Understanding the Effect of

Metamictization on the Efficiency of

Zircon Milling
Emma Jones, Matthew Smith, Stuart Blackburn, Richard Greenwood
In acknowledging the support and input from the following members of the ZIA Technical
, United Kingdom Committee:
Angelika Priese (Imerys), Jorge Masbate (Iluka Resources),
Miguel Ten (Iluka Resources), Iván Raro (Chilches Materials), Gavin Diener (TZMI), Benoit
Robitaille (Eramet), Johan Human (Tronox) and Andrew Romeo (Chemours).
 Introduction

University of Birmingham, UK

Ceramics Group: • Milling • Refractories • Sintering

• Materials • Extrusion • Surface Behaviour • Rheology
 Introduction
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

Metamictization is a term used to describe the natural process by which

the crystal structure of a mineral is destroyed by alpha radiation.

[1]
eU = effective U concentration
[1] A. K. Ault, W. R. Guenthner, A. C. Moser, G. H. Miller, and K. A. Refsnider, "Zircon grain selection reveals (de)coupled
metamictization, radiation damage, and He diffusivity," Chemical Geology, vol. 490, pp. 1-12, 2018/06/25/ 2018, doi:
https://doi.org/10.1016/j.chemgeo.2018.04.023.
 Impact of Metamictization
With increasing radiation dose:

• Decrease in hardness and density [2,3,4]

• Hardness reducing by up to 48%
• Fracture toughness has been shown to increase by 31.8% [3]

• Decrease in refractive index and birefringence [5,6]

• Colour change [7]

• Crystal structure changes [6, 8, 9]

[2] Beirau, et al., 2016; [3] Chakoumakos, et al., 1991; [4] Murakami, et al., 1991
[5] Vance and Anderson, 1972; [6] Holland and Gottfried, 1955, [7] Speer, 1980.
[8] Woodhead et al., 1991; [9] Weber, 1990.
 Key Knowledge Gaps
Key properties affected by
metamictization: density, refractive No defined system for ranking
index, hardness. zircons based on metamictization.
A distinct relationship has been
established between uranium
content and each of these
properties, individually.

Heat treatment can be

Effect of metamictization used to reverse the effects
on various physical properties of metamictization.
has been investigated
No corresponding investigation into the
– but no investigation into milling
effect of heat treatment on milling
impact specifically.
performance was carried out.
 Key Knowledge Gaps
Key properties affected by
metamictization: density, refractive No defined system for ranking
index, hardness. zircons based on metamictization.
A distinct relationship has been
established between uranium
content and each of these
properties, individually.

Heat treatment can be

Effect of metamictization used to reverse the effects
on various physical properties of metamictization.
has been investigated
No corresponding investigation into the
– but no investigation into milling
effect of heat treatment on milling
impact specifically.
performance was carried out.
 Key Knowledge Gaps
Key properties affected by
metamictization: density, refractive No defined system for ranking
index, hardness. zircons based on metamictization.
A distinct relationship has been
established between uranium
content and each of these
properties, individually.

Heat treatment can be

Effect of metamictization used to reverse the effects
on various physical properties of metamictization.
has been investigated
No corresponding investigation into the
– but no investigation into milling
effect of heat treatment on milling
impact specifically.
performance was carried out.
 Key Knowledge Gaps
Key properties affected by
metamictization: density, refractive No defined system for ranking
index, hardness. zircons based on metamictization.
A distinct relationship has been
established between uranium
content and each of these
properties, individually.

Heat treatment can be

Effect of metamictization used to reverse the effects
on various physical properties of metamictization.
has been investigated
No corresponding investigation into the
– but no investigation into milling
effect of heat treatment on milling
impact specifically.
performance was carried out.
 Research Aims
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

Develop a Assess the

To identify Assess the
classification of relationship
any impact of impact of heat
zircon sands between
based on impurities on treatment of
metamictization
metamictization milling zircon on milling
level and milling
level behaviour behaviour
efficiency
 Samples
To maintain anonymity of supplier companies, each sand sample was assigned a unique
code for identification purposes.
It must be noted a limited range of actinide content was observed across samples, typically
between 350 - 500 ppm, with the exception of one sample. Investigating the impact of high
or low actinide content may have a more notable impact on milling behaviour.
Samples were screened via several characterisation methods to develop a classification of
zircons based on the level of metamictization:
• Analysis of Actinide Data and Impurity • Particle Size
• True Density • Colour
• Crystal structure • Qualitative analysis of particle shape
• Surface Area
 Characterisation Techniques
Particle Size Crystal Structure
[11]

