Thermal insulation material and method for making the same
The present invention relates to a cellular structure thermal insulation material, a mineral
foam from which to obtain said thermal insulation material as well as the methods for making
such materials.
5 There is nowadays a substantially increasing demand for thermal insulation materials.
Indeed, one believes that the building industry in France accounts for about 46% of total energy
costs and for 25% of carbon dioxide total emission. Building energy performance regulations
makes provision for substantial reductions in domestic energy consumption.
To be able to aim at those objectives, not only consumers will have to deeply change
10 their life habits but also fundamental innovations in the field of building thermal insulation
technologies will have to be achieved.
In addition, in order to efficiently perform the renovation of the existing home park, it is
important for such new technologies to be readily implemented by users, while being financially
compatible with home owner budgets.
15 Amongst the insulation techniques, the distinction should be made, especially on the
renovation market, between techniques dedicated to inner insulation and to outer insulation.
Innovative building techniques are also emerging such as Monowall bricks and the use
of bearing panels of the sandwich type comprising a framework filled with insulation materials.
Insulation materials that are traditionally used nowadays in the hereabove mentioned
20 insulation techniques do vary in nature:
- mineral: glass wools, rock wool, vermiculites,
- polymers: expanded polystyrene foam (EPS) and extruded polystyrene foam (XPS),
polyurethane foam (PU), polyisocyanurate foam (polyisocyanurate),
- naturally originating from plants or animals: bulk cellulose or injected cellulose, hemp,
25 flax, wood (fibers, chips, board), straw, cork, cotton, Coco, sheep's wool, duck feathers.
Their intrinsic performance as regards thermal insulation is characterized by the
coefficient of thermal conductivity A. This coefficient A corresponds to the heat flux crossing over
1 m2 of a 1 m-thick wall, when the difference in temperature between both sides equals
1 degree (A is expressed in W / m.°C (Celsius or Kelvin)). The lower such coefficient is, the
30 more performant the material from the thermal insulation point of view.
All the previously mentioned materials suffer from drawbacks and use limitations. Rock
wool, glass wool and vermiculites tend to "pack down" over time leading to efficiency loss. In
addition, to satisfy the requirements of the new regulations governing energy performance
(2005 Thermal Regulation), it is necessary for achieving such performances to increase the
35 thickness of the materials, which causes problems of useful space loss (for example: 400 mm of
thickness for glass wool...). The improvements in the intrinsic efficiency of this type of materials
by increasing the density thereof remain limited.
2
Polymers which possess thermal conductivity values within the lower range (0.029 for
polyisocyanurate ) suffer from drawbacks that are related to the problematic recycling, and
especially to the need to separate the polymer from the building materials for waste disposal.
Moreover, they do raise problems of fire resistance and potential release of toxic fumes in case
5 of fire ( PU foams very especially).
The materials of natural origin by definition have performances that do "vary " from one
batch to the other and suffer from durability problems due to the compaction phenomenon.
For the sake of clarity hereafter , the following conventions will be adopted:
All weight percentages , unless otherwise specified , are expressed as related to the
10 weight of dry matter in the compositions.
a Cement slurry:
As used herein , a cement slurry is intended to mean a composition in its plastic state
obtained by adding at least one mineral hydraulic binder , water, and optionally specific
additives, calcium sulfate, and fillers.
15 a Aqueous foam:
As used herein , aqueous foams are intended to mean those foams composed of at least
one gas, in particular air, and one solvent which may be water . Those foams do not contain any
mineral binder.
They are characterized in the initial time by their initial coefficient of expansion = total
20 volume in the initial time/ volume of solution used for generating the foam.
As used herein , the initial time is intended to mean the moment when the operator has
achieved the air entrainment for generating the foam , such as described in the patent
FR2913351 (Al).
Inherently unstable , they are further characterized by their stability over time , commonly
25 measured through half -life, that is to say the time required for obtaining a drainE +ge equivalent to
the half of the whole liquid used for producing the same.
The stability of these foams may be improved by suitably selecting surfactants combined
with foam stabilizers such as for example alkanolamides , hydrocolloids , proteins mentioned in
the patent applications and the patents WO/2008/020246. WO/2006/067064 and US 4,218,490.
30 a Mineral foam:
As used herein , a mineral foam is intended to mean a foam comprising at least one gas,
in particular air, at least one solvent which may be water , at least one mineral hydraulic binder
and at least one filler, notably a fine, in the hereunder defined amounts.
These foams like the preceding ones will change over time and will be only stabilized when the
35 mineral binder will have reacted to "freeze" the structure of the material.
a Hardened mineral foam:
As used herein , mineral foams are intended to mean those mineral foams that are finally
obtained after the reaction (hydration ) of the hydraulic binder which will "freeze", via the
3
percolation of the hydrate network, the backbone of the mineral foam. A mineral foam also
means the cellular structure thermal insulation material obtained through hardening of the
mineral foam.
As an alternative of the invention, the thermal insulation material is obtained from a
cement slurry based on an aluminous hydraulic binder comprising low-density hollow fillers,
through hardening of the cement slurry.
® Aluminous hydraulic binder (abbreviated AHB):
As used herein, aluminous hydraulic binders are intended to mean hydraulic binders
comprising at least one phase selected from C3A, CA, C12A7, C11A7CaF2, C4A3$ (Yee
10 lemite), C2A(1-x)Fx (where x belongs to 10,1]), hydraulic amorphous phases having a C/A
molar ratio ranging from 0.3 to 15 and such that cumulated amounts of AI203 in these phases
range from 3 to 70% by weight of the hydraulic binder total weight, preferably from 7 to 50% by
weight and better from 20 to 30% by weight.
In particular embodiments, this binder may also optionally contain, by weight as related
15 to the binder total weight:
- from 0 to 90%, preferably up to 70%, even more preferably up to 50% and most
preferably up to 40% of calcium sulfate or of a calcium sulfate source, and,
- from 0 to 10%, preferably from 0 to less than 5% of Portland cement. At the same time,
hardened mineral foams based on hydraulic binder have been developed for various
20 applications. Many patents describe especially how to make cellular concretes by incorporating
aqueous foams or by generating gases in situ through aluminium metal decomposition.
Lightweight concretes having improved freezing-thawing resistance properties thanks to
an air bubble network absorbing stresses and restraining the crack propagation have been
extensively documented and published. The patent US 7,288,147 may especially be mentioned.
25 It is also known to use light-weight cement slurries for cementing oil wells in unstable
rocks and lands such as the deep-sea sedimentary environments described in the patent
application US 2005/126781.
Hardened mineral foams are known from GB-1,506,417, that are obtained from binders
of the ettringite type, that is to say from mixtures of aluminous cement and calcium sulfate. US-
30 4,670,055 also describes binders based on aluminate and calcium sulfate. However, these
binders are used for making calcium silicate-based foam blocks with a very high density.
Hardened mineral foams are known from GB-1578470 and GB-2162506, that are obtained from
aluminous cement and high amounts of silicates. The cellular materials obtained after
hardening of these mineral foams as a drawback suffer from having poor mechanical resistance
35 properties and very high densities.
WO00/23395 describes aerated mortar compositions based on calcium aluminate and
comprising a filler in the form of aggregate. The insulation materials obtained from these
compositions have a very high density and therefore insufficient performances as regards
4
insulation. The document RU2365087 describes hardened mineral foams based on calcium
aluminate, gypsum and sand. Insulation materials obtained in this document have a high
thermal conductivity and a high density. Hardened mineral foams have also been developed for
fire protection applications wherein, thanks to their intrinsic non combustibility characteristics or
5 even refractory properties , they offer an obvious advantage over materials comprising organic
base or polymer components . However, while these hardened mineral foams fully meet the fire
protection requirements, the conductivity values thereof A remain too high for applications of the
thermal insulation type, which require conductivity values at 20° C lower than or equal to
0.2 W/m .° C, even more preferably lower than or equal to 0.15 W/m .°C, even lower than or equal
10 to 0.08 W/m.°C and most preferably lower than or equal to 0.045 W/ m.°C. Properties of
0.2 W/m .° C have been obtained with silica-derived materials , as described in DE3227079.
However such materials as a drawback suffer from possessing high densities (400 to
600 kg/m3), poor mechanical performances and poor fire resistance properties. Low thermal
conductivity materials have also been described in EP 2 093 201. There are lime-based foams
15 obtained from a mixture of hydraulic lime and cement . However, the use of hydraulic lime
unfortunately leads to the formation of products with a very high density. Aluminous cements
have also been described in JP-06056497 to obtain such conductivity performances. However
these materials are substantially based on pumice , and have a very high density (800 kg/m3)
because they are poorly aerated. And yet it is technically very difficult to attain these thermal
20 conductivity values at 20 °C while keeping a material having a minimal mechanical behavior and
preserving its physical integrity, that is to say a material that will not collapse under its own
weight. Moreover obtaining materials with a lower density than that of the prior art is, also a
problem which has been solved by the present invention.
The intrinsic insulating performance of a material resulting from a hardened cement
25 based mineral foam will be the higher as the gas bubbles fraction in the material will be high
and said bubbles will be as fine as possible and not connected so as to avoid thermal bridges.
And yet an increase in the pore volume for a given pore size distribution , that is good for the
insulating character also results in an increased weakness of the material which explains how
fire-resistant hardened mineral foams do reach such limit.
30 Finally, a method for making thermo-insulating hardened mineral foams is described in
the patent EP 0 121 524 comprising the provision of an aqueous foam stream through
mechanical foaming with air, of an aqueous solution of polyvinyl alcohol and a dispersant
followed with the addition to the aqueous foam stream of an aqueous solution comprising
magnesium oxide and barium metaborate . In this patent, the provision of a stable aqueous foam
35 is enabled through the combined use of polyvinyl alcohol and sodium or barium metaborate.
Boric acid salt acts here as a crosslinking agent for polyvinyl alcohol enabling to fix the size of
the air bubbles included in the material. A chemical stabilization of the aqueous foam therefore
occurs.
5
There is thus a need for new solutions that would be at the same time efficient, easy to
implement and cost effective while respecting the safety of the operators and users and
enabling to obtain a good compromise between workability, mechanical behavior, low density
and thermal insulation.
i The applicant discovered surprisingly that particular aluminous hydraulic binder
compositions make it possible to incorporate great amounts of air in a finely divided form,
especially in the form of bubbles, or in the form of low density hollow fillers and to obtain after
hardening of the binder a material with a low thermal conductivity and a high mechanical
strength , especially a high compressive strength. Thus a cellular structure material could be
10 obtained from a hardened cement based mineral foam having outstanding thermal insulation
properties but also with a sufficient short-term mechanical strength for this material to be used
in many applications requiring especially the placing in situ of said material.
Such compressive strength values cannot be obtained when binders are used that are
essentially made of Portland cement. The present invention relates to a cellular structure
15 thermal insulation material comprising by weight as compared to the material total weight:
a) from 4 to 96% of a cement matrix obtained by hydration of a hydraulic binder that is
characterized , prior to being contacted with water, in that it comprises at least one phase
selected from C3A, CA, C12A7, CI1A7CaF2, C4A3$ (Yee lemite), C2A(1-x) Fx (where x
belongs to ]0 , 1]), hydraulic amorphous phases having a C/A molar ratio ranging from 0.3 to 15
20 and such that cumulated amounts of AI203 of these phases be ranging from 3 to 70% by
weight of the hydraulic binder total weight, preferably from 7 to 50 % by weight and preferably
from 20 to 30% by weight,
b) from 4 to 96% of at least one filler, preferably a fine.
Said material advantageously has a coefficient of thermal conductivity at 20°C, lower than or
25 equal to 0 .2 W/m°C, better lower than or equal to 0.15 W/m°C, preferably lower than or equal to
0.08 W/m°C, even more preferably lower than or equal to 0.045 W/m°C, and most preferably,
lower than or equal to 0.04 W/m°C.
