(19)

*EP002970003B1*
(11) EP 2 970 003 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C04B 18/08 (2006.01) C04B 38/02 (2006.01)
06.05.2020 Bulletin 2020/19 C04B 28/00 (2006.01)

(21) Application number: 14762280.7 (86) International application number:

PCT/IB2014/059599
(22) Date of filing: 10.03.2014
(87) International publication number:
WO 2014/141051 (18.09.2014 Gazette 2014/38)

(54) HIGH-STRENGTH GEOPOLYMER COMPOSITE CELLULAR CONCRETE

HOCHFESTER GEOPOLYMERVERBUNDZELLENBETON
BÉTON CELLULAIRE COMPOSITE GÉOPOLYMÈRE DE GRANDE RÉSISTANCE

(84) Designated Contracting States: • PEGG, Ian L.

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Alexandria, Virginia 22310 (US)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO
PL PT RO RS SE SI SK SM TR (74) Representative: Balder IP Law, S.L.
Paseo de la Castellana 93
(30) Priority: 14.03.2013 US 201361781885 P 5ª planta
28.02.2014 US 201414193001 28046 Madrid (ES)

(43) Date of publication of application: (56) References cited:

20.01.2016 Bulletin 2016/03 WO-A2-2012/069024 US-A1- 2010 058 957
US-A1- 2011 271 876 US-A1- 2012 024 196
(73) Proprietor: THE CATHOLIC UNIVERSITY OF US-A1- 2012 152 153 US-A1- 2012 172 469
AMERICA US-B2- 8 202 362
Washington, DC 20064 (US)
• R. ARELLANO AGUILAR ET AL: "Lightweight
(72) Inventors: concretes of activated metakaolin-fly ash
• GONG, Weiliang binders, with blast furnace slag aggregates",
Rockville, Maryland 20850 (US) CONSTRUCTION AND BUILDING MATERIALS,
• LUTZE, Werner vol. 24, no. 7, 1 July 2010 (2010-07-01), pages
Chevy Chase, Maryland 20815 (US) 1166-1175, XP55146920, ISSN: 0950-0618, DOI:
10.1016/j.conbuildmat.2009.12.024
EP 2 970 003 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 2 970 003 B1

Description

BACKGROUND

5 Field of the Invention

[0001] This invention relates generally to methods of high strength low-density geopolymer composite cellular concrete
compositions (GCCCs).

10 Related Art

[0002] There is a growing need to develop, green, low cost, non-autoclaving processes to manufacture high strength
lightweight cellular concrete for both thermal insulation and structural applications.

15 SUMMARY

[0003] According to a first aspect, the present invention provides a product comprising: a composite binder comprising:

one or more Class F fly ash materials,

20 one or more gelation enhancers,
one or more hardening enhancers,
one or more alkaline activators,
one or more aggregates, and
one or more foaming agents;
25 wherein each of the one or more Class F fly ash materials comprises 15 wt.% or less calcium oxide,
wherein the one or more alkaline activators comprise an alkaline activator solution comprising one or more metal
hydroxides, one or more metal silicates, and water,
wherein the one or more gelation enhancers are selected from the group consisting of metakaolin, metahalloysite,
micron and nanoparticles of silica and alumina, and pozzolanic aluminosilicate materials that have a low alkali-earth
30 oxide content and a high dissolution rate in alkaline solution,
wherein the one or more hardening enhancers are selected from the group consisting of ground granulated blast
furnace slag, Class C fly ash, vitreous calcium aluminosilicate, kiln dust, CaO-rich pozzolanic aluminosilicates, and
combinations thereof,
wherein the one or more foaming agents comprise aluminum powder or a peroxide-based foaming agent,
35 wherein the geopolymer composite binder is a Portland cement-free binder,
wherein the product is a geopolymer composite cellular concrete (GCCC);
wherein an amount of the one or more Class F fly ash materials is 1 to 50 wt.% of the product, an amount of the
one or more gelation enhancers is 1 to 50 wt.% of the product, and an amount of the one or more hardening
enhancers is 1 to 50 wt.% of the product; and
40 wherein the product has an apparent density of 1200 kg/m3 to 1800 kg/m3 and a 28-day compressive strength of
at least 17 MPa or 2500 psi.

[0004] Disclosed but not claimed is a method comprising the following steps:

45 (a) mixing together one or more Class F fly ash materials, one or more gelation enhancers and one or more hardening
enhancers to thereby form a composite binder,

(b) mixing the composite binder with one or more alkaline activators to thereby form an activated mixture,

50 (c) mixing the activated mixture with one or more aggregates to thereby form a concrete mixture,

(d) mixing the concrete mixture with one or more foaming agents to thereby form a geopolymer composite cellular
concrete mixture,

55 (e) pouring the geopolymer composite cellular concrete mixture into a mold, and (f) maintaining the geopolymer
composite cellular concrete mixture in the mold at a temperature of at least room temperature to thereby allow the
geopolymer composite cellular concrete mixture to foam, expand, set, harden and cure and thereby form a geopol-
ymer composite cellular concrete product, wherein each of the one or more Class F fly ash materials comprises 15

2
 EP 2 970 003 B1

wt.% or less calcium oxide.

[0005] Also disclosed but not claimed is a method comprising the following steps:

5 (a) mixing together one or more Class F fly ash materials, one or more gelation enhancers and/or one or more
hardening enhancers to thereby form a composite binder,
(b) mixing the composite binder with one or more alkaline activators to thereby form an activated mixture,
(c) mixing the activated mixture with one or more foaming agents to thereby form a geopolymer composite cellular
concrete mixture,
10 (d) pouring the geopolymer composite cellular concrete mixture into a mold, and
(e) maintaining the geopolymer composite cellular concrete mixture in the mold at a temperature of at least room
temperature to thereby allow the geopolymer composite cellular concrete mixture to foam, expand, set, harden and
cure and thereby form a geopolymer composite cellular concrete product,

15 wherein each of the one or more Class F fly ash materials comprises 15 wt.% or less calcium oxide, and
wherein the geopolymer composite cellular concrete product has an apparent density of about 400 kg/m3 to about 1200
kg/m3 and a 28-day compressive strength of about 3 to about 17 MPa.
[0006] According to a second aspect, the present invention provides a method for the manufacture of a geopolymer
composite cellular concrete, comprising the following steps:
20
(a) mixing together one or more Class F fly ash materials, one or more gelation enhancers and one or more hardening
enhancers to thereby produce a blend of composite binder components,
(b) mixing the blend of composite binder components with one or more alkaline activators to thereby produce an
activated mixture,
25 (c) mixing the activated mixture with one or more aggregates, one or more foaming agents to thereby produce a
geopolymer composite cellular concrete (GCCC) paste,
(d) pouring the geopolymer composite cellular concrete paste into a mold, and allowing the geopolymer composite
cellular concrete paste to foam, expand, set, and harden at room temperature, thereby producing a hardened GCCC
body;
30 (e) removing the hardened GCCC body from the mold and curing the hardened GCCC body at room temperature,
thereby producing a geopolymer composite cellular concrete product, wherein each of the one or more Class F fly
ash materials comprises 15 wt.% or less calcium oxide,

wherein the one or more alkaline activators comprise an alkaline activator solution comprising one or more metal hy-
35 droxides, one or more metal silicates, and water;
wherein the one or more gelation enhancers are selected from the group consisting of metakaolin, metahalloysite, micron
and nanoparticles of silica and alumina, and pozzolanic aluminosilicate materials that have a low alkali-earth oxide
content and a high dissolution rate in alkaline solution;
wherein the one or more hardening enhancers are selected from the group consisting of ground granulated blast furnace
40 slag, Class C fly ash, vitreous calcium aluminosilicate, kiln dust, CaO-rich pozzolanic aluminosilicates, and combinations
thereof;
wherein the one or more foaming agents comprise aluminum powder or a peroxide-based foaming agent;
wherein an amount of the one or more Class F fly ash materials is 1 to 50 wt.% of the GCCC paste, an amount of the
one or more gelation enhancers is 1 to 50 wt.% of the GCCC paste, and an amount of the one or more hardening
45 enhancers is 1 to 50 wt.% of the GCCC paste; and
wherein the geopolymer composite cellular concrete product has an apparent density of about 1200 kg/m3 to about
1800 kg/m3 and a 28-day compressive strength of at least 17 MPa.

BRIEF DESCRIPTION OF THE DRAWINGS

50
[0007]

FIG. 1 is a photo of a geopolymer composite cellular concrete for structural application showing homogeneous
cellular structure.
55
FIG. 2 is a photo of a geopolymer composite cellular concrete for thermal insulation showing homogeneous cellular
structure, disclosed but not claimed.

3
 EP 2 970 003 B1

FIG 3 shows a ternary composition diagram of geopolymer composite binders for cellular concrete.

FIG. 4 is a graph showing compressive strength of a geopolymer composite cellular concrete product for structural
applications as a function of apparent product density according to one embodiment of the present invention.
5
FIG. 5 is a graph showing compressive strength of a geopolymer composite cellular concrete product for thermal
insulation as a function of the products’ apparent density according to a not-claimed disclosure.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

10
Definitions

[0008] Where the definition of terms departs from the commonly used meaning of the term, applicant intends to utilize
the definitions provided below, unless specifically indicated.
15 [0009] For purposes of the present invention, the term "low alkali-earth oxide content" refers to pozzolans with less
than 15 wt.% CaO+MgO.
[0010] For purposes of the present invention, the term "high dissolution rate in alkaline solution" refers to certain
pozzolanic materials which have a high reactivity in an alkaline solution, e.g., at an apparent rate constant of more than
10-2 to 10-3 hour-1 at ambient temperatures.
20 [0011] For purposes of the present invention, the term "binder for concrete" refers to a binder material or cementitious
material (non Portland cement) that may be mixed with an air or solid lightweight aggregate material to form a hardened
material.
[0012] For purposes of the present invention, the term "Class C fly ash" refers to "Class C fly ash" as defined by the
American society for Testing and Materials (ASTM C618).
25 [0013] For purposes of the present invention, the term "Class F fly ash" refers to "Class F fly ash" as defined by the
American society for Testing and Materials (ASTM C618).
[0014] For purposes of the present invention, the term "coarse aggregate" and the term "coarse aggregate material"
refer to a coarse aggregate as defined by the American society for Testing and Materials (ASTM C33). Examples of
coarse aggregates include: granite, metamorphic, limestone etc.
30 [0015] For the purposes of present invention, the term "coarse lightweight aggregate" is referred to a coarse lightweight
aggregate as defined by the American society for Testing and Materials (ASTM C332 and C330 for insulating and
structural concretes, respectively).
[0016] For purposes of the present invention, the term "fine aggregate" refers to an aggregate as defined by the
American society for Testing and Materials (ASTM C33). Examples of fine aggregates include masonry sand and calcined
35 bauxite sand. A fine lightweight aggregate is a fine aggregate that is also lightweight as defined by the American society
for Testing and Materials (ASTM C332 and C330 for insulating and structural concretes, respectively).
[0017] For purposes of the present invention, the term "foaming agent" refers to materials that may be used to introduce
or generate foam in fresh concrete. Examples of foaming agents include aluminum powder, hydrogen peroxide, alkali
peroxides, alkali perborate, etc.
40 [0018] For purposes of the present invention, the term "highly reactive aluminosilicates" refers to pozzolanic materials,
which are low in alkali-earth oxide (e.g., less than 5 wt.%) and are able to dissolve very quickly in alkaline solution at
ambient temperatures, e.g., at apparent rate constant of more than 10-2 hour-1._. An example of a highly reactive
aluminosilicate is metakaolin.
[0019] For purposes of the present invention, the term "ground granulated blast-furnace slag" refers to the material
45 as defined by American society for Testing and Materials (ASTM C989). The furnace slag is usually produced by
quenching molten iron slag from a blast furnace in water or steam to form a glassy granular product and then drying
and grinding the glassy into a fine powder.
[0020] For purposes of the present invention, the term "lightweight aggregate" refers to any aggregate having a density
of 50 kg/m3 to about 1000 kg/m3.
50 [0021] For purposes of the present invention, the term "low calcium Class F fly ash" refers to Class F fly ash having
a calcium content of less than_8 wt.% or less than 15 wt.%.
[0022] For purposes of the present invention, the term "Portland cement-free binder" refers to a binder composition
that does not contain Portland cement.
[0023] For purposes of the present invention, the term "reactive amorphous alkali-earth aluminosilicate" refers to the
55 pozzolanic materials containing alkali-earth oxides (CaO+MgO) more than 15 wt.%. Examples of reactive amorphous
alkali-earth almuninosilicates include ground granulated blast-furnace slag, vitreous calcium silicate, Class C fly ash, etc.
[0024] For purposes of the present invention, the term "silica fume" and "microsilica" refers to the conventional meaning,
i.e., an amorphous (non-crystalline) form of silica (silicon dioxide) with a particle size less than 0.1 mm.

4
 EP 2 970 003 B1

[0025] For purposes of the present invention, the term "submicron" refers to particles that are less than 1 mm in diameter.
[0026] For purposes of the present invention, the term "ultrafine" refers to particles that are less than or equal to about
15 mm in diameter.

5 Description

[0027] Conventional Cellular Concrete is a versatile, lightweight, building material. Other names frequently used in
the literature are aerated concrete, aircrete, and foamed concrete. Cellular concrete can be made with a wide range of
densities and compressive strength and it is used for many different applications. In many cases cellular concrete can
10 provide cost and performance benefits when compared with traditional building materials. Essentially, the basic definition
of cellular concrete is that "it is mortar or mortar-like material with discrete air bubbles in it." The air content of conventional
cellular concrete may be up to 85 % by volume. It can have a range of dry densities typically from 400 kg/m3 (25 lbs/ft3)
to 1600 kg/m3 (100 lbs/ft3) with compressive strength between 1 to 15 MPa. Generally the cellular concrete offers a
number of benefits such as generally lower in cost than alternative load-reducing materials, relatively high compressive
15 strength in relation to its weight, absorption of shock waves, high thermal insulation due to content of up to 85 vol.% air,
and high fire resistance (cellular concrete is approximately twice as fire resistant as dense concrete.
[0028] A large number of proprietary methods and agents are used to make cellular concrete but essentially they can
be divided into two groups: those using a chemical reaction and those relying on mix foaming to entrain air into the
concrete. The lightweight concrete made by gasification from a chemical reaction is called in this patent application
20 aerated concrete or Aerated Cellular Concrete (ACC). Since this process usually employs an autoclave, it is also called
Autoclaved Cellular Concrete (ACC). The lightweight concrete made by using aqueous foams is called foamed concrete
or aircrete. The foamed concrete derived from aqueous foams is typically proportioned to achieve only low compressive
strengths as compared to ACC and only suitable for use in void fill and trench reinstatement, and thus the material is
largely disregarded for use in weight-bearing and structural applications.
25 [0029] In a typical ACC manufacturing process, quartz sand or fly ash, lime, cement, aluminum powder, and water
are mixed together. During mixing, the lime reacts with the water to form calcium hydroxide, and heat is generated.
When the mix is cast in forms, the aluminum powder, reacting with calcium hydroxide and water generates hydrogen,
expands or foams the concrete mix to about twice its original volume or more. After expansion has occurred the porous
mass is cut to a desired size and shape and is placed in an autoclave filled with pressurized steam. The autoclaving
30 process lasts typically 10-12 hours with temperature of 180-200 °C and the pressure reaching 12 bars. The ACC process
is more suitable for precast plants than for use in the field. Production is associated with relatively large initial capital
investment in equipment and facility and operation costs. There has been a worldwide increase in the use of AAC
materials and new production plants are being built in Eastern Europe, Israel, China, Bahrain, India, and Australia. Most
of the attempts over the last few decades to introduce AAC to the US hardly made a significant impact on the construction
35 industry. The tens of millions of dollars of initial capital investment needed to make AAC compared with a conventional
precast plant is justan important reason for failure as reported in the literature. The abundance of inexpensive wood
products in the United States explains the lack of incentive for the development of new building technologies.
[0030] The autoclaved cellular concrete uses significant amounts of Portland cement and lime (calcium hydroxide). It
is well known that production of Portland cement and lime emits carbon dioxide, which contributes to global warming.
40 High temperature/pressure autoclaving is an energy- intensive process.
[0031] Foresight groups around the world have identified the future need for construction materials that are light,
durable, and simple to use, economic, yet green and environmentally sustainable. A low temperature process to man-
ufacture high strength cellular concrete is desirable.
[0032] In the past decades, the potential of geopolymers has been explored as a substitute for Portland cement.
45 Geopolymer is a term used to describe inorganic polymers based on aluminosilicate, which can be produced by reacting
pozzolanic compounds, i.e., aluminosilicate source materials, with highly alkaline solutions. Geopolymers consist of
silicon and aluminum atoms bonded via oxygen atoms into a polymer network. Charge balance is provided by alkali
ions. Geopolymers are prepared by dissolution and subsequent poly-condensation reactions between a reactive alumi-
nosilicate material and an alkaline silicate solution, such as a mixture of an alkali metal silicate and metal hydroxide.
50 Examples of a reactive aluminosilicate material are industrial by-products such as Class F fly ash (FFA), Class C fly ash
(CFA) and ground granulated blast furnace slag (BFS). The reactive aluminosilicate source can also be a natural mineral
such as kaolinite, clay, zeolite and volcanic ash. Thus geopolymers are essentially ’green and sustainable’.
[0033] U. S. Patent No. 5,605,570 (Reference 5) describes a foamed geopolymer material made from blast furnace
slag. Sodium peroxide acts as the foaming agent and the alkaline activator. Sodium peroxide reacts with water to produce
55 a sodium hydroxide solution that activates the slag to form the geopolymer and oxygen gas develops to induce volume
expansion. Sodium peroxide is expensive and therefore, the process is economically not viable.
[0034] Esmaily and Nuranian (2012) (Reference 1) have used aluminum powder and/or an organic foaming agent to
prepare lightweight materials from furnace slag activated by sodium silicate solution.

