EP3894611A1

EP3894611A1 - Chemical vapour infiltration or deposition process

Info

Publication number: EP3894611A1
Application number: EP19842373.3A
Authority: EP
Inventors: Jean-François Daniel René POTIN
Original assignee: Safran Ceramics SA
Current assignee: Safran Ceramics SA
Priority date: 2018-12-14
Filing date: 2019-11-25
Publication date: 2021-10-20
Also published as: US20220041513A1; FR3090011A1; FR3090011B1; CN113242914A; WO2020120857A1

Abstract

The present invention relates to a chemical vapour infiltration or deposition process, comprising at least: - the formation of pyrocarbon in the porosity of a porous substrate or on a surface of a substrate, wherein the substrate is placed in a reaction chamber and the pyrocarbon is formed from a gas phase introduced into the reaction chamber, this gas phase comprising at least pyrocarbon precursor compound and carbon dioxide.

Description

Title of the invention: Process for infiltration or chemical vapor deposition

Technical area

The present invention relates to a chemical vapor infiltration or deposition process in which pyrocarbon is formed from a gas phase comprising a pyrocarbon precursor compound and carbon dioxide.

Prior art

It is known to coat or densify substrates with pyrocarbon (also called pyrolytic carbon) by placing these substrates in an oven into which a reactive gas containing a pyrocarbon precursor consisting of a hydrocarbon is introduced. The pressure and the temperature in the oven are adjusted to produce the coating or the matrix of pyrocarbon by decomposition of the

hydrocarbon precursor.

The effluent gas containing reaction by-products is removed from the furnace by pumping. The reaction by-products include organic compounds which have a fairly high solidification temperature, in particular polycyclic aromatic hydrocarbons (PAH) such as, in particular, naphthalene, pyrene, anthracene or acenaphthylene.

By condensation, these reaction by-products form tars which tend to deposit in the furnace outlet pipes when the effluent gas cools. These tars are also found in the pumping device, for example in the vacuum pump oil or in the condensers of steam ejectors.

It is therefore desirable to improve the pyrocarbon formation processes by limiting the generation of PAHs.

Statement of the invention The invention relates, according to a first aspect, to a method of infiltration or chemical vapor deposition, comprising at least:

the formation of pyrocarbon in the porosity of a porous substrate or on a surface of a substrate, the substrate being placed in a reaction vessel and the pyrocarbon being formed from a gaseous phase introduced into the reaction vessel, this gas phase comprising at least one precursor compound of pyrocarbon and carbon dioxide.

The pyrocarbon precursor compound constitutes a compound known per se making it possible to obtain pyrocarbon by infiltration technique or chemical vapor deposition. The introduction of carbon dioxide CO2 into the reaction vessel in addition to the precursor compound of pyrocarbon allows

advantageously to produce dihydrogen during the formation of the pyrocarbon which makes it possible to limit the production of PAHs.

In an exemplary embodiment, a volume content of carbon dioxide in the gas phase is imposed less than or equal to 15%, this content being taken at the time of the introduction of the gas phase into the reaction vessel.

It is advantageous to limit the content of carbon dioxide in the gas phase in order to limit the oxidizing nature of the latter.

In particular, the volume content of carbon dioxide in the gas phase may be less than or equal to 10%, for example less than or equal to 7%, or even less than or equal to 5%. The volume content of carbon dioxide in the gas phase may be greater than or equal to 2%, for example greater than or equal to 3%.

In particular, the volume content of carbon dioxide in the gas phase can be between 2% and 15%, for example between 2% and 10%, for example between 2% and 7%. The volume content of carbon dioxide in the gas phase may in particular be between 3% and 15%, for example between 3% and 10%, or even between 3% and 7%.

In an exemplary embodiment, the pyrocarbon precursor compound is a hydrocarbon. In particular, the pyrocarbon precursor compound can be a linear hydrocarbon.

The use of a linear hydrocarbon is advantageous because it improves the kinetics of formation of dihydrogen and therefore further limits the production of PAHs. The invention is not however limited to the use of a hydrocarbon as a precursor compound of pyrocarbon. The pyrocarbon precursor compound may alternatively be an alcohol or a polyalcohol. By "alcohol" is meant a compound having a single alcohol function. By “polyalcohol” is meant a compound having several alcohol functions. The invention also relates to a process for manufacturing a part made of a matrix composite material at least partially made of pyrocarbon, the process comprising at least:

- densification of the porous substrate forming a fibrous preform of the part to be obtained by a pyrocarbon matrix phase by chemical vapor infiltration by carrying out a process as described above.