Preferably , the binder of the insulating material of the invention comprises in addition as
related to the binder total weight
30 - from 0 to 90%, preferably up to 70%, even more preferably up to 50 % and most
preferably up to 40% of calcium sulfate or of a calcium sulfate source, and,
-froth 0 to less than 5% of Portland cement.
Preferably the cement matrix accounts for 10 to 80%, and better for 20 to 60% by weight
of the cellular structure thermal insulation material.
35 As used herein, "hydration of a hydraulic binder" is intended to mean the contacting of
the hydraulic binder with water , the weight ratio of water to hydraulic binder ranging typically
from 0.1 to 0.7, preferably from 0.15 to 0.5.
Advantageously, the mineral foams of the invention are prepared by using water as a
solvent and this weight ratio characterizes the mineral foams of the invention.
Such hydration may be effected when preparing the cement slurry as described
hereafter, or at any time by introducing water or an aqueous solvent when preparing the mineral
5 foam.
The invention further relates to a method for making the thermal insulation material, or
hardened mineral foam, this method comprising the production of a mineral foam or a cement
slurry comprising low-density hollow fillers which will be described hereunder and a step of
setting or hardening, which will take more or less time depending on the additives used.
10 The invention further relates to the mineral foam enabling to obtain, after hardening, the
thermal insulation material as well as the method for making the mineral foam.
The invention moreover relates to the cement slurry comprising low-density hollow fillers
enabling to obtain, after hardening, the thermal insulation material as well as the method for
making this cement slurry.
15
For attaining thermal conductivity values compatible with applications of the thermal
insulation type, it is not only necessary to form a very fine aqueous foam in the initial state, but
also it is advisable to have a hydraulic matrix which enables to obtain a mineral foam having on
the one hand a sufficient workability to allow the placing thereof and on the other hand the very
20 early development of a hydrate network for stabilizing the mineral foam in its plastic
configuration before the Ostwald ripening phenomenon occurs.
The applicant discovered that the use of aluminous hydraulic binders AHB is particularly
well adapted to obtain a compromise between workability properties of the foam and the early
development of the hydrate network.
25 In an alternative, these properties may be obtained by using low density hollow fillers
dispersed in a cement slurry based on such aluminous hydraulic binders AHB.
In a preferred alternative, these properties are improved by using fillers selected from
reactive fillers.
The very high hydraulic potential of these phases, which develops as soon as the
30 binders AHB is contacted with water, immediately leads to the nucleation of a great amount of
small-sized hydrates (which may have a submicrometer to micrometer size) which:
- firstly stabilize the mineral foam in its plastic phase (thus preventing the Ostwald
ripening) for a time period which may be adjusted depending on the desired workability,
between 5 and 30 minutes, even to more than 30 minutes
35 - secondly enable through percolation the formation of a mineral hydrated skeleton
which will ensure the early acquisition of the mechanical performances and allow the provision
of the hardened mineral foam of the invention and/or of the thermal insulation material of the
invention.
5
7
It is particularly interesting to use hydraulic binders comprising calcium sulfate or a
source of calcium sulfate , so as to promote the production of ettringitic and hydrated alumina
phases which have both advantages to reinforce the mechanical properties of the hardened
mineral foam and to also improve the fire resistance of the latter.
These binders are particularly interesting for the provision of a high early mechanical
strength . At 24 h, the materials of the invention possess at least 80% of their final mechanical
strength, which is not the case for those materials of which the binder is essentially made of
Portland cement.
These binders also enable to control and to limit the shrinkage of the material upon
10 hardening.
The use of hydraulic binder AHB of the invention enables to obtain hardened mineral
foams that are free of polymers, especially of EPS, XPS, PU and PIR type polymers, these
hardened mineral foams having the expected properties of thermal conductivity and good fire
resistance.
15 This type of hydraulic binders AHB enables therefore to improve the fire resistance of the
materials, which represents a clear improvement over foams based on polymers of the EPS,
XPS, PU and PIR type.
Moreover the use of this type of hydraulic binder AHB improves the mineral foam
production reliability in industrial conditions since the susceptibility to Ostwald ripening becomes
20 less problematic and since the optimization of the surfactant and foam stabilizer system
becomes therefore less crucial.
As non limitative examples, the binders of the invention will be able to contain aluminous
cements and cements of the calcium sulphoaluminate type which will be able to be optionally
associated with a source of calcium sulfate.
25 Non limitative examples of commercially available aluminous cements include for
example Secar 71, Secar 51, Fondu cement, Ternal RG, Ternal EV marketed by the Kerneos
company, and aluminous cements marketed by the Calucem, Cementos Molins companies and
by the TMC and Denka companies in Japan. Non limitative examples of commercially available
sulpho-aluminous cements include for example Rapidset marketed by CTS, Alipre cement
30 marketed by the Italcementi company, calcium sulpho-aluminates marketed by Polarbear and
Lionhead.
The aluminous hydraulic binders AHB of the invention, as a consequence of their
reactivity, enable to rapidly develop a hydrate network which percolates, freezes the bubble
diameter and forms the mineral skeleton of the hardened mineral foam. This phenomenon
35 occurs whatever the agent used to obtain the aqueous foam, that is to say whatever the
foaming agent, the air-entraining agent or the gas-generating agent. Indeed, it seems that the
mechanisms underlying the invention correspond to a mineral stabilization obtained thanks to
the formation of the hydrates which freeze at an early stage the gas or air inclusions. Therefore
8
a hardened mineral foam is thus obtained, having small-sized bubbles that are very
homogeneously distributed.
The invention therefore differs from the hardened mineral foam compositions described
in the prior art and especially in the patent EP 0 121 524 in the specific choice of a hydraulic
5 binder AHB. Indeed, the high reactivity of the mineral compounds used enables to obtain a
hardened mineral foam of a superior quality without requiring for example the use of the
polyvinyl alcohol + boric acid salt combination. For this reason, the mineral foam as well as the
hardened mineral foam and the cellular structure thermal insulation material of the invention do
preferably not contain the polyvinyl alcohol + boric acid salt combination.
10 As compared to the prior art which deals with the optimization of the surfactant systems
in order to limit the Ostwald ripening, the present invention enables therefore to manage the
setting of the mineral system in the early stages and to overcome, amongst others, the Ostwald
ripening which results in an increase in the bubble size and thus in an increase in the coefficient
of thermal conductivity and a reduction of the mechanical strength.
15 The stabilization of the hardened mineral foam or of the cement slurry obtained thanks to
the high reactivity of the hydraulic binders AHB associated, or not, with calcium sulphates
according to the invention enables, as compared to an improvement of the aqueous foam
stability or of the mineral foam stability obtained by the relevant selection of surfactants
combined with polymers or other aqueous foam stabilizers well known from the person skilled in
20 the art such as proteins, polymers of natural or synthetic origin, to obtain in a reliable and robust
manner a hardened mineral foam having a fine and homogeneous bubble network leading after
setting to a cellular structure thermal insulation material having a lower thermal conductivity
while retaining good mechanical strength characteristics.
As compared to the mineral foams of the prior art comprising large amounts of silicates,
25 the hardened mineral foams of the invention have a lower density associated with a high
mechanical strength.
As an alternative of the invention, the porosity may be provided by the presence of low
density hollow fillers in the cement slurry, optionally associated with an aqueous foam.
The systems of the invention as a non negligible additional advantage have a good
30 short-term mechanical strength expressing especially through the following compressive
strength values after 3 hours:
- CS values higher than 0.2 MPa, preferably higher than 0.3 MPa, and even more
preferably higher than or equal to 0.5 MPa for materials having lambda values lower
than 0.08 W/m°C
35 - CS values higher than 0.8 MPa, preferably higher than 1 MPa and even more preferably
higher than 1.5 MPa for lambda values ranging from 0.08 to 0.2W/m°C.
The systems of the invention are characterized by the following compressive strength values
after 24 hours:
9
CS values higher than 0.3 MPa, preferably higher than or equal to 0.5 MPa for materials
having lambda values lower than 0.08 W/m°C
CS values higher than 1 MPa preferably higher than 1.5 MPa for lambda values ranging
from 0.08 to 0.2W/rn°C.
5 The thermal insulation materials of the invention are also characterized by a shrinkage
value lower than 500 pm/rn, preferably lower than 400 pm/m, advantageously lower than
300 pm/m and even more preferably lower than 200 pm/m. This shrinkage is measured
according to the method taught by the NF EN 128 08-4 standard.
This property advantageously provides the materials of the invention with a good
10 adhesion to walls for filling hollow building elements and a better stability over time. This
property is particularly important when placing the foam in situ: building renovation, composite
slab construction, to avoid the formation of thermal bridges.
Finally, the mineral foams of the invention as a further advantage allow to modulate the
setting time. This is profitable as compared to mineral foams comprising essentially Portland
15 cement as a binder which does not intrinsically develop a so high hydrate nucleation in the early
stages.
Mineral foams based on Portland cement (without accelerator systems) have, typically,
setting times exceeding 2 hours.
The mineral foams and cement slurries of the invention may have a workability as short
20 as 5 minutes (flash setting) or as long as 30 minutes. The mineral foam of the invention
therefore has a workability which can be easily adjusted to values ranging from 5 to 30 minutes,
or even to values exceeding 30 minutes. The fact for the setting time to be adjustable is
advantageous in that for making precasts, a quick setting of from 20 to 30 minutes is interesting
whereas for applications requiring the placing in situ of the mineral foam, longer setting times,
25 exceeding 30 minutes, or even exceeding 1h or 2 hours, may be advantageous. Thus, with
hydraulic binders AHB workabilities of more than one hour, or even of more than two hours may
be obtained, while retaining a fast mechanical performance acquisition kinetics after the period
of workability. Small-sized hydrates precipitated during the period of workability make the
mineral foam stabilize without affecting the plastic, characteristics thereof, which is known from
30 the person skilled in the art.
The compromise between workability time and mechanical performance acquisition may
be readily adjusted by using the accelerator /retarder additive systems known from the person
skilled in the art and described hereafter.
The, rest of the description does refer to appended Figures which show:
35 On Figure 1, a diagram of a device for making an aqueous foam or a mineral foam of the
invention;
10
On Figures 2 a) to 2 c), a photograph of a cellular structure thermal insulation material or
hardened mineral foam of the invention (2a), of a material based on Portland cement without
setting accelerator (2b) and with setting accelerator (2c); and
On Figures 3a and 3b, optical microscopy images (x5) of cross-sections of the material
5 of the Figure 2a.
Figures 4 to 10 show optical microscopy images (x5) of cross-sections of the materials of
examples 3 to 7 and 9.
The cellular structure thermal insulation material or hardened mineral foam of the
invention does moreover possess the following characteristics, either alone or in combination:
10 - it has a pore volume ranging from 70% to 95%, preferably from 80% to 95%;
- it has a density lower than or equal to 500 KgIm 3, preferably lower than or equal to 300
Kg/m3. Advantageously, it has a density which may be from 80 to 250 Kg/m3;
- it has a cell mean size of less than 500 pm, preferably of less than 400 pm,
advantageously of less than 300 pm. Such cell sizes have been observed through optical
15 microscopy of cross-sections of materials;
- it has a compressive strength Cs at 3 hours higher than or equal to 0.2 MPa, preferably
higher than or equal to 0.3 and even more preferably higher than or equal to 0.5 MPa,
- it has a fire resistance at 600°C, preferably at 900°C and even more preferably at
1 200°C for three hours.
20 Surprisingly, as compared to materials of the hardened mineral foam type of the prior art,
the thermal insulation materials of the invention may have a high pore volume and a low density
while retaining a very good mechanical strength. The combination of these properties results
from the choice of a particular aluminous hydraulic binder composition which enables to
incorporate a high amount of air bubbles or a high amount of hollow fillers while retaining a
25 mineral network provided with a strong cohesion.
