EP2558430A1

EP2558430A1 - Matrix based on nanocrystalline cristobalite for a thermostructural fibrous composite material

Info

Publication number: EP2558430A1
Application number: EP11732501A
Authority: EP
Inventors: Michel Davidovics
Original assignee: PYROMERAL SYSTEMS SA
Current assignee: PYROMERAL SYSTEMS SA
Priority date: 2010-04-14
Filing date: 2011-03-28
Publication date: 2013-02-20
Also published as: WO2011128521A4; WO2011128521A1; US8975201B2; US20130130886A1; FR2958934A1

Abstract

The invention relates to a matrix for thermostructural fibrous composite materials, which is obtained by geopolymer synthesis based on nanocrystalline cristobalite resulting from the crystallization of geopolymer micelles of potassium polysiloxonate K-(Si-O-Si-O)n. The nanocrystalline cristobalite is in the form of micelles and/or microspheres which have dimensions of less than 1 μm, preferably less than 500 nm, and are interconnected by an amorphous phase. It contains at least 85 wt % oxide S1O2 with at most 15 wt %, preferably at most 10 wt %, alkaline oxide K20. The nanocrystalline cristobalite results from the crystallization of geopolymer micelles of potassium polysiloxonate by a thermal treatment at a temperature which is preferably between 600°C and 800°C, for a duration of less than 30 min. The fibrous composite material impregnated with said matrix is thermostructural.

Description

NANO-CRYSTALLINE CRYSTOBALITY MATRIX FOR

THERMOSTRUCTURAL FIBROUS COMPOSITE MATERIAL.

FIELD OF THE INVENTION

The invention relates to composite materials and processes for obtaining such materials, and more particularly to a thermostructural composite material comprising a fiber reinforcement and a matrix based on nano-crystalline cristobalite.

Thermostructural composites retain their mechanical properties (tensile strength, flexion, modulus of elasticity, etc.) at a high

temperature, for several hours, even for several thousand hours. They should not be confused with fire-resistant composites, which, even though they are non-flammable, like some matrix composites

geopolymer, see their mechanical properties greatly decrease from the first hours of use at temperatures above 400 ° C.

Obviously, the thermostructural composite material according to the present invention is, by nature, also fire resistant.

There are normally two types of composite materials

thermostructural, those with a vitroceramic matrix, also called a glass matrix, and those with a CMC ceramic matrix, without oxide. In this second category, the SiC, Si3N4 and C matrices are found. The material of the present invention is classified in the first category, that is to say that of the glass-ceramic matrix. But all this is just a convention. This does not imply that this matrix is made of glass.

In the case of the present invention, the thermostructural composite material comprises a matrix consisting essentially of a mineral based on nano-crystalline cristobalite as defined by its X-ray diffraction spectrum. The main object of the invention is the description of this matrix based on nano-crystalline cristobalite. A second object is the description of its method of obtaining which includes a geopolymeric synthesis of a binder of the type Potassium polysiloxonate K- (Si-O-Si-O) _n , and a third object relates to the description of the composite materials thus obtained.

PRIOR ART

The glass ceramic matrix composite materials are appreciated in the industry, in particular aeronautics and aerospace as well as in the automotive industry. These thermostructural materials would allow the realization of structures having good thermomechanical properties. Their development is envisaged for applications requiring a good behavior in continuous use (of several hundreds, or even thousands of hours) at temperatures of the order of 300 to 1000 ° C.

However, most of the materials of this type developed to date, is not entirely satisfactory, both in terms of their final properties and in terms of their method of preparation. Indeed, new applications require fibrous composite materials with matrices that have the following characteristics:

- a procedure meeting the following three criteria: a) manufacturing process taking place at low and medium temperatures; b) methods respecting the thermal properties of the reinforcing fibers; c) system allowing the realization of complex parts and or of big dimension.

- good resistance to thermal shock;

- Average thermal expansion coefficients slightly higher than those of the reinforcing fibers.

There is a mineral used in ceramics, with these thermal characteristics but whose traditional manufacturing process involves very high

temperatures. This is cristobalite, consisting essentially of crystalline silica SiO2. It was therefore necessary to develop a cristobalite-based matrix whose manufacturing process can easily be implemented at low temperatures to produce thermostructural fibrous composites. In addition, this matrix must be the result of the hardening of a binder in which the size of the minerals is less than 2 microns, preferably less than 1 micron, to ensure perfect impregnation between the fibers. The matrix then contains a nano-crystalline cristobalite, the geopolymeric particles or micelles of which are smaller than 1 micron, preferably less than 500 nanometers. This is the main object of the present invention.

In the prior art, the glass-ceramic matrix composite materials are generally referred to as silica-based. This does not mean that the glass-ceramic matrix is essentially composed of silica S1O2, as is the case for special composites containing vitreous silica, especially those used to manufacture radomes transparent to radar waves. On the contrary, these silica-based matrices indicate that they contain silicon Si, in the form of lithium aluminosilicate (LAS), LiO2.Al2O3.SiO2,

magnesium aluminosilicate (MAS), MgO.Al2O3.SiO2, barium salt aluminosilicate (BAS), BaO.Al ₂ O ₃ .SiO ₂ , calcium aluminosilicate (CAS),

CaO.Al2O3.SiO2, as can be read in patent EP0819657.

As shown in Table 1, the amount of S1O2 for these prior art materials varies between 19% and 31.2% by weight of the matrix and the so-called silica-based glass ceramic matrix is therefore inaccurate.

