Lixiviation

Salsola Kali plant,

used in Mediterranean glassmaking

in the 17th century.

A long time ago, perhaps as long ago as the Stone Age, our ancestors discovered that mixing water with the ashes from the previous night's fire makes a good washing-up liquid. Not the solids, but what dissolves in the water forms a mildly caustic lye solution. It cleans dirty hands, and oily hair. The more concentrated the lye, the more pronounced the cleansing effect. When the solids are strained out and the liquid is evaporated, left behind is a crystalline salt known as potash. This process of extracting the soluble components of charred plant material is known as lixiviation. Potash had several applications in the ancient world that played a critical role in the advancement of civilization. Mix potash with tallow (rendered animal fat) and you have soap, spread it on your fields and you have a good fertilizer, put it in a very hot furnace with powdered sand, and you have glass. In simple everyday human activity, we see the roots of modern chemistry. The English word ‘potash’ is derived directly from the process described above: made in a pot with plant ash. It lends its name to the chemical element potassium, a major constituent and a key ingredient for many glass recipes.

Besides potassium, plant ash can also contain significant quantities of sodium, magnesium and calcium. They occur in different amounts depending on the species and on its habitat. Plants are literally composed of the nutrients in the soil from which they grow. Mineral compounds that dissolve in water are brought in through the roots and become part of the plant. In northern European forests, salt from the ash of oak and beech trees and fern plants was used for potassium glass as far back as the middle ages. In the more arid Mediterranean regions, scrub vegetation from the coastal marshes made both sodium and potassium glass, namely with the soda and kali plants. The soda plant lends its name to sodium and the kali plant lends its name to a group of chemical elements, which we now call the alkali group. Of these two plants, salsola soda is high in sodium and very low in potassium, salsola kali is more equal between the two. The high sodium carbonate content of the soda plant and a few other species is unusual, but soda accounts for most glass made, even today. Most other plants are potassium rich. 

To make glass, the material was lixiviated: boiled, filtered, purified and dried. The raw plant material was lightly charred to reduce moisture content; this prevented rotting and reduced volume and weight significantly for shipping. Neri experimented with the ash of many other plants as well and he does not hesitate to mix salt from different sources to achieve a desired effect. He found suitable glass salts can be made from ferns, blackberries, broad bean (fava) husks, cabbage, thorn bushes, millet, rush and marsh reeds. What Neri did not know was that virtually all of these plants produced a salt that was heavily laden with potassium. Potash glass has a fundamentally different character than soda glass. He knew quite well that fern glass had a different workability and appearance from soda glass, but he was over a century too early to understand why. Highly purified, potash glass sparkles in the light more than soda glass. It is denser, giving better refraction of light, yet it is also more difficult to work since it stiffens quickly on the blowpipe.

* This post first appeared here on 29 September 2014.

Top Physician

Frontispiece from Ricettario Fiorentino 1597 ed.

In 1580, when Antonio Neri was four years old, just after the birth of his brother Vincenzio, both his father and grandfather were together granted full Florentine citizenship by Grand Duke Francesco I de' Medici. In Tuscany, citizen status was an honor conferred to a small fraction of the population and often through inheritance at around the age of thirty. The fact that Neri Neri gained citizenship at the age of forty and did so together with his father, Jacopo, shows it was not legacy, but perhaps their medical prowess that lead to the award. Antonio's father was a celebrated physician, and his grandfather was a well regarded barber surgeon. This period also corresponds to the first appearance of the unique coat of arms that distinguish this branch of the family. The same arms adorn the central panel of the vestibule ceiling at the Neri's residence. Citizen status bestowed the advantage of direct representation in the government and the right to hold public office. It also carried responsibilities to the city, to its leaders and to the Church. One requirement of citizenship was possession of a domicile within Florence. The baptism register listed Antonio and all of his siblings as residents of San Pier Maggiore parish long before the citizenship grant. However, it is in the 1580s that we see the first reference to Neri Neri's ownership of the palazzo at what is now 27 Borgo Pinti. 