5
 EP 2 970 003 B1

[0035] Vlcek et al. (2010) (Reference 2) have studied the effect of fly ash addition on properties of lightweight geopol-
ymer materials based on alkali activated iron and steel slag using aluminum powder as the foaming agent.
[0036] Augilar et al. (2010) (Reference 3) have reported a lightweight concrete made of alkali activated metakaolin-
flyash binder. Aluminum powder was used as the foaming agent. Blast furnace slag sands were used as aggregates.
5 [0037] Henon et al. (2013) (Reference 4) have published a method to prepare metakaolin-based geopolymer foams
made with silica fume as the pore-forming agent. Silica fume, a waste product from the Si-Fe metallurgy, contains usually
less than 1 wt.% silicon. Silicon is a foaming agent when it reacts with alkali hydroxide solution giving off hydrogen.
Large amounts of silica fume are needed and the foaming process requires stimulation at elevated temperature. WO
2012/069024 (Reference 8) discloses acid and high temperature resistant cement composites comprising Class F fly
10 ash and /or ground slag and an alkali activator.
[0038] Fly ash is a fine powder byproduct formed during combustion of pulverized coal in electrical power plants. The
American Society for Testing and Materials (ASTM) C618 standard recognizes two major classes of fly ashes for use
in concrete: Class C and Class F. The lower limit of SiO2 + Al2O3 + Fe2O3 for Class F fly ash is 70% and that for Class
C fly ash is 50%. Class F fly ashes generally have a calcium oxide content of about 15 wt.% or less, whereas Class C
15 fly ashes generally have a higher calcium oxide content (e.g., 20 to 40 wt.%). High calcium oxide content makes Class
C fly ashes possess cementitious properties leading to the formation of calcium silicate and calcium aluminate hydrates
when mixed with water. Ground granulated blast furnace slag (GGBFS) is a glassy granular material that varies, from
a coarse, popcorn-like friable structure to greater dense, sand-size grains. Grinding reduces the particle size to cement
fineness, allowing its use as a supplementary cementitious material in Portland cement-based concrete. Typical ground
20 granulated blast furnace slag includes 27-38% SiO2, 7-12% Al2O3, 34-43% CaO, 7-15% MgO, 0.2-1.6% Fe2O3,
0.15-0.76% MnO and 1.0-1.9% by weight. Since GGBFS is almost 100% glassy (amorphous), it is much more reactive
than Class F fly ashes. The higher proportion of the strength-enhancing calcium silicate hydrate (CSH) than in Portland
cement results in higher ultimate strength than concrete made only with Portland cement.
[0039] Challenges associated with the use of ground granulated furnace slag and Class C fly ashes in geopolymers
25 include difficult control of setting during alkali activation and large shrinkage of the final products.
[0040] One particular challenge is that the geopolymer paste made with Class F fly ash sets and hardens very slowly
and usually has low final strength, particularly when cured at low temperatures (e.g., room temperature).
[0041] To overcome this and other challenges, the present inventors have developed new Geopolymer Composite
Cellular Concretes (GCCCs) that reach high final strength, even when cured at room temperature. At the same time
30 these geopolymer composites exhibit optimal rheological properties for stabilizing the cellular structure and exhibit a
sufficiently long set time to allow desirable volumetric expansion. These compositions and methods of high strength
Geopolymer Composite Cellular Concrete (GCCC), can be widely used in structural applications in the construction
industry.
[0042] Disclosed but not claimed are geopolymer composite compositions and methods to make cellular concrete for
35 nonstructural thermal insulation applications including: (i) one Class F fly ash; (ii) at least one hardening enhancer, e.g.,
ground granulated blast furnace slag or vitreous calcium aluminosilicate, or Class C fly ash; (iii) at least one gelation
enhancer, e.g., metakaolin or ground pumice powder or micron- or submicron particles of silica fume and aluminum
hydroxide; (iii) one or more alkaline activators; and iv) at least one foaming agent such as aluminum powder, Fe-Si
powder, hydrogen peroxide, alkali peroxides, alkali perborates, alkali perchlorides. The components (i), (ii) and (iii)
40 constitute a ternary geopolymer composite binder for cellular concrete.
[0043] An embodiment according to the invention provides geopolymer composite compositions and methods to make
a high strength cellular concrete for structural applications. The methods comprise mixing of: (i) at least one hardening
enhancer, e.g., ground granulated blast furnace slag, vitreous calcium silicate, kiln dust, Class C fly ash; (ii) at least one
gelation enhancer, e.g., metakaolin; (iii) Class F fly ash; (iv) at least one aggregate, e.g., river sand, lightweight aggregate
45 (LWA), pumice, cenosphere, hollow glass or ceramic particles; (v) at least one alkali silicate activator; and (vi) at least
one foaming agent. The components from i) to iii) constitute a ternary geopolymer composite binder for cellular concrete.
[0044] In some embodiments, a GCCC of the present invention may contain one or more accelerators, e.g., alkali
fluoride, calcium salts such as CaCl2, alkali oxalate, and alkali sulfate. Addition of these admixtures may improve early
and final strength of the cellular concrete products. Optionally a GCCC composition may contain gypsum, reactive
50 magnesium oxide (MgO) or certain commercially available shrinkage reducing admixtures to reduce shrinkage of the
cellular concrete. To vary the set time, a GCCC composition may also contain one or more set retarders such as sodium
metaphosphate, borax, boric acid, alkali citrates such as sodium citrate, barium hydroxide, and barium nitrate and barium
chloride, zinc nitrate and chloride, alkali phosphate compounds such as sodium metaphosphate. In some embodiments,
a GCCC composition may contain one or more chopped fibers, e.g., organic fiber, glass fiber, basalt fiber, mineral fiber
55 for reinforcement. In some embodiments, a GCCC composition may contain one or more superplasticizers to further
reduce water demand and improve rheological properties of the paste for optimal volumetric expansion and a stable
cellular structure.
[0045] The GCCC has a 28-day compressive strength of at least 2500 psi (17 MPa) with a density of 1200 to 1800

6
 EP 2 970 003 B1

kg/m3. In some embodiments, the GCCC has a 28-day compressive strength of at least 3000 psi (about 21 MPa) with
a density of 1200 kg/m3. In one embodiment, the GCCC has a 28-day compressive strength of at least 8000 psi (about
56 MPa) with a density of 1500 kg/m3. In some embodiments, the GCCC is cured at room temperatures, e.g., 20 °C.
[0046] In one embodiment, the GCCC is cured at elevated temperatures such as between 30 °C and about 90 °C.
5 The GCCC products exhibit a gasification-induced porosity of about 10% to about 90%.
[0047] Disclosed but not claimed are compositions and methods of preparation of geopolymer composite cellular
concrete for thermal insulation. The GCCC mix can include: i) one Class F fly ash; and ii) at least one hardening enhancer
such as ground granulated blast furnace slag, Class C fly ash, vitreous calcium aluminosilicate, and kiln dust; iii) at least
one gelation enhancer such as metakaolin, certain dehydrated clays, dehydrated zeolite, micron particles of silica (in-
10 cluding silica fume, colloidal silica, etc.) and alumina in appropriate proportions, and volcanic ash (pumice); iv) one or
more alkali silicate activators; and v) at least one foaming agent, e.g., aluminum powder, Fe-Si powder, hydrogen
peroxide, alkali peroxides, and alkali perborates.
[0048] In one embodiment, the present invention provides methods of making a high strength GCCC for structural
applications. The methods comprise mixing: (i) at least one hardening enhancer, e.g., ground granulated blast furnace
15 slag, vitreous calcium aluminosilicate, Class C fly ash and kiln dust; (ii) at least one gelation enhancer, e.g., metakaolin;
(iii) one Class F fly ash; (iv) at least one aggregate, e.g., river sand, lightweight aggregate (LWA), pumice, cenosphere,
and hollow glass particles; (v) at least one alkaline activator; and (vi) at least one foaming agent.
[0049] In some embodiments, one or more setting retarders, such as boric acid, borax, alkali citrate, barium hydroxide,
barium chloride, barium nitrate, zinc nitrate, alkali phosphate compounds such as sodium meta phosphate may be added
20 to a GCCC composition to extend set times, in particular when temperature rise in the paste is significant due to heat
released from reactions of foaming agent and water and when blast furnace slag is a major ingredient in a geopolymer
composite composition. In some embodiments, one or more accelerators, such as alkali fluoride, calcium salts, alkali
oxalate may be added to improve early and/or final strength. Both set retarder and accelerator may be used to regulate
set times for optimal volumetric expansion.
25 [0050] In some embodiments of the present invention, one or more types of chopped fibers, e.g., organic fiber, glass
fiber, carbon fiber, basalt fiber, mineral fiber may be included for reinforcement.
[0051] In some embodiments of the present invention, one or more superplasticizers may be included to further reduce
water demand and improve rheological properties of the paste for optimal bubble formation and stable volumetric ex-
pansion.
30 [0052] In some embodiments of the present invention, one or more kinds of ultrafine and/or submicron filler particles
such as silica fume, ultrafine fly ash, ultrafine furnace slag, and submicron calcium carbonate powder may be included
to decrease water demand of a cellular concrete mix and improve rheological properties of the paste, and to enhance
product strength by producing additional alkali aluminosilicate and/or CSH gels.
[0053] The GCCC products have a density of about 1200 to 1800 kg/m3 with a 28-day compressive strength of about
35 17 MPa to about 100 MPa. In some embodiments, the GCCC composition is cured at room temperatures, e.g., 20 °C.
In some embodiments, the GCCC composition is cured at elevated temperatures such as between 30° C and about 90°
C or higher. GCCC products comprise a gasification-induced porosity of about 10% to about 90%. In some embodiments,
GCCC products comprise porosity of about 10% to about 50% introduced by lightweight aggregates.
[0054] Important factors in successfully manufacturing geopolymer composite cellular concretes of the present inven-
40 tion for structural applications include, (i) use of geopolymer composite binder compositions; (ii) optimization of the
composition of the alkaline activator; (iii) control of paste properties for efficient volumetric expansion and stabilization
of the cellular structure; and (iv) use of chemical foaming agents and/or low cost lightweight aggregates to achieve low
density and high strength products.
[0055] The performance of geopolymer products depends on both the reactivity of pozzolans and mass of gel formed
45 during alkali activation. The inventors have found that alkali activation of reactive aluminosilicate materials, such as
metakaolin, generates large amounts of alkali aluminosilicate gel (AAS gel). However, reactivity of Class F fly ash in
alkaline solution is very slow at room temperature and the paste usually does not develop enough strength even after
curing for 7 days. Little alkali-aluminosilicate gel (AAS) forms to increase strength.
[0056] In prior art an alkali silicate solution was used to provide additional dissolved silica. The present inventors find
50 that the dissolved silica and/or alumina can come from sources other than alkali silicate solution. For example, a group
of aluminosilicate materials may be used as additional sources of dissolved silica and/or alumina in Class F fly-ash-
based geopolymers. The pozzolans should desirably dissolve in an alkaline solution at a much faster rate than Class F
fly ash. This group of materials is herein referred to as "gelation enhancer". Examples of this group of materials are
metakaolin, zeolitic phases, and micron/submicron particles of silica fume and alumina in an appropriate proportion. The
55 addition of these gelation enhancers does not substantially affect the reactivity of the fly ash, while it increases the
amount of AAS gel, which results in a substantial improvement of compressive strength of the products.
[0057] A large body of the literature shows that the AAS gel can coexist with the calcium silicate hydrate (CSH) and/or
related gels (e.g., calcium aluminosilicate gel, CASH) and/or crystalline calcium aluminosilicate phases in alkali-activated

7
 EP 2 970 003 B1

furnace slag materials. As disclosed in US patent application # 20120024196, the present inventors find coexistence of
AAS and CSH gel in the geopolymer composite products containing mostly Class F fly ash. Additional metakaolin and
blast furnace slag help achieve a higher rate of strength gain as well as a high final strength of the mortar and concrete
products even when cured at room temperature. As disclosed in US patent application # 2012/0152153 A1, the present
5 inventors find that optimal ratios of AAS and CSH gels can be obtained by appropriate proportioning of geopolymer
composite compositions, which will then result in ultrahigh performance of mortar and concrete products. The pozzolanic
materials that produce more CSH and/or related gels during alkali activation process are referred to as "hardening
enhancers," and are described in more detail below. Examples of these hardening enhancers are in general reactive
alkali-earth aluminosilicates including Class C fly ash, blast furnace slag, kiln dust, and vitreous calcium aluminosilicate
10 (VCAS).
[0058] Geopolymer composite binders offer a great flexibility in formulating cellular concrete compositions and the
properties of their pastes (e.g., set times, viscosity, workability) can be tailored for production of excellent cellular struc-
tures. Product density and strengths can be controlled to meet specific structural and nonstructural design requirements.
A typical ternary geopolymer composite binder consists of one Class F fly ash, at least one hardening enhancer such
15 as ground granulated blast furnace slag, and at least one gelation enhancer such as metakaolin. In particular, the present
invention provides compositions and methods of using mostly Class F fly ash or blast furnace slag to produce low cost,
high performance cellular concrete manufactured at room or slightly elevated temperatures but without applying pressure.

Class F Fly Ash

20
[0059] The first ingredient of the GCCC composition is a Class F fly ash, which is considered to be the main ingredient
in a typical geopolymer composite cellular concrete. Class F fly ash is a low cost waste product and readily accessible
worldwide. The classification of fly ash is based on ASTM C618, which is generally known in the art. One embodiment
of the geopolymer composite binder of the present invention comprises Class F fly ash in the amount of, at least about
25 10 wt.%, such as at least about 40 wt.%, such as at least about 60 wt.% of the dry mixture of a geopolymer composite
binder, for example 10 to 90 wt.% of the dry mixture, such as 50 to 80 wt.%. In one embodiment, the dry mixture contains
a maximum of about 90 wt.% of Class F fly ash.
[0060] A portion of the fly ash is an amorphous aluminosilicate phase (i.e., a glassy material), which is reactive in
strongly alkaline solutions. The magnitude of the portion can vary, depending on the origin of the fly ash material. The
30 reactivity of Class F fly ash can depend on the amount of the amorphous phase contained therein and on the particle
size of the fly ash. In one embodiment, the fly ash should contain at least 75 wt.% amorphous aluminosilicate phase
and have a particle diameter of 60 mm or less, such as 50 mm or less, such as 45 mm or less, such as 30 mm or less.
In one embodiment, Class F fly ash with up to 12 wt.% of loss on ignition (LOI) is used. In one embodiment, Class F fly
ash has a CaO (and, thus, Ca) content of less than 8 wt.%. In one embodiment, Class F fly ash has a CaO content of
35 about 8 to 15 wt.%.

Hardening enhancer

[0061] The second ingredient in the GCCC composition is the hardening enhancer, which can be less than about 80
40 wt.%, such as less than about 50 wt.%, such as less than about 25 wt.%, of the geopolymer composite binder. In one
embodiment, the hardening enhancer can be at least about 5 wt.% of the dry mixture of a geopolymer composite binder,
for example 5 to 80 wt.%, such as 10 to 25 wt.% of the dry mixture. A hardening enhancer is selected from the group
consisting of: ground granulated blast furnace slag, Class C fly ash, kiln dust, CaO-rich pozzolanic aluminosilicates,
vitreous calcium aluminosilicate (VCAS) and combinations thereof. These alkali-earth aluminosilicate pozzolans are
45 much more reactive than Class F fly ash - they dissolve more readily in alkaline solutions because most of these materials
are glassy. The greater reactivity of these components produces a higher concentration of ions, such as silicate, aluminate,
calcium hydroxide, which in turn react to produce a denser network of polymer chains (alkali or alkali-earth aluminosilicate)
and/or cementitious CSH and/or related gel/CASH phases, and, as a result, higher strength. The present inventors use
ground granulated blast furnace slag covered by ASTM C989 in geopolymer composite cellular concrete with grades of
50 at least 80, such as grade 100, such as grade 120.
[0062] Ultrafine furnace slag is more reactive than furnace slag grade 120. Ultrafine furnace slag usually has particle
sizes less than about 15 mm and a specific surface area of more than 800 m2/kg. An example of commercially available
ultrafine slag is MC-300 Micro-fine Cement from De Neef Construction Chemicals. Ultrafine furnace slag improves
workability and reduces the water demand. It reduces cracking due to autogenous and plastic shrinkage and ensures
55 excellent durability of the products.
[0063] Examples of calcium-rich pozzolanic materials are kiln dust, bottom ash, and vitreous calcium aluminosilicate
(VCAS). VCAS is a waste product of fiberglass production. In a typical glass fiber manufacturing facility, about 10-20
wt.% of the processed glass material is not converted into a final product and is rejected as a by-product or waste and

8
 EP 2 970 003 B1

sent for disposal to a landfill. VCAS is 100% amorphous and its composition is fairly constant, mainly containing 50-55
wt.% SiO2, 15-20 wt.% Al2O3, and 20-25 wt.% CaO. Ground VCAS exhibits pozzolanic activity comparable to silica fume
and metakaolin when tested in accordance with ASTM C618 and C1240. Therefore, it can be a very effective hardening
enhancer by forming additional cementitious compounds such as CSH and CASH gels. Cement Kiln Dust (CKD) is a
5 by-product of the manufacture of Portland cement, therefore an industrial waste. Over 30 million tons of CKD are produced
worldwide annually. Significant amounts of CKD are currently put into landfills. Typical CKD contains 38-64 wt.% CaO,
9-16 wt.% SiO2, 2.6-6.0 wt.% Al2O3, 1.0-4.0 wt.% Fe2O3, 0. -3.2 wt.% MgO, 2.4-13 wt.% K2O, 0.2.0 wt.% Na2O. 1.6-18
wt.% SO3, 0. -5.3 wt.% Cl, and 5.0-25 wt.% LOI. CKD is generally a very fine powder (4600-14000 cm 2/g specific surface
area) and is a good hardening enhancer. When CKD is used in a geopolymer composite binder for cellular concrete,
10 elevated concentrations of the alkali oxides contained in it enhance geopolymerization. Additional formation of CSH gel,
ettringite (3CaO·Al2O3·3CaSO4·32H2O), and/or syngenite (a mixed alkali-calcium sulfate) can help develop high early
strength of a geopolymer composite cellular concrete when cured at room temperature.

