Even after watching the video, I still don’t quite believe it. A March 28, 2018 news item on ScienceDaily announces the work,
Scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab [or LBNL]) have developed a way to print 3-D structures composed entirely of liquids. Using a modified 3-D printer, they injected threads of water into silicone oil — sculpting tubes made of one liquid within another liquid.
They envision their all-liquid material could be used to construct liquid electronics that power flexible, stretchable devices. The scientists also foresee chemically tuning the tubes and flowing molecules through them, leading to new ways to separate molecules or precisely deliver nanoscale building blocks to under-construction compounds.
The researchers have printed threads of water between 10 microns and 1 millimeter in diameter, and in a variety of spiraling and branching shapes up to several meters in length. What’s more, the material can conform to its surroundings and repeatedly change shape.
“It’s a new class of material that can reconfigure itself, and it has the potential to be customized into liquid reaction vessels for many uses, from chemical synthesis to ion transport to catalysis,” said Tom Russell, a visiting faculty scientist in Berkeley Lab’s Materials Sciences Division. He developed the material with Joe Forth, a postdoctoral researcher in the Materials Sciences Division, as well as other scientists from Berkeley Lab and several other institutions. They report their research March 24  in the journal Advanced Materials.
The material owes its origins to two advances: learning how to create liquid tubes inside another liquid, and then automating the process.
For the first step, the scientists developed a way to sheathe tubes of water in a special nanoparticle-derived surfactant that locks the water in place. The surfactant, essentially soap, prevents the tubes from breaking up into droplets. Their surfactant is so good at its job, the scientists call it a nanoparticle supersoap.
The supersoap was achieved by dispersing gold nanoparticles into water and polymer ligands into oil. The gold nanoparticles and polymer ligands want to attach to each other, but they also want to remain in their respective water and oil mediums. The ligands were developed with help from Brett Helms at the Molecular Foundry, a DOE Office of Science User Facility located at Berkeley Lab.
In practice, soon after the water is injected into the oil, dozens of ligands in the oil attach to individual nanoparticles in the water, forming a nanoparticle supersoap. These supersoaps jam together and vitrify, like glass, which stabilizes the interface between oil and water and locks the liquid structures in position.
“This stability means we can stretch water into a tube, and it remains a tube. Or we can shape water into an ellipsoid, and it remains an ellipsoid,” said Russell. “We’ve used these nanoparticle supersoaps to print tubes of water that last for several months.”
Next came automation. Forth modified an off-the-shelf 3-D printer by removing the components designed to print plastic and replacing them with a syringe pump and needle that extrudes liquid. He then programmed the printer to insert the needle into the oil substrate and inject water in a predetermined pattern.
“We can squeeze liquid from a needle, and place threads of water anywhere we want in three dimensions,” said Forth. “We can also ping the material with an external force, which momentarily breaks the supersoap’s stability and changes the shape of the water threads. The structures are endlessly reconfigurable.”
This image illustrates how the water is printed,
These schematics show the printing of water in oil using a nanoparticle supersoap. Gold nanoparticles in the water combine with polymer ligands in the oil to form an elastic film (nanoparticle supersoap) at the interface, locking the structure in place. (Credit: Berkeley Lab)
Here’s a link to and a citation for the paper,
Reconfigurable Printed Liquids by Joe Forth, Xubo Liu, Jaffar Hasnain, Anju Toor, Karol Miszta, Shaowei Shi, Phillip L. Geissler, Todd Emrick, Brett A. Helms, Thomas P. Russell. Advanced Materials https://doi.org/10.1002/adma.201707603 First published: 24 March 2018
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.
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.
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)
A 3-D view of a hyperbranched nanoparticle with complex structure, made possible by Tomviz 1.0, a new open-source software platform developed by researchers at the University of Michigan, Cornell University and Kitware Inc. Image credit: Robert Hovden, Michigan Engineering
Now it’s possible for anyone to see and share 3-D nanoscale imagery with a new open-source software platform developed by researchers at the University of Michigan, Cornell University and open-source software company Kitware Inc.
Tomviz 1.0 is the first open-source tool that enables researchers to easily create 3-D images from electron tomography data, then share and manipulate those images in a single platform.
The world of nanoscale materials—things 100 nanometers and smaller—is an important place for scientists and engineers who are designing the stuff of the future: semiconductors, metal alloys and other advanced materials.
Seeing in 3-D how nanoscale flecks of platinum arrange themselves in a car’s catalytic converter, for example, or how spiky dendrites can cause short circuits inside lithium-ion batteries, could spur advances like safer, longer-lasting batteries; lighter, more fuel efficient cars; and more powerful computers.
“3-D nanoscale imagery is useful in a variety of fields, including the auto industry, semiconductors and even geology,” said Robert Hovden, U-M assistant professor of materials science engineering and one of the creators of the program. “Now you don’t have to be a tomography expert to work with these images in a meaningful way.”
Tomviz solves a key challenge: the difficulty of interpreting data from the electron microscopes that examine nanoscale objects in 3-D. The machines shoot electron beams through nanoparticles from different angles. The beams form projections as they travel through the object, a bit like nanoscale shadow puppets.
Once the machine does its work, it’s up to researchers to piece hundreds of shadows into a single three-dimensional image. It’s as difficult as it sounds—an art as well as a science. Like staining a traditional microscope slide, researchers often add shading or color to 3-D images to highlight certain attributes.
A 3-D view of a particle used in a hydrogen fuel cell powered vehicle. The gray structure is carbon; the red and blue particles are nanoscale flecks of platinum. The image is made possible by Tomviz 1.0. Image credit: Elliot Padget, Cornell UniversityTraditionally, they’ve have had to rely on a hodgepodge of proprietary software to do the heavy lifting. The work is expensive and time-consuming; so much so that even big companies like automakers struggle with it. And once a 3-D image is created, it’s often impossible for other researchers to reproduce it or to share it with others.
Tomviz dramatically simplifies the process and reduces the amount of time and computing power needed to make it happen, its designers say. It also enables researchers to readily collaborate by sharing all the steps that went into creating a given image and enabling them to make tweaks of their own.
“These images are far different from the 3-D graphics you’d see at a movie theater, which are essentially cleverly lit surfaces,” Hovden said. “Tomviz explores both the surface and the interior of a nanoscale object, with detailed information about its density and structure. In some cases, we can see individual atoms.”
