Tag Archives: Huajian Gao

Wood’s natural nanotechnology

“Wood’s natural nanotechnology: is an unusual term and it comes at the end of this February 7, 2018 University of Maryland (US) news release about a technique which will make wood stronger than titanium alloy,

Engineers at the University of Maryland in College Park have found a way to make wood more than ten times times stronger and tougher than before, creating a natural substance that is stronger than titanium alloy.

“This new way to treat wood makes it twelve times stronger than natural wood and ten times tougher,” said Liangbing Hu, the leader of the team that did the research, to be published on Thursday [February 7, 2018] in the journal Nature. “This could be a competitor to steel or even titanium alloys, it is so strong and durable. It’s also comparable to carbon fiber, but much less expensive.” Hu is an associate professor of materials science and engineering and a member of the Maryland Energy Innovation Institute.

“It is both strong and tough, which is a combination not usually found in nature,” said Teng Li, the co-leader of the team and the Samuel P. Langley associate professor of mechanical engineering at the University of Maryland. His team measured the dense wood’s mechanical properties.  “It is as strong as steel, but six times lighter. It takes 10 times more energy to fracture than natural wood. It can even be bent and molded at the beginning of the process.”

The team’s process begins by removing the wood’s lignin, the part of the wood that makes it both rigid and brown in color. Then it is compressed under mild heat, at about 150 F. This causes the cellulose fibers to become very tightly packed. Any defects like holes or knots are crushed together.  The treatment process was extended a little further with a coat of paint.

The scientists found that the wood’s fibers are pressed together so tightly that they can form strong hydrogen bonds, like a crowd of people who can’t budge – who are also holding hands. The compression makes the wood five times thinner than its original size.

The team also tested the material by shooting a bullet-like projectile at it. Unlike natural wood, which was blown straight through, the fully treated wood actually stopped the projectile partway through.

“Soft woods like pine or balsa, which grow fast and are more environmentally friendly, could replace slower-growing but denser woods like teak, in furniture or buildings,” Hu said.

“The paper provides a highly promising route to the design of light weight high performance structural materials, with tremendous potential for a broad range of applications where high strength, large toughness and superior ballistic resistance are desired, “ said Dr. Huajian Gao, a professor at Brown University, who was not involved in the study. “It is particularly exciting to note that the method is versatile for various species of wood and fairly easy to implement.”

“This kind of wood could be used in cars, airplanes, buildings – any application where steel is used,” Hu said.

“The two-step process reported in this paper achieves exceptionally high strength, much beyond what [is] reported in the literature,” said Dr. Zhigang Suo, a professor of mechanics and materials at Harvard University, also not involved with the study. “Given the abundance of wood, as well as other cellulose-rich plants, this paper inspires imagination.”

“The most outstanding observation, in my view, is the existence of a limiting concentration of lignin, the glue between wood cells, to maximize the mechanical performance of the densified wood. Too little or too much removal lower the strength compared to a maximum value achieved at intermediate or partial lignin removal. This reveals the subtle balance between hydrogen bonding and the adhesion imparted by such polyphenolic compound. Moreover, of outstanding interest, is the fact that that wood densification leads to both, increased strength and toughness, two properties that usually offset each other,” said Orlando J. Rojas, a professor at Aalto University in Finland.

Hu’s research has explored the capacities of wood’s natural nanotechnology [emphasis mine]. They previously made a range of emerging technologies out of nanocellulose related materials: (1) super clear paper for replacing plastic; (2) photonic paper for improving solar cell efficiency by 30%; (3) a battery and a supercapacitor out of wood; (4) a battery from a leaf; (5) transparent wood for energy efficient buildings; (6) solar water desalination for drinking and specifically filtering out toxic dyes. These wood-based emerging technologies are being commercialized through a UMD spinoff company, Inventwood LLC.

At a guess, “wood’s natural nanotechnology” refers to the properties of wood and other forms of cellulose at the nanoscale.

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

Processing bulk natural wood into a high-performance structural material by Jianwei Song, Chaoji Chen, Shuze Zhu, Mingwei Zhu, Jiaqi Dai, Upamanyu Ray, Yiju Li, Yudi Kuang, Yongfeng Li, Nelson Quispe, Yonggang Yao, Amy Gong, Ulrich H. Leiste, Hugh A. Bruck, J. Y. Zhu, Azhar Vellore, Heng Li, Marilyn L. Minus, Zheng Jia, Ashlie Martini, Teng Li, & Liangbing Hu. Nature volume 554, pages 224–228 (08 February 2018) doi:10.1038/nature25476 Published online: 07 February 2018

This paper is behind a paywall.

h/t Feb. 7, 2018 news item on Nanowerk and, finally, you can find out more about the wood-based emerging technologies being commcercialized by the University of Maryland here on the Inventwood website.

