MANUFACTURE OF KAOLIN/QUARTZ POROUS CERAMICS

INTRODUCTION According to the 2012 update of Progress on drinking water and sanitation published by WHO and UNICEF, over 780 million people are still without access to improved sources of drinking water and 2.5 billion lack improved sanitation (WHO, 2012). While it is not possible to quantify the proportion of deaths directly due to unsafe drinking water and not attributed to other transmission routes, access to clean drinking water and proper sanitation can provide substantial improvements in health. The presence of water borne pathogens (protozoa, bacteria and virus) constitutes the greatest treat to human health in relation to unsafe drinking water. These problems of public health treat to worsen in the near future due to population growth and the continuous worsening of the quality of water sources due to the indiscriminate discharge of both domestic and industrial effluents without adequate treatments. (F. Macedonio, 2012) (Jonathon Brame, 2011) (Meng Nan Chong, 2010) (S. Malato, 2009) (Nora Savage, 2005) (Chunjian Shi, 2012). Addressing these problems calls out for a tremendous amount of research to be conducted to identify robust new methods of water disinfection at lower cost and with less energy, while at the same time minimizing the use of chemicals and impact on the environment (S. Malato, 2009). Approaches relying solely on centralized solutions for drinking water disinfection may work in some regions, whereas in many cases structural problems such as: drawing water from highly contaminated sources, contamination of drinking water during distribution, storage or handling, lack of financial resources and unprofessional operation, maintenance and management; lead to their failure. In this case, promoting alternative decentralized water treatment options such as household treatment is often the most feasible way of improving drinking water quality (Maryna PeterVarbanets, 2010) (Michen, 2010) (WHO, 2011). Household water treatment technologies are also known as point-of-use and point-of-entry water treatment technologies (WHO, 2011). Point-of-use (POU) systems treat only the part of water used for drinking. The minimum requirement for drinking water amounts to about 2 l per person per day, while the maximum for drinking and cooking is 8 l per day. Point-of-entry (POE) systems refer to the treatment of all the water supplied to a household. The treatment capacity is therefore much higher than for POU systems in the order of 100150 l per person per day (Maryna Peter-Varbanets, 2010) (Nora Savage, 2005). Water disinfection methods include: (i) strong oxidants-based systems, (ii) heat and UV-based systems, (iii) physical systems, and (iv) combined systems. Most of these methods can be adapted for either large scale or household drinking water disinfection. One great advantage of physical systems such as filtration, if compared to strong oxidant- and UV-based treatments, is the simultaneous and rapid removal of turbidity and microorganisms in a one-stage process. In filtration, two major processes may be distinguished, namely surface filtration and depth filtration. Surface filtration relies to a great extend on the sieving effect, which is the physical straining of particles that are larger than the pore dimension of the filter media (Michen, 2010). In contrast, in depth filtration contaminated water is passed through a filter medium with micron-scale open porosity, and microbes are retain by a combination of physical and chemical processes, including physical straining, natural die-off, biological action and adsorption. Adsorption on the pore walls takes place under the main influence of van der Waals, electrostatic forces and hydrophobic interactions. Because of the relatively coarse porosity (compared to surface filters), the flow rates are high at low applied pressures, and the system cost is reduced because of the less demanding

materials processing required and the absence of high-pressure pumps (Markus Wegmann B. M., 2008) (WHO, 2011). Fired-clay depth filters are concidered sustainable and affective options for retention of pathogenic microrganisms. Their main drawback is their low virus retention capacity. Virus retention has been improve by filter surface functionalization using metal oxides and hydroxides with isoelectric points (IEPs) generally above 7. This aproximation besides increasing the surface charge increases the filter surface area; however coating loss during operation is common (Markus Wegmann B. M., 2008). An alternative to reduce such problem and simultaneously reduce the number of operations require to manufacture the filter, is to add the adsorbent material to the raw material mixture. The sucess of this approch is relative sice reported filter structural quality is low (Michen, 2010). The ceramic process is a series of systematic operations leading to the transformation of particle system into an object of pre-defined shape or a part of an object such as a coating. In order to achieve this, material properties must be modified and controlled in every operation. The defects introduced in any one operation are retained in the following one due to the sequential nature of the process, leading to non-uniform microstructures and defective objects. Therefore knowledge of the material response in every operation of the process is the key to successful design of ceramic materials with controlled microstructure (Moreno, 2003) (Evans, 2008) (Olga Burgos-Montes, 2009). The manufacture process of a ceramic product starts with the selection and conditioning of powdered raw materials. Followed by the shaping of that powder into the desire object, and thermal treatment. The shaping operation can be performed via different techniques that in general, can be classified in three groups related to water content, namely: powder pressing, plastic molding and suspension casting. The use of suspensions has acquire renew relevance due to its great versatility in relation to object geometry, complex microstructure design and improve reliability (Moreno, 2003) (Evans, 2008). Mentioned characteristics are crucial in the manufacture of fired clay filters for drinking water disinfection, consequently suspension casting was selected as the shaping technique. Suspension casting processes are characterized by state change, and the use of a surface to define the final object shape; other characteristics such as reduction of free volume do not always take place. When free volume collapse is non-uniform throughout the object residual stresses develops and deformation occurs upon thermal treatment. State change mechanisms in suspension casting includes: (i) liquid phase removal by filtration, (ii) formation of a physical network of particles via suspension destabilization either by shifting the pH towards the isoelectric point or by double layer compression, (iii) formation of a gel by reaction or modification of additives and (iv) freezing the liquid phase and consecutive sublimation (Moreno, 2003) (Evans, 2008). Among the alternatives within suspension casting thecniques, slip casting will be used for this initial approach. In this technique phase separation is achieve via filtration in a porous mold made of plaster of Paris. Using concentrated clay-based suspensions (above 40 vol%) is possible to cast green bodies with relative density values above 0.65 (Moreno, 2003) (Santacruz M. I. Nieto, 2003). These levels are above those predicted from rheological measurements and are a direct consequence of the high span in particle size distribution of natural raw materials, which allow higher packing efficiencies than those calculated for monosized rigid spheres (Moreno, 2003). Nevertheless, slip casting technique has drawbacks, the cast thickness is proportional to the square root of casting time, hence the first layers cast faster with lower packing efficiency, generating density gradients (Evans, 2008). Furthermore, increased casting time allows the occurrence of sedimentation and crack forming (Moreno, 2003).

