Transcript Historical Use of Materials

Mech 473 Lectures
Professor Rodney Herring
Historical Use of Materials
Introduction
• Through out the history of man, those countries that produced
metals of exception quality became wealthy lands.
• For example, Britain learned to produce a high-quality steel that
enable it to conquer 1/5 of the world.
• The USA become wealthy in the 1900 because of its excellent
steel and,
• Japan has become wealthy recently because of its electronic
materials.
Historical Use of Materials
Introduction
• Often a country was invaded because of the metal ores that were
know to exist there. This happened throughout history.
• For example, Rome invaded England for its Tin mines. Rome
invaded Spain for its lead mines, and so forth.
• As well, Kings spent fortunes trying to find the secret of the
Philosopher’s stone where Lead could be turned into Gold with
the transmutation agent being able to right bodily imperfections,
cure all illnesses and confer long life.
• For a long time, mercury (Hg) was thought to be this agent,
however, it ended up poisoning countless people playing with its
properties.
Historical Use of Materials
Introduction (cont’d)
• For most of man’s history, every generation went to war, every
generation suffered some lose of their kindred.
• The people and countries that exist today are here because their
ancestors kept up with the pace of producing new materials for
defense technologies.
• Let us look briefly at the ages of man through the looking glass
of its metals.
Historical Use of Materials
Stone Age
Through archeological digs we know that:
• ~500,000 yrs ago, early man used flint, bones and stones
•~100,000 yrs ago, Piltdown man used stone for knives, axes,
and borers
• this period ended only ~6000 yrs ago but it is still in existence
today in some restricted places (S. America, Africa and
Indonesia).
• The stone age was also still in existence in early with the
natives of North America and South America, which gave the
Europeans a significant advantage to concur the native peoples.
Historical Use of Materials
Metal Age
• the real history of metals and man starts ~35,000 yrs ago when
homo sapiens displaced Neanderthals
• gold was first to be discovered and used for ornaments.
• iron from meteorites was used for tools such as starting fires
with flint, a silica-based stone.
• even though iron was the first “really hard” material to be
used, it took the longest to be produced by man into useful tools.
• Learning how to produce iron or steel still continues today.
• Today 90% of man-made materials is iron-based.
Historical Use of Materials
Copper Age
• Copper was the first metal produced by early man.
• ~6,000 BC, copper has been discovered in parts of the Middle
East where is seems likely that the art of metallurgy, like
agriculture, was first practiced.
• Copper was probably discovered by chance when man built
his fires in a hearth of rocks containing copper mineral, which
was reduced to metal by the charcoal providing a reducing
atmosphere – the camp fire theory.
• In a copper-rich region this would have happen many times
increasing its chance to be noticed.
• After the Great Flood, ~4,000 BC, the art of melting and
casting copper, silver and gold was established over a 2000 year
period as seen in ornaments and weapons excavated.
• Findings occur in Egypt, Babylon (Ur) and India.
Historical Use of Materials
Bronze Age
• Copper is a rather soft material so harder is desirable.
• ~1,200 BC, probably by accident again, Bronze was produced
from mixing Copper (Cu) with Tin (Sn) when Cu was made
from CuO ore in SnO2 hearths.
• The Sn leached into the Cu to make Bronze.
• Bronze is much stronger and harder than Cu producing a
better product.
• the use of Bronze quickly spread throughout Europe as far as
the Baltic, then to India and then to China.
• development can be easily followed by the axes, swords and
farm implements produced.
• even today, places in India, and its surrounding countries
such as Nepal, Burma, Pakistan, Malaysia and Indonesia, still
produce and use the finest quality of Bronze.
Historical Use of Materials
Lead
• There was no Lead Age but it played a significant role in the
history of man.
• Lead, being easily shaped, was widely used for water ducts and
eating utensils (cups, plates, knives, spoons and forks) and personal
hygiene implements (eg., combs, hair pins, etc) afforded by the rich.
• The people of the Roman Empire and especially the Romans used
lead for their daily needs.
• Lead poisoning creates confusion and the inability to make
rational decisions, which caused the Fall of Rome in 700 AD, which
changed the face of civilization in Europe, Asia and Africa.
• Thus, lead had a significant impact of human civilization.
Historical Use of Materials
Brass
• There was no Brass Age but it played a significant role in the
history of man.
• Brass was produced from Copper and Zinc oxide.
