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Reducing nitrogen with boron and beer

Humankind is reliant on the ammonium in synthetic fertiliser for food. However, producing ammonia from nitrogen is extremely energy-intensive and requires the use of transition metals.

Researchers from Julius-Maximilians-Universität (JMU) Würzburg in Bavaria, Germany, have now achieved the conversion of nitrogen to ammonium at room temperature and low pressure without the need for transition metals. This was reported by a research group led by JMU scientist Holger Braunschweig in the journal Nature Chemistry.

A new toolbox for binding nitrogen

The industrial production of ammonia, the so-called Haber-Bosch process, requires high temperatures and pressures, and is estimated to consume roughly two percent of all energy produced on earth. This process also relies on transition metal elements, relatively heavy and reactive atoms.

In 2018, Professor Braunschweig’s team reported the binding and chemical conversion of nitrogen using a molecule constituted only of lighter, non-metal atoms. A year later, they used a similar system to demonstrate the first combination of two nitrogen molecules in the laboratory, a reaction that had otherwise only been seen in Earth’s upper atmosphere and under plasma conditions.

The key in both of these discoveries was the use of boron, the fifth lightest element, as the atom to which the nitrogen binds. “After these two discoveries, it was clear that we had a pretty special system on our hands,” says Braunschweig.

Just add water

Although their system binds and converts nitrogen, only half of the puzzle pieces were in place. “We knew that completing the conversion of nitrogen to ammonia would be a major challenge, as it requires a complex sequence of chemical reactions that are often incompatible with each other,” explains the JMU professor.

The breakthrough came from the most simple of reagents: traces of water left behind in a sample were enough to promote a sequential reaction that brought the team only a single step away from the target ammonium. It was later discovered that the key reactions could be done using a solid acid, allowing the reactions to occur sequentially in a single reaction flask, all at room temperature.

Making ammonium with beer

Realising that the acidification step of the process appeared to work even with simple reagents such as water, the team repeated the reaction using locally brewed Würzburger Hofbräu beer. To their delight, they were able to detect the pre-ammonium product in the reaction mixture.

“This experiment was in part a bit of fun, but it also shows how tolerant the system is to water and other compounds,” explains Dr. Marc-André Légaré, the postdoctoral researcher who initiated the study. “The reduction of nitrogen to ammonia is one of the most important chemical reactions for humankind. This is undoubtedly the first time it has been done using beer, and it is particularly fitting that it was done in Germany!” says Dr. Rian Dewhurst, Akademischer Oberrat and coauthor of the study.

Much work left to be done

The reaction, while exciting, is still far from being a truly practical process for industrially producing ammonium. Ideally, finding a way to re-form the active species will be needed to make the process energy efficient and economical.

Nevertheless, the discovery is an exciting demonstration that the lighter elements can tackle even the biggest challenges in chemistry. “There is much left to be done here, but boron and the other light elements have already surprised us so many times. They are clearly capable of so much more,” says Holger Braunschweig.

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Shift in how we build computers: Photonics

Information technology continues to progress at a rapid pace. However, the growing demands of data centers have pushed electrical input-output systems to their physical limit, which has created a bottleneck. Maintaining this growth will require a shift in how we built computers. The future is optical.

Over the last decade, photonics has provided a solution to the chip-to-chip bandwidth problem in the electronic world by increasing the link distance between servers with higher bandwidth, far less energy and lower latency compared to electrical interconnects.

One element of this revolution, silicon photonics, was advanced 15 years ago by the demonstration from UC Santa Barbara and Intel of a silicon laser technology. This has since triggered an explosion of this field. Intel is now delivering millions of silicon photonic transceivers for data centers all around the world.

A new discovery in silicon photonics by a collaboration of UC Santa Barbara, Caltech and the Swiss Federal Institute of Technology Lausanne (EPFL) reveals another revolution in this field. The group managed to simplify and condense a complex optical system onto a single silicon photonic chip. The achievement, featured in Nature, significantly lowers the cost of production and allows for easy integration with traditional, silicon chip production.

“The entire internet is driven by photonics now,” said John Bowers, who holds the Fred Kavli Chair in Nanotechnology at UC Santa Barbara, directs the campus’s Institute for Energy Efficiency and led the collaborative research effort.

