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Granular Chains & Polymer Systems: Jamming Transition Perspective, Notas de estudo de Física

The similarities between the behavior of granular chains and real polymer systems, suggesting that the glass transition in polymers might be a jamming transition caused by the formation of rigid semiloops. The document also highlights the potential implications of this discovery for polymer science and the possibility of observing monopoles in spin ices.

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www.sciencemag.org SCIENCE VOL 326 16 OCTOBER 2009 375
PERSPECTIVES
during chain packing act as if they are large
hollow monomers that can pack together to
form a jammed (shear-resisting) confi gura-
tion. A two-dimensional simulation of granu-
lar chains at low chain density, where the sys-
tem is unjammed (has no resistance to shear)
(see the fi gure, panel A), contains randomly
configured chains. At high chain density
when the system is jammed (see the fi gure,
panel B), semiloop structures appear. Zou et
al. revealed that semiloop formation is cru-
cial to the behavior of the granular chain sys-
tem. The presence of semiloops lowers the
jamming density of the system, and this effect
is more pronounced in longer chains where
there are fewer chains per unit volume.
Real polymer systems undergo a transi-
tion to a glassy state below some temperature.
It is known that this glass transition tempera-
ture increases with polymer length and satu-
rates for long polymers ( 4). In the granular
chain polymer model system, there is no tem-
perature; instead, the inverse density serves
as a quantity analogous to temperature. When
Zou et al. compare the behavior of the inverse
density of the granular chains as a function of
chain length to the glass transition tempera-
ture of a real polymer as a function of poly-
mer length, they fi nd that the behaviors are
nearly identical. This remarkable result could
imply that the glass transition in real polymers
might be a jamming transition governed by
the formation of rigid polymer semiloops. It
would be extremely interesting to determine
whether this type of semiloop actually occurs
in real polymer systems. Semiloops should
form much more easily than complete loops
because the two ends of the polymer do not
need to be near each other. If semiloops play
a role in real polymer systems, this would be
one of the most beautiful examples of where
a macroscopic toy system explains the phys-
ics on a molecular scale. Such a result would
also confi rm that the ideas of jamming origi-
nally proposed for granular assemblies ( 57)
are applicable to a wide variety of molecular
systems.
Granular polymers also represent a new
form of granular matter and most likely will
exhibit new kinds of phenomena that do not
occur in real polymers or in granular systems
composed of individual grains. As the jam-
ming density of the granular polymer sys-
tem can be controlled readily by adjusting
the length of the granular chains, introducing
chains into other systems that exhibit jam-
ming may allow for a much more precise con-
trol of the jamming of these materials.
The experimental demonstration by Zou et
al. that granular polymers can give insight into
molecular polymer systems potentially opens
Observing Monopoles in
a Magnetic Analog of Ice
PHYSICS
Michel J. P. Gingras
Experimental evidence has been found that magnetic poles within metal oxide magnets can be
separated.
A bar magnet has a north and south
pole, and cutting it in half just cre-
ates two new poles, not two sepa-
rated monopoles. However, a recent theo-
retical proposal suggested that defects in the
spin alignment of certain oxide magnets can
create separated effective magnetic mono-
poles ( 1). These materials are called spin ices
because the lowest-energy orientation of the
magnetic spins closely mimics the most sta-
ble arrangement of protons in water ice ( 2).
On pages 415 and 411 of this issue, Fennell
et al. ( 3) and Morris et al. ( 4) report measure-
ments from neutron-scattering experiments
showing that the low-energy excitations in
spin ices are reminiscent of Dirac’s elemen-
tary magnetic monopoles ( 5) that have so far
eluded the searches of high-energy physicists.
These dissociated north and south poles dif-
fuse away from each other ( 6) in these oxides
and leave behind a “Dirac string” of reversed
spins that can be seen as patterns in the inten-
sity of scattered neutrons.
The materials studied, holmium titan-
ate (Ho2Ti2O7) ( 3) and dysprosium titanate
(Dy2Ti2O7) ( 4), are geometrically frustrated
ferromagnets ( 7, 8); they are unusual para-
magnets with strong spin-spin correlations
( 8) that become magnetized in a magnetic
eld. These oxides have a pyrochlore struc-
ture; the Ho3+ and Dy3+ ions within these crys-
tals form a lattice of corner-sharing tetrahe-
dra (see the fi gure, panel A). The magnetic
moments of Ho3+ and Dy3+ act like two states,
or Ising model spins, and are constrained by
anisotropic forces to point “in” or “out” of the
tetrahedra. The minimum energy condition,
or rule, is that there must be two spins point-
ing “in” and two spins pointing “out” on each
tetrahedron ( 7, 8).
The “two-in, two-out” rule is analogous to
the Bernal-Fowler ice rule, which states that
for energetic reasons, two protons must be
“close” and two protons must be “far” from
any given oxygen in common water ice ( 2).
As explained by Pauling ( 2), the very large
number of two-in, two-out confi gurations in
a macroscopic ice sample leads to a measur-
able residual entropy in ice at low tempera-
tures ( 9, 10). Correspondingly, Ho2Ti2O7 and
Dy2Ti2O7 also exhibit a residual low-temper-
ature “Pauling entropy” ( 11).
A tetrahedron fulfi lling the two-in, two-
out rule amounts to an effective “magnetic
charge neutrality” where four (two positive,
two negative) magnetic charges cancel out
at the center of the tetrahedron ( 1). A spin
ipped by thermal fl uctuations creates two
defective adjoining tetrahedra—a monopole-
antimonopole pair (see the fi gure, panel B).
Once formed, these particles can diffuse away
from each other by reversing spins along the
path they trace as they separate, which recon-
Department of Physics and Astronomy, University of
Waterloo, Waterloo, Ontario N2L 3G1, Canada, and Cana-
dian Institute for Advanced Research/Quantum Materi-
als Program, Toronto, Ontario MSG 1Z8, Canada. E-mail:
a new avenue of research for polymer sci-
ence. For example, polymer systems under
shear often exhibit very complex dynamics.
Perhaps by shearing granular polymers, the
microscopic motions of the shearing pro-
cess can be studied directly, along with other
analogous phenomena such as entanglement
and polymer mechanical properties ( 1, 2).
One can imagine going even further and cre-
ating increasingly intricate granular poly-
mers to model biological polymers, such as
proteins or DNA.
References
1. M. Rubenstein, R. H. Colby, Polymer Physics (Oxford
Univ. Press, New York, 2003).
2. P. De Gennes, Scaling Concepts in Polymer Physics (Cor-
nell Univ. Press, Ithaca, NY, 1979).
3. L.-N. Zou, X. Cheng, M. L. Rivers, H. M. Jaeger, S. R.
Nagel, Science 326, 408 (2009).
4. T. J. Fox, P. J. Flory, J. Appl. Phys. 21, 581 (1950).
5. A. J. Liu, S. R. Nagel, Nature 396, 21 (1998).
6. C. S. O’Hern, L. E. Silbert, A. J. Liu, S. R. Nagel, Phys. Rev.
E Stat. Nonlin. Soft Matter Phys. 68, 011306 (2003).
7. J. A. Drocco, M. B. Hastings, C. J. Olson Reichhardt, C.
Reichhardt, Phys. Rev. Lett. 95, 088001 (2005).
10.1126/science.1180973
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www.sciencemag.org SCIENCE VOL 326 16 OCTOBER 2009 (^375)