• Brass having 21-28% Zn was used for coins that didn’t corrode,
establishing our currency system, which had a significant impact on
the known world for trade.
• Other metals corroded and there was too little gold.
• Rome conquered Spain just to obtain its Cu and Zn mines.
• The brass currency helped Rome solidify its empire by enabling
trade between its countries.
Historical Use of Materials
Concrete
•There was no Concrete Age but it played a significant role in the
history of man.
• The Romans invented concrete who used it for their buildings,
which still stand today, and for their roads.
• Rome’s army was kept fit by building concrete roads during quiet
periods, establishing trade routes.
• The Roman built roads that connected the countries of Europe.
• Rome’s roads are still being used throughout Europe today!
• In fact, only recently did civil engineers discover the secret of
making roads that enable them to last a long time without suffering
from the freeze-thaw exposures due to weather. Does anyone know
the secret?
Historical Use of Materials
Iron Age
• The use of Iron very slowly replaced that of Bronze.
• Iron first really started to be produced and used in the Middle
East by the Hittites in Ur. Ur is now Iraq.
• Because of their iron, the Hittites were feared by Egypt. In 1,200
BC, when the Egyptian Pharaoh received a high-quality iron knife
as a gift from the Hittite King, the Pharaoh had his army attack
and destroy the Hittites’s mines and furnaces.
• This loss significantly slowed the development of iron during this
period.
Historical Use of Materials
Iron Age
• ~400 BC, the Greeks (and later Romans) learned that water
quenched and tempered iron was much harder, stronger and less
brittle than slowly-cooled forged iron. Why?
• The Romans defeated the Gauls because they had better weapons.
• The Gauls had to straighten their softer and weaker weapons after
taking the first thrust on their spears and armor while the Romans,
not having to stop, cut them down with their stronger, superior
weapons.
• At the end of this course, we will study how modern technology
has recently replaced steel and urania penetrators with tungsten.
Historical Use of Materials
Iron Age
• Even up to the 17th and 18th century, there was no clear pathway
for metallurgists to proceed to produce better, higher quality
metals, including iron, relying instead on the Greek philosophies of
earth, wind, fire and ice as the foundation for their development.
• The Arabs lead the way between the 700 AD and 1200 AD by
producing furnaces, referred to as the Philosophers egg or Vase of
Hermes, that had high chimneys.
• The high chimneys produced higher temperatures and thus purer
metals. These evolved into the Blast Furnaces today.
• From iron ore and charred wood (charcoal), high-quality iron was
produced for wrought iron (forged at high temperatures, red hot >
600 C) and cast iron (poured into a mold).
Historical Use of Materials
Iron (cont’d)
• Wrought iron guns (rifles) also started to be made, which shot
lead balls made in shot towers located in every city, usually in their
centers. You can still see these towers if you look for them.
• England, Germany and Scandinavia also began producing iron
during the middle ages by medieval metallurgists as they had plenty
of iron ore and forests, preferably hard wood, for charcoal.
• So much hardwood for the iron industry was being cut down in
England that it was banned by its Parliament so England started to
import iron from European Iron Mongers (mostly Swedish who
made 1/3 of the world production).
• This created a net flow of capital out of the country, so Iron was
then restricted for import by the British Parliament.
Historical Use of Materials
Iron Age (cont’d)
• This restriction severely affected the production of the Caxton’s
press for making newspapers and books.
• Three books on steel making were published around this time:
• 1) The Pirotechnia by Vannoccino Biringuccio
• 2) De Re Metallica by Georgius Agricola
• 3) Autobiography by Benvenuto Cellini (a metallurgist)
• These became the metallurgists bibles and were used by many to
start iron works.
Historical Use of Materials
Iron Age (cont’d)
• Making Iron in America was first attempted in Jamestown,
Virginia but failed.
• In 1644 an iron plant was established in Hammersmith,
Massachusetts, which was successful.
• Eventually, the Americans produced so much iron that they would
sell iron to Britain. America had large forests with no charcoal
restrictions.
Historical Use of Materials
Iron Age (cont’d)
• In the 1700s coal, and shortly thereafter coke, began to be used for
iron-making in Britain, which over came the shortage of charcoal
and brought new life to its industry.
• During the next 100 years, Britain was the greatest iron producer
in the world and lead the world for ~300 years making its industry
and Kingdom thrive.
• Because Britain had plenty of high-quality iron, it lead the world
militarily up to ~1950.
