Tag Archives: gold

Deriving gold from electronic waste

Caption: The gold nugget obtained from computer motherboards in three parts. The largest of these parts is around five millimetres wide. Credit: (Photograph: ETH Zurich / Alan Kovacevic)

A March 1, 2024 ETH Zurich press release (also on EurekAlert but published February 29, 2024) by Fabio Bergamin describes research into reclaiming gold from electronic waste, Note: A link has been removed.

In brief

  • Protein fibril sponges made by ETH Zurich researchers are hugely effective at recovering gold from electronic waste.
  • From 20 old computer motherboards, the researchers retrieved a 22-​carat gold nugget weighing 450 milligrams.
  • Because the method utilises various waste and industry byproducts, it is not only sustainable but cost effective as well.

Transforming base materials into gold was one of the elusive goals of the alchemists of yore. Now Professor Raffaele Mezzenga from the Department of Health Sciences and Technology at ETH Zurich has accomplished something in that vein. He has not of course transformed another chemical element into gold, as the alchemists sought to do. But he has managed to recover gold from electronic waste using a byproduct of the cheesemaking process.

Electronic waste contains a variety of valuable metals, including copper, cobalt, and even significant amounts of gold. Recovering this gold from disused smartphones and computers is an attractive proposition in view of the rising demand for the precious metal. However, the recovery methods devised to date are energy-​intensive and often require the use of highly toxic chemicals. Now, a group led by ETH Professor Mezzenga has come up with a very efficient, cost-​effective, and above all far more sustainable method: with a sponge made from a protein matrix, the researchers have successfully extracted gold from electronic waste.

Selective gold adsorption

To manufacture the sponge, Mohammad Peydayesh, a senior scientist in Mezzenga’s Group, and his colleagues denatured whey proteins under acidic conditions and high temperatures, so that they aggregated into protein nanofibrils in a gel. The scientists then dried the gel, creating a sponge out of these protein fibrils.

To recover gold in the laboratory experiment, the team salvaged the electronic motherboards from 20 old computer motherboards and extracted the metal parts. They dissolved these parts in an acid bath so as to ionise the metals.

When they placed the protein fibre sponge in the metal ion solution, the gold ions adhered to the protein fibres. Other metal ions can also adhere to the fibres, but gold ions do so much more efficiently. The researchers demonstrated this in their paper, which they have published in the journal Advanced Materials.

As the next step, the researchers heated the sponge. This reduced the gold ions into flakes, which the scientists subsequently melted down into a gold nugget. In this way, they obtained a nugget of around 450 milligrams out of the 20 computer motherboards. The nugget was 91 percent gold (the remainder being copper), which corresponds to 22 carats.

Economically viable

The new technology is commercially viable, as Mezzenga’s calculations show: procurement costs for the source materials added to the energy costs for the entire process are 50 times lower than the value of the gold that can be recovered.

Next, the researchers want to develop the technology to ready it for the market. Although electronic waste is the most promising starting product from which they want to extract gold, there are other possible sources. These include industrial waste from microchip manufacturing or from gold-​plating processes. In addition, the scientists plan to investigate whether they can manufacture the protein fibril sponges out of other protein-​rich byproducts or waste products from the food industry.

“The fact I love the most is that we’re using a food industry byproduct to obtain gold from electronic waste,” Mezzenga says. In a very real sense, he observes, the method transforms two waste products into gold. “You can’t get much more sustainable than that!”

If you have a problem accessing either of the two previously provided links to the press release, you can try this February 29, 2024 news item on ScienceDaily.

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

Gold Recovery from E-Waste by Food-Waste Amyloid Aerogels by Mohammad Peydayesh, Enrico Boschi, Felix Donat, Raffaele Mezzenga. DOI: https://doi.org/10.1002/adma.202310642 First published online: 23 January 2024

This paper is open access.

Gold glue?

If you’re hoping for gold flecks in your glue, this is not going to satisfy you, given that it’s all at the nanoscale. An August 7, 2019 news item on Nanowerk briefly describes this gold glue (Note: A link has been removed),

It has long been known that gold can be used to do things that philosophers have never even dreamed of. The Institute of Nuclear Physics of the Polish Academy of Sciences in Cracow has confirmed the existence of ‘gold glue’: bonds involving gold atoms, capable of permanently bonding protein rings. Skilfully used by an international team of scientists, the bonds have made it possible to construct molecular nanocages with a structure so far unparalleled in nature or even in mathematics (Nature, “An ultra-stable gold-coordinated protein cage displaying reversible assembly”).

Caption: The ‘impossible’ sphere, i.e. a molecular nanocage of 24 protein rings, each of which has an 11-sided structure. The rings are connected by bonds with the participation of gold atoms, here marked in yellow. Depending on their position in the structure, not all gold atoms have to be used to attach adjacent proteins (an unused gold atom is marked in red). Credit: Source: UJ, IFJ PAN

An August 6, 2019 Polish Academy of Sciences press release (also on EurekAlert but published August 7, 2019), which originated the news item, expands on the theme,

The world of science has been interested in molecular cages for years. Not without reason. Chemical molecules, including those that would under normal conditions enter into chemical reactions, can be enclosed within their empty interiors. The particles of the enclosed compound, separated by the walls of the cage from the environment, have nothing to bond with. These cages can be therefore be used, for example, to transport drugs safely into a cancer cell, only releasing the drug when they are inside it.

Molecular cages are polyhedra made up of smaller ‘bricks’, usually protein molecules. The bricks can’t be of any shape. For example, if we wanted to build a molecular polyhedron using only objects with the outline of an equilateral triangle, geometry would limit us to only three solid figures: a tetrahedron, an octahedron or an icosahedron. So far, there have been no other structural possibilities.

“Fortunately, Platonic idealism is not a dogma of the physical world. If you accept certain inaccuracies in the solid figure being constructed, you can create structures with shapes that are not found in nature, what’s more, with very interesting properties,” says Dr. Tomasz Wrobel from the Cracow Institute of Nuclear Physics of the Polish Academy of Sciences (IFJ PAN).

