Title of Invention

"BRAZED JOINT BETWEEN A METAL PART AND A CERAMIC PART"

Abstract An assembly comprising a metal piece, a piece made of ceramic material, and at least one intermediate connection element assembled to each of said pieces by brazing, said intermediate connection element (10') being constituted by a deformable sheet presenting at least two flat zones (11, 12) brazed to respective ones of said pieces, said two flat zones (11, 12) being interconnected by a deformable zone (13') presenting at least two free undulations (19, 20) oriented in alternation towards said metal piece and towards said piece made of ceramic material.
Full Text Title of the invention
A brazed assembly of a metal piece and a piece made of
ceramic material
Background of the invention
The present invention relates to the general field
of brazing together two materials that present different
thermomechanical properties.
More precisely, the invention applies to brazing
together a metal piece and a piece made of ceramic
material, e.g. based on silicon carbide (SiC) and/or
carbon.
The piece made of ceramic material may be
constituted by solid silicon carbide. It may also be
constituted by a thermostructural composite, and in
particular by a ceramic matrix composite (CMC) reinforced
by silicon carbide or carbon fibers.
Thermostructural composite materials are
characterized by mechanical properties that make them
suitable for constituting structural parts, while also
conserving these mechanical properties at high
temperatures. They are constituted by fiber
reinforcement densified by a matrix of refractory
material that fills in the pores of the fiber
reinforcement, at least in part. The choice of materials
for the fibers and for the ceramic is typically made
amongst carbon and ceramics (i.e. materials that are
neither metallic nor organic), and in particular silicon
carbide (SiC).
By way of example, the invention can be used for
assembling together a piece made of ceramic material with
a metal piece made of an alloy of titanium, aluminum, and
vanadium (TA6V) or of Inconel 718 (registered trademark),
an alloy based on nickel and having the composition
NiCrl9Fel9Nb5Mo3.
The mechanical properties of pieces made of ceramic
material and the fact that these properties are conservedat high temperature make them materials that are
particularly suitable for making pieces that are
subjected to high levels of thermomechanical stress, in
particular in aviation applications (engine parts,
fairingr elements). When ceramic materials are reinforced
by silicon carbide or carbon fibers, they constitute an
alternative to metallic materials, presenting numerous
advantages, in particular in terms of weight savings and
of operational lifetime.
Conventionally, pieces made of ceramic material and
metal pieces are assembled together by a mechanical
connection of the riveting or bolting type, but such a
connection can sometimes be unsuitable for reasons of
size, difficulty of implementation, or weight.
Furthermore, known homogeneous assembly methods for
use with ceramic materials and involving organic
precursors of ceramics are not suitable for heterogeneous
assemblies between a ceramic material and a metal.
Known brazing techniques used for making homogeneous
connections between two ceramic materials can be
difficult to use for heterogeneously brazing a ceramic
material on a metal because of the very different
thermomechanical and chemical behaviors of ceramic
materials and metals.
A metal alloy based on titanium, aluminum, and
vanadium presents a coefficient of expansion that is
about two to three times greater than that of ceramic
materials.
More precisely, the coefficient of expansion of such
an alloy at 500°C is about lOxlO-6K-1 ± 15%, while the
coefficient for a CMC is' about 2.5XlO-6K-1 to -l.OxlO^K"1 +
15%.
Thus, for a 30 millimeter (mm) assembly, an
expansion offset of 0.2 mm is observed on cooling the
assembly from the solidification temperature of the
brazing composition to ambient temperature.