Within a few years, Antonio's father's work on cures for paralysis were published. By the end of the decade he was appointed personal physician to the new grand duke, Ferdinando de' Medici, and to the royal family. The 1590's saw Antonio taking vows, and beginning his career in the Church. The road to priesthood ran on a parallel track to an apprenticeship in a trade. The completion of a trial period led to becoming a novice at the age of sixteen, then deacon and finally priest at around twenty-two. Meanwhile, Antonio's father, along with another doctor and two apothecaries was chosen by the entire Florentine College of Physicians to revise and update the famed Ricettario Fiorentino.[1] This book was the gold standard of doctors and pharmacists in Tuscany and throughout much of Europe. The Ricettario was an official reference for medicinal cures and prescriptions. The law required every apothecary to own a copy and to supply its listed formulas to customers. Many regard this volume as the first European pharmacopoeia. It was a systematic standardization of drug recipes and dosages. Throughout the Medici reign, updated editions appeared as knowledge progressed. The book is a major landmark in the history of medicine. The edition authored by Neri's father and colleagues, in 1597, proved so popular that in 1621 it was reissued without change.

There can be no doubt that Antonio's father and his work had a profound influence on the priest. In the introduction to his book on glassmaking, L'Arte Vetraria,[2] he proclaims his desire to publish his own work on chemical and medical [spagyric] arts, saying "I believe there is no greater thing in nature in the service of humanity." In his recipes he uses the terminology of physicians; adding chemicals in 'doses' and measuring 'ana' (in equal parts). In a 1608 letter to a friend, [3] Antonio describes his great success with medicinal cures of Paracelsus, "to the great wonderment of Antwerp." The priest also references experiments he carried out in Brussels and at the Hospital of Malines. Following in the footsteps of his father and grandfather, medicine would continue to be practiced in the Neri family for generations to come. 

[1] Neri, Benadù, Rosselli, Galletti 1597.
[2]Neri 1612.
[3]Neri 1608.
This post was first published here in a slightly different form on 16 October 2013.

Band of Alchemists

"The Alchemist" 1558, Pieter Brugle the Elder.

Mention the word 'alchemist' and the images that spring to mind are likely the same ones that have been around for centuries. Perhaps you will imagine something like Pieter Brugle’s 1558 depiction; a fool, whose head is filled with fantasies of conjuring gold. He spends all his earnings on exotic chemicals while his children go shoeless, the cupboard goes bare and his family starves. No? Then perhaps a more classical rendition; a white bearded mystic stirring a cauldron in a deserted castle, summoning unearthly forces, bending the will of nature.    

It is true that outlandish characters like these have existed, but as a fringe element at best.  For every secluded wizard or "get rich quick" schemer there were many more alchemists who lived otherwise unremarkable lives and went to work every day. They interacted with colleagues and used their knowledge to provide valuable services like making painter's pigments or medicines or refining metals. Seventeenth century glassmaker and Catholic priest Antonio Neri fell into the latter category. Another departure from the typical caricature of alchemy is that it was very much a plural endeavor; it was practiced not primarily in isolation but by well connected networks of people, at least in late sixteenth century Florence.

Anibal and Martin

Neri's father was the chief physician to the grand duke of Tuscany, and as such probably had something to do with Antonio's education and with the position that he landed in Florence at the renowned "Casino di San Marco," the laboratory of Medici prince Don Antonio, inherited from his father grand duke Francesco. Even before his prestigious appointment, Neri wrote an illustrated manuscript in which he shows a number of young men and some women his own age working at the business of alchemy. A few of them are identified by name and must have been Antonio’s friends: Anibal, Martin, Hiroem and Pietro. [1] 

Female alchemist depicted in Neri's
"Tesoro del Mondo"

The female alchemists depicted in the manuscript are not specifically identified, but a strong possibility is that they were nuns from one of the nearby convents. These facilities often maintained their own pharmacies and ran cottage industries that produced and sold goods to raise funds. Alchemy practiced by women is an area of study which still needs much research, but it is known that convents used alchemical techniques to distill their own medicinal remedies and produced their own paint pigments. The famous painter Suor Plautilla Nelli resided in the Dominican convent across the street from the Medici's Casino laboratory. Sculptor Suor Caterina Eletta was a nun at the same convent around Neri's time and was the daughter of Stefano Rosselli, the royal apothecary, another profession steeped in alchemy. Her uncle Fra Anselmo ran the Dominican's apothecary at San Marco, literally a few steps from the laboratory's front door. Suor Caterina was surrounded by relatives deeply involved in alchemy, how could she not be familiar with the subject?

