Pore size distribution, mercury intrusion

Fig. 3J3 Calculation of pore size distribution in ink-bottle" pores, from mercury intrusion-extrusion experiment." (After Reverberi. )...

Fig. 12. Mercury intrusion pore size distribution for an unactivated sample of CFCMS monolith.

Another property of importance is the pore volume. It can be measured indirectly from the adsorption and/or desorption isotherms of equilibrium quantities of gas absorbed or desorbed over a range of relative pressures. Pore volume can also be measured by mercury intrusion techniques, whereby a hydrostatic pressure is used to force mercury into the pores to generate a plot of penetration volume versus pres- sure. Since the size of the pore openings is related to the pressure, mercury intrusion techniques provide information on the pore size distribution and the total pore volume. 

Porosity and surface area are routinely measured by nitrogen absorption-desorption, mercury intrusion, and low-angle X ray. The electron microscope (EM) provides direct visual evidence of pore size and pore-size distribution. Thus, a combination of EM and conventional methods of pore-size measurement should provide reliable information on the pore structure of polymers. 

The physical characterisation of membrane structure is important if the correct membrane is to be selected for a given application. The pore structure of microfiltration membranes is relatively easy to characterise, SEM and AFM being the most convenient method and allowing three-dimensional structure of the membrane to be determined. Other techniques such as the bubble point, mercury intrusion or permeability methods use measurements of the permeability of membranes to fluids. Both the maximum pore size and the pore size distribution may be determined.1315 A parameter often quoted in manufacturer s literature is the nominal... 

In addition, mercury intrusion porosimetry results are shown together with the pore size distribution in Figure 3.7.3(B). The overlay of the two sets of data provides a direct comparison of the two aspects of the pore geometry that are vital to fluid flow in porous media. In short, conventional mercury porosimetry measures the distribution of pore throat sizes. On the other hand, DDIF measures both the pore body and pore throat. The overlay of the two data sets immediately identify which part of the pore space is the pore body and which is the throat, thus obtaining a model of the pore space. In the case of Berea sandstone, it is clear from Figure 3.7.3(B) that the pore space consists of a large cavity of about 85 pm and they are connected via 15-pm channels or throats. 

With the advent of mercury intrusion porosimeters, it is advantageous to perform a pore size distribution of investigational batches of a drug [43]. The Washburn equation [44] states that the pressure, P, necessary to intrude a pore is given by... 

The pore size distribution of the dried sample was measured by a Aminco 60,000 psi Mercury-Intrusion Porosimeter. 

Figure 4. Pore Size Distribution By Mercury Intrusion.

Although a number of methods are available to characterize the interstitial voids of a solid, the most useful of these is mercury intrusion porosimetry [52], This method is widely used to determine the pore-size distribution of a porous material, and the void size of tablets and compacts. The method is based on the capillary rise phenomenon, in which excess pressure is required to force a nonwetting liquid into a narrow volume. 

One of the most popular methods to measure the pore size distribution in diffusion layers is mercury intrusion porosimetry (MIP) this technique is... 

For membranes with pore diameters smaller than 3.5 nm, the nitrogen adsorption/desorption method based on the widely used BET theory ean be employed. This measurement technique, however, is good only for pore diameters ranging from 1.5 nm to 100 nm ( = 0.1 micron). Typical data from this method are split into two portions adsorption and desorption. The nitrogen desorption curve is usually used to describe the pore size distribution and corresponds better to the mercury intrusion curve. Given in Figure... 

The pore diameter on the abscissa is calculated by employing a particular pore model, usually to the intrusion branch. As a matter of convenience, a cylindrical pore model is traditionally applied. On the ordinate, steep changes in the cumulative diagram are reflected as peak maxima in the incremental curve. From several possible representations (incremental, differential, log differential), the log differential plot seems to be the most revealing, since the areas under the peaks are proportional to the pore volume [79]. Data that can easily derived from mercury intrusion are the pore size distribution, median or average pore size, pore volume, pore area, bulk and skeletal density, and porosity. 

Fig. 1.18A shows the pore size distribution for nonporous methacrylate based polymer beads with a mean particle size of about 250 pm [100]. The black hne indicates the vast range of mercury intrusion, starting at 40 pm because interparticle spaces are filled, and down to 0.003 pm at highest pressure. Apparent porosity is revealed below a pore size of 0.1 pm, although the dashed hne derived from nitrogen adsorption shows no porosity at aU. The presence or absence of meso- and micropores is definitely being indicated in the nitrogen sorption experiment. 