Historical Use of Materials
Steel Age
• Slowly, very slowly the Iron age turned into the Steel Age as
impurities were removed from the iron and Steel Alloys began
being produced.
• The steel age, which some would argue is still continuing today,
has had a major impact on modern man (ships, buildings, cars, etc.
etc. etc.).
• As Iron furnaces improved, the quality or purity of Iron turned it
into Steel, which is an Iron-Carbon alloy, as we will learn in detail
in this course.
Historical Use of Materials
Steel Age
• Archeologists have found iron-carbon, i.e., steel, being made a
various times throughout history but the methods didn’t survive.
• The first “Steel” is considered to be Wootz steel made in India
~500 BC using a type of blast furnace that used clay pots as the
crucible to hold the charge but it wasn’t very reproducible.
• Damascus steel involved fusing together layers of steel and iron by
hammering to form a type of composite, which was stronger than
other steels of its time. The steel was naturally produced in the
furnace on the surface of the metal from the charcoal.
• Much later the Damascus method was refined by the Japanese
who took it to a much higher level for their samurai swords.
Historical Use of Materials
Steel
• A low quality steel, called Blister Steel, which used a primitive
carburizing technique that formed blisters on it surface, was
produced in Egypt in the 1300s but came to an end due to the Black
Death or Black Plague that ravaged the known world.
• In the 1400’s metallurgists remelted cast iron and refined it by
removing impurities, known as “refining”, which produced a steel
that was more malleable.
• Methods to refine continued to improve steel into the 1700’s such
that it replaced Bronze and Brass to make cannons, as well as, for
making cannon balls, which up to that time were made of stone.
Their shots became much more accurate with steel balls.
Historical Use of Materials
Steel Age
• Similar to Wootz steel, Benjamin Huntsman used a crucible
process in 1740 to produce the first steel that was sufficiently
reliable to be accepted and used in many parts of the world.
• This steel enabled the Industrial Revolution to occur in Western
Europe. It had a major impact on society.
• The crucibles became larger with time enabling larger charges of
steel to be made.
• Crucible steel making reached an all-time high in the United
States, which took the lead in steel production from Britain in 1890.
Historical Use of Materials
Steel Age
• An English inventor, Henry Bessemer in 1854 applied for a patent
for “Improvements in the Manufacture of Iron and Steel”, which
involved decarburizing the molten steel by blowing air over it using
a fireclay pipe such that the iron became free of carbon (0.1% to
1.5% C) and other impurities.
• In his method, the heat generated by the oxidation process was
sufficient to keep the iron molten, when, in fact, to Bessemer’s
surprise it became hotter. He initially thought the air would cool the
molten iron.
Historical Use of Materials
Steel Age
• Even today, every person in the UK learns of Sir Henry Bessemer
who became a national hero, of sorts.
• Bessemer’s invention was the first step towards blowing oxygen
into steel to clean it. He never got the chance to try pure oxygen
because pure oxygen didn’t exist, i.e., it hadn’t been made yet.
• Bessemer’s invention eventually culminated into the Basic Oxygen
Furnace (BOF) method, first developed by Canadians, as discussed
later.
Historical Use of Materials
Steel Age
• There was problems with Bessemer’s method.
• Stopping the blow of air at a good carbon content was still a
problem called hot-shortness that brittled the steel so it could not
be forged when hot.
• Hot shortness was solved by blowing all the carbon out and then
adding a small amount of spiegelsen (a type of pig iron containing
15-30 % Manganese and 4-7% C) where Mn helped make the steel
become malleable.
Historical Use of Materials
Steel Age
• the Bessemer process reduced the price of steel sufficiently that it
could be used in large quantities such as rails and girders for the
railway industry and plates for battleships.
• In 1885, the British government accepted Bessemer steel for its
guns and naval shipbuilding.
Historical Use of Materials
Steel Age
• Another inventor, Charles Siemens, a German who settled in
England in 1844 modified a reverberatory furnace that developed
into the Open Hearth method of steel making which became the
most popular method during the 1900s.
• The Open Hearth method became the most popular method used
by all countries to make steel.
Historical Use of Materials
Steel Age
• For the Open Hearth method, a reverberatory furnace used the
flames of gas burners put over the steel melt or hearth to heat the
steel along with the heat reflected from the furnace roof.
• As well, instead of the hot burned gases going up a chimney, they
were redirected through brickwork chambers to preheat incoming
air and gas, i.e., heat exchanger, which enabled higher temperatures
of steel to be produced.