Table 1: SiO ₂ % by weight in the vitroceramic matrices of the prior art (LAS), LiO2.Al2O3.SiO2 31, 2%

(MAS), MgO.Al2O3.SiO2 29.7%

(BAS), BaO.AI2O3.SiO2 19.0%

(CAS), CaO.Al2O3.SiO2 25.7%

Of course, an excess of silica may be included in the manufacturing process, which will remain as a filler in the matrix. Thus, patent EP 0404632 claims a glass-ceramic matrix in which this amount of silica S102 is between 25 and 70%, the glass-ceramic matrix consisting essentially of aluminosilicate containing alkaline earth oxides and rare earth oxides.

On the contrary, in the present invention, the term glass ceramic matrix to Silica base is correct since the amount of SiO ₂ is greater than 85% by weight of the matrix. Indeed, the matrix according to the invention is based on nano-crystalline cristobalite containing essentially at least 85% by weight of silica. In addition, in all these cases of the prior art, the method of manufacturing the thermostructural composite material requires densification at a temperature of at least 850 ° C, preferably between 900 ° C and 1100 ° C, all under one embodiment. isostatic pressure of at least 3 MPa, for several hours, followed by another heat treatment between 1100 ° C and 1200 ° C, or even 1350 ° C.

More recently, patent application WO 2005/030662 describes a method for manufacturing a lithium aluminosilicate (LAS) glass-ceramic matrix in which the densification temperature is carried out at a significantly lower temperature, around 500 ° C. . The so-called sol-gel impregnation technique is used for this purpose.

In contrast, in the present invention, the manufacturing method follows the technology developed for the geopolymer matrices, that is to say by means of a densification (a polycondensation) carried out at a temperature below 200 ° C. under vacuum cover in autoclave. In the context of the invention, the potassium polysiloxonate K- (Si-O-Si-O) _n type geopolymeric compound is used. When a short heat treatment is applied to this geopolymeric matrix at a temperature of 700 ° C., without exerting pressure, it crystallizes in the form of a mineral based on nano-crystalline cristobalite as defined by its diffraction spectrum. X-ray with the three main 2-theta lines 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for CuKal radiation However, the X-ray diffraction spectrum is always accompanied by a 2-theta stripe 21 degrees attributable to tridymite (hkl 100).

In the article by Y. Imanaka & al. "Cristobalite phase formation in glass-ceramic composite", J. Amer. Ceram. 1995, the goal is to avoid crystallization of cristobalite. Otherwise, the crystallization is carried out at a temperature above 1000 ° C, with a treatment of at least 5 hours. In a European patent application EP 1991/0401345, a composite material is presented having a glass-ceramic matrix based on silica, alumina and lithium oxides, namely LAS. already described previously. It reads in particular that the manufacturing process is carried out in such a way that, again, "the occurrence of harmful crystalline phases, such as cristobalite ..." is avoided. On the contrary, the process according to the present invention describes a heat treatment at a temperature above 500 ° C, preferably between 600 ° C and 800 ° C, allowing the crystallization of a mineral based on nano-crystalline cristobalite.

A fluoroaluminosilicate geopolymeric binder described in patent FR 2,659,320 is also known. This binder can be used, inter alia, to impregnate fiber reinforcements. It comprises a poly (sialate-siloxo) fluoropolymer (MF) -PSDS type geopolymer accompanied by an alkaline aluminum fluoride, cryolite Na ₃ AIF ₆ or elpasolite K ₂ NaAIF ₆ , and a siliceous phase of Opal type. CT, ie hydrated silica. The amount of this siliceous phase can vary between 10 and 95 parts by weight of the geopolymeric binder. As we can read in the

description on page 6, lines 11 to 19, the siliceous phase comes from the

precipitation of the alkali silicate present in the reaction mixture with sodium fluosilicate Na ₂ SiF ₆ . It also reads that the characteristic of this siliceous phase is that it is X-ray amorphous. On the other hand, it is noted that this siliceous phase of Opal CT type confers dilatometric properties in temperature, quite particular. For example, line 22-23 on page 4 states that it is not crystalline cristobalite, although this Opal CT silica phase has a characteristic dilatometric curve of SiO ₂ in the cristobalite phase. In fact, we also learn in lines 7 to 15 on page 7, "[...] In what follows the cristobalitic character is defined by the very characteristic step of the shrinkage expansion curve, shrinkage phase at 200 ° C. The Opal CT-type SiO ₂ concentration can be monitored by the intensity of the cristobalitic setback and by the value of the linear thermal expansion coefficient Δλ.10 ^_6 / ° Ο [...] "

Those skilled in the art know that crystalline cristobalite has this dilatometric behavior, namely, a high expansion of 0 to 210 ° C, of the order of 15. 0 ⁶ / ° C and, after the offset to 200 -210 ° C, a small expansion of the order of 2 to 5. 10 ^"6 / ° C. This is the first dilatometric phase, the one with high expansion which is claimed in patent FR 2 659 320. This expansion is essentially depending on the amount of SiO ₂ silica of the Opal CT type. Thus for 10 to 25 parts of Opal CT, the coefficient is less than ΙΟ.Ι Ο ^ /. For 26 to 75 parts of Opal CT it is between 10.10 ^"6 and 20.10 ^{" 6} / ° C and for 76 to 95 parts of Opal CT, it is greater than 20.10 ^"6 / ° C.

