Glass Salt

Diderot & d'Alembert, L'Encyclopédie (1772)Raking Out Roasted Frit

Making glass from raw materials involves several steps. In his 1612 book on glassmaking, L'Arte Vetraria, Antonio Neri breaks the process down into parts so that, "given a bit of experience and practice, as long as you do not purposely foul-up, it will be impossible to fail." Pure white sand, or preferably quartz river stones which Neri calls "tarso" is broken up and pulverized into a fine powder. The initial work can be done by heating the stones in a furnace, then dropping them into a vat of clean cold water, where they will fracture due to the thermal shock. The process was often repeated multiple times. From there, the pieces are pulverized in a stone mortar and pestle. Stone, because metal tools would contaminate the quartz, and in the end tint the glass. Finally, a powder is obtained by grinding with a stone tool on a flat granite "porphyry stone." This powdered quartz is the main ingredient of glass.

The second critical ingredient is the flux, what Neri calls "glass salt" or "soda." This can be obtained from mineral sources, but European glassmakers in the seventeenth century extracted all their salt from certain plants. The powdered quartz was mixed with the salt and a third ingredient, which is critical, lime. Lime is simply calcium oxide used by builders to make cement. It is nothing more than pulverized seashells roasted to a high temperature. Neri advises using two pounds of lime for every hundred pounds of salt. He specifies that it should be added to all his frit recipes, but it is not clear that he understood its critical importance; without lime, the glass would be subject to attack by mere water, eventually decomposing. This mixture of soda, lime and silica when heated in a kiln would chemically react forming "frit." The combined materials were raked around in a kiln for a long period (many hours) and finally formed nut sized pieces. It was cooled and heaped into piles in dry cellars where it was aged for a time. This is where some real "magic" in glassmaking takes place. The glass salt or soda dramatically lowers the melting temperature of the quartz, all the way down to a point that was easily achieved in a wood fired furnace. When a batch of glass was made, the aged frit was then melted in furnace crucibles and skimmed to remove excess salt, which floated on the surface; it could foul the glass, and smelled terrible. The melted glass, now ready to work, was sometimes colored and finally made into objects by gaffers. 

Neri obtained his glass salt from products shipped by traders from the Levant (eastern Mediterranean). It was supplied as the dried, partially charred remains of special plants that grow in arid seaside conditions. Shipping them this way cut down on weight and volume, and prevented rotting. These Soda and Kali plants contain large amounts of sodium carbonates. This is a white powder, chemically identical to what we know as "washing soda." He advises, 

In buying either of these make sure it is richly salted. This may be determined by touching it with the tongue in order to taste its saltiness; but the surest way of all is to do a test in a crucible and to see if it contains much sand or stones, a thing common in this art and very well known by glass conciatori.

He crushes any large pieces of the product in a stone mortar, and sifts the result through a fine screen, ensuring that most of what remains is salt.  

As the common proverb of the art of glassmaking says: a fine sieve and dry wood bring honor to the furnace. Then with any of these sodas, 100 pounds of soda ordinarily requires 85 to 90 pounds of tarso.

Neri sets up large cauldrons of clean water over brickwork stoves, adds the plant product and boils the water. He strains the insoluble parts out and reduces the liquid by evaporation until crystals of the salt start to form on the surface. He skims these off and continues the process. Finally he carefully dries the product. Our glassmaker describes several variations of this process, including one in which he takes extreme measures to ensure the purity of the salt and clarity of the finished glass. In all, this is a task that could easily take several weeks to perform for the amount of frit to fill a single pot for the gaffer to work.

Not content with the established materials, our glassmaker experimented extensively with other plants: 

[U]se the husks and stalks of fava beans after the farmhands have thrashed and shelled them. With the rules and diligence prescribed for the Levantine polverino salt, extract the salt from this ash, which will be marvelous, and from which a frit can be made using well-sifted white tarso, as is described throughout this work. A very noble frit will result, which in the crucible will make a crystal of all beauty. The same may be made from the ashes of cabbages, or a thorn bush that bears small fruit, called the blackberry, even from millet, rush, marsh reeds, and from many other plants that will relinquish their salt. *

*These other plants produce potassium carbonate salts with similar properties to sodium carbonate.