Despite the great success of photonics in the Internet backbone, challenges still exist. The explosion of data traffic puts a growing requirement on the data rate each individual silicon photonic chip can handle. Using multicolor laser light to transmit information is the most efficient way to address this demand. The more laser colors, the more information that can be carried.

However, this poses a problem for integrated lasers, which can generate only one color of laser light at a time. “You might literally need 50 or more lasers in that chip for that purpose” said Bowers. And using 50 lasers has a number of drawbacks. It’s expensive, and rather inefficient in terms of power. What’s more, the frequency of light each laser produces can fluctuate slightly due to noise and heat. With multiple lasers, the frequencies can even drift into each other, much like early radio stations did.

A technology called “optical frequency combs” provide a promising solution to address this problem. It refers to a collection of equally spaced frequencies of laser light. Plotting the frequencies reveals spikes and dips that resemble a hair comb — hence the name. However, generating combs required bulky, expensive equipment. Using an integrated photonics approach, Bowers’ team has demonstrated the smallest comb generator in the world, which resolves all of these problems.

The configuration of the system is rather simple, consisting of a commercially distributed feedback laser and a silicon nitride photonic chip. “What we have is a source that generates all these colors out of one laser and one chip. That’s what’s significant about this,” Bowers said.

The simple structure leads to a significant reduction of scale, power and cost. The whole setup now fits in a package smaller than a match box, whose overall price and power consumption are smaller than previous systems.

What’s more, the new technology is also much more convenient to operate. Previously, generating a stable comb had been a tricky endeavor. Researchers had to modulate the frequency and adjust power just right to produce a coherent comb state, called soliton. That process was not guaranteed to generate such state every time. “The new approach makes the process as easy as switching on a room light,” said coauthor Kerry Vahala, a professor of applied physics and information science and technology at Caltech.

“What is remarkable about the result is the reproducibility with which frequency combs can be generated on demand,” added Tobias J. Kippenberg, professor of physics at EPFL who provided the low loss silicon nitride photonics chips, a technology already commercialized via LIGENTEC. “This process used to require elaborate control in the past.”

The magic behind all these improvements lies in an interesting physical phenomenon. When the pump laser and resonator are integrated, the interaction between them forms a highly coupled system that is self-injection locking and simultaneously generates “solitons,” pulses that circulate indefinitely inside the resonator and give rise to optical frequency combs. “Such interaction is the key to directly generating the comb and operating it in the soliton state” explained coauthor Lin Chang, a postdoctoral researcher in Bowers’ lab.

This new technology will have a big impact on photonics. In addition to addressing the demands of multicolor light sources in communication related products, it also opens up a lot of new opportunities in many applications. One example is optical clocks, which provide the most accurate time standard in the world and have many uses — from navigation in daily life to measurements of physical constants.

“Optical clocks used to be large, heavy and expensive,” Bowers noted, “and there are only a few in the world. With integrated photonics, we can make something that could fit in a wristwatch, and you could afford it. Low noise integrated optical microcombs will enable a new generation of optical clocks, communications and sensors. We should see more compact, more sensitive GPS receivers coming out of this approach.”

All in all, the future looks bright for photonics. “It is the key step to transfer the frequency comb technology from the laboratory to the real world.” Bowers said. “It will change photonics and our daily lives.”

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New ‘whirling’ state of matter discovered in an element of the periodic table

The strongest permanent magnets today contain a mix of the elements neodymium and iron. However, neodymium on its own does not behave like any known magnet, confounding researchers for more than half a century. Physicists at Radboud University and Uppsala University have shown that neodymium behaves like a so-called ‘self-induced spin glass,’ meaning that it is composed of a rippled sea of many tiny whirling magnets circulating at different speeds and constantly evolving over time. Understanding this new type of magnetic behaviour refines our understanding of elements on the periodic table and eventually could pave the way for new materials for artificial intelligence. The results will be published on 29th of May, in Science.

“In a jar of honey, you may think that the once clear areas that turned milky yellow have gone bad. But rather, the jar of honey starts to crystallize. That’s how you could perceive the ‘aging’ process in neodymium.” Alexander Khajetoorians, professor in Scanning probe microscopy, together with professor Mikhail Katsnelson and assistant professor Daniel Wegner, found that the material neodymium behaves in a complex magnetic way that no one ever saw before in an element on the periodic table.

