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Steadystate Studies in The Conventional Verneuil Process-A Working Model For Burnout
Steadystate Studies in The Conventional Verneuil Process-A Working Model For Burnout
Burnout
R. C. Pastor
Citation: The Journal of Chemical Physics 45, 321 (1966); doi: 10.1063/1.1727327
View online: http://dx.doi.org/10.1063/1.1727327
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/45/1?ver=pdfcov
Published by the AIP Publishing
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THE JOURNAL OF CHEMICAL PHYSICS VOLUME 45, NUMBER I 1 JULY 1966
A working model for burnout of additives is presented for the flame fusion ~r?wth of cry.stals (Ver.neuil
process). The case of a-AhOa:Cr3+ (ruby) is of special interest since the additive (.chronuum) mamfests
more than one valence state in the powder, the conventional form of the feed matenal.
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322 R. C. PASTOR
further with the spherically symmetric species which From Eqs. (1), (3), and (5), partition equilibrium
are the more volatile, i.e., Fe3+ vs FeH and MnH vs yields
Mn4+. It is, in fact, this dependence on the oxidation fJ. = w,,/w. (6)
state which causes burnout to depend not only on the
nature of the host-additive combination and the start- The symbol showing dependence on time (t) is dropped
ing concentration, but also on impurity content and to signify equilibrium values. Equations (1) and (2)
thermal treatment of the powder. Burnout is a signifi- hold also for equilibrium. From Eqs. (2) and (6) it
cant specification of a steady-state operation pertinent follows that
to crystal growth (d. Part II). The object in the (7)
following discussion is to provide a working model.
The dependence of w. and w" on w is derived from (1)
II. SUGGESTED MODEL AND PRELIMINARY and (7),
(8)
OBSERVATIONS
and
In the pyrolytic production of the powder, the ad- (9)
ditive partitions between the bulk and the surface. The following experimental results (d. Part II) are
At the conditions prevailing during calcination (low- pertinent:
level doping), the partition' is "reproducible and reversi-
ble (d. Part I) . - .. (1) The powder in transit thermally loads the tra-
Let w represent the mole percent of the additive. jection (melting) zone and flattens out the axial tem-
The conservation relation in the powder is perature profile.
(2) For a given heat balance (steady-state opera-
(1) tion) , the trajection length (distance of growth zone
from burner orifice) is fixed. The radial temperature
w.(t) refers to the additive incorporated in bulk and profile determines the growth diameter of the crystal
w,,(t) to that present on the surface at time t. Since (boule) .
the material has a high specific surface, bulk incor- (3) The residence time of the melt is short and
poration is quite limited. The saturation coefficient as burnout occurs mainly through trajection.
a function of time is given by (4) Burnout is sensitively dependent on the thermal
profiles but not on the chemical nature of the fuel.
fJs(t) =ws(t) /w so. (2)
It may be assumed that the concentration in the boule
w 8 0 is the saturation concentration of the bulk. Wb is equal to the sum of w" and w,' each weighted by a
The flow of additive from the surface to the bulk is retention coefficient,
described by
(10)
dw,,(t) /dt= - k"8[1-fJ. (t) Jw,,(t) +k."fJ.(t)ws(t). (3)
It is of course expected that
The constraint arising from Eq. (1) is
(11)
dw"(t)/dt = -dw8 (t)/dt. (4)
Hence, from Eqs. (1), (7), and (10), it can be shown
From Eqs. (3) and (4) it is appreciated that k". is the that
probability per unit time that the additive on the
p" W)
Pow,ow
surface moves to the bulk phase when completely Wb= ( 1+-- --
P. w.o w.o+w·
(12)
empty (fJs=O). Similarly, kau measures the probability
per unit time that the additive moves from the bulk In ruby more than one valence state of the additive
to the surface when the bulk phase is completely filled occurs in w" (d. Part I). The additives on the surface
(fJ,=1). have a large escaping tendency (d. Part II). For this
In Eq. (3) it is assumed that k." and k"o are inde- case, it is assumed that p,,:::::;O, and
pendent of concentration and hence of time. Consider
a surface to intervene between two bulk phases, fJ.= 1 (13)
and fJ.=O. When the surface region is made to dis-
appear by bringing the two bulk phases together, the A further approximation follows from (13), in the
diffusion through the imaginary boundary (constant dilute region where
temperature) depends only on the concentration dif- w«w.o, (14)
ference if and
k.u= k"•. (5) (15)
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STEADY STATE IN THE VERNEUIL PROCESS 323
Recent data on ruby in the dilute region suggest Sil'nichenko and Gritsenko. 8 A more extensive range
P.~O.S (or a burnout ~~SO%).6 This is in agreement in W would provide a test of Eq. (13). In addition, an
with earlier data provided by Olt, where a range of assessment of w.o can be made.9
P. from 0.7 to 0.4 is seen.7 In this case, the logarithmic
ACKNOWLEDGMENT
scales on both wand Wb defy the detection of a slight
curvature, according to Eq. (13), in the higher range The author would like to thank A. C. Pastor for
of W where Inequality (14) does not hold. Such a helpful discussions.
curvature is indeed seen in the more recent data of
8 V. G. Sil'nichenko and M. M. Gritsenko, Soviet Phys.-Cryst.
9, 647 (1965) [Kristallografiya 9, 763 (1964)].
6 See Fig. 5 of Part II for both oxyhydrogen and oxygas burners. 9 The curve described by Eq. (13) is easily rectified by plotting
7 R. D. Olt, App!. Opt. 1, 25 (1962). W/Wb against w. The slope and the intercept yield p, and w,o.
We consider a classical system of particles interacting via a pair potential consisting of a strong short-
range repulsion u.(r) and a weak long-range potential of the form ul(r) ="1 F(-yr), where the range "I-I
is long compared with the range of u•. The systematic expansion of the thermodynamic quantities in the
ratio of the two ranges has been developed previously and is briefly reviewed. The expansion breaks down
when the inverse compressibility of the fluid vanishes. Explicit calculations of the equation of state for
special choices of the two parts of the intermolecular potential are presented and compared with the corre-
sponding experimental results for argon. It is also shown that to first order in the expansion parameter the
specific heat Cv has a maximum near the critical isochore.
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