Such an offset leads to high levels of stress
appearing in the two pieces, and in particular to
compression forces in zones of the brazed joint adjacent
to the ceramic, and traction forces in zones adjacent to
the metal piece. These stresses can give rise to local
deformations that might cause one of the pieces to break
or lead to reduced strength of the brazed joint.
Such deformations are irreversible in the metal
piece. In the ceramic piece, in particular when made of
a CMC, these deformations can lead to brittle type
breakage. Such breakage can occur suddenly if the stress
is too high. Breakage can also occur by damage building
up successively under cyclical stressing.
Object and summary of the invention
A main object of the present invention is thus to
mitigate such drawbacks by proposing an assembly
comprising a metal piece, a piece made of ceramic
material, and at least one intermediate connection
element assembled to each of said pieces by brazing, the
intermediate connection element being constituted by a
deformable sheet presenting brazed flat zones and
deformable zones.
By way of example, a brazing composition of the Ag-
Mn or Ag-Cu-Ti type may be selected, thus making it
possible to obtain an assembly that is strong at high
temperatures of as much as 500°C.
In accordance with the invention, the differential
expansion between the piece made of ceramic material and
the metal piece is absorbed by the deformable sheet.
The assembly thus presents thermomechanical
adaptation to differential expansion, while remaining as
much as possible within the elastic domain. In order to
be able to withstand cooling after brazing and thermal
cycling in operation, it is necessary to accommodate the
differential expansion between the piece made of ceramic
material and the metal piece.
In a preferred embodiment, the piece made of ceramic
material is based on silicon carbide,and/or carbon.
For example, the ceramic material piece is made of
solid silicon carbide.
In another embodiment, the ceramic material piece
comprises a ceramic matrix reinforced by silicon carbide
or carbon fibers.
In a preferred embodiment, the deformable sheet
includes at least two deformable undulations oriented in
alternation towards the metal piece and towards the piece
made of ceramic material.
Preferably, at least one of the deformable
undulations is free, such a free undulation guaranteeing
increased flexibility for the brazed connection.
The height of the free undulation may advantageously
be used for modifying rigidity in the fold direction.
In a first variant embodiment, the deformable
undulations are concentric.
In an embodiment of this first variant, the
intermediate connection element comprises a first flat
zone that is substantially circular about an axis, a
second flat zone that is substantially annular, coaxial
about the first flat zone, and having an inside diameter
greater than the diameter of said first zone, and
undulations presenting symmetry of revolution about the
above-mentioned axis.
Because of this symmetry, such a connection element
presents behavior that is identical regardless of the
direction of the line of greatest stress.
In another variant embodiment the connection element
is generally in the form of a concertina-folded tape.
In an advantageous embodiment of the invention, the
assembly comprises a plurality of intermediate connection
elements that are disposed radially around a fixed point.
With such a connection element, the stresses are low
in the brazed joints and rigidity can be modulated.
Placing the intermediate connection elements in a
radial star disposition advantageously presents
concentric undulations that are interrupted radially (the
interruptions being constituted by empty gaps along a
plurality of radial directions), thus making it possible
to reduce or eliminate tangential stresses from such
concentric circles.
Preferably, the intermediate connection elements are
arranged in a plurality of radial directions around the
fixed point.
Such an embodiment enables the stiffness of the
assembly between the metal piece and the piece of ceramic
material to be increased.
Around the fixed point as defined above, the offset
due to the expansion of the metal piece increases with
distance from the fixed point.
In a particular embodiment of this configuration,
the intermediate connection elements are of increasing
flexibility on going away from the fixed point.
Such an embodiment serves to compensate for the
above-mentioned increase in offset.
The invention also provides a turbomachine nozzle
including at least one assembly as mentioned above in
which the metal piece is a casing of said nozzle (or a
lever), and the piece made of ceramic material is a flap
of the nozzle.
The invention also seeks to provide a turbomachine
combustion chamber including at least one assembly as
mentioned above in which the metal piece is a casing of
said chamber (or a component part thereof, or a joint -
i.e. a connection element - therein), and the piece made
of ceramic material is a component part of said chamber.
The invention also provides post-combustion
equipment for a turbomachine including at least one
assembly as mentioned above in which the metal piece is a
post-combustion casing (or a platform of post-combustionequipment), and the piece made of .ceramic material is a
flame-holder arm.
The invention also provides a turboinachine including
at least one assembly as mentioned above.
Brief description of the drawings
Other characteristics and advantages of the present
invention appear from the following description with
reference to the accompanying drawings that show
embodiments having no limiting character. In the
figures:
• Figure 1 shows a connection element suitable for
use in a first assembly in accordance with the invention;
• Figure 2 is a section through an eissembly of the
invention using the connection piece of Figure 1;
• Figure 3 shows a connection element suitable for
use in a second assembly, in accordance with the
invention;
• Figure 4 shows a connection element suitable for
use in a third assembly in accordance with the invention;
• Figure 5 is a fragmentary section through the
connection element of Figures 3 and 4;
• Figure 6 shows an undulating surface from which
intermediate connection elements of the kind shown in
Figure 5 are obtained;
• Figure 7 shows an advantageous embodiment of the
invention;
• Figure 8 shows a particular embodiment of a piece
having openings formed therein to facilitate positioning
and anchoring connection elements for assembly in
accordance with the invention; and
. Figures 9A and 9B are curves showing mechanical
properties as a function of temperature for materials
suitable for use in making intermediate elements,
respectively elements that are ductile and elements that
are reversibly deformable.
Detailed description of embodiments
Figure 1 shows a connection element 10 suitable for
use in a first assembly in accordance with the invention.
By way of example it is constituted by a plane deformable
material stamped as to form a first flat zone 11 that is
circular about an axis A, and a second flat zone 12 that
is annular about the axis A, these two zones being
interconnected by a deformable zone 13 forming
substantially a truncated cone. The inside diameter of
the annular zone 12 is greater than the diameter of the
circular zone 11. The substantially conical walls 13 may
