Lime

Vintage 1920's Water Glass Label.

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

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

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

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

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

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

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

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

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

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

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

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

Lime

Vintage 1920's Water Glass Label.

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

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

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

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

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

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

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

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

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

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

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

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

Lime

Vintage 1920's Water Glass Label.

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

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

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

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

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

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

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

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

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

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

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

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

Lime

Vintage 1920's Water Glass Label.

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

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

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

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

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

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

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

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

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

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

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

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

Neri's Cabinet #7: Lime

Vintage 1920's Water Glass Label.

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

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

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

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

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

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

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

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

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

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

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

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

Glass as Pasta

Paste gem and gold finger ring
Museum of London, 1600s

Antonio Neri devoted the fifth part of his book on glassmaking, L'Arte Vetraria, entirely to the production of "paste gems." These are pieces of intensely colored brilliant glass crystal used to imitate gemstones. The name "paste" comes from the way they were produced. A finely ground powder, resembling pasta flour, was mixed wet in small batches like dough. The mixture starts with crystal clear pieces of quartz rock crystal. Neri "dresses" them by chipping off any impurities or dirt. He then repeatedly heats the quartz in a covered crucible and then dumps it out into clean cold water, which causes it to fracture into smaller and smaller pieces. He advises doing this at least twelve times, stressing the importance of keeping out contamination, avoiding embers and fly ash, which require a clean burning fire.

Next, he works the fractured quartz, which should "crumble and decompose like refined sugar." He grinds it on the porphyry stone with a muller to reduce it to the finest powder; "like sifted grain flour. […] Grind it one time, grind it again and then make another pass. Always put only a little onto the porphyry, which is to say half a spoonful at a time." In another part of the book, Neri recounts a glassmaker's proverb which is apt for this process: "A fine sieve and dry wood bring honor to the furnace."

He mixes in a quantity of "minium" which is an orange or red mineral consisting of lead oxide. This material acts as a "flux," which dramatically lowers the melting temperature of the quartz, and at the same time creates the highly refractive "fire" for which gems are known. In an improvement to this "standard" way of making paste gems, Neri substitutes "Sugar of Saturn" –what we know as lead acetate. This is a water soluble (and highly toxic) lead compound which can be produced in the laboratory, in an extremely purified state. Chemically, minium and lead acetate will reduce the same way in glass; the advantage of the latter is in its higher purity. 

The last part of the formula is to mix in various pigments to give the glass the characteristic colors of different gems. Neri uses "zaffer" (cobalt oxide) for sapphires, copper for emeralds, etc. He presents a number of possibilities, even using real gems as pigment. He also gives advice of how to achieve the correct level of tint for different applications:

Be aware that the colors for the pastes described above can be made more or less saturated according to your will, and inclination, and according to the works in which they will be used. In order to make small stones for rings, the color must be deeper, for larger stones use less color, for earrings, and pendants, concentrate the color. Remit this matter to the discretion of whoever is doing the work. There are no true rules here; the rules given by me above serve only to illuminate the intellect of the curious artisan. To this end, you can always invent and find better colors than the ones that I describe here, other than verdigris, zaffer, and manganese. The curious and noble spirit will be able to get a marvelous red from gold, yet another beautiful red from iron, a most beautiful green from copper, a golden yellow color from lead, a celestial one from silver and a sky blue even more beautiful from the garnets of Bohemia. You will find the small garnets inexpensive, and you can extract their tincture, as I have done many times in Flanders. These materials result in notable effects, and you may do the same with rubies, sapphires, and other gems. All of these things are manageable by a practical chemist. To require me to write such things here would be too much of a tedious matter, especially since I wish to speak succinctly in the present work. However, with the colors described above, you can make very appealing pieces.

The mixed "pasta" is dried and loaded into small terracotta pots, covered with a lid, and sealed shut with a special mixture of clay called "lute." Many of these pots can be prepared and fired at the same time in a pottery furnace. The pots are fired continuously for twenty-four hours or longer. They are allowed to cool slowly, along with the furnace. The lid is then unsealed and lifted very carefully: 

Because it is such a significant matter, I will repeat once more, that when the pastes are not cooked or purified enough, you should return them to cook again in the same crucibles, taking care not to break them. If the pastes are not satisfactorily cooked and purified, putting them into other crucibles will cause many impurities to form. They will have adhesions from the crucibles, and be loaded with dirt; they will be useless, and not usable for any work. When they are not cooked or purified well, then you should not break the crucibles in any way, but re-lute and return them to the furnace or kiln to cook again. Then they will become pure, and beautiful, to be used in any kind of work that you might want to make.

Tin into Silver

The Alchymist, (Joseph Wright of Derby, 1771)

In Discorso sopra la chimica, a manuscript written by Antonio Neri in 1613, he discusses his philosophy of chemistry and gives several examples of recipes for the transmutation of metals. An instructive example is his conversion of tin into silver. He starts with a ball of pure English tin. He encases it in lute—clay that can withstand high temperatures—and then forces it below the surface of a bath of molten silver. After a time, the ball is removed and cooled. The clay is then cracked away to reveal that the tin inside is now silver. Neri explains that the "spirit" of the silver has penetrated the clay ball and its noble properties have converted the tin. 

In the light of current knowledge it is not hard to assign a more accurate understanding of what was taking place. Tin is a much less dense metal than silver and melts at a lower temperature. By forcing the luted ball down into the liquid silver, the tin inside quickly melts and its buoyancy forces it out of any small holes or cracks in the clay, even if microscopic in size. Much the same way as a sealed rubber balloon filled with helium deflates over time. As tin escapes the rigid ball it is replaced by silver from the surrounding melt, pushing inward. Once the tin escapes the clay, it will rise to the surface, but it also mixes, diffusing into the silver. Depending on the quantities and the temperature of the melt, a thin layer of alloyed silver-tin might form on the surface and some would evaporate into the air. Neri describes this as "malignant fumes" of the tin and goes on to say anyone discovering something "that would repress these vapors would have a very great secret."

Even though the clay encasement might appear to be a solid barrier, buoyancy forces cause much of the tin to escape the ball and to be replaced by silver. If the process of mixing were allowed to complete, the comparatively small amount of tin in the ball would disperse throughout the much larger silver melt. An assay would reveal a high silver content in the luted metal. Given the historical lore of alchemy and the level of scientific knowledge at the time, this was a very persuasive argument in favor of transmutation, even for seasoned experts. A valid criticism of Neri's explanation is that he was simply not skeptical enough; the presence of silver inside the sealed ball does not, in itself, prove transmutation. Indeed, a careful accounting of all the materials involved would have revealed to him that the total amount of silver had not changed in the experiment. 

For the viewers of such a demonstration there are other considerations. There was an unmistakable theatrical flair to these events. Audiences often included princes and other royals. Even before the demonstration begins, there is an air of anticipation, the expectation to witness something extraordinary. It is not hard to imagine the same sort of performance atmosphere for Neri's demonstration that was and is still a critical part of legerdemain and conjuring acts. Even if not intentional, this charged setting leads to a suspension of disbelief. It can have a powerful effect on our perceptions. The same state of mind that allows us to be amazed by a "magic act" can blind us to seeing nature as it is in truth. Despite his interpretation, Neri’s experiment does involve repeatable chemistry, conducted without trickery that has a legitimate explanation, even if not the same one advanced in the early seventeenth century.

For further reading, see M. G. Grazzini 2012, p. 351.