Journal of Supercritical Fluids 21 (2001) 61 – 70

www.elsevier.com/locate/supflu

Controlled release system formed by supercritical

anti-solvent coprecipitation of a herbicide and a
biodegradable polymer
S. Taki, E. Badens *, G. Charbit
Laboratoire d’Etudes et d’Applications de Procédés Séparatifs, Faculté des Sciences et Techniques de Saint-Jérôme, Case 512,
A6enue Escadrille Normandie-Niemen, 13397 Marseille cedex 20, France
Received 4 September 2000; received in revised form 18 January 2001; accepted 5 February 2001

Abstract

Coprecipitation using a supercritical antisolvent technique seems to be a promising way for the elaboration of
controlled herbicide delivery system since it allows the preparation of a herbicide (diuron) loaded in amorphous
microparticles of a biodegradable polymer (L-polylactic acid, L-PLA). Coprecipitation was successfully realized in
methylene chloride. The concentrations of the two components had a major influence upon morphology and shape
of the final product. Spherical particles of L-PLA entrapping diuron were obtained provided that the initial
concentrations of L-PLA and diuron did not exceed, respectively 3 wt.% and 0.1 wt.% in methylene chloride at 10
MPa and 308 K. A parallel study of the precipitation of diuron by the SAS process showed the formation of long
needle-like crystals with a mean length of 500 mm. The precipitation time being very short during the SAS process,
the growth rates observed are 10 000 times higher than the growth rates of diuron in aqueous solution. © 2001
Elsevier Science B.V. All rights reserved.

Keywords: Supercritical anti-solvent; Precipitation; Herbicide; Controlled release system

1. Introduction of active substance and the cost of labor. In this

The search for high profitability in agriculture
implies having more active pesticide products with
longer term effects. A reduction in treatment fre-
quency is both environmentally and economically
of interest in order to reduce the required quantity
* Corresponding author. Tel.: + 33-491-288411; fax: +33-
491-023572.
E-mail address: elisabeth.badens@leaps.u-3mrs.fr (E.
Badens).
context, the controlled release system of a herbi-
cide seems to offer these advantages compared to
the conventional formulations which consist of
suspensions of herbicides in aqueous media.
Several controlled release systems of drugs have
been elaborated using supercritical fluid processes
[1–6]. Indeed, recent techniques using a supercrit-
ical fluid as a solvent or as an anti-solvent are
considered to be useful alternatives to produce
fine powders and coprecipitation can be realized

