SteadyState Studies in the Conventional Verneuil Process—A Working Model for

Burnout
R. C. Pastor

Citation: The Journal of Chemical Physics 45, 321 (1966); doi: 10.1063/1.1727327
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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 45, NUMBER I 1 JULY 1966

Steady-State Studies in the Conventional Verneuil Process-A Working Model

for Burnout*
R. C. PASTOR

Korad Corporation, A Subsidiary of Union Carbide Corporation, Santa Monica, California

(Received 1 November 1965)

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.

1. INTRODUCTION heats by collision transfer. Unfortunately, this situ-

ation exaggerates volatility losses.
N the growth of mixed crystals for lasers, two control
I problems characterize the substitutional incorp?ra-
tion of an additive-valence state and concentratIOn.
In the crystal growth of ruby at 20S0°C, the tri-
valent state of the additive (chromium) is the stable
form. However, it has been shown that the same case
These two features are linked through the dependence
does not obtain in the powder. s A considerable differ-
of escaping tendency on oxidation state. Through this
ence in volatility is associated with the various oxida-
dependence, charge compensation (impurities or va-
tion states. For instance, Cr(VI) content of typical
cancies) further complicates the control of the level
powders 20%-40% of the total, accounts for what
and uniformity of additive concentration. In these solid
becomes'lost instantly upon entry into the heat zone.
solutions the concentration level corresponds to a mole
In addition since Cr20a is more volatile than AI20 a,
fraction ~f 10-4 (3d additive) to 10-2 (4f additive).
further loss' is incurred through the Cr(III) species
Control of concentration is easier when the additive
during trajection to an extent dependent upon the
incorporates predominantly in the desired valence state.
thermal profile encountered. Typical values range from
The task is rendered difficult in the crystal growth of
3%-7% cm-1 depending on the boule diameter.4
refractory materials at temperatures above 2000°C due
Controlled incorporation of the additive is of para-
to incompatibility (corrosion problems) between the
mount importance in the growth of laser crystals where
melt and the container as well as the protective atmos-
the attainment and maintenance of a given steady-
phere. The method developed by Verneui! (viz., flame
state concentration must be effected through a time
fusion) avoids these problems. 1 In this method the
interval commensurate with the desired size of the
material enters the melting region in powder form.2
monocrystal. In the case of ruby, '"'-'2S0-g size boules
Rigid monitoring of powder flow is necessary since the
are produced for laser fabrication (cylinder, i-in. di-
material provides the main heat sink in the growth
ameterX4-in. length) with growth rates of 6-10 g·h- l •
zone. Consequently, flow control serves as the mam
To achieve '"'-'80% utilization, rigid control of crystal
objective in powder processing.
growth must be exercised for about one day.
The problems of powder flow are germ.ane to ~he
The net accounting in the additive is expressed as
conventional Verneuil. Such a method for mtroducmg
burnout, which simply measures the discrepancy be-
and maintaining the nourishment to crystal growth,
tween the starting concentration (powder) and the
although subject to modifications (e.g., vapor trans-
final (crystal). Past measurements have provided a
port), is basic to the control of thickness and per~pheral
crude scale of volatilities at ~ 2000°C (increasing order
extension of the melt. This feature allows contamment
shown) with the burnout ({3) range as follows: Si <
of the melt by interfacial tensions, thus obviating the
Fe<Mn, 80%<13<100%; Cu<Ca<Mg<Cr, 40%<
use of crucibles. A high specific surface of the powder
13<60%; and Ti<V, {3 ~40%.6 The scale is subject to
is desired for quick attainment of sensible and latent
the distribution of the oxidation states of the ions.
* This work was sponsored by the U.S. Air Force Systems The effect of electronic configurations is appreciated
Command (Wright-Patterson Air Force Base, Ohio) under Con-
tract No. AF33(657)-11395. . a R. C. Pastor, H. Kimura, L. Podoksik, and l\f. A.. Pear~on,
1 A. Verneuil, Compt. Rend. 135, 791 (1902); Ann. Chlm. J. Chern. Phys. 43, 3948 (1965). In the followmg discussIOn,
Phys. 3, 20 (1904). this will be referred to as Part 1.
2 An extensive discussion on the engin~eri~g aspects of !he 4 R. C. Pastor, A. C. Pastor, H. Kimura, and K. Arita, J. C:hem.
technology applied to sapphire and ruby IS give!"! m an article Phys. 44, 4486 (1966). In the following discussion, this Will be
by S. K.Popov, in Growth of Crystals,A. V. ~hubnikov and N. N. referred to as Part II.
Sheftal, Eds., (Consultants Bureau Enterpnses, Inc., New York, 6 K. Arita and H. Kimura, oxyhydrogen Verneuil gro~th of
1959), Vol. 2, p. 103. mixed crystals (low-level doping) in corundum (unpublished).
321