Gelation Enhancer
15
[0064] The third ingredient in a GCCC composition of the present invention is the gelation enhancer, which is less
than 85 wt.%, such as less than 50 wt.%, such as less than 25 wt.%, such as less than 15 wt.% of the dry mixture of
geopolymer composite binders. In one embodiment, the gelation enhancer is at least about 5 wt.% of the dry mixture of
a geopolymer composite binder, for example 3 to 80 wt.%, such as 10 to 25 wt.% of the dry composite binder mixture.
20 The gelation enhancer is selected from the group consisting of: metakaolin, metahalloysite, micron/submicron particles
of amorphous silica such as silica fume and alumina and pozzolanic aluminosilicate materials that have a low alkali-
earth oxide content and a high dissolution rate in alkaline solution.
[0065] Examples of other gelation enhancers include diatomaceous earth, micro-silica, which is a highly reactive
pozzolan processed from siliceous material from natural deposits, dehydrated clay minerals and various zeolite phases.
25 The pozzolanic materials should be much more reactive than Class F fly ash in alkaline solutions and thus produce
abundant AAS gel to support strength development.
[0066] One gelation enhancer that may be used in various embodiments of the present invention is metakaolin as it
is readily available and has a small particle size (∼5 mm). The rates of metakaolin dissolution and polymerization in an
alkaline solution can be high (i.e., from minutes to hours), and the water expelled during geopolymerization can help
30 improve the workability of the paste and enhance the hydration process of a hardening enhancer such as ground
granulated blast furnace slag.
[0067] The geopolymer composite binder dry mixture is mixed with an alkaline activator solution to form a paste for
cellular concrete. The present inventors have discovered that metakaolin increases or decreases the setting time of the
GCCC paste depending on the compositions of geopolymer composite binders for cellular concrete. Metakaolin favorably
35 extends the usually short set time of a GCCC composition containing a significant amount of furnace slag or Class C
fly ash or VCAS or kiln dust. In contrast, metakaolin also shortens the usually long setting times of GCCC compositions
high in Class F fly ash in the geopolymer composite binder. In addition, mixing metakaolin first with a hardening enhancer
such as furnace slag for at least 3 minutes can extend set times of the composite binder systems. In general, by including
metakaolin in the composite binder composition, initial setting of the paste for cellular concrete can be extended up to
40 1 hour or longer compared with paste without metakaolin.
[0068] The three ingredients described above, i.e., the Class F fly ash, the hardening enhancer and the gelation
enhancer, constitute the dry mixture of a ternary geopolymer composite binder composition for cellular concrete, totaling
100 wt.%.

45 Alkaline Activator

[0069] The fourth ingredient in a GCCC composition of the present invention is an alkaline activator. In addition to the
above mentioned geopolymer composite binder components, an alkaline activation solution ("alkaline activator") must
be added to the dry mixture of a geopolymer composite binder to form a complete GCCC composition. The alkaline
50 activator is in effect a solution of metal hydroxide and metal silicate. In one embodiment, the metal hydroxide used in
the process can be an alkali metal hydroxide. The metal in the metal hydroxide may be an alkali metal such as sodium
or potassium or both.
[0070] The metal silicate can be an alkali metal silicate and/or alkaline earth metal silicate. The alkali metals include
potassium and sodium. Alkali metal silicates, particularly sodium silicate solution, are desirable due to their relatively
55 low cost though potassium silicate has better performance such as decreasing significantly water demand in the GCCC
composition. Silica fume, a waste product from ferrosilicon industry is usually used to make the activation solution by
dissolving it in an alkali hydroxide solution. Commercially available water glass may be also used to prepare an alkaline
activator solution by dissolving it in alkali hydroxide solution. In one embodiment, sodium silicate with a mass ratio of

9
 EP 2 970 003 B1

SiO 2/Na2O (modulus) equal to about 2 to 3.2 may be used. In one embodiment, the sodium silicate solution may comprise
about 38 to 55 wt.% alkali silicate solids and about 45 to 62 wt.% water. Alternatively, alkali silicate glass powders can
be dissolved in an alkali hydroxide solution to prepare an alkaline activator. Examples of soluble alkali silicate glass
commercially available are SS® sodium silicate and Kasolv® potassium silicate from PQ Corporation.
5
Foaming agents

[0071] The fifth ingredient in a GCCC composition of the present invention is a foaming agent. Bubbles are made by
adding at least one foaming agent to the GCCC slurry usually near the end of the mixing process. The at least one
10 foaming agent comprises aluminum powder or a peroxide based foaming agent. Chemical reaction of a foaming agent
with the alkaline activator solution generates gas which forms bubbles (cells) and thus the cellular structure within the
geopolymer paste. Examples of foaming agents include aluminum powder, Fe-Si powders, zinc, hydrogen peroxide,
alkali peroxides such as sodium peroxide, alkali perborates, and alkali and alkali-earth hypochlorites such as sodium or
calcium hypochlorite.
15 [0072] Aluminum powder is used due to its efficiency in volumetric expansion and its low cost. The aluminum powder
has a particle size between 1 and 75 mm. Reaction of aluminum powder with alkaline solution in the GCCC composition
gives off hydrogen which expands the paste until a desirable volume is reached. Hydrogen is a volatile gas and is
replaced rapidly by air. Addition of aluminum powder may be from about 0.01 to about 0.5 wt.% of a GCCC composition
to produce geopolymer composite cellular concrete with a density ranging from about 500 to about 1800 kg/m3.
20 [0073] Peroxide-based foaming agents usually release oxygen bubbles when exposed to the alkaline solution in a
GCCC paste. Examples of peroxides include hydrogen peroxide, sodium peroxide, calcium peroxide, alkali perborate
such as sodium perborate, and the like. In one embodiment of the present invention, hydrogen peroxide solution may
be used due to its low cost and easy use. Concentrations of hydrogen peroxide can be about 5wt.% to 40 wt.% and 20
to 35 wt.%. Hydrogen peroxide solution is added in a range from about 0.01 wt.% to about 1.25 wt.% (calculated as
25 hydrogen peroxide) to a GCCC composition to produce geopolymer composite cellular concrete with a density ranging
from about 400 to about 1800 kg/m3.

Aggregate

30 [0074] One or more aggregates are added to improve final strength of geopolymer composite cellular concrete, for
structural applications. Structural lightweight concrete usually has an in-place density of 1440 to 1840 kg/m 3 compared
to normal weight concrete with a density of 2240 to 2400 kg/m3. For structural applications, the concrete strength should
be greater than 2500 psi (17 MPa). The primary use of structural lightweight concrete is to reduce the dead load of a
concrete structure and thus allow reduce the size of columns, footing and other load bearing elements. The lightweight
35 structural concrete should exhibit comparable or better mechanical and chemical durability than normal concrete. Struc-
tural lightweight concrete provides a higher strength-to-weight ratio resulting in lower overall costs, in particular when
geopolymer composite binders are used as in the present invention. Examples of aggregates include normal-weight fine
aggregates such as river sand or masonry sand, coarse and fine lightweight aggregates (meet ASTM Specification
C330). Examples of lightweight aggregates (LWA) include expanded slag, expanded slate, expanded shale, expanded
40 clay, expanded perlite, pumice, scoria, and expanded palletized fly ash. In one embodiment of the present invention,
lightweight aggregates with a density of about 50 kg/m3 to about 1000 kg/m3 may be used. Fine river sand is added to
improve the strength of a geopolymer composite cellular concrete Addition of lightweight aggregates instead of fine river
sand could further decrease the product density without decreasing the performance of the final product. High perform-
ance geopolymer composite cellular concrete for structural applications can be made simply by adding coarse and/or
45 fine lightweight aggregate without using a foaming agent.
[0075] Low density of about 1200 to about 1800 kg/m3 can be achieved by incorporating lightweight aggregates without
introducing additional air bubbles.
[0076] River sand or lightweight aggregates would be added to the GCCC composition in the range of about zero to
about 60 wt.%, such as about 0 to about 40 wt.%, such as about 20 to 50 wt.%.
50 [0077] While river sand or lightweight aggregate is not usually used for a GCCC composition for thermal insulation
applications with a density of from about 400 to about 1000 kg/m3, some lightweight fillers could be added if bubbles
are produced as well, e.g., by chemical reaction of a foaming agent with the alkaline solution. Use of these fine lightweight
particles as fillers in a GCCC composition can improve strength significantly while keeping the product density low.
Examples of lightweight filler particles include fine expanded perlite, cenosphere, and hollow glass particles and certain
55 organic particles such as expanded polystyrene. Use of these lightweight particles will further improve performance of
a geopolymer composite cellular concrete.
[0078] Perlite is a volcanic glass that shows relatively high water absorption and is typically formed by hydration of
obsidian. When the material reaches temperatures of 850-900 °C, water trapped in the structure of the material vaporizes

10
 EP 2 970 003 B1

and escapes. This causes the expansion of the material to 7-16 times its original volume. Unexpanded raw perlite has
a bulk density of about 1100 kg/m3 while expanded perlite has a bulk density of about 30-150 kg/m 3.
[0079] Cenosphere is a lightweight, inert, hollow sphere made largely of silica and alumina and filled with air or inert
gas, typically produced as a byproduct of coal combustion in power plants. The color of cenospheres varies from gray
5 to almost white and their density is about 0.4-0.8 g/cm3.
[0080] In some embodiments, one or more aggregates are added to the geopolymer composite dry mixture. In some
embodiments, one or more aggregates are added toward end of mixing when a homogeneous paste consistency is
obtained.

10 Paste modifiers

[0081] In some embodiments, paste modifiers may be needed. Viscosity and initial set time are two very important
properties of the pastes produced to make cellular structures. Ideally, a GCCC paste must have a viscosity that not only
prevents individual bubbles from coalescing (destabilization of cellular structure) but also from not rising. The initial set
15 time must be long enough for the paste to reach the intended volumetric expansion. Set times longer than necessary
may alter and deteriorate the cellular structure. The paste must harden when expansion is complete. In some embodi-
ments, one or more paste modifiers may be added to a GCCC composition to regulate paste properties for optimal
volumetric expansion and cellular structure stabilization.
[0082] In some embodiments with proper proportioning of a ternary binder composition and optimization of an alkaline
20 activator solution, a GCCC paste with appropriate paste properties for intended volumetric expansion and cellular struc-
ture stabilization can be obtained without use of any paste modifiers. However, in some embodiments having a high
content of a hardening enhancer such as ground granulated furnace slag one or more set retarders may be needed to
extend set times. Heat generated from reaction between a chemical foaming agent and the alkaline solution may shorten
the set time of a GCCC paste more than acceptable. If the paste becomes too thick too early, the intended volumetric
25 expansion will be incomplete and a set retarder must be used. Examples of set retarders include certain phosphate
compounds such as alkali metaphosphate, phosphoric acid, borax, boric acid, alkali citrates such as sodium citrate,
barium hydroxide, barium nitrate, barium chloride, zinc nitrate, and gypsum. In one embodiment of the present invention,
one or more set retarders may be added in an amount of less than about 5 wt.%. In one embodiment of the present
invention, one or more set retarders may be added in an amount of 0.1 to 2 wt.% of a GCCC composition. In one
30 embodiment of the present invention, sodium metaphosphate, borax and barium chloride may be used as set retarders.
While some set retarders such as barium chloride may be added to the alkaline activator solution together with dry
mixture of geopolymer composite binders, the present inventors find that the retarding effect is improved if sodium
metaphosphate or borax is dissolved in the alkaline activator solution prior to adding the composite binder.
[0083] In one embodiment where Class F fly ash is used as the main ingredient in a composite binder composition,
35 the GCCC paste may set very slowly resulting in destabilizing the cellular structure and low strength. One or more
accelerators may be included in the cellular concrete mix to obtain a GCCC paste with appropriate set time and viscosity
to obtain a stable cellular structure with high product strength. Examples of accelerators include but are not limited to
alkali fluorides such as sodium fluoride, calcium salts such as calcium chloride, alkali oxalates such as sodium oxalate,
and alkali sulfates such as sodium sulfate. In one embodiment of the present invention, one or more accelerators may
40 be added in a range of about 0 to 5 wt.%. In one embodiment of the present invention, one or more accelerators may
be added in a range of about 0.5 to 2.5 wt.% of the geopolymer composite dry mixture.
[0084] In some embodiments with high contents of hardening enhancers such as Class C fly ash, the cellular concrete
products may have unacceptably large shrinkage. In one embodiment of the present invention, one or more shrinkage
reducers may be added in an amount of about 0 to about 20 wt.% of the GCCC composition, In one embodiment of the
45 present invention, one or more shrinkage reducers may be added in an amount of 0 wt.% to about 10 wt,% of a GCCC
composition. Examples of shrinkage reducers include reactive MgO, gypsum, and commercially available shrinkage
reducing admixtures. Shrinkage reducers are usually mixed together with the geopolymer composite binder components.
[0085] In some embodiments, water reducers or superplasticizer solids may be used to not only decrease the amount
of water needed to prepare an alkaline activator solution for a GCCC composition but also to modify the paste viscosity.
50 Superplasticizer solids belong to a class of water reducers capable of reducing water content by about 30 % for Portland
cement based concretes. More recent superplasticizers include polycarboxylic compounds, such as polyacrylates, al-
though any superplasticizer known in the art may be used in the GCCC process.
[0086] In one embodiment of the present invention, superplasticizer solids may comprise about 0.0 to about 1 wt.%
of a GCCC composition. In one embodiment of the present invention, superplasticizer solids may comprise about 0.0
55 to about 0.5 wt.% of a GCCC composition. In one embodiment of the present invention, superplasticizer solids may
comprise about 0.0 to about 0.25 wt.% of a GCCC composition.

11
 EP 2 970 003 B1

Ultrafine and submicron fillers

[0087] In some embodiments, ultrafine and/or submicron fillers with a particle size ranging from about 0.05 to about
10 mm may be used to significantly improve rheological properties of a GCCC paste when little water is used. The present
5 inventors find that a GCCC composition with optimal or near optimal water-to-geopolymer solids ratio exhibits a char-
acteristic progression of stages, i.e., visual characteristics while mixing is never interrupted. The mix initially assumes
a sand- or granule-like structure, suggesting deficiency in water. After having added ultrafine or submicron filler particles
the mix assumes a dough-like structure, which turns into a homogeneous, lump-free paste while one or more foaming
agents are added. After pouring the paste into one mold, the paste undergoes volumetric expansion assuming a homo-
10 geneous, cellular structure eventually.
[0088] Examples of ultrafine or submicron fillers include silica fume, precipitated silica, ultrafine fly ash (UFFA), ultrafine
blast furnace slag (UBFS) and submicron calcium carbonate with silica fume being one material that may be used. UFFA
is a product processed by mechanically separating an ultrafine fraction with a mean particle size of about 1 to 10 mm
from the parent fly ash. Silica fume is the most readily available submicron material, which is a by-product of Fe-Si
15 metallurgy. It appears gray in color due to a few percentage of unburnt carbon. White silica fume contains almost no
carbon, but silicon, e.g., from Elkon Products Inc. Preliminary tests conducted by the present inventors show that addition
of only a few weight percent of white silica fume to a GCCC composition can result in a volumetric expansion up to 50%.
Therefore, while the white silica fume functions as submicron filler, it is also an efficient foaming agent. Coal gasification
fly ash is discharged from respective power stations. This fly ash is usually a Si02-rich material consisting mainly of
20 spherical particles with a maximum particle size of about 5 to 10 mm. Thus, coal gasification fly ash is also a suitable filler.
[0089] In one embodiment, the ultrafine and submicron filler may comprise from 1 to about 12 wt.% of a GCCC
composition. In one embodiment, the ultrafine and submicron filler may comprise from about 1 to about 5 wt.% of a
GCCC composition

25 Fibers for Reinforcement

[0090] Optionally, fiber can be added to a GCCC composition up to about 5 wt.%, such as up to about 2.5 wt.%, such
as up to about 1 wt.%, such as up to 0.5 in order to improve flexural strength of cellular concrete products. Addition of
short fibers may also enhance stabilization of the cellular structure during volumetric expansion. Fibers include organic
30 fibers (e.g., polyvinyl alcohol fibers and polyacrylonitrile fibers); glass fibers (e.g., basalt fibers); and carbon fibers.
[0091] A process for the manufacture of geopolymer composite cellular concrete comprises the following steps:

a. Premixing ternary geopolymer composite binder components, shrinking reducers if any, river sand if any, fibers
if any, and lightweight aggregate if any
35 b. Mixing the blend of composite binder components with at least one alkaline activator solution, which comprises
water, alkali hydroxide, alkali silicate, set retarder if any, accelerator if any, and superplasticizer if any.
c. Adding ultrafine and/or submicron particles, if any, during mixing
d. Adding at least one foaming agent near the end of mixing
e. Pouring the mixture of step (d) into a mold and allowing it to foam, expand, set, and harden
40 f. Removing the hardened body from the mold
g. Optionally cutting and shaping the hardened body
h. Curing the geopolymer composite cellular concrete products at room temperature or at higher temperatures