[10] [12]

Laser Diffraction X-ray Diffraction

[13]
Surface Area

Nitrogen Adsorption

[10] Malvern Panalytical. (2019, July 4). Mastersizer 3000. Retrieved from Malvern Panalytical:
https://www.malvernpanalytical.com/en/products/product-range/mastersizer-range/mastersizer-3000
[11] Malvern Panalytical, “Laser Diffraction,” Malvern Panalytical, 11 May 2012. [Online]. Available:
https://www.malvernpanalytical.com/en/products/technology/light-scattering/laser-diffraction. [Accessed 7 April 2018].
[12] B. Fultz and J. M. Howe, “Diffraction and the X-Ray Powder Diffractometer,” in Transmission Electron Microscopy and Diffractometry of
Materials, Springer, 2013, pp. 1-57.
[13] A. Connelly, “BET surface area,” 13 March 2017. [Online]. Available: https://andyjconnelly.wordpress.com/2017/03/13/bet-surface-area/.
 Characterisation Techniques
True Density 1: Inert gas flows into the sample chamber
2: Gas equilibrium achieved
3: Valve b opens, gas flows into second chamber
4: Gas equilibrium achieved
5: Sample weight divided by volume
[14] 6: Pressure vented off to atmosphere

Gas Pycnometer

Surface Features [15]

Scanning Electron
Microscopy with Energy
dispersive X-ray
spectroscopy

[14] mictomeritics, “Gas Displacement Pycnometry System ACCUPYC II 1345,” mictomeritics, 2021.
[15] Jeol, "Products - Scanning Electron Microscope (SEM)," 9 April 2017. [Online]. Available:
https://www.jeol.co.jp/en/products/list_sem.html.
 Characterisation Techniques
Image Analysis Colour

[16]

Image attained using Scanning Electron

Microscopy.
Image analysis using ImageJ.
Colorimeter

[16] Carolina, G., Rodica, S., Turcanu, D., Covaliov, E., 2021. Walnut Meal Whitening and the Impact of Whitening Factors
on Its Quality. Food and Nutrition Sciences, 12(1), 1-12.
 Experimental Techniques
Milling Technique
Milling was carried out on a laboratory scale using
a cylindrical ceramic vessel.
A ball to powder mass ratio of 10:1 was selected.
At pre-selected intervals during the milling
procedure, samples of powder were extracted from
the mill for the purpose of particle size analysis:
To monitor particle size reduction: Rotary Ball Mill
1 hour, 2 hours, 4 hours & 8 hours
Assess the long term milling behaviour and to locate the plateau:
24 hours, 48 hours & 72 hours

Thermal Treatment
A ramp rate of 10 K min-1 to 1000 K, held at temperature and ramped down at 5 K min-1
Classification of Zircon Sands Based on
Metamictization Level
Classification of Zircon Sands Based on
Metamictization Level

~ 4.60 Largest

~ 4.65 Mid

~ 4.70 Smallest
Relationship between Metamictization
Level and Milling
Relationship between Metamictization
Level and Milling
Relationship between Metamictization
Level and Milling
Relationship between Metamictization
Level and Milling
Relationship between Metamictization
Level and Milling
 Relationship between
Zircon Properties and Milling
XRD Peak Intensity Density Pre-Milled Surface Area

Key: High Metamict Medium Metamict Low Metamict

 Impact of Impurities on
Milling Behaviour
Alumina Iron Oxide

Key: High Metamict Medium Metamict Low Metamict

Impact of Heat Treatment of Zircon on
Milling Behaviour
 Conclusion
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

Develop a Assess the

To identify Assess the
classification of relationship
any impact of impact of heat
zircon sands between
based on impurities on treatment of
metamictization
metamictization milling zircon on milling
level and milling
level behaviour behaviour
efficiency
 Conclusion
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

• Characterisation of samples allowed for inference of

metamictization level in zircon based on a range of experimental
Develop a data.
classification of • However, the relationship between each measured characteristic
zircon sands was not found strictly linear.
based on
metamictization • A true comparative ranking of metamictization levels is difficult to
level define among zircons with similar actinide content.
• Nature of metamictization as a geological process facilities
variation in the overall change observed.
 Conclusion
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