** This post first appeared here 9 December 2013.

Sulfur

Alchemical Symbol for Sulfur

Bright yellow elemental sulfur or “brimstone” as it was often called, occupied a central place in the cabinets of seventeenth century alchemists. Antonio Neri used it in many of his preparations and specifically in pigments for glass. When sulfur is heated with thin sheets or shavings of metal, foul smelling chemical reactions can take place that reduce the metal to a powdered compound and some of these turn out to be effective glass colorants. Neri’s 1612 book, L’Arte Vetraria, offers a variety of recipes, which specifically prepare iron and copper using sulfur to form pigments. In reality, the resultant chemicals were mixtures of oxides and sulfur compounds. Since these also chemically interact with each other in the glass melt, many different effects are possible. Modern glass artists sometimes specifically use both oxide and sulfide pigmented glass side by side in the same piece; a striking effect can be the spontaneous formation of a third color along the boundary. As Neri says in the closing line of his book:

Although I have placed here the way to make this powder with much clarity, do not presuppose that I have described a way to make something ordinary, but rather a true treasure of nature, and this for the delight of kind and curious spirits.[1]

Keep in mind that the thinking of alchemist Neri was that the sulfur acted upon the metal, but did not necessarily combine with it. From his point of view, the exposure resulted in the metal’s infusion with new properties. The Aristotelian conception of the world was that everything under the sun contained various amounts of four elemental essences: air, water, fire and earth. Sulfur was seen to be dominated by the latter two, ‘fire’ because it burned easily and ‘earth’ because it occurs as a solid.

In the sixteenth century, a Swiss physician named Paracelsus developed an extension of the four-element system. After his death, his writings enjoyed a new popularity among chemical experimenters in the period that Neri came of age. Since his teenage years, the work of Paracelsus was a strong influence on both Neri and separately on his benefactor, Florentine prince Don Antonio de’ Medici. According to Paracelsus, sulfur was one of a triad of “principles” consisting of salt, sulfur and mercury. These three had philosophical as well as physical interpretations attached to them. Besides other applications, like in medicine, the three physical materials figured prominently in efforts to transmute one metal into another. 

In fact, sulfur in particular played a starring role in a very convincing demonstration that purported to turn iron into copper. Mining operations often utilized water to clean or separate ore from tailings. Other times, water was used to keep dust down, or simply flowed naturally through underground springs. When sulfur-bearing earth is exposed to air and moisture, the result can be the formation of dilute sulfuric acid. This “vitriol” was an irritant to the eyes and skin, and very unpopular with the miners. However, in at least one location, it seemed to have a miraculous property. When this “vitriolated water” flowed out of the mine, it seemed to transform bits of iron into copper. [2]

Chemically, copper had already been dissolved in the acid, forming a copper sulfate solution. But sulfuric acid shows a preference for iron. When the copper solution flowed over iron tools, it took up the iron and dropped the copper, depositing it in a thin layer. The effect appeared to be a transmutation of iron into copper. Further testing and scrutiny confirmed that pure iron, when exposed to the mine fluids resulted in real copper. Neri for one was well aware that the vitriolated water might have arrived containing copper, as he explains in his manuscript Discorso. [3] But apparently, it did not occur to him that the water leaving the scene might have contained the iron. If he had made the connection, the observation would have advanced the understanding of both ion-exchange chemistry and the principal of conservation of matter; these were two ideas that would not be explored seriously for another hundred years.

Well into the eighteenth century, the mine at Smolnik, (now in Slovakia), was a highly touted tourist destination for chemical experimenters. [4] For some, it was considered among the strongest evidence that transmutation could and did take place in the natural world. I like this demonstration so much because it works the same way as a parlor trick; while we are so intently focused on the metal changing before our eyes, Mother Nature quietly slips the copper in with one hand and takes the iron away with the other, no one the wiser.


[1] Neri 1612, p.114.
[2] See this post for a more detailed description  http://www.conciatore.org/2014/01/turning-iron-into-copper.html
[3] Grazzini 2102.
[4] The effect had previously been described Georgius Agricola, in book 5 [9] of Nature Fossilium. See edition, transl. from the first Latin edition of 1546 by Mark Chance Bandy, Jean A. Bandy (New York: Mineralogical Society of America, 1955), p. 188.

