The Critical Point

David Pacchioli
May 1, 2001

"Near the critical point," Moses Chan says, "is where things get
interesting."

James Collins

Custom-built cryostat for cooling samples close to absolute zero.

He pops up from his chair and walks to a file cabinet, rummaging a

moment before producing what looks like a small red-handled hammer,
holds it up for inspection. The head is a stainless-steel cube, with a small
round window. The chamber is half-filled with clear liquid.Chan, Evan
Pugh professor of physics at Penn State and recently elected member of
the National Academy of Sciences, motions me to follow, out of his office
and down the hall to the faculty lounge. There's a kitchenette, and an
electric hot pot on the counter. Chan removes the lid and plunges the
instrument into the pot. The sealed chamber is now a pressure cooker.
"We'll heat this liquid, freon, beyond its critical pointthat's 80 degrees C
then watch what happens," he says. He hurries to the adjacent
conference room to flip on an overhead projector, then dashes back to the
pot.
It's hot enough. Using paper towels to protect his fingers, he plucks the
instrument out by the handle, shakes it twice, hustles back to the
conference room, and lays it on the projector.

Enlarged on the wall screen the round window is completely transparent.

Gone is the meniscus, the curved line that marked the level of liquid.
"Above the critical point, the distinction between liquid and vapor simply
disappears," Chan says. "There's only a single, undifferentiated fluid.
"Now watch what happens as it cools."
In a few seconds, the little porthole turns a milky yellow; in another it fades
to black. A few more seconds and the darkness resolves, and what reemerges is two distinct phases: liquid and vapor.
Back in his office, Chan explains. As the chamber is heated, the liquid
expands, becoming less dense. The vapor pressure increases, and the
gas grows denser. In an ordinary tea kettle, the liquid would eventually
come to a boil, with heat escaping the liquid in bubbles rising to the
surface and leaving the kettle as steam. Here, though, in a sealed
environment, there's nowhere for the steam to go.
Instead, near the critical point, the densities of the two phases are
fluctuating wildly. If the molecules in a liquid are a tethered cluster of
tennis balls, those in a gas are cut loose and bouncing off the walls.
During fluctuation in density, the distance between molecules in each
phase is yo-yoing back and forth: moving closer, then farther apart.
When the temperature gets above 80 degrees, the dueling densities
simply merge. The two phases become indistinguishable. As the chamber
cools back down, however, the fluctuations return. At the critical point their
scale reaches a length of 4000 angstromswhich just happens to match
the wavelength of visible light. The reason why everything goes black,
Chan concludes, is that the fluctuations of the freon cancel out the light
waves trying to pass through it. The light is scattered, deflected -"like the
beam of your headlights when you're driving in a fog." Critical
opalescence, the phenomenon is called. Another degree cooler and it
passes.
Every substance has a critical point. Not only that, but critical points, with
their unusual properties, are not limited to the liquid-to-vapor shift. The
same rules describe other sorts of transitions as well. A magnet, for
instance, has a critical point. Heated to a certain temperature, it abruptly
loses its magnetism. Just before it does, there's a period of fluctuation.
For Chan, who has spent 30 years studying the nature of critical
transitions, what's fascinating is that shaky in-between time, when
molecules share a different sort of communication.

James Collins

Moses Chan and a super-cooling apparatus. "Finding something a little different from the prediction is what we
experimenters like the most," says Chan.

One of the properties that governs molecules in a bulk material, he

explains, is what physicists call symmetry, which to hear Chan explain it,
is something like peer pressure. "It's like a teenager who buys a baseball
cap," he says. "Before he sees how his neighbors wear their hats, he is
equally likely to wear it with the brim forward or back. But when he sees
that all the others wear it backwards, there is peer pressurea lowering
of potential energyand he conforms."
Similarly, if you think of a magnet as a lot of tiny arrows all in a row (as the
German-American physicist Ernst Ising did back in 1925) at low
temperature, Chan says, "they like to line up, all pointing in the same
direction. Even if one arrow gets the urge to flip, the peer pressure is too
great. It will soon flip back to conformity." This is the magnetized state.
"It requires energy to break the mold," Chan continues. In this case,
kinetic energy, or heat. Apply enough of it, and "molecules will defect."
Above the critical point, those arrows are constantly flipping, back and