Whirling magnets and glasses

Magnets are defined by a north and south pole. Dissecting a regular fridge magnet, one finds many atomic magnets, so-called ‘spins’, that are all aligned along the same direction and define the north and south pole. Quite differently, some alloy materials can be a ‘spin glass,’ randomly placed spins point in all kinds of directions. Spin glasses derive their name-sake from the amorphous evolving structure of the atoms in a piece of glass. In this way, spin glasses link magnetic behaviour to phenomena in softer matter, like liquids and gels.

Spin glasses have been known to sometimes occur in alloys, which are combinations of metals with one or more other elements and with an amorphous structure, but never in pure elements of the periodic table. Surprisingly, Radboud researchers found that the atomic spins of a perfectly ordered piece of the rare-earth element neodymium form patterns that whirl like a helix but constantly change the exact pattern of the helix. This is the manifestation of a new state of matter called a ‘self-induced spin glass’.

Seeing the magnetic structure

“In Nijmegen, we are specialists in scanning tunnelling microscopy (STM). It allows us to see the structure of individual atoms, and we can resolve the north and south poles of the atoms,” Wegner explains. “With this advancement in high-precision imaging, we were able to discover the behaviour in neodymium, because we could resolve the incredibly small changes in the magnetic structure. That’s not an easy thing to do.”

A material that behaves like neurons

This finding opens up the possibility that this complex and glassy magnetic behaviour could also be observed in uncountable new materials, including other elements on the periodic table. Khajetoorians: “It will refine textbook knowledge of the basic properties of matter. But it will also provide a proving ground to develop new theories where we can link physics to other fields, for example, theoretical neuroscience.”

“The complex evolution of neodymium may be a platform to mimic basic behaviour used in artificial intelligence,” Khajetoorians continues. “All the complex patterns which can be stored in this material can be linked to image recognition.”

With the advancement of AI and its large energy footprint, there is increasing demand to create materials that can perform brain-like tasks directly in hardware. “You could never build a brain-inspired computer with simple magnets, but materials with this complex behaviour could be suitable candidates,” Khajetoorians says.

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Microbial cyborgs: Bacteria supplying power

Electronic devices are still made of lifeless materials. One day, however, “microbial cyborgs” might be used in fuel cells, biosensors, or bioreactors. Scientists of Karlsruhe Institute of Technology (KIT) have created the necessary prerequisite by developing a programmable, biohybrid system consisting of a nanocomposite and the Shewanella oneidensis bacterium that produces electrons. The material serves as a scaffold for the bacteria and, at the same time, conducts the microbially produced current. The findings are reported in ACS Applied Materials & Interfaces.

The bacterium Shewanella oneidensis belongs to the so-called exoelectrogenic bacteria. These bacteria can produce electrons in the metabolic process and transport them to the cell’s exterior. However, use of this type of electricity has always been limited by the restricted interaction of organisms and electrode. Contrary to conventional batteries, the material of this “organic battery” does not only have to conduct electrons to an electrode, but also to optimally connect as many bacteria as possible to this electrode. So far, conductive materials in which bacteria can be embedded have been inefficient or it has been impossible to control the electric current.

The team of Professor Christof M. Niemeyer has now succeeded in developing a nanocomposite that supports the growth of exoelectrogenic bacteria and, at the same time, conducts current in a controlled way. “We produced a porous hydrogel that consists of carbon nanotubes and silica nanoparticles interwoven by DNA strands,” Niemeyer says. Then, the group added the bacterium Shewanella oneidensis and a liquid nutrient medium to the scaffold. And this combination of materials and microbes worked. “Cultivation of Shewanella oneidensis in conductive materials demonstrates that exoelectrogenic bacteria settle on the scaffold, while other bacteria, such as Escherichia coli, remain on the surface of the matrix,” microbiologist Professor Johannes Gescher explains. In addition, the team proved that electron flow increased with an increasing number of bacterial cells settling on the conductive, synthetic matrix. This biohybrid composite remained stable for several days and exhibited electrochemical activity, which confirms that the composite can efficiently conduct electrons produced by the bacteria to an electrode.

Such a system does not only have to be conductive, it also must be able to control the process. This was achieved in the experiment: To switch off the current, the researchers added an enzyme that cuts the DNA strands, as a result of which the composite is decomposed.

