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Scripta Materialia 56 (2007) 859–862 www.actamat-journals.

com

On measuring wettability in infiltration processing
´ Veronique Michauda,* and Andreas Mortensenb
a

´ ´ Laboratory for Polymer and Composite Technology (LTC), Ecole Polytechnique Federale de Lausanne (EPFL), Station 12, CH-1015 Lausanne, Switzerland b ´ ´ Laboratory for Mechanical Metallurgy, Ecole Polytechnique Federale de Lausanne (EPFL), Station 12, CH-1015 Lausanne, Switzerland
Received 3 January 2007; revised 31 January 2007; accepted 1 February 2007 Available online 26 February 2007

Capillary pressures encountered in composite processing are often evaluated by measuring infiltration rates as a function of applied pressure. Such data are generally interpreted assuming slug-flow. Using the Brooks–Corey correlations we relax this assumption, to indicate possible pitfalls of the slug-flow approach and to show how such data can nonetheless be used to derive meaningful capillary parameters. Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Infiltration; Composites; Capillary phenomena; Wetting; Threshold pressure

Many composite materials are produced by infiltration. This process is largely governed by capillarity, which acts to drive or oppose motion of the infiltrating fluid into the porous solid preform to be infiltrated. Quantifying capillary forces, by analysis or measurement, is of obvious importance in understanding the process. In the absence of interfacial reactions (which are important in some systems but complicate the problem immensely), the relevant thermodynamic parameter is the work of immersion Wi [1,2]. According to Young’s equation [3]: W i ¼ rlv cosðhÞ ¼ rsv À rsl ð1Þ where rlv is the surface tension of the liquid infiltrant, h ir its wetting angle on a flat solid substrate, and rsv and rsl are the solid/atmosphere and solid/liquid interfacial energy, respectively. Both rlv and h, and hence Wi, are measurable directly using the sessile drop technique [3]; however, this technique is often not usable for systems of relevance to composite processing. Reinforcement materials are generally not available as flat and large substrates. Also, wetting in infiltration is dynamic, which can influence h [3–5]. Direct methods are therefore often used to

measure capillary forces in infiltration; these come in two classes. The first relies on the slug-flow assumption [1,2,4,6,7]. In slug-flow, infiltration takes place with a fully saturated infiltration front, across which there is a single pressure difference, DPc, caused by curved menisci of the liquid surface – as with a liquid in a straight capillary tube. The second approach is based on methods that were developed in soil science and reservoir engineering. Here, capillary forces are quantified, not with a single pressure difference but with curves plotting the capillary pressure vs. the fraction of filled void space (or ‘‘saturation’’), called drainage or imbibition curves, respectively, when the infiltrating fluid does not wet, or wets, the solid [1,2,8–13]. This approach is more complex and also somewhat more cumbersome experimentally, hence it is more rarely adopted in the study of composite processing. However, it is fundamentally more correct. The point of this note is to examine the former approach in light of theory underlying the second. Consider the first method. It rests on Darcy’s law written for fully saturated flow, which states that the rate of flow of a Newtonian and incompressible fluid through a solid at sufficiently low Reynolds number (typical of infiltration processing) is proportional to the local gradient of pressure P within the fluid: vo ¼ À K rP g ð2Þ

* Corresponding author. Tel.: +41 21 693 49 23; fax: +41 21 693 58 80; e-mail: veronique.michaud@epfl.ch

1359-6462/$ - see front matter Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.scriptamat.2007.02.002

