm	yellow-brown
Titanium	Ti	golden brown
Vanadium	V	green


Color Range^[8]^[9]	Dopant Used
yellow-orange-red	${\ce {CeO2}}$ , ${\ce {Ce2O3}}$
yellow-amber-brown	${\ce {CuO, Fe2O3, NiO, Pr2O3, TiO2}}$
pink	${\ce {Er2O3, Eu2O3, Ho2O3}}$
green-olive	${\ce {Cr2O3, Tm2O3, V2O3}}$
lilac-violet	${\ce {Co2O3, MnO2, Nd2O3}}$

Purple cubic zirconia with checkerboard cut
Multi-colour cubic zirconia
Three-tone cubic zirconia gems

Primary growth defects

The vast majority of YCZ (yttrium bearing cubic zirconia) crystals clear with high optical perfection and with gradients of the refractive index lower than $5\times 10^{-5}$ .^[8] However some samples contain defects with the most characteristic and common ones listed below.

Growth striations: These are located perpendicular to the growth direction of the crystal and is caused mainly by either fluctuations in the crystal growth rate or the non-congruent nature of liquid-solid transition, thus leading to nonuniform distribution of ${\textstyle {\ce {Y2O3}}}$ .

Light scattering phase inclusions: Caused by contaminants in the crystal (primarily precipitates of silicates or aluminates of yttrium) typically of magnitude 0.03-10 μm.

Mechanical stresses: Typically caused from the high temperature gradients of the growth and cooling processes causing the crystal to form with internal mechanical stresses acting on it. This causes refractive index values of up to ${\textstyle 8\times 10^{-4}}$ although the effect of this can be reduced by annealing at 2100 °C followed by a slow enough cooling process.

Dislocations: Similar to mechanical stresses, dislocations can be greatly reduced by annealing.

Uses outside jewelry

Due to its optical properties YCZ (yttrium cubic zirconia) has been used for window, lenses, prisms, filters and laser elements. Particularly in the chemical industry it is used as window material for the monitoring of corrosive liquids due to its chemical stability and mechanical toughness. YCZ has also been used as a substrate for semiconductor and superconductor films in similar industries.^[8]

Mechanical properties of partially stabilized zirconia (high hardness and shock resistance, low friction coefficient, high chemical and thermal resistance as well as high wear and tear resistance) allow it to be used as a very particular building material. Particularly in the bio-engineering industry, it has been used to make reliable super sharp medical scalpels for doctors that are compatible with bio tissues and contain an edge much smoother than one made of steel.^[8]

Innovations

In recent years manufacturers have sought ways of distinguishing their product by supposedly "improving" cubic zirconia. Coating finished cubic zirconia with a film of diamond-like carbon (DLC) is one such innovation, a process using chemical vapor deposition. The resulting material is purportedly harder, more lustrous and more like diamond overall. The coating is thought to quench the excess fire of cubic zirconia, while improving its refractive index, thus making it appear more like diamond. Additionally, because of the high percentage of diamond bonds in the amorphous diamond coating, the finished simulant will show a positive diamond signature in Raman spectra.

Another technique first applied to quartz and topaz has also been adapted to cubic zirconia: vacuum-sputtering an extremely thin layer of a precious metal (typically gold) or even certain metal oxides or nitrides amongst other coatings onto the finished stones creates an iridescent effect.^[10] This material is marketed as "mystic" by many dealers. Unlike diamond-like carbon and other hard synthetic ceramic coatings, the effect is not durable with decorative precious metal coatings due to their extremely low hardness compared to the substrate along with poor abrasion wear properties.

Cubic zirconia versus diamond

There are a few key features of cubic zirconia which distinguish it from diamond:

Hardness: cubic zirconia has a rating of approximately 8 on Mohs hardness scale vs. a rating of 10 for diamond.^[1] This causes sharp edges in cut crystals to dull and round off in CZ, while with diamond the edges remain sharp. Furthermore, when polished, diamond will rarely show polish marks and those seen will travel in different directions on adjoining facets while CZ will show polishing marks along the same direction of the polish.^[9]
Specific gravity: the density of cubic zirconia is about 1.7 times that of diamond. This difference allows skilled gem identifiers to tell the difference between the two by weight. This property can also be exploited by dropping the stones in heavy liquids and compare their relative sink times (diamond will sink more slowly than CZ).^[9]
Refractive index: cubic zirconia has a refractive index of 2.15–2.18, compared to a diamond's 2.42. This led to the development of immersion techniques of identification. In this method, stones with refractive indices higher than that of the liquid used will have dark borders around the girdle and light facet edges while those with indices lower than the liquid will have light borders around the girdle and dark facet junctions.^[9]
Dispersion is very high at 0.058–0.066, exceeding a diamond's 0.044.
Cut: cubic zirconia gemstones may be cut differently from diamonds. The facet edges can be rounded or "smooth".
Color: only the rarest of diamonds are truly colorless, most having a tinge of yellow or brown to some extent. A cubic zirconia is often entirely colorless: equivalent to a perfect "D" on diamond's color grading scale. Other desirable colors of cubic zirconia can be produced including near colorless, yellow, pink, purple, green, and even multicolored.
Thermal conductivity: Cubic zirconia is a thermal insulator whereas diamond is a very good thermal conductor. This provided the basis for Wenckus’ identification method (currently the most successful identification method)^[8]

Cubic zirconia and the diamond market

Cubic Zirconia, as a diamond substituent and jewel competitor, has been seen as a potential solution against conflict diamonds and the controversy surrounding the rarity and value of diamonds.^[11]^[12]