Fired-clay ceramics are usually produced from natural raw materials such as clays, quartz and feldspar (Santacruz M. I. Nieto, 2003). The raw materials mixture use for both dense and porous bodies contain a balanced proportion of plastic materials and non-plastic materials (around 50/50 wt%). In dense bodies the non-plastic material content is roughly 50 wt% quartz and 50 wt% feldspar (Mustafa Salih Eygi, 2008). In porous bodies non-plastic material proportions are about 60 wt% quartz, 10 wt% feldspar and 30 wt% calcium carbonate (J. L. Amors, 2010). Specifically, for the manufacture of fired-clay filters the following proportions between plastic and non-plastic materials has been reported. L. palacio et. al. use mixtures of 25 wt% plastic components (clay) and 75 wt% of non-plastic compoents (alumina and quartz); B.K. Nandi et. al. and D. Vansanth et. al. use mixtures with 50 wt% of plastic (kaolin) material and 50 wt% of non-plastic materials (quartz and calcium carbonate) and M. C. Almandoz et. al. prepared ceramic filters using mixtures of ball clay, kaolin, quartz, alumina and calcium carbonate. Plastic materials proportions used were 60, 45 and 15 wt% (L. Palacio P. P.) (B. K. Nandi, Treatment of oily waste water using low-cost ceramic membrane: Flux decline mechanism and economic feasibility, 2009) (D. Vasanth G. P., Fabrication and properties of low cost ceramic microfiltration membranes for separation of oil and bacteria from its solution, 2011) (M. C. Almandoz J. M., 2004). In general is common not to add the flux phase (feldspar) when the final purpose is to obtain a ceramic filter, however alternative ways to improve mixture sinterability are reported. When compared to dense ceramics, porous structures poses a range of interesting intrinsic properties, such as low thermal mass, low thermal conductivity, pre-design permeability, high surface area, low density and high specific mechanical strength (Andr R. Studart, 2006) (Isabel Santacruz R. M., 2008) (M. Montero, 2010). These structures are classified according to pore size as macroporous (pores > 50 nm), mesoporous (2 < pores < 50 nm) and microporous (pores < 2 nm) (Andr R. Studart, 2006). However, the functionality of porous ceramics is defined by additional parameters such as pore density, morphology, degree of order, and interconnection level (Marcus Liew Kai Hoa, 2006) (Andr R. Studart, 2006) (Ilke Akartuna, 2008) (Isabel Santacruz R. M., 2008) (M. Montero, 2010). These structural features are highly influenced by raw materials selection, processing route and thermal treatment. The methods for producing porous ceramic structures can be divided by the kind of template used in hard and soft. Hard templates include porous structures, particles or fibers made of polymers, silica, and carbon, among other materials. While soft templates include, polymer micelles, liquid droplets, gas bubbles and microorganisms (Zeng, 2006). The main advantages of using hard particles, as template is the possibility to pre-design porosity level, pore size distribution and pore morphology through particle selection (Andr R. Studart, 2006). However if an even distribution of the template particles is not achieved, due to for example the aggregation of template particles, the mentioned advantages are lost and the reliability of the porous ceramic is compromised (Jean-Marc Tulliani, 2009). Within reviewed literature dealing with the manufacture of fired clay filters, the pore generation techniques cited are: addition of hard template materials such as carbon or starch that are completely eliminate upon thermal treatment or calcite and dolomite wich are only partially eliminated and basic (NaOH) leaching of amorphous silica (Mansoor Kazemimoghadam, 2004) (Mohsen Abbasi A. S., 2010) (D. Laux, 2006) (Jilali Bentama K. Q., 2002) (S. Rakib, 2001) (S. Khemakhem, 2009) (S. Fakhfakh, 2010) (N. Saffaj, 2004) (L. Palacio Y. B., 2009) (B. K. Nandi, Treatment of oily waste water using low-cost ceramic membrane: Flux decline mechanism and economic feasibility, 2009) (M. C. Almandoz J. M., 2004) (Ashwin Potdar, 2002) (Anupam Shukla, Characterization of chemically modified zeolite-clay composite membranes using separation of trivalent cations, 2005) (Anupam Shukla, Separation of Cr(VI) by zeolite-clay composite membranes modified by reaction with NOx, 2007) (Solomon Workneh, 2008)

(Anupam Shukla, Analysis of separation of chromic acid by zeolite-clay composite membrane using space-charge model, 2004) (Anupam Shukla, Modeling of separation of aqueous solutions of FeCl3 and AlCl3 by zeolite-clay composite membranes using a space-charge model, 2004) (Manoj Kumar, 2006) (Abhijit Majhi, 2009) (D. Vasanth G. P., Fabrication and properties of low cost ceramic microfiltration membranes for separation of oil and bacteria from its solution, 2011) (D. Vasanth R. U., 2011) (Jianer Zhou, 2010) (Gangling Chen, 2008) (Mohsen Abbasi M. M., 2010). In the case of ceramic filters, the main demands are high fracture resistance and permeability; in addition depth filters need large surface area and enhanced tortuosity to maximize the filter adsorption capacity and the probability to generate collisions between microorganisms and the filter surface. If relatively inhomogeneous particle packing is obtained during shaping, the consolidated filter is, in general, permeable and its toughness is low. This is because permeability consistently rises with increase of porosity and pore size (particle size) and fracture resistance consistently drops under the same conditions. For more homogeneous packing, the contrary applies (P. Maarten Biesheuvel, 1999) (M. L. Mottern, 2008) (Jeonghwan Kim, 2010) (Murilo D. M. Innocentini, 1998). Consequently, fracture resistance and permeability depend on the preparation of a dispersed suspension, porosity level, coarsest pore size, coarsest particle size, and sintering temperature, because they determine the size of the largest flaw within the porous structure (P. Maarten Biesheuvel, 1999) (J. L. Amors, 2010). In addition, physical models have indicate that contrary to permeability, which consistently increases with porosity and pore size, mass flow reaches a maximun at porosity (open) levels arround 30% and raw materials particle sizes between 0.5 - 5 microns (P. Maarten Biesheuvel, 1999). The final goal of the ongoing investigation is to manufacture a ceramic filter using silica sand, kaolin and hematite nanoparticles with capacity to retain protozoan parasites via straining and viruses by adsortion. The capacity of hematite to retain viruses and its stability in aqueous systems have been tested, these makes it a suitable material to manufacture the ceramic filter with a reduce number of operations. In this article the structure of silica sand - kaolin porous ceramics manufacture by casting onto plaster of Paris surfaces will be characterized and the manufacture route leading to the best results within the options tested will be discussed.

MATERIALS AND METHODS MATERIALS Kaolin marketed as Kaofine was supplied by Thiele Kaolin Company (Sandersville, Georgia, U.S.), silica sand traded under the name MIN-U-SIL 5 was provided by U.S. Silica Company (Frederick, Maryland, U.S.) and synthetic graphite marketed as KS 6 was supplied by TIMCAL Graphite & Carbon (Bodio, Switzerland) were used as raw materials in this work. Kaolin clay (1:1 dioctahedral phyllosilicate) particles have a hexagonal platelet-like shape; with typical diameters bellow 10 m, thickness above 20 nm and surface areas between 5 and 25 m2/g. Kaolin provides plasticity and green strength to the raw material mixture (F. Andreola, 2006) (J. C. Baird, The effects of added nanoparticles on aqueous kaolinite suspensions I. Structural effects, 2006) (Joao B. Rodriguez Neto R. M., 2007) (C. Chassagne, 2009). Silica sand (Quartz) acts mainly as filler and contributes to dimensional stability by reducing dimensional change during sintering and synthetic graphite is used as hard template to tailor the pore structure. Particles in suspension tend to form aggregate units under the influence of Van der Waals attraction. There are three ways to overcome the van der Waals attraction: electrostatic, steric and

