Development of deuterated polystyrene shells for laser fusion by means of a density

matched emulsion method

M. Takagi, T. Norimatsu, T. Yamanaka, and S. Nakai

Citation: Journal of Vacuum Science & Technology A 9, 2145 (1991); doi: 10.1116/1.577241
View online: http://dx.doi.org/10.1116/1.577241
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 Development of deuterated polystyrene shells for laser fusion by means
of a density~matched emulsion method
M. Takagi, T. Norimatsu, T. Yamanaka, and S. Nakai
Instituteo/Laser Engineering. Osaka University. 2-6, Yamada-oka, Suita, Osaka 565, Japan
(Received 15 August 1990; accepted 16 February 1991)
High quality, microdeuterated polystyrene shells were fabricated using a density-matched
emulsion method. The diameter and wall thickness of the shell ranged from 100 to 1500 and 3 to
15 pm, respectively. The sphericity, the wall thickness unifonnity, and the surface smoothness
were 99.8%, 99.3% and < 0.1 11m, respectively. A defect on the inner surface of the shell was
smeared by replacing water in the shell with ethanol prior to the final drying process.

I. INTRODUCTION removing the solvent by heating the emulsion, DPS shells

In laser fusion experiments, a glass microbaHoon (GMB) containing water inside are obtained. The DPS shells are
has been used for a fuel container since it has high sphericity, then immersed in ethanol to replace the WI with ethanol to
wall uniformity, and good fuel retention characteristics. 1-3 obtain defect-free surfaces. Without this replacement, im-
However, the GMB is not appropriate for achieving high- purities in the WI deposit at the bottom of the shell during
density compression, due to x-ray preheat caused by the sili- the final drying process. The ethanol reduces the wetting
con of the glass, and Rayleigh-Taylor instabilities which de- angle of the WI and uniformly disperses the impurities on
velop between the waH and the fuel during the stagnation the inner surface. Finally the DPS shells with ethanol are
phase of the implosion. dried in the air to obtain hollow DPS shells.
A plastic shell can reduce the preheat and the instability Deuterated polystyrene was synthesized to study the ef-
because of its relatively low atomic number and mass den- fects of the molecular weight on the shell quality. The start-
sity. Moreover, it can be used to study implosion dynamics ing material was a deuterated styrene monomer which was
offuel in the shape of a shell and the physics of highly com- purchased from Commissariat a I'Energie Atomique. 98%
pressed fuel plasmas by replacing the hydrogen by deuter- of the hydrogen in the polystyrene is replaced with deuter-
ium and tritium which emit thermonuclear reaction prod- ium. The monomer was mixed with a 0.2- to O,8-wt. % poly-
ucts useful for diagnosing implosion experiments.
Many reports have been published on fabrication of the
plastic shells4-9 intended for use as fuel containers. How-
ever, they have noted some drawbacks such as low yield for
high quality shells.
We have developed a technique to make high quality, deu-
terated polystyrene shells with high yield for use in high-
density compression experiments. An emulsion method was
used to fabricate the shells. The important improvements ----OC-W8ter Glcbule
over previous reports are that the densities of the oil and
water phases are adjusted to remove the effect of gravity, and
W,/O/W 2
Emulsicn ~ «:» a-Phase
that the molecular weight of polystyrene (PS) is controlled
in order to obtain bubble-free walls. We have successfully ~~e_·r_w_a_t_e~=I)=fY=i-"-!!J""'1 W-Phase (W 2 )
fabricated high quality, bubble-free deuterated plastic shells.
Sclidification:.c:- t!! t \ ~..::CICH2CH2CI· CsHs
The specifications for fabricated shells are as follows; diame- of O-Phase - 0 -
Evapcrates at 82°C
ter 500 to 1500 pm; wall thickness, 4 to 15 pm; and spheri- Drive cut \\
city and wall uniformity, > 99%. The detailed technique is Solvent by \ Water
Heating in Water Solid Pclystyrene Shell
described in the foHowing sections. Replacement of deuter-
ium with tritium will be reported elsewhere.
[!eplace W, with EthancU
T-----·-·-~-

II. FABRICATION PROCESS

A. SyntheSiS of polystyrene and encapsulation
The basic process of the emulsion method is shown in Fig.
1, which is similar to that developed by Kubo et 01.4
Deuterated polystyrene (DPS) is dissolved in a solvent to
make an oil phase (0). Water (Wj ) is poured into the
stirred solution to make a WI 10 emulsion which contains
water globules. The emulsion is, in turn, poured into a sec-
ond water bath ( W2 ) to form a WI /0 I W2 emulsion. After
G--VOid
Polystyrene Shell
A Final Product!
FIG. I. Fabrication process for deuterated polystyrene shells with high
sphericity and wall uniformity. Molecular weight of deuterated polysty-
rene, density matching through WI' oil phase to W2 , and replacement of
water with ethanol are all important to obtain high quality sheils.

