ceramic materials science in society
TRANSCRIPT
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
Annu. Rev. Mater. Sci. 1989. 19: 1-20 Copyright © 1989 by Annual Reviews Inc. All rights reserved
CERAMIC MATERIALS
SCIENCE IN SOCIETY
W. David Kingery
Department of Materials Science and Engineering, and Department of Anthropology, University of Arizona, Tucson, Arizona 85721
INTRODUCTION
It is easy for an academic or research-minded materials scientist to become so fascinated with the process of solving materials science problems that this activity is seen as an end in itself. Thomas S. Kuhn has suggested that, "Bringing a normal research problem to a conclusion is achieving the anticipated in a new way and it requires the solution of all sorts of complex instrumental, conceptual and mathematical puzzles. The man who succeeds proves himself an expert puzzle-solver and the challenge of the puzzle is an important part of what usually drives him on" (1). But materials science is much more than solving puzzles. It is an enabling science that makes possible new, improved, more reliable, and effective materials technology. The discoveries and scientific explanations of materials science are important primarily as they relate to this technology-the alteration and manipulation of the material world to obtain socially desired objectives. In sequence, materials technology is much more than manipulating materials; it is an enabling technology that makes possible new and improved devices, products, and systems. That is, the materials produced are important as they relate to devices and products that incorporate them and fit into larger systems that meet objectives and desires of the society in which they are embedded. This hierarchical nature of materials sciencematerials technology-devices and products-technological systemssocietal needs and desires suggests that an appreciation of the relationships between these different components should be an essential part of the intellectual kit of every materials scientist.
For this purpose ceramic science and technology is a wonderful field. It extends from 25,000 BC up to the present day. Ceramic manufacture was
0084-6600/89/0801-0001$02.00
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
2 KINGERY
one of man's earliest technical successes .. European porcelain development and marketing were central to the scientific, industrial, economic, and consumer revolutions of the eighteenth century. New high-tech ceramics were important for the development of electrical technology a hundred years ago and have been central to the post-World War II electronic information and communications revolution. Ceramic superconductors may revolutionize technology of the next century. With opportunities to control form, texture, translucency, opalescence, and color, ceramics are a wonderful art medium. Pottery shards are the fundamental data of archaeology. In short, ceramics are a crossroads for art, archaeology, history, science, and technology and thei� relation to societal and human values. As such, they present a marvelous opportunity to investigate the interaction of materials science with the technical, economic, and human concerns of society.
CLASSIFICATION OF TECHNOLOGY
Technology and its history have come to be studied in categories more or less reflecting departmental structures of university schools of engineering-agriculture, transportation, building construction, electrical engineering, and so forth. Remembering that the encyclopedists of the eighteenth century changed the way that people thought about branches of knowledge (2), there may be value in considering alternate classification schemes. The usual industry-focused classifications of technology are shown as vertical columns in Figure 1. Peer groups based on university degree join professional societies, attend professional meetings, are elected to national academies, and otherwise reinforce the scheme. Another equally rational classification of technology is what we shall call taskfocused and is illustrated by the horizontal cuts in the matrix of Figure 1.
Generalized Textile Electronic Civil Engineer Technology Technology Technology Technology
Materials Acquisition Starting S i lk Silicon Iron
Technology- Material Fiber Powder Bar
Materials Engineering Shaped Silk Silicon Iron Technololll Object Thread Crystal I-beam
Device Production Intermediate Silk Transister Iron Technololll Devices Cloth Chip Truss
Product Manufacture Product
Wedding P.C. Railroad Technology Gown Computer Bridge
System Design System
Marriage Publication Transportation Technology System System System
Figure 1 The usual industry-focused classifications of technology are shown as vertical
columns. Task-focused classifications are shown as horizontal rows.
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 3
In every industry there are a series of tasks of increasing structural complexity that begin with materials acquisition, preparation, and shaping. These materials are assembled to form products and devices that are the industry's output. Products are used in systems that may be based on one or several different industries. Materials science and engineering, systems design and, increasingly, manufacturing engineering are firmly in place or are becoming established as engineering departments at many universities. One of the advantages of a task-focused classification is that it recognizes commonalities in the tasks faced in manufacturing quite different product lines. It may also be appropriate for teaching technology to humanities students, management professionals, and other non-technologists. Task focusing achieves an industry-free generality and allows industry-craftarchaeology-ethnography continuities and comparisons to be seen more easily.
A different and equally rational classification is to focus on the technological systems associated with a specific individual product-a ceramic capacitor, a semiconductor chip, a temple, a television set. This productfocused technology is a particularly natural classification for archaeology and material culture studies; it implies the existence of a technological system consisting of materials acquisition, materials distribution, design, manufacturing, distribution, as well as product reception, perception, and use and various reuse and discard technologies (Table 1). A general illustration of such a system is shown as Figure 2.
