June 10, 2013

Scientists at the U.S. Department of Energy’s (DOE) Ames Laboratory have discovered a new family of rare-earth quasicrystals using an algorithm they developed to help pinpoint them. Quasicrystalline materials may be found close to crystalline phases that contain similar atomic motifs, called crystalline approximants. And just like fishing experts know that casting a line in the right habitat hooks the big catch, the scientists used their knowledge to hone in on just the right spot for new quasicrystal materials discovery.

Their research resulted in finding the only known magnetic rare earth icosahedral binary quasicrystals, now providing a “matched set” of magnetic quasicrystals and their closely related periodic cousins.

The discovery has been published online by the journal Nature Materials in an article, “A family of binary magnetic icosahedral quasicrystals based on rare earth and cadmium.”

“This discovery of binary magnetic quasicrystals provides us with a  means of doing a cleaner comparison of structural and magnetic  properties between a quasicrystal and its periodic approximant,” said  Alan Goldman, Ames Laboratory faculty scientist and a distinguished  professor at Iowa State University. “It’s a tremendously exciting  thing.”

Goldman is part of the Ames Laboratory’s research group  which studies the microscopic properties of crystals through neutron and  x-ray scattering performed at Argonne National Laboratory’s Advanced  Photon Source. His collaborator, Ames Laboratory faculty scientist and  Iowa State University distinguished professor  Paul Canfield, was one of  the first scientists able to grow single-grain, rare-earth  quasicrystals, and his work continues in discovering, growing, and  characterizing them.

Since the 1982 discovery of quasicrystals--  intermetallic compounds that are ordered but not periodic--by Nobel  Prize winning chemist Dan Shechtman, many have been synthesized by  researchers worldwide, and one has even been discovered occurring  naturally.

But scientists at the Ames Laboratory, with their  expertise in rare earths and magnetism, were beginning to look for the  next step after that revolutionary first discovery.

“For the  last ten years, we have been moving beyond just the innate beauty of  these quasicrystalline structures to find out what else is interesting  about them. Are the electrical properties any different? Are the  magnetic qualities unusual?” Goldman asked.

Goldman and  Canfield, like many researchers around the world began to wonder what  magnetic properties would do, extended to the unique design of  quasicrystals.

“If you could place magnetism on these quasicrystal structures, what  would it look like?” Canfield said the researchers wondered. “You can  have antiferromagnets or ferromagnets in the crystalline or periodic  example. You have a disordered magnet or spin glass with the amorphous  system. This is known. But with quasicrystals, you have an aperiodic  arrangement. Will it affect the magnetism in some weird or novel way?  It’s a strange environment for magnetism.”

“There’s been a lot of theoretical and experimental work on magnetic quasicrystals and mathematically there’s no reason why magnetic ordering can’t happen,” said Goldman. “But experimentally it was never observed. Why? What does this teach us about magnetism in complex environments?”

A few years ago, a series of periodic approximants of rare-earth cadmium were discovered that did order magnetically by research colleagues in Japan. The Ames Laboratory scientists worked to characterize by scattering the magnetic structures in collaboration with other researchers from France, Japan, and the United States.

Goldman and Canfield suspected that there could be quasicrystals very close to these rare earth cadmium approximants, hidden in very limited regions of temperature and composition space in the phase diagram, and most easily attainable through the flux growth method Canfield has used to grow other quasicrystals. Together with Ames Lab scientists Sergey Bud’ko, Andreas Kreyssig, Kevin Dennis, Mehmet Ramazanoglu, Anton Jesche, and physics graduate student Tai Kong, Goldman and Canfield initiated a new search for magnetic quasicrystals.

Goldman asked Canfield to start by growing the approximant, but Canfield was shooting for both.

“My intent was not just to go to the approximant, but to cool this as far as I could before everything solidified; I was fishing for the binary quasicrystal,” Canfield said. “It was an attempt to survey the system. I know there’s an approximant in there, but is there another surprise?”

And sure enough, there was.  Canfield had grown the approximant, but he also found the presence of faceted pentagonal dodecahedra, one of the signatures of quasicrystals. Goldman’s x-ray scattering work confirmed the material as a quasicrystal.

In the rare earth cadmium approximants, there is magnetic order. In the quasicrystalline materials, however, the scientists found spin glass behavior, similar to the magnetic behavior in amorphous materials.

“What we have here is proof of principle. Yes, you can find quasicrystals near approximants; you just have to search the right way,” said Canfield.

“There’s still work to be done; it’s my hope that there is lurking out there a quasicrystalline antiferromagnet, which means an ordered magnetic structure. It hasn’t been theoretically ruled out,” said Goldman. “What I do know is that quasicrystals continue to surprise me.”

High-energy x-ray diffraction patterns from a single grain of i-Gd-Cd were taken at the Advanced Photon Source at Argonne National Laboratory with the beam parallel to the five-fold axis.

The research was supported by DOE’s Office of Science.

The Ames Laboratory is a U.S. Department of Energy Office of Science national laboratory operated by Iowa State University. The Ames Laboratory creates innovative materials, technologies and energy solutions. We use our expertise, unique capabilities and interdisciplinary collaborations to solve global problems.

The Advanced Photon Source at Argonne National Laboratory is one of five national synchrotron radiation light sources supported by the U.S. Department of Energy’s Office of Science to carry out applied and basic research to understand, predict, and ultimately control matter and energy at the electronic, atomic, and molecular levels, provide the foundations for new energy technologies, and support DOE missions in energy, environment, and national security. To learn more about the DOE Office of Science X-ray user facilities, visit the DOE Office of Science website.

DOE’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time. For more information, please visit science.energy.gov.