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Applied Ceramic Technology

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Applied Ceramic Technology

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Applied
Ceramic
Technology

Volume I
Copyright 2005 SACMI IMOLA
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Tel. 0542/607111 - Fax 0542/642354
www.sacmi.it
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(microfilm and photocopy included), whole or partial, is prohibited.

ISBN 88-88108-48-3

Editrice La Mandragora s.r.l.


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e-mail: info@editricelamandragora.it
CONTENTS

To the reader................................................................................................................................. 9
Introduction ................................................................................................................................ 11
The production process ........................................................................................................... 22

Chapter I – Identification and characterisation of ceramic raw materials ....... 25


Sampling ...................................................................................................................................... 26
Chemical analysis ....................................................................................................................... 27
Mineralogical (or crystallographic) analysis ...................................................................... 32
Thermal analyses ....................................................................................................................... 33
Plastic, semi-plastic and non-plastic raw materials .......................................................... 41

Chapter II – Rocks .................................................................................................................. 45


The rock cycle ............................................................................................................................ 45
Magma .......................................................................................................................................... 47
Clays and rocks .......................................................................................................................... 47
Primary rocks ............................................................................................................................. 48
Main minerals in the earth’s crust ........................................................................................ 51
Structure of clayey minerals .................................................................................................. 52
Characteristics of the main clayey minerals ...................................................................... 58

Chapter III – Raw materials for ceramic bodies.......................................................... 59


Kaolinite ....................................................................................................................................... 59
Illite ............................................................................................................................................... 67
Montmorillonite (smectite) ..................................................................................................... 74
Chlorite......................................................................................................................................... 80
Talc ................................................................................................................................................ 86
“Non-plastic” materials ............................................................................................................ 92
Silica ............................................................................................................................................. 92
Feldspathic minerals ................................................................................................................. 99
Pyrophyllite ............................................................................................................................. 105
Wollastonite ............................................................................................................................. 109
Carbonates ................................................................................................................................ 112
Accessory minerals present in ceramic raw materials .................................................. 118
Halloysite .................................................................................................................................. 118
Attapulgite, Sepiolite, Vermiculite ..................................................................................... 122
Micas .......................................................................................................................................... 126
Mineral hydroxides ................................................................................................................ 128
Soluble salts ............................................................................................................................. 129
Vegetable substances and reducers .................................................................................... 134
Sulphur and sulphides (alunite)........................................................................................... 136
Vitreous materials .................................................