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History of Quenching

  • Quaker Houghton

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Iron seemeth a simple metal, but in its nature are many mysteries, and men who bend to them their minds shall, in arriving days, gather therefrom great profit, not to themselves alone but to all mankind…….attributed to Joseph Glanvill (1636–80) The basic concept of heat-treating, and specifically quenching, is intertwined with the history of civilization. It is the efforts of these pre-industrialized people that laid the foundation for modern metallurgy, and our understanding of materials behavior. In this paper, the early history of quenching will be described from the dawn of civilization to the early industrial age. The focus will be primarily on the contributions of Europeans, Indian, Chinese and Japanese civilizations.
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History of Quenching
D. Scott MacKenzie
Houghton International, Inc., Valley Forge, PA, USA
Iron seemeth a simple metal, but in its nature are
many mysteries, and men who bend to them their
minds shall, in arriving days, gather therefrom great
profit, not to themselves alone but to all
mankind…….attributed to Joseph Glanvill (1636–80)
The basic concept of heat-treating, and specifically
quenching, is intertwined with the history of civilization.
It is the efforts of these pre-industrialized people that
laid the foundation for modern metallurgy, and our
understanding of materials behavior. In this paper, the
early history of quenching will be described from the
dawn of civilization to the early industrial age. The
focus will be primarily on the contributions of
Europeans, Indian, Chinese and Japanese civilizations.
Much of the history of quenching is shrouded in mystery
– especially from roughly 400 BC to approximately
1500 AD. This is thought to be a result of the general
education of the people, and the desire to protect
intellectual property by the many blacksmiths and
guilds. It was only until much later, that many of the
quenchants, and the methods of quenching were
described. The methods of quenching were determined
through empirical research, and much experimentation.
It was only until much later, after approximately 1850
AD, that the science of quantifying the effects of
quenchants and alloying elements was developed. Steel
hardenability, martensite formation and the mechanism
of quenching would have to wait until the necessary
analytical tools were developed.
Much of the history of quenching is interlaced with the
early production of iron. Probably one of the earliest
references to smelting and blacksmithing is from the Old
Testament [1] in Genesis 4:22:
Figure 1 - Jubal and Tubalcain in the smithery. UNKNOWN;
Illustrator of 'Speculum humanae salvationis', Cologne, c.
1450. Museum Meermanno Westreenianum, The Hague.
“Zillah also had a son, Tubal-Cain, who was an
artificer of bronze and iron.”
Interestingly, the name “Cain” is a cognate with the
Arabic qayin “smith”. The name Cainities is also the
description of the Midianite tribe, which some have
inferred to be the Hittites [2].
It is not known when steel was first created, or who first
created steel. It is suggested from tradition (Herodotus,
Xenophon and Strabo) and archaeological
evidence[3][4] that iron working developed in the
Middle East, in Turkey, near the plateau of Anatolia in
1400-1200 BC by the Hittites [5][6][7]. Iron smelting
was well known by the second millennium, and
described by Homeric poems (880 BC), the History of
Herodotus (446 BC) and Aristotle [8] (350BC). Because
of ore variation, and the skill of the individual craftsman,
the production of steel was often poor quality, and
limited in production [9].
One of the first mentions of quenching is from Homer
(circa 800BC):
“As when a man who works as a blacksmith
plunges a screaming great axe blade or adze into
cold water, treating it for temper, since this is the
way steel is made strong, even so Cyclops’ eye
sizzled about the beam of the olive….” Odyssey
9.389-9394, translation by R Lattimore
This dramatic image of quenching indicates familiarity
with the concept of quenching of steel. Much of the
history of quenching has been shrouded in mystery and
One of the earliest myths perpetrated regarding
quenching ancient steel, was the idea that slaves or
virgins were used as a quenching medium. The idea
being that the hot sword or knife would be plunged into
the body of a slave would impart special properties.
Slaves as a quenching medium was first presented with a
tounge-in-cheek by Douglas Fisher [10]. This was
subsequently noted by John Sullivan [11]. From a
practical perspective, it is not likely that slaves or virgins
were used as a quenching medium. The physical force
required to plunge a blade while hot would likely cause
the blade to deflect and warp. Further, it is likely that
the slaves would tend to writhe about, causing distortion
to the blade. Lastly, slaves and virgins are not
renewable. Any large production would certainly
exceed the available supply.
