6 INDUSTRIAL CARBON CHEMICAL VAPOR INFILTRATION (CVI) PROCESSES I.Golecki 1 Introduction Carbon-Carbon(C-C)fiber-matrix composite materials-C-Cs(Buckley and Edie,1993; Savage,1993;Thomas,1993)possess several extraordinary sets of properties.Foremost,C-Cs have densities in the range of 1.6-2.2 gcm3,much lower than those of most metals and ceramics.Lower densities can be translated into lower component weights,an important con- sideration,especially for applications in flying platforms.C-Cs also have excellent mechan- ical and thermal properties.The mechanical strengths of C-Cs increase with temperature,in contrast to the strengths of the majority of other fiber-matrix composites and those of metals and ceramics,which decrease with increasing temperature.C-Cs evidence high toughness and graceful failure under load,as do some other fiber-matrix composites,in con- trast to the more abrupt brittle behavior of most monolithic materials.No melting occurs in C-Cs at increasing temperatures,although carbon evaporates above=2,500C.Appropriately processed,pitch-fiber based C-C's possess higher thermal conductivities than copper and sil- ver and they exhibit,by far,the highest thermal conductivity per unit density among thermal management materials,e.g.400(Wm-k/(g cm-3)(Golecki et al.,1998).In addition,the thermal expansion coefficient of C-Cs in the fiber direction at 20C to =1,000C is between -1 and 1 ppm/C,much lower than that of most other structural materials.Consequently, thermal stresses in C-C articles are,in principle,also lower.All of these properties of C-Cs can be tailored by design,using different fibers,matrices,processing methods and schedules. While C-C articles can be used from cryogenic temperatures to over 3,000C,and in severe and chemically aggressive environments,they require protection from oxidation for continu- ous use above =350C.The practical effect of oxidation is to diminish the structural and functional integrity of the article.Effective engineering solutions for protecting C-C articles from oxidation have been demonstrated for different types of articles and different tempera- ture-time envelopes (Buckley and Edie,1993;Savage,1993;Sheehan et al.,1994;Golecki et al.,2000).Current and potential future applications of C-Cs include disc brake pads for commercial and military airplanes and racing cars,uncooled engine parts,rocket leading- edge sections,furnace heating elements,heat sinks for high-power electronics,heat exchang- ers,and bipolar plates for proton-exchange-membrane fuel cells. Carbon-Carbon articles generally comprise(a)continuous or chopped carbon fibers pro- duced from rayon,polyacrilonitrile(PAN)or pitch precursors and(b)one or more types of ©2003 Taylor&Francis
6 INDUSTRIAL CARBON CHEMICAL VAPOR INFILTRATION (CVI) PROCESSES I. Golecki 1 Introduction Carbon–Carbon (C–C) fiber-matrix composite materials – C–Cs (Buckley and Edie, 1993; Savage, 1993; Thomas, 1993) possess several extraordinary sets of properties. Foremost, C–Cs have densities in the range of 1.6–2.2 g cm3 , much lower than those of most metals and ceramics. Lower densities can be translated into lower component weights, an important consideration, especially for applications in flying platforms. C–Cs also have excellent mechanical and thermal properties. The mechanical strengths of C–Cs increase with temperature, in contrast to the strengths of the majority of other fiber–matrix composites and those of metals and ceramics, which decrease with increasing temperature. C–Cs evidence high toughness and graceful failure under load, as do some other fiber-matrix composites, in contrast to the more abrupt brittle behavior of most monolithic materials. No melting occurs in C–Cs at increasing temperatures, although carbon evaporates above ≈2,500 C. Appropriately processed, pitch-fiber based C–C’s possess higher thermal conductivities than copper and silver and they exhibit, by far, the highest thermal conductivity per unit density among thermal management materials, e.g. 400 (Wm1 k1 )/(g cm3 ) (Golecki et al., 1998). In addition, the thermal expansion coefficient of C–Cs in the fiber direction at 20 C to ≈1,000 C is between 1 and 1 ppm/C, much lower than that of most other structural materials. Consequently, thermal stresses in C–C articles are, in principle, also lower. All of these properties of C–Cs can be tailored by design, using different fibers, matrices, processing methods and schedules. While C–C articles can be used from cryogenic temperatures to over 3,000 C, and in severe and chemically