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Ancient and modern concretes: what is the real difference

Article · December 1987

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 Geopolymer '88 -93-

Geopolymer '88, Vol.1, pp. 93-106

7. Geopolymeric Reactions in
Archaeological Cements and in
Modern Blended Cements.

Joseph Davidovits

Reprint of:"Ancient and modern concretes: what is the real difference?" published in
"Concrete International,", December 1987, Vol.9, pp. 23-29, a publication of the American
Concrete Institute (ACI), USA. Data Bank: Chemical Abstracts 108-80768t.

7.1 Introduction

When did the history of concrete begin. Emery Farkas, then president of ACI,
contemplated this question in his August 1985 President's memo [1] entitled,
"How old is concrete? Engineering versus Chemistry."
"It is an accepted fact that the origin of portland cement goes back to the
early 19th century when an English bricklayer, Joseph Aspdin, created a
cementitious product which when hardened looked similar to building stone
found in the island of Portland in England.
The history of concrete, however, goes back to ancient times. The Greeks
and Romans used calcined limestone and later developed the pozzolanic
cement by grinding together lime and volcanic ash called "pozzolan" which
was first found near Port Pozzuoli, Italy. The late Henry L. Kennedy, a past
president of ACI in the middle 50's, had on his desk a sample of pozzolanic
concrete which had been under water in the harbour of Pozzuoli for over
2,000 years.
Sometime ago, an article in Omni magazine [2] dealt with a fascinating
idea which would put the origin of concrete much earlier... According to this
theory [13]...to built a pyramid....Egyptian workers could have carried
crushed limestone to the work site in buckets, mixed it with Nile River for
the needed aluminium and silicon binder, and added salts available locally as
catalysts to make the solution alkaline. They could have dumped the
-94- Archaeological & Modern Cements

ingredients into wooden molds and a few hours in the desert heat would have
dried the mixture to hard rock. This could have been done with neither
massive ramps nor difficult tooling....This is a fascinating theory but it is
totally rejected by archaeologists who support the "engineering" aspect
against the "chemistry" theory.
Whoever is right, it is interesting to note that concrete may be much older
than we think and that in ancient structures it might have been
"engineering" or "chemistry" while in today's construction it is "engineering"
and "chemistry" together which create the marvellous modern structures."

7.2 The longevity of ancient cements

What strikes many observers of ancient architecture is the vast difference in

quality between the restored and original portions of structures.
Investigations of Roman structures of the 1st century AD by Malinowski and
co-workers [3, 4] revealed that while the lime concrete and mortar of these
structures remains unaffected by severely corrosive conditions, such as
flowing freshwater, seashore or salt- laden air, salt-water, and hot spring
water, modern concrete made with portland cement has suffered extensive
damage in the same localities and under the same conditions. Under certain
climatic conditions, some portland cement structures that are only ten years
old are being severely eroded, whereas two thousand year old cement in
structures in the same locations remain unaffected.
Unfortunately, only cements and mortars of surviving monuments can be
investigated, since monuments made with poor mortars or cements no longer
exist. The concrete or "opus caementitium" described by the Roman writer,
Vitruvius, a first century B.C. Roman architect and engineer, in his work
entitled "de architectura", is generally assumed to be a material of Roman
origin. However, pozzolanic concrete walls of the cistern at Kameiros, on the
Greek island of Rhodes, however, built about 500 BC, show that this type of
material can last at least 2,500 years [5].
A comparison between the ancient and modern restorations of Egypt's
Great Sphinx demonstrates how damaging modern restoration material is
compared to that of antiquity. Modern gypsum plaster between ten and fifty
 Geopolymer '88 -95-

years old is already damaging a restoration of the Sphinx. On the other hand,
repairs made over 3,500 years ago with gypsum prevented damage by
causing a protective duricrust to form on the surface (Gauri) [6].
Because of the poor quality of modern cements, restorations on the Step
Pyramid at Saqqara, Egypt, are no longer carried out with white cement. I
observed cracked concrete blocks in this structure that are no more than forty
years old. These blocks cannot be expected to remain intact more than a
hundred years. More recent restorations are therefore being made with
limestone blocks. The natural stone restoration would ordinarily last longer,
but, like the Sphinx, it too will be adversely affected by adjoining mortar.

