Showing posts with label potassium. Show all posts
Showing posts with label potassium. Show all posts

Monday, December 28, 2020

Golden Yellow Glass

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. However, his actual glass recipes tend to contradict this advice. 

Neri says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color, paradoxically, one of them, in direct contradiction to his previous advice, is tartar: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.

Friday, May 1, 2020

Laughing in the Fern

Alain Manesson Mallet  1719,
"Der Mont. – Lune"
In Chapter 5 of L'Arte Vetraria, Antonio Neri shows how to extract salt for glass from fern plants in an evocative recipe. Fern was and still is widely abundant in Tuscany. It presented a ready source material for glassmakers of the region. Neri directs that harvesting of the plants be done in the spring:
Cut this herb from the ground when it is green, between the end of the month of May and mid June. The moon should be waxing and close to its opposition with the sun, because at this point the plant is in its perfection and gives a lot of salt, more than it would at other times and of better nature, strength and whiteness.
At first, it is tempting to dismiss this lunar influence as the product of a fertile imagination, but let us take a closer look. Even today, grandmothers throughout Italy remember the advice to pick vegetables from the garden and bring them into the kitchen at a half-moon. Can nona be completely off-track? The fact is that tidal forces of the moon do subtly affect plants, fish and animals in ways that can be measured. A closer look at Neri’s advice reveals reasoning that is hard to dismiss as mere astrological superstition. When the moon is waxing, tides rise and so do water tables. According to folklore, this is when sap rises from the roots of plants into stems and leaves. Sap carries the dissolved mineral salts required for glass. Neri also stipulates that harvesting should take place during lunar opposition. When the moon is 'opposed' to the sun, it is on the opposite side of the earth from the sun. In opposition, the moon is near full and rises as the sun sets. Plants see more light at night, leading to increased photosynthesis and growth.

In contrast, violin makers from Cremona valued high alpine spruce called moon wood which contain a minimum of sap. Trees were felled in the wintertime, when lunar tides were low. This minimized the amount of vibration deadening sap in the wood. In his Natural History, Pliny relates Cato’s advice on felling trees in accordance with the lunar cycle. In fact, centuries-old tradition specified lunar conditions for a host of needs from construction timbers to cheese boxes. In this case the advice relates to picking ferns for use in glass.

Fern ash is high in potassium carbonates. If carefully purified it can make an exceedingly clear glass, rivaling or even surpassing Venetian cristallo. It has the additional advantage of being physically tough, making it ideal for engraving or diamond-point work. On the other hand, once out of the furnace it stiffens quickly, giving it a short 'working life' for the hot glass artisan. This limits designs to simple basic forms. While soda-based glass was the norm for the Mediterranean region, throughout the Middle Ages and into the Renaissance, northern Europeans were more likely to be making potash-based glass. They utilized the potassium rich local trees and plants of the northern forests. In France, fern glass is called verre de fougère. In the considered opinion of some connoisseurs, wine tasted better when sipped from verre de fougère cups, hence the delightful expression 'le vin rit dans la fougère' [wine laughs (sparkles) in the fern].

Since the middle ages, fern glass became part of everyday life in northern Europe. It was familiar enough to find its way into literary verse on matters of the heart. There is a nice reference to fern glass by Geoffrey Chaucer, in The Squires Tale:
But notwithstanding, some said that it was
Wondrous to make fern-ashes into glass,
Since glass is nothing like the ash of fern;
But since long since of this thing men did learn,
Chaucer, in turn, borrowed this reference from an epic twenty-two thousand line French poem from the late thirteenth century, when the technique of making glass from ferns was already ancient.

* This post is a mashup of material that first appeared here on 5-7 August 2013.

Monday, February 17, 2020

Golden Yellow Glass

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. However, his actual glass recipes tend to contradict this advice. 

Neri says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color, paradoxically, one of them, in direct contradiction to his previous advice, is tartar: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.

Monday, July 8, 2019

Golden Yellow Glass

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. However, his actual glass recipes tend to contradict this advice. 

Neri says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color, paradoxically, one of them, in direct contradiction to his previous advice, is tartar: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.

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.