*This post first appeared here on 7 November 2014.

Lime

Vintage 1920's Water Glass Label.

The temperature of 1500 degrees (825 C) was comfortably within reach of seventeenth century glassmakers like Antonio Neri. It was also achievable in much earlier times and was used in one of the earliest chemical reactions of  human industry; the production of "lime" by heating seashells or limestone to the above mentioned temperature. This is the point at which these materials give up the carbon dioxide gas bound into their chemical structure, leaving behind calcium oxide, otherwise known as lime.

What makes lime so useful is a property early Roman engineers knew well; that when mixed with water, lime undergoes a chemical reaction that releases heat and quickly solidifies into a rock-hard mass that is impervious to the elements. The Romans used it as a construction material; they mixed it with ash, clay, sand and stones to form mortar, cement and concrete. It has played a critical role ever since in the construction of buildings, roads and monuments.

Today it is perhaps not an obvious choice in imagining the supplies of a seventeenth century alchemist’s cabinet; lime does not require exotic methods to produce, it was made in industrial quantities and readily available as a construction material. Nevertheless, lime played an important part in many diverse chemical preparations of the day. Antonio Neri mentions it numerous times in his writing. He used it in his lute recipe; a hard, cement like coating which protected alchemical glassware in direct flame and sealed joints. He also used it to extract the color from flowers in the production of paints. Most notably, he used lime as an ingredient in the formulation of glass itself. 

Lime turns out to be a rather critical ingredient in glassmaking and the central player in a mystery about the history of glass that to this day has not been satisfactorily explained. Neri obtained the white powder from suppliers as "lime cake." Early in his book, L'Arte Vetraria, he states it should be used in all his glass recipes. 

Take lime salt, which is used for building. Purify this salt and mix it with ordinary Levantine polverino salt in the proportion of 2 pounds per 100, which is 2 pounds of lime salt, to every 100 pounds of polverino salt, purified and well made, as previously described. With this salt mixture, you can make yourself ordinary frit, and put it in the crucible to clarify. I will refer to this frit from now on in the recipes for cristallino, cristallo, and common glass. This way you will have cristallo quite subtle and beautiful.[1]

The above excerpt is the full extent of Neri's discussion on lime in glassmaking. An interesting point here is that he does not say why lime is so necessary. [2] He must have known that adding too much lime will cause glass to become cloudy, the exact opposite effect that he is after. What is not so clear is if Neri (or anyone else) understood that too little lime allows glass to dissolve slowly when exposed to water. 

One of the great enduring mysteries in the history of glassmaking is the question of exactly when it was understood that lime was so important. The subject became a matter of deliberate chemical investigation in the eighteenth century, but the use of lime extends much earlier. Some of the earliest glass fragments known contain healthy amounts of lime. Neri's ambiguous endorsement is the first mention in print, but even among much earlier manuscripts, its role is unclear. In the first century, Roman author Pliny made a cryptic reference to adding seashells to the glass melt, but again, without further explanation. [3] Analysis of ancient glass often shows a significant lime content; seemingly more than could be reasonably accounted for by happy accident or contamination. The ingredient is never mentioned in most surviving early recipes. Of course, it may be that  lime is present in many ancient glass artifacts precisely because those artifacts are the ones that have survived without dissolving.

Some have speculated that calcium could have been introduced inadvertently as seashell fragments when sand was crushed into powder for glassmaking. This hypothesis is certainly possible, but it seems suspect considering just how much seashell would be required and how fussy the glassmakers were in obtaining pure white sand from particular locations. However, a distinction must be made between knowing that sand from a particular location makes good glass, and knowing what is in that sand. 