7.3 The chemical difference

Only in recent years have studies been undertaken to determine why ancient
mortars and concretes are so much more durable than their modern
conterparts. It is assumed that the make-up of the ancient cements is similar
to that of modern cements (Langton and Roy) [7], the major difference
between ancient and modern cements being a higher degree of carbonation of
lime Ca(OH)2 in the ancient products. The assumption is that this process
causes portland cement to deteriorate, due to a significant volume
modification of the cement matrix (about 11%]. In ancient cement, however,
this high degree of carbonation has not been deleterious to durability. Their
chemistry, therefore, cannot be the same.
An optical investigation of various Roman concretes and mortars led
Malinowsky [3, 8] to conclude that the ancient binders consist of extremely
fine calcite (CaCO3) microcrystals in the range of 1 to 5 microns in size. Also
X-ray diffraction analysis of ancient cements from Greece, Cyprus, and Italy
indicate that calcite is the predominant crystalline phase of the ancient
cements [7]. However, X-ray amorphous material (silicates and silico-
aluminates) and X-ray cryptocrystalline zeolitic phases of the analcime type,
Na2O.Al2O3.4SiO2.2H2O, accompany the microcrystalline calcite.
This research assumed that, as in portland cement, the binding property
of the ancient cements is due to the production of calcium silicate hydrates
(C-S-H gel), which are mainly amorphous colloidal precipitates and have a
-96- Archaeological & Modern Cements

rather variable composition. As previously stated, however, the chemistry of

ancient cements cannot be the same as that of portland cement. The ancient
matrix must be of a more complicated nature. And, indeed, chemical analysis
reveals a relatively high amount of Al203+Fe203+SiO2 in the ancient
mortars.
Studies of durable Roman cements, concentrating on pozzolana,
demonstrate the benefits of zeolitic materials (Tavasci) [9] (Eitel) [10]. When
combined with lime, the pozzolanic cement converted into either calcite,
calcium aluminates, calcium silicate hydrates (of the C-S-H type), calcium
silico-aluminates, or gehlenite hydrate or hydrogarnet (Roberts) [11]. The
Rhineland trasses of the Eifel Mountains, in West Germany, which played an
important role in the preparation of the ancient lime mortars of Roman
constructions located in Germany, underwent a pozzolanic reaction resulting
in end products of calcium silico-aluminates, calcium zeolites of the
phillipsite type (3CaO.3Al2O3.10SiO2.12H2O) (Ludwig and Schwiete) [12].
We detected a zeolite in a coating on a casing stone from the Pyramid of
Cheops, built about 2650 BC (Davidovits) [13, 14]. Lime mortars which are
older, such as those of Jericho, in the Jordan Valley, and Tel-Ramad, Syria,
date as far back as 7000 BC and contain up to 40% by weight of the zeolite,
analcime [15, 16, 17] (see our discussion below). The presence of analcime in
various ancient cements confirms that this zeolite is the final, stable phase of
the long-term hydrothermal conversion of zeolitic materials (Hoss and Roy)
[18].
Although C-S-H gel is the main constituent of modern portland cement
and is also part of the make-up of ancient cements, we think it is erroneous
to conclude that this component is responsible for durability. Modern
cements containing C-S-H gel deteriorate under conditions in which ancient
cements, with an uncertain C-S-H gel content, remain intact. Instead, it is
silico-aluminates (zeolitic or amorphous materials) which produce long-term
durability.
 Geopolymer '88 -97-