Key to making Tomviz happen was getting tomography experts and software developers together to collaborate, Hovden said. Their first challenge was gaining access to a large volume of high-quality tomography. The team rallied experts at Cornell, Berkeley Lab and UCLA to contribute their data, and also created their own using U-M’s microscopy center. To turn raw data into code, Hovden’s team worked with open-source software maker Kitware.
With the release of Tomviz 1.0, Hovden is looking toward the next stages of the project, where he hopes to integrate the software directly with microscopes. He believes that U-M’s atom probe tomography facilities and expertise could help him design a version that could ultimately uncover the chemistry of all atoms in 3-D.
“We are unlocking access to see new 3D nanomaterials that will power the next generation of technology,” Hovden said. “I’m very interested in pushing the boundaries of understanding materials in 3-D.”
Identification of the precise 3-D coordinates of iron, shown in red, and platinum atoms in an iron-platinum nanoparticle.. Courtesy of Colin Ophus and Florian Nickel/Berkeley Lab
The image of the iron-platinum nanoparticle (referenced in the headline) reminds of foetal ultrasound images. A Feb. 1, 2017 news item on ScienceDaily tells us more,
In the world of the very tiny, perfection is rare: virtually all materials have defects on the atomic level. These imperfections — missing atoms, atoms of one type swapped for another, and misaligned atoms — can uniquely determine a material’s properties and function. Now, UCLA [University of California at Los Angeles] physicists and collaborators have mapped the coordinates of more than 23,000 individual atoms in a tiny iron-platinum nanoparticle to reveal the material’s defects.
The results demonstrate that the positions of tens of thousands of atoms can be precisely identified and then fed into quantum mechanics calculations to correlate imperfections and defects with material properties at the single-atom level.
Jianwei “John” Miao, a UCLA professor of physics and astronomy and a member of UCLA’s California NanoSystems Institute, led the international team in mapping the atomic-level details of the bimetallic nanoparticle, more than a trillion of which could fit within a grain of sand.
“No one has seen this kind of three-dimensional structural complexity with such detail before,” said Miao, who is also a deputy director of the Science and Technology Center on Real-Time Functional Imaging. This new National Science Foundation-funded consortium consists of scientists at UCLA and five other colleges and universities who are using high-resolution imaging to address questions in the physical sciences, life sciences and engineering.
Miao and his team focused on an iron-platinum alloy, a very promising material for next-generation magnetic storage media and permanent magnet applications.
By taking multiple images of the iron-platinum nanoparticle with an advanced electron microscope at Lawrence Berkeley National Laboratory and using powerful reconstruction algorithms developed at UCLA, the researchers determined the precise three-dimensional arrangement of atoms in the nanoparticle.
“For the first time, we can see individual atoms and chemical composition in three dimensions. Everything we look at, it’s new,” Miao said.
The team identified and located more than 6,500 iron and 16,600 platinum atoms and showed how the atoms are arranged in nine grains, each of which contains different ratios of iron and platinum atoms. Miao and his colleagues showed that atoms closer to the interior of the grains are more regularly arranged than those near the surfaces. They also observed that the interfaces between grains, called grain boundaries, are more disordered.
“Understanding the three-dimensional structures of grain boundaries is a major challenge in materials science because they strongly influence the properties of materials,” Miao said. “Now we are able to address this challenge by precisely mapping out the three-dimensional atomic positions at the grain boundaries for the first time.”
The researchers then used the three-dimensional coordinates of the atoms as inputs into quantum mechanics calculations to determine the magnetic properties of the iron-platinum nanoparticle. They observed abrupt changes in magnetic properties at the grain boundaries.
“This work makes significant advances in characterization capabilities and expands our fundamental understanding of structure-property relationships, which is expected to find broad applications in physics, chemistry, materials science, nanoscience and nanotechnology,” Miao said.
In the future, as the researchers continue to determine the three-dimensional atomic coordinates of more materials, they plan to establish an online databank for the physical sciences, analogous to protein databanks for the biological and life sciences. “Researchers can use this databank to study material properties truly on the single-atom level,” Miao said.
Miao and his team also look forward to applying their method called GENFIRE (GENeralized Fourier Iterative Reconstruction) to biological and medical applications. “Our three-dimensional reconstruction algorithm might be useful for imaging like CT scans,” Miao said. Compared with conventional reconstruction methods, GENFIRE requires fewer images to compile an accurate three-dimensional structure.
That means that radiation-sensitive objects can be imaged with lower doses of radiation.
The US Dept. of Energy (DOE) Lawrence Berkeley National Laboratory issued their own Feb. 1, 2017 news release (also on EurekAlert) about the work with a focus on how their equipment made this breakthrough possible (it repeats a little of the info. from the UCLA news release),
Scientists used one of the world’s most powerful electron microscopes to map the precise location and chemical type of 23,000 atoms in an extremely small particle made of iron and platinum.
The 3-D reconstruction reveals the arrangement of atoms in unprecedented detail, enabling the scientists to measure chemical order and disorder in individual grains, which sheds light on the material’s properties at the single-atom level. Insights gained from the particle’s structure could lead to new ways to improve its magnetic performance for use in high-density, next-generation hard drives.
What’s more, the technique used to create the reconstruction, atomic electron tomography (which is like an incredibly high-resolution CT scan), lays the foundation for precisely mapping the atomic composition of other useful nanoparticles. This could reveal how to optimize the particles for more efficient catalysts, stronger materials, and disease-detecting fluorescent tags.
Microscopy data was obtained and analyzed by scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) at the Molecular Foundry, in collaboration with Foundry users from UCLA, Oak Ridge National Laboratory, and the United Kingdom’s University of Birmingham. …
Atoms are the building blocks of matter, and the patterns in which they’re arranged dictate a material’s properties. These patterns can also be exploited to greatly improve a material’s function, which is why scientists are eager to determine the 3-D structure of nanoparticles at the smallest scale possible.