electrosteric stabilization (Moreno, 2003) (P. Marco J. L., 2009) (Tadros, 2011). Electrostatic stabilization occurs when a double layer develops as a result of the presence of a surface charge generated by ionization of surface groups and the presence of adsorbed ionic species around particles immersed in a polar liquid (Tadros, 2011) (Olga Burgos-Montes, 2009). When charged particles in dispersion approach each other such that the double layers begin to overlap, repulsion occurs. Since the individual double layers can no longer develop unrestrictedly (complete potential decay is not allowed). This repulsion that is determined by the extent of the double layer, may overcome the van der Waals attraction, leading to a stable system. On the other hand if the repulsive force is not sufficiently large (e.g. when the double layers are compressed), the van der Waals attraction dominates and aggregation takes place (Tadros, 2011). Particle aggregation depends on double layer extension (1/), particle size (R) and zeta potential (). The larger and 1/ the lower the tendency towards particle aggregation. Steric stabilization arises when nonionic surfactants and/or polymers are adsorbed at the particle surface. In this case one can define an adsorbed layer thickness for the surfactant or polymer and hence an effective radius (Reff = R+). When two particles each with a radius R and containing an adsorbed polymer layer with a thickness , approach each other to a surface-surface separation distance that is smaller than 2, the polymer layers interact with each other resulting in two main situations: (i) polymer chains may overlap with each other and (ii) polymer layer may undergo some compression. In both cases, there will be an increase in the local segment density of the polymer chains in the interaction region (Tadros, 2011). Provided the dangling chains are in a good solvent, this local increase in segment density in the interaction zone will result in strong repulsion as a result of two main effects: increase in the osmotic pressure in the overlap region as a result of the unfavorable mixing of the polymer chains and (ii) reduction of the configurational entropy of the chains in the interaction zone. Combination of these two energies is usually referred to as the steric interaction free energy (Tadros, 2011). Steric repulsion will overcome the Van der Waals attraction showing a rapid increase at distances smaller than twice the adsorbed layer thickness (Tadros, 2011) (Olga Burgos-Montes, 2009). The occurrence of Particle aggregation depends on the Hamaker constant (A), the particle size (R) and adsorbed layer thickness (). The larger the value of /R, the stronger the adsorption and the higher the surface coverage, the smaller the tendency towards particle aggregation (Tadros, 2011) (Zhongwu Zhou, 2001). Electrosteric stabilization arises from the combination of the other two, due to the action of charged polymers (polyelectrolites) which combine the steric barrier provided by the polymer at short separation distances with the electrostatic repulsion related to the double layer overlap (Olga Burgos-Montes, 2009). Electrosteric forces can be manipulated by controlling the type, size and concentration of the adsorbed species (Zhongwu Zhou, 2001). Additives commonly used for stabilization of concentrated kaolin suspensions include electrostatic deflocculants such as: sodium polyphosphates and sodium silicates and anionic electrosteric deflocculants such as: poly(carboxilic) acid (sodium salt), poly(methyl-acrylic) acid and synthetic polyelectrolites, among others. (Prashant Shankar, 2010) (Joao B. Rodriguez Neto R. M., 2007). (Jos Luis Amors, 2010) (Maxim Loginov, 2008) (F. Andreola, 2006) (Mustafa Salih Eygi, 2008) (J. C. Baird, The effects of added nanoparticles on aqueous kaolinite suspensions I. Structural effects, 2006) (Santacruz M. I. Nieto, 2003) (P. Marco J. L., 2009) (C. Chassagne, 2009). In some cases mixtures of these two types are also used. Highly dispersed carbon materials (e.g. natural graphite, carbon black etc.) display a strong tendency to agglomerate and form highly disordered ramified aggregates (Vasily Moraru, 2003). Hence an effective deflocculant is required to prepare a dispersed graphite suspension. It has

been shown that aqueous carbon suspensions can be stabilized though adsorption of anionic and non-ionic polymers via electrosteric and steric mechanisms, respectively. Besides these mechanisms the adsorption of water-soluble polymers reduces the surface tension between phases; i.e. reduces the hydrophobic character of carbon. Deflocculants used include: polyacrylates, polyolefins, polystyrene sulfonates, humic acids, among others (S. L. Khilko, 2008) (Phillip R. Tudor, 1996) (Pawlik, 2005) (H. Huai, 1998) (Vasily Moraru, 2003). Marek Pawlik et. al. compared the dispersion capacity of anionic and non-ionic polymers in aqueous of relatively large carbon particles (average particle size was 50 m). The authors stated that stabilization depends on the polymer ionic character and its ability to increase carbon wettability. In addition it was concluded that even though observed surface coverage of anionic polymers was less dense, the electrosteric mechanism gave rise to stronger stabilization (Pawlik, 2005). In contrast, H. Huai et. al. showed that in suspensions of micron sized carbon particles non-ionic deflocculants were more efficient, requiring lower addition levels when compare to anionic additives (H. Huai, 1998). Since stronger stabilization is the priority in this work anionic polyelectrolites will be used instead of non-ionic surfactants (e.g. triton X-305). Deflocculants tested in this work include: Dolapix PC 67, Dolapix PCN and Giessfix 162 produced by Zschimmer & Schwarz GmbH & CO KG (Lahnstein, Germany); Darvan 811D provided by R.T. Vanderbilt Company, Inc. (Norwalk, Connecticut, U.S.); sodium hexametaphosphate purchased from R.A. Chemicals (Bogota, Colombia); and poly(acrylic) acid produced by Polysciences Inc. (Warrington, Pennsylvania, U.S.). Table 1 includes type, chemical basis, active matter content and molecular weight of tested deflocculants. ELEMENTAL AND MINERALOGICAL ANALYSIS Chemical analysis of raw materials was performed using a wavelength-dispersive X-Ray fluorescence spectrometer ZSX Primus (Rigaku Industrial Corporation, Japan). Measurements were performed using the standard rhodium (Rh) X-ray tube excited at 50 kV and 50 mA, four crystals (LiF200, Ge, PET and RX25) were used for the measurement of different wavelength fluorescent Xrays and detection of wavelengths bellow 0.336 nm and above 0.154 nm was achieved using a scintillation counter and a gas flow type proportional counter, respectively. Mineralogical analysis of raw materials was performed by powder diffraction using a SmartLab X-ray diffraction system (Rigaku Industrial Corporation, Japan). Measurements were carried out using a standard copper (Cu) target X-ray tube (40 kV and 40 mA), at a scan rate of 0.02 per five seconds within the 2 - 70 2 range. X-ray diffraction was also used to identify phase transformations that take place upon thermal treatment of kaolin and the long-range order phases present in consolidated bodies. PARTICLE SIZE DISTRIBUTION AND -POTENTIAL Particle size distribution was determined by laser light scattering at two different wavelengths 633 nm (He-Ne) and 470 nm (LED) using a Mastersizer 3000 (Malvern Instruments Ltd., U.K.). The zeta potential () was determined using the microelectrophoresis system incorporated into the Zetasizer Nano ZS (Malvern Instruments Ltd., U.K.). In this equipment, the movement of charged particles in an alternating electric field is determined by the frequency shift between a reference laser beam (He-Ne; =633 nm) and the light scattered by the charged particles (Doppler Effect). Based on the frequency shift, the particles velocity () can be determined. The electrophoretic mobility (E) of the particles can be calculated under consideration of the applied electrical field (E). The E can be converted into with the help of the equation derived by Henry (Eq. 1).

(Eq. 1)

This takes into account the electric permittivity of a vacuum (0), the relative permittivity of the suspension media (r), the viscosity of the suspension () as well as the Henry function (f(a)), with a as the particle radius (i.e. the physical model is valid for spherical particles) and as the DebyeHckel parameter (1/ is the distance at which the Stern potential has fallen to the value 1/e, this value is commonly taken as the double layer thickness). Therefore a measures the ratio of the particle radius to electrical double layer thickness. The Henry function can take values between 1 (Hckel approximation; for a << 1) and 1.5 (Smoluchowski approximation; for a >> 1). For the -3 materials tested (Dv10 > 500 nm) and the fixed ionic strength of 1x10 mol NaCl/l, the Smoluchowski approximation (i.e. f(a)=1.5) is favored since a will be above 50 (the value of a is derived from Dv[4,3]). Diluted suspensions (0.01 wt% solids) pH was modified by addition of 0.1 and 0.01 mol/l solutions of NaOH and HCl. The measured of non-spherical particles is considered only as an indicative value related to the nature of electrostatic interactions among raw materials particles in suspension. Hence it is use to access the electrostatic stability of suspensions in a qualitative manner and to compare the measured data with data reported in cited literature. RHEOLOGY In micromechanics, suspensions (i.e. the dispersion of particles in a liquid medium) are considered as multiphase mixtures and effective material properties are defined for the mixture as a whole. The minimum amount of microstructural information necessary for a suspension is the solid phase effective volume fraction (eff) (Pabst, 2004). When suspended particles are of colloidal size (i.e bellow one micron) thermal motion and surface forces rules over hydrodynamic forces and a random stable distribution of suspended particles can be obtained. Suspension preparation, transport, storage and shaping is based on the study and manipulation of the balance between thermal force, hydrodynamic force and net surface force, which ultimately determines the suspension rheological behavior (Moreno, 2003) (Evans, 2008) (Olga Burgos-Montes, 2009) (R. Benavente, 2011) (Arnaldo J. Milln R. M., 2002) (M. Bostrom, 2006) (Tadros, 2011) (Jan Mewis, Current trends in suspension rheology, 2009) (Zhongwu Zhou, 2001). These three forces are determined by four main parameters: (i) the solids effective volume fraction eff, (ii) the particle shape and size distribution span, (iii) the net balance between them, and (iv) the balance between repulsive and attractive surface forces (Tadros, 2011). In the concentrated suspensions use for shaping ceramic objects, the effective volume fraction (eff) is sufficiently high for many-body interactions to occur and both hydrodynamic and surface forces play a major role in determining the properties of the system. Additionally, the particle-particle distances are comparable to the (effective) particle size and this allows thermal motion and the properties of the system show time dependence. Consequently concentrated suspensions show non-Newtonian flow and their relative (shear) viscosity is a time-dependent complex function of eff (Tadros, 2011). More often that not, concentrated ceramic suspensions display a plastic flow behavior evidenced by the existence of a yield stress and a shear thinning viscosity. When the yield stress is zero, the rheological behavior is clasified as peudoplastic. The simplest description of the rheological behavior of concentrated ceramic suspensions is based on the assumption that surface forces are screened and suspended particles are hard-spheres. In this case the balance between thermal motion and hydrodynamic forces determines the rheology of the suspension (Tadros, 2011). Many attempts to the solution for the hard sphere suspensions have led to numerous (semi) empirical equations for the description of the concentration

