COMPOSITE MATERIAL HAVING AN ALUMINOSILICATE MATRIX IN PARTICULAR MADE FROM BARIUM ALUMINOSILICATE (BAS) REINFORCED WITH METAL OXIDE REINFORCEMENTS, AND METHOD FOR PREPARING SAME

Abstract

A composite material consisting of a matrix made of at least one aluminosilicate notably selected from barium aluminosilicate BAS, barium and strontium aluminosilicate BSAS, strontium aluminosilicate SAS, and mixtures thereof, reinforced by reinforcements made of at least one metal or metalloid oxide, the expansion coefficient of which is close to that of said at least one aluminosilicate.

A method for preparing said composite material.

A composite material according to the invention notably finding its application in the aeronautical or aerospace field, for example for the manufacture of radomes.

Claims

1-21. (canceled)

22. A method for preparing a composite material consisting of a matrix made of at least one aluminosilicate, reinforced by reinforcements made of at least one metal oxide or metalloid oxide, the expansion coefficient of which is close to that of said at least one aluminosilicate, the method comprising the following successive steps a) to d): a) placing into contact a powder of at least one aluminosilicate selected from barium aluminosilicate BAS, barium and strontium aluminosilicate BSAS, strontium aluminosilicate SAS, and mixtures thereof, with reinforcements made of at least one metal oxide or metalloid oxide, the expansion coefficient of which is close to that of said at least one aluminosilicate; b) sintering the powder of at least one aluminosilicate and the reinforcements made of at least one metal oxide or metalloid oxide by a hot sintering method using a pulsed electric field; c) cooling the sintered powder and reinforcements; and d) recovering the composite material.

23. The method according to claim 22, wherein the powder of at least one aluminosilicate is barium aluminosilicate BAS powder.

24. The method according to claim 22, wherein the BAS in majority by mass comprises BAS of hexagonal structure.

25. The method according to claim 24, wherein the BAS powder, wherein in majority by mass comprises BAS of hexagonal structure, is prepared by carrying out the following successive steps: mixing BaCO.sub.3 powder and SiO.sub.2 powder in a molar ratio of 1 BaCO.sub.3 for 2 SiO.sub.2; drying and then sintering the mixture of the BaCO.sub.3 powder and of the SiO.sub.2 powder to obtain a compound in majority consisting of the compound BaSi.sub.2O.sub.5; milling the compound in majority consisting of BaSi.sub.2O.sub.5 is to obtain a powder of said compound in majority consisting of BaSi.sub.2O.sub.5; mixing the powder of the compound in majority consisting of BaSi.sub.2O.sub.5, and the Al.sub.2O.sub.3 powder, in a molar ratio of 1 BaSi.sub.2O.sub.5 for 1 Al.sub.2O.sub.3; drying and then sintering the mixture of the powder of the compound in majority consisting of BaSi2O5, and of the Al2O3 powder; and milling the sintered mixture to obtain a BAS powder which in majority by mass comprises BAS of hexagonal structure.

26. The method according to claim 24, wherein the reinforcements are made of alumina.

27. The method according to claim 22, wherein the BAS in majority by mass comprises BAS of monoclinic structure.

28. The method according to claim 27, wherein the reinforcements are made of silica and/or made of mullite.

29. The method according to claim 22, wherein the reinforcements made of at least one metal oxide or metalloid oxide appear in one or more form(s) selected from particles and fabrics of fibers.

30. The method according to claim 29, wherein the particles are selected from long fibers and short fibers also called whiskers.

31. The method according to claim 22, wherein the step a) further comprises preparing a mixture of the powder of at least one aluminosilicate, such as barium aluminosilicate powder, and of particles made of at least one metal oxide or metalloid oxide.

32. The method according to claim 22, wherein the step a) further comprises impregnating a fabric of fibers made of at least one metal oxide or metalloid oxide with a slip (slurry) of the powder of at least one aluminosilicate, such as barium aluminosilicate powder.

33. The method according to claim 22, wherein the matrix represents 99 to 50% by mass of the material, and the reinforcements represent 1 to 50% by mass of the material.

34. The method according to claim 22, which is a dense material with a density from 80% to 100% of the theoretical density.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0099] Other features and advantages of the invention will become better apparent upon reading the description which follows, given as an illustration and not as a limitation with reference to the appended figures, wherein:

[0100] FIG. 1 is a schematic vertical sectional view of an exemplary SPS device for applying the method according to the invention;

[0101] FIG. 2 is a graph which shows a thermal cycle used during the sintering step by SPS of the method according to the invention.

[0102] Time (in minutes) is plotted in abscissas and the temperature (in ° C.) is plotted in ordinates.

[0103] FIG. 3 is a diffractogram obtained during XRD analysis (X-Ray Diffraction on a powder) of a pellet consisting of a mixture of BaCO.sub.3 and SiO.sub.2 powders having been subject to a first heat treatment of sintering with a plateau at 1,150° C. for 4 hours in a tubular oven.

[0104] 2 Theta (in angle degrees) is plotted in abscissas and Lin (in counts) is plotted in ordinates.

[0105] FIG. 4 shows a micrograph obtained with a scanning electron microscope of a cut of a pellet consisting of a mixture of BaCO.sub.3 and SiO.sub.2 powders having been subject to a heat sintering treatment with a plateau at 1,150° C. for 4 hours in a tubular oven.

[0106] The scale plotted in FIG. 4 represents 5 μm.

[0107] FIG. 5 is a diffractogram obtained during XRD analysis of a pellet obtained after a second sintering treatment in a tubular oven with a plateau at 1,200° C. for 6 hours.