forth. This too, however, represents a kind of unanimity: that of the nonmagnetized state.
Near the critical point, however, the propensity to line up matches the
propensity to flip, and neither dominates. The system doesn't know
whether it wants to be magnetic or non-magnetic." Now push it just a little
further, to the cool side. "One arrow may flip for good, and it has an
influence on its neighbor. The next one wants to follow suit, and the next,
and the next."
"Symmetry-breaking," Chan says, "is the making of a choice, forsaking an
alternative. And the amazing thing is these molecules act in coordination.
At the right temperature, all you need is someone to incite a riot and the
disturbance can propagate out to a very long distance.
"According to the cosmologists," Chan says, "the Big Bang is a symmetrybreaking event. When the universe is very hot, there is no difference
between energy and matter. At the Big Bang, there is a transition. A choice
is madeto break down and settle into this universe we happen to be in."
Condensed-matter physicists, working with huge numbers of particles,
have to rely on tatistical models to describe phase-transition processes.
Such models must be tremendously simplified. Ising's was onedimensional: a string of magnets in a row. Lars Onsager, the NorwegianAmerican chemist who would later win a Nobel prize, tackled the more
difficult and more interesting problem of magnets arrayed on a twodimensional lattice. "It's more interesting," Chan says, "because this
system exhibits a phase transition at the critical point." Onsager's 1944
result, extended in 1952 by another eventual Nobel laureate, the ChineseAmerican physicist C. N. Yang, is one of the most famous papers in
statistical mechanics.
So complex are the mathematics involved that no one has yet completely
solved the magnet problem in three dimensions. But in 1984, 32 years
after the two-dimensional Ising model was proposed, it was confirmed
experimentally by Chan and his student Hyung-kook Kim at Penn State.
After earning his Ph.D. at Cornell in 1974, Chan, an experimentalist, had
set out to explore the effect of dimensionalitywith symmetry a basic
property of bulk materialson liquid-to-vapor phase changes. He wanted
to see how a transition taking place on a flat surface, the heating of a thin
film of liquid, say, compared to the same transition in a depth of liquid. Did
the two models differ in fundamental ways?

Experimenting in two-dimensional matter, Chan says, is like peering down

at tiny skaters on an ice rink. "A single skater is like a gas molecule, free
to move anywhere across the ice, but unable to rise above it. If I put more
skaters on the rink, eventually there will be collisions." That would be the
vapor phase. "A liquid in two dimensions is a cluster of moleculesa
bunch of skaters tired of colliding who have decided to join hands.
We did experiments on graphite, not ice," he says. He and Kim introduced
methane vapor into a small metal cell containing a graphite sample. As
the cell cooled, the methane settled onto the graphite surface in liquid and
vapor patches. Then the experimenters slowly varied the temperature in
the cell and mapped out the densities of the two phases. What we
measured was precisely what Onsager and Yang predicted," Chan says.
Since that time, Chan and his students have created experimental
systems that have confirmedor refuteda number of theoretical
predictions. ("Finding something a little different from the prediction is
what we experimenters like the most," he confesses.) In most of these
studies, the material of choice has been liquid helium, which, Chan says,
in addition to demonstrating the properties common to all fluids, also
offers the unique advantage that "at very low temperatures it very clearly
manifests its quantum-mechanical nature."
Helium, he explains, is the only substance that will not solidify even if
cooled to absolute zero. At very low temperatures -below 2.17 degrees K
it becomes a superfluid: a liquid with no viscosity, that is, no resistance
to flow. Chan picks up a cup of coffee that has been sitting neglected at
his elbow, removes the lid. "If this were a superfluid," he explains, "and if I
were to take a spoon and stir it, the coffee would go on rotating forever."
Pause. "Well, not exactly," he amends. "The rotation will slowly decay. But
the time of decay is longer than the age of the universe."
To precisely determine the onset of superfluidity in adsorbed helium films,
Chan's students used a torsional pendulum fixed to a porous bob. The
pendulum is rotated back and forth at a specific frequency. When helium
is adsorbed on the surface of the bob, the mass of the bob increases,
measurably lowering the frequency of rotation. When cooled below 2.17
degrees, however, the helium turns to superfluid, at which point "it is
completely decoupled from the twisting motion, as if it is not there," Chan
says. The pendulum rotates without resistance.
"This property doesn't show up in other fluidsthey freeze solid first,"
Chan says. "So we use this systemthe superfluid transition in helium