aggressive environments, they require protection from oxidation for continuous use above ≈350 C. The practical effect of oxidation is to diminish the structural and functional integrity of the article. Effective engineering solutions for protecting C–C articles from oxidation have been demonstrated for different types of articles and different temperature-time envelopes (Buckley and Edie, 1993; Savage, 1993; Sheehan et al., 1994; Golecki et al., 2000). Current and potential future applications of C–Cs include disc brake pads for commercial and military airplanes and racing cars, uncooled engine parts, rocket leadingedge sections, furnace heating elements, heat sinks for high-power electronics, heat exchangers, and bipolar plates for proton-exchange-membrane fuel cells. Carbon–Carbon articles generally comprise (a) continuous or chopped carbon fibers produced from rayon, polyacrilonitrile (PAN) or pitch precursors and (b) one or more types of © 2003 Taylor & Francis
carbon matrices(Savage,1993).One of the most common fabrication methods of C-C arti- cles is densification of a porous preform having the desired shape,so-called near-net pro- cessing.The preform consists only or principally of fibers.The initial geometrical density of such preforms varies in the range 10-80%of the theoretical value at full density. Preforms may be fabricated using e.g.weaving of continuous fibers,lay-up of fibrous mats or fabrics,needle-punching,or mixing of chopped fibers with resins and powders,followed, as needed,by thermal treatment in the 200-1,000C range to evaporate organic binders or residues(Savage,1993).Fabricating,cutting and machining a porous preform is easier and faster than machining a fully-dense C-C bar,which often requires diamond tooling.The densification of the preform can be achieved either from the vapor phase,conventionally by means of isothermal isobaric chemical vapor deposition and infiltration(CVD/CVD),or by liquid-phase resin infiltration and annealing,or by a combination of these two approaches. Both approaches involve heating the preforms to about 1,000C,either during CVI or after resin has been placed inside the preforms.Conventionally,in either densification approach, several steps are required to effect sufficient densification of the preforms.Minimum final density values are necessary for achieving the desired mechanical and thermal properties. All densification methods leave typically 1-10%of voids in the composite.The average density of a composite article,Pav,is equal to: EpiXi=PrX+pmiXml +pm2Xm2+ (1) where the X;denote the respective volume fractions (X;=1-X)and the subscripts f,mi, and v denote fiber,matrix no.i,and void,respectively.After densification is complete,the C-C article may just need to be lightly machined to final tolerances.Additional processing steps involved in the manufacture of C-C articles often include high-temperature (1,000-3,000C)annealing in an inert ambient,called graphitization,in order to achieve desired properties,and oxidation protection treatment. In this chapter,a brief review is provided of CVI routes to the densification of C-C's, from an industrial perspective,with emphasis placed on published approaches demonstrated to reduce the processing time of functional components or that show potential for the same; a more extensive review of this subject was published recently (Golecki,1997). 2 Overview of carbon CVI CVI and CVD (Pierson,1992;Hitchman and Jensen,1993)involve flowing one or several streams of precursor vapors containing the desired element or compound,e.g.methane (CH4),over and around the porous parts,while keeping these parts in a furnace at a suffi- ciently high temperature to decompose the precursor.Each flow rate is usually controlled by means of an electronic mass flow controller and the total pressure in the furnace can be con- trolled independently by means of a throttle valve,which varies the flow conductance to the vacuum pumps.The terms CVD and CVI are often used interchangeably,but strictly speak- ing,they denote different processes.The purpose of CVD is to deposit a functional,thin coating on a dense substrate;e.g.the coating may serve as the active part of an electronic device or as a protective layer.The coating produced by CVD generally adds less than 1% of weight to the substrate and the deposition time is of the order of a few minutes to a few hours.The primary purpose of CVL,on the other hand,is to increase the density of a porous body by 100-900%,in order to obtain a material with desirable properties.In addition to achieving the desired density,a specific carbon matrix microstructure may be required, ©2003 Taylor&Francis