[0108] 2 Theta (in °) is plotted in abscissas, and Lin (in counts) is plotted in ordinates.

[0109] FIG. 6 shows a micrograph, obtained with a scanning electron microscope, of a cut of a pellet obtained after a second sintering treatment in a tubular oven with a plateau at 1,200° C. for 6 hours.

[0110] The scale plotted in FIG. 6 represents 5 μm.

[0111] FIG. 7 shows a micrograph, obtained with a scanning electron microscope of a composite material with a BAS matrix reinforced by alumina fibers, prepared by sintering by SPS at a temperature of 1,000° C. for 5 minutes.

[0112] The scale plotted in FIG. 7 represents 30 μm.

[0113] FIG. 8 shows a micrograph, obtained with a scanning electron microscope of a composite material with a BAS matrix reinforced by alumina fibers, prepared by sintering by SPS at a temperature of 1,200° C. for 5 minutes.

[0114] The scale plotted in FIG. 8 represents 30 μm.

[0115] FIG. 9 shows a micrograph obtained with a scanning electron microscope at a magnification of 200 of a composite material with a BAS matrix reinforced by alumina fibers, prepared by sintering by SPS at a temperature of 1,200° C. for 5 minutes.

[0116] The scale plotted in FIG. 9 represents 200 μm.

[0117] FIG. 10 shows a micrograph, obtained with a scanning electron microscope at a magnification of 6,000 of a composite material with a BAS matrix reinforced by alumina fibers, prepared by sintering by SPS at a temperature of 1,200° C. for 5 minutes.

[0118] The scale plotted in FIG. 10 represents 5 μm.

[0119] FIG. 11 is a diffractogram obtained during XRD analysis of the core of a composite material with a BAS matrix reinforced by alumina fibers, prepared by sintering by SPS at a temperature of 1,200° C. for 5 minutes.

[0120] 2 Theta (in °) is plotted in abscissas, and Lin (in counts) is plotted in ordinates.

[0121] FIG. 12 is a diffractogram obtained during XRD analysis of a pellet consisting of the three BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 powders after sintering by SPS at 1,000° C. for 5 minutes.

[0122] 2 Theta (in °) is plotted in abscissas, and Lin (in counts) is plotted in ordinates.

[0123] FIG. 13 shows a micrograph, obtained with a scanning electron microscope of a cut of a pellet formed by the three BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 powders after sintering by SPS at 1,000° C. for 5 minutes.

[0124] The scale plotted in FIG. 13 represents 5 μm.

[0125] FIG. 14 is a diffractogram obtained during XRD analysis of a pellet consisting of the three BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 powders, the SiO.sub.2 powder being coarser and the Al.sub.2O.sub.3 powder being finer, after sintering by SPS at 1,000° C. for 5 minutes.

[0126] 2 Theta (in °) is plotted in abscissas, and Lin (in counts) is plotted in ordinates.

[0127] FIG. 15 shows a micrograph obtained by a scanning electron microscope of a cut of a pellet consisting of the three BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 powders, the SiO.sub.2 powder being coarser and the Al.sub.2O.sub.3 powder being finer, after sintering by SPS at 1,000° C. for 5 minutes.

[0128] The scale plotted in FIG. 15 represents 10 μm.

[0129] FIG. 16 is a diffractogram obtained during XRD analysis of a pellet after an annealing treatment with a plateau at 1,150° C. for 4 hours.

[0130] 2 Theta (in °) is plotted in abscissas, and Lin (in counts) is plotted in ordinates.

[0131] FIG. 17 shows a micrograph, obtained with a scanning electron microscope of a pellet after an annealing treatment with a plateau at 1,150° C. for 4 hours.

[0132] The scale plotted in FIG. 17 represents 5 μm.

DETAILED DISCUSSION OF PARTICULAR EMBODIMENTS

[0133] The description which follows is rather made, by convenience, with reference to the method for preparing the composite material according to the invention but it is quite obvious that it also contains teachings which apply to the composite material according to the invention.

[0134] The description which follows is also rather made with reference to the preparation of a composite material for which the matrix is in a single aluminosilicate, i.e. BAS. But it is quite obvious that this description may be easily adapted by one skilled in the art, for allowing the preparation of a composite material, the matrix of which is generally at least one aluminosilicate, whichever this or these aluminosilicate(s).

[0135] This aluminosilicate may for example be selected from barium aluminosilicate BAS, barium and strontium aluminosilicate BSAS, strontium aluminosilicate SAS and mixtures thereof.

[0136] In the first step of the method according to the invention, a barium aluminosilicate BAS powder and reinforcements made of at least one metal or metalloid oxide, the expansion coefficient of which being close to that of barium aluminosilicate, are put into contact.

[0137] The barium aluminosilicate BAS powder may in majority comprise BAS with a hexagonal structure.

[0138] By «in majority», is generally meant that the BAS powder comprises more than 50% by mass, preferably more than 80% by mass of BAS with a hexagonal structure, still preferably 100% by mass of BAS of hexagonal structure.

[0139] The remainder of the BAS powder may comprise as a minority, one or several impurities for example selected from alumina, silica and barium silicates such as Ba.sub.5Si.sub.8O.sub.21 and Ba.sub.3Si.sub.5O.sub.13.

[0140] As this is specified later on, when the BAS powder in majority comprises BAS with a hexagonal structure, the reinforcements are then made of alumina.

[0141] Or else, the barium aluminosilicate BAS powder may in majority comprise BAS of monoclinic structure.

[0142] By «in majority», is generally meant that the BAS powder comprises more than 50% by mass, preferably more than 80% by mass of BAS of monoclinic structure, still preferably 100% by mass of BAS of monoclinic structure.