In the first millennium, few technological advances were
made in Europe. Some Icelandic sagas spoke of
searching through many kingdoms to find the proper
water to harden the sword Ekkisax and weapons that are
hardened in blood. Predominately, the advances in
metallurgical technology were located in the Arab
World, India, China and Japan. While European armor
blacksmiths were improving, and gradually perfecting
their craft, the Crusaders of the 12th century had no steel
that was the equal of Islamic metallurgy. The Japanese
sword was even better than the Islamic sword by an even
greater margin [12].
The primary contribution of India was the production of
high quality steel called Wootz steel. The quality of the
steel was excellent, and exported to Europe, China, and
the Middle East. The 12th century Arab Idrisi wrote
The Hindus excel in the manufacture of iron. It is
impossible to find anything to surpass the edge from
Indian steel.”[13].
The first real production of steel on a large scale was
produced in India around 500 B.C. [14]. This steel,
which even in relatively modern times, was known for
its high quality:
‘…there is a cake which is supposed to be steel from
India and the kind to be rated most highly in Egypt. I
could find no artisan in Paris who succeeded in forging
a tool out of it.’ Rene Antoine Ferchault de Reaumur,
(1722) [15]
Figure 1 – Figure showing Indian blacksmiths creating
swords, from the cover of “India’s Legendary Wootz Steel: An
Advanced Material of the Ancient World [16]
Sherby[17], describing the production of Wootz steel,
indicates that wrought iron is broken into pieces in a
sealed crucible, with a pre-measured amount of charcoal.
The crucible is heated to approximately 1200ºC. The
wrought iron absorbs the carbon, and the melting point is
lowered. The process is completed when the crucible is
shaken, and the sound of molten iron is heard. The
crucible is slow cooled over several days. Large grains
of Cementite are formed, and a homogeneous alloy of
1.5-2% carbon is formed.
These buttons are then heated to a relatively narrow
range of 600º-850ºC. In this temperature range the
Cementite does not completely dissolve. Upon forging
or hammering, the Cementite grains are broken up,
resulting in a mixed, banded microstructure, with the
trademark swirl of Damascus Steels [18]. This forging
technique explains the strength, toughness and ductility,
and the mythology of Damascus steels, which have been
produced since 330BC. This steel was exported to
China, Persia, Arabia and eventually Europe.
Figure 2 – Damask pattern, courtesy of Manfred Sachse.
Middle East
Not much is known of the methods of quenching in the
Islamic world. It was known that the swords of the
Islamic world were high quality. A writer from the
Crusades, regarding the quality of Damascus blades
fashioned from Wootz steel described the quality of the
blade as “One blow of a Damascus sword would cleave
a European helmet without turning the edge, or cut
through a silk handkerchief drawn across it.”[19].
al-Biruni, writing in the Kitab al-jamahir fi ma'rifat al-
jawahir, in the 11th century AD, specifies what dawa is
in Indian practice. He writes [20] “…in the process of
quenching the sword they coat the flat of the blade
(matn) with hot clay, cow dung and salt, like an
ointment, and clean the two edges with two fingers….
This is similar to the process of making Japanese blades,
and the application of yakaba-tsuchi clay.
The account of Second Captain Massalski, as published
in Annuaire du Journal des Mines de Russie, 1841, says
Persians quenched their Wootz steel in pre-heated hemp
oil. The Captain says some smiths added a little grease
and bone marrow to the quenchant.
"If it is a dagger it is held flat; if it is a sabre, it is
quenched little by little, beginning by the end of the
cutting edge, holding the latter toward the bath. This
manoeuvre is repeated until the oil stops smoking,
which proves that the blade has cooled. After
quenching the blade is always soiled with burnt oil.
This dirt is removed by heating it enough to set light
to a piece of wood, and by rubbing with a rag from a
English Translation by Graham Cross.
Pretextat Lecomte is a French painter and mosaic artist
who lived in the end of 19th century, and was invited to
Istanbul for the restoration and reconstruction of some
historical art pieces. He spent many years in Istanbul,
and from his studies of oriental arts, he wrote the "Arts
and Crafts of the Orient" in 1903. (Les Arts et Metieres
de la Turquie de l'Orient, published in Paris in 1902).