present inclination to a greater or lesser extent
relative to the direction perpendicular to the flat zones
11 and 12.
Figure 2 shows a section II-II (see Figure 1)
through an assembly 14 of the invention made using a
connection element 10 as shown in Figure 1.
In this assembly, a first brazed joint 15 is made
between a metal piece 16 and the circular flat zone 11 of
the connection element 10. A second brazed joint 17,
preferably using the same brazing composition, is made
between a piece 18 of ceramic material, e.g. a CMC, and
the annular flat zone 12 of the connection element 10.
The connection element 10 shown and used in
Figures 1 and 2, can be obtained from a plate of
deformable material, by cutting out and stamping using a
substantially cylindrical stamping element.
A vertical height or size for the connection element
of about 2 mm is appropriate for aviation applications,
however it will be understood that this size can be
modified as a function of requirements specific to
different applications. The proportions of the various
portions of the connection element 10 may also be
modified as a function the intended application.
On this topic, it should be observed that modifying
the geometrical parameters of the connection element 10 makes it possible to modify the magnitude of the stresses
observed.
The proposed size of 2 mm enables flexibility to be
obtained in the tangential direction for pieces having a
size of the order of about ten centimeters. Under the
effect of differential expansion, for example during a
thermal cycle, the conical portion 13 of the connection
element 10 can absorb this expansion differential
completely, or in part, without endangering the strength
of the assembly. Since the material from, which the
connection element is made is deformable, the deformation
of the cylindrical portion is of no consequence for the
assembly as a whole.
Nevertheless, in the embodiment shown in Figure 2,
high levels of stress can be observed in the brazed
joints and in shear in the membrane in the connection
element.
The connection element 10' described below with
reference to Figure 3 serves to mitigate this drawback.
The connection element 10' has a deformable zone 13'
that is axially symmetrical about an axis A, this zone
13' being shaped so as to comprise at least two free
undulations 19 and 2 0 oriented alternately upwards and
downwards relative to the flat zones 11 and 12 that are
respectively circular and annular about the axis A. The
structure is still advantageously made of stamped
deformable material. The presence of undulations that
are free, i.e. not brazed, in the deformable zone 13'
makes the structure more flexible.
Figure 5 shows a section V-V (see Figure 3) of the
connection element 10'. The flat zones 11 and 12 are
interconnected by the deformable zone 13' that presents
two free undulations 19 and 20.
It should be observed that in Figures 3 and 5, the
undulations 19 and 20 are shown as being substantially
flat, however they could equally well have other shapes,
for example they could be sinusoidal.
Considerations of size, bulk, and proportion similar
to those mentioned for the connection element shown in
Figure 1 apply likewise to the element of Figure 3.
It should be observed that changes in the thickness
of the stamped sheet, radii of curvature rl, r2, r3, r4,
r5, and r6 of the undulations, dimensions £1, £2 of the
undulations, heights h1, h2, and h3 characterizing the
undulations 19 and 20, angles alpl, alp2, and alp3
between the undulations and the perpendicular to the flat
zones, and sizes £0, £2 of said flat zones are all to be
envisaged and constitute as many parameters for refining
the stresses and the stiffness properties of the element.
In the embodiments of Figures 1 and 3, the rigidity
of the resulting assembly in shear presents the advantage
of being isotropic in the assembly plane.
The shear stresses observed at the brazed joints in
an assembly using a connection element having the
characteristics shown in Figure 3 are smaller than those
observed in an assembly using a connection element as
shown in Figure 1.
Figure 4 shows a connection element 10" that can be
used in another assembly in accordance with the
invention. In this embodiment, the connection element
10" is generally in the form of a concertina-folded tape.
In the example shown in Figure 4, the section of the tape
is the same as that shown in Figure 5. Such a connection
element could also be a stamped structure or could
advantageously be obtained by folding, or by extrusion in
a straight line along the direction Y. If extruded, and
as shown in Figure 6, an undulating surface 2 2 is
obtained with corrugations that extend along the
direction Y.
The connection elements 10" are then cut once every
L millimeters from said undulating surface 22.
It is also possible to envisage machining a piece
made of metal such as Inconel 718, e.g. by wire
machining.
The intermediate element 10" in this embodiment has
a preferred direction for deformation constituted by the
direction X (tangential rigidity) and a rigid direction
constituted by the direction Y (transverse rigidity).
The stresses observed in the brazed joints in this
embodiment are low. The resulting assembly then presents
lower rigidity than that observed in the other
embodiments based on an axially symmetrical connection
element 10 or 10', as shown in Figures 1 and 3.
The geometrical parameters of the tape can be
modified in order to obtain the lowest maximum stress in
the brazed joints and in the structure itself for the
lowest tangential rigidity (i.e. in the direction X), and
the highest normal rigidity (in the direction Z).
Thus, it is possible to modify the thickness e_ of
the tape, the radii of curvature rl, r2, r3, r4, r5, and
r6 of the undulations, the dimensions £1, £2 of the
undulations, the heights h1, h.2, and b.3 of the
undulations, the angles alpl, alp2, and alp3 made by the
undulations relative to the perpendicular to the flat
zones, and the dimensions £0, £3 of the flat zones.
The three heights h1, h2, h.3 characterize the two
free undulations 19 and 20 of the deformable zone 13'.
These first, second, and third heights h1, h2, h3
correspond, as shown in Figure 5, to the heights of the
portions of the tape that are substantially rectilinear
in profile extending respectively between the first flat
zone 11 and the bottom of the undulation 19, between the
bottom of the undulation 19 and the top of the undulation
20, and between the top of the undulation 2 0 and the
second flat zone 12. '
The person skilled in the art will understand that
the height h2 is selected to be less than or equal to the
height h1.
Nevertheless, it is advantageous also to take
account of the minimum radii of curvature for the free
undulations. The value of h2 is then advantageously
selected to be greater than or equal to 1/3 of h1.
In the example described herein, the values that
have been selected and that are proposed are limited to a
few tenths of a millimeter since it is required that the
connection between the assembled pieces should not exceed
2 mm. That said, the greater h1 and h2, the more the
deformations are spread and the lower the stresses.
The table below shows an example of a set of
geometrical parameters suitable for obtaining a good
compromise between maximum stress and rigidity with an
alloy tape made of Inconel 718 (trade name).