Fig. 1.18 Pore size distribution from mercury intrusion...

Fig. 1.19 Pore size distribution from mercury intrusion (-) and nitrogen adsorption (.) data for mesoporous methacrylate-based (A) and...

Characterization. When silica gel is used as an adsorbent, the pore structure determines the gel adsorption capacity. Pores are characterized by specific surface area, specific pore volume (total volume of pores per gram of solid), average pore diameter, pore size distribution, and the degree to which entrance to larger pores is restricted by smaller pores. These parameters are derived from measuring vapor adsorption isotherms, mercury intrusion, low angle x-ray scattering, electron microscopy, gas permeability, ion or molecule exclusion, or the volume of imbibed liquid (1). 

Pore size distributions are often determined by the technique of mercury intrusion porosimetry. The volume of mercury (contact angle c. 140° with most solids) which can be forced into the pores of the solid is measured as a function of pressure. The pore size distribution is calculated in accordance with the equation for the pressure difference across a curved liquid interface,... 

A diameter of 20 A represents approximately the limiting pore size that can be measured by mercury intrusion. In pores smaller than this, transport becomes increasingly affected by molecule-pore wall interactions, and conventional theories based on molecular and Knudsen diffusion break down. The classification is somewhat arbitrary, however, since the point at which such effects become important also depends on the size of the diffusing molecule. Adsorption equilibrium in microporous adsorbents also depends to some extent on the pore size as well as on the nature of the surface, so control of the pore size distribution is important in the manufacture of an adsorbent for a particular separation. 

FIGURE 5 Pore size distribution by the mercury intrusion method. 

The poly-[HIPE] sample intrusion mercury porosimetry study reported in Figure 4.67 was carried out in a Micromeritics, Atlanta, GA, USA, AutoPore IV-9500 automatic mercury porosimeter.1 The sample holder chamber was evacuated up to 5 x 10-5 Torr the contact angle and surface tension of mercury applied by the AutoPore software in the Washburn equation to obtain the pore size distribution was 130° and 485mN/m, respectively. Besides, the equilibration time was 10 s, and the mercury intrusion pressure range was from 0.0037 to 414 MPa, that is, the pores size range was from 335.7 to 0.003 pm. The poly-(HIPE) sample was prepared by polymerizing styrene (90%) and divinylbenzene (10%) [157],... 

Scaffold porosity and information on the pore size distribution can be obtained from intrusion techniques. The most commonly used methods are mercury porosimetry and capillary flow porometry. In mercury porosimetry the pressure required to fill a tissue scaffold with non-wetting mercury is monitored over a set period of time. Higher pressures are required to fill small pores than large pores a fact that can be exploited using the Washburn equation13 to extract structural information where D is the diameter of the pore at a particular differential... 

Table 4. Porosities and pore size distributions derived from mercury intrusion porosimetry.

Figure 5 compares the pore size distributions of the scaffold computed from the intrusive techniques of capillary flow porosimetry and mercury porometry. From this figure it is apparent that the range of pore sizes derived from capillary flow porometry occurs over a smaller length scale than those based on mercury porometry data. This difference is expected since underlying physics of the... 

Experimental techniques commonly used to measure pore size distribution, such as mercury porosimetry or BET analysis (Gregg and Sing, 1982), yield pore size distribution data that are not uniquely related to the pore space morphology. They are generated by interpreting mercury intrusion-extrusion or sorption hysteresis curves on the basis of an equivalent cylindrical pore assumption. To make direct comparison with digitally reconstructed porous media possible, morphology characterization methods based on simulated mercury porosimetry or simulated capillary condensation (Stepanek et al., 1999) should be used. 

Nitrogen adsorption/condensation is used for the determination of specific surface areas (relative pressure < 0.3) and pore size distributions in the pore size range of 1 to 100 nm (relative pressure > 0.3). As with mercury porosimetry, surface area and PSD information are obtained from the same instrument. Typically, the desorption branch of the isotherm is used (which corresponds to the porosimetry intrusion curve). However, if the isotherm does not plateau at high relative pressure, the calculated PSD will be in error. For PSD s, nitrogen condensation suffers from many of the same disadvantages as porosimetry such as network/percolation effects and pore shape effects. In addition, adsorption/condensation analysis can be quite time consuming with analysis times greater than 1 day for PSD s with reasonable resolution. 

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