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Making diamonds at ambient pressure

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Making diamonds at ambient pressure


Did you know that 99% of synthetic diamonds are currently produced using high-pressure and high-temperature (HPHT) methods?[2] A prevailing paradigm is that diamonds can only be grown using liquid metal catalysts in the gigapascal pressure range (typically 5-6 GPa, where 1 GPa is about 10,000 atm), and typically within the temperature range of 1300-1600 °C. However, the diamonds produced using HPHT are always limited to sizes of approximately one cubic centimeter due to the components involved. That is — achieving such high pressures can only be done at a relatively small length scale. Discovering alternative methods to make diamonds in liquid metal under milder conditions (particularly at lower pressure) is an intriguing basic science challenge that if achieved could revolutionize diamond manufacturing. Could the prevailing paradigm be challenged?

A team of researchers led by Director Rod RUOFF at the Center for Multidimensional Carbon Materials (CMCM) within the Institute for Basic Science (IBS), including graduate students at the Ulsan National Institute of Science and Technology (UNIST), have grown diamonds under conditions of 1 atmosphere pressure and at 1025 °C using a liquid metal alloy composed of gallium, iron, nickel, and silicon, thus breaking the existing paradigm. The discovery of this new growth method opens many possibilities for further basic science studies and for scaling up the growth of diamonds in new ways.

Director Ruoff, who is also a UNIST Distinguished Professor notes, “This pioneering breakthrough was the result of human ingenuity, unremitting efforts, and the concerted cooperation of many collaborators.” Researchers led by Ruoff conducted a series of experiments, involving several hundred parameter adjustments and a variety of experimental approaches before they finally succeeded in growing diamonds using a ‘home-built’ cold-wall vacuum system.

Ruoff notes “We had been running our parametric studies in a large chamber (named RSR-A with an interior volume of 100 liters) and our search for parameters that would yield growth of diamond was slowed due to the time needed to pump out air (about 3 minutes), purge with inert gas (90 minutes), followed by pumping down again to vacuum level (3 minutes) so that the chamber could then be filled with 1 atmosphere pressure of quite pure hydrogen/methane mixture (again 90 minutes); that is over 3 hours before the experiment could be started! I asked Dr. Won Kyung SEONG to design & build a much smaller chamber to greatly reduce the time needed to start (and finish!) the experiment with the liquid metal exposed to the mixture of methane and hydrogen.” Seong adds, “Our new homebuilt system (named RSR-S, with an interior volume of only 9 liters) can be pumped out, purged, pumped out, and filled with methane/hydrogen mixture, in a total time of 15 minutes. Parametric studies were greatly accelerated, and this helped us discover the parameters for which diamond grows in the liquid metal!”

The team discovered that diamond grows in the sub-surface of a liquid metal alloy consisting of a 77.75/11.00/11.00/0.25 mix (atomic percentages) of gallium/nickel/iron/silicon when exposed to methane and hydrogen under 1 atm pressure at ~1025 °C.

Yan GONG, UNIST graduate student and first author, explains “One day with the RSR-S system when I ran the experiment and then cooled down the graphite crucible to solidify the liquid metal, and removed the solidified liquid metal piece, I noticed a ‘rainbow pattern’ spread over a few millimeters on the bottom surface of this piece. We found out that the rainbow colors were due to diamonds! This allowed us to to identify parameters that favored the reproducible growth of diamond.”

The initial formation occurs without the need for diamond or other seed particles commonly used in conventional HPHT and chemical vapor deposition synthesis methods. Once formed, the diamond particles merge to form a film, which can be easily detached and transferred to other substrates, for further studies and potential applications.

The synchrotron two-dimensional X-ray diffraction measurements confirmed that the synthesized diamond film has a very high purity of the diamond phase. Another intriguing aspect is the presence of silicon-vacancy color centers in the diamond structure, as an intense zero-phonon line at 738.5 nm in the photoluminescence spectrum excited by using a 532 nm laser was found.

Coauthor Dr. Meihui WANG notes, “This synthesized diamond with silicon-vacancy color centers may find applications in magnetic sensing and quantum computing.”

The research team delved deeply into possible mechanisms for diamonds to nucleate and grow under these new conditions. High-resolution transmission electron microscope (TEM) imaging on cross-sections of the samples showed about 30-40 nm thick amorphous subsurface region in the solidified liquid metal that was directly in contact with the diamonds. Coauthor Dr. Myeonggi CHOE notes, “Approximately 27 percent of atoms that were present at the top surface of this amorphous region were carbon atoms, with the carbon concentration decreasing with depth.”