0896-8446/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 8 9 6 - 8 4 4 6 ( 0 1 ) 0 0 0 7 6 - 6
62 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
in one step. The general concept of using super-
critical fluid as anti-solvent is relatively well estab-
lished [7]. Supercritical carbon dioxide offers
various advantages compared with organic sol-
vents widely used in microencapsulation pro-
cesses. Carbon dioxide is environmentally
acceptable, non-flammable, non-toxic, abundant,
its critical coordinates are moderate and it is
gaseous under ambient conditions of pressure and
temperature.
In the supercritical fluid antisolvent techniques,
carbon dioxide is used as an antisolvent for the
solute but as a solvent with respect to the organic
solvent. Different acronyms were used by various
authors to denote micronization processes: aero-
sol solvent extraction system (ASES) [8], precipi-
tation with a compressed fluid anti-solvent (PCA)
[9 – 11], gas anti-solvent (GAS) [12,13], solution
enhanced dispersion by supercritical fluids
(SEDS) and supercritical anti-solvent (SAS). The
SAS process involves the spraying of the solution
composed of the solute and of the organic solvent
into a continuous supercritical phase flowing co-
currently [5]. The simultaneous dissolution of the
supercritical fluid in the liquid droplet and the
evaporation of the organic solvent towards the
supercritical phase induce a supersaturation of the
solute in the liquid phase which then precipitates.
Compared to the other anti-solvent techniques,
the SAS process offers two advantages:
“ Because of the dispersion of the liquid phase,
very fine droplets are formed and a high spe-
cific surface area is available for the mass
transfer.
“ Since the carbon dioxide and the organic sol-
vent are continuously drained off from the
vessel, the precipitated solid is the only species
remaining inside. Thus, relatively high amounts
of liquid solution can be processed before re-
covering the solid.
The aim of this work was to study the feasibil-
ity of the encapsulaltion of a herbicide within a
biodegradable polymer using the SAS process.
The diuron was chosen as the herbicide because
of its wide use in agricultural treatments. We
specially turned our attention to the recrystalliza-
tion of this species since very interesting results
were obtained. The biodegradable polymer used
in the study is the L-PLA which has been the
subject of a number of studies [2,13,14]. This
paper reports the first results of this work and
concerns the influence of various process parame-
ters upon the size and morphology of the particles
formed, i.e. pressure, temperature, composition
and flow rates.
2. Experimental
2.1. Materials
The following chemicals were used as received:
L-polylactic acid (L-PLA), molecular weight:
29 000, inherent viscosity (in chloroform, 25°C):
0.97 dl g − 1, Purac Biochem, the Netherlands.
3-(3,4-Dichlorophenyl)-1,1-dimethyl-urea (di-
uron), purity 98%, Aldrich, France. Methylene
chloride, purity 99.8%, Aldrich, France. Tetrahy-
drofuran (THF), purity 99.7%, Aldrich, France.
Carbon dioxide, purity 99.7%, Air liquide Méd-
iterranée, France.
2.2. Obser6ation and characterization
2.2.1. Scanning electron microscopy (SEM)
Solid particles were observed with a PHILIPS
model 515 SEM. Samples were sputter coated for
80 s with gold–palladium to a thickness of ap-
proximately 100 A, using a BALZERS SCD sput-
ter coater. SEM images were collected using the
EDAX Scan Generator software.
2.2.2. X-Ray diffraction (XRD)
X-Ray diffraction analyses were carried out in
order to characterize crystalline products. The
Debye –Scherrer diagrams were obtained using
X-rays with a wavelength l equal to 1.540598 A,
and an exposure time of 1800 s. The detector used
was an INEL CPS 120 System.
2.2.3. Energy dispersi6e X-ray (EDX) analysis
Element compositions were determined using a
PHILIPS EDAX apparatus and DX-4 software.
We proceeded with an acquisition time of approx-
imately 600 s. The tension used was 20 kV and
spatial resolution was approximately 1–2 mm.
 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
2.3. Apparatus and procedure
2.3.1. Preliminary studies: determination of
solubilities and phase diagrams
2.3.1.1. Solubility. Solubilities were determined us-
ing thermostated glass cells. Successive small
masses of diuron were introduced into a certain
volume of solvent. When the liquid solution be-
came cloudy, successive volumes of solvent were
added to obtain a homogeneous solution. The
solubility S (g l − 1) was calculated from the total
amount of solid and of the solvent used.
2.3.1.2. Phase diagrams. The phase boundaries of
the ternary systems: polymer/carbon dioxide/sol-
vent and herbicide/carbon dioxide/solvent were
visually determined in a high-pressure view cell
equipped with a sapphire window, temperature
and pressure gauges, a movable piston and a
camera linked to a TV monitor. Detailed descrip-
tions of the apparatus and operating procedures
have been published elsewhere [15].
2.3.2. SAS precipitation
A schematic diagram of the SAS apparatus is
shown in Fig. 1. The central feature of the ap-
paratus consisted of a 6.3-cm i.d., 500-ml 316
stainless steel precipitation vessel provided by the
Exenia group (Italy). Two high pressure pumps
deliver the liquid solution (Gilson model 307
pump, Villiers Le Bel, France) and the supercriti-
cal antisolvent (Dosapro Milton Roy, Pont-Saint-
Fig. 1. The SAS apparatus for precipitation.
63
Pierre, France). Pressure and temperature gauges,
security rupture disks and valves complete the
plant.
Carbon dioxide was preliminary introduced
into the precipitator through a frit filter to set the
operating pressure. When the experimental condi-
tions of pressure were reached, a vent was created
in order to maintain the chosen pressure in the
precipitator and a constant carbon dioxide feed
rate of 400 g h − 1. The liquid solution was then
introduced at various feed rates through a 150-mm
internal diameter capillary (Chrompack, les Ulis,
France), during times of approximately 30 min.
The liquid solution flow was then stopped and a
pure constant carbon dioxide flow was maintained
in order to completely change the volume of the
precipitator and thus to remove the residual sol-
vent. After this washing step which lasted approx-
imately 90 min, the autoclave was depressurized
for 30 min at the experimental temperature. The
collected solid particles were then observed by
SEM and characterized by XRD and EDX analy-
sis if necessary.
3. Results and discussion
3.1. Preliminary studies: determination of
solubilities and phase diagrams
3.1.1. Solubilities
To be successful, the coprecipitation implies
two conditions:
1. the solubility of the diuron and of the polymer
must not be infinite; and
2. the diuron has to precipitate first.
Methylene chloride, chloroform and tetrahy-
drofuran are generally good solvents for poly-
mers. Methylene chloride is more interesting than
chloroform because of its higher volatility which
makes the removal of the solvent easier. The
boiling point of methylene chloride (313 K) is
lower than chloroform (334.8 K) and tetrahydro-
furan (339.1 K). Diuron is soluble in practically
all organic solvents.
Solubilities of diuron and of L-PLA in methyl-
ene chloride and in tetrahydrofuran at 298 K are
reported in Table 1. Solubilities of diuron in
64 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70