dependence of the viscosity. Within which, the most commonly used model is the KriegerDougherty model (Zhongwu Zhou, 2001). However, as mention before particles in suspension tend to form aggregate units under the influence of Van der Waals attraction and each stabilization technique results in a characteristic rheological behavior (Moreno, 2003) (P. Marco J. L., 2009) (Tadros, 2011). The rheological behavior of electrostatically stabilized suspensions is mainly determined by the relative importance of the hydrodynamic force to the net surface force and the relative magnitude of the Debye length (1/) to the mean particle-particle separation (2d), which can be approximated for spherical particles using equations 2 and 3, respectively. In equation 2, I is the ionic strength of the dispersion medium, e is the elementary charge, 0 is the permittivity of free space, w is the dielectric constant of water, k is the Boltzmann constant and T is the absolute temperature. Mentioned relations depend on parameters such as: shear rate (or shear stress), effective particle volume fraction, particle size, zeta potential, and ionic strength (Zhongwu Zhou, 2001) (Tadros, 2011). =

(Eq. 2) (Eq. 3)

In steric stabilized suspensions the repulsive force is relatively hard and short-range. If the adsorbed polymers are short, densely packed and in a good solvent, a steric stabilized suspension can be treated as a hard sphere system by using an effective volume fraction that includes the thickness () of the adsorbed polymer layer (Zhongwu Zhou, 2001) (Tadros, 2011). In the case of electrosteric stabilization rheological behavior depends on a combination of the already mention parameters, noticing that steric mechanisms rule over electrostatic at surface separation distances bellow 2. Equation 4 can be used to approximate the polyelectrolyte length by assuming an ideal freely joint chain. In this equation, M is the molecular weight (average) of the polymer specified by the producer, m is the unit molecular weight and l is the unit length. < > = (Eq. 4)

Independently of the stabilization technique, when particle dimensions are larger than a few micrometers, hydrodynamic forces dominate the rheological behavior and the lack of thermal motion makes it impossible to achieve a random distribution of particles; consequently rheological test results depend on initial conditions and shear history. Additionally, in real systems containing polydisperse non-spherical particles (e.g. ellipsoids, platelets, and other irregular shapes), particleparticle interactions become more complex and packing efficiency is altered (Jan Mewis, Current trends in suspension rheology, 2009) (Zhongwu Zhou, 2001). In non-Newtonian fluids, the apparent (shear) viscosity is defined as the ratio between shear stress and shear rate at a given shear rate. This continuum description for suspensions rheology is a valid approach, as long as suspensions are measured at a macroscopic length scale. This means that the external characteristic length (e.g. the gap between rotor and cup wall) should be much larger than the intrinsic characteristic length of the microscopic heterogeneities (e.g. the size of suspended particles) (Pabst, 2004). Rheological measurements (continium description) can be use to assess the stability of a concentrate ceramic suspension and even to determine particle-particle net surface interaction force. For example: flow curves, in which the shear stress is ploted

versus the shear rate are commonly used to characterize suspension stability. Normally a lower shear stress or shear viscosity is related to better stabilization (target deflocculant addition), because aggregate formation trap a portions of the dispersion medium, leading to higher shear viscosity. Also, one can determine if the net force between particles is repulsive or attractive by measuring the yield stress or the elastic modulus of a suspension. Since an increasing attractive particle-particle interaction consistently raises both properties (Moreno, 2003) (Zhongwu Zhou, 2001) (M. Bostrom, 2006) (J. C. Baird, The effects of added nanoparticles on aqueous kaolinite suspensions II. Rheological effects, 2007). In this work aqueous suspensions with 40 vol% of solids were prepared and homogenized (30 min) using a mechanical mixer (Dispermat D-58580, VMA-GETZMANN GMBH, Germany). Improve suspension homogenization was achieved using a high shear mixer (Silent Crusher M, Heidolph Instruments GmbH & Co, Germany) for three minutes or via high energy milling (Mill 2B, Gabbrielli, Italy) for thirty minutes, these methods are commoly used for homogenization (Santacruz M. I. Nieto, 2003) (J. L. Amors, 2010) (S. Deniel, 2010) (Joao B. Rodriguez Neto R. M., 2007). The rheological behavior of concentrated kaolin suspensions was characterized as a function of deflocculant type and content, quartz content, homogenization technique, pH and graphite content. In this work flow curves were obtained at controlled rate conditions (CR) with a three-stage 1 measuring program with a linear increase of shear rate from 0.1 to 300 s in 180 s, a plateau at 1 -1 300 s for 60 s, and a further decrease to 0.1 s in 180 s. Thixotropy was calculated as the area between the up-curve and the down-curve within the shear -1 rate range 0.1 240 s . Green and Weltmann introduced this hysteresis technique. Which consists in systematically increased and decreased the shear rate between zero and a maximum value. The change can be a continuous ramp (as it was done) or a series of small steps. When the transient data are plotted as shear stress versus shear rate (flow curve), a thixotropic sample will describe a hysteresis loop because the stress will lag behind the shear rate. It should be pointed out that also irreversible changes in the sample could generate a hysteresis loop. Performing the experiment slower will lead to less difference between the ascending and descending curves as the microstructure has more time to come closed to the steady state one (Jan Mewis, Thixotropy, 2009). This is why hysteresis area was taken as a relative measure of suspension thixotropy. Measurements were performed using a magnetic bearing rheometer (AR-G2, TA Instruments Ltd., U.S.) with a vane rotor/cup sensor configuration and setting a 4000 m gap between the rotor and the cup bottom, as specified by the equipment manufacturer. The gap between rotor and the cup wall is 500 m (>50 times the Dv90 of the coarsest powder) ensuring a macroscopic measurement of suspension rheology. A single controlled stress measurement was made to prove the yield stress measured using the control rate program. The three-stage measurement program consists of a linear increase of shear stress from 0.1 to 15 Pa in 120 s, a plateau at 15 Pa for 60 s, and a further decrease to 0.1 Pa in 120 s. MANUFACTURE AND STRUCTURAL CHARACTERIZATION

Ceramics pieces were shaped into tablets (50x50 mm) and cylinders (10 mm diameter) via slip casting onto plaster of Paris surfaces using stainless steel bottomless molds. Green geometrical densities were determined for casted tablets after 48 72 hours room temperature drying. The geometrical density of thermally treated pieces was determined as a function of sintering temperature (1200, 1300 and 1400C) and graphite content (5, 10 and 15 vol%) for a single sintering time of four hours. Microstructure of consolidated pieces was observed in images taken using scanning electron microscope (Jeol JSM-6490LV). Samples were polished using a 6 mm suspension and coated with a thin gold layer to avoid charging during the observation. Secondary electron images were taken at an accelerating voltage of 10 keV. The influence of graphite addition on, open pores fraction, total (close and open) pore size distribution and specific surface area of consolidated pieces were determined via water intrusion, mercury intrusion porosimetry (AutoPore IV 9500 manufactured by Micrometrics Instruments Co.) and gas adsorption (B.E.T analysis), respectively.

