Gaseous Diffusion and Pore Structure in Nuclear Graphites
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GASEOUS DIFFUSION AND PORE STRUCTURE IN NUCLEAR GRAPHITES T.J. MAYS, B. McENANEY, B.T. KELLY School of Materials Science, Bath University, XA9642926 Bath, United Kingdom Abstract With the incentive of providing more information for oxidation and lifecycle studies of moderators in thermal reactors, a new method has been developed to estimate pore structure in nuclear graphites. This method involves the measurement of room-temperature binary gas diffusion in graphite samples using an apparatus that was specially-built to operate at pressures below 100 Torr In these conditions diffusion in graphite pores is in the transition regime between Knudsen and bulk or molecular diffusion. Transition diffusion measurements are analysed for nuclear-grade graphites to yield pore size distributions. Results from the new method are compared with pore structure data obtained using porosimetry. pycnometry and established gas flow techniques. 1. INTRODUCTION Synthetic graphites used as moderators in thermal nuclear reactors contain pores, mostly in the macropore size range (larger than 50 nm [1]), which arise initially during their manufacture. Subsequently these pores are developed by radiolytic oxidation in the CO2 coolant during service. This leads to a reduction in graphite density, and hence to degradations in mechanical and other properties which have implications for moderator lifecycles. It is therefore important to determine pore structure in nuclear graphites in order to understand and predict radiolytic oxidation and property changes in moderators [2]. The nuclear industry in the UK recognised the need for this approach, and consequently used and developed methods such as porosimetry and permeability for macropore structure determination in moderator graphites. However, certain problems with these methods are well-known, such as the limited information available from permeability data [3]. This paper describes a new method to estimate pore structure that might supplement established methods. The new method is based on room-temperature measurements of gas diffusion in graphite samples that are made at pressures < 100 Torr. In these conditions flow in macropores is in the transition regime between Knudsen and bulk or molecular diffusion [4]. This compares with established fluid flow methods for pore structure determination which work at higher pressures where transport is mainly in the bulk regime. The structure of this paper is as follows. First, a simple theory of gaseous diffusion in porous solids is outlined. From this theory, a generalised, transition diffusion equation is obtained which lays the ground for experimental measurements. The second part of the paper deals briefly with the apparatus that was built to measure transition diffusion in graphites. Third, results from the new apparatus - essentially pore size distributions - are reported and discussed, and compared with results from established pore structure techniques, such as porosimetry 2. THEORY OF GASEOUS DIFFUSION IN POROUS SOLIDS A gas flow conductivity, C, may be defined as the molar flux through a solid sample per unit concentration gradient. For component i in a gas mixture, C may be written as 329 C =JlLL2_ (!) 1 Ac, / L where J! is the molar flow rate of i through the sampie, A is the cross-section area of the sample perpendicular to the macroscopic direction of flow and Ac; is the concentration difference of i across the length, LT of the sample parallel to flow The gas flow conductivity is a measure of the ease with which a component of a gas mixture flows through a solid, and is analogous to the thermal conductivity for the flow of heat. For the isothermal, isobaric, steady-state diffusion of component i in an ideal mixture of ideal gases, Eqn (1) becomes r =D =—* (T\ where D! is the effective diffusivity of the solid for component i. R is the gas constant, T is absolute temperature, p is pressure and Ayj is the mole fraction difference of i across L. The effective diffusivity depends on the flowing gas, the pore and surface structure of the solid and on environmental conditions (pressure, temperature and external gas composition). Experimentally, Dj can be calculated from Eqn (2) using experimental measurements of Ji, T, p and Ay; and sample dimensions. A cornerstone of this paper is the relationship between effective diffusivity and pore structure, using which experimental measurements of the former can yield estimates of the latter. This relationship involves a model of gaseous diffusion in porous solids. The model used here for nuclear graphites, which was originally proposed by Hewitt [5] and has more recently been described critically in [3], is as follows. The first part of the model refers to the pore