Method mercury porosimetry

Mercury Porosimetry Method Mercury is a nonwetting liquid that must be forced to enter a pore by application of external pressure. Consequently it is an extremely useful and convenient liquid for measuring the density of powders and/or particles. This method can measure the apparent and true density of one sample by... 

The precision of the mercury porosimetry method on the material class cementitious mortar was investigated by an interlaboratory study of six different samples. The results are summarized in the following points. 

Chemical characterization total metal analysis has been performed using atomic adsorption spectroscopy (Varian Techtron analyzer). Metals were reported in % by weight (bulk) of total metal oxides in the support (W, Ni, Pt / Al-Si support). See Table 1. Physical method Surface, pore volume, and average pore diameter were measured using standard nitrogen adsorption and mercury porosimetry methods. See Table 1. 

Lindstrom and Boersma (1971) pioneered the prediction of breakthrough curves from equivalent cylindrical pore size distributions, determined by either the water retention or mercury porosimetry methods. The model developed by these authors includes the effects of bothintra- and interpore dispersion. In general, dispersion due to differences in tube size has a much greater influence on the shape and position of the breakthrough curve than mixing within tubes due to microscopic velocity profiles (Rao et al., 1976). For completeness, however, it is preferable to include both effects. Lindstrom and Boersma (1971) defined a CDE for each tube, so that C/C0 for the bundle as a whole is given by ... 

The action of capillary pressure underlies the mercury porosimetry method, which is commonly used for the determination of pore size distribution in ceramics, adsorbents, catalysts and other porous materials [15]. Mercury is known to wet non-metallic surfaces poorly, and thus the capillary pressure, equal to 2o/r (where r is the pore radius, or the average radius of pores having complex shape), prevents its spontaneous penetration into the pores. The pore size distribution can be established by measuring the volume... 

The sample porous structure was defined using the mercury porosimetry method. 

The results obtained from the indirect methods are often controversial, because actually it is not a pore system that is examined but rather the processes applied in these methods the results reflect only the pore size distribution response. Any established value of pore diameter has only conventional meaning and may be different than diameters obtained from other methods. The indirect methods more or less influence the object of observation and measurements because the interventions disrupt material structure. Determining of distribution of pore diameters in cement paste is performed by the mercury porosimetry method and the results are partly confirmed by observations and counting the pores by computer image analysis, but mercury intrusion may damage and alter the material microstructure. Furthermore, the intrusion of mercury into a pore is related to the orifice of the pore rather than to its real dimension (Diamond 2000). Other methods, like capillary condensation, give considerably different values. 

Mercury Porosimetry and Capillary Flow Porometry - Pore Size Determination In a mercury porosimetry measurement, pressure is used to force mercury into filling the pores and voids of the material. The method is based on the capillary rise phenomenon which exists when a non-wetting liquid climbs up a narrow capillary. As the pressure is increased, mercury infiltrates the pores to occupy a subset of the total pore space, the extent of which depends on the applied external pressure. The injected volume of mercury as a function of pressure is recorded. The pore size and distribution can be resolved using the Young and Laplace model [43]. The pore sizes that can be determined by mercury porosimetry range from a few nanometers to a few hundreds of microns. The method is invasive in that not all the mercury will be expelled from the pores and pores may collapse as a result of the high pressures. Due to this and environmental concerns about mercury pollution mercury porosimetry method is becoming less popular. 

Fig. 3 shows the comparison of the pore volume distributions calculated by macromolecular and mercury porosimetry methods for two macroporous silica samples C-80 and CX-2. Porograms found by mercury porosimetry were obtained in Kamaiikhov lab at Institute of Catalysis (Novosibirsk, USSR). This figure demonstrates satisfactory agreement between the maxima positions of these distributions. 

The technique of mercury porosimetry consists essentially in measuring the extent of mercury penetration into an evacuated solid as a function of the applied hydrostatic pressure. The full scope of the method first became apparent in 1945 when Ritter and Drake developed a technique for ... 

Since in practice the lower limit of mercury porosimetry is around 35 A, and the upper limit of the gas adsorption method is in the region 100-200 A (cf. p. 133) the two methods need to be used in conjunction if the complete curve of total pore volume against pore radius is to be obtained. 

Whereas at the lower end of its range mercury porosimetry overlaps with the gas adsorption method, at its upper end it overlaps with photomicrography. An instructive example is provided by the work of Dullien and his associates on samples of sandstone. By stereological measurements they were able to arrive at a curve of pore size distribution, which was extremely broad and extended to very coarse macropores the size distribution from mercury porosimetry on the other hand was quite narrow and showed a sharp peak at a much lower figure, 10nm (Fig. 3.31). The apparent contradiction is readily explained in terms of wide cavities which are revealed by photomicrography, and are entered through narrower constrictions which are shown up by mercury porosimetry. 

Mercury porosimetry is generally regarded as the best method available for the routine determination of pore size in the macropore and upper mesopore range. The apparatus is relatively simple in principle (though not inexpensive) and the experimental procedure is less demanding than gas adsorption measurements, in either time or skill. Perhaps on account of the simplicity of the method there is some temptation to overlook the assumptions, often tacit, that are involved, and also the potential sources of error. 

The incorporation of the new material without any increase in the overall length of the book has been achieved in part by extensive re-writing, with the compression of earlier material, and in part by restricting the scope to the physical adsorption of gases (apart from a section on mercury porosimetry). The topics of chemisorption and adsorption from solution, both of which were dealt with in some detail in the first edition, have been omitted chemisorption processes are obviously dependent on the chemical nature of the surface and therefore cannot be relied upon for the determination of the total surface area and methods based on adsorption from solution have not been developed, as was once hoped, into routine procedures for surface area determination. Likewise omitted, on grounds of... 