Ruoff elaborates, “The presence of such a high concentration of carbon ‘dissolved’ in a gallium-rich alloy could be unexpected, as carbon is reported to be not soluble in gallium. This may explain why this region is amorphous — while all other regions of the solidified liquid metal are crystalline. This sub-surface region is where our diamonds nucleate and grow and we thus focused on it.”

Researchers exposed the Ga-Fe-Ni-Si liquid metal to the methane/hydrogen for short periods of time to try to understand the early growth stage — well prior to the formation of a continuous diamond film. They then analyzed the concentrations of carbon in the subsurface regions using time-of-flight secondary ion mass spectrometry depth profiling. After a 10-minute run, no diamond particles were evident but there were ~65 at% carbon atoms present in the region where the diamond typically grows. Diamond particles began to be found after a 15-minute run, and there was a lower subsurface C atom concentration of ~27 at%.

Ruoff explains, “The concentration of subsurface carbon atoms is so high at around 10 minutes that this time exposure is close to or at supersaturation, leading to the nucleation of diamonds either at 10 minutes or sometime between 10 and 15 minutes. The growth of diamond particles is expected to occur very rapidly after nucleation, at some time between about 10 minutes and 15 minutes.”

The temperature in 27 different locations in the liquid metal was measured with an attachment to the growth chamber having an array of nine thermocouples that was designed and built by Seong. The central region of the liquid metal was found to be at a lower temperature compared to the corners and sides of the chamber. It is thought that this temperature gradient is what drives carbon diffusion towards the central region, facilitating diamond growth.

The team also discovered that silicon plays a critical role in this new growth of diamond. The size of the grown diamonds becomes smaller and their density higher as the concentration of silicon in the alloy was increased from the optimal value. Diamonds could not be grown at all without the addition of silicon, which suggests that silicon may be involved in the initial nucleation of diamond.

This was supported by the various theoretical calculations conducted to uncover the factors that may be responsible for the growth of diamonds in this new liquid metal environment. Researchers found that silicon promotes the formation and stabilization of certain carbon clusters by predominantly forming sp3 bonds like carbon. It is thought that small carbon clusters containing Si atoms might serve as the ‘pre-nuclei’, which can then grow further to nucleate a diamond. It is predicted that the likely size range for an initial nucleus is around 20 to 50 C atoms.

Ruoff states, “Our discovery of nucleation and growth of diamond in this liquid metal is fascinating and offers many exciting opportunities for more basic science. We are now exploring when nucleation, and thus the rapid subsequent growth of diamond, happens. Also ‘temperature drop’ experiments where we first achieve supersaturation of carbon and other needed elements, followed by rapidly lowering the temperature to trigger nucleation — are some studies that seem promising to us.”

The team discovered their growth method offers significant flexibility in the composition of liquid metals. Researcher Dr. Da LUO remarks, “Our optimized growth was achieved using the gallium/nickel/iron/silicon liquid alloy. However, we also found that high-quality diamond can be grown by substituting nickel with cobalt or by replacing gallium with a gallium-indium mixture.”

Ruoff concludes, “Diamond might be grown in a wide variety of relatively low melting point liquid metal alloys such as containing one or more of indium, tin, lead, bismuth, gallium, and potentially antimony and tellurium — and including in the molten alloy other elements such as manganese, iron, nickel, cobalt and so on as catalysts, and others as dopants that yield color centers. And there is a wide range of carbon precursors available besides methane (various gases, and also solid carbons). New designs and methods for introducing carbon atoms and/or small carbon clusters into liquid metals for diamond growth will surely be important, and the creativity and technical ingenuity of the worldwide research community seem likely to me, based on our discovery, to rapidly lead to other related approaches and experimental configurations. There are numerous intriguing avenues to explore!”

This research was supported by the Institute for Basic Science and has been published in the journal Nature.



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A new study reveals that marine cyanobacteria communicate

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A new study reveals that marine cyanobacteria communicate


Three years ago María del Carmen Muñoz, a researcher at the University of Cordoba, was peering into an electron microscope to study the vesicles of marine cyanobacteria and found, almost accidentally, something she did not expect: structures that, although they had already been discovered years ago in other bacteria, had never been found in this type of living being, responsible for producing more than half of the oxygen on Earth. Thus began an extensive study carried out by a multidisciplinary team. Today their work comes out, its results having just been published in the journal Science Advances.