to try to understand aspects of critical phenomena not available in other

systems."
In the idealized world of physical "systems," until recently, Chan has
written, "disorder and impurities were often viewed as unavoidable
nuisances that masked . . . true behavior." Particularly the behavior of
critical-phase transitions. "The old way of thinking was if you put any kind
of junk into a pure system, the critical transition would be ruined.

James Collins

Making final adjustments to measure fluctuations near the liquid-vapor critical point of nitrogen. Chan is joined by
graduate student Sarah Weber, left, and visiting professor Klaus Knorr.

But the real world is never pure," he says. A recent thrust in his lab,
therefore, has been to see just what does happen when impurities are
introduced. One major obstacle has been finding a way to introduce
impurities in precisely controlled amounts.
Chan opens a desk drawer, and pulls out a pinky-sized vial. Unscrewing
the lid, he removes what looks like a skinny translucent cork or a glue
stick, and motions me to hold out my palm. "Be careful with it," he says.
"It's glass." Strands of silica, actually, woven into a mesh of microscopic
fineness. An aerogel. It's featherlight, and no wonder. "This particular one
is only eight times the density of air."
First made by chemist Steven Kistler of Stanford in the 1930s, silica
aerogels are formed by a sol-gel process: particles of silica dust are
suspended in a solvent which then sets as a gel. Subsequent drying
leaves only the porous glass frame, or "host," a perfect sample of
controlled disorder. Injected with liquid helium, Chan explains, "the

aerogel itself becomes the impurity." To get the precise amount of impurity
you want, you simply adjust the amount of the starting chemical that forms
the silica network.
When helium-filled aerogels are cooled to the superfluid critical point,
Chan has found, a phase transition still takes place. This level of disorder,
at least, doesn't change that physical fact. What's surprising, Chan says,
is that the helium's properties at transitionthe patterns of fluctuation
near the critical pointare completely changed. "The presence of
disorder seems to alter how the material approaches the critical point," he
says. "It seems to follow a completely different path." This change, he
says, seems related to the structure of the aerogelthe way the silica
strands are connected. "There are very few of them, and so they have to
be connected at a long length scale. The speculation is that the fluctuation
in density of the helium is at the same length scale."
The National Science Foundation recently established a Materials
Research Science and Engineering Center at Penn State to exploit just
this type of behavior. The Center for Collective Phenomena in Restricted
Geometries, one of 29 MRSECs across the country, will bring together 13
Penn State researchers from the departments of physics, electrical
engineering, chemistry, and materials science to explore the science and
the possible uses of aerogel-type hosts. Possible technologies include
nanometer-sized superconducting wires and tunable light-controlled
crystals, which might someday become optical switches speeding signalprocessing along the Internet.
For Chan, the director of the new center, this kind of technologically
relevant, interdisciplinary work is a new experience. "But I have learned a
lot already," he says. "And I have enjoyed the interaction.
"You might have got the impression that I like to work on very esoteric
thingsand I do. But I have found that doing interesting things and doing
useful things don't have to be exclusive."
Moses H.W. Chan, Ph.D., is Evan Pugh professor of physics in the
Eberly College of Science, 104 Davey Laboratory, University
Park, PA 16802; 814-863-2622; chan@phys.psu.edu. Hyung-kook
Kim, Ph.D., is professor and head of the department of physics at
Pusan National University in Korea.