Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.

8-16

Geopolymer Institute

1996

ALL RIGTHS RESERVED

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Geopolymer Institute
02100 SAINT-QUENTIN - France
www.geopolymer.org

From Ancient
CONCRETE TO GEOPOLYMERS
The act of creating a business cannot be reduced to the offer of competence and
given products at an appropriate time. It often implies particular kinds of people, because the path, filled with obstacles, always makes the course difficult. Even though
these people may have a certain number of qualities in common, like willpower or a
goal-oriented spirit, they differ greatly in their character and in the situations they are
faced with.
We were given the opportunity to
meet Prof. Joseph Davidovits, and to discover the path that made him start as an
organic-polymer chemist and become a
mineral-polymer chemist. And this path
is not dull.
In 1970, a horrible fire burned down
the French nightclub "Cinq/Sept.This
was cruel proof that polyester-type decoration materials represent an unthinkable danger. At the time, Joseph Davidovits was in charge of a textile research
laboratory in Saint Quentin, France. In
his field, he was on several occasions
confronted with the danger of flammable nylon stockings and overalls, which caused
several severe accidents in the workplace.
Given the situation, it was absolutely necessary to bring non-flammable materials
to the market. Everyone in the chemical industry knew that this was possible by introducing phosphides into the chain. However, phosphides are toxic products that one
cannot conceive of using, for it would be substituting one evil for another. In fires, the
greatest danger is not the flame, but rather the release of toxic smoke. Joseph Davidovits decided to actively address this problem and start his own business in 1972.

Learned Language is mandatory

The whole problem was to create non-flammable plastic materials, not based on
carbon chemistry. The solution was to use silicon based geological elements. But one
had to overcome the difficulty of getting the operation to work at low temperature.
"Thus", explains Joseph Davidovits, "we discovered that some mineral chemistry
reactions are similar to some used in organic chemistry." This observation led to the
first applications based on the transformation of clay at low temperature. An interesting application was the manufacture of non-flammable wood-chip panels. Their utilization could undoubtedly have prevented, in the early seventies, the disastrous Edouard
Pailleron high school fire, in Paris. The corporation Saint Gobain was very interested in
the product, and programmed a complete prototype manufacturing line. There was an
important market. But the 1973 oil crisis disrupted further progress.

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Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.8-16

Getting rid of the art

The crisis stalled development of the product to the
of firing
Silico-aluminate: synonymous of point at which Joseph Davidovits was

The first objec- polysialate.