To increase rigidity in shear parallel to the
assembly plane, a plurality of intermediate connection
elements 10' are disposed radially around a fixed point
23, as shown in Figure 7.
In this embodiment, the deformable sheets are
directed towards the fixed point 23. By placing the
connection elements 10" in concentric manner, zero
relative displacement is forced between the assembled
pieces for the central point 2 3 of the concentric
arrangement. This stiffens the assembly in the assembly
plane. The intermediate elements 10" can be placed in
such a manner that their own deformation directions point
towards the fixed point 23.
This disposition.mitigates the lack of rigidity in
the tangential direction. Relative deformation during
cooling of the two pieces to be assembled together is
then oriented towaards the center of the assembly, which
is the fixed point 23, so there is no relative movement
between the two pieces that are to be assembled. The
deformation due to differential expansion is then
absorbed concentrically. Overall rigidity is obtained
because of the greater rigidity of the structures in the
direction perpendicular to the preferred deformation
direction.
In addition, given that the relative displacement
between the pieces for assembly is zero at the fixed
point and that it increases out to the periphery, it is
advantageous to make use of structures of increasingly
flexibility on going away from the fixed point. This
serves to improve tangential rigidity in the region of
the fixed point.
Figure 8 shows a particular embodiment of an
assembly piece 3 0 having openings or cavities 31 formed
therein for the purpose of positioning intermediate
connection elements 10" in a star configuration
corresponding to that shown in Figure 7. This
arrangement enables the intermediate connection elements
10" to be anchored in the piece 3 0 which is preferably
the metal piece, or possibly the piece made of ceramic
material.
Implementing the invention requires the intermediate
elements to be made of a material that is selected to
remain within its elastic domain. It is also important
to fabricate the intermediate connection elements out of
a material that is as strong as possible in order to have
greater latitude in mechanical weakening, i.e. improved
flexibility.
Figures 9A and 9B show properties that need to be
taken into account when selecting the material for the
intermediate element. In Figure 9A, curve IMD
representing the mechanical properties of an intermediate
connection element that is solid and ductile is given for
comparison with the curve HX for the metal piece that is
to be assembled. A loss in mechanical properties PP
(elastic limit, rupture strength) can be observed.
The curve MP represents the potentially ideal
mechanical properties of an intermediate connection element for brazing at a temperature Ts corresponding to
the solidification temperature of the brazing compound.
Below the solidification temperature Ts, the
intermediate element should ideally have mechanical
properties that are weaker than those of the metal piece
for assembly (HX) so as to enable it to act as a ductile
material. It also needs to have mechanical strength
properties that are at least sufficient at an operating
temperature TF, where the operating temperature TF is
empirically about 2/3 of the above-mentioned
solidification temperature Ts, in degrees Celsius, which
can be written as follows:
(Figure Removed)
where Ts and TF are expressed in degrees Celsius.
However, the person skilled in the art knows that
these requirements, represented by the curve MP cannot be
achieved with an intermediate element that is solid and
ductile. To mitigate the loss of property PP observed
with such a material, it is necessary for the assembly to
be overdimensioned.
Figure 9B shows a curve ISC for the mechanical
properties of a material for a deformable intermediate
connection element that is advantageously suitable for
use in the invention. This curve corresponds to a highly
refractory material (e.g. alloys based on iron, nickel,
chromium, aluminum, titanium) having mechanical
properties that degrade little at high operating
temperature.
Instead of observing a loss of property PP as in
Figure 9A, there can be seen a structural weakening
margin MAS. This margin is controllable and used for
adjusting the flexibility of the structure at will.
The deformable intermediate connection elements may
also be in the form, of a one-dimensional (1D) undulating
sheet, a stamped sheet, or indeed a sheet with
corrugeitions crossing in two dimensions (2D) .
By way of example, materials for making these
structures can be selected from the following list: ID
undulating sheet of alloy based on FeCrAlY; 2D corrugated
sheet of Haynes 230 (stamped sheet); crossed 2D
corrugated sheets of Nimonic 7 5 (one-dimensional
corrugated tape inserted and brazed in the corrugation
recesses of a one-dimensional corrugated sheet,
embodiment not shown).
Such structures can be used in particular for
assembling parts made of ceramic material based on SiC
with metal parts based on Inconel 718 or TA6V alloy, this
list not being limiting.

