In contrast to the two previolls typologies, this product-focused classification scheme has little to offer in a direct way for the primary organization of technologist training or for professional societies. I believe it has much to offer in understanding how technology exists as a system within society-the first step in appreciating the interactions of materials science, materials technology, and society as components of culture. It also provides a way for seeing the system in which the work of materials scientists
Table 1 A series of technologies are required for the
design. production and use of any product
Product-Centered Classification of Technologies
Materials acquisition technology Design technology
Manufacturing technology
Distribution technology
Use technology Re-use technology
Discard technology
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
4 KINGERY
PARTIAL DISCARD
or
OTHER USE
PARTIAL DISCARD
or
OTHER USE
SELECTED DESIGN
ALL
EVALUATED WITH
A SSOCIATIONS AND IN
CONTEXT
NEW FUNCTION and USE
DISCARD or
OTHER USE
Figure 2 The components of a product-focused classification of technology are interrelated and interact to fonn a technological/social system.
and materials technologists must be embodied. In particular, it shows that the principal feedback loop affecting design technology and manufacturing technology is generated by the reception and perception of a product by its users. This is not surprising-sometime ago I discussed the tendency of technology to reach the level of its market (3), and von Hippel has recently shown that industrial innovation is mostly a user-inspired activity
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 5
(4). However, this understanding that not only the needs, but also the reactions and perceptions of users are an essential context of design and manufacturing technology is often a new thought to engineering students.
In the history of ceramics the influence of Augustus the Strong, Elector of Saxony and owner of the largest European collection of Oriental ceramics, in directing the eighteenth century invention of European porcelain is well known (5). Modern ceramics was born in response to the needs of the age of electricity (6). The recent dominant role of Japanese ceramic technology has been explained by Hiroaki Yanagida of Tokyo University (7): "The rapid growth of the electronics indu!'ltry has created an intense requirement for better materials."
Thomas Alva Edison's first invention, patented in 1868, was an electrical vote recorder. He took the device to Washington and demonstrated it to a committee of the House of Representatives. It worked very well. Edison recounted that the chairman of the committee, after seeing how perfectly it worked, said "Young man, if there is any invention on earth that we don't want down here it is this. One of the greatest weapons in the hands of a minority to prevent bad legislation is filibustering on votes, and this instrument would prevent that" (8). The experience taught Edison to "turn his efforts towards inventing things that not only were needed, but were wanted as well." Good advice.
EUROPEAN PORCELAIN
Throughout the seventeenth century Chinese porcelain was extensively imported into Europe. Tt had a translucence, whiteness, and ring that could not be reproduced using European methods. Porcelain was beginning to be used for utilitarian purposes as coffee, chocolate, and tea were becoming more common, but mostly it was displayed as exotica from the East. This was a period of centralization of authority and establishment of autocratic rule after the model of Louis XIV in France. There were chemistry and physics experiments exploring new phenomena as well as exploitation of natural resources and development of new manufacturing methods as part of a mercantile economic policy. In Saxony, Augustus the Strong, Elector from 1694--1735, and also King of Poland, had a special interest in porcelain; his personal collection was the largest in Europe. He and his court supported one of the first truly modern research efforts; it was aimed at porcelain manufacture (9).
An important participant in this study was Count von Tschirnhaus, who had studied mathematics and physics at Leyden and carried out many experiments on materials behavior using high temperatures achieved by
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
6 KINGERY
focusing sunlight in a solar furnace such as illustrated in Figure 3. He had found that calcium oxide was not melted in his furnace, nor was pure quartz. However, a mixture of the two, for which the lower melting temperature or eutectic is 1436°C, could be fused. Thus, his solar furnace reached at least this temperature, much higher than those used in ordinary practice. A budding alchemist, Johann Friedrich Bottger, whose demonstration transforming mercury into gold had got him into difficulties with the authorities, was enrolled as principal investigator. In 1705 he was given some assistants to work with him and entered into a research program aimed at porcelain manufacture. One of his helpers was Paul Wildenstein, a Freiburg miner, who reported to an investigation commission in 1736 (10). He recalled:
Figure 3 Solar furnace or "burning lens" such as used by Count von Tschirnhaus for porcelain experiments.
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 7
In 1706, I came to Meissen to the Baron Bottger, to the secret laboratory, and we were
shut in there for 18 weeks. Even the windows had been walled up to half of their height, and Herr von Tzschirnhaussen [sic] from Dresden was often with us as well as the mining councillor Pabst from Freyberg. We had a laboratory with 24 kilns, and the baron and
Tzschirnhaussen had already made specimens of red porcelain in the shape of small
slabs and marbled slab stones.
Herr von Tzschirnhaussen, too, was giving instructions, and they began to research.
Among other things, specimens of red porcelain were made, as well as white. Kohler
and I had to stand nearly every day by the large burning-glass to test the minerals. There
I ruined my eyes, so that I now can perceive very little at a distance.