He mentions that most of the Ottoman sword blades
were made in Damascus (Today's Syria was a part of the
Ottoman Empire during that time), and those blades had
a superior steel which was made in a totally different
way than Europeans:
"...Steel is iron, mixed with charcoal. In Damascus,
10-12 kilograms of iron was required for making one
sword blade. Craftsmen mixed this ore with charcoal
dust, melted it again and again, until it came to a
consistency of their mind."
"...Now it was required to quench it in order to give it
the necessary strength, and that was the interesting
point of the procedure: Europeans quench the steel in
water, vegetable oil, or cattle fat, but in the East they
were doing it on air. When the craftsmen were done
with the processing of the metal, they heated it until
totally red, and gave it to a cavalry man waiting on
his horse, ready for a ride. The cavalry man rode his
horse in the wilderness, waving the blade in the air
with crazy screams to make his horse ride faster."
Lecomte concludes with that although swords were still
made in Damascus during his time, this craft had already
disappeared for economical reasons: The swordsmiths in
Damascus started using imported steel from Britain
because it was much cheaper.
On the other hand, “air quenching” was certainly not the
only method for making “superior steel” in the Ottoman
period. Kemankes (translation is Bowman) Mustafa Aga
gives a special formula in his book, “The Book of
Arrow” [21], for making armor-piercing arrowheads and
sword blades. His quenching medium consists of:
1 okka Quick Lime (CaO)
½ okka Soda (NaCO)
½ okka Carbonas Cupricus (Copper Oxide?)
½ okka Arsenic Sulphate (AsS)
2 okka Radish juice
1 okka Wild Onion juice
½ okka Valonia ash
1 okka Tar
(Okka is a weight unit and corresponds to 1283
The earliest known Chinese word for quench-hardening
is cui [22] and is still used in the modern term for
quenching cuihuo [22]. Water was predominately the
preferred quenchant:
When a skilled metallurgical worker ‘casts’ [zhu] the
material of a Gan Jiang [sword], quench-hardening
[cui] its tip with pure water and grinding its edge
with a whetstone from Yue, then in the water it can
slice water-dragons, and on land it can cut
rhinoceros hide as quickly as sweeping and
sprinkling or drawing in mud.
Sheng zhu dexian chen song presented to the Emperor
Xuan-di (73 BC to 49 BC) by Wang Bao [22]
There is some thought that the idea of quenching was a
Han Dynasty innovation [22]. Early Tang texts
indicated that the Yunnan quench-hardened steel in “the
blood of a white horse”22. Various texts indicate that
different waters were good for quenching, while others
were inadequate. The Qingzhand and the Longguan
Rivers were noted for being good for quenching: [22]
“The Han River is sluggish and weak and is not
suitable for quench-hardening. The Shu River is
bold and vigorous…..”[19]
This empirical line of thinking appears to be universal.
The Elder Pliny, in the 1st century, also indicated that
certain waters were good for quenching. [23]
Quenching in vinegar was considered to be poor practice
“making it brittle and easy to break” [22]. It is not
known why this practice would be considered to be poor
practice, as it should give similar performance to a brine-
type quench.
It seems that quenching in urine was a common practice,
with quenching in the urine of five sacrificial animals or
the fat of five sacrificial animals. It was given that “such
a sword could penetrate thirty layers of armor” [22].
There was also an understanding of the effects of
different quenchants, and the effect on performance. In
6 AD, the blacksmith Qiwu Huaiwen used animal urine
and animal grease to effect different quench rates. The
characters used differentiated this: cui was denoting
quenching in animal grease, while yu was designated for
quenching in urine. Song Yingxing discusses quenching
in oil, which provides a softer quench, “since the
strength of steel lies in quenching”. Further it was noted
that barbarians quench in di son, the “urine of the earth”,
a kind of oil not produced in China [22]. This perhaps is
the first possible mention of quenching in petroleum-
based oils. Japan
The metallurgical state-of-the-art was very advanced in
Japan. The science and craftsmanship of the Japanese
sword is still revered today for being beautiful and
effective, capable of maintaining a sharp edge and the
unique curve of the blade.