Monday, May 13, 2019

Laughing in the Fern

Alain Manesson Mallet  1719,
"Der Mont. – Lune"
In Chapter 5 of L'Arte Vetraria, Antonio Neri shows how to extract salt for glass from fern plants in an evocative recipe. Fern was and still is widely abundant in Tuscany. It presented a ready source material for glassmakers of the region. Neri directs that harvesting of the plants be done in the spring:
Cut this herb from the ground when it is green, between the end of the month of May and mid June. The moon should be waxing and close to its opposition with the sun, because at this point the plant is in its perfection and gives a lot of salt, more than it would at other times and of better nature, strength and whiteness.
At first, it is tempting to dismiss this lunar influence as the product of a fertile imagination, but let us take a closer look. Even today, grandmothers throughout Italy remember the advice to pick vegetables from the garden and bring them into the kitchen at a half-moon. Can nona be completely off-track? The fact is that tidal forces of the moon do subtly affect plants, fish and animals in ways that can be measured. A closer look at Neri’s advice reveals reasoning that is hard to dismiss as mere astrological superstition. When the moon is waxing, tides rise and so do water tables. According to folklore, this is when sap rises from the roots of plants into stems and leaves. Sap carries the dissolved mineral salts required for glass. Neri also stipulates that harvesting should take place during lunar opposition. When the moon is 'opposed' to the sun, it is on the opposite side of the earth from the sun. In opposition, the moon is near full and rises as the sun sets. Plants see more light at night, leading to increased photosynthesis and growth.

In contrast, violin makers from Cremona valued high alpine spruce called moon wood which contain a minimum of sap. Trees were felled in the wintertime, when lunar tides were low. This minimized the amount of vibration deadening sap in the wood. In his Natural History, Pliny relates Cato’s advice on felling trees in accordance with the lunar cycle. In fact, centuries-old tradition specified lunar conditions for a host of needs from construction timbers to cheese boxes. In this case the advice relates to picking ferns for use in glass.

Fern ash is high in potassium carbonates. If carefully purified it can make an exceedingly clear glass, rivaling or even surpassing Venetian cristallo. It has the additional advantage of being physically tough, making it ideal for engraving or diamond-point work. On the other hand, once out of the furnace it stiffens quickly, giving it a short 'working life' for the hot glass artisan. This limits designs to simple basic forms. While soda-based glass was the norm for the Mediterranean region, throughout the Middle Ages and into the Renaissance, northern Europeans were more likely to be making potash-based glass. They utilized the potassium rich local trees and plants of the northern forests. In France, fern glass is called verre de fougère. In the considered opinion of some connoisseurs, wine tasted better when sipped from verre de fougère cups, hence the delightful expression 'le vin rit dans la fougère' [wine laughs (sparkles) in the fern].

Since the middle ages, fern glass became part of everyday life in northern Europe. It was familiar enough to find its way into literary verse on matters of the heart. There is a nice reference to fern glass by Geoffrey Chaucer, in The Squires Tale:
But notwithstanding, some said that it was
Wondrous to make fern-ashes into glass,
Since glass is nothing like the ash of fern;
But since long since of this thing men did learn,
Chaucer, in turn, borrowed this reference from an epic twenty-two thousand line French poem from the late thirteenth century, when the technique of making glass from ferns was already ancient.

* This post is a mashup of material that first appeared here on 5-7 August 2013.

Wednesday, December 12, 2018

Laughing in the Fern

Allain Manesson Mallet  1719,
"Der Mont. – Lune"
In Chapter 5 of L'Arte Vetraria, Antonio Neri shows how to extract salt for glass from fern plants in an evocative recipe. Fern was and still is widely abundant in Tuscany. It presented a ready source material for glassmakers of the region. Neri directs that harvesting of the plants be done in the spring:
Cut this herb from the ground when it is green, between the end of the month of May and mid June. The moon should be waxing and close to its opposition with the sun, because at this point the plant is in its perfection and gives a lot of salt, more than it would at other times and of better nature, strength and whiteness.
At first, it is tempting to dismiss this lunar influence as the product of a fertile imagination, but let us take a closer look. Even today, grandmothers throughout Italy remember the advice to pick vegetables from the garden and bring them into the kitchen at a half-moon. Can nona be completely off-track? The fact is that tidal forces of the moon do subtly affect plants, fish and animals in ways that can be measured. A closer look at Neri’s advice reveals reasoning that is hard to dismiss as mere astrological superstition. When the moon is waxing, tides rise and so do water tables. According to folklore, this is when sap rises from the roots of plants into stems and leaves. Sap carries the dissolved mineral salts required for glass. Neri also stipulates that harvesting should take place during lunar opposition. When the moon is 'opposed' to the sun, it is on the opposite side of the earth from the sun. In opposition, the moon is near full and rises as the sun sets. Plants see more light at night, leading to increased photosynthesis and growth.

