Tag Archives: Brett Helms

Liquid circuitry, shape-shifting fluids and more

I’d have to see it to believe it but researchers at the US Dept. of Energy (DOE) Lawrence Berkeley National Laboratory (LBNL) have developed a new kind of ‘bijel’ which would allow for some pretty nifty robotics. From a Sept. 25, 2017 news item on ScienceDaily,

A new two-dimensional film, made of polymers and nanoparticles and developed by researchers at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), can direct two different non-mixing liquids into a variety of exotic architectures. This finding could lead to soft robotics, liquid circuitry, shape-shifting fluids, and a host of new materials that use soft, rather than solid, substances.

The study, reported today in the journal Nature Nanotechnology, presents the newest entry in a class of substances known as bicontinuous jammed emulsion gels, or bijels, which hold promise as a malleable liquid that can support catalytic reactions, electrical conductivity, and energy conversion.

A Sept. 25, 2017 LBNL news release (also on EurekAlert), which originated the news item, expands on the theme,

Bijels are typically made of immiscible, or non-mixing, liquids. People who shake their bottle of vinaigrette before pouring the dressing on their salad are familiar with such liquids. As soon as the shaking stops, the liquids start to separate again, with the lower density liquid – often oil – rising to the top.

Trapping, or jamming, particles where these immiscible liquids meet can prevent the liquids from completely separating, stabilizing the substance into a bijel. What makes bijels remarkable is that, rather than just making the spherical droplets that we normally see when we try to mix oil and water, the particles at the interface shape the liquids into complex networks of interconnected fluid channels.

Bijels are notoriously difficult to make, however, involving exact temperatures at precisely timed stages. In addition, the liquid channels are normally more than 5 micrometers across, making them too large to be useful in energy conversion and catalysis.

“Bijels have long been of interest as next-generation materials for energy applications and chemical synthesis,” said study lead author Caili Huang. “The problem has been making enough of them, and with features of the right size. In this work, we crack that problem.”

Huang started the work as a graduate student with Thomas Russell, the study’s principal investigator, at Berkeley Lab’s Materials Sciences Division, and he continued the project as a postdoctoral researcher at DOE’s Oak Ridge National Laboratory.

Creating a new bijel recipe

The method described in this new study simplifies the bijel process by first using specially coated particles about 10-20 nanometers in diameter. The smaller-sized particles line the liquid interfaces much more quickly than the ones used in traditional bijels, making the smaller channels that are highly valued for applications.

Illustration shows key stages of bijel formation. Clockwise from top left, two non-mixing liquids are shown. Ligands (shown in yellow) with amine groups are dispersed throughout the oil or solvent, and nanoparticles coated with carboxylic acids (shown as blue dots) are scattered in the water. With vigorous shaking, the nanoparticles and ligands form a “supersoap” that gets trapped at the interface of the two liquids. The bottom panel is a magnified view of the jammed nanoparticle supersoap. (Credit: Caili Huang/ORNL)

“We’ve basically taken liquids like oil and water and given them a structure, and it’s a structure that can be changed,” said Russell, a visiting faculty scientist at Berkeley Lab. “If the nanoparticles are responsive to electrical, magnetic, or mechanical stimuli, the bijels can become reconfigurable and re-shaped on demand by an external field.”

The researchers were able to prepare new bijels from a variety of common organic, water-insoluble solvents, such as toluene, that had ligands dissolved in it, and deionized water, which contained the nanoparticles. To ensure thorough mixing of the liquids, they subjected the emulsion to a vortex spinning at 3,200 revolutions per minute.

“This extreme shaking creates a whole bunch of new places where these particles and polymers can meet each other,” said study co-author Joe Forth, a postdoctoral fellow at Berkeley Lab’s Materials Sciences Division. “You’re synthesizing a lot of this material, which is in effect a thin, 2-D coating of the liquid surfaces in the system.”

The liquids remained a bijel even after one week, a sign of the system’s stability.

Russell, who is also a professor of polymer science and engineering at the University of Massachusetts-Amherst, added that these shape-shifting characteristics would be valuable in microreactors, microfluidic devices, and soft actuators.

Nanoparticle supersoap

Nanoparticles had not been seriously considered in bijels before because their small size made them hard to trap in the liquid interface. To resolve that problem, the researchers coated nano-sized particles with carboxylic acids and put them in water. They then took polymers with an added amine group – a derivative of ammonia – and dissolved them in the toluene.

At left is a vial of bijel stabilized with nanoparticle surfactants. On the right is the same vial after a week of inversion, showing that the nanoparticle kept the liquids from moving. (Credit: Caili Huang/ORNL)

This configuration took advantage of the amine group’s affinity to water, a characteristic that is comparable to surfactants, like soap. Their nanoparticle “supersoap” was designed so that the nanoparticles join ligands, forming an octopus-like shape with a polar head and nonpolar legs that get jammed at the interface, the researchers said.

“Bijels are really a new material, and also excitingly weird in that they are kinetically arrested in these unusual configurations,” said study co-author Brett Helms, a staff scientist at Berkeley Lab’s Molecular Foundry. “The discovery that you can make these bijels with simple ingredients is a surprise. We all have access to oils and water and nanocrystals, allowing broad tunability in bijel properties. This platform also allows us to experiment with new ways to control their shape and function since they are both responsive and reconfigurable.”

The nanoparticles were made of silica, but the researchers noted that in previous studies they used graphene and carbon nanotubes to form nanoparticle surfactants.

“The key is that the nanoparticles can be made of many materials,” said Russell.  “The most important thing is what’s on the surface.”

