Tag Archives: boron nitride nanotubes

Double-walled carbon nanotubes have superior electrical properties?

A March 27, 2020 news item on Nanowerk suggests that double-walled carbon nanotubes (DWCNTs) may offer some advantages over single-walled carbon nanotubes (SWCNTs), NOTE: A link has been removed,

One nanotube could be great for electronics applications, but there’s new evidence that two could be tops.

Rice University engineers already knew that size matters when using single-walled carbon nanotubes for their electrical properties. But until now, nobody had studied how electrons act when confronted with the Russian doll-like structure of multiwalled tubes.

There’s a diagram representing the work,

Caption: Rice University theorists have calculated flexoelectric effects in double-walled carbon nanotubes. The electrical potential (P) of atoms on either side of a graphene sheet (top) are identical, but not when the sheet is curved into a nanotube. Double-walled nanotubes (bottom) show unique effects as band gaps in inner and outer tubes are staggered. Credit: Yakobson Research Group/Rice University

A March 27, 2020 Rice University news release (also on EurekAlert), which originated the news item, delves further (NOTE: Links have been removed),

The Rice lab of materials theorist Boris Yakobson has now calculated the impact of curvature of semiconducting double-wall carbon nanotubes on their flexoelectric voltage, a measure of electrical imbalance between the nanotube’s inner and outer walls.

This affects how suitable nested nanotube pairs may be for nanoelectronics applications, especially photovoltaics.

The theoretical research by Yakobson’s Brown School of Engineering group appears in the American Chemical Society journal Nano Letters.

In an 2002 study, Yakobson and his Rice colleagues had revealed how charge transfer, the difference between positive and negative poles that allows voltage to exist between one and the other, scales linearly to the curvature of the nanotube wall. The width of the tube dictates curvature, and the lab found that the thinner the nanotube (and thus larger the curvature), the greater the potential voltage.

When carbon atoms form flat graphene, the charge density of the atoms on either side of the plane are identical, Yakobson said. Curving the graphene sheet into a tube breaks that symmetry, changing the balance.

That creates a flexoelectric local dipole in the direction of, and proportional to, the curvature, according to the researchers, who noted that the flexoelectricity of 2D carbon “is a remarkable but also fairly subtle effect.”

But more than one wall greatly complicates the balance, altering the distribution of electrons. In double-walled nanotubes, the curvature of the inner and outer tubes differ, giving each a distinct band gap. Additionally, the models showed the flexoelectric voltage of the outer wall shifts the band gap of the inner wall, creating a staggered band alignment in the nested system.

“The novelty is that the inserted tube, the ‘baby’ (inside) matryoshka has all of its quantum energy levels shifted because of the voltage created by exterior nanotube,” Yakobson said. The interplay of different curvatures, he said, causes a straddling-to-staggered band gap transition that takes place at an estimated critical diameter of about 2.4 nanometers.

“This is a huge advantage for solar cells, essentially a prerequisite for separating positive and negative charges to create a current,” Yakobson said. “When light is absorbed, an electron always jumps from the top of an occupied valence band (leaving a ‘plus’ hole behind) to the lowest state of empty conductance band.

“But in a staggered configuration they happen to be in different tubes, or layers,” he said. “The ‘plus’ and ‘minus’ get separated between the tubes and can flow away by generating current in a circuit.”

The team’s calculations also showed that modifying the nanotubes’ surfaces with either positive or negative atoms could create “substantial voltages of either sign” up to three volts. “Although functionalization could strongly perturb the electronic properties of nanotubes, it may be a very powerful way of inducing voltage for certain applications,” the researchers wrote.

The team suggested its findings may apply to other types of nanotubes, including boron nitride and molybdenum disulfide, on their own or as hybrids with carbon nanotubes.

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

Flexoelectricity and charge separation in carbon nanotubes by Vasilii I. Artyukhov, Sunny Gupta, Alex Kutana, Boris I. Yakobson. Nano Lett. 2020, XXXX, XXX, XXX-XXX DOI: https://doi.org/10.1021/acs.nanolett.9b05345 [Online] Publication Date:March 10, 2020 Copyright © 2020 American Chemical Society

This paper is behind a paywall.

Change the shape of water with nanotubes

An August 24, 2018 news item on ScienceDaily describes a ‘shapeshifting’ water technique,

First, according to Rice University engineers, get a nanotube hole. Then insert water. If the nanotube is just the right width, the water molecules will align into a square rod.

Rice materials scientist Rouzbeh Shahsavari and his team used molecular models to demonstrate their theory that weak van der Waals forces between the inner surface of the nanotube and the water molecules are strong enough to snap the oxygen and hydrogen atoms into place.

Shahsavari referred to the contents as two-dimensional “ice,” because the molecules freeze regardless of the temperature. He said the research provides valuable insight on ways to leverage atomic interactions between nanotubes and water molecules to fabricate nanochannels and energy-storing nanocapacitors.

