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. Using 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 in glass. 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.

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. Using 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 in glass. 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.

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. Using 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 in glass. 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.

Roasting the Frit

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 chemical "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; 'Kali' and 'Soda'. Shipping them this way cut down on weight and volume, and prevented rotting. These 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.

Solid Water

Rock crystal cup , around 1550,

 Museo degli Argenti, Palazzo Pitti, Florence

(click to enlarge)

In the ancient world, certain natural materials commanded a premium and rock crystal was among the most coveted. Large completely transparent crystals of quartz were found in caves and glacial moraines and craftsmen managed to work them into exquisite cups, vessels and ceremonial objects. By the time the Renaissance arrived, unfulfilled demand for rock crystal drove much of the innovation in glassmaking. Indeed, clear glass was very much sought after and thought of as an artificially produced form of rock crystal.

A standard line in the historical narrative tells that the ancient Greeks believed that rock crystal was a form of solidified water, the word “krystallos” meaning ice. Enough written material survives from the likes of Herodotus, Pliny, Seneca and Saint Jerome to know for certain that one version or another of this idea has been around for a few thousand years. It is a line that usually gets attention for all the wrong reasons; when stated so glibly, it does not throw any light on ancient culture or our connection to it and worse, it plays into the fiction that we are somehow very much more astute than our relatives of 150 generations ago, that our progenitors were quaintly uninformed. 

Instead, think of “solidified water” as part of a working model of the world. It was consistent with the prevailing conception of nature in the same way that, for modern physicists, string theory serves; it seems to be correct, to the best of our knowledge, but the chances are good that there is more to the story yet to figure out. Like string theory, solid water is not a concept that would have a strong bearing on the daily lives of most people. For specialized artisans, it did make good sense; to thinking of rock crystal in this way would be a reminder that if treated too roughly, the material would shatter into pieces as if it were ice.

In the fifteenth century, the Venetian island of Murano became the center of the universe for glassmakers, and it stayed that way for the next four centuries. Of all the many forms that glass can take, the one that made Murano most famous was cristallo; named after the mineral it so closely imitates. The genius of cristallo was in bringing together diverse techniques and ingredients to form a product that was clear like water, yet could be worked thinner and in more complex designs than was possible with carved rock crystal.

 The hallmark of cristallo was the specific use of Levantine soda ash and white quartz river stones (tarso) as opposed to sand and it became the pinnacle of the glassmaker’s art. For the first time, artisans combine best practices with premium raw material sources, the extra purification steps, the careful avoidance of iron contamination, the hot glass washing process, the clean burning hardwood fire and the manganese color correction. In Venetian furnaces, even the clay for the crucibles was a special product imported from Constantinople, which did not contaminate the melt.

In 1450 the Christian world was dealt a severe blow by the Byzantine Empire’s fall to the Ottomans and with it went the Venetian’s major trading partners. That same year, the Murano glassmaker Angelo Barovier is given credit for the development of cristallo. He was the man responsible for bringing together the ultimate refinements that elevated glass to a new level of perfection and created a national product for Venice when they sorely needed it. These techniques and materials were all available and utilized by glassmakers individually at least fifty years earlier, but not together in a single product. Barovier had attended lectures by noted alchemist Paola de Pergola, at the School of Rialto. This indicates that he was thinking along the lines of a chemist in putting together a repeatable regimen for an exceptionally clear, bright, workable product. Barovier’s innovation would become a tradition that was carried on by countless glassmakers and ultimately by our Florentine priest Neri more than a century and a half later.

In seventeenth century Florence, Grand Duke Cosimo I de' Medici negotiated for Venetian masters to teach and practice their coveted techniques in Tuscany. Royal architect and polymath Bernardo Buontalenti was credited with the development of an artificial rock crystal, Tuscany’s own version of cristallo. It is an open question whether we see his hand in Neri’s recipe number seventy-six in which actual precious rock crystal is crushed and used as raw material for glass. In any case, Buontalenti’s continued presence at the Casino must have been an influential experience for his former pupil Don Antonio de' Medici, Neri’s sponsor. Our glassmaking priest was impressed enough with this technique to use rock crystal as the basis for his artificial gems. In turn, Neri’s chapter on artificial gems received the most attention, by far, of any other single subject in his groundbreaking book on glassmaking, L’Arte Vetraria. His work on this subject took on a life of its own and was the subject of plagiarism and unattributed derivative works well into the nineteenth century. An argument can be made that his lead glass based gems fueled the revolution pioneered by English glassmaker George Ravenscroft in what has become the current pinnacle of clear glass: lead crystal.

