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Contents
I Polymers and Geopolymers
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Introduction
1.1 Geopolymer technology . . . . . . . . . . . . . . . . . .
1.1.1
The invention of the first mineral resin, October
1.2 The scope of the book . . . . . . . . . . . . . . . . . . .
1.3 Early observations . . . . . . . . . . . . . . . . . . . . .
1.4 Phosphate-based geopolymer . . . . . . . . . . . . . . .
1.4.1
Phosphate geopolymers . . . . . . . . . . . . . .
1.4.2
High-molecular phosphate-based geopolymers:
balitic AlPO4 . . . . . . . . . . . . . . . . . . .
1.5 Organo-mineral geopolymers . . . . . . . . . . . . . . . .
1.5.1
Silicone . . . . . . . . . . . . . . . . . . . . . . .
1.5.2
Hybrid organo-mineral geopolymers . . . . . . .
1.5.3
Humic-acid based: kerogen geopolymer . . . . .
The
2.1
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Contents
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.16
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Contents
8.3
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Contents
13 Phosphate-based geopolymers
13.1 A 4500 year-old Egyptian technology! . . . . . . . . . . . . . .
13.2 Brief survey of phosphate chemistry . . . . . . . . . . . . . . .
13.2.1 Ortho-, di-, tri- and poly-phosphoric acid . . . . . . . .
13.2.2 Polyphosphate linear chains . . . . . . . . . . . . . . .
13.3 Low-molecular phosphate-based geopolymers . . . . . . . . . .
13.4 Poly(sialate-siloxo) / phosphate composites . . . . . . . . . . .
13.5 Phospho-siloxonate geopolymer, -Si-O-P-O-Si- . . . . . . . . . .
13.5.1 Caphospho-silicate . . . . . . . . . . . . . . . . . . . .
13.6 AlPO4 -based geopolymers . . . . . . . . . . . . . . . . . . . . .
13.6.1 Polymeric structures of AlPO4 -geopolymers: 27 Al and
31
P NMR. . . . . . . . . . . . . . . . . . . . . . . . . .
13.6.2 Synthesis of AlPO4 -geopolymers: the solution and solgel routes . . . . . . . . . . . . . . . . . . . . . . . . .
13.6.3 Synthesis of AlPO4 -geopolymers: the modified Al2 O3
routes . . . . . . . . . . . . . . . . . . . . . . . . . . .
13.6.4 MK-750 metakaolin-based AlPO4 -geopolymer . . . . .
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14 Organic-mineral geopolymer
14.1 Poly-organo-siloxanes / silicones . . . . . . . . . . . . . . . . . .
14.1.1 Geopolymeric identity . . . . . . . . . . . . . . . . . .
14.1.2 Two polymerization mechanisms: acidic and basic . . .
14.1.3 Depolymerization and cleavage . . . . . . . . . . . . .
14.1.4 Properties of technical silicones . . . . . . . . . . . . .
14.2 Kerogen-geopolymer . . . . . . . . . . . . . . . . . . . . . . . .
14.3 Organo-geopolymer compounds . . . . . . . . . . . . . . . . . .
14.3.1 Inclusion of hydrophilic polymers, poly(ethylene glycol)
14.3.2 Reaction with isocyanate R-N=C=O . . . . . . . . . .
14.3.3 Reaction with poly(acrylic acid) R-C(=O)-OH . . . . .
14.3.4 Reaction with aqueous phenolic resin and poly(styrene
butadiene) latex . . . . . . . . . . . . . . . . . . . . .
14.3.5 Reaction with hydrophobic polymers: epoxy, phenolic,
silicone . . . . . . . . . . . . . . . . . . . . . . . . . . .
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III Properties
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IV Applications
18 Quality control
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Contents
18.1 Raw-materials . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18.1.1 Solid elemental composition . . . . . . . . . . . . . . .
18.1.2 pH determination of the raw-materials . . . . . . . . .
