Experimental Evaluation of a New Flocculation-Filtration Model for Ceramic Shape Forming Processes

The effect of suspension rheology on the casting mechanics of 37 vol% aqueous silicon carbide slips was examined. Slip viscosities of 180, 120, 90, and 58 mPa.s were evaluated. The 58 mPa.s slip was considered to be fully deflocculated; the others were underdeflocculated to varying degrees. The fully deflocculated slip cast according to parabolic rate behavior, while the others cast at a faster than parabolic rate. Deviations from parabolic rate behavior were correlated with a nonuniform cake structure observed through ultrasound and mercury porosimetry measurements. The observed casting behavior was explained on the basis of a suspension flocculation-filtration model. From rheological measurements, it was found that flocculation of the SiC particles during casting in the underdeflocculated suspensions caused the local void volume within the forming cake to increase as a function of cake thickness. The fully deflocculated slip was rheologically stable, and therefore cast with a uniform microstructure.     

Influence of the aging time of yttria stabilized zirconia slips on the cracking behavior during drying and green properties of cast tapes

Tape-casting process was used to produce yttria stabilized zirconia (YSZ) substrates in an aqueous system using a low amount of an acrylic latex binder. Concentrated suspensions with different aging times were cast, and the influence of the slip aging time on the drying kinetics and cracking behavior of the tapes were studied. In addition, the effect of the slip aging time on the properties of the resultant green tapes was investigated. The latex particles consolidated by coalescence during the aging time of the slips and resulted in an increase in the smaller pore size of the cast tapes. The pore radius increased with increasing the slip aging time up to 14 days thereby decreasing the capillary pressure in the liquid. Aging times over 14 days did not change the pore radius and consequently the capillary pressure. The capillary tension drove the consolidation; the tapes produced from slips with lower aging times which had higher capillary pressure shrank more, had lower pore volume and consequently higher green density. Cracking was found in tapes prepared from slips with aging times shorter than 14 days; the crack area decreased with increasing the slip aging time. For slip aging time ≥14 days cracking was not observed. Aging before casting up to 14 days reduced cracking in tapes prepared with low amounts of latex; however, the lower capillary pressure resulted in low green density of the cast tapes.     

PROPERTIES OF CLAY CASTING SLIPS*

Nine casting slips were prepared, using bodies of the sanitary porcelain type. The electrolyte was a combination of 60%“N” brand sodium silicate and 40% sodium carbonate. Its amount was adjusted in each body slip to produce a cast having the right characteristics according to the “feel” test; the specific gravity of each slip was constant. The grain-size distribution of each slip was determined as well as the casting rate, consistency, and pH when the casting slips were first prepared and again after 24-, 48-, and 96-hour aging periods. There is a reasonably close relation between castability and the grain-size distribution. The pH of the body compositions differed, but there was little or no change in its value with the age of the casting slip up to 96 hours. It is concluded that the determination of grain size and pH should be of considerable aid in the control of casting slips.     

Microstructural Characterization of Alumina and Silicon Carbide Slip-Cast Cakes

The effect of solids loading, particle-size distribution, and suspension viscosity on the resultant microstructure of slipcast monolithic ceramics prepared from aqueous suspensions of alumina and silicon carbide was studied. Unimodal alumina suspensions (average particle size = 0.6 μm) were prepared at 35, 37, and 42 vol%. Silicon carbide suspensions (average particle size = 0.7 μm) were produced with different quantities of dispersant at 37 vol%. Similarly, aqueous alumina suspensions of 42 and 50 vol% were produced with a bimodal particle-size distribution. The slip-cast microstructures were characterized by mercury porosimetry and small-angle neutron scattering, which provided pore size (distribution), pore fraction, and pore morphology. Essentially, the combination of these techniques deciphered packing differences obtained in the cake microstructures. For the alumina cakes produced from the 35,37, and 42 vol% suspensions, the individual characterization techniques, mercury intrusion, and the neutron scattering measurements showed that the cake microstructures were similar in pore size and quantity. However, comparison of the techniques and their assumptions showed differences in the pore shape. Mercury porosimetry and neutron scattering showed bimodal porosity for the cake produced from a mixture of 85% 6-μm particles and 15% 0.6-μm particles. Pore volume fraction and pore size increases were correlated with increased viscosity in the silicon carbide suspensions. In addition, the silicon carbide cake microstructures were measured, and homogeneity was evaluated as a function of position in the cast.     

Assessment of permeation quality of concrete through mercury intrusion porosimetry

Permeation quality of laboratory cast concrete beams was determined through initial surface absorption test (ISAT). The pore system characteristics of the same concrete beam specimens were determined through mercury intrusion porosimetry (MIP). Data so obtained on the measured initial surface absorption rate of water by concrete and characteristics of pore system of concrete estimated from porosimetry results were used to develop correlations between them. Through these correlations, potential of MIP in assessing the durability quality of concrete in actual structure is demonstrated.     

