Process Engineering

The Physics of Selecting Ball Clays

Introduction
The art of doing Physics requires the ability to describe a scientific problem in such a way that useful, quantitative predictions may be made, ideally by using as simple a mathematical form as possible. Indeed many of the principal physical laws are striking in their simplicity, such as: kinetic energy = mv2, radiative power of a black body = T4, and so on. Furthermore, a physical law is to be regarded as being of general validity within a particular, well defined area of application. What could Physics possibly have to do with ball clays, which are renowned for their awkwardness and variability? Furthermore, is it worthwhile to attempt a general, physical description of ball clays? The answer is yes, because a general, physically based approach has the potential of delivering ball clays with improved consistency in their ceramic properties, whilst also reducing the quality control overhead. A challenge to the development of a Physics of Selecting Ball Clays is presented by the way in which many clay mining companies successfully supply hundreds of thousands of tonnes of consistent raw materials annually. The technique of blending is generally used to attain this level of invariance. This, in itself, suggests that individual ball clay seams can be impressively consistent in their ceramic properties. Furthermore, experience shows that, at least on a limited scale, blends of several raw clays may be used to substitute other, individual ball clay seams in short supply. In general, mining companies exploit their experience of the raw materials, backed up by ceramic and quality control tests. However, these tests alone generally fall short of a complete physical description. The challenge is therefore to identify a physical approach that will mirror the successful, existing practices of mining operations. If successful, it will also point to deficiencies in operating practices and be
1 Dr.

Noel W. Thomas1 Fachhochschule Koblenz D-56203 HhrGrenzhausen, thomas@fhkoblenz.de

capable of extension to further clay systems.

Approaches to the Global Characterisation of Ball Clays

Clarity of purpose is required here, since the objective is not to characterise an individual ball clay fully, but rather to compare different ball clays within a global, quantitative framework.

Chemistry
The technique of X-ray fluorescence (XRF) is readily able to give quantitatively reliable information on the chemical composition of a given ball clay. In general, the concentrations of eight oxides are monitored, i.e. SiO2, TiO2, Al2O3, Fe2O3, CaO, MgO, K2O and Na2O. Attention is also generally paid to the loss-on-ignition of a ball clay, this being symptomatic of the types of clay minerals present and their concentrations, as well as reflecting the presence of hydrocarbons. The power of this technique lies in the quantitatively exact information provided. The problem is, however, that this information is not directly linked to the ceramic properties of the clay, since the distribution of these oxides over the minerals present is not known. In order to attempt a link-up with ceramic properties, it follows that a consideration of the mineralogy of ball clays is necessary.

Clay Mineralogy
Most ceramists who have looked into texts on clay mineralogy will have formed the view that clay mineralogy is a difficult subject. Also likely is the view that the seemingly large variability in the ceramic properties of ball clays must, in some way, be a result of changes in this underlying, complex mineralogy. Following this argument through, the key to success in selecting ball clays would be to develop an improved analytical description of the clay

mineralogy. An alternative approach would be to focus on clay rheology, rather than mineralogy, but the central belief would be similar: only careful, sometimes long-winded analysis would provide any hope of selecting ball clays by a scientific method. Clay mineralogy doesnt have to be difficult! The key to making it simpler is to concentrate on the similarities between clay minerals, rather than their differences. What general statements can be made about all clay minerals, in particular their structures? a) They are a sub-class of aluminosilicate minerals b) They form two-dimensional atomic framework structures, socalled layered structures, in which the frameworks are either 2:1 or 1:1 in nature c) The frameworks themselves contain Si, Al, Fe and Mg cations d) Ca, K and Na ions occupy sites in the minerals in between the layers. Ti ions tend not to form aluminosilicate minerals. Fortunately much of clay mineralogy can be understood in terms of two elementary physical attributes of the ions present, i.e. charge and radius. The first of these allows the condition of charge neutrality to be applied, in order to limit which clay minerals can exist for a given, chemical composition of a clay. The following charges are generally applied in an ionic model: Si4+, Ti4+, Al3+, Fe3+, Ca2+, Mg2+, K+, Na+. The only controversial choice here is that of Fe, which also commonly exists in oxidation state +2. The second attribute, that of ionic radius, has wide-reaching consequences: Si4+ exists only in four-fold coordination, i.e. in SiO44- tetrahedra; Mg2+ exists only in six-fold coordination, i.e. as MgO6-x(OH)x-10+x octahedra, whereas Al3+ can exist in either four- or sixfold coordination. This seemingly maverick behaviour of aluminium is routinely exploited by nature in aluminosilicate minerals, in order to accommodate Ca2+,

Noel Thomas has been Professor of Mineralogy and Functional Ceramics at Koblenz University of Applied Sciences since October 2006 and was previously Principal Scientist of WBB Technology, latterly WBB Minerals. 2 A splitting of the atom is not required here! The presence of two aluminium ions in tetrahedral coordination is accompanied by the presence of one calcium ion.