structure. The transport porosity in graphites, i. e., that part of the accessible or open porosity through which fluid flows in the steady state, is assumed to comprise Nv non-intersecting, straight, cylindrical capillaries per unit volume. Isotropy is also assumed, so that there are Nv / 3 capillaries per face of a unit cube of material. The length, 1, of each capillary is assumed to be constant but may exceed the length, L, of the sample, by a factor q = 1 / L > 1, called the tortuosity. Finally, capillary radii, r, are assume to be distributed with a probability density function, f(r). In this model, the fractional transport pore volume, Vj, is given by 2 VT =7tNv < r >q (3) where < > denotes a mean value. It should be recognised that this model is a necessary simplification of the complicated pore structure in graphites. The second part of the model of gaseous diffusion in porous solids refers to flow in capillaries. From simple kinetic theory arguments, see [4], the isothermal, steady-state molar flow rate, ji, of a component i in an inert, ideal, binary mixture of ideal gases diffusing through a single, straight capillary of radius r and length 1» r is given by = 7trpDm rinyl2mKil Jl amRTl U-ainyli+Dm/DKJ where D^ is the bulk or molecular binary diffusion coefficient for the mixture (i = 1, n = 2 or i = 2, n =1). The sub-subscripts 1 and 2 for mole fraction, y, refer to opposite ends of the capillary. The flow rate ratio a is given by 330 (5) where M is molecular weight. Assuming completely diffuse (random) reflection of molecules after collision with pore walls, the Knudsen diffusion coefficient DK is given by DK, = | r < v, > (6) where the mean molecular speed, < v; >, of gas molecules is given by < v, > = ^RT/TIM,) (7) It is useful at this stage to note that bulk or molecular diffusion refers to flow that involves only intermolecular collisions in the gas phase (i. e., for high pressures and large pores) and Knudsen diffusion refers to flow that only involves molecule-pore wall collisions (low pressures, small pores). Transition diffusion refers to the case where both gas-gas and gas-solid collisions are important in flow. It should also be noted that capillary diffusion, Eq (4), depends in a complex way on pore radius, mainly due to the radius-dependence of the Knudsen diffusion coefficient in the logarithmic term. The total molar flow rate, Ji, through an area A of material is simply the sum of flows through each of the (Nv A / 3) capillaries in this area. Accounting for the distribution of pore radii, f(r), this gives (8) Combining Eqns (2), (4) and (8), remembering that q = 1 / L and for convenience defining the diffusivity ratio X, = D i / D in, gives two equations S() (9) J +D ainAy1 Q U /D J which in the model diffusivity ratio equation, and JRTL (10) ApAyiD m which is the experimental diffusivity ratio equation. A detailed derivation of these equations in contained in [6], together with a commentary on the properties of the generalised transition diffusion equation, Eqn (9). But here it is sufficient to note that, in principle, it appears to be possible to estimate the unknown, characteristic pore structure function [(Ny / q) f(r)] from the use of Eqn (9) as a model for experimental values of diffusivity ratio that are calculated using Eqn (10). The following sections summarise how this estimation is carried out. 331 3 EXPERIMENTAL Experimentally the aim is to measure the factors on the right hand side of Eq (10) and hence to calculate the diffusivity ratio as a function of pressure. In this work the only unknown is the molar flow rate since all other factors are fixed (R = 8.314 J K"1 mol" , T = 300 K, L / A « 0.012, Ay; « 1 and Din can be calculated for binary gases from empirical functions of p and T [6]). For He-Ar diffusion, it turns out for this work that X, /1000 = 3.914 (V^imols"1), i = HeorAr (11) Measurements of molar flow rate for each gas were made using a Wicke-Kallenbach cell [3], that operated at pressures < 100 Torr (13.3 kPa), in which conditions mean free path calculations indicated that transition diffusion would occur in the graphites. In this cell, pure He was directed through a mass flowmeter to one side of a sample, pure Ar was directed to the other side through another mass flowmeter, and the amounts of each gas diffusing through the sample into the other stream were determined using a mass spectrometer. Details of the apparatus that was built specially for this work are in [7]. The three nuclear-grade graphites selected for study are: AXF (a moulded, petroleum coke filler-coal tar pitch binder graphite made by POCO Graphite Inc., Decateur, TX, USA); Isograph-50 or IG-50 (an isostatically-pressed graphite made in Osaka, Japan by Toyo Tanso Co. Ltd.) and ATJ (similar to AXP but made by Union Carbide in Sheffield, UK). 4. RESULTS AND DISCUSSION Fig.