Fusing graphene flakes for 3D graphene structures that are 10x as strong as steel

A Jan. 6, 2017 news item on Nanowerk describes how geometry may have as much or more to do with the strength of 3D graphene structures than the graphene used to create them,

A team of researchers at MIT [Massachusetts Institute of Technology] has designed one of the strongest lightweight materials known, by compressing and fusing flakes of graphene, a two-dimensional form of carbon. The new material, a sponge-like configuration with a density of just 5 percent, can have a strength 10 times that of steel.

In its two-dimensional form, graphene is thought to be the strongest of all known materials. But researchers until now have had a hard time translating that two-dimensional strength into useful three-dimensional materials.

The new findings show that the crucial aspect of the new 3-D forms has more to do with their unusual geometrical configuration than with the material itself, which suggests that similar strong, lightweight materials could be made from a variety of materials by creating similar geometric features.

The findings are being reported today [Jan. 6, 2017\ in the journal Science Advances, in a paper by Markus Buehler, the head of MIT’s Department of Civil and Environmental Engineering (CEE) and the McAfee Professor of Engineering; Zhao Qin, a CEE research scientist; Gang Seob Jung, a graduate student; and Min Jeong Kang MEng ’16, a recent graduate.

A Jan. 6, 2017 MIT news release (also on EurekAlert), which originated the news item, describes the research in more detail,

Other groups had suggested the possibility of such lightweight structures, but lab experiments so far had failed to match predictions, with some results exhibiting several orders of magnitude less strength than expected. The MIT team decided to solve the mystery by analyzing the material’s behavior down to the level of individual atoms within the structure. They were able to produce a mathematical framework that very closely matches experimental observations.

Two-dimensional materials — basically flat sheets that are just one atom in thickness but can be indefinitely large in the other dimensions — have exceptional strength as well as unique electrical properties. But because of their extraordinary thinness, “they are not very useful for making 3-D materials that could be used in vehicles, buildings, or devices,” Buehler says. “What we’ve done is to realize the wish of translating these 2-D materials into three-dimensional structures.”

The team was able to compress small flakes of graphene using a combination of heat and pressure. This process produced a strong, stable structure whose form resembles that of some corals and microscopic creatures called diatoms. These shapes, which have an enormous surface area in proportion to their volume, proved to be remarkably strong. “Once we created these 3-D structures, we wanted to see what’s the limit — what’s the strongest possible material we can produce,” says Qin. To do that, they created a variety of 3-D models and then subjected them to various tests. In computational simulations, which mimic the loading conditions in the tensile and compression tests performed in a tensile loading machine, “one of our samples has 5 percent the density of steel, but 10 times the strength,” Qin says.

Buehler says that what happens to their 3-D graphene material, which is composed of curved surfaces under deformation, resembles what would happen with sheets of paper. Paper has little strength along its length and width, and can be easily crumpled up. But when made into certain shapes, for example rolled into a tube, suddenly the strength along the length of the tube is much greater and can support substantial weight. Similarly, the geometric arrangement of the graphene flakes after treatment naturally forms a very strong configuration.

The new configurations have been made in the lab using a high-resolution, multimaterial 3-D printer. They were mechanically tested for their tensile and compressive properties, and their mechanical response under loading was simulated using the team’s theoretical models. The results from the experiments and simulations matched accurately.

The new, more accurate results, based on atomistic computational modeling by the MIT team, ruled out a possibility proposed previously by other teams: that it might be possible to make 3-D graphene structures so lightweight that they would actually be lighter than air, and could be used as a durable replacement for helium in balloons. The current work shows, however, that at such low densities, the material would not have sufficient strength and would collapse from the surrounding air pressure.

But many other possible applications of the material could eventually be feasible, the researchers say, for uses that require a combination of extreme strength and light weight. “You could either use the real graphene material or use the geometry we discovered with other materials, like polymers or metals,” Buehler says, to gain similar advantages of strength combined with advantages in cost, processing methods, or other material properties (such as transparency or electrical conductivity).

“You can replace the material itself with anything,” Buehler says. “The geometry is the dominant factor. It’s something that has the potential to transfer to many things.”