“Our research is a big step in this direction. We can now take a snapshot that shows the positions of all the atoms in a nanoparticle at a specific point in its growth. This will help us learn how nanoparticles grow atom by atom, and it sets the stage for a materials-design approach starting from the smallest building blocks,” says Mary Scott, who conducted the research while she was a Foundry user, and who is now a staff scientist. Scott and fellow Foundry scientists Peter Ercius and Colin Ophus developed the method in close collaboration with Jianwei Miao, a UCLA professor of physics and astronomy.
Their nanoparticle reconstruction builds on an achievement they reported last year in which they measured the coordinates of more than 3,000 atoms in a tungsten needle to a precision of 19 trillionths of a meter (19 picometers), which is many times smaller than a hydrogen atom. Now, they’ve taken the same precision, added the ability to distinguish different elements, and scaled up the reconstruction to include tens of thousands of atoms.
Importantly, their method maps the position of each atom in a single, unique nanoparticle. In contrast, X-ray crystallography and cryo-electron microscopy plot the average position of atoms from many identical samples. These methods make assumptions about the arrangement of atoms, which isn’t a good fit for nanoparticles because no two are alike.
“We need to determine the location and type of each atom to truly understand how a nanoparticle functions at the atomic scale,” says Ercius.
A TEAM approach
The scientists’ latest accomplishment hinged on the use of one of the highest-resolution transmission electron microscopes in the world, called TEAM I. It’s located at the National Center for Electron Microscopy, which is a Molecular Foundry facility. The microscope scans a sample with a focused beam of electrons, and then measures how the electrons interact with the atoms in the sample. It also has a piezo-controlled stage that positions samples with unmatched stability and position-control accuracy.
The researchers began growing an iron-platinum nanoparticle from its constituent elements, and then stopped the particle’s growth before it was fully formed. They placed the “partially baked” particle in the TEAM I stage, obtained a 2-D projection of its atomic structure, rotated it a few degrees, obtained another projection, and so on. Each 2-D projection provides a little more information about the full 3-D structure of the nanoparticle.
They sent the projections to Miao at UCLA, who used a sophisticated computer algorithm to convert the 2-D projections into a 3-D reconstruction of the particle. The individual atomic coordinates and chemical types were then traced from the 3-D density based on the knowledge that iron atoms are lighter than platinum atoms. The resulting atomic structure contains 6,569 iron atoms and 16,627 platinum atoms, with each atom’s coordinates precisely plotted to less than the width of a hydrogen atom.
Translating the data into scientific insights
Interesting features emerged at this extreme scale after Molecular Foundry scientists used code they developed to analyze the atomic structure. For example, the analysis revealed chemical order and disorder in interlocking grains, in which the iron and platinum atoms are arranged in different patterns. This has large implications for how the particle grew and its real-world magnetic properties. The analysis also revealed single-atom defects and the width of disordered boundaries between grains, which was not previously possible in complex 3-D boundaries.
“The important materials science problem we are tackling is how this material transforms from a highly randomized structure, what we call a chemically-disordered structure, into a regular highly-ordered structure with the desired magnetic properties,” says Ophus.
To explore how the various arrangements of atoms affect the nanoparticle’s magnetic properties, scientists from DOE’s Oak Ridge National Laboratory ran computer calculations on the Titan supercomputer at ORNL–using the coordinates and chemical type of each atom–to simulate the nanoparticle’s behavior in a magnetic field. This allowed the scientists to see patterns of atoms that are very magnetic, which is ideal for hard drives. They also saw patterns with poor magnetic properties that could sap a hard drive’s performance.
“This could help scientists learn how to steer the growth of iron-platinum nanoparticles so they develop more highly magnetic patterns of atoms,” says Ercius.
Adds Scott, “More broadly, the imaging technique will shed light on the nucleation and growth of ordered phases within nanoparticles, which isn’t fully theoretically understood but is critically important to several scientific disciplines and technologies.”
The folks at the Berkeley Lab have created a video (notice where the still image from the beginning of this post appears),
The Oak Ridge National Laboratory (ORNL), not wanting to be left out, has been mentioned in a Feb. 3, 2017 news item on ScienceDaily,
… researchers working with magnetic nanoparticles at the University of California, Los Angeles (UCLA), and the US Department of Energy’s (DOE’s) Lawrence Berkeley National Laboratory (Berkeley Lab) approached computational scientists at DOE’s Oak Ridge National Laboratory (ORNL) to help solve a unique problem: to model magnetism at the atomic level using experimental data from a real nanoparticle.
“These types of calculations have been done for ideal particles with ideal crystal structures but not for real particles,” said Markus Eisenbach, a computational scientist at the Oak Ridge Leadership Computing Facility (OLCF), a DOE Office of Science User Facility located at ORNL.
Eisenbach develops quantum mechanical electronic structure simulations that predict magnetic properties in materials. Working with Paul Kent, a computational materials scientist at ORNL’s Center for Nanophase Materials Sciences, the team collaborated with researchers at UCLA and Berkeley Lab’s Molecular Foundry to combine world-class experimental data with world-class computing to do something new–simulate magnetism atom by atom in a real nanoparticle.
Using the new data from the research teams on the West Coast, Eisenbach and Kent were able to precisely model the measured atomic structure, including defects, from a unique iron-platinum (FePt) nanoparticle and simulate its magnetic properties on the 27-petaflop Titan supercomputer at the OLCF.
Electronic structure codes take atomic and chemical structure and solve for the corresponding magnetic properties. However, these structures are typically derived from many 2-D electron microscopy or x-ray crystallography images averaged together, resulting in a representative, but not true, 3-D structure.
“In this case, researchers were able to get the precise 3-D structure for a real particle,” Eisenbach said. “The UCLA group has developed a new experimental technique where they can tell where the atoms are–the coordinates–and the chemical resolution, or what they are — iron or platinum.”
The ORNL news release goes on to describe the work from the perspective of the people who ran the supercompute simulationsr,
A Supercomputing Milestone
Magnetism at the atomic level is driven by quantum mechanics — a fact that has shaken up classical physics calculations and called for increasingly complex, first-principle calculations, or calculations working forward from fundamental physics equations rather than relying on assumptions that reduce computational workload.
For magnetic recording and storage devices, researchers are particularly interested in magnetic anisotropy, or what direction magnetism favors in an atom.
“If the anisotropy is too weak, a bit written to the nanoparticle might flip at room temperature,” Kent said.
To solve for magnetic anisotropy, Eisenbach and Kent used two computational codes to compare and validate results.