“As far as we know, such a complex, functional biohybrid material has now been described for the first time. Altogether, our results suggest that potential applications of such materials might even extend beyond microbial biosensors, bioreactors, and fuel cell systems,” Niemeyer emphasizes.

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Microsystem for faster, more sustainable industrial chemistry

The synthesis of plastic precursors, such as polymers, involves specialized catalysts. However, the traditional batch-based method of finding and screening the right ones for a given result consumes liters of solvent, generates large quantities of chemical waste, and is an expensive, time-consuming process involving multiple trials.

Ryan Hartman, professor of chemical and biomolecular engineering at the NYU Tandon School of Engineering, and his laboratory developed a lab-based “intelligent microsystem” employing machine learning, for modeling chemical reactions that shows promise for eliminating this costly process and minimizing environmental harm.

In their research, “Combining automated microfluidic experimentation with machine learning for efficient polymerization design,” published in Nature Machine Intelligence, the collaborators, including doctoral student Benjamin Rizkin, employed a custom-designed, rapidly prototyped microreactor in conjunction with automation and in situ infrared thermography to study exothermic (heat generating) polymerization — reactions that are notoriously difficult to control when limited experimental kinetic data are available. By pairing efficient microfluidic technology with machine learning algorithms to obtain high-fidelity datasets based on minimal iterations, they were able to reduce chemical waste by two orders of magnitude and catalytic discovery from weeks to hours.

Hartman explained that designing the microfluidic setup required the team to first estimate the thermodynamics of polymerization reactions, in this case involving a class of metallocene catalysts, widely used in industrial-scale polymerization of polyethylene and other thermoplastic polymers.

“We first developed an order-of-magnitude estimation of heat and mass transport,” said Hartman. “Knowledge of these quantities enabled us to design a microfluidic device that can screen the activity of catalysts and offer scalable mechanisms mimicking the intrinsic kinetics needed for industrial-scale processes.”

Hartman added that such a benchtop system could open the door to a range of other experimental data. “It could provide context for analyzing other properties of interest such as how stream mixing, dispersion, heat transfer, mass transfer, and the reaction kinetics influence polymer characteristics,” he explained.

Using a class of zirconocene-based polymer catalysts, the research team paired microfluidics — proven in research of other exothermic reactions — with an automated pump and infrared thermography to detect changes in reactivity based on exotherms (compounds that give off heat during their formation) resulting in efficient, high-speed experimentation to map the catalyst’s reaction space. Since the process was conducted in a small reactor, they were able to introduce the catalyst dissolved in liquid, eliminating the need for extreme conditions to induce catalysis.

“The fact is, most plastics are made using metallocene catalysts bound to silica particles, creating a heterogenous substrate that polymerizes monomers like propylene and ethylene,” said Hartman. “Recent advances in homogenous catalyst of dissolved metallocene allow milder reaction conditions.”

Hartman’s group previously demonstrated that artificial neural networks (ANN) can be used as a tool for modelling and understanding polymerization pathways. In the new research they applied ANNs to modeling the zirconocene-catalyzed exothermic polymerization. Using MATLAB and LabVIEW systems to control the reactions, interface with external devices, and generate advanced computational algorithms, the researchers generated a series of ANNs to model and optimize catalysis based on experimental results.

“Chemical companies typically use 100-milliliter to 10-liter reactors to screen hundreds of catalysts that in turn could be scaled up to manufacture plastics. Here we are using less than a milliliter, and by scaling down the footprint of lab experiments you scale down the facilities needed, so the whole footprint is reduced. Our work provides a useful tool for both scientific and technoeconomic analysis of complex catalytic polymerizations,” said Hartman.

Hartman and his lab’s discoveries open doors to new types of research, primarily involving the concept of automated, or “robotic” chemistry, increasing throughput, data fidelity, and the safe handling of highly exothermic polymerizations.

He explained that, in principle, the method could lead to more efficient design and more environmentally benign plastics, since screening catalysts and polymers faster allows the ability to more quickly tailor processes to more environmentally friendly polymers.