After numerous experiments based on the idea of a flux to provide the lower temperature eutectic melting, there is little known about the details of experiments studying the response of different clays and clay mixtures under the high temperatures developed by von Tschirnhaus' lenses. The use of lime as the fluxing material required high temperatures and, in fact, this was the main sticking point for the experimental program. Wilden stein testified (10):
We couldn't manage to make a strong fire in the new kiln; all our toil was fruitless and
the fire remained weak. While it was burning, we had to make the fire walls sometimes
higher, sometimes lower, but it was no use until we finally discovered the fault in the
casing. The coals wouldn't burn all the way down, so we had to pull them out every
thirty minutes . . .. Our hair was scorched and the floor had grown so hot that our feet
were covered with large blisters.
While most descriptions of the invention of European porcelain focus on the composition and clay used, there were really three principal requirements leading to success: first, the concept of partially fluxing a white clay with lime; second, the experimental testing of suitable compositions with von Tschirnhaus' burning lenses; third, achieving the high kiln temperature necessary for satisfactory firing. A temperature near 1400°C is required to fire the composition of Bottger porcelain so that a viscous liquid phase bonds the material together. This was an unheard of temperature for firing at the time and the secret of success was more related to the design of a kiln with multiple fireboxes of good design than to the particular clay used.
The resulting microstructure illustrated in Figure 4 is a mass of mullite crystals held together with a refractory glass, giving strength and resistance to thermal shock that remained a characteristic of the Meissen formula, one which is quite different from the Chinese compositions. One of the results of this is an extraordinary resistance to thermal shock. Wilden stein (10) described a visit of Augustus the Strong to Bottger's Jungfernbastei laboratory to view a firing.
His Majesty arrived with the Prince of Fiirstenberg, but when they entered the laboratory and felt the terrible fire, they would rather have turned back. Since, however, the baron-looking like a sooty charcoal-burner-was so close to him, His Majesty entered
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
8 KINGERY
(8)
(b)
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 9
and urged the prince to come in, too. The baron told us to stop firing for a while and to open the kiln, and during this time the prince said several times, "Oh, Jesus." The king, however, laughed and said to him that it was in no way to be compared to Purgatory! The kiln was opened, and all was bathed in white heat so that nothing could be seen.' The king looked in and said to the prince, "Look Egon, they say that porcelain is in there!" The prince said he couldn't see anything either but finally the kiln grew red, since it was open, so they could see the porcelain. I had to draw out a specimen, which was a saggar containing a small teapot.
A tubful of water stood nearby, so that the flowing iron could be extinguished. The baron immediately seized the tongs, drew the teapot out, and threw it into the water. Suddenly a loud bang was heard, and the king said, "Oh, it's smashed." But the baron replied, "No, Your Majesty, it must stand this test." He then rolled up his sleeves and took it out of the tub. It indeed proved to be intact.
T was a bit doubtful about this story, but students in my laboratory repeated the experiment with the same result. The composition and microstructure are similar to some of the spark plug porcelains developed during the early years of high-compression automobile and aircraft engines.
The method of manufacturing hard porcelain developed at Meissen spread throughout Western Europe entirely by the movement of workers, first from Meissen to Vienna, who took with them the necessary compositional and kiln technology. Workmen went from Vienna to Venice and later other workmen to Hochst, Furstenberg, Nymphenberg, Strasburg, Frankenthal, St. Petersburg and so forth. In 1762 at the end of the Seven Years War, Frederick the Great occupied Dresden and brought back with him models, molds, and workers to establish the royal porcelain manufactory in Berlin.
All in all, the development of European hard porcelain was an epochal event in the history of materials science and technology. To achieve the mercantile, social, and symbolic goals of Augustus the Strong, a dedicated research program led to new materials science, new materials technology, and new manufacturing methods.
THE AGE OF ELECTRICITY
Until the end of the eighteenth century the only source of electricity was generation by friction, a source known since ancient times. In 1600,
'Note: color temperatures are 1300°C, dull white; l400°C, bright white.
Figure 4 Microstructures of a Bottger porcelain. (a) A sample from 1715 heavily etched (12 minutes in 2% hydrofluoric acid) shows mullite needles in a glass matrix that has been etched away (1500 x). (Courtesy of W. Schulle & B. Ullrich.) (b) Replica prepared in author's laboratory that has been polished and lightly etched (ten seconds, I % hydrofluoric acid) that also shows mullite crystals in a glass matrix (2000 x).
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
10 KINGERY
. electricity and magnetism were the topics of one of the first books on experimental science (11). A machine for providing electricity was first made by Otto von Guericke in 1660; many more elaborate and effective models were manufactured in the eighteenth century. Then, about 1750, E. G. von Kleist devised the Leyden jar for storing the elusive electrical fluid; but electricity remained a substance for scientific, scholarly, and public amusement. In a famous late century demonstration Abbe Jean Antoine Nollet charged a Leyden jar, formed a rank of 180 soldiers holding hands and had the ends of the rank grasp wires connected to the Leyden jar; the entire company jumped simultaneously in perfect unison. The experiment was so impressive that King Louis repeated it with 700 Carthusian monks (12).