To simulate a supercell of about 1,300 atoms from strongly magnetic regions of the 23,000-atom nanoparticle, they used the Linear Scaling Multiple Scattering (LSMS) code, a first-principles density functional theory code developed at ORNL.
“The LSMS code was developed for large magnetic systems and can tackle lots of atoms,” Kent said.
As principal investigator on 2017, 2016, and previous INCITE program awards, Eisenbach has scaled the LSMS code to Titan for a range of magnetic materials projects, and the in-house code has been optimized for Titan’s accelerated architecture, speeding up calculations more than 8 times on the machine’s GPUs. Exceptionally capable of crunching large magnetic systems quickly, the LSMS code received an Association for Computing Machinery Gordon Bell Prize in high-performance computing achievement in 1998 and 2009, and developments continue to enhance the code for new architectures.
Working with Renat Sabirianov at the University of Nebraska at Omaha, the team also ran VASP, a simulation package that is better suited for smaller atom counts, to simulate regions of about 32 atoms.
“With both approaches, we were able to confirm that the local VASP results were consistent with the LSMS results, so we have a high confidence in the simulations,” Eisenbach said.
Computer simulations revealed that grain boundaries have a strong effect on magnetism. “We found that the magnetic anisotropy energy suddenly transitions at the grain boundaries. These magnetic properties are very important,” Miao said.
In the future, researchers hope that advances in computing and simulation will make a full-particle simulation possible — as first-principles calculations are currently too intensive to solve small-scale magnetism for regions larger than a few thousand atoms.
Also, future simulations like these could show how different fabrication processes, such as the temperature at which nanoparticles are formed, influence magnetism and performance.
“There’s a hope going forward that one would be able to use these techniques to look at nanoparticle growth and understand how to optimize growth for performance,” Kent said.
Finally, here’s a link to and a citation for the paper,
Nanoengineers at the University of California San Diego [UCSD], in collaboration with the Materials Project at Lawrence Berkeley National Laboratory (Berkeley Lab), have created the world’s largest database of elemental crystal surfaces and shapes to date. Dubbed Crystalium, this new open-source database can help researchers design new materials for technologies in which surfaces and interfaces play an important role, such as fuel cells, catalytic converters in cars, computer microchips, nanomaterials and solid-state batteries.
Crystalium is a new open-source database with the largest collection of elemental crystal surfaces and shapes to date. Image courtesy of the Materials Virtual Lab at UC San Diego
“This work is an important starting point for studying the material surfaces and interfaces, where many novel properties can be found. We’ve developed a new resource that can be used to better understand surface science and find better materials for surface-driven technologies,” said Shyue Ping Ong, a nanoengineering professor at UC San Diego and senior author of the study.
For example, fuel cell performance is partly influenced by the reaction of molecules such as hydrogen and oxygen on the surfaces of metal catalysts. Also, interfaces between the electrodes and electrolyte in a rechargeable lithium-ion battery host a variety of chemical reactions that can limit the battery’s performance. The work in this study is useful for these applications, said Ong, who is also part of a larger effort by the UC San Diego Sustainable Power and Energy Center to design better battery materials.
“Researchers can use this database to figure out which elements or materials are more likely to be viable catalysts for processes like ammonia production or making hydrogen gas from water,” said Richard Tran, a nanoengineering PhD student in Ong’s Materials Virtual Lab and the study’s first author. Tran did this work while he was an undergraduate at UC San Diego.
The work, published Sept. 13  in the journal Scientific Data, provides the surface energies and equilibrium crystal shapes of more than 100 polymorphs of 72 elements in the periodic table. Surface energy describes the stability of a surface; it is a measure of the excess energy of atoms on the surface relative to those in the bulk material. Knowing surface energies is useful for designing materials that perform their functions primarily on their surfaces, like catalysts and nanoparticles.
The surface energies of some elements in their crystal form have been measured experimentally, but this is not a trivial task. It involves melting the crystal, measuring the resulting liquid’s surface tension at the melting temperature, then extrapolating that value back to room temperature. This process also requires that the sample have a clean surface, which is challenging because other atoms and molecules (like oxygen and water) can easily adsorb to the surface and modify the surface energy.
Surface energies obtained by this method are averaged values that lack the facet-specific resolution that is necessary for design, Ong said. “This is one of the areas where the ’virtual laboratory’ can create the most value—by allowing us to precisely control the models and conditions in a way that is extremely difficult to do in experiments.”
Also, the surface energy is not just a single number for each crystal because it depends on the crystal’s orientation. “A crystal is a regular arrangement of atoms. When you cut a crystal in different places and at different angles, you expose different facets with unique arrangements of atoms,” explained Ong, who teaches the course NANO106 – Crystallography of Materials at UC San Diego.
To carry out this ambitious project, Ong and his team developed highly sophisticated automated workflows to calculate surface energies from first principles. These workflows are built on the popular open-source Python Materials Genomics library and FireWorks workflow codes of the Materials Project, which were co-authored by Ong.
“The techniques for calculating surface energies have been known for decades. The major accomplishment is the codification of how to generate surface models and run these complex calculations in a robust and efficient manner,” Tran said. The surface model generation software code developed by the team has already been extended by others to study substrates and interfaces. Powerful supercomputers at the San Diego Supercomputer Center and the National Energy Research Scientific Computing Center at the Lawrence Berkeley National Lab were used for the calculations.
Ong’s team worked with researchers from the Berkeley Lab’s Materials Project to develop and construct Crystalium’s website. Co-founded and directed by Berkeley Lab scientist Kristin Persson, the Materials Project is a Google-like database of material properties calculated by supercomputers.
“The Materials Project was designed to be an open and accessible tool for scientists and engineers to accelerate materials innovation,” Persson said. “In five years, it has attracted more than 20,000 users working on everything from batteries to photovoltaics to thermoelectrics, and it’s extremely gratifying to see scientists like Ong providing lots of high quality computed data of high interest and making it freely available and easily accessible to the public.”
The researchers pointed out that their database is the most extensive collection of calculated surface energies for elemental crystalline solids to date. Compared to previous compilations, Crystalium contains surface energies for far more elements, including both metals and non-metals, and for more facets in each crystal. The elements that have been excluded from their calculations are gases and radioactive elements. Notably, Ong and his team have validated their calculated surface energies with those from experiments, and the values are in excellent agreement.