Use of X-ray tomography to study the porosity and morphology of granules

X-ray computed tomography (XRCT) is a technique that uses X-ray images to reconstruct the internal microstructure of objects. Known as a CAT scan in medicine, it has found wide application for whole-body and partial-body imaging of hard tissues (e.g., bone). A modern tabletop XRCT system with a resolution of about 4 μm was used to characterize some pharmaceutical granules. Total porosity, pore size distribution, and geometric structure of pores in granules produced using different conditions and materials were studied. The results were compared to data obtained from mercury porosimetry. It was found that while XRCT is less precise in the determination of total porosity in comparison to mercury porosimetry, it provides detailed morphological information such as pore shape, spatial distribution, and connectivity. The method is nondestructive and accurate down to the resolution of the instrument.Tomographic images show that the pore network of individual granules comprises relatively large cavities connected by narrow pore necks. The major structural difference between granules produced at different conditions of compaction and shear is a reduction in the pore neck diameter; the cavity size is relatively insensitive to these conditions. Comparison of pore size distributions determined from tomographic images and mercury porosimetry indicates that mercury intrusion measures the pore neck size distribution, while tomography measures the true size distribution of pores ca. 4 μm or larger (the instrument resolution).     

Study on some factors affecting the results in the use of MIP method in concrete research

Effects of rate of pressure application and forms and type of sample on porosity and pore size distribution of concrete estimated through mercury intrusion porosimetry (MIP) are presented in this experimental work. Two different forms of concrete sample, namely, crushed chunks of concrete and small core drilled out from the concrete beam specimens, were used for this study. The results exhibit that the rate of pressure application in mercury porosimetry has little effect on porosity and pore size distribution of concrete. It is also demonstrated that small cores drilled out from large concrete specimens are preferable as samples for performing porosimetry test on concrete.     

低场核磁法测定凝胶过滤介质的孔径分布

凝胶过滤介质在蛋白质、多糖等生物大分子的分离纯化过程中具有非常重要的作用,其中介质的孔径分布是决定分离纯化效果的关键因素。由于绝大部分凝胶过滤介质是软凝胶,因此很难用常规的方法如压汞法、低温氮吸附法等测定其孔径分布。本文探索了利用低场核磁共振测定凝胶过滤介质的孔径分布的方法。首先通过抽滤、自制琼脂糖凝胶块等实验确定了峰的归属,明确了介质孔内水、介质间隙水和自由水在核磁共振横向弛豫时间(T₂)图谱上的分布范围;随后与逆体积排阻层析法(ISEC)测定的结果相对比,得出层析介质孔径和介质孔内水弛豫时间的关系;最后通过高斯正态拟合得到了介质的孔径分布。实验结果证实了低场核磁共振法测定凝胶过滤介质孔径分布的可行性。该法操作简单、测定迅速,并可以为其他层析介质孔径分布的测定提供参考。     

Clarification of liquids using filter aids Part I. Mechanisms of filtration

Filter aids were characterized by an effective particle diameter and a pore diameter in the filter aid cake, calculated from the specific cake resistance using the Kozeny equation. The results agreed well with those from mercury porosimetry. The transition from surface filtration to depth filtration by filter-aid cakes was studied with uniform polystyrene particles as a model impurity. The critical ratio between pore diameter and impurity diameter was between 2 and 3. At conditions of non-surface filtration, an important concentration of impurity exists in the liquid flowing through the cake causing a danger of blocking. When pre-coat and body feed were used with polystyrene particles as an impurity, the blocking appeared to occur rather easily on top of the original pre-coat and on the filter medium. The type of pre-coat and the way in which it was formed were very important. In beer filtration, which is mainly a surface filtration, a small concentration of passing impurity was able to block the pre-coat layer, when the filter aid of the body feed was coarser than that of the pre-coat.     

Evaluating Pore Space in Macroporous Ceramics with Water‐Based Porosimetry

We show that water‐based porosimetry (WBP), a facile, simple, and nondestructive porosimetry technique, accurately evaluates both the pore size distribution and throat size distribution of sacrificially templated macroporous alumina. The pore size distribution and throat size distribution derived from the WBP evaluation in uptake (imbibition) and release (drainage) mode, respectively, were corroborated by mercury porosimetry and X‐ray micro‐computed tomography (μ‐CT). In contrast with mercury porosimetry, the WBP also provided information on the presence of “dead‐end pores” in the macroporous alumina.     