An August 24, 2018 Rice University news release (also on EurekAlert and received via email), which originated the news item, delves further,

Shahsavari and his colleagues built molecular models of carbon and boron nitride nanotubes with adjustable widths. They discovered boron nitride is best at constraining the shape of water when the nanotubes are 10.5 angstroms wide. (One angstrom is one hundred-millionth of a centimeter.)

The researchers already knew that hydrogen atoms in tightly confined water take on interesting structural properties. Recent experiments by other labs showed strong evidence for the formation of nanotube ice and prompted the researchers to build density functional theory models to analyze the forces responsible.

Shahsavari’s team modeled water molecules, which are about 3 angstroms wide, inside carbon and boron nitride nanotubes of various chiralities (the angles of their atomic lattices) and between 8 and 12 angstroms in diameter. They discovered that nanotubes in the middle diameters had the most impact on the balance between molecular interactions and van der Waals pressure that prompted the transition from a square water tube to ice.

“If the nanotube is too small and you can only fit one water molecule, you can’t judge much,” Shahsavari said. “If it’s too large, the water keeps its amorphous shape. But at about 8 angstroms, the nanotubes’ van der Waals force [if you’re not familiar with the term, see below the link and citation for my brief explanation] starts to push water molecules into organized square shapes.”

He said the strongest interactions were found in boron nitride nanotubes due to the particular polarization of their atoms.

Shahsavari said nanotube ice could find use in molecular machines or as nanoscale capillaries, or foster ways to deliver a few molecules of water or sequestered drugs to targeted cells, like a nanoscale syringe.

Lead author Farzaneh Shayeganfar, a former visiting scholar at Rice, is an instructor at Shahid Rajaee Teacher Training University in Tehran, Iran. Co-principal investigator Javad Beheshtian is a professor at Amirkabir University, Tehran.

Supercomputer resources were provided with support from the [US] National Institutes of Health and an IBM Shared Rice University Research grant.

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

First Principles Study of Water Nanotubes Captured Inside Carbon/Boron Nitride Nanotubes by Farzaneh Shayeganfar, Javad Beheshtian, and Rouzbeh Shahsavari. Langmuir, DOI: 10.1021/acs.langmuir.8b00856 Publication Date (Web): August 23, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

For the purposes of the posting, van der Waals force(s) are weak adhesive forces measured at the nanoscale. Humans don’t feel them (we’re too big) but gecko lizards can exploit those forces which is why they are able to hang from the ceiling by a single toe.  There’s a more informed description here in the van der Waals force entry on Wikipedia.

Boron nitride nanotubes

Most of the talk about nanotubes is focused on carbon nanotubes but there are other kinds as a May 21, 2018 Rice University news release (also received via email and on EurekAlert and in a May 21, 2018 news item on ScienceDaily), notes,

Boron nitride nanotubes are primed to become effective building blocks for next-generation composite and polymer materials based on a new discovery at Rice University – and a previous one.

Scientists at known-for-nano Rice have found a way to enhance a unique class of nanotubes using a chemical process pioneered at the university. The Rice lab of chemist Angel Martí took advantage of the Billups-Birch reaction process to enhance boron nitride nanotubes.

The work is described in the American Chemical Society journal ACS Applied Nano Materials.

Boron nitride nanotubes, like their carbon cousins, are rolled sheets of hexagonal arrays. Unlike carbon nanotubes, they’re electrically insulating hybrids made of alternating boron and nitrogen atoms.

Insulating nanotubes that can be functionalized will be a valuable building block for nanoengineering projects, Martí said. “Carbon nanotubes have outstanding properties, but you can only get them in semiconducting or metallic conducting types,” he said. “Boron nitride nanotubes are complementary materials that can fill that gap.”

Until now, these nanotubes have steadfastly resisted functionalization, the “decorating” of structures with chemical additives that allows them to be customized for applications. The very properties that give boron nitride nanotubes strength and stability, especially at high temperatures, also make them hard to modify for their use in the production of advanced materials.

But the Billups-Birch reaction developed by Rice Professor Emeritus of Chemistry Edward Billups, which frees electrons to bind with other atoms, allowed Martí and lead author Carlos de los Reyes to give the electrically inert boron nitride nanotubes a negative charge.

That, in turn, opened them up to functionalization with other small molecules, including aliphatic carbon chains.

“Functionalizing the nanotubes modifies or tunes their properties,” Martí said. “When they’re pristine they are dispersible in water, but once we attach these alkyl chains, they are extremely hydrophobic (water-avoiding). Then, if you put them in very hydrophobic solvents like those with long-chain hydrocarbons, they are more dispersible than their pristine form.

“This allows us to tune the properties of the nanotubes and will make it easier to take the next step toward composites,” he said. “For that, the materials need to be compatible.”