which are well established in soil science. is predicted. DPc is inversely proportional to the average preform pore diameter) [20. and (ii) a ‘‘pore size distribution index’’ k that measures the spread in effective pore diameter within the preform (the greater the spread. intersecting the horizontal axis at p = 1. IL). DPc is the capillary pressure. the governing equation becomes: h i dP d À2 K dV l dV l du g u¼ ð6Þ dV l to be solved with boundary conditions: u ¼ 0 ði:e: x ¼ 0 and t > 0Þ. Champ paign. when the front position is not dynamically tracked. P. this. at x = L. then the position of the infiltration front. Pb is inversely proportional to the average pore diameter. [20. We now consider the same experiment. A. the Brooks and Corey correlation reads:  k Vl Pb ¼1À ð9Þ Sl ¼ 1ÀVs P and h i ð2þkÞ K ¼ K sat S 2 1 À ð1 À S l Þ k l ð10Þ where x = 0 is the preform entrance. all else being constant. The infiltration front position. V l ¼ V l ðDP T Þ ð7Þ Here. which is generally the case in composite processing. Methods vary. DPT. [23. these are known in the form of semiempirical correlations. (3) applies. (6) and integrating once subject to Eq. including in composite material processing [8.9. however. (8) yields: Àðkþ1Þ Z du S l K sat P b ð1 À S l Þ k uðsÞ ds ¼ À2 dS l 0 ð1 À V s Þg k  S 2 ½1 À ð1 À S l Þ l ð2þkÞ=k Š ð11Þ This non-linear integro-differential equation is solved numerically for the function u(Sl) subject to Eq. increases. k tends towards infinity since the preform structure tends towards one of perfectly uniform pores (e. (7) using Mathematica (Wolfram Research Inc.g. after substitution of Eqs. We use hereafter the correlations of Brooks and Corey.34]. of course. Mortensen / Scripta Materialia 56 (2007) 859–862 where the fluid ‘‘superficial velocity’’ vo is the volume of fluid passing through a unit surface cut across the porous medium per unit time. Infiltration thus proceeds gradually. but reproducible values that obey expectations are often obtained (e. We define: x ð5Þ u ¼ pffi t and. Michaud. namely the infiltration along a single direction (x) of a non-deforming preform driven by a constant pressure. L2 for a fixed infiltration time t) vs.38–40].2. (3).. Mass conservation dictates: ovo oV l ¼À ð4Þ ox ot where Vl is the local volume fraction liquid in the preform.g. all curves gradually become straight lines of slope unity. Measurements of capillary pressure drop values conducted in this manner have been published by many authors. for unidirectional infiltration driven by a constant pressure the problem can be solved using the Boltzman transformation [8.g.35–37]. (4) and (2) into Eq. and Vl itself varies between 0 and (1 À Vs) as the local pressure in the liquid. which is the first pressure at which the liquid penetrates the preform.31]. the liquid saturation Sl depends on P via (i) the ‘‘bubbling pressure’’ Pb. a bundle of straight capillaries) and Eq. Substituting Eqs. as p increases. over a range of pressures described by the drainage–imbibition curve [1. and have been successfully confronted with experimental data [32. defining the infiltration front position as TM F ¼ ðufront Þ 2 ð1 À V s Þg 2K sat P b ð12Þ while dimensionless applied pressure is defined as p¼ P Pb ð13Þ This adimensionalization of pressure and infiltration velocity is such that infiltration under slug-flow will give a straight line of slope 1. The results of this calculation are plotted in Figure 1 in adimensional form. The method.32]. ufront t. When h > (p/2).31]. and Vs is the volume fraction of solid phase in the preform. Solving the problem requires knowledge of the two functions K(Vl) and Vl(P). As is well known. When the total pressure differential DPT driving the motion of the fluid is kept constant. assumes slug-flow while in many such experiments there is clear evidence that flow is not fully saturated (e. in this case DPc = Pb. DPT then yields a straight line that intersects the abscissa axis at DPT = DPc. an extensive review of the subject is given in Refs. .27]). As seen. Practically.10–13. The permeability K is now a function of Vl. Plotting L2/t (or. In slug-flow continuity dictates that vo be constant everywhere along the infiltrated preform. (9) and (10) in Eq. Ksat is the permeability of the fully saturated preform. is: L2 ¼ 2Kt ðDP T À DP c Þ gð1 À V s Þ ð3Þ and u ¼ ufront .6. but assume unsaturated flow. to measure DPc one produces an experimental set-up such that infiltration of a homogeneous and non-deforming preform takes place along a single direction parallel to a principal direction (Ox) of K.860 V.33. for both polymer and metal composite systems [4. (3)). the smaller is k). Indeed. K is the permeability of the porous medium (in the most general case a tensor and of units m2) and g is the viscosity of the fluid (in Pa s). Vl ¼0 ð8Þ where Vl(DPT) is the fraction liquid in the preform for P = DPT and ufront is the value of u at the tip of the liquid front advancing into the preform. is the measured quantity L in slug-flow infiltration experiments (Eq.14–30]. counted positive when it opposes infiltration.

