The Core-Rim Interface of
Interstellar Graphite Onions
Dori Witt
2000
Undergraduate Intern
Advisor:
Dr. Phil Fraundorf
University
of Missouri-St. Louis
Many
scientists have waited a long time to be able to study cosmic dust in the their
own laboratories. In the nineteenth
century, the existence of interstellar matter was discovered. Evidence of this matter in space was looked
for in meteorites, but scientific equipment was not advanced enough to
differentiate between matter from space and matter from Earth. In the 1910s, stable isotopes were
discovered (Thomson, 1912), which sparked a search for cosmic dust. Scientists started getting results in the
early sixties (Reynolds, 1960). Presolar grains can be identified by isotopic
ratios different from our Sun’s ratios
(Bernatowicz & Walker, 1997).
The first evidence for interstellar material in meteorites was found in
1973 (Clayton et al, 1973). In the
mid-eighties, presolar grains were found inside meteorites (Wasserburg and
Papanastassiou, 1982). This, along with
the laboratory study of interplanetary dust, has opened up the field of
materials astronomy, in which astrophysical objects are studied with
microscopes as well as telescopes.
Interstellar
graphite onions are one of the few presolar relics that have survived the trip
to earth. They are called onions
because they are round and their outside portions are layered. These graphite onions make up about one
third of all presolar graphite (Zinner, 1998).
More
than 80% of interstellar graphite onions have a strange core formed of carbon
material that does not contain much order.
Images of these cores suggest randomly oriented, fine crystals. Diffraction indicates graphene sheets, or
graphenes, which are atom-thick sheets of carbon in hexagonal rings. Basically, graphene is graphite that does
not have layering in the third dimension. (Bernatowicz et al, 1996).
Diffraction
patterns suggest that the mass-weighted average diameter for graphene sheets is
between three and four nanometers (Bernatowicz, Gibbons, Amari, & Lewis,
1995). Graphenes of this size contain
several hundred carbon atoms and comprise the bulk of the mass in the cores of
the interstellar graphite onions. Only
one quarter of the mass comes from graphene sheets with diameters less than or
equal to a nanometer. However, these
tiny graphenes outnumber the large ones by far (Bernatowicz et al, 1996).
Materials
astronomers have no simple explanation why the onion cores do not show this
layering. Although curvature of the sheets (Bernatowicz et al, 1995), for
example due to the occasional replacement of hexagonal rings in the graphene
sheet with pentagonal or heptagonal ones (Bernatowicz et al, 1996) has been
suggested as an explanation, this does not explain the abrupt transition to
layered growth between core and rim.
Moreover, the observed 4 nm coherence widths are much larger than the
coherence widths of layered carbon nanotubes, and work by Wackenhut here shows
that the curvature due to even a single pentagonal insert would destroy this
coherence.
The cores of interstellar graphite
onions have often been compared to polycyclic aromatic hydrocarbons (PAHs),
which are a type of organic molecule that are sheets of carbon atoms with
hydrogen at the edges (Messenger et al, 1995).
PAHs have been discovered to contribute less than 10% of interstellar
graphite onion cores’ volume (Bernatowicz et al, 1995) but 5 to 25% of the core
mass (Bernatowicz et al, 1996).
The
rims of these spherical graphite onions consist of three-dimensional van der Waals
bonded graphite layers with 0.34 nm spacing (as shown in Fig. 1) that curve
like the layers of an onion. The
three-dimensional graphite of the rim always surrounds the two-dimensional
graphite of the core, never vice versa.
Three fourths of interstellar graphite onions have been found to have
rim thicknesses between 0.1 and 0.4 microns.
Small graphite onions do not have direct correlation between their size
and rim thickness, while onions with a diameter of about one micron or more
have thicker rims than smaller onions (Bernatowicz et al, 1996).
Astronomical
observation has estimated the mean interstellar grain size to be 0.025 to 0.25
microns (Amari, Lewis, & Anders, 1994); however, the mean size for a
graphite onion is 1.5 microns. The
smallest interstellar graphite onion has been measured to be 0.3 microns
(Bernatowicz et al, 1996), while the largest measured is 20 microns (Zinner,
1998).
The
density of onion cores is found to be greater than that of amorphous carbon and
a little less than the density of regular graphite (Bernatowicz et al,
1996). The density of the whole onion
ranges from 2 to 2.2 grams per cubic centimeter (Anders & Zinner. 1993).
Because presolar
grains are such a small part of meteorites (5 parts per million), they were
previously overlooked. Scientists
dissolved meteorites with acid to study the isotopic composition of selected
components. The presolar grains
identified so far are highly insoluble and hence did not dissolve with the rest
of the meteorite. Scientists soon
discovered that the mound of dust left over was mostly material that outdated
our solar system (Bernatowicz & Walker, 1997).