PERSPECTIVES

during chain packing act as if they are large hollow monomers that can pack together to form a jammed (shear-resisting) configura- tion. A two-dimensional simulation of granu- lar chains at low chain density, where the sys- tem is unjammed (has no resistance to shear) (see the figure, panel A), contains randomly configured chains. At high chain density when the system is jammed (see the figure, panel B), semiloop structures appear. Zou et al. revealed that semiloop formation is cru- cial to the behavior of the granular chain sys- tem. The presence of semiloops lowers the jamming density of the system, and this effect is more pronounced in longer chains where there are fewer chains per unit volume. Real polymer systems undergo a transi- tion to a glassy state below some temperature. It is known that this glass transition tempera- ture increases with polymer length and satu- rates for long polymers ( 4 ). In the granular chain polymer model system, there is no tem- perature; instead, the inverse density serves as a quantity analogous to temperature. When Zou et al. compare the behavior of the inverse density of the granular chains as a function of chain length to the glass transition tempera- ture of a real polymer as a function of poly- mer length, they find that the behaviors are nearly identical. This remarkable result could imply that the glass transition in real polymers might be a jamming transition governed by the formation of rigid polymer semiloops. It would be extremely interesting to determine whether this type of semiloop actually occurs in real polymer systems. Semiloops should form much more easily than complete loops because the two ends of the polymer do not need to be near each other. If semiloops play a role in real polymer systems, this would be one of the most beautiful examples of where a macroscopic toy system explains the phys- ics on a molecular scale. Such a result would also confirm that the ideas of jamming origi- nally proposed for granular assemblies ( 57 ) are applicable to a wide variety of molecular systems. Granular polymers also represent a new form of granular matter and most likely will exhibit new kinds of phenomena that do not occur in real polymers or in granular systems composed of individual grains. As the jam- ming density of the granular polymer sys- tem can be controlled readily by adjusting the length of the granular chains, introducing chains into other systems that exhibit jam- ming may allow for a much more precise con- trol of the jamming of these materials. The experimental demonstration by Zou et al. that granular polymers can give insight into molecular polymer systems potentially opens