Table 1
Solubilities of diuron and L-PLA in methylene chloride and in
tetrahydrofuran at 298 K

Solute Solubility in Solubility in

methylene tetrahydrofuran
chloride (g l−1) (g l−1)

Diuron 20.9 89.4

L-Polylactic \100 Insoluble
acid

Fig. 2. Phase diagram of the ternary system: CO2 (45%)/di-

methylene chloride and in tetrahydrofuran at dif-
ferent temperatures are reported in Table 2.
As L-PLA is insoluble in THF, we chose to use
methylene chloride. It is worth noting that, in this
solvent, L-PLA is more soluble than diuron. This
condition is necessary because diuron has to pre-
cipitate first in order to be coated by the polymer
which has to precipitate next.
From the results presented in Table 2, we note
that the solubility of diuron in both solvents
increases when temperature increases.
3.1.2. Phase diagrams
A key role in the precipitation process is played
by the different phase transitions of the multicom-
ponent system. The phase diagram allows selec-
tion of the best operating conditions for the SAS
process.
Fig. 2 shows the general shape of the phase
diagram of the ternary system: CH2Cl2 (solvent)/
CO2 (anti-solvent)/diuron (solute). The two phase
boundaries define three regions: vapor– liquid (V–
L), vapor –liquid –solid (V– L – S) and solid– su-
uron (0.9 wt.%)/methylene chloride.
percritical fluid equilibrium (S–SCF). Operating
conditions in the (S– SCF) region will lead to
herbicide precipitation and to easy removal of the
solvent. The same diagram could not be deter-
mined for the L-PLA/diuron/CH2Cl2/CO2 system.
Indeed, because of the turbidity of the solution,
the V–L to V–L–S transition was not visible.
Figs. 3 and 4 show the experimentally measured
phase boundary for the two ternary systems, re-
spectively: diuron/CH2Cl2/CO2 and L-PLA/
CH2Cl2/CO2 under various experimental
conditions. The lines denote transitions from the
(V–L–S) region to the (S–SFC) region for vari-
ous compositions.
Two main conclusions may be drawn from
these measurements:
1. At a given temperature, the transition pressure
increases slightly with an increase in the weight
fraction of carbon dioxide (Fig. 3). The same
observation was made for the L-PLA/CH2Cl2/
CO2 system [16].

Table 2
Solublities of diuron in methylene chloride and in tetrahydro-
furan at different temperatures

Temperature (K) Solubility in Solubility in

methylene tetrahydrofuran
chloride (g l−1) (g l−1)