By comparison, in the context of the present invention, the matrix is formed of a nano-crystalline cristobalite-based mineral as defined by its X-ray diffraction spectrum. It is not made entirely of Opal CT hydrated silica. X-ray amorphous, but on the contrary, its diffraction spectrum is extremely precise and well characterized crystalline cristobalite. In the context of the invention it is even nanocrystalline, that is to say composed of nanocrystals of dimensions less than 1 micron, preferably less than 500 nanometers.

It is also known that the fiber-reinforced composite made using the geopolymeric matrix of (F, M) -PSDS type of the patent FR 2 659 320 does not meet the definition given above for the thermostructural composite material. Obviously, like all geopolymer matrices, it is fire resistant, but its use is limited to average temperatures, generally below 500 ° C. As can be learned in the book "Geopolymer Chemistry & Applications" by Joseph Davidovits, (2008), published by the Geopolymer Institute (Geopolymer Institute), ISBN 978-2-9514-8201-2, according to the nature of the fiber which constitutes the reinforcement, the flexural strength drops sharply above 400 ° C with the carbon fiber, or above 600 ° C with the SiC fiber (see Chapter 21, Figures 21.11 and 21) .12). This sudden drop in strength is mainly due to the softening of the geopolymer matrix accompanied by a strong expansion, because it contains a very large amount of melting agent: cryolite and elpasolite.

In contrast, the thermostructural composite material comprising a fiber reinforcement and a nano-crystalline cristobalite matrix according to the present invention does not contain cryolite or elpasolite. As can be seen, its X-ray diffraction spectrum only describes cristobalite with its main 2-theta crystallographic planes 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for CuKal radiation It can be used continuously, at temperatures above 500 ° C, up to 1000 ° C, without undergoing significant degradation or loss of mechanical strength throughout the duration of its operation. The operating temperatures are essentially determined by the nature of the reinforcing fibers containing at least one of the Si, B, O, N and C elements. Those skilled in the art know that in the case of carbon fiber , we avoid the

degradation of it by working in a non-oxidizing atmosphere.

In the prior art, it is known to synthesize crystalline cristobalite from amorphous silica. For example, the diatomaceous earth is composed of hydrated amorphous silica which is industrially heat treated at a temperature above 900 ° C., most often above 1000 ° C. Calcined diatomaceous earth, used in the production of filters for the food industry, is obtained which contains between 40 and 60% by weight of crystalline cristobalite, the size of which is generally greater than 2 microns. We can read in the patent

EP0463927: "The calcination of diatomites for the production of filtering agents therefore also aims to agglomerate diatoms and their debris a few microns in length aggregates of 10 pm or more, in order to reduce the rate of It is obviously a partial agglomeration, which must be controlled so as to avoid the complete melting of the diatomic skeletons and the formation of aggregates larger than 50 μm which have the serious disadvantage of decanting or depositing in the low points of pipes or filters during filtration operations. "

This cristobalitic diatom could be used to manufacture a thermostructural composite material comprising a fiber reinforcement and a matrix based on nano-crystalline cristobalite, by impregnating the fibrous reinforcement with a mineral binder (for example a geopolymer binder) containing a size cristobalite. very small. For this, it should be grinded very finely, at least below 2 microns, preferably below 1 micron, or employ a manufacturing process that would avoid any agglomeration of siliceous skeletons smaller than 2 microns. WO 88/02741 indicates that in the case of a geopolymeric ceramic matrix composite material, the dimension of the charges must be less than 2 microns. Now it is very difficult and very expensive to achieve a grain size of this type by simple grinding, and therefore, to the knowledge of the applicant, we can not achieve the object of the invention by this method.

In a European patent application EP 1996/0903002 describes the manufacture of a silica glass containing cristobalite particles of size between 0.1 microns and 1000 microns. However, in the examples given in this patent to illustrate this silica glass, the size of the cristobalite particles is never less than 40 microns. There is no production process for nano-crystalline cristobalite, less than one micron in size, and the extension to the 0.1 micron range, seems to be just a sentence of style (it does not is not included in the claims). However, here too, the final product is a solid silica glass that will have to be milled to a size of less than 2 microns, as in the case of the calcined diatom, mentioned above. In addition, the method of manufacturing cristobalite passes through the melting phase, that is to say involves temperatures between 1630 ° C and 1720 ° C. This is not the case of the present invention in which the nano-crystalline cristobalite-based mineral is crystallized at a much lower temperature, higher than 500 ° C, preferably between 600 and 800 ° C.

In the article by M. A. Saltzberg & al. «Synthesis of Chemically Stabilized

Cristobalite, J.Amer. Ceram. Soc., 75 (1), 89-95 (1992), cristobalite is produced starting from an amorphous silica gel to which doping products are added: Al, Na, Sr, K, Ca. Here again, the temperature of the transformation into cristobalite is at least 1000 ° C, for 24 hours. In the Si: AI.Ca system, it is 8 hours at 1100 ° C. In the Si: AI: K system it takes at least 24 hours at 1100 ° C. The Si: Al: K system is the preferred one in the examples of the present invention which, unlike the prior art, produces nano-crystalline cristobalite at a temperature well below 1100 ° C, only between 500 ° C. and 800 ° C. In addition, the crystallization time is very short since at 700 ° C it is only 10 to 15 minutes.

