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ADVANCES in 13Th CENTURY GLASS MANUFACTURING and THEIR EFFECT on CHEMICAL PROGRESS Seth C

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ADVANCES in 13Th CENTURY GLASS MANUFACTURING and THEIR EFFECT on CHEMICAL PROGRESS Seth C 28 Bull. Hist. Chem., VOLUME 33, Number 1 (2008) ADVANCES IN 13th CENTURY GLASS MANUFACTURING AND THEIR EFFECT ON CHEMICAL PROGRESS Seth C. Rasmussen, North Dakota State University, Fargo, ND Introduction progress (5, 7). The ability to produce more laboratory apparatus and vessels from glass allowed much greater The technology of glass production is thought to have freedom and versatility in their design; no matter what been known since ~2500 BC (1-3) and had become fairly shape was needed, it could be made of glass. Addition- advanced within the Roman Empire (4). At that time glass ally, pieces of glass could be melted together, forming was widely used for blown vessels, pitchers, beakers, a seal without cement. It is difficult to imagine modern bowls, and other tableware, with such glass objects be- chemistry without glass apparatus. coming as widespread as pottery (1-3,5). The use of glass The goal of this study is to attempt to bring together for laboratory apparatus, however, was rather limited various partial works in history, chemistry, and glass because of a lack of durability under rapid temperature studies in order to give for the first time a detailed picture changes and poor chemical resistance. For example, of how and why the Venetian glass of the 13th century the combination of poor quality and the thick, irregular nature of the glass resulted in the frequent breaking of the vessels during distillation (6). With the collapse of the Roman Empire, glass pro- duction declined for a time as glassmakers moved either into the East or to the outer regions of the old empire (1, 3). These glassmakers, however, not only preserved many of the Roman glassmaking techniques, but also began developing new patterns and styles. One such glassmaking center flourished in Venice and Murano (Fig. 1) during the 13th through 16th centuries (1, 3, 7), and it was here that improved glass was produced begin- ning in the second half of the 13th century (3, 4, 8). The strength of the Venetian glass made it especially practical for glass vessels, and its high melting point made it useful for laboratory apparatus (1). The glass industry received great impetus from the growing general use of glass for chemical vessels. At the same time, the flourishing in- dustry at Venice and Murano greatly influenced chemical Figure 1. The Venetian territory of the 14th century (9) Bull. Hist. Chem., VOLUME 33, Number 1 (2008) 29 became suitable for use in chemical apparatus and what salts would then be converted to lime during the fusion effect this new glass had on the progress of labora- processes. Thus, the actual composition of medieval tory practitioners. For example, it could be argued that glasses depended heavily on both the specific raw materi- this improved glass technology led to the invention of als and how those materials were treated prior to use. eyeglasses and a vast improvement in still design, both As discussed above, the source of silica could affect of which occurred shortly after the introduction of the the resulting glass composition. It could be argued, how- improved glass and within close geographical proximity ever, that the largest difference between the glass compo- to Venice. As a result of better stills, important materials sitions of the previous Roman period and the improved were isolated in pure forms for the first time, most notably Venetian material was due to the source of alkali. Most alcohol and the mineral acids. The availability of these Roman glasses were prepared with natron as the alkali of materials then greatly changed the evolving fields of both choice (2, 18). The Venetians, however, favored the use chemistry and medicine. of plant ashes, in particular the ashes from the salt marsh plant salsola kali, which were imported from the Levant The Composition of Medieval Glass (modern Syria, Libya, and Egypt) (8, 12-16, 18). These Levantine ashes, called allume catino (19), were used The majority of medieval glasses adhered rather closely almost exclusively in Murano until the end of the 1600s to a formula consisting of three primary components: (16). During this time their use was even protected by the silica, lime, and an alkali, typically either potash (K CO ) 2 3 Venetian government, and the use of other plant ashes for or soda (Na CO ) (10-12). The alkali is used to reduce the 2 3 glassmaking was expressly prohibited (13, 16). Allume rather high melting point of the silica (~1710 °C) to below catino had relatively high soda content (up to 30%), as 1000o C (10). The addition of calcium salts can result in well as quite large amounts of calcium and magnesium an even greater reduction than alkali alone, resulting in carbonates (8, 12-14, 16, 18), but the exact source of the the lowest temperature of the triple eutectic at ~725° C ash could also play a factor in its composition. For ex- and giving a typical soda-lime glass of the composition ample, the ash of Syria was regarded to be better than that 21.3% Na O, 5.2% CaO, and 73.5% SiO (10). 