7.4 Erroneous classification

Since 1972, we have been involved with the development and applications of
zeolitic binders and cements called geopolymers. Comparative studies of
ancient ceramics, cements, mortars, and concretes demonstrate the
exceptional durability of geopolymeric products (Davidovits and co-workers)
[19, 20, 21, 22]. Ancient cements have been classified into two main
categories:
- Hydrated Pozzolana-Lime Cements
- Hydrated Hydraulic Siliceous Lime Cements
These classifications are misleading, however, because cements of these
types are precisely the poor quality products in use when portland cement
was first developed.
Of the lime cements we studied which date from as far back as 7000 BC
[17], some are very weak and pulverulent while others have the consistency
of hard limestone after 9000 years of burial. Chemical analysis revealed that
the weak cements are essentially made of recarbonated lime. The durable
cements contain various amounts of siliceous and silico-aluminous
ingredients, indicating that they are hydrated siliceous lime cements.
Most studies of ancient lime cements have been essentially carried out
optically and microscopically. Studies using thin sections have concluded that
cementation was the result of lime recarbonation. According to these studies,
the durability of the lime mortars is essentially dependent on the speed and
intensity of the recarbonation of free lime [3] [7][15]. This opinion
characterizes the majority of studies on ancient cements. But uncertainty
still prevails about why the ancient lime cements are so durable.
Microscopic examinations detect only highly crystalline minerals. Those
minerals, such as cryptocrystalline zeolitic minerals, with dimensions too
small to be seen through an optical microscope, are overlooked.
This problem has been solved using X-ray diffraction [16, 17] which
indicates that the ancient lime mortars contain a synthetic silico-aluminate
or zeolite of the analcime type. The amount of analcime present ranges from
10 to 40 percent by weight. We concluded that the primary binding agent is
not recarbonated lime, but instead the cryptocrystalline zeolite, analcime.
-98- Archaeological & Modern Cements

While the recarbonation or hardening of lime takes place slowly, over

several days or months,the geopolymerization of analcime can occur in a few
hours. Therefore, the recarbonated lime appears to act as an inert filler when
combined with a geopolymeric matrix of analcime. The previously used
classification categories for ancient cements are therefore inadequate. A new
category called blended geopolymer-lime should be added.
The highly durable ancient lime cements presently classified as hydrated
hydraulic siliceous lime cements have not been studied for the purpose of
identifying a geopolymeric matrix. Table 7.1 lists the main oxides values of
Tel-Ramad blended geopolymer-lime and of ancient Greek mortars, as
extrapolated from the studies of Langton and Roy [7].

TABLE 7.1: Chemical Analysis of Blended Geopolymer-Lime: (main oxides)

----------------------------------------------------------
Greece, Lavrion Tel-Ramad, Syria,
350-300 BC 7000 BC
----------------------------------------------------------
SiO2 18.0 25.6 24.6
Al2O3 4.3 6.2 4.92
Na2O,K2O 1.44 1.0 1.55
CaO,MgO 45.94 40.0 41.8
CO2 23.11 14.44 25.96
----------------------------------------------------------
The extraordinarily low amount of the alkali Na2O,K2O (1.55%) in the
Tel-Ramad blended lime activated the synthesis of a 40% by weight
geopolymeric compound constituting the blended geopolymer-lime. This
geopolymeric compound has following formula:
(0.1Na2O;0.1K2O;0.45CaO;0.25MgO):Al2O3:4.27SiO2:2.13H20
This compound is 94% by weight geopolymer of the analcime type,
(Na,K,Ca,Mg)-PSS, poly(sialate-siloxo) and 6% by weight of CaO:5SiO2:H2O
(a pentamer of C-S-H gel).
The fabrication of the blended geopolymer-lime involved calcination at
700°C (1300°F) for limestone, dolomite, and kaolinitic soils, which are very
common in the Mediterranean regions [17]. Calcined kaolin (also called
metakaolin) is known for its pozzolanic properties. The addition of natron
(Na2CO3) or plant ashes (K2CO3, Na2CO3) produces NaOH and KOH,
which react strongly with calcined kaolin, yielding the synthesis of a
 Geopolymer '88 -99-

geopolymeric binder of the analcime type [20].