carbon matrices (Savage, 1993). One of the most common fabrication methods of C–C articles is densification of a porous preform having the desired shape, so-called near-net processing. The preform consists only or principally of fibers. The initial geometrical density of such preforms varies in the range 10–80% of the theoretical value at full density. Preforms may be fabricated using e.g. weaving of continuous fibers, lay-up of fibrous mats or fabrics, needle-punching, or mixing of chopped fibers with resins and powders, followed, as needed, by thermal treatment in the 200–1,000 C range to evaporate organic binders or residues (Savage, 1993). Fabricating, cutting and machining a porous preform is easier and faster than machining a fully-dense C–C bar, which often requires diamond tooling. The densification of the preform can be achieved either from the vapor phase, conventionally by means of isothermal isobaric chemical vapor deposition and infiltration (CVD/CVI), or by liquid-phase resin infiltration and annealing, or by a combination of these two approaches. Both approaches involve heating the preforms to about 1,000 C, either during CVI or after resin has been placed inside the preforms. Conventionally, in either densification approach, several steps are required to effect sufficient densification of the preforms. Minimum final density values are necessary for achieving the desired mechanical and thermal properties. All densification methods leave typically 1–10% of voids in the composite. The average density of a composite article, av, is equal to: iXi fXf m1Xm1 m2Xm2 … (1) where the Xi denote the respective volume fractions (Xi 1 Xv) and the subscripts f, mi, and v denote fiber, matrix no. i, and void, respectively. After densification is complete, the C–C article may just need to be lightly machined to final tolerances. Additional processing steps involved in the manufacture of C–C articles often include high-temperature (1,000–3,000 C) annealing in an inert ambient, called graphitization, in order to achieve desired properties, and oxidation protection treatment. In this chapter, a brief review is provided of CVI routes to the densification of C–C’s, from an industrial perspective, with emphasis placed on published approaches demonstrated to reduce the processing time of functional components or that show potential for the same; a more extensive review of this subject was published recently (Golecki, 1997). 2 Overview of carbon CVI CVI and CVD (Pierson, 1992; Hitchman and Jensen, 1993) involve flowing one or several streams of precursor vapors containing the desired element or compound, e.g. methane (CH4), over and around the porous parts, while keeping these parts in a furnace at a sufficiently high temperature to decompose the precursor. Each flow rate is usually controlled by means of an electronic mass flow controller and the total pressure in the furnace can be controlled independently by means of a throttle valve, which varies the flow conductance to the vacuum pumps. The terms CVD and CVI are often used interchangeably, but strictly speaking, they denote different processes. The purpose of CVD is to deposit a functional, thin coating on a dense substrate; e.g. the coating may serve as the active part of an electronic device or as a protective layer. The coating produced by CVD generally adds less than 1% of weight to the substrate and the deposition time is of the order of a few minutes to a few hours. The primary purpose of CVI, on the other hand, is to increase the density of a porous body by 100–900%, in order to obtain a material with desirable properties. In addition to achieving the desired density, a specific carbon matrix microstructure may be required, © 2003 Taylor & Francis