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K+ and Na+ ions. In many minerals, for example feldspars, nephelines, micas and clay minerals, the presence of each aluminium ion in fourfold coordination is accompanied by the presence either of an alkali ion (K+,Na+) or of half an alkaline earth ion (Ca2+).2 Otherwise the aluminium ion would be present in six-fold coordination. All the Ca2+, K+ and Na+ ions, whose concentrations have been quantitatively determined by XRF, must be accommodated in electrically neutral aluminosilicate minerals. This requirement enables an exact calculation of the relative numbers of aluminium ions in tetrahedral (fourfold) and octahedral (six-fold) coordination. How are the atoms put together in ball clays? A helpful approach, which is of general validity, is to consider just two building blocks, tetrahedra and polyhedra (Fig. 1). The molar concentrations of tetrahedral and octahedral building blocks, i.e. [tet]total and [oct]total, are known from the following two equations. [tet]total = [Si4+] + [Al3+]IV [oct]total = [Mg2+] + [Al3+]VI (1) (2) sent in a given ball clay. The blueprints for constructing these minerals are given in Fig. 2. 1:1 clay minerals are so called because they consist of one tetrahedral atomic layer followed by one octahedral atomic layer in open sandwich structure. 2:1 clay minerals, by comparison, are made up of a tet-oct-tet closed sandwich sequence, in which there are twice as many tetrahedral as octahedral units. The power of this reduction lies in its generality. 1:1 clay minerals encompass kaolinites, fireclays and halloysites. 2:1 clay minerals encompass illites, smectites, illite-smectite mixed layer minerals, chlorites (with appropriate treatment) and dioctahedral mica minerals. 1:0 minerals are not clay minerals, but encompass quartz, feldspars and feldspathoids. They are made up of tetrahedra alone, which share corners with one another. By counting the numbers of tetrahedral and octahedral building blocks in Fig. 2, the 1:1, 2:1 and 1:0 minerals can be represented as follows: 2:1 tet4oct2 ; 1:1 tet2 oct2; 1:0: tet. Accordingly, the following numberbalance equations can be written. [tet]total = 4[2:1] + 2[1:1] + [1:0] (5) [oct]total = 2[2:1] + 2[1:1] (6)

The square brackets signify molar concentrations and the Roman superscripts IV and VI tetrahedral and octahedral coordination, respectively. The division of aluminium ions between [Al3+]IV and [Al3+]VI is calculated by means of the following two equations. [Al3+]IV = [K+] + [Na+] + 2[Ca2+] [Mg2+] (3) [Al3+]VI = [Al3+]total - [Al3+]IV (4)

Fig. 1 The building blocks of clay minerals. (a) MO4n- tetrahedra; (b) MO2(OH)4p- octahedra; (c) MO4(OH)2q- octahedra. Metal ions M are located within the polyhedra. Oxygen ions are drawn in red and the hydrogen atoms of hydroxide ions in white.

Fig. 2 The three relevant classes of minerals seen from the viewpoint of tetrahedral and octahedral building blocks. (a) 1:1 clay minerals (here in kaolinite); (b) 2:1 clay minerals (here in illite); (c) 1:0 minerals (here in a feldspar). The blue spheres represent metal ions K+, Na+ or Ca2+ Tab. 1 Method of derivation of [tet]total and [oct]total for a representative ball clay.
[%] SiO2 Experimental results [mass-%]: Oxide molar masses [g] Cation stoichiometry Molar ion concentrations Fraction in aluminosilicates Effective molar ion concentrations RESULTS OF ANALYSIS [Al3+]IV (by equation (3)) [Al3+]VI (by equation (4)) [tet]total (by equation (1)) [oct]total (by equation (2)) 60,32 60,084 1 [Si4+] 1,0039 1,0 1,0039

Magnesium ions enter equation (3) with a coefficient of -1, since their presence in the octahedral sites of clay minerals, for example in smectites and illites, consumes alkali and alkaline earth ions, leaving fewer left for the formation of [Al3+]IV. The iron ions present in a ball clay give rise to a small difficulty, since they can be accommodated either in the aluminosilicate or in the non-aluminosilicate fraction. Furthermore, their influence on structure will depend on oxidation state: an Fe2+ ion will behave similarly to an Mg2+ ion, whereas an Fe3+ ion will resemble an Al3+ ion. This implies that a pragmatic approach would be to treat iron ions as virtual magnesium and/or virtual aluminium ions, depending on the type of ball clay under consideration. In so far as this analysis is concerned, the sole purpose of XRF is to inform us how many tetrahedral building blocks, [tet]total and octahedral building blocks, [oct]total, we have at our disposal when constructing a model of the aluminosilicate minerals pre[%] Al2O3 25,87 101,961 2 [Al3+] 0,5074 1,0 0,5135 [%] Fe2O3 0,97 159,677 2 [Fe3+] 0,0122 0,5