RESULTS AND DISCUSSION ELEMENTAL AND MINERALOGICAL CHARACTERIZATION Table 2 present the mass fractions of main elements identified in raw material samples. The diffractogram obtained for the oriented Kaofine sample without thermal treatment (see figure 1a) shows that the material belongs to the kaolin group - Al2Si2O5(OH)4 (PDF 01-078-2109); Furthermore the extensive sample orientation indicated by the high intensity of (001), (002) and (003) reflections confirm non-spherical morphology of the particles and by means of the Scherrer formula using the FWHM of (001) and (002) planes the average crystal thickness calculated was 41 and 43 nm, respectively. Upon thermal treatment at 550C for 2 hours the long range structural order of kaolin is lost and the diffractogram (see figure 1b) shows a minor fraction of anatase-TiO2 (PDF 01-070-7348), this is in agreement with the elemental analysis performed by XRF (see table 2). After thermal treatment of kaolinite clay at 1200C the crystalline phases in the sample is made up of cristobalite- (PDF 01-071-6248), mullite (PDF 01-080-2645) and a minor fraction of titanium dioxide (See figure 3). Crystalline phases identified in MIN-U-SIL 5 and KS 6 samples are -quartz (PDF 01-070-3755) and graphite (PDF 01-089-8487), respectively. As for kaolin, the orientation in the graphite sample confirms its reported non-spherical morphology (Vasily Moraru, 2003). PARTICLE SIZE DISTRIBUTION AND -POTENTIAL Particle size distribution, size span (Dv90-Dv10/Dv50), density and surface area (calculated from measured particle size distributions assuming non-porous spheres) of raw materials are presented in table 3. Kaolin has the largest size span (5) and graphite the lowest (1.5) while silica sand and kaolin mixtures (K-SS) present similar intermediate size spans around 2. Kaolin particle size distribution was measured in deionized water, at natural (6.5) and basic pH (9) and as function of deflocculant content (0.1 1.5 wt% Darvan 811D), showing no difference in obtained particle size distribution. Furthermore, homogenization using either the high shear mixer (3 and 15 min) or the high-energy mill (30 and 60 min) has no relevant effect on particle size distribution of kaolin.

The prediction of stability through zeta potential measurements is common practice. This predictive method can be used to select the pH conditions for the preparation of a stable suspension (Olga Burgos-Montes, 2009). Figure 4 shows the variation of zeta potential of the starting powders in presence of selected deflocculants as a function of pH (3-10). All three powders have a negative zeta potential at pH above 4. In general, 25 mV is considered the minimum zeta potential required to produce electrostatically stabilized suspensions (Joao B. Rodriguez Neto R. M., 2007). Nevertheless, C. Chassagne et. al. indicate that the minimum zeta-potential needed for the electrostatic stabilization of the kaolin suspensions was 40 mV, this value was similar to the values reported by other researchers: 44 mV, using sodium polyacrylate; 40 mV, using sodium carboxymethyl cellulose; and 43 mV, by setting dispersion pH at 10 (C. Chassagne, 2009). Based on the measured -potential, suspension pH should be above five for effective electrostatic stabilization. For kaolin and silica sand the -potential absolute value continuously increases with increasing pH, while for graphite in the presence of PAA a maximum value was measured around pH 6. RHEOLOGY The clay-water system was the first colloidal systems to receive scientific attention. In addition, it was also the first colloidal system use in a manufacture process involving an engineering methodology (Moreno, 2003). The rheological behavior of concentrated clay suspensions is complex, due to a number of factors including: non-spherical morphology, wide particle size span, heterogeneous surface charge distribution and wet state plasticity. Heterogeneous surface charge and plasticity are directly related to their lamellar structure, in which the crystal structure has welldefined sheets interlinked by weak bonds (Santacruz M. I. Nieto, 2003) (Joao B. Rodriguez Neto R. M., 2007) (Bulelwa Ndlovu, 2011). Surface charge cease to be heterogeneous at pH > 8 when aluminum oxide surfaces become negatively charged (Vishal Gupta, 2011). However the adsorption of anionic polyelectrolytes displace the EIP of the aluminum oxide surfaces to lower pH values allowing homogeneous charge distribution at pH values bellow 8. This is evidenced by roughly constant -potential measure for kaolin at pH values above 6 (see figure 4). Different models has been proposed to predict the rheological behavior of concentrated suspensions, in which there is a maximum concentration above which the suspension behaves as a solid (m). According to this concept, a monosized rigid sphere suspensions can be described using the semi empiric relation proposed by Krieger-Dougherty (Moreno, 2003). The equation describing this model is:

(Eq. 5)

However, industrial ceramic suspensions are no composed of uniform spheres, consequently the Krieger-Dougherty model (Eq. 2) should be modified changing the expoential factor ([]m) for a general value n, this exponent indicates how much the particle shape deviates from a sphere and particle size distribution deviates from a single value (Moreno, 2003). The effective volumen fraction (eff) was determined using equation 6. In which, is an approximate polyelectrolyte length -1 determined from equation 4 and the inverse Debye length ( ) was taken as the electrostatic layer thickness. The radius (a) in equation 6 was derive from Dv[4,3] (i.e. the diameter of the equivalent average volume of suspended particles). = +
!!

(Eq. 6)

As a ceramic suspension become more concentrated plastic and viscoelastic behaviors are observed, because the translational and rotational motion of the particles are limited as the particleparticle distance decrease (i.e. excluded volume interactions increase). As a result, rheological properties (yield stress, storage modulus, etc.) increased sharply with the effective volume fraction (C. Chassagne, 2009). The rheological behavior measured for all the silica sand - kaolin suspensions was shear-thinning; this is in agreement with results reported by several authors (P. Marco J. L., 2009) (Joao B. Rodriguez Neto R. M., 2008) (C. Chassagne, 2009) (Jos Luis Amors, 2010). Plastic behavior has been reported for kaolin concentrated suspensions. According to the authors the plastic behavior is characteristic of dense dispersions of plate shaped colloidal particles, which are well stabilized by electrostatic repulsion (C. Chassagne, 2009) (Jos Luis Amors, 2010). Though, the rheological measurement performed using a control stress program indicates that the suspension composed entirely of kaolin has a pseudoplastic behavior (see figure 5) and that the yield stress showed in control rate measurements is an apparent value. Joao B. Rodriguez and Rodrigo Moreno showed that suspensions prepared from mixtures of kaolin, alumina and talc also exhibit an apparent yield stress (Joao B. Rodriguez Neto R. M., 2008). Since pure kaolin suspensions show the higher apparent yield stress in control rate measurements, it is assumed that suspensions of kaolin-silica sand mixtures are also pseudoplastic. This assumption is in agreement with previously reported findings for kaolin-quartz-feldspar concentrated (around 40 vol%) suspensions (M. C. Almandoz J. M., 2004). Rheological studies were first performed using a variety of commercial deflocculants in order to select that one leading to lower shear stress and thixotropy of the suspension. In general, it is indicated that electrosteric deflocculants provide a more homogenous dispersion of kaolin particles in suspension than electrostatic deflocculants (Mustafa Salih Eygi, 2008) (P. Marco J. L., 2009). In this work the addition of electrostatic defloculants (HMF-Na and Giessfix) lead to suspensions of lower viscosity when compared with electrosteric defloculants (see figure 6); Giessfix 162 outperforms Na-HMF. Nevertheless, electrostatic deflocculants induce the aggregation of nanoparticles in suspension. Since the final goal of the ongoing research is to add hematite nanoparticles to the raw materials suspension in order to modify the surface properties of the porous ceramic, this type of deflocculants will not be further studied. Within the tested electrosteric deflocculants Dolapix PC67 and Darvan 811D produce concentrated kaolin suspensions with analogous rheological behavior, when added at 0.25 wt% of the solids content (see table 4), and superior to those obtained with Dolapix PCN. Hence the effect of deflocculant content will be assessed for both. A higher deflocculant content (range 0.05 1 wt%) produce suspensions of higher viscosity, in comparison variation in tixotrophy is not relevant within this range. The lowest viscosity was measured for suspensions containing 0.05 wt% of Dolapix PC67 (see tables 5 and 6). Reported deflocculant contents related to an optimum rheological behavior of concentrated claybased suspensions commonly rages from 0.1 to 1.5wt% of the solids content on dry basis. In contrast, the adsorbed polyelectrolyte fractions reported by P. Marco et. al. for concentrated kaolin suspensions range between 0,07 and 0.02 wt% of the solids content, this results are in agreement with the deflocculant addition level leading the best rheological behavior measured in this work. Furthermore, it was stated that the high adsorption limit was related to the strong interaction between carboxyl groups and kaolin particles (P. Marco J. L., 2009). Which is the functional group of polycarboxilic acid.