Effect of Particle Packing on the Filtration and Rheology Behavior of Extended Size Distribution Alumina Suspensions

The effect of particle packing on the rheology and casting behavior and cast cake characteristics of aqueous alumina suspensions (5O vol%) was investigated using the Andreasen approach. Varied packing was produced by blending two starting materials that differed in average size by a factor of 10. Formulations closest to ideal packing lowered viscosity. Specifically, the lowest viscosity suspension, 196 mPa s, was produced with the distribution closest to the ideal packing distribution. Typically, a well-dispersed suspension (characterized by low viscosity) casts slower than one of poorer dispersion given the same solids content. However, the suspension that provided the lowest viscosity cast at a rate of 0.41 mm²/s, which was the fastest rate of the compared formulations. Therefore, suspensions consisting of extended size distributions do not necessitate slow filtration rates. The colloidal properties of the individual starting materials, low shear rate rheology, and mercury porosimetry were used to explain the unexpected casting behavior. The dispersion and structure formation within the suspension were investigated using electrokinetic sonic amplitude measurements. Mercury porosimetry characterized the flow channels that developed in the casts. Low shear rate rheology confirmed the presence of flocculation that was first suggested by the porosimetry results.     

Characterisation of porous solids using integrated nitrogen sorption and mercury porosimetry

The two different techniques of nitrogen sorption and mercury porosimetry, which are generally utilised completely separately, have been integrated into the same experiment to improve upon the information obtained from both methods. Nitrogen sorption isotherms have been run both before and after a mercury porosimetry experiment on the same sample. This experiment has revealed that for a particular type of sol-gel silica catalyst support the entrapped mercury is confined to only the very largest pores in the material. Light micrograph studies have shown that the spatial distribution of entrapped mercury is highly heterogeneous. These results suggest that mercury entrapment within the material is caused by a mechanism involving macroscopic () heterogeneities in the pore structure. These findings conflict with the usual assumptions generally made in simulations of porosimetry based on random pore bond network models. The new work has shown that, in conjunction with computer simulations involving the correct mercury retraction mechanism, mercury porosimetry and nitrogen sorption can be used to study the spatial distribution of all pore sizes within a mesoporous material. A percolation analysis of the nitrogen sorption data, obtained both before and after mercury entrapment, allowed broad features of the spatial disposition of variously sized pores to be determined. The results reported here also support the use of new, semi-empirical alternatives to the Washburn Equation to analyse raw mercury porosimetry data, rather than the traditional approach.     

Monoclinic Zirconia Microfiltration Membranes: Preparation and Characterization

Microfiltration zirconia membranes were prepared by slip casting from two pure zirconia powders derived from different processing techniques. Powders had almost the same mean particle size but were different in surface area, particle size distribution and morphology. Rheology of zirconia slips was studied in order to prepare a well-dispersed slip suitable for slip casting. The powders showed different dispersibility in the preparation of slips by colloidal processing. The effect of sintering temperature and holding time on porosity, pore size distribution, phase composition, microhardness and microstructure of unsupported membranes are studied and discussed in relation to the membrane processing and properties of powders resulting from different processing routes. Pore size distribution of membranes reflected the differences in morphology of particles and the state of agglomeration in the green samples.Isothermal sintering at 1100°C resulted in some tetragonal phase retained at room temperature in the monoclinic structure. Cracking occurred in membranes sintered above 1150°C due to the volume change in phase transformation. Densification behavior, removal of porosity and the hardness property showed differences that are attributed to the differences in powder processing and characteristics of powders. Crackfree membranes can be prepared by sintering at 1100°C from both powders.     

Capillary porosity in hydrated tricalcium silicate pastes

A survey of the capillary pore size distribution in hydrated tricalcium silicate pastes was made using mercury intrusion porosimetry. The results are interpreted in terms of microstructural features revealed by scanning electron microscopy, and also compared with earlier studies on cement pastes. Certain soluble calcium salts which influence the kinetics of the hydration of tricalcium silicate alter the morphology of the hydration products. This morphological change can be correlated with a change in pore size distribution observed with mercury porosimetry.     

Porosity, pore size distribution and in situ strength of concrete

In this study, in situ strength of concrete was determined through compression test of cores drilled out from laboratory cast beams. The apparent porosity and pore size distribution of the same concrete were determined through mercury intrusion porosimetry, performed on small-drilled cores. The normal-strength concrete mixes used in the experimental investigation were designed to exhibit a wide variation in their strengths. To ensure further variation in porosity, pore size distribution and strength, two modes of compaction, two varieties of coarse aggregates, different levels of age, curing period and exposure condition of concrete were also introduced in experimental scheme. With the data so generated, an appraisal of the most frequently referred relationships involving strength, porosity and pore size of cement-based materials was carried out. Finally, a new empirical model relating the in situ strength of concrete with porosity, pore size characteristics, cement content, aggregate type, exposure conditions, etc., is presented.     