Here [2:1], [1:1] and [1:0] signify molar concentrations of 2:1, 1:1 and 1:0 minerals, respectively. Thus we have just two equations linking three unknowns. In order to provide a third equation, we may now consider the framework water associated with 1:1 and 2:1 clay minerals, as shown in Fig. 1. 1:1 clay minerals are associated with MO2(OH)4p- octahedra and 2:1 clay minerals with MO4(OH)2q- octahedra. Since the dehydroxylation reaction that takes place during the thermal decomposition of a ball clay can
[%] K2O [%] Na2O 3,18 94,195 2 [K+] 0,0676 1,0 0,0676 0,19 61,979 2 [Na+] 0,0063 1,0 0,0063 [%] LOI 7,38 18,015 1 [H2O] 0,4097 1,0 0,4097

[%] TiO2 1,35 79,898 1 [Ti4+] 0,0169 0,0

[%] CaO [%] MgO 0,20 56,079 1 [Ca2+] 0,0036 1,0 0,0036 0,53 40,304 1 [Mg2+] 0,0131 1,0 0,0131

0,0681 0,4454 1,0720 0,4585

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be represented as 2OH- O2- + H2O, one water molecule is associated with two OH- ions. Furthermore, each OH- ion is shared by two octahedra in the structures. Accordingly, 1:1 minerals have one H2O molecule per octahedral building block and 2:1 minerals just one half. Herein lies the third equation: [H2O]framework = [2:1] + 2[1:1] (7) the contribution of hydrocarbons to the loss-on-ignition. A further constraint can be used to find a reliable solution, indeed by a method that is more robust than the explicit use of framework water concentration. This is to consider the structures of the 2:1 layer minerals in a ball clay. These are characterised not just by their framework structures but also by the presence of interlayer cations, K+, Na+ and Ca2+, which are located between the 2:1 units. The degree of occupancy, or loading, of these sites by these ions varies significantly between different types of 2:1 layer minerals. Since these sites are generally fully occupied in mica minerals containing alkali ions, a site loading-factor, fL, equal to one may be assigned to them. The degree of loading falls off in illites, to which fL-values of the order of 0,8 apply. Some of the sites not occupied by K+, Na+ or Ca2+ ions are thought to be occupied either by H2O molecules or by hydroxonium ions, H3O+. In smectites, moreover, the loading factor fL falls off to yet lower values. In sodium montmorillonite, for example, with an idealised formula of Na1/2Al3/2Mg1/2Si4O10(OH)2, fL = 0,5. A general treatment of this factor would require the following equation:
[K+] + [Na+] + [Ca2+] = [2:1] fL + [FS]/4 (11)

The system of eq. (5),(6),(7) gives rise to an exact solution, provided that [H2O]framework is known. Although this can ultimately be derived from the loss on ignition of a ball clay, difficulties in partitioning the loss between framework water, interlayer water, hydrocarbons and (in rare cares) other minerals suggest that a graphical approach should be adopted towards finding the solution, whereby [H2O]framework is the independent, x-axis variable. Solutions to eq. (5),(6),(7) are therefore as follows. [2:1] = [oct]total - [H2O]framework [1:1] = [H2O]framework - [oct]total (8) (9)

Fig. 3 The graphical method of solution for [2:1], [1:1] and [1:0]

[1:0] = [tet]total - 3[oct]total + 2[H2O]framework

(10) This method of solution is now demonstrated by reference to a set of experimental XRF and loss-onignition results obtained in 2001 for an arbitrary clay seam from the Petschmorgen quarry in the Westerwald (see Tab. 1). The assumption is made here that TiO2 does not enter the aluminosilicate mineral fraction. Further, it is assumed that one half of the iron ions enter the aluminosilicate fraction, in an oxidation state of +3, so that they behave effectively as aluminiumions. The derived values of [tet]total and [oct]total are now used to find the solution for [2:1], [1:1] and [1:0] graphically, as shown in Fig. 3. The range of possible solutions is indicated by the outer limits, which are defined by the values [H2O]framework for which all three mineral concentrations [2:1], [1:0] and [1:1] are positive. Initial guidance to the point along the x-axis corresponding to the actual solution is provided by the measured loss-on-ignition value, [H2O]LOI ,which corresponds to the value of 0,4097 mol (see Table 1). The value of [H2O]framework for the solution cannot be greater than [H2O]LOI, and is likely to be slightly smaller than this value, because of c/Ber. DKG 85 (2008) No. 3

Fig. 4 Use of triangular plots in order compare the mineralogy of different ball clays (units of mass-%). Each point in the plot here corresponds to an individual clay seam from the Westerwald.

