Tag Archives: Art Institute of Chicago

Richard Van Duyne solves mystery of Renoir’s red with surface-enhanced Raman spectroscopy (SERS) and Canadian scientists uncover forgeries

The only things these two items have in common is that they are concerned with visual art. and with solving mysteries The first item concerns research by Richard Van Duyne into the nature of the red paint used in one of Renoir’s paintings. A February 14, 2014 news item on Azonano describes some of the art conservation work that Van Duyne’s (nanoish) technology has made possible along with details about this most recent work,

Scientists are using powerful analytical and imaging tools to study artworks from all ages, delving deep below the surface to reveal the process and materials used by some of the world’s greatest artists.

Northwestern University chemist Richard P. Van Duyne, in collaboration with conservation scientists at the Art Institute of Chicago, has been using a scientific method he discovered nearly four decades ago to investigate masterpieces by Pierre-Auguste Renoir, Winslow Homer and Mary Cassatt.

Van Duyne recently identified the chemical components of paint, now partially faded, used by Renoir in his oil painting “Madame Léon Clapisson.” Van Duyne discovered the artist used carmine lake, a brilliant but light-sensitive red pigment, on this colorful canvas. The scientific investigation is the cornerstone of a new exhibition at the Art Institute of Chicago.

The Art Institute of Chicago’s exhibition is called, Renoir’s True Colors: Science Solves a Mystery. being held from Feb. 12, 2014 – April 27, 2014. Here is an image of the Renoir painting in question and an image featuring the equipment being used,

Renoir-Madame-Leon-Clapisson.Art Institute of Chicago.

Renoir-Madame-Leon-Clapisson.Art Institute of Chicago.

Renoir and surface-enhanced Raman spectroscopy (SERS). Art Institute of Chicago

Renoir and surface-enhanced Raman spectroscopy (SERS). Art Institute of Chicago

The Feb. 13, 2014 Northwestern University news release (also on EurekAlert) by Megan Fellman, which originated the news item, gives a brief description of Van Duyne’s technique and its impact on conservation at the Art Institute of Chicago (Note: A link has been removed),

To see what the naked eye cannot see, Van Duyne used surface-enhanced Raman spectroscopy (SERS) to uncover details of Renoir’s paint. SERS, discovered by Van Duyne in 1977, is widely recognized as the most sensitive form of spectroscopy capable of identifying molecules.

Van Duyne and his colleagues’ detective work informed the production of a new digital visualization of the painting’s original colors by the Art Institute’s conservation department. The re-colorized reproduction and the original painting (presented in a case that offers 360-degree views) can be viewed side by side at the exhibition “Renoir’s True Colors: Science Solves a Mystery” through April 27 [2014] at the Art Institute.

I first wrote about Van Duyne’s technique in my wiki, The NanoTech Mysteries. From the Scientists get artful page (Note: A footnote was removed),

Richard Van Duyne, then a chemist at Northwestern University, developed the technique in 1977. Van Duyne’s technology, based on Raman spectroscopy which has been around since the 1920s, is called surface-enhanced Raman spectroscopy’ or SERS “[and] uses laser light and nanoparticles of precious metals to interact with molecules to show the chemical make-up of a particular dye.”

This next item is about forgery detection. A March 5, 2014 news release on EurekAlert describes the latest developments,

Gallery owners, private collectors, conservators, museums and art dealers face many problems in protecting and evaluating their collections such as determining origin, authenticity and discovery of forgery, as well as conservation issues. Today these problems are more accurately addressed through the application of modern, non-destructive, “hi-tech” techniques.

Dmitry Gavrilov, a PhD student in the Department of Physics at the University of Windsor (Windsor, Canada), along with Dr. Roman Gr. Maev, the Department of Physics Professor at the University of Windsor (Windsor, Canada) and Professor Dr. Darryl Almond of the University of Bath (Bath, UK) have been busy applying modern techniques to this age-old field. Infrared imaging, thermography, spectroscopy, UV fluorescence analysis, and acoustic microscopy are among the innovative approaches they are using to conduct pre-restoration analysis of works of art. Some fascinating results from their applications are published today in the Canadian Journal of Physics.