In an article by F. Aumento "Stability, Lattice Parameters, and Thermal Expansion of β-Cristobalite ", The American Mineralogists, Vol. 81, 1167-1176, July 1966, the manufacture of cristobalite is proposed from the thermal degradation of a zeolite, stilbite, calcium aluminosilicate. Cristobalite crystallization occurs only at a temperature above 920 ° C, in fact above 965 ° C, and even closer to 1000 ° C, for 24 hours. In the method of the present invention, this crystallization of cristobalite takes place much lower, around 700 ° C, for a time less than 30 minutes, generally between 10 to 15 minutes.

In an article by W. Kriven and S.J. Lee "Toughning of Mullite / Cordierite

Laminated Composites by Transformation Weakening of β-Cristobalite

Interphases »J. Am. Ceram. Soc, 86 [6] 1521-1528 (2005), we study the

behavior of a mullite / cordierite composite containing a cristobalite interface. It is learned that the crystallization takes place at 1300 ° C and the size of the cristobalite particles is of the order of 4 microns.

In an article by AJ Perrotta & al. "Chemical Stabilization of β-Cristobalite", J. Amer. Ceram., 72 [3] 441-47 (1989) describes how to make cristobalite by thermal crystallization of synthetic gels and zeolites, thus from sodium and calcium aluminosilicate, whose chemistry is close to that of geopolymers. The manufacture of cristobalite is essentially a function of the Si: Al atomic ratio of the aluminosilicate. Thus in Table IV, for Si: Al = 25 (SiO ₂ : Al ₂ O ₃ = 50), the crystallization temperature is 1200 ° C; with a ratio Si: Al = 7 (SiO ₂ : Al ₂ O ₃ = 14), the crystallization temperature is 850 ° C. (it is therefore different from that given in FIG. 3, example C which, for the same aluminosilicate, indicates 800 ° C, which could be a simple hardware error because it does not fit with the logic of the mixtures described in Table IV). However, the aluminosilicate matrix requires extremely long crystallization times, at least 24 hours and contains less than 80% by weight silica oxide S102. The mineral used in Example 5 of the present invention has an Si: Al = 30 ratio, which would imply a temperature of 1250 ° C. according to the method described in this article by AJ Perrotta et al. Now, the

The plaintiff discovered to his great surprise that it was possible to manufacture a glass-ceramic matrix by promoting the formation of nanocrystalline cristobalite. crystalline with a very rapid crystallization, of the order of 10 to 15 minutes at 700 ° C. The matrix is present in the form of micelles and / or microspheres of dimensions less than 1 micron, preferably less than 500 nanometers. The said micelles and / or microspheres are interconnected by an amorphous alveolated phase consisting of closed cells.

The scientific article by Zhu et al. sets forth the rules for obtaining a nano-crystalline cristobalite (see Y. Zhu, K. Yanagisawa, A. Onda and K. Kajiyoshi, "The preparation of nano-crystallized cristobalite under hydrothermal conditions" Journal of Materials Science, 40, 3829 The starting material is a colloidal silica, a silica gel, whose micelle size (particles) is of the order of 18-20 nanometers.

Nano-crystalline cristobalite is carried out at average temperatures between 200 ° C and 400 ° C, but it depends solely on the nature of the alkaline salts and the alkaline solutions used during the experiment. It reveals that cristobalite is only formed with the alkaline salts NaF and KF (with a preference for NaF), but that, on the other hand, the action of NaOH always leads to the formation of quartz. However, the presence of the NaF and KF alkaline salts prevents this nano-crystalline cristobalite from forming a matrix having thermostructural properties. In fact, these alkaline salts act as fluxing agents which, at higher temperatures, will transform the matrix into glass. We then find ourselves in the same unfavorable practical conditions at high temperature as those encountered for geopolymer binders of (M, F) -PSDS type, mentioned above in the patent FR 2 659 320.

In this scientific article by Zhu et al., The use of NaOH generates the formation of quartz instead of cristobalite. Indeed, in an example presented below, and under the conditions of the process according to the invention, the X-ray diffraction pattern of the matrix thus obtained does not contain crystalline cristobalite. In the article by Zhu et al., It is also discovered that one skilled in the art knows that in a strongly alkaline medium, quartz is always formed, not cristobalite. It could be deduced that it would be the same with another alkaline hydroxide, potash KOH. Now, to the great surprise of the

applicant, the method according to the invention, is characterized in that the matrix nano-crystalline cristobalite base results from the crystallization of a geopolymeric micelle of potassium polysiloxonate K- (Si-O-Si-O) _n , by action of potassium hydroxide KOH, which seems contrary to the teaching provided by the prior art. In addition, contrary to what is taught in Zhu et al.'S article, the geopolymeric synthesis of the matrix is carried out at a temperature below 200 ° C., followed by a heat treatment at a temperature above 500 ° C. preferably between 600 ° C and 800 ° C. However, according to Zhu et al., Above 400 ° C, quartz is always formed.

In the present invention, the nano-crystalline cristobalite matrix is in the form of micelles and / or microspheres of dimensions less than 1 micron, preferably less than 500 nanometers. This nano-crystalline cristobalite matrix of the present invention enables the manufacture of a thermostructural composite material comprising a fiber reinforcement. It contains, apart from oxygen and carbon, the following principal elements: Si, K, Al, Zr, of which at least 75 per cent by weight of Si atom. These principal elements are those which, in the elemental analysis of the matrix under an electron microscope are present at more than 0.2% by weight of atom. As an indication, the chemical composition of said matrix contains at least 85% by weight of oxide SiO ₂ , at most 3% by weight of Al ₂ O ₃ , at most 10% by weight of K ₂ O, at most 4% by weight of ZrO ₂ . The absence of formative agents or glass modifiers is found as claimed in the WO application

2007/141455. The fiber reinforcement of the thermostructural composite material contains at least one of the elements Si, B, O, N and C. In addition, the amount of nano-crystalline cristobalite matrix is between 40 and 70, preferably between 45 and 55 percent of the total weight of said composite material.