Here the presence of the term [FS] allows a non-zero feldspar concentration, it being divided by four, since a standard feldspar concentration would be KAlSi3O8 or CaAl2Si2O8, for example, i.e. K tet4 or Ca tet4. Since the coefficient of the [1:0] term in eq. (5) is one, these feldspars would be represented as K1/4 tet and Ca1/4 tet in this approach. It may generally be assumed that [FS] 0 for ball clays, as feldspars weather easily. Consequently all the alkali and alkaline earth ions can be assigned to 2:1 clay minerals. This loading factor is essentially a matter of packing: sufficient interlay[%] SiO2 60,32 -17,20 -26,51 16,61 [%] TiO2 1,35

er ions must be present in order to provide mechanical support for the 2:1 layer-frameworks. The charges of the ions are no longer relevant, since the requirements of charge neutrality have already been taken into account in equations (8) to (10). For our example clay, loading factors in the range 0,8 to 1,0 would be expected. From Tab. 1, [Ca2+] + [K+] + [Na+] = 0,0775 mol. For a loading factor of 0,8, [2:1] will be 0,0775/0,8 = 0,0969 mol and for a loading factor of 0,9, [2:1] will be 0,0775/0,9 = 0,0861 mol. From eq. (8), the corresponding values of [H2O]framework for loading factors 0,8, 0,9 and 1,0 are therefore 0,3616, 0,3724 and 0,3810, respectively. Since the maximum possible value of [H2O]framework for this clay is therefore 0,3810 mol, additional contributions to the L.o.I., e.g. from hydrocarbons and interlayer water/hydroxonium ions are
[%] Al2O3 25,87 -14,59 [%] Fe2O3 0,97 [%] CaO [%] MgO 0,20 0,53

Tab. 2 Calculation of the mass-%-concentration of the 2:1 clay mineral fraction

[%] Na2O 0,19

Experimental results [mass-%]: in kaolinite in quartz in non-aluminosilicate fraction in 2:1 mineral

[% ]K2O 3,18

-1,35 0,00

11,28

-0,49 0,49

0,20

0,53

3,18

0,19

32,49 SUM

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required for self-consistency. Alternatively the presence of a small, nonzero feldspar concentration would lead to smaller values of [2:1] and therefore larger values of [1:1]. This would cause higher values of [H2O]framework (see Fig. 3). Such considerations would be made, where necessary, on a case-by-case basis, taking into account additional experimental evidence, for example from XRD or from measurements of carbon concentrations. For such a purpose, a graphical computer interface would be best suited for bringing all the available information together, in order to find the correct solution. The computer would also handle the reverse conversion from molar concentrations to mass-% values that are conventionally used in ceramics. By way of an example, let us assume that [FS] = 0, and that the solution chosen here corresponds to a loading factor, fL = 0,9. In this case, [2:1] = 0,0861 and [H2O]framework = 0,3724. Corresponding values of [1:1] and [1:0] are 0,1431 and 0,4412 respectively, according to eq. (9) and (10). Assuming idealised kaolinite and quartz formulae of Al2O3.2SiO2.2H2O and SiO2, which have molecular mass of 258.159 and 60,084 g mol-1, the clay contains 36,95 mass-% kaolinite and 26,51 mass-% quartz. Manual calculation of the mass-% 2:1 clay mineral fraction is cumbersome, because of its ability to accommodate all ion-types except titanium. Therefore it is best performed computationally, as indicated in Tab. 2. The metal oxides sum to 32,49 mass-%, on to which is added the framework water contribution of (0,3724 2 x 0,1431) x 18,015 = 1,55 mass-%, leading to a 2:1-mineral concentration of 34,04 mass-%. The sum of the three mineral concentrations amounts to 97,50 mass-%. The discrepancy of 2,50 mass-% is accounted by 1,35 mass-% TiO2, half the FeO2O3, i.e. 0,485 mass-% and the remaining contribution to the L.o.I., which has not been accounted for.