Since the early 1900s, using infrared imaging in various wave bands, scientists have been able to see what parts of artworks have been retouched or altered and sometimes even reveal the artist’s original sketches beneath layers of the paint. Thermography is a relatively new approach in art analysis that allows for deep subsurface investigation to find defects and past reparations. To a conservator these new methods are key in saving priceless works from further damage.

Gavrilov explains, “We applied new approaches in processing thermographic data, materials spectra data, and also the technique referred to as craquelure pattern analysis. The latter is based on advanced morphological processing of images of surface cracks. These cracks, caused by a number of factors such as structure of canvas, paints and binders used, can uncover important clues on the origins of a painting.”

“Air-coupled acoustic imaging and acoustic microscopy are other innovative approaches which have been developed and introduced into art analysis by our team under supervision of Dr. Roman Gr. Maev. The technique has proven to be extremely sensitive to small layer detachments and allows for the detection of early stages of degradation. It is based on the same principles as medical and industrial ultrasound, namely, the sending a sound wave to the sample and receiving it back. ”

Spectroscopy is a technique that has been useful in the fight against art fraud. It can determine chemical composition of pigments and binders, which is essential information in the hands of an art specialist in revealing fakes. As described in the paper, “…according to the FBI, the value of art fraud, forgery and theft is up to $6 billion per year, which makes it the third most lucrative crime in the world after drug trafficking and the illegal weapons trade.”

One might wonder how these modern applications can be safe for delicate works of art when even flash photography is banned in art galleries. The authors discuss this and other safety concerns, describing both historic and modern-day implications of flash bulbs and exhibit illumination and scientific methods. As the paper concludes, the authors suggest that we can expect that the number of “hi-tech” techniques will only increase. In the future, art experts will likely have a variety of tools to help them solve many of the mysteries hiding beneath the layers.

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

A review of imaging methods in analysis of works of art: Thermographic imaging method in art analysis by D. Gavrilov, R.Gr. Maev, and D.P. Almond. Canadian Journal of Physics, 10.1139/cjp-2013-0128

This paper is open access.

Picasso, paint, and the hard x-ray nanoprobe

There’s the paint you put on your walls and there’s the paint you put on your body and there’s the paint artists use for their works of art. Well, it turns out that a very well known artist used common house paint to create some of his masterpieces,

Among the Picasso paintings in the Art Institute of Chicago collection, The Red Armchair is the most emblematic of his Ripolin usage and is the painting that was examined with APS X-rays at Argonne National Laboratory. To view a larger version of the image, click on it. Courtesy Art Institute of Chicago, Gift of Mr. and Mrs. Daniel Saidenberg (AIC 1957.72) © Estate of Pablo Picasso / Artists Rights Society (ARS), New York [downloaded from http://www.anl.gov/articles/high-energy-x-rays-shine-light-mystery-picasso-s-paints]

Among the Picasso paintings in the Art Institute of Chicago collection, The Red Armchair is the most emblematic of his Ripolin usage and is the painting that was examined with APS X-rays at Argonne National Laboratory. To view a larger version of the image, click on it. Courtesy Art Institute of Chicago, Gift of Mr. and Mrs. Daniel Saidenberg (AIC 1957.72) © Estate of Pablo Picasso / Artists Rights Society (ARS), New York [downloaded from http://www.anl.gov/articles/high-energy-x-rays-shine-light-mystery-picasso-s-paints]

The Art Institute of Chicago teamed with the US Argonne National Laboratory to solve a decades-long mystery as to what kind of paint Picasso used. From the Feb. 8, 2013 news item on Azonano,

The Art Institute of Chicago teamed up with Argonne National Laboratory to unravel a decades-long debate among art scholars about what kind of paint Picasso used to create his masterpieces.