As in the case of kaolin the addition of 0.25 wt% of Dolapix PC67 and Darvan 811D produce concentrated silica sand suspension with analogous rheological properties. Flow curves measured for 40 vol% silica sand suspensions as a function of Dolapix PC67 addition are presented in figure 9. The lowest viscosity within the tested range was measured for suspension containing 0.1 wt% of deflocculant. Viscosity decreases as deflocculant content was reduced; in comparison variation in tixotropy follows the opposite trend (see table 7), hence lower deflocculant addition levels where not tested. The deflocculant content for suspensions containing kaolin and silica sand was set by unification of the rheological behavior of pure kaolin and silica sand suspensions (40 vol%) at the -1 maximum shear rate (300 s ). This unification takes place at deflocculant contents of 0.05 (0.1) wt% and 0.1 (0.25) wt% for kaolin and silica sand, respectively (see table 6 and 7). Figure 10 show the flow curves of kaolin - silica sand mixtures. From this figure is clear that silica sand addition -1 effectively reduces shear stress at shear rates below 10 s when compared to the pure kaolin suspension. The effect of silica sand addition was not studied for the lowest deflocculant contents (i.e. 0.05 wt% for kaolin and 0.1 wt% for silica sand) due to the probability to increase the suspended powder surface area by the grinding effect of hard silica particles over soft clay particles during mechanical mixing. For clay-based suspensions (kaolin, feldspar and quartz) the maximum packing factor is around 0.6 and the exponential factor n is close to 4, this value implies the presence of nonspherical particles of multiple sizes (Moreno, 2003) (Joao B. Rodriguez Neto R. M., 2008). Since -1 particles in suspension are relatively large, hydrodynamic forces should dominate at high (300 s ) -1 and low (3 s ) shear rates, this is supported by the Peclet number (Pe=/th - the radius to -1 determine the thermal stress is derived from Dv[4,3]) at 3s taking values above 400. The maximum packing fraction was assumed to be 0.6 in order to compare the exponent n of prepared mixtures. This exponent ranges from 4.7 for pure kaolin to 3 for pure silica sand (at low shear rate -1 3s ) Indicating that additions of silica sand reduce the shear stress and viscosity by decreasing the shape factor of suspended particles, these changes in rheological behavior can not be related to the narrower size span, since this lowers the packing efficiency, increasing shear stress and -1 viscosity for a given volume fraction. However the fact that for the high shear rate (300 s ) the n exponent has a value around 2.5 for pure kaolin and silica sand suspensions, compromises the validity of the previous statement (see table 8). The lowest viscosity and thixotropy within the tested range was measured for the suspension composed of 30 wt% kaolin and 70 wt% silica sand with 0.085 wt% of Dolapix PC67 (see table 8). Therefore, the effect of enhanced homogenization using the high shear mixer and the high-energy mill will be studied in this suspension alone.

As mention before milling and high shear mixing has no significant effects on size distribution. However, Peclet number is reduced from 900 to 600 and 400 upon high shear mixing and high energy milling, respectively. When compare to the suspension prepare by mechanical helix mixer alone. This increase indicates a larger influence of thermal stress in relation to the measured shear stress, which is related to size reduction. The observed reduction in shear stress can be related to a reduction of the shape factor, which is supported by the reduction in the exponent n calculated for a maximum packing fraction of 0.6 at a given shear rate (see table 10). The lowest suspension shear stress was measured after 30 min of high energy milling at the natural suspension pH (see tables 9 and 10 and figures 11 and 12). The increase of pH has no positive effects on the suspension rheological behavior, as evidenced in figure 12 and table 10. The milling procedure has three main drawbacks when compared to high shear mixing, namely: (i) it requires minimum twice the amount of suspension, (ii) it requires a longer time, and (iii) solids particles in suspension are lost during the process due to electrostatic attraction between negatively charge kaolin and silica sand particles to positively charged alumina grinding elements and jar walls; though no changes in suspension density were measured. In view of the mentioned issues it was decided to use high shear mixing in further experiments. In electrostercally stabilized systems composed of relatively large non-spherical particles as the ones tested, complex hydrodynamic forces and surface forces (electrostatic and steric) generated by added deflocculats determine rheological behavior. A way to improve the rheological behavior (i.e. reduce shear stress and thixotropy) at low shear rates is to add silica sand particles with a lower shape factor than kaolin. The best rheological behavior for the more efficient (faster and less material demand) suspension preparation method was obtained for the suspension prepared by combine mechanical helix and high shear mixing adding 0.085 wt% of Dolapix PC 67 for a mixture of 30 wt% of kaolin and 70 wt% of silica sand at the natural suspension pH. It is concluded that the main parameter controlling the rheology of the suspensions was the shape of suspended particles. Graphite suspensions with 14 vol% of solids were stabilized using polyacrylic acid (polycarboxilic acid) with a molecular weight of 50000 and setting the pH value around 6 by addition of a NaOH solution (5 mol/l). The preparation of graphite suspensions at 14 vol% of solids was not possible using either Dolapix PC 67 (polycarboxilic acid, sodium salt @ 0.85 wt%) or Darvan C-N (ammonium polyacrylate @ 0.75 wt%). The calculated PAA length is roughly 16 nm and addition of 0.1 ml NaOH solution required to rise the solution pH to around 6 (5 mol/l) give an extension of the double layer of around 4 nm, the effective radius of suspended particles will be increased by approximately 20 nm, in a similar way the extension of the double layer when dolapix PC 67 is used is around 4 nm and the polymer length (assuming a MW of 10000 g/mol) is roughly 3 nm, however both formulations have a similar effect on the effective volume due to the relatively large size of suspended graphite particles, although the main stabilization mechanism is different, indicating that the steric component plays a mayor role in the reparation of graphite suspensions. While, potential of graphite reach maximum at pH 6 the absolute value remains over 50 mV until pH 11, this indicative value can be considered high enough to provide effective electrostatic stabilization. Until know there is no satisfactory explanation why carboxylic acid (PAA) + NaOH allows the preparation of 14 and 16 vol% graphite suspensions and carboxylic acid sodium salt do not.