[0143] As this is specified later on, when the BAS powder in majority comprises BAS of monoclinic structure, the reinforcements are then made of silica and/or made of mullite.

[0144] The barium aluminosilicate powder may consist of particles of any shape for example of a spherical or spheroidal shape.

[0145] The average size—defined by their largest dimension—of the particles of the barium aluminosilicate powder is generally from 10 nm to 100 microns, preferably from 1 micron to 10 microns.

[0146] A new procedure, operating method was developed according to the invention which gives the possibility of obtaining a BAS powder which in majority comprises BAS of hexagonal structure.

[0147] This operating method, a procedure, which has already been described above consists of reacting successively and not in one go, the BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 compounds [16].

[0148] This operating method therefore comprises the following successive steps:

[0149] (1) The BaCO.sub.3 powder and the SiO.sub.2 powder are mixed in a molar ratio of 1 BaCO.sub.3 for 2 SiO.sub.2.

[0150] This mixture may be carried out via a wet route in a liquid such as ethanol.

[0151] Thus, it will for example be possible to mix the BaCO.sub.3 powder and the SiO.sub.2 powder for 30 minutes for example in a liquid such as ethanol, in a milling machine such as a RETSCH milling machine (ball milling machine) made of WC (tungsten carbide).

[0152] (2) The mixture of the BaCO.sub.3 powder and of the SiO.sub.2 powder is dried and then sintered.

[0153] This drying and this sintering may be carried out for a period from 1 to 10 hours, for example 4 hours, at a temperature from 1,000° C. to 1,400° C., for example 1,150° C., for example in air, in a device such as a tubular oven. At the end of this step, a sintered mixture of the BaCO.sub.3 powder and of the SiO.sub.2 powder is obtained, in majority consisting in moles (chemical composition), of BaSi.sub.2O.sub.5. This compound is then milled for a period from 10 minutes to 2 hours, for example for a period of 1 hour. This milling may be carried out via a wet route in a liquid such as ethanol.

[0154] For example a RETSCH milling machine (ball milling machine) made of WC may be used.

[0155] (3) The obtained product at the end of the step (2) is mixed with Al.sub.2O.sub.3 powder in a molar ratio of 1 BaSi.sub.2O.sub.5 for 1 Al.sub.2O.sub.3.

[0156] This mixing may be achieved via a wet route in a liquid such as ethanol.

[0157] Thus, it will for example be possible to mix the sintered mixture with Al.sub.2O.sub.3 powder for example for 30 minutes in a liquid such as ethanol, in a milling machine such as for example a RETSCH milling machine (ball milling machine) made of WC.

[0158] (4) The obtained mixture at the end of step (3) is dried and then sintered.

[0159] This drying and this sintering may be carried out for a period from 1 to 10 hours, for example 6 hours, at a temperature from 1,000° C. to 1,400° C., for example 1,200° C., for example in air in a device such as a tubular oven.

[0160] The product obtained at the end of this step in majority consists, i.e. at more than 50%, or even at more than 80% by mass of hexagonal BAS. However, there still remains alumina, and barium silicate but these secondary phases are not redhibitory for the remainder of the method.

[0161] This product, obtained at the end of step (4), is milled for a period from 1 minute to 2 hours, for example for a period of 1 hour.

[0162] A powder in majority consisting of hexagonal BAS is then obtained.

[0163] This milling may be carried out via a wet route in a liquid such as ethanol.

[0164] For example a RETSCH milling machine (ball milling machine) made of WC may be used.

[0165] It should be noted that by extending the duration of the second heat treatment of step (4), for example up to a duration from 6 hours to 20 hours, for example 10 hours, it is possible to reduce the amount of secondary phases.

[0166] When it is desired to use monoclinic BAS and not hexagonal BAS, an extended heat treatment for example for a duration from 1 hour to 10 hours, at a low temperature, for example around 300° C., gives the possibility of transforming the hexagonal BAS into monoclinic BAS.

[0167] Said metal or metalloid oxide may be selected from alumina, silica and mullite.

[0168] According to the invention, the barium aluminosilicate BAS and said at least one metal or metalloid oxide have “close” expansion coefficients.

[0169] By “close” in the sense of the invention, is generally meant that the expansion coefficient of barium aluminosilicate BAS and the expansion coefficient of said at least one metal or metalloid oxide do not differ by more than 30%, preferably no more than 10%.

[0170] The man skilled in the art can easily determine from among metal or metalloid oxides which are the metal or metalloid oxides which satisfy this condition as to the expansion coefficient and which may therefore be used in the material according to the invention.

[0171] The BAS with a hexagonal structure has a thermal expansion coefficient of 8.10.sup.−6° C..sup.−1, it will therefore be compatible with alumina which has an expansion coefficient close to 8.10.sup.−6° C..sup.−1.

[0172] The BAS of monoclinic structure as for it has a thermal expansion coefficient of 2.3.10.sup.6° C..sup.−1 for its vitroceramic form, to 4.5.10.sup.6° C..sup.−1 for its monolithic form (both of these forms may be used), it will therefore be rather compatible with silica or mullite.

[0173] In an embodiment, during step a), a mixture of the barium aluminosilicate powder and of particles of said at least one metal or metalloid oxide is prepared.

[0174] These particles may have any shape.

[0175] These may for example be grains with a spherical or spheroidal shape, long fibers or further short fibers also-called whiskers.

[0176] The fibers generally have a circular or quasi-circular cross-section.

[0177] The long fibers generally have a length from 100 microns to 10 mm, and a diameter from 3 microns to 20 microns.