At Don Antonio's laboratory, the Casino di San Marco, or the Royal Foundry as it also became known, Neri worked closely with Agnolo della Casa, another Florentine of the same age. In fact, all three men, Neri, Della Casa and Don Antonio were all born within a year of each other around 1576. Della Casa took notes on Antonio Neri's experiments in Florence over a period that spanned more than a decade. He filled literally thousands of pages. Much of this material is devoted to transmutation and the philosophers stone, both were subjects dear to Don Antonio de' Medici, their boss. The notebooks also indicate a lively correspondence with other chemical experimenters around Italy and wider Europe. Neri himself carried on a correspondence with his friend Emmanuel Ximenes who lived in Antwerp, a city that would become Antonio's home for seven years. 

The network of alchemy in Florence reached outwards to other experimenters and it also reached forward in time. Knowledge was passed from one generation to the next by schooling children in the art. From another branch of Della Casa's family came two brothers, Ottavio (1596) and Jacinto (Giacinto) Talducci della Casa (1601).  As youngsters they were said to have learned alchemy at the knee of Don Antonio. A century later, historian Giovanni Targioni-Tozzetti chronicled that these boys would go on to serve Grand Duke Ferdinando II de' Medici  and continue the work by directing the Real Fonderia when, after Don Antonio's death, it was moved from the Casino to the Boboli Gardens. Ottavio would become director of the Royal Foundry. [2]  

Jacinto Talducci Della Casa

Jacinto became a parish priest a few kilometers east of Florence, but he was pressed back into service as an alchemist after his brother died. He succeeded Ottavio as director of the Royal Foundry under Francesco Redi. Little is known about Jacinto's contributions to chemistry, but it must have been a remarkable life. He saw the germ of experimentalism really take hold; it would continue to grow and become the basis of our own modern science. Jacinto died in 1700 at the age of 99, he was the last surviving member of Don Antonio's band of alchemists and quite likely the last living soul to have personally met Antonio Neri.

[1] Neri 1598-1600, ff. 22r, 23r, 24r.
[2] Targioni-Tozzetti 1780, p. 127. Don Antonio de' Medici died in 1621.

* This post first appeared here on 26 September 2014.

Deadly Fumes

Memento mori, 1605.
Nikolaus Alexander  Mair von Landshut.

17th century glassmaker and alchemist Antonio Neri handled very dangerous materials on a daily basis. He used strong acids, which if splattered could easily burn flesh, or cause blindness. He handled poisonous compounds containing arsenic, mercury and lead. If ingested, or inhaled as fumes these materials caused progressive, irreversible damage to internal organs and especially to the nervous system. There is no question that Neri did take chances with his health, but he was not naive. He knew very well many of the potential dangers and others he could well imagine. In chapter 74 of his book L'Arte Vetraria, he describes a way to tint rock crystal with beautiful colors. He wrote: 

Take orpiment of that really tawny orange-yellow color and pulverize 2 ounces of this along with 2 ounces of powdered crystalline arsenic, 1 ounce of pulverized crude antimony, and 1 ounce of sal ammoniac. […] Perform this entire operation under a large chimney to draw the fumes out of the room. These fumes are not only harmful but also quite deadly. Return to see if the coals have died down, because for the work to come out nicely, they must be burning well and full. For the remainder, leave and let the fire run its course with no one in the room with the work, for it is dangerous; the harsh materials will smoke quite a bit. Leave it to finish all fuming by itself and then extinguish the fire and spread the coals.[1]

In the spring of 1603, Neri was working in Pisa and became seriously ill. The specific cause and symptoms of his ailment are not known. He could have been harmed by one of his own experiments, or just as easily fallen prey to an infection or one of many other maladies prevalent in the early seventeenth century. He postponed his planned visit to Antwerp in order to recuperate. Finally, on 2 May 1603, his friend Emmanuel Ximenes wrote: "Praise God that your indisposition has ended ... if the Pisan air is suited to your recovery then do not change it." [2]

In the winter of 1603-4 Neri embarked on what would become a seven-year-long visit to his friend's palace in Antwerp. There, he would learn many new techniques, and ultimately have special glass vessels made and presented to Philip William, Prince of Orange. Upon his return to Tuscany in 1611, he sat down to write the book for which he is most remembered, L'Arte Vetraria. Two years after publication, in 1614, the priest would be dead. According to the only known account, printed over two centuries later by Francesco Inghirami.