Perhaps the most famous such site for good glassmaking sand is the "Belus" [Na'aman] River outlet in what is now northern Israel. This is where the story of the discovery of glass takes place, as told by Pliny and other early writers. Sailors were driven here by a storm, they used natron (glassmaking salt) [4] from their cargo to hold their cooking pots up over a beach fire, and when the natron mixed with the sand in the fire, glass was formed. Or so the story tells. The nearby Phoenician cities of Tyre and Sidon are known to have hosted a thriving glass industry. The sand in this area is composed of exceptionally pure quartz, with a healthy amount of calcium from shells ground down from wave action. Together these make an ideal mix for stable glass. 

There is some evidence that experimenters such as Basil Valentine were aware that glass without lime would dissolve as early as 1520. [5] For what it is worth, I can contribute some anecdotal evidence from the twentieth century. There is a well-known product called water-glass that is essentially composed of dissolved glass without the lime. [6] My glass artist friend Emilio tells me that growing up on Murano in Venice, his mother regularly preserved fresh eggs by dipping them in water-glass, which when dry, formed a hard seal over the existing shell. Presumably, she learned the technique from her own mother. I do not know of any early references, but the use of water-glass clearly indicates a knowledge of the role lime played.

There are other explanations possible for the addition of lime to glass. Lime was a commodity that was made since ancient times, in furnaces very similar to the ones producing glass. In fact, Neri specifies the use of a “limekiln” for the production of his enamels. The archaeological remains of Tyre and Sidon show prolific use of lime based plaster and mortar in their construction practices and there are indications of lime making facilities. It seems only good business sense that the same furnaces making glass may have also been making lime. Cross contamination, and even experimentation would be a natural outcome. 

[1] Neri 1612, ch 7.
[2] As an aside, magnesia (MgO) can also serve as a stabilizer in glass.
[3] Pliny, Natural History v.36, ch. 66.192.
[4] Natron is a mix of sodium carbonates. 
[5] Basil Valentine, et al. see footnote 6 of the Wikipedia article on sodium silicate for a discussion.
[6] Sodium Silicate.
* This post first appeared here in a slightly different form on 10 October 2014.

Saltpeter

Saltpeter beds, 1683 English ed.
Beschreibung allerfurnemisten mineralischen Ertzt 
by Lazarus Ercker. (Prague, 1574).

In the era of glassmaker and alchemist Antonio Neri (the early seventeenth century), it was commonly assumed there was a direct causal connection between the "macrocosm" (stars, planets etc.) and the "microcosm" (the very small), with human life on earth standing in the balance, in-between the two. This philosophy forms the basis for astrology, which in Neri's time was utilized for all sorts of decisions and the planning of events. Even so, there was much debate about what the exact connections were and how they worked. This cosmic theory of the very large being directly connected to the very small is an ancient idea that precedes even the discovery of saltpeter, today's topic of discussion. Saltpeter was the critical ingredient of gunpowder, fireworks, fertilizers, medicines and as we will see, even the preparation of materials for glassmaking. It undoubtedly held an important place in Antonio Neri's alchemical cabinet. 

From our vantage point on Earth, Sirius is the brightest star in the heavens. As such, it has a rich history in almost every ancient culture. The Egyptians used it to base their calendar; when the star made its last appearance for the year, rising just ahead of the sun, it foreshadowed the coming season of Nile flooding (and abundant crops). To the ancient Greeks, this event signaled a hot, dry summer ahead. In the constellation Canis Major, the main star is Sirius, which  is also commonly known as the "dog star," hence the expression, "dog days of summer." [1]

Next Month in September, Sirius makes its reappearance in the evening sky. Just after dusk, you can find it following the sun toward the horizon to the west. Since it is the brightest star in the night sky, it tends to be visible before other stars. In Renaissance Italy, this evening event heralded the end of summer’s heat and the start of cool autumn rains. Which, among other things, meant it was time to harvest the saltpeter, before it washed away. 

Chemically, saltpeter is potassium nitrate, [2] although several similar compounds have traditionally been referred to by the same name. The term derives not from the name Peter, but from the Latin word for rock "petra"; it often forms on the walls of caves as mineral deposits, hence "salt from rocks." 

In China, where saltpeter was first put to use in gunpowder, it was widely collected from caves. Eventually it was discovered to be more prevalent where bat droppings were to be found. As a result, a new  "organic" open air method of production soon gained favor.