[0178] The short fibers, or whiskers generally have a length of 0.5 microns to less than 100 microns (in other words from 0.5 micron to 100 microns, the value of 100 microns being excluded) and a diameter from 0.5 micron to 3 microns.

[0179] Thus, it will for example be possible to use alumina fibers with a diameter of 10 μm, and with a length after being cut out of about 1 mm.

[0180] The alumina fibers are generally deenzymated beforehand for example by a heat treatment in an oven at 500° C. in air.

[0181] Such fibers are generally available from 3M® under the name of NEXTEL.

[0182] The mixing of the barium aluminosilicate powder, for example of the hexagonal BAS powder, and of the particles of at least one metal or metalloid oxide, for example of alumina fibers may be carried out by any known mixing method.

[0183] This mixing may be carried out via a wet route in a liquid such as ethanol.

[0184] Thus, it will for example be possible to carry out this mixing for a duration of 0.5 minute to 60 minutes, for example 1 minute, in a liquid such as ethanol, in a milling machine such as for example a RETSCH milling machine (ball milling machine) made of WC.

[0185] In another embodiment, during step a), the contacting is achieved by impregnating a fabric of fibers made of at least one metal or metalloid oxide with a slip (slurry) of the barium aluminosilicate powder. In other words, in this embodiment, the reinforcement is a fibrous reinforcement consisting of woven long fibers.

[0186] Sintering of the barium aluminosilicate powder and of the reinforcements made of at least one metal or metalloid oxide is then achieved by a hot sintering method with a pulsed electric field.

[0187] The hot sintering technology with a pulsed electric field (“spark plasma sintering” or “SPS”) is also known under the name of “field activated sintering technique” or FAST or further under the name of “flash sintering”. This method notably allows rapid densification of powders.

[0188] “SPS” is a sintering technique which consists of simultaneously applying on the powdery sample to be densified an uniaxial pressure and pulses of a high intensity current which cause a rise in temperature of the sample. The current is applied as trains of current pulses, for example with a period of 3.2 ms, the intensity of which may attain several thousands of amperes, for example up to 8,000 A, or even 50,000 A.

[0189] The current is applied to the sample via an assembly of graphite plates and pistons, the mixture of the BAS powder and of the particles of at least one oxide is inserted into the inside of a matrix, sleeve, tableting machine, or graphite mould.

[0190] The assembly formed by the sleeve, tableting machine, or mould, the pistons and plates, is the only assembly in the vacuum chamber to rise in temperature.

[0191] More exactly, the operating principle of an SPS device is illustrated in FIG. 1, suitable for applying the method according to the invention, and its main members. The mixture of the BAS powder and of the particles of at least one oxide (1) (or the impregnated fabric of fibers), is placed in a mould, a sleeve, a matrix, a graphite tableting machine (2), between two pistons also in graphite (3). Pressure (4) is applied to these pistons (3), and a DC current (5) is applied to electrodes (6). The mixture of the BAS powder and of the particles of at least one oxide (1), the pistons (3), the graphite sleeve (2) and a portion of the electrodes (6) are placed inside a vacuum chamber (7).

[0192] The temperature is tracked via an optical pyrometer which also controls the electric power injected into the assembly.

[0193] The main benefit of “SPS” technology is to rise the temperature with a minimum of heat energy and to densify the mixture of powder and of particles in relatively short times of the order of a few minutes, for example from 5 to 10 minutes.

[0194] The rapidity of the sintering allows limitation of the diffusion or grain growth phenomena which has the effect of retaining submicron grain sizes and complex architectures such as those of composite materials. It is possible to attain a density close to 100%.

[0195] Generally one begins by placing the mixture of the BAS powder and of the particles of at least one oxide inside the mould, the tableting machine, the sleeve, the graphite matrix of the machine, the “SPS” device, described above.

[0196] Generally, a flexible graphite sheet such as the product marketed under the commercial name of PAPYEX® by Carbone Lorraine is placed between the mixture of powder and particles and the internal walls of the mould and between the powder and the pistons. This sheet has the purpose of preventing the powders from reacting with the mould and the pistons and of preserving them.

[0197] The PAPYEX® may be coated on one of its faces, i.e. the face in contact with the mixture of powder and particles, with a boron nitride BN layer.

[0198] The BN plays the role of a diffusion barrier between the oxides and the graphite.

[0199] The graphite mould may also be covered with a graphite felt for limiting radiation.

[0200] The tableting machine, the matrix, the sleeve, the graphite mould and the pistons are then placed in the SPS machine such as the machine described in FIG. 1.

[0201] The vacuum chamber is closed and then application of a vacuum is initiated. When the desired vacuum is attained, i.e. when the pressure is generally less than 10 Pa, the sintering operation by SPS strictly speaking may then begin.

[0202] A sufficient pressure is applied to said mixture of BAS powder and of particles of at least one oxide, and simultaneously a sufficient pulsed electric current is applied to said mixture in order to raise the temperature of the part up to a sufficient temperature in order to cause sintering of the mixture of the BAS powder and of the particles of at least one oxide.

[0203] In other words, when anything is in contact (tableting machine, pistons, mixture), it is possible to generate an electric current in order to generate the rise in temperature. Generally, the maximum number of amperes which a matrix may support is notably related to its diameter. Thus, for a sample diameter of 8 mm, it is possible to apply 2,000 A without any risk of deteriorating the matrix. For larger diameters such as 20 mm, it is possible to apply 4,000 A or more.

[0204] The applied pulsed electric current is generally from 1 A to 50,000 A in order to generate a rise in temperature up to a temperature (plateau temperature) comprised between 1,000° C. and 2,500° C. The pressure which is applied at the same time corresponds to an applied force from 0.01 MPa to 500 MPa.