forced to lay off his employees, and he
tive of Pr. Joseph
found himself alone. The business had
Davidovits' research on
to be re-thought by analysing any mistakes. The system
"geopolymer" materials was to
had to be changed, and the business had to be oriented
create an alternative to polytowards high-end applications. In high-tech applications,
mers with regard to ease of use.
geopolymers have a role to play. The mineral resins are
The success of plastic
silico-aluminates. They withstand temperatures of 1000C
materials is primarily due to
to 2000C. With this established, specific outlets had to
low temperature setting. Plasbe found for the products. "In my mind," notes Joseph
tics do not require a firing proDavidovits, "I thought to show the technological commucedure, and unlike to ceramnity the importance of developing a new branch of mineral
ics and metals, temperatures
chemistry. But oddly enough, the potential applications
under 100C are sufficient.
did not attract attention. They were thought to be only the
By substituting mineral
return to the processing of clay, which was considered
elements, such as sodium or potrivial even though an intelligent retransformation."
tassium silico-aluminates, for
A wall of misunderstanding had been instantly
organics, the manufacturing
erected. The influence of high technology is such that it
process of geopolymer becomes
rejects anything that could be acquainted with a de-voluthat of a mineral polymer. It
tion process. Within such a mind set, clay
therefore naturally Polysialate: large molecular chain was no longer interesting. The idea of recdisplays an excep- made of silicon, oxygen, and aluminum. reating clay was not considered a noble
tional fire-resistance It is one of the main constituents of course of action. Under such circumquality, which may be GEOPOLYMER.
stances, the promotion of clay technolput to use in fire pro- Mineral polymer: a polymer is a very ogy did not seem credible. Thus, our intection applications long chain of atoms which repeats itself. terviewee sourly realized that Moliere's
A mineral polymer is primarily made of
(panels, doors, and silicium, oxygen and aluminum.
learned people would continue to rage
the frame of airplane
and that one had to serve them with the
flight recorders). Al- Organic polymer: long chain made of language they desired. " This is why I
carbon, nitrogen, oxygen and hydrogen
though the geopoly- atoms. It is also called carbon chain, and eradicated from my vocabulary the term
meric manufacturing is the prime constituent of all living clay," says Joseph Davidovits. "I talked
process eliminates beings, crude oil, and plastics.
instead about polysialates. And I did lecfiring, fire may Geopolymer matrix composites: tures." The first of these public appearpresent an indispen- composite materials are made of fiber ances took place in Stockholm, in 1976.
sable need for its uti- glass, carbon, or graphite fabric; the My topic was "the heat stability of minbinder which is used to harden this fabric
lization!
eral polymers (as opposed to organic polyis called a matrix.
Here, the matrix of the composite is the mers)." But it was in 1979, in Los AngeFuture appli- Geopolymer binder.
les, that a real reference to geopolymers
cations
was made. Into the field of reinforced texGeopolymers are at the dawn
tiles, Joseph Davidovits introduced the novel idea of a geof their use, especially in the
opolymeric matrix by showing the thermal stability of texarea of high-technology. So far,
tile fibers. As interesting as this may be, his research was
geopolymeric molds exist to
at the time far from complete. It was not yet possible to
form titanium alloy for aerocreate geopolymer-matrix composites.
nautical components Thermoplastics: materials which
Nevertheless, -and this may illustrate why
and ladles that endure become soft through heat (iron, steel
the innovator must promote his findingspermanent contact at 800C, PVC at 180C, Nylon at
250C, etc...) and behave their shape the property of thermal stability attracted
with molten alumi- upon cooling.
attention. The Dassault corporation, in
num. But these have
particular, showed interest in the idea.
not been widely industrialized.
This company consequently oriented the research of
The main problem for
Joseph Davidovits' team towards the aeronautics field.
this type of new product is deIn the beginning (1980), the property of thermal stasigners' habits. We are all fability was used in the transformation of thermoplastics.
miliar with the way spheroidal
The scope was then widened to the casting of super-plasgraphite cast iron was brought

Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.8-16

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tic aluminum, which is processed in a 500C to 550 C