These strange structures are called membrane nanotubes, and the most relevant thing is that, according to the study, these small tubes make it possible for these living beings to transfer material by generating an exchange bridge, a kind of hose that connects with nearby cells, allowing them to transfer substances from some cyanobacteria to others. Since the discovery of these organisms, this is the first time that physical and direct contact between them has been demonstrated.

“This finding has enormous implications, and strengthens the idea that we need to change the way we think about cyanobacteria,” said researcher José Manuel García. Challenging the idea that these organisms operate in isolation, the study suggests that they could act as a kind of network in which they interact, a premise of great relevance considering that these living beings are the most abundant photosynthetic organisms on the planet, representing a veritable “lung” for the oceans, and being indispensable for the sustenance of life as we know it.

In recent years the study, led by principal investigator María del Carmen Muñoz, has mobilized a multidisciplinary group composed of, among others, the UCO’s Departments of Biochemistry, Molecular Biology, and Cell Biology; the Maimonides Institute for Biomedical Research (Cordoba), the University of Cádiz’s University Institute of Marine Research, the Institute of Plant Biochemistry and Photosynthesis (Seville), and oceanographer Sallie W. Chisholm, a member of the Massachusetts Institute of Technology and discoverer of the Prochlorococcus genus of cyanobacteria.

Key details

Since the study began, and after reviewing the literature available on these nanotubes in other bacteria, the team has launched different experiments in the laboratory, such as the use of fluorescent proteins and their monitoring by fluorescence microscopy; and the use of electron microscopy for the characterization of these structures. Through these tests they have been able to confirm that there is an exchange of material from the interior of one cell to the other. In addition, as doctoral student and the study’s first author Elisa Angulo explained, the work has shown that this transfer of substances not only occurs in cyanobacteria of the same lineage, but also between those of different genders, something that has been verified not only at the laboratory level, but also in natural ocean samples.

New questions

As is often the case in science, these findings now open the door to new questions: is this transfer of molecules a support mechanism or a weapon to compete for survival? What other substances could be exchanged, beyond proteins? Is there any relationship between this mechanism and the amount of food available in the environment? Elisa Angulo, a researcher at the University of Cordoba, is already trying to answer this last question, and has just concluded a voyage on the high seas in which she has been researching the behavior of these living beings in oligotrophic areas of the Pacific poor in nutrients. We will have to wait for the next few months to continue acquiring knowledge about these marine bacteria, the living beings that invented photosynthesis and that, more than 3.5 billion years old, represent one of the oldest known forms of life. Their study, therefore, is not only of vital importance for ecosystems, but also to understand fundamental processes in the vast field of Biology.



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People feel more connected to ‘tweezer-like’ bionic tools that don’t resemble human hands

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People feel more connected to ‘tweezer-like’ bionic tools that don’t resemble human hands


Some say the next step in human evolution will be the integration of technology with flesh. Now, researchers have used virtual reality to test whether humans can feel embodiment — the sense that something is part of one’s body — toward prosthetic “hands” that resemble a pair of tweezers. They report June 6 in the journal iScience that participants felt an equal degree of embodiment for the tweezer-hands and were also faster and more accurate in completing motor tasks in virtual reality than when they were equipped with a virtual human hand.

“For our biology to merge seamlessly with tools, we need to feel that the tools are part of our body,” says first author and cognitive neuroscientist Ottavia Maddaluno, who conducted the work at the Sapienza University of Rome and the Santa Lucia Foundation IRCCS with Viviana Betti. “Our findings demonstrate that humans can experience a grafted tool as an integral part of their own body.”

Previous studies have shown that tool use induces plastic changes in the human brain, as does the use of anthropomorphic prosthetic limbs. However, an open scientific question is whether humans can embody bionic tools or prostheses that don’t resemble human anatomy.

To investigate this possibility, the researchers used virtual reality to conduct a series of experiments on healthy participants. In the virtual reality environment, participants had either a human-like hand or “bionic tool” resembling a large pair of tweezers grafted onto the end of their wrist. To test their motor ability and dexterity, participants were asked to pop bubbles of a specific color (by pinching them with their tweezers or between their index finger and thumb). For this simple task, the researchers found that participants were faster and more accurate at popping virtual bubbles when they had tweezer-hands.