Testing for self-consistency by means of X-ray diffraction

The above analysis of XRF-derived information from ball clays has been developed in as general a manner as possible, using well established physical principles of ionic charge and radius. Further, the whole of clay mineralogy has been brought together into a unified treatment by focusing on the two fundamental structural frameworks, i.e. 1:1 and 2:1 clay minerals. Therefore it is natural to expect broad agreement with the information provided by the complementary technique of Xray diffraction (XRD). In order to test for self-consistency, attention was given to the intensities of just two reflections in the XRD patterns of some 260 ball clay seams analysed in 2001, as part of a study carried out within the company WBB Fuchs. These ball clays originated mainly from the Westerwald area of Germany. The two reflections monitored corresponded to the {212} quartz maximum at approximately 50,14 2 for CuK1 radiation and the (002) kaolinite reflection at approximately 24,89 2. Choice of this quartz reflection is standard practice, since its intensity is not influenced by overlaps from reflections due to the other minerals present. In the case of kaolinite, this reflection was selected, because it is not influenced by the degree of order of the kaolinite. What is the structural basis of disorder in kaolinite? This is associated with random displacements of adjacent 1:1 layers by 0, -b/3 or +b/3 relative to one another along the crystallographic y-axis 3. This situation is to be compared with ordered kaolinite, in which adjacent 1:1 layers always have displacements relative to each other of zero (Fig. 5). Since this mechanism of disorder does not affect the separation of adjacent 1:1 layers along the stackaxis, it follows that the only reflections whose intensities are not affected by disorder in kaolinite are basal reflections (00l), l=1,2,3 If the information provided by the two techniques of XRF and XRD is self-consistent, the expectation is that the two reflection intensities of quartz and kaolinite in XRD will be proportional to their concentrations derived from XRF, once these intensities have been corrected for com-

Fig. 5 Schematic comparison of ordered and disordered kaolinite, whereby the red blocks represent 1:1 layers topped by OH- ions. Oxygen ions form the bottom atomic layer.

Graphical Presentation of Results

The previous section has demonstrated how it is possible to deal with the mineralogy of ball clays (as well as kaolins, loams and other aluminosilicates) quantitatively and generally. The method advocated leads to robust solutions, whereby local, known variations in mineralogy can also be accommodated by choosing appropriate partitioning of iron oxides, as well as different 2:1 clay mineral loading factors or feldspar concentrations. Although sufficient detail has been given in order to satisfy the sceptical analyst, the ceramist generally requires a more intuitive grasp of the mineralogical composition of ball clays. For this purpose, the use of triangular plots is advocated, as shown in Fig. 4. The triangular coordinate system demands that the concentrations of the 1:0-, 2:1- and 1:1- minerals sum to 100 mass-%. Therefore a normalisation factor, FN, is applied to the derived concentrations, in order to force this. FN = 100 / [c(1:0) + c(2:1) + c(1:1)] (12) The twenty-five points in the plot indicate that most of these clays are slightly richer in 1:1- than 2:1 minerals, with the 1:0 component, i.e. quartz acting as a diluent of the clay minerals.

Fig. 6 The correlation between quartz concentrations derived from XRF and from XRD, which is generally acceptable. The solid line corresponds to a quadratic trend-line.
3

b is the length of the unit cell along the y-axis.

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position-dependent X-ray absorption effects. In the case of quartz, the agreement is acceptable, given that no particular effort was made to coerce agreement by attending to the 260 samples individually: a global 2:1 clay mineral loading factor of 0,9 was merely applied (Fig. 6). In the case of kaolinite, the agreement between the two techniques is extremely poor (Fig. 7). The red line is the quadratic trendline, whereas the pink straight line is another alternative based on the premise that XRD intensity loss is important. Maximum discrepancies along the x-axis are of the order of 40 mass-%, as indicated by the two arrows. Two conclusions follow from this exercise of seeking self-consistency: a) The derived quartz concentration is a reliable and appropriate parameter for quantifying ball clays b) A new interpretation is required of the information provided by XRF and XRD regarding the kaolinite fraction. In connection with b), the potential for reinterpreting XRF results is limited, because the quantitative method of interpretation has been defined so generally and fundamentally. The only possibility would be to hypothesize the widespread existence of a hydrous illite with H3O+ and H2O molecules in the interlayer sites. This is because it is possible to generate a hypothetical 2:1 clay mineral structure with identical stoichiometry to the 1:1 structure of kaolinite: 3/2[Al2O3.2SiO2.2H2O] = 3/2[Si2O5.Al2(OH)4] (kaolinite) = Si3/2Al1/2O5.Al2(OH)2.Si3/2Al1/2O5.[H3 O+.H2O] (hydrous illite) (13) Such a mineral would allow the large-scale reassignation of kaolinite to the 2:1 clay mineral fraction, thereby permitting a forced agreement with kaolinite concentrations implied by XRD. In reality, such an illite would not consist merely of [H3O+.H2O] in interlayer sites, but also contain K+, Na+, Ca2+ ions. However, this option would be extremely drastic, and it is therefore not being proposed as a means of reconciling the discrepancy between XRF and XRD. It follows that attention should rather be focused on the interpretation of XRD results. However, the dis4