This situation changed dramatically on March 20, 1800 when Alessandro Volta sent a communication to the Royal Society of London, which was read on June 26 of that year (13). He described a method of continuous current generation from a "pile" of dissimilar metals. The reaction was sensational. In England William Nicholson and Anthony Carlisle had seen part of the letter and, in less than a month (on April 30, 1800), observed the electrolytic decomposition of water. Volta himself was invited to Paris and demonstrated his discoveries at the Institute of France during November 1801. The emperor Napoleon attended and witnessed experiments that included the decomposition of water and heating an iron wire to incandescence. It had long been known that an electric current could be transmitted by wire long distances, and by 1805 Salva used electrolytic decomposition as an indicator in an elementary method of communicating signals over a long distance. Sir Humphrey Davy, lecturer at the Royal Institution in London, installed the largest voltaic apparatus of the time. He showed that impurities were needed for the electrolysis of water (1806), electro lysed fused salts to form elemental potassium (1807), discovered chlorine (1808), heated platinum to incandescence (1802), and displayed the first electric arc lamp (1808). Davy was an exciting lecturer who used lots of demonstrations and whose performances were major public attractions. Reminiscent of the recent discovery of high-temperature ceramic superconductors, there was intense scientific and public excitement and optimism about the nature and uses of electricity. In 1812 Davy hired Michael Faraday, who became his successor, and went on to discover the principle of the dynamo in 1831-that is, the possibility of transforming mechanical energy into electrical current.
The basic ideas for using electricity for chemical purposes, communication, and lighting were all well established in the first few years after Volta's cell was announced. However, it was a century or more before the possibilities of electricity were fully realized and the world had telegraphic,
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 1 1
telephone and radio communication, electric light, recorded sound, electric motors, widespread electric power distribution, radios, t.v. and, more recently, transistors, computers, and a world full of electronic devices. The practical achievement of all these things was limited by, and required the discovery and development of new materials.
Edison's Carbon Microphone
After a series of inventions and successful manufacturing of various electrical devices, Thomas Alva Edison set himself up in a laboratory at Menlo Park devoted to the business of invention ( 14). That same year, 1876, Alexander Graham Bell announced the telephone at the Philadelphia Centennial Exhibition. His device was astounding, but crude and ineffective. A single instrument, both transmitter and receiver, had a flexible diaphragm that vibrated an armature facing an electromagnet, thus inducing a modulated current transformed hack to sound by the reverse
process. The current generated was weak. The problem of developing a better transmitter was immediately recognized by many inventors in the emerging field of electrical devices. Long distance telegraphy had grown to become a big business and there was no question in anyone's mind that a major market awaited a practical telephone.
In his new Menlo Park laboratory early in 1877, Edison characteristically tried a number of tacks for transforming sound vibrations into electrical oscillations. He tested moving coils, vibrating condensors, needles immersed in mercury and in electrolytic solutions. His success, the carbon microphone, was based on earlier experiments in which he had discovered the effect of prcssure on contact resistance, when he constructed a carbon rheostat in 1873 (15). For that, he used layers of silk discs saturated with fine particles of graphite contained in an insulating cylinder. When pressure was applied with a screw drive to a plate that compressed the stack, its resistance changed by an order of magnitude. When experiments were begun to develop a better telephone transmitter, a pressed tablet of graphite mounted behind a vibrating platinum disc gave good initial results when included in the primary circuit of an induction coil (16). This touched off a whole series of electromechanical improvements. In addition, Edison instituted a materials research program on the influence of pressure on contact resistance; it was this that set him apart from other electromechanical inventors of the time.
Edison tested thousands of different materials placed between plates connected to a battery and galvanometer; the change in resistance was measured as weights were added. The results of these experiments were described by Prescott (1879):
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
12 KINGERY
The value of different substances to be used as buttons in the telephone is given below, the first mentioned being the best, and the others in the order given:
Lampblack Hyperoxide of lead Iodide of copper Graphite Gas carbon Platinum black
Finely divided materials which do not oxidize in the air, such as osmium, ruthenium, silicon, boron, iridium and platinum, give results proportionate to this minute division, but many of them are such good conductors that it is necessary to mix some very fine nonconducting material with them before moulding (17).
Edison patented the use of lampblack in the telephone transmitter in February 1878 ( I8). Western Union manufactured the Edison telephone transmitter in New York until they retired from the telephone business in a compromise with the Bell companies in 1879. During this period the critical lampblack carbon discs continued to be produced at Menlo Park. A battery of smoking kerosene lamps produced soot that was scraped off, carefully weighed and pressed into 300 mg discs. According to Francis Jehl,
The process of smoking chimneys was not so simple as it sounds. It was very essential that the soot should be deposited at the lowest possible temperature, and the flame could not be allowed to play upon the deposit, as otherwise it acquired a high resistance and was wholly unsuited to use in the transmitters.
The first step after the chimney had been scraped was to take away the portions that had a hrownish tinge. The remainder was then finely ground and placed in the press, or mould. Each button was supposed to weigh three hundred milligrams. Afterward, the buttons were packed in shallow wooden boxes padded with cotton, and shipped thus to New York City (19).
This was the first application of modern high-technology materials science, research, development, and production by an electrical company completely independent of the metal and ceramic industries (Figure 5).