The results published last month in the journal Applied Physics A: Materials Science & Processing adds significant weight to the widely held theory that Picasso was one of the first master painters to use common house paint rather than traditional artists’ paint. That switch in painting material gave birth to a new style of art marked by canvasses covered in glossy images with marbling, muted edges, and occasional errant paint drips but devoid of brush marks. Fast-drying enamel house paint enabled this dramatic departure from the slow-drying heavily blended oil paintings that dominated the art world up until Picasso’s time.

The key to decoding this long-standing mystery was the development of a unique high-energy X-ray instrument, called the hard X-ray nanoprobe, at the U.S. Department of Energy’s Advanced Photon Source (APS) X-ray facility and the Center for Nanoscale Materials, both housed at Argonne. The nanoprobe is designed to advance the development of high-performance materials and sustainable energies by giving scientists a close up view of the type and arraignment of chemical elements in material.

At that submicroscopic level is where science and art crossed paths.

The Argonne National Laboratory Feb. 6, 2013 news release by Tona Kunz, which originated the news item,  provides more  technical detail,

Volker Rose, a physicist at Argonne, uses the nanoprobe at the APS [Advanced Photon Source]/CNM [Center for Nanoscale Materials] to study zinc oxide, a key chemical used in wide-band-gap semiconductors. White paint contains the same chemical in varying amounts, depending on the type and brand of paint, which makes it a valuable clue for learning about Picasso’s work.

By comparing decades-old paint samples collected through e-Bay purchases with samples from Picasso paintings, scientists were able to learn that the chemical makeup of paint used by Picasso matched the chemical makeup of the first commercial house paint, Ripolin. Scientists also learned about the correlation of the spacing of impurities at the nanoscale in zinc oxide, offering important clues to how zinc oxide could be modified to improve performance in a variety of products, including sensors for radiation detection, LEDs and energy-saving windows as well as liquid-crystal displays for computers, TVs and instrument panels.

“Everything that we learn about how materials are structured and how chemicals react at the nanolevel can help us in our quest to design a better and more sustainable future,” Rose said.

Physicists weren’t the first to investigate the question,

Many art conservators and historians have tried over the years to use traditional optical and electron microscopes to determine whether Picasso or one of his contemporaries was the first to break with the cultural tradition of professional painters using expensive paints designed specifically for their craft. Those art world detectives all failed, because traditional tools wouldn’t let them see deeply enough into the layers of paint or with enough resolution to distinguish between store-bought enamel paint and techniques designed to mimic its appearance.

“Appearances can deceive, so this is where art can benefit from scientific research,” said Francesca Casadio, senior conservator scientist at the Art Institute of Chicago, and co-lead author on the result publication. “We needed to reverse-engineer the paint so that we could figure out if there was a fingerprint that we could then go look for in the pictures around the world that are suspected to be painted with Ripolin, the first commercial brand of house paint.”

Just as criminals leave a signature at a crime scene, each batch of paint has a chemical signature determined by its ingredients and impurities from the area and time period it was made. These signatures can’t be imitated and lie in the nanoscale range.

Yet until now, it was difficult to differentiate the chemical components of the paint pigments from the chemical components in the binders, fillers, other additives and contaminates that were mixed in with the pigments or layered on top of them. Only the nanoprobe at the APS /CNM can distinguish that level of detail: elemental composition and nanoscale distribution of elements within individualized submicrometeric pigment particles.

“The nanoprobe at the APS and CNM allowed unprecedented visualization of information about chemical composition within a singe grain of paint pigment, significantly reducing doubt that Picasso used common house paint in some of his most famous works,” said Rose, co-lead author on the result publication titled “High-Resolution Fluorescence Mapping of Impurities in the Historical Zinc Oxide Pigments: Hard X-ray Nanoprobe Applications to the Paints of Pablo Picasso.”

The nanoprobe’s high spatial resolution and micro-focusing abilities gave it the unique ability to identify individual chemical elements and distinguish between the size of paint particles crushed by hand in artists’ studios and those crushed even smaller by manufacturing equipment. The nanoprobe peered deeper than previous similar paint studies limited to a one-micrometer viewing resolution. The nanoprobe gave scientists an unprecedented look at 30-nanometer-wide particles of paint and impurities from the paint manufacturing process. For comparison, a typical sheet of copier paper is 100,000 nanometers thick.