temperature range.
Presently, the trials deal with titanium alloy tools
operating between 900C and 950 C. So far, the results
seem promising. To date, these geopolymeric products,
geared towards the aeronautics industry, are technically
and economically competitive. Their share of the European market has recently started to increase. But Joseph
Davidovits notes that it has taken them 10 years to specifically meet the needs of this industry.
"One thing is certain," he says, "we were at the time
technologically far ahead. But we weren't given the opportunity to benefit from it." He points out that French products are often faced with a lack of credibility in their own
country, whereas American products are
The mortars
blindly granted credibility. In order to fosMortars are made of
ter the superiority of his product, the
lime or cement, which
French industrialist has to make considact as binders for the
erable amounts of risky investments and
so-called fillers. Lime
undertake considerable financial efforts
is made by calcining
to gain operational stage. This was done
limestone (calcium
without any immediate commercial comcarbonate CaCO3 dipensation, to the risk of jeopardizing the
viding in lime CaO
whole enterprise. The problem is even
and carbon dioxide Roman mortar (Trier, Germany). more complicated when everything dealCO2). Regular lime is Made of white lime and red ing with high-technology (and not only
brick (testa in Latin) .The
hardened through the powdered
testa contains the elements in this field) seems to be built on the
action of carbon diox- necessary to start
the American market, which is very hard to
ide contained in the geopolymeric reaction and the penetrate. In fact, notes our interviewee,
atmosphere; a mortar hardening of the mortar.
the promotion of a European product
containing this lime will not
begins on American soil. "That's exactly what happened
withstand erosion because its
with our material." Everything really started in Los Angemechanical properties are meles, in 1990, with a presentation, followed by another one
diocre.
at a symposium in San Diego. It is a sad fact, but from
If the limestone contains
now on the U.S. seems to be a mandatory route to suca portion of silico-aluminates,
cess.
or if clay is added to it, the
The American based presentations keep French and
product will harden, after calEuropean engineers informed on trends, evolution, and
cination, without the presence
new products. Each year, a certain amount of time is dediof air, for instance under wacated to conferences and meetings, which are often held
ter. In that case, lime is called
in Florida and California. It is also, indirectly and in a
"hydraulic," and its mechanisubtle manner, how America watches the developments of
cal properties have been imEuropean technology.
proved.
If the portion of silicoBeing able to measure ones Lead
aluminate added is significant,
Entrepreneurs, having a high-value-added material
along with other elements,
available, and a seemingly promising future, cannot wait
such as aluminum, iron, magfor success to knock on their doors. They
nesium oxides, and so
Crystallization: sugar is made of must seek their battle grounds, especially
on, then a cement is crystalline powder, whereas caramel has
when dealing with a new product like
obtained. Mechanical an homogenuous amorphous structure
geopolymers that is aimed specifically toproperties will vary and is more difficult to break apart than
wards the aeronautics industry. Joseph
according to the pro- regular sugar. When a poly mer
Davidovits explains that the different
portion and nature of crystallizes it becomes generally weaker.
potential applications for mineral polyeach element included.
mers had to be carefully studied. Let us recall that the

into use, by an accidental fall

from a great height of tubes
made out of this type of cast
iron. Against all expectations,
theses tube were bent without
breaking, as if they were made
out of steel. The traditional
idea that cast iron was brittle
was eradicated and permitted
the fabulous development opportunities that ensured for security elements made of spheroidal graphite cast iron.

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Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.8-16

difference with organic polymers (PVC, polyacrilates) lies

in the absence of a carbon chain. One can, in that case, at
an industrial level, resort to the chemistry of polymerisation, using sodium or potassium silicoaluminates. The operation of crystalization is thus avoided. And from that
point, it is possible to obtain not only a resin but also a
binder and a cement.
Cements were precisely the option chosen by Joseph
Davidovits . As with all innovators, he had to innovate.
Research was oriented along two main lines: new kinds of
cement, and hazardous and radioactive waste management. Joseph Davidovits and his team have been developing a new kind of cement with exceptional
characteristics. This cement, used by the
If...
U.S. Air Force and others, enables the conLet us suppose that the abbey of
struction of a runway in a very short time.
Cluny (France) was built out of
A Boeing can land on it only 4 hours after
rubble stones (concrete) or morcompletion. These properties are believed
tar-bonded bricks rather than
to be useful for other fields, such as hazcarved limestones. This monuardous and radioactive waste manment would certainly not have
agement. Joseph Davidovits pointed
been demolished after the
Pr. Joseph
out that such a cement would be an
Davidovits
French Revolution in 1789 due
ideal material for the long-term conto the low value of these matefinement (trapping) of heavy metals, because it recreates
rials.
natural rock. And once again the product was too adSince the decline of Anvanced for the needs of its time. "In 1987", Davidovits concient Greece, it is apparent that
tinues, "only two countries were demonstrated to us an
every construction, marble pilinterest, Canada and Sweden. It was therefore not in the
lar or squared-off stone is a poU.S., where I was working at the time, that I could begin
tential quarry! But in order to
trials, but in Canada. I had to negotiate very hard to begin
build edifices with rubble
these trials, which would prove that my technology could
stones, more erosion resistant
really trap toxic materials such as mercury. I finally found
binders than regular lime must
a laboratory in Toronto, and a partner in Ottawa." Howbe available.
ever, the price outweighed the results of the trials. The
The high-quality mortars
material was too expensive, and so this means of
used by the Romans more than
stabilization was disregarded. One must add that in 1987,
two thousand years before, were
the environment was not a major political issue. The "green"
unknown in Burgundy at that
parties were not being courted by those in office. Joseph
time. However, the Saint Sofia
Davidovits tells us the innovator's greatest challenge. One
Church of Constantinople was
must know how to innovate by taking
built in the year AD Calcining calcium carbonate: means just enough lead to raise interest. To
532 using the Roman the burning of limestone, yielding lime. much lead creates a reference vacuum,
concrete technology. Adding water to lime, results in a binder which is likely to scare the end-user
The same applies to the which has been the basic formulation of away. Will the product be trustworthy?
cathedral of Irevas. It all mortars since 10,000 years
Will it not modify my behavior as a user?
is by trying to match the propIs it not better to wait for a competing product to appear
erties of binders used in the fawhich will benefit from the flaws of the first one? Moreomous buildings of ancient Rome
ver, unforeseeable economic and sociological consequences
that Aspdin invented Portland
weigh upon these questions (such as the soaring of the
cement. He was calcining clays
"green" parties). With the new geopolymer cements, Davifrom the Leeds area. Meandovits now possesses a material tailored to the market.
while, the French Vicat was doWe keep in mind that the manufacture of traditional Porting the same to clays from the
land cement requires calcining calcium carbonate. This
area of Grenoble. This took
yields calcium oxide and so the emission of carbon dioxplace less than half a century
ide gas. In low quantities, this not considered a major conafter the demolition of Cluny III!
cern. This changes on a global scale. What is happening
Pozzolans are volcanic minerals, mainly made up of
aluminum, iron and silicon oxides. These naturally possess
hydraulic properties. This explains the durability of Roman
monuments built with mortars
containing pozzolans from the
Vesuvius volcano! These properties can be re-created by calcining clay or using fly ashes
collected at electricity coal
power plants.

Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.8-16

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The Souillac Bridge

today is the soaring of worldwide cement and concrete

After his graduation from the
needs, especially in industrializing countries (Asia).
Ecole Polytechnique, Louis Vicat,
The first stage of all industrialization, increasing
based in Perigueux as a civil enstandards of living, requires concrete for building ingineer, was in charge of a bridge
frastructures. The example of China is significant, given
construction project over the river
that its production started from 40 million tons in 1976
Dordogne, at Souillac.
and has presently reached 250 million tons. Countries
Very little was
such as India, South Korea, and
known concerning morto a lesser extent Taiwan and
tars in 1811, and Vicat
Thailand, are among the worlds
decided to research bindlargest producers.
ers suited for bridge conThe emission of carbon
struction. The underwadioxide is, therefore, becoming a
ter part of the bridge imgrowing concern; it is an imporperatively required a hytant contributor to the greendraulic hardening binder.
house effect. As it regards develHe published his first
opment statistics, the worldwide
findings in 1818 under
level of cement production, estithe title "Recherches The granular structure of Portland cement mated at 1.8 billion tons by the
Exprimentales sur la surrounding sand explains its weakness year 2000, is expected to reach
Chaux de Construction, because the structure is not compact.
3.5 billion tons in 2015. This
les Btons et les Mortiers" (Exwould put the share in the global pollution (all human
perimental Research on Construcactivities combined) at 18%. "One can easily under tion Lime, Concretes and Morstand," explains Joseph Davidovits, "the importance of
tars). His second paper entitled
these new geopolymer based cements, which would lower
"Rsum des Connaissances
the cement-related emission of CO2 by 90%." Such a
Actuelles sur les Mortiers et les
prospect could greatly increase the feasible production
Ciments Calcaires" (Summary of
of cement and concrete in the developing countries. The
today's knowledge on limestone
drastic limitations planned by the EEC and the USA
mortars and cements) was pubwould also be eased.
lished in 1828. It was to become a
standard reference.
A Disturbing Hypothesis
However, four years earOur interviewee made
lier, the Englishmen
clear to us that all his reflections
Joseph Aspdin invented
on cement derived from questionPortland cement by caling the nature of ancient Egypcining a mixture of clay
tian and Roman mortars. Their
and limestone.
resistance presents a mystery
that lay in the materials they contain. What are the ingredients,
Regular lime does not
which, when added to lime, gave
withstand the test of time.
these materials such strength?
The majority of the consmooth and homogenuous structure The common interpretation is
structions using this The
of Geopolymer cement surrounding sand, that it is a lime-based mortar, and
binder have long since yields a stronger cement.
all materials are "inert" (without
disappeared. How can it
chemical reaction) except for the lime. "Our interpretabe explained then, that certain edition," states Davidovits, "is just the opposite. It is that
fices are still standing, and that
reactive ingredients combine with lime, leaving the extheir mortar is as resistant as our
cess lime as inert." The makeup of the mortars varys
best hydraulic binders? It is likely
according to the archeological site, that is, according to
that works built to last were made
its geological environment. A mortar will be good if comwith specific know-how, whereas
ponents are selected from an appropriate site.
eroded buildings lacked it. The duIn 1979, at an Egyptology congress, Joseph Davirability of this ancient mortar is
dovits set forth the hypothesis that the pyramid blocks
mainly due to fillers such as
were cast as concrete, instead of carved. Such a theory
alumino-silicates. Regular lime
The missing link