Next, the team used a test called the “cross-modal congruency task” to compare implicit or unconscious embodiment for the virtual hand and bionic tool. During this test, the researchers applied small vibrations to the participants’ fingertips and asked them to identify which fingers were stimulated. At the same time, a flickering light was displayed on the virtual reality screen, either on the same finger as the tactile stimulus or on a different finger. By comparing the participants’ accuracy and reaction times during trials with matched and mismatched stimuli, the researchers were able to assess how distracted they were by the visual stimulus.

“This is an index of how much of a mismatch there is in your brain between what you feel and what you see,” says Maddaluno. “But this mismatch could only happen if your brain thinks that what you see is part of your own body; if I don’t feel that the bionic tool that I’m seeing through virtual reality is part of my own body, the visual stimulus should not give any interference.”

In both cases, participants were faster and more accurate at identifying which of their real fingers were stimulated during trials with matched tactile and visual stimuli, indicating that participants felt a sense of embodiment toward both the virtual human hand and the tweezer-hands.

However, there was a bigger difference between matched and mismatched trials when participants had tweezer- rather than human hands, indicating that the non-anthropomorphic prosthesis resulted in an even greater sense of embodiment. The researchers speculate that this is due to the tweezer-hands’ relative simplicity compared to a human-like hand, which might make it easy for the brain to compute and accept.

“In terms of the pinching task, the tweezers are functionally similar to a human hand, but simpler, and simple is also better computationally for the brain.” says Maddaluno.

They note that it could also relate to the “uncanny valley” hypothesis, since the virtual human hands might have been too eerily similar yet distinct for perfect embodiment.

In addition to the tweezer-hands, the researchers also tested a wrench-shaped bionic tool and a virtual human hand holding a pair of tweezers. They found evidence of embodiment in all cases, but the participants had higher embodiment and were more dexterous when the tweezers were grafted directly onto their virtual wrists than when they held them in their virtual hand.

Participants also displayed a higher sense of embodiment for the bionic tools when they had the opportunity to explore the virtual reality environment before undertaking the cross-modal congruency test. “During the cross-modal congruency task participants had to stay still, whereas during the motor task, they actively interacted with the virtual environment, and these interactions in the virtual environment induce a sense of agency,” says Maddaluno.

Ultimately, the researchers say that this study could inform robotics and prosthetic limb design. “The next step is to study if these bionic tools could be embodied in patients that have lost limbs,” says Maddaluno. “And we also want to investigate the plastic changes that this kind of bionic tool can induce in the brains of both healthy participants and amputees.”



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Planet-forming disks around very low-mass stars are different

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Planet-forming disks around very low-mass stars are different


Planets form in disks of gas and dust, orbiting young stars. The MIRI Mid-INfrared Disk Survey (MINDS), led by Thomas Henning from the Max Planck Institute for Astronomy (MPIA) in Heidelberg, Germany, aims to establish a representative disk sample. By exploring their chemistry and physical properties with MIRI (Mid-Infrared Instrument) on board the James Webb Space Telescope (JWST), the collaboration links those disks to the properties of planets potentially forming there. In a new study, a team of researchers explored the vicinity of a very low-mass star of 0.11 solar masses (known as ISO-ChaI 147), whose results appear in the journal Science.

JWST opens a new window to the chemistry of planet-forming disks

“These observations are not possible from Earth because the relevant gas emissions are absorbed by its atmosphere,” explained lead author Aditya Arabhavi of the University of Groningen in the Netherlands. “Previously, we could only identify acetylene (C2H2) emission from this object. However, JWST’s higher sensitivity and the spectral resolution of its instruments allowed us to detect weak emission from less abundant molecules.”

The MINDS collaboration found gas at temperatures around 300 Kelvin (ca. 30 degrees Celsius), strongly enriched with carbon-bearing molecules but lacking oxygen-rich species. “This is profoundly different from the composition we see in disks around solar-type stars, where oxygen-bearing molecules such as water and carbon dioxide dominate,” added team member Inga Kamp, University of Groningen.