• This method was also used for glass making, which needs to reach
high temperatures, ~2000 oC and is still the method used today.
Historical Use of Materials
Steel Age
• So much heat was produced by the Open Hearth method that very
large charges could be made that included steel scrap, which
substantially reduced its cost.
• High-quality steel can be produced as there is time for measuring
its impurity content and alloy levels.
• the Open Hearth method dominated steel making right up into the
1990s, however, it has now been replaced by the BOF method (Basic
Oxygen Furnace) as it takes too long, sometimes longer than a
week, for one charge to finish, whereas, the BOF method takes 20 –
25 minutes for one charge.
Historical Use of Materials
Steel Age
• Bessemer steel makers became aware of two deficiencies of the
process; the inevitable nitrogen pick-up in the steel from the air
blast and the difficulty in judging the end of the after-blow (final C
removal).
• Bauxite, an aluminum ore, can be used to remove the impurities
but it adds too much to the cost.
• These problems were solved by blowing pure oxygen into the steel
bath using a lance inserted from the top of the vessel in a way that
Bessemer described in a patent in 1855 but he was never able to
realize because of the high heat and lack of pure oxygen.
Historical Use of Materials
Steel Age
• The Basic Oxygen Furnace (BOF) was first invented in Austria,
called the Linz-Donawitz process. A water cooled lance is used to
blow oxygen into the charge for a short time.
• In 1953, the steel company, Dofasco in Hamilton, Canada secured
the exclusive rights to the basic oxygen furnace technology from the
Austrians and with the expertise of engineering immigrants from
Austria, German and the UK, was able to pioneer many of the
important developments of the basic oxygen steelmaking process
such that by the 1970’s, the BOF started to dominate steel
production in North American.
Historical Use of Materials
Steel Age
• Stelco using the Open Hearth method was Canada’s largest steel
producer
• Dofasco took over Stelco as the largest producer in the 1990s and
provides much of the steel used in North American cars and
buildings today.
• Over the decades, the BOF method as developed in Canada has
become the common method for all steelmaking around the globe.
• This success has obviously made Canada one of the best, if not the
world leader, in producing high-quality steel.
Historical Use of Materials
Canada
• Apart from iron ore, which was mined prior to the British
conquest of Canada in 1763, minerals do not play an important
part in Canada’s economic history until the late 1800s.
• Mining really started in Sudbury, Ontario, where large copper
and nickel deposits were found during the construction of the
Canadian Pacific Railway in 1883.
• The large nickel and iron originated from a large meteor hitting
the earth enabling nickel to be produced at times as high as 90% of
world production and at 50% of the world’s production today.
Historical Use of Materials
Canada
• Mining pulled Canada out of being essentially a farming, fur
trapping, and fishing community during the 1800s and 1900s to
being a “developed” country, now that it had the necessary
ingredients, i.e., abundant energy and materials.
Historical Use of Materials
Canada
• Ontario has also been producing cobalt, silver, gold and, more
recently, diamonds.
• Quebec produces copper and for a period, asbestos, which was
used for insulation but found to be carcinogenic so has mostly
discontinued. Asbestos is still used for special, high-temperature
processes.
• Manitoba produces Zinc.
Historical Use of Materials
Canada
• British Columbia produces copper, lead and zinc, along with other
high value materials such as antimony, indium, gallium and arsenic.
The major producer is Cominco founded in 1906.
• Huge iron ore and coal deposits have been found in Labrador that
are semi-processed into pellets and shipped to Hamilton for use by
the Steel Industry.
• Canada is currently the world’s largest supplier of uranium from
its northlands, which may become increasingly valuable as we try
to reduce global warming by using nuclear power.
Periodic Table
How did we determine the presence of all the elements of the
Periodic Table?
• Before the 1900s, very few elements were known. The known
ones included gold, silver, lead, tin, zinc, copper, iron and
antimony (reduced from antimony sulphide).
• X-ray were discovered in 1895 by RÖntgen.
• X-rays were found to fluoresce from materials when they were
irradiated by high energy x-rays, electrons or ion beams.
• The energy of the x-ray fluorescence could be used to determine
the elements present and, eventually, their composition. By this
means, missing elements from the periodic table could be found
and even created by man.