Edison's Electric Light
One of the results of relatively successful arc lighting systems developed in the nineteenth century was an invigoration of the research for an incandescent lamp. Thomas Edison visited the factory of WiIIiam Wallace on September 8, 1878 and saw a demonstration of the Wallace dynamo lighting, a system of eight arc lamps. Beginning thc next day, he devoted the resources of his Menlo Park invention factory to producing a practical incandescent lamp (20). One major challenge of electric lighting was the invention of a workable filament. To accomplish this, Edison had available at Menlo Park not only the capability for electrical experimentation, but
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 13
Figure 5 A magazine illustration showing how lamp chimneys were smoked to produce the soot used in the carbon telephone
transmitters. This was the beginning of modern materials technology. [Jehl (8), p. 13 1.]
also an in-house machine shop, vacuum equipment, chemical laboratory, and glass blower.
Edison first saw the problem as one of feedback controls to allow the use of platinum at a temperature near, but not exceeding, its melting point. Then he found that platinum worked better in vacuo, particularly if it were heated to remove occluded gases prior to having the vacuum sealed. Since a vacuum tube was indicated in any event, and Edison wanted a relatively high resistance (to use lamps connected in a parallel circuit), he turncd
, back to carbon as the filament material. In order to achieve a long life, he specified a completely sealed glass envelope with platinum lead-through wires. This combination of carbon filament, platinum lead-through wires, and heating the filament while evacuated in a glass bulb that was then sealed to maintain the vacuum, was successful-a success that depended on the entire lamp system, all elements of which were essential (21).
The Nernst Lamp
Walther Hermann Nernst was only 29 years old in 1893 when the first edition of his book, Theoretical Chemistry, was helping establish the new field of physical chemistry; his work integrating electrochemistry and thermodynamics was well underway. A new laboratory was established for him at the University of Gottingen and the brilliant young professor had a team of research students working for the doctorate degree, most
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
14 KINGERY
of whom were destined for careers in industry. By this time, the unification of Germany under Bismarck's Prussian leadership had led to an expansionist and nationalist fervor that affected all fields of endeavor. There was rapid industrial growth and university programs were promoted to produce the scientists and engineers needed for industry. The growth of chemical manufacturing and chemistry in the universities was particularly notable. In addition to providing for students, active faculty participation in new technological enterprises was both expected and encouraged. When an opportunity to develop the practical benefits of his new field of physical chemistry appeared, it is hardly surprising that Nernst rose to the occasion.
In the l 890s, Edison's basic patents had run out and there was a surge of research and invention aimed at a better light bulb (22). In 1897, Nernst filed a basic patent application for such a solid-state incandescent conductor "of the second class" (i.e. ionic, such as sulfuric acid rather than electronic, such as carbon or metal) (23). In this first patent, the conductor (Figure 6) was illustrated as heated with a Bunsen burner. Mendelssohn (24) recounts that Nernst amused the Kaiser by lighting his electric lamp with a match and then demonstrating that it could be blown out like a candle. For the solid electrolyte, Nernst indicated, "Such substances as lime, magnesia, zirconia, and other rare earths." His example was "burnt magnesia." [However, pure magnesia such as would be found in a physical chemistry laboratory is a good insulator and does not work, as was quickly discovered by those trying to imitate his art (25).] All in all, the first disclosure indicates an idea with good possibilities, but entirely impractical.
Figure 6 Drawing from Nernst's first patent application for the Nernst Glower Lamp. US Patent No. 653.349.
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 15
Emil Rathenau, who had bought the rights for Edison's lamp seventeen years before, also bought the German rights to Nernst's lamp. (He is reported to have paid a million marks which made Nernst a rich professor. Nernst indulged himself with sport cars and comfortable estates.) A Westinghouse employee at G6ttingen, Henry Noel Potter, brought Nernst to East Pittsburgh early in 1898 where George Westinghouse bought the American rights to his invention (26).
When George Westinghouse bought the American rights, he set up a technical staff of chemists, physicists, and engineers working in cooperation with researchers at G6ttingen (26, 27). Fortunately, it was soon discovered that a solid solution of zirconia with yttria is highly refractory, can be repeatedly heated and cooled, and has a good electrolytic electrical conductivity. [E. Ryskewitch reports that this discovery was made by A. Lukas in the Nernst Laboratory (28).] In a patent filed November 9, 1900, a mixture of 70-90% zirconia with 30-10% yttria is specified. In subsequent patents, 85% zirconia-15% yttria is indicated (29). Analysis of
a 1901 lamp indicates the actual composition was 88% Zr02-12% Y203 with solid-state sintered microstructure shown in Figure 7 (30). In addition to developing the composition used for the glower, new manufacturing
Figure 7 Microstructme of the zirconia-yttria solid solution Nernst electrolytic glower from
a 1901 lamp (1000 x).
