Tag Archives: Middle Ages

Gold at the nanoscale in medieval textiles

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It takes a while (i.e., you have to read the abstract for the paper) to get to the nanoscale part of the story. In the meantime, here are the broad brushstrokes (as it were) from a group of researchers in Hungary, from an Oct. 11, 2017 American Chemical Society (ACS) news release (also on EurekAlert),

Gold has long been valued for its luxurious glitter and hue, and threads of the gleaming metal have graced clothing and tapestries for centuries. Determining how artisans accomplished these adornments in the distant past can help scientists restore, preserve and date artifacts, but solutions to these puzzles have been elusive. Now scientists, reporting in ACS’ journal Analytical Chemistry, have revealed that medieval artisans used a gilding technology that has endured for centuries.

Researchers can learn a lot about vanished cultures from objects left behind. But one detail that has escaped understanding has been the manufacturing method of gold-coated silver threads found in textiles from the Middle Ages. Four decades of intensive research yielded some clues, but the findings have been very limited. Study of the materials has been hindered by their extremely small size: A single metal thread is sometimes only as thick as a human hair, and the thickness of its gold coating is a hundredth of that. Tamás G. Weiszburg, Katalin Gherdán and colleagues set out to fill this gap.

Using a suite of lab techniques, the researchers examined medieval gilded silver threads, and silver and gold strips produced during and after the Middle Ages. The items come from European cultures spanning the 13th to 17th centuries. The researchers characterized the chemistry of the silver thread, its gold coating, the interactions between the two and the shape of metal strips’ edges. To characterize the threads and strips, the researchers combined high-resolution scanning electron microscopy, electron back-scattered diffraction with energy-dispersive electron probe microanalysis and other analytical methods. Though previous studies indicated that these tiny objects were manufactured by a mercury-based method in fashion at that time, the new results suggest that the threads were gilded exclusively by using an ancient method that survived for a millennium. The goldsmiths simply heated and hammered the silver sheets and the gold foil together, and then cut them into strips. It was also possible to determine whether scissor- or knife-like tools were used for cutting. The results also show that this process was used widely in the region well into the 17th century.

The authors acknowledge funding from the European Social Fund.

Here’s an image of medieval bling,

Caption: A new study unravels how medieval artisans embellished textiles with gold. Credit: The American Chemical Society

Finally, here’s the abstract with the information about the nanoscale elements (link to paper follows abstract),

Although gilt silver threads were widely used for decorating historical textiles, their manufacturing techniques have been elusive for centuries. Contemporary written sources give only limited, sometimes ambiguous information, and detailed cross-sectional study of the microscale soft noble metal objects has been hindered by sample preparation. In this work, to give a thorough characterization of historical gilt silver threads, nano- and microscale textural, chemical, and structural data on cross sections, prepared by focused ion beam milling, were collected, using various electron-optical methods (high-resolution scanning electron microscopy (SEM), wavelength-dispersive electron probe microanalysis (EPMA), electron backscattered diffraction (EBSD) combined with energy-dispersive electron probe microanalysis (EDX), transmission electron microscopy (TEM) combined with EDX, and micro-Raman spectroscopy. The thickness of the gold coating varied between 70–400 nm [emphasis mine]. Data reveal nano- and microscale metallurgy-related, gilding-related and corrosion-related inhomogeneities in the silver base. These inhomogeneities account for the limitations of surface analysis when tracking gilding methods of historical metal threads, and explain why chemical information has to be connected to 3D texture on submicrometre scale. The geometry and chemical composition (lack of mercury, copper) of the gold/silver interface prove that the ancient gilding technology was diffusion bonding. The observed differences in the copper content of the silver base of the different thread types suggest intentional technological choice. Among the examined textiles of different ages (13th–17th centuries) and provenances narrow technological variation has been found.

Here’s a link to the paper,

Medieval Gilding Technology of Historical Metal Threads Revealed by Electron Optical and Micro-Raman Spectroscopic Study of Focused Ion Beam-Milled Cross Sections by Tamás G. Weiszburg, Katalin Gherdán, Kitti Ratter, Norbert Zajzon, Zsolt Bendő, György Radnóczi, Ágnes Takács, Tamás Váczi, Gábor Varga and György Szakmány. Anal. Chem., Article ASAP DOI: 10.1021/acs.analchem.7b01917 Publication Date (Web): September 19, 2017

Copyright © 2017 American Chemical Society

This paper is behind a paywall.