In contrast, violin makers from Cremona valued high alpine spruce called moon wood. Trees were felled in the wintertime, when lunar tides were low. This minimized the amount of vibration deadening sap in the wood. In his Natural History, Pliny relates Cato’s advice on felling trees in accordance with the lunar cycle. In fact, centuries-old tradition specified lunar conditions for a host of needs from construction timbers to cheese boxes. In this case the advice relates to picking ferns for use in glass.

Fern ash is high in potassium carbonates. If carefully purified it can make an exceedingly clear glass, rivaling or even surpassing Venetian cristallo. It has the additional advantage of being physically tough, making it ideal for engraving or diamond-point work. On the other hand, once out of the furnace it stiffens quickly, giving it a short 'working life' for the hot glass artisan. This limits designs to simple basic forms. While soda-based glass was the norm for the Mediterranean region, throughout the Middle Ages and into the Renaissance, northern Europeans were more likely to be making potash-based glass. They utilized the potassium rich local trees and plants of the northern forests. In France, fern glass is called verre de fougère. In the considered opinion of some connoisseurs, wine tasted better when sipped from verre de fougère cups, hence the delightful expression 'le vin rit dans la fougère' [wine laughs (sparkles) in the fern].

Since the middle ages, fern glass became part of everyday life in northern Europe. It was familiar enough to find its way into literary verse on matters of the heart. There is a nice reference to fern glass by Geoffrey Chaucer, in The Squires Tale:
But notwithstanding, some said that it was
Wondrous to make fern-ashes into glass,
Since glass is nothing like the ash of fern;
But since long since of this thing men did learn,
Chaucer, in turn, borrowed this reference from an epic twenty-two thousand line French poem from the late thirteenth century, when the technique of making glass from ferns was already ancient.

* This post is a mashup of material that first appeared here on 5-7 August 2013.

Wednesday, September 26, 2018

Golden Yellow Glass

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. However, his actual glass recipes tend to contradict this advice. 

Neri says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color, paradoxically, one of them, in direct contradiction to his previous advice, is tartar: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.

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.

Monday, February 12, 2018

Laughing in the Ferm

Allain Manesson Mallet  1719,
"Der Mont. – Lune"
In Chapter 5 of L'Arte Vetraria, Antonio Neri shows how to extract salt for glass from fern plants in an evocative recipe. Fern was and still is widely abundant in Tuscany. It presented a ready source material for glassmakers of the region. Neri directs that harvesting of the plants be done in the spring:
Cut this herb from the ground when it is green, between the end of the month of May and mid June. The moon should be waxing and close to its opposition with the sun, because at this point the plant is in its perfection and gives a lot of salt, more than it would at other times and of better nature, strength and whiteness.
At first, it is tempting to dismiss this lunar influence as the product of a fertile imagination, but let us take a closer look. Even today, grandmothers throughout Italy remember the advice to pick vegetables from the garden and bring them into the kitchen at a half-moon. Can nona be completely off-track? The fact is that tidal forces of the moon do subtly affect plants, fish and animals in ways that can be measured. A closer look at Neri’s advice reveals reasoning that is hard to dismiss as mere astrological superstition. When the moon is waxing, tides rise and so do water tables. According to folklore, this is when sap rises from the roots of plants into stems and leaves. Sap carries the dissolved mineral salts required for glass. Neri also stipulates that harvesting should take place during lunar opposition. When the moon is 'opposed' to the sun, it is on the opposite side of the earth from the sun. In opposition, the moon is near full and rises as the sun sets. Plants see more light at night, leading to increased photosynthesis and growth.