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3D Printing Industry

Albirght Silicone introduces 3D printing capabilities; WACKER launches new ACEO silicone 3D printing material

3D printing with silicone is a rather niche area, however, activity does appear to be heating up. The two companies in this news update both offer 3D printing solutions for users who want to access the benefits and material properties of silicones. Albright Silicone, a Massachusetts-based engineering company, has launched a new 3D printing silicone […]

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New kind of soft elastic material has medical and technological applications

Gel-like materials have a wide range of applications, especially in chemistry and medicine. However, their usefulness is sometimes limited by their inherent random and disordered nature. Researchers from the University of Tokyo’s Institute for Solid State Physics have found a way to produce a new kind of gel which overcomes this limitation. It is still malleable and adaptable like existing gels, but it has a more ordered structure, which can open up a new range of possible uses in various fields.

When you hear the word “gel,” you probably conjure up the image of something wobbly and viscous like some cosmetic substance or the inside of a memory-foam mattress. But in the world of scientific research, gels have a more specific definition. Strictly speaking, gels are three-dimensional networks of polymers — chains of molecules — with microscopic pores between these chemical strands. The nature and arrangement of these polymers give gels different functions leading to common applications, such as chemical filtration or drug delivery.

The creation of polymer network gels is difficult to control, so they are very disordered and contain many structural inconsistencies or defects. They are said to be heterogeneous, meaning their forms vary widely throughout their structures. However, Research Associate Xiang Li and colleagues have found a novel way to maintain a high level of order while fabricating polymer gels. The result is a homogeneous gel, one that is more consistent throughout its structure whilst still providing the benefits of a highly porous and malleable material.

“We demonstrated that it’s actually quite easy to synthesize an extremely homogeneous gel network,” said Li. “First, we tightly packed some star-shaped polymers together in a solvent and added some chemicals which, when activated, join these star polymers together. We activated the joining or ‘cross-linking’ chemicals in a controlled manner; this in turn led to a more ordered polymer gel network than one might ordinarily expect from this kind of process.”

The fabrication process, based on a concept known as bond percolation, is very effective at producing ordered gel networks — so much so that researchers feel it forces them to redefine what actually constitutes a gel. Previously a gel was assumed to contain disorder and defects, however these are no longer key properties. But all this work is not just for the sake of making something new; it has a strong purpose and it could lead to some interesting advancements.

“Ordered yet flexible gel networks could be used in applications like high-performance chemical filters, flexible sensors, mechanical actuators, controlled drug release and even ultraclear optical fibers,” explained Li. “We want to encourage others to build on our work here and find other ways to synthesize new polymer gels based on what we have started. Although our method was very specific, it lays the foundations for a more general experimental platform.”

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Curved nanochannels allow independent tuning of charge and spin currents

To increase the efficiency of microchips, 3D structures are now being investigated. However, spintronic components, which rely on electron spin rather than charge, are always flat. To investigate how to connect these to 3D electronics, University of Groningen physicist Dr. Kumar Sourav Das created curved spin transport channels. Together with his colleagues, he discovered that this new geometry makes it possible to independently tune charge and spin currents. The results were published online by the journal Nano Letters on 13 September 2019.

Das started with two main questions: how to tune spin current using geometry, and how to create spin transport in a 3D nanostructure. Electron spin is a quantum mechanical property, a magnetic moment that can be used to transfer or store information. Spin is already used in memory storage, and could also be used in logic circuits.

Curved architecture

‘So far, most spintronic devices have been based on a flat structure. We wanted to find out how the spin currents behave in a curved channel’, says Das. Using silicon oxide substrates with trenches created by an ion beam, designed at the HZDR in Dresden by Dr. Denys Makarov, Das grew aluminum nanochannels that crossed the trenches. In this curved architecture, the thickness of the aluminum varies at nanoscale dimensions, shorter than the spin relaxation length.

Das used different sized trenches and measured both spin resistance and charge currents. ‘What we discovered is that variations in the trench size affect spin and charge transport in the channel differently’, Das explains. ‘We were therefore able to independently tune both spin and charge currents based on the channel geometry.’

Novel functionalities

His colleague Dr. Carmine Ortix from Utrecht University created a theoretical model describing this phenomenon. ‘Our theory clearly demonstrates that it is possible to independently tune the spin and charge characteristics using the shape of the materials alone. This possibility overcomes the existing technological hurdles for the applicability of spintronics in modern electronics’, says Dr. Ortix. ‘Extending low-dimensional structures into the three-dimensional space can provide the means to modify conventional functionalities or even launch completely novel functionalities by suitably tailoring the shape of real materials.’