Meanwhile, Neri became gravely ill, so he called the prince to come to him, having the promised the secret [of the philosophers stone]. But the Medici, who was in the countryside, took too much time; the patient died before the prince could be with him. Don Antonio was not quieted and he questioned all of Neri’s friends to see if he could find the information, but his efforts were in vain, as they should be in so groundless a science, although Giacinto Salducci [sic.] said that he had seen great things, specifically a powder that fixed mercury into gold. [3]

[1] Neri 1612, ch. 74.
[2] Ximenes 1601–11, also see Zecchin 1987–89, v. 1, pp. 165–169.
[3] Inghirami 1841–44,v. 13, pp. 457–458 probably based on Targioni-Tozzetti  189.

This post first appeared here in a slightly shorter form on 30 October 2013.

Encomium for a Female Glassblower

Woman flameworking glass
(Attribution Unknown, late 19th cent.)

In 1743, Britain was ruled by George II, although the Jacobites in Scotland were plotting to install Bonnie Prince Charlie to the throne. That year, Samuel Johnson was a 33 year old struggling writer and his still-to-be famed biographer James Boswell was just a toddler in Edinburgh. Also in Edinburgh, in 1743, exhibiting for a short time only, was Mrs. Johnston, an itinerant fancy glassblower.

‘Fancy' glassblowing refers to the process of working, not at a furnace, but at a table over an oil lamp with rods of glass. The artist formed the glass into small objects; rigged ships, animals, flowers, religious icons, beads and other ornaments. Glass spinning was a related process in which the heat of the lamp flame was used to draw an extremely fine continuous filament of glass that was collected on a large spinning wheel. The result was a mass of almost silk-like floss that was soft and flexible; nothing like the brittle glass of a cup or a window pane. Spinning demonstrations never failed to fascinate audiences and were a staple of fancy glass blowing acts well into the twentieth century.

Artists would often take suggestions from spectators on what to make and then form the piece on the spot. A common technique was to repeatedly touch a thin rod of glass, called a stringer, along the piece under construction forming a series of little loops in the flame. Rows of loops build up a surface that resembles knitting and a skilled artist can form finished pieces quickly. Eventually, both spinning and the knitting techniques became known generically as ‘spun glass’.

Although not well chronicled, this type of demonstration was performed at fairs and other shows as far back as the fifteenth century, and probably earlier. Because of their popularity with women and children, female fancy glass workers were not only well accepted, but commanded a premium at these events.

Below is a lovely correspondence appearing in the local Edinburgh newspaper in January of 1743. The writer is so taken by Mrs. Johnston’s demonstration that he or she was moved to compose a poem. In terms of documenting eighteenth century glass artists, it simply does not get any better:

“To The Publishers of the Caledonian Mercury. Reading a former letter of Leonora’s, curiosity inclined me to see Mrs Johnston the glass spinner, and was agreeably surprised to find the encomiums given her fall short of the character she justly deserves; so I hope the gentlemen, as well as the ladies, will solicit in the behalf of the celebrated artist, as is due her merit.  Therefore,

Let Britain quite enjoy its transport round,

Or Johnston’s praise to all the nation sound;

For me, to humble distance I’ll retire,

There gaze, and with secret joy admire:

My native Scotland such a one can boast,

On whom the praises of the world are lost,

For her own works do justly praise her most.

By giving this a place in your paper, you will oblige, yours, etcetera  -- Torisment. [1]

Two weeks later, appearing in the same paper is Mrs. Johnston’s reaction:

“When a person is obliged to persons unknown, the best way is to return them thanks in the most public manner: therefore Mrs. Johnston, the glass blower and spinner, returns thanks to all the gentlemen and ladies who have honored her with their presence; but more especially the gentleman and lady who did her that honour in the public paper: She cannot show her gratitude in any other way than by her best prayers for their felicity, which she shall always think herself to do both for them and all other her benefactors. Her stay being short in this kingdom, she performs now for the small price of sixpence per piece. [2]

[1] The Caledonian Mercury, Edinburgh, Scotland, 10 Jan 1743, p. 3.