After he discovered the phenomenon, de los Reyes spent months trying to reproduce it reliably. “There was a period where I had to do a reaction every day to achieve reproducibility,” he said. But that turned out to be an advantage, as the process only required about a day from start to finish. “That’s the advantage over other processes to functionalize carbon nanotubes. There are some that are very effective, but they may take a few days.”

The process begins with adding pure ammonia gas to the nanotubes and cooling it to -70 degrees Celsius (-94 degrees Fahrenheit). “When it combines with sodium, lithium or potassium — we use lithium — it creates a sea of electrons,” Martí said. “When the lithium dissolves in the ammonia, it expels the electrons.”

The freed electrons quickly bind with the nanotubes and provide hooks for other molecules. De los Reyes enhanced Billups-Birch when he found that adding the alkyl chains slowly, rather than all at once, improved their ability to bind.

The researchers also discovered the process is reversible. Unlike carbon nanotubes that burn away, boron nitride nanotubes can stand the heat. Placing functionalized boron nitride tubes into a furnace at 600 degrees Celsius (1,112 degrees Fahrenheit) stripped them of the added molecules and returned them to their nearly pristine state.

“We call it defunctionalization,” Martí said. “You can functionalize them for an application and then remove the chemical groups to regain the pristine material. That’s something else the material brings that is a little different.”

The researchers have provided this pretty illustration of boron nitride nanotube,

Caption: Rice University researchers have discovered a way to ‘decorate’ electrically insulating boron nitride nanotubes with functional groups, making them more suitable for use with polymers and composite materials. Credit: Martí Research Group/Rice University

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

Chemical Decoration of Boron Nitride Nanotubes Using the Billups-Birch Reaction: Toward Enhanced Thermostable Reinforced Polymer and Ceramic Nanocomposites by Carlos A. de los Reyes, Kendahl L. Walz Mitra, Ashleigh D. Smith, Sadegh Yazdi, Axel Loredo, Frank J. Frankovsky, Emilie Ringe, Matteo Pasquali, and Angel A. Martí. ACS Appl. Nano Mater., Article ASAP DOI: 10.1021/acsanm.8b00633 Publication Date (Web): May 16, 2018

Copyright © 2018 American Chemical Society

This paper is behind a paywall.

Getting a more complete picture of aerosol particles at the nanoscale

What is in the air we breathe? In addition to the gases we learned about in school there are particles, not just the dust particles you can see, but micro- and nanoparticles too and scientists would like to know more about them.

An August 23, 2017 news item on Nanowerk features work which may help scientists in their quest,

They may be tiny and invisible, says Xiaoji Xu, but the aerosol particles suspended in gases play a role in cloud formation and environmental pollution and can be detrimental to human health.

Aerosol particles, which are found in haze, dust and vehicle exhaust, measure in the microns. One micron is one-millionth of a meter; a thin human hair is about 30 microns thick.

The particles, says Xu, are among the many materials whose chemical and mechanical properties cannot be fully measured until scientists develop a better method of studying materials at the microscale as well as the much smaller nanoscale (1 nm is one-billionth of a meter).

Xu, an assistant professor of chemistry, has developed such a method and utilized it to perform noninvasive chemical imaging of a variety of materials, as well as mechanical mapping with a spatial resolution of 10 nanometers.

The technique, called peak force infrared (PFIR) microscopy, combines spectroscopy and scanning probe microscopy. In addition to shedding light on aerosol particles, Xu says, PFIR will help scientists study micro- and nanoscale phenomena in a variety of inhomogeneous materials.

The lower portion of this image by Xiaoji Xu’s group shows the operational scheme of peak force infrared (PFIR) microscopy. The upper portion shows the topography of nanoscale PS-b-PMMA polymer islands on a gold substrate. (Image courtesy of Xiaoji Xu)

An August 22, 2017 Lehih University news release by Kurt Pfitzer (also on EurekAlert), which originated the news item, explains the research in more detail (Note: A link has been removed),

“Materials in nature are rarely homogeneous,” says Xu. “Functional polymer materials often consist of nanoscale domains that have specific tasks. Cellular membranes are embedded with proteins that are nanometers in size. Nanoscale defects of materials exist that affect their mechanical and chemical properties.

“PFIR microscopy represents a fundamental breakthrough that will enable multiple innovations in areas ranging from the study of aerosol particles to the investigation of heterogeneous and biological materials,” says Xu.

Xu and his group recently reported their results in an article titled “Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy.” The article was published in Science Advances, a journal of the American Association for the Advancement of Science, which also publishes Science magazine.

The article’s lead author is Le Wang, a Ph.D. student at Lehigh. Coauthors include Xu and Lehigh Ph.D. students Haomin Wang and Devon S. Jakob, as well as Martin Wagner of Bruker Nano in Santa Barbara, Calif., and Yong Yan of the New Jersey Institute of Technology.

“PFIR microscopy enables reliable chemical imaging, the collection of broadband spectra, and simultaneous mechanical mapping in one simple setup with a spatial resolution of ~10 nm,” the group wrote.