which is a function of the CVI process conditions.The infiltration time in conventional CVI methods is therefore much longer than the deposition time in CVD. The most important quantity describing a CVD process is the deposition rate of the coat- ing,r,which may vary from =10-2-103umh.The most important parameter influencing the deposition rate for a given material system is the substrate temperature.The deposition rate can be expressed (Grove,1967)as: r=Ce[kshg/(ks hg)l/Ns, (2) where C is the chemical concentration in the gas phase,ks is the rate constant for hetero- geneous decomposition of the chemical into the film on the surface of the substrate,hg is the gas-phase mass-transfer coefficient of the chemical to the substrate,and Ns is a normal- izing constant.This chemical may be,but often is not the input precursor (e.g.CH4)intro- duced into the reactor.Often a complex series of chemical reactions lead from the input gas to the solid film.The gas-phase mass-transfer coefficient can be expressed as h=D/dp, where D is the gas-phase diffusivity and do is the thickness of the boundary layer.When kshg,r=kC INs and the process is surface-reaction controlled.Under these conditions, the reaction rate constant ks and hence the deposition rate r usually increase exponentially with temperature according to the Arrhenius law: ks=ksoexp(-E/kT),r=(ksoCg/N3)p"exp(-E/kT), (3) where Ea is the activation energy for the controlling surface reaction,T is the absolute tem- perature in K,and Boltzmann's constant k=1.3805X 10-16 ergK-1=8.614X 10-5eVK-1 (see Fig.6.1).For carbon,E2-4eV/molecule.Pressure signifies the pressure in the reactor chamber. At higher temperature,when khr=hC/N,and the process is gas-phase diffusion controlled.Under these conditions,transport of the precursor through the gas phase to the substrate becomes the limiting factor,while the surface chemical kinetics are relatively more rapid.In this regime,the deposition rate increases with temperature much more slowly,as r=ATb,where b=0.5-1,due to the temperature dependence of the gas-phase diffusivity. At still higher temperature,the deposition rate decreases with increasing temperature,due to competing reactions,such as homogeneous gas-phase nucleation or powder formation and sometimes etching of the surface of the film.Generally,lower temperatures,lower pres- sures,increased dilution,and higher flow rates(i.e.milder CVD conditions)minimize unde- sirable processes at the expense of growth rate.The choice of precursor may also influence the deposition rate and the properties of the deposited coating(Tesner,1984;Duan and Don, 1995;Huttinger,2001). Gas-phaseGas-phase!Surface nucleation mass chemical transport kinetics 1T(K-) Figure 6.I Three temperature regimes in chemical vapor deposition. ©2003 Taylor&Francis
which is a function of the CVI process conditions. The infiltration time in conventional CVI methods is therefore much longer than the deposition time in CVD. The most important quantity describing a CVD process is the deposition rate of the coating, r, which may vary from ≈102 –103mh1 . The most important parameter influencing the deposition rate for a given material system is the substrate temperature. The deposition rate can be expressed (Grove, 1967) as: r Cg[kshg/(ks hg)]/Ns, (2) where Cg is the chemical concentration in the gas phase, ks is the rate constant for heterogeneous decomposition of the chemical into the film on the surface of the substrate, hg is the gas-phase mass-transfer coefficient of the chemical to the substrate, and Ns is a normalizing constant. This chemical may be, but often is not the input precursor (e.g. CH4) introduced into the reactor. Often a complex series of chemical reactions lead from the input gas to the solid film. The gas-phase mass-transfer coefficient can be expressed as hg D/db, where D is the gas-phase diffusivity and db is the thickness of the boundary layer. When ks << hg, r ≈ ksCg/Ns and the process is surface-reaction controlled. Under these conditions, the reaction rate constant ks and hence the deposition rate r usually increase exponentially with temperature according to the Arrhenius law: ks ksoexp(Ea/kT ), r (ksoCg/Ns)pn exp(Ea/kT ), (3) where Ea is the activation energy for the controlling surface reaction, T is the absolute temperature in K, and Boltzmann’s constant k 1.3805 1016 ergK1 8.614 105 eVK1 (see Fig. 6.1). For carbon, Ea ≈ 2 4 eV/molecule. Pressure signifies the pressure in the reactor chamber. At higher temperature, when ks >> hg, r ≈ hgCg/Ns and the process is gas-phase diffusion controlled. Under these conditions, transport of the precursor through the gas phase to the substrate becomes the limiting factor, while the surface chemical kinetics are relatively more rapid. In this regime, the deposition rate increases with temperature much more slowly, as r ATb , where b ≈ 0.5 1, due to the temperature dependence of the gas-phase diffusivity. At still higher temperature, the deposition rate decreases with increasing temperature, due to competing reactions, such as homogeneous gas-phase nucleation or powder formation and sometimes etching of the surface of the film. Generally, lower temperatures, lower pressures, increased dilution, and higher flow rates (i.e. milder CVD conditions) minimize undesirable processes at the expense of growth rate. The choice of precursor may also influence the deposition rate and the properties of the deposited coating (Tesner, 1984; Duan and Don, 1995; Hüttinger, 2001). Figure 6.1 Three temperature regimes in chemical vapor deposition. 1/T (K–1) Gas-phase nucleation Gas-phase mass transport Surface chemical kinetics Log deposition rate, r (µm h–1) © 2003 Taylor & Francis