crepancy cannot be ascribed to variations in kaolinite order, because the (002) reflection is insensitive to this. Assigning the discrepancy to preferred orientation is also not an option, since this effect could only ever increase the kaolinite (002) intensity of a ball clay, and not lead to a dramatic fall-off in intensity. There must be some other influences leading to large-scale intensity variations in kaolinites. Tentative ceramic support for a physical basis of the discrepancy between XRF and XRD is provided by the fact that the two clay seams associated with maximum discrepancies along the X-axis (Fig. 7) are extremely plastic. A complementary plot, indicating y-axis deviations from the quadratic trend-line is given in Fig. 8 Those quarries with predominantly negative deviations from the trendline were generally perceived within the company WBB Fuchs to be associated with highly plastic clays, whereas clays with positive deviations from the line were significantly less plastic. Since ceramic logic conventionally associates plasticity with a fine particle size, it follows that the discrepancy between XRF and XRD results may be telling us something amount clay particle size. Further explicit consideration of the influence of particle size on XRD is deferred until Section 4.

Fig. 7 The poor correlation between kaolinite concentrations derived from XRF and from XRD

Fig. 8 Deviations in area of (002) kaolinite reflection in XRD from the quadratic trend line, plotted on a quarry-by-quarry basis. Each quarry is represented in its own colour.

Taking Ball Clay Particle Size into Account

It has been established that the quartz concentration of a ball clay may be reliably determined. Further, the question of particle size has revealed itself potentially as the area in which to look for a reconciliation of the information provided by XRF and XRD. The present objective is to search for a second, particle-size related parameter to be used in conjunction with quartz concentrations, in order to produce a two-dimensional mapping of ball clays. The use of particle size distributions to characterise ball clays is a well established ceramic practice. However their use here would not be expected to provide the level of differentiation needed to characterise different ball clays. The desired map will ideally have its value along the xaxis determined by the quartz concentration and the value along the y-

axis given by a parameter which is essentially controlled by the clay minerals within a ball clay, but not significantly influenced by the quartz concentration. In this way the values along the x- and y-axes will be essentially independent of one another. The experimental technique to be used to yield the independent parameter for the y-axis is to measure the specific surface area of ball clays.

Specific Surface Area (SSA)

The specific surface area (SSA) of a material corresponds to the total surface area per mass unit. The total surface area of a ball clay can straightforwardly be measured by means of nitrogen adsorption at 77 K at a range of vapour pressures, utilising the BET isotherm to interpret the experimental data obtained. The results are generally obtained in the form of a single value for the specific surface area, such as 15,55 m2 g-1. As is always the case in Physics, approximations are called for, in order to interpret the experimental data simply and meaningfully.

A better approximation could be made without difficulty, for example by assuming that the quartz particles made a contribution to the specific surface area in proportion to their concentration in the clay. This could be regarded as a future refinement of the approach.

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Although clay mineral particles are generally plate-like, the assumption of plates would require three parameters (length, breadth and height) to be specified. The simplest threedimensional form however, requiring just one parameter, is a sphere of radius r. This will have surface area 4 r2 and volume 4/3 r3. A system of mono-sized spheres of radius r and density would therefore have a specific surface area of 3
r

Fig. 9 SEM image of a quartz-rich ball clay from the Westerwald (courtesy of A. Gros, FH Koblenz)

Fig. 10 Definition of the proposed two-dimensional mapping. The x-axis value is calculated from 100% - c(quartz) and the y-axis value from 100 . SSA / x. Along a given contour, the SSA value is constant.

This result is of great importance, since it shows how the dominant contribution to the specific surface area will come from the finer particles of smaller radius. This insight may be used to make a second approximation, in the interests of producing a good 2D-mapping. This is that the coarse quartz particles make no contribution to the specific surface area of a ball clay. An equivalent statement would be that the specific surface area of a ball clay is caused by the clay minerals alone 4. General support for an approach of this is provided by the SEM secondary electron image of a quartzrich ball clay from the Westerwald (Fig. 9). It is seen here that large quartz particles are coordinated by platey clay particles that are very much smaller. The physical picture underlying the proposed mapping may now be defined. The value along x-axis is given by the concentration of clay minerals in the ball clay, which is approximated as 100- mass-% quartz concentration. The value along the y-axis is the surface area per mass unit of clay mineral. Thus both axes of the map concern the clay minerals present in a ball clay.

example a ball clay consisting of 50 % quartz with a measured SSA of 20 m2 g-1 (i.e. Clay A in Fig. 10) would have a clay mineral specific surface area of 40 m2 g-1. Similarly, a ball clay also of SSA 20 m2 g-1 but consisting of 20 % quartz, and therefore 80 % clay minerals, would have a CMSSA value of 20/0,8 = m2g-1(i.e. Clay B in Fig. 10). The physical insight here is that the SSA value of ball clay can be increased in two ways, either by increasing the concentration of clay minerals or by having finer clay particles. The derived CMSSA parameter is a direct measure of the fineness of the clay particles. Accordingly, contours can be drawn in the proposed xy-map, along which SSA values remain constant (Fig. 10). The two approximations of sphericity of particles and there being no contribution to the SSA from quartz particles allow clear physical meanings to be ascribed to the quantities plotted along the x- and y-axes. Their use is further justified by applying the maps to the selection of ball clays.