Regarding the latter, the main argument presented being that the paradigm where diamonds were seen as rare due to their visual beauty is no longer the case and instead has been replaced by an artificially rarity reflected in their price.^[11]^[12] This is attributed to confirmed evidence that there was price-fixing practices taken by the major producers of rough diamonds, in majority attributed to De Beers Company known as to holding a monopoly on the market from the 1870s to early 2000s.^[11]^[13] The company plead guilty to these charges in an Ohio court in 13 July 2004 .^[13] However, De Beers and Co do not have as much power over the market, the price of diamonds continues to increase due to the increased demand in emerging markets such as India and China.^[11] Therefore, with the emergence of artificial stones, such as Cubic Zirconia, that have optic properties highly similar to that of diamonds (see section above), it has been presented that these could be a better alternative for jewelry buyers given their lower price and unconvoluted history.

A closely related issue to this monopoly was the emergence of conflict diamonds. The Kimberley Process was established in order to deter the illicit trade of diamonds to fund civil wars in Angola and Sierra Leone.^[14] However, it has been shown that KP is not as effective in decreasing the number of conflict diamonds reaching the European and American markets. The main problem being its definition is too narrow and does not properly include forced labor conditions or human right violations.^[14]^[15] A 2015 study from the Enough Project, showed that groups in the Central African Republic have reaped between US$3 millions and US$6 millions annually from blood diamonds .^[16] UN reports shows that more than US$24 millions in conflict diamonds have been smuggled since the establishment of the KP.^[17] Diamond substituents therefore have become an alternative to boycott altogether the funding of such unethical practices.^[16]^[18] Terms have emerged for these artificial stones such as “Eco-friendly Jewelry” that define them as conflict free origin and environmentally sustainable .^[19] However, concerns from mining countries such as the Democratic Republic of Congo are that a boycott in purchases of diamonds would only worsen their economy. According to the Ministry of Mines in Congo, 10% of its population relies in the income from diamonds.^[14] Therefore, it is argued that in the short term diamonds substituents could be an alternative to reduce conflict around the market of diamond mining but a long term solution would be establish a more rigorous system of identifying the origin of these stones.

References

^ ^a ^b "Mohs' Hardness of Abrasives". Archived from the original on 17 October 2009. Retrieved 6 June 2009. {{cite web}}: Unknown parameter |deadurl= ignored (|url-status= suggested) (help)
^ Bayanova, T.B. (2006). "Baddeleyite: A promising geochronometer for alkaline and basic magmatism". Petrology. 14 (2): 187. doi:10.1134/S0869591106020032.
^ ^a ^b ^c ^d Dhanaraj, Govindhan; Byrappa, Kullaiah; Prasad, Vishwanath (2010). Springer Handbook of Crystal Growth. Springer. pp. 443–. ISBN 978-3-540-74761-1. Retrieved 1 February 2013.
^ Stackelberg, M. von; Chudoba, K. (1937). "Dichte und Struktur des Zirkons; II". Zeitschrift für Kristallographie. 97: 252–262.
^ ^a ^b "Understanding more about Cubic Zirconia". Chic Jewelry. 2013. Archived from the original on 14 December 2013. Retrieved 6 December 2013. {{cite web}}: Unknown parameter |deadurl= ignored (|url-status= suggested) (help)
^ Hesse, Rayner W. Jewelrymaking Through History: An Encyclopedia. Greenwood Publishing Group. p. 72. ISBN 978-0-313-33507-5.
^ ^a ^b Fletcher, Andrew, ed. (1993). ""7.7 Glass and Gemstones."". Zirconia. Vol. 1 (3 ed.). ScienceDirect: Mitchell Market Reports. pp. 31–93.
^ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ Lomonova, E. E.; Osiko, V. V. (2004). Growth of Zirconia Crystals by Skull‐Melting Technique. Chichester, West Sussex: J. Wiley. pp. 461–484.
^ ^a ^b ^c ^d ^e ^f ^g Nassau, Kurt (Spring 1981). ""Cubic zirconia: An Update."". Gems & Gemology. 1: 9–19.
^ "Designer Enhanced Gemstones". Azotic Coating Technology, Inc. 2010. Retrieved 3 November 2010.
^ ^a ^b ^c ^d Dhar, Robin (19 March 2013). "Diamonds Are Bullshit". Priceonomics. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ ^a ^b Muller, Richard (3 July 2017). "Why Smart People Buy Cubic Zirconia Engagement Rings". Forbes. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ ^a ^b Johannesburg; Windhoek (15 July 2004). "The Diamond Cartel". The Economist. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ ^a ^b ^c Baker, Aryn. "Blood Diamonds". Time. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ k., Greg (2 December 2014). "A Simple Way To Stop Blood Diamonds". Brilliant Earth. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ ^a ^b "Why the illicit diamond trade is (almost) gone, but not yet forgotten". SCMP. 21 February 2017. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ Flynn, Daniel (5 November 2014). "Gold, diamonds fuelling conflict in Central African Republic: U.N. panel". Reuters. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)
^ "Blood Diamonds". Cubic Zirconia Platinum Jewelry. 8 May 2013. {{cite web}}: Check |url= value (help); Cite has empty unknown parameter: |dead-url= (help)
^ Hoffower, Hillary (21 April 2018). "15 Moissanite Engagement Rings for the Eco-Friendly Bride". Brides. {{cite web}}: Cite has empty unknown parameter: |dead-url= (help)