‘This discovery is important because it allows us to tune spintronic components to match both the spin current and the charge current of electronic circuits’, says Das. ‘It enables the efficient integration of spin injectors and detectors or spin transistors into modern 3D circuitry.’ This could help to create more energy-efficient electronics, as spintronics is an attractive way of creating low-power devices. ‘And we can now use our model to purpose-design channels.’

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Nanocatalyst makes heavy work of formic acid

Hydrogen occurs in nature as H2 molecules; however when deuterium isotopes — so called “heavy hydrogen” — are introduced, the result can be deuterium hydride (HD) or deuterium gas (D2). These compounds are useful starting materials in fine chemical production; however, the natural abundance of these gases is low and the techniques used for producing D2 are expensive and energy intensive. Researchers from Osaka University have now developed a catalyst that promotes selective production of D2 and HD from the inexpensive starting material formic acid in the presence of D2O. Their findings are published in Nature Communications.

Formic acid (FA) has low toxicity, high hydrogen content, and is also low-cost and non flammable, making it an attractive hydrogen storage material. Significant effort has therefore been devoted to optimizing the use of FA as a source of hydrogen. However, previously reported reactions to produce deuterium gases from FA have required the expensive deuterium form of FA as a starting material and high toxicity materials. In addition, the use of homogenous processes, where the catalyst and the reactants are the same phase, has made the recovery of the catalysts challenging and expensive on a large scale.

The researchers report a heterogeneously catalyzed process, in which the catalyst is a different phase to the reactants, using a palladium-based alloy nanocatalyst (PdAg). The catalyst is supported on a silica substrate modified with amine groups that promote the reaction. The amine groups were found to be central to the viability of the reaction and a correlation between the basicity of the amine groups used and the selectivity of the reaction was demonstrated.

“Heterogeneously catalyzed processes are advantageous as they reduce the need for challenging separations,” study lead author Kohsuke Mori explains. “Further advantages of our process are the cost-effective formic acid starting material and the control over the product gas we have demonstrated by tuning the amine groups on the catalyst surface. We also showed that the H/D exchange reaction that leads to the formation of the hydrogen isotope gases involves a quantum tunneling effect.”

Molecules that contain deuterium in place of hydrogen are extremely useful research tools in chemistry and life sciences owing to their distinct properties of deuterium nuclei compared with hydrogen equivalents.

“The demand for deuterated products continues to increase as their applications are developed and become more widespread; therefore, it is important to make the production of precursors more accessible,” study corresponding author Hiromi Yamashita explains. “Japan in particular relies heavily on imported materials, so we hope that our catalyst will lead to viable low-cost systems that will be able to satisfy the increasing global demand.”

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Make Your Own Wine Spill Art Over the Internet

Spilling wine is generally a bad thing; however, if you’re not the person who has to clean it up, such a faux pas does make interesting patterns. This was the thinking of marketing firm KPS3 as they developed the “Santa Maria Swirl Machine,” which swirls wine in a normally-unreasonable manner, then flings it onto paper to make artwork.

The Swirl Machine lets you produce your own wine art online using Raspberry Pi and Arduino. (📷: KPS3)

The process is live streamed using a rig with a Raspberry Pi 3B+ along with a Pi 4 and two cameras, and employs a third to take a photo of the art itself. An Arduino Micro is also used in the art creation process, where a piece of paper is first picked up out of a stack using a suction device, and moved into place with a linear actuator. A generous portion of wine is then poured into a glass inside the “spill chamber” where it’s spun at a high rate of speed until it’s pushed with quite a bit of force toward the paper. Wine then splatters onto it, creating a unique picture.

According to TechRepublic:

The website is a single-page React.js app stored in S3, served via CloudFront, with the platform running on a MySQL and Redis database, with a Node.js/Koa REST API server that communicates with an API worker that manages the queue and communicates with the machine through gRPC. A Lambda media worker is used for image processing, and Mux.com is used for live streaming the video captured on the Raspberry Pi 3B+.

Since everything is automated and viewable over the Internet, you don’t even have to be present to make this wine artwork; presumably someone else even cleans the spill chamber. Sign up here to give it a try yourself!

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Author: Jeremy S. Cook