HISTORiCAL NOTE

Energetic Materials, for firearms and military devices; the so-

dium nitrate version used the letter B and
was used for most other industrial applica-
tions.

Part I: Black Powder, Black powder may hâve been used for
blasting mines in Germany as early as
1613, and almost certainly was used in
Schemnitz, Hungary, by 1627. For the re-

Nitroglycerin, and mainder of that cenrury, the use of black

powder in mining spread slowly because
pf its high cost, the miners' fear of roof col-
lapse, and the lack of efficient tools for

Dynamite drilling boreholes. In 1679, black powder

was used for blasting the Malpas Tunnel of
the Canal du Midi in France.
But because it is a deflagrating explosive
material, black powder has a severe draw-
An explosive, according to the dictio- nited by flame or heat. In the early days, back in mining—it tends to ignite coal gas
nary, is "any substance that can be made to torches, hot iron rods or glowing tinder and coal dust, which led to many mine ex-
produce a volume of rapidly expanding were used to set off black powder, usually plosions. By 1800, several European gov-
gas in an extremely brief period." This His- by igniting a trail of powder leading to the emments had set up testing stations to
torical Note and the next one will look at main charge, giving people time to take search for safer substitute materials.
the development of energetic materials cover before the explosion. Around the turn of the 18th cenrury, the
used as industrial and military explosives. Since the déflagration of black powder is first "high" explosive—mercury fulmi-
This first part will focus on black powder, a surface phenomenon, coarse granula- nate—was discovered. Mercury fulminate
used thousands of years ago, through the tions burn more slowly thàn fine grains. is very sensitive, easily ignited, and has a
création of nitroglycerin, to the discovery Grain sizes are designated with a compli- rapid deflagration-to-detonation transi-
of dynamite. Next month's Historical Note cated System of letters and numerals. tion.
will describe the development of nitrocel- The beginnings of modem energetic
lulosic explosives such as gun-cotton, as materials research, however, did not begin
well as TNT and other explosives used in until a cenrury later, when Italian chemist
World Warsl and E. Italian chemist Ascania Ascanio Sobrero discovered nitroglycerin
Dynamite, discovered by Alfred B. No- in 1846. At first Sobrero called his concoc-
bel in 1866, was one of the first detonating, Sobrero discovered tion pyroglycerin, or blasting oil.
or "high" explosives, which are character- "blasting-oil" Nitroglycerin was extremely dangerous,
ized by extremely rapid décomposition with great risks inhérent in its manufacture
and the development of high-pressure —nitroglycerin— and application. No dependable means
shocks. Earlier materials used deflagrating in 1846. could be found to detonate it other than the
or "low" explosives, which were simply chancey ignition Systems known at the
fast-burning powders that produced rela- time. Pure nitroglycerin is relatively insen-
tively low pressures. The most familiar low sitive when frozen, and since it freezes at
explosive had been used for many The saltpeter for black powder was origi- 52 °F (11 °C), merely packing it in ice will
centuries—black powder. nally extracted from compost piles and ani- keep it safe.
For perhaps 2000 years the Chinese used mal dung; later, large deposits in India By the 1850s some nitroglycerin was be-
black powder in their fireworks and to supplied manufacturing needs. During ing used instead of black powder for cer-
send smoke signais. Called "Greek fire," the 1850s, enormous quantifies of sodium tain applications, but the "blasting oil" was
black powder (or some similar low explo- nitrate, which could be converted to saltpe- seen as merely a laboratory curiosity. How-
sive) was also used for pyrotechnies in east- ter through reaction with readily available ever, about a décade later, Swedish re-
ern Europe in the 700s A.D. By the late potassium chloride, were discovered in searchers Immanuel Nobel and his son
13th cenrury, the Arabs were using black Chile. Alfred began working (independently) on
powder in a "gun"—a bamboo tube rein- Chilean sodium nitrate absorbed a great the commercial potentials of large-scale
forced with iron, which used an explosive deal of moisture, fhough, and manufactur- production and application of nitroglyc-
charge to fire an arrow. About this same ers did not initially consider it good erin.
time, on another continent, English médi- enough for use in black powder. In 1858, The elder Nobel had been working on
éval scholar Roger Bacon at Oxford Univer- American industrialist Lammot du Pont developing munitions, especially subma-
sity included thorough instructions for began to make sodium nitrate, from which rine mines, charged with black powder for
preparing black powder in a published he made his own blasting powder. Du the Russian Tsar. At the same time, young
volume—but he encoded the détails in a Pont's sodium nitrate blasting powder pro- Alfred Nobel had been studying in the
difficult Latin anagram to conceal the in- duced an explosive inferior to black pow- United States for four years; he saw a wild
structions. der, but it remained good enough for many country being opened up for civilization,
Black powder, a mixture of 75% saltpe- mining and construction applications— and he envisioned roads and canals
ter (potassium nitrate), 10% sulfur, and and it was a good deal cheaper. The potas- blasted out of the rock through the con-
15% charcoal (carbon), is relatively insensi- sium nitrate composition came to be called trolled use of explosive materials. Alfred
tive to shôck and friction, but is easily ig- "blasting powder A" and was used mainly returned to his father, who had just dem-