Figure 13 show flow curves measured for graphite suspensions with 14 vol% of solids, minimum viscosity and tixotropy was measured for graphite suspension with 0.85 wt% of PAA, as can be seen in table 11. Using the shear viscosity at 300 s-1 for samples with 14 and 16 vol% of solids the maximum packing fraction (m) value calculated (using the modified Krieger-Dougherty relation) was in the order of 0.2, this gave an exponent n around 3 at low shear rate (3s-1) and a variation between 2.7-2.1 at high shear rate (300s-1) depending on polyelectrolyte addition for samples with 14 vol% of solids (see table 11). The low maximum packing fraction of graphite compare to that of kaolin can be related to its narrower particle size distribution and its larger shape factor, reflected by a value of the intrinsic viscosity ([]=n/m) in the order of 15. The shape of the hysteresis loops in most kaolin and kaolin-silica sand suspensions, indicates a lag in shear stress with respect to share rate. This is supported by fact that kaolin suspensions show an analogous flow curve upon replication of CR measurements, ruling out irreversible structural changes. In graphite suspensions shear induces a structure formation and the hysteresis loop take different shapes depending on deflocculant addition level. The increasing addition of graphite to the kaolin-silica sand suspension consistently rises shear stress, in comparison a markedly increase in thixotropy was only measured for the kaolin silica sand suspension with 15 vol% of graphite (see figure 14 and table 12). MANUFACTURE AND STRUCTURAL CHARACTERIZATION Tablets produced from pure kaolin slips show a casting texture and a high density of macro defects (see figure 15). These casting defects are not correct by altering the rheological behavior of the suspension via type of deflocculant or content, neither via pH rise or enhance slip homogenization by high energy milling and high shear mixing. Only the additions of hard silica sand particles prove to be an effective alternative to solve this problem. Figures 16-18 show that macro size defects are no longer observed in pieces casted using the slip containing 70 wt% of silica sand. This improvement in green body quality is related to the effective reduction of suspension shear stress -1 within the shear rate range characteristic of the shaping process (<10 s ), the faster casting kinetics (see figure 19) of silica sand containing suspensions and the inhibition of extensive orientation of clay particles during phase separation. The casting rate obtained for pure kaolin suspension was in the order of 0.15 mm /min for suspensions prepared using either electrostatic or electrosteric defloculants with evidently different rheological behavior (see table 13), in contrast upon addition of silica sand the casting rate was 2 increased to 0.7 mm /min. Mustafa Salih reported casting rates for kaolin suspensions between 1.4 2 0.6 mm /min; the maximum casting rates were reached with the addition of sodium silicate while the addition of sodium polyacrylate allow the minimum casting rates. Intermediate casting rates were obtained for suspensions prepared using Dolapix G-6 (Polycarboxylic acid, sodium salt) and Dolapix SPC-7 (silicate-polycarbonate) (Mustafa Salih Eygi, 2008). The high casting rate limits were obtain for kaolin powders with a particle size span of 12.6 (Dv90=16,51 Dv50=1,27 and Dv10=0,47), while the low limit casting rate was obtain with kaolin with a lower particle size span of 7.3 (Dv90=12,42 Dv50=1,64 and Dv10=0,50) (Mustafa Salih Eygi, 2008). In contrast, in this work the opposite behavior was observed, i.e. the higher casting rate was obtained for a narrower particle size distribution. This is because a smaller span in particle size is related to lower packing efficiency, hence to a more permeable casted body. Consequently it can be concluded that improve casting kinetics are related to both, smaller particle size distribution span and reduce viscosity at shear rates characteristic of the slip casting process.
2

The relative green densities of dry slip cast tablets shaped from suspensions prepare using the mechanical helix mixer were around 0.6 of the theoretical raw material mixture density (2,645 g/cm3), upon enhanced homogenization relative green densities were increased to 0.65, as in the case of rheological behavior pH rise show no improvement of green density (see table 14). The additions of graphite reduce back the relative green density to levels around 0.6. Obtained green density values are among the values reported in literature 0.6 - 0.7 (Joao B. Rodriguez Neto R. M., 2007) (Joao B. Rodriguez Neto R. M., 2008) (Moreno, 2003). Thermal characterization of kaolin as reported in literature reveals a specific water loss at 130 C, followed by a loss of structural hydroxyl groups at 530 C due to the transformation of kaolinite to metakaolinite, the formation of a pre-mullite due to the transformation of metakaolinite at temperatures from 900 to 1000 C and the formation of thermodynamically stable mullite phase at temperatures above 1050 C. (D. Vasanth G. P., Fabrication and properties of low cost ceramic microfiltration membranes for separation of oil and bacteria from its solution, 2011). Mullite crystallization depends on the used clay minerals and on interaction with other components. Using kaolinite, the solid-state reaction ensures slow crystallization and growth of crystals. The shape of mullite crystals is always elongated. While small (1050 nm) rod-like crystals form at lowest temperatures, larger (315 m) acicular crystals are generally observed at highest temperature ranges (S. Deniel, 2010). Quartz (grain size and content) has relevant effects on the mechanical properties of dense and porous bodies. For dense bodies, with abundant glassy phase and low porosity, the principal factor influencing strength is considered to be quartz particle size. This effect is basically caused by two simultaneously acting mechanisms related to the difference between the coefficients of thermal expansion of the quartz and of the glassy matrix: on one hand, the difference in thermal expansion between both materials has a strengthening effect, by subjecting the glassy matrix to local residual compressive stress; on the other, the magnitude of the stress can produce cracks around quartz particles when quartz particle size exceeds a critical size, thereby causing partial stress relaxation and increasing microstructural damage. This microstructural damage adversely affects the final product mechanical properties. In porous bodies, whose microstructure and composition differ from those of dense bodies (higher porosity and smaller glassy phase content), the foregoing two mechanisms also need to be considered (J. L. Amors, 2010). Though, the second would have a more relevant effect on the mechanical strength of the fired-clay porous object. Because, the sudden volumetric shrinkage of quartz (2%) during transition from to at 573C during cooling break particle-particle contacts created during sintering. The results obtained by J. L. Amors et. al. indicate that the fired properties of porous fired-clay tiles may be considerably enhanced, while holding low shrinkage and high porosity, by reducing quartz particle size to Dv90 < 1015 m (J. L. Amors, 2010). Green pieces were thermally treated following the program shown in figure 20. Samples are heated slowly to allow water elimination, quartz phase transformation and graphite elimination to take place in a smooth fashion, in addition cooling from the sintering temperature to 575C was controlled and this temperature was hold for 2 hours to allow temperature homogenization within the entire body to minimize crack formation by promoting the quartz phase transformation (shrinkage) to occur simultaneusly within the entire ceramic body. Three different sintering temperatures were apply 1200, 1300 and 1400C, while heating rate and holding times were set to 2C/min and 4 hours, respectively.

Due to the lack of a flux phase (i.e. feldspar) in the raw material mixture there is no densification and the relative amount of open pores is high at the tested temperature range. Formation of particle-particle contacts only takes place via solid state diffusion, aided at temperatures below 1200C by the release of short range order silica during mullite formation. No increase in relative density (density of the thermally treated kaolin-silica sand mixture is 2.69 gr/cm3) was observed with rising sintering temperature, similar observations have been reported for porous fired-clay ceramics (J. L. Amors, 2010). In contrast the rise of mechanical strength was evident between pieces sintered at 1200C and those sintered at 1300 and 1400C, This observation is related to both the higher green density and sintering temperature. Furthermore it is evidenced by the increase in particle-particle contact area showed en figures 21 - 23. The relative amount of open pores in sintered bodies with out graphite addition consistently decreases as the sintering temperature rises from around 0.92 at 1200C to 0.76 at 1400C. Total and open porosity values measured (see table 14) are comparable to those reported for fired clay porous bodies. For example M. C. Almadoz et. al. obtained total porosities of 0.45 and 0.35 from slips with average particles sizes of 2.5 and 1 m, respectively and J. L. Amors et. al. obtained porous ceramics with total porosity (determined from bulk density) within 0.32 - 0.36 and open porosity (determined from water intrusion) within 0.29 - 0.34 (M. C. Almandoz, 2004) (J. L. Amors, 2010). Since the final objective of the present work is to obtain porous bodies with high permeability. Additions of graphite were used to increase porosity (compare figure 22 with figures 24-26). The rise in total porosity is proportional to the addition of graphite, and congruent with those obtained by Jilali Bentama et. al. using carbon additions between 5 and 20 wt% (Jilali Bentama, 2002). In contrast, no changes in the total open porosity were measured between sample sintered at 1300C containing 10 and 15 vol% of graphite. Thermally treated samples exhibit noticeable bending; the geometric distortion observed increases when graphite is added and indicates that the bottom part of the tablet experienced a larger volumetric change. Since slip-casting (phase separation) kinetics is gradually reduced upon wall formation the initial layers form faster and with lower density, this phenomenon is inherent to the process and is related to green pieces bending during thermal treatment. Porosity decreases continuously when the sintering time or temperature is raised. For a given sintering time or temperature, porosities are roughly the same for different average particle sizes, when the green density is comparable (P. Maarten Biesheuvel, 1999) (D. Vasanth G. P., Fabrication and properties of low cost ceramic microfiltration membranes for separation of oil and bacteria from its solution, 2011), In contrast average particle size determines the size of open pores (L. Palacio P. P.) and increasing sintering induces appreciable inhomogeneous particle and void growth that results in the formation of larger pores (flaws) and wider pore size distribution in the final product (P. Maarten Biesheuvel, 1999) (J. L. Amors, 2010) (Somen Jana M. K., 2010) (L. Palacio P. P.) (D. Vasanth G. P., Fabrication and properties of low cost ceramic microfiltration membranes for separation of oil and bacteria from its solution, 2011). Consequently, a controlled thermal treatment allows to control the mechanical resistance and pore structure of the sintered bodies.. Secondary electron images of polished samples show that manufactured pieces have highly irregular surface, low density of defects and elongated pores of sizes bellow 10 m.