[0092] The dry constituents described above, except for the micron/submicron filler are premixed in an appropriate
45 mixer, such as an intensive mixer. Then, the alkaline activation solution, together with the superplasticizer (if any) and/or
accelerator (if any), are poured into the dry mixture and mixed. In some embodiments, retarding compounds such as
barium chloride, borax and sodium metaphosphate are dissolved in the alkaline activator solution before mixing with the
geopolymer composite dry mixture. The foaming agent is added near the end of the mixing process. The volumetric
expansion decreases the density of the not-foamed product about 1.25 to about 4.0 times.
50
Constraining Parameters

[0093] Constraining parameters are defined as either molar ratios or mass fractions and their ranges. Constraining
parameters can be used to define certain non-limiting formulations of geopolymer composite cellular concrete composition
55 for thermal insulation and structural applications. The constraining parameters are set for the specific ingredients used
in the geopolymer composite binder compositions.
[0094] The constraining parameters for metakaolin as a gelation enhancer include a set of molar ratios of SiO2/Al2O3,
M2O/Al2O 3, and H2O/M2O, where M represents alkali metals (Na, K, Li) or alkali-earth metals (Ca, Mg). The molar

12
 EP 2 970 003 B1

SiO 2/Al2O3 ratio in metakaolin is about 2. Alkali hydroxide and alkali silicate are added to the solution to obtain the
required values for the molar ratios characteristic of a metakaolin based AAS gel. For example, the SiO 2/Al2O3 molar
ratio in the AAS gel ranges from about 2.5 to 6.0, such as 3.0 to 4.0; M2O/Al2O3 ranges from about 0.7 to 1.5, such as
from 0.9 to 1.25; and H2O/M2O ranges from about 5 to 18, such as from about 6 to 10.
5 [0095] The constraining parameters for Class F fly ash (as a main ingredient), Class C fly ash, VCAS, kiln dust, or
blast furnace slag (as a hardening enhancer) require a set of mass fractions of M2O, SiO2, H2O and molar ratio SiO2/M 2O
that are used to formulate an activation solution. Mass fractions of M2O or SiO2 of the pozzolanic materials, either as a
main ingredient or a hardening enhancer can range from about 0.01 to 0.15, such as about 0.04 to 0.075. The molar
SiO 2/M2O ranges from about 0.2 to 2.5, such as about 0.5 to 1.8, such as 1.0 to 1.8. The mass fraction of H2O of the
10 main ingredient or a hardening enhancer can range from about 0.20 to 0.50, such as from about 0.25 to 0.30. Alkali
metals can be Na, K, or Li, and Na in particular can be used to save costs. The amounts of alkali hydroxide, alkali silicate,
and water needed for each geopolymer composite binder component are summed up to formulate a GCCC activation
solution composition.
[0096] The water-to-geopolymer solids mass ratio (w/c) is a key parameter for a GCCC composition. As used herein,
15 the term "geopolymer solids" is defined as the sum of the masses of reactive constituents in the composite binder (i.e.,
Class F fly ash, hardening enhancer and gelation enhancer) and masses of alkali oxide and silicon dioxide dissolved in
the alkaline activator solution. The w/c ratio is determined by a set of constraining parameters such as the molar ratio
H2O/M2O for metakaolin, mass fraction of H2O for Class F fly ash and reactive alkali-earth aluminosilicate as hardening
enhancer, and whether and how much superplasticizer and/or ultrafine and/or submicron filler is applied. In some em-
20 bodiments for structural applications, masonry sand with moisture absorption of about 2.5 wt.% is used as a fine aggregate.
If the moisture content of the fine aggregate deviates from about 2.5 wt.%, the GCCC composition must be corrected
to comply with a prescribed w/c. In some embodiments where hydrogen peroxide is applied as a foaming agent, the mix
must be corrected taking into account of H2O in H2O2 (e.g. 35 wt.% H2O2 in H2O). Typically, w/c ratios in GCCC
compositions range from about 0.20 to 0.55, such as about 0.30 to 0.45.
25 [0097] The water-to-geopolymer solids mass ratio (w/c) determines almost exclusively the viscosity of a GCCC paste.
A good GCCC paste should not be so thin that bubbles coalesce and rise to the surface and not so thick that volumetric
expansion is not optimal. A superplasticizer reduces the demand of water and decreases the plastic viscosity such that
volumetric expansion can take place. Addition of an ultrafine and/or submicron filler tends to decrease the plastic viscosity
and yield stress while reducing water demand. However, addition of an accelerator may render the paste thicker. Another
30 important property of a GCCC paste is set times. The present inventors find that a right GCCC paste should have an
initial set time of about 30 to about 90 min. The flexibility of the geopolymer composite binder compositions according
to one embodiment of the present invention offers a great opportunity to design cellular concrete mixes with ideal paste
properties. Additions of set retarders and other admixtures such as an accelerator, a superplasticizer, ultrafine and/or
submicron filler also help obtain an optimal paste for cellular concrete.
35 [0098] The present inventors have developed a procedure, which they use to determine whether a GCCC composition
has a right paste for high strength cellular concrete. A GCCC composition with optimal or near optimal w/c ratio exhibits
a characteristic progression through various stages under continued intensive mixing. The mix initially develops a sand-
or granule-like consistency. With continued mixing after adding ultrafine or submicron filler particles the sand- or granule-
like mixture assumes a dough-like consistency, which turns into a homogeneous paste when metal powder is added
40 toward the end of mixing. The sand- or granule-like particles are about 0.5 to about 2 cm thick. Alternatively, if 35%
hydrogen peroxide solution is used as a foaming agent, then this is usually added toward the end of mixing. In one
embodiment of the present invention the ideal particle size should be less than 1 cm. In one embodiment of the present
invention the ideal particle size should be less than about 0.5 cm. The water contained in hydrogen peroxide solution
will render the sand-or granule-like consistency into a homogeneous paste with the right viscosity for optimal bubble
45 formation and stable cellular structure. When hydrogen peroxide solution is used as a foaming agent, ultrafine and/or
submicron filler may not be needed.
[0099] Table 1 below shows constraining parameters used to formulate alkaline activator solutions for GCCC compo-
sitions.

50 Table 1
Constraints and preferred ranges for alkaline activator solution
Constituents Ratio Range Preferred Range
H2O/FFA 0.20-0.40 0.25-0.30
55
Class F fly ash (Mass ratio) SiO2/FFA 0.04-0.10 0.05-0.08
M2O/FFA (M= K, Na, or both) 0.04-0.15 0.05-0.08

13
 EP 2 970 003 B1

(continued)

Constraints and preferred ranges for alkaline activator solution

Constituents Ratio Range Preferred Range
5
H2O/HDE 0.20-0.40 0.25-0.30
Hardening enhancer (Mass ratio) SiO2/HDE 0.02-0.10 0.04-0.08
M2O/HDE (M= K, Na, or both) 0.02-0.10 0.04-0.08
10 SiO2/Al2O3 3.0-5.0 3.5-3.9
Gelation enhancer (Molar ratio) M2O/Al2O3 0.70-1.50 0.90-1.25
H2O/M2O (M=K, Na, or both) 5-18 6-10
* HDE = Hardening enhancer
15

[0100] Table 2 shows constituents and their proportions for GCCC recipes to make products for thermal insulation,
disclosed but not claimed.

20 Table 2
Constituents and their preferred proportions in GCCC composition for thermal insulation applications, disclosed but
not claimed
Type of materials Constituents Range I (wt.%) Range II (wt.%)
25 Class F fly ash 2 - 60 10 - 50
Composite binder Hardening enhancer 2 - 60 10 - 50
Gelation enhancer 2 - 60 3 - 25
M2O (M =K, Na, or both) 2 - 12 4-8
30
Alkaline activator SiO2 2 - 15 6 - 10
Water 10 - 30 15 - 22
Ultrafine and/or submicron filler 0 - 12 0-2
35 Fine lightweight aggregate 0 - 50 0 - 20
Shrinkage reducer 0 - 10 0 - 5.0
Al powder 0.01 - 0.50 0.025 - 0.25
Foaming agent*
Hydrogen peroxide (35 wt.%) 0.10 - 3.00 0.25 - 2.00
40
Accelerator 0-5 0 - 2.5
Paste modifiers
Set retarder 0-5 0.5 - 2.0
Superplasticizer solids 0-2 0 - 0.5
45 Chopped fiber 0-5 0.25 - 2.5
Sum 100 100
* 35 wt.% hydrogen peroxide is usually used as an example. Hydrogen peroxide solutions with other concentrations
can be used. Higher weight percentages are required for the same density if other foaming agents are used, such as
50 alkali peroxide and alkali hypochlorites.

[0101] Table 3 shows constituents and their proportions for GCCC recipes to make products for structural applications
according to the present invention.
55

14
 EP 2 970 003 B1

Table 3
Constituents and their preferred proportions in GCCC compositions for structural applications according to the
invention
5
Materials Constituents Range I (wt.%) Range II (wt.%)
Class F fly ash 1- 50 10 - 30
Composite binder Hardening enhancer 1 - 50 10 - 35
10 Gelation enhancer 1 - 50 8 - 25
M2O (M =K, Na, or both) 2 - 12 3.5 - 8
Alkaline activator SiO2 2 - 15 3.5 - 8
Water 6 - 25 8 - 16
15
Shrinkage reducer 0 - 10 0 - 5.0
Ultrafine and/or submicron filler 0 - 12 2-5
River sand 0 - 60 20 -50
Aggregate
20 Lightweight aggregate 0 - 40 0 - 25
Al powder 0.01 - 0.50 0.02 -0.15
Foaming agent**
Hydrogen peroxide* 0.01 - 2.00 0.25 -1.25
Accelerator 0-5 0 - 2.5
25
Paste modifiers Set retarder 0-5 0.5 - 2.0
Superplasticizer solids 0-2 0.25 - 0.50
Chopped fiber** 0-5 0.25 - 0.5
30
Sum 100 100
* Assume 35 wt.% hydrogen peroxide. Optimal weight percentages of other types of foaming agents can be determined
by trial testing.

35
[0102] In one embodiment of the present invention, molar concentrations of alkaline hydroxide (e.g., KOH and NaOH)
in alkaline activator solutions are in the range from about 3 to 15 M. In one embodiment of the present invention, molar
concentrations of alkaline hydroxide in alkaline activator solutions are in the range from about 5 to 10 M. The moisture
present in the aggregate (if any) and the water in a foaming agent (i.e., in 35 wt.% hydrogen peroxide solution) are
included in the above calculations.
40
[0103] Provided herein is a general approach to obtain an applicable formulation for a GCCC composition. In one
embodiment, the dry mixture of a geopolymer composite comprises three ingredients, as described above. The sum of
these three ingredients is 100 wt.%. Then masses of the composite binder ingredients are set in desired proportions.
The composition of an activation solution is formulated based on a set of constraining parameters and their respective
ranges for each geopolymer composite binder component (e.g., Class F fly ash, gelation enhancer and hardening
45
enhancer) by summing up the needed amounts of alkali hydroxide, dissolved silica, and water. When the weight per-
centages of foaming agent, set retarder if any, accelerator if any, ultrafine and/or submicron filler if any, aggregate if
any, and fiber if any are determined, respectively, in a GCCC composition, the compositions of the dry binder and the
activation solution are re-normalized so that the total of the dry binder, the activation solution and the additional com-
ponents amount to 100 wt.%.
50
[0104] Manipulation of the composite constituent proportions within their ranges (see, e.g., Tables 1-3) and subsequent
testing allow for optimization of a GCCC composition in terms of paste properties for optimal volume expansion, stable
cellular structure, rapid growth of strength and high final strength after curing at room temperature. GCCC compositions
according to one embodiment of the present invention may be cured at elevated temperatures.
[0105] Initial set times for GCCC compositions according to one embodiment of the present invention range between
55
about 0.25 to about 3 hours, such as about 0.5 to 1 hour. After the composition sets, it is cured for 24 hours, such as
24 hours to one week or longer, at a curing temperature between about 20 °C and about 75 °C. Specific set times can
be obtained by adjusting binder and filler compositions, e.g., by selecting binder and filler compositions with different

15
 EP 2 970 003 B1

reactivity in alkaline solutions, or by other methods known in the art such as adding a retarding compound.
[0106] In one embodiment of a GCCC composition of the present invention that includes one or more aggregates, the
one or more aggregates may have a particle size of about 0.025 to about 10 mm, and wherein the one or more aggregates
comprise about 5 to 70 wt.% of the GCCC composition. In one embodiment of a GCCC composition of the present
5 invention that include one or more lightweight aggregates, the one or more lightweight aggregates may have a particle
size of about 0.025 and 20 mm, and wherein the one or more lightweight aggregates comprise about 5 to 50 wt.% of
the GCCC composition.
[0107] In one embodiment of a GCCC composition of the present invention that includes one or more fine lightweight
aggregates that comprise about 1 to about 25 wt.% of the GCCC composition.
10 [0108] In one embodiment of a GCCC composition of the present invention that includes one or more set retarders,
the one or more set retarders may comprise about 0.05 to about 5 wt.% of the GCCC composition. In one embodiment
of a GCCC composition of the present invention that include set retarders, the one or more set retarders may comprise
about 0.5 to 2 wt.% of the GCCC composition.
[0109] In one embodiment of a GCCC composition of the present invention that includes one or more fiber materials,
15 the one or more fiber materials may comprise about 0.1 to about 5 wt.% of the GCCC composition. In one embodiment
of a GCCC composition of the present invention that includes one or more fiber materials, the one or more fiber materials
may comprise about 0.25 to about 2.5 wt.% of the GCCC composition.
[0110] In one embodiment of a GCCC composition of the present invention that includes one or more submicron fillers,
the one or more submicron fillers may comprise about 2 to about 5 wt.% of the GCCC composition. In one embodiment
20 of a GCCC composition of the present invention that includes one or more submicron fillers, the one or more submicron
fillers may comprise about 2 to about 5 wt.% of the GCCC composition.
[0111] In one embodiment of a GCCC composition of the present invention that includes one or more superplasticizer
solids, the one or more superplasticizer solids may comprise 0.01 to about 1 wt.% of the GCCC composition.
[0112] The foregoing description of the embodiments of the invention has been presented for purposes of illustration
25 and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications
and variations are possible in light of the above teaching or may be acquired from practice of the invention. The embod-
iments have been chosen and described in order to explain the principles of the invention and as a practical application
to enable one skilled in the art to utilize the invention in various embodiments and with various modifications suited to
the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto.
30
EXAMPLES

[0113] In the following examples, all the GCCC pastes were cured at room temperatures, e.g., at about 20 °C, except
where other curing temperatures are specified.
35 [0114] Masonry sand from Aggregates Industries was used as fine aggregate, which has a particle size between 50
and 600 mm with a median size of about 250 mm. The moisture in the fine aggregate was about 2.5 wt.% at room
temperature. The moisture in the fine aggregate was included to calculate molar concentrations of alkali hydroxide and
water to geopolymeric solids ratio. wt.%
[0115] Metakaolin (Kaorock) was from Thiele Kaolin Company, Sandersville, GA. The metakaolin had a particle size
40 between 0.5 and 50 mm with 50 vol.% less than 4 mm.
[0116] Ground granulated blast furnace slag grade 120 (NewCem Slag cement) was from Lafarge, North America Inc.
(Baltimore Terminal). The furnace slag had a particle size between 0.5 to 60 mm, with 50 vol.% less than 7 mm.
[0117] Silica fume, an industrial waste product from Fe-Si alloying, was from Norchem Inc. The silica fume contained
2.42 wt.% carbon. The silica fume was used to prepare alkaline activator solutions by dissolving silica fume in alkali
45 hydroxide solution, or added as submicron filler.
[0118] Commercially available sodium silicate solution (Ru™ sodium silicate solution, PQ Corp) was used to prepare
an alkaline activator solution. The sodium silicate solution contained about 14 wt.% Na2O, 33 wt.% SiO 2 and 53 wt.% water.
[0119] One Class F fly ash from Brandon Shores Power Station, Baltimore, MD, was from Separation Technologies
LLC. The Brandon Shores fly ash had lower CaO (0.9 wt.%) and a low loss on ignition (<1.5 wt.%) and was marketed
50 under the name ProAsh. The Brandon Shores fly ash had a particle size between 0.6 and 300 mm with 50 vol.% below
26 mm. Another Class F fly ash from SEFA Group (South Carolina, USA) was produced by a thermal beneficiation
process. The fly ash contained about 1.5 wt.% CaO and had a particle size between 0.5 and 300 mm with 50 vol.%
below 15 mm. Yet another fly ash was Orland fly ash from Headwaters Incorporation. The fly ash had a very high loss
on ignition, e.g., 7 to 9 wt.%.
55 [0120] Synthetic polypropylene fibers (20 mm in length) from Grace Construction Products were used for reinforcement.
[0121] Compressive strength was measured on a Test Mark CM-4000-SD compression machine. During testing, all
cylindrical samples were capped with compression caps from Delauriers, Inc.
[0122] The foaming agent, accelerator, set retarder, chopped fiber, and superplasticizer solids if any are not included

16
 EP 2 970 003 B1

in a GCCC formulation given in the examples below. These components were weighed in the amount of wt.% of a GCCC
formulation. Adding them to the other solids yielded the final GCCC composition (not shown in the examples). The water
in the hydrogen peroxide solution is part of a GCCC formulation.