2145 J. Vac. Sci. Technol. A 9 (4), Jull Aug 1991 0734-21011911042145-04$01.00 @ 1991 American Vacuum Society 2145

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 2146 Takagi et sl.: Development of deuterated polystyrene shells for laser fusion 2146

merization initiator of 2,2-azobis-iso-butyronitrile (hereaf- TABLE 1. Molecular weight of deuterate<! polystyrene polymerized by 2,2-
ter referred as AIBN) in a test tube. After the mixture was azobis-iso-butyronitrile (AIBN) with different concentrations at 7S"C.
frozen by liquid nitrogen, the test tube was evacuated, filled
with argon, and sealed by melting the top of the tube. The AIBN concentration (wt. %) Molecular weight
sealed tube was kept at 75 ·C for 12 h and at 120°C for 5 h to 0.2 (1,5-2.0) X 10'
complete the polymerization. After cooling and breaking the 0.5 (0.8-1.5) X 105
test tube, the DPS polymer was obtained. 0.8 (0.3-1.0) X 10'
The solvent for the DPS was an equivolume mixture of
benzene [boiling point (bp) = 80.1 DC, d!5 =0.8787 10 )
and 1.2 dichloroethane (bp = 83 ·C, d ~o = 1.2569 10 ). These
solvents were chosen because they have almost the same make concentric interference patterns in the shell image.
boiling temperature, temperature dependence of vapor pres- When the deviation of the interference pattern and the sheH
sure, and heat of vaporization, which should prevent center is (jr, the nonuniform term Of is given approximately
changes in density ofthe solution during the drying process. by
The concentration of DPS in the mixed solution was varied
from 3 to 5 wt. %. The solution was filtered with a Teflon
Of = ort Ir, 0)
sieve with 0.1 p,m in pore size to eliminate particles of dust. where rand t are the average radius and the wall thickness,
The specific gravities of the solution at 22 and 82°C were respectively.
1.065 and 0.993, respectively. The surface finish and the cross section of the wall were
Water with O.OS-wt. % surfactant (Daikin Co., DS-IOt) observed with a scanning electron microscope (SEM). A
was used for the WI phase. The specific gravity of the WI shell was frozen with liquid nitrogen and broken to produce
phase was L002 at 22°C and 0.977 at 82 dc. The W2 phase a dear cross section of the waH.
consisted of water and 5-wt. % polyvinylalcohol (PVA)
whose degree of polymerization was 500. The specific gravi- III. EXPERIMENTAL RESUI..TS
ty of the W2 phase was 1.013 at 22°C and 0.987 at 82 dc. A. Molecular weight of deuterated polystyrene
These water phases were also filtered to remove particles.
The molecular weight of polymerized DPS depended on
Five grams of the WI phase was added to the 109 of the
the temperature during polymerization and the concentra-
stirred oil phase in a 20-ml vessel to form a WI 10 emulsion.
tion of AIBN. The molecular weight of DPS's polymerized
This emulsion was poured into 500 ml of the W2 phase
at 75 ce, with various AIBN concentrations, are shown in
which was contained in a beaker placed in a 82 DC bath. The
Table 1. These molecular weights were estimated from the
emulsion was stirred with a 3-cm-diam propeller rotated at
viscosity of the solutions with a same concentration at room
400 rpm for the first 10 to 30 s and at 200 rpm after sufficient
temperature.
dispersion ofthe WI 10 emulsion had occurred. The beaker
The best results were obtained using DPS of
in the hot bath was also shaken in a horizontal plane with
(0.8 to 1.5) X 105 molecular weight. Figure 2 shows the
stroke lengths of 15 mm to produce random but gentle mo-
completed shell with high sphericity and waH uniformity.
tion of the emulsion. It took 3 h to remove the solvent from
The shell had no bubbles in its wall and surface smoothness
the oil phase through the W2 • The DPS shells containing the
was better than 0.1 p,m. High quality shens were obtained
WI were washed with distilled water to remove the PVA and
were immersed in ethanol for 48 h to replace the WI with
ethanol. This replacement smeared away the defect on the
inner surface which will be mentioned later. The DPS shells
were completed after the ethanol was evaporated by drying
in the air for 48 h.

B. Characterization
Sphericity was measured using an optical microscope
equipped with a digital scaler. A DPS shell was picked up
with a vacuum chuck and the diameter was measured at six
different angles by rotating the vacuum chuck. The shell was
then mounted on another vacuum chuck oriented perpen-
dicular to the former to measure the diameter at six other
points including the poles.
The uniformity of wall thickness was measured with an
interference microscope in a similar way using the orthogo-
nal vacuum chucks. Since the interference microscope mea-
sures the summation of the top and bottom wall thickness,
the sensitivity for nonuniformity in mode III (the noncon-
centricity of inner and outer surfaces) is low. The probe FIG. 2. Highly spherical deuterated polystyrene sheU with a uniform wall.
beam was interfered with the parallel reference beam to No bubbles and cracks are seen in the wall.