Geopolymer matrices of the K-nano-poly (siloxo) or K-nano-poly (sialate) type are already known in the prior art. They are described in the book Geopolymer, Green Chemistry and Sustainable Development Solutions, Proceedings of the World Geopolymer Congress 2005, edited by Joseph Davidovits, Institute

Geopolymer (Geopolymer Institute) ISBN 2-9514820-0-0 (2005), pages 1-12, as well as in the book already cited above, Geopolymer Chemistry & Applications, in Chapter 1 1, Section 1 1.6, entitled Poly ( siloxo) and poly (sialate) cross-links, nacocomposite geopolymer. In these publications of the prior art, the nano-composite geopolymer is defined in that it comprises two phases:

1. a nodular phase of silica fume composed of nanospheres of diameter less than 1 micron, preferably less than 500 nanometers.

2. a polymeric phase, fully amorphous under the observation at

optical microscope, consisting of poly (silanol) linear chains more or less crosslinked by a siloxo bridge (-Si-O-Si-O-), or a sialate bridge (Si-O-AI-O-).

The X-ray spectrum of this nano-poly (silanol) geopolymer matrix is entirely amorphous. Then, again in the book Geopolymer Chemistry & Applications, we follow the evolution of this matrix as a function of temperature, with the formation of siloxo bridges, at 200 ° C. and 500 ° C. The X-ray spectra of this nano-poly (siloxo) matrix at 250 ° C and 500 ° C are identical, and fully amorphous. But the conversion of silanol groups into a siloxo bridge results in the production of water from dehydroxylation. This results in an expansion of the geopolymer which is quite important since, at 250 ° C its volume is tripled (300% expansion) and 850 ° C is reached an expansion rate of 488%. It is thus explained that the composite materials containing this matrix do not have the thermostructural character, but that their mechanical strength decreases sharply as a function of temperature. On the contrary, the composite material according to the present invention, has little or no expansion, and it has the thermostructural character, with constant mechanical strength for several or even several thousand hours in the temperature range of 200 ° C and 1000 ° C.

In the prior art, this expansion is eliminated by introducing sialate bonds or bridges (Si-O-Al-O-). This gives a three-dimensional crosslinking known as nano-poly (sialate-siloxo). It is also described in the prior art (Proceedings of Geopolymer 2005) as well as in Chapter 11 of the book "Geopolymer Chemistry & Applications". The disadvantage of this poly (sialate-siloxo) matrix is that, during the rise in temperature, shrinkage and a very marked embrittlement of the composite material are observed. It is this defect that the process described in the WO application has attempted to solve

2007/141455. In this patent, embrittlement is prevented by incorporating glass forming agents in the process of making the matrix. Then, by heat treatment, and under the effect of glass forming agents, this poly (sialate-siloxo) matrix will melt. This implies that once the fusion is complete, it will cool the material to solidify. For example, in the description of WO 2007/141455, lines 15-17, page 23 read: "The melting temperature of the matrix is preferably between 600 and 1200 ° C, and depends on the nature of the glass to be formed. ... ", then to claim 35" Part formed of composite material with fiber reinforcement and matrix

mainly glass, .... " Those skilled in the art know that a glass obtained by melting, then solidified, is X-ray amorphous. The material described in this patent WO 2007/141455 is therefore an amorphous X-ray glass.

In the present invention there is crystallization of a nano-crystalline cristobalite-type mineral without going through the melting stage. The method for manufacturing the glass-ceramic matrix of the nano-crystalline cristobalite type first comprises the synthesis, according to the methods already described above, of a compound based on nano-poly (siloxo) type geopolymeric micelles. Here we write this compound in its more precise form of potassium polysiloxonate, K- (Si-O-Si-O) _n . It contains at least 85% by weight of amorphous silica S1O2 with not more than 15%, preferably not more than 10% by weight, of potassium oxide K ₂ O. As can be seen, even after treatment at 500 ° C. there is no crystallization of nano-crystalline cristobalite, the X-ray diffraction spectrum being amorphous. Then a very short heat treatment (of the order of 10 minutes) is carried out to obtain the nano-crystalline cristobalite-based mineral. This results from the crystallization of potassium polysiloxonate geopolymeric micelles by a heat treatment at a temperature above 500 ° C, preferably between 600 ° C and 800 ° C, for a period of less than 30 minutes.

Still in application WO 2007/141455, we saw above that claim 35 specified that in the piece formed, the matrix was a glass, and the characteristic of this glass is developed in lines 20-28 of page 25:

"In this formed part, the matrix presents at least one of the

characteristics: - it has a 29Si NMR spectrum with all three following reference areas: -87 + -5 ppm, -98 + -5ppm, -107 + -5ppm .... ". The resonance at -87ppm characterizes the Si atom of type Q2, which is found mainly in glasses, the one at -98ppm corresponds to the Si type (Q.3), also present in glasses, and at the surface of the nodular phase. Finally, the resonance -107ppm, type Si (Q _4), characterized quartz or within the nodule Si0 ₂ from amorphous structure. In the matrix according to the present invention, the spectrum 29SINMR is different since it is essentially that of cristobalite, consisting of SiO 2 Si (Q ₄ ), with a single major resonance at -109 ppm (see in the book: High Resolution Solid-State NMR of Silicates and Zeolites, by G. Engelhardt and D. Michel, John Willey & Sons, 1987, page 170 Silica

polymorpha).