TABLES

Table 1: Characteristics of tested deflocculants.

Table 2: Mass fractions of main elements identified in raw materials samples.

Material Kaolin Silica Sand Graphite Element Si 0,425 >0,99 0,009 Al 0,446 <0,01 0,001 Fe 0,008 <0,001 0,007 Mn <0,001 Mg 0,001 Ti 0,022 <0,001 <0,001 Cr <0,001 Ca 0,009 0,009 Na K P 0,005 Balance Water N/A Carbon

Table 3: Particle size distribution of raw materials

Table 4: Rheological data obtained for 40 vol% kaolin suspension stabilized with different deflocculants at 0.25 wt% of the solids content.

Table 5: Rheological data obtained for 40 vol% kaolin suspension stabilized with Darvan 811D.
Material Solids cont. vol% Deflocculant Defloculant cont. wt% 0,05 0,1 0,25 Darvan 811D 0,5 0,75 1 Viscosity @ 3 s-1 mPa*s 164 174 740 1390 2128 3018 Viscosity @ 300 s-1 mPa*s 15 15 26 37 50 66 Stress @ 300 s-1 Pa 4,5 4,5 7,9 11 14,9 19,7 A @ 0.1-240 s-1 Pa/s 133 127 133 134 132 134

Kaolin

40

Table 6: Rheological data obtained for 40 vol% kaolin suspension stabilized with Dolapix PC 67.
Material Solids cont. vol% Defloculant cont. wt% 0,05 0,1 0,25 Dolapix PC67 0,5 0,75 1 Deflocculant Viscosity @ 3 s-1 mPa*s 119 207 737 1798 2997 4028 Viscosity @ 300 s-1 mPa*s 14 16 26 45 66 86 Stress @ 300 s-1 Pa 4,1 4,7 7,8 13,5 19,9 25,8 A @ 0.1-240 s-1 Pa/s 127 126 129 141 154 126

Kaolin

40

Table 7: Rheological data obtained for 40 vol% silica sand suspensions stabilized with Dolapix PC 67.

Table 8: Rheological data obtained for 40 vol% silica sand - kaolin suspensions stabilized with Dolapix PC 67.

Table 9: Rheological data obtained for 40 vol% silica sand - kaolin suspensions after high energy milling and high shear mixing

Table 10: Rheological data obtained for 40 vol% silica sand - kaolin suspensions after pH modification.
Material Solids cont. vol% 40 Defloculant cont. Viscosity @ 3 s-1 Viscosity @ 300 s-1 Stress @ 300 s-1 A @ 0.1-240 s-1 wt% mPa*s mPa*s Pa Pa/s 18 10 3,1 124 20 10 3,1 124 Dolapix PC67 0,085 23 11 3,2 125 27 11 3,3 123 Deflocculant pH 6,5 7,5 9 10

K30-SS72-HEM

Table 11: Rheological data obtained for 14 vol% graphite suspension for different deflocculant contents.

Table 12: Rheological data of suspensions with different graphite contents.

Solids cont. Defloculant cont. Viscosity @ 3 s-1 Viscosity @ 300 s-1 Stress @ 300 s-1 A @ 0.1-240 s-1 Deflocculant vol% wt% mPa*s mPa*s Pa Pa/s 0 vol% Graphite - HSM 40 Dolapix PC67 0,085 23 12 3,7 125 5 vol% Graphite - HSM 46 16 4,8 123 Dolapix PC67 10 vol% Graphite - HSM 40 0,085 - 0,85 77 20 6 123 - PAA 15 vol% Graphite - HSM 171 30 8,9 226 Material

Table 13: Rheological characteristics of the slips used for casting kinetics determination

Table 14: Properties of green and sintered bodies

Sintering T. (C) RD - green body 1200 1300 1400 0,61 0,65 0,60 0,61 0,58 0,66 HSM (min) 0 3 3 3 3 3 RD - Sintered body 0,60 0,64 0,57 0,53 0,48 0,63 Total porosity 0,40 0,36 0,43 0,47 0,52 0,37 Total open porosity 0,37 0,31 0,37 0,40 0,40 0,28 Graphite (vol%) 0 0 5 10 15 0

FIGURES

Figure1: (a) Diffractogram of the oriented kaolin sample without thermal treatment. The identified long-range order phase was kaolinite (K). (b) Diffractogram of the oriented kaolin sample after thermal treatment at 500C for two hours. After lost of long-range order of kaolinite, the anatase phase of titania (T) was identified. (c) Diffractogram of non-oriented kaolin sample after thermal treatment at 1200 C for two hours. The crystallographic phases identified were, mullite (M), cristobalite (C) and titania (T).

Figure 2: Diffractogram of silica sand sample. The identified long-range order phase was quartz (Q).

Figure 3: Diffractogram of oriented KS-6 sample. The identified long-range order phase was graphite (G).

Figure 4: (a) Variation of z-potential as function of pH for the raw materials used under the conditions used for the preparation of suspensions. (b), (c) and (d) Variation of z-potential as a function of pH with and without deflocculants for the raw materials used.

Figure 5: Comparison between flow curves obtained from controlled rate and controlled stress for suspensions composed entirely of kaolin.

Figure 6: Deflocculation curves of 40 vol% kaolin suspensions

Figure 7: Flow curves of 40 vol% kaolin suspension stabilized with Darvan 811D.

Figure 8: Flow curves of 40 vol% kaolin suspension stabilized with Dolaix PC 67.

Figure 9: Flow curves of 40 vol% silica sand and silica sand - kaolin suspension stabilized with Dolaix PC 67.

Figure 10: Flow curves of 40 vol% silica sand - kaolin suspension stabilized with Dolaix PC 67.

Figure 11: Effect of high-energy milling and high shear mixing in flow curves of 40 vol% silica sand kaolin suspensions.

Figure 12: Effect of pH in flow curves of 40 vol% silica sand - kaolin suspensions.

Figure 13: Flow curves of graphite suspensions with 14 vol% of solids.

Figure 14: Flow curves of kaolin silica sand suspension with different contents of graphite.

Figure 15: Fracture surface kaolin 100 wt%

Figure 16: Fracture surface kaolin 70wt% silica sand 30wt%

Figure 17: Fracture surface kaolin 50wt% silica sand 50wt%

Figure 18: Fracture surface kaolin 30wt% silica sand 70wt%

Figure 19: Casting kinetics

Figure 20: Thermal treatment

Figure 21: Piece sintered at 1200C with out graphite additon.

Figure 22: Piece sintered at 1300C with out graphite additon.

Figure 23: Piece sintered at 1400C with out graphite additon.

Figure 24: Piece sintered at 1300C with 5 vol% graphite additon.

Figure 25: Piece sintered at 1300C with 10 vol% graphite additon.

Figure 26: Piece sintered at 1300C with 15 vol% graphite additon.

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