CLAIMS
1. An assembly (14) comprising a metal piece (16) and a
piece (18) made of ceramic material, the assembly being
characterized in that it includes at least one
intermediate connection element (10', 10") assembled to
each of said pieces (16, 18) by brazing, said
intermediate connection element being constituted by a
deformable sheet presenting at least two flat zones (11,
12) brazed respectively to said two pieces (16, 18), the
two flat zones (11, 12) being interconnected by a
deformable zone (13') presenting at least two free
undulations (19, 20) oriented in alternation towards said
metal piece (16) and towards said piece (18) made of
ceramic material.
2. An assembly according to claim 1, in which said piece
(18) made of ceramic material is based on silicon carbide
and/or carbon.
3. An assembly according to claim 2, in which said piece
(18) made of ceramic material is made of solid silicon
carbide.
4. An assembly according to claim 2, in which said piece
(18) made of ceramic material comprises a ceramic matrix
reinforced by silicon carbide or carbon fibers.
5. An assembly according to any one of claims 1 to 4, in
which said deformable zone (13') presents two free
undulations (19, 20) characterized by three heights (hi,
h2, h3), these three heights being such that the value of
the second height (h2) is greater than or equal to 1/3 of
the value of the first height (h1).
6. An assembly according to any one of claims 1 to 5, in
which said free undulations (19, 20) are concentric.
7. An assembly according to any one of claims 1 to 6, in
which said intermediate connection element (10')
comprises a first flat zone (11) that is substantially
circular about an axis (A), a second flat zone (12) that
is substantially annular, coaxial about said first zone,
and of inside diameter greater than the diameter of said
first zone, and three undulations presenting symmetry of
revolution about said axis (A).
8. An assembly according to any one of claims 1 to 5, in
which said intermediate connection element (10") is
generally in the form of a tape that is concertina-folded
in a main direction (X).
9. An assembly according to claim 8, in which a plurality
of intermediate connection elements (10") are arranged
radially around a fixed point (23).