18.1.3 Granulometry . . . . . . . . . . . . . . . . . . . . . . .
18.2 Determination of the geopolymeric reactivity . . . . . . . . . .
18.3 Working time (pot-life), resin and paste . . . . . . . . . . . . .
18.3.1 Working time (pot-life) . . . . . . . . . . . . . . . . . .
18.3.2 Role of additional water . . . . . . . . . . . . . . . . .
18.3.3 Control on the hardening paste: penetrometer . . . . .
18.3.4 Plasticizers and retarders . . . . . . . . . . . . . . . . .
18.4 Compressive strength and tensile strength . . . . . . . . . . . .
18.4.1 Compressive strength . . . . . . . . . . . . . . . . . . .
18.4.2 Tensile strength . . . . . . . . . . . . . . . . . . . . . .
18.5 Additional fast testing on hardened geopolymers . . . . . . . .
18.5.1 Boiling water / steam . . . . . . . . . . . . . . . . . . .
18.5.2 Freeze-Thaw / Wet-Dry . . . . . . . . . . . . . . . . .
18.5.3 Thermal behavior, expansion at 250C, thermal dilatometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19 Development of user-friendly systems
19.1 Definitions . . . . . . . . . . . . . . .
19.2 The need for user-friendly systems .
19.3 The position of civil engineers . . . .
19.4 The pH values of geopolymers . . . .
19.5 K+ versus Na+ . . . . . . . . . . . .
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applications
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21.4
21.5
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21.10
22 Foamed geopolymer
22.1 Geopolymer foam fabrication . . . . . . . . . . .
22.1.1 Foaming with Na perborate . . . . . . .
22.1.2 Foaming with H2 O2 . . . . . . . . . . . .
22.1.3 Insulating value of geopolymer foam . .
22.2 High-temperature insulation . . . . . . . . . . . .
22.3 Passive cooling of buildings in hot / arid climate
22.4 Passive Cooling in big cities . . . . . . . . . . . .
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xi
Part I
Chapter 1
Introduction
The discovery of a new class of inorganic materials, geopolymer
resins, binders, cements and concretes, resulted in wide scientific interest and kaleidoscopic development of applications. From the first
industrial research eorts in 1972 at the Cordi-Gopolymre private
research laboratory, Saint-Quentin, France, until the end of 2013,
hundreds of papers and patents were published dealing with geopolymer science and technology. On August 31. 2005, the Geopolymer
Institute (a non-profit scientific organization founded in 1979) was
proud to announce in its News on line (www.geopolymer.org): "Since
1997, 80000 papers have been downloaded by 15000 scientists around
the world at the geopolymer.org website". The extent of international
scientific and commercial interest in geopolymers was evidenced by
several large conferences. In France, the First European Conference on Soft Mineralurgy, organized by the Geopolymer Institute
and sponsored by the European Economic Commission, was held at
the University of Technology of Compigne in June 1988 (Geopolymer 88 ). Eleven years later in June-July 1999, the Geopolymer Institute organized the Second International Conference Geopolymere
99, held in Saint-Quentin; the published proceedings included 32
papers presented to the 100 scientists from over 12 countries. The
Third International Conference, Geopolymer 2002 was held in Australia in October 2002. Organized by the University of Melbourne
and chaired by J.S.J. van Deventer, it focused on the ways needed to
"Turn Potential into Profit".
Since 2003, several national and international scientific institutions have organized "geopolymer sessions", "geopolymer seminars"
3
1. Introduction
1.1
Geopolymer technology
Geopolymer technology
wide variety of potential applications includes: fire resistant materials, decorative stone artifacts, thermal insulation, low-tech building
materials, low energy ceramic tiles, refractory items, thermal shock
refractories, bio-technologies (materials for medicinal applications),
foundry industry, cements and concretes, composites for infrastructures repair and strengthening, high-tech composites for aircraft interior and automobile, high-tech resin systems, radioactive and toxic
waste containment, arts and decoration, cultural heritage, archaeology and history of sciences.
My chemistry background had focused on organic polymer chemistry and in the aftermath of various catastrophic fires in France
between 197072, which involved common organic plastic, research
on nonflammable and noncombustible plastic materials became my
objective. In 1972, I founded the private research company Cordi
SA, later called Cordi-Gopolymre. In my pursuit to develop new
inorganic polymer materials, I was struck by the fact that the same
simple hydrothermal conditions governed the synthesis of some organic plastics in alkali medium, as well as mineral feldspathoids and
zeolites.
Thus, phenol and formaldehyde polycondense into the famous
Bakelite invented by Bakeland at the beginning of the 20th Century,
one of the oldest man-made plastic (Figure 1.1).
1. Introduction
1.1.1
Geopolymer technology
1. Introduction
Geopolymer technology
1. Introduction
ments based concretes, which are performing better than had ever
been expected for high-quality concretes.
In the field of so-called high-tech applications, since 1982, the
French aeronautic company Dassault Aviation (Vautey, 1990) has
used geopolymer molds and tooling in the development of French
Airforce fighters (Davidovits et al. 1991). More than a hundred tooling and other items have been delivered for aeronautic applications
and SPF Aluminum processing. In 1994 the American Federal Aviation Administration (FAA) with R. Lyon, initiated a cooperative
research program to develop environmentally friendly, fire resistant
matrix materials for aircraft composites and cabin interior applications. The Geopolymer composites were selected by FAA as the best
candidate for this program (Lyon, 1997).
