A Brief History of Chemistry and Materials Science

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A Brief History of Chemistry and Materials Science

• Bernard A. Boukamp
• Inorganic Materials Science

AT colloquium, 14 October 2009
Rodin, le Penseur
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The three princes of Serendip
Serendipity!
The king of Serendippo had three sons, which he
send out into the world

• They encountered a merchant who has lost a camel
• They ask him
• Is he blind on one eye,
• Lame
• Missing a tooth
• Carrying a pregnant woman
• Bearing honey on one side
• And butter on the other side?
• (which turns out to be all correct!)

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Materials Science
Our far removed ancestors knew how to shape
materials and make tools.
Bronze age flint arrowhead www.dartfordarchive.org
.uk
Serendipity?
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Technique!
Hitting flint stone at an appropriate angle
results in a sharp, shell shaped edge.
www.suffolkcc.gov.uk
Stone age ended 6000 2500 BC
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Bronze age
3000-800 BC transition from stone to bronze for
tools arts
N. Afghanistan, 2200-1800 B.C.
Bronze Cu Sn Tm 950C
Turkey, 3000-2000 B.C.
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Bronze age not only bronze but also gold and
silver.
Why not iron?
Iron is harder than bronze, keeping its cutting
edge.
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A-tomos
On philosophical grounds There must be a
smallest indivisible particle. Arrangement of
different particles at micro-scale determine
properties at macro-scale.
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It started with
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Science?
Founder of Logic and Methodology as tools for
Science and Philosophy
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• Elements recognized in the middle ages.
• Metals
• Gold
• Silver
• Iron
• Tin
• Mercury
• Copper
• Lead
• Non metals
• Carbon
• Sulphur
• Antimony

Known elements
Alchemists Lead least noble, through
transformations to be turned into gold?
Important discoveries 1649 - Hennig Brand
Phosphorous 1766 Cavendish Hydrogen
gas 1774 Priestley Oxygen
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Centuries of Materials Science Knowledge
transferred from father to son, master to
apprentice.
The art of materials
Combination of tough and hard
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Newton published in 1687 Philosphiae Naturalis
Principia Mathematica,
Newton ! (1643-1727)
while the alchemists were still in the dark
ages.
Origin of classical mechanics Gravitational
force Movement of the planets
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Grandfather of crystallography
Abbé René-Just Haüy (1743-1822)
Dropped accidentally a calcite crystal. Saw the
same arrangement of side-planes in the broken
pieces. Deduced from this molécules
intégrates as basic building bloc.
CaCO3
Essai d'une théorie sur la structure des crystaux
(1784)
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Steps smooth?
Pyrite or Fools gold
Not a true five-fold symmetry!!
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End of 17th century, begining of 18th
Flogiston?
J. J. Becher
In all flammable materials there is present
phlogiston, a substance without color, odor,
taste, or weight that is given off in burning.
Phlogisticated substances are those that
contain phlogiston and, on being burned, are
dephlogisticated. The ash of the burned
material is held to be the true material.
Denounced by A. L. Lavoisier (1743-94) through
his research. (But he accepted calorium as
element.)
F.W.J. Schelling (1803) Ist Chemie als
Wissenschaft möglich?
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Lavoisiers calcination set-up
Bring out the sun!
1743 1794 (beheaded by the Guillotine)
Prominent tax collector in the Ancient Régime.
Antione Laurent Lavoisier Father of modern
chemistry First to formulate conservation law
for matter. Observed that oxygen reacted with
Cavendishs burning air to form a dew, which
Priestly proved to be water. Calcination
experiments
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The power of physics
Atomic weights early 1800?
(trying to get order in the chaos)
Dulong and Petit Potential and kinetic energy
½ kT / degree of freedom In solid 3
degrees of freedom ? 3kT energy per atom It
follows heat capacitance/mol 3k x NA 3R
25 J/mol.K
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Atomic weights more clarity with the help of
physics.
Berzelius!
M Murium, an unknown element that, together
with oxygen, forms HCl (muriatic acid, HMO).
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Sir Humphry Davy (1778-1829)
Put electrons to work!
Used electrochemistry to separate salts. He
discovered the alkali metals and many other
compounds. Became famous for inventing the
mineworkers lamp.
He used a white hot gun barrel and a Zn/Ag
Volta pile for the electrolysis of potash,
leading to the discovery of Potassium (K)
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Regularities in atomic weights
Triades !!!
1817 Johann Dobereiner (and others) noticed
relations between atomic weights of similar
elements
Dumas (1851) N 14 P 14 17 31 As 14
17 44 75 Sb 14 17 88 119 Bi 14 17
176 207
Li 7 Na 7 16 23 K 23 16 39
Mg 12 Ca 12 8 20 Sr 20 24 44 Ba
44 24 68
Also lateral relations were observed Cl - P
Br - As I - Sb 5
This led eventually to
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Mendeleèff
Start of the modern Periodic Table
Mendeleev and simultaneously Meyers ordening
according to atomic weights and similar
properties.
Based on his system Mendeleev did correct
predictions of still unknown, missing elements.
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The original
Atomic weights, not atomic numbers!
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The Spectroscopists
Advances in understanding
Robert Wilhelm Bunsen and Robert Gustav Kirchoff
developed the spectrograph (1860), based on the
colourless (!) Bunsen burner.
Many new elements were discovered based on their
unique emission spectra. Within a few month
cesium and rubidium were discovered.
R.W. Bunsen
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H-spectrum
Emission spectrum of hydrogen
S Scharf P Prinzpal D Diffuse F
Feinstruktuur
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19th Century
Meanwhile demands of society on materials
grew Bigger, larger, faster . But materials
science was still largely empirical.
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The era of steam
Factories, commerce, travel placed ever
increasing demands on iron
Fundamental knowledge of iron steel?
The Firth of Forth Bridge, 2.5 km. Built
from 1883-1890.
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While in Paris
Construction of the Eiffeltower. World exhibition
1889.
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Enigma?
Work hardening strength.
On theoretical grounds Force to deform metals
100 1000 times higher than in practice!
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Postulate dislocations!
Vito Volterra, 1860-1940 Mathematician /
physicist 1905 theory of dislocations in
crystals.
Volterras dislocation models
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Real dislocations
Deformation by stepwise moving of a half-plane
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Lack of understanding
Second World War (1940 - 1945)
Liberty Ships cracked in the Northern Ice Sea
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Invisible rays
Wilhelm Conrad Röntgen Discovered the Röntgen
rays in 1895.Named these Xrays.
Nobel prize 1901
Radiation went straight through a closed, black
carton, hitting a fluorescent screen.
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Enigma X-rays could not be diffracted by
regular grids.
Max von Laue
Nobel prize 1914
Max von Laue assumed the X-ray wavelength to be
in the order of atom-atom distances in a crystal.
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Sir William Henry Bragg He saw the shortcomings
of the Von Laue method. His solution rotating
single crystal.
Braggs law
Noble prize 1915!
Conditions for reflection
The most important thing in science is not so
much to obtain new facts as to discover new ways
of thinking about them.
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From art to science
Materials science became a real science due to
the development of modern analysis and imaging
techniques. Modern analysis and imaging
techniques become possible due to developments in
the materials science
Turn of the century
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1890-1900
Microscopes!