Surface Area and Permeability or Porosity. Gas or solute adsorption is typicaUy used to evaluate surface area (74,75), and mercury porosimetry is used, ia coajuactioa with at least oae other particle-size analysis, eg, electron microscopy, to assess permeabUity (76). Experimental techniques and theoretical models have been developed to elucidate the nature and quantity of pores (74,77). These iaclude the kinetic approach to gas adsorptioa of Bmaauer, Emmett, and TeUer (78), known as the BET method and which is based on Langmuir s adsorption model (79), the potential theory of Polanyi (25,80) for gas adsorption, the experimental aspects of solute adsorption (25,81), and the principles of mercury porosimetry, based on the Young-Duprn expression (24,25). 

In order to describe the geometrical and structural properties of several anode electrodes of the molten carbonate fuel cell (MCFC), a fractal analysis has been applied. Four kinds of the anode electrodes, such as Ni, Ni-Cr (lOwt.%), Ni-NiaAl (7wt.%), Ni-Cr (5wt.%)-NijAl(5wt.%) were prepared [1,2] and their fractal dimensions were evaluated by nitrogen adsorption (fractal FHH equation) and mercury porosimetry. These methods of fractal analysis and the resulting values are discussed and compared with other characteristic methods and the performances as anode of MCFC. 

The wetting ability of the anode electrode was evaluated as the contact angle measured by the capillary rise method. The value of fractal dimension of anode electrode of MCFC was calculated by use of the nitrogen adsorption (fractal FHH equation) and the mercury porosimetry. 

As described before, the pore size of porous material ranges widely from atomic size to millimeter order. Different pore sizes are required for different applications of porous materials. Most porous materials do not have uniform pores. Pore size distribution is also an important property. Narrow pore size distribution, i.e., uniform pore size, is required for instance for filters and bioreactor beds. Mercury porosimetry and gas adsorption methods are commonly used to measure pores size and pores distribution. 

This short overview illustrates the large complexity of the SEC processes and explains the absence of a quantitative theory, which would a priori express dependence between pore size distribution of the column packing—determined for example by mercury porosimetry—and distribution constant K in Equation 16.4. Therefore SEC is not an absolute method. The SEC columns must be either calibrated or the molar mass of polymer species in the column effluent continuously monitored (Section 16.9.1). 

Both deBoer s t-method and Brunauer s MP method are based on the assumption that the BET measured surface area is valid for micropores. Shields and Lowell, using this same assumption, have proposed a method for the determination of the micropore surface area using mercury porosimetric data. The surface area of micropores is determined as the difference between the BET surface area and that obtained from mercury porosimetry (see Section 11.5). Since mercury porosimetry is capable of measuring pore sizes only as small as approximately 18 A radius, this technique affords a means of calculating the surface area of all... 

The experimental method of mercury porosimetry for the determination of the porous properties of solids is dependent on several variables. One of these is the wetting or contact angle between mercury and the surface of the solid. 

According to the Washburn equation (10.23) a capillary of sufficiently small radius will require more than one atmosphere of pressure differential in order for a nonwetting liquid to enter the capillary. In fact, a capillary with a radius of 18 A (18 x 10 ° m) would require nearly 60 000 pounds per square inch of pressure before mercury would enter-so great is the capillary depression. The method of mercury porosimetry requires evacuation of the sample and subsequent pressurization to force mercury into the pores. Since the pressure difference across the mercury interface is then the applied pressure, equation (10.23) reduces to... 

The experimental method employed in mercury porosimetry, discussed more extensively in Chapter 20, involves the evacuation of all gas from the volume containing the sample. Mercury is then transferred into the sample container while under vacuum. Finally, pressure is applied to force mercury into the interparticle voids and intraparticle pores. A means of monitoring both the applied pressure and the intruded volume are integral parts of all mercury porosimeters. 

Mercury porosimetry has somewhat the same constraints at the narrow pore end of its range, in that the same questions arise regarding the constancy of surface tension and wetting angle for mercury as exist for an adsorbate. Consequently, both methods have nearly the same lower limit which is about 18 A pore radius for mercury intrusion (e.g. bOOOOpsia). However, at the wide-pore end porosimetry does not have the limitation of the Kelvin equation and for example, at 1.0 psia pore volumes can be measured in pores of 107 micrometer radius or 1.07 x 10 A. 

Mercury porosimetry provides a convenient method for measuring the density of powders. This technique gives the true density of those powders which do not possess pores or voids smaller than those into which intrusion occurs at the highest pressure attainable in the porosimeter and provides apparent densities for those powders that have pores smaller than those corresponding to the highest pressure. 

Methods of measurement of coal density include use of a gas pycnometer and particle density by mercury porosimetry. However, the difference in density values using different gases must be recognized since, for example, density values measured by nitrogen may be greater than those obtained when helium is used. Density measurement depends on adsorption of gas molecules, and differences (between nitrogen and helium) may be due to nitrogen adsorption on the coal surface. 

Another method of estimating the pore size distribution of meso- and macropores is by mercury porosimetry. Here one measures the volume of mercury, a nonwetting liquid, which is forced under pressure into the pores ofa catalyst sample immersed in mercury. The pressure required to intrude mercury into the sample s pores is inversely proportional to the pore size [86]. For cylindrical pores of radius r, this... 

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