Using the nanoprobe, scientists were able to determine that Picasso used enamel paint to create in 1931 The Red Armchair, on display at the Art Institute of Chicago. They were also able to determine the paint brand and from what manufacturing region the paint originated.

X-ray analysis of white paints produced under the Ripolin brand and used in artists’ traditional tube paints revealed that both contained nearly contaminate-free zinc oxide pigment. However, artists’ tube paints contained more fillers of other white-colored pigments than did the Ripolin, which was mostly pure zinc oxide.

Casaido [sic] views this type of chemical characterization of paints as a having a much wider application than just the study of Picasso’s paintings. By studying the chemical composition of art materials, she said, historians can learn about trade movements in ancient times, better determine the time period a piece was created, and even learn about the artist themselves through their choice of materials.

Perhaps not so coincidentally, the Art Institute of Chicago is celebrating the 100 year relationship between Picasso and Chicago, excerpted from their Jan. 14, 2013 news release,

THE ART INSTITUTE HONORS 100-YEAR RELATIONSHIP BETWEEN PICASSO AND CHICAGO WITH LANDMARK MUSEUM–WIDE CELEBRATION

First Large-Scale Picasso Exhibition Presented by the Art Institute in 30 Years Commemorates Centennial Anniversary of the Armory Show

Picasso and Chicago on View Exclusively at the Art Institute February 20–May 12, 2013

This winter, the Art Institute of Chicago celebrates the unique relationship between Chicago and one of the preeminent artists of the 20th century—Pablo Picasso—with special presentations, singular paintings on loan from the Philadelphia Museum of Art, and programs throughout the museum befitting the artist’s unparalleled range and influence. The centerpiece of this celebration is the major exhibition Picasso and Chicago, on view from February 20 through May 12, 2013 in the Art Institute’s Regenstein Hall, which features more than 250 works selected from the museum’s own exceptional holdings and from private collections throughout Chicago. Representing Picasso’s innovations in nearly every media—paintings, sculpture, prints, drawings, and ceramics—the works not only tell the story of Picasso’s artistic development but also the city’s great interest in and support for the artist since the Armory Show of 1913, a signal event in the history of modern art.

The Art Institute of Chicago, Francesca Casadio, and art conservation (specifically in regard to Winslow Homer) were mentioned here in an April 11, 2011 posting.

GlaxoSmithKline (with roots in the 18th century) makes 21st century deal with Liquidia Technologies

The GlaxoSmithKline (GSK) company history starts in the 1700s (1715 to be exact) when “Plough Court pharmacy, the forerunner of Allen and Hanburys Ltd, is established in London by Silvanus Bevan” (from the Company History webpage). As you’ve probably guessed, GSK is a pharmaceutical company (from the About Us, Our Company page),

We are a science-led global healthcare company

We have a challenging and inspiring mission: to improve the quality of human life by enabling people to do more, feel better and live longer. This mission gives us the purpose to develop innovative medicines and products that help millions of people around the world.

Headquartered in the UK, we are a global organisation with offices in over 100 countries and major research centres in the UK, USA, Spain, Belgium and China.

But being a leader brings responsibility. This means that we care about the impact that we have on the people and places touched by our mission to improve health around the world.

It also means that we must help developing countries where debilitating disease affects millions of people and access to life-changing medicines and vaccines is a problem. To meet this challenge, we are committed to providing discounted medicines where they are needed the most.

We are one of the few healthcare companies researching both medicines and vaccines for the World Health Organization’s three priority diseases – HIV/AIDS, tuberculosis and malaria, and are very proud to have developed some of the leading global medicines in these fields.

We produce medicines that treat major disease areas such as asthma, anti-virals, infections, mental health, diabetes, cardiovascular and digestive conditions. In addition, we are a leader in the important area of vaccines and are developing new treatments for cancer.