Dr. Wrobel is one of the members of an international team of researchers who have recently carried out the ‘impossible’: they built a cage similar in shape to a sphere out of eleven-walled proteins. The main authors of this spectacular success are scientists from the group of Prof. Jonathan Heddle from the Malopolska Biotechnology Centre of the Jagiellonian University in Cracow and the Japanese RIKEN Institute in Wako. The work described in Nature magazine took place with the participation of researchers from universities in Osaka and Tsukuba (Japan), Durham (Great Britain), Waterloo (Canada) and other research centres.

Each of the walls of the new nanocages was formed by a protein ring from which eleven cysteine molecules stuck out at regular intervals. It was to the sulphur atom found in each cysteine molecule that the ‘glue’, i.e. the gold atom, was planned to be attached. In the appropriate conditions, it could bind with one more sulphur atom, in the cysteine of a next ring. In this way a permanent chemical bond would be formed between the two rings. But would the gold atom under these conditions really be able to form a bond between the rings?

“In the Spectroscopic Imaging Laboratory of IFJ PAS we used Raman spectroscopy and X-ray photoelectron spectroscopy to show that in the samples provided to us with the test nanocages, the gold really did form bonds with sulphur atoms in cysteines. In other words, in a difficult, direct measurement, we proved that gold ‘glue’ for bonding protein rings in cages really does exist,” explains Dr. Wrobel.

Each gold atom can be treated as a stand-alone clip that makes it possible to attach another ring. The road to the ‘impossible’ begins when we realize that we don’t always have to use all of the clips! So, although all the rings of the new nanocages are physically the same, depending on their place in the structure they connect with their neighbours with a different number of gold atoms, and thus function as polygons with different numbers of vertices. 24 nanocage walls presented by the researchers were held together by 120 gold atoms. The outer diameter of the cages was 22 nanometres and the inner diameter was 16 nm.

Using gold atoms as a binder for nanocages is also important due to its possible applications. In earlier molecular structures, proteins were glued together using many weak chemical bonds. The complexity of the bonds and their similarity to the bonds responsible for the existence of the protein rings themselves did not allow for precise control over the decomposition of the cages. This is not the case in the new structures. On the one hand, gold-bonded nanocages are chemically and thermally stable (for example, they withstand hours of boiling in water). On the other hand, however, gold bonds are sensitive to an increase in acidity. By its increase, the nanocage can be decomposed in a controlled way and the contents can be released into the environment. Since the acidity within cells is greater than outside them, gold-bonded nanocages are ideal for biomedical applications.

The ‘impossible’ nanocage is the presentation of a qualitatively new approach to the construction of molecular cages, with gold atoms in the role of loose clips. The demonstrated flexibility of the gold bonds will make it possible in the future to create nanocages with sizes and features precisely tailored to specific needs.

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

An ultra-stable gold-coordinated protein cage displaying reversible assembly by Ali D. Malay, Naoyuki Miyazaki, Artur Biela, Soumyananda Chakraborti, Karolina Majsterkiewicz, Izabela Stupka, Craig S. Kaplan, Agnieszka Kowalczyk, Bernard M. A. G. Piette, Georg K. A. Hochberg, Di Wu, Tomasz P. Wrobel, Adam Fineberg, Manish S. Kushwah, Mitja Kelemen, Primož Vavpetič, Primož Pelicon, Philipp Kukura, Justin L. P. Benesch, Kenji Iwasaki & Jonathan G. Heddle Nature volume 569, pages438–442 (2019) Issue Date: 16 May 2019 DOI: https://doi.org/10.1038/s41586-019-1185-4 Published online: 08 May 2019

This paper is behind a paywall.

Gold sheets that are two atoms thick

The gold sheets in question are effectively 2D. I’m surprised they haven’t named them ‘goldene’ as everything else that’s 2D seems to have an ‘ene’ suffix (e.g. graphene, germanene, tellurene).

Of course, these gold sheets are not composed of single atoms but of two according to an August 6, 2019 news item on Nanowerk,

Scientists at the University of Leeds [UK] have created a new form of gold which is just two atoms thick – the thinnest unsupported gold ever created.

The researchers measured the thickness of the gold to be 0.47 nanometres – that is one million times thinner than a human finger nail. The material is regarded as 2D because it comprises just two layers of atoms sitting on top of one another. All atoms are surface atoms – there are no ‘bulk’ atoms hidden beneath the surface.

Caption: Image shows gold nanosheets that are just two atoms thick Credit: University of Leeds

I’m pretty sure they’ve added colour to those images and not just in the background; they’ve likely added a gold colour to the gold.

An August 6, 2019 University of Leeds press release (also on EurekAlert), which originated the news item, gives some insight into the scientists’ ambitions and some technical details about the work,

The material could have wide-scale applications in the medical device and electronics industries – and also as a catalyst to speed up chemical reactions in a range of industrial processes.

Laboratory tests show that the ultra-thin gold is 10 times more efficient as a catalytic substrate than the currently used gold nanoparticles, which are 3D materials with the majority of atoms residing in the bulk rather than at the surface.

Scientists believe the new material could also form the basis of artificial enzymes that could be applied in rapid, point-of-care medical diagnostic tests and in water purification systems.

The announcement that the ultra-thin metal had been successfully synthesised was made in the journal Advanced Science.

The lead author of the paper, Dr Sunjie Ye, from Leeds’ Molecular and Nanoscale Physics Group and the Leeds Institute of Medical Research, said: “This work amounts to a landmark achievement.

“Not only does it open up the possibility that gold can be used more efficiently in existing technologies, it is providing a route which would allow material scientists to develop other 2D metals.

“This method could innovate nanomaterial manufacturing.”

The research team are looking to work with industry on ways of scaling-up the process.

Synthesising the gold nanosheet takes place in an aqueous solution and starts with chloroauric acid, an inorganic substance that contains gold. It is reduced to its metallic form in the presence of a ‘confinement agent’ – a chemical that encourages the gold to form as a sheet, just two atoms thick.

Because of the gold’s nanoscale dimensions, it appears green in water – and given its shape, the researchers describe it as gold nanoseaweed.