The fibrous preform can be formed from wires made of ceramic material or carbon.

In an exemplary embodiment, the fiber preform has an annular shape and is made of carbon fibers.

In an exemplary embodiment, the fiber preform can be formed in one piece by three-dimensional weaving or from a plurality of two-dimensional fiber layers.

In an exemplary embodiment, the part is a friction part, for example a brake disc such as an airplane brake disc.

Alternatively, the friction part may be a brake disc for a land vehicle, in particular an automobile, or a friction part other than a disc, in particular a brake shoe.

Description of the embodiments

We will now describe the steps of an embodiment where a porous substrate is densified by a pyrocarbon matrix phase. In this case, it is set uses a chemical vapor infiltration technique (“Chemical Vapor Infiltration”; “CVI”).

Alternatively, the pyrocarbon can be formed on the outer surface of the substrate. In this case, a chemical vapor deposition technique (“CVD”) is used.

The following description describes an example of CVI technique but applies mutatis mutandis in case a CVD technique is implemented. The person skilled in the art knows from his general knowledge to adapt the operating conditions to move from the CVI technique to the CVD technique or from the CVD technique to the CVI technique.

The porous substrate is first formed during a first step. The porous substrate has an accessible porosity intended to be wholly or partly filled with pyrocarbon from the gas phase.

The porous substrate can be a fibrous preform having the shape of a part made of composite material to be obtained. The fibrous preform is intended to constitute the fibrous reinforcement of the part to be obtained.

The fiber preform may include a plurality of ceramic or carbon threads or a mixture of such threads. One can for example use silicon carbide wires supplied by the Japanese company NGS under the reference "Nicalon", "Hi-Nicalon" or even "Hi-Nicalon Type S". The carbon wires which can be used are, for example, supplied under the name Torayca T300 3K by the company Toray.

The fiber preform can be obtained from at least one textile operation using the threads.

According to one example, the fibrous preform can be produced by superimposing layers cut from a fibrous texture into son of carbon precursor, bonding the layers together, for example by needling, and transformation of the precursor into carbon by heat treatment. The preform can also be produced directly from layers of fibrous texture made of carbon threads which are superimposed and bonded together for example by needling.

It is also possible to produce an annular preform by winding in turns

superimposed with a helical fabric in carbon precursor threads, bonding of the turns between them, for example by needling, and transformation of the precursor by heat treatment. We can for example refer to documents US 5,792,715, US 6,009,605 and US 6,363,593.

According to a variant, the fibrous preform can be obtained by multilayer or three-dimensional weaving of such threads. By “three-dimensional weaving” or “3D weaving”, it is necessary to understand a mode of weaving by which at least some of the warp threads link weft threads on several layers of weft. A reversal of the roles between warp and weft is possible in the present text and should be considered as also covered by the claims. The fibrous preform may, for example, have a multi-satin weave, that is to say be a fabric obtained by three-dimensional weaving with several layers of weft threads, the base weave of each layer of which is equivalent to one weave of the classic satin type but with certain points of the weave which link the layers of weft threads together. Alternatively, the fiber preform may have interlock weave. By “interlock weave or fabric”, it is necessary to understand a 3D weaving weave in which each layer of warp threads links several layers of weft threads with all the threads of the same warp column having the same movement in the plane of the armor. Different multilayer weaving modes which can be used to form the fibrous preform are described in document WO 2006/136755. It is also possible to start from fibrous textures such as fabrics

two-dimensional or unidirectional sheets, and to obtain the fibrous preform by draping such fibrous textures on a form. These textures can optionally be linked together, for example by sewing or implanting threads to form the fibrous preform. Once obtained, the porous substrate is densified by a pyrocarbon matrix phase obtained from the gas phase. The matrix coats the threads of the fibrous preform. The preform wires are present in the matrix.

The invention can be implemented in a known CVI installation suitable for densification with pyrocarbon comprising an introduction line

additional for injecting carbon dioxide gas into the reaction vessel. Carbon dioxide can be introduced into the reaction vessel by means known per se commonly used in CVI to introduce the precursor in gaseous state. The pyrocarbon precursor compound and carbon dioxide can be introduced separately (by different injection points) into the reaction vessel. Alternatively, the pyrocarbon precursor compound and carbon dioxide can be introduced directly into the reaction vessel as a mixture (via the same injection point). Preferably, the mixture of the precursor compound of pyrocarbon and of carbon dioxide is carried out before the temperature rise of the reaction vessel enabling infiltration or chemical vapor deposition to be carried out.