The unusual geometric shapes that graphene naturally forms under heat and pressure look something like a Nerf ball — round, but full of holes. These shapes, known as gyroids, are so complex that “actually making them using conventional manufacturing methods is probably impossible,” Buehler says. The team used 3-D-printed models of the structure, enlarged to thousands of times their natural size, for testing purposes.

For actual synthesis, the researchers say, one possibility is to use the polymer or metal particles as templates, coat them with graphene by chemical vapor deposit before heat and pressure treatments, and then chemically or physically remove the polymer or metal phases to leave 3-D graphene in the gyroid form. For this, the computational model given in the current study provides a guideline to evaluate the mechanical quality of the synthesis output.

The same geometry could even be applied to large-scale structural materials, they suggest. For example, concrete for a structure such a bridge might be made with this porous geometry, providing comparable strength with a fraction of the weight. This approach would have the additional benefit of providing good insulation because of the large amount of enclosed airspace within it.

Because the shape is riddled with very tiny pore spaces, the material might also find application in some filtration systems, for either water or chemical processing. The mathematical descriptions derived by this group could facilitate the development of a variety of applications, the researchers say.

“This is an inspiring study on the mechanics of 3-D graphene assembly,” says Huajian Gao, a professor of engineering at Brown University, who was not involved in this work. “The combination of computational modeling with 3-D-printing-based experiments used in this paper is a powerful new approach in engineering research. It is impressive to see the scaling laws initially derived from nanoscale simulations resurface in macroscale experiments under the help of 3-D printing,” he says.

This work, Gao says, “shows a promising direction of bringing the strength of 2-D materials and the power of material architecture design together.”

There’s a video describing the work,

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

The mechanics and design of a lightweight three-dimensional graphene assembly by Zhao Qin, Gang Seob Jung, Min Jeong Kang, and Markus J. Buehler. Science Advances  06 Jan 2017: Vol. 3, no. 1, e1601536 DOI: 10.1126/sciadv.1601536  04 January 2017

This paper appears to be open access.

Bioceramic armour: tough and clear

This story about a mollusk and its armour eventually led me back to one of my favourite science writers, David L. Chandler at the Massachusetts Institute of Technology (MIT). First, here’s an excerpt from a March 30, 2014 news item on ScienceDaily,

The shells of a sea creature, the mollusk Placuna placenta, are not only exceptionally tough, but also clear enough to read through. Now, researchers at MIT have analyzed these shells to determine exactly why they are so resistant to penetration and damage — even though they are 99 percent calcite, a weak, brittle mineral.

The shells’ unique properties emerge from a specialized nanostructure that allows optical clarity, as well as efficient energy dissipation and the ability to localize deformation, the researchers found. The results are published this week in the journal Nature Materials, in a paper co-authored by MIT graduate student Ling Li and professor Christine Ortiz.

A March 30, 2014 MIT press release (I’m not positive Chandler wrote this but he is the press contact) describes both the engineered bioceramic armour and the mollusk’s naturally occurring armour,

Engineered ceramic-based armor, while designed to resist penetration, often lacks the ability to withstand multiple blows, due to large-scale deformation and fracture that can compromise its structural integrity, Ortiz says. In transparent armor systems, such deformation can also obscure visibility.

Creatures that have evolved natural exoskeletons — many of them ceramic-based — have developed ingenious designs that can withstand multiple penetrating attacks from predators. The shells of a few species, such as Placuna placenta, are also optically clear.

To test exactly how the shells — which combine calcite with about 1 percent organic material — respond to penetration, the researchers subjected samples to indentation tests, using a sharp diamond tip in an experimental setup that could measure loads precisely. They then used high-resolution analysis methods, such as electron microscopy and diffraction, to examine the resulting damage.

The material initially isolates damage through an atomic-level process called “twinning” within the individual ceramic building blocks: A crystal breaks up into a pair of mirror-image regions that share a common boundary, rather like a butterfly’s wings. This twinning process occurs all around the stressed region, helping to form a kind of boundary that keeps the damage from spreading outward.

The MIT researchers found that twinning then activates “a series of additional energy-dissipation mechanisms … which preserve the mechanical and optical integrity of the surrounding material,” Li says. This produces a material that is 10 times more efficient in dissipating energy than the pure mineral, Li adds.

The properties of this natural armor make it a promising template for the development of bio-inspired synthetic materials for both commercial and military applications — such as eye and face protection for soldiers, windows and windshields, and blast shields, Ortiz says.