One final comment, if you read the abstract, you’ll see how many technologies the researchers needed to use to examine the textiles. How did medieval artisans create nanoscale and microscale gilding when they couldn’t see it? I realize there are now some optical microscopes that can provide a view of the nanoscale but presumably those artisans of the Middle Ages did not have access to that kind of equipment. So, how did they create those textiles with the technology of the day?

Revisiting the scientific past for new breakthroughs

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A March 2, 2017 article on phys.org features a thought-provoking (and, for some of us, confirming) take on scientific progress  (Note: Links have been removed),

The idea that science isn’t a process of constant progress might make some modern scientists feel a bit twitchy. Surely we know more now than we did 100 years ago? We’ve sequenced the genome, explored space and considerably lengthened the average human lifespan. We’ve invented aircraft, computers and nuclear energy. We’ve developed theories of relativity and quantum mechanics to explain how the universe works.

However, treating the history of science as a linear story of progression doesn’t reflect wholly how ideas emerge and are adapted, forgotten, rediscovered or ignored. While we are happy with the notion that the arts can return to old ideas, for example in neoclassicism, this idea is not commonly recognised in science. Is this constraint really present in principle? Or is it more a comment on received practice or, worse, on the general ignorance of the scientific community of its own intellectual history?

For one thing, not all lines of scientific enquiry are pursued to conclusion. For example, a few years ago, historian of science Hasok Chang undertook a careful examination of notebooks from scientists working in the 19th century. He unearthed notes from experiments in electrochemistry whose results received no explanation at the time. After repeating the experiments himself, Chang showed the results still don’t have a full explanation today. These research programmes had not been completed, simply put to one side and forgotten.

A March 1, 2017 essay by Giles Gasper (Durham University), Hannah Smithson (University of Oxford) and Tom Mcleish (Durham University) for The Conversation, which originated the article, expands on the theme (Note: Links have been removed),

… looping back into forgotten scientific history might also provide an alternative, regenerative way of thinking that doesn’t rely on what has come immediately before it.

Collaborating with an international team of colleagues, we have taken this hypothesis further by bringing scientists into close contact with scientific treatises from the early 13th century. The treatises were composed by the English polymath Robert Grosseteste – who later became Bishop of Lincoln – between 1195 and 1230. They cover a wide range of topics we would recognise as key to modern physics, including sound, light, colour, comets, the planets, the origin of the cosmos and more.

We have worked with paleographers (handwriting experts) and Latinists to decipher Grosseteste’s manuscripts, and with philosophers, theologians, historians and scientists to provide intellectual interpretation and context to his work. As a result, we’ve discovered that scientific and mathematical minds today still resonate with Grosseteste’s deeply physical and structured thinking.

Our first intuition and hope was that the scientists might bring a new analytic perspective to these very technical texts. And so it proved: the deep mathematical structure of a small treatise on colour, the De colore, was shown to describe what we would now call a three-dimensional abstract co-ordinate space for colour.

But more was true. During the examination of each treatise, at some point one of the group would say: “Did anyone ever try doing …?” or “What would happen if we followed through with this calculation, supposing he meant …”. Responding to this thinker from eight centuries ago has, to our delight and surprise, inspired new scientific work of a rather fresh cut. It isn’t connected in a linear way to current research programmes, but sheds light on them from new directions.

I encourage you to read the essay in its entirety.

Magic nano ink

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Colour changes © Nature Communications 2017 / MPI [Max Planck Institute] for Intelligent Systems

A March 1, 2017 news item on Nanowerk helps to explain the image seen above (Note: A link has been removed),

Plasmonic printing produces resolutions several times greater than conventional printing methods. In plasmonic printing, colours are formed on the surfaces of tiny metallic particles when light excites their electrons to oscillate. Researchers at the Max Planck Institute for Intelligent Systems in Stuttgart have now shown how the colours of such metallic particles can be altered with hydrogen (Nature Communications, “Dynamic plasmonic colour display”).

The technique could open the way for animating ultra-high-resolution images and for developing extremely sharp displays. At the same time, it provides new approaches for encrypting information and detecting counterfeits.