You may have noticed this; when animal dung sits in the barnyard for a while and there has not been any rain, a powdery white deposit starts to form on what is exposed to the air. That white powder is saltpeter. In France, saltpeter production turned into a cottage industry, with large beds being maintained, covered from the rain. Beds were prepared several ways, but the most straightforward was to mix dung with potassium rich wood ash and straw and let it sit for up to a year, then flush out the saltpeter with water. The liquid was carefully collected and further purified.

As far as I know, Antonio Neri does not speculate in any of his writing about the natural process by which saltpeter forms, but one of his contemporaries does. Polish born alchemist and medical doctor Michele Sendivogius made a name for himself at the court of Holy Roman Emperor Rudolf II, in Prague. Sendivogius was convinced that saltpeter was a product of the air around us. He thought it was the congealed spirits of air and considered it "the food of life." He supported his argument with the fact that saltpeter makes a wonderful fertilizer for plants. He outlines his theories in A New Chemical Light which published in Frankfort in 1604, the same year Neri would have attended the spring fair there, assuming he followed the travel advice of his friend Emmanuel Ximenes. It was the year Neri embarked on what would become a seven year visit to Antwerp. [3]

While he was visiting in Antwerp, Neri makes particular use of saltpeter in his recipes for his colorful chalcedony glass "adorned with so many graceful and beautiful areas of undulations and enhanced with the play of diverse, lively, flaming colors." [4] He presented "His Excellency, the Prince of Orange, with two vessels of this chalcedony, which delighted him greatly." [5] In the recipe for this exotic glass, he makes extensive use of aqua fortis, acids for which saltpeter was an essential ingredient. These were the strongest acids known and the only way to dissolve precious metals like silver and gold. Neri uses a few gallons of these acids in the preparation of the ingredients for a single batch of his chalcedony glass. These acids were themselves thought to be composed of common water that had been infused with "powerful spirits." If Neri shared Sendivogius' reasoning, he might have thought that the process of making the acid was one of transferring the spirits of the air into water.

[1] Due to precession of the equinoxes, the date when Sirius rises and sets with the sun has shifted later by  about 25 days. In the Egyptian calendar of 3000 BCE the start of "dog days" coincided with the summer solstice.
[2] It is also called niter, with the chemical formula KNO3, composed of potassium, nitrogen and oxygen. 
[3] Again, there is no direct evidence of Neri's route, or that he was familiar with Sendivogius or the book. In Discorso (Neri 1613), he does mention alchemist Alessandro Scotus, who was released from prison by Sendivogius in 1590, after a conviction of practicing alchemy in public. See Grazzini 2012 p.346, n.55. 
[4] Neri 1612, p. 34.
[5] Ibid, p. 48.

* This post first appeared here on 19 September 2014.

Sulfur of Saturn

The Roman Goddess Ops, 'sweet'-heart (and wife)

of Saturn, Peter Paul Rubens c. 1630,

“Abundance (Abundantia).” [1]

Antonio Neri’s book on glassmaking, L'Arte Vetraria, devotes an entire chapter to making artificial gems. These are made with an especially dense, refractive form of lead glass—what today would be called lead crystal. He made it in small batches, in sealed ceramic vessels; each infused with various metal oxide pigments to give characteristic jewel tone colors.  His secret ingredient for making the finest artificial gems was a material known as "sulfur of Saturn." He writes:

You will have jewels of marvelous beauty in every color, which by far surpass those described above, made with ordinary minium. Because with this true sulfur of Saturn, they will surpass all others by far more than I can write here, as I have seen and made many times in Antwerp.[2]

This "ordinary minium" that he speaks of is one of several oxide forms of lead, also known as 'red lead,' it is bright red or orange in color. As a stable red pigment it was well known to ancient Byzantine and Persian illuminators. [3] It was so popular, in fact, that the word used to describe small intricate pictures 'miniature,' is derived directly from 'minium.' [4] The intricate embellishments in manuscripts ultimately took on the name of the scribes' favorite color.  In glass, minium does not impart red or any other color on its own, but does add 'sparkle' and made Neri's jewels highly refractive to light. 

