Characterization mercury porosimetry

The new composite (SC-155) and some of its precursors and derivatives were characterized by LOI (loss on ignition), XRD ( X ray diffraction), 1R (infrared spectra), BET specific surface area, nitrogen adsorption desorption isotherms, pore size distribution (mercury porosimetry), dynamic methylene blue adsorption and SEM (Scanning Electron... 

Since the porosity of carbons is responsible for their adsorption properties, the analysis of the different types of pores (size and shape), as well as the PSD, is very important to foresee the behavior of these porous solids in final applications. We can state that the complete characterization of the porous carbons is complex and needs a combination of techniques, due to the heterogeneity in the chemistry and structure of these materials. There exist several techniques for the analysis of the porous texture, from which we can underline the physical adsorption of gases, mercury porosimetry, small angle scattering (SAS) (either neutrons—SANS or x-rays—SAXS), transmission and scanning electron microscopy (TEM and SEM), scanning tunnel microscopy, immersion calorimetry, etc. 

Mercury porosimetry is the most suitable method for the characterization of the pore size distribution of porous materials in the macropore range that can as well be applied in the mesopore range [147-155], To obtain the theoretical foundation of mercury porosimetry, Washburn [147] applied the Young-Laplace equation... 

Table 4 lists porosity values determined from mercury porosimetry. These preliminary values agree with those expected based on the proportion of porogen used to make the scaffolds for samples B and E. However there are significant differences between the porosity estimates for samples A and C and those expected based on sample composition. Intrusion methods were not suitable to characterize sample D due to its low permeability. 

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. 

The applied pressure is related to the desired pore size via the Washburn Equation [1] which implies a cylindrical pore shape assumption. Mercury porosimetry is widely applied for catalyst characterization in both QC and research applications for several reasons including rapid reproducible analysis, a wide pore size range ( 2 nm to >100 / m, depending on the pressure range of the instrument), and the ability to obtain specific surface area and pore size distribution information from the same measurement. Accuracy of the method suffers from several factors including contact angle and surface tension uncertainty, pore shape effects, and sample compression. However, the largest discrepancy between a mercury porosimetry-derived pore size distribution (PSD) and the actual PSD usually... 

Incorporation of appropriate contact angles in textural characterization by mercury porosimetry... 

Physico-chemical techniques are widely used for characterization of catalysts and porous materials in general. Well-known methods based on physical adsorption of inert gases (N2 and CO2) and penetration of mercury at elevated pressures provide information on the total surface area, pore volume, and pore size distribution (PSD) of the sample [1,2]. Gas adsorption and mercury porosimetry are often compared since they generate data of similar nature in the pore size range 4 - 100 nm. 

The texture properties of the ultrathin porous glass membranes prepared in our laboratory were initially characterized by the equilibrium based methods nitrogen gas adsorption and mercury porosimetry. The nitrogen sorption isotherms of two membranes are shown in Fig. 1. The fully reversible isotherm of the membrane in Fig. 1 (A) can be classified as a type I isotherm according to the lUPAC nomenclature which is characteristic for microporous materials. The membrane in Fig. 1 (B) shows a typical type IV isotherm shape with hysteresis of type FIl (lUPAC classification). This indicates the presence of fairly uniform mesopores. The texture characteristics of selected porous glass membranes are summarized in Tab. 1. The variable texture demanded the application of various characterization techniques and methods of evaluation. 

The authors thank Sutcliffe Speakman Carbons for providing the carbon samples and characterizing them using N2 adsorption and mercury porosimetry. This work was supported by the European Conununity through contract No. ENK6-CT-2000-00053.1. E. acknowledges the financial support of FCT/MCT (grant PRAXIS XXI/BD/19832/99). 

We now consider application of percolation theory to describing mercury intrusion into porous solids. First we briefly recall the main physical principles of mercury porosimetry (in particular, the Washburn equation). These principles are treated in detail in many textbooks [e.g., Lowell and Shields 49)]. The following discussions (Sections IV,B and IV,C) introduce general equations describing mercury penetration and demonstrate the effect of various factors characterizing the pore structure on this process. Mercury extrusion from porous solids is briefly discussed in Section IV,D. 

The stochastic pore network visualized in Fig. 5 can now be examined with respect to the widely used characterization techniques of mercury porosimetry and low-temperature capillary gas adsorption. Both these equilibrium processes can be computed on a pore-by-pore basis. 