Environmentally-driven geopolymer applications are based on the
implementation of (K,Ca)poly(sialate-siloxo) / (K,Ca)poly(sialatedisiloxo) cements. In industrialized countries (Western countries)
emphasis is put on toxic waste (heavy metals) and radioactive waste
safe containment. On the other hand, in emerging countries, the
applications relate to sustainable development, essentially geopolymeric cements with very low CO2 emission. Both fields of application
are strongly dependent on politically driven decisions. Heavy metal
waste encapsulation with geopolymer started in 1987, in Canada,
with the financial support of CANMET Ottawa, Ontario Research
Foundation, Toronto, and Comrie Consulting (Davidovits and Comrie, 1988). The safe containment of uranium mine tailings and radioactive sludge started in 1994 within the European research project
GEOCISTEM, funded by the European Union. The GEOCISTEM
project was aimed at manufacturing cost-eectively new geopolymeric cements (Geocistem, 1997). It was experimented on two important uranium-mining locations of Wismut, former East Germany,
with the collaboration of BPS Engineering, Germany. Our results
clearly show that solidification with geopolymeric cement (K,Ca)
poly(sialate-siloxo) is a prime candidate to cost-eciently fill the gap
between conventional concrete technology and vitrification methods
(Hermann et al., 1999).
Major eorts were dedicated to greenhouse CO2 mitigation with
the development of low CO2 geopolymer cements. My research on
this very important geopolymer application started in 1990 at PennState University, Materials Research Laboratory, USA. The production of 1 tonne of kaolin based-geopolymeric cement generates 0.180
10
1.2
1.3
Early observations
1. Introduction
Alkali-activation
(slag)
Hydrosodalite
(kaolin)
1940 : Purdon
(Belgium)
1934 : Olsen
(Netherland)
1945 : US Bureau
of Standard (USA)
1949 : Borchert,
Keidel (Germany)
1930
1940
1950
1960
1970
1945 : Barrer
(UK)
1953 : Barrer,
White (UK)
1956 : Milton
(USA)
Geopolymer
1976 : Davidovits
(IUPAC terminology)
1979 : Davidovits
(France)
Geopolymer
Early observations
extraction process involved the precipitation of a sodalite-like compound. Borchert and Keidel (1949) prepared hydrosodalite (NaPS)
by reacting kaolinite in a concentrated NaOH solution, at 100C.
Howell (1963) obtained a Zeolite A type, using calcined kaolin (metakaolin) instead of kaolinite, preventing the formation of hydrosodalite.
In 1972, the ceramicist team Jean Paul Latapie and Michel Davidovics confirmed that water-resistant ceramic tiles could be fabricated at temperatures lower than 450C, i.e. without firing. One
component of clay, kaolinite, reacted with caustic soda at 150C. In
fact, the industrial application of this kaolinite reaction with alkali
began in the ceramic industry with Niels Olsen (1934) and was later
on reinvented in 1964 by Berg et al. (1970), a Russian team, but
without any successful industrial implementation.
In 1969, Besson, Caillre and Hnin at the French Museum of
Natural History, Paris, carried out the synthesis of hydrosodalite
from various phyllosilicates (kaolinite, montmorillonite, halloysite)
at 100C in concentrated NaOH solution, (Besson et al., 1969).
In 1972, at CORDI laboratory in Saint-Quentin, we developed a
technology based on this geosynthesis, which has been disclosed in
various patents issued on the applications of the so-called "SilifaceProcess" (Davidovits and Legrand, 1974). To a natural kaolinite/quartz
blend (50/50 weight ratio) was added and mixed solid NaOH in the
proportion of 2 moles or less of NaOH for 1 mole Al2 O3 of the contained kaolinite, and water (11.5 g water for 1 g NaOH). The resulting granules were cold-pressed at 15 MPa into a green body, which
was then hot-pressed (thermosetting process) in a mold equipped
with a porous layer for water evaporation.
The thermosetting parameters were:
Temperature: 130C to 180C;
Applied hydraulic pressure: higher than the saturated vapor
pressure of water, for the selected temperature, i.e. 10 to 30
bars;
Time: one minute per millimeter thickness at 150C or 10 minutes for a 10 millimeters thick plate. 65 to 75 % of the total
time is devoted to degassing water.
The setting time is relatively short. In the absence of any pervious
device, i.e. when degassing is not working, the polycondensation into
hydrosodalite occurs very rapidly in a time as short as 1520 seconds
per millimeter thickness, at 180C and 40 kg/cm2 hydraulic pressure.