In the recipe, he uses white vinegar and he reacts it with finely ground minium through a laborious process. The acetic acid in vinegar chemically combines with the minium to form lead acetate, which alchemists called "sugar of Saturn" because it had a distinctively sweet taste (more on that later). [5] Lead (Saturn) could be added to the melt in a number of different forms including acetate, carbonate and various oxides. The heat of the furnace reduces them all and the result is essentially identical glass from any of these sources. The lead acetate has one major advantage that set it apart from the others. Lead acetate is soluble in water and therefore it can easily be purified of contaminants and to a much higher degree. It can be filtered, allowed to stand and decanted after any insoluble impurities settle out.

In other references "sugar of Saturn" and "sulfur of Saturn" are considered synonyms. This is not the case with Neri, for him they are two different substances; the 'sugar' is a precursor for his final product, sulfur of Saturn:

Left in the bottom will be a salt as white as snow, and as sweet as sugar. Repeat the dissolution, and filtering, and evaporation with common water three times. This is the required sugar of Saturn. 

Keep it to calcine in sand in a glass flask or ball in a furnace over a moderated fire for many days. It will further calcine to a color that is much redder than cinnabar, and more finely impalpable than sifted grain flour. This is the required true sulfur of Saturn; purified from the sediment, foulness and blackness that were upon the lead at first. [6]

It would be a reasonable guess that by heating the acetate for "many days" he is reducing it back to minium, its more basic, bright red oxide state, but this time in a greatly purified form.

Unfortunately for his health, in this recipe for sulfur of Saturn, Antonio makes extensive use of heating and evaporation. Even more unfortunate is that in a number of steps he judges the potency of his product by taste. Lead acetate is highly toxic; because it is soluble in water, it enters the bloodstream easily. It attacks the nervous system, accumulates in the bones and can cause organ failure. It is quite likely that by breathing the fumes and tasting crystals of sugar of Saturn, Neri was contributing to his own demise at the relatively young age of thirty-eight. Lead acetate was not the only toxic substance he handled regularly, but it was certainly one of the worst for his health. 

 It does not follow that he was totally ignorant of the risks he was taking. The dangers of heavy metals were recognized from early times. Pliny speaks of the noxious fumes from lead furnaces, and Plutarch opined that lead and mercury mines were "unwholesome and pestilent places." Neri’s own father followed the work of Dioscorides, who wrote that ceruse (lead carbonate), taken internally, could be fatal and that certain sweet wines could adversely affect the abdomen and the nerves.

Ancient Romans discovered that when wine started to turn to vinegar, it could be boiled down in lead lined pots to produce a highly sweet syrup called sapa. A late Roman cookbook made extensive use of sapa, which presumably contained considerable lead acetate. [7] It has been conjectured that  lead laced sapa contributed to poisoning among the Roman aristocracy. While lead acetate is a deadly poison, it is a step too far to imply that it contributed to the fall of the Roman Empire.

[1] Alchemical tradition does provide for an association between the metal lead and the Roman god Saturn. However, there is no such association between 'sugar of Saturn' and either of his consorts Ops or Lua, although Ops, the goddess of abundance (opulence) does rather nicely represent the chemical that made Neri's most opulent artificial gems possible.
[2] Neri 1612, ch. 91.
[3] Chemically, this is Pb3O4, also known as Lead (II,IV) oxide, triplumbic tetroxide. Historically, it was called minium and red lead.
[4] The accepted etymology of ‘miniature’ is from ‘minium,’ but may have been influenced by similar Latin terms such as  minor, minimus, minutus, etc.
[5] Lead acetate comes in two forms; Pb (C2H3O2)4 and Pb (C2H3O2)2, both are toxic; the later variety is soluble in water.
[6] Neri 1612, ch. 91.
[7] “Saba” endures today as a popular grape syrup, albeit without the lead.
* This post forst appeared here on 12 September 2014.

Tartar Salt

So-called "wine diamonds," (harmless)

Potassium bitartrate deposits which can accumulate

in bottles and barrels of wine.