Swords made by the traditional method are
manufactured from steel produced by the tatara method.
This steel, or tamahagane, is produced from iron sands
that have very low Phosphorus and Sulfur.
The basic process is similar to that practiced by the
Europeans in the 5-6th century AD. The sharp edge
consists of high carbon steel to retain an edge, and the
interior of the blade consisting of lower carbon steel for
toughness and ductility. However, the Europeans
immersed the entire sword in the water, with the entire
surface of the sword quenched rapidly. In the Japanese
method, controlled quenching is achieved at specific
rates at different locations on the blade.
Prior to heating, the Japanese sword maker applies a
closely guarded secret clay mixture (called yakiba-
tsuchi), that consists of stone powder, clay and charcoal.
The stone powder helps prevent the clay from cracking
during heating of the blade; the charcoal is burned out
during heating, producing a site for initiation of nucleate
boiling, depressing the formation of the vapor phase.
The thickness of the clay determines the quench rate.
The clay is thinnest at the edge of the blade, and thickest
at the ridge of the blade – opposite the edge. The blade
is immersed in water in the water box or mizubune. The
edge is quenched with the highest heat transfer rate and
produces martensite, while the ridge experiences a much
milder quench and transforms to a mixture of pearlite
and ferrite. The interface between the pearlite and
martensite is called the hamon.
This unique and ingenuous method of quenching also
produces the characteristic curvature of the blade. As
the blade is quenched, the edge contracts, and reverse
bending occurs, called gyaku-sori. At the martensite
transformation, the sori, or normal bending occurs, due
to the volumetric transformation of martensite. Gyaku-
sori appears again at the pearlite transformation at the
ridge of the blade. Finally, the final curvature or sori
appears as the pearlite contracts due to thermal
contraction, contributing to strong compressive residual
stress at the blade edge. Final tempering of the blade, or
aidori, is done in a charcoal fire. This understanding of
the quenching process, practiced since the 5-6 century,
shows the advanced nature of the Japanese metalsmiths.
Probably the first significant work in Medieval Europe
was written by Theophilus (1125), a 12th century
German Monk. The “Diver Arts” describe several good
quenchants. His recommendations for quenchants were
very specific:
"Tools are also given a harder tempering in the urine
of a small, red-headed boy than in ordinary water."
Other recommendations for quenchants included the
urine of goats fed ferns for three days.
Giambattista della Porta (ca. 1535-1615) in his books
“Natural Magic,” described the temperatures of steel to
be quenched:
“When the iron is sparkling red hot, that it can not be
hotter, that it twinkles, they call it Silver; and then it
must not be quenched, for it would be consumed. But
if it be of a yellow or red color, they call it Gold or
Rose color; and then quenched in Liquors, it grows
harder. This color requires them to quench it. But
observe that if all the Iron be tempered, the colour
must be blue or violet color, as the edge of a Sword,
Razor, or Lancet; for observe the second colors;
namely, when the iron is quenched, and so plunged
in, grows hard. The last is Ash color; and after this if
it be quenched, it will be the least of all made hard.”
This was a critical observation. He indicates a critical
range for quenching, based on the colors of the heated
steel. Only when the steel is rose or yellow will the steel
be hardened properly. Further, the observation of
tempering colors was indicated. As Cyril Stanley
Smith28 pointed out, it led Della Porta to realize the
advantages of the two-stage quench over a direct quench,
and reject some of the more exotic quenching baths that
was cited in earlier metallurgical literature.
Figure 1 - Process in creating a Japanese Sword, from top to
bottom: The steel is heated prior to the forging process in a
charcoal fire; After hammering the steel out, it is cut in half
and folded; The folded steel is then hammer welded together,
as the forging process continues; The smith then continues to
shape the blade, first with a power hammer and then with a
hand held hammer; After forging, the blade is shaped by hand,
and then coated with clay, prior to the hardening process;
After the claying of the blade, it is heated to critical (about
1450°F) and then quenched in water, creating the martensite
edge and pearlite body of the sword; The blade is then final
shaped and polished. This sharpens the blade and reveals the
hamon that is created by the hardening process. Figures
courtesy Bugei Trading Company.