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
16 KINGERY
methods were required. As part of the East Pittsburgh manufacturing plant, there was a chemical department in which oxides were prepared, mixed with a binding material and water; the plastic mass was forced through a small hole to extrude a filament using the same general method as was used in "squirting" incandescent carbon filaments of the time. After drying, the glowers were slowly heated to eliminate the binder and then sintered at high temperature in an electrical furnace or by passing a fiber through an electric arc for "fast firing."
New methods had to be developed for attaching platinum conductor wires to the glowers (31). Heaters were required to bring the glowers to'a low-red heat where they would conduct; platinum wire wound on porous low-heat-capacity insulators in varying configurations was used (32). Special machines for winding the discs for extrusion and resistance on an extended rod were required, Figure 8 (33). During the years 1900-1902 more than 70 patents describing materials and design details of the Nernst lamp were assigned to George Westinghouse and the Nernst Lamp Company (34). They, and the lamps themselves, evidence careful materials selection and manufacture of the essential lamp components from chemically processed materials much in advance of ceramic industry practices. The Nernst Lamp Company chemical department prepared the carefully
Figure 8 Vertical single glower lamp with
platinum resistance heater wound around
rod. US Patent No. 652,638.
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 17
controlled new materials. Advanced methods for shaping, firing, and testing the ceramic components were employed. In every way, the Nernst Lamp Company had a fully articulated high-tech fine ceramic processing unit as part of its manufacturing operation. For a few years it was the outstanding lamp on the market.
Improved Lamp Filaments
With the invention of Edison's (and Swan's) carbon filament lamps in 1878, the concerns of electric companies turned to other system components. Swan in 1883 developed a method of squirting a viscous nitro-cellulose solution through a die to form a "structureless" filament; Edison Electric continued to use bamboo filaments until 1892. Initially used by Sawyer and Man, "treated" carbon filaments were "flashed" by a chemical vapor deposition process. First evacuated, gasoline vapor was admitted to a filament chamber; when the filament was heated, a surface layer of graphite was deposited that adjusted the filament resistance and improved its emissivity. In the 1890s, particularly on the Continent where patent restrictions were less stringent, a growing number of efforts were aimed at obtaining filaments with long life at higher operating temperatures (35, 36).
In 1906, Carl Auer von Welsbach, inventor of the 99% Th02-1 % Ce02 gas mantle, patented a filament made of sintered osmium metal. Osmium has a high melting point, but is brittle and cannot be drawn into wire. We Is bach mixed osmium powder with an organic binder and extruded the paste through a die as had been done with cellulose for carbon filaments and with zirconia-yttria for Nernst glowers. After heating to remove the binder, the filament was sintered by passing current through the wire in a hydrogen atmosphere. The filament was weak and friable; in one configuration, Auer used a sintered thoria rod as a ceramic oxide refractory support (37). Auer later used a mixture of osmium (enormously expensive) and tungsten, gradually shifting his production completely over to tungsten. von Bolton, working at Siemens, found that filaments could be made of tantalum if sufficiently purified. The tantalum filament was patented in 1902. At the General Electric Research Laboratory W. R. Whitney found that if a carbon filament is first heated in vacuo, then flashed, and finally heated in a carbon furnace at an even higher temperature to consolidate the coating, it has a longer life at a higher operating temperature; this was the GEM filament.
All of these materials and processes were overwhelmed by the development of tungsten filaments. Various manufacturing methods were devised that included chemical vapor deposition, solid state sintering, and sintering with a liquid phase. Tungsten filament lamps were marketed in Europe
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
18 KINGERY
during 1906 and in the United States the following year. About that same time, W. D. Coolidge at the General Electric Research Laboratories began experiments that led to a successful process for making drawn tungsten wire, which was much stronger than the sintered variety. These lamps were put on the market in 1911; unsold sintered filament lamps were withdrawn and scrapped.
DISCUSSION
In the early eighteenth century the performance goals of high-value-added ceramics in western Europe were the visual and mechanical properties associated with Oriental porcelain. Its manufacture was perceived as a social, symbolic, economic, nationalist goal. That goal was achieved by application of new materials science and the development of new manufacturing technology in a classic materials research program. The application of materials science led to a new materials technology in response to a perceived goal of western European society.
Toward the end of the nineteenth century the successes of telegraphy and arc lighting made it clear that there was a tremendous demand and an assured market for a feasible electrical technology. Among other parts of the overall system, this required new materials and new materials technology.
The use of manufactured lampblack for the carbon microphone, the use of extruded carbonized lamp filaments, the use of thorium oxide cerium oxide alloys in Auer's incandescent gas lamp mantle, the use of zirconiayttria glowers in the Nernst lamp, and the use of thorium oxide supports in Auer's osmium lamp are all rational candidates as progenitors of modern high-tech ceramic materials technology. Perhaps we should also include the chemical vapor deposition flashing process for treating carbon filaments in a hydrocarbon atmosphere. One thing all these novel products and processes have in common is a role in bringing forth practical fruits of the new age of electricity. A second common element is that they were all done independent of the traditional ceramic clayworking industry; no one at the time thought of them as ceramics. Finally, each of these developments owes a great debt to the evolving chemical science.