Tartar salt is an example of an alchemist's chemical that is a byproduct of another process, in this case winemaking. In his book L'Arte Vetraria, [1] Antonio Neri uses it in his glassmaking for two very different effects. The first application is to improve the appearance of the glass and the other is to modify colors. In addition to uses in glass, tartar also finds its way into his recipes for red paint made from the dried kermes insect [2] and for cast bronze mirrors, as a flux. (In foundries, a flux keeps the metal bright and shiny while in a molten state). [3]

Neri notes that tartar also went by the name of "gruma" to which we can add the synonyms greppola and argol. He warns readers several times to "leave behind the [dried] powder of the [raw] tartar, which is no good" and that "you should have tartar, from the dregs of red wine, which is better than white wine." [4] Nevertheless, he does specifically use white wine tartar in his recipes for rosichiero, a transparent dark red enamel. [5] In his recipe for producing tartar salt [6] he directs the reader to obtain the raw material from emptied wine barrels, but elsewhere in the book he seems to prefer to use the large crystals of tartar that have “vitrified naturally in bottles of wine.” [7] Chemically, tartar is a potassium compound formed through a reaction with tartaric acid, a major constituent of grape juice. [8] 

The effect of tartar in improving the appearance of glass can be readily explained. Most of the glass that was made in Italy in the seventeenth century used sodium-based additives to lower the melting temperature of finely ground quartz powder; these formulations are known as soda-based glasses. Potassium compounds can have the same effect and these 'potash' based glasses were predominantly produced in northern Europe where trees and plants rich in potassium were used. Potassium is a heavier element and it produces a denser, more refractive glass, giving it more sparkle, although not as much as lead imparts to crystal. Unfortunately, potassium also makes the glass harder to work for the artisan. Potash glass stiffens more quickly as it cools, whereas soda glass remains workable for a longer time before requiring reheating in the furnace. Many of Neri's recipes blend the two additives, which we can imagine gives some of the advantages of both.

Neri also used tartar to modify color in glass. The effects of tartar are exemplified in a number of passages throughout the book. He uses it as the sole pigment in his recipe for pearl colored glass, but he warns, "Once obtained, you must work the color quickly, because it will dissipate." [9] Conversely, he also uses tartar to produce a black colored enamel, combining it with manganese [oxide], which by itself imparts a magenta color. [10] 

The first step in making Neri's purified tartar salt is to obtain the raw "gruma, from barrels of red wine in which it forms large lumps." Next, he gently roasts it in terracotta pots "until it becomes calcined black and all its sliminess is roasted away. It then will begin to whiten, but do not let it become white, because if you do the salt will be no good." Now, he boils it in water for two hours, evaporating off three-quarters of the liquid. After filtering, he lets the remaining liquid "lye" cool in pans, allowing any sediment to settle to the bottom. He gently pours off  (decants)  the liquid which is further processed on the stove, this time in glass containers. The result, after full evaporation over a slow fire is a “white salt” left in the vessel. He dissolves this in hot water, filters it again and allows more sediment to settle out for a period of two days. Again, the liquid is decanted and evaporated in a glass container. The filtering and evaporation process is repeated four times, resulting in a product that is "whiter than snow."

Neri's final remarks for this chapter are as follows:

“When mixed with sifted polverino, or rocchetta, with its doses of tarso or sand, this salt will make a frit that in crucibles will produce the most beautiful cristallino and common glass, which one cannot make without the accompaniment of tartar salt. Without it, good fine cristallino can be made, nevertheless with it, it will be the absolute most beautiful.” [11]

[1] Neri 1612.
[2] Ibid, ch 116, 117.
[3] Ibid, ch 113. Note that in glassmaking, the term 'flux' has a different meaning than in metallurgy.
[4] Ibid,  ch 41. 
[5] Ibid, ch 125.
[6] Ibid, ch 11.
[7] Ibid. ch 46.
[8] Pure tartar takes the form potassium bitartrate KHC4H4O6.
[9] Neri 1612, ch 60.
[10] Ibid, ch 102.
[11] Ibid, ch 11. Polverino and rocchetta are thought to be forms of dried Salsola Kali plants. Tarso is Neri's term for white quartz river stones. Cristallino was a Venetian style glass that in quality fell between common glass and the premium cristallo, for which Murano became famous.