Observing Monopoles in

a Magnetic Analog of Ice

PHYSICS

Michel J. P. Gingras

Experimental evidence has been found that magnetic poles within metal oxide magnets can be separated.

A

bar magnet has a north and south pole, and cutting it in half just cre- ates two new poles, not two sepa- rated monopoles. However, a recent theo- retical proposal suggested that defects in the spin alignment of certain oxide magnets can create separated effective magnetic mono- poles ( 1 ). These materials are called spin ices because the lowest-energy orientation of the magnetic spins closely mimics the most sta- ble arrangement of protons in water ice ( 2 ). On pages 415 and 411 of this issue, Fennell et al. ( 3 ) and Morris et al. ( 4 ) report measure- ments from neutron-scattering experiments showing that the low-energy excitations in spin ices are reminiscent of Dirac’s elemen- tary magnetic monopoles ( 5 ) that have so far eluded the searches of high-energy physicists. These dissociated north and south poles dif- fuse away from each other ( 6 ) in these oxides and leave behind a “Dirac string” of reversed spins that can be seen as patterns in the inten- sity of scattered neutrons. The materials studied, holmium titan- ate (Ho 2 Ti 2 O 7 ) ( 3 ) and dysprosium titanate (Dy 2 Ti 2 O 7 ) ( 4 ), are geometrically frustrated ferromagnets ( 7 , 8 ); they are unusual para- magnets with strong spin-spin correlations ( 8 ) that become magnetized in a magnetic

field. These oxides have a pyrochlore struc- ture; the Ho3+^ and Dy3+^ ions within these crys- tals form a lattice of corner-sharing tetrahe- dra (see the figure, panel A). The magnetic moments of Ho3+^ and Dy3+^ act like two states, or Ising model spins, and are constrained by anisotropic forces to point “in” or “out” of the tetrahedra. The minimum energy condition, or rule, is that there must be two spins point- ing “in” and two spins pointing “out” on each tetrahedron ( 7 , 8 ). The “two-in, two-out” rule is analogous to the Bernal-Fowler ice rule, which states that for energetic reasons, two protons must be “close” and two protons must be “far” from any given oxygen in common water ice ( 2 ). As explained by Pauling ( 2 ), the very large number of two-in, two-out configurations in a macroscopic ice sample leads to a measur- able residual entropy in ice at low tempera- tures ( 9 , 10 ). Correspondingly, Ho 2 Ti 2 O 7 and Dy 2 Ti 2 O 7 also exhibit a residual low-temper- ature “Pauling entropy” ( 11 ). A tetrahedron fulfilling the two-in, two- out rule amounts to an effective “magnetic charge neutrality” where four (two positive, two negative) magnetic charges cancel out at the center of the tetrahedron ( 1 ). A spin flipped by thermal fluctuations creates two defective adjoining tetrahedra—a monopole- antimonopole pair (see the figure, panel B). Once formed, these particles can diffuse away from each other by reversing spins along the path they trace as they separate, which recon-

Department of Physics and Astronomy, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada, and Cana- dian Institute for Advanced Research/Quantum Materi- als Program, Toronto, Ontario MSG 1Z8, Canada. E-mail: [email protected]

a new avenue of research for polymer sci- ence. For example, polymer systems under shear often exhibit very complex dynamics. Perhaps by shearing granular polymers, the microscopic motions of the shearing pro- cess can be studied directly, along with other analogous phenomena such as entanglement and polymer mechanical properties ( 1 , 2 ). One can imagine going even further and cre- ating increasingly intricate granular poly- mers to model biological polymers, such as proteins or DNA.