This role of ceramics as critical components determining the effectiveness and value of larger devices and systems was a new one. Novel arrangements and accommodations were required. At the outset, in order to control the properties of critical new materials, ceramics were manufactured and shaped by the electrical companies. This was done by Westinghouse at the Nernst Electric Lamp Company; subsequently tungsten filaments were manufactured at General Electric. This integration of chemical, ceramic,
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
CERAMIC MATERIALS IN SOCIETY 19
and metallurgical manufacturing within the developing electrical industry began with Edison, for whom chemical studies were an integral part of his invention factory. [He had a copy of Nernst's Theoretical Chemistry on his bookshelf (38).] It continued and expanded with the development of corporate research laboratories by the large electrical companies. These research laboratories attended to all the needs of their systems, including development of new materials and processes. The successful plan by C. p. Steinmetz in 1900 that the General Electric Company set up a central research laboratory "entirely separate from the factory" proposed four targets for the initial work that included a substantial commitment to materials science: mercury vapor lamps, Nernst-type lamps, new filaments, and new materials for arc lamp electrodes (39). This combination of integrated high-tech ceramic manufacturing and integrated research programs, including materials, was the innovation that assured the development of modern materials science, technology and engineering in its present form.
The age of electricity gradually metamorphosed into the age of electronics with a continuing need for new materials and opportunities for applying novel materials discoveries. The pattern continued of new materials research being focused in user laboratories, which have included those of national defense and atomic energy establishments, steel makers, automobile manufacturers, the nuclear power industry, and others. But the prime mover has been electronics.
In histories of materials science, that enterprise has most often been pictured as a development of metallurgy and applied physics-microstructures of steel, X-ray diffraction, spectroscopy, quantum theory. In contrast, high-tech ceramics (and modern materials technology) developed in response to needs of the growing electrical industry. Its success is almost entirely a story of chemists and applied chemistry, beginning with Edison and continuing with Acheson, Moisson, Auer, von Welsbach, and Nernst. The first complete research, development, and manufacturing program meeting all the criteria of modern high-tech fine ceramics was the electrolytic conductors and high-temperature insulators developed for the Nernst lamp. If Edison, famous as an inventor, is the founder of modern materials technology, perhaps Nernst, famous as a physical chemist, should be considered the father of modern ceramics. This would be particularly fitting if it reinforced the importance of chemistry for the future of ceramic materials science and technology.
ACKNOWLEDGMENTS
Dr. Joseph E. Burke was the person who first suggested to me that the source of modern materials science and technology lay in the needs of the
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
20 KINGERY
lighting and electrical industry at the turn of the century, and I am grateful for his stimulating ideas and suggestions. Susan Rosevear at M.LT. and Mary Voss at Johns Hopkins University have been enormously helpful as research assistants and in manuscript preparation.
Literature Cited
I. Kuhn, T. S. 1970. The Structureof Scientific Revolution, p. 36. Chicago: Univ. Chicago. 2nd ed.
2. Lough, J. 1971. The Encyclopedie. New York: McKay
3. Kingery, W. D. 1967. Transactions of the 10th International Ceramic Congress, ed. C. Brosset, C. He1gesson, pp. 3-17. Gothenberg, Sweden
4. von Hippel, E. 1987. Ceramics and Civilization. Vol. 3. High Technology Ceramics: Past, Present and Future, ed. W. D. Kingery, pp. 325-34. Westerville, Ohio: The Am. Ceram. Soc.
5. Kingery, W. D. 1987. See Ref. 4, pp. 153-80
6. Kingery, W. D. 1988. An Unseen Revolution: The Birth of High-Tech Ceramic.�. Presented at Ann. Meet. Am. Ceram. Soc., Cincinnati
7. Yanagida, H. 1987. Fine Ceramics, ed. S. Saito, p. 239. New York: Elsevier
8. JeW, F. 1937. Menlo Park Reminiscences, p. 41. Dearborn, Mich: Edison Inst.
9. Kingery, W. D. 1987. See Ref. 4, pp. 153-80
10. Wilden stein, P. 1736. Manufactory Commission Report (WA 1 A 24a/312 If), cited in Walcha, O. 1980. Meissen Porcelain, p. 440. London: Studio Vista/ Christies
1 I . Gilbert, W. 1600. On the Magnet. London: Chiswick (1900 reprint)
12. Dibner, B. 1964. Alessandro Volta and the Electric Battery, p. 18. New York: Franklin Watts
13. Dibner, B. See Ref. 12, pp. I I I If 14. Josephson, M. 1959. Edison. New York:
McGraw-Hill 15. Jehl, F. 1937. See Ref. 8, p. 41 16. Edison, T. A. 1878. US Patent No.
203013 17. Jehl, F. 1937. See Ref. 8, pp. 122-23 18. Edison, T. A. 1878. US Patent No.
203015 19. Jehl, F. 1937. See Ref. 8, p. 132 20. Friedel, R., Israel, P., Finn, B. S. 1987.