We also market other consumer products, many of which are among the market leaders:

  • over-the-counter (OTC) medicines including Gaviscon and Panadol
  • dental products such as Aquafresh and Sensodyne
  • smoking control products Nicorette/Niquitin
  • nutritional healthcare drinks such as Lucozade, Ribena and Horlicks skincare products marketed by Stiefel Laboratories

The other partner in this deal, nanomedicine company  Liquidia Technologies offers a less expansive description of their healthcare interests while a more market-oriented approach (from the home page),

Over the next decade, nanotechnology has the potential to influence virtually every aspect of our lives, including our energy, food, water, buildings, and medicines. According to a recently published report by BCC Research, the market value of the worldwide nanomedicine industry alone is estimated to grow at a CAGR [compound annual growth rate] of 12.5% to reach $130.9 billion by the fiscal year 2016. However, in order to realize this broad potential robust, cost-effective, regulatory-friendly manufacturing technologies will be required. Through its novel nanoparticle technology platform and expansive intellectual property, Liquidia is poised to be a leader in the development of nanotechnology-based healthcare products and a catalyst for the growth anticipated across this industry.

Here’s more about the deal and the technology, from the June 20,2012 news item on Nanowerk,

Liquidia Technologies today announced the initiation of a broad, multi-year collaboration with GlaxoSmithKline (GSK), which has acquired exclusive rights to research and develop certain vaccine and inhaled product candidates using the company’s proprietary PRINT® (Particle Replication In Non-Wetting Templates) technology. Liquidia’s PRINT technology is a powerful and versatile nanoparticle technology product development and manufacturing platform that is changing the way companies engineer healthcare products.

“We are very pleased to have the opportunity to work with GSK, a company known for its commitment to scientific excellence, medicinal chemistry expertise and expansive library of proprietary compounds that could potentially benefit from Liquidia’s PRINT technology,” said Neal Fowler, Chief Executive Officer at Liquidia, “The strength of this collaboration is based on the strong and successful heritage of GSK’s vaccine and inhaled therapy franchises and the transformative particle engineering and manufacturing capabilities of Liquidia’s PRINT technology, which when combined, we believe will yield a next generation of life saving therapeutics.”

Here’s my description of Liquidia’s PRINT technology (it’s not possible to cut and past from the company’s Product Platform page). The company has copied lithographic techniques used in the semiconductor industry to develop templates, probably polymer-based, that look like cupcake tins to me. Somehow a bunch of dots (nanoparticles) are attracted to these cupcake tin moulds, which can be different shapes, and somehow the nanoparticles are induced to remain in the shape prescribed by the mould as it disintegrates leaving the newly moulded nanoparticle shape ready for use.

Here’s more from the June 20, 2012 news item,

According to the agreement, Liquidia will receive an upfront payment, comprised of cash and equity, R&D funding, as well as potential for additional licensing fees, development milestones, and royalties. Upfront payment, R&D funding, licensing, and development and regulatory milestone payments under this collaboration could total up to several hundred million dollars upon all contingent payments coming due. Through this agreement, Liquidia has also retained the ability to independently develop certain respiratory and vaccine products in addition to using the PRINT platform to develop products in other therapeutic areas.

It certainly seems as if Liquidia Technologies (the source for the June 20, 2012 news item)  is more interested in communicating about business and markets than about any health benefits for the rest of us.

Winslow Homer, Van Gogh, and nanotechnology

A few years back I wrote up a story about Winslow Homer and his painting, For to Be a Farmer’s Boy, which had a nanotechnology angle. The painting,part f the Art Institute of Chicago’s (AIC) collection, was examined using the Surface Enhanced Raman Spectrometry (SERS) technique and I found the art conservation application so interesting I included the story in my The Nanotech Mysteries wiki on the Scientists get artful page.