References

  1. M. Rubenstein, R. H. Colby, Polymer Physics (Oxford Univ. Press, New York, 2003).
  2. P. De Gennes, Scaling Concepts in Polymer Physics (Cor- nell Univ. Press, Ithaca, NY, 1979).
  3. L.-N. Zou, X. Cheng, M. L. Rivers, H. M. Jaeger, S. R. Nagel, Science 326 , 408 (2009).
  4. T. J. Fox, P. J. Flory, J. Appl. Phys. 21 , 581 (1950).
  5. A. J. Liu, S. R. Nagel, Nature 396 , 21 (1998).
  6. C. S. O’Hern, L. E. Silbert, A. J. Liu, S. R. Nagel, Phys. Rev. E Stat. Nonlin. Soft Matter Phys. 68 , 011306 (2003).
  7. J. A. Drocco, M. B. Hastings, C. J. Olson Reichhardt, C. Reichhardt, Phys. Rev. Lett. 95 , 088001 (2005).

10.1126/science.

Published by AAAS

on June 6, 2010

www.sciencemag.org

Downloaded from

376 16 OCTOBER 2009^ VOL 326^ SCIENCE^ www.sciencemag.org

PERSPECTIVES

stitutes tetrahedra that obey the ice rule along the path ( 6 ). In his effort to alter the standard theory of electromagnetism as little as possi- ble ( 12 ), Dirac ( 5 ) postulated that a monopole- antimonopole pair is connected by an unob- servable “string” or tightly wound magnetic solenoids. In spin ices, the “Dirac strings” of reversed spins have direct consequences ( 3 ) and are observable ( 4 ). Because all tetrahe- dra, except the two adjoining the north and south poles, fulfill the ice rule, the string is without tension and the energy to separate the poles by an infinite distance is finite ( 1 )—the defects are dissociated, or deconfined. The monopoles in spin ice act like mag- netic charges: They obey analogous electric field laws and exhibit an effective Coulomb’s law for their interaction strength. At zero tem- perature, the spin-ice state can be viewed as a “vacuum” free of monopoles and is referred to as a “magnetic Coulomb phase” ( 3 ). This analogy affords a mathematical framework for calculating the underlying spin correla- tions of the rare-earth magnetic moments. Thermal fluctuations that create dissociated monopoles are sources of the analogous elec- tric field that modifies the spin correlations ( 3 , 4 ) and the dissociated monopoles can be used to describe the low-temperature thermo- dynamic properties of the material ( 1 , 4 ). Neutron scattering can probe the “Cou- lomb phase” nature of the spin-ice state by measuring the spin-spin correlation function, C ( r ), where r is the distance between spins. In the absence of thermally induced monopoles, C ( r ) does not decay exponentially with r , as would be the case for a conventional thermally disordered paramagnet. Rather, C ( r ) is theo-

retically expected to display the same spa- tial anisotropy and r – decay as a dipolar inter- action. These correla- tions are manifest in the neutron scattering as “bow-tie” pinch-point singularities at par- ticular neutron-scattering directions of wave vectors Q , which correspond to a “reciprocal space” of the real-space lattice in the crystals. The theoretical argument for the magnetic Coulomb phase ( 1 ) is highly compelling, but all previous neutron-scattering experiments, such as those on Ho 2 Ti 2 O 7 ( 13 ) and Dy 2 Ti 2 O 7 ( 14 ), failed to find an unmistakable signature of the pinch points. Unlike prior studies, Fen- nell et al. performed a polarized neutron-scat- tering experiment where the scattering signal is separated in two components. The pinch points are clearly revealed in the component where the neutron spin is flipped, confirming the theoretical prediction. The pinch points are obscured in the more intense “non-spin flip” signal, which helps to explain why previ- ous studies were inconclusive. In their analysis, Fennell et al. introduced a parameter that cuts off the pinch-point singu- larities in reciprocal space, which they associ- ate with the typical length of the Dirac strings. Whereas their experiment was performed in zero magnetic field and did not directly probe those strings, Morris et al. applied a mag- netic field B along the [100] crystal direc- tion to induce a magnetically polarized state where the ice rule and the minimum magnetic field energy, or Zeeman energy, are satisfied simultaneously (see the figure, panel C). The magnetic field strength can be tuned near a transition where thermally excited mono- pole-antimonopole pairs start to proliferate. The resulting flipped spins of the Dirac string are then oriented against the magnetic field direction, with the strings causing cone-like features observable in the scattering inten-