5 Example 1

[0123] KOH (assay 90%) and NaOH (assay 99%) were dissolved in tap water to make alkaline solution using a
mechanical stirrer. Silica fume from Norchem Inc. was then dissolved in the KOH and/or NaOH solution under stirring.
The alkaline activator solution was black due to undissolved carbon. The alkaline activator solution was aged for up to
10 7 days before sample preparation.
[0124] To prepare the GCCC for structural applications, the following constituents were mixed dry:

Brandon Shore Class F fly ash (10.00 wt.%)

15 Metakaolin as gelation enhancer (5.64 wt.%),

Ground granulated blast furnace slag as hardening enhancer (14.55 wt.%),

Masonry sand as fine aggregate (50.00 wt.%) and

20
Synthetic polypropylene fiber (0.5 wt.%).

[0125] Then, the alkaline activator solution was prepared by mixing:

25 Na2O (1.36 wt.%) as NaOH,

K2O (3.08 wt.%) as KOH,

SiO2 (3.92 wt.%) as silica fume, and

30
H2O (9.45 wt.%).

[0126] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume (2 wt.%) as submicron filler was added under continued
35 mixing for another 3 minutes. 1 minute before end of mixing, aluminum powder (20 mm median size, 0.05 wt.% of the
GCCC composition) was added as a foaming agent. The paste was poured in 3"36" cylindrical molds, allowed to expand
and fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored
at room temperature. After curing for 28 days, the apparent density was determined to be 1403 kg/m3 and compressive
strength was measured to be 3637 psi or 25.08 MPa (Sample # 1, Table 4).
40 [0127] Additional GCCC samples were prepared with the same composition and procedure described in Example 1
wt.%but varying the amount of aluminum powder (20mm median size). The wt.%aluminum powder concentration, the
apparent density and the compressive strength of the additional samples are shown in Table 4.

Table 4
45
Compressive
Sample Al powder (wt.%) Mixing of Al Fiber (wt.%) Density (kg/m3) strength
psi MPa
#1 0.025 1 min 0.5 1403 3637 25.08
50
#2 0.010 1 min 0.5 1614 6509 44.88
#3 0.075 1 min 0.5 1235 2234 15.40
#4 0.015 1 min 0.5 1723 6269 43.22
55 #5 0.020 1 min 0.5 1493 2898 19.98
#5a 0.05 1 min 0.5 1201 2979 20.54

17
 EP 2 970 003 B1

Example 2

[0128] To prepare the GCCC for structural applications, the following constituents were first mixed dry:

5 Brandon Shore Class F fly ash (16.00 wt.%)

Metakaolin as gelation enhancer (9.92 wt.%),

Ground granulated blast furnace slag as hardening enhancer (25.60 wt.%),

10
Masonry sand as fine aggregate (20.00 wt.%) and

Synthetic polypropylene fiber (0.5 wt.%)

15 [0129] Then, the alkaline activator solution was prepared by mixing:

Na2O (1.94 wt.%) as NaOH,

K2O (3.90 wt.%) as KOH,

20
SiO2 (6.63 wt.%) as silica fume, and

H2O (14.00 wt.%)

25 [0130] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume (2 wt.%) as submicron filler was added under continued
mixing for another 3 minutes. 1 minute toward before end of mixing, aluminum powder (20 mm median size, 0.08 wt.%
of the GCCC composition) was added. The paste was poured in a 3"x6" cylindrical mold, allowed to expand and fill the
mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room
30 temperature. After curing for 28 days, the apparent density was determined to be 1202 kg/m3 and compressive strength
was measured to be 3159 psi or 21.78 MPa (Sample#6).

Example 3 (Comparative)

35 [0131] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry:

Brandon Shore Class F fly ash (16.00 wt.%)

40 Metakaolin as gelation enhancer (9.92 wt.%),

Ground granulated blast furnace slag as hardening enhancer (25.60 wt.%),

Masonry sand as fine aggregate (20.00 wt.%) and

45
Synthetic polypropylene fiber (0.3 wt.%).

[0132] Then, the alkaline activator solution was prepared by mixing:

50 Na2O (1.94 wt.%) as NaOH,

K2O (3.90 wt.%) as KOH,

SiO2 (6.63 wt.%) as silica fume, and

55
H2O (14.00 wt.%).

[0133] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer

18
 EP 2 970 003 B1

(20L K-Lab Mixer from Lancaster Products). Then, silica fume (2 wt.%) as submicron filler was added under continued
mixing for another 3 minutes. 1 minute toward ending of mixing, aluminum powder (20 mm median size, 0.15 wt.% of
the GCCC composition) was added. The paste was poured in a 3"36" cylindrical mold, allowed to expand and fill the
mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room
5 temperature. After curing for 28 days, the apparent density was determined to be 880 kg/m3 and the compressive strength
was measured to be 1282 psi or 8.84 MPa (Sample #7, Table 5).
[0134] Additional GCCC samples were prepared with the same composition and procedure in Sample 7 but with
different wt.%amounts of aluminum powder as well as different median particle sizes. The wt.%aluminum powder con-
centration, the Al particle size, the apparent density and the compressive strength of the additional samples are shown
10 in Table 5.

Table 5
Compressive
Sample Al powder(wt. %) Al median size Fiber (wt. %) Density (kg/m3) strength
15
psi MPa
#7 0.15 20 mm 0.3 880 1282 8.84
#8 0.25 20 mm 0.3 839 1120 7.72
20 #9 0.25 20 mm 0.0 788 582 4.01
#10 0.35 20 mm 0.3 774 812 5.60
#11 0.30 9 mm 0.0 680 461 3.18
#12 0.30 35 mm 0.0 770 679 4.68
25
#13 0.30 20 mm 0.0 817 697 4.81

Example 4 (Comparative)
30
[0135] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry:

Brandon Shore Class F fly ash (10.00 wt.%)

35
Metakaolin as gelation enhancer (5.64 wt.%),

Ground granulated blast furnace slag as hardening enhancer (14.55 wt.%), and

Masonry sand as fine aggregate (50.00 wt.%).

40

[0136] Then, the alkaline activator solution was prepared by mixing:

Na2O (1.36 wt.%) as NaOH,

45
K2O (3.08 wt.%) as KOH,

SiO2 (3.92 wt.%) as silica fume, and

H2O (9.45 wt.%).

50

[0137] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume (2 wt.%) as submicron filler was added and continued
mixing for another 3 minutes. 1 minute before end of mixing, aluminum powder (20 mm median size, 0.08 wt.% of the
GCCC composition) was added. The paste was poured in a 3"36" cylindrical mold, allowed to expand and fill the mold,
55
and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room temperature.
After curing for 28 days, the apparent density was determined to be 1098.35 kg/m3 and the compressive strength was
measured to be 1537 psi or 10.64 MPa (Sample #14).

19
 EP 2 970 003 B1

Example 5 (Comparative)

[0138] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry:
5
Brandon Shore Class F fly ash (12.50 wt.%)

Metakaolin as gelation enhancer (11.58 wt.%),

10 Ground granulated blast furnace slag as hardening enhancer (12.50 wt.%),

Masonry sand as fine aggregate (12.50 wt.%) and

Synthetic polypropylene fiber (0.3 wt.%).

15
[0139] Then, the alkaline activator solution was prepared by mixing:

Na2O (5.42 wt.%) as NaOH,

20 K2O (0.47 wt.%) as KOH,

SiO2 (7.79 wt.%) as silica fume, and

H2O (17.85 wt.%).

25
[0140] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume as submicron filler (2 wt.%) was added under continued
mixing for another 3 minutes. 1 minute before end of mixing, aluminum powder (20 mm median size, 0.05 wt.% of the
GCCC composition) was added. The paste was poured in a 3"36" cylindrical mold, allowed to expand and fill the mold,
30 and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room temperature.
After curing for 28 days, the apparent density was determined to be 910 kg/m3 and the compressive strength was
measured to be 1712 psi or 11.80 MPa (Sample #15).

Example 6 (Comparative)
35
[0141] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry:

Brandon Shore Class F fly ash (19.00 wt.%)

40
Metakaolin as gelation enhancer (13.13 wt.%),

Ground granulated blast furnace slag as hardening enhancer (33.89 wt.%), and

45 Synthetic polypropylene fiber (0.3 wt.%).

[0142] Then, the alkaline activator solution was prepared by mixing:

Na2O (5.37 wt.%) as NaOH,

50
K2O (1.00 wt.%) as KOH,

SiO2 (8.76 wt.%) as silica fume, and

55 H2O (16.85 wt.%).

[0143] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume (2 wt.%) as submicron filler was added under continued

20
 EP 2 970 003 B1

mixing for another 3 minutes. 1 before end of mixing, aluminum powder (20 mm median size, 0.25 wt.% of the GCCC
composition) was added. The paste was poured in a 3"’36" cylindrical mold, allowed to expand and fill the mold, and
subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room temperature.
After curing for 28 days, the apparent density was determined to be 730 kg/m 3 and the compressive strength was
5 measured to be 831 psi or 5.73 MPa (Sample #16).

Example 7 (Comparative)

[0144] To prepare the GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
10 were first mixed dry:

Brandon Shore Class F fly ash (18.66 wt.%)

Metakaolin as gelation enhancer (12.89 wt.%),

15
Ground granulated blast furnace slag as hardening enhancer (33.27 wt.%), and

Synthetic polypropylene fiber (0.03 wt.%).

20 [0145] Then, the alkaline activator solution was prepared by mixing:

Na2O (5.28 wt.%) as NaOH,

K2O (0.98 wt.%) as KOH,

25
SiO2 (8.60 wt.%) as silica fume, and

H2O (18.35 wt.%).

30 [0146] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume (1.96 wt.%) as submicron filler was added under continued
mixing for another 3 minutes. 1 minute before end of mixing, aluminum powder (20 mm median size, 0.15 wt.% of the
GCCC composition) was added. The paste was poured in a 3"36" cylindrical mold, allowed to expand and fill the mold,
and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room temperature.
35 After curing for 28 days, the apparent density was determined to be 790 kg/m3 and the compressive strength was
measured to be 1132 psi or 7.80 MPa (Sample #17).

Example 8 (Comparative)

40 [0147] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry:

Brandon Shore Class F fly ash (11.90 wt.%) and

45 Ground granulated blast furnace slag as hardening enhancer (54.21 wt.%).

[0148] The alkaline activator solution (modulus ∼1.65) was prepared by mixing sodium hydroxide solution and Ru™
sodium silicate solution (PQ Inc) such that the following concentrations were obtainedin the GCCC composition:

50 Na2O (4.96 wt.%)

SiO2 (7.93 wt.%), and

H2O (20.00 wt.%).

55
[0149] The alkaline activator solution was mixed with the premixed dry constituents for 3 minutes in an intensive mixer
(20L K-Lab Mixer from Lancaster Products). Then, silica fume as submicron filler was added under continued mixing
for another 3 minutes. 1 minute before end of mixing, aluminum powder (20 mm median size, 0.25 wt.% of the GCCC

21
 EP 2 970 003 B1

composition) was added. The paste was poured in 3"x6"cylindrical molds and allowed to expand and fill the mold and
subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored at room temperature.
After curing for 28 days, the apparent density was determined to be 597.3 kg/m3 and the compressive strength was
measured to be 870 psi or 6.0 MPa (Sample# 18, Tables 6 and 7).
5 [0150] Additional samples were prepared in the similar way but the paste was poured in 4"34"316" beam molds
instead and allowed to expand, and subsequently cured at room temperature. After 7 days, the samples were de-molded
and were sawed wet into 4" cubes. After drying for 3 days in ambient environment, the apparent density and compressive
strength were measured (Sample# 19-21, Tables 6 and 7 below).

10 Table 6
GCCC Composition (wt.%)
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#18 11.90 0.00 54.21 1.00 7.93 4.96 20.00 100.00
15
#19 13.35 0.00 53.39 1.00 8.01 5.01 19.25 100.00
#20 20.17 0.00 47.06 1.00 7.89 4.93 18.95 100.00
#21 13.35 0.00 53.39 1.00 8.01 5.01 19.25 100.00
20

Table 7
Compressive
Sample Retarder (wt.%) Al (wt.%) Fiber (wt.%) W/C NaOH (M) Density (kg/m3) strength
25
psi MPa
#18 None 0.25 0.40 0.25 8.00 777 1595 11.00
#19 None 0.15 0.15 0.24 8.39 725 415 2.86
30 #20 None 0.175 0.30 0.24 8.39 733 ND ND
#21 None 0.145 0.00 0.24 8.39 ND ND ND
ND = Not determined

35
Example 9 (Comparative)

[0151] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following constituents
were first mixed dry in an intensive mixer (20L K-Lab Mixer from Lancaster Products):
40
Brandon Shore Class F fly ash (13.69 wt.%)

Ground granulated blast furnace slag as hardening enhancer (54.75 wt.%), and

45 Additional synthetic polypropylene fiber (0.3 wt.% of the GCC mix).

[0152] Then, an alkaline activator solution (modulus ∼1.6) was prepared by mixing sodium hydroxide solution powder
in Ru™ sodium silicate solution (PQ Inc) such that the following concentrations were obtained in the GCCC composition:

50 Na2O (5.13 wt.%) as NaOH,

SiO2 (8.21 wt.%) as silica fume, and

H2O (17.19 wt.%).

55
[0153] Borax as a set retarder was dissolved in the alkaline activator solution in the amount of 1.00 wt.% of the GCCC
composition. The alkaline activator solution with borax was mixed with the pre-blended dry mixture in an intensive mixer
(20L K-Lab Mixer from Lancaster Products) for 3 min.

22
 EP 2 970 003 B1

[0154] Then, silica fume (1.03 wt.%) as submicron filler was added under continued mixing for another 3 minutes. 45
seconds before end of mixing, 35% hydrogen peroxide solution was added as a foaming agent into the mixture in the
amount of 1.75 wt.% of the GCCC composition. The paste was poured in a 3"36" cylindrical mold, allowed to expand
and fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored
5 at room temperature. After curing for 28 days, the apparent density was determined to be 777 kg/m3 and the compressive
strength was measured to be 1595 psi or 11.00 MPa (Sample #22, Tables 8 and 9).
[0155] Additional GCCC samples were prepared with similar compositions and preparation procedures as used in
Sample #22. Compositions,, apparent densities and compressive strengths of the additional samples (#22 to #25) are
given in Tables 8 and 9.
10
Table 8
GCCC composition (wt.%)
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
15 #22 13.69 0.00 54.75 1.03 8.21 5.13 17.19 100.00
#23 13.58 0.00 54.32 1.02 8.15 5.09 17.84 100.00
#24 13.61 0.00 54.45 1.02 8.17 5.10 17.65 100.00
#25 13.30 0.00 53.19 1.00 7.98 4.99 19.55 100.00
20

Table 9
Compressive strength
25 Sample Retarder (wt.%) H2O2 (wt.%) Fiber (wt.%) W/C NaOH (M) Density (kg/m3)
psi MPa
#22 1.00* 1.75 0.30 0.21 9.63 777 1595 11.00
#23 1.20** 1.75 0.30 0.22 9.21 585 600 4.14
30 #24 1.20** 1.50 0.30 0.21 9.33 672 1145 10.15
#25 1.00** 0.20$ 0.30 0.24 8.23 813 986 6.80
* Borax; ** Sodium trimetaphosphate; $ metal aluminum powder (20 micron size)

35
Example 10 (Comparative)

[0156] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
(modulus ∼1.6) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) such that
40 the following concentrations were obtained in the GCCC composition:

Na2O (5.04 wt.%)

SiO2 (7.78 wt.%), and

45
H2O (19.73 wt.%).

[0157] The blend of following blend of three constituents were added to the alkaline activator solution with sodium
hexametaphosphate (SHMP) dissolved in it:
50
Brandon Shore Class F fly ash (13.29 wt.%)

Ground granulated blast furnace slag as hardening enhancer (43.19 wt.%), and

55 Synthetic polypropylene fiber (0.03 wt.% of the GCCC composition).

Mixing lasted for 3 minutes.

23
 EP 2 970 003 B1

[0158] Then, silica fume (0.99 wt.%) as submicron filler was added under continued mixing for another 3 minutes. 1
minute before end of mixing, hydrogen peroxide solution (37 wt.% concentration) was added as a foaming agent into
the mixture in the amount of 2.25 wt.% of the GCCC composition. The paste was poured in a 3"x6" cylindrical mold,
allowed to expand and fill the mold, and subsequently cured at room temperature. The initial set time was determined
5 to be 43 minutes. After 24 hours, the sample was de-molded and stored at room temperature. After curing for 28 days,
the apparent density was determined to be 574 kg/m 3 and the compressive strength was measured to be 649 psi or
4.47 MPa (Sample #26, Tables 10 and 11).
[0159] Additional GCCC samples were prepared with similar compositions, the same amount of SHMP as a set retarder
and the preparation procedure described in Sample #26. Compositions, apparent densities and compressive strengths
10 of the additional samples (#27 to #30) are given in Table 10 and 11.

Table 10
GCCC composition (wt.%)
Sample
15 FFA MK BFS SF SiO2 Na2O Water Sum
#26 13.29 9.97 43.19 0.99 7.78 5.04 19.73 100.00
#27 13.31 9.98 43.25 1.00 7.82 5.07 19.56 100.00
#28 13.44 10.08 43.67 1.00 7.87 5.10 18.85 100.00
20
#29 13.23 9.92 43.00 1.00 7.78 5.04 20.02 100.00
#30 13.35 10.01 43.39 1.00 7.82 5.07 19.37 100.00

25
Table 11
Compressive
SHMP (wt. H2O2 (wt. Fiber NaOH Initial set Density strength
Sample W/C
%) %) (wt.%) (M) (min) (kg/m3)
psi MPa
30
#26 0.85 2.25 0.25 0.25 8.25 43 574 649 4.47
#27 0.85 1.75 0.35 0.24 8.37 >38 644 835 5.76
#28 0.85 1.75 0.20 0.23 8.73 32 ND ND ND
35 #29 0.85 1.85 0.30 0.25 8.13 34 638 806 5.56
#30 0.85 2.15 0.20 0.24 8.44 31 596.69 610 4.21
ND = Not determined

40
Example 11 (Comparative)

[0160] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
(modulus ∼1.56) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) such
45
that the following concentrations were obtained in the GCCC composition:

Na2O (4.92 wt.%)

SiO2 (7.66 wt.%), and

50
H2O (19.07 wt.%).

[0161] Sodium hexametaphosphate (SHMP) as a set retarder was dissolved in the alkaline activator solution in the
amount of 1.00 wt.% of the GCCC composition. The alkaline activator solution with sodium hexametaphosphate in it
55
was mixed with metakaolin (6.73 wt.%) in an intensive mixer (20L K-Lab Mixer from Lancaster Products) for 12 minutes.
[0162] Subsequently the following constituents were added and mixed for 3 minutes:

Brandon Shore Class F fly ash (13.47 wt.%)

24
 EP 2 970 003 B1

Ground granulated blast furnace slag as hardening enhancer (47.14 wt.%), and

Synthetic polypropylene fiber (0.2 wt.% of the GCCC composition).