Geopolymer chemistry, when associated with portland cement, yields
cementitious materials with remarkable properties, such as ultra-rapid
usable strength gain, natural sulphate resistance, and freeze/thaw resistance
(Kirkpatrick) [23]. Modern blended geopolymer-cements can also be expected
to offer long-term stability. Table 7.2 compares the main oxides values of
ancient pozzolanic mortars, extrapolated from the data of Langton and Roy
[7], with that of blended geopolymer-portland cement [24]:

TABLE 7.2: A Chemical Analysis of Ancient Cement and Modern, Blended Geopolymeric
Cement (main oxides)
----------------------------------------------------------
Rome, 160-140 BC Geopolymer-Portland
----------------------------------------------------------
SiO2 42.0 39.56 32.5 to 40.1
Al2O3 14.48 14.01 9.9 to 14.1
Na2O,K2O 4.21 4.02 3.6 to 7.5
CaO,MgO 39.22 42.35 37.5 to 46.3
----------------------------------------------------------
One difference between ancient and modern geopolymeric cements is the
nature of the alkalis which activate geopolymeric setting. In ancient cements,
an ion exchange between the Ca++ and the natural zeolite contained in the
pozzolana resulted in free Na+ and K+. In the modern formula, alkalis are
added to the slurry. But we think that to accelerate setting time, small
amounts of alkalis were also added to ancient cements. The alkalis were
probably sodium carbonate (natron) or potassium carbonate (derived from
plant ashes), which react with lime to yield NaOH or KOH in the slurry [21].
Studies carried out by Alexander [25] have demonstrated that a small
amount of only 1% NaOH, equivalent to O.64Na2O, activates the setting of
pozzolana-lime cement. Geopolymerization should have occurred before the
recarbonation of lime.

7.5 Geopolymeric pyramid stone

A concrete made with 90% by weight natural limestone and 10% by weight of
a blended geopolymer-lime of the Tel-Ramad type (approximately 450 pounds
per cubic yard of stone, i.e., a medium-quality concrete) would contain a very
-100- Archaeological & Modern Cements

low amount of reactive ingredients. Nevertheless, it does produce a

geopolymeric limestone (GP-limestone) concrete. With time, the
recarbonation of the non-reacted lime would have transformed the Ca(OH)2
into calcite. Bulk chemical analysis does not produce a distinction between
the different types of Ca++ constituting such a geopolymeric limestone
concrete. Furthermore, natural calcite and recarbonated Ca(OH)2 and Ca++,
the latter resulting from geopolymeric silico-aluminates, are usually not
analytically separated.
Table 7.3 compares the chemical analysis of pyramid stone samples, using
data extrapolated from Brown [26] and Iskander [27], with our analysis of
limestone from Turah [14, 28] and our geopolymeric limestone concrete.

TABLE 7.3: Chemical Analysis of Limestone of the Egyptian Pyramids, Associated Quarries,
and GP-Limestone Concrete (main oxides)
----------------------------------------------------------
Turah Cheops Chefren Teti Seneferu GP-limestone
Quarries Pyramid Pyramid Pyramid Pyramid Concrete
----------------------------------------------------------
Calcite 97-99 94 94-96 92 86 95
SiO2 0.52-1.60 3.1 3-5 4.3 9.54 2.46
Al2O3 0.25-0.63 0.50 0.3-0.5 0.82 2.92 0.49
Na2O O.05-0.08 0.18 0.2-0.3 0.18 ? 0.15
----------------------------------------------------------
Chemically speaking, the casing stones of the pyramids built for pharaohs
Cheops, Chefren, Seneferu, and Teti were produced by mixing a blended
geopolymer-lime cement with limestone rubble from Turah. The core
masonry was agglomerated using local Giza limestone comprised of fossil
shells, mostly nummulites. These flat, round nummulitic shells lay
horizontally in the bed-rock conforming to natural sedimentary layering. In
the pyramid blocks, however, the shells are randomly oriented, as would
occur when agglomerating nummulitic limestone rubble into concrete. This
alone is substantial proof that the pyramid blocks are concrete.
An X-ray diffraction of the noncarbonate clastic fraction of Giza limestone
provides additional data to support this. According to Gauri [29], the
noncarbonate fraction of the nummulitic limestone constituting the body of
the Sphinx contains clays of the kaolinite type Si2O5, Al2(OH)4, in the range
of 0.5% to 4% by weight of the total amount of limestone. The limestone
 Geopolymer '88 -101-