- the hydraulic binder AHB may comprise by weight as related to the hydraulic binder
total weight:
- from 10 to 90%, preferably from 10 to 70%, even more preferably from 10 to 50% and
most preferably from 20 to 40% by weight of calcium sulfate.
30 - the hydraulic binder AHB may further comprise from 0 to 10% by weight of Portland
cement, preferably from 0 to less than 5% and even more preferably from 2 to less than 5% of
Portland cement.
- The hydraulic binder may further comprise one or more additives included selected
from foaming agents and foam crosslinking agents, setting accelerators, setting retarders,
35 rheology modifiers and water retaining agents, dispersants and superplasticizers, preferably
said additive(s) accounting for up to 15% by weight, preferably up to 10% and typically for 5% or
less of the hydraulic binder total weight.
11
Especially setting-time controlling agents selected from setting accelerators and setting
retarders may represent from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight as
related to the hydraulic binder total weight.
Fillers or fines (fillers which particle size by convention is of less than 100 pm) are
5 typically selected from silica fume, blast furnace slag, steel slag, fly ash, limestone fillers,
particulate silica, silicas including pyrogenated and precipitated silicas, silicas recovered in rice
husks, diatomaceous silicas, calcium carbonates, calcium silicates, barium sulfate, metakaolins,
titanium, iron, zinc, chromium, zirconia, magnesium metal oxides, alumina under its various
forms (hydrated or not), alumina hollow beads, boron nitride, lithopone, barium metaborate,
10 calcinated, standard or expanded clays, perlite, vermiculite, pumices, rhyolite, chamotte, talc,
mica, optionally hollow, glass beads or expanded glass granules, silicate foam grains, silica
aerogels, sands, broken gravels, gravels, pebbles, carbonate black, silicon carbide, corundum,
rubber granules, wood, straw.
According to the invention, fines are mineral fillers the components of which have a size
15 of less than 100 micrometers.
The hardened mineral foam may further comprise one or more other components such
as additives introduced when preparing the binder or the mineral foam, preferably said
additive(s) represent up to 15% by weight, typically from 3 to 10% of the material total weight.
These additives may be selected from foaming agents and foam stabilizers, setting
20 accelerators, setting retarders, rheology modifiers and water retaining agents, dispersants or
superplastifiants.
- The hardened mineral foam or the cement slurry may also contain other additives such
as waterproofing agents as well as thermoplastic or thermosetting polymers introduced for all or
part thereof, either when preparing the binder or the mineral foam or by spraying or
25 impregnating onto the hardened mineral foam. When used, these additives represent typically
from 0.5 to 25%, preferably from 1 to 15% by weight of the cellular structure thermal insulation
material total weight.
The hardened mineral foam or the cement slurry of the invention may further comprise
fibers or microfibers, for example cellulose, polyvinyl alcohol, polyamide, polyethylene,
30 polypropylene, silicone, metal and/or glass fibers, fibers of natural origin such as hemp fibers,
coco fibers, cotton fibers, wood fibers; having preferably a length ranging from 20 pm to 6 mm
and a diameter of from 10 to 800 pm.
- These fibers are introduced into the binder composition or into the mineral foam and
may represent up to 2% by weight of the cellular structure thermal insulation material total
35 weight.
The cellular structure thermal insulation materials of the invention have preferably a
density lower than or equal to 500 Kg/m3 preferably lower than or equal to 300 Kg/m3.
Advantageously, they have a density which may be from 80 to 250 Kg/m3.
12
Preferably the thermal insulation material of the invention contains from 1 to 40% of low
density hollow fillers, advantageously from 5 to 30% by weight as compared to the thermal
insulation material total weight.
In one embodiment, the cellular structure thermal insulation material has advantageously
5 the following composition by weight as compared to the material total weight:
a) from 50 to 96%, preferably from 70 to 96% and even more preferably from 90 to 96%
of a hydraulic binder AHB such as defined hereabove containing:
- from 10 to 90 %, preferably from 10 to 70%, even more preferably from 10 to 50%
and even more preferably from 20 to 40% by weight of calcium sulfate, and,
10 b) from 1 to 40% of at least one material selected from reactive fillers,
c) from 0.5 to 5% of a material selected from reactive filler activators,
d) from 0 to 2%, preferably from 0 to 1% of fibers or microfibers, and
e) from 0 to 15% of additives selected from foaming agents and stabilizers or foam
crosslinking agents, setting accelerators, setting retarders , rheology modifiers and water
15 retaining agents, dispersants and superplastifiants.
In another embodiment of the invention, the cellular structure thermal insulation material
has advantageously the following composition by weight as compared to the material total
weight:
a) from 50 to 96%, preferably from 70 to 96% and even more preferably from 90 to 96%
20 of a hydraulic binder AHB such as defined hereabove containing:
from 10 to 90%, preferably from 10 to 70%, even more preferably from 10 to 50%
and even more preferably from 20 to 40% by weight of calcium sulfate, and,
b) from 1 to 80%, preferably from 1 to 60%, advantageously from 1 to 40% of at least
one material selected from low density hollow fillers,
25 c) from 0 to 2%, preferably from 0 to 1% of fibers or microfibers,and
d) from 0 to 15% of additives selected from foaming agents and stabilizers or foam
crosslinking agents, setting accelerators, setting retarders, rheology modifiers and water
retaining agents, dispersants and superplastifiants.
In one embodiment, the cellular structure thermal insulation material has, advantageously
30 the following composition by weight as compared to the material total weight:
a) from 50 to 96%, preferably from 70 to 96% and even more preferably from 90 to 96%
of a hydraulic binder AHB such as defined hereabove containing:
- from 10 to 90%, preferably from 10 to 70%, even more preferably from 10 to 50%
and even more preferably from 20 to 40% by weight of calcium sulfate, and,
35 - from 0 to less than 5% by weight of Portland cement,
b) from 4 to 50%, preferably from 4 to 30% and even more preferably from 4 to 10% of
fines,
c) from 0 to 2%, preferably from 0 to 1% of fibers or microfibers, and
13
d) from 0 to 15% of additives selected from foaming agents and stabilizers or
foam crosslinking agents, setting accelerators , setting retarders , rheology modifiers and water
retaining agents, dispersants and superplastifiants . The material of the invention may possess
an open- or closed-cell structure, typically both open and closed.
5 The invention further relates to the mineral foam which acts as a precursor for obtaining
the cellular structure thermal insulation material (hardened mineral foam) of the invention.
The mineral foam of the invention used for making the cellular structure thermal
insulation material described hereabove may have the following characteristics , either alone or
in combination:
10 ® it comprises:
15
- at least one hydraulic binder AHB such as described hereabove optionally
containing calcium sulfate, and /or optionally containing Portland cement,
- at least one filler, preferably fines,
- at least one aqueous and/or non aqueous solvent and
- at least one gas such as air, carbon dioxide or nitrogen.
The invention further relates to a hollow filler-containing cement slurry which acts as a
precursor for obtaining the cellular structure thermal insulation material (hardened mineral foam)
of the invention.
The hollow filler-containing cement slurry of the invention used for making the cellular
20 structure thermal insulation material described hereabove may have the following
characteristics, either alone or in combination:
it comprises:
at least one hydraulic binder AHB optionally containing calcium sulfate,
25
and /or optionally containing Portland cement,
- at least one low density hollow filler,
- at least one aqueous and/or non aqueous solvent.
In the cement slurries or the mineral foams of the invention, the low density hollow filler is
introduced in amounts ranging from 1 to 80%, preferably from 1 to 60%, advantageously from 1
to 40% most preferably from 5 to 30% by weight as compared to the dry matter total weight in
30 the cement slurry or in the mineral foam.
The compositions of mineral foam and cement slurry used for implementing the present
invention advantageously comprise:
An aluminous hydraulic binder such as defined hereabove.
Preferably the binder comprises from 10 to 90% by weight, as related to the binder total
35 weight, of calcium sulfate.
Advantageously, these mineral foam or cement slurry compositions contain in addition at
least one filler selected from reactive fillers. They may also contain low-density hollow fillers.
14
As used herein, a reactive filler is intended to mean a filler, which takes part to the
hydration reaction of the hydraulic binder. According to the present invention, the category of
materials called " reactive fillers " does neither include Portland cement nor calcium silicate.
Preferably , the mineral foam or cement slurry composition comprises , for making the
5 hardened mineral foam material of the invention, from 1 to 30% by weight, preferably from 1.5
to 15%, advantageously from 2 to 10%, this percentage being related to the dry matter total
weight in the mineral foam , of at least one filler selected from reactive fillers.
Advantageously, the mineral foam or cement slurry composition comprises, for making
the hardened mineral foam material of the invention from 0.5 to 5%, by weight as compared to
10 the mineral foam composition total weight of at least one reactive filler activating compound.
As used herein, a reactive filler activating compound is intended to mean a compound
selected from alkaline and alkaline earth metal salts, especially alkaline and alkaline earth metal
carbonates and sulfates . In addition to the reactive fillers and low density hollow fillers that are
mentioned hereabove, the mineral foam composition of the invention may contain chemically
15 inert fillers or fines. They represent advantageously from 10 to 70% by weight of the mineral
foam o r cement slurry dry matter weight.
In particular embodiments , the binder may also optionally contain , as related to the
binder total weight from 0 to less than 5% of Portland cement.
Calcium silicate is one of the components of Portland cement, and traditionally
20 represents from 40 to 60% of Portland cement by weight of the composition.
Advantageously , the binders of the invention may contain from 0 to less than 3%, most
preferably to less than 2 %, by weight of alkaline or alkaline earth metal silicate, this component
being employed alone or being incorporated as a contribution of Portland cement.
They may contain from 0 to less than 5% by weight of calcium hydroxide and calcium
25 oxide, in cumulated % by weight for both materials , as related to the mineral foam or cement
slurry weight.
Suitable reactive fillers or fines (fillers which particle size by convention is of less than
100 pm) to be used in the binders of the invention include especially: silica fume, blast furnace
slag, steel slag, fly ash, metakaolins , silicas including pyrogenated and precipitated silicas,
30 silicas recovered in rice husks , diatomaceous silicas, alumina under its various forms (hydrated
or not), alumina hollow beads, calcinated, standard or expanded clays, silica aerogels,
pozzolans . Amongst the chemical materials which may be used in the present invention as a
reactive filler, some exist in various particle sizes. Amongst the existing particle sizes for these
materials, some correspond to a chemically inert structure. The use of reactive fillers in the
35 present invention is intended as being related to a material in a form which actually enables this
material to take part to the hydration reaction of the hydraulic binder. When present, Portland
cement does not come into the category of reactive fillers.
15
Preferably the reactive fillers used in the invention have a median diameter D50 lower
than or equal to 30 pm, advantageously lower than or equal to 15 pm.
Preferably the reactive fillers used in the invention have a median diameter D90 lower
than or equal to 80 pm, advantageously lower than or equal to 35 pm.
5 As used herein a median diameter D. lower than or equal to y pm is intended to mean
that x% of the particles have a diameter lower than y pm. The measure is effected using a laser
granulometer of the Malvern type.
Non reactive fillers or fines (fillers which particle size by convention is of less than
100 pm) are typically selected from limestone fillers , particulate silica , calcium carbonates,
10 barium sulfate, titanium , iron, zinc, chromium ,zirconia, magnesium metal oxides , boron nitride,
lithopone, barium metaborate , perlite, vermiculite , pumices, rhyolite , chamotte, talc, mica,
optionally hollow , glass beads or expanded glass granules, silicate foam grains , sands, broken
gravels, gravels , pebbles, carbonate black, silicon carbide , corundum , rubber granules, wood,
straw.