A March 1, 2017 Max Planck Institute press release, which originated the news item, provides more  history and more detail about the research,

Glass artisans in medieval times exploited the effect long before it was even known. They coloured the magnificent windows of gothic cathedrals with nanoparticles of gold, which glowed red in the light. It was not until the middle of the 20th century that the underlying physical phenomenon was given a name: plasmons. These collective oscillations of free electrons are stimulated by the absorption of incident electromagnetic radiation. The smaller the metallic particles, the shorter the wavelength of the absorbed radiation. In some cases, the resonance frequency, i.e., the absorption maximum, falls within the visible light spectrum. The unabsorbed part of the spectrum is then scattered or reflected, creating an impression of colour. The metallic particles, which usually appear silvery, copper-coloured or golden, then take on entirely new colours.

A resolution of 100,000 dots per inch

Researchers are also taking advantage of the effect to develop plasmonic printing, in which tailor-made square metal particles are arranged in specific patterns on a substrate. The edge length of the particles is in the order of less than 100 nanometres (100 billionths of a metre). This allows a resolution of 100,000 dots per inch – several times greater than what today’s printers and displays can achieve.

For metallic particles measuring several 100 nanometres across, the resonance frequency of the plasmons lies within the visible light spectrum. When white light falls on such particles, they appear in a specific colour, for example red or blue. The colour of the metal in question is determined by the size of the particles and their distance from each other. These adjustment parameters therefore serve the same purpose in plasmonic printing as the palette of colours in painting.

The trick with the chemical reaction

The Smart Nanoplasmonics Research Group at the Max Planck Institute for Intelligent Systems in Stuttgart also makes use of this colour variability. They are currently working on making dynamic plasmonic printing. They have now presented an approach that allows them to alter the colours of the pixels predictably – even after an image has been printed. “The trick is to use magnesium. It can undergo a reversible chemical reaction in which the metallic character of the element is lost,” explains Laura Na Liu, who leads the Stuttgart research group. “Magnesium can absorb up to 7.6% of hydrogen by weight to form magnesium hydride, or MgH2”, Liu continues. The researchers coat the magnesium with palladium, which acts as a catalyst in the reaction.

During the continuous transition of metallic magnesium into non-metallic MgH2, the colour of some of the pixels changes several times. The colour change and the speed of the rate at which it proceeds follow a clear pattern. This is determined both by the size of and the distance between the individual magnesium particles as well as by the amount of hydrogen present.

In the case of total hydrogen saturation, the colour disappears completely, and the pixels reflect all the white light that falls on them. This is because the magnesium is no longer present in metallic form but only as MgH2. Hence, there are also no free metal electrons that can be made to oscillate.

Minerva’s vanishing act

The scientists demonstrated the effect of such dynamic colour behaviour on a plasmonic print of Minerva, the Roman goddess of wisdom, which also bore the logo of the Max Planck Society. They chose the size of their magnesium particles so that Minerva’s hair first appeared reddish, the head covering yellow, the feather crest red and the laurel wreath and outline of her face blue. They then washed the micro-print with hydrogen. A time-lapse film shows how the individual colours change. Yellow turns red, red turns blue, and blue turns white. After a few minutes all the colours disappear, revealing a white surface instead of Minerva.

The scientists also showed that this process is reversible by replacing the hydrogen stream with a stream of oxygen. The oxygen reacts with the hydrogen in the magnesium hydride to form water, so that the magnesium particles become metallic again. The pixels then change back in reverse order, and in the end Minerva appears in her original colours.

In a similar manner the researchers first made the micro image of a famous Van Gogh painting disappear and then reappear. They also produced complex animations that give the impression of fireworks.

The principle of a new encryption technique

Laura Na Liu can imagine using this principle in a new encryption technology. To demonstrate this, the group formed various letters with magnesium pixels. The addition of hydrogen then caused some letters to disappear over time, like the image of Minerva. “As for the rest of the letters, a thin oxide layer formed on the magnesium particles after exposing the sample in air for a short time before palladium deposition,” Liu explains. This layer is impermeable to hydrogen. The magnesium lying under the oxide layer therefore remains metallic − and visible − because light is able to excite the plasmons in the magnesium.