One striking example of an oxygen-rich disk is the one of PDS 70, where the MINDS program recently found large amounts of water vapour. Considering earlier observations, astronomers deduce that disks around very low-mass stars evolve differently than those around more massive stars such as the Sun, with potential implications for finding rocky planets with Earth-like characteristics there. Since the environments in such disks set the conditions in which new planets form, any such planet may be rocky but quite unlike Earth in other aspects.

What does it mean for rocky planets orbiting very low-mass stars?

The amount of material and its distribution across those disks limits the number and sizes of planets the disk can supply with the necessary material. Consequently, observations indicate that rocky planets with sizes similar to Earth form more efficiently than Jupiter-like gas giants in the disks around very low-mass stars, the most common stars in the Universe. As a result, very low-mass stars host the majority of terrestrial planets by far.

“Many primary atmospheres of those planets will probably be dominated by hydrocarbon compounds and not so much by oxygen-rich gases such as water and carbon dioxide,” Thomas Henning pointed out. “We showed in an earlier study that the transport of carbon-rich gas into the zone where terrestrial planets usually form happens faster and is more efficient in those disks than the ones of more massive stars.”

Although it seems clear that disks around very low-mass stars contain more carbon than oxygen, the mechanism for this imbalance is still unknown. The disk composition is the result of either carbon enrichment or the reduction of oxygen. If the carbon is enriched, the cause is probably solid particles in the disk, whose carbon is vaporised and released into the gaseous component of the disk. The dust grains, stripped of their original carbon, eventually form rocky planetary bodies. Those planets would be carbon-poor, as is Earth. Still, carbon-based chemistry would likely dominate at least their primary atmospheres provided by disk gas. Therefore, very low-mass stars may not offer the best environments for finding planets akin to Earth.

JWST discovers a wealth of organic molecules

To identify the disk gases, the team used MIRI’s spectrograph to decompose the infrared radiation received from the disk into signatures of small wavelength ranges — similar to sunlight being split into a rainbow. This way, the team isolated a wealth of individual signatures attributed to various molecules.

As a result, the observed disk contains the richest hydrocarbon chemistry seen to date in a protoplanetary disk, consisting of 13 carbon-bearing molecules up to benzene (C6H6). They include the first extrasolar ethane (C2H6) detection, the largest fully-saturated hydrocarbon detected outside the Solar System. The team also successfully detected ethylene (C2H4), propyne (C3H4), and the methyl radical CH3 for the first time in a protoplanetary disk. In contrast, the data contained no hint of water or carbon monoxide in the disk.

Sharpening the view of disks around very low-mass stars

Next, the science team intends to expand their study to a larger sample of such disks around very low-mass stars to develop their understanding of how common such exotic carbon-rich terrestrial planet-forming regions are. “Expanding our study will also allow us to understand better how these molecules can form,” Thomas Henning explained. “Several features in the data are also still unidentified, warranting additional spectroscopy to interpret our observations fully.”

Background information

The study was funded in the framework of the ERC Advanced Grant “Origins — From Planet-Forming Disks to Giant Planets” (Grant ID: 832428, PI: Thomas Henning, DOI: 10.3030/832428).

The MPIA scientists involved in this study are Thomas Henning, Matthias Samland, Giulia Perotti, Jeroen Bouwman, Silvia Scheithauer, Riccardo Franceschi, Jürgen Schreiber, and Kamber Schwartz.

Other researchers include Aditya Arabhavi (University of Groningen, the Netherlands [Groningen]), Inga Kamp (Groningen), Ewine van Dishoeck (Leiden University, the Netherlands and Max Planck Institute for Extraterrestrial Physics, Garching, Germany), Valentin Christiaens (University of Liege, Belgium), and Agnes Perrin (Laboratoire de Météorologie Dynamique/IPSL CNRS, Palaiseau, France).

The MIRI consortium consists of the ESA member states Belgium, Denmark, France, Germany, Ireland, the Netherlands, Spain, Sweden, Switzerland, and the United Kingdom. The national science organisations fund the consortium’s work — in Germany, the Max Planck Society (MPG) and the German Aerospace Center (DLR). The participating German institutions are the Max Planck Institute for Astronomy in Heidelberg, the University of Cologne, and Hensoldt AG in Oberkochen, formerly Carl Zeiss Optronics.

JWST is the world’s premier space science observatory. It is an international program led by NASA jointly with its partners, ESA (European Space Agency) and CSA (Canadian Space Agency).



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