rubble of Giza, some of which was generated when the bed-rock was
excavated in order to sculpt the body of the Sphinx, was ideal for producing
pyramid blocks because it contains the highly reactive, natural alumino-
silicate clay.
Since 1972, I have been developing products based on reactions of
kaolinite with alkalis (NaOH, KOH), yielding the synthesis ofrock-forming
minerals or, more specifically, geopolymers of the feldspathoidic
hydrosodalite group [19]. These reactions produce high-quality building
materials at temperatures which are within the range of the climate of
Egypt. I commonly use kaolinitic and lateritic soils (both alumina and silica
sources) of Africa and other parts of the world [21, 30, 31]. Generally, the
addition to these soils of an alkali, in the amount of 3 to 6 percent by
weight,is sufficient to produce water-resistant, durable bricks at ambient
temperatures.
The stabilization of kaolinitic soils with lime has been studied [32]. A
slurry consisting of water, lime Ca(OH)2, and natron Na2CO3, for the in situ
production of NaOH, produces a geopolymeric binder when the kaolinitic
Giza limestone. This is confirmed by our studies made when using X-ray
diffraction. The d-spacings for the noncarbonate materials of the samples
analysed, one from Cheops and one from Chefren, match those of the
following geopolymers:
- Hydrosodalite, Nan(Si-O-Al-O-)n
- Analcime, (Na,Ca,Mg)n(Si-O-Al-O-Si-O-)n
- Various Synthetic Ca-silico-aluminates, Na-silico-aluminates, called
Kaolin-Ca(OH)2 and Kaolin-NaOH by Willoughby and co-workers [32].
The X-ray analysis data indicates that the noncarbonate material in the
Giza pyramid samples are the result of a reaction of the kaolinite in the Giza
limestone with the alkalis NaOH and CaO. In other words, the d-spacings
indicate deliberate chemical reactions which are geopolymeric. The published
results from examinations by highly qualified geologists and geochemists are
amazingly scarce, perhaps resulting from less than conclusive data.
Cooperative investigations are being sought with the Egyptian Antiquities
Organization in Cairo in order to extend our knowledge of early Egyptian
concrete technology.
-102- Archaeological & Modern Cements

7.6 Conclusion

In the preface of his book "Cement Replacement Materials," R.N. Swamy [33]
says, "the search for alternative binders or cement replacement materials has
thus become a challenge for national development and forward
planning...From the economic, technological, and ecological point of view,
cement replacement materials have an undisputed role to play in the future
of the construction industry." These replacement materials are pozzolanic
materials, slags, condensed silica fume, rice husk ash, and pulverized fuel
ash. With the exception of condensed silica fume, these materials were
available and used thousand of years ago to produce various highly durable
blended geopolymeric cements.

The durability of geopolymers is demonstrated by the longevity of the

ancient cements, and this property is essential for certain modern
applications. For example, after the nuclear accident in Chernobyl was
contained, it was asserted that the damaged reactor was safely isolated for
centuries by a sarcophagus, as it was called by the Soviet press, of thick
concrete walls. The entombed plant looks like an ancient Mayan temple with
its rows of terraces. It is assumed that the structure will last for centuries.
The harsh climatic conditions, however, coupled with the enormous amount
of heat stored within the reactor itself, raises serious questions about the
reactor's stability.
The concrete used for entombment is made with portland cement, which is
known to deteriorate very rapidly in hydrothermal conditions. A portland
cement restoration of the Roman baths of Tiberias, near the Tiberian Sea
(Sea of Galilee) in Israel is such an example. While the portland cement
restoration is being dramatically eroded by hot spring water, the 2000 year
old Roman concrete bath itself remains intact [3]. The prevailing conditions
in the Roman baths are close to those expected to occur at Chernobyl: High
temperatures from the reactor combined with high humidity from rain, snow,
and underground water mean eventual disaster. And it seems likely that
most, if not all, operating nuclear reactors will have to be entombed in
 Geopolymer '88 -103-

concrete once their service lives are spent. The most likely candidate will be a
concrete that experiences no volume change- geopolymer.

