Showing posts with label potash. Show all posts
Showing posts with label potash. Show all posts

Monday, November 30, 2020

Lead Crystal

 

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's 1612 book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Wednesday, April 22, 2020

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.

Friday, February 7, 2020

Lead Crystal

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's 1612 book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Wednesday, December 11, 2019

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.

Friday, July 5, 2019

Lead Crystal

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's 1612 book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Friday, May 31, 2019

Sweet Lixiviation

Salsola Kali plant,
used in Mediterranean glassmaking
in the 17th century.
A long time ago, perhaps as long ago as the Stone Age, our ancestors discovered that mixing water with the ashes from the previous night's fire makes a good washing-up liquid. Not the solids, but what dissolves in the water forms a mildly caustic lye solution. It cleans dirty hands, and oily hair. The more concentrated the lye, the more pronounced the cleansing effect. When the solids are strained out and the liquid is evaporated, left behind is a crystalline salt known as potash. This process of extracting the soluble components of charred plant material is known as lixiviation. Potash had several applications in the ancient world that played a critical role in the advancement of civilization. Mix potash with tallow (rendered animal fat) and you have soap, spread it on your fields and you have a good fertilizer, put it in a very hot furnace with powdered sand, and you have glass. In simple everyday human activity, we see the roots of modern chemistry. The English word ‘potash’ is derived directly from the process described above: made in a pot with plant ash. It lends its name to the chemical element potassium, a major constituent and a key ingredient for many glass recipes.

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

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

* This post first appeared here on 29 September 2014.

Wednesday, April 24, 2019

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.

Monday, September 24, 2018

Lead Crystal

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Friday, August 3, 2018

Lixiviation

Salsola Kali plant,
used in Mediterranean glassmaking
in the 17th century.
A long time ago, perhaps as long ago as the Stone Age, our ancestors discovered that mixing water with the ashes from the previous night's fire makes a good washing-up liquid. Not the solids, but what dissolves in the water forms a mildly caustic lye solution. It cleans dirty hands, and oily hair. The more concentrated the lye, the more pronounced the cleansing effect. When the solids are strained out and the liquid is evaporated, left behind is a crystalline salt known as potash. This process of extracting the soluble components of charred plant material is known as lixiviation. Potash had several applications in the ancient world that played a critical role in the advancement of civilization. Mix potash with tallow (rendered animal fat) and you have soap, spread it on your fields and you have a good fertilizer, put it in a very hot furnace with powdered sand, and you have glass. In simple everyday human activity, we see the roots of modern chemistry. The English word ‘potash’ is derived directly from the process described above: made in a pot with plant ash. It lends its name to the chemical element potassium, a major constituent and a key ingredient for many glass recipes.

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

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

* This post first appeared here on 29 September 2014.

Friday, June 29, 2018

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.

Monday, November 6, 2017

Lead Crystal

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Wednesday, September 6, 2017

Lixiviation

Salsola Kali plant,
used in Mediterranean glassmaking
in the 17th century.
A long time ago, perhaps as long ago as the Stone Age, our ancestors discovered that mixing water with the ashes from the previous night's fire makes a good washing-up liquid. Not the solids, but what dissolves in the water forms a mildly caustic lye solution. It cleans dirty hands, and oily hair. The more concentrated the lye, the more pronounced the cleansing effect. When the solids are strained out and the liquid is evaporated, left behind is a crystalline salt known as potash. This process of extracting the soluble components of charred plant material is known as lixiviation. Potash had several applications in the ancient world that played a critical role in the advancement of civilization. Mix potash with tallow (rendered animal fat) and you have soap, spread it on your fields and you have a good fertilizer, put it in a very hot furnace with powdered sand, and you have glass. In simple everyday human activity, we see the roots of modern chemistry. The English word ‘potash’ is derived directly from the process described above: made in a pot with plant ash. It lends its name to the chemical element potassium, a major constituent and a key ingredient for many glass recipes.

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

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

* This post first appeared here on 29 September 2014.

Monday, August 7, 2017

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.

Monday, November 21, 2016

Lead Crystal

Roemer type drinking glass c. 1677,
George Ravenscroft.
The entire fourth part of Antonio Neri's book L'Arte Vetraria is devoted to the preparation of lead glass, a forerunner of what is now commonly known as lead crystal. This section is unique in the book in that it contains the only instance of the author giving direct advice to glass artists themselves:
"To work lead glass into various drinking glasses or other vessels, or even to draw cane for beadmaking, it is necessary to raise the punty [out of the melt], and to make a gather of glass by turning. Take it out, let it cool somewhat and then work it on a well-cleaned marble [marver]. The marble should be somewhat cool, and well bathed with water before use."
He goes on to describe what might be termed a kind of dance with the glass. As with a human partner, gentle patience is required in learning the boundaries of what can and cannot be done. Ultimately, an artist must come to understand the material's behavior and personality in order to result in a great partnership. For the artist who makes unrealistic demands, glass can be a heartbreaker.  
"This sort of glass, lead glass, is so runny that were it not cooled, and taken up by turning [the punty] to wind a gather, it would be impossible to work. It is so runny that it would not even hold onto the punty, because it is as loose as soup. This arises out of [the fact that] the lead calx causes it to become very fluid."
"Namely, gather the glass little by little, allow it to cool, and work it over marble frequently bathed in water. Furthermore, make sure to keep the pot of glass rather calm, and in a place in the furnace where it will not see too much heat, otherwise it will not be possible to work this glass at all."
The formulation of lead crystal as we know it is a relatively recent development. This is a composition of crushed silica (sand or quartz), potash (potassium carbonates) and lead oxide substituting for calcium to stabilize the composition. It is also true that lead has been added to glass since its invention a few thousand years ago. It is not clear that this addition was always intentional, but a Babylonian tablet of 1700 BCE gives a recipe for pottery glaze that explicitly contains lead. At some point, a discovery showed that small amounts of lead and pigment smeared on glass and fired made stained glass paintings possible. The earliest known examples of colored stained glass windows date to 800-820 (San Vicenzo Abbey excavation in Volturno, Italy.)  In medieval Europe, leading up to Antonio Neri's time, lead glass was used in mosaic tesserae and in artificial gems.

Finally, it is worth noting that Neri's childhood church in Florence, Cestello (now called Santa Maria Maddalena dei Pazzi), was then run by Cistercian monks. It was the Cistercian luminary St. Bernard of Clairvaux who, in the twelfth century, built the first church with large windows, urging, "The soul shall seek the light by following the light."

This post first appeared here 15 November 2013.

Friday, September 16, 2016

Lixiviation

Salsola Kali plant,
used in Mediterranean glassmaking
in the 17th century.
A long time ago, perhaps as long ago as the Stone Age, our ancestors discovered that mixing water with the ashes from the previous night's fire makes a good washing-up liquid. Not the solids, but what dissolves in the water forms a mildly caustic lye solution. It cleans dirty hands, and oily hair. The more concentrated the lye, the more pronounced the cleansing effect. When the solids are strained out and the liquid is evaporated, left behind is a crystalline salt known as potash. This process of extracting the soluble components of charred plant material is known as lixiviation. Potash had several applications in the ancient world that played a critical role in the advancement of civilization. Mix potash with tallow (rendered animal fat) and you have soap, spread it on your fields and you have a good fertilizer, put it in a very hot furnace with powdered sand, and you have glass. In simple everyday human activity, we see the roots of modern chemistry. The English word ‘potash’ is derived directly from the process described above: made in a pot with plant ash. It lends its name to the chemical element potassium, a major constituent and a key ingredient for many glass recipes.

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

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

* This post first appeared here on 29 September 2014.