In contrast, violin makers from Cremona valued high alpine spruce called moon wood. Trees were felled in the wintertime, when lunar tides were low. This minimized the amount of vibration deadening sap in the wood. In his Natural History, Pliny relates Cato’s advice on felling trees in accordance with the lunar cycle. In fact, centuries-old tradition specified lunar conditions for a host of needs from construction timbers to cheese boxes. In this case the advice relates to picking ferns for use in glass.

Fern ash is high in potassium carbonates. If carefully purified it can make an exceedingly clear glass, rivaling or even surpassing Venetian cristallo. It has the additional advantage of being physically tough, making it ideal for engraving or diamond-point work. On the other hand, once out of the furnace it stiffens quickly, giving it a short 'working life' for the hot glass artisan. This limits designs to simple basic forms. While soda-based glass was the norm for the Mediterranean region, throughout the Middle Ages and into the Renaissance, northern Europeans were more likely to be making potash-based glass. They utilized the potassium rich local trees and plants of the northern forests. In France, fern glass is called verre de fougère. In the considered opinion of some connoisseurs, wine tasted better when sipped from verre de fougère cups, hence the delightful expression 'le vin rit dans la fougère' [wine laughs (sparkles) in the fern].

Since the middle ages, fern glass became part of everyday life in northern Europe. It was familiar enough to find its way into literary verse on matters of the heart. There is a nice reference to fern glass by Geoffrey Chaucer, in The Squires Tale:
But notwithstanding, some said that it was
Wondrous to make fern-ashes into glass,
Since glass is nothing like the ash of fern;
But since long since of this thing men did learn,
Chaucer, in turn, borrowed this reference from an epic twenty-two thousand line French poem from the late thirteenth century, when the technique of making glass from ferns was already ancient.

* This post is a mashup of material that first appeared here on 5-7 August 2013.

Monday, December 18, 2017

Like Snow From Heaven

28th December 2005 in Florence
Photo by Marco De La Pierre
In its simplest incarnation, glass is nothing more than crushed quartz or sand mixed with 'glass salt'. This salt is the alkali carbonates of sodium or potassium. Essentially, the ash of certain plants that reduces to oxide in the furnace and dramatically lowers the melting point of the sand.

In Pliny's ancient account of the discovery of glass, the process takes place in a single step. The ingredients came together accidentally in a fire and "glass trickled out." The problem is that pure quartz does not react with the salt until it gets very hot and even then, it does so reluctantly. In a wood-fired furnace, quartz stones, even small pebbles or sand would melt with excruciating slowness. As Neri advises, "... this would only succeed after a protracted period of time and a great amount of trouble." 

'Fritting' is an intermediate step that speeds the process considerably. Glassmakers reduce the quartz to a fine powder and then mix it with the alkali salt. In the heat of a kiln, the entire content of each stone is thus exposed to the salt right from the beginning. This roasting process starts a chemical reaction between the ingredients. In the late Renaissance, the combination was then cooled and 'aged' for several months before use. When made from pure quartz river stones and the best Levantine ash, the result was what Neri calls 'bollito,' "white and pure like snow from heaven."

A third ingredient of glass, critical to its long-term stability is lime, or calcium oxide. Without the lime, glass is susceptible to attack by water. The water actually dissolves the glass, or less dramatically makes it subject to 'glass disease' or 'crizzling', a condition where the glass slowly decomposes due to humidity in the air. Waterglass is a product made without the lime. On Murano and elsewhere, it was dissolved in water and painted onto the shells of eggs to seal and preserve them. In Neri's era, lime was produced by roasting seashells. It was a key ingredient of cement, and as such was readily available. It had been a major commodity throughout the Mediterranean since the Roman Empire. Neri advises to add lime to all his glass recipes, but it is not so clear that he himself understood why it was so important.


*This post first appeared here on 11 October 2013.

Wednesday, November 8, 2017

Golden Yellow

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. However, his actual glass recipes tend to contradict this advice. 

Neri says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color, paradoxically, one of them, in direct contradiction to his previous advice, is tartar: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.

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.