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. Using 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 in glass. 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.

Roasting the Frit

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 chemical "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; 'Kali' and 'Soda'. Shipping them this way cut down on weight and volume, and prevented rotting. These 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.

Solid Water

Rock crystal cup , around 1550,

 Museo degli Argenti, Palazzo Pitti, Florence

(click to enlarge)

In the ancient world, certain natural materials commanded a premium and rock crystal was among the most coveted. Large completely transparent crystals of quartz were found in caves and glacial moraines and craftsmen managed to work them into exquisite cups, vessels and ceremonial objects. By the time the Renaissance arrived, the demand for rock crystal drove much of the innovation in glassmaking. Indeed, clear glass was very much sought after and thought of as an artificially produced form of rock crystal.

A standard line in the historical narrative tells that the ancient Greeks believed that rock crystal was a form of solidified water, the word “krystallos” meaning ice. Enough written material survives from the likes of Herodotus, Pliny, Seneca and Saint Jerome to know for certain that one version or another of this idea has been around for a few thousand years. It is a line that usually gets attention for all the wrong reasons; when stated so glibly, it does not throw any light on ancient culture or our connection to it and worse, it plays into the fiction that we are somehow very much more astute than our relatives of 150 generations ago, that our progenitors were quaintly uninformed. 

Instead, think of “solidified water” as part of a working model of the world. It was consistent with the prevailing conception of nature in the same way that, for modern physicists, string theory serves; it seems to be correct, to the best of our knowledge, but the chances are good that there is more to the story yet to figure out. Like string theory, solid water is not a concept that would have a strong bearing on the daily lives of most people. For specialized artisans, it did make good sense; to thinking of rock crystal in this way would be a reminder that if treated too roughly, the material would shatter into pieces as if it were ice.

In the fifteenth century, the Venetian island of Murano became the center of the universe for glassmakers, and it stayed that way for the next four centuries. Of all the many forms that glass can take, the one that made Murano most famous was cristallo; named after the mineral it so closely imitates. The genius of cristallo was in bringing together diverse techniques and ingredients to form a product that was clear like water, yet could be worked thinner and in more complex designs than was possible with carved rock crystal.

 The hallmark of cristallo was the specific use of Levantine soda ash and white quartz river stones (tarso) as opposed to sand and it became the pinnacle of the glassmaker’s art. For the first time, artisans combine best practices with premium raw material sources, the extra purification steps, the careful avoidance of iron contamination, the hot glass washing process, the clean burning hardwood fire and the manganese color correction. In Venetian furnaces, even the clay for the crucibles was a special product imported from Constantinople, which did not contaminate the melt.

In 1450 the Christian world was dealt a severe blow by the Byzantine Empire’s fall to the Ottomans and with it went the Venetian’s major trading partners. That same year, the Murano glassmaker Angelo Barovier is given credit for the development of cristallo. He was the man responsible for bringing together the ultimate refinements that elevated glass to a new level of perfection and created a national product for Venice when they sorely needed it. These techniques and materials were all available and utilized by glassmakers individually at least fifty years earlier, but not together in a single product. Barovier had attended lectures by noted alchemist Paola de Pergola, at the School of Rialto. This indicates that he was thinking along the lines of a chemist in putting together a repeatable regimen for an exceptionally clear, bright, workable product. Barovier’s innovation would become a tradition that was carried on by countless glassmakers and ultimately by our Florentine priest Neri more than a century and a half later.

In seventeenth century Florence, Grand Duke Cosimo I de' Medici negotiated for Venetian masters to teach and practice their coveted techniques in Tuscany. Royal architect and polymath Bernardo Buontalenti was credited with the development of an artificial rock crystal, Tuscany’s own version of cristallo. It is an open question whether we see his hand in Neri’s recipe number seventy-six in which actual precious rock crystal is crushed and used as raw material for glass. In any case, Buontalenti’s continued presence at the Casino must have been an influential experience for his former pupil Don Antonio de' Medici, Neri’s sponsor. Our glassmaking priest was impressed enough with this technique to use rock crystal as the basis for his artificial gems. In turn, Neri’s chapter on artificial gems received the most attention, by far, of any other single subject in his groundbreaking book on glassmaking, L’Arte Vetraria. His work on this subject took on a life of its own and was the subject of plagiarism and unattributed derivative works well into the nineteenth century. An argument can be made that his lead glass based gems fueled the revolution pioneered by English glassmaker George Ravenscroft in what has become the current pinnacle of clear glass: lead crystal.