Validation by Reference to Mining Practices

The practical application of this mapping approach may be demonstrated by reference to ball clay operations within the company WBB Minerals during 2004, in the county of Devon in South West England. This operation is successful in supplying highly differentiated ball clay blends for diverse ceramic applications, ranging from plastic blends for tiles through to blends for high density slips, as might be used for slipand pressure-casting. The key to this success is the careful and informed selection of ball clay seams, coupled with stringent quality control testing. The question arises as to whether the proposed two-dimensional mapping, with concentration of clay minerals along the x-axis and CMSSA along the y-axis, is able to mirror the existing good practice of this operation. Such a map is shown in Fig. 11, following the analysis of some 200 clay seams. The mapping is successful, in that the 30 clay selections under consideration generally occupy characteristic regions within the two-dimensional space. It therefore mirrors mining practice. In cases where selections overlap, the potential for reducing the number of selections

Clay Mineral Specific Surface Area (CMSSA)

Fig. 11 Application of the mapping defined in Fig. 10 to ball clays from Devon in England. Each unique colour/symbol signifies a particular clay selection.

The derived quantity to be plotted along the y-axis of the map could also be termed the clay mineral specific surface area (CMSSA). For

Fig. 12 Method used to reduce the computational overhead needed to use the Debye equation. (a) The separation of the two red atoms is not calculated directly, but by means of the alternative path proceeding via the arrows shown. The two black cells drawn are the crystallographic unit cells to which the red atoms belong. (b) The vectors in this alternative path. (c) Reduction of the five vectors in (b) to just three.

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exists. Conversely, if a particular selection occupies too broad a region in the map, attention should be given to mining practices, in order to avoid problems of inconsistent product blends. The horizontal line drawn at a CMSSA value of 35 m2 g-1 effectively separates clays from South Devon from those originating from North Devon, the two regions being associated with different geological conditions of formation. Exceptions to this generalisation are given by some North Devon seams with significant hydrocarbon concentrations, with the implication here that the hydrocarbons present bind the finer particles together into coarser ones.
Fig. 13 The variation of atomic scattering factors with diffraction angle for atomtypes Si, Al, O and H

Measuring Clay Particle Size by X-ray Diffraction

The foregoing discussion has indicated how the discrepancy between XRF and XRD-derived information on ball clays could be due to the influence of particle size on the intensities of X-ray diffraction peaks. The central problem here is that the variations in intensity of the (002)reflections in the XRD patterns cannot be correlated with the concentrations of kaolinite derived from XRF. Further, the SSA measurements carried out suggest that particle size is an essential parameter to consider. Most modern approaches to treating X-ray diffraction, such as the Rietveld Method [3], start from the ideal of infinite, perfect crystals, and consider the effects of defects and smaller particle sizes as corrections to this ideal. A head-on approach to our problem, however, would be to build small particles of kaolinite in the computer, and to calculate the total X-ray diffraction pattern for different particle sizes. Initial work here has made use of the Debye scattering equation, as proposed almost 100 years ago [2].

Fig. 14 A Debye simulation of the X-ray diffraction pattern of ordered kaolinite, assuming cylindrical particles of diameters ranging between 120 and 20 nm and a fixed height:diameter ratio of 1:10.

Fig. 15 A Debye simulation of the X-ray diffraction pattern of kaolinite with degrees of order of 100 %, 50 % and 0 %, for cylindrical particles of fixed diameter 100 nm and a height:diameter ratio of 1:10.

I( k ) =
with

fmfn

sin k r mn k r mn

k=

4 sin

Here fm and fn signify the scattering factors of atoms m and n and rmn their separation. For radiation of fixed wavelength , the value of k varies only with angle , where 2 is c/Ber. DKG 85 (2008) No. 3

the diffraction angle. The equation is directly applicable to powder X-ray scattering, as discussed, for example, by Warren [4]. It is used here to compute the diffraction pattern due to a clay particle of given size and shape as part of a randomly oriented powder. Although the Debye scattering equation makes no prior assumptions about the arrangement of atoms within a given particle, the main problem in using it is the enormous computational overhead required to calculate each interatomic separation rmn separately. Therefore, for the purposes of the present work, it was necessary to back-engineer some crystalline peri-

odicity into the structure, in order that a conventional PC could be used. An approach was adopted whereby a given kaolinite particle was regarded as a circular disk. A two-dimensional periodicity was assumed within the plane of this disk. For this purpose, the a,b and lattice parameters of kaolinite obtained from a structural refinement by Bish[1] were used: a = 5,1535 ; b = 8,9419 ; = 89,797 (Fig. 12). The advantage of the representation in Fig. 12c is that the lattice vectors in the xy-plane and along z are repeated many times, as are the vectors between pairs of atoms within a