5 [0163] Then, silica fume (1.00 wt.%) as submicron filler was added under continued mixing for another 3 minutes. 30
seconds before end of mixing, 35% hydrogen peroxide solution was added as a foaming agent into the mixture in the
amount of 2.00 wt.% of the GCCC composition. The paste was poured in a 3"36" cylindrical mold, allowed to expand
and fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and stored
at room temperature. After curing for 28 days, the apparent density was determined to be 658 kg/m3 and the compressive
10 strength was measured to be 704 psi or 4.85 MPa (Sample #31, Tables 12 and 13).
[0164] Additional GCCC samples were prepared with the same geopolymer composite composition and procedure in
Sample #31 but the paste was poured into a 4"34"316" beam mold. Compositions, apparent densities and compressive
strengths of the additional samples are given in Tables 12 and 13.

15 Table 12
GCCC composition (wt.%)
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#31 13.47 6.73 47.14 1.00 7.66 4.92 19.07 100.00
20
#32 13.49 6.74 47.21 1.00 7.68 4.93 18.95 100.00
#33 13.45 6.73 47.09 1.00 7.66 4.92 19.16 100.00
#34 13.34 6.67 46.70 0.99 7.59 4.88 19.82 100.00
25

Table 13

Initial Compressive
SHMP (wt. H2O2 (wt. Fiber (wt. NaOH Density strength
Sample W/C set
30 %) %) %) (M) (kg/m3)
(min) psi MPa
#31 1.00 2.00 0.20 0.24 8.33 30 658 704 4.85
#32* 0.90 1.75 0.25 0.23 8.40 42 ND ND ND
35 #33* 0.90 1.75 0.35 0.24 8.29 32 ND ND ND
#34* 0.70 1.85 0.35 0.25 7.94 19 ND ND ND
* The alkaline activator solution was mixed with all dry components together. ND = Not determined

40
Example 12 (Comparative)

[0165] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
(modulus ∼1.39) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) such
45 that the following concentrations were obtained in the GCCC composition:

Na2O (5.02 wt.%)

SiO2 (6.97 wt.%), and
H2O (19.25 wt.%).
50
[0166] Sodium hexametaphosphate (SHMP) as a set retarder was dissolved in the alkaline activator solution in the
amount of 0.90 wt.% of the GCCC composition. The alkaline activator solution with sodium hexametaphosphate first
mixed with metakaolin (6.88 wt.%) in an intensive mixer (20L K-Lab Mixer from Lancaster Products) for 12 minutes.
[0167] Subsequently the following dry constituents were added and mixed for 6 minutes:
55
Brandon Shore Class F fly ash (20.63 wt.%)
Ground granulated blast furnace slag as hardening enhancer (41.25 wt.%), and
Synthetic polypropylene fiber (0.3 wt.% of the GCCC composition).

25
 EP 2 970 003 B1

[0168] 1 minute before the end of mixing, 35% hydrogen peroxide solution was added as a foaming agent into the
mixture in the amount of 2.50 wt.% of the GCCC composition. The paste was poured in a 3"36" cylindrical mold, allowed
to expand and fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded
and stored at room temperature. After curing for 28 days, the apparent density was determined to be 502 kg/m3 and
5 compressive strength was measured to be 445 psi or 3.07 MPa (Sample #35, Tables 14 and 15).
[0169] Additional GCCC samples were prepared with the same composite binder composition and procedure in Sample
#35. Compositions, apparent densities and compressive strengths of the additional samples are given in Tables 14 and 15.

Table 14
10
GCCC composition (wt.%)
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#35 20.63 6.88 41.25 0.00 6.97 5.02 19.25 100.00

15 #36 20.63 6.88 41.25 0.00 6.97 5.02 19.25 100.00

#37 20.45 6.82 40.89 0.00 6.91 4.98 19.96 100.00
#38 20.53 6.84 41.06 0.00 6.94 5.00 19.62 100.00

20
Table 15

Initial Compressive
SHMP (wt. H2O2 (wt. Fiber (wt. NaOH Density strength
Sample W/C set
%) %) %) (M) (kg/m3)
25 (min) psi MPa
#35 0.90 2.50 0.30 0.24 8.42 35 502 445 3.07
#36 0.12 2.50 0.30 0.24 8.42 36 532 324 2.23
#37 0.90 0.185** 0.30 0.25 8.05 56 ND ND ND
30
#38* 1.90 1.85 0.30 0.24 8.23 21 ND ND ND
* The alkaline activator solution was mixed with all dry components together. Calcium nitrate and sodium sulfate in
a mass ratio of 1:5 were added a set retarder. ** Aluminum powder (20mm size) as the foaming agent. #35 and #37
were prepared by pouring the paste into 4"34"316" beam molds.
35

Example 13 (Comparative)

[0170] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
40 (modulus ∼1.39) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) such
that the following concentrations were obtained in the GCCC composition:

Na2O (5.73 wt.%)

SiO2 (7.98 wt.%), and
45 H2O (19.28 wt.%).

[0171] Sodium hexametaphosphate (SHMP) as a set retarder was dissolved in the alkaline activator solution in the
amount of 0.85 wt.% of the GCCC composition. The alkaline activator solution with sodium hexametaphosphate was
mixed with metakaolin (10.05 wt.%) in an intensive mixer (20L K-Lab Mixer from Lancaster Products) for 12 minutes.
50 [0172] Subsequently the following constituents were added and mixed for 6 minutes:

SEFA Class F fly ash (20.10 wt.%)

Ground granulated blast furnace slag as hardening enhancer (36.86 wt.%), and
55
Synthetic polypropylene fiber (0.03 wt.% of the GCCC composition).

[0173] 30 seconds before end of mixing, 35% hydrogen peroxide solution was added as a foaming agent into the

26
 EP 2 970 003 B1

mixture in the amount of 1.85 wt.% of the GCCC composition. The paste was poured in a 3"36" cylindrical mold, allowed
to expand and fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded
and stored at room temperature. After curing for 28 days, the apparent density was determined to be 566 kg/m3 and the
compressive strength was measured to be 619 psi or 4.27 MPa (Sample #39, Tables 16 and 17).
5 [0174] Additional GCCC samples were prepared with the same composite binder composition and procedure in Sample
#39, except that the paste was poured into a 4"34"316 beam mold. Brandon Shore Class F fly ash was used to prepare
additional GCCC samples. Up to 3 times volumetric increases were observed in all additional samples. Compositions,
apparent densities and compressive strengths of the additional samples are given in Tables 16 and 17.

10 Table 16
GCCC composition (wt.%)
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#39 20.10 10.05 36.86 0.00 7.98 5.73 19.28 100.00
15
#40 19.47 9.74 35.70 0.00 7.72 5.55 21.83 100.00
#41 19.60 9.80 35.94 0.00 7.78 5.58 21.29 100.00
#42 19.60 9.80 35.94 0.00 7.78 5.58 21.29 100.00
20 #43 19.86 9.93 36.41 0.00 7.88 5.66 20.26 100.00
#44 19.79 9.90 36.28 0.00 7.85 5.64 20.54 100.00
#45 19.81 9.91 36.33 0.00 7.86 5.64 20.45 100.00
#46 19.96 9.98 36.59 0.00 7.92 5.69 19.88 100.00
25

Table 17
Compressive
30 SHMP H2O2 (wt. Fiber (wt. Initial set Density strength
Sample W/C NaOH
(wt.%) %) %) (min) (kg/m3)
psi MPa
#39 0.85 1.85 0.30 0.24 9.58 >32 565.63 619 4.27
#40 0.85 1.75 0.30 0.28 8.20 52 ND ND ND
35
#41 0.85 1.85 0.30 0.27 8.46 63 ND ND ND
#42 0.85 1.85 0.30 0.27 8.46 90 ND ND ND
#43 0.85 1.85 0.30 0.25 9.10 65 ND ND ND
40
#44 0.85 2.50 0.30 0.26 8.86 60 ND ND ND
#45 0.85 2.90 0.30 0.26 8.91 85 ND ND ND
#46 0.85 2.00 0.30 0.25 9.23 26 541.80 529 3.65

45
[0175] Additional GCCC samples were prepared with the same composite binder composition and procedure described
in Sample #39 except that no set retarder was used. Either Brandon Shore or SEFA Class F fly ash was used to prepare
additional GCCC samples. Mix characteristics, apparent density and compressive strength of the additional samples
are shown in Tables 18 and 19.
50
Table 18
GCCC composition
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
55 #47 19.92 9.96 36.52 0.00 7.90 5.67 20.02 100.00
#48 19.95 9.98 36.58 0.00 7.92 5.68 19.89 100.00
#49 19.76 9.88 36.23 0.00 7.84 5.63 20.65 100.00

27
 EP 2 970 003 B1

Table 19
Compressive
SHMP H2O2 Fiber NaOH Initial Density strength
Sample W/C
5 (wt%) (wt%) (wt%) (M) Set (kg/m3)
psi MPa
#47* 0 2.50 0.30 0.25 9.14 48 min 513 518 3.57
#48** 0 1.85 0.30 0.24 9.22 34 min 597 479 3.30
10 #49** 0 2.15 0.30 0.26 8.80 35 min 557 613 4.23
* SEFA fly ash; ** Brandon Shore fly ash

Example 14 (Comparative)
15

[0176] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
(Modulus= 1.39) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) to obtain
weight percents of the following components in the GCCC composition:

20 Na2O (5.72 wt%)

SiO2 (7.97 wt%), and

H2O (19.39 wt%).

25

[0177] Borax as a set retarder was dissolved in the alkaline activator solution in the amount of 0.85 wt% of the GCCC
composition. The alkaline activator solution dissolved with borax was first mixed with metakaolin (10.04 wt%) in an
intensive mixer (20L K-Lab Mixer from Lancaster Products) for 12 minutes.
[0178] Subsequently the following constituents were added and mixed for 3 minutes:
30

Brandon Shore Class F fly ash (20.08 wt%)

Ground granulated blast furnace slag as hardening enhancer (36.81 wt%), and

35 Synthetic polypropylene fiber (0.03 wt% of the GCCC composition).

75 seconds toward ending of mixing, 35% hydrogen peroxide solution was added as a foaming agent into the mixture
in the amount of 1.85 wt% of the GCCC composition. The paste was poured in a 3"36" cylindrical mold, allowed to
expand to fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was de-molded and
40 stored at room temperature. After curing for 28 days, the apparent density was determined to be 561 kg/m3 and com-
pressive strength was measured to be 687 psi or 4.74 MPa (Sample #50, Tables 20 and 21).
[0179] Additional GCCC samples were prepared with the same composite binder composition and procedure described
in Sample #50. Borax was used as the set retarder throughout all the additional samples. Either Brandon Shore or SEFA
Class F fly ash was used to prepare additional GCCC samples. Samples #54 and 55 were estimated to have a volumetric
45 expansion about 3 to 4 times. Mix characteristics, apparent density and compressive strength of the additional samples
are shown in Tables 20 and 21.

Table 20
GCCC composition
50 Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#50 20.08 10.04 36.81 0.00 7.97 5.72 19.39 100.00
#51 20.10 10.05 36.85 0.00 7.97 5.73 19.30 100.00
55 #52 20.09 10.04 36.83 0.00 7.97 5.72 19.35 100.00
#53 20.06 10.03 36.78 0.00 7.96 5.72 19.44 100.00

28
 EP 2 970 003 B1

(continued)

GCCC composition
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
5
#54 19.92 9.96 36.51 0.00 7.90 5.67 20.04 100.00
#55 19.91 9.96 36.51 0.00 7.90 5.67 20.05 100.00

10
Table 21
Compressive
Borax H 2 O2 Fiber NaOH Initial Density strength
Sample W/C
(wt%) (wt%) (wt%) (M) set (kg/m3)
psi MPa
15
#50* 0.85 1.85 0.30 0.24 9.52 91 min 561 687 4.74
#51** 0.85 1.50 0.30 0.24 9.57 96 min 625 882 6.08
120
#52** 0.85 1.20 0.30 0.24 9.54 726 1472 10.15
20 min
#53* 0.85 2.15 0.30 0.24 9.49 73 min 492 451 3.11
#54* 0.85 2.50 0.30 0.25 9.14 90 min ND ND ND
#55* 0.85 1.75# 0.30 0.25 9.13 33 min ND ND ND
25
* Brandon Shore fly ash ; ** SEFA fly ash; # Additionally metal aluminum powder was added together with hydrogen
peroxide in the amount of 0.05 wt% of the GCCC composition.

Example 15 (Comparative)
30
[0180] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, an alkaline activator solution
(Modulus= 1.39) was prepared by mixing sodium hydroxide solution and Ru™ sodium silicate solution (PQ Inc) to obtain
weight percents of the following components in the GCCC composition: Na2O (5.60 wt%) SiO2 (7.80 wt%), and H2O
(17.71 wt%).
35 [0181] The alkaline activator solution (no retarder was used) was first mixed with metakaolin (20.36 wt%) in an intensive
mixer (20L K-Lab Mixer from Lancaster Products) for 10 minutes.
[0182] Subsequently the following constituents were added and mixed for 6 minutes: SEFA Class F fly ash (40.72
wt%), ground granulated blast furnace slag as hardening enhancer (6.79 wt%), and synthetic polypropylene fiber (0.03
wt% of the GCCC composition)
40 [0183] At 45 seconds toward ending of mixing, metal aluminum powder (20 mm median size) was added as a foaming
agent into the mixture in the amount of 1.85 wt% of the GCCC composition. The paste was poured in a 3"x6" cylindrical
mold, allowed to expand to fill the mold, and subsequently cured at room temperature. After 24 hours, the sample was
de-molded and stored at room temperature. After curing for 28 days, the apparent density was determined to be 689
kg/m3 and compressive strength was measured to be 751 psi or 5.18MPa (Sample #56, Tables 22 and 23).
45 [0184] Sample #57 was prepared with the same procedure described in Sample #58 but with a different composite
binder composite and no retarder was added. Samples # 58 and 59 were prepared in the same procedure described in
Sample #56 except that borax was used as the set retarder. Mix characteristics, apparent density and compressive
strength of all the samples are shown in Tables 22 and 23.

50 Table 22
GCCC composition
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#56 40.72 20.36 6.79 1.02 7.80 5.60 17.71 100.00
55
#57 47.57 13.59 6.80 1.02 7.81 5.61 17.61 100.00
#58 27.65 34.56 6.91 0.00 7.95 5.71 17.22 100.00

29
 EP 2 970 003 B1

(continued)

GCCC composition
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
5
#59 48.38 13.82 6.91 0.00 7.95 5.71 17.22 100.00

Table 23
10
Compressive
Borax H2O2 Al Fiber NaOH Initial Density strength
Sample W/C
(wt%) (wt%) (wt%) (wt%) (M) set (kg/m3)
psi MPa
#56 0.85 - 0.185 0.30 0.22 10.21 46 min 689 751 5.18
15
#57 0.85 - 0.185 0.30 0.21 10.28 35 min 656 559 3.85
>46 ND ND ND
#58 0.85 1.85 - 0.30
0.21 10.70 min

20 #59 0.85 1.85 - 0.30 0.21 10.70 N/A 531 362 2.50

Example 16 (Comparative)

[0185] To prepare a GCCC for thermal insulation applications, disclosed but not claimed, the following dry ingredients
25
were first mixed:

Orlando Class F fly ash (54.77 wt%)

Ground granulated blast furnace slag as hardening enhancer (5.00 wt%), and
Metakaolin (5.00 wt%)
30

[0186] Then an alkaline activator solution (Modulus ∼1.05) was prepared by mixing sodium hydroxide solution and
Ru™ sodium silicate solution (PQ Inc) to obtain weight percents of the following components in the GCCC composition:

Na2O (5.58 wt%)

35
SiO2 (5.88 wt%), and
H2O (20.77 wt%).

[0187] The activator solution was mixed in a 7-quart planetary mixer for 3 minutes. Then silica fume (3 wt%) as
submicron filler was added and continued mixing for 3 minutes. Metal aluminum powder (0.08 wt% of the GCCC com-
40
position) was added and continued mixing for another 3 minutes. The paste was poured in a 2"34" cylindrical mold,
allowed to expand to fill the mold, and cured at and 70 °C for 24 hours. After 24 hours, the sample was de-molded and
stored at room temperature. After curing for 28 days, the apparent density was determined to be 923 g/m 3 and compressive
strength was measured to be 881 psi or 6.07 MPa (Sample #60, Tables 24 and 25).
[0188] More GCCC samples with similar composition were prepared with the same procedure described in Sample
45
#60. Mix characteristics, apparent density and compressive strength of the additional samples are shown in Tables 24
and 25.

Table 24

50
GCCC composition
Sample
FFA MK BFS SF SiO2 Na2O Water Sum
#60 54.77 5.00 5.00 3.00 5.88 5.58 20.77 100.00
#61 53.37 7.44 4.87 2.92 5.73 5.44 20.23 100.00
55
#62 53.98 6.40 4.93 2.96 5.79 5.50 20.45 100.00
#63 54.06 8.40 4.93 0.82 5.80 5.51 20.48 100.00

30
 EP 2 970 003 B1

Table 25
Compressive
Sample Al (wt%) W/C NaOH (M) Density (kg/m3) strength
5 Curing
psi MPa
#60 70 0.08 0.26 8.67 923 881 6.07
#61 70 0.06 0.25 8.67 844 403 2.78
10 #62 50 0.04 0.26 8.67 907 813 5.61
#63 70 0.02 0.26 8.68 1136 1853 12.78

[0189] Selected compositions of the ternary geopolymer composite binders exemplified by Examples 1 to 16 are
15 shown in FIG. 3.