Figure 5. Sequence of quenching a Japanese Tanto: This
blade was coated with clay (yakiba-tscuchi); The nose or tip
of the blade (kissaki) is down showing gyaku-sori; Blade is
now straight again; Nose is up as in the typical final curvature
of a Japanese blade (sori). Photographs courtesy of Jesus
Hernandez and Walter Sorrells.
He emphasized the necessity of using clear quenching
liquids so that the tempering colors could be observed,
and recommended rubbing a blade with soap before
heating it, "that it may have a better color from the fire."
Porta was one of the first people to recognize that there
were various tempers of steel, and described methods to
achieve those tempers. In describing the “Temper of
Files” in his Thirteenth Book of Natural Magic:
“…take the chest out from the coals with iron
pinchers, and plunge the files into very cold water,
and so they will become extremely hard. This is the
usual temper for files, for we fear not if the files
should be wrested by cold waters.”
Porta also showed an excellent understanding of the
reason why many quenchants were effective, and some
of the underlying principles:
“If you quench red hot iron in distilled vinegar, it
will grow hard. The same will happen, if you do it
into distilled urine, by reason of the salt it contains in
it. If you temper it with dew, that in the month of
May is found on vetches leaves, it will grow most
hard. For what is collected above them, is salt, as I
taught elsewhere out of Theophrastus. Vinegar, in
which Salt Ammoniac is dissolved, will make a most
strong temper. But if you temper Iron with Salt of
Urine and Saltpeter dissolved in water, it will be very
hard. Or if you powder Saltpeter and Salt
Ammoniac, and shut them up in a glass vessel with a
long neck, in dung, or moist places, till they resolve
into water, and quench the red hot Iron in the water,
you shall do better. Also Iron dipped into a Liquor of
Quicklime, and Salt of Soda purified with a Sponge,
will become extreme hard. All these are excellent
things, and will do the work.”
There was also an understanding of the cause of quench
cracking, and the results of quenching in other than
water for “The Temper for Instruments to let blood”:
“It is quenched in oil, and grows hard, because it is
tender and subtle. For should it be quenched in
water, it would be wrested and broken.”
Various authors, describe other quenchants: pigeon
droppings, flour, honey, olive oil and milk [25][26][27].
Other quenchants, including urine, water and solubilized
animal fats and whale oil are described by Smith [28],
Biringuccio [29], Agricola [30] and others:
Figure 6. Coverplate from John Baptist Porta, “Natural
Magick in 20 Bookes”
"Take clarified honey, fresh urine of a he-goat, alum,
borax, olive oil, and salt; mix everything well
together and quench therein."
"Take varnish, dragon's blood, horn scrapings, half
as much salt, juice made from earthworms, radish
juice, tallow, and vervain and quench therein. It is
also very advantageous in hardening if a piece that is
to be hardened is first thoroughly cleaned and well
Excerpts from Von Stahel und Eysen (1532)[31]
Haedke [27] indicated that the swords and knives made
in Toledo, Spain were known to be of high quality as
early as the ninth century. Heat-treating occurred on a
night with a warm south wind, and clouds obscured the
stars. A cherry red heat was taken on the blade, and it
was quenched immediately in the Tajo River.
Hanko Doebringer's writings on swordsmanship from
about 1389 [32]. In the same manuscript, there are
formulas for hardening, tempering, and annealing metal.
Wiltu stol herten / und gar gute sneiden machen zo nym
buglossam / blateloze mit worcze und mit al und sewt das
in kaldem wasser / und herte was du wilt
An approximate translation is:
“If you wish to harden steel, and make extremely good
blades, then take Buglossam without the leaves, including
the root, with [eels? oil?] and steep that in cold water.
And use this to harden whatever you want.” [Note:
Buglossam is an herb, also called Porrago or Borras.]
A quench for hardening a stonemason's hammer:
Wiltu hemer herten do man steyne mete hewt / So
nym rupen saff / Do lesche dy hemer gluende dorynne
“..If you wish to harden a hammer so that it can be
used to cut stone, then take turnip juice, and quench
the hammer in it while it is glowing.
The term rupen saff could also be Rubensaft, which
could be turnip juice, beet juice, or rapeseed juice.
Rapeseed oil is commonly used as a lubricant for
machines, so this may be a possible translation.