which is simply computed from Eq. and (ii) the pore size distribution index k. Analyzing results from the present calculations. Graphic validation of the correlation given in Eq. i. for k = 1. as a simple function of Pb and k. it turns out that Pex can be expressed. for various values of k. drainage/imbibition curves can then be used to measure directly the work of immersion Wi. as the degree of pore uniformity decreases. If. such as 2 [8. namely:   k þ 0:71 ð14Þ P ex ¼ P b kÀ1 as shown in Figure 3. Therefore.V. i. (14). (3).38–40]. which is measured directly. method described above. as k decreases. DPc. the curve becomes increasingly linear. According to Eq.9. Given the finite experimental error that comes in such experiments. Also. which increasingly exceeds Pb as k decreases. then taking the intercept of the resulting straight line with the horizontal axis. Ref. if infiltration of the porous solid preform by the liquid takes place quasi-statically. as the degree of uniformity of pore size and pore geometry within the preform increases. Pex. slug-flow-based. (1) – provided again that infiltration takes place quasi-statically. a sufficiently wide range of applied pressures is explored that the strictly linear portion of the curve is obtained. Suppose now that a series of experiments be conducted to measure the capillary pressure according to the first. the difference between Pex and Pb is quite significant (Fig. over the range of k explored here. Then. Since Rl can be measured directly using the BET technique. showing extensive non-linearity at lower values of P and illustrating the definition of Pex. experiments of the first type. it is still possible to use the data to arrive Figure 2.57 (observed with Saffil alumina short fibres). vs. provided the range of pressures explored in experiments of the first type is made sufficiently wide to obtain both (i) a trustworthy value for the lowest (or ‘‘bubbling’’) pressure Pb at which the infiltrant first penetrates the preform and (ii) the strictly linear. A. Figure 3. Now. For realistic values of k. [25]). Rl. although Pex itself has no direct fundamental significance. data are most conveniently plotted as L2 divided by t (i. will yield a pressure. the fact that it increasingly deviates from Pb as k decreases suggests that the deviation between the two may be used to access the pore size distribution index.e. defined in Eq. (ufront)2). (14) as: k¼ P ex þ 0:71P b P ex À P b ð15Þ We also note that. Adimensional infiltration front kinetic parameter F as a function of P/Pb. Michaud. namely (i) the bubbling pressure Pb. on the other hand. the integral of the drainage curve Z 1 Z 1 k ¼ W i Rl P dS l ¼ P b ð1 À S l ÞÀ1=k dS l ¼ P b ðk À 1Þ 0 0 ð16Þ is the work of immersion Wi. (14). this is a pitfall that will easily be encountered in practice. 1). at the two parameters that describe the drainage curve according to the Brooks and Corey correlation. inserting Eq. that has no physical meaning. k. Adimensional infiltration front kinetic parameter F as a function of P/Pb. can also be used to assess Wi as: . Running a straight line through a limited set of data and extrapolating to the horizontal axis will then lead to a measured apparent capillary pressure drop.g. as illustrated in Figure 2 for a low value of k. Examining Figure 1. as k increases. high-pressure portion of the curves in Figure 1.e. multiplied by the total area of preform/infiltrant interface created per unit volume of liquid infiltrated into the preform. (16) into Eq. examples of non-linear plots such as those in Figure 1 can be found in many studies (e. much of the data from experiments of this type may lie within the non-linear portion of the curve. Mortensen / Scripta Materialia 56 (2007) 859–862 861 Figure 1. DPT: this is simply a dimensional form of Figure 1.e. conducted over a sufficiently wide range of pressures to measure both Pb and Pex.

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