Image-based characterization of cement pore structure using wood’s metal intrusion

Mercury intrusion porosimetry is a widely used technique for characterization of the pore size distribution of cement-based materials. However, the technique has several limitations, among which are the ink bottle effect and a cylindrical pore geometry assumption that lead to inaccurate pore size distribution curves. By substituting Wood’s metal for mercury as the intruding liquid, scanning electron microscopy and imaging techniques can be applied to the sample after intrusion. The molten Wood’s metal solidifies within the pore structure of the sample, which allows it to be sectioned and observed in the scanning electron microscopy. From here, the sample can be analyzed both qualitatively, by observing the changes in the appearance of the sample as the intrusion process progresses, and quantitatively, by applying image analysis techniques. This study provides insight for better interpretation of mercury intrusion porosimetry results and the possibility for quantitative characterization of the spatial geometry of pores in cement-based materials.     

Sintering Effects on the Porous Characteristics of Functionally Gradient Ceramic Membrane Structures

A method to drain cast porous ceramics has been conceived and established, where samples were shown to have a functionally gradient cross-section with a continuously increasing mean particle size between the two principal surfaces.Ceramic discs approximately 45 mm in diameter, and 3.3 mm thick were cast by sedimentation. These green bodies were dried prior to sintering. Maximum sintering temperature and the length of the sintering soak time were varied for samples made from suspensions of both 5 and 10 volume percent solids. Mercury porosimetry was used to obtain the porosity and pore size distribution in each sample. Additionally, a number of atomic force microscopy (AFM) measurements were made on some samples in order to correlate bulk porous properties with those on the outside surfaces.The results showed that as the sintering temperature increased, the densification of the bodies proceeded more rapidly. In general, the longer the sintering soak time, the denser the samples became as well. For the samples prepared at the lower temperatures however, the porosity showed less of a soak time dependence. The green body had a clustered and asymmetric microstructure, which contributed to differing degrees of localized densification and coarsening effects depending on the sintering temperature. Densification effects were more pronounced with the samples made from the more concentrated suspenisions.There was an inverse correlation between the bulk and surface pore dimensions, attributable to the different size scales of particles in the two regions. The much finer surface layer particles were able to undergo some amount of densification while surface diffusion sintering mechanisms were primarily at work elsewhere in the structure.     

A grain size distribution model for non-catalytic gassolid reactions

A new model to describe the non-catalytic conversion of a solid by a reactant gas is proposed. This so-called grain size distribution (GSD) model presumes the porous particle to be a collection of grains of various sizes. The size distribution of the grains is derived from mercury porosimetry measurements. The measured pore size distribution is converted into a grain size distribution through a so-called pore-tosphere factor whose value is also derived from the porosimetry measurements. The grains are divided into a number of size classes. For each class the conversion rate is calculated either according to the shrinking core model, involving core reaction and product layer diffusion as rate-determining steps or according to a new model in which some reaction at the grain surface is assumed to be limiting. The GSD model accounts for the phenomenon of pore blocking by calculating the maximum attainable conversion degree for each size class. In order to verify the model, two types of precalcined limestone particles with quite different microstructures were sulphided as well as sulphated. Furthermore, a single sample of sulphided dolomite was regenerated with a mixture of carbon dioxide and steam. For each reaction good agreement was attained between measured and simulated conversion vs. time behaviour.     

Microstructural comparison of porous oxide ceramics from the system Al2O3–ZrO2 prepared with starch as a pore-forming agent

In this paper we show examples of microstructures of porous oxide ceramics prepared by traditional slip casting (TSC) and starch consolidation casting (SCC) and present results obtained using different microstructural characterization techniques; Archimedes method (open and total porosity), shrinkage measurement, mercury intrusion porosimetry (pore size distribution) and microscopic methods – optical microscopy with microscopic image analysis (pore size distribution) and scanning electron microscopy (detailed investigation of the local microstructure). In particular, microstructures are compared for porous ceramics from the system Al₂O₃–ZrO₂ prepared with rice and corn starch. It is shown that maximum values of the total porosity of porous ceramics prepared with starch as a pore-forming agent were approx. 50%. A major finding by using SEM with respect to starch-produced porous ceramics is the existence of pore fillings in the form of small sintered ceramic shell inside the pores, as a result of starch granule shrinkage during the drying and burn-out steps.     

Application of partial sintering of waste glasses for preparation of porous glass bodies

Porous glasses were prepared by partial sintering of waste glasses. Polyvinyl alcohol was added as a binder to the glass powder and the mixture was un-axially cold pressed under two different forces, followed by sintering at 700 °C. The effects of thermal history, particle size of glass powder, binder content and applied pressing forces on pore size and total porosity of fabricated porous glasses were investigated and final products with the porosity of 15–32 % were prepared. The average pore size of the specimens was determined using mercury porosimetry. The morphology of the porous glasses was observed by scanning electron microscopy. These produced porous glasses can be used for selective and accurate filtration.