Moving forward, the team will work on expanding the scope of the database beyond single elements to multi-element compounds like alloys, which are made of two or more different metals, and binary oxides, which are made of oxygen and one other element. Efforts are also underway to study the effect of common adsorbates, such as hydrogen, on surface energies, which is key to understanding the stability of surfaces in aqueous media.
“As we continue to build this database, we hope that the research community will see it as a useful resource for the rational design of target surface or interfacial properties,” said Ong,
Here’s a link to and a citation for the paper,
Surface energies of elemental crystals by Richard Tran, Zihan Xu, Balachandran Radhakrishnan, Donald Winston, Wenhao Sun, Kristin A. Persson, & Shyue Ping Ong. Scientific Data 3, Article number: 160080 (2016) doi:10.1038/sdata.2016.80 Published online: 13 September 2016
1. A DIY paint-on coating for energy efficient windows
This “cool” DIY retrofit tech could improve the energy efficiency of windows and save money. Researchers are developing a polymer-based heat-reflective coating that makes use of the unusual molecular architecture of a polymer.
It has the potential to be painted on windows at one-tenth the cost of current retrofit approaches. Window films on the market today reflect infrared solar energy back to the sky while allowing visible light to pass through, but a professional contractor is needed to install them. A low-cost option could significantly expand adoption and result in potential annual energy savings equivalent to taking 5 million cars off the road.
2. Nanowires that move data at light speed
Researchers have found a new way to produce nanoscale wires that can serve as tiny, tunable lasers. The excellent performance of these tiny lasers is promising for the field of optoelectronics, which is focused on combining electronics and light to transmit data, among other applications. Miniaturizing lasers to the nanoscale could further revolutionize computing, bringing light-speed data transmission to desktop, and ultimately, handheld computing devices.
3. Nano sponges that fight climate change
Scientists are developing nano sponges that could capture carbon from power plants before it enters the atmosphere. Initial tests show the hybrid membrane, composed of nano-sized cages (called metal-organic frameworks) and a polymer, is eight times more carbon dioxide permeable than membranes composed only of the polymer.
Boosting carbon dioxide permeability is a big goal in efforts to develop carbon capture materials that are energy efficient and cost competitive. Watch this video for more on this technology.
4. Custom-made chemical factories
Scientists have recently reengineered a building block of a nanocompartment that occurs naturally in bacteria, greatly expanding the potential of nanocompartments to serve as custom-made chemical factories. Researchers hope to tailor this new use to produce high-value chemical products, such as medicines, on demand
The sturdy nanocompartments are formed by hundreds of copies of just three different types of proteins. Their natural counterparts, known as bacterial microcompartments, encase a wide variety of enzymes that carry out highly specialized chemistry in bacteria.
5. Nanotubes that assemble themselves
Researchers have discovered a family of nature-inspired polymers that, when placed in water, spontaneously assemble into hollow crystalline nanotubes. What’s more, the nanotubes can be tuned to all have the same diameter of between five and ten nanometers.
Controlling the diameter of nanotubes, and the chemical groups exposed in their interior, enables scientists to control what goes through. Nanotubes have the potential to be incredibly useful, from delivering cancer-fighting drugs inside cells to desalinating seawater.
It’s nice to see projects grouped together like that as it gives you a bigger picture of what’s taking place at the lab than you’re likely to get reading news releases about individual projects and breakthroughs.
Berkeley Lab has also got an introductory video which does one of the best jobs I’ve seen of conveying the concept of the nanoscale,
This atomic force microscopy image of the grainy surface of a perovskite solar cell reveals a new path to much greater efficiency. Individual grains are outlined in black, low-performing facets are red, and high-performing facets are green. A big jump in efficiency could possibly be obtained if the material can be grown so that more high-performing facets develop. (Credit: Berkeley Lab)
It’s always fascinating to observe a trend (or a craze) in science, an endeavour that outsiders (like me) tend to think of as impervious to such vagaries. Perovskite seems to be making its way past the trend/craze phase and moving into a more meaningful phase. From a July 4, 2016 news item on Nanowerk,
Scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have discovered a possible secret to dramatically boosting the efficiency of perovskite solar cells hidden in the nanoscale peaks and valleys of the crystalline material.
Solar cells made from compounds that have the crystal structure of the mineral perovskite have captured scientists’ imaginations. They’re inexpensive and easy to fabricate, like organic solar cells. Even more intriguing, the efficiency at which perovskite solar cells convert photons to electricity has increased more rapidly than any other material to date, starting at three percent in 2009 — when researchers first began exploring the material’s photovoltaic capabilities — to 22 percent today. This is in the ballpark of the efficiency of silicon solar cells.
Now, as reported online July 4, 2016 in the journal Nature Energy (“Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite”), a team of scientists from the Molecular Foundry and the Joint Center for Artificial Photosynthesis, both at Berkeley Lab, found a surprising characteristic of a perovskite solar cell that could be exploited for even higher efficiencies, possibly up to 31 percent.
Using photoconductive atomic force microscopy, the scientists mapped two properties on the active layer of the solar cell that relate to its photovoltaic efficiency. The maps revealed a bumpy surface composed of grains about 200 nanometers in length, and each grain has multi-angled facets like the faces of a gemstone.
Unexpectedly, the scientists discovered a huge difference in energy conversion efficiency between facets on individual grains. They found poorly performing facets adjacent to highly efficient facets, with some facets approaching the material’s theoretical energy conversion limit of 31 percent.
The scientists say these top-performing facets could hold the secret to highly efficient solar cells, although more research is needed.
“If the material can be synthesized so that only very efficient facets develop, then we could see a big jump in the efficiency of perovskite solar cells, possibly approaching 31 percent,” says Sibel Leblebici, a postdoctoral researcher at the Molecular Foundry.
Leblebici works in the lab of Alexander Weber-Bargioni, who is a corresponding author of the paper that describes this research. Ian Sharp, also a corresponding author, is a Berkeley Lab scientist at the Joint Center for Artificial Photosynthesis. Other Berkeley Lab scientists who contributed include Linn Leppert, Francesca Toma, and Jeff Neaton, the director of the Molecular Foundry.