References

[0190] The following references are referred to above:

20

1. Esmaily, H. and H. Nuranian, Non-autoclaved high strength cellular concrete from alkali activated slag, Construc-
tion and Building Materials, 26 (1), 200-206 (2012).
ˇ
2. Vlcek, ˇ
J., H. Eleková, V. Tomková, V. Matekja, ˇ ˇ Lightweight materials based on slag from production
and F. Ovcacik,
of iron and steel (published on-line) (2010).
25 3. Aguilar, R.A., O.B. Diaz, J.I. Escalante Garcia, Lightweight concretes of activated metakaolin-fly ash binders,
with blast furnace slag aggregates, Construction and Building Materials, 24 (7), 1166-1175 (2010). To produce this
lightweight alkali activated concrete, Al powder is used as foaming agent.
4. Joseph Henon, J., A. Alzina, J. Absi, D.S. Smith, and S. Rossignol, Potassium geopolymer foams made with
silica fume pore forming agent for thermal insulation, Journal of Porous Materials, 20(1), 37-46 (2013).
30 5. U.S. Patent No. 5,605,570, Alkali-activated glassy silicate foamed concrete (1997).
6. U.S Patent Application: 2012/0024196, Tailored geopolymer composite binders for cement and concrete appli-
cations (2012).
7. U.S. Patent Application: 2012/0152153, Geopolymer composite for ultra high performance concrete (2012).
8. Patent application WO 2012/069024, Acid and high temperature resistant cement composites.
35

Claims

1. A product comprising:
40

a geopolymer composite binder comprising:

one or more Class F fly ash materials,

one or more gelation enhancers, and
45 one or more hardening enhancers;
one or more alkaline activators;
one or more aggregates; and
one or more foaming agents;

50 wherein each of the one or more Class F fly ash materials comprises 15 wt.% or less calcium oxide;
wherein the one or more alkaline activators comprise an alkaline activator solution comprising one or more
metal hydroxides, one or more metal silicates, and water;
wherein the one or more gelation enhancers are selected from the group consisting of metakaolin, metahalloysite,
micron and nanoparticles of silica and alumina, and pozzolanic aluminosilicate materials that have a low alkali-
55 earth oxide content and a high dissolution rate in alkaline solution;
wherein the one or more hardening enhancers are selected from the group consisting of ground granulated
blast furnace slag, Class C fly ash, vitreous calcium aluminosilicate, kiln dust, CaO-rich pozzolanic aluminosil-

31
 EP 2 970 003 B1

icates, and combinations thereof;

wherein the one or more foaming agents comprise aluminum powder or a peroxide-based foaming agent;
wherein the geopolymer composite binder is a Portland cement-free binder;
wherein the product is a geopolymer composite cellular concrete (GCCC);
5 wherein an amount of the one or more Class F fly ash materials is 1 to 50 wt.% of the product, an amount of
the one or more gelation enhancers is 1 to 50 wt.% of the product, and an amount of the one or more hardening
enhancers is 1 to 50 wt.% of the product; and
wherein the product has an apparent density of 1200 kg/m 3 to 1800 kg/m3 and a 28-day compressive strength
of at least 17 MPa or 2500 psi.
10
2. The product of claim 1, wherein the one or more metal hydroxides comprise alkali-metal oxides including sodium
hydroxide and/or potassium hydroxide; wherein an amount of the one or more metal hydroxides, as alkali-metal
oxides, is 2 to 12 wt.% of the product; wherein the one or more metal silicates comprise one or both members of
the group consisting of sodium silicate and potassium silicate and wherein an amount of the one or more metal
15 silicates, as soluble silica, is 2 to 15 wt.% of the product.

3. The product of any one of the preceding claims, wherein the peroxide-based foaming agent is selected from the
group consisting of hydrogen peroxide solution, sodium peroxide, calcium peroxide, and alkali perborate.

20 4. The product of claim 3, wherein the concentration of the hydrogen peroxide solution is 35 wt.%; and wherein the
hydrogen peroxide comprises 0.01 wt.% to 2.00 wt.% of the product.

5. The product of any one of claims 1-2, wherein the aluminum powder has a particle size of between 1 and 75 microns;
wherein the aluminum powder comprises 0.01 to 0.5 wt.% of the product.
25
6. The product of any one of the preceding claims, wherein a mass ratio of water to solid ranges from 0.20 to 0.55.

7. The product of any one of the preceding claims,

wherein the product comprises one or more aggregates including river sand and/or one or more lightweight aggre-
30 gates;
wherein the one or more lightweight aggregates comprise one or more fine or coarse lightweight aggregates com-
prising expanded slag, expanded slate, expanded shale, expanded clay, expanded perlite, pumice, scoria, or ex-
panded pelletized fly ash; wherein each of the one or more lightweight aggregates has a density of 50 kg/m3 to
1000 kg/m3;
35 wherein an amount of the one or more lightweight aggregates is 40 wt.% or less of the product; and
wherein an amount of the river sand is 60 wt.% or less of the product.

8. The product of any one of the preceding claims,

wherein the product further comprises one or more ultrafine and/or submicron fillers;
40 wherein the one or more ultrafine and/or submicron fillers have a particle size ranging from 0.05 to 10 mm, and
wherein the one or more ultrafine and/or submicron fillers is 12 wt.% or less of the product.

9. The product of claim 3, wherein the product further comprises one or more set retarders selected from the group
consisting of sodium metaphosphate, phosphoric acid, borax, boric acid, alkali citrates, barium hydroxide, barium
45 nitrate, barium chloride, zinc nitrate, and gypsum; and wherein the one or more set retarders is 5 wt.% or less of
the product.

10. The product of any one of the above claims, wherein the product further comprises one or more fiber materials
selected from the group consisting of organic fiber, glass fiber, mineral fiber, basalt fiber, and carbon fiber; wherein
50 the one or more fiber materials is 5 wt.% or less of the product.

11. The product of any one of the preceding claims,

wherein the product further comprises one or more accelerators selected from the group consisting of sodium sulfate,
sodium oxalate, sodium fluoride,
55 wherein the one or more accelerators is 5 wt.% or less of the product.

12. A method for the manufacture of a geopolymer composite cellular concrete (GCCC) comprising:

32
 EP 2 970 003 B1

(a) mixing together one or more Class F fly ash materials, one or more gelation enhancers and one or more
hardening enhancers, thereby producing a blend of composite binder components;
(b) mixing the blend of composite binder components with one or more alkaline activators, thereby producing
an activated mixture;
5 (c) mixing the activated mixture with one or more aggregates, one or more foaming agents, thereby producing
a geopolymer composite cellular concrete (GCCC) paste;
(d) pouring the GCCC paste into a mold and allowing the GCCC paste to foam, expand, set, and harden at
room temperature, thereby producing a hardened GCCC body;
(e) removing the hardened GCCC body from the mold and curing the hardened GCCC body at room temperature,
10 thereby producing a GCCC product;

wherein each of the one or more Class F fly ash materials comprises 15 wt.% or less calcium oxide;
wherein the one or more alkaline activators comprise an alkaline activator solution comprising one or more metal
hydroxides, one or more metal silicates, and water; wherein the one or more gelation enhancers are selected from
15 the group consisting of metakaolin, metahalloysite, micron and nanoparticles of silica and alumina, and pozzolanic
aluminosilicate materials that have a low alkali-earth oxide content and a high dissolution rate in alkaline solution;
wherein the one or more hardening enhancers are selected from the group consisting of ground granulated blast
furnace slag, Class C fly ash, vitreous calcium aluminosilicate, kiln dust, CaO-rich pozzolanic aluminosilicates, and
combinations thereof;
20 wherein the one or more foaming agents comprise aluminum powder or a peroxide-based foaming agent;
wherein the composite binder is a Portland cement-free binder;
wherein an amount of the one or more Class F fly ash materials is 1 to 50 wt.% of the GCCC paste, an amount of
the one or more gelation enhancers is 1 to 50 wt.% of the GCCC paste, and an amount of the one or more hardening
enhancers is 1 to 50 wt.% of the GCCC paste; and
25 wherein the GCCC product has an apparent density of 1200 kg/m3 to 1800 kg/m3 and a 28-day compressive strength
of at least 17 MPa or 2500 psi.

13. The method of claim 12,

wherein an amount of the one or more metal hydroxides, as alkali-metal oxides, is 2 to 12 wt.% of the GCCC paste;
30 wherein an amount of the one or more metal silicates, as soluble silica, is 2 to 15 wt.% of the GCCC paste; and
wherein a mass ratio of water to solid components in the GCCC paste ranges from 0.20 to 0.55.

14. The method of claim 13,

wherein step (b) comprises mixing the blend of composite binder components with one or more members of the
35 group consisting of a set retarder, an accelerator, an aggregate, an ultrafine and/or submicron filler, and a fiber
material;
wherein the set retarder amounts to 5 wt.% or less of the GCCC paste and is selected from the group consisting of
sodium metaphosphate, phosphoric acid, borax, boric acid, alkali citrates, barium hydroxide, barium nitrate, barium
chloride, zinc nitrate, and gypsum;
40 wherein the accelerator amounts to 5 wt.% or less of the GCCC paste and is selected from the group consisting of
sodium sulfate, sodium oxalate, sodium fluoride;
wherein the aggregate comprises river sand being 60 wt.% or less of the GCCC paste or a lightweight aggregate
being 40 wt.% or less of the GCCC paste; wherein the one or more lightweight aggregates comprise one or more
fine or coarse lightweight aggregates comprising expanded slag, expanded slate, expanded shale, expanded clay,
45 expanded perlite, pumice, scoria, or expanded pelletized fly ash;
wherein each of the one or more lightweight aggregates has a density of 50 kg/m3 to 1000 kg/m 3 ;
wherein the ultrafine and/or submicron filler has a particle size ranging from 0.05 to 10 mm, and amounts to 12 wt
% or less of the GCCC paste; and
wherein the fiber material amounts to 5 wt.% or less of the GCCC paste and is selected from the group consisting
50 of organic fiber, glass fiber, mineral fiber, basalt fiber, and carbon fiber.

Patentansprüche

55 1. Ein Produkt, bestehend aus:

einem Geopolymer-Verbundbindemittel, bestehend aus:

33
 EP 2 970 003 B1

einem oder mehr Flugaschematerialien der Klasse F,

einem oder mehr Gelierungsverstärken, und
einem oder mehr Härtungsverstärken;
einem oder mehr alkalischen Aktivatoren;
5 einem oder mehr Zuschlagstoffen; und
einem oder mehr Schäummittel;

wobei jedes der einzelnen Flugaschematerialien der Klasse F maximal 15 Massenanteile Calciumoxid enthält;
wobei einer oder mehrere der alkalischen Aktivatoren eine alkalische Aktivatorlösung enthalten, die aus einem
10 oder mehreren Metallhydroxiden, einem oder mehr Metallsilikaten und Wasser besteht;
wobei mindestens einer der Gelierungsverstärker aus der Gruppe gewählt wird, die aus Metakaolin, Metahal-
loysit, Mikro- und Nanopartikeln aus Siliciumdioxid und Aluminiumoxid und puzzolanischen Aluminiumsilikaten
mit geringen Anteilen an Erdalkalimetalloxiden und einer hohen Auflösungsrate in alkalischen Lösungen besteht;
wobei mindestens einer der Härtungsverstärker aus der Gruppe gewählt wird, die aus gemahlener granulierter
15 Hochofenschlacke, Flugasche der Klasse C, glasartigem Calcium-Aluminiumsilikat, Ofenstaub, puzzolanischen
Aluminiumsilikaten mit hohem CaO-Anteil und Kombinationen hieraus besteht;
wobei mindestens eines der Schäummittel Aluminiumspulver oder eine peroxidbasiertes Schäummittel enthält;
wobei das Geopolymer-Verbundbindemittel frei von Portlandzement ist;
wobei das Produkt ein Geopolymer-Verbundstoff-Porenbeton (GVP) ist;
20 wobei die Anteile eines oder mehrerer Flugaschematerialien der Klasse F zwischen 1 und 50 Masseanteilen
des Produktes, der Masseanteil eines oder mehrerer Gelierungsverstärker zwischen 1 und 50 Masseanteilen
des Produktes und der Anteil eines oder mehrerer Härtungsverstärker zwischen 1 und 50 Masseanteilen des
Produktes liegen; und
wobei das Produkt eine Rohdichte von 1200 kg/m3 bis zu 1800 kg/m3 sowie eine 28-Tage-Druckfestigkeit von
25 mindestens 17 MPa oder 2500 psi aufweist.

2. Das Produkt aus Antrag 1, wobei eines oder mehrere Metallhydroxide zu den Alkalimetalloxiden gehören, ein-
schließlich Natriumhydroxid und/oder Kaliumhydroxid; wobei der Anteil eines oder mehrerer Metallhydroxide als
Alkalimetalloxide zwischen 2 und 12 Massenanteilen des Produkts liegt; wobei eines oder mehrere der Metallsilikate
30 eines oder beide Mitglieder der Gruppe aus Natriumsilikat und Kaliumsilikat beinhaltet und wobei ein Anteil eines
oder mehrerer Metallsilikate, wie lösliche Kieselsäure, zwischen 2 und 15 Masseneinheiten des Produkts liegt.

3. Das Produkt aus einem der vorstehenden Anträge, wobei das peroxidbasierte Schäummittel aus der Gruppe Was-
serstoffperoxidlösung, Natriumperoxid, Calciumperoxid und Alkaliperborat gewählt wird.
35
4. Das Produkt aus Antrag 3, wobei die Konzentration der Wasserstoffperoxidlösung 35 Massenanteile beträgt; und
wobei der Anteil des Wasserstoffperoxids zwischen 0,01 und 2,00 Massenanteilen des Produkts liegt.

5. Das Produkt aus den Anträgen 1 oder 2, wobei die Partikelgröße des Aluminiumpulvers zwischen 1 und 75 mm
40 beträgt; wobei der Anteil des Aluminiumpulvers zwischen 0,01 und 0,5 Massenanteilen des Produkts liegt.

6. Das Produkt aus einem der vorstehenden Anträge, wobei das Massenverhältnis von Wasser zu Feststoffen zwischen
0,20 und 0,55 liegt.

45 7. Das Produkt aus einem der vorstehenden Anträge, wobei das Produkt einen oder mehrere Zuschlagstoffe enthält,
einschließlich Flusssand, und/oder einen oder mehrere leichte Zuschlagstoffe;
wobei einer oder mehrere der leichten Zuschlagstoffe einen oder mehrere der feinen oder groben Zuschlagstoffe
geblähte Schlacke, geblähter Tonschiefer, geblähter Schiefer, Blähton, Blähperlit, Bimsstein, Schlacke oder geblähte
pelletisierte Flugasche umfasst;
50 wobei der leichte Zuschlagstoff oder die leichten Zuschlagstoffe eine Dichte von 50 kg/m3 bis 1000 kg/m 3 aufweisen;
wobei ein Anteil des oder der leichten Zuschlagstoffe bei 40 Massenanteilen oder weniger des Produkts liegt; und
wobei ein Anteil an Flusssand bei 60 Massenanteilen oder weniger des Produkts liegt.

8. Das Produkt aus einem der vorstehenden Anträge,

55 wobei das Produkt weiterhin einen oder mehrere ultrafeine und/oder Submikron-Füllstoffe enthält;
wobei die Partikelgrößen der ultrafeinen und/oder Submikron-Füllstoffe zwischen 0,05 und 10 mm liegen, und wobei
der Anteil des oder der ultrafeinen und/oder Submikron-Füllstoffe bei 12 Massenanteilen oder weniger des Produkts
liegen.

34
 EP 2 970 003 B1

9. Das Produkt aus Antrag 3, wobei das Produkt weiterhin einen oder mehrere Abbindeverzögerer enthält, die aus
der Gruppe Natriummetaphosphat, Phosphorsäure, Borax, Borsäure, Alkalicitrate, Bariumhydroxid, Bariumnitrat,
Bariumchlorid, Zinknitrat und Gips ausgewählt wird; und wobei der oder die Abbindeverzögerer 5 Massenanteile
oder weniger des Produkts liegen.
5
10. Das Produkt aus einem der vorstehenden Anträge, wobei das Produkt weiterhin eines oder mehrere Fasermaterialien
enthält, die aus der Gruppe organische Fasern, Glasfaser, Mineralfaser, B asaltfaser und Carbonfaser ausgewählt
werden; wobei das oder die Fasermaterialien 5 Massenanteile oder weniger des Produkts liegen.

10 11. Das Produkt aus einem der vorstehenden Anträge,

wobei das Produkt weiterhin einen oder mehrere Beschleuniger enthält, die aus der Gruppe Natriumsulfat, Natri-
umoxalat und Natriumfluorid gewählt werden, wobei der Anteil des oder der Beschleuniger bei 5 Massenanteilen
oder weniger des Produkts liegt.