J. VilC. Sci. Technol. A, Vol. 9, No.4, JullAug 1991

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 2147 Takagi et al.: Development of deuterated polystyrene shells for laser fusion 2147

Bars in the figure represent variations of wall thicknesses in a

batch. The wall thickness of the shell can be changed from 2
to 15 flm by adjusting the concentration of DPS in the oil
phase.
Typical sphericity of shens in a batch around 500-jlm
diam was 99.8 ± 0.2%. The sphericity s was defined as
(2)

10 11m
FIG. 3. Bubbles in a deuterated polystyrene shell. These bubbles were often
found in the shell wall if the shells were fabricated using a deuterated poly"
styrene shell of (l.S-2.Q) X 10' in molecular weight.
similarly from an equimolar mixture of DPS's with low and
high molecular weights. However, the shells made of
(0.3-1.0) X 105 molecular weight DPS, were fragile and
many cracks were found" If shells were fabricated from D PS
of (1.5-2.0) X 105 in molecular weight, shells became opa-
que and contained many bubbles in their walls as shown in
Fig. 3.
B. Sphericity and uniformity
A relation between the wall thickness of DPS shells and
the concentration of DPS in the oil phase is shown in Fig. 4.
16
where Rmax and Rav are the maximum and average radii of
the shell, respectively, as obtained by measurements taken in
12 orientations for each shell. The variation of ± 0.7% re-
sults from the resolution ofthe microscope 0.5 ,urn and mea-
surement error of ± 0.2%.
Figure 5 shows concentric interference patterns from a
uniform shell. Nonuniformity of wall thickness in mode 1
was < 1%. We can say the uniformity in wall thickness of
DPS shens fabricated by the density-matched emulsion
method is better than 99%.
Kubo et al." used dichloromethane for the solvent of the
oil phase. The dichloromethane has a low boiling point suit-
able for easy removal of the solvent through the W2 • How-
ever, its density is 1.3255 which is much larger than that of
the WI . During removal of the solvent in the oil phase, the
WI droplet in the oil phase floats due to buoyancy, resulting
in a nonuniformity of waH thickness in mode 1.
Co Surface finish
The cuter surface of the DPS shell is shown in Fig. 6. The
surface roughness of our shells was < 0.1 flm. With regard to
the inner surface, the above value was obtained by replacing
WI with ethanol before the final drying process.
Without this replacement, a disk-type defect shown in
Fig. 7 appears at the bottom of the inner surface. The defect
was 10 to 30 Ji-m in diameter and 0.5 j..tm in thickness. From
x-ray framing images during implosion of the shell indicated
this defect contained higher atomic number elements than
hydrogen and carbon. We do not understand what the mate-

14

12

E
2: 8
III
In
t!!
C
.:t:
U
...
:E
'is
~

o 2 4 6 10 12

Polymer concentration (wt%)

FIG. 4. Wall thickness of a deuterated polystyrene shell can be changed by FIG. 5. Interference patterns in a deuterated polystyrene shell. Uniformity
adjusting the concentration of polystyrene in the oil phase. of wall thickness was better than 99%.

J. Vac. Sci. Techno!. A, Vol. 9, No.4, JlIi/Aug 1991

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 2148 Takagi et af.: Development of deuterated polystyrene shells for laser fusion
FIG. 6. Surface of a deuterated polystyrene shell imaged with an electron
microscope.
rial of the defect is. However, the defect is independent of the
purity of the WI and the molecular weight seems to be high,
since it cannot diffuse through the wall. This material might
consist of solvent molecules combined with deuterated poly-
styrene. If the WI in the shell is replaced with ethanol, these
molecules become uniformly distributed over the inner sur-
face of the shell.
IV. CONCLUSIONS
Deuterated polystyrene shells with high sphericity and
wall uniformity were fabricated by a density-matched emul-
sion method in which the influence of gravity was eliminat-
ed. The sphericity and wall uniformity of the shell were bet-
ter than 99.8% and 99%, respectively.
Molecular weight of deuterated polystyrene CDPS) suit-
able for fabricating shells was found to be (0.8-1.5) X 105 •
Shells fabricated with DPS of higher molecular weight ex-
hibited bubbles in their walls and shells with lower molecu-
lar weight were unacceptably fragile.
Irregularities in the surface finish of the shell were < 0.1
/-Lm and the defect on the inner surface, which often re-
mained after previous emulsion methods were used, was
smeared if water in the shell was replaced with ethanol be-
fore the final drying process.
J. Vac. ScI. Techno!. A, Vol. 9, No.4, JullAug 1991
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2148
FIG. 7. Defect appearing at the bottom of the inner surface of the shell if the
shell was dried without the replacement of waier with ethanol.
This technique is applicable to the fabrication of normal-
hydrogen polystyrene shells which may be used as fuel con-
tainers for cryogenic targets.
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