298 20.9 89.4

303 26.4 99.1
308 29.8 116.2
313 41.3 134 Fig. 3. Phase diagrams of the ternary systems: CO2/diuron (0.9
wt.%)/methylene chloride with different CO2 compositions.
 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
Fig. 4. Phase diagram of the system: CO2/L-PLA/methylene
chloride with different CO2 and L-PLA compositions.
2. At a given temperature and within the range
of compositions studied here, the transition
pressure is quite insensitive to small changes in
polymer concentrations (Fig. 4), in agreement
with the results of Magnan [15] and of Yeo et
al. [17]. The same observation was made for
the diuron/CH2Cl2/CO2 system [16].
3.2. Precipitation of L-PLA by SAS process
For the following range of pressure and solu-
tion flow rate:
“ P: 8 –10 MPa; and
“ solution flow rate: 18– 30 ml h − 1,
spherical and non-aggregated particles were ob-
tained at 308 K for concentrations lower than 3
wt.% and polymeric fibers with cobweb-like
macrostructure were obtained for upper
concentrations.
Fig. 5. L-PLA particles precipitated from methylene chloride
at 8 MPa, 308 K, 1 wt.%, 18 ml h − 1.
65
Fig. 6. L-PLA fibers precipitated from methylene chloride at
10 MPa, 308 K, 6 wt.%, 30 ml h − 1.
Fig. 5 shows a sample obtained by spraying a 1
wt.% solution into CO2 at 8 MPa, 308 K and with
a solution flow rate of 18 ml h − 1. Small mi-
croparticles are produced with size ranging from 1
to 5 mm. Similar spherical particles of L-PLA are
also obtained at 10 MPa, 308 K and with a
solution flow rate of 30 ml h − 1. In contrast, Fig.
6 shows polymeric fibers obtained by spraying a 6
wt.% solution at 10 MPa, 308 K and with a
solution flow rate of 30 ml h − 1. This polymeric
fibrous network has already been observed by
Bodmeier et al. [14]. The whole SEM photographs
of L-PLA particles obtained by SAS process are
shown elsewhere [16].
Microparticles of polymers will precipitate on
condition that the jet of liquid solution breaks up
at the outlet of the capillary, thus forming individ-
ual droplets. The size of these droplets is governed
by a number of parameters such as the internal
diameter of the capillary, the density and the flow
rate of the liquid solution. The viscosity of the
polymer solution is another important factor. In-
creasing the polymer concentration will result in
higher viscosities that have a stabilizing effect on
the jet and yield bigger droplets. High polymer
concentrations may even reduce the atomization
forces to such a low level that they are not
sufficient to break up the jet into droplets [14]. In
that condition, the precipitation kinetic is much
fast than the droplet formation kinetic and fibers
are formed rather than microparticles.
66 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
Fig. 7. Crystals of diuron precipitated from methylene chloride
at 10 MPa, 308 K, 0.9 wt.%, 18 ml h − 1.
3.3. Precipitation of diuron by SAS process
For the following range of pressure and solu-
tion flow rate:
“ P: 10–11 MPa,
“ solution flow rate: 18– 30 ml h − 1,
needle-like crystals of diuron were obtained at 308
K from methylene chloride solutions with concen-
trations varying from 0.1 to 1 wt.%. Fig. 7 shows
diuron crystals precipitated from solutions with a
diuron concentration of 0.9 wt.%. Fig. 8 shows
the Debye –Scherrer diagram of the raw diuron
provided by Aldrich (a) and of the diuron crystals
obtained by SAS process (b). Diagram (b) is
similar to the one of the raw material, this means
Fig. 8. Debye – Scherrer diagrams of diuron provided by
Aldrich (a) and of diuron precipitated from methylene chloride
(b).
that both products have the same crystal lattices
(identical intereticular distances d) and the same
structure (comparable intensities).
In conventional crystallization in solution, di-
uron is known to give crystals with good crys-
tallinity in very short times; typical values of 0.03
mm s − 1 were reported [18]. Although this growth
rate depends on several parameters, such as super-
saturation, its value remains of this order of
magnitude.
In our experiments, needles of diuron with a
mean length of 500 mn were formed (Fig. 7). This
implies very high growth rates that can be esti-
mated if the precipitation time is known. This
precipitation time was evaluated to be a few sec-
onds referring to:
1. an experimental observation; and
2. literature.
(i) A few needle-like crystals were formed and
settled in the upper part of the precipitation ves-
sel. This indicates that the precipitation time is
very short. Indeed, the liquid solution is intro-
duced in the autoclave with a rate varying from
28 to 47 cm s − 1.
(ii) Kikic et al. [19] have studied the amount of
precipitated solid as a function of the axial coor-
dinate, h, of a cylindrical precipitator. Depending
on the nature of the solute, the amount of precip-
itated solid may be a function of the ratio be-