Images taken from an electron microscope reveal the way the gold atoms have formed into a highly organised lattice. Other images show gold nanoseaweed that has been artificially coloured. The images are available for download: https://drive.google.com/drive/folders/

Professor Stephen Evans, head of the Leeds’ Molecular and Nanoscale Research Group who supervised the research, said the considerable gains that could be achieved from using these ultra-thin gold sheets are down to their high surface-area to volume ratio.

He said: “Gold is a highly effective catalyst. Because the nanosheets are so thin, just about every gold atom plays a part in the catalysis. It means the process is highly efficient.”

Standard benchmark tests revealed that gold nanoscale sheets were ten times more efficient than the gold nanoparticles conventionally used in industry.

Professor Evans said: “Our data suggests that industry could get the same effect from using a smaller amount of gold, and this has economic advantages when you are talking about a precious metal.”

Similar benchmark tests revealed that the gold sheets could act as highly effective artificial enzymes.

The flakes are also flexible, meaning they could form the basis of electronic components for bendable screens, electronic inks and transparent conducting displays.

Professor Evans thinks there will inevitably be comparisons made between the 2D gold and the very first 2D material ever created – graphene, which was fabricated at the University of Manchester in 2004.

He said: “The translation of any new material into working products can take a long time and you can’t force it to do everything you might like to. With graphene, people have thought that it could be good for electronics or for transparent coatings – or as carbon nanotubes that could make an elevator to take us into space because of its super strength.

“I think with 2D gold we have got some very definite ideas about where it could be used, particularly in catalytic reactions and enzymatic reactions. We know it will be more effective than existing technologies – so we have something that we believe people will be interested in developing with us.”

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

Sub‐Nanometer Thick Gold Nanosheets as Highly Efficient Catalysts by Sunjie Ye, Andy P. Brown, Ashley C. Stammers, Neil H. Thomson, Jin Wen, Lucien Roach, Richard J. Bushby, Patricia Louise Coletta, Kevin Critchley, Simon D. Connell, Alexander F. Markham, Rik Brydson, Stephen D. Evans. Advnaced Science https://doi.org/10.1002/advs.201900911 First published: 06 August 2019

This paper is open access.

Unusual appetite for gold

This bacterium (bacteria being the plural) loves gold, which is lucky for anyone trying to develop artificial photosynthesis.From an October 9, 2018 news item on ScienceDaily,

A bacterium named Moorella thermoacetica won’t work for free. But UC Berkeley [University of California at Berkeley] researchers have figured out it has an appetite for gold. And in exchange for this special treat, the bacterium has revealed a more efficient path to producing solar fuels through artificial photosynthesis.

An October 5, 2018 UC Berkeley news release by Theresa Duque (also on EurekAlert but published on October 9, 2018), which originated the news item, expands on the theme,

M. thermoacetica first made its debut as the first non-photosensitive bacterium to carry out artificial photosynthesis (link is external) in a study led by Peidong Yang, a professor in UC Berkeley’s College of Chemistry. By attaching light-absorbing nanoparticles made of cadmium sulfide (CdS) to the bacterial membrane exterior, the researchers turned M. thermoacetica into a tiny photosynthesis machine, converting sunlight and carbon dioxide into useful chemicals.

Now Yang and his team of researchers have found a better way to entice this CO2-hungry bacterium into being even more productive. By placing light-absorbing gold nanoclusters inside the bacterium, they have created a biohybrid system that produces a higher yield of chemical products than previously demonstrated. The research, funded by the National Institutes of Health, was published on Oct. 1 in Nature Nanotechnology (link is external).

For the first hybrid model, M. thermoacetica-CdS, the researchers chose cadmium sulfide as the semiconductor for its ability to absorb visible light. But because cadmium sulfide is toxic to bacteria, the nanoparticles had to be attached to the cell membrane “extracellularly,” or outside the M. thermoacetica-CdS system. Sunlight excites each cadmium-sulfide nanoparticle into generating a charged particle known as an electron. As these light-generated electrons travel through the bacterium, they interact with multiple enzymes in a process known as “CO2 reduction,” triggering a cascade of reactions that eventually turns CO2 into acetate, a valuable chemical for making solar fuels.

But within the extracellular model, the electrons end up interacting with other chemicals that have no part in turning CO2 into acetate. And as a result, some electrons are lost and never reach the enzymes. So to improve what’s known as “quantum efficiency,” or the bacterium’s ability to produce acetate each time it gains an electron, the researchers found another semiconductor: nanoclusters made of 22 gold atoms (Au22), a material that M. thermoacetica took a surprising shine to.

A single nanocluster of 22 gold atoms

Figure: A single nanocluster of 22 gold atoms – Au22 – is only 1 nanometer in diameter, allowing it to easily slip through the bacterial cell wall.

“We selected Au22 because it’s ideal for absorbing visible light and has the potential for driving the CO2 reduction process, but we weren’t sure whether it would be compatible with the bacteria,” Yang said. “When we inspected them under the microscope, we discovered that the bacteria were loaded with these Au22 clusters – and were still happily alive.”

Imaging of the M. thermoacetica-Au22 system was done at UC Berkeley’s Molecular Imaging Center (link is external).

The researchers also selected Au22 ­– dubbed by the researchers as “magic” gold nanoclusters – for its ultrasmall size: A single Au22nanocluster is only 1 nanometer in diameter, allowing each nanocluster to easily slip through the bacterial cell wall.

“By feeding bacteria with Au22 nanoclusters, we’ve effectively streamlined the electron transfer process for the CO2 reduction pathway inside the bacteria, as evidenced by a 2.86 percent quantum efficiency – or 33 percent more acetate produced within the M. thermoacetica-Au22 system than the CdS model,” Yang said.

The magic gold nanocluster is the latest discovery coming out of Yang’s lab, which for the past six years has focused on using biohybrid nanostructures to convert CO2 into useful chemicals as part of an ongoing effort to find affordable, abundant resources for renewable fuels, and potential solutions to thwart the effects of climate change.

