Patent Application
20180328429
The present disclosure is directed to a carbon-carbon composite materials and techniques for forming carbon-carbon composite materials.
Some carbon-carbon composite bodies, such as some carbon-carbon composite brake discs that are used in the aerospace industry, may be manufactured from porous preforms. The preforms may be densified using one of several processes, such as chemical vapor deposition/chemical vapor infiltration (CVD/CVI), vacuum/pressure infiltration (VPI) or resin transfer molding (RIM) followed by carbonization, which may apply carbon within the porous preform.
In some examples, the disclosure describes a method of forming a carbon-carbon composite component including depositing an initial carbon material into a porous preform using chemical vapor deposition (CVI)) or chemical vapor infiltration (CVI) to form a rigidized porous preform, infusing the rigidized porous preform with an isotropic resin, pyrolyzing the infused isotropic resin to form an isotropic carbon within pores of the rigidized porous preform, and encapsulating the isotropic carbon with a graphitizable carbon to form the carbon-carbon composite component,
In some examples, the disclosure describes a method of forming a carbon-carbon composite component including depositing an initial carbon material into a porous preform using chemical vapor deposition (CVD) or chemical vapor infiltration (CVI) to form a rigidized porous preform, infusing the rigidized porous preform with an isotropic resin, pyrolyzing the infused isotropic resin to form an isotropic carbon within pores of the rigidized porous preform, and depositing a graphitizable carbon over the isotropic carbon using CVD or CVI to form the carbon-carbon composite component.
In some examples, the disclosure describes a carbon-carbon composite component that includes a rigidized, porous carbon fiber preform having plurality of carbon coated fibers that define a plurality of pores between the carbon coated fibers, an isotropic carbon within the plurality of pores and on the carbon coated fibers, and a graphitizable carbon on the isotropic carbon.
The details of one or more examples are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the disclosure will be apparent from the description and drawings, and from the claims.
The present disclosure describes carbon-carbon composite materials and techniques for forming carbon-carbon composite materials. In some examples, the carbon-carbon composite materials may be produced from a carbon fiber preform that includes a plurality of carbon fibers or carbon precursor fibers. In some examples, the carbon fiber preform may be subjected to an initial chemical vapor deposition/chemical vapor infiltration (CVD/CVI) to rigidize the carbon fiber preform. Following the initial CVD/CVI cycle, the rigidized carbon fiber preform may be subjected to one more resin infiltration/carbonization cycles using isotropic resin materials (e.g., phenolic resin or furan resin) to form isotropic carbon within the rigidized carbon fiber preform. In some examples, the isotropic carbon formed by the phenolic or furan resin materials may extend substantially throughout a volume of the rigidized carbon fiber preform to increase the amount of carbon material and overall density of the resultant densified preform. The densified preform may then be subjected to one or more final densification steps to at least partially encapsulate the isotropic carbon with a graphitizable carbon (e.g., rough laminar carbon), resulting in a carbon-carbon composite.
The isotropic resin, materials used during the intermediate stages provides a relatively inexpensive and efficient means of building up the density and carbon material within the resultant article. For example, in some examples, the isotropic resin materials may include relatively fast thermosetting resin materials that, once cured, remain set within the rigidized carbon fiber preform during the carbonization process (e.g., the isotropic resin materials do not melt or flow from the preform during carbonizations). In some examples, the isotropic resin materials may significantly reduce or eliminate the duration of the stabilization cycle times associated with non-isotropic resins or pitch infiltrant materials. Additionally or alternatively, isotropic resin materials may over a relatively low cost alternative compared to traditional non-isotropic resin or pitch infiltrant materials.
Once carbonized, the isotropic resin materials are converted in to isotropic carbon that adheres to the rigidized carbon fiber preform. In some examples, the isotropic carbon may be relatively hard and fragile. The isotropic carbon provides good structural support for the resultant component, but provides poor frictional characteristics compared to non-isotropic carbon (e.g., carbon produced from non-isotropic resins or pitch infiltrant materials). For example, due to the brittle nature of the isotropic carbon, fictional and slicer forces applied to the resultant component during braking) causes the isotropic carbon to fracture, break apart, and become dislodged from the component, ultimately leading to reduce wear properties and service life of the component.
