Often viewed as primarily a tool for basic
research, the Lab's Advanced Light Source (ALS) nonetheless has its share
of industrial users seeking solutions to their problems. Recently, the
people who manufacture materials for disposable baby diapers set up shop
at the ALS.
The global market for disposable diapers is $20 billion annually, but
manufacturers face a twofold challenge. To keep the baby dry, the diaper
must be able to take up a large quantity of liquid and then, as baby
diaper scientists describe it, "hold it under load" as the baby
moves around.
Parents don't make matters any easier. These consumers demand
thin diapers, and through their buying habits, have ruled out the
extensive use of the bulky cellulose fluff that was once the stuff of
disposable baby diapers.
Today, "superabsorbent polymers," materials with long chains
of intertwining molecules that are able to soak up lots of liquid, now
dominate the disposable diaper market.
By means of chemical reactions on the surfaces of submillimeter-sized
superabsorbent polymer beads, manufacturers fashion thin shells of tightly
"crosslinked" polymer in which the strands are connected at the
cross links. The shell makes it more difficult for liquid to leak out, but
actual performance depends on the microscopic details of the shell
structure, such as variations in the crosslinking through and around the
shell.
Examining this kind of structural detail has been difficult, but
researchers now have found a way, using the synchrotron radiation produced
at the ALS.
Researchers from The Dow Chemical Company teamed with academic
colleagues and used an x-ray microscopy technique to analyze a variety of
shells formed in different ways. Researchers were able to map the
variation in crosslink density of the different shells, providing a way to
gauge the effect of shell-formation processes at the microscopic level and
thereby, to improve the production process.
The experiments were such a success that Dow has been able to use the
results to help develop the process technology now being designed for a
new superabsorbent polymer manufacturing plant. Because of this and
related work on x-ray spectromicroscopy of polymeric materials, Dow's
Analytical Sciences division has conferred its highest internal award on
researchers Gary Mitchell and Ed Rightor.
Superabsorbent polymers are used not only in baby diapers
but in a wide range of products. They are an example of a polymer gel.
Occurring in both natural and synthetic forms, polymer
gels exhibit an intriguing combination of the properties of both liquids
and solids. One feature that makes gels useful is their ability to respond
strongly to very weak external stimuli, such as minute changes in pH or
temperature. For example, a polymer gel might first absorb a quantity of
liquid and later release it as the external conditions change. Timed
release of pharmaceuticals is one example among many in which a control
stimulus determines the rate of release. Crosslinking is a key feature of
the polymer microstructure that governs actual performance.
Dow sells superabsorbent polymers in the form of small (less than 1.0
mm in size) beads of sodium polyacrylate that are lightly crosslinked to
form an insoluble, hydrophilic gel. The ability to soak up great
quantities of fluid makes superabsorbent polymers attractive for use in
diapers. But, like a sponge when compressed, some of the fluid is squeezed
back out when the baby moves, negating part of the benefit. The strategy
for preventing leakage under weight-bearing load is the formation of a
thin shell of more tightly crosslinked polymer. The effectiveness of the
shell depends in part on the density profile of the crosslinking through
the shell, a distance of several microns. Several different methods have
been developed to make surface crosslinked superabsorbent polymers gels,
but up until now there has been no good way to visualize and assess the
resulting core-shell structure and the crosslink density profile.
To obtain the desired information, the researchers turned to near-edge
x-ray absorption fine structure spectromicroscopy, using a scanning
transmission x-ray microscope at the Advanced Light Source. They
were able to make images of the polymers in the fully hydrated state (in
excess water). Because the x-ray energy could be tuned to a value where
the carbon in the polymer absorbs and the water is almost transparent,
they could map the areas where crosslinking was higher by observing the
increased carbon content in these regions.
Crosslinking was stimulated by treating the surface of the
superabsorbent polymer beads with varying solutions. Sectioned beads were
then exposed to a saline solution to put them in the fully swollen state
for imaging. Analysis of the images yielded two extreme cases for the
crosslink profile through the shell. In one, the crosslink density
decreased smoothly over a distance of 18 microns from a maximum at the
outer surface. In the other, the density was uniform over a distance of
five microns and then dropped abruptly.
These differences reflect a complicated interplay between the dynamics
of the swelling of the bead in water, the diffusion rate of the
crosslinker in the water phase, and the rate of the crosslinking reaction.
And, this interplay can make or break a better baby diaper.
Dow was able to use this information to help guide the design of new
superabsorbent polymer fabrication plant.
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