“Next, we’d like to find a way to reduce costs, improve the lifetimes for these biohybrid systems, and improve quantum efficiency,” Yang said. “By continuing to look at the fundamental aspect of how gold nanoclusters are being photoactivated, and by following the electron transfer process within the CO2 reduction pathway, we hope to find even better solutions.”

Co-authors with Yang are UC Berkeley graduate student Hao Zhang and former postdoctoral fellow Hao Liu, now at Donghua University in Shanghai, China.

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

Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production by Hao Zhang, Hao Liu, Zhiquan Tian, Dylan Lu, Yi Yu, Stefano Cestellos-Blanco, Kelsey K. Sakimoto, & Peidong Yang. Nature Nanotechnologyvolume 13, pages900–905 (2018). DOI: https://doi.org/10.1038/s41565-018-0267-z Published: 01 October 2018

This paper is behind a paywall.

For lovers of animation, the folks at UC Berkeley have produced this piece about the ‘gold-loving’ bacterium,

Chinese scientists strike gold in plant tissues

I have heard of phytomining in soil remediation efforts (reclaiming nanoscale metals in plants near mining operations; you can find a more detailed definition here at Wiktionary) but, in this case, scientists have discovered plant tissues with nanoscale gold in an area which has no known deposits of gold. From a June 14, 2018 news item on Nanowwerk (Note: A link has been removed),

Plants containing the element gold are already widely known. The flowering perennial plant alfafa, for example, has been cultivated by scientists to contain pure gold in its plant tissue. Now researchers from the Sun Yat-sen University in China have identified and investigated the characteristics of gold nanoparticles in two plant species growing in their natural environments.

The study, led by Xiaoen Luo, is published in Environmental Chemistry Letters (“Discovery of nano-sized gold particles in natural plant tissues”) and has implications for the way gold nanoparticles are produced and absorbed from the environment.

A June 14, 2018 Springer Publications press release, which originated the news item, delves further and proposes a solution to the mystery,

Xiaoen Luo and her colleagues investigated the perennial shrub B. nivea and the annual or biennial weed Erigeron Canadensis. The researchers collected and prepared samples of both plants so that they could be examined using the specialist analytical tool called field-emission transmission electron microscope (TEM).

Gold-bearing nanoparticles – tiny gold particles fused with another element such as oxygen or copper – were found in both types of plant. In E. Canadensis these particles were around 20-50 nm in diameter and had an irregular form. The gold-bearing particles in B. nivea were circular, elliptical or bone-rod shaped with smooth edges and were 5-15 nm.

“The abundance of gold in the crust is very low and there was no metal deposit in the sampling area so we speculate that the source of these gold nanoparticles is a nearby electroplating plant that uses gold in its operations, “ explains Jianjin Cao who is a co-author of the study.

Most of the characteristics of the nanoparticles matched those of artificial particles rather than naturally occurring nanoparticles, which would support this theory. The researchers believe that the gold-bearing particles were absorbed through the pores of the plants directly, indicating that gold could be accumulated from the soil, water or air.

“Discovering gold-bearing nanoparticles in natural plant tissues is of great significance and allows new possibilities to clean up areas contaminated with nanoparticles, and also to enrich gold nanoparticles using plants,” says Xiaoen Luo.

The researchers plan to further study the migration mechanism, storage locations and growth patterns of gold nanoparticles in plants and also verify the absorbing capacity of different plants for gold nanoparticles in polluted areas.

For anyone who’d like to find out more about electroplating, there’s this January 25, 2018 article by Anne Marie Helmenstine for ThoughtCo.

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

Discovery of nano-sized gold particles in natural plant tissues by Xiaoen Luo (Luo, X.) and Jianjin Cao (Cao, J.). Environ Chem Lett (2018) pp 1–8 https://doi.org/10.1007/s10311-018-0749-0 First published online 14 June 2018

This paper appears to be open access.

Golden nanoglue

This starts out as a graphene story before taking an abrupt turn. From a June 5, 2018 news item on Nanowerk,

Graphene has undoubtedly been the most popular research subject of nanotechnology during recent years. Made of pure carbon, this material is in principle easy to manufacture: take ordinary graphite and peel one layer off with Scotch tape. The material thus obtained is two-dimensional, yielding unique properties, different from those in three-dimensional materials.

Graphene, however, lacks one important property, semiconductivity, which complicates its usage in electronics applications. Scientists have therefore started the quest of other two-dimensional materials with this desired property.

Molybdenum disulfide, MoS2 is among the most promising candidates. Like graphene, MoS2 consists of layers, interacting weakly with one another. In addition to being a semiconductor, the semiconducting properties of MoS2 change depending on the number of atomic layers.

A June 5, 2018 University of Oulu press release, which originated the news item,  gives more detail about the work,

For the one or few layer MoS2 to be useful in applications, one must be able to join it to other components. What is thus needed is such a metallic conductor that electric current can easily flow between the conductor and the semiconductor. In the case of MoS2, a promising conductor is provided by nickel, which also has other desired properties from the applications point of view.

However, an international collaboration, led by the Nano and molecular systems research unit at the University of Oulu has recently discovered that nanoparticles made of nickel do not attach to MoS2. One needs gold, which ‘glues’ the conductor and the component together. Says docent Wei Cao of NANOMO: “The synthesis is performed through a sonochemical method.” Sonochemistry is a method where chemical reactions are established using ultrasound. NANOMO scientist Xinying Shi adds: “The semiconductor and metal can be bridged either by the crystallized gold nanoparticles, or by the newly formed MoS2-Au-Ni ternary alloy.”

The nanojunction so established has a very small electrical resistivity. It also preserves the semiconducting and magnetic properties of MoS2. In addition, the new material has desirable properties beyond those of the original constituents. For example, it acts as a photocatalyst, which works much more efficiently than pure MoS2. Manufacturing the golden nanojunction is easy and cheap, which makes the new material attractive from the applications point of view.