Data from studies of ancient cementitious materials can be extrapolated

to demonstrate the longevity of materials made with silico-aluminates or
zeolitic materials. Hydroxylated zeolitic phases have been developed for
nuclear waste encapsulation to maintain maximum stability under repository
conditions [34]. Radwastes adsorbed onto natural zeolites are solidified using
portland cement [36]. Concrete structures made of either geopolymeric
cement or a blend of geopolymeric and portland cement, which would contain
either natural or man-made zeolitic phases, should effect safe, long-term
disposal for radioactive and other toxic wastes. Ancient constructions can
serve to demonstrate the longevity of geopolymeric concrete (Davidovits)
[35].
In a recent report discussing geopolymers titled, "Potential for Use of
Alkali-Activated Silico-Aluminate Binders in Military Applications," the US
Army Corps of Engineers [36] has identified potential uses for alumino-
silicate binders which result in the formation of calcium-alkali alumino-
silicates or zeolites and hydrogarnets, geopolymers of the poly(sialate-siloxo)
(Si-O-Al-O-Si-O-) or the poly(sialate) (Si-O-Al-O-) type. This alkali-activation
of various minerals, which we call geopolymerization, improves the
properties of cements.
The unique properties of the geopolymeric binders include: high early
strength, low shrinkage, freeze-thaw resistance, sulphate resistance,
corrosion resistance, and low alkali-aggregate expansion. In addition,
geopolymeric cements possess another remarkable property. Using
appropriate aggregates, beautiful synthetic stone objects can be created,
since geopolymeric concrete has the beautiful appearance of and is as long-
lasting as natural stone.

Chemical research at the Geopolymer Institute has allowed to replicate

ancient cements, mortars, and concretes. Our goal at the Institute for
Applied Archaeological Sciences is to use this knowledge, combined with
informations gained through scientific and archaeological research, to revive
-104- Archaeological & Modern Cements

and introduce other useful ancient technology for the purpose of enhancing
modern science and technology. We believe we can advance technology by
offering geopolymeric products that can be evaluated by comparing them
with the surviving cementitious products of antiquity.

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8, p. 5 (1985).
2. STARR, D. 'The Pyramids: a Bold New Theory', Omni magazine (USA), p. 50, February
1983.
3. MALINOWSKI, R.; SLATKINE, A.; BEN YAIR, M. 'Durability of roman mortars and
concretes for hydraulic structures at Caesarea and Tiberias', Preprint R.I.L.E.M. Inter.
Symp. on durability of Concrete, Prague, (Aug. 1961).
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5. MALINOWSKI, R. 'Betontechnische Probleml"sung bei antiken Wasserbauten',
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6. GAURI, K.L. 'Deterioration of the stone of the Great Sphinx', Newsletter Amer. Res.
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(1982).
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 Geopolymer '88 -105-

17. DAVIDOVITS, J. and COURTOIS, L. 'D.T.A. detection of intra-ceramic geopolymeric

setting in archaeological ceramics and mortars' Abstracts of Papers 21st Symposium on
Archaeometry, Brookhaven, New York; p. 22 (1981).
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4 472 199, 1984; British Patent 1 434 807, 1976; British Patent 1 518 605, 1978.;
European Patent 0026687, 1981; European Patent 0066571 (PCT WO 82/00816), 1982;
DAVIDOVITS J. and LEGRAND, J.J., U.S. Patent 4 028 454, 1977; British Patent 1 481
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Patent 0153097, 1985.
21. DAVIDOVITS, J. 'Détermination de la provenance des céramiques par l'analyse des
Géopolymères', Revue d'Archéométrie (Proc. 20°Symp. Intern. Archaeometry, Paris,
1980), 3, pp. 53-56 (1981); see also BOUTTERIN, C. and DAVIDOVITS, J., 'Low
Temperature Geopolymeric Setting of Ceramics', in: A. Espinal & S.E. Warren (ed.), The
Proc. 22nd Symp. on Archaeometry, Univ. of Bradford U.K.; pp. 213-217 (1982).
22. DAVIDOVITS, J. 'Le calcaire des pierres des Grandes Pyramides d'Egypte serait un
béton géopolymère vieux de 4,600 ans', Revue des Questions Scientifiques, Brussels, 157
(2); pp. 199-225 (1986).
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