2 2 of Egypt, as the Syrian ash was blacker in color because The importance of lime, however, was not initially of its higher carbon content (14). It has been proposed recognized and it was not intentionally added as a major that Venice’s close economic ties to the Levant, including constituent before the end of the 17th century (2, 11- access to Syrian glass technology and craftsmen, greatly 13). Prior to that time, all lime content in the medieval influenced Venetian glassmaking and thus resulted in a glasses was a result of impurities in either the silica or blending of the plant ash-based methods of the Levant alkali source. Until the beginning of the 14th century, with the previous Roman methods (3, 4, 18). the nearly exclusive source of silica used by the Venetian In addition to allume catino, the Venetian glassmak- glassmakers was various Sicilian sands (13). These sands ers also utilized barilla or Spanish ash, obtained from are thought to have provided also considerable alumina, the burning of marine plants (salsola sativa, halogeton as well as iron oxide, lime, magnesia, and frequently sativus, salsola kali, and suaeda maritima) from the small amounts of manganese (2, 8). These sands were salt marshes of Alicante, Spain and other parts of the gradually replaced with quartz pebbles (~98% silica), Mediterranean (14, 17). The highest quality barilla for which reduced impurities that contributed to coloring glassmaking was called agua azul, of which Alicante was of the glass (iron, chromium, etc.) (13-15). The two the sole source (17). The source of this form of barilla primary sources of alkali were natron, a natural sodium was described as a shrub with blue green berries, thought sesquicarbonate (Na CO ·NaHCO ·2H O) found in 2 3 3 2 to be salsola sativa, which gave this particular barilla Egypt and Syria, and various types of plant ash (2, 12- ash a blue color (14, 17). Like allume catino, barilla 17). The actual composition of natron, however, often was a soda-rich ash (up to 30%) containing significant varied widely because of chloride and sulfate impurities quantities of calcium salts (12, 15). While it is believed (12, 14, 15). As one might imagine, the composition of that both the Levantine and some barilla ashes may have plant ash could be even more complex and variable. In been derived from salsola kali, it is important to note that addition to providing sodium and potassium carbonates, plant ash composition depended largely on the soil in plant ash often furnished sodium and potassium chlorides which the plants grew. This is best illustrated by the fact and sulfates, as well as calcium and magnesium salts of that plants grown in salty soil or near the sea produced carbonate and phosphate (8, 12-14, 18). These calcium ash high in soda, while those grown inland gave ash with 30 Bull. Hist. Chem., VOLUME 33, Number 1 (2008) higher potash content (2). As a result, the Levantine and magnesium content shows a slight advantage over lime barilla ashes may have been similar, but distinct, raw for improved water and acid resistance, but lime imparts materials, with allume catino being the initial and pre- a markedly improved resistance to alkaline solutions in ferred material and barilla becoming more common by comparison to magnesium. the 16th century (12). Neri later wrote of both materials, The second critical property for laboratory glass- also expressing a preference for the Levantine ash over ware, its thermal durability, is also dependent on chemical barilla (20). This preference was due to the fact that glass composition. Like most solids, glass undergoes thermal from barilla would tend to suffer from some light blue expansion that can result in increased stress during coloring (14, 17, 20), which has been proposed to be a rapid temperature changes. For simple soda glasses, the result of iron oxide content in the ash (14). thermal expansion actually increases with soda content, Another significant contribution to the advancement thus resulting in glasses with low thermal durability and of the Venetian methods was the introduction of new a tendency to break under rapid heating. Substitution processes for the preparation of the alkali raw materi- of sodium oxide by another oxide results in decreased als. The plant ash (either barilla or allume catino) was thermal expansion with increased content of the new shipped to Venice as hard pieces of calcined residue. oxide. Both magnesium and calcium oxides, discussed Although these chunks of calcined residue then required above, result in significantly decreased thermal expan- pulverization after arrival, it was preferred over ash that sion, with the addition of magnesium oxide providing arrived in powdered form (8, 13, 16).
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