15 12. Eine Herstellungsmethode für einen Geopolymer-Verbundstoff-Porenbeton (GVP), bestehend aus:

(a) dem Mischen eines oder mehrerer Flugasche Materialien der Klasse F, eines oder mehrerer Gelierungs-
verstärker und einem oder mehrerer Härtungsverstärker, wodurch eine Mischung aus Verbundbindemittel-
Komponenten entsteht;
20 (b) dem Mischen der Mischung aus Verbundbindemittel-Komponenten mit einem oder mehreren alkalischen
Aktivatoren, wodurch eine aktivierte Mischung entsteht;
(c) dem Mischen der aktivierten Mischung mit einem oder mehreren Zuschlagstoffen sowie einem oder mehreren
Schäummitteln, wodurch eine Paste aus Geopolymer-Verbundstoff-Porenbeton (GVP) entsteht;
(d) dem Gießen der GVP-Paste in eine Form, in welcher die GVP-Paste bei Raumtemperatur schäumen, sich
25 ausdehnen, abbinden und aushärten kann, wodurch ein abgebundener GVP-Körper entsteht;
(e) dem Entfernen des abgebundenen GVP-Körpers aus der Form, um den abgebundenen GVP-Körper bei
Raumtemperatur aushärten zu lassen, wodurch ein GVP-Produkt entsteht;

wobei jedes einzelne der Flugaschematerialien der Klasse F 15 Massenanteile oder weniger Calciumoxid enthält;
30 wobei der oder die alkalischen Aktivatoren eine alkalische Aktivatorlösung enthalten, die aus einem oder mehreren
Metallhydroxiden, einem oder mehreren Metallsilikaten und Wasser besteht; wobei der oder die Gelierungsverstärker
aus der Gruppe Metakaolin, Metahalloysit, Mikro- und Nanopartikeln aus Siliciumdioxid und Aluminiumoxid und
puzzolanischen Aluminiumsilikaten mit geringen Anteilen an Erdalkalimetalloxiden und einer hohen Auflösungsrate
in alkalischen Lösungen gewählt werden;
35 wobei der oder die Härtungsverstärker aus der Gruppe gemahlene granulierte Hochofenschlacke, Flugasche der
Klasse C, glasartiges Calcium-Aluminiumsilikat, Ofenstaub, puzzolanische Aluminiumsilikate mit hohem CaO-Anteil
und Kombinationen hieraus gewählt wird;
wobei das oder die Schäummittel aus Aluminiumpulver oder einem peroxidbasierten Schäummittel besteht;
wobei das Verbundbindemittel frei von Portlandzement ist;
40 wobei die Anteile eines oder mehrerer Flugaschematerialien der Klasse F zwischen 1 und 50 Masseanteilen des
Produktes, der Masseanteil eines oder mehrerer Gelierungsverstärker zwischen 1 und 50 Masseanteilen des Pro-
duktes und der Anteil eines oder mehrerer Härtungsverstärker zwischen 1 und 50 Masseanteilen der GVP-Paste
liegen; und
wobei das GVP-Produkt eine Rohdichte von 1200 kg/m3 bis zu 1800 kg/m 3 sowie eine 28-Tage-Druckfestigkeit von
45 mindestens 17 MPa oder 2500 psi aufweist.

13. Die Methode aus Antrag 12,

wobei ein Anteil eines oder mehrerer Metallhydroxide, beispielsweise Alkalimetalloxide, zwischen 2 und 12 Mas-
seanteilen der GVP-Paste liegt;
50 wobei ein Anteil eines oder mehrerer Metallsilikate, beispielsweise lösliche Kieselsäure, zwischen 2 und 15 Mas-
seanteilen der GVP-Paste liegt; und
wobei das Massenverhältnis von Wasser zu Feststoffen in der GVP-Paste zwischen 0,20 und 0,55 liegt.

14. Die Methode aus Antrag 13, wobei Schritt (b) daraus besteht, die Mischung aus Verbundbindemittel-Komponenten
55 mit einem oder mehreren Mitgliedern der Gruppe, die aus einem Abbindeverzögerer, einem Beschleuniger, einem
Zuschlagstoff, einem ultrafeinen und/oder Submikron-Füllstoff und einem Fasermaterial besteht, zu mischen;
wobei der Anteil des Abbindeverzögerers bei 5 Massenanteilen oder weniger der GVP-Paste liegt und aus der
Gruppe Natriummetaphosphat, Phosphorsäure, Borax, Borsäure, Alkalicitrate, Bariumhydroxid, Bariumnitrat, Bari-

35
 EP 2 970 003 B1

umchlorid, Zinknitrat und Gips ausgewählt wird;

wobei der Anteil des Beschleunigers bei 5 Masseanteilen oder weniger der GVP-Paste liegt und aus der Gruppe
Natriumsulfat, Natriumoxalat und Natriumfluorid ausgewählt wird;
wobei der Zuschlagstoff Flusssand mit einem Anteil von 60 Masseanteilen oder weniger an der GVP-Paste oder
5 einen leichten Zuschlagstoff mit einem Anteil von 40 Masseanteilen oder weniger an der GVP Paste umfasst; wobei
einer oder mehrere der leichten Zuschlagstoffe einen oder mehrere der feinen oder groben Zuschlagstoffe geblähte
Schlacke, geblähter Tonschiefer, geblähter Schiefer, Blähton, Blähperlit, Bimsstein, Schlacke oder geblähte pelle-
tisierte Flugasche umfasst;
wobei der leichte Zuschlagstoff oder die leichten Zuschlagstoffe eine Dichte von 50 kg/m3 bis 1000 kg/m 3 aufweisen;
10 wobei die Partikelgrößen der ultrafeinen und/oder Submikron-Füllstoffe zwischen 0,05 und 10 mm liegen und deren
Anteil bei 12 Massenanteilen oder weniger der GVP-Paste liegt; und
wobei der Anteil der Fasermaterialien bei 5 Masseanteilen oder weniger der GVP-Paste liegt und diese aus der
Gruppe organische Fasern, Glasfasern, Mineralfasern, Basaltfasern und Carbonfasern gewählt werden.

15
Revendications

1. Un produit comprenant :

20 un liant composite géopolymère comprenant:

un ou plusieurs matériaux de cendres volantes de Classe F,

un ou plusieurs exhausteurs de gélification, et
un ou plusieurs exhausteurs de durcissement;
25 un ou plusieurs activateurs alcalins;
un ou plusieurs agrégats; et
un ou plusieurs agents moussants;

dans lequel chacun des un ou plusieurs matériaux de cendres volantes de classe F comprend 15% en poids
30 ou moins d’oxyde de calcium ;
dans lequel le ou les activateurs alcalins comprennent une solution d’activateur alcalin comprenant un ou
plusieurs hydroxydes métalliques, un ou plusieurs silicates métalliques et de l’eau;
dans lequel le ou les exhausteurs de gélification sont choisis dans le groupe constitué par le métakaolin, le
métahalloysite, le micron et les nanoparticules de silice et d’alumine, et les matériaux d’aluminosilicate pouzzo-
35 lanique qui ont une faible teneur en oxyde alcalino-terreux et une vitesse de dissolution élevée dans une solution
alcaline ;
dans lequel le ou les exhausteurs de durcissement sont choisis dans le groupe comprenant les scories de haut
fourneau granulées broyées, les cendres volantes de classe C, l’aluminosilicate de calcium vitreux, la poussière
de four, les aluminosilicates pouzzolaniques riches en CaO et leurs combinaisons ;
40 dans lequel le ou les agents moussants comprennent de la poudre d’aluminium ou un agent moussant à base
de peroxyde;
dans lequel le liant composite géopolymère est un liant sans ciment de Portland;
dans lequel le produit est un béton cellulaire composite géopolymère (GCCC);
dans lequel une quantité d’un ou plusieurs matériaux de cendres volantes de classe F est de 1 à 50% en poids
45 du produit, une quantité de ou des exhausteurs de gélification est de 1 à 50% en poids du produit et une quantité
de l’un ou plusieurs exhausteurs de durcissement représentent 1 à 50% en poids du produit; et
dans lequel le produit a une densité apparente de 1200 kg / m3 à 1800 kg / m 3 et une résistance à la compression
de 28 jours d’au moins 17 MPa ou 2500 psi.

50 2. Produit selon l’affirmation 1, dans lequel le ou les hydroxydes métalliques comprennent des oxydes alcalins com-
prenant l’hydroxyde de sodium et / ou l’hydroxyde de potassium ;
dans lequel une quantité du ou des hydroxydes métalliques, sous forme d’oxydes de métaux alcalins, est de 2 à
12% en poids du produit; dans lequel le ou les silicates métalliques comprennent l’un ou les deux membres du
groupe consistant en silicate de sodium et en silicate de potassium et dans lequel une quantité du ou des silicates
55 métalliques, sous forme de silice soluble, est de 2 à 15% en poids du produit.

3. Produit selon l’une quelconque des affirmations précédentes, dans lequel l’agent moussant à base de peroxyde
est choisi dans le groupe consistant en une solution de peroxyde d’hydrogène, du peroxyde sodium, du peroxyde

36
 EP 2 970 003 B1

de calcium et du perborate alcalin.

4. Produit selon l’affirmation 3, dans lequel la concentration de la solution de peroxyde d’hydrogène est de 35% en
poids ; et dans lequel le peroxyde d’hydrogène représente 0,01% en poids à 2,00% en poids du produit.
5
5. Produit selon l’une quelconque des affirmations 1 à 2, dans lequel la poudre d’aluminium a une granulométrie
comprise entre 1 et 75 microns ; dans lequel la poudre d’aluminium représente 0,01 à 0,5% en poids du produit.

6. Produit selon l’une quelconque des affirmations précédentes, dans lequel un rapport massique de l’eau au solide
10 varie de 0,20 à 0,55.

7. Produit selon l’une quelconque des affirmations précédentes,

dans lequel le produit comprend un ou plusieurs agrégats comprenant du sable de rivière et / ou un ou plusieurs
agrégats légers;
15 dans lequel le ou les agrégats légers comprennent un ou plusieurs agrégats légers fins ou grossiers comprenant
du laitier amplifié, de l’ardoise amplifiée, du schiste amplifié, de l’argile amplifiée, de la perlite amplifiée, de la pierre
ponce, de la scorie ou des cendres volantes granulées amplifiées;
dans lequel chacun de un ou plusieurs agrégats légers a une densité de 50 kg / m3 à 1000 kg / m3 ;
dans lequel une quantité de ou des agrégats légers est de 40% en poids ou moins du produit; et
20 dans lequel une quantité de sable de rivière représente 60% en poids ou moins du produit.

8. Produit selon l’une quelconque des affirmations précédentes,

dans lequel le produit comprend en outre une ou plusieurs charges ultrafines et / ou submicroniques;
dans lequel la ou les charges ultrafines et / ou submicroniques ont une granulométrie allant de 0,05 à 10 mm, et
25 dans lequel la ou les charges ultrafines et / ou submicroniques représentent 12% en poids ou moins du produit.

9. Produit de l’affirmation
dans lequel le produit comprend en outre un ou plusieurs retardateurs de prise choisis dans le groupe constitué par
le métaphosphate de sodium, l’acide phosphorique, le borax, l’acide borique, les citrates alcalins, l’hydroxyde de
30 baryum, le nitrate de baryum, le chlorure de baryum, le nitrate de zinc et le gypse; et dans lequel le ou les retardateurs
de prise représentent 5% en poids ou moins du produit.

10. Produit selon l’une quelconque des affirmations ci-dessus, dans lequel le produit comprend en outre une ou plusieurs
matières fibreuses choisies dans le groupe consistant en fibre organique, fibre de verre, fibre minérale, fibre de
35 basalte et fibre de carbone ; dans lequel la ou les matières fibreuses représentent 5% en poids ou moins du produit.

11. Produit selon l’une quelconque des affirmations précédentes,

dans lequel le produit comprend en outre un ou plusieurs accélérateurs choisis dans le groupe consistant en sulfate
de sodium, oxalate de sodium, fluorure de sodium,
40 dans lequel le ou les accélérateurs représentent 5% en poids ou moins du produit.

12. Procédé de fabrication d’un béton cellulaire composite géopolymère (GCCC) comprenant :

(a) mélanger ensemble un ou plusieurs matériaux de cendres volantes de classe F, un ou plusieurs activateurs
45 de gélification et un ou plusieurs activateurs de durcissement, produisant ainsi un mélange de composants de
liant composite ;
(b) mélanger le mélange de composants de liant composite avec un ou plusieurs activateurs alcalins, produisant
ainsi un mélange activé ;
(c) mélanger le mélange activé avec un ou plusieurs agrégats, un ou plusieurs agents moussants, produisant
50 ainsi une pâte de béton cellulaire composite géopolymère (GCCC) ;
(d) verser la pâte GCCC dans un moule et laisser la pâte GCCC mousser, se dilater, prendre prise et durcir à
température ambiante, produisant ainsi une masse GCCC durcie ;
(e) retirer la masse du GCCC durcie du moule et laisser durcir la masse GCCC durcie à température ambiante,
produisant ainsi un produit GCCC ;
55
dans lequel chacun des un ou plusieurs matériaux de cendres volantes de classe F comprend 15% en poids ou
moins d’oxyde de calcium ;
dans lequel le ou les activateurs alcalins comprennent une solution d’activateur alcalin comprenant un ou plusieurs

37
 EP 2 970 003 B1

hydroxydes métalliques, un ou plusieurs silicates métalliques et de l’eau;

dans lequel le ou les exhausteurs de gélification sont choisis dans le groupe comprenant le métakaolin, le méta-
halloysite, le micron et les nanoparticules de silice et d’alumine, et les matériaux d’aluminosilicate pouzzolanique
qui ont une faible teneur en oxyde alcalino-terreux et une vitesse de dissolution élevée dans une solution alcaline;
5 dans lequel le ou les exhausteurs de durcissement sont choisis dans le groupe comprenant les scories de haut
fourneau granulées broyées, les cendres volantes de classe C, l’aluminosilicate de calcium vitreux, la poussière de
four, les aluminosilicates pouzzolaniques riches en CaO et leurs combinaisons;
dans lequel le ou les agents moussants comprennent de la poudre d’aluminium ou un agent moussant à base de
peroxyde ;
10 dans lequel le liant composite est un liant sans ciment de Portland;
dans lequel une quantité d’un ou plusieurs matériaux de cendres volantes de classe F est de 1 à 50% en poids de
la pâte GCCC, une quantité du ou des exhausteurs de gélification est de 1 à 50% en poids de la pâte GCCC, et
une quantité d’un ou plusieurs exhausteurs de durcissement représente 1 à 50% en poids de la pâte GCCC; et
dans lequel le produit GCCC a une densité apparente de 1200 kg / m 3 à 1800 kg / m3 et une résistance à la
15 compression de 28 jours d’au moins 17 MPa ou 2500 psi.

13. Procédé selon l’affirmation 12,

dans lequel une quantité de ou des hydroxydes métalliques, sous forme d’oxydes de métaux alcalins, est de 2 à
12% en poids de la pâte GCCC;
20 dans lequel une quantité de ou des silicates métalliques, sous forme de silice soluble, est de 2 à 15% en poids de
la pâte GCCC; et
dans lequel un rapport massique de l’eau aux composants solides dans la pâte GCCC varie de 0,20 à 0,55.

14. Procédé selon l’affirmation 13,

25 dans lequel l’étape (b) comprend le mélange du mélange de composants de liant composite avec un ou plusieurs
membres du groupe constitué d’un retardateur de prise, d’un accélérateur, d’un agrégat, d’une charge ultrafine et
/ ou submicronique, et d’un matériau fibreux;
dans lequel le retardateur de prise représente 5% en poids ou moins de la pâte GCCC et est choisi dans le groupe
constitué par le métaphosphate de sodium, l’acide phosphorique, le borax, l’acide borique, les citrates alcalins,
30 l’hydroxyde de baryum, le nitrate de baryum, le chlorure de baryum, le zinc nitrate et gypse;
dans lequel l’accélérateur représente 5% en poids ou moins de la pâte GCCC et est choisi dans le groupe consistant
en sulfate de sodium, oxalate de sodium, fluorure de sodium;
dans lequel l’agrégat comprend, du sable de rivière représentant 60% en poids ou moins de la pâte GCCC ou un
agrégat léger représentant 40% en poids ou moins de la pâte GCCC ; dans lequel le ou les agrégats légers com-
35 prennent un ou plusieurs agrégats légers fins ou grossiers comprenant du laitier amplifié, de l’ardoise amplifiée, du
schiste amplifié, de l’argile amplifiée, de la perlite amplifiée, de la pierre ponce, de la scorie ou des cendres volantes
granulées amplifiées ;
dans lequel chacun de un ou plusieurs agrégats légers a une densité de 50 kg / m3 à 1000 kg / m3;
dans lequel la charge ultrafine et / ou submicronique a une taille de particules allant de 0,05 à 10 um et représente
40 12% en poids ou moins de la pâte GCCC; et
dans lequel le matériau fibreux représente 5% en poids ou moins de la pâte GCCC et est choisi dans le groupe
constitué de fibre organique, fibre de verre, fibre minérale, fibre de basalte et fibre de carbone.

45

50

55

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39
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40
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41
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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 5605570 A [0033] [0190] • US 20120152153 A1 [0057]

• WO 2012069024 A [0037] [0190] • US 20120152153 A [0190]
• US 20120024196 A [0057] [0190]

Non-patent literature cited in the description

• ESMAILY, H. ; H. NURANIAN. Non-autoclaved high • AGUILAR, R.A. ; O.B. DIAZ ; J.I. ESCALANTE
strength cellular concrete from alkali activated slag. GARCIA. Lightweight concretes of activated metaka-
Construction and Building Materials, 2012, vol. 26 (1), olin-fly ash binders, with blast furnace slag aggre-
200-206 [0190] gates. Construction and Building Materials, 2010, vol.
• ˇ
VLCEK, J. ; H. ELEKOVÁ ; V. TOMKOVÁ ; V. 24 (7), 1166-1175 [0190]
ˇ
MATEKJA ˇ ˇ
; F. OVCACIK. Lightweight materials • JOSEPH HENON, J. ; A. ALZINA ; J. ABSI ; D.S.
based on slag from production of iron and steel, 2010 SMITH ; S. ROSSIGNOL. Potassium geopolymer
[0190] foams made with silica fume pore forming agent for
thermal insulation. Journal of Porous Materials, 2013,
vol. 20 (1), 37-46 [0190]

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