15 The mineral foam or slurry composition comprising hollow fillers is further characterized in
that:
® it may further comprise preferably a compound selected from surfactants, air-entraining
agents and/or gas-generating agents
® it has a workability which may be adjusted to 5 -30 minutes or a workability longer than
20 30 minutes,
- the solvent(s) represent(s) from 10 to 40% by weight of the mineral foam
total weight, preferably from 20 to 30% by weight,
® it may further comprise one or more additives selected from foaming agents and
stabilizers or foam crosslinking agents, setting accelerators , setting retarders, rheology
25 modifiers and water retaining agents, dispersants and superplasticizers
it may further comprise other additives selected from waterproofing agents, fibers,
thermoplastic or thermosetting polymers.
A suitable mineral foam composition according to the invention has advantageously the
30
35
following composition, by weight as compared to the mineral foam total weight:
- from 50 to 80%, preferably from 60 to 70% of hydraulic binder AHBIO, for
40%, preferably from 20 to 30% of solvent,
from 2 to 10%, preferably from 2 to 5% of fines, and optionally
from 0.1 to 15%, preferably from 3 to 10% of an additive selected from
foaming agents and stabilizers or foam crosslinking agents, setting
accelerators, setting retarders, rheology modifiers and water retaining
agents, dispersants and superplastifiants
amongst which, especially:
- from 0.1 to 2% of a foaming agent,
16
- from 0.1 to 2% of a crosslinking agent,
- from 0.1 to 2% of a dispersant,
- from 0.1 to 10% of setting accelerators or retarders.
5 The invention further relates to a method for making a mineral foam such as described
above. The methods and devices for making foams are known and described for example in the
patents US2005/0,126,781 and US 4,731,389.
The method of the invention comprises the following steps, consisting in:
a) preparing an aqueous foam from a composition comprising at least water and at least
10 one compound selected from foaming agents, air-entraining agents and gas-generating agents,
b) preparing a cement slurry comprising
- mixing the binder with a solvent and optionally at least one compound selected from
surfactants, air-entraining agents and gas-generating agents,
c) introducing one or more filler(s) for all or part of them into the aqueous foam and/or
15 cement slurry,
d) mixing the aqueous foam and the slurry together.
According to another embodiment, the mineral foam may be prepared according to a
preparation method comprising the following steps, consisting in:
20 a) preparing a cement slurry comprising:
mixing the binder together with a solvent and optionally at least one compound selected
from surfactants, air-entraining agents and gas-generating agents,
b) injecting a gas into the slurry while maximizing the contact surface between the gas
and the cement slurry,
25 c) incorporating one or more fillers for all or part of them during or after the step a), or
during or after the step b).
According to another embodiment, the hollow filler-containing cement slurry of the
invention may be prepared according to a preparation method comprising the following steps,
30 consisting in:
a) preparing a cement slurry comprising:
mixing the binder AHB together with a solvent,
b) incorporating into the slurry at least one low density hollow filler,
c) incorporating one or more fillers for all or part of them during or after the step a), or
35 during or after the step b).
1 7
When used in the preparation of the hollow filler--containing mineral foams or cement
slurries of the invention, the reactive filler activating compound may be introduced into the
cement slurry or with the fillers.
In all three embodiments described hereabove , the additives , such as setting activators
5 and so on , may be introduced for all or part of them into the slurry or into the foam or after
having combined the foam and the slurry.
The maximization of the contact surface between the gas and the cement slurry may be
obtained, for example by using a static mixer. Moreover , introducing for all or part of them the
filler into the slurry at the same time as the gas increases the contact surface between the gas
10 and the slurry.
According to another embodiment , the mineral foam may be generated without adding
surfactants through simple air entrainment when preparing a cement slurry comprising a
hydraulic binder AHB , optionally containing calcium sulfate , a solvent, and optionally fillers,
which may be introduced for all or part thereof either when preparing the slurry , or after this
15 step.
Finally, the invention relates to the use of the mineral foam or hardened mineral foam as
a cellular structure thermal insulation material for making thermal insulating materials:
for making precast panels comprising at least one insulating layer based on mineral
foam or hardened mineral foam,
20 - for filling hollow parts in building elements for facilities by placing in situ said mineral
fcam such as walls, ceilings, hollow blocks, doors, ducts,
- for making hot floors by placing in situ the foam in contact with the under-surfaces of.
pipes,
for applying outdoors a monolayer having an insulation function for facing a building by
25 placing in situ said mineral foam.
When the hardened mineral foam is used for preparing materials dedicated to these
applications (thermal insulation), a coefficient of thermal conductivity at 20°C lower than or
equal to 0.045 W/m.°C is particularly advantageous.
The invention further relates to the use of the mineral foam or hardened mineral foam in
30 applications for insulating refractories:
- for making refractory bricks,
- for making monolithic concretes by placing in situ said mineral foam.
When the mineral foam or hardened mineral foam is used for preparing materials
dedicated to applications for insulating refractories, the structure is typically reinforced through
35 the use of light fillers previously mentioned in order to limit the shrinkage after burning and to
increase the mechanical strength.
Moreover a coefficient of thermal conductivity at 20°C lower than or equal to 0.2 W/m°C
and preferably lower than or equal to 0.15 W/m°C is sufficient in this application.
1S
Preferably, the binder of the invention is an ettringite binder. As used herein, an ettringite
binder is intended to mean a hydraulic binder which components, upon hydration under normal
conditions of use, give ettringite as the main hydrate, which is a trisulfocalcium alurninate having
the formula 3CaO,AI203.3CaSO4.32H20. Calcium sulfate-containing binders AHB through
5 hydration lead to the formation of ettringite. For this reason, the hydraulic binder AHB of the
invention comprises, preferably from 10 to 90% by weight of calcium sulfate as related to the
hydraulic binder total weight, preferably from 10 to 70%, even more preferably from 10 to 50%,
and most preferably from 20 to 40%.
Calcium sulfate originates from compounds of natural or synthetic origin, or from the
10 treatment of by-products selected from anhydrites, semi-hydrates, gypsums and combinations
thereof. The use of a hydraulic binder AHB comprising highly reactive materials enables to
obtain mineral foams, cement slurries and thermal insulation materials having very low binder
ratios, for example lower than 20%, preferably lower than 10%, or even of 4% by weight as
compared to the composition total weight.
15 Depending on the applications, the cellular structure thermal insulation materials of the
invention preferably comprise at most 70% by weight of fillers, even more preferably at most
60% of fillers.
Thus, the hydraulic binders of the invention may predominantly comprise an aluminous
cement and (or) a calcium sulfoaluminate cement. However, they may comprise Portland
20 cement as a minor component, preferably in a maximal amount of 5% by weight as related to
the hydraulic binder total weight.
The materials of the invention also have outstanding properties of fire resistance. It can
be observed that this property is more pronounced when using an ettringite binder thanks to the
great amount of bound water present in the ettringite molecular structure.
25 Preferably, the hydraulic binder of the invention comprises setting-time controlling
additives such as setting accelerators or setting retarders. They represent from 0.1 to 15% by
weight, preferably from 0.1 to 10% by weight as related to the hydraulic binder total weight.
The setting accelerators used in the present invention may be of any type known. Their
use enables to adjust the workability of the mineral foam or of the cement slurry. To be
30 mentioned as illustrative examples are sodium aluminate, sodium silicate, potassium aluminate,
aluminium sulfate, potassium carbonate, lithium salts such as lithium hydroxide, lithium sulfate
and lithium carbonate to be used alone or in combination.
The setting retarders used in the present invention may be of any type known, and to be
especially mentioned as illustrative examples are citric acid, tartaric acid, gluconate, and boric
35 acid and salts thereof to be used alone or in combination.
Water retaining agents and rheology modifiers may be selected in the family including
cellulose ethers, guar ethers, starch ethers, associative polymers, polymers obtained through
biofermentation such as xanthan gums, wellan gums...
19
In order to limit the moisture transfers inside the hardened mineral foam, which
significantly increase the coefficient of thermal conductivity and therefore significantly reduce
the thermal insulation efficiency, it is interesting to incorporate a waterproofing agent introduced
for all or part of it either into the mineral foam or into the cement slurry mass during the
5 preparation thereof, or through impregnation of the hardened mineral foam. To be mentioned as
illustrative, non limitative examples of suitable waterproofing agents are:
- silicon oils of the polydimethylsiloxane type which may be functionalized or not with
reactive groups of the Si-H, Si (OMe), Si (OEt) type, the aqueous emulsions derived from these
oils such as for example described in the patent US 5,373,079;
10 - organosilanes such as trialkoxysilanes and silazanes described in the patent US 2,005,
018,217,4;
- siliconates such as for example potassium methylsiliconate;
- paraffins, waxes of the stearate and oleate types, vegetable oils and their derivatives
such as marketed by the Novance company.
15 These waterproofing agents will be used depending on their nature, either neat or diluted
in a solvent, or dispersed or emulsioned in water.
In order to reinforce the mechanical properties of the hardened mineral foam, it is
interesting to introduce polymers during the preparation of the mineral foam or of the cement
slurry such as for example polyvinyl alcohols, polyamides, latexes in a liquid form or in a
20 powdered form.
As used herein, a latex is intended to mean an emulsion of one or more polymers
obtained through radical polymerization of ethylenically unsaturated monomers selected from
styrene, styrene derivatives, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl
propionate, vinyl n-butyrate, vinyl laurate, vinyl pivalate and vinyl stearate, VEOVA° 9 to 11,
25 (meth)acrylamide, (C1-C20)alkyl esters of methacrylic acid, (C2-C20) alkenyl esters of
methacrylic acid with alkanols of from 1 to 12 carbon atoms, such as methylester, ettylester, nbutylester,
isobutylester, t-butylester and 2-ethylhexylester of acrylic and methacrylic acids,
nitriles, acrylonitriles, dienes, such as 1,3-butadiene, isoprene, monomers carrying two vinyl
groups, two vinylidene groups or two alkylene groups.
30 It can also be envisaged to introduce some thermosetting or photo-crosslinkable
polymers, for all or part thereof, either during the preparation of the mineral foam or of the
cement slurry, or by spraying or impregnating onto the hardened mineral foam.
Suitable examples of thermosetting polymers (which do crosslink under the action of
heat or a radiation) include as non limitative examples polyurethanes, epoxies and polyesters.
35 The fillers used in the invention are typically inert materials used as a filling agent. In an
especially advantageous embodiment, it is envisaged to use reactive fillers in the mineral foam.
In another advantageous alternative it is envisaged to use low-density hollow fillers in the
mineral foam or in the cement slurry. The fillers may be mineral or organic in nature. The
20
mineral fillers may be for example selected from silica fume, blast furnace slag, steel slag, fly
ash, limestone fillers, particulate silica, silicas which pyrogenated and precipitated silicas, silicas
recovered in rice husks, diatomaceous silicas, calcium carbonates, barium sulfate, metakaolins,
titanium, iron, zinc, chromium, zirconium, magnesium metal oxides, alumina under its various
5 forms (hydrated or not), alumina hollow beads, boron nitride, lithopone, barium metaborate,
calcinated, standard or expanded clays, perlite, vermiculite, pumices, rhyolite, chamotte, talc,
mica, optionally hollow, glass beads or expanded glass granules, silica aerogels, silicate foam
grains, sands, broken gravels, gravels and/or pebbles. The organic fillers may be selected in the
group made of organic polymer beads (polytetrafluoroethylene, polyethylene, polypropylene,
10 polystyrene, polyvinyl chloride, polydimethylsiloxane), rubber granules, wood such as cork
powder, filler wood, straw and/or polystyrene flakes.