• 1931 Max Knoll and Ernst Ruska
• build first electron microscope
• 1933 Ruska developes an EM with
• higher resolution than an optical
• microscope
• 1937 The first scanning electron
• microscope is built
• 1939 Siemens brings the first
• commercial EM on the market
• 1965 First commercial SEM (Oatley)

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Beyond our imagination
Impact of high resolution microscopic images.
Tremendous depth of sharpness!
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Max Planck (1858-1947) quantum theory E h
? 1913 Niels Bohr electron orbits, Explanation
of principal quantum numbers, n 1, 2, 3 .. and
lines prectrum of H and He
Enter the physics!
Quantum mechanics provided a consistent theory
Linus Pauling (Cal. Tech), on a study tour in
Europe, used quantum mechanics to explain the
chemical bond The Nature of the Chemical Bond
(1939). And chemistry became a real science.

• Pauling visited in Europe
• Louis de Broglie
• Erwin Schrödinger
• Wolfgang Pauli
• Paul Dirac
• Max Born
• Walter Heitler
• Fritz London

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Greatest impact from/on materials science?
Start of the Silicon age!
23 December 1947. Brattain and Bardeens pnp
pointcontact germanium transistor workt as an
18-times amplifier!
Nobel prize 1956
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Where are we going now?
Quest for nano!

• Electronics require ever smaller structures
  (Moores law)
• more transistors, higher frequencies
• new lithography techniques!
• self assembling structures

nano !
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The ultimate tool
Atoms become visible! 1982 - Scanning Tunneling
Microscope Gerd Binnig (IBM) 1986 -
Atomic Force Microscope Uses van der Waals
Force All materials surfaces can be studied.
One can drag atoms across the surface, Make new
compounds, Infinite possibilities!
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Conclusion
Expect the unexpected Look for the details Have
an open mind Science is still a great adventure
Thanks for your kind attention