• Highly metamict
zircons were found to • Data
Assess the exhibit a broader inconclusive.
particle size To identify
relationship
between
distribution after any impact of • Further research
extensive milling impurities on recommended
metamictization compared to a less including doping
milling
level and milling metamict zircon. of samples and
behaviour testing samples
efficiency
• Marginally smaller containing
average particle size different
concentrations
attained for low (the extremes).
metamict zircons.
 Conclusion
Understanding the Effect of Metamictization on the
Efficiency of Zircon Milling

• Thermal treatment shown to have a significant effect on milling

behaviour across all metamictization levels.
Assess the • Milling process was shown to be less efficient for heat-treated
impact of heat samples (heat treated via the method in this research)
treatment of compared to the same sample untreated.
zircon on milling • May be attributed to hardness restored.
behaviour • Heat treatment may be beneficial to other properties.
• Difference between annealed and non-annealed milling
behaviour as not observed to vary greatly as a function of
metamictization.
 Closing Remarks
“The findings are relevant to industrial applications where precise
ranges of zircon particle sizes are required. Low metamict samples
were found to be most suitable for this, but [if using] high metamict
samples, industrial millers may need to consider additional sieving
Matt Smith steps to reduce the variation in milled particle size observed.”
MRes

Thank you for your time.

Any questions?
 References
[1] A. K. AULT, W. R. GUENTHNER, A. C. MOSER, G. H. MILLER, AND K. A. REFSNIDER. 2018. Zircon grain
selection reveals (de)coupled metamictization, radiation damage, and He diffusivity. Chemical Geology,
vol. 490, pp. 1-12.
[2] BEIRAU, T., NIX, W., BISMAYER, U., BOATNER, L., ISAACSON, S. & EWING, R. 2016. Anisotropic
mechanical properties of zircon and the effect of radiation damage. Phys Chem Minerals, 43, 627-638
[3] CHAKOUMAKOS, B., LUMPKIN, G. & EWING, R. 1991. Hardness and elastic modulus of zircon as a
function of heavy-particle irradiation dose: I. In situ α-decay event damage. Radiation Effects and
Defects in Solids, 118, 393-403.
[4] MURAKAMI, T., CHAKOUMAKOS, B., EWING, R., LUMPKIN, G. & WEBER, W. 1991. Alpha-Decay Event
Damage in Zircon. American Mineralogist, 76, 1510-1532.
[5] VANCE, E. R., ANDERSON, B. W. 1972. Study of metamict Ceylon zircons. Mineralogical Magazine,
38(197), 605-613
[6] HOLLAND, H., GOTTFRIED, D., 1955. The effect of nuclear radiation on the structure of zircon. Acta
Crystallographica, 8(6), 291-300.
[7] SPEER, J. 1980. Zircon. Reviews in Mineralogy, 5, 67-112
[8] WOODHEAD, J., ROSSMAN, G., SILVER, L., 1991. The metamictization of zircon: Radiation dose-
dependent structural characteristics. American Mineralogist, 76(1-2), 74-82.
[9] WEBER, W. J., 1990. Radiation-induced defects and amorphization in zircon. Journal of Materials
Research, 5(11), 2687-2697.
 References
[10] MALVERN PANALYTICAL. (2019, July 4). Mastersizer 3000. Retrieved from Malvern Panalytical:
https://www.malvernpanalytical.com/en/products/product-range/mastersizer-range/mastersizer-3000
[11] MALVERN PANALYTICAL, “Laser Diffraction,” Malvern Panalytical, 11 May 2012. [Online]. Available:
https://www.malvernpanalytical.com/en/products/technology/light-scattering/laser-diffraction.
[Accessed 7 April 2018].
[12] B. FULTZ AND J. M. HOWE, “Diffraction and the X-Ray Powder Diffractometer,” in Transmission
Electron Microscopy and Diffractometry of Materials, Springer, 2013, pp. 1-57.
[13] A. CONNELLY, “BET surface area,” 13 March 2017. [Online]. Available:
https://andyjconnelly.wordpress.com/2017/03/13/bet-surface-area/.
[14] MICTOMERITICS, “Gas Displacement Pycnometry System ACCUPYC II 1345,” mictomeritics, 2021.
[15] JEOL, "Products - Scanning Electron Microscope (SEM)," 9 April 2017. [Online]. Available:
https://www.jeol.co.jp/en/products/list_sem.html.
[16] CAROLINA, G., RODICA, S., TURCANU, D., COVALIOV, E., 2021. Walnut Meal Whitening and the Impact
of Whitening Factors on Its Quality. Food and Nutrition Sciences, 12(1), 1-12.