In this way it is possible to conceal a message, for example by mixing real and nonsensical information. Only the intended recipient is able to make the nonsensical information disappear and filter out the real message. For example, after decoding the message “Hartford” with hydrogen, only the words “art or” would remain visible. To make it more difficult to crack such encrypted messages, the group is currently working on a process that would require a precisely adjusted hydrogen concentration for deciphering.

Liu believes that the technology could also be used some day in the fight against counterfeiting. “For example, plasmonic security features could be printed on banknotes or pharmaceutical packs, which could later be checked or read only under specific conditions unknown to counterfeiters.”

It doesn’t necessarily have to be hydrogen

Laura Na Liu knows that the use of hydrogen makes some applications difficult and impractical for everyday use such as in mobile displays. “We see our work as a starting shot for a new principle: the use of chemical reactions for dynamic printing,” the Stuttgart physicist says. It is certainly conceivable that the research will soon lead to the discovery of chemical reactions for colour changes other than the phase transition between magnesium and magnesium dihydride, for example, reactions that require no gaseous reactants.

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

Dynamic plasmonic colour display by Xiaoyang Duan, Simon Kamin, & Na Liu. Nature Communications 8, Article number: 14606 (2017) doi:10.1038/ncomms14606 Published online: 24 February 2017

This paper is open access.

Making lead look like gold (so to speak)

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Apparently you can make lead ‘look’ like gold if you can get it to reflect light in the same way. From a Feb. 28, 2017 news item on Nanowerk (Note: A link has been removed),

Since the Middle Ages, alchemists have sought to transmute elements, the most famous example being the long quest to turn lead into gold. Transmutation has been realized in modern times, but on a minute scale using a massive particle accelerator.

Now, theorists at Princeton University have proposed a different approach to this ancient ambition — just make one material behave like another. A computational theory published Feb. 24 [2017] in the journal Physical Review Letters (“How to Make Distinct Dynamical Systems Appear Spectrally Identical”) demonstrates that any two systems can be made to look alike, even if just for the smallest fraction of a second.

In this context, for two objects to “look” like each other, they need to reflect light in the same way. The Princeton researchers’ method involves using light to make non-permanent changes to a substance’s molecules so that they mimic the reflective properties of another substance’s molecules. This ability could have implications for optical computing, a type of computing in which electrons are replaced by photons that could greatly enhance processing power but has proven extremely difficult to engineer. It also could be applied to molecular detection and experiments in which expensive samples could be replaced by cheaper alternatives.

A Feb. 28, 2017 Princeton University news release (also on EurekAlert) by Tien Nguyen, which originated the news item, expands on the theme (Note: Links have been removed),

“It was a big shock for us that such a general statement as ‘any two objects can be made to look alike’ could be made,” said co-author Denys Bondar, an associate research scholar in the laboratory of co-author Herschel Rabitz, Princeton’s Charles Phelps Smyth ’16 *17 Professor of Chemistry.

The Princeton researchers posited that they could control the light that bounces off a molecule or any substance by controlling the light shone on it, which would allow them to alter how it looks. This type of manipulation requires a powerful light source such as an ultrafast laser and would last for only a femtosecond, or one quadrillionth of a second. Unlike normal light sources, this ultrafast laser pulse is strong enough to interact with molecules and distort their electron cloud while not actually changing their identity.

“The light emitted by a molecule depends on the shape of its electron cloud, which can be sculptured by modern lasers,” Bondar said. Using advanced computational theory, the research team developed a method called “spectral dynamic mimicry” that allowed them to calculate the laser pulse shape, which includes timing and wavelength, to produce any desired spectral output. In other words, making any two systems look alike.

Conversely, this spectral control could also be used to make two systems look as different from one another as possible. This differentiation, the researchers suggested, could prove valuable for applications of molecular detections such as identifying toxic versus safe chemicals.

Shaul Mukamel, a chemistry professor at the University of California-Irvine, said that the Princeton research is a step forward in an important and active research field called coherent control, in which light can be manipulated to control behavior at the molecular level. Mukamel, who has collaborated with the Rabitz lab but was not involved in the current work, said that the Rabitz group has had a prominent role in this field for decades, advancing technology such as quantum computing and using light to drive artificial chemical reactivity.