“We have investigated three types of representative materials, namely, soft polymers, perovskite crystals and boron nitride nanotubes, all of which provide a strong PFIR resonance for unambiguous nanochemical identification. Many other materials should be suited as well for the multimodal characterization that PFIR microscopy has to offer.

“In summary, PFIR microscopy will provide a powerful analytical tool for explorations at the nanoscale across wide disciplines.”

Xu and Le Wang also published a recent article about the use of PFIR to study aerosols. Titled “Nanoscale spectroscopic and mechanical characterization of individual aerosol particles using peak force infrared microscopy,” the article appeared in an “Emerging Investigators” issue of Chemical Communications, a journal of the Royal Society of Chemistry. Xu was featured as one of the emerging investigators in the issue. The article was coauthored with researchers from the University of Macau and the City University of Hong Kong, both in China.

PFIR simultaneously obtains chemical and mechanical information, says Xu. It enables researchers to analyze a material at various places, and to determine its chemical compositions and mechanical properties at each of these places, at the nanoscale.

“A material is not often homogeneous,” says Xu. “Its mechanical properties can vary from one region to another. Biological systems such as cell walls are inhomogeneous, and so are materials with defects. The features of a cell wall measure about 100 nanometers in size, placing them well within range of PFIR and its capabilities.”

PFIR has several advantages over scanning near-field optical microscopy (SNOM), the current method of measuring material properties, says Xu. First, PFIR obtains a fuller infrared spectrum and a sharper image—6-nm spatial resolution—of a wider variety of materials than does SNOM. SNOM works well with inorganic materials, but does not obtain as strong an infrared signal as the Lehigh technique does from softer materials such as polymers or biological materials.

“Our technique is more robust,” says Xu. “It works better with soft materials, chemical as well as biological.”

The second advantage of PFIR is that it can perform what Xu calls point spectroscopy.

“If there is something of interest chemically on a surface,” Xu says, “I put an AFM [atomic force microscopy] probe to that location to measure the peak-force infrared response.

“It is very difficult to obtain these spectra with current scattering-type scanning near-field optical microscopy. It can be done, but it requires very expensive light sources. Our method uses a narrow-band infrared laser and costs about $100,000. The existing method uses a broadband light source and costs about $300,000.”

A third advantage, says Xu, is that PFIR obtains a mechanical as well as a chemical response from a material.

“No other spectroscopy method can do this,” says Xu. “Is a material rigid or soft? Is it inhomogeneous—is it soft in one area and rigid in another? How does the composition vary from the soft to the rigid areas? A material can be relatively rigid and have one type of chemical composition in one area, and be relatively soft with another type of composition in another area.

“Our method simultaneously obtains chemical and mechanical information. It will be useful for analyzing a material at various places and determining its compositions and mechanical properties at each of these places, at the nanoscale.”

A fourth advantage of PFIR is its size, says Xu.

“We use a table-top laser to get infrared spectra. Ours is a very compact light source, as opposed to the much larger sizes of competing light sources. Our laser is responsible for gathering information concerning chemical composition. We get mechanical information from the AFM [atomic force microscope]. We integrate the two types of measurements into one device to simultaneously obtain two channels of information.”

Although PFIR does not work with liquid samples, says Xu, it can measure the properties of dried biological samples, including cell walls and protein aggregates, achieving a 10-nm spatial resolution without staining or genetic modification.

This looks like very exciting work.

Here are links and citations for both studies mentioned in the news release (the most recently published being cited first),

Nanoscale simultaneous chemical and mechanical imaging via peak force infrared microscopy by Le Wang, Haomin Wang, Martin Wagner, Yong Yan, Devon S. Jakob, and Xiaoji G. Xu. Science Advances 23 Jun 2017: Vol. 3, no. 6, e1700255 DOI: 10.1126/sciadv.1700255

Nanoscale spectroscopic and mechanical characterization of individual aerosol particles using peak force infrared microscopy by Le Wang, Dandan Huang, Chak K. Chan, Yong Jie Li, and Xiaoji G. Xu. Chem. Commun., 2017,53, 7397-7400 DOI: 10.1039/C7CC02301D First published on 16 Jun 2017

The June 23, 2017 paper is open access while the June 16, 2017 paper is behind a paywall.

Boron nitride-graphene hybrid nanostructures could lead to next generation ‘green’ cars

An Oct. 24, 2016 phys.org news item describes research which may lead to improved fuel storage in ‘green’ cars,

Layers of graphene separated by nanotube pillars of boron nitride may be a suitable material to store hydrogen fuel in cars, according to Rice University scientists.

The Department of Energy has set benchmarks for storage materials that would make hydrogen a practical fuel for light-duty vehicles. The Rice lab of materials scientist Rouzbeh Shahsavari determined in a new computational study that pillared boron nitride and graphene could be a candidate.