To sum,the basic steps in CVD are:(1)transport of the gaseous precursor from the center of the gas stream to the boundary layer,(2)diffusion of the precursor across the boundary layer to the surface of the substrate,and(3)decomposition of the precursor on the surface of the substrate to form the solid coating.The last step includes adsorption of precursor-derived moieties on the surface,desorption of other moieties from the surface, surface diffusion and chemical reactions.The conditions during CVD are usually far from thermodynamic equilibrium.Only a few systems,such as Si and GaAs,have been studied in relative depth.An accurate description of the CVD mechanism requires numerically solv- ing the combined chemical and flow equations for the particular reactor configuration.In spite of the progress achieved,quantitative modeling of CVD processes in general cases is limited.Porting of a process from one reactor to another reactor of different geometry and/or size may not be trivial.Therefore,reliable data must be acquired experimentally. In CVL,an additional gas-phase diffusion step needs to occur after the second step in CVD, namely diffusion from the surface of the preform into the interior pore.Such diffusion may be driven by a concentration gradient (isobaric CVD)or by a pressure gradient (forced-flow CVD). Porous fiber preforms generally have a complex pore size distribution,which may consist of several median size ranges.Continuous fibers,with diameters of 5-15 um,are arranged in bundles or tows,with 500-3,000 or more fibers per bundle (Lovell,1995).Pore sizes between individual fibers are of the order of 1-15 pm,those between fiber bundles and between cloth layers are typically 50-500 um.Because flow conductances are proportional to the opening diameter to the third or fourth power,the partial pressure of a precursor inside a small pore in a preform may be different than its value in the reactor.Also,the characteristic dimensions(s), a,for the reactor(1-500cm)and for the interior of the preform (1-500 um)differ by many orders of magnitude.For example,for a mean free path A =17um (methane molecules at 1,000C and 10 Torr=1.3 x 103 Pa),and assuming the same pressure in the pore as in the reactor,the flow would be laminar outside the preform(A<a)and laminar,mixed or molec- ular inside a pore in the preform.Therefore,both the gas-phase diffusion and the CVD depo- sition mechanisms may differ in the reactor and inside a pore:while on the surface of the preform,the CVD process may be in the surface-reaction controlled regime,within an interior pore there may be significant depletion of the precursor due to slow gas-phase diffusion in the molecular regime and the process may be gas-phase diffusion controlled.This state of affairs may lead to non-uniform densification observed in isothermal,isobaric CVI of thick preforms, where the outer surface of the preform has a higher density than the interior regions. A helpful dimensionless number in CVI is the Thiele modulus (Thiele,1939): 0=(kL21Da)0.5 (4) where a and L are the pore diameter and length,respectively.The Thiele modulus gives the relative importance of chemical reaction rate versus gas-phase diffusion.Solution of the per- tinent differential equations for mass transfer,diffusion and change of pore geometry under simplifying assumptions results in the following expression for the concentration profile, C(z),of the precursor species along the pore (0L): C(z)/C(0)=cosh[(1-2z/L)0]/cosh 0. (5) As shown in Fig.6.2,the gas-phase concentration within the pore and therefore the deposi- tion rate of the solid will be more uniform the smaller the Thiele modulus,i.e.the larger the gas-phase diffusivity compared to the surface reaction rate,and the smaller the aspect ratio L/a.It is generally preferable in CVD and CVI to operate in the surface-reaction controlled ©2003 Taylor&Francis