Friday, March 31, 2017

Laughing in the Fern

Allain Manesson Mallet  1719,
"Der Mont. – Lune"
In Chapter 5 of L'Arte Vetraria, Antonio Neri shows how to extract salt for glass from fern plants in an evocative recipe. Fern was and still is widely abundant in Tuscany. It presented a ready source material for glassmakers of the region. Neri directs that harvesting of the plants be done in the spring:
Cut this herb from the ground when it is green, between the end of the month of May and mid June. The moon should be waxing and close to its opposition with the sun, because at this point the plant is in its perfection and gives a lot of salt, more than it would at other times and of better nature, strength and whiteness.
At first, it is tempting to dismiss this lunar influence as the product of a fertile imagination, but let us take a closer look. Even today, grandmothers throughout Italy remember the advice to pick vegetables from the garden and bring them into the kitchen at a half-moon. Can nona be completely off-track? The fact is that tidal forces of the moon do subtly affect plants, fish and animals in ways that can be measured. A closer look at Neri’s advice reveals reasoning that is hard to dismiss as mere astrological superstition. When the moon is waxing, tides rise and so do water tables. According to folklore, this is when sap rises from the roots of plants into stems and leaves. Sap carries the dissolved mineral salts required for glass. Neri also stipulates that harvesting should take place during lunar opposition. When the moon is 'opposed' to the sun, it is on the opposite side of the earth from the sun. In opposition, the moon is near full and rises as the sun sets. Plants see more light at night, leading to increased photosynthesis and growth.

In contrast, violin makers from Cremona valued high alpine spruce called moon wood. Trees were felled in the wintertime, when lunar tides were low. This minimized the amount of vibration deadening sap in the wood. In his Natural History, Pliny relates Cato’s advice on felling trees in accordance with the lunar cycle. In fact, centuries-old tradition specified lunar conditions for a host of needs from construction timbers to cheese boxes. In this case the advice relates to picking ferns for use in glass.

Fern ash is high in potassium carbonates. If carefully purified it can make an exceedingly clear glass, rivaling or even surpassing Venetian cristallo. It has the additional advantage of being physically tough, making it ideal for engraving or diamond-point work. On the other hand, once out of the furnace it stiffens quickly, giving it a short 'working life' for the hot glass artisan. This limits designs to simple basic forms. While soda-based glass was the norm for the Mediterranean region, throughout the Middle Ages and into the Renaissance, northern Europeans were more likely to be making potash-based glass. They utilized the potassium rich local trees and plants of the northern forests. In France, fern glass is called verre de fougère. In the considered opinion of some connoisseurs, wine tasted better when sipped from verre de fougère cups, hence the delightful expression 'le vin rit dans la fougère' [wine laughs (sparkles) in the fern].

Since the middle ages, fern glass became part of everyday life in northern Europe. It was familiar enough to find its way into literary verse on matters of the heart. There is a nice reference to fern glass by Geoffrey Chaucer, in The Squires Tale:
But notwithstanding, some said that it was
Wondrous to make fern-ashes into glass,
Since glass is nothing like the ash of fern;
But since long since of this thing men did learn,
Chaucer, in turn, borrowed this reference from an epic twenty-two thousand line French poem from the late thirteenth century, when the technique of making glass from ferns was already ancient.

* This post is a mashup of material that first appeared here on 5-7 August 2013.

Friday, January 20, 2017

Like Snow from Heaven

28th December 2005 in Florence
Photo by Marco De La Pierre
In its simplest incarnation, glass is nothing more than crushed quartz or sand mixed with 'glass salt'. This salt is the alkali carbonates of sodium or potassium. Essentially, the ash of certain plants that reduces to oxide in the furnace and dramatically lowers the melting point of the sand.

In Pliny's ancient account of the discovery of glass, the process takes place in a single step. The ingredients came together accidentally in a fire and "glass trickled out." The problem is that pure quartz does not react with the salt until it gets very hot and even then, it does so reluctantly. In a wood-fired furnace, quartz stones, even small pebbles or sand would melt with excruciating slowness. As Neri advises, "... this would only succeed after a protracted period of time and a great amount of trouble." 

'Fritting' is an intermediate step that speeds the process considerably. Glassmakers reduce the quartz to a fine powder and then mix it with the alkali salt. In the heat of a kiln, the entire content of each stone is thus exposed to the salt right from the beginning. This roasting process starts a chemical reaction between the ingredients. In the late Renaissance, the combination was then cooled and 'aged' for several months before use. When made from pure quartz river stones and the best Levantine ash, the result was what Neri calls 'bollito,' "white and pure like snow from heaven."