An Oct. 24, 2016 Rice University news release (also on EurekAlert), which originated the news item, provides more detail (Note: Links have been removed),

Shahsavari’s lab had already determined through computer models how tough and resilient pillared graphene structures would be, and later worked boron nitride nanotubes into the mix to model a unique three-dimensional architecture. (Samples of boron nitride nanotubes seamlessly bonded to graphene have been made.)

Just as pillars in a building make space between floors for people, pillars in boron nitride graphene make space for hydrogen atoms. The challenge is to make them enter and stay in sufficient numbers and exit upon demand.

In their latest molecular dynamics simulations, the researchers found that either pillared graphene or pillared boron nitride graphene would offer abundant surface area (about 2,547 square meters per gram) with good recyclable properties under ambient conditions. Their models showed adding oxygen or lithium to the materials would make them even better at binding hydrogen.

They focused the simulations on four variants: pillared structures of boron nitride or pillared boron nitride graphene doped with either oxygen or lithium. At room temperature and in ambient pressure, oxygen-doped boron nitride graphene proved the best, holding 11.6 percent of its weight in hydrogen (its gravimetric capacity) and about 60 grams per liter (its volumetric capacity); it easily beat competing technologies like porous boron nitride, metal oxide frameworks and carbon nanotubes.

At a chilly -321 degrees Fahrenheit, the material held 14.77 percent of its weight in hydrogen.

The Department of Energy’s current target for economic storage media is the ability to store more than 5.5 percent of its weight and 40 grams per liter in hydrogen under moderate conditions. The ultimate targets are 7.5 weight percent and 70 grams per liter.

Shahsavari said hydrogen atoms adsorbed to the undoped pillared boron nitride graphene, thanks to  weak van der Waals forces. When the material was doped with oxygen, the atoms bonded strongly with the hybrid and created a better surface for incoming hydrogen, which Shahsavari said would likely be delivered under pressure and would exit when pressure is released.

“Adding oxygen to the substrate gives us good bonding because of the nature of the charges and their interactions,” he said. “Oxygen and hydrogen are known to have good chemical affinity.”

He said the polarized nature of the boron nitride where it bonds with the graphene and the electron mobility of the graphene itself make the material highly tunable for applications.

“What we’re looking for is the sweet spot,” Shahsavari said, describing the ideal conditions as a balance between the material’s surface area and weight, as well as the operating temperatures and pressures. “This is only practical through computational modeling, because we can test a lot of variations very quickly. It would take experimentalists months to do what takes us only days.”

He said the structures should be robust enough to easily surpass the Department of Energy requirement that a hydrogen fuel tank be able to withstand 1,500 charge-discharge cycles.

Shayeganfar [Farzaneh Shayeganfar], a former visiting scholar at Rice, is an instructor at Shahid Rajaee Teacher Training University in Tehran, Iran.

 

Caption: Simulations by Rice University scientists show that pillared graphene boron nitride may be a suitable storage medium for hydrogen-powered vehicles. Above, the pink (boron) and blue (nitrogen) pillars serve as spacers for carbon graphene sheets (gray). The researchers showed the material worked best when doped with oxygen atoms (red), which enhanced its ability to adsorb and desorb hydrogen (white). Credit: Lei Tao/Rice University

Caption: Simulations by Rice University scientists show that pillared graphene boron nitride may be a suitable storage medium for hydrogen-powered vehicles. Above, the pink (boron) and blue (nitrogen) pillars serve as spacers for carbon graphene sheets (gray). The researchers showed the material worked best when doped with oxygen atoms (red), which enhanced its ability to adsorb and desorb hydrogen (white). Credit: Lei Tao/Rice University

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

Oxygen and Lithium Doped Hybrid Boron-Nitride/Carbon Networks for Hydrogen Storage by Farzaneh Shayeganfar and Rouzbeh Shahsavari. Langmuir,  DOI: 10.1021/acs.langmuir.6b02997 Publication Date (Web): October 23, 2016

Copyright © 2016 American Chemical Society

This paper is behind a paywall.

I last featured research by Shayeganfar and  Shahsavari on graphene and boron nitride in a Jan. 14, 2016 posting.

The nanotube of a thousand faces (similar nanomaterials behaving differently)

Kudos to any one who recognizes the reference to the ‘man of a thousand faces’, Lon Chaney, a silent film horror star. As for the nanotubes, there’s this Sept. 14, 2016 news item on ScienceDaily,

Nanotubes can be used for many things: electrical circuits, batteries, innovative fabrics and more. Scientists have noted, however, that nanotubes, whose structures appear similar, can actually exhibit different properties, with important consequences in their applications. Carbon nanotubes and boron nitride nanotubes, for example, while nearly indistinguishable in their structure, can be different when it comes to friction. A study conducted by SISSA/CNR-IOM and Tel Aviv University created computer models of these crystals and studied their characteristics in detail and observed differences related to the material’s chirality. …

A Sept. 14, 2016 Scuola Internazionale Superiore di Studi Avanzati (SISSA) press release (PDF), which originated the news item, describes the research in more detail,

“We began with a series of experimental observations which showed that very similar nanotubes exhibit different frictional properties, with intensities ranging up to two orders of magnitude,” says Roberto Guerra, a researcher at CNR-IOM and the International School for Advanced Studies (SISSA) in Trieste, first author of the study. “This led us to hypothesize that the chirality of the materials may play a role in this phenomenon.” The study involving also Andrea Vanossi (CNR-IOM) and Erio Tosatti (SISSA), was conducted in collaboration with the University of Tel Aviv.