84 MRS BULLETIN/NOVEMBER1989

https://doi.org/10.1557/S0883769400061303 Published online by Cambridge University Press

 HISTORICAL NOTE

onstrated a comparatively simple way of glycerin and black powder for most though, that the inert substance of the
producing nitroglycerin, simÛar to So- blasting purposes. kieselguhr added nothing to the explosive
brero's original method. Dynamite is a ductile and easily handled power (and actually detracted, since it ab-
That year, 1862, Immanuel and Alfred energetic material. The heat liberated in a sorbed some of the heat). He began to use
Nobel built a nitroglycerin plant, Nitro- dynamite explosion ranges from about 900 active materials such as wood pulp, rye
glycerin, Ltd., at Heleneborg, Sweden. to 1200 calories per gram, depending on its flour, starch, and sugarcane pith for the ni-
American chemist George Mowbray nitroglycerin content. High-nitroglycerin troglycerin absorbents, and sodium nitrate
began his work with nitroglycerin by dynamites can produce a shock pressure of for an oxidizing agent; he also added cal-
founding a manufacturing plant in Massa- atmost a million pounds per square inch, cium carbonate as an anti-acid. By varying
chusetts in 1867. Much of Mowbray's prod- traveling between 2000 and 4000 meters thèse "doping" materials, Nobel could
uct was used in blasting the Hoosac Tunnel per second. The shattering effect of this manufacture dynamites of differing
in nearby North Adams, Massachusetts. shock is useful for breaking hard rock. strengths. Thèse became classed as
Before he was forced to shut down his Other dynamite recipes create lower shock "straight dynamites," according to their
plant several years later, Mowbray safely pressures, down to about 60,000 pounds percentage of nitroglycerin. For example,
shipped about a million pounds of frozen per square inch, which are useful for min- 40% straight dynamite (a standard used by
nitroglycerin throughout the eastern ing soft coal in large chunks. the U.S. Bureau of Mines) contains 40% ni-
United States and Canada. Dynamite's abifîty to detonate also dé- troglycerin, 44% sodium nitrate, 15%
In 1863 Alfred Nobel patented his inven- pends on its porous and granular struc- wood pulp, and 1% calcium carbonate.
tion of the blasting cap, which allowed ture. Coarse-grained dynamites hâve a less In later years, Nobel continued his string
safe, reliable détonation of nitroglycerin shattering action. When dynamites are of inventions, developing blasting gelatin
from a distance. The blasting cap used a highly compressed, détonation is likely to and smokeless powder, as well as working
tiny charge of mercury fulminate in a métal fail. By appropriate compounding and on some non-explosive materials, such as
cap, which could then be detonated when granulation, explosives can be prepared to synthetic rubber and artificial silk.
desired. Instead of applying heat, the break soft minerais (i.e., coal) or shatter Through his many patented inventions,
strong shock from the mercury fulminate hard rock. and also through successful exploitation of
detonated the nitroglycerin. This proved to Nobel's "Dynamite No. 1" was 75% ni- the Baku oil fields in Russia, Nobel became
be a tremendously important break- troglycerin and 25% of the diatomaceous- one of the world's richest men. He died on
through for the safe use of explosive mate- earth kieselguhr. Nobel soon realized, December 10,1896, in San Remo, Italy.
rials.
On September 3,1864, Nobel's Helene- KEVIN J.ANDERSON
borg plant exploded, killing several work-
ers including Alfred Nobel's youngest
brother, Emil Oskar. Other explosions con-
tinued to claim lives in applications and in
production plants for liquid nitroglycerin.
Many of the accidents were caused by care-
less handling and by workers who did not
appreciate the danger of the material they
were dealing with. For a time, in order to
be away from potential victims, Alfred No-
bel even lived on a barge moored in the
middle of a lake while conducting his ex-
periments to find a safer energetic mate-
rial.
In 1866, at a newly established explo-
sives factory in Krummel, Germany, Nobel
came across a cask of nitroglycerin that had
leaked into its diatomaceous-earth packing
material, called "kieselguhr." The kiesel-
guhr, impregnated with nitroglycerin, had Get the Facts On TVivac®
dried into granules. Q Compact Design
Nobel experimented with the powder, Q Low Noise Level
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nearly as much force as pure liquid nitro- Ask for the 7 Golden
glycerin. Being so insensitive to shocks, Rules for use in
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diatomaceous-earth/nitroglycerin mixture
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 FIRST ANNOUNCEMENT
Owing to an enormous increase in the amount of high quality research in the fields of electronic and médical materials
Chapman and Hall are launching two new companion journals to Journal of Materials Science in 1990.
thèse twô new journals will maintain the high production and refereeing standards ôf the Journal of Materials
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Journal of Materials Science: Materials in Electronics