A team effort
The research started when Leblebici was searching for a new project. “I thought perovskites are the most exciting thing in solar right now, and I really wanted to see how they work at the nanoscale, which has not been widely studied,” she says.
She didn’t have to go far to find the material. For the past two years, scientists at the nearby Joint Center for Artificial Photosynthesis have been making thin films of perovskite-based compounds, and studying their ability to convert sunlight and CO2 into useful chemicals such as fuel. Switching gears, they created pervoskite solar cells composed of methylammonium lead iodide. They also analyzed the cells’ performance at the macroscale.
The scientists also made a second set of half cells that didn’t have an electrode layer. They packed eight of these cells on a thin film measuring one square centimeter. These films were analyzed at the Molecular Foundry, where researchers mapped the cells’ surface topography at a resolution of ten nanometers. They also mapped two properties that relate to the cells’ photovoltaic efficiency: photocurrent generation and open circuit voltage.
This was performed using a state-of-the-art atomic force microscopy technique, developed in collaboration with Park Systems, which utilizes a conductive tip to scan the material’s surface. The method also eliminates friction between the tip and the sample. This is important because the material is so rough and soft that friction can damage the tip and sample, and cause artifacts in the photocurrent.
Surprise discovery could lead to better solar cells
The resulting maps revealed an order of magnitude difference in photocurrent generation, and a 0.6-volt difference in open circuit voltage, between facets on the same grain. In addition, facets with high photocurrent generation had high open circuit voltage, and facets with low photocurrent generation had low open circuit voltage.
“This was a big surprise. It shows, for the first time, that perovskite solar cells exhibit facet-dependent photovoltaic efficiency,” says Weber-Bargioni.
Adds Toma, “These results open the door to exploring new ways to control the development of the material’s facets to dramatically increase efficiency.”
In practice, the facets behave like billions of tiny solar cells, all connected in parallel. As the scientists discovered, some cells operate extremely well and others very poorly. In this scenario, the current flows towards the bad cells, lowering the overall performance of the material. But if the material can be optimized so that only highly efficient facets interface with the electrode, the losses incurred by the poor facets would be eliminated.
“This means, at the macroscale, the material could possibly approach its theoretical energy conversion limit of 31 percent,” says Sharp.
A theoretical model that describes the experimental results predicts these facets should also impact the emission of light when used as an LED. …
The Molecular Foundry is a DOE Office of Science User Facility located at Berkeley Lab. The Joint Center for Artificial Photosynthesis is a DOE Energy Innovation Hub led by the California Institute of Technology in partnership with Berkeley Lab.
Here’s a link to and a citation for the paper,
Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite by Sibel Y. Leblebici, Linn Leppert, Yanbo Li, Sebastian E. Reyes-Lillo, Sebastian Wickenburg, Ed Wong, Jiye Lee, Mauro Melli, Dominik Ziegler, Daniel K. Angell, D. Frank Ogletree, Paul D. Ashby, Francesca M. Toma, Jeffrey B. Neaton, Ian D. Sharp, & Alexander Weber-Bargioni. Nature Energy 1, Article number: 16093 (2016 doi:10.1038/nenergy.2016.93 Published online: 04 July 2016
This paper is behind a paywall.
Dexter Johnson’s July 6, 2016 posting on his Nanoclast blog (on the IEEE [Institute of Electrical and Electronics Engineers] website} presents his take on the impact that this new finding may have,
The rise of the crystal perovskite as a potential replacement for silicon in photovoltaics has been impressive over the last decade, with its conversion efficiency improving from 3.8 to 22.1 percent over that time period. Nonetheless, there has been a vague sense that this rise is beginning to peter out of late, largely because when a solar cell made from perovskite gets larger than 1 square centimeter the best conversion efficiency had been around 15.6 percent. …
A June 14, 2016 news item on ScienceDaily focuses on memristors. (It’s been about two months since my last memristor posting on April 22, 2016 regarding electronic synapses and neural networks). This piece announces new insight into how memristors function at the atomic scale,
In experiments at two Department of Energy national labs — SLAC National Accelerator Laboratory and Lawrence Berkeley National Laboratory — scientists at Hewlett Packard Enterprise (HPE) [also referred to as HP Labs or Hewlett Packard Laboratories] have experimentally confirmed critical aspects of how a new type of microelectronic device, the memristor, works at an atomic scale.
This result is an important step in designing these solid-state devices for use in future computer memories that operate much faster, last longer and use less energy than today’s flash memory. …
“We need information like this to be able to design memristors that will succeed commercially,” said Suhas Kumar, an HPE scientist and first author on the group’s technical paper.
The memristor was proposed theoretically [by Dr. Leon Chua] in 1971 as the fourth basic electrical device element alongside the resistor, capacitor and inductor. At its heart is a tiny piece of a transition metal oxide sandwiched between two electrodes. Applying a positive or negative voltage pulse dramatically increases or decreases the memristor’s electrical resistance. This behavior makes it suitable for use as a “non-volatile” computer memory that, like flash memory, can retain its state without being refreshed with additional power.
Over the past decade, an HPE group led by senior fellow R. Stanley Williams has explored memristor designs, materials and behavior in detail. Since 2009 they have used intense synchrotron X-rays to reveal the movements of atoms in memristors during switching. Despite advances in understanding the nature of this switching, critical details that would be important in designing commercially successful circuits remained controversial. For example, the forces that move the atoms, resulting in dramatic resistance changes during switching, remain under debate.
In recent years, the group examined memristors made with oxides of titanium, tantalum and vanadium. Initial experiments revealed that switching in the tantalum oxide devices could be controlled most easily, so it was chosen for further exploration at two DOE Office of Science User Facilities – SLAC’s Stanford Synchrotron Radiation Lightsource (SSRL) and Berkeley Lab’s Advanced Light Source (ALS).
At ALS, the HPE researchers mapped the positions of oxygen atoms before and after switching. For this, they used a scanning transmission X-ray microscope and an apparatus they built to precisely control the position of their sample and the timing and intensity of the 500-electronvolt ALS X-rays, which were tuned to see oxygen.