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unit cell. The lengths of these vectors only need to be calculated once. What also needs to be calculated, however, is the number of times they occur in the Debye summation for kaolinite particles of different sizes. This second calculation does not require a significant computational overhead, and allows considerations of particle size and shape, i.e. aspect ratio to be taken into account directly. The set of interatomic distances within the unit cell is defined by the crystal structure of kaolinite, as also determined by Bish[1]. The parameterization adopted had just three variable parameters: a) diameter of the disk b) thickness of the disk c) degree of order of the kaolinite. The diameter of the disk determines the numbers of different lattice vectors in the xy-plane and its thickness the number of lattice vectors along z. Kaolinite disorder was modelled by allowing random additional displacements to the z lattice vectors by 0, b/3 along the y-axis (Fig. 5). The values of atomic scattering factors fm,fn and their assumed angular dependence are shown in Fig. 13. No account was taken of the Lorentz-polarisation factor or of atomic temperature factors in this initial work. The Debye simulations for fully ordered kaolinite are given in Fig. 14, for disk-diameters between 20 and 120 nm and a fixed height:diameter ratio of 1:10. These correspond, for this cylindrical geometry, to CMSSA values of 458 and 76,4 m2 g-1 respectively, for an assumed density of 2,62 g cm-3, so that the CMSSA value of the 120 nm-diameter particles has almost reached the average values of CMSSA that are typical of ball clays. It is seen that the kaolinite (002) reflection becomes successively weaker as the diameter is reduced from 120 nm downwards, implying that the observed loss in intensity in the kaolinite (002) reflection of ball clays could indeed be a size effect. If this were the case, a distribution of particle diameters about the average values would be required, in order to give rise to the extremely fine particles for which the (002) intensity is significantly reduced. Fig. 15 confirms that the intensity of the kaolinite (002) reflection is not affected by the degree of kaolinite order. By comparison, many of other peaks associated with ordered kaolinite become progressively weaker, or adopt changed profiles as the degree of disorder increases. The Debye simulation method therefore opens the door to new possibilities for the quantitative interpretation of X-ray diffraction from fine particles. This is particularly so in that it models the whole diffraction pattern without recourse to idealised peak profiles, as required in the Rietveld method [3]. There is also considerable scope for extending this introductory work to other clay minerals, e.g. 2:1 clay minerals and halloysites, as well as to the whole area of synthetic nanoceramic powders. quartz concentration is important. t would be welcome indeed if approaches similar to the Debye method would revitalise the XRD technique in characterising ball clays. All too often the experimental technique is used just for search/match phase identification purposes or for impurity-screening, with little regard paid to the additional quantitative information it is capable of yielding about the majority phases present. The predominant influence of very fine particles in determining the plasticity of many ball clays also suggests the need for a paradigm-shift in analysing their rheological behaviour. Whereas in English a commonly used word in this context is deflocculation, the German word Verflssigung, meaning fluidization, is perhaps more appropriate. This word has the advantage of not implying that all ball clays naturally exist in a flocculated state within a water slip. Perhaps the relationship of ball clays (or at least Tone (Germ.)) to kaolins, for which deflocculation is undoubtedly the correct word, is more distant than is often assumed.

Outlook
The foregoing discussion suggests that the focus for selecting ball clays should lie firmly in the Ceramics domain, in which considerations of particle size have always been essential. However, a shift in practice is called for, so that attention is focused on the very fine particles. Measurement of the specific surface area has proved effective in this regard. Clearly the chemical compositional information provided by XRF is crucial when ball clays are also to be selected on the basis of fired colour, and the ability of this technique to yield a robust value for

Acknowledgement
The financial support of all companies contributing to my Stiftungsprofessur is gratefully acknowledged.

References
[1] Bish, D.L., Rietveld refinement of the kaolinite structure at 1.5 K, Clays & Clay Minerals, 41(1993) 738-744 [2] Debye, P., Ann. Physik 46 (1915)809 [3] McClusker, L.B., von Dreele, R.B., Cox, D.E., Louer, D., Scardi, P. Rietveld refinement guidelines, J. Appl. Cryst. 32 (1999) 36-50 [4] Warren, B.E., X-ray Diffraction, Addison-Wesley (1969)

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