DETAILED PRESENTATION OF THE INVENTION

The matrix according to the invention is characterized in that it contains a mineral based on nano-crystalline cristobalite which results from the crystallization of geopolymeric micelles of potassium polysiloxonate. These are obtained by geopolymeric synthesis at a temperature below 200 ° C. The matrix is then subjected to a heat treatment at a temperature above 500 ° C., preferably between 600 ° C. and 800 ° C. The nano-crystalline cristobalite is in the form of micelles and / or microspheres of dimensions less than 1 micron, preferably less than 500 nanometers, interconnected by an amorphous phase. This amorphous phase may also be weakly cellular, consisting mainly of closed cells. The whole forms the matrix based on nano-crystalline cristobalite as defined by its X-ray diffraction spectrum with the three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36, 4 (hkl 200), for CuKal radiation. The X-ray diffraction spectrum is also accompanied by a 21-degree 2-theta line that can be attributed to tridymite (hkl 100).

The nano-crystalline cristobalite matrices according to the present invention are generally employed in the manufacture of fibrous reinforcing composites for use at high temperature, in the range of 300 ° C to 1000 ° C, continuously, during hundreds or thousands of hours. The temperatures of use are essentially determined by the nature of the reinforcing fibers containing at least one of Si, B, O, N and C. Those skilled in the art know that in the case of carbon fiber, avoids the degradation thereof by working in a non-oxidizing atmosphere. In addition, the amount of nano-crystalline cristobalite matrix is from 40 to 70, preferably from 45 to 55 percent of the total weight of said composite material. Its linear expansion coefficient is Δλ> W 0 / ° C from 0 ° C to 210 ° C and then Δλ <6.10 ^"6 / ° Ο above 210 ° C

These matrices can also be used in the manufacture of ceramic objects containing well-referenced mineral fillers. In the case of the fibrous reinforcement composite, the fiber is first impregnated with a potassium polysiloxonate K- (Si-O-Si-O) _n geopolymer binder, and the geopolymeric synthesis is then carried out. autoclaving at 200 ° C. Finally, the composite material thus produced is subjected to a heat treatment at a temperature above 500 ° C, preferably between 600 ° C and 800 ° C, for a relatively short time between 10 minutes and 30 minutes. After heat treatment, the composite material contains the thermostructural matrix consisting essentially of a mineral based on nano-crystalline cristobalite as defined by its X-ray diffraction spectrum, namely the three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for CuKa radiation

The starting raw material is amorphous silica consisting of amorphous particles smaller than 1 micron, preferably less than 500 nanometers. There are several types:

- colloidal silica,

- silica gel

- silica fume.

They are described in Chapter 1 1 of "Geopolymer Chemistry &Applications" already mentioned above, as well as their products obtained by geopolymeric synthesis. These silicas produce X-ray diffraction patterns that are entirely amorphous. It therefore seems difficult to know their molecular structure. However, thanks to the Nuclear Magnetic Resonance, it is known that the molecular structure of these different amorphous silicas consists of regions having the faces hkl 100 and hkl 1 1 1 of β-cristobalite; see DW Sindorf and GE Maciel, "29Si NMR Study of Dehydrated / Rehydrated Silica Gel Using Cross Polarization and Magic-Angle Spinning", J. Am. Chem. Soc. , Flight. 105, No. 61487-1493 (1983). It was therefore necessary to find a method that would crystallize this cristobalite structure already present in the disorganized state in amorphous and colloidal silicas, without leading to the crystallization of quartz. In addition, this method had to produce a matrix free of fluxing agent and glass former, to ensure the thermostructural properties of the fibrous composite material obtained by this method.

The nano-crystalline cristobalite matrix for thermostructural fibrous composite material of the present invention is illustrated by the following examples. They do not have a limiting character on the overall scope of the invention as presented in the claims.

Example 1

The geopolymeric synthesis of the nano-poly (siloxo) described in Chapter 11 of "Geopolymer Chemistry & Applications", section 1 1.6, page 264-266 is carried out. For this, silica fume is reacted from the electrofusion at 2000 ° C of a natural silicate, with potassium silicate. 245 g of geopolymeric mixture containing

H ₂ O: 3.5 moles

K ₂ O: 0.276 moles

SiO ₂ : 2.509 moles.

SiO ₂ comes from silica fume and potassium silicate of molar ratio SiO ₂ : K ₂ O = 1.25. K ₂ O comes from potassium silicate. The ratio between the oxides is:

SiO ₂ : H ₂ O = 0.72

SiO ₂ : K ₂ O = 9.1

After polycondensation at 80 ° C. for 2 hours, the evolution of the

nano-poly (siloxo) geopolymer as a function of temperature up to 500 ° C. For this, the oven temperature increases by 10 ° C per minute and a plateau is set at 500 ° C for 30 minutes before allowing to cool. It is confirmed that at 500 ° C the X-ray pattern is amorphous. There is no crystallization of quartz as should have been the case according to the article by Zhu et al. described above. There is also no cristobalite. However, accidentally, the heat treatment was continued up to 750 ° C, with a plateau at 750 ° C for 15 minutes. The X-ray diffraction pattern then shows the lines very

characteristics of cristobalite with three main lines at 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for CuKal radiation. The molecular structure formed by the cristobalite faces hk1 100 and hk1 1 1 1 of silica fume (amorphous) was therefore revealed at this temperature of 750 ° C., after a duration of less than 30 minutes.