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

Metallic Contact between MoS2 and Ni via Au Nanoglue by Xinying Shi, Sergei Posysaev, Marko Huttula, Vladimir Pankratov, Joanna Hoszowska, Jean‐Claude Dousse, Faisal Zeeshan, Yuran Niu, Alexei Zakharov, Taohai Li. Small Volume 14, Issue22 May 29, 2018 1704526 First published online: 24 April 2018 https://doi.org/10.1002/smll.201704526

This paper is behind a paywall.

There is a pretty illustration of the ‘golden nanojunctions’,

Golden nanoglue (Courtesy of the University of Oulu)

Create gold nanoparticles and nanowires with water droplets.

For some reason it took a lot longer than usual to find this research paper despite having the journal (Nature Communications), the title (Spontaneous formation …), and the authors’ names. Thankfully, success was wrested from the jaws of defeat (I don’t care if that is trite; it’s how I felt) and links, etc. follow at the end as usual.

An April 19, 2018 Stanford University news release (also on EurekAlert) spins fascinating tale,

An experiment that, by design, was not supposed to turn up anything of note instead produced a “bewildering” surprise, according to the Stanford scientists who made the discovery: a new way of creating gold nanoparticles and nanowires using water droplets.

The technique, detailed April 19 [2018] in the journal Nature Communications, is the latest discovery in the new field of on-droplet chemistry and could lead to more environmentally friendly ways to produce nanoparticles of gold and other metals, said study leader Richard Zare, a chemist in the School of Humanities and Sciences and a co-founder of Stanford Bio-X.

“Being able to do reactions in water means you don’t have to worry about contamination. It’s green chemistry,” said Zare, who is the Marguerite Blake Wilbur Professor in Natural Science at Stanford.

Noble metal

Gold is known as a noble metal because it is relatively unreactive. Unlike base metals such as nickel and copper, gold is resistant to corrosion and oxidation, which is one reason it is such a popular metal for jewelry.

Around the mid-1980s, however, scientists discovered that gold’s chemical aloofness only manifests at large, or macroscopic, scales. At the nanometer scale, gold particles are very chemically reactive and make excellent catalysts. Today, gold nanostructures have found a role in a wide variety of applications, including bio-imaging, drug delivery, toxic gas detection and biosensors.

Until now, however, the only reliable way to make gold nanoparticles was to combine the gold precursor chloroauric acid with a reducing agent such as sodium borohydride.

The reaction transfers electrons from the reducing agent to the chloroauric acid, liberating gold atoms in the process. Depending on how the gold atoms then clump together, they can form nano-size beads, wires, rods, prisms and more.

A spritz of gold

Recently, Zare and his colleagues wondered whether this gold-producing reaction would proceed any differently with tiny, micron-size droplets of chloroauric acid and sodium borohydide. How large is a microdroplet? “It is like squeezing a perfume bottle and out spritzes a mist of microdroplets,” Zare said.

From previous experiments, the scientists knew that some chemical reactions proceed much faster in microdroplets than in larger solution volumes.

Indeed, the team observed that gold nanoparticle grew over 100,000 times faster in microdroplets. However, the most striking observation came while running a control experiment in which they replaced the reducing agent – which ordinarily releases the gold particles – with microdroplets of water.

“Much to our bewilderment, we found that gold nanostructures could be made without any added reducing agents,” said study first author Jae Kyoo Lee, a research associate.

Viewed under an electron microscope, the gold nanoparticles and nanowires appear fused together like berry clusters on a branch.

The surprise finding means that pure water microdroplets can serve as microreactors for the production of gold nanostructures. “This is yet more evidence that reactions in water droplets can be fundamentally different from those in bulk water,” said study coauthor Devleena Samanta, a former graduate student in Zare’s lab and co-author on the paper.

If the process can be scaled up, it could eliminate the need for potentially toxic reducing agents that have harmful health side effects or that can pollute waterways, Zare said.

It’s still unclear why water microdroplets are able to replace a reducing agent in this reaction. One possibility is that transforming the water into microdroplets greatly increases its surface area, creating the opportunity for a strong electric field to form at the air-water interface, which may promote the formation of gold nanoparticles and nanowires.

“The surface area atop a one-liter beaker of water is less than one square meter. But if you turn the water in that beaker into microdroplets, you will get about 3,000 square meters of surface area – about the size of half a football field,” Zare said.

The team is exploring ways to utilize the nanostructures for various catalytic and biomedical applications and to refine their technique to create gold films.

“We observed a network of nanowires that may allow the formation of a thin layer of nanowires,” Samanta said.

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

Spontaneous formation of gold nanostructures in aqueous microdroplets by Jae Kyoo Lee, Devleena Samanta, Hong Gil Nam, & Richard N. Zare. Nature Communicationsvolume 9, Article number: 1562 (2018) doi:10.1038/s41467-018-04023-z Published online: 19 April 2018

Not unsurprisingly given Zare’s history as recounted in the news release, this paper is open access.

Mixing the unmixable for all new nanoparticles

This news comes out of the University of Maryland and the discovery could led to nanoparticles that have never before been imagined. From a March 29, 2018 news item on ScienceDaily,

Making a giant leap in the ‘tiny’ field of nanoscience, a multi-institutional team of researchers is the first to create nanoscale particles composed of up to eight distinct elements generally known to be immiscible, or incapable of being mixed or blended together. The blending of multiple, unmixable elements into a unified, homogenous nanostructure, called a high entropy alloy nanoparticle, greatly expands the landscape of nanomaterials — and what we can do with them.

This research makes a significant advance on previous efforts that have typically produced nanoparticles limited to only three different elements and to structures that do not mix evenly. Essentially, it is extremely difficult to squeeze and blend different elements into individual particles at the nanoscale. The team, which includes lead researchers at University of Maryland, College Park (UMD)’s A. James Clark School of Engineering, published a peer-reviewed paper based on the research featured on the March 30 [2018] cover of Science.

A March 29, 2018 University of Maryland press release (also on EurekAlert), which originated the news item, delves further (Note: Links have been removed),

“Imagine the elements that combine to make nanoparticles as Lego building blocks. If you have only one to three colors and sizes, then you are limited by what combinations you can use and what structures you can assemble,” explains Liangbing Hu, associate professor of materials science and engineering at UMD and one of the corresponding authors of the paper. “What our team has done is essentially enlarged the toy chest in nanoparticle synthesis; now, we are able to build nanomaterials with nearly all metallic and semiconductor elements.”