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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
P.~O.S (or a burnout ~~SO%).6 This is in agreement
with earlier data provided by Olt, where a range of
P. from 0.7 to 0.4 is seen.7 In this case, the logarithmic
scales on both wand Wb defy the detection of a slight
curvature, according to Eq. (13), in the higher range
of W where Inequality (14) does not hold. Such a
curvature is indeed seen in the more recent data of
6 See Fig. 5 of Part II for both oxyhydrogen and oxygas burners.
7 R. D. Olt, App!. Opt. 1, 25 (1962).
Sil'nichenko and Gritsenko. 8 A more extensive range
in W would provide a test of Eq. (13). In addition, an
assessment of w.o can be made.9
ACKNOWLEDGMENT
The author would like to thank A. C. Pastor for
helpful discussions.
8 V. G. Sil'nichenko and M. M. Gritsenko, Soviet Phys.-Cryst.
9, 647 (1965) [Kristallografiya 9, 763 (1964)].
9 The curve described by Eq. (13) is easily rectified by plotting
W/Wb against w. The slope and the intercept yield p, and w,o.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 45, NUMBER 1 1 JULY 1966

Fluids with Weak Long-Range Forces

E. HIlS HAUGE* AND P. C. HEMMER
Instituttfor Teoretisk Fysikk, Norges Tekniske Hpgskole, Trondheim, Norway
(Received 13 January 1966)

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.

1. INTRODUCTION A different and perhaps equally interesting approach,

based on the fact that the intermolecular potential is
HILE the thermodynamic properties of a classical
W fluid of N particles can, in principle, be calcu-
lated from the 3N-dimensional configuration integral,
known to contain a strongly repulsive short-range part
plus a weaker attractive part of longer range, uses the
dimensionless ratio ~ of the repulsive interaction volume
such a direct evaluation is of course not feasible. In-
to the attractive interaction volume as a small param-
sisting on a systematic procedure of successive approxi-
eter.3.4
mations one looks for a small parameter in the problem.
The main interest stems from the fact that already
The theory of imperfect gases has been dominated by
the zeroth approximation-which is equivalent to a
the virial expansion,! where the small parameter is the
van der Waals or mean-field theory-includes a phase
ratio of the interaction volume to the volume per
transition. An important stimulus for efforts in this
particle. The actual calculations for a realistic potentia.l
direction has been the Kac one-dimensional model, 5
have not progressed beyond the third order, and it is
which is exactly solvable as an integral equation
clear that the virial expansion becomes questionable at
problem. This model can be used to check any general
high densities. Many workers have, therefore, de-
result obtained by dimensionality independent tech-
veloped methods, in which certain contributions in this
niques (in the present case graphs).
expansion, selected mainly for mathematical reasons,
In Sec. II we discuss briefly the expansion method
are summed to infinite order of the density.2
which is described in more detail elsewhere,3 and give
* Present ad,\ress: The Rockefeller University, New York, New
York 10021. s P. C. Hemmer, J. Math. Phys. 5, 75 (1964).
I For a clear discussion see G. E. Uhlenbeck and G. W. Ford 4 Recent work by M. Coopersmith and R. Broul, Phys. Rev.
in Studies in Statistical Mechanics (North-Holland Pub!. Co., 130, 2539 (1963); and by J. L. Lebowitz, G. Stell, and S. Baer,
Amsterdam, 1962), Vo!' 1, Part B. J. Math. Phys. 6, 1282 (1965), is closely related to Ref. 3. Other
2 A good review of these attempts, notably the hypernetted related works are surveyed by E. Helfand in Ref. 2 Sec. III-6.
chain and the Percus-Yevick approximations, is given by G. The extension to mixtures has been done by E. H. Hauge, J.
Stell, in The Equilibrium Theory of Classical Fluids (W. A. Benja- Chern. Phys. 44, 2249 (1966).
min, Inc., New York, 1964), Sec. II-4. 1M. Kac, Phys. Fluids 2,8 (1959).

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