[2] Op. cit., 24 Jan 1743, p. 3.

The Discovery of Glass

Giovan Maria Butteri,

"The Discovery of Glass"
Studiolo of Francesco I de' Medici

Any self-respecting Roman historian living in the first century could tell you the story that glass was first discovered by Phoenician sailors. They were temporarily grounded at the bay of Haifa, near the Belus River, in the shadow of Mount Carmel, forced ashore by a storm. Needing to eat, they improvised a fire on the beach in order to cook their food. Using natron, a mineral they were carrying as cargo on the ship, they built up a stove. To their amazement, in the heat of the fire, the natron mixed with the beach sand started to melt and liquid glass trickled out.

Actually, starting with Pliny the Elder, the author of most famous version of this story, skepticism abounds about how much of it was true. Nevertheless, if we gently tease apart the loose threads of this yarn we find that it is not without substance. First, there is the location; not just any port in a storm, this region was the site of a thriving glass industry as early as the sixth century BCE, due to the exceptional, pure white sand at the outlet of the Belus river. Archaeologists have excavated ancient glass furnaces at the nearby cities of Tyre and Sidon.

Next, the sodium carbonates in natron do indeed form glass when mixed with fine sand and brought to a high temperature, but this takes strong, concentrated heat, likely more than could be provided by a cook's beach fire. Natron is a hydroscopic mineral – this means it pulls moisture out of the surrounding environment. The water is locked into its solid crystal structure, where it remains until it is released either chemically or through heat. Natron can hold a remarkable amount of water, up to two-thirds of its weight. This is why it was used extensively to preserve mummies in Egypt; it dried out the bodies, quickly preserving them. While the story of the Phoenician sailors deserves a healthy dose of skepticism, it is also easy to see how the decomposition of the natron in the fire, resulting in the release of briny liquor, might be misinterpreted as glass.

In the early 1600s glassmaker and alchemist Antonio Neri published the first printed book of glass recipes, and in his introduction he too recounts the tale. However, in Neri's telling, natron does not make an appearance. Instead, the sailors use 'kali,' a coastal plant that is rich in alkali salts, to fuel their fire. The salts in kali are substantially similar to natron and, according to the story, triggered a similar result. In this period, Kali ash was a well-known ingredient in glass making. Neri used it in his own recipes, so the substitution is not surprising, but in this respect, Neri's version of the story does appear to be unique in the literature. It is interesting to note that Lodovico Domenichi, who was good friends with Neri's grandfather, tells a version of this story in his Italian translation of Pliny's Natural History. Here the sailors use natron, but in the next paragraph, Domenichi describes how local natives later used the plants to make their own glass.

The above depiction of the discovery of glass was painted by Butteri, one of a select group of painters for the Medici court in Florence. The work was commissioned to hang in the secret "studiolo" of Francesco de' Medici, a concealed barrel vaulted room tucked under a staircase in the Palazzo Vecchio in the early 1570's. It was only accessible through secret passages, one leading from Francesco's bed chamber. Another led from the chamber to an unmarked door on the street and a third passage led from the chamber to the secret treasury room once used by his father, Grand Duke Cosimo I. The walls and ceiling were entirely filled with paintings, the lower ones concealing cabinets full of oddities of nature, precious gems, coins, alchemical concoctions, and other treasures. Presumably, the cabinet behind Butteri's "Discovery of glass" would house some of the intricate Venetian glass vessels for which the craftsmen of Murano had become world famous. Shortly before the room was completed, a small number of these glass masters were allowed to teach their secrets in Florence by special arrangement with the Venetian government.

This post first appeared in a shorter form here on 9 October 2013.

Alchemy of Plants

Antonio Neri, Tesoro del Mondo, f. 9r.

"Arts Preparatio frugu vel Piantar."