In some examples, by depositing a subsequent layer of graphitizable carbon (e.g., CVI/CVD rough laminar carbon) over the isotropic carbon, the wear performance properties of the resultant component may be significantly improved. The graphitizable carbon may at least partially encapsulate the isotropic carbon. The graphitizable carbon may help prevent the isotropic carbon from fracturing and becoming dislodged from component. Additionally, the encapsulating graphitizable carbon may exhibit better friction characteristics compared to isotropic carbon resulting in better braking performance. For example, depositing, a layer of graphitizable carbon over the isotropic carbon may improve high energy friction performance, such, as during rejected take off (RTO) braking, as well as reducing wear rates through the formation of friction films while minimizing variation in friction and wear performance at different stages of brake wear (new and worn brake conditions). Additionally or alternatively, the graphitizable carbons may improve the thermal and structural properties of the carbon composite material.
The technique of
In some examples where porous preform 20 include fibers 24, the fibers may include carbon fibers or carbon precursor fibers such as polyacrylonitrile (PAN) fibers, oxidized polyacrylonitrile (O-PAN) fibers, rayon fibers, or the like, which may be subsequently pyrolyzed to form carbon fibers prior to the initial CVI/CVD processing cycle (10). As used herein, the term “carbon fibers” is used to describe both preforms that include carbon fibers or carbon precursor fibers that have been subsequently converted to carbon fibers.
In some examples, porous preform 20 may be in the form of a disc, e.g., for use as a brake disc, that includes central aperture 26 extending through an axial thickness of the preform and defined by inner diameter (ID) and an outer diameter (OD). In other examples, porous preform 20 may define a different geometry. For example, the geometry of porous preform 20 may be similar to or substantially the same as the desired geometry for the finished part formed by the carbon-carbon composite component 50. Porous preform 20 may also define an axial thickness T measured in a direction substantially orthogonal to the direction in which inner diameter ID and outer diameter OD are measured. In some examples, the porosity of porous preform 20 may extend substantially throughout the thickness of porous preform 20. Fibers 24 and pores 22 are not necessarily shown to scale in
During the initial CVI/CVD deposition process (10), an initial deposit of carbon, is applied within pores 22 of porous preform 20 to at least partially coat fibers 24 with carbon (e.g. carbon coated fibers 28) and increase the rigidity of the preform resulting in rigidized porous preform 30.
In some examples, the initial CVI/CVD deposition process (10) may be carried out using a carbonaceous gas to deposit the initial carbon on and around fibers 24. Any suitable carbonaceous gas may be used during the CVI/CVD processing including, for example, carbon-based gases such as natural gas, methane, ethane, propane, butane, propylene, or acetylene, or a combination of at least two of these gases. In some examples, the initial carbon material may be deposited in porous preform 20 by applying one or more cycles of the CVI/CVD. In some examples, the application of the carbonaceous gas to porous preform 20 via the initial CVI/CVD deposition process (10) may occur substantially in a vacuum space e,g, a vessel with an internal environment at less than 100 Torr (e.g., 133.3 kPa)) or under an inert gas environment so as to control the chemical deposition reaction. In some examples, during application of the CVI/CVD gas, the environment including porous preform 20 may be heated to an elevated temperature, for example between about 900° C. and about 1200° C., to promote the chemical deposition reaction of the initial carbon material to form carbon coated fibers 28.
In some examples, the density of rigidized porous preform 30 may be between to about 0.8 g/cm3 and about 1.7 g/cm'prior to proceeding to infusing of rigidized porous preform 30 with isotropic resin (12).