The gas phase comprises (i) at least one precursor compound of pyrocarbon in the gaseous state, (ii) carbon dioxide in the gaseous state, and optionally (iii) a diluent gas such as a neutral gas such as argon. The gas phase can be

essentially constituted by said at least one precursor compound of

pyrocarbon, carbon dioxide and any diluent gas present.

The simplified mechanism for the formation of the proposed pyrocarbon is indicated below in the case where the precursor compound is a hydrocarbon. In the chemical equations below, C _x H _y denotes the pyrocarbon precursor hydrocarbon and the radical compounds are marked with the symbol *.

C _X Hy + C0 ₂ -> CO + OH * + CxHy- _l *

OH * + CxH _yl * -> H ₂ 0 + CxH _y-2

H ₂ 0 + CO -> C0 ₂ + H ₂ .

As indicated in the chemical equations above, carbon dioxide initially reacts with the hydrocarbon C _x H _y in the gas phase in order to obtain carbon monoxide and radical reaction intermediates OH * and CxH _y .i *. These OH * and C _x H _y -i * reaction intermediates then react together to form CxH _y.2 which has a C = C double bond and from which the

pyrocarbon is obtained. Carbon monoxide reacts with water vapor present in the gas phase to form dihydrogen

to limit the formation of PAHs.

When the precursor compound is a hydrocarbon, the latter may contain at least two carbon atoms. The number of carbon atoms in the hydrocarbon can be between 2 and 5, and for example be equal to 3. The hydrocarbon can for example be propane. Alternatively, the pyrocarbon precursor compound can be an alcohol or polyalcohol. The alcohol or polyalcohol can be C ₂ to C ₆ . For example, ethanol can be used as a pyrocarbon precursor.

During the formation of the pyrocarbon, the temperature in the reaction chamber can be between 980 ° C and 1050 ° C, for example between 1000 ° C and 1020 ° C, and the pressure in the reaction chamber can be between 1 kPa and 2 kPa, for example between 1.3 kPa and 1.7 kPa.

During the formation of the pyrocarbon, it is possible to impose a carbon dioxide content in the gas phase of at most 15% by volume, this content being taken at the time of the introduction of the gas phase into the reaction vessel.

The content of carbon dioxide in the gas phase is, unless otherwise stated, equal to the following ratio [volume of carbon dioxide introduced into the reaction vessel] / [total volume of gaseous phase introduced into the vessel

reactionary].

The pyrocarbon matrix phase formed from the gas phase can occupy at least 50%, or even at least 75%, of the initial porosity of the porous substrate. The porous substrate can be fully densified with the pyrocarbon from this gas phase. Alternatively, only part of the matrix densifying the porous substrate can be formed by the pyrocarbon from this gas phase, the rest of the matrix having a different composition. The rest of the matrix may for example be made of a ceramic material other than pyrocarbon, for example silicon carbide.

Whatever the embodiment considered (CVI or CVD), a plurality of substrates can be simultaneously treated with the gas phase in the same reaction vessel.

The expression "included between ... and ..." must be understood as including the limits.

Claims

[Claim 1] Process for infiltration or chemical vapor deposition, comprising at least:

the formation of pyrocarbon in the porosity of a porous substrate or on a surface of a substrate, the substrate being placed in a reaction vessel and the pyrocarbon being formed from a gaseous phase introduced into the reaction vessel, this gas phase comprising at least precursor compound of pyrocarbon and carbon dioxide.

[Claim 2] A method according to claim 1, in which a volume content of carbon dioxide in the gas phase is imposed less than or equal to 15%, this content being taken at the time of

the introduction of the gas phase into the reaction vessel.

[Claim 3] The method of claim 2, wherein the volume content of carbon dioxide in the gas phase is less than or equal to 10%.

[Claim 4] The method of claim 3, wherein the volume content of carbon dioxide in the gas phase is between 2% and 7%.

[Claim 5] A method according to any one of claims 1 to 4, wherein the pyrocarbon precursor compound is a hydrocarbon.

[Claim 6] The method of claim 5, wherein the pyrocarbon precursor compound is a linear hydrocarbon.

[Claim 7] Process according to any one of Claims 1 to 4, in which the pyrocarbon precursor compound is an alcohol or a polyalcohol.

[Claim 8] Method for manufacturing a part made of a matrix composite material at least partially made of pyrocarbon, the method comprising at least:

the densification of the porous substrate forming a fibrous preform of the part to be obtained by a phase of pyrocarbon matrix by chemical vapor infiltration by carrying out a process according to any one of claims 1 to 7.

[Claim 9] The method of claim 8, wherein the part is a friction part.

[Claim 10] The method of claim 9, wherein the part is a brake disc.