tween the gas and liquid flow rates. In the case of
phenanthrene precipitated with toluene as solvent
and CO2 as antisolvent, this amount can reach
80% (with respect to the total amount of compo-
nent in the initial solution) at h equals 2 cm
whatever the ratio of flow rates. Moreover, Kikic
has evaluated the time at which the droplet disap-
pears depending on the nozzle diameter. The or-
der of magnitude is the second. On the contrary,
the amount of solid precipitated is strongly depen-
dent of the ratio of gas and liquid flow rates for
naphthalene precipitated in the same conditions.
This amount can be of only 5% at h equals 20 cm.
In this study, the presence of crystals on the
upper inner wall of the precipitator, i.e. just below
the end of the capillary, implies that a certain
amount of diuron is precipitated early. Consider-
ing these results, we can estimate a precipitation
time on the order of a second or of a few seconds
 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
for the precipitation of diuron in the experimental
conditions studied here, that is to say growth
rates of approximately 100 mm s − 1.
The very rapid growth observed for diuron is
contradictory to the idea that a rapid volumetric
expansion of the liquid phase (liquid droplets in
SAS process) leads to the formation of small
crystals [12]. The influence, during the GAS pro-
cess, of the pressure rise on the nucleation and
growth of the crystal has been discussed by Gal-
lagher. During the GAS process, the liquid solu-
tion is expanded less rapidly than during the SAS
process. During both processes, the solute in solu-
tion is depleted owing to the formation of nuclei
and to the crystal growth. A rapid increase in the
supersaturation generally leads to a high nucle-
ation rate which results then in little and numer-
ous crystals. So, the GAS process is supposed to
imply higher growth rates and thus to give larger
crystals. Our results show that there is a competi-
tion between nucleation and growth, even if su-
persaturation increases rapidly. Berends et al. [20]
observe growth rates varying from 0.01 to 0.14
mm s − 1 for the precipitation of phenanthrene in
toluene by the GAS process. The growth rate
observed for the diuron precipitated by SAS pro-
cess is 104 times bigger than growth rates ob-
served for the crystallization of diuron in liquid
solution under ambient conditions or for the crys-
tallization of phenanthrene during GAS process.
3.4. Coprecipitation of diuron and L -PLA by
SAS process
Diuron and L-PLA were coprecipitated from a
single liquid solution by SAS process using meth-
ylene chloride as solvent.
It has been shown in the literature that the
temperature may greatly influence the precipita-
tion of polymers. In particular, the morphology of
the solid formed may differ depending on whether
the operating temperature is higher or lower than
the glassy transition point. Notwithstanding this
fact, the effect of the temperature was not investi-
gated in this study; pressure, flow rates and com-
position of the liquid phase were the only
parameters varied. Dramatic changes in the mor-
phology of the particles formed were observed by
67
Fig. 9. Crystals of diuron and L-PLA particles precipitated
from methylene chloride at respectively 0.9 wt.% and 1.8 wt.%,
at 10 MPa, 308 K, 18 ml h − 1.
varying the composition of the liquid solution and
to a certain extent by varying the pressure. The
former parameter has a preponderant effect since
the coprecipitate formed can look like acicular
diuron crystals with microparticles of L-PLA ag-
gregated or like small diuron crystals entrapped in
polymer.
Fig. 9 shows a failed encapsulation of diuron
yielding the formation of long needles of diuron
with aggregated microspheres of L-PLA. Obvi-
ously in that case, too much time separates the
precipitation of the two species and long needles
of diuron could develop before the precipitation
of L-PLA. Such a result is due to an excessive
concentration of diuron which results in an early
precipitation of this compound.
Figs. 10 and 11 show the results of successful
encapsulations leading to spherical particles of
L-PLA entrapping small crystals of diuron. In
these two cases, the experimental conditions were
the same except for the concentration of L-PLA
which varies from 0.1 to 1 wt.% (Figs. 10 and 11).
The particles which size ranged from 1 to 5 mm,
were similar in appearance to diuron-free mi-
croparticles. In order to check the presence of
diuron inside the L-PLA particles, we carried out
an energy dispersive X-ray analysis. During the
observation with the scanning electron micro-
scope, the electron beam was directed towards the
center of one particle of coprecipitate in order
that it entered the bulk of the spherical particle.
68 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
Fig. 10. Particles of diuron coated by L-PLA precipitated from