The porous structure of active carbons can be characterized by various techniques adsorption of gases (Ni, Ar, Kr, CO ) [5.39] or vapors (benzene, water) [5,39] by static (volumetric or gravimetric) or dynamic methods [39] adsorption from liquid solutions of solutes with a limited solubility and of solutes that are completely miscible with the solvent in all proportions [39] gas chromatography [40] immersion calorimetry [3,41J flow microcalorimetry [42] temperature-programmed desorption [43] mercury porosimetry [36,41] transmission electron microscopy (TEM) [44] and scanning electron microscopy (SEM) [44] small-angle x-ray scattering (SAXS) [44] x-ray diffraction (XRD) [44]. 

The precursor and the calcined catalyst were characterized by various techniques such as nitrogen adsorption, mercury porosimetry, X-ray diffraction (XRD), atomic emission spectrometry by inductively coupled plasma (ICP), thermogravimetric analysis, and temperature-programmed reduction (TPR). More details about the catalyst preparation and characterization can be found in a previous work (22). 

In the present work the meso- and macro-structural characteristics of the mesoporous adsorbent MCM-41 have been estimated with the help of various techniques. The structure is found to comprise four different length scales that of the mesopores, the crystaUites, the grains and of the particles. It was found that the surface area estimated by the use of small angle scattering techniques is higher, while that estimated by mercury porosimetry is much lower, than that obtained from gas adsorption methods. Based on the macropore characterization by mercury porosimetry, and the considerable macropore area determined, it is seen that the actual mesopore area of MCM-41 may be significantly lower than the BET area. TEM studies indicated that MCM-41 does not have an ideal mesopore structure however, it may still be treated as a model mesoporous material for gas adsorption studies because of the large radius of curvature of the channels. 

On the basis of the results of various characterization techniques, it was found that MCM-41 consists of 4 levels of structure mesopores, crystaUites, grains and particles. AU these levels have been successfuUy characterized. Estimates of surface area by SAXS and SANS are higher, while those from mercury porosimetry are much lower, than those estimates by BET methods the estimates obtained from geometrical consideration using variable waU thickness are close to the BET results. It was confirmed that mesopores in MCM-41 are curved rather than straight channels and, even though they do not have an ideal mesopore structure, they can be considered as model mesoporous materials for gas adsorption studies. 

In gas adsorption for micro-, meso- and macropores, the pores are characterized by adsorbing gas, such as nitrogen at liquid-nitrogen temperature. This method is used for pores in the ranges of approximately <2 nm micropores), 2 to 50 nm (mesopores), and >50 nm macropores) (ISO/FDIS 15901-2, Pore Size Distribution and Porosity of Solid Materials—Evaluation by Mercury Porosimetry and Gas Adsorption, Part 2 Analysis of Meso-pores and Macro-pores by Gas Adsorption ISO/FDIS 15901-3, Part 3 Analysis of Micro-pores by Gas Adsorption). An isotherm is generated of the amount of gas adsorbed versus gas pressure, and the amount of gas required to form a monolayer is determined. 

Several determination methods of a porous texture can be used for characterizing the supports. Certain of these methods (i.e., scanning electron microscopy, mercury porosimetry) are described in other chapters of this book. We shall only report here the specific methods of support characterization. 

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. 

The aim of this work is to explore the applicability of the sol-gel method for the preparation of Ag/Si02 and Cu/Si02 catalysts and to see whether such a method can yield silver and copper species stabilized by the carrier. Characterization of the catalyst structure by several physical and chemical techniques, including N2 adsorption-desorption isotherms, mercury porosimetry measurements, X-ray diffraction and transmission electron microscopy, has been used to correlate the microstructure of Ag/Si02 and Cu/Si02 catalysts with their catalytic performance. 

The composition, the textural and surface properties of the catalysts were studied by AAS, mercury porosimetry, XRD, XPS and TG-DTA [16,17]. The amount of metallic copper on the surface of catalyst was determined by titration with N2O [18]. The characterization of bulk and surface properties of the catalysts is given elsewhere [14,16,17]. 

Giesche, H. (2006). Mercury porosimetry A general (practical) overview. Particle and Particle Systems Characterization, 23(1), 9-19. 

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