To sum, the basic steps in CVD are: (1) transport of the gaseous precursor from the center of the gas stream to the boundary layer, (2) diffusion of the precursor across the boundary layer to the surface of the substrate, and (3) decomposition of the precursor on the surface of the substrate to form the solid coating. The last step includes adsorption of precursor-derived moieties on the surface, desorption of other moieties from the surface, surface diffusion and chemical reactions. The conditions during CVD are usually far from thermodynamic equilibrium. Only a few systems, such as Si and GaAs, have been studied in relative depth. An accurate description of the CVD mechanism requires numerically solving the combined chemical and flow equations for the particular reactor configuration. In spite of the progress achieved, quantitative modeling of CVD processes in general cases is limited. Porting of a process from one reactor to another reactor of different geometry and/or size may not be trivial. Therefore, reliable data must be acquired experimentally. In CVI, an additional gas-phase diffusion step needs to occur after the second step in CVD, namely diffusion from the surface of the preform into the interior pore. Such diffusion may be driven by a concentration gradient (isobaric CVI) or by a pressure gradient (forced-flow CVI). Porous fiber preforms generally have a complex pore size distribution, which may consist of several median size ranges. Continuous fibers, with diameters of 5–15m, are arranged in bundles or tows, with 500–3,000 or more fibers per bundle (Lovell, 1995). Pore sizes between individual fibers are of the order of 1–15m, those between fiber bundles and between cloth layers are typically 50–500m. Because flow conductances are proportional to the opening diameter to the third or fourth power, the partial pressure of a precursor inside a small pore in a preform may be different than its value in the reactor. Also, the characteristic dimensions(s), a, for the reactor (1–500cm) and for the interior of the preform (1–500m) differ by many orders of magnitude. For example, for a mean free path 17m (methane molecules at 1,000 C and 10 Torr1.3 103Pa), and assuming the same pressure in the pore as in the reactor, the flow would be laminar outside the preform ( <<a) and laminar, mixed or molecular inside a pore in the preform. Therefore, both the gas-phase diffusion and the CVD deposition mechanisms may differ in the reactor and inside a pore: while on the surface of the preform, the CVD process may be in the surface-reaction controlled regime, within an interior pore there may be significant depletion of the precursor due to slow gas-phase diffusion in the molecular regime and the process may be gas-phase diffusion controlled. This state of affairs may lead to non-uniform densification observed in isothermal, isobaric CVI of thick preforms, where the outer surface of the preform has a higher density than the interior regions. A helpful dimensionless number in CVI is the Thiele modulus (Thiele, 1939): (ksL2 /Da) 0.5 (4) where a and L are the pore diameter and length, respectively. The Thiele modulus gives the relative importance of chemical reaction rate versus gas-phase diffusion. Solution of the pertinent differential equations for mass transfer, diffusion and change of pore geometry under simplifying assumptions results in the following expression for the concentration profile, C(z), of the precursor species along the pore (0 z L): C(z)/C(0) cosh[(1 2z/L) ]/cosh . (5) As shown in Fig. 6.2, the gas-phase concentration within the pore and therefore the deposition rate of the solid will be more uniform the smaller the Thiele modulus, i.e. the larger the gas-phase diffusivity compared to the surface reaction rate, and the smaller the aspect ratio L/a. It is generally preferable in CVD and CVI to operate in the surface-reaction controlled © 2003 Taylor & Francis
1.0 0=0.1 0.3 0.8 0.5 巨0.6 60.4 0.2 10 0.0420 0.00.10.20.30.40.5 z/L Figure 6.2 Calculated relative deposition rate along a pore axis,z,for different values of the Thiele modulus,0;L=pore length. regime,where D/ks is large.For Fickian diffusion,the diffusivity D is inversely proportional to pressure and thus operating at lower pressures will decrease 6 and result in a more uni- form infiltration profile (Kotlensky,1973;Naslain et al.,1989;Pierson,1992;Savage, 1993)and a more uniform microstructure (Pierson and Lieberman,1975)in the pore.The value of the Thiele modulus will change during infiltration,because both the gas-related quantities and the aspect ratio of the pore will change.The above simplifying assumptions include a first-order chemical reaction with no change in volume and no homogeneous gas-phase