Low-density hollow fillers are preferably used. Preferably, the fillers have a lower density
as that of fresh mortar (which is of less than 3). Typically the low density hollow fillers have a
density of less than 0.5, preferably of less than 0.1, advantageously of less than 0.05. The
15 hollow filler size is preferably ranging from 10 pm to 2.5 mm. Hydrophobic fillers, for example of
calcium carbonate, are preferably used. The fine fillers, that is to say fillers having a mean
diameter D90 lower than or equal to 5 pm, preferably lower than 1 pm reinforce the mineral
foam. Preferably, the material of the invention comprises fillers of mean diameter (D90) lower
than or equal to 5 pm.
20 To be mentioned as foam glass granules are the granules marketed under trademark
Poraver® having a bulk density as a function of the particle size ranging from 140 to 530 Kg/m3.
For example, granules with a standard particle size of 4 - 8 mm have a bulk density of 180
kg/m3 and granules with a particle size of 0.1 - 0.3 mm have a density of 400 kg/m3. To be
mentioned are also the foam glass granules Liaver, the particle size of which does range from
25 0.25 to 4 mm as well as grains with a higher particle size (0 - 72 mm) marketed under the trade
name Misapor®.
To be mentioned as hollow glass beads are the glass beads marketed by the 3M,
Potters PQ and Akzo Nobel Expancel companies, with a particle size ranging from 20 pm to
110 pm and a density of about 100 kg/m3.
30 To be used as cenospheres are the products marketed by the Trelleborg Fillite, Potters
PQ, Omega Minerals companies. These fillers are cenospheres with a particle size of 0 -
0.5 mm, the bulk density of which does range from 350 to 450 kg/m3.
To be mentioned as silicate foam grains are the grains SLS®20 which are very
lightweight grains, hydrophobic in nature.
35 To be used as expanded clays are for example those with a particle size of 0 - 4 mm
and having a bulk density of about 200 kg/m3.
21
The pumices or pumice stones are highly porous volcanic rocks with a low density often
of less than 1. Preferably , pumices have a particle size ranging from 0.3 to 8 mm. This product
is marketed by the Quick Mix company.
Expanded clays used according to the invention preferably have a particle size ranging
5 from 1 to 8 mm and a bulk density ranging from 280 to 650 kg/m3. These products are marketed
by the Maxit Fibo and Liapor companies. Surface-treated expanded clays may be chosen for
reducing water demand.
The expanded shales used according to the invention preferably have a particle size
ranging from 2 to 8 mm. These products are marketed by the Berwilit company.
10 Perlite used according to the invention preferably has a particle size ranging from 0 to
6 mm and a bulk density ranging from 39 to 95 kg/m3. This product is marketed for example by
the Knauf and Pavatex companies.
Vermiculite used according to the invention preferably has a particle size ranging from 0
to 2 mm and a bulk density ranging from 60 to 160 kg /m3. This product is marketed for example
15 by the Isola-Mineralwblle Werke, CMMP and Reppel companies.
Rhyolite used according to the invention preferably has a particle size ranging from 10 to
350 l im and a bulk density ranging from 180 to 350 kg /m3. This product is marketed for example
by the Lafarge Noblite company.
Other types of additives may also be used, such as for example water retaining agents
20 and rheology modifiers which may be selected from the family of cellulose ethers, guar ethers,
starch ethers , polyvinyl alcohols, polyacrylamides , associative polymers, polymers obtained
through biofermentation such as xanthan gums, wellan gums, pyrogene silicas, precipitated
silicas, laponites, bentonites, hectorites...
Dispersants may also be used, such as for example lignosulfonates, naphthalene
25 sulfonates, melamine sulfonates , caseins, modified polycarboxylates , polymers comprising
phosphonate units, phosphates and phosphonates.
The mineral foam or the hollow filler-containing cement slurry are obtained from a
cement slurry . The cement slurry may be prepared extemporaneously , that is to say just before
use. In this case, the hydraulic binder components may firstly be mixed together with the
30 setting-time controlling agents and optionally the fillers and/or other additives so as to form a
powdered mixture, then the thus obtained mixture be mixed with water or a solvent to form a
cement slurry.
It is also possible to employ a ready-to-use aqueous slurry, that is to say a slurry that
has been prepared beforehand. In this case, the slurry should be stabilized to exhibit a high life-
35 time, that is to say of at least one month, even more preferably of two months, preferably 3
months or more, and even more preferably of at least 6 months, in order to saveguard storage
life or delivery times.
22
As used herein , the "life-time" is intended to mean the time during which a component
remains in the form of an aqueous or non aqueous suspension of solid products , more or less
fluid, that is able to return to the aqueous or non aqueous suspension state through a simple
mechanical stirring, without setting.
5 The slurry in aqueous phase should be stabilized (or retarded) for several months. Boric
acid or one salt thereof suspended in water may be used to that end for example . It will
therefore be required for initiating the setting to "release " the cement contained in the slurry
before use . To that purpose, a material is typically used, that is able to "release" the retarded
aluminous cement and optionally a catalyst enabling to accelerate the setting of the cement, for
10 example , a mixture of lime and lithium hydroxide. The patents EP 0241 230 and EP 0 113 593
disclose systems of this type.
To obtain the mineral foam of the invention, the cement slurry described hereabove may
be combined with an aqueous foam comprising at least one compound selected from foaming
agents, air-entraining agents and gas-generating agents . An instrumentation can be used, such
15 as illustrated on Figure 1 for preparing the aqueous foam. A mixture of water and foaming
agents or air-entraining agents 1 is pumped by means of a metering pump 2 and is co-injected
with a gas 3 in a mixing device 5 for example a static mixer (or a tube filled with beads). The
gas, for example air, nitrogen or carbon dioxide is collected from a gas source 3. The injected
gas flow rate is monitored using a flowmeter 4. According to another embodiment , the mixture
20 of gas and water, of foaming agents and /or air-entraining agents flows through several bead
stirrers 5 and 6 having beads of continuously decreasing diameters. Finally the aqueous foam is
recovered in a container 7.
According to another embodiment of the invention , to the cement slurry is directly added
at least one compound selected from foaming agents , air-entraining agents and gas-;generating
25 agents, then a gas is injected into this slurry so as to form the mineral foam. The gas injection is
effected by maximizing the interaction surface between the gas and the slurry so as to obtain a
plentiful and stable mineral foam. An instrumentation may be used such as that described on
Figure 1 by replacing the combination of water and foaming agents or air-entraining agents by
the additived cement slurry.
30 According to another embodiment , the mineral foam may be generated without adding
surfactants by air entrainment when preparing a cement slurry comprising a hydraulic binder
AHB, a solvent, fillers, preferably reactive fillers or low-density hollow fillers, or for example
fillers, which may be introduced for all or part thereof either when preparing the slurry, or after
this step.
35 According to another embodiment , hollow fillers are incorporated into the cement slurry
so as to generate pores.
The mineral foam or the cement slurry thus obtained may be directly used for making a
cellular structure thermal insulation material (or hardened mineral foam) of the invention. The
23
mineral foam or the cement slurry or the hardened mineral foam of the invention
advantageously does not require any chemical treatment, especially any expensive
hydrothermal treatment. The cellular structure thermal insulation material of the invention may
therefore be obtained without any chemical or hydrothermal treatment.
5 According to the invention, any foaming agent traditionally used for foaming cement can
be suitably used, such as anionic, non ionic surfactants and combinations thereof. An additive
for stabilizing the aqueous foam may optionally be added. The stabilizing additives may be
either surfactants, or polymers, long-chain alcohols, in a liquid form or as solid particles such as
for example alkanolamides, hydrocolloids, proteins mentioned in the patents WO/2008/020246,
10 WO/2006/067064, and US 4,218,490. The foam of the invention may not comprise any foaming
agent or foam stabilizer.
The air-entraining agents are compounds which make it possible to stabilize the air
bubbles entrapped by the turbulences resulting from stirring. To be mentioned as air-entraining
agents are wood natural resins, sulfate or sulfonate compounds, synthetic detergents and
15 organic fatty acids.
The gas-generating agents used according to the invention may for example be selected
from compounds producing nitrogen, oxygen, hydrogen, carbon dioxide, carbon monoxide,
ammoniac or methane. The patent US 2005/0,126,781 mentions a plurality of gas-generating
agents, which can be used according to the invention. To be mentioned as illustrative examples
20 are compounds containing hydrazine or azo groups such as hydrazine, azodicarbonamide,
azobis (isobutyronitrile), p-toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide,
carbohydrazide, p-p'-oxybis (benzenesulfonyl hydrazide) and combinations thereof. Examples
of nitrogen-producing agents which do not contain any hydrazine or azo group include organic
or inorganic acid ammonium salts, hydroxylamine sulfate, carbamides and combinations
25 thereof. Examples of oxygen-producing agents are for example the bleaching agents that are
traditionally used in detergent field, such as for example peroxides, percarbonates, persulfates,
peroxycarbonates. The material (hardened mineral foam) or the mineral foam or the hollow
filler-containing cement slurry of the invention are particularly useful for improving the thermal
insulation and the fire resistance in facilities. Indeed, the material (hardened mineral foam) or
30 the mineral foam or the cement slurry may be used for making precast panels comprising at
least one insulating layer based on that material (hardened mineral foam) such as:
- for making panels for replacing polystyrene panels used in thermal insulation systems
from the outside,
- for making sandwich panels, wherein the mineral foam, or the hollow filler-containing
35 cement slurry, is introduced between two walls of building material (wood, plywood,
polystyrene, plaster, concrete),
- for making load-bearing or not, insulating pre-walls, or hollow blocks and bricks to be
used for construction,
2/1
- for making panels for replacing composite slab panels with glass fibers or PU inside,
used for the inner thermal insulation of a house.
The material (hardened mineral foam ) or the mineral foam or the hollow filler-containing
cement slurry may also be used for placing in situ the mineral foam for filling hollow parts in
5 building elements for facilities , such as walls , ceilings, hollow blocks, doors , ducts...
The material or the mineral foam may also be used for placing in situ the mineral foam
as under-surface in contact with the pipes for hot floors.
The material or the mineral foam or the hollow filler-containing cement slurry may also
be used for applying in situ the mineral foam on the. outside, as a monolayer having an
10 insulating function for rendering buildings, where such monolayer may be covered with an
aesthetic finishing coat.
The material , or the mineral foam of the invention, or the hollow filler -containing cement
slurry is also especially useful for making insulating concretes or bricks for refractory
applications including the production of refractory bricks and the placing in situ of the mineral
15 foam for making monolithic concretes.
Finally , the mineral foam or the hollow filler-containing cement slurry of the invention
may be used as a ready -to-use concrete from which to obtain a thermo -insulating material used
in following applications:
- structures , studs, cross walls and slabs in Monowall elements thus enabling to reduce
20 thermal bridges at the junctions,
- outer concrete shells enabling the reduction of thermal bridges between the various
floors of a building,
- slabs on earth platforms,
- filling of double-walls,
25 - roof and terrace insulation.
Examples
I - Definition of protocols
1. 1 - Determination of thermal conductivity and thermal shrinkage.
30 - Measurement of the thermal conductivity, A at 20°C.
Thermal conductivity values have been measured according to the standard EN
12667:2001 "Thermal performance of building materials and products. Determination of thermal
resistance by means of guarded hot plates and heat flow meter methods. Products of high and
medium thermal resistance".
35 1.2 - Determination of compressive strength.
The compressive strength was determined according to the standard EN 196-1 with
concrete cubes of 100x100x100 mm after 3 and 24 hours.