For materials, such as those used in the study, chirality is linked to the three-dimensional arrangement of the weft that form the nanotube. “If we wrap a sheet of lined paper around itself to form a tube, the angle that the lines form with the axis of the tube determines its chirality,” says Guerra. “In our work we reconstructed the behavior of double-walled nanototubes, which can be imagined as two tubes of slightly different diameters, one inside the other. We observed that the difference in chirality between the inner tube and the outer tube has a remarkable effect on the three-dimensional shape of the nanotubes.”

A polygonal tube

“If we continue with the paper metaphor, the difference in orientation between the lattice on the inner tube and the outer tube determine to what extent, and, in what way, planar regions (faces) along the tube will form,” says Guerra. To better understand what is meant by “faces,” imagine a cross section of the tube, which is polygonal rather than perfectly circular. “The smaller the difference in chirality, the clearer and more obvious the faces,” concludes Guerra. If, however, the difference in chirality becomes too large, the faces disappear and the nanotubes take on the classic cylindrical shape.

The faces appear spontaneously depending on the characteristics of the material. Double-walled carbon nanotubes tend to form with a greater difference in internal and external chirality compared to boron nitride. Therefore, the former usually maintains a cylindrical shape that allows for less friction. In further studies, Guerra and colleagues intend to work directly on measuring the level of friction between nanotubes.

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

Multiwalled nanotube faceting unravelled by Itai Leven, Roberto Guerra, Andrea Vanossi, Erio Tosatti, & Oded Hod. Nature Nanotechnology (2016) doi:10.1038/nnano.2016.151 Published online 22 August 2016

This paper is behind a paywall.

Graphene-boron nitride material research from Rice University (US) and Polytechnique Montréal (Canada)

A Jan. 13, 2016 Rice University news release (also on EurekAlert) highlights computational research on hybrid material (graphene-boron nitride),

Developing novel materials from the atoms up goes faster when some of the trial and error is eliminated. A new Rice University and Montreal Polytechnic study aims to do that for graphene and boron nitride hybrids.

Rice materials scientist Rouzbeh Shahsavari and Farzaneh Shayeganfar, a postdoctoral researcher at Montreal Polytechnic (also known as École Polytechnique de Montréal or Polytechnique de Montréal), designed computer simulations that combine graphene, the atom-thick form of carbon, with either carbon or boron nitride nanotubes.

Their hope is that such hybrids can leverage the best aspects of their constituent materials. Defining the properties of various combinations would simplify development for manufacturers who want to use these exotic materials in next-generation electronics. The researchers found not only electronic but also magnetic properties that could be useful.

Shahsavari’s lab studies materials to see how they can be made more efficient, functional and environmentally friendly. They include macroscale materials like cement and ceramics as well as nanoscale hybrids with unique properties.

“Whether it’s on the macro- or microscale, if we can know specifically what a hybrid will do before anyone goes to the trouble of fabricating it, we can save cost and time and perhaps enable new properties not possible with any of the constituents,” Shahsavari said.

His lab’s computer models simulate how the intrinsic energies of atoms influence each other as they bond into molecules. For the new work, the researchers modeled hybrid structures of graphene and carbon nanotubes and of graphene and boron nitride nanotubes.

“We wanted to investigate and compare the electronic and potentially magnetic properties of different junction configurations, including their stability, electronic band gaps and charge transfer,” he said. “Then we designed three different nanostructures with different junction geometry.”

Two were hybrids with graphene layers seamlessly joined to carbon nanotubes. The other was similar but, for the first time, they modeled a hybrid with boron nitride nanotubes. How the sheets and tubes merged determined the hybrid’s properties. They also built versions with nanotubes sandwiched between graphene layers.

Graphene is a perfect conductor when its atoms align as hexagonal rings, but the material becomes strained when it deforms to accommodate nanotubes in hybrids. The atoms balance their energies at these junctions by forming five-, seven- or eight-member rings. These all induce changes in the way electricity flows across the junctions, turning the hybrid material into a valuable semiconductor.

The researchers’ calculations allowed them to map out a number of effects. For example, it turned out the junctions of the hybrid system create pseudomagnetic fields.

“The pseudomagnetic field due to strain was reported earlier for graphene, but not these hybrid boron nitride and carbon nanostructures where strain is inherent to the system,” Shahsavari said. He noted the effect may be useful in spintronic and nano-transistor applications.