10. An assembly according to claim 9, in which said
intermediate connection elements (10") are arranged in
such a manner that their main directions (X) are in
alignment on a plurality of radial directions about said
fixed point (23).
11. An assembly according to claim 9 or claim 10, in
which the plurality of intermediate connection elements
is such that the intermediate elements (10") are of
increasing flexibility on going away from said fixed
point (23).
12. A turbomachine nozzle including at least one assembly
according to any one of claims 1 to 11, in which said
metal piece (16) is a casing of said nozzle and said
piece (18) made of ceramic material is a flap of said
nozzle.
13. A turbomachine combustion chamber including at least
one assembly according to any one of claims 1 to 11, in
which said metal piece (16) is a casing of said chamber
and said piece (18) made of ceramic material is a
component part of said chamber.
14. Post-combustion equipment of a turbomachine including
at least one assembly according to any one of claims 1 to
11, in which said metal piece (16) is a post-combustion
casing and said piece (18) of ceramic material is a
flame-holder arm.
15. A turbomachine including at least one assembly
according to any one of claims 1 to 11.



Documents:

4881-delnp-2008-Abstract-(26-08-2014).pdf

4881-DELNP-2008-Abstract.pdf

4881-delnp-2008-Claims-(16-10-2014).pdf

4881-delnp-2008-Claims-(26-08-2014).pdf

4881-DELNP-2008-Claims.pdf

4881-delnp-2008-Correspondence Others-(08-05-2014).pdf

4881-delnp-2008-Correspondence Others-(14-03-2014).pdf

4881-delnp-2008-Correspondence Others-(16-10-2014).pdf

4881-delnp-2008-Correspondence Others-(26-08-2014).pdf

4881-DELNP-2008-Correspondence-Others-(04-11-2009).pdf

4881-delnp-2008-correspondence-others.pdf

4881-delnp-2008-Description (Complete)-(16-10-2014).pdf

4881-DELNP-2008-Description (Complete).pdf

4881-delnp-2008-Drawings-(26-08-2014).pdf

4881-DELNP-2008-Drawings.pdf

4881-delnp-2008-Form-1-(16-10-2014).pdf

4881-DELNP-2008-Form-1.pdf

4881-DELNP-2008-Form-18-(04-11-2009).pdf

4881-DELNP-2008-Form-2.pdf

4881-DELNP-2008-Form-3.pdf

4881-delnp-2008-Form-5-(26-08-2014).pdf

4881-DELNP-2008-From-5.pdf

4881-delnp-2008-GPA-(14-03-2014).pdf

Petition (4881-DELNP-2008).pdf

Petition (4881-DELNP-2008)Form 1.pdf


Patent Number 263628
Indian Patent Application Number 4881/DELNP/2008
PG Journal Number 46/2014
Publication Date 14-Nov-2014
Grant Date 08-Nov-2014
Date of Filing 06-Jun-2008
Name of Patentee SNECMA
Applicant Address 2 BOULEVARD DU GENERAL MARTIAL VALIN, 75015 PARIS, FRANCE.
Inventors:
# Inventor's Name Inventor's Address
1 JOEL MICHEL BENOIT 5 SQUARE DE L'ELAN, F-77240 CESSON LA FORET, FRANCE.
2 JEAN FRANCOIS FROMENTIN 16 ALLEE DES NEFLIERS, RESIDENCE LES TENNIS, F-77240 CESSON LA FORET, FRANCE.
3 OLIVIER GILLIA 22 RUE DES LILAS, F-38360 SASSENAGE, FRANCE.
4 PASCAL REVIRAND 7 RUE DES ECHELLES, F-38120 SAINT EGREVE, FRANCE.
PCT International Classification Number C04B 37/02
PCT International Application Number PCT/FR2006/051319
PCT International Filing date 2006-12-08
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0553793 2005-12-08 France