[0205] Preferably, the applied pressure according to the invention is generally from 1 to 200 MPa and the applied intensity is preferably from 500 to 8,000 A. Preferably, the pressure is from 10 to 150 MPa, still preferably from 20 to 100 MPa, for example 40 MPa.

[0206] Preferably, the intensity is from 200 to 6,000 A, still preferably from 300 to 1,000 A.

[0207] The pressure and intensity values are selected inside the ranges above so that the temperature of the mixture of BAS powder and of particles of at least one oxide is raised to a temperature (plateau temperature) allowing sintering of the mixture of BAS powder and of particles of at least one oxide and its densification, preferably its total densification.

[0208] Such a temperature is generally from 700° C. to 2,000° C., preferably from 1,000° C. to 1,500° C., still preferably from 1,100° C. to 1,300° C., for example 1,200° C.

[0209] The duration during which said temperature (still called a plateau temperature) for example 1,200° C. is maintained, a duration which may also be called a plateau duration or time is a short duration generally from 0 to 10 minutes, preferably from 0 to 7 minutes, for example 5 minutes.

[0210] When the plateau time is equal to 0, this means that a rise in temperature up to the maximum temperature is carried out and then the temperature is lowered to room temperature without observing any plateau.

[0211] It will be noted that this plateau duration is in every case very short, with regard to the other sintering methods.

[0212] Such a very short sintering duration is particularly advantageous in the case when BAS is hexagonal BAS, since it gives the possibility of “setting” the metastable hexagonal high temperature phase of BAS.

[0213] Also, the cycle time excluding cooling, and the total overall duration of the complete cycle with cooling are reduced.

[0214] This cycle time is for example from 10 to 30 minutes, notably from 20 to only 22 minutes, and the duration of the complete cycle is of about one hour, which is another advantage of the method according to the invention.

[0215] Generally it is important to control the lowering of the temperature and of the pressure in order to avoid cracking of the composite material.

[0216] The cooling of the material is generally carried out in a not too sudden way as one skilled in the art in this field of the art may understand. Thus, generally a cooling rate from 1° C. to 600° C. per minute, for example from 10° C. to 100 T/min will be observed from the temperature plateau.

[0217] Preferably, the cooling is carried out with successive ramps having different slopes, thus the cooling may for example be carried out as follows: 45° C./min from the plateau temperature up to 600° C.; and then cooling depending on the inertia of the machine from 600° C. to room temperature.

[0218] It is obvious for the man skilled in the art that the temperature-pressure cycle has to be optimized for each type of mixture of BAS powder and of particles of at least one oxide, which is applied. On the other hand, regardless of the rises, lowerings or durations of the plateaus in temperature and pressure, simultaneity of the temperature and of the pressure is indispensable for good sintering of the mixture of the BAS powder and of the particles of at least one oxide.

[0219] Advantageously, the temperature and therefore intensity parameters and pressure parameters (or of the applied force, the pressure depending on the supporting surface according to the well known relationship P=F/S) are not from room temperature and a pressure of 0 MPa, applied in a sudden way, instantaneously, but are gradually raised from room temperature and a pressure of 0 MPa.

[0220] For the temperature (governed by the intensity), a gradual rise will thus preferably be carried out with a ramp, or several ramps optionally having different slopes, these ramps being optionally separated by intermediate plateaus, in order to attain the maximum temperature mentioned above, also called a plateau or sintering temperature.

[0221] Said temperature ramp(s) is(are) preferentially a slope from 50° C. to 200 T/min, for example 80T/min or 100 T/min.

[0222] For the pressure, in the same way it is possible to advantageously produce a gradual rise with a ramp, or several ramps optionally having different slopes, these ramps being optionally separated by intermediate plateaus, in order to reach the maximum pressure indicated above, also called a plateau or sintering pressure.

[0223] Said pressure ramp(s) is(are) generally a slope from 1 MPa/min to 20 MPa/min, preferably from 5 to 10 MPa/min.

[0224] The rise in temperature and the rise in pressure whether they are progressive or not, are preferably achieved simultaneously, concomitantly, within a same duration.

[0225] If several pressure ramps and several temperature ramps are performed, the corresponding pressure and temperature ramps preferably have the same duration.

[0226] By applying the temperature (and therefore intensity) and/or pressure (and therefore applied force) parameters gradually and not abrupt, sudden, instantaneous, subjecting the material to too strong stresses is thereby avoided and no breaking of the material is reported.

[0227] As an example, a rise in temperature, from room temperature (generally 20° C. to 25° C.) up to 1,000° C., may be carried out in the following way (see FIG. 2; it should be noted that the cycle of FIG. 2 up to 1,000° C. is compliant with the invention, but it does not give the most dense material): [0228] room temperature to 570° C.: about 5 minutes; [0229] 570° C. to 600° C.: about 4 minutes; [0230] 600° C. to 1,000° C.: about 5 minutes; [0231] plateau at 1,000° C.: about 5 minutes; [0232] cooling from 1,000° C. to room temperature: a duration conditioned by the thermal inertia of the machine, for example from 10 minutes to 30 minutes, notably 15 minutes.

[0233] During the same time, the pressure varies in the following way: [0234] from 0 to 3.2 kN, 40 MPa: rise in 1 minute; [0235] plateau at 3.2 kN, 40 MPa: 20 minutes; [0236] lowering from 3.2 kN to 0 kN: 1 minute.