* This post first appeared here on 5 Sept. 2014.

Vitriol of Venus

Crystals of Copper Sulfate Pentahydrate

(Vitriol of Venus)

Vitriol of Venus was one of the most cherished items in Antonio Neri’s chemical library. In his book, L'Arte Vetraria, he describes its effect in glass this way:

To your great contentment, you will be astonished at what you see. I do not know of anybody else who has tried it this way and I Priest Antonio Neri trying it found it most marvelous, as said above, and it is of my own invention. [1]

To be clear, Neri is claiming a novel preparation technique for a chemical substance that was known since antiquity. I think it is quite reasonable to say that a particular personality trait led him down this path of discovery; his almost maniacal drive for purification. For a seventeenth century alchemist, it is a trait that served him well. Where other practitioners were content to use contaminated or substitute ingredients in their formulations, Neri always goes the extra mile in verifying his ingredients and using any extra filtering steps that might be warranted, no matter how time consuming. More than anything else this is what led him to such success in glass formulation, the assurance of exceptionally clear product and bright colors.

He is so proud of his creation that he spreads the description of his method over four full chapters of the book, going into a level of meticulous detail that is extreme, even for Neri. Rest assured, dear readers, that I have taken the liberty of distilling said description down to a more manageable form for your reading pleasure. Nevertheless, our priest-alchemist clearly puts great stock in this preparation, going so far as to drop hints that this material has uses that go far beyond glassmaking: "Many things could be said here, which are omitted as not being pertinent to the art of glassmaking, which perhaps upon another occasion you will be able to judge." [2]

Before starting, he gives some general advice:

You should make the sulfurs, vitriols, ammoniac salts, and similar materials slowly, over a low fire, so they are well prepared and well opened, because a violent fire will cause great damage to them.[3]

To begin, Neri cuts thin copper sheet into small pieces half the size of a small coin. filling a crucible, he layers the copper pieces with common sulfur (known as brimstone).  He cements the vessel shut with a lid and then buries it in the hot coals of a drafted furnace for two hours.

The dark purple contents are then ground and sifted through a fine screen, mixed with six ounces of pulverized sulfur per pound and then heated in a round terracotta pan, which is sitting in the hot coals. When the sulfur starts to burn, he stirs the mixture, rolling it into balls with an iron hook so it does not stick to the pan, continuing until it stops smoking. He removes the mixture from the heat, grinds it finely, adds more sulfur and repeats the entire process three times.

Neri grinds the resulting reddish tawny colored material into powder, putting a pound of it into a large glass vessel containing six pounds of clean water and gently evaporate away a third of the water. The liquid is carefully poured off and saved. The residual solids are dried and recycled in the process. Now more solids are allowed to settle out of the "beautiful blue" liquid over a two-day period and then the liquid is filtered through a felt cone.

He heats the liquid again, this time evaporating two thirds and then puts the remaining third into glazed terracotta pans, and leaves them in a cold damp place overnight. "You will find the vitriol of copper has formed into crystalline points that mimic true oriental emeralds." The crystals are removed, dried and the liquid is further evaporated in order to obtain more crystals. To the chemist, this material is copper sulfate pentahydrate [4]; today it is sold inexpensively as a fungicide for swimming pools. One reason it was so valuable to alchemists is that when gently heated or added to water this chemical forms a sulfuric acid solution. 

This is the true flaming azure blue [tincture], with which marvelous things are made. It is most potent, and as sharp as anything known in nature today, as can easily be perceived from its odor.

However important this was in other areas of alchemy, those applications do not have any particular relevance to the blue-green tint it imparts to glass, which he does make use of throughout the book. The full recipe was so long that he continued it several times and finished as the final chapter of L'Arte Vetraria. Here are the closing words to the book:

Although I have placed here the way to make this powder with much clarity, do not presuppose that I have described a way to make something ordinary, but rather a true treasure of nature, and this for the delight of kind and curious spirits.[5]

[1] Neri 1612, ch. 31.
[2] Ibid, ch. 133.
[3] Ibid, ch. 37.
[4] CuSO4•5H2O

[5] Ibid, ch 133.
* This post first appeared here on 29 Aug 2014.