“It’s a very general and nice application of coherent control,” Mukamel said. “It demonstrates that you can, by shaping the optical paths, bring the molecules to do things that you want beforehand — it could potentially be very significant.”

Since the Middle Ages, alchemists have sought to transmute elements, the most famous example being the long quest to turn lead into gold. Now, theorists at Princeton University have proposed a different approach to this ancient ambition — just make one material behave like another, even if just for the smallest fraction of a second. The researchers are, left to right, Renan Cabrera, an associate research scholar in chemistry; Herschel Rabitz, Princeton’s Charles Phelps Smyth ’16 *17 Professor of Chemistry; associate research scholar in chemistry Denys Bondar; and graduate student Andre Campos. (Photo by C. Todd Reichart, Department of Chemistry)

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

How to Make Distinct Dynamical Systems Appear Spectrally Identical by
Andre G. Campos, Denys I. Bondar, Renan Cabrera, and Herschel A. Rabitz.
Phys. Rev. Lett. 118, 083201 (Vol. 118, Iss. 8) DOI:https://doi.org/10.1103/PhysRevLett.118.083201 Published 24 February 2017

© 2017 American Physical Society

This paper is behind a paywall.

Medieval chain mail inspires physicists

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A Feb. 9, 2017 news item on Nanowerk describes new research at the Karlsruhe Institute of Technology (KIT), which takes its inspiration from medieval chain mail,

The Middle Ages certainly were far from being science-friendly: Whoever looked for new findings off the beaten track faced the threat of being burned at the stake. Hence, the contribution of this era to technical progress is deemed to be rather small. Scientists of Karlsruhe Institute of Technology (KIT), however, were inspired by medieval mail armor when producing a new metamaterial with novel properties. They succeeded in reversing the Hall coefficient of a material.

The Hall effect is the occurrence of a transverse electric voltage across an electric conductor passed by current flow, if this conductor is located in a magnetic field. This effect is a basic phenomenon of physics and allows to measure [sic] the strength of magnetic fields. It is the basis of magnetic speed sensors in cars or compasses in smartphones. Apart from measuring magnetic fields, the Hall effect can also be used to characterize metals and semiconductors and in particular to determine charge carrier density of the material. The sign of the measured Hall voltage allows conclusions to be drawn as to whether charge carriers in the semiconductor element carry positive or negative charge.

The ring structure of the metamaterial was inspired by mail armor of medieval knights. (Photo: KIT)

A Feb. ?, 2017 KIT press release (also on EurekAlert), which originated the news item, expands on the theme,

Mathematicians already predicted theoretically that it is possible to reverse the Hall coefficient of a material (such as gold or silicon), i.e. to reverse its sign. This was expected to be achieved by a three-dimensional ring structure resembling medieval mail armor. How-ever, this was considered difficult, as the ring mesh of millionths of a meter in size would have to be composed of three different components.

 

Die Ringstruktur des Metamaterials wurde von Kettenhemden aus der Ritterzeit inspiriert. (Bild: KIT)
The ring mesh of millionths of a meter in size. (Photo: KIT)

Christian Kern, Muamer Kadic, and Martin Wegener of KIT’s Institute of Applied Physics now found that a single basic material is sufficient, provided that the ring structure chosen follows a certain geometric arrangement. First, they produced polymer scaffolds with a highest-resolution 3D printer. Then, they coated these scaffolds with semiconducting zinc oxide.

The result of the experiment: The scientists can produce meta-materials with a positive coefficient, even though their components have negative coefficients. This sounds a bit like the philosopher’s stone, the formula, by means of which medieval alchemists tried to convert one substance into another. But here, no conversion takes place. “The charge carriers in the metamaterial remain negatively charged electrons,” Christian Kern explains. “Hall measurements only make them appear positively charged, as the structure forces them to take detours.”

Kern admits that this discovery so far is of no practical use. There are sufficient solids with both negative and positive Hall coefficients. But Kern wants to continue research. The next step will be the production of anisotropic structures with a Hall voltage in the direction of the magnetic field. Normally, Hall voltage is directed vertically to current and magnetic fields. Such unconventional materials might be applied in novel sensors for the direct measurement of magnetic field eddies.

The researchers do not seem to have published a paper about this work.