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. Using 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 in glass. 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.

The Material of All Enamels

Léonard Limosin, Allegory of Catherine de' Medici as Juno,

French, 1573, Polychrome enamel  on copper and silver.

In L'Arte Vetraria, Antonio Neri's recipe book on glassmaking, he devotes the sixth chapter to making enamel. For Neri, this was a tinted form of opaque glass favored by jewelers and goldsmiths. The material was ground into a fine powder, added to a binder and painted onto glass or metals, usually copper, gold or silver. Once dry, the item was fired over a flame or in a kiln so the enamel would fuse to form a durable glossy coating. Talented workers could use various colors to paint entire scenes.

“We see ornate enameled metals in many colors and they make a pleasant and noble sight; they entice others to look and take notice.”

Neri begins by showing how to produce what he calls “the material to make all enamels.” This is a neutral-white base to which he then adds various metal oxide pigments to produce color.

He starts by mixing together thirty pounds of pure lead and thirty-three pounds of pure tin, both in a finely divided state. He heats them in a low temperature kiln that has a wide, accessible hearth. He roasts or "calcines" the metals, raking the powders around with special iron tools for many hours. This has the effect of oxidizing the metals without melting them.

He sifts the mixture and boils it in a kettle of pure clean water. The kettle is removed from the heat and the contents are allowed to settle for a while. The water is then carefully poured off, carrying with it only the finest particles still in suspension. This liquid is saved, while the sediment at the bottom of the kettle is sent back for reprocessing in the kiln. He repeats the "decanting" procedure many times, and then carefully evaporates the accumulated liquid over a low fire. What remains is an extremely fine powdered tin and lead oxide mixture.

Neri tells us that fifty pounds of this oxide is to be mixed with an equal weight of powdered cristallo frit. Cristallo was the coveted glass perfected by the Venetians on the island of Murano. "Frit" is the granulated glass before it is put into the furnace and melted. The recipe for cristallo had remained a state secret for over a century. It was the clearest, finest glass that money could buy and items made from it commanded top dollar among the richest families in Europe. Even after production methods became known to outsiders, Venice still controlled many of the raw materials through exclusive trade agreements around the Mediterranean. Neri was first to actually publish the recipes for making cristallo, in this very same book. It was made with pure white quartz pebbles from Pavia, mixed with purified salts derived from the Levantine kali plant, and decolorized with manganese from Piedmont.

In order to complete the enamel base material, Neri adds eight ounces of white tartar salt (made from the dregs of wine), sifts the mix and carefully heats it in terracotta pots for ten hours. The result is ground again and stored in a in a dry place, in a sealed container for future use.

The rest of the chapter is devoted to coloring this enamel base material; he always starts with a batch of either four or six pounds. He uses a large furnace pot to melt the enamel because even though the amount is relatively small, some of the pigments cause the batch to froth and swell violently. After adding the pigments, he lets the glass cook for a while, adjusts the color as necessary and then "washes" it several times. In this process, he throws ladlefuls of molten glass from the furnace-pot into large vats of cold clean water. The effect is to remove excess plant salts from the glass, which would ultimately foul the enamel. Finally, he forms the glass into individual dollops of about five ounces each; a size to which the goldsmiths were accustomed.

For green enamel, Neri uses copper and iron oxides in various proportions, for blues he uses "zaffer," which is a cobalt oxide. He mixes green and blue pigments to obtain turquoise colors. Manganese produced a red wine color, for yellow, he adds the unrefined dregs of red wine (potassium) with a pinch of manganese. Violet is a mix of manganese and copper oxides.

Finally, a word to the wise: Do not attempt to duplicate these recipes; fine lead powder is dangerous enough, molten lead enamel will evolve fumes that cause heavy metal poisoning. Remember that Antonio Neri was dead by age thirty-eight.

* This post first appeared here 11 July 2014.

Roasting the Frit

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

Making glass from raw materials involves several steps. In his 1612 book on glass- making, 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 chemical "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; 'Kali' and 'Soda'. Shipping them this way cut down on weight and volume, and prevented rotting. These 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: 

Use 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.