25
1.3 - Determination of the apparent porosity of a concrete according to the standard: EN
993-1
1.3.1 - Instrumentation
- Weighing scale 0.1 g fitted with a fastening device for the basket receiving the sample
- Vacuum bell
- Vacuum pump with pressure gauge
- Water jar at 20°C
- Pail of water at 20°C
10 1.3.2 - Procedure
- Dry the sample in oven at 60 ° C (civil engineering) or at 110°C (refractory) for 24h
- Weigh the dry sample (P1)
- Introduce the sample in the vacuum bell
- Create vacuum and control pressure gauge (< 50 mBar)
15 - While maintaining suction, slowly introduce water in the vacuum bell until covering the
sample with 2 cm water (submerge the sample under vacuum)
- Maintain suction to the end of water ebullition (=>to remove air from the pores)
- Shut the valve of the vacuum bell. off and turn the pump off
- Allow impregnation under vacuum to proceed for a minimum of 3 hours (degassing
20 time of the sample)
- Bring the bell back to atmospheric pressure
- Remove the sample to test and remove excess water with a damp sponge (do not dry
the sample)
- Weigh the water-saturated sample (P2)
25 - Tare the weighing scale with the water-saturated sample on the plate
- Introduce the sample in the metallic basket suspended under the weighing scale
- Immerge the whole in a pail under approximately 10 cm water
Read the weight (P3), which enables to measure the water weight displacement and
therefore the volume of the sample (buoyancy measurement on the water-saturated specimen)
30 POROSITY (%) = (Water-saturated weight - Dry weight) / Volume x 100
POROSITY (%) = (P2 - P1)/P3 X100
1-4: Determination of true density and apparent porosity by the pycnometer method
1-4-1: Instrumentation
3 5 - Pycnometer Micromeritics ACCUPYC 11 1340.
- Precision weighing scale of the Mettler type + /- 0.0001 g.
- Bottle + pressure regulator helium (99.995% mini) 1.5 bars (21.5 psi)
26
1-4-2: Range of validity - accuracy
- Measuring range: > 0.2g /cm3
- Measurement accuracy: 0.05%
5 I-4-3: Procedure
Preparation of samples:
The sample should be placed in an oven at 60°C (mini 2h), then cooled down so as to remove
water and stabilize more.rapidly the measure (5 identical successive measurements).
Tare the sample supporting cell and fill the same to 2/3. Save the exact mass. Introduce the cell
10 in the pycnometer and close the cover.
Initiate the measurement cycle through the computer program.
Results:
Determination of true density of a solid (g/cm3) based on the measurement of the volume
15 occupied by a known mass of material present in the cell.
20
25
The result corresponds to the average of the five last results within the device confidence
interval (0.02% in volume variation).
The computerized results to within 0.01 g / cm3 express the value.
POROSITY (%) = 1-(1/bulk density measured ® 1/true density) x 100
1-5: Measurement of pore diameters through optical microscopy
The hardened mineral foam is impregnated with a hardenable resin (epoxy resin) to be
observable under optical microscopy. After 12h hardening, the sample is cut out transversally to
plates of about 4 cm* 4cm, with a thickness ranging from 0.05 to 3 mm. The observation of the
sample transversal surface is effected under magnification X5.
11 - Examples of compositions of the invention and evaluation of the thermal conductivity and
compressive strength of insulation materials of the invention
30 II. A. Exam1:
II. A. 1 - Preparation of binders
Following components were added to a container:
35
27
Component Binder of
the invention
L1
Hydraulic binder :
Calcium aluminate from the TMC company 70 g
Gypsum 30 g
Lithium carbonate 0.05 g*
Citric acid 0.18 g*
Dispersant:
Mighty 21 PZ® (Polycarboxylate ether powdered) 0.22 g
Cellulose ether 0.19
Microfibers of cellulose:
Arbocel® 40 (CFF) length 0.45-1 tam. 0.5
Filler:
silica fume Rw Q1 Fuller 5g
Water: 22.5
Crosslinking agent:
LithoFoam®NWFS .5 g
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
is thus obtained.
5 II. A. 2 - Production of the aqueous foam
Mix in a bowl following products:
- 6 g of a foaming agent Lithofoam® SL400-L (protein of 20000 to 120000 D altons),
- 0.40 g of cellulose ether,
- 80 g of water.
10 The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced.
II. A. 3 - Preparation of the mineral foam
20 grams of the aqueous foam are incorporated into the cement slurry prepared
15 hereabove by means of the electric mixer for 3 minutes at medium speed (graduation 3).
II. A. 4 - Pouring and drying of the mineral foam
The mineral foam is poured into molds of 4 cm*4 cm*16 cm previously lubricated with a
mold oil.
20
II. A. 5 - Mineral foam composition
25
28
Composition Amounts
(parts by weight)
%
(by weight)
Binder 94.5 66.8%
Water 38.6 (21.2 + 17.4) 27.3%
Foaming agent 1.3 0.9%
Crosslinking agent 1.4 1%
Fillers 5.2 3.7%
Other additives 0.4 (0.3 + 0.1) 0,3%
II. A. 6 - Characterization of the insulating material obtained
- Density: 125 Kg/ma
5
- Compressive strength at 3 hours: Cs = 0.3 MPa
- Coefficient of thermal conductivity: A = 0.044 W/m.°C
- No default due to Ostwald ripening
- Porosity >90%.
II. B. Example 2: Comparison between the insulating material of the invention and an
10 insulating material based on Portland cement 52.5 R
11131.- Preparation of binders
Following components were added
Componen
Hydraulic binder:
Portland cement 52.5R (Lafarge Le Havre)
Calcium aluminate Ternal RG ® (Kerneos)
Anhydrite
Lithium carbonate
Sodium carbonate
Citric acid
o a container:
Dispersant:
Mighty® 21 PZ (Polycarboxylate ether
powdered)
Microfibers of cellulose:
Arbocel® 40 (CFF) length 0.45-1 pm
Fillers:
silica fume Rw Q1 Fuller
Water:
Foam curing agent:
Lithofoam® NWFS (solution = 30% dry
matter)
Binder of Comparative Comparative
the invention Binder I Bonder 2
L2 LCI LC2
4.76 g - 100 g 100 g
66.67 g
28.7 g
0.05 g
0.4 g
0.18 g
0.2g 0.2 g 0.2 g
0.2 g 0.2 g 0.2 g
5g 5 g
22.59 22.5 g 22.5 g
1.5 g 1.5 g 1.5 g
15
29.
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5).
II. B.2 - Production of the aqueous foam
Mix in a bowl following products:
- 5 g of a foaming agent Lithofoam ® SL400-L ( protein of 20000 to 120000 Daltons)
- 80 g of water.
The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced.
10
II. B.3 - Preparation of the mineral foam
20 grams of the aqueous foam are incorporated into 100 grams of binder by means of
the electric mixer for 3 minutes at medium speed (graduation 3).
The mineral foam of the invention is all the more easy to obtain as the aqueous foam
15 readily incorporates into the binding phase and the whale is homogeneous.
The comparative assay mineral foam 2 was difficult to obtain because the binder was
not fluid enough.
II.B.4 - Pouring and drying of the mineral foam
20 The mineral foam is poured into molds of 4 cm* 4 cm" 16 cm previously lubricated with a
mold oil.
The mineral foams are thereafter dried at 23°C and 60 % RH for 24h in order to obtain
the cellular structure thermo-insulating material of the invention.
It could be observed that the mineral foam predominantly based on Portland cement
25 obtained with the comparative binder LC1 collapsed (Figure 2b) as opposed to the mineral foam
of the invention predominantly based on aluminous cement L2 which did not collapse
(Figure 2a). Figure 2 c) represents the insulating material predominantly based on Portland
cement LC2 . A lesser collapse could be observed but a high inhomogeneity also within the
cellular structure thermo-insulating material obtained.
30
II. B.5 - Characterization of the cellular structure thermo-insulating material of the
invention.
Measurement of pore volume and density:
The density of the cellular structure thermo-insulating material is measured using a pycnometer,
35 this measure being compared to the result obtained through water porosimetry. Both methods
made it possible to measure a density of 0.29 and a pore volume of 85% for the insulating
material of the invention comprising an aluminous cement-, calcium sulfate- and Portland
cement-based binder.
30
Measurement of insulating material pore diameters:
The hardened mineral foam is impregnated with a hardenable resin (epoxy resin) in order to be
observable under optical microscopy. After 12h hardening, the sample is cut out transversally to
plates of about 4 cm* 4cm", with a thickness ranging from 0.05 to 3 mm.
5 The observation of the sample transversal surface is effected under magnification X5
and is illustrated on Figures 3 a) and 3 b).
As shown on Figures 2a to 2c, the hardened mineral foam of the invention (1-2. Figure 2a) has
an outstanding mechanical behavior, whereas the hardened mineral foams only based on
Portland cement, (LC1. Figure 2b and LC2. Figure 3b) collapsed upon contacting the aqueous
10 foam with the slurry.
The hardened mineral foam of the invention (L2. Figure 3a) comprises regularly
distributed (4 to 5 bubbles per mm2) and regularly sized bubbles, whereas the hardened mineral
foam of comparative example LCI (Figure 3b) has a heterogeneous bubble size and bubble
distribution.
15
II. C. Example 3: ettringitic binders with hollow fillers and comparison with
Portland cement 52.5R-based material
II. C. 1 - Preparation of binders
Following components were added to a container:
20
Component Binder of the
invention L3 with
hollow and reactive
fillers
Comparative/ Binder
1 LC3 without
hollow fillers
Comparative
binder 100% OPC
/ Binder I LC4
Hydraulic binder:
Portland cement 52.5R
(Lafarge Le Havre)
Calcium aluminate Secar
51 ® (Kerneos)
Anhydrite
Sodium carbonate
Citric acid
7.15 g
35.75 g
12.5g
0.1 g
7.15 g
35.75 g
12.5 g
0.1 g
100 g
.4 g
0.1 g
Hollow filler
Thermosilit® (h) 11.0 g
Reactive fillers:
silica fume Rw Q1 Fuller 5.03 g 5.03 g 5.03 g
Dispersant:
Conpac 500 0.36 g 0.36 g 0.36 g
Cellulose ether:
Tylose H300P2 1 0.11 g I 0.11 g _1_ 0.11 g
31
Resin
Vinnapass 5011 L
Fillers:
Durcal 2
Sand Palvadeau
0.315 mm
Water for mixing
finder of the Comparative/ Binder
invention L3 with I LC3 without
hollow and reactive hollow fillers
fillers
Comparative
binder 100% OP
/ Binder 1 LC4
(*) Thermosilit ® is a hollow filler of expanded perlite type which presents the following
characteristics:
Particle size: 0 - 2.5 mm
Density: 80 - 100 kg/m3
5
The components are mixed using an electric mixer for 30 seconds at low speed (graduation 1),
then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry is thus
obtained.
II. C. 2 - Production of the aqueous foam
10 Mix in a bowl following products:
- 4 g of a foaming agent Empicol ESC/3L (sodium laureth ether sulfate),
- 0.1 g of xanthan gum,
- 0.1 g of lithium sulfate,
- 92.8 g of water.
15
The whole is mixed with the electric mixer at high speed for 5 minutes until a homogeneous and
compact aqueous foam is produced , with a density of 50 kg.m3.
II. G. 3 - Preparation of the mineral foam
20 30 grams of aqueous foam are incorporated into 100 g of cement slurry prepared hereabove by
means of the electric mixer for 3 minutes at medium speed (graduation 3).
II. C. 4 - Pouring and drying of the mineral foam
The mineral foam is poured into molds of 4 cm*4 cm*16 cm or 10 cm *10 cm *10 cm in
25 polystyrene.
The mineral foams are thereafter dried at 23°C and 60% RH for 24h in order to obtain the
cellular structure thereto-insulating material of the invention.
It could be observed that the mineral foam predominantly based on Portland obtained with the
comparative binder LC3 collapsed as opposed to the mineral foam of the invention
32
predominantly based on aluminous cement 13 with reactive fillers and hollow fillers which did
not collapse.