In a 1598 manuscript devoted to "all of alchemy", Antonio Neri singled out four particular practices, each of which he made the subject of a detailed illustration. Each is devoted to a different "art"; preparing animals, stone/minerals, plants and metals. The manuscript was produced over a period of two years starting when he was just twenty-two years old. He began writing shortly after his ordination as priest and the work was completed before he was employed making glass for the royal Medici family in Florence. 

Neri is best known for writing the first printed book of glassmaking recipes, so we might expect to find that subject covered in the early manuscript, but nothing appears aside from a single recipe for artificial ruby which makes use of glass. Indeed, the general conclusion of historians is that his involvement in making glass did not start until 1600 or 1601. Absent of any direct citation of that art, the manuscript does show a familiarity with the kind of individual skills required. Among the things Neri would need to know was the ability to make "glass salt" from certain dried plants. Presently we will look into the third of the illustrations mentioned above, which he titled "The Art of Preparing Fruits or Plants." [1] All of the activities depicted here relate to food and drink, yet they could easily be applied toward other purposes.

While there is scant reference to glass in the text, the pictures are filled with examples of specialized vessels for chemical production and investigation. From these figures we know Neri at least received an exposure to the glassmaking profession earlier. He must have started his training in alchemy as a teenager while still studying for the priesthood. This is not hard to imagine since his father was the chief physician to the grand duke of Tuscany, and would have a strong grounding in alchemical techniques for producing medicines. Indeed, the first sentence of Antonio's 1612 book on glassmaking, L'Arte Vetraria, begins: "I have spent years of my youth laboring around the glassmaking craft, and experimented with many fine and marvelous effects." [2]

At center-left of the illustration at hand, we see a male farmer holding a flail, perhaps going about the business of threshing wheat, which appears in a bale behind him. Figuring prominently above the farmer (upper left) is a large mechanical apparatus that appears to be a gristmill powered by a waterwheel. A conical bag feeds grain or possibly corn from above into the central hole of a horizontal grinding stone supported by a large rectangular box. We can easily imagine that the gears shown on the front of the box control the drive or the gap between the stones. Wheat, of course, was an ancient well established staple. Corn was introduced as a direct result of Columbus' voyage to Cuba and by Neri's time, corn was being widely cultivated throughout southern Europe, northern Africa, and even as far as China.

Returning to the illustration, on the immediate left of the mill is a woman, who we can guess, is fashioning rolls or small loaves of bread from dough made with flour from the mill. Below her, (center right) is a boy using a long paddle to put the balls of dough into a baking oven. In effect, Neri is showing us the full chain of events from harvesting to finished baked goods. 

Further down, another woman works over a large basket of herbs, which appear destined for three large glassware stills to her right. In his book, Neri presents numerous recipes for extracting paint pigments from flowers using similar methods.

At the bottom of the illustration, a third woman stands in a large wooden tub crushing grapes with her bare feet, as grape juice runs into a pan on the right. To her left are three wine barrels standing side-by-side. 

For us, the connection to alchemy might seem tenuous with the possible exception of the distilling stations. For Neri, there was a deep lesson here about the way nature works; in his later manuscript Discorso, he uses the growth of grain as a metaphor for "multiplying" the "seeds" of gold inherent in primordial material left over from the creation of the world. 

This is confirmed by the example of seeds, of which a single grain is capable of producing a hundred or a thousand, as long as you sow them in a commensurate place. Take the further example of fermentation, in which one small part is sufficient to ferment a large mass. Nor is it contradictory to say that the metals do not produce seeds, like herbs and plants, because even though nature by itself has no power to take the seed out of gold, however, aided and encouraged by art, [nature] will do that which it does not do by itself. So that art begins where nature ends, and art will perfect the seed, which in gold is merely begun. [3] 

Given knowledge of how to work in harmony with nature and bring about the right conditions, he was convinced that a small quantity of material could be converted into a large amount of precious metal. The illustration on the art of preparing plants simply showed a different manifestation of the same principle; he is showing how grain multiplies in the fertile earth, it is then transformed through the addition of water and fire into nourishment.

[1] Neri 1598–1600, f. 9r.
[2] Neri 1612, p. ii.
[3] Grazzini 2012, p. 454, (Neri, 1613).

* This post first appeared here in a slightly different form on 10 Sept 2014.