Other types of
presolar dust in meteorites go through many purification processes. These diminish the number of particles but
decrease their contamination. Because
interstellar graphite onions are so rare in meteorites, their quantity is
preserved, independent of purity. Still,
many small graphite onions are probably lost in their retrieval (Amari et al,
1994). The interstellar graphite onion
samples studied today came from only two meteorites, Murchison and Tieschitz
(Zinner, Amari, Wopenka, & Lewis, 1995).
Whole micron-sized grains are kept for study in scanning electron
microscopes and for ion microprobe analysis.
Most samples used in transmission electron microscopes (TEMs) are
separated by size, cut with a diamond ultramicrotome knife to about 100 nm
thick, and deposited on a TEM grid (Bernatowicz & Walker, 1997).
Observations
I took a survey of the specimen of sliced
onions KFC1AE from the Murchison meteorite in a 300 kV Philips TEM.
Example of a cleanly sliced onion is shown in Fig. 2. Fifty-six onions were noted, described,
measured, and mapped. Measurements were
approximated using the 5-mm diameter ring on the screen of the microscope for
reference. Mapping was done by marking
the position of the specific onion on a low magnitude image of the grid square.
Data from this survey is available on
the web. The size distribution of
sliced onions ranged from 0.4 to 2.2 microns in diameter with a mean of about
one micron. More than 90% of the onions
seen showed signs of a core. Regions of
thin core material suitable for high-resolution electron microscopy were also
identified. High-resolution images
taken in our lab in some cases (cf. Fig. 3) show the smooth graphite (hk0)
fringes characteristic of core material.
Since
slicing of the onions alters the size distribution and the core-rim ratio of
the sample, we requested a sample of small, whole graphite onions deposited on
a TEM grid from Roy Lewis at the University of Chicago. A survey has revealed thirteen whole onions,
which have been noted, measured, and mapped.
Measurements have been carried out the same way, but mapping was done by
drawing the sample. For the whole
onions, the size distribution has ranged from 0.3 to 3.5 microns with a mean of
about 1.4 microns. We took a series of
dark field images while rotating the incident beam to help us search for cores
in the whole onions. Some of these
evidenced inclusions of the sort expected for non core-rim onions, as shown in
Fig. 4, while others evidenced a decrease in (002) diffraction toward the
particle center even though no sharp core-rim boundary could be observed (cf.
Fig. 5).
One of
the smaller whole onions exhibited an
obvious core, as shown in Fig. 6. A
tilt of the specimen by 15 degrees has shown this onion’s core to be
spherically symmetric, while its rim is not.
Its diameter was an average of 0.5 microns. At the rim’s thickest point, this onion’s core-rim ratio is 0.44,
but at the rim’s thinnest point, the onion’s core-rim ratio is 0.63.
DISCUSSION
The sliced onions without a core are likely
the slices from the very top and bottom of the spherules. The many whole onions without a core are
much more mysterious. At least two
possible conclusions can be drawn from the lack of cores in the whole onion
sample. First, onions from the unsliced
set we were provided do not usually have cores. Alternatively, cores are difficult to detect in larger
onions. In either case, the onion with
an obvious core remains the exception in our collection of unsliced onions,
even though the majority of onions in the set microtomed by Tom Bernatowicz are
of the core-rim type.
David
Dawkins, during his research here, deduced that the thickness of the rim of
particles, subject to the expulsion by radiation during rim formation near the
surface of the star, might depend on core-radius r, according to the simple
relationship:
where
D=deposition rate of graphite, L=luminosity of the star, r=radius of the
particle, R=distance from the star to the particle, and r*=maximum radius of a
particle (Dawkins, 1996). For red
giants, r* is much greater than 1 micron, so the thickness of the rim is
proportional to r-1/2. For
our single onion with a well-defined core, the average constant of
proportionality is 0.12. The resulting
deposition rate, so inferred, exceeds the rate one might expect in regions of
“average density” in 2000 degree Celsius regions of a red giant
atmosphere. If these particles do form
in stellar atmospheres, regions of significantly increased carbon gas density are
likely required.
Overall, we have inventoried 56 microtomed
and 13 unsliced interstellar graphite onions.
A subset of the former have regions of torn core material that ramp down
to thicknesses less than the 10 nm suitable for high resolution study. Some images taken from these regions already
show the power spectrum signature of the core material, and work to both
analyze the contrast and compare with simulations is presently underway. For example, is the relationship between
graphene sheets dendritic, is it random, or does it show evidence of bending
due to pentagonal or heptagonal loop defects in the sheets? This information is crucial to understanding
the processes by which they are formed, as well as the nature of the abrupt
transition to layered growth in the onion rims. The unsliced onions show promise for providing core-rim ratios
not broadened by the onion slicing process, which helps for comparison to
models of transport out of the star’s gravitational well by radiation pressure
after they are formed. More statistics
are needed for firm conclusions at this point in time.
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