The technique of
The isotropic resin may include a carbon precursor that, once pyrolyzed, forms an isotropic carbon 42. In some examples, the term “isotropic resin” may be used to characterize a resin that, under standard free-state pyrolysis conditions independent of the preform (e.g., pyrolyzing the isotropic resin independent of the preform so that the preform architecture, pore size distributions, density, and the like does not influence the pyrolyzation process), forms carbon that substantially includes an isotropic phase (e.g., more than about 90% of the carbon formed by pyrolyzing the isotropic resin under standard free-state pyrolysis conditions is isotropic carbon). In some examples, the carbon generated by the pyrolysis of the isotropic resin under standard free-state pyrolysis conditions may include more than about 95% isotropic carbon, and in some examples more than about 98% isotropic carbon. The degree of isotropic carbon 42 formed within the rigidized porous preform 30 may depend on a variety of factors including, for example, the initial density of rigidized porous preform 30. For example, the lower the initial density of rigidized porous preform 30 (e.g., 0.8 g/cc density) the more isotropic carbon 42 will be produced from pyrolyzing the isotropic resin. In some examples, the carbon material produced by pyrolyzing the isotropic carbon within the rigidized porous preform 30 may include majority isotropic carbon. In some examples, the carbon material produced by pyrolyzing the isotropic carbon within the rigidized porous preform 30 may include at least 80% isotropic carbon.
Suitable isotropic resins may include, for example, a phenolic resin such as resol; a polymerizable aldehyde such as novolac; a furan resin such as furfuryl alcohol, furthryl alcohol anhydride, or furfural-acetone that can be polymerized to from a furan resin (e.g., poly(furfuryl alcohol)); or combinations thereof. In some examples, the isotropic resin infiltrated into rigidized porous preform 30 may consist essentially of isotropic resin.
In some examples, the isotropic resin may include a thermoset resin that once infused into porous preform 10, sets to form an insoluble polymer that will not melt or leech out of porous preform 30 during the pyrolysis process (14). In some examples, an isotropic resin in the form of a thermoset resin furfuryl alcohol) may substantially reduce the processing times and costs associated with densifying porous preform 30. For example, traditional pitch materials (e.g., mesophase or coal tar pitch) used during the densification processes require extended stabilization cycles on the order of several days at elevated temperatures to allow the pitch materials to crosslink and network within a porous preform structure (e.g., rigidized porous preform 30). Absent such extended stabilization cycles, the temperature increase during the pyrolysis cycle may cause a some of the pitch materials to soften and flow/leech from the porous preform structure before the pitch is converted to carbon. This leeching effect can be wasteful, costly, and highly inefficient. Additionally the leeching effect may lead to density non-uniformity within the resultant composite structure, reduced density values, or both. By using, the isotropic resin to build up the density of rigidized porous preform 30, the efficiency and cost associated with densifying the rigidized porous preform 30 may be significantly improved.
In some examples, the isotropic resin may define a relatively low viscosity (e.g., compared to non-isotropic resins or pitch materials) so that the isotropic resin may be infused substantially throughout the entire volume of rigidized porous preform 30. In some examples, the isotropic resin may be relatively non-viscous. In one example, the viscosity of the isotropic resin may be between about 4 centipoise (cp) and 200 cp at the infusion temperature (e.g., the temperature in which the isotropic resin is infiltrated into rigidized porous preform 30, which may be a target temperature between about 25° C. and about 180° C.). For example, furfuryl alcohol has a viscosity of about 4.6 cp (e.g., 4.6 mPa) at 25° C.
The isotropic resin may be infused into rigidized porous preform 30 using any suitable technique including, for example, a resin transfer mold (RTM) vacuum pressure infiltration (VPI). For example, VPI may include immersing rigidized porous preform 30 in the isotropic resin and subjecting rigidized porous preform 30 and the isotropic resin to a vacuum, such that the resin is drawn into rigidized porous preform 30. In some examples, the VPI may be performed at room temperature (e.g., about 25° C.) or may be performed at elevated infusion temperature (e.g., about 40° C. or up to 180° C. depending on the resin) to aid infusion of the isotropic resin into pores >22 of rigidized porous preform 30.