13
1. Introduction
Yet, due to the high internal pressure of water and the danger of
explosion, the press must be equipped with safety devices (see for
more details in Chapter 7). Otherwise, it is recommended to wait
until the item has cooled down to room temperature before opening
the press.
1.4
Phosphate-based geopolymer
1.4.1
Phosphate geopolymers
(1)
(2)
Phosphate-based geopolymer
(3)
(4)
where X is Fe or Mn.
1.4.2
1. Introduction
1.5
1.5.1
Organo-mineral geopolymers
Silicone
1.5.2
1.5.3
T.K. Yen and his team, working on the transformation of geomolecules through geochemical processes during diagenesis, (Kim et al.,
2004, 2006) have drawn attention to the concept of geopolymer in
association with kerogen and petroleum. Kerogen-geopolymer is the
16
Organo-mineral geopolymers
most stable material and the final alternating product in the Earth.
Some geopolymeric materials can last for a long time due to their
unique geopolymeric structure, so-called three-dimensional crosslink.
Geopolymers can be classified into two major groups: pure inorganic
geopolymers and organic containing geopolymers, synthetic analogue
of naturally occurring macromolecules (Kim et al., 2004, 2006). The
small content of organics is a key parameter governing the strength
and durability of material in a large volume of inorganics. Organic
compounds can be incorporated into refractory macromolecules such
as lignin and melanodin or humic materials (Henrichs 1992). Humic
materials represent an inorganic-organic structure.
1. Introduction
more organics and less inorganics, while others have the opposite. It
is, however, evident that both inorganics and organics are required
in a mix at a certain ratio, which will result in a geopolymeric structure. This geopolymeric structure exhibits a similar organization
to human bone and teeth, typical inorganic-organic composites that
show extreme durability and mechanical strength. The mechanism of
geomacromolecule formation involves the crosslink reaction between
the inorganic and organic materials.
References
Almennigen, A., Bastiansen, O., Ewing, V., Hedberg, K. and Traetteberg, M.,
(1963), Acta Chem. Scand. 17, 24552460.
Berg L.C., Demidenko B.A., Reminikova V.I. and Nisamov N.S., (1970), Stroitelnye Materialy (USSR), 10, 22.
Besson H., Caillre S. and Henin S., (1969), Conditions de prparation de lhydrosodalite basse temprature, C. Rend. Acad. Sci., D269, 1367.
Borchert W. and Keidel J., (1949), Heidelb. Beitr. z. Min. u. Petr., 1. 2.
Davidovits J., (1972), Procd de fabrication de panneaux agglomrs et panneaux resultant de lapplication de ce procd, French Patent Application
FR 72.38746 (FR 2,204,999) and FR 73.35979 (FR 2,246,382); US Patent
3,950,470, Process for the fabrication of sintered panels and panels resulting
from the application of this process.
Davidovits J. and Legrand J.-J., (1974) French Patent FR 2,324,427 filed Jan.
11. 1974; see also US Patent 4,028,454 (1977), filed Dec. 31. 1974 ; United
Kingdom Patent UK 1.481.479 (1977), filed Jan. 9, 1975; German Patent DE
25 00 151 (1979), filed Jan. 3, 1975.
Davidovits J., (1976), Solid phase synthesis of a mineral blockpolymer by low
temperature polycondensation of aluminosilicate polymers, IUPAC International Symposium on Macromolecules Stockholm; Sept. 1976; Topic III, New
Polymers of high stability.
Davidovits J., (1979), Polymre Minral, French Patent Application FR 79.22041
(FR 2,464,227) and FR 80.18970 (FR 2,489,290); US Patent 4,349,386, Mineral polymer.
Davidovits J., (1993), Carbon-Dioxide Greenhouse-Warming: What Future for
Portland Cement, Proceedings, Emerging Technologies Symposium on Cement
and Concrees in the Global Environment, 21p, Portland Cement Association,
Chicago, Illinois, March 1993.
Davidovits J. and Sawyer J.L., (1985), Early high-strength mineral polymer, US
Patent 4,509,985, 1985, filed February 22, 1984.
Davidovits J. and Comrie D., (1988), Archaeological long-term durability of hazardous waste disposal: preliminary results with geopolymer technologies, Division of Environmental Chemistry, American Chemical Society, Toronto, 1988,
Extended Abstracts, 237240. See also: Long Term Durability of Hazardous
Toxic and Nuclear Waste Disposals, Geopolymer 88 Proceedings, 125134.
18
Organo-mineral geopolymers
19
1. Introduction
20
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