Editor: Professor Arthur Willoughby, Professorof Electronic Materials,
Southampton University, Southampton $09 5NH, UK
Journal of Materials Science: Materials in Electronics is à new refereed quarterly compahion to the Journal of Materials
Science which will publish papers on materials and their applications in modem eiectronics.
The Journal will cover the ground between the fundamental science, such as semiconductor physics, and work concemed
solely with applications. It will feature nbt only the growth ànd préparation of new materials, but also their processing,
fabrication, bonding and encapsulàtion, together with the reliability, failure analysis, quality assurance ànd characterisation
relatéd to the whole range of applications in eiectronics.
It will encourage papers in newly developing fields such as low-dimensional structures and devices, optoelectronics
including IM-V compounds, glasses and linear/non-linear crystal materials and iasers, high Te superconductors, conducting
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techniques, as well as bulk crystal growth will be covered, while ail aspects of the technology and fabrication of
semiconductor devices and circuits, together with their assessment and reliability, will be included. Materials used in more
conventional applications such as resistors, inductors, conductors, capacitors, power semiconductor devices, dielectrics,
ferroelectrics, insulàtors and magnetic applications will equallybe encouraged.
The journal will bring together those working on the materiais themselves, and those concemed with their applications. It will
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Authors should submit two copies of their paper, with any original artwork, to the Editor, Professor Willoughby. Full
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Journal of Materials Science: Materials in Medicine

Officiai publication of the European Biomaterials Society
Editors: Professor William Bonfield, Professorof Materials, Queen Mary Collège,
Mile End Road, London E1 4NS, UK
Professor D. F. Williams, Institute of Médical and Dental Bioengineering,
University fo Liverpool, P.O. Box 147, Liverpool LB69 3BX, UK
It hàs become apparent that progress in the field of biomédical materials, particularly in the development of second
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https://doi.org/10.1557/S0883769400061303 Published online by Cambridge University Press