In examples where an RTM is used, rigidized porous preform 30 may be placed into a mold matching the desired part geometry. The isotropic resin may be injected at low temperature (50° C. to 150° C.) using pressure or induced under vacuum, into rigidized porous preform 30 contained within a mold. The isotropic resin is cured within the mold before being removed from the mold. In some examples, the isotropic resin may be rapidly injected into mold 40, within between about 10 seconds and about 40 seconds, such as about between about 15 seconds and about 40 seconds, using an injection apparatus.
In some examples, the isotropic carbon 42 may be formed using furfuryl alcohol as the isotropic resin. In such examples, the furfuryl alcohol may be infused into rigidized porous preform 30 using a VPI or RIM process. The furfuryl alcohol has low viscosities which makes the alcohol easy to process and infiltrate into rigidized porous preform 30. Further the furfuryl alcohol is comparatively less prone to blocking or otherwise occluding the pores of rigidized porous preform 30 upon conversion into isotropic carbon 42 thereby allowing for subsequent infiltration by the graphitizable carbon material as described further below. The infiltration of the rigidized preform with a furan resin (e.g., furfuryl alcohol or furfuryl acetone) may be performed under vacuum anator pressure. The rigidized porous preform 30 containing the furan resin may be polymerized using an acid bath (e.g., sulfuric acid, phosphoric acid, or the like) followed by placing the infiltrated rigidized porous preform 30 in another bath to neutralize the excess acid and rinsed with de-ionized water. Rigidized porous preform 30 may then be subsequently processed to pyrolyze the polymerized furan resin.
After infusing the isotropic resin into rigidized porous preform 30 (12), the technique of
Additionally or alternatively, the isotropic resin may be infused (12) and pyrolyzed (14) at lower temperatures to produce isotropic carbon 42. The process steps (12) and (14) may be repeated (16) one or more times to create a buildup of isotropic carbon 42. The resultant intermediate composite structure 40 may then be subsequently heat treated (e,g., heated to a temperature greater between about 1600° C. (about 2900° F.) and about 2700° C. (about 4890° F.)) to develop porosity within isotropic carbon 42.
The isotropic carbon may be used to increase the carbon content, density, and strength of rigidized porous preform 30. Additionally or alternatively, the isotropic carbon may further enhance the rigidity and/or the stability of rigidized porous preform 30.
The resultant density of intermediate composite component 40 may be dependent on a variety of factors including, for example, the initial density of rigidized porous preform 30, the initial porosity of rigidized porous preform 30, the number of isotropic resin infusion cycles applied to rigidized porous preform 30, and the like. In some examples, the density of intermediate composite component 40 may be increased to about 1.3 g/cm3 and about 1.85 g/cm3 (e.g., between about 1.7 g/cm3 to about 1.85 g/cm3) prior to proceeding to encapsulating isotropic carbon 42 with a graphitizable carbon 52 (18).
After the completion of one or more cycles (16) of infusing rigidized porous preform 30 with an isotropic resin (14) and pyrolyzing the isotropic resin to produce an isotropic carbon (14), isotropic carbon 42 may be encapsulated with a graphitizable carbon 52 to form a carbon-carbon composite component 50, as shown in
In some examples, by encapsulating isotropic carbon 42 with graphitizable carbon 52 may substantially improve the frictional performance and mechanical durability of carbon-carbon composite component 50 compared to a component with a non-encapsulated isotropic carbon. For example, isotropic carbon 42 on its own may be hard yet relatively fragile. During braking operations of a carbon-carbon composite component that includes isotropic carbon 42 as an outer layer (e.g., use of intermediate composite component 40 absent a subsequent application, graphitizable carbon) may cause the fragile isotropic carbon 42 to fracture and break apart under the sheer and frictional loads, applied to the carbon composite component. The fracturing of the isotropic carbon 42 may cause chunks isotropic carbon 42 to become dislodged from the carbon composite component leading to reduced frictional power of the component and reduced durability and service life of the resultant component.