A third ingredient of glass, critical to its long-term stability is lime, or calcium oxide. Without the lime, glass is susceptible to attack by water. The water actually dissolves the glass, or less dramatically makes it subject to 'glass disease' or 'crizzling', a condition where the glass slowly decomposes due to humidity in the air. Waterglass is a product made without the lime. On Murano and elsewhere, it was dissolved in water and painted onto the shells of eggs to seal and preserve them. In Neri's era, lime was produced by roasting seashells. It was a key ingredient of cement, and as such was readily available. It had been a major commodity throughout the Mediterranean since the Roman Empire. Neri advises to add lime to all his glass recipes, but it is not so clear that he himself understood why it was so important.


*This post first appeared here on 11 October 2013.

Wednesday, November 23, 2016

Yellow Glass

Yellow Neon Chandelier, 1995
Dale Chihuly.
(Columbus, Indiana Visitors Center). 
"Very few people know how to make colors like golden yellow and solid red well. These are difficult and troublesome in the art of glassmaking, since in making them you must stick precisely to the doses, the timing, the details and the materials as prescribed. The smallest error will cause everything to be ruined, and the colors to be irreparably spoiled. Therefore, you must be on guard not to make mistakes. [1]
So says Antonio Neri in his groundbreaking 1612 book of glass recipes, L’Arte Vetraria. Elsewhere he warns in several places not to add “tartar” to any glass destined for yellow pigmentation. Tartar was a common additive to boost the ‘sparkle’ of a glass because it contained a high level of potassium carbonates. These converted to potassium oxide in the melt, which has a higher refractive index than the usual glass flux, sodium oxide. 

However, the reason for the mismatch is not clear, since Neri also says of his “fern glass,” which is entirely potassium based:
…This frit can be given a wonderful golden yellow color provided there is no tartar salt within, as described in the caution, because then golden yellow will not emerge. This crystal is given to a golden yellow that is far more beautiful and pleasant than can be achieved in cristallo made with Levantine polverino salt and with this crystal unlike the other, every kind of job can be done. [2]
“Polverino” was a sodium based plant product used in many of Neri’s glass recipes, which he says was derived from the Kali plant grown in the Levant. The plot thickens when, for yellow, he recommends substituting ‘rocchetta’ another soda based Kali derivative. 

His primary recipe for golden yellow is #46, in which he reveals two ingredients responsible for the color: “For every 100 pounds of [glass], add 1 pound of tartar from the dregs of red wine. Use large pieces well vitrified naturally in bottles of wine, because the powder is no good. Crush these raw dregs well, and pass them through a fine sieve. For every 1 pound of these dregs, add 1 pound of prepared Piedmont manganese…” [3] To this he adds the advice that “the powder is always given in parts and given [to the frit], not to the fused glass, because then it will not tint.”

He also offers advice to add more or less pigment depending on the intended use of the glass: more for thin items, less for heavier ones. “For larger [thick] spit beads, it is said that at Murano they reduce the dose of [wine] dregs and manganese by nearly half.”

For Neri’s lead glass, he uses a different combination, this time pairing copper sulfate with iron oxide: “Take 16 pounds of cristallo frit and 16 pounds of lead calx. Mix them well and pass them through a sieve. To this material, add 6 ounces of thrice cooked copper, made with flakes of the kettle-smiths [chapter 28], and 2 pennyweight of iron crocus made with vinegar [chapter 17].” He goes on to advise, “If it leans toward greenishness, add a little iron crocus, which will remove the greenishness and will bring out a yellow color of the most beautiful gold.

Yellow is one of several colors that iron oxide can form in glass, and is used frequently in low-fire pottery glazes. In that realm, it has a reputation as a difficult, unstable color, as Neri alludes to in his warnings. But in modern, higher temperature borosilicate glass, iron oxide is relied on for a nice yellow. In modern soda-lime glass, cadmium, titanium or the exotic praseodymium are more likely choices. They produced bright reliable color that is stable at the higher temperatures of modern operations. In lead glass, selenium is the modern favorite for yellow.

[1] Neri 1612, ch. 45.
[2] ibid, ch 5.
[3] ibid, ch 46.