[0237] Still as an example, a rise in temperature, from room temperature (generally 20° C. to 25° C.), this time up to 1,200° C., may be carried out in the following way (this cycle may be illustrated by slightly adapting FIG. 2): [0238] room temperature to 570° C.: about 5 minutes; [0239] 570° C. to 600° C.: about 4 minutes; [0240] 600° C. to 1,200° C.: about 7.5 minutes; [0241] plateau at 1,200° C.: about 5 minutes; [0242] cooling from 1,200° C. to room temperature: a duration conditioned by the thermal inertia of the machine, for example from 10 minutes to 30 minutes, notably 20 minutes.

[0243] During the same time, the pressure varies in the following way: [0244] from 0 to 3.2 kN, 40 MPa: rise in 1 minute; [0245] plateau at 3.2 kN, 40 MPa: 22.5 minutes; [0246] lowering from 3.2 kN to 0 kN: 1 minute.

[0247] The current is applied in the form of series, trains of pulses; each series, train, consisting of a determined and adjustable number of “pulses”. The series (trains) are separated from each other by a period during which the applied current is zero.

[0248] In the method according to the invention, pulses from 1 to 5 ms, for example from 3.3 ms of period, generally assembled as a train from 1 to 15, for example 12 pulses are generally used, each train being generally separated by 1 to 15 periods, for example 2 periods, with the duration (such as 3.3 ms) above, without any current.

[0249] It is possible to change these values but the current should always keep the same geometry, i.e.: more or less pulse trains separated by variable periods without any current.

[0250] The applied voltage is of a few volts, generally from 1 to 8 volts, preferably from 2 to 7 volts, typically 3 volts for 500 A.

[0251] At the end of the cooling, generally down to room temperature, for example from 20° C. to 25° C., the composite material is recovered in the “SPS” device.

[0252] The material according to the invention, because of its excellent mechanical and strength properties at high temperatures finds its application in fields as diverse as aeronautics, aerospace for example for manufacturing radomes, the chemical industry and generally in all the fields where excellent mechanical properties at high temperatures are required.

[0253] The invention will now be described with reference to the following examples, given as an illustration and not as a limitation.

EXAMPLES

[0254] Examples 2 to 4 are examples which show that it is preferable to use the procedure discussed above for obtaining certainly hexagonal BAS.

1. Raw materials used.

[0255] a. Alumina (Al.sub.2O.sub.3).

[0256] Alumina powder of reference 265497 comes from SIGMA-ALDRICH. The d.sub.50 of the particles is 10 μm and its purity is 99.7%

[0257] b. Silica (SiO.sub.2).

[0258] The silica powder is from SIGMA-ALDRICH, its reference is 55631. This is SiO.sub.2 in quartz form with a purity close to 99%, and a grain size comprised between 0.5 and 10 μm, for which 80% of them is between 1 and 5 μm.

[0259] c. Barium carbonate (BaCO.sub.3).

[0260] The barium carbonate powder is from SIGMA-ALDRICH, its reference is 237108. Its average grain size is 5 μm, and its purity is greater than 99%.

[0261] d. Alumina fibers (Al.sub.2O.sub.3).

[0262] Alumina fibers Nextel 610®, from 3M®, are used as a reinforcement for the composite. The fibers are deenzymated beforehand in an oven at 500° C. in air. They have a diameter of 10 μm and they are cut out with a pair of scissors to a length of about 1 mm.

2. Experimental procedure.

[0263] a. Procedure for mixing the powders.

[0264] The powders are weighed on METTLER AE260 DeltaRange® scales in the proportions indicated in Table 1.

[0265] The powders are then placed in Retsch minijars in tungsten carbide (WC). 1 g of ethanol is added to the mixture of powders. Ethanol is used as a solvent for the mixture.

[0266] Two balls of 7 mm and five balls with a diameter of 3 mm made of WC are used as milling bodies for the mixture.

[0267] The minijars are then closed and stirred for 30 min at 25 Hz by means of a vibratory milling machine Retsch MM200. Once the mixing is achieved, the obtained suspension is emptied into a crystallizer and the minijars rinsed with ethanol. The rinsing liquid is also poured into the crystallizer. The crystallizer is then heated (STUART CR162) to 100° C. in order to evaporate the ethanol. Once the ethanol is removed, the powder is scraped by means of an aluminium spatula and recovered in flasks.

TABLE-US-00001 TABLE 1 Amount of material to be mixed BaCO.sub.3 Al.sub.2O.sub.3 SiO.sub.2 Mass (g) 0.47 0.24 0.29 Mole (mg) 1 1 2

[0268] b. Preparation of the BAS powder.

[0269] The BAS is synthesized in a tubular oven according to a two-step procedure.

[0270] The first step consists of mixing the BaCO.sub.3 and SiO.sub.2 powders in a molar ratio of 1 BaCO.sub.3 for 2 SiO.sub.2, and then of sintering the mixture of powders at 1,150° C. in air for 4 h in a Carbolite tubular oven.

[0271] The mixture of powders is then transformed into BaSi.sub.2O.sub.5.

[0272] Next, in a second step, the BaSi.sub.2O.sub.5 compound is milled in the vibratory milling machine Retsch for 1 h, and then mixed with alumina with a molar ratio of 1 BaSi.sub.2O.sub.5 for 1 Al.sub.2O.sub.3. This new mixture is then sintered in a Carbolite tubular oven at 1,200° C. in air for 6 h.

[0273] This separation into two steps gives the possibility of improving the reaction kinetics and thus promoting the appearance and the preponderance of the BaAl.sub.2Si.sub.2O.sub.8 (BAS) compound.

[0274] c. Preparation of the composite material according to the invention.

[0275] The BAS is milled and reduced into powder by means of the vibratory milling machine Retsch for 2 h.