The experiments revealed that even weak voltage pulses create a thin conductive path through the memristor. During the pulse the path heats up, which creates a force that pushes oxygen atoms away from the path, making it even more conductive. Reversing the voltage pulse resets the memristor by sucking some of oxygen atoms back into the conducting path, thereby increasing the device’s resistance. The memristor’s resistance changes between 10-fold and 1 million-fold, depending on operating parameters like the voltage-pulse amplitude. This resistance change is dramatic enough to exploit commercially.
To be sure of their conclusion, the researchers also needed to understand if the tantalum atoms were moving along with the oxygen during switching. Imaging tantalum required higher-energy, 10,000-electronvolt X-rays, which they obtained at SSRL’s Beam Line 6-2. In a single session there, they determined that the tantalum remained stationary.
“That sealed the deal, convincing us that our hypothesis was correct,” said HPE scientist Catherine Graves, who had worked at SSRL as a Stanford graduate student. She added that discussions with SLAC experts were critical in guiding the HPE team toward the X-ray techniques that would allow them to see the tantalum accurately.
Kumar said the most promising aspect of the tantalum oxide results was that the scientists saw no degradation in switching over more than a billion voltage pulses of a magnitude suitable for commercial use. He added that this knowledge helped his group build memristors that lasted nearly a billion switching cycles, about a thousand-fold improvement.
“This is much longer endurance than is possible with today’s flash memory devices,” Kumar said. “In addition, we also used much higher voltage pulses to accelerate and observe memristor failures, which is also important in understanding how these devices work. Failures occurred when oxygen atoms were forced so far away that they did not return to their initial positions.”
“Transistors are big and bulky compared to memristors,” he said. “Memristors are also much better suited for creating the neuron-like voltage spikes that characterize neuromorphic circuits.”
The researchers have provided an animation illustrating how memristors can fail,
This animation shows how millions of high-voltage switching cycles can cause memristors to fail. The high-voltage switching eventually creates regions that are permanently rich (blue pits) or deficient (red peaks) in oxygen and cannot be switched back. Switching at lower voltages that would be suitable for commercial devices did not show this performance degradation. These observations allowed the researchers to develop materials processing and operating conditions that improved the memristors’ endurance by nearly a thousand times. (Suhas Kumar) Courtesy: SLAC
Some of the ‘memristor story’ is contested and you can find a brief overview of the discussion in this Wikipedia memristor entry in the section on ‘definition and criticism’. There is also a history of the memristor which dates back to the 19th century featured in my May 22, 2012 posting.
The Materials Project, a Google-like database of material properties aimed at accelerating innovation, has released an enormous trove of data to the public, giving scientists working on fuel cells, photovoltaics, thermoelectrics, and a host of other advanced materials a powerful tool to explore new research avenues. But it has become a particularly important resource for researchers working on batteries. Co-founded and directed by Lawrence Berkeley National Laboratory (Berkeley Lab) scientist Kristin Persson, the Materials Project uses supercomputers to calculate the properties of materials based on first-principles quantum-mechanical frameworks. It was launched in 2011 by the U.S. Department of Energy’s (DOE) Office of Science.
The idea behind the Materials Project is that it can save researchers time by predicting material properties without needing to synthesize the materials first in the lab. It can also suggest new candidate materials that experimentalists had not previously dreamed up. With a user-friendly web interface, users can look up the calculated properties, such as voltage, capacity, band gap, and density, for tens of thousands of materials.
Two sets of data were released last month: nearly 1,500 compounds investigated for multivalent intercalation electrodes and more than 21,000 organic molecules relevant for liquid electrolytes as well as a host of other research applications. Batteries with multivalent cathodes (which have multiple electrons per mobile ion available for charge transfer) are promising candidates for reducing cost and achieving higher energy density than that available with current lithium-ion technology.
The sheer volume and scope of the data is unprecedented, said Persson, who is also a professor in UC Berkeley’s Department of Materials Science and Engineering. “As far as the multivalent cathodes, there’s nothing similar in the world that exists,” she said. “To give you an idea, experimentalists are usually able to focus on one of these materials at a time. Using calculations, we’ve added data on 1,500 different compositions.”
While other research groups have made their data publicly available, what makes the Materials Project so useful are the online tools to search all that data. The recent release includes two new web apps—the Molecules Explorer and the Redox Flow Battery Dashboard—plus an add-on to the Battery Explorer web app enabling researchers to work with other ions in addition to lithium.
“Not only do we give the data freely, we also give algorithms and software to interpret or search over the data,” Persson said.
The Redox Flow Battery app gives scientific parameters as well as techno-economic ones, so battery designers can quickly rule out a molecule that might work well but be prohibitively expensive. The Molecules Explorer app will be useful to researchers far beyond the battery community.
“For multivalent batteries it’s so hard to get good experimental data,” Persson said. “The calculations provide rich and robust benchmarks to assess whether the experiments are actually measuring a valid intercalation process or a side reaction, which is particularly difficult for multivalent energy technology because there are so many problems with testing these batteries.”
Here’s a screen capture from the Battery Explorer app,
The Materials Project’s Battery Explorer app now allows researchers to work with other ions in addition to lithium. Courtesy: The Materials Project
The news release goes on to describe a new discovery made possible by The Materials Project (Note: A link has been removed),
Together with Persson, Berkeley Lab scientist Gerbrand Ceder, postdoctoral associate Miao Liu, and MIT graduate student Ziqin Rong, the Materials Project team investigated some of the more promising materials in detail for high multivalent ion mobility, which is the most difficult property to achieve in these cathodes. This led the team to materials known as thiospinels. One of these thiospinels has double the capacity of the currently known multivalent cathodes and was recently synthesized and tested in the lab by JCESR researcher Linda Nazar of the University of Waterloo, Canada.
“These materials may not work well the first time you make them,” Persson said. “You have to be persistent; for example you may have to make the material very phase pure or smaller than a particular particle size and you have to test them under very controlled conditions. There are people who have actually tried this material before and discarded it because they thought it didn’t work particularly well. The power of the computations and the design metrics we have uncovered with their help is that it gives us the confidence to keep trying.”
The researchers were able to double the energy capacity of what had previously been achieved for this kind of multivalent battery. The study has been published in the journal Energy & Environmental Science in an article titled, “A High Capacity Thiospinel Cathode for Mg Batteries.”
“The new multivalent battery works really well,” Persson said. “It’s a significant advance and an excellent proof-of-concept for computational predictions as a valuable new tool for battery research.”