reactions;solutions for other cases were published (Thiele,1939).In many CVI processes,including carbon CVI,there is a net increase in the volume of the gaseous materials due to the decomposition of the precursor.Thus,fresh precursor species have to diffuse into the pores against an opposite,higher flow of by-product species.For carbon CVI,temperatures can vary,e.g,in the 600-2,000C range,depending on the par- ticular chemistry and system;total pressures in the reactor are generally in the range 0.13-1.3×105Pa(10-3-103Tor). CVI has several advantages compared to other densification methods.CVI allows penetra- tion of the desired atoms or molecules into the smallest pores of the preform and does not require post-densification treatment to remove organics.CVI produces uniform and conformal coatings around each accessible fiber and surface in the preform.The matrix produced by CVI is purer than that obtained by hot pressing.The final shape of an article densified by CVI is closest to the desired shape.CVI minimizes the mechanical damage to the fibers as a result of the much lower pressures and temperatures employed.The published methods described here of infiltrating composites using CVI are listed in Table 6.1 and depicted schematically in Fig. 6.3(Golecki,1997).These CVI methods can be divided into several categories,depending on: (i)spatially uniform temperature (isothermal)or not(thermal gradient); (ii)heating method-radiative or inductive; (iii)type of reactor-cold wall or hot wall; (iv)method of extraction of heat from the preform (e.g.radiative,convective,conductive); (v)pressure regime-atmospheric or low pressure; (vi)uniform pressure (isobaric)or pressure gradient (forced flow,pulsed pressure); (vii)whether a plasma is used; (viii)whether immersion in a liquid is required. ©2003 Taylor&Francis
regime, where D/ks is large. For Fickian diffusion, the diffusivity D is inversely proportional to pressure and thus operating at lower pressures will decrease and result in a more uniform infiltration profile (Kotlensky, 1973; Naslain et al., 1989; Pierson, 1992; Savage, 1993) and a more uniform microstructure (Pierson and Lieberman, 1975) in the pore. The value of the Thiele modulus will change during infiltration, because both the gas-related quantities and the aspect ratio of the pore will change. The above simplifying assumptions include a first-order chemical reaction with no change in volume and no homogeneous gas-phase reactions; solutions for other cases were published (Thiele, 1939). In many CVI processes, including carbon CVI, there is a net increase in the volume of the gaseous materials due to the decomposition of the precursor. Thus, fresh precursor species have to diffuse into the pores against an opposite, higher flow of by-product species. For carbon CVI, temperatures can vary, e.g, in the 600–2,000 C range, depending on the particular chemistry and system; total pressures in the reactor are generally in the range 0.13 1.3 105 Pa (103 103 Torr). CVI has several advantages compared to other densification methods. CVI allows penetration of the desired atoms or molecules into the smallest pores of the preform and does not require post-densification treatment to remove organics. CVI produces uniform and conformal coatings around each accessible fiber and surface in the preform. The matrix produced by CVI is purer than that obtained by hot pressing. The final shape of an article densified by CVI is closest to the desired shape. CVI minimizes the mechanical damage to the fibers as a result of the much lower pressures and temperatures employed. The published methods described here of infiltrating composites using CVI are listed in Table 6.1 and depicted schematically in Fig. 6.3 (Golecki, 1997). These CVI methods can be divided into several categories, depending on: (i) spatially uniform temperature (isothermal) or not (thermal gradient); (ii) heating method – radiative or inductive; (iii) type of reactor – cold wall or hot wall; (iv) method of extraction of heat from the preform (e.g. radiative, convective, conductive); (v) pressure regime – atmospheric or low pressure; (vi) uniform pressure (isobaric) or pressure gradient (forced flow, pulsed pressure); (vii) whether a plasma is used; (viii) whether immersion in a liquid is required. Figure 6.2 Calculated relative deposition rate along a pore axis, z, for different values of the Thiele modulus, ; L pore length. 1.0 0.8 0.6 0.4 C(z)/ C(0) 0.2 20 5 2 1 0.5 0.3 = 0.1 10 0.0 0.0 0.1 0.2 z /L 0.3 0.4 0.5 © 2003 Taylor & Francis