Binder
II. C. 5 - Mineral foam composition (Binder L3 with reactive fillers and hollow fillers)
Composition
Hollow filler
Reactive filler
Filler
Water
Foaming agent
Other additives
L3%
(by weight)
32.78
6.51
2.98
14.79
39.75
0.30
3.19
II. C. 6 - Characterization of the insulating material obtained
- Density: 194 Kg/m3.
- Porosity: 91%
10 - Compressive strength at 3hours : 0.5MPa, at 24 hours: Cs = 0.8 MPa
- Coefficient of thermal conductivity : A = 0.07 W/m.°C
The comparative assay mineral foam with Portland cement LC4 could not be obtained due to
the collapse of the mineral foam. The causes of such collapse result from the low reactivity of
this system.
15 Measurement of the insulating material pore diameters:
Figure 4 shows pores which sizes range approximately from 100 to 550 pm.
II. D. Example 4: low concentration of binder without Ordinary Portland Cement (OPC),
with reactive fillers and hollow fillers
20 Il. D. 1 - Preparation of binders
Following components were added to a container:
Component
Hydraulic binder
Portland cement 52.5R (Lafarge LE
Havre)
Calcium aluminate Secar 51 ° (Kerneos)
Anhydrite Francis Flower
Semi-hydrate Prestia Creation
Ettringite binder with
hollow and reactive
fillers L4
9.1 g
3.51 g
0.39 g
Comparative binder
100% OPC /Ettringite
binder LC5
13.3 a
Air-slaked lime 1 0.3 g 1 0.3 g
33
Component Ettringite binder with
hollow and reactive
fillers L4
Comparative binder
100% OPC /Ettringite
binder LC5
Hollow filler
Silica aerogel Isogel® 5.0 g 5.0 g
Reactive fillers:
Slag (h) 5g 5g
silica fume Rw Q1 Fuller 5g 5g
Dispersant:
Compac 500 0.36 g 0.36 g
Cellulose ether:
Tylose MH15003P6 0.10 g 0.11 g
Fillers:
Durcal 130
Sand Sifraco BR36
33 g
37.5 g
25 g
11 g
(*)
The characteristics of the slag used in all examples are as follows:
Specific surface (Blaine): 2900cm2/g
True density: 2.913 g/cm3
5 Particle size (pm):
D10 3.49
D20 5.60
D50 12.65
D80 24.76
D90 33.22
The components are mixed using an electric mixer for 30 seconds at low speed (graduation 1),
thereafter 3 minutes and 30 seconds at high speed (graduation 5). A mineral foam is thus
10 obtained.
It. D. 2 - Production of the aqueous foam
Mix in a bowl following products:
4 g of a foaming agent Empicol CSC/3L (sodium laureth ether sulfate),
- 0.1 g of xanthan gum,
15 - 0.1 g of lithium sulfate,
34
- 92.8 g of water.
The whole is mixed with the electric mixer at high speed for 5 minutes until a homogeneous and
compact aqueous foam is produced, with a density of 50 kg.m3.
II. D. 3 - Preparation of the mineral foam
15 grams of aqueous foam are incorporated into 100 g of cement slurry prepared hereabove by
means of the electric mixer for 3 minutes at medium speed (graduation 3).
10 II D.4 - Mineral foam composition
Composition
Binder L3
Hollow filler
Reactive filler
Filler
Water
Foaming agent
Other additives
(by weight)
9.27
50.88
15
II. D.4- Characterization of the insulating material obtained
- Density: 232 Kg/ma
- Compressive strength at 3 hours: Cs = 0.2 MPa
- Coefficient of thermal conductivity : A = 0.0712 W/m.°C
- Porosity: 86%
The comparative assay mineral foam LC5 with Portland cement could not be obtained due to
the collapse of the mineral foam. The causes of such collapse result from the low reactivity of
20 this system.
25
Measurement of the insulating material pore diameters:
On Figure 5 , pores with a size of less than 300 pm can be observed
II E -Example 5: Production of foam in situ in the slurry with reactive filler and hollow
filler
II. E. 1 - Preparation of binders
30
Following components were added to a container:
Component
Hydraulic binder:
Portland cement 52.5R (Lafarge Le Havre)
Calcium aluminate Secar 51 ® (Kerneos)
Anhydrite Francis Flower
Semi-hydrate Prestia Creation
Air-slaked lime
Hollow filler
5
Thermosilit®
Reactive fillers:
Slag (*)
silica fume Rw Q1 Fuller
Dispersant:
Conpac 500
Cellulose ether:
Tylose H300P2
Fillers:
Durcal 130
Sand Sifraco BR36
Foaming system:
Empicol ESC/3L
Lithium sulfate
Xanthan gu
Water for mixing
7g
2.7 g
0.3 g
0.3 g
20.0 g
5g
5g
0.36 g
0.08 g
26 g
30.5 g
1g
0.1g
0.015
40 g
(*) cf example 4
The. components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), thereafter 3 minutes and 30 seconds at high speed (graduation 5). A mineral
foam is thus obtained.
II.E.2 -Pouring and drying of the mineral foam
Same method as lI.D.2.
II. E. 3 - Mineral foam composition
Ettringite
binder with
hollow and
eactive fillers
L5
10
Composition
(by
weight)
Binder 7.23
Hollow filler 14.46
Reactive filler 7.23
Filler 40.84
Water 28.91
Foaming agent 0.72
Other additives 0.56
II. E. 4- Characterization of the insulating material obtained
- Density: 287 Kg/m3.
- Compressive strength at 3 hours: Cs < 0.2 MPa, at 24 hours: Cs= 0.2 MPa
- Coefficient of thermal conductivity : A = 0.0821 W/m.°C
- Porosity: 88.5%
Measurement of the insulating material pore diameters: the size of the pores that can be
observed on Figure 6 is essentially lower than 200 pm.
10 II. F. Example 6: high binder ratio with OPC with hollow filler and with or without
reactive filler
II. F. 1 - Preparation of binders
Following components were added to a container:
Component Ettringite binder with
hollow and reactive
fillers L6
Ettringite binder with
hollow fillers and
without Slag 1-7
Hydraulic binder :
Portland cement 52.5R ( Lafarge Le
Havre)
4.5 g 4.5 g
Calcium aluminate Secar
(Kerneos)
51 ° 35.06 g 35.06 g
Anhydrite Francis Flower 10.52 g 10.52 g
Semi-hydrate Prestia Creation
Reactive fillers:
1.17g 1.17 g
Slag (") 5g
Silica fume Rw Q1 Fuller 5g 5g
Dispersant:
Compac 500 0.36 g 0.36 g
Cellulose ether:
Tylose H300P2 1 0.10 g 1 0.10 g
37
Component Ettringite binder with
hollow and reactive
fillers L6
Ettringite binder with
hollow fillers and
without Slag L7
Fillers:
Durcal 2 log 15 g
Sand Sifraco BR36 28 g 28 g
Water for mixing 22 g 22 g
(*) cf example 4
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
is thus obtained.
5 II. F. 2 - Production of the aqueous foam
Mix in a bowl following products:
- 4 g of a foaming agent Empicol ESC/3L (sodium laureth ether sulfate),
- 0.1 g of xanthan gum,
- 0.1 g of lithium sulfate,
10 - 92.8 g of water.
The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced , with a density of 50 kg.m3.
15 11. F. 3 - Preparation of the mineral foam
30 grams of aqueous foam are incorporated into 100 g of cement slurry prepared
hereabove by means of the electric mixer for 3 minutes at medium speed (graduation 3).
II. F. 4 - Pouring and drying of the mineral foam
20 The same as in II.C.4
II. F. 5 - Mineral foam composition (Binder 1 with Slags and hollow fillers and Binder 1
with hollow fillers without Slags)
Compositi
Binder 132.31
Reactive filler 6.31
Filler 124.08
Other additives
25
% (weight)
Binder L7
32.31
27.23
35.95
10
38
II. F. 6 - Characterization of the insulating material obtained
- Density: with binder L6 194 Kg/m3
With binder L7 143 Kg/m3
- Porosity: with binder L6 91 %
With binder L7 94%
- Compressive strength at 3 hours:
With binder L6 Cs = 0.2 MPa
With binder L7 Cs < 0.2 MPa
- Coefficient of thermal conductivity:
With binder L6 A = 0.053 W/m.°C
With binder L7 A = 0.045 W/m.°C
Measurement of the insulating material pore diameters:
With binder L6: the pore size that is observed on Figure 7 is essentially lower than
400 pm.
15 With binder L7: the pore size that is observed on Figure 8 is essentially lower than
350 pm.
II. G. Example 7: high binder ratio, without OPC, with hollow filler of silica aerogel type
II. G. 1 - Preparation of the binder
Following components were added to a container
Component Ettringite binder with
hollow and reactive
fillers L8
Cellulose ether
Tylose H300P2 0.11 g
9
Component
Fillers:
Durcal 2
Water for mixing
23 g
30 g
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
is thus obtained.
5 II. G. 2 - Production of the aqueous foam
Mix in a bowl following products:
- 4 g of a foaming agent Empicol (sodium laureth ether sulfate),
- 0.1 g of lithium sulfate,
- 92.8 g of water.
10
The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced, with a density of 50 kg.m3.
II. G. 3 - Preparation of the mineral foam
15 30 grams of aqueous foam are incorporated into 100 g of cement slurry prepared
hereabove by means of the electric mixer for 3 minutes at medium speed (graduation 3).
II. G. 4- Pouring and drying of the mineral foam
The same as in II. C
20 II. G. 5 - Mineral foam composition
Composition
Binder
Reactive filler
Hollow filler
Filler
Water
Foaming agent
Other additives
L8%
(by weight)
35.50
3.08
6.51
13.61
39.83
0.92
0.53
Ettringite binder with
hollow and reactive
fillers L8
II. G. 6 - Characterization of the insulating material obtained
- Density: 236 Kg/m3
40
- Porosity: 90.3%
- Compressive strength at 3 and 24 hours: Cs <0.2 MPa, Cs 28 f=days= 0.4 MPa
- Coefficient of thermal conductivity: A = 0.061 W/m.°C
Measurement of the insulating material pore diameters: on Figure 9 the pore size that is
observed on Figure 450 pm
II. H. Example 8: high binder ratio with OPC reactive filler of silica fume type
It. H. 1 - Preparation of the binder
Following components were added to a container
Componen Ettringite binder with
hollow and reactive
fillers L9
Ettringite binder with
hollow and reactive
fillers L10
Hydraulic binder:
Portland cement 52.5R (Lafarge Le
Havre)
Calcium aluminate Secar 51 °
(Kerneos)
Anhydrite Francis Flower
Tartaric acid
Reactive fillers:
Slag (*)
Silica fume Rw Q1 Fuller
8,25 g
35.06 g
11.69 g
0.1 g
5.20 g
8,25 g
35.06 g
11.69 g
0.1 g
5.0 g
5.20 g
Dispersant:
Compac 500 0.38 g 0.11 g
Resin
Vinnapass 5011 L
3.20 g 3.20 g
Cellulose ether
Tylose H300P2 0.11 g 0.11 g
Fillers:
Sand Palvacleau 0-0.315 mm
Durcal 2
16.51 g
19.5 g
16.51 g
14.5 g
Water for mixing 22 g 22 g
10 (*) cf example 4
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
is thus obtained.
15
41
II. H.2 - Production of the aqueous foam
Mix in a bowl following products:
- 1 g of foaming agent Glucopon CSUP 600 (alkyl polyglucoside ether),
- 0.3 g of Gluadin (wheat protein hydrolyzate),
5 - 0.3 g of lithium carbonate
- 0.1 g of cellulose ether H300P2
- 98.3 g of water.
The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced , with a density of 50 kg.m'.