sity pattern. The conic features transform in inclined sheets of scattering when the field direction is tilted away from the [100] direc- tion, in close concordance with the calcula- tions of Morris et al. for this state. The spe- cific heat in zero magnetic field can also be described well in terms of a dilute gas of ther- mally excited monopoles ( 4 ). The demonstration that dissociated mono- pole-like excitations in spin ices can be observed and manipulated may help guide future studies of similar topological excita- tions in other exotic condensed matter sys- tems. Of particular interest is the exploration of geometrically frustrated magnetic systems with large quantum mechanical zero-point fluctuations of the magnetic moments away from the classical Ising spin directions ( 15 , 16 ) enforced in the Ho 2 Ti 2 O 7 and Dy 2 Ti 2 O 7 spin ices considered in ( 3 , 4 ). Such quan- tum magnets could provide condensed matter physicists with systems that mimic the phys- ics of quantum electrodynamics.

References

  1. C. Castelnovo, R. Moessner, S. L. Sondhi, Nature 451 , 42 (2008).
  2. L. Pauling, J. Am. Chem. Soc. 57 , 2680 (1935).
  3. T. Fennell et al ., Science 326 , 415 (2009); published online 3 September 2009 (10.1126/science.1177582).
  4. D. J. P. Morris et al., Science 326 , 411 (2009); published online 3 September 2009 (10.1126/science.1178868).
  5. P. A. M. Dirac, Proc. R. Soc. London Ser. A 133 , 60 (1931).
  6. L. D. C. Jaubert, P. C. W. Holdsworth, Nat. Phys. 5 , 258 (2009).
  7. M. J. Harris et al ., Phys. Rev. Lett. 79 , 2554 (1997).
  8. S. T. Bramwell, M. J. P. Gingras, Science 294 , 1495 (2001).
  9. W. F. Giauque, M. F. Ashley, Phys. Rev. 43 , 81 (1933).
  10. W. F. Giauque, J. W. Stout, J. Am. Chem. Soc. 58 , 1144 (1936).
  11. A. P. Ramirez et al ., Nature 399 , 333 (1999).
  12. R. J. Jackson, Classical Electrodynamics (Wiley, New York, 1998), pp. 273–280.
  13. T. Fennell et al ., Nat. Phys. 3 , 566 (2007).
  14. T. Yavor’skii et al ., Phys. Rev. Lett. 101 , 037204 (2008).
  15. M. Hermele, M. P. A. Fisher, L. Balents, Phys. Rev. B 69 , 064404 (2004).
  16. H. R. Molavian, M. J. P. Gingras, B. Canals, Phys. Rev. Lett. 98 , 157204 (2007). 10.1126/science.

Magnetic field direction

A

C

B

Spin excitations creating magnetic monopoles. (A) Spins on two adjacent tet- rahedra for magnetic ions in the pyrochlore lattice satisfy a rule that requires two spins pointing in and two spins pointing out, similar to the arrangement of pro- tons in water ice. (B) The reversal of a spin connecting two tetrahedra amounts to the creation of a “monopole” and an “antimonopole” that differ in magnetic “charge.” At finite temperature, monopole-antimonopole pairs are created by thermal fluctuations. The monopoles can separate, leaving behind a “Dirac string” of reversed spins. Their signature was deduced in spin-polarized neutron scatter- ing by Fennell et al. in zero applied magnetic field, where the Dirac strings have no preferred orientation. (C) For a magnetic field applied along the crystallographic [100] direction shown, the ground state has the magnetic moments on each tetra- hedron pointing with the field, which still maintains the two-in, two-out rule. Two separated tetrahedra, each with a flipped spin (three in, red; three out, blue) leads to a pair of monopoles connected by a string (green) of spins reversed against the field. Morris et al. observed a signature for this string in their neutron-scattering data by carefully tuning the applied magnetic field.

Published by AAAS

on June 6, 2010

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Downloaded from