However, medieval and Renaissance sources such as
Serranus of Nuremberg, 1539 [33], more commonly use
"rupe" to mean a kind of tuber.
Eyne ander gute herte / Nym der wuerme engerlinge
czweiteil / und regen worme das dritteteil / und czu
stos sy und druck das saff durch eyn tuch / dorczu tu
auch saff von steyn krawtes worczel / und stos doryn
eyn gluende eizen ader was du herten wilt
Another good hardening method: Take two parts
[rain-]worm larvae [or grubs] and three parts
rainworm and mash them together. Press the juice
through a cloth, and then add the juice of the
Steinkraut root. And plunge the glowing iron in this,
or whatever else you wish to harden.
The Latin botanical name for Steinkraut is Lobularia
Maritima, or Sweet Alyssum in English. Regenwurm
appears to be the same as English "earthworm", the kind
of worm that comes out after it rains.
A formula for tempering blades:
Wiltu dy herte von dem eizen entloezen So nym
menschen blut / Und los das sten bis das wasser
dorof stet und wert / zo seige denne das wasser in eyn
glas / und halt das / Und wen du denne dy herte
entloesen wilt / zo nym das geherte wofen und halt
das czu dem fewer bis das is zo heis werde das is das
wasser slinde / zo stich daz wasser mit eyner veder
an dy sneide zo entlet sich dy herte und wirt linder /
If you wish to temper the hardness away from iron,
then take human blood, and let that stand until the
water stands on top of it, and stays separated. Then
drain off the water into a glass, and set that aside.
And when you wish to take the hardness away, then
take the hardened weapon and hold it in the fire until
it becomes so hot that water sizzles [presumably,
when a drop of water is placed on the blade]. And
then paint the water [from the blood] onto the blade
with a feather; this will take away the hardness and
make it tempered.
The "water" is the serum from the blood, which
separates from the more solid parts when the blood is
left to stand.
Formula for annealing iron:
wiltu eisen weich machen und czehe / zo nym
canomillen blumen eynteil / und eyn teil kranches
snabel das hat bloe blun und eynteil veitbomes / Und
das lege alles mit eynander / in heis wasser / und tu
is in eynen tap / und decke is / das der broden icht
aus moege gen und laz is wol siden Dorynne lesche
gluende eisen / das wirt gar weich und czehe /
If you wish to make iron soft and tough, then take one
part Camomille flowers, and one part Veitpommes,
and one part stork's beak of the kind that has blue
markings. And put that all together in hot water, put
it in a pot, and cover it, so that the broth cannot
escape. And let it simmer for a long time. Then
quench glowing iron in it; this will make it soft and
tough. [Note: Veitpommes is a kind of fruit or berry.]
Another formula for annealing iron:
wiltu eizen weich machen / zo nym horn und schabe
das of eyn leder und menge das mit sal armoniaco /
und seiche dorof / und winde das uem das eisen und
laz das leder alzo of dem eisen vorbruen zo wirt is
weich /
If you wish to make iron soft, then take horn and
scrape that on [or "rub it into"] a piece of leather
and mix that with Sal Armoniac. And then urinate on
it, and wrap that around the iron. And then leave the
leather to steep around the iron; this will make it soft.
[Note: Sal Armoniac is Ammonium Chloride.]
Only late in medieval times, did sufficient technical
advances in steel-making occur in Europe. In was only
in the late 18th century that difference between iron and
steel was identified as being associated with different
quantities of carbon present [34][35].
It was not until 1890 that Adolf Martens made the
discovery of the hardenable phase in steel, that we now
call Martensite. It is remarkable that the ancient
metallurgists, and blacksmiths were able to achieve the
results they did, using only empirical methods.
Conclusions and Summary
From the earliest times, at the beginning of the Iron Age,
quenching has played an important role in the growth of
civilization throughout the World. Much of the
development of quenching was developed out of
mysticism, and empirical experimentation. It was not
until much later, at the beginning of the Industrial Age
(1850 AD or so), that mankind started on a quest to
understand and quantify the mechanism of quenching
and heat treatment. While much of the empirical
technology developed was used to increase the
effectiveness of swords, knives and armor, there has
been a technology transfer to other devices important to
the arriving Industrial Age. Today, there is a firm grasp
on heat treatment, and the mechanism of quenching,
enabling special quenchants to be tailored to specific
application. It was these original philosophers,
alchemists and blacksmiths that are the foundation of the
Science and Art of Metallurgy today.