10 II. H. 3 - Preparation of the mineral foam
30 grams of aqueous foam are incorporated into 100 g of cement slurry prepared
hereabove by means of the electric mixer for 3 minutes at medium speed (graduation 3).
II. H. 4 - Pouring and drying of the mineral foam
15 The same as in II. C. 4.
II. H. 5 - Mineral foam composition
Composition L9% I L10%
(by weight) I (by weight)
Binder
Reactive filler
Filler
Water
Foaming agent
Other additives
34.68
3.28
22.70
36.23
0.62
2.49
34.68
6.56
19,43
36.23
0.62
2.49
II. H. 6 - Characterization of the insulating material obtained
20 - Density: without Slag 212 Kg/m3. With Slag 300 Kg/m3
- Porosity: without Slag 90.3%, with Slag 80%
Compressive strength at 3 hours: Cs < 0.2 MPa, Cs at 24 hours: 0.5 MPa with slag and
<0.5 MPa without slag. Cs at 28 days without slag: 0.6 MPa
- Coefficient of thermal conductivity: A = W/m.°C, with slag: 0.102 W/m.°C
25
II. I. Example 9: high binder ratio with OPC reactive filler of silica fume tube +
hydrophobic agent
30
II. I. 1 - Preparation of the binder
Following components were added to a container
42
Component Ettringite binder with
reactive fillers LId 1
Hydraulic binder :
Portland cement 52.5R (Lafarge
Le Havre)
Calcium aluminate Secar 51
(Kerneos)
Semi-hydrate Prestia creation
Tartaric acid
Reactive fillers:
silica fume Rw Q1 Fuller
8,25 g
35.06 g
11.69 g
0.1 g
4g
Dispersant:
Compac 500 0.38 g
Resin
Vinnapass 8031H 0.7 g
Cellulose ether
Tylose H300P2 0.11 g
Fillers:
Sand Palvadeau 0-0.315 mm
Durcal 2
17.8 g
22 g
Water for mixing 22 g
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
5 is thus obtained.
10
II. 1.2 - Production of the aqueous foam
Mix in a bowl following products:
- 7 g of a foaming agent Neopor®600 (animal protein),
- 0.3 g of lithium carbonate
- 92.7 g of water
The whole is mixed with the electric mixer at high speed for 5 minutes until a
homogeneous and compact aqueous foam is produced, with a density of 50 kg.m3.
II. 1.4 - Pouring and drying of the mineral foam
15 The same as in II.C.4
II. 1.5 - Mineral foam composition
43
(by weight)
Binder 134.68
Reactive filler 2.52
Filler 25M9
Water 35.85
Foaming agent 1.00
Other additives
II. 1.6 - Characterization of the insulating material obtained
- Density: 214 Kg/m
- Porosity: 90.1%,
5 - Compressive strength at 3 hours: Cs < 0.2 MPa, Cs at 28 days: 0.7 MPa
- Coefficient of thermal conductivity: A = 0.0545 W/m.°C.
The pore diameters that can be observed on Figure 10 are essentially lower than 300 pm.
II. J. Example 10: non foam slurry with hollow filler
10 II. J. 1 - Preparation of the binder
Following components were added to a container
Component
Hydraulic binder:
Portland cement 52.5R (Lafarge Le
Havre)
Calcium aluminate Secar 51
(Kerneos)
Anhydrite Francis Flower
Air-slaked lime
Semi-hydrate Prestia creation
Sodium carbonate
Lithium carbonate
Citric acid
Reactive fillers:
Slag (*)
Silica fume RW Q1 Fuller
Hollow fillers
Thermosilit
Dispersant:
Conpac 500
Cellulose ether
Tylose H300P2
Fillers:
Sand Sifraco BR36
Composition I Formula Li 1 %
Ettringite binder with
hollow and reactive
fillers L12
Comparative binder
100% OPC Ettringite
binder LC6
7g
2.70 g
1.0 g
0.3 g
0.066 g
0.05 g
10.0 g
.5 g
5.0 g
5.0 g
20 g
5.0 g
5.0 g
20 g
0.36 g 0.36 g
0.08 g 0.08 g
30.5 g 30.5 g
44
=ttringite binder with
hollow and reactive
fillers L12
26.0 g
(*) cf example 4
The components are mixed using an electric mixer for 30 seconds at low speed
(graduation 1), then for 1 minute and 30 seconds at high speed (graduation 5). A cement slurry
is thus obtained.
5 II. J.2 - Characterization of the insulating material obtained
Mechanical strength;.
Reflection at 24h (Mpa) 1.3 -
Reflection at 3h M pa) 1.5 0.9
Compressive strength (3h M a) 2.3 --
Compressive strength 24h (Mpa) 3.1 1.3
omparative binder
100% OPC Ettringite
binder LC6
45
CLAWS
1. A cellular structure thermal insulation material, comprising by weight as compared to
5 the material total weight:
a) from 4 to 96% of a cement matrix obtained by hydration of a hydraulic binder that is
characterized prior to being contacted with water, in that it comprises at least one phase
selected from C3A, CA, C12A7, C11A7CaF2, C4A3$ (Yee lemite), C2A(1-x)Fx (where x
belongs to ]0, 1 ]), hydraulic amorphous phases having a C/A molar ratio ranging from 0.3 to 15
10 and such that cumulated amounts of AI203 of these phases be ranging from 3 to 70% by
weight of the hydraulic binder total weight,
b) from 4 to 96% of at least one filler,
said material having a pore volume ranging from 70% to 95%.
2. A cellular structure thermal insulation material according to claim 1, which presents a
15 shrinkage lower than 500 pm/m.
3. A cellular structure thermal insulation material according to claim 1 or 2, which presents
a compressive strength Cs at 3 hours higher than or equal to 0.2 MPa and a coefficient of
thermal conductivity at 20°C, lower than or equal to 0.2 W/m.°C.
4. A cellular structure thermal insulation material according to any of claims 1 to 3, which
20 contains from 1 to 80% by weight, as compared to the material total weight, of low density
hollow fillers.
5. A mineral foam that may be used for making a material according to any of claims 1 to
4, comprising:
- a hydraulic binder that is characterized, prior to being contacted with water, in that it
25 comprises at least one phase selected from C3A, CA, C12A7, C11A7CaF2, C4A3 (Yee lemite),
C2A(1-x)Fx (where x belongs to ]0, 1]), hydraulic amorphous phases having a C/A molar ratio
ranging from 0.3 to 15 and such that cumulated amounts of A1203 of these phases be ranging
from 3 to 70% by weight of the hydraulic binder total weight,
- from -1 to 30% by weight, this percentage being related to the dry matter total weight in
30 the mineral foam, of at least one filler selected from reactive fillers,
- at least one aqueous and/or non aqueous solvent and
a gas such as air, carbon dioxide or nitrogen.
6. A mineral foam that may be used for making a material according to any of claims 1 to
4, comprising:
35 - a hydraulic binder that is characterized, prior to being contacted with water, in that it
comprises at least one phase selected from C3A, CA, C12A7, C11A7CaF2, C4A3 (Yee lemite),
C2A(1-x) Fx (where x belongs to ]0, 1]), hydraulic amorphous phases having a C/A molar ratio
ranging from 0.3 to 15 and such that cumulated amounts of AI203 of these phases be ranging
46
from 3 to 70% by weight of the hydraulic binder total weight, and from 0 to less than 5% by
weight of Portland cement,
- at least one aqueous and/or non aqueous solvent and
- a gas such as air, carbon dioxide or nitrogen.
5 7. A mineral foam that may be used for making a material according to any of claims 1 to
4, comprising:
- a hydraulic binder that is characterized, prior to being contacted with water, in that it
comprises at least one phase selected from C3A, CA, C12A7, C11A7CaF2, C4A3 (Yee lemite),
C2A(1-x)Fx (where x belongs to ]0, 1]), hydraulic amorphous phases having a C/A molar ratio
10 ranging from 0.3 to 15 and such that cumulated amounts of AI203 of these phases be ranging
from 3 to 70% by weight of the hydraulic binder total weight,
- from 1 to 80% by weight, this percentage being related to the mineral foam dry matter
total weight, of at least one filler selected amongst the hollow fillers,
- at least one aqueous and/or non aqueous solvent and
15 - a gas such as air, carbon dioxide or nitrogen.
8. A mineral foam according to any of claims 5 to 7, which comprises in addition a
compound selected from foaming agents, air-entraining agents and/or gas-generating agents.
9. A cement slurry that may be used for making a material according to any of claims 1 to
4, comprising:
20 - at least one hydraulic binder that is characterized, prior to being contacted with water, in
that it comprises at least one phase selected from C3A, CA, C12A7, C11A7CaF2, C4A3 (Yee
lemite), C2A(l-x)Fx (where x belongs to ]0, 1]), hydraulic amorphous phases having a C/A
molar ratio ranging from 0.3 to 15 and such that cumulated amounts of AI203 of these phases
be ranging from 3 to 70% by weight of the hydraulic binder total weight,
25 - at least one low density hollow filler,
- at least one aqueous and/or non aqueous solvent.
10. A mineral foam or cement slurry according to any of claims 5 to 9, wherein the binder
comprises from 10 to 90% by weight of calcium sulfate, as compared to the binder total weight.
11. A mineral foam or cement slurry according to any of claims 5 to 10, wherein the
30 solvent is water and the water/ hydraulic binder weight ratio is ranging from 0.1 to 0.7.
12. A mineral foam or cement slurry according to any of claims 5 to 11, which comprises
at least one reactive filler and between 0.5 to 5% by weight as compared to the composition
total weight of at least one reactive filler activating compound.
13. A method for making a mineral foam according to any of claims 4 to 8 and 10 to 12
35 comprising the following steps, consisting in:
a) preparing an aqueous foam from a composition comprising at least water and at least
one compound selected from foaming agents, air-entraining agents and gas-generating agents,
b) preparing a cement slurry comprising
47
- the mixing with a solvent and optionally at least one compound selected from
surfactants, air-entraining agents and gas-generating agents, of the binder,
c) introducing one or more filler(s) for all or part of them into the aqueous foam and/or
cement slurry,
5 d) mixing the aqueous foam and the slurry together.
14. A method for making a mineral foam according to any of claims 4 to 8 and 10 to 12
comprising the following steps, consisting in:
a) preparing a cement slurry comprising:
the mixing with a solvent and optionally at least one compound selected from
10 surfactants, air-entraining agents and gas-generating agents, of the binder,
b) injecting a gas into the slurry by maximizing the contact surface between the air and the
cement slurry, for example by using a static mixer.
c) incorporating one or more fillers, for all or part of them, during or after the step a).
15. A method for making a'cement slurry according to any of claims 9 to 12, comprising
15 the following steps, consisting in:
a) preparing a cement slurry comprising:
mixing the binder together with a solvent,
b) incorporating into the slurry at least one low density hollow filler,
c) incorporating one or more fillers, for all or part of them, during or after the step a), or
20 during or after the step b).
'16. Use of the mineral foam or the cement slurry according to any of claims 5 to 12 or of
the hardened mineral foam according to any of claims I to 4 as a component for making a
thermal insulation:
25 - for making precast panels comprising at least one insulating layer based on mineral
foam,
- for making sandwich panels,
- for filling hollow parts in building elements for facilities by placing in situ said mineral
foam such as walls, ceilings, hollow blocks, doors, ducts,
30 - for making hot floors by placing in situ the foam in contact with the under-surfaces of
pipes,
- for applying outdoors a monolayer having an insulation function for facing a building by
placing in situ said mineral foam.
'17. Use of the mineral foam or the cement slurry according to any of claims 5 to 12 or of
35 the hardened mineral foam according to any of claims 'I to 4 as refractory materials:
- for making refractory bricks,
- for making monolithic concretes by placing in situ said mineral foam.