Here’s a link to and a citation for the paper,
A high capacity thiospinel cathode for Mg batteries by Xiaoqi Sun, Patrick Bonnick, Victor Duffort, Miao Liu, Ziqin Rong, Kristin A. Persson, Gerbrand Ceder and Linda F. Nazar. Energy Environ. Sci., 2016, Advance Article DOI: 10.1039/C6EE00724D First published online 24 May 2016
This paper seems to be behind a paywall.
Getting back to the news release, there’s more about The Materials Project in relationship to its membership,
The Materials Project has attracted more than 20,000 users since launching five years ago. Every day about 20 new users register and 300 to 400 people log in to do research.
One of those users is Dane Morgan, a professor of engineering at the University of Wisconsin-Madison who develops new materials for a wide range of applications, including highly active catalysts for fuel cells, stable low-work function electron emitter cathodes for high-powered microwave devices, and efficient, inexpensive, and environmentally safe solar materials.
“The Materials Project has enabled some of the most exciting research in my group,” said Morgan, who also serves on the Materials Project’s advisory board. “By providing easy access to a huge database, as well as tools to process that data for thermodynamic predictions, the Materials Project has enabled my group to rapidly take on materials design projects that would have been prohibitive just a few years ago.”
More materials are being calculated and added to the database every day. In two years, Persson expects another trove of data to be released to the public.
“This is the way to reach a significant part of the research community, to reach students while they’re still learning material science,” she said. “It’s a teaching tool. It’s a science tool. It’s unprecedented.”
Supercomputing clusters at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility hosted at Berkeley Lab, provide the infrastructure for the Materials Project.
Funding for the Materials Project is provided by the Office of Science (US Department of Energy], including support through JCESR [Joint Center for Energy Storage Research].
A March 29, 2016 news item on Nanotechnology Now announces a new technique for nature-inspired self-assembling polymer nanotubes,
When it comes to the various nanowidgets scientists are developing, nanotubes are especially intriguing. That’s because hollow tubes that have diameters of only a few billionths of a meter have the potential to be incredibly useful, from delivering cancer-fighting drugs inside cells to desalinating seawater.
But building nanostructures is difficult. And creating a large quantity of nanostructures with the same trait, such as millions of nanotubes with identical diameters, is even more difficult. This kind of precision manufacturing is needed to create the nanotechnologies of tomorrow.
Help could be on the way. As reported online the week of March 28  in the journal Proceedings of the National Academy of Sciences [PNAS], researchers at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have discovered a family of nature-inspired polymers that, when placed in water, spontaneously assemble into hollow crystalline nanotubes. What’s more, the nanotubes can be tuned to all have the same diameter of between five and ten nanometers, depending on the length of the polymer chain.
The polymers have two chemically distinct blocks that are the same size and shape. The scientists learned these blocks act like molecular tiles that form rings, which stack together to form nanotubes up to 100 nanometers long, all with the same diameter.
“This points to a new way we can use synthetic polymers to create complex nanostructures in a very precise way,” says Ron Zuckermann, who directs the Biological Nanostructures Facility in Berkeley Lab’s Molecular Foundry, where much of this research was conducted.
Several other Berkeley Lab scientists contributed to this research, including Nitash Balsara of the Materials Sciences Division and Ken Downing of the Molecular Biophysics and Integrated Bioimaging Division.
“Creating uniform structures in high yield is a goal in nanotechnology,” adds Zuckermann. “For example, if you can control the diameter of nanotubes, and the chemical groups exposed in their interior, then you can control what goes through—which could lead to new filtration and desalination technologies, to name a few examples.”
The research is the latest in the effort to build nanostructures that approach the complexity and function of nature’s proteins, but are made of durable materials. In this work, the Berkeley Lab scientists studied a polymer that is a member of the peptoid family. Peptoids are rugged synthetic polymers that mimic peptides, which nature uses to form proteins. They can be tuned at the atomic scale to carry out specific functions.
For the past several years, the scientists have studied a particular type of peptoid, called a diblock copolypeptoid, because it binds with lithium ions and could be used as a battery electrolyte. Along the way, they serendipitously found the compounds form nanotubes in water. How exactly these nanotubes form has yet to be determined, but this latest research sheds light on their structure, and hints at a new design principle that could be used to build nanotubes and other complex nanostructures.
Diblock copolypeptoids are composed of two peptoid blocks, one that’s hydrophobic one that’s hydrophilic. The scientists discovered both blocks crystallize when they meet in water, and form rings consisting of two to three individual peptoids. The rings then form hollow nanotubes.
Cryo-electron microscopy imaging of 50 of the nanotubes showed the diameter of each tube is highly uniform along its length, as well as from tube to tube. This analysis also revealed a striped pattern across the width of the nanotubes, which indicates the rings stack together to form tubes, and rules out other packing arrangements. In addition, the peptoids are thought to arrange themselves in a brick-like pattern, with hydrophobic blocks lining up with other hydrophobic blocks, and the same for hydrophilic blocks.
“Images of the tubes captured by electron microscopy were essential for establishing the presence of this unusual structure,” says Balsara. “The formation of tubular structures with a hydrophobic core is common for synthetic polymers dispersed in water, so we were quite surprised to see the formation of hollow tubes without a hydrophobic core.”
X-ray scattering analyses conducted at beamline 7.3.3 of the Advanced Light Source revealed even more about the nanotubes’ structure. For example, it showed that one of the peptoid blocks, which is usually amorphous, is actually crystalline.
Remarkably, the nanotubes assemble themselves without the usual nano-construction aids, such as electrostatic interactions or hydrogen bond networks.
“You wouldn’t expect something as intricate as this could be created without these crutches,” says Zuckermann. “But it turns out the chemical interactions that hold the nanotubes together are very simple. What’s special here is that the two peptoid blocks are chemically distinct, yet almost exactly the same size, which allows the chains to pack together in a very regular way. These insights could help us design useful nanotubes and other structures that are rugged and tunable—and which have uniform structures.”
This cryo-electron microscopy image shows the self-assembling nanotubes have the same diameter. The circles are head-on views of nanotubes. The dark-striped features likely result from crystallized peptoid blocks. (Credit: Berkeley Lab)