The researchers say this advance in nanoscience opens vast opportunities for a wide range of applications that includes catalysis (the acceleration of a chemical reaction by a catalyst), energy storage (batteries or supercapacitors), and bio/plasmonic imaging, among others.

To create the high entropy alloy nanoparticles, the researchers employed a two-step method of flash heating followed by flash cooling. Metallic elements such as platinum, nickel, iron, cobalt, gold, copper, and others were exposed to a rapid thermal shock of approximately 3,000 degrees Fahrenheit, or about half the temperature of the sun, for 0.055 seconds. The extremely high temperature resulted in uniform mixtures of the multiple elements. The subsequent rapid cooling (more than 100,000 degrees Fahrenheit per second) stabilized the newly mixed elements into the uniform nanomaterial.

“Our method is simple, but one that nobody else has applied to the creation of nanoparticles. By using a physical science approach, rather than a traditional chemistry approach, we have achieved something unprecedented,” says Yonggang Yao, a Ph.D. student at UMD and one of the lead authors of the paper.

To demonstrate one potential use of the nanoparticles, the research team used them as advanced catalysts for ammonia oxidation, which is a key step in the production of nitric acid (a liquid acid that is used in the production of ammonium nitrate for fertilizers, making plastics, and in the manufacturing of dyes). They were able to achieve 100 percent oxidation of ammonia and 99 percent selectivity toward desired products with the high entropy alloy nanoparticles, proving their ability as highly efficient catalysts.

Yao says another potential use of the nanoparticles as catalysts could be the generation of chemicals or fuels from carbon dioxide.

“The potential applications for high entropy alloy nanoparticles are not limited to the field of catalysis. With cross-discipline curiosity, the demonstrated applications of these particles will become even more widespread,” says Steven D. Lacey, a Ph.D. student at UMD and also one of the lead authors of the paper.

This research was performed through a multi-institutional collaboration of Prof. Liangbing Hu’s group at the University of Maryland, College Park; Prof. Reza Shahbazian-Yassar’s group at University of Illinois at Chicago; Prof. Ju Li’s group at the Massachusetts Institute of Technology; Prof. Chao Wang’s group at Johns Hopkins University; and Prof. Michael Zachariah’s group at the University of Maryland, College Park.

What outside experts are saying about this research:

“This is quite amazing; Dr. Hu creatively came up with this powerful technique, carbo-thermal shock synthesis, to produce high entropy alloys of up to eight different elements in a single nanoparticle. This is indeed unthinkable for bulk materials synthesis. This is yet another beautiful example of nanoscience!,” says Peidong Yang, the S.K. and Angela Chan Distinguished Professor of Energy and professor of chemistry at the University of California, Berkeley and member of the American Academy of Arts and Sciences.

“This discovery opens many new directions. There are simulation opportunities to understand the electronic structure of the various compositions and phases that are important for the next generation of catalyst design. Also, finding correlations among synthesis routes, composition, and phase structure and performance enables a paradigm shift toward guided synthesis,” says George Crabtree, Argonne Distinguished Fellow and director of the Joint Center for Energy Storage Research at Argonne National Laboratory.

More from the research coauthors:

“Understanding the atomic order and crystalline structure in these multi-element nanoparticles reveals how the synthesis can be tuned to optimize their performance. It would be quite interesting to further explore the underlying atomistic mechanisms of the nucleation and growth of high entropy alloy nanoparticle,” says Reza Shahbazian-Yassar, associate professor at the University of Illinois at Chicago and a corresponding author of the paper.

“Carbon metabolism drives ‘living’ metal catalysts that frequently move around, split, or merge, resulting in a nanoparticle size distribution that’s far from the ordinary, and highly tunable,” says Ju Li, professor at the Massachusetts Institute of Technology and a corresponding author of the paper.

“This method enables new combinations of metals that do not exist in nature and do not otherwise go together. It enables robust tuning of the composition of catalytic materials to optimize the activity, selectivity, and stability, and the application will be very broad in energy conversions and chemical transformations,” says Chao Wang, assistant professor of chemical and biomolecular engineering at Johns Hopkins University and one of the study’s authors.

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

Carbothermal shock synthesis of high-entropy-alloy nanoparticles by Yonggang Yao, Zhennan Huang, Pengfei Xie, Steven D. Lacey, Rohit Jiji Jacob, Hua Xie, Fengjuan Chen, Anmin Nie, Tiancheng Pu, Miles Rehwoldt, Daiwei Yu, Michael R. Zachariah, Chao Wang, Reza Shahbazian-Yassar, Ju Li, Liangbing Hu. Science 30 Mar 2018: Vol. 359, Issue 6383, pp. 1489-1494 DOI: 10.1126/science.aan5412

This paper is behind a paywall.

Gold’s origin in the universe due to cosmic collision

An hypothesis for gold’s origins was first mentioned here in a May 26, 2016 posting,

The link between this research and my side project on gold nanoparticles is a bit tenuous but this work on the origins for gold and other precious metals being found in the stars is so fascinating and I’m determined to find a connection.

An artist's impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

An artist’s impression of two neutron stars colliding. (Credit: Dana Berry / Skyworks Digital, Inc.) Courtesy: Kavli Foundation

From a May 19, 2016 news item on phys.org,

The origin of many of the most precious elements on the periodic table, such as gold, silver and platinum, has perplexed scientists for more than six decades. Now a recent study has an answer, evocatively conveyed in the faint starlight from a distant dwarf galaxy.

In a roundtable discussion, published today [May 19, 2016?], The Kavli Foundation spoke to two of the researchers behind the discovery about why the source of these heavy elements, collectively called “r-process” elements, has been so hard to crack.