This is an animation of the bijel

3-D rendering of the nanoparticle bijel taken by confocal microscope. (Credit: Caili Huang/ORNL [Oak Ridge National Laboratory] and Joe Forth/Berkeley Lab)

Here’s a link to and a citation for the paper,

Bicontinuous structured liquids with sub-micrometre domains using nanoparticle surfactants by Caili Huang, Joe Forth, Weiyu Wang, Kunlun Hong, Gregory S. Smith, Brett A. Helms & Thomas P. Russell. Nature Nanotechnology (2017) doi:10.1038/nnano.2017.182 25 September 2017

This paper is behind a paywall.

Smart windows from Texas (US)

I’ve been waiting for ‘smart’ windows and/or self-cleaning windows since 2008. While this research on ‘smart’ windows at the University of Texas at Austin looks promising I suspect it will be years before these things are in the marketplace. A July 22, 2015 news item on Nanotechnology Now announces the latest research,

Researchers in the Cockrell School of Engineering at The University of Texas at Austin are one step closer to delivering smart windows with a new level of energy efficiency, engineering materials that allow windows to reveal light without transferring heat and, conversely, to block light while allowing heat transmission, as described in two new research papers.

By allowing indoor occupants to more precisely control the energy and sunlight passing through a window, the new materials could significantly reduce costs for heating and cooling buildings.

In 2013, chemical engineering professor Delia Milliron and her team became the first to develop dual-band electrochromic materials that blend two materials with distinct optical properties for selective control of visible and heat-producing near-infrared light (NIR). In a 2013 issue of Nature, Milliron’s research group demonstrated how, using a small jolt of electricity, a nanocrystal material could be switched back and forth, enabling independent control of light and energy.

A July 23, 2015 University of Texas at Austin news release, which originated the news item, provides more details about the research which has spawned two recently published papers,

The team now has engineered two new advancements in electrochromic materials — a highly selective cool mode and a warm mode — not thought possible several years ago.

The cool mode material is a major step toward a commercialized product because it enables control of 90 percent of NIR and 80 percent of the visible light from the sun and takes only minutes to switch between modes. The previously reported material could require hours.

To achieve this high performance, Milliron and a team, including Cockrell School postdoctoral researcher Jongwook Kim and collaborator Brett Helms of the Lawrence Berkeley National Lab, developed a new nanostructured architecture for electrochromic materials that allows for a cool mode to block near-infrared light while allowing the visible light to shine through. This could help reduce energy costs for cooling buildings and homes during the summer. The researchers reported the new architecture in Nano Letters on July 20.

“We believe our new architected nanocomposite could be seen as a model material, establishing the ideal design for a dual-band electrochromic material,” Milliron said. “This material could be ideal for application as a smart electrochromic window for buildings.”

In the paper, the team demonstrates how the new material can strongly and selectively modulate visible light and NIR by applying a small voltage.

To optimize the performance of electrochromics for practical use, the team organized the two components of the composite material to create a porous interpenetrating network. The framework architecture provides channels for transport of electronic and ionic change. This organization enables substantially faster switching between modes.
Smart Window

The researchers are now working to produce a similarly structured nanocomposite material by simple methods, suitable for low-cost manufacturing.

In a second research paper, Milliron and her team, including Cockrell School graduate student Clayton Dahlman, have reported a proof-of-concept demonstrating how they can achieve optical control properties in windows from a well-crafted, single-component film. The concept includes a simple coating that creates a new warm mode, in which visible light can be blocked, while near-infrared light can enter. This new setting could be most useful on a sunny winter day, when an occupant would want infrared radiation to pass into a building for warmth, but the glare from sunlight to be reduced.

In this paper, published in the Journal of the American Chemical Society, Milliron proved that a coating containing a single component ­— doped titania nanocrystals — could demonstrate dynamic control over the transmittance of solar radiation. Because of two distinct charging mechanisms found at different applied voltages, this material can selectively block visible or infrared radiation.

“These two advancements show that sophisticated dynamic control of sunlight is possible,” Milliron said. “We believe our deliberately crafted nanocrystal-based materials could meet the performance and cost targets needed to progress toward commercialization of smart windows.”

Interestingly, the news release includes this statement,

The University of Texas at Austin is committed to transparency and disclosure of all potential conflicts of interest. The lead UT investigator involved with this project, Delia Milliron, is the chief scientific officer and owns an equity position in Heliotrope Technologies, an early-stage company developing new materials and manufacturing processes for electrochromic devices with an emphasis on energy-saving smart windows. Milliron is associated with patents at Lawrence Berkeley National Laboratory licensed to Heliotrope Technologies. Collaborator Brett Helms serves on the scientific advisory board of Heliotrope and owns equity in the company.

Here are links to and citations for the two papers,

Nanocomposite Architecture for Rapid, Spectrally-Selective Electrochromic Modulation of Solar Transmittance by Jongwook Kim, Gary K. Ong, Yang Wang, Gabriel LeBlanc, Teresa E. Williams, Tracy M. Mattox, Brett A. Helms, and Delia J. Milliron. Nano Lett., Article ASAP DOI: 10.1021/acs.nanolett.5b02197 Publication Date (Web): July 20, 2015

Copyright © 2015 American Chemical Society

Spectroelectrochemical Signatures of Capacitive Charging and Ion Insertion in Doped Anatase Titania Nanocrystals by Clayton J. Dahlman, Yizheng Tan, Matthew A. Marcus, and Delia J. Milliron. J. Am. Chem. Soc., 2015, 137 (28), pp 9160–9166 DOI: 10.1021/jacs.5b04933 Publication Date (Web): July 8, 2015

Copyright © 2015 American Chemical Society

These papers are behind paywalls.