“The pseudomagnetic field causes charge carriers in the hybrid to circulate as if under the influence of an applied external magnetic field,” he said. “Thus, in view of the exceptional flexibility, strength and thermal conductivity of hybrid carbon and boron nitride systems, we propose the pseudomagnetic field may be a viable way to control the electronic structure of new materials.”

All the effects serve as a road map for nanoengineering applications, Shahsavari said.

“We’re laying the foundations for a range of tunable hybrid architectures, especially for boron nitride, which is as promising as graphene but much less explored,” he said. “Scientists have been studying all-carbon structures for years, but the development of boron nitride and other two-dimensional materials and their various combinations with each other gives us a rich set of possibilities for the design of materials with never-seen-before properties.”

Shahsavari is an assistant professor of civil and environmental engineering and of materials science and nanoengineering.

###

Rice supported the research, and computational resources were provided by Calcul Quebec and Compute Canada.

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

Electronic and pseudomagnetic properties of hybrid carbon/boron-nitride nanomaterials via ab-initio calculations and elasticity theory by Farzaneh Shayeganfar and Rouzbeh Shahsavari. Carbon Volume 99, April 2016, Pages 523–532 doi:10.1016/j.carbon.2015.12.050

This paper is behind a paywall.

Here’s an image illustrating the hybrid material,

Caption: The calculated properties of a three-dimensional hybrid of graphene and boron nitride nanotubes would have pseudomagnetic properties, according to researchers at Rice University and Montreal Polytechnic. Credit: Shahsavari Lab/Rice University

Caption: The calculated properties of a three-dimensional hybrid of graphene and boron nitride nanotubes would have pseudomagnetic properties, according to researchers at Rice University and Montreal Polytechnic. Credit: Shahsavari Lab/Rice University

Boron nitride nanotubes muscle aside carbon nanotubes

Boron nitride has been exciting members of the scientific community most recently as an alternative to carbon. A Dec. 22, 2015 news item on ScienceDaily,

When mixed with lightweight polymers, tiny carbon tubes reinforce the material, promising lightweight and strong materials for airplanes, spaceships, cars and even sports equipment. While such carbon nanotube-polymer nanocomposites have attracted enormous interest from the materials research community, a group of scientists now has evidence that a different nanotube — made from boron nitride — could offer even more strength per unit of weight.

A Dec. 22, 2015 American Institute of Physics (AIP) news release by Catherine Meyers, which originated the news item, describes why carbon nanotubes have interested scientists and the advantages presented by boron nitride nanotubes (Note: A link has been removed),

Carbon nanotubes are legendary in their strength — at least 30 times stronger than bullet-stopping Kevlar by some estimates. When mixed with lightweight polymers such as plastics and epoxy resins, the tiny tubes reinforce the material, like the rebar in a block of concrete, promising lightweight and strong materials for airplanes, spaceships, cars and even sports equipment.

While such carbon nanotube-polymer nanocomposites have attracted enormous interest from the materials research community, a group of scientists now has evidence that a different nanotube — made from boron nitride — could offer even more strength per unit of weight. …

Boron nitride, like carbon, can form single-atom-thick sheets that are rolled into cylinders to create nanotubes. By themselves boron nitride nanotubes are almost as strong as carbon nanotubes, but their real advantage in a composite material comes from the way they stick strongly to the polymer.

“The weakest link in these nanocomposites is the interface between the polymer and the nanotubes,” said Changhong Ke, an associate professor in the mechanical engineering department at the State University of New York at Binghamton. If you break a composite, the nanotubes left sticking out have clean surfaces, as opposed to having chunks of polymer still stuck to them. The clean break indicates that the connection between the tubes and the polymer fails, Ke noted.

Plucking Nanotubes

Ke and his colleagues devised a novel way to test the strength of the nanotube-polymer link. They sandwiched boron nitride nanotubes between two thin layers of polymer, with some of the nanotubes left sticking out. They selected only the tubes that were sticking straight out of the polymer, and then welded the nanotube to the tip of a tiny cantilever beam. The team applied a force on the beam and tugged increasingly harder on the nanotube until it was ripped free of the polymer.

The researchers found that the force required to pluck out a nanotube at first increased with the nanotube length, but then plateaued. The behavior is a sign that the connection between the nanotube and the polymer is failing through a crack that forms and then spreads, Ke said.

The researchers tested two forms of polymer: epoxy and poly(methyl methacrylate), or PMMA, which is the same material used for Plexiglas. They found that the epoxy-boron nitride nanotube interface was stronger than the PMMA-nanotube interface. They also found that both polymer-boron nitride nanotube binding strengths were higher than those reported for carbon nanotubes — 35 percent higher for the PMMA interface and approximately 20 percent higher for the epoxy interface.