Figure 7. Museum quality armor created using modern
quenchants. Photograph courtesy of Robert MacPherson,
Armoror (
I wish to thank the people on the Bladesmith’ Forum
( and the International Sword
Forum, ( for their help and
encouragement in writing this short article. Their
patience is greatly appreciated.
I would also like to thank Robert MacPherson, for
showing me his intricate and beautiful work, and his
patient help in explaining many of the techniques used.
[1] Guillaume, “Metallurgy in the Old Testament,” Palestine
Exploration Quarterly (1962), 129-132.
[2] Sawyer, J.F.A., “Cain and Hephaestus: Possible Relics of
Metalworking Traditions in Genesis 4,” Abr-Nahrain 24
(1986), 155-166.
[3] Wertime, T.A., “Man’s First Encounters with Metallurgy,”
Science 146 (1964) 1257-1267.
[4] Wertime, T.A., “The Beginnings of Metallurgy,”, Science
182 (1973) 857-887.
[5] Yener, K.A., “Swords, Armor and Figurines,Biblical
Archaeologist, 58 (1995) 2.
[6] Fensham, F.C., “Iron in Ugaritic Texts, Oriens Antiquus 8
(1969) 209-213.
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... In Europe, in the first millennium, some technologies were made to harden the swords and weapons. However, the advances in heat treatment techniques were done in the Arab-world, India, China and Japan [2]. Surface roughness can be considered as the measurement of the small-scale variation in the height of a physical surface. ...
... Quenching generally prevents low-temperature processes by reducing the window of time during which these processes are both thermodynamically favorable and kinetically accessible. [155] In this work, the samples were heated for 10 minutes above T C (i.e. to 150 • C) and then dropped into water for cooling. The fast cooling freezes the movement of oxygen vacancies, preventing the formation of defect dipoles as a result. ...
Ferroelectric materials are famous for their multiple properties, including large permittivity, high piezoelectric response, pyroelectric, and optical properties, and so on. To make ferroelectric materials better applied in commercial applications and meet miniaturization requirements and needs of an environment-friendly society, lead-free ferroelectric BaTiO3 has been intensively developed through a continuous worldwide research efforts. Massive microstructural engineering and chemical modifications have been investigated to enhance the properties of lead-free ferroelectric BaTiO3. In this PhD work, we shall introduce acceptors and oxygen vacancies to form defect dipoles, the ferroelectric domain rotations are controlled, which enables tuning the properties of lead-free ferroelectric BaTiO3 ceramics. The acceptors Cu2+ (rCu2+ = 87 pm) and Fe3+ (rFe3+ = 78.5 (69) pm for high (low) spin) are selected to substitute for the Ti ions (rTi4+ = 74.5 pm) on the B site of the perovskite structure of BaTiO3 through traditional solid-state synthesis method. The Fe and Cu substitutions in BaTiO3 are demonstrated by the EPR spectra. Combined with the SEM images, Rietveld-refined XRD patterns, and Raman spectra, the perovskite structure of doped BaTiO3 ceramics with a single tetragonal phase (P4mm) at room temperature are determined. The homogeneous Cu distributions are observed on the EDX maps. The oxygen vacancies, either trapped by dopants or accumulated at grain boundaries, create an internal electric field, playing a crucial role to harden acceptor-doped ferroelectrics. According to these two trapping positions for the oxygen vancancies, the hardening mechanism is generally explained by the volume effect or the surface effect, respectively. Resiscope measured the resistance reduction of the interior of the grains (ΔRG) and grain boundary when hardened 0.4 at%Cu-coped BaTiO3 became the relaxed. The higher reduction of the interior of the grains resistance (ΔRG) than the reduction of grain boundary resistance (ΔRGB)n demonstrates that the volume effect is the principal hardening mechanism in polycrystalline acceptor-doped ferroelectrics. The movements of ferroelectric domain walls are restricted by the defect dipoles that are created as oxygen vacancies reach positions nearest-neighbor to dopants. Inspired by this defect dipole-domain interaction, we design several strategies including thermal and field excitation to control the oxygen vacancies migration, and manipulate the orientation of defect dipoles. Consequently, the domain walls movements are controlled, which makes the acceptordoped BaTiO3 present different hysteresis loops, including de-aging process, re-aging process, shifting process. Through DFT calculations, the lowest energy barrier of oxygen vacancies movement following the spontaneous polarization of rhombohedral acceptor doped BaTiO3 ceramics is established. This result is consistent with the symmetry-conforming principle of point defects. In addition, the lower energy barriers of oxygen vacancies diffusion in Fe-doped BaTiO3 than in Cu-doped BaTiO3 are calculated, which indicates the higher mobility of oxygen vacancies in Fe-doped BaTiO3. These DFT calculation results are backed up by two experiments : field cooling measurement and fatigue measurement.