Adapted from Arts et Mtiers Magazine N180, Sept. 1993, p.8-16

page -6-

does not have a binding function in this case. This knowledge appears to have been lost
after the fall of the Roman
Empire, for concrete disappeared from masonry uses and
for many centuries. It was only
in the 19th century, after the
publication of Vicat's works in
1828, that knowledge expanded again, and explained
the increase of mechanical
properties through hydration
reaction. This led the way to
fabulous developments such as
reinforced and prestressed concrete.
Roman cement

Ancient cement such as the

Romans made, gives us an idea
about the durability of geopolymeric cements. This is important because it is possible to
extrapolate the durability to
hazardous waste management
systems.

The
project

was great disruptive to the orthodox theory with its hundreds of thousand of workers taking part in this gigantic
endeavor.
But in the course of his research, and after performing chemical analysis on the cement materials, he concluded
that ancient Roman cement and the Great Pyramid blocks
were the result of a geopolymeric reaction or in other words,
a "geosynthesis." And thanks to this historical reference,
he was able to demonstrate that Geopolymers have the same
strength and endurance than natural rock.
Of course, Joseph Davidovits is innovative. He uses
archeology as a data bank, to validate his discoveries. This
shows the originality of his scientific and industrial approach.
But his approach has its difficulties, as it requires a
critical examination of data that is thousands of years old.
Imagine the numbers of natural processes that have had
time to act on the ancient mortars. There is a risk of misinterpretation, so one must proceed caustiously. Another
source of potential errors arises from ancient scriptures,
which have been translated through the centuries in diverse ways. Interpretations devoid of the new information
increase confusion, and these are standard references.
What is required are new translations employing the new
science along with knowledge of antiquity, as well as a formidable creative capacity.

GEOCISTEM
Adapted from Arts et Mtiers magazine, Jacqueline Delatte et Grard Facy, 09/93.

The European Community, under the "Brite-Euram" research funding program, is

supporting the European industrial research program
named GEOCISTEM.
Its purpose is to develop
the technology and equipment
necessary for the manufacture
of geopolymeric cements on an
industrial scale, at a cost close
to that of traditional cements.
Joseph Davidovits is the coordinator of the project.
GEOCISTEM stands for Cost
Effective GEOpolymeric Cements
for
Innocuous
Stabilization of Toxic Elements.
A street of the Roman city Pompei

GEOPOLYMERE

What is geosynthesis?
Geosynthesis is the science of manufacturing artificial rock at a
temperature below 100C, in order to obtain natural characteristics
(hardness, longevity, heat stability, etc.). The Geopolymer materials and
the Geopolymer-based mortars, cements, and binders, are geosynthetic
materials. This word was coined to broadly define the geopolymeric
chemistry.