Is this a simple physical transformation of silica fume nanospheres at this temperature or does this cristobalite crystallization result from the action of the alkaline portion of potassium silicate? To know it carrying us a sample of silica fume at the temperature of 750 ° C, under the same conditions as above, namely an elevation of 10 ° C per minute and a bearing at 750 ° C for 15 minutes. The X-ray diffraction pattern remains entirely amorphous, there is no formation of nano-crystalline cristobalite. In the case of the nano-poly (siloxo) of this Example 1, the formation of nano-crystalline cristobalite would likely be the result of the "dopant" action of K ₂ O.

But, we know that this geopolymer has a serious disadvantage that makes it absolutely not able to fulfill the matrix function for thermostructural composite material, as claimed by the present invention. Also in the book "Geopolymer Chemistry &Applications", we learn that between 20 ° C and 850 ° C, this geopolymer undergoes an expansion of nearly 500% by volume. It is not stable in temperature. Crosslinking in poly (sialate-siloxo) does not meet this criterion either, because they induce shrinkage, and, moreover, according to the prior art, the presence of free alumina in the geopolymeric medium prevents the formation of cristobalite. . Example 2

The geopolymeric synthesis of a potassium polysiloxonate K- (Si-O-Si-O) _{n is carried out} by reacting silica fume from the electrofusion at 2000 ° C of a natural silicate with carbon dioxide. potassium hydroxide KOH. 674 g of geopolymeric mixture containing

H ₂ O: 7.22 moles

K ₂ O: 0.5 moles

SiO ₂ : 7.08 moles.

SiO ₂ comes from silica fume, K ₂ O and H ₂ O come from an aqueous solution of KOH. The ratio between the oxides is:

SiO ₂ : H ₂ O = 0.98

SiO ₂ : K ₂ O = 14.16

After polycondensation at 80 ° C. for 2 hours, the evolution of the

geopolymer potassium polysiloxonate as a function of temperature, up to 750 ° C, as in Example 1. It is confirmed that at 500 ° C, the X-ray pattern is amorphous. But after the heat treatment at 750 ° C. for 15 minutes, the X-ray diffraction pattern then shows the very characteristic lines of cristobalite with three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for the CuKal radiation In addition, the

The geopolymer has undergone a very small expansion of less than 3% by volume.

Example 3

The geopolymeric synthesis is repeated according to Example 2, but replacing the potassium hydroxide with sodium hydroxide NaOH. After the heat treatment at 750 ° C, the X-ray diffraction pattern remains amorphous. The nano-crystalline cristobalite phase did not develop.

Example 4

The geopolymeric synthesis is repeated according to Example 2, but replacing the silica fume by colloidal silica type Ludox or equivalent. After polycondensation at 80 ° C. for 2 hours, the evolution of the potassium polysiloxonate geopolymer as a function of temperature is followed, up to 750 ° C., as in Example 1. It is confirmed that, at 500 ° C., the X-ray is amorphous. But after the heat treatment at 750 ° C for 15 minutes, the X-ray diffraction pattern then shows the very characteristic lines of cristobalite with three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), In addition, the geopolymer has undergone very little expansion, less than 3% by volume.

Example 5

A geopolymeric mixture is carried out according to Example 2 to serve as a matrix for a thermostable composite material. For this, various ingredients known in the prior art are added to the geopolymeric mixture to facilitate the impregnation and to modify the rheology of the binders resulting from geopolymeric synthesis and traditional alkaline silicates. Examples include wetting agents and surface tension modifiers, usable in strongly alkaline medium; also other organic products such as polyols and polyglycols (soluble in alkaline medium), generally used as adjuvants in very small amounts, generally less than 2% by weight of the matrix.

After maturation for 1 hour, a fabric of silicon carbide fiber (SiC), orientation 0/90 to 200 g / m2, is impregnated. We make sure that the ratio between the weight of the geopolymeric mixture and the weight of fiber is 55/45. This produces a formable composite material containing 10 layers of impregnated fabric, then placed on a metal plate, the assembly being covered with a vacuum cover. The mixture is evacuated for 1 hour at ambient temperature, and the complex is then placed in an autoclave at 120 ° C. under 6 bars of pressure for 3 hours. After cooling, the plates are removed and subjected to heat treatment at 750 ° C. for 15 minutes. For this, the sample is placed in the oven at 20 ° C. and the temperature is raised at a rate of 10 ° per minute, and then, when the 750 ° C. are reached, a plateau of 15 minutes is reached. Then, let cool in the oven.

After cooling, the examination of the X-ray diffraction spectrum of the matrix shows the three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 (hkl 200), for the CuKal radiation. The X-ray diffraction spectrum is also accompanied by a 2-theta 21-degree line attributed to tridymite (hkl 100).

In the composite material, the nano-crystalline cristobalite matrix weight ratio and SiC fiber weight is 49/51.