Edison's Electric Light. New Brunswick, NJ: Rutgers Univ. Press
21. Edison, T. A. 1880 .. US Patent No. 223,898
22. Bright, A. A. Jr. 1949. The Electric Lamp Industry. New York: Macmillan
23. Nernst, W. 1899. US Patent No. 653,349 24. Mendelssohn, K. 1973. The World of
Walther Nernst, p. 46. Pittsburgh: Univ. Pittsburgh Press
25. Davenport, C. B. 1899. Science NS 9(221): 456
26. Wurts,A.J.190 I . AIEETrans.18:545-71
27. "The Nernst Lamp." 1904. anon. Electrical World 43: 981-85
28. Ryskewitch, E. 1960. Oxide Ceramics, p. 391. New York: Academic
29. Nernst, W. 1901. US Patent No. 685,725; US Patent No. 685,729; US Patent No. 685,730
30. Kingery, W. D. 1989. Ceramics and Civilization, Vol. 5, ed. W. D. Kingery. Westerville, Ohio: The Am. Ceram. Soc. In press
31. Hanks, M. W. 1900. US Patent No. 652,607
32. Potter, H. N. 1900. US Patent No. 652,637
33. Potter, H. N. 1900. US Patent No. 652,638
34. The Nernst Lamp, More Light for Less Money. 1902. anon. Pittsburgh: Nernst Lamp Co.
35. Bright, A. A. Jr. 1949. See Ref. 22 36. Howell, J. W., Schroeder, H. 1927.
History of the Incandescent Lamp. Schenectady, New York: The Maqua Co.
37. von We1sbach, C. A. 1906. US Patent No. 814,632
38. Mendelssohn, K. 1973. See Ref. 24, p. 43
39. Wise, G. 1985. Willis R. Whitney, General Electric and the Origins of u.s. Industrial Research, p. 76. New York: Columbia Univ.
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
Annual Review of Materials Science Volume 19,1989
CONTENTS
PREFATORY CHAPTER
Ceramic Materials Science in Society, W. David Kingery
EXPERIMENTAL AND THEORETICAL METHODS
Dynamical Diffraction Imaging (Topography) with X-Ray Synchrotron Radiation, M. Kuriyama, B. W. Steiner, and R. C. Dobbyn 183
Use of Laser Techniques to Study the Dynamics of Molecular-Surface Interaction, J. Hager and H. Walther 265
Towards Unified Computer Models for Predicting Fracture of Solids, Alan K. Miller 439
Fractal Phenomena in Disordered Systems, R. Orbach 497
PREPARATION, PROCESSING, AND STRUCTURAL CHANGES
Gas-Source Molecular Beam Epitaxy, Morton B. Panish and Henryk Temkin 209
Photo electrochemical Methods for III-V Compound Semiconductor Device Processing, P. A. Kohl and F. W. Ostermayer, Jr. 379
Ion Beam Processing for Surface Modification, J. K. Hirvonen 401
Rapid Omnidirectional Compaction (ROC) of Powder, C. A. Kelto, E. E. Timm, and A. J. Pyzik 527
PROPERTIES AND PHENOMENA
Chemically Induced Interface Migration in Solids, Duk N. Yoon 43
Materials Synthesis by Mechanical Alloying, C. C. Koch 121
The Structures of Electrodeposits and the Properties that Depend on Them, Rolf Wei! 165
Polymer Interdiffusion, H. H. Kausch and M. Tirrell 341
Structural Relaxation in Metastable Strained-Layer Semiconductors, Brian W. Dodson and Jeffrey Y. Tsao 419
vii
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.
viii CONTENTS (continued)
SPECIAL MATERIALS
Fluoride Glasses, J. M. Parker 21
Very Low Thermal Expansion Coefficient Materials, Rustum Roy, D. K. Agrawal, and H. A. McKinstry 59
Electroluminescent Display Materials, H. Ohnishi 83
Composite Electrolytes, Nancy J. Dudney 103
Hardmetals and Cermets, P. Ettmayer 145
Intermetallic Compounds for Strong High-Temperature Materials: Status and Potential, R. L. Fleischer, D. M. Dimiduk,
and H. A. Lipsitt 231
Structural Properties of Ionomers, C. W. Lantman, W. J. MacKnight, and R. D. Lundberg 295
Crystal Chemistry and Properties of Mixed Valence Copper
Oxides, B. Raveau and C. Michel 319
Synthesis, Stabilization, and Electronic Structure of Quantum
Semiconductor Nanoclusters, Michael L. Steigerwald and
Louis E. Brus 471
INDEXES
Subject Index 551 Cumulative Index of Contributing Authors, Volumes 15-19 557 Cumulative Index of Chapter Titles, Volumes 15-19 559
Ann
u. R
ev. M
ater
. Sci
. 198
9.19
:1-2
1. D
ownl
oade
d fr
om w
ww
.ann
ualr
evie
ws.
org
by M
osco
w S
tate
Uni
vers
ity -
Sci
entif
ic L
ibra
ry o
f L
omon
osov
on
11/0
2/13
. For
per
sona
l use
onl
y.