methylene chloride at respectively 0.1 wt.% and 1 wt.%, at 10
MPa, 308 K, 30 ml h − 1.
X-Rays of the emitted rays were then examined.
The X-ray peak positions, along the energy scale
identify the elements present in the solid particle.
This analysis was repeated for approximately 20
particles. Fig. 12 shows the superimposition of the
EDX spectra of L-PLA precipitated from methyl-
ene chloride and of the product of the coprecipita-
tion of L-PLA and diuron in the same solvent; all
other experimental conditions are identical. The
spectrum of (diuron+ L-PLA) shows the presence
of nitrogen and chlorine; these two elements are
not present in L-PLA but only in diuron whose
developed formula is also given in Fig. 12. This
main point of our results shows obviously that
Fig. 11. Particles of diuron coated by L-PLA precipitated from
methylene chloride at respectively 0.1 wt.% and 1 wt.%, at 10
MPa, 308 K, 30 ml h − 1.
Fig. 12. Energy dispersive X-ray spectra of L-PLA and diuron
coprecipitated.
diuron is really entrapped inside the spherical
particle of L-PLA.
It is worth noting here that we did not detect
the presence of chlorine arising from methylene
chloride in the spectrum of L-PLA alone. Obvi-
ously, the solvent is quite completely removed
during the washing step.
The weight percentage of diuron in the mi-
croparticle should be equal to 10%. Indeed, this
percentage corresponds to the weight ratio of
L-PLA and diuron in the liquid solution sprayed
since:
“ the whole quantity of L-PLA and diuron intro-
duced in the vessel precipitate (no solid was
recovered in the cold trap); and
“ the SEM observations showed particles abso-
lutely similar to the one of L-PLA obtained by
SAS process without diuron (Figs. 5 and 11).
All the diuron is then probably entrapped in
the microparticles.
Our experiments led us to the conclusion that
the main parameters controlling the encapsulation
of diuron by L-PLA are the absolute concentra-
tions of the two components, rather than the ratio
of these concentrations. The concentration of
 S. Taki et al. / J. of Supercritical Fluids 21 (2001) 61–70
each component has an upper limit, 3 wt.% for
L-PLA and 0.1 wt.% for diuron and the encapsu-
lation is successful when the two concentrations
are below these thresholds. Fig. 13 illustrates this
observation for experiments carried out at 10
MPa, 308 K and with a solution flow rate of 30
ml h − 1. For other values of the pressure, the
respective concentrations remain the main
parameters controlling the encapsulation but the
thresholds are slightly shifted towards higher val-
ues as the pressure is increased.
4. Conclusion
This study shows that encapsulating diuron by
L-PLA can be achieved by a one-step SAS pro-
cess. More broadly speaking, even though the
species to be encapsulated crystallizes under an
acicular form, it has been possible to process the
coprecipitation by acting on the concentration of
the active molecule and of the coating material.
Such a result may be interesting if the method
could be transposed to pharmaceuticals that gen-
erally crystallize with acicular habit.
The highest concentration of solid (herbicide+
polymer) in the liquid solution that can be pro-
cessed is of 3.1 wt.% in methylene chloride at 10
MPa and 308 K. This limit may seem low but the
method offers a high degree of flexibility as con-
cerns the ratio between the concentrations of the
two species.
From an economical point of view, encapsulat-
ing an herbicide by a rather expensive polymer
Fig. 13. Schematic diagram of the results of SAS coprecipita-
tion (10 MPa, 308 K).
69
may not seem realistic. It must be kept in mind
that reducing the treatment frequency may be the
key point in specific cases where the cost of labor
is of the same order of magnitude as the cost of
the raw material (treatment of railway, roads
shoulder).
In other respects, commercial herbicides like
diuron are generally available as aqueous suspen-
sions called ‘Flows’. We can imagine these flows
being prepared in the precipitation vessel intro-
ducing the aqueous medium just after the depres-
surization step of the SAS process.
The data reported here constitute the prelimi-
nary part of the study which is at the present time
been extended in order to improve the method
and complete results have not yet been obtained.
The three studies in progress deal with:
“ the kinetic of the herbicide’s release;
“ the percentage of herbicide entrapped; and
“ the search for less expensive coating material.
Acknowledgements
The Research Laboratory CRMC2 (Centre de
Recherche sur les Mécanismes de la Croissance
Cristalline, Campus de Luminy, Marseille) is
gratefully acknowledged. The authors want to
thank particularly Dr S. Veesler and J.P. Astier.
The authors are also indebted to PURAC
biochem for the supply of L-PLA.
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