From the Spring 2016 Kavli Foundation webpage hosting the  “Galactic ‘Gold Mine’ Explains the Origin of Nature’s Heaviest Elements” Roundtable ,

Astronomers studying a galaxy called Reticulum II have just discovered that its stars contain whopping amounts of these metals—collectively known as “r-process” elements (See “What is the R-Process?”). Of the 10 dwarf galaxies that have been similarly studied so far, only Reticulum II bears such strong chemical signatures. The finding suggests some unusual event took place billions of years ago that created ample amounts of heavy elements and then strew them throughout the galaxy’s reservoir of gas and dust. This r-process-enriched material then went on to form Reticulum II’s standout stars.

Based on the new study, from a team of researchers at the Kavli Institute at the Massachusetts Institute of Technology, the unusual event in Reticulum II was likely the collision of two, ultra-dense objects called neutron stars. Scientists have hypothesized for decades that these collisions could serve as a primary source for r-process elements, yet the idea had lacked solid observational evidence. Now armed with this information, scientists can further hope to retrace the histories of galaxies based on the contents of their stars, in effect conducting “stellar archeology.”

Researchers have confirmed the hypothesis according to an Oct. 16, 2017 news item on phys.org,

Gold’s origin in the Universe has finally been confirmed, after a gravitational wave source was seen and heard for the first time ever by an international collaboration of researchers, with astronomers at the University of Warwick playing a leading role.

Members of Warwick’s Astronomy and Astrophysics Group, Professor Andrew Levan, Dr Joe Lyman, Dr Sam Oates and Dr Danny Steeghs, led observations which captured the light of two colliding neutron stars, shortly after being detected through gravitational waves – perhaps the most eagerly anticipated phenomenon in modern astronomy.

Marina Koren’s Oct. 16, 2017 article for The Atlantic presents a richly evocative view (Note: Links have been removed),

Some 130 million years ago, in another galaxy, two neutron stars spiraled closer and closer together until they smashed into each other in spectacular fashion. The violent collision produced gravitational waves, cosmic ripples powerful enough to stretch and squeeze the fabric of the universe. There was a brief flash of light a million trillion times as bright as the sun, and then a hot cloud of radioactive debris. The afterglow hung for several days, shifting from bright blue to dull red as the ejected material cooled in the emptiness of space.

Astronomers detected the aftermath of the merger on Earth on August 17. For the first time, they could see the source of universe-warping forces Albert Einstein predicted a century ago. Unlike with black-hole collisions, they had visible proof, and it looked like a bright jewel in the night sky.

But the merger of two neutron stars is more than fireworks. It’s a factory.

Using infrared telescopes, astronomers studied the spectra—the chemical composition of cosmic objects—of the collision and found that the plume ejected by the merger contained a host of newly formed heavy chemical elements, including gold, silver, platinum, and others. Scientists estimate the amount of cosmic bling totals about 10,000 Earth-masses of heavy elements.

I’m not sure exactly what this image signifies but it did accompany Koren’s article so presumably it’s a representation of colliding neutron stars,

NSF / LIGO / Sonoma State University /A. Simonnet. Downloaded from: https://www.theatlantic.com/science/archive/2017/10/the-making-of-cosmic-bling/543030/

An Oct. 16, 2017 University of Warwick press release (also on EurekAlert), which originated the news item on phys.org, provides more detail,

Huge amounts of gold, platinum, uranium and other heavy elements were created in the collision of these compact stellar remnants, and were pumped out into the universe – unlocking the mystery of how gold on wedding rings and jewellery is originally formed.

The collision produced as much gold as the mass of the Earth. [emphasis mine]

This discovery has also confirmed conclusively that short gamma-ray bursts are directly caused by the merging of two neutron stars.

The neutron stars were very dense – as heavy as our Sun yet only 10 kilometres across – and they collided with each other 130 million years ago, when dinosaurs roamed the Earth, in a relatively old galaxy that was no longer forming many stars.

They drew towards each other over millions of light years, and revolved around each other increasingly quickly as they got closer – eventually spinning around each other five hundred times per second.

Their merging sent ripples through the fabric of space and time – and these ripples are the elusive gravitational waves spotted by the astronomers.

The gravitational waves were detected by the Advanced Laser Interferometer Gravitational-Wave Observatory (Adv-LIGO) on 17 August this year [2017], with a short duration gamma-ray burst detected by the Fermi satellite just two seconds later.

This led to a flurry of observations as night fell in Chile, with a first report of a new source from the Swope 1m telescope.

Longstanding collaborators Professor Levan and Professor Nial Tanvir (from the University of Leicester) used the facilities of the European Southern Observatory to pinpoint the source in infrared light.

Professor Levan’s team was the first one to get observations of this new source with the Hubble Space Telescope. It comes from a galaxy called NGC 4993, 130 million light years away.

Andrew Levan, Professor in the Astronomy & Astrophysics group at the University of Warwick, commented: “Once we saw the data, we realised we had caught a new kind of astrophysical object. This ushers in the era of multi-messenger astronomy, it is like being able to see and hear for the first time.”

Dr Joe Lyman, who was observing at the European Southern Observatory at the time was the first to alert the community that the source was unlike any seen before.

He commented: “The exquisite observations obtained in a few days showed we were observing a kilonova, an object whose light is powered by extreme nuclear reactions. This tells us that the heavy elements, like the gold or platinum in jewellery are the cinders, forged in the billion degree remnants of a merging neutron star.”

Dr Samantha Oates added: “This discovery has answered three questions that astronomers have been puzzling for decades: what happens when neutron stars merge? What causes the short duration gamma-ray bursts? Where are the heavy elements, like gold, made? In the space of about a week all three of these mysteries were solved.”

Dr Danny Steeghs said: “This is a new chapter in astrophysics. We hope that in the next few years we will detect many more events like this. Indeed, in Warwick we have just finished building a telescope designed to do just this job, and we expect it to pinpoint these sources in this new era of multi-messenger astronomy”.

Congratulations to all of the researchers involved in this work!

