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Alex M. Maldonado
Abstract
Pharmaceuticals rely heavily on controlled drug release and their synthesis can be enhanced or
controlled by encapsulating the active drug with SiO2/MgSt core/shell nanoparticles less than 20
to a desired nucleus size and composition. A temperature infinitesimally under 200 degrees
Celsius with a high degree of saturation would be ideal for small nucleus size. More
experimentation for compound characteristics such as surface energies and molar volume are
Problem Statement
process of forming solid particles within an aqueous solution. We will be examining the
Task Identified
because heterogeneous nucleation has a significantly lower nucleation barrier. The lower
nucleation barrier is due to the lowering of the surface energy cost of forming a nucleus
(Zhigilei, 2016).
The ideal solution would be a single reactor with the capability to control standard
thermodynamic variables to direct the synthesis reaction. The general steps of the synthesis
process would be forming a solution, nucleation, cluster formation, and crystallization. The
nucleation step will be analyzed, discussed, and recommendations will be made to achieve the
ideal reaction.
Parameters Selected
requirements and particle size. Only variables that can be independently controlled or affected to
change particle size will be considered; these variables include temperature of reactor and
Background
Homogeneous nucleation is when a second phase spontaneously appears out of a parent phase
(Zhigilei, 2016). For an aqueous solution the phase is solid and phase is liquid.
Heterogeneous nucleation occurs when nucleation and growth initiates on other species already
in the phase which typically are walls of the reaction vessel or impurities in the solution
(Kornfield & Greer, 2016). Any heterogeneous nucleation would incorporate impurities into the
structure and cannot be utilized. Therefore only homogeneous nucleation will be analyzed.
the melting temperature Tm. At any point where a liquid is cooled below its melting temperature
the system will solidify to decrease the free energy by, = . This difference in
The total free energy is given by (Thanh, Maclean, & Mahiddine, 2014) as
4 ln()
= 4 2 3 (1)
3
Where r is the radius of a spherical particle, is the surface energy of the species, kb is
Boltzmanns constant, T is the temperature, S is the supersaturation of the solution, and v is the
molar volume of the solution. The positive term in the free energy equation is the surface term
THERMODYNAMICS OF NUCLEATION 5
associated with the formation of new interfacial area between phases. The negative term is the
volume term associated with the bulk condensation energy (Zhigilei, 2016).
equal to zero, ( ) = 0, gives us (Thanh, Maclean, &
Mahiddine, 2014):
4 2
2
= (2) = (3)
3 ln()
Figure 2: Free energy with respect
The critical radius rcrit corresponds to the minimum size a to radius of nucleus (Thanh,
Maclean, & Mahiddine, 2014).
particle must maintain to avoid being dissolved back into the
parent phase. The energy barrier required to reach this size is the critical free energy Gcrit.
There are three thermodynamic regimes when regarding particle size and free energy. When r is
increasing and r < r*, Gr increases and therefore the particle is not thermodynamically stable
and particles dissolve back into the bulk phase. When r = r* and r is still increasing there is still
a positive Gr; however, it starts to decrease but is still thermodynamically unfavorable. Once
the size reaches r0 any further increase in size leads to Gr becoming negative and leads to the
Approach
In order to produce a stable solid nanoparticle without having it dissolve back into the
solution, but not start solidification, the size of the nucleus needs to stay between r* and r0. If the
THERMODYNAMICS OF NUCLEATION 6
particle size reaches r0 the reactor would being spontaneous solidification and nanoparticle
higher temperature would produce a larger particle size. A reaction temperature closer to the
fusion temperature would be ideal for small stable nuclei. The other independent variable that
affects rcrit is degree of supersaturation S which shares the same relationship with rcrit as
Description
The fusion temperature for Magnesium Stearate (MgSt) is 200 degrees Celsius (Sigma-
Aldrich, 2016). Fusion data for colloidal silica could not be found, but is assumed to be lower
than 200 degrees Celsius. At a temperature lightly below 200 degrees Celsius the MgSt can start
nucleation while the colloidal silica can remain in the liquid phase without having to worry about
solidification. Currently, there is no available data for the surface energies of MgSt or colloidal
optimum temperature of reactor. Molar volume v cannot be calculated without knowing the
Conclusions
concentration for the overall synthesis of SiO2/MgSt core/shell nanoparticles. Once the solution
is made, the temperature should be as close to the fusion temperature of MgSt as possible while
still overcoming the free energy barrier. The degree of supersaturation should be higher to lower
References
Kornfield, J., & Greer, J. (2016, April 2016). MS 133. Kinetics of Solid Phase Transformations.
Retrieved December 2016, from Julia R. Green Professor of Materials Science and
Mechanics:
http://jrgreer.caltech.edu/content/teaching/MS133_SP_2016/Lecture_Notes/week5_2.pdf
http://www.sigmaaldrich.com/catalog/product/usp/1374340?lang=en®ion=US
Thanh, N. T., Maclean, N., & Mahiddine, S. (2014). Mechanisms of Nucleation and Growth of
doi:dx.doi.org/10.1021/cr400544s
Virkar, A. (2016, January 1). Lecture notes and other materials for MSE 5034 & 6034. Retrieved
December 2016, from The University of Utah Department of Materials Science &
Engineering: http://www.eng.utah.edu/~lzang/mse5034&6034.html
Zhigilei, L. (2016, January). MSE 3050: Thermodynamics and Kinetics of Materials. Retrieved
Engineering`: http://www.people.virginia.edu/~lz2n/mse305/
THERMODYNAMICS OF NUCLEATION 8
Figures
Figure 1. At point Tm the chemical potential of a pure substance is equal for the liquid and solid
phase. When the solution is at T* you have a difference in temperature of T. At T* the chemical
potential of the liquid GVL is greater than the chemical potential of the solid GVS; this difference
of Gv is the driving force of the phase transition from liquid to solid (Zhigilei, 2016).
Figure 2. This figure demonstrates the relationship of free energy G to the radius of a nucleus.
The Gv represents the change of free energy due to the increasing volume of the solid phase.
The Gs represents the change of free energy due to new interfacial area between solid and
liquid. The G is the total free energy where Gcrit is the maximum free energy barrier obtained at