Fluorescence energy, E ~ Z2, where Z is atomic number
Periodic Table
How did we determine the presence of all the elements of the
Periodic Table? (cont’d)
• The invention of the Period Table is attributed to Dmitri
Mendeleev in 1869 who intended to illustrate recurring trends in
the properties of the elements.
•
Its layout has been refined and extended over the years as new
elements have been discovered and new models have been
developed to explain chemical behavior.
• So far, 118 elements have been discovered and new ones are
being reported all the time.
From Alchemy to Metallurgy
• During the 1600s/1700s, the people developing materials
gradually started to understand some of the whys and ways of
the techniques they were using.
• If one had to state categorically whose work this gradual
enlightenment depended upon, it would be Robert Boyle, a
seventeenth century chemist who made a distinction between
elements, compounds and mixtures and laid the foundations for
modern chemistry, clearing away the decaying alchemical
philosophy based on earth, water, air and fire that outlived its
usefulness.
• In 1722, a book was published entitled, “Memoirs on Steel and
Iron” by Rene Réaumur that included practical theories on
processes such as malleabilizing cast iron and heat treating
steels.
From Alchemy to Metallurgy
• Surface polishing techniques were developed in 1863 by Sorby
by using successively finer abrasives to produce a mirror-like
finish, which enabled grains to be seen using an optical
microscope for the first time.
• RÖntgen’s x-rays were used by William Bragg to determine a
material’s crystal structures that determines much of its
mechanical and other physical properties.
• From this work, Bragg’s Law was realized.
  d hkl sin  Bragg angle
Where  is the wavelength of radiation, d is the atomic plane of
Miller indices, h, k, l and  is the Bragg angle of diffraction.
From Alchemy to Metallurgy
• The electron microscope was first proposed by Knoll and Ruska
in 1932 where they introduced the concept of electron lenses.
(Ruska received the Nobel prize for this in 1986)
• The first electron microscope built in a configuration as we
know it today, was in 1938 by the Canadians; James Hillier and
Albert Prebus at the University of Toronto.
• This type of microscope can now see smaller than an atom as is
possible with UVic’s STEHM (Scanning Transmision Electron
Holography Microscope).
• This spatial resolution is ~1,000,000x better than an optical
microscope’s.
• It has enabled, and will continue to enable, development of
advance materials that previously were only seen in sci-fi
movies.
The First EM in N. America
The First EM in N. America
Compositional Analysis
• The quality of any material is largely dependent on its impurity
concentration. The following methods are used to determine the
presence and concentration of impurities and alloying additions.
• Gas Flame spectroscopy – a small sample of material is burned in
a flame and the flame’s colour and its intensity is used to
determine the material’s composition. It is fast and effectively
used during the making of steels by Dofasco, Stelco and Algoma.
It can measure a fraction of 1% composition.
Compositional Analysis
• Mass spectroscopy – a small amount of material is dissolved in an
acidic solution, which is vaporized by heating. The vapor is
injected into a tube with an inert carrier gas such as argon where
the light elements travel quickly and the heavy elements travel
slowly through the tube. At a meter or so from the beginning,
magnetic induction measures changes in the gas due to the
elements. Time and degree of change in inductance determine the
elements present and their composition. Mass spectroscopy can
measure parts per million (ppm).
Compositional Analysis
• SIMS (Secondary Ion Mass Spectrometry) – An ion beam is fired
at a material sample, which loses surface atoms (now ions) by
sputtering, which are collected and analyzed by a mass
spectrometer. It is the most sensitive technique for elemental,
isotopic or molecular composition being able to detect elements
present in the parts per billion (ppb) range.
Compositional Analysis
• X-ray spectroscopy – High energy ions from an ion gun or a
radioactive source or electrons from an electron microscope
impinge a material sample causing x-rays to fluorescence from the
k, l, and m shells of electrons orbiting the atoms, which are
detected using an energy dispersive spectrometer (EDS) that can
determine the composition of the material to a fraction of 1%. Its
advantage is the small volume of material that can be analyzed
(~1 nm3).
Compositional Analysis
• Electron Energy Loss Spectroscopy (EELS) - High energy
electrons from an electron microscope pass through a material
sample losing energy to the atom’s electronic structure. It can
determine the composition of a small volume of material to a
fraction of 1%.
• EELS is similar to EDS but the peaks in their spectrums are not
the same so if a material has elements whose peaks overlap in
EDS, which makes it difficult to determine the composition of the
elements, the peaks likely won’t be overlapping in EELS and visa
versa.
The End
Any questions or comments?