Deformation of Titanium alloys close to optimal superplastic condition i.e. near superplastic regime of deformation leads to significant change in microstructures.VT-9 titanium alloy was used in order to find out those parameters of microstructure which are varying significantly during near superplastic regime of deformation. Tensile tests were carried out at 930°C up to fracture with a constant strain rate of 5*10⁻⁴ s-1 and a jump wise varying strain rate of 1*10-4 s-1 & 5*10⁻⁴ s⁻¹ .The microstructural parameters of both air-cooled and water quenched portion i.e. size of alpha phase, percentages of alpha phase and parameter of non-uniaxiality of alpha phase were found to change significantly during near superplastic regime of deformation. It has been found that in the near superplastic regime of deformation percentage of α-phase decreased from 90% to 13%. As the β-transus temperature of this alloy is 970°C, this significant change in percentage of α-phase is attributed to deformation induced phase transformation. Optical microscopes, micro Vickers hardness test, XRD, FESEM have been used to characterize the microstructure of the material.
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Professor R. Pleiner of the Institute of Archaeology, Prague, who has provided this review of Dr Tylecote’s book, is one of theforemost authorities on the origins of ironmaking. He is Secretary of the Comite pour la Siderurgie Ancienne de I’Union Internationale des Sciences Prehistoriques et Protohistoriques, whose offices are also in Prague. Professor Pleiner has made a special study of replica-smelting of early furnaces and some of his recent publications include ‘Metallographic report on early iron artefacts’ (Stockholm, 1975), ‘Origins of the shaft furnace in European ironmaking’ (Prague, 1975),!‘Ironmaking in pre-medieval Central Europe’ (Miinster, 1975), ‘The problem of the beginningof the iron age in India’ (Berlin, 1972), ‘Forging and blacksmiths’ art in Moravia’ (Krakow, i971), ‘Experimental smelting of steel in early medievalfurnaces’ (Prague, 1969), ‘The beginnings of the iron age in ancient Persia’ (Prague, 1967), and ‘The work of the early European smith’ (Prague, 1962).
Metal mining and manufacture were critical high technologies in the ancient world: metal provided the standard of value, medium of exchange, and the raw material of tool and weapon industries. Analysis of the "fingerprints" of ores and artifacts has begun to display the complex tableau of ancient metal industries. Lead-isotope analysis clarifies the dynamics of provisioning metal in the Late Bronze Age Hittite empire.
A study was carried out to evaluate the role of the impurity elements found in Damascus steels on the origin of the cementite (Cm) particles that produce the characteristic pattern of Damascus blades. It is shown that the high phosphorous (P) impurity levels of Damascus steels could have controlled the mechanism of Cm formation. Experiments on small steel castings with impurity compositions matching that of Damascus steels reveal that the P impurity content produces two significant effects: 1) it results in formation of primary Cm between austenite dendrites upon solidification that could lead to the damask pattern of the final sword; and 2) it causes a graphitization of Cm on certain heat-treat cycles, which destroys the damask pattern. The origin of the Cm particles in casting and forging a Damascus steel blade is discussed in view of these results.
Iron objects excavated at the turn of the century at Thebes in Egypt,but possibly of Assyrian or Urartian origin, were examined chemically and metallurgically. Three objects consist of wrought iron containing appreciable amounts of slag. Two had been case-hardened along their cutting edges, increasing the hardness about threefold. Two specimens were of fairly homogeneous steel (0.1-0.2% C) which had been hardened by quenching.