The Advantages of Boron Nitride Nanotubes

Boron nitride nanotubes likely bind more strongly to polymers because of the way the electrons are arranged in the molecules, Ke explained. In carbon nanotubes, all carbon atoms have equal charges in their nucleus, so the atoms share electrons equally. In boron nitride, the nitrogen atom has more protons than the boron atom, so it hogs more of the electrons in the bond. The unequal charge distribution leads to a stronger attraction between the boron nitride and the polymer molecules, as verified by molecular dynamics simulations performed by Ke’s colleagues in Dr. Xianqiao Wang’s group at the University of Georgia.

Boron nitride nanotubes also have additional advantages over carbon nanotubes, Ke said. They are more stable at high temperatures and they can better absorb neutron radiation, both advantageous properties in the extreme environment of outer space. In addition, boron nitride nanotubes are piezoelectric, which means they can generate an electric charge when stretched. This property means the material offers energy harvesting as well as sensing and actuation capabilities.

The news release does note that boron nitride nanotubes have a drawback ,

The main drawback to boron nitride nanotubes is the cost. Currently they sell for about $1,000 per gram, compared to the $10-20 per gram for carbon nanotubes, Ke said. He is optimistic that the price will come down, though, noting that carbon nanotubes were similarly expensive when they were first developed.

“I think boron nitride nanotubes are the future for making polymer composites for the aerospace industry,” he said.

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

Mechanical strength of boron nitride nanotube-polymer interfaces by Xiaoming Chen, Liuyang Zhang, Cheol Park, Catharine C. Fay, Xianqiao Wang, and Changhong Ke. Appl. Phys. Lett. 107, 253105 (2015); http://dx.doi.org/10.1063/1.4936755

This paper appears to be open access.

You gotta shake, shake, shake those nanomaterials out of the water

A team at Michigan Technological University (Michigan Tech) has developed a simple technique for clearing nanoparticles from water according to a Dec. 10, 2015 news item on Nanotechnology Now,

Nano implies small—and that’s great for use in medical devices, beauty products and smartphones—but it’s also a problem. The tiny nanoparticles, nanowires, nanotubes and other nanomaterials that make up our technology eventually find their way into water. The Environmental Protection Agency says more 1,300 commercial products use some kind of nanomaterial. And we just don’t know the full impact on health and the environment.

A Dec. 10, 2015 Michigan Tech news release, which originated the news item, describes the concept and the research in more detail,

“Look at plastic,” says Yoke Khin Yap, a professor of physics at Michigan Technological University. “These materials changed the world over the past decades—but can we clean up all the plastic in the ocean? We struggle to clean up meter-scale plastics, so what happens when we need to clean on the nano-scale?”

The method sounds like a salad dressing recipe: take water, sprinkle in nanomaterials, add oil and shake.

Water and oil don’t mix, of course, but shaking them together is what makes salad dressing so great. Only instead of emulsifying and capturing bits of shitake or basil in tiny olive oil bubbles, this mixture grabs nanomaterials.

Dongyan Zhang, a research professor of physics at Michigan Tech, led the experiments, which covered tests on carbon nanotubes, graphene, boron nitride nanotubes, boron nitride nanosheets and zinc oxide nanowires. Those are used in everything from carbon fiber golf clubs to sunscreen.

“These materials are very, very tiny, and that means if you try to remove them and clean them out of contaminated water, that it’s quite difficult,” Zhang says, adding that techniques like filter paper or meshes often don’t work.

What makes shaking work is the shape of one- and two-dimensional nanomaterials. As the oil and water separate after some rigorous shaking, the wires, tubes and sheets settle at the bottom of the oil, just above the water. The oils trap them. However, zero-dimensional nanomaterials, such as nanospheres do not get trapped.

The researchers, according to the news release, are attempting to anticipate the potential contamination of our water supply by nanomaterials and provide a solution before it happens,

We don’t have to wait until the final vote is in on whether nanomaterials have a positive or negative impact on people’s health and environmental health. With the simplicity of this technique, and how prolific nanomaterials are becoming, removing nanomaterials makes sense. Also, finding ways to effectively remove nanomaterials sooner rather than later could improve the technology’s market potential.

“Ideally for a new technology to be successfully implemented, it needs to be shown that the technology does not cause adverse effects to the environment,” Yap, Zhang and their co-authors write. “Therefore, unless the potential risks of introducing nanomaterials into the environment are properly addressed, it will hinder the industrialization of products incorporating nanotechnology.”

Purifying water and greening nanotechnology could be as simple as shaking a vial of water and oil.

Here’s a video about the research supplied by Michigan Tech,

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

A Simple and Universal Technique To Extract One- and Two-Dimensional Nanomaterials from Contaminated Water by Bishnu Tiwari, Dongyan Zhang, Dustin Winslow, Chee Huei Lee, Boyi Hao, and Yoke Khin Yap. ACS Appl. Mater. Interfaces, 2015, 7 (47), pp 26108–26116 DOI: 10.1021/acsami.5b07542 Publication Date (Web): November 9, 2015

Copyright © 2015 American Chemical Society

This paper is behind a paywall.