Mechanochemical Activation of Minerals

DMR Sekhar

Mechanochemical activation of minerals may open up the possibilities of directly using

minerals in agriculture.

Introduction
Mechanochemical action is about causing chemical changes in a material/ mineral due to
mechanical action on the mineral/ material. Mechanical action may be through pestle and
mortar, ball mill or planetary mill1 or ultra sound2. The chemical changes that result are
breaking chemical bonds, inclusion of foreign atoms, creation of gaps etc. The changed
chemical properties are mainly due to the reduction of mineral particle sizes to micron/nano
scale. Unlike the atoms in the bulk of the mineral, atoms on the surface are bonded with
other atoms below the surface and have broken bonds on the surface. As we grind the
mineral to finer and finer sizes the population of broken bonds increase and in other words
the mineral loses crystallinity and tends to be amorphous. An important application is size
reduction of insoluble drugs for easy dispensation.

Planetary Mills
Planetary mills are used to grind hard materials such as cemented tungsten carbide and
coated tungsten carbide (WC/CO) to micron and sub- micron sizes in a matter of minutes3.
Industrial scale planetary mills can produce 20 70 Kg per hour to 3 to 5 tons per hour to
yield product sizes of -10 microns. The productivity per unit volume of working chamber of
planetary mills is said to be at least 10 times higher than conventional ball mills. The
accelerations of planetary mills is reported to be 20 times of g. Planetary mills have one or
more vertical cylindrical grinding chambers with balls as grinding media rotating around a
central axis while simultaneously rotating around the axis of the vertical cylindrical
chambers.
A feed size of 1 mm of WC/CO material after 8 mins of grinding in a planetary is reduced
to 40 microns having d90 at 7.8 microns and d50 at 1.6 microns and more interestingly the
size distribution is multi modal3 having a major peak at 1.5 microns followed by 4 and 9.5
microns. Multimodal distribution indicates that the grinding process inside the planetary
mill is not uniform but the material being ground undergoes multiple process settings.
Planetary mills are used5 to grind unusually difficult materials such as hair. Hair contains
16% nitrogen which may work6 as slow release N fertilizer if it can be ground to fine size.

Figure 1: Movement of Supporting Disc, Grinding Chamber (bowl) and Grinding Media in a
Planetary Mill - courtesy, Tanja Scherer, Fritsch GmbH4, Germany.

Solubility of Phosphate Rocks

Phosphate rock in principle is Ca3 (PO4)2 that is tricalcium phosphate and in nature it is
associated with CaF2 association gives the name fluorapatite. PO4 may be replaced by CO3 or
OH isomorphycally. Tricalcium Phosphate it -self is insoluble in water while CaHPO4
dicalcium phosphate is soluble in 2% citric acid and Ca.2(H2PO4) monocalcium phosphate is
soluble in water. Plants take up P if it is either in water or 2% citric soluble form. Some
phosphate rocks of sedimentary origin with isomorphic replacement of CO3 or OH show
citric acid solubility (CAS). Rocks having CAS content of P are directly used as P fertilizers in
acidic soils. Phosphate rocks of igneous origin show very low CAS and hence are thought to
be not eligible for use as direct application fertilizers. As it may be noted phosphate rocks
including those of igneous origin show7, 8 significantly higher CAS as they are ground to finer
and finer sizes which may be noted from figure 2. After fine grinding of phosphate rocks if
accompanied by sufficient quantity of organic manure or N containing fertilizers such as
urea or ammonium nitrate work as efficiently9 as di ammonium phosphate (DAP) even in
alkaline soils.
While citric acid solubility of phosphate rocks is dependent on the geological origin of the
phosphate rock it also depends on the size of the mineral particles. Specifying the size of
phosphate rock particles is invariably important while specifying CAS content of P 2O5 in the
phosphate rock particles.
On the lines of mechanochemical activation of phosphate rock followed by its application
in agriculture many other agri minerals such as potassium feldspar, magnesite, can be
tested/developed. Both K and Mg are major plant nutrients. Minerals containing
micronutrients may also be tested.

Figure 2: Increasing P2O5 soluble in 2% citric acid as percent of total P2O5 as size of mineral
decreases due to grinding.

References:

(1) Leos Benes, http://www.fritsch-milling.com/products/milling/planetary-mills/

(2) Hovig Kouyoumdjian, Sonochemical and Mechanochemical Applications in
Organic Synthesis, 2010
http://www2.chemistry.msu.edu/courses/cem958/FS09_SS10%5CKouyoumdjian.pdf
(3) Fokina, E. L., Budim, N. I. , Kochnev, V. G. and Chernik, G. G., Planetary mills of
periodic and continuous action, Journal of materials science, Vol 39, pp 5217 5221,
2004.
(4) Tanja Scherer, http://www.fritsch-milling.com/products/milling/planetary-mills/
(5) Kensaku Okamoto, Masatoshi Morita, Hao Quan, Takashi Uehiro, and Kelichiro Fuwa,
Preparation and Certification of Human Hair Powder Reference Material, CLINICAL
CHEMISTRY, Vol. 31, No. 10, pp 1592-1597, 1985.
http://www.canaltlabs.com/pictures/site131/content6873/media/Preparationand_C
ertificationof_HumanHair_PowderReferenceMateria.pdf
(6) Andrea Thompson, Human Hair Makes Good Fertilizer, Live Science, January 05,
2009.
(7) Sekhar, DMR, Principles of Phosphate Fertilization and PROM Progress Review
2012.
https://www.researchgate.net/publication/235918492_Principles_of_Phosphate_Fe
rtilization_and_PROM__Progress_Review_2012
(8) Sekhar, D.M.R., Prabulingaiah., G., Gupta, D.K. and Katewa, M.K, In PROM Review2005, Udaipur, 2005.
(9) Pareek, D.K., Masih, M.R., Banani Singh and Ashok Chowdary, In PROM Review-2005,
Udaipur 2005.