a brief history of chemistry and materials science

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A Brief History of Chemistry

and Materials Science

Bernard A. BoukampInorganic Materials Science

AT colloquium, 14 October 2009 Rodin, le Penseur



Serendipity!

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

The three princes of Serendip

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 !)



Our far removed

ancestors knew howto shape materials

and make tools.

Bronze age flintarrowhead

www.dartfordarchive.org.uk

Materials

‘Science’ …

Serendipity?



www.suffolkcc.gov.uk

Hitting flint stone atan appropriate angleresults in a sharp,

„shell shaped‟ edge.

Technique!

Stone age ended 6000 – 2500 BC



3000-800 BCtransition fromstone to bronzefor tools & arts

Turkey, 3000-2000 B.C.

N. Afghanistan, 2200-1800 B.C.

Bronze age

Bronze:Cu + SnT m 950°C



Bronze age: not only bronzebut also gold and silver.

Why not iron?

More complexprocess,

Higher temperature> ~1200°C

Reduction of orewith charcoal

Obtaining charcoal

Iron is harder thanbronze, keeping itscutting edge.



A-tomos

Democritus460-~370 BC

On philosophicalgrounds:

There must be asmallest indivisibleparticle.

Arrangement of differentparticles at micro-scaledetermine properties atmacro-scale.



Aristoteles384-322 BC

fire

water

earthair

hotdry

wet cold

The four elements

from ancient times

It started

with …



Aristoteles384-322 BC

Founder of Logic and Methodology as tools for

Science andPhilosophy

Science?



Important discoveries:

1649 - Hennig Brand: Phosphorous

1766 – Cavendish: Hydrogen gas

1774 – Priestley: Oxygen

Known

elements

Elements recognized in the middle ages.Metals:

• Gold

• Silver• Iron• Tin• Mercury• Copper• Lead

Non metals:• Carbon

• Sulphur• Antimony

Alchemists:Lead least noble,through transformationsto be turned into gold ?



Centuries of Materials Science

„Knowledge‟ transferred

from father to son,master to apprentice.

Damascener sword

1100-1700

The art of

materials

Combination of tough and hard



Newton !(1643-1727)

Newton published in 1687:‘Philosphiae Naturalis

Principia Mathematica’,

Origin of classicalmechanics

Gravitational force

Movement of theplanets

Newton(by Godfrey Kneller, 1689)

… while the alchemists were

still in the ‘dark ages’.



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

Abbé René-Just Haüy (1743-1822)Grandfather of

crystallography

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



Not a true five- fold symmetry!!

Pyrite or ‘Fools gold’

Steps =

smooth?



In all flammable materials there ispresent phlogiston, a substance without color,odor, taste, or weight that is given off in burning.

“Phlogisticated” substances are those thatcontain phlogiston and, on being burned, are“dephlogisticated.”

The ash of the burned material is held to be the

true material.

J. J. Becher :

Denounced by A. L. Lavoisier (1743-94) through hisresearch. (But he accepted ‘calorium’ as element.)

F.W.J. Schelling (1803): „Ist Chemie als Wissenschaft möglich?‟

End of 17th century,begining of 18th: Flogiston?



Lavoisier’s ‘calcination’ set-up Bring out

the sun!1743 – 1794 (beheaded by the Guillotine)Prominent tax collector in the ‘Ancient Régime’.

Antione Laurent LavoisierFather of modern chemistry

First to formulate conservationlaw for matter.

Observed that oxygen reacted

with Cavendish‟s „burning air‟to form a dew, which Priestlyproved to be water.

„Calcination experiments‟



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 N A = 3R = 25 J/mol.K

The power

of physicsAtomic weights early 1800?(trying to get order in the chaos)



1814 1818 1826 Modern

O 16 16 16 16

S 32.16 32.19 32.19 32.07

P 26.80 31.88x2 31.38x2 30.98

M 22.33 22.82 -- --

Cl -- -- 35.41 35.46

C 11.99 12.05 12.23 12.01

H 1.062 0.995 0.998 1.008

M = „Murium‟, an unknown element that, together

with oxygen, forms „HCl‟ (muriatic acid, „HMO‟).

Berzelius!Atomic weights:more clarity with thehelp of physics.



Sir Humphry Davy (1778-1829)

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)

Put electrons

to work!Used „electrochemistry‟ to

separate salts.He discovered the alkali metalsand many other compounds.

Became famous for inventingthe mineworkers lamp.