Many, many research teams were  involved. Here’s a sampling of their news releases which focus on their areas of research,

University of the Witwatersrand (South Africa)


Weizmann Institute of Science (Israel)


Carnegie Institution for Science (US)


Northwestern University (US)


National Radio Astronomy Observatory (US)


Max-Planck-Gesellschaft (Germany)


Penn State (Pennsylvania State University; US)


University of California – Davis


The American Association for the Advancement of Science’s (AAAS) magazine, Science, has published seven papers on this research. Here’s an Oct. 16, 2017 AAAS news release with an overview of the papers,


I’m sure there are more news releases out there and that there will be many more papers published in many journals, so if this interests, I encourage you to keep looking.

Two final pieces I’d like to draw your attention to: one answers basic questions and another focuses on how artists knew what to draw when neutron stars collide.

Keith A Spencer’s Oct. 18, 2017 piece on salon.com answers a lot of basic questions for those of us who don’t have a background in astronomy. Here are a couple of examples,

What is a neutron star?

Okay, you know how atoms have protons, neutrons, and electrons in them? And you know how protons are positively charged, and electrons are negatively charged, and neutrons are neutral?

Yeah, I remember that from watching Bill Nye as a kid.

Totally. Anyway, have you ever wondered why the negatively-charged electrons and the positively-charged protons don’t just merge into each other and form a neutral neutron? I mean, they’re sitting there in the atom’s nucleus pretty close to each other. Like, if you had two magnets that close, they’d stick together immediately.

I guess now that you mention it, yeah, it is weird.

Well, it’s because there’s another force deep in the atom that’s preventing them from merging.

It’s really really strong.

The only way to overcome this force is to have a huge amount of matter in a really hot, dense space — basically shove them into each other until they give up and stick together and become a neutron. This happens in very large stars that have been around for a while — the core collapses, and in the aftermath, the electrons in the star are so close to the protons, and under so much pressure, that they suddenly merge. There’s a big explosion and the outer material of the star is sloughed off.

Okay, so you’re saying under a lot of pressure and in certain conditions, some stars collapse and become big balls of neutrons?

Pretty much, yeah.

So why do the neutrons just stick around in a huge ball? Aren’t they neutral? What’s keeping them together? 

Gravity, mostly. But also the strong nuclear force, that aforementioned weird strong force. This isn’t something you’d encounter on a macroscopic scale — the strong force only really works at the type of distances typified by particles in atomic nuclei. And it’s different, fundamentally, than the electromagnetic force, which is what makes magnets attract and repel and what makes your hair stick up when you rub a balloon on it.

So these neutrons in a big ball are bound by gravity, but also sticking together by virtue of the strong nuclear force. 

So basically, the new ball of neutrons is really small, at least, compared to how heavy it is. That’s because the neutrons are all clumped together as if this neutron star is one giant atomic nucleus — which it kinda is. It’s like a giant atom made only of neutrons. If our sun were a neutron star, it would be less than 20 miles wide. It would also not be something you would ever want to get near.

Got it. That means two giant balls of neutrons that weighed like, more than our sun and were only ten-ish miles wide, suddenly smashed into each other, and in the aftermath created a black hole, and we are just now detecting it on Earth?

Exactly. Pretty weird, no?

Spencer does a good job of gradually taking you through increasingly complex explanations.

For those with artistic interests, Neel V. Patel tries to answer a question about how artists knew what draw when neutron stars collided in his Oct. 18, 2017 piece for Slate.com,

All of these things make this discovery easy to marvel at and somewhat impossible to picture. Luckily, artists have taken up the task of imagining it for us, which you’ve likely seen if you’ve already stumbled on coverage of the discovery. Two bright, furious spheres of light and gas spiraling quickly into one another, resulting in a massive swell of lit-up matter along with light and gravitational waves rippling off speedily in all directions, towards parts unknown. These illustrations aren’t just alluring interpretations of a rare phenomenon; they are, to some extent, the translation of raw data and numbers into a tangible visual that gives scientists and nonscientists alike some way of grasping what just happened. But are these visualizations realistic? Is this what it actually looked like? No one has any idea. Which is what makes the scientific illustrators’ work all the more fascinating.

“My goal is to represent what the scientists found,” says Aurore Simmonet, a scientific illustrator based at Sonoma State University in Rohnert Park, California. Even though she said she doesn’t have a rigorous science background (she certainly didn’t know what a kilonova was before being tasked to illustrate one), she also doesn’t believe that type of experience is an absolute necessity. More critical, she says, is for the artist to have an interest in the subject matter and in learning new things, as well as a capacity to speak directly to scientists about their work.

Illustrators like Simmonet usually start off work on an illustration by asking the scientist what’s the biggest takeaway a viewer should grasp when looking at a visual. Unfortunately, this latest discovery yielded a multitude of papers emphasizing different conclusions and highlights. With so many scientific angles, there’s a stark challenge in trying to cram every important thing into a single drawing.

Clearly, however, the illustrations needed to center around the kilonova. Simmonet loves colors, so she began by discussing with the researchers what kind of color scheme would work best. The smash of two neutron stars lends itself well to deep, vibrant hues. Simmonet and Robin Dienel at the Carnegie Institution for Science elected to use a wide array of colors and drew bright cracking to show pressure forming at the merging. Others, like Luis Calcada at the European Southern Observatory, limited the color scheme in favor of emphasizing the bright moment of collision and the signal waves created by the kilonova.

Animators have even more freedom to show the event, since they have much more than a single frame to play with. The Conceptual Image Lab at NASA’s [US National Aeronautics and Space Administration] Goddard Space Flight Center created a short video about the new findings, and lead animator Brian Monroe says the video he and his colleagues designed shows off the evolution of the entire process: the rising action, climax, and resolution of the kilonova event.

The illustrators try to adhere to what the likely physics of the event entailed, soliciting feedback from the scientists to make sure they’re getting it right. The swirling of gas, the direction of ejected matter upon impact, the reflection of light, the proportions of the objects—all of these things are deliberately framed such that they make scientific sense. …

Do take a look at Patel’s piece, if for no other reason than to see all of the images he has embedded there. You may recognize Aurore Simmonet’s name from the credit line in the second image I have embedded here.

Gold at the nanoscale in medieval textiles

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?