[0276] The BAS powder and the reinforcing fibers are then mixed for only 1 min, with the vibratory milling machine Retsch, in order not to damage the fibers too much. The total mass of powder and fiber is set to 1 g, including 20% by mass of fiber. The mixture is carried out via a liquid route in ethanol (about 1 g).

[0277] d. Sintering of the mixture of the BAS powder and of the fibers by a hot sintering method with a pulsed electric field («spark plasma sintering» or «SPS»).

[0278] The sintering of the mixture of the BAS powder and of the fibers is carried out according to the invention by a hot sintering method with a pulsed electric field («spark plasma sintering» or «SPS»), or flash sintering.

[0279] The SPS method may be carried out with a device such as the one illustrated in FIG. 1, already described above.

[0280] A sheet of Papyex® (graphite sheet) is cut out to the internal dimensions of the graphite mould, and then it is optionally partly coated with BN, for example by spraying with an aerosol spray can, and is then rolled and placed in this mould.

[0281] The lower graphite piston is then inserted into the mould.

[0282] A disc of Papyex® of the same dimension as the piston is deposited at the bottom of the mould.

[0283] The mixture of BAS powder and of reinforcing fibers prepared as described above, is introduced by means of a spatula into the graphite mould.

[0284] This mixture of BAS powder and of reinforcing fibers is then covered with another disc of Papyex®, and the upper graphite piston is then inserted.

[0285] As this has been indicated already above, it is also possible to cover the Papyex® with a boron nitride (BN) layer. This deposition may be carried out for example by spraying on a portion of a simple face of each sheet, disc, by means of an aerosol spray can.

[0286] The graphite mould is finally covered with a graphite felt for limiting radiation and preventing a possible explosion of the mould.

[0287] The mould is placed in the machine as indicated in the schematic view of FIG. 1.

[0288] The chamber is first closed and then application of a vacuum is initiated. When the vacuum attains a few Pascal (less than 10 Pa), sintering may begin. The applied pressure is 40 MPa and the temperature ramps are 80° C./min between 600° C. and 1,000° C. or 1,200° C.

[0289] The temperature cycle used for 1,000° C. is illustrated in FIG. 2.

Example 1

[0290] In this example, a composite material according to the invention is prepared.

[0291] a. Preparation of the BAS.

[0292] i. First heat treatment carried out at 1,150° C. for 4 h, on a mixture of BaCO.sub.3 and SiO.sub.2 powders.

[0293] A first heat treatment is carried out with a mixture of BaCO.sub.3 (SIGMA-ALDRICH) and of SiO.sub.2 (SIGMA-ALDRICH) at 1,150° C., for 4 hours. The obtained sintered material is very white and quite brittle.

[0294] Further, FIGS. 3 and 4 show that the reaction between SiO.sub.2 and BaCO.sub.3 is not complete.

[0295] There exist several phases and EDS analysis allows determination of the atoms constituting said phases.

[0296] Thus, there remains a non-negligible amount of unreacted SiO.sub.2. The matrix therefore consists of one third of SiO.sub.2 and of two thirds of a phase based on Ba, Si and O. The silica is not detected on the diffractogram of FIG. 3 since it should be in an amorphous form.

[0297] ii. Second heat treatment, carried out at 1,200° C. for 6 h on a mixture of the material obtained at the end of the first heat treatment and of an Al.sub.2O.sub.3 powder.

[0298] The material obtained earlier, milled, at the end of the first heat treatment is mixed with Al.sub.2O.sub.3 (SIGMA-ALDRICH) and then the whole is heat treated at 1,200° C. for 6 hours.

[0299] The obtained sintered material is not brittle.

[0300] The micrograph of FIG. 6 indicates the presence of a phase corresponding to BAS which represents more than half of the material (see also the diffractogram of FIG. 5).

[0301] However, there remain particles consisting of aluminium and oxygen atoms. These particles are residual alumina. There exists a pale gray phase not containing any aluminium. The reaction is therefore incomplete. Moreover, it is interesting to note the total disappearance of the silica.

[0302] b) Elaboration of the Composite Material According to the Invention.

[0303] The BAS obtained at the end of the second heat treatment described above is mixed with alumina fibers and then sintered by SPS according to the procedure described above.

[0304] Sintering tests are conducted by observing a plateau at a temperature of 1,000° C. for 5 minutes, and other sintering tests are conducted by observing a plateau at a temperature of 1,200° C. for 5 minutes.

[0305] As shown by the micrograph of FIG. 7, sintering by SPS at 1,000° C. does not sufficiently densify the matrix of the composite.

[0306] At 1,200° C., (FIG. 8), the densification seems to be total and the fibers do not show any deformations related to the heat treatment or to the pressure.

[0307] FIGS. 9 and 10 and notably FIG. 10 show that the matrix actually penetrates into the small spaces between the fibers.

[0308] Further, the fibers do not have any decohesion or reaction with the matrix.

[0309] Many dark fragments may be observed in FIGS. 9 and 10. These fragments are made of alumina and certainly come from the fibers.

[0310] It would be the mixture which would have generated these fragments. The diffractogram of FIG. 11 indicates that the structure no longer contains any barium silicate on the one hand, and that a small portion of the hexagonal phase (“hexacelsian”) has become monoclinic (“celsian”) on the other hand.

[0311] If there is no more silicate, this means that the whole matrix consists of BaAl.sub.2Si.sub.2O.sub.8. No cracking is observed.

[0312] In the examples 2 to 4 which follow, it is seen that it is preferable to use a BAS prepared by the procedure described above, when it is desired to prepare a composite material comprising a BAS matrix with a hexagonal structure, and reinforcement fibers made of alumina.