Huajian Gao, a professor of engineering at Brown University who was not involved in this research, calls it “an excellent and elegant piece of work.” He says it “successfully demonstrates the effectiveness of nanoscale deformation twins in energy dissipation in bioceramics, and should be able to inspire and guide the development of manmade ceramic materials.” He adds, “As a first-of-its-kind [demonstration of] the effectiveness of deformation twins in natural materials, this work should have huge practical impact.”

The work was supported by the National Science Foundation; the U.S. Army Research Office through the MIT Institute for Soldier Nanotechnologies; the National Security Science and Engineering Faculty Fellowships Program; and the Office of the Assistant Secretary of Defense for Research and Engineering.

The researchers have produced an image showing how the mollusk shell reacts to being damaged,

A Scanning Electron Microscope (SEM) image of the region surrounding an indentation the researchers made in a piece of shell from Placuna placenta. The image shows the localization of damage to the area immediately surrounding the stress. Image: Ling Li and James C. Weaver. Courtesy: MIT

A Scanning Electron Microscope (SEM) image of the region surrounding an indentation the researchers made in a piece of shell from Placuna placenta. The image shows the localization of damage to the area immediately surrounding the stress.
Image: Ling Li and James C. Weaver. Courtesy: MIT

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

Pervasive nanoscale deformation twinning as a catalyst for efficient energy dissipation in a bioceramic armour by Ling Li & Christine Ortiz. Nature Materials (2014) doi:10.1038/nmat3920 Published online 30 March 2014

This paper is behind a paywall.

Why asbestos and carbon nanotubes are so dangerous to cells

Sphere or spear? Apparently cells can’t tell that an asbestos fibre or long carbon nanotube are spears due to their rounded tips according to researchers at Brown University. From the Sept. 18, 2011 news item on Nanowerk,

Through molecular simulations and experiments, the team reports in Nature Nanotechnology that certain nanomaterials, such as carbon nanotubes, enter cells tip-first and almost always at a 90-degree angle. The orientation ends up fooling the cell; by taking in the rounded tip first, the cell mistakes the particle for a sphere, rather than a long cylinder. By the time the cell realizes the material is too long to be fully ingested, it’s too late.

Here’s a representation of what the scientists mean,

 

Something perpendicular this way comes Cells ingest things by engulfing them. When a long perpendicular fiber comes near, the cell senses only its tip, mistakes it for a sphere, and begins engulfing something too long to handle. Credit: Gao Lab/Brown University

Here’s what happens when a cell encounters a carbon nanotube, asbestos fibre, gold nanowires, and other materials that are long and perpendicular with rounded tips,

Like asbestos fibers, commercially available carbon nanotubes and gold nanowires have rounded tips that often range from 10 to 100 nanometers in diameter. Size is important here; the diameter fits well within the cell’s parameters for what it can handle. Brushing up against the nanotube, special proteins called receptors on the cell spring into action, clustering and bending the membrane wall to wrap the cell around the nanotube tip in a sequence that the authors call “tip recognition.” As this occurs, the nanotube is tipped to a 90-degree angle, which reduces the amount of energy needed for the cell to engulf the particle.

Once the engulfing — endocytosis — begins, there is no turning back. Within minutes, the cell senses it can’t fully engulf the nanostructure and essentially dials 911. “At this stage, it’s too late,” Gao [Huajian Gao] said. “It’s in trouble and calls for help, triggering an immune response that can cause repeated inflammation.”

I gather this is the starting point for mesothelioma. Here’s a description of the process (from the Brown University Sept. 18, 2011 news release,

“We thought the tube was going to lie on the cell membrane to obtain more binding sites. However, our simulations revealed the tube steadily rotating to a high-entry degree, with its tip being fully wrapped,” said Xinghua Shi, first author on the paper who earned his doctorate at Brown and is at the Chinese Academy of Sciences in Beijing. “It is counter-intuitive and is mainly due to the bending energy release as the membrane is wrapping the tube.”

Here’s a video from Brown illustrating the process,

Cells bite off more than they can chew from Brown PAUR on Vimeo.

The whole thing has me wondering about long vs. short carbon nanotubes. Does this mean that short carbon nanotubes can be ingested successfully? If so, at what point does short become too long to ingest? It doesn’t seem like my questions are going to be answered too soon since the team would like to go in this direction (from the Brown news release),

The team would like to study whether nanotubes without rounded tips — or less rigid nanomaterials such as nanoribbons — pose the same dilemma for cells.

“Interestingly, if the rounded tip of a carbon nanotube is cut off (meaning the tube is open and hollow), the tube lies on the cell membrane, instead of entering the cell at a high-degree-angle,” Shi said.