New hybrid state of matter is a mix of solid and liquid
The boundary between a substance’s liquid and solid phases may not be as clear-cut as previously believed. A new state of matter that is a hybrid of both has emerged in research by scientists at the University of Nottingham, UK and the University of Ulm, Germany, and they say the discovery could have applications in catalysis and other thermally-activated processes.
In liquids, atoms move rapidly, sliding over and around each other in a random fashion. In solids, they are fixed in place. The transition between the two states, solidification, occurs when random atomic motion transitions to an ordered crystalline structure.
At least, that’s what we thought. Thanks to a specialist microscopy technique, researchers led by Nottingham’s Andrei Khlobystov found that this simple picture isn’t entirely accurate. In fact, liquid metal nanoparticles can contain stationary atoms – and as the liquid cools, their number and position play a significant role in solidification.
Some atoms remain stationary
The team used a method called spherical and chromatic aberration-corrected high-resolution transmission electron microscopy (Cc/Cs-corrected HRTEM) at the low-voltage SALVE instrument at Ulm to study melted metal nanoparticles (such as platinum, gold and palladium) deposited on an atomically thin layer of graphene. This carbon-based material acted a sort of “hob” for heating the particles, says team member Christopher Leist, who was in charge of the HRTEM experiments. “As they melted, the atoms in the nanoparticles began to move rapidly, as expected,” Leist says. “To our surprise, however, we found that some atoms remained stationary.”
At high temperatures, these static atoms bind strongly to point defects in the graphene support. When the researchers used the electron beam from the transmission microscope to increase the number of these defects, the number of stationary atoms within the liquid increased, too. Khlobystov says that this had a knock-on effect on how the liquid solidified: when the stationary atoms are few in number, a crystal forms directly from the liquid and continues to grow until the entire particle has solidified. When their numbers increase, the crystallization process cannot take place and no crystals form.
“The effect is particularly striking when stationary atoms create a ring (corral) that surrounds and confines the liquid,” he says. “In this unique state, the atoms within the liquid droplet are in motion, while the atoms forming the corral remain motionless, even at temperatures well below the freezing point of the liquid.”
Unprecedented level of detail
The researchers chose to use Cc/Cs-corrected HRTEM in their study because minimizing spherical and chromatic aberrations through specialized hardware installed on the microscope enabled them to resolve single atoms in their images.
“Additionally, we can control both the energy of the electron beam and the sample temperature (the latter using MEMS-heated chip technology),” Khlobystov explains. “As a result, we can study metal samples at temperatures of up to 800 °C, even in a molten state, without sacrificing atomic resolution. We can therefore observe atomic behaviour during crystallization while actively manipulating the environment around the metal particles using the electron beam or by cooling the particles. This level of detail under such extreme conditions is unprecedented.”
Effect could be harnessed for catalysis
The Nottingham-Ulm researchers, who report their work in ACS Nano, say they obtained their results by chance while working on an EPSRC-funded project on 1-2 nm metal particles for catalysis applications. “Our approach involves assembling catalysts from individual metal atoms, utilizing on-surface phenomena to control their assembly and dynamics,” explains Khlobystov. “To gain this control, we needed to investigate the behaviour of metal atoms at varying temperatures and within different local environments on a support material.
“We suspected that the interplay between vacancy defects in the support and the sample temperature creates a powerful mechanism for controlling the size and structure of the metal particles,” he tells Physics World. “Indeed, this study revealed the fundamental mechanisms behind this process with atomic precision.”
The experiments were far from easy, he recalls, with one of the key challenges being to identify a thin, robust and thermally conductive support material for the metal. Happily, graphene meets all these criteria.
“Another significant hurdle to overcome was to be able to control the number of defect sites surrounding each particle,” he adds. “We successfully accomplished this by using the TEM’s electron beam not just as an imaging tool, but also as a means to modify the environment around the particles by creating defects.”
The researchers say they would now like to explore whether the effect can be harnessed for catalysis. To do this, Khlobystov says it will be essential to improve control over defect production and its scale. “We also want to image the corralled particles in a gas environment to understand how the phenomenon is influenced by reaction conditions, since our present measurements were conducted in a vacuum,” he adds.
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