Example 2

[0313] In this example, the simultaneous mixing in a single step of the three initial powders of BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 is performed and then it is proceeded with sintering by SPS of this mixture of powders (without any fibers).

[0314] The powders used in this example are the powders described in points 1.a., 1.b., and 1.c. above.

[0315] The three initial powders are weighed and mixed according to the procedure shown in point 2.a. above. However, unlike the procedure shown in point 2.b., the three powders are simultaneously mixed in a single step, in the proportions of table 1.

[0316] Sintering by SPS is then carried out with a plateau at 1,000° C. for 5 minutes, of the thereby obtained mixture of powders.

[0317] The micrograph of the section of a thereby obtained pellet by sintering by SPS of the mixture of the three BaCO.sub.3, Al.sub.2O.sub.3 and SiO.sub.2 powders (SIGMA-ALDRICH) according to the cycle shown in FIG. 2 with a plateau at 1,000° C. for 5 minutes, is shown in FIG. 13.

[0318] In this section, the silica grains are all coated with a pale shell rich in barium. On the contrary, the alumina grains do not have any particular surroundings, they do not seem to have reacted.

[0319] Moreover, the diffractogram of FIG. 12 reveals the presence of a phase close to the over-stoichiometric BAS in Si. This phase indicates that the formation of the BAS has nevertheless begun.

[0320] The synthesis of BAS by SPS shows that the reaction between BaCO.sub.3 and SiO.sub.2 is promoted.

Example 3

[0321] In this example, the simultaneous mixing in a single step of the three initial powders of BaCO.sub.3, Al.sub.2O.sub.3, and SiO.sub.2 is carried out and then it is proceeded with sintering by SPS of this mixture of powders (without any fibers).

[0322] The powders used in this example are not the powders described in points 1.a., 1.b., and 1.c. above. Indeed, instead of slowing down the reaction by SPS, between the BaCO.sub.3 and SiO.sub.2, and to allow reaction with Al.sub.2O.sub.3, it was decided to use in this example, a coarser powder of SiO.sub.2 (PROLABO) (d50=100 μm) and a finer Al.sub.2O.sub.3 powder (ATOCHEM) (d50=5 μm).

[0323] The three initial powders are weighed and mixed according to the procedure shown in point 2.a. above. However, unlike the procedure shown in point 2.b., the three powders are simultaneously mixed in a single step, in the proportions of table 1.

[0324] Sintering by SPS is then carried out with a plateau at 1,000° C. for 5 minutes, of the thereby obtained mixture of powders.

[0325] The micrograph of the section of a thereby obtained pellet by sintering by SPS of the mixture of the three powders of BaCO.sub.3, Al.sub.2O.sub.3 and SiO.sub.2 (SIGMA-ALDRICH) according to the cycle shown in FIG. 2 with a plateau at 1,000° C. for 5 minutes, is shown in FIG. 15.

[0326] The micrograph of FIG. 15 shows several phases. The darkest spots correspond to silicon and oxygen. These are certainly large silica grains. Around these grains a pale gray casing has formed of a mixture of Ba, Si and C. A phase consisting of Ba, Al, Si and O appears in dark grey. This phase may be the sought BAS. There also exist Al and O platelets which would likely be alumina platelets. These platelets moreover seem to be in equilibrium with the dark grey Ba—Al—Si—O phase. Finally, it is possible to note the presence of a very pale phase containing tungsten. This tungsten comes from the mixing operation.

[0327] The pellets characterized in XRD (FIG. 14) reveal the presence of BAS in a hexagonal form. This phase is certainly the one observed in dark grey in SEM. Also there are probably barium silicates such as sanbornite (BaSi.sub.2O.sub.5) and Ba.sub.5Si.sub.8O.sub.21 which would be in the pale areas close to the SiO.sub.2 grains. Alumina in the form of corundum may be residual platelets. The silica does not appear on the spectrum, the residual silica is no doubt amorphous.

Example 4

[0328] In this example, annealing is carried out with a plateau at a temperature of 1,150° C. for 4 hours of the pellets prepared in example 3.

[0329] The annealing operations are carried out in a Carbolite tubular oven.

[0330] The ramps are 500° C..Math.h.sup.−1 and the plateau is 4 h at 1,150° C. This treatment is carried out in air. The annealing has the purpose of homogenizing the structure of the material.

[0331] The material after annealing essentially consists of BaAl.sub.2Si.sub.2O.sub.8 as shown by the diffractogram and the micrograph of FIGS. 16 and 17.

[0332] However, this BAS has been subject to a transformation of a hexagonal phase into a monoclinic phase.

[0333] Thus, the structure of the material of the pellet has been subject to significant stresses which have caused cracks visible in FIG. 17.

[0334] Moreover, the residual phases are either alumina or a compound based on Ba, Si and O.

[0335] The reaction is almost complete, the annealing has actually played its role for homogenizing material. However, it is not desirable to obtain the monoclinic form, when use of alumina reinforcements is desired. Thus, annealing of this type is not to be used in the case when use of alumina reinforcements is desired.

[0336] Examples 2 to 4 clearly show that it is not possible to obtain hexagonal BAS by simultaneously mixing the three initial powders BaCO.sub.3, Al.sub.2O.sub.3 and SiO.sub.2, even by acting on the grain size of the powders and by carrying out an annealing step.

[0337] Indeed, this annealing step promotes the formation of the monoclinic phase of BAS which is incompatible with an alumina fiber reinforcement since the difference in the fiber/matrix expansion coefficients is too high which has the consequence of generating cracks within the material.

REFERENCES

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