The April 5, 2011 article [ETA: Link added Feb. 10, 2013] by Francesca Casadio on physorg.com  has more technical detail about the conservation process and the painting. It also mentions The Bedroom by Van Gogh,

… they are both displayed at the Art Institute of Chicago (AIC). Homer’s painting represents a high point in the career of America’s premiere watercolorist, while Van Gogh’s painting is perhaps one of most recognizable paintings in the world. However, they also share a key physical trait.

“These breathtaking artworks are both painted with colorants that are sensitive to light, or, as we say in museums, they are ‘fugitive,’ meaning they quickly vanish if exposed to too much light,” says Francesca Casadio, A.W. Mellon senior conservation scientist at the AIC. “Fading can dramatically change the color balance of fragile works of art and go so far as to obfuscate, in part, the artist’s intended effect.”

Here’s how it works,

By using a colloidal suspension of silver nanoparticles as a “performance enhancing drug,” researchers, for the first time, can identify natural organic colorants on a single grain of pigment otherwise invisible to the naked eye.

SERS analysis
Indeed, only a handful of pigment particles were available from the Homer watercolor. Compared to reference 19th century watercolor pigments available at AIC, these colorants were identified as Indian purple (cochineal precipitated with copper sulfate) and madder purple, two natural dyestuffs derived from an insect and vegetable-root sources, respectively.
The results indicate that in Homer’s For to Be a Farmer’s Boy, the “empty” sky once depicted a vibrant autumn sunset, with organic purples and reds, in addition to inorganic reds and yellows.

The Art Institute of Chicago has a page about this painting where they have a digital simulation that allows you to see the original before and after the restoration.

I did cover Van Gogh’s The Bedroom in a March 16, 2010 posting (scroll down) about the Amsterdam Museum and its restoration efforts. The museum staff wrote a blog about the painting and the process as they restored it. The last posting on the blog indicates that The Bedroom was going to be in Japan until April 10, 2011 and then it was being returned to the Amsterdam Museum. I wonder if the painting’s current residency at the AIC is a consequence of the earthquake, tsunami, and reactor situations in Japan.

UK’s National Gallery holds an art/science exhibition

Priceless art works need to be restored, cleaned, and, sometimes even centuries later, authenticated. Art conservators at the UK’s National Gallery have been collaborating for years with EPSRC (Engineering and Physical Sciences Research Council) scientists to find ways to make these activities less damaging. Generally, this is not considered the most exciting topic but in a bold move, the National Gallery has opened an exhibition (Close Examination) featuring their art/science collaboration with EPSRC. From the news item on physorg.com,

Close Examination explores the pioneering work of the National Gallery’s Scientific Department by presenting the varied and fascinating stories behind more than 40 paintings in the National Gallery’s collection. The exhibition is arranged over six rooms, representing some of the major challenges faced by Gallery experts: Deception and Deceit; Transformations and Modifications; Mistakes; Secrets and Conundrums; Redemption and Recovery; and a special focus room relating to Botticelli. [emphases mine] The exhibition features works by Raphael, Dürer, Gossaert, Rembrandt and others.

The partnership between the National Gallery and EPSRC has highlighted the contribution that science and scientists make in the world of art and shows the intellectual value that emerges when scientific and artistic traditions come together. EPSRC, together with Arts and Humanities Research Council, funds a Science and Heritage Programme which aims to increase knowledge and the resilience of our cultural heritage in the face of twenty first century challenges.

I came across a similar collaboration between the Art Institute of Chicago and a chemist at Northwestern University who’d created a technique for another use altogether that the Institute’s conservators adapted. From The Nanotech Mysteries wiki page,

Richard Van Duyne, then a chemist at Northwestern University, developed the technique in 1977. Van Duyne’s technology, based on Raman spectroscopy which has been around since the 1920s, is called surface-enhanced Raman spectroscopy’ or SERS “[and] uses laser light and nanoparticles of precious metals to interact with molecules to show the chemical make-up of a particular dye.”

The conservators at the Institute were able to scrape off the most minute amounts of paint from a Winslow Homer painting in their efforts to examine the pigments and eventually restore the painting to its original colours. You can go here to see the painting that the conservators were trying to restore and to slide a button that will change the colours to their original shades.