A sample of this composite material is subjected to various analyzes, namely: a) elementary chemical analysis of the matrix, by electron microscopy, in% by weight of the matrix:

SiO ₂ = 86.6%

AI ₂ O ₃ = 2.5%

K ₂ O = 8.94%

ZrO ₂ = 1, 8%

The molar ratios are

SiO ₂ : K ₂ O = 15.15

SiO ₂ : Al ₂ O 3 = 60 is an atomic ratio Si: Al = 30

Zirconium oxide, to the knowledge of the applicant, does not react in the geopolymeric synthesis. It remains an integral part of the micelle

geopolymer.

b) coefficient of thermal expansion:

- in the fiber direction Δλ = 4,510 ^"6

- in the thickness:

from 20 ° C to 210 ° C, Δλ = 13.51 ° ^"6

from 210 ° C. to 900 ° C., Δλ = 5.510 ^"6

The composite material thus produced has a flexural strength of 158 MPa at 20 ° C; this is maintained at 142 MPa after 100 hours at 700 ° C. and is still at 124 MPa after 1000 hours at 700 ° C.

Example 6

A composite material is produced according to Example 5, but the source of SiO ₂ consists of silica fume (see Example 2) and colloidal silica (see Example 4) in a 50/50 ratio by weight of SiO ₂ . The nanocrystalline cristobalite matrix is obtained and the weight ratio of matrix and weight of SiC fiber is 48/52. A sample of this composite material is subjected to elemental chemical analysis of the matrix, by electron microscopy, in% by weight of the matrix:

SiO ₂ = 88.75%

AI ₂ O ₃ = 1, 25%

K ₂ O = 8.94%

ZrO ₂ = 0.9%

The molar ratios are

SiO ₂ : K ₂ O = 15.5

SiO ₂ : Al ₂ O 3 = 123 is an atomic ratio Si: Al = 61.5.

Those skilled in the art may add in the geopolymeric synthesis any other mineral or organic auxiliary agent known to increase the quality of the impregnation, reduce the amount of air included in the matrix, or facilitate the development of the composite material. Various modifications can therefore be made by those skilled in the art to the process for preparing the nanco-crystalline cristobalite matrix which has just been described by way of example, without departing from the scope of the invention.

Claims

1) Matrix consisting of a mineral based on nano-crystalline cristobalite, for thermostructural fibrous composite material, characterized in that it is the result of the geopolymeric synthesis of a reaction mixture containing amorphous silica S1O2 in the presence of potassium hydroxide KOH and / or potassium silicate. Said geopolymeric synthesis is carried out at a temperature below 200 ° C, then said matrix is subjected to a heat treatment at a temperature above 500 ° C, preferably between 600 ° C and 800 ° C. The said nano-crystalline cristobalite-based mineral is characterized by its X-ray diffraction spectrum, namely the three main lines with 2 theta 21, 9 (hkl 101), 31, 4 (hkl 102), 36.4 ( hkl 200), for CuKal radiation. The said X-ray diffraction pattern is also accompanied by a 21-degree 2-theta line attributed to tridymite (hkl 100).

2) Matrix for thermostructural fibrous composite material according to claim 1), characterized in that said nano-crystalline cristobalite-based mineral results from the crystallization of geopolymeric micelles of potassium polysiloxonate K- (Si-O-Si-O) _n .

3) Matrix for thermostructural fibrous composite material according to one

any of claims 1 to 2, characterized in that its linear coefficient of expansion is Δλ> 10.10 ^"6 / ° C from 0 ° C to 210 ° C and then Δλ <6.10 ^{" 6} / ^Ο ΰ above 210 ° C.

4) Matrix for thermostructural fibrous composite material according to one

any of claims 1 to 3, characterized in that it contains, apart from oxygen and carbon, the following main elements: Si, K, Al, Zr, of which at least 75 atomic percent by atom of Si.

5) Matrix for thermostructural fibrous composite material according to one

any of claims 1 to 4, characterized in that it contains at least 85 weight percent S1O2 oxide. 6) Matrix for thermostructural fibrous composite material according to one

any one of claims 1 to 5, characterized in that said nano-crystalline cristobalite-based mineral is in the form of micelles and / or microspheres of dimensions less than 1 micron, preferably less than 500 nanometers, interconnected by an amorphous phase.

7) Process for manufacturing a thermostructural fibrous composite material obtained by impregnating a fibrous reinforcement with a nano-crystalline cristobalite-based matrix according to any one of claims 1 to 6, characterized in that said geopolymeric micelles result from the geopolymeric synthesis of potassium polysiloxonate, K- (Si-O-Si-O) _n , containing at least 85% by weight of nano-crystalline silica nanoparticles with at most 15%, preferably at most 10% by weight alkaline oxide K ₂ 0.

8) Process for producing a thermostructural fibrous composite material obtained by impregnating a fibrous reinforcement with a nano-crystalline cristobalite-based matrix according to any one of Claims 1 to 6, characterized in that the nano-crystalline cristobalite results from the crystallization of micelles

geopolymeric potassium polysiloxonate by heat treatment at a temperature above 500 ° C, preferably between 600 ° C and 800 ° C, for a period of less than 30 minutes.

9) thermostructural fibrous composite material obtained according to any one of claims 7 to 8, characterized in that said fiber reinforcement contains at least one of the elements Si, B, O, N and C.

10) thermostructural fibrous composite material according to claim 9, characterized in that the amount of nano-crystalline cristobalite matrix is between 40 and 70, preferably between 45 and 55 percent of the total weight of said composite material.