By encapsulating isotropic carbon 43 with an exterior application of graphitizable carbon 52, the otherwise poor frictional and mechanical aspects of isotropic carbon 42 may be significantly reduced or prevented. For example, without wanting to be bound to a specific scientific theory, it is believed that the graphitizable carbon 52 has better fracture resistance compared to isotropic carbon 42. By at least partially encapsulating the isotropic carbon 42 with graphitizable carbon 52, the graphitizable carbon 52 performs as a binder to help prevent the fracturing of isotropic carbon 42 and its general dislodgement from the final carbon-carbon composite component 50. Additionally, graphitizable carbon 52 exhibits a higher coefficient of friction but may exhibit a reduced strength (e.g., hardness) compared to isotropic carbon 42. Thus, carbon-carbon composite component 50 may exhibit improved braking strength and coefficient of friction compared to a component including either graphitizable carbon 52 or isotropic carbon 42 independently,
Graphitizable carbon 52 may be applied to isotropic carbon 42 using any suitable technique. For example, in some examples, graphitizable carbon 52 may be produced by infusing and pyrolyzing intermediate composite component 40 with an anisotropic pitch material using one or more cycles of RTM/VPI using similar techniques to those described above. Example anisotropic pitch materials suitable for generating graphitizable carbon 52 may include, for example, synthetic mesophase pitches, coal-tar derived pitches, such as thermally or chemically treated coal tar, petroleum-derived pitches, synthetic-pitch derivatives, thermally treated pitches.
Additionally or alternatively, the graphitizable carbon 52 may be produced using one or more cycles of CVI/CVD. Depending on die processing parameters including for example, the deposition temperature, selection/composition of carbonaceous gas, carbonaceous gas flow rate, typo of deposition equipment, duration of the application, and the like, a CVI/CVD deposition process may be configured to produce semi-isotropic carbon, smooth laminar carbon, or rough laminar carbon. The CVI/CVD deposition process may be configured to produce a rough laminar carbon microstructure. In some examples, the resultant deposit of graphitizable carbon 52 may be characterized as having a rough laminar carbon microstructure that includes a non-isotropic carbon material and defines about a 16 degree to about a 24 degree extinction angle as measured by optical microscopy using polarized light.
Example carbonaceous gas materials that are more prone to forming rough laminar carbon may include, for example, propane. In some examples, the formation of the rough laminar carbon using the CVI/CVD deposition process may be increased by using higher process temperatures. In some examples, graphitizable carbon 52 exhibiting a rough laminar carbon microstructure may be produced by conducting the CVI/CVD process at temperature of about 1025° C. with at least 6% of propane by volume added to natural gas.
In some examples, encapsulating isotropic carbon 42 with graphitizable carbon 52 using one or more CVI/CVD deposition process may provide a more uniform application of graphitizable carbon 52 over isotropic carbon 42 compared to a RTM/VPI process. In some examples, graphitizable carbon 52 may be produced using a combination of one or more CVI/CVD and RTM/VPI cycles.
In some examples, graphitizable carbon 52 may form the final (e.g., exterior) coating of carbon material on carbon-carbon composite component 50 such that no additional carbon material is applied to carbon-carbon composite component 50 upon the completion of encapsulating isotropic carbon 42 with graphitizable carbon 52 (18). In some examples, the completed carbon-carbon composite component 50 may define a final density between about 1.7 g/cm3 and about 1.9 g/cm3 (e.g., between about 1.72 g/cm3 to about 1.87 g/cm3).
In some examples, carbon-carbon composite component 50 may be shaped (e.g., mechanically machined) into a brake disc alter encapsulating isotropic carbon 42 with graphitizable carbon 52 (18). In some examples, following the encapsulation of the isotropic carbon 42 with graphitizable carbon 52, carbon-carbon composite component 50 may go through a final heat treatment process (e.g., heat treated at temperatures greater than about 1800° C.) to increase the degree of graphitic carbon within graphitizable carbon 52, and are then machined to final dimensions. Additionally or alternatively, carbon-carbon composite component 50 may be coated with an anti-oxidant protection system.
Various examples have been described. These and other examples are within the scope of the following claims.
