A Brief History of Chemistry and Materials Science

Bernard A. Boukamp
Inorganic Materials Science

Rodin, le Penseur

AT colloquium, 14 October 2009

The three princes of Serendip The king of Serendippo had three sons, which he send out into the world

Serendipity!

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!)

Materials
Science

Our far removed ancestors knew how to shape materials and make tools.
Bronze age flint arrowhead
www.dartfordarchive.org.uk

Serendipity?

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

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.

Bronze age: not only bronze but also gold and silver.

Why not iron?

Iron is harder than bronze, keeping its cutting edge. More complex process,
Higher temperature > ~1200C Reduction of ore with charcoal Obtaining charcoal

A-tomos

On philosophical grounds:
There must be a smallest indivisible particle.

Democritus 460-~370 BC

Arrangement of different particles at micro-scale determine properties at macro-scale.

It started with
fire dry air hot earth wet water The four elements from ancient times cold

Aristoteles
384-322 BC

Science?

Aristoteles
384-322 BC

Founder of Logic and Methodology as tools for Science and Philosophy

Elements recognized in the middle ages. Known Metals: elements Gold Silver Iron Tin Mercury Alchemists: Copper Lead least noble, Lead through transformations to be turned into gold? Non metals: Carbon Sulphur Important discoveries: Antimony 1649 - Hennig Brand: Phosphorous 1766 Cavendish: Hydrogen gas 1774 Priestley: Oxygen

Centuries of Materials Science Knowledge transferred from father to son, master to apprentice.

The art of materials

Damascener sword

11001700

Combination of tough and hard

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
Newton (by Godfrey Kneller, 1689)

Movement of the planets

Abb Ren-Just Hay (1743-1822)

Dropped accidentally a calcite crystal. Saw the same arrangement of sideplanes in the broken pieces. Deduced from this: molcules intgrates as basic building bloc.

Grandfather of crystallography

CaCO3

Essai d'une thorie sur la structure des crystaux (1784)

Steps = smooth?

Pyrite or Fools gold

Not a true fivefold symmetry!!

End of 17th century, begining of 18th:

J. J. Becher :

Flogiston?

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 mglich?

Lavoisiers calcination set-up

1743 1794 (beheaded by the Guillotine) Prominent tax collector in the Ancient Rgime.

Bring out the sun!

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

Atomic weights early 1800?

(trying to get order in the chaos)

The power of physics

Dulong and Petit: Potential and kinetic energy = 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

Atomic weights: more clarity with the help of physics.

1814 O S 16 32.16 1818 16 32.19 1826 16 32.19

Berzelius!
Modern 16 32.07

P
M Cl C H

26.80
22.33 -11.99 1.062

31.88x2
22.82 -12.05 0.995

31.38x2
-35.41 12.23 0.998

30.98
-35.46 12.01 1.008

M = Murium, an unknown element that, together with oxygen, forms HCl (muriatic acid, HMO).

Sir Humphry Davy (1778-1829)

Used electrochemistry to separate salts. He discovered the alkali metals and many other compounds. Became famous for inventing the mineworkers lamp.

Put electrons to work!

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)

Regularities in atomic weights 1817: Johann Dobereiner (and others) noticed relations between atomic weights of similar elements:
Li = 7

Triades !!!

Dumas (1851):

N = 14
P = 14+ 17 = 31 As = 14 + 17 + 44 =75 Sb = 14 + 17 + 88 = 119 Bi = 14 + 17 + 176 = 207

Na = 7 + 16 = 23
Mg = 12 K = 23 + 16 = 39

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

Mendeleff
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.

Atomic weights, not atomic numbers!

The original

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.

The Spectroscopists

R.W. Bunsen

H-spectrum

Emission spectrum of hydrogen S = Scharf P = Prinzpal D = Diffuse F = Feinstruktuur

19th Century

Meanwhile demands of society on materials grew:

Bigger, larger, faster .

But materials science was still largely empirical.

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.

While in Paris

Construction of the Eiffeltower. World exhibition 1889.

Enigma?

Work hardening & strength.

On theoretical grounds: Force to deform metals 100 1000 times higher than in practice!

Postulate: dislocations!

Vito Volterra, 1860-1940 Mathematician / physicist 1905: theory of dislocations in crystals.

Volterras dislocation models

Deformation by stepwise moving of a half-plane

Real dislocations

Second World War (1940 - 1945)

Lack of understanding

Liberty Ships cracked in the Northern Ice Sea Influence % carbon on brittleness.

Wilhelm Conrad Rntgen Discovered the Rntgen rays in 1895.Named these X=rays.

Invisible rays

Radiation went straight through a closed, black carton, hitting a fluorescent screen.

Nobel prize 1901

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. Red Beryl: Al2Be3Si6O18 Beryl Modern Laue diagram, using white radiation.

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:

2d sin n

The most important thing in science is not so much to obtain new facts as to discover new ways of thinking about them.

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

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)

Impact of high resolution microscopic images.

Beyond our imagination

Tremendous depth of sharpness!

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 Schrdinger Wolfgang Pauli Paul Dirac Max Born Walter Heitler Fritz London

Greatest impact from/on materials science? 23 December 1947. Brattain and Bardeens pnp pointcontact germanium transistor workt as an 18-times amplifier!

Start of the Silicon age!

Nobel prize 1956

Where are we going now?

Postulated in 1965 !

Quest for nano!

Electronics require ever smaller structures (Moores law):

more transistors, higher frequencies

new lithography techniques! self assembling structures

www.intel.com/research/silicon/mooreslaw.htm

= nano !

Atoms become visible!

1982 - Scanning Tunneling Microscope Gerd Binnig (IBM)

The ultimate tool

1986 - Atomic Force Microscope Uses van der Waals Force All materials surfaces can be studied.

Graphite One can drag atoms across the surface, Make new compounds, Infinite possibilities! silicium

Conclusion
Expect the unexpected

Look for the details Have an open mind

Science is still a great adventure

Thanks for your kind attention