1817: Johann Dobereiner

(and others) noticedrelations between atomicweights of similar elements:

Mg = 12

Ca = 12 + 8 =20

Sr = 20 + 24 = 44

Ba = 44 + 24 = 68

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

Also „lateral relations‟ were

observed:

Cl - P = Br - As = I - Sb = 5

This led eventually to …

Triades !!!Regularities in atomic weights



Mendeleev and simultaneouslyMeyers: ordening according to atomic

weights and similar properties.

Start of themodern

Periodic Table

Based on his system Mendeleevdid correct predictions of still

unknown, missing elements.

Mendeleèff



The originalAtomic weights, not atomic numbers!



Robert Wilhelm Bunsen and RobertGustav Kirchoff developed thespectrograph (1860), based on thecolourless (!) Bunsen burner.

Many new elements werediscovered based on theirunique emission spectra.

Within a few month cesiumand rubidium werediscovered.

The

Spectroscopists

R.W. Bunsen

Advances in understanding



Emission spectrum of hydrogen

H-spectrum

S = ScharfP = PrinzpalD = Diffuse

F = Feinstruktuur



Meanwhile demands of society onmaterials grew:

Bigger, larger, faster ….

But materials science was stilllargely empirical.

19th Century



Factories, commerce, travel …

placed ever increasingdemands on iron

The “Firth of Forth” Bridge, 2.5 km. Built from 1883-1890.

Fundamentalknowledge ofiron & steel?

The era of

steam …



Construction of the Eiffeltower.World exhibition 1889.

While in Paris



On ‘theoretical’ grounds: Force to deform metals 100 – 1000

times higher than in practice!

Enigma?

Work hardening& strength.



Vito Volterra, 1860-1940Mathematician / physicist1905: theory of dislocations in crystals.

Postulate:

dislocations!

Volterra‟s dislocation models



Real

dislocations

Deformation by stepwisemoving of a half-plane



Influence % carbon on brittleness.

„Liberty Ships‟

cracked in theNorthern Ice Sea

Lack of

understanding

Second World War (1940 - 1945)



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

Nobel prize1901

Invisible

rays

Wilhelm Conrad Röntgen

Discovered the „Röntgen‟ rays in

1895.Named these „X=rays‟.



Red Beryl

Enigma: ‘X-rays’ could not be

diffracted by regular grids.

Max von Laue assumed the„X-ray‟ wavelength to be in the

order of atom-atom distances

in a crystal.

Nobel prize1914

Max von Laue

Modern „Laue diagram‟,

using „white radiation‟.

Beryl: Al2Be3Si6O18



Sir William Henry Bragg:

He saw the shortcomings of the VonLaue method.

His solution: rotating single crystal.

The most important thing in science is not so much to obtain

new facts as to discover new ways of thinking about them.

2d nsin Conditions for reflection:

Nobleprize1915!

Bragg’s law



Materials science became a real sciencedue to the development of modern analysis

and imaging techniques.Modern analysis and imaging techniquesbecome possible due to developments in

the materials science ……

Turn of the century

From art

to science



1890-1900

• 1931 Max Knoll and Ernst Ruskabuild first electron microscope

• 1933 Ruska developes an EM withhigher resolution than an opticalmicroscope

• 1937 The first scanning electron

microscope is built

• 1939 Siemens brings the firstcommercial EM on the market

• 1965 First commercial SEM (Oatley)

Microscopes!



Tremendous depth

of sharpness!

Impact of high resolutionmicroscopic images.

Beyond our

imagination



Pauling visited in Europe:• Louis de Broglie• Erwin Schrödinger

• Wolfgang Pauli• Paul Dirac• Max Born• Walter Heitler

• Fritz London

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+

Linus Pauling (Cal. Tech), on astudy tour in Europe, usedquantum mechanics to explainthe chemical bond:

„The Nature of the Chemical Bond ‟ (1939).

And chemistry became a

real science.

Enter the

physics!

Quantum mechanics provided a consistent theory



23 December 1947.

Brattain and Bardeen’s pnppointcontact germanium transistorworkt as an 18-times amplifier!

Nobel prize 1956

Greatest impact from/onmaterials science?

Start of the

Silicon age!



Electronics require ever smaller structures(Moore‟s law):

• more transistors, higher frequencies• new lithography techniques!

• self assembling structures

= nano !

Postulated in 1965 !

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

Quest for

nano!

Where are we going now?



Atoms become visible!

1982 - Scanning Tunneling Microscope

Gerd Binnig (IBM)

1986 - Atomic Force MicroscopeUses van der Waals ForceAll materials surfaces can be studied.

One can drag atoms across the surface,

Make new compounds,

Infinite possibilities!

Graphite

silicium

The ultimate

tool



Conclusion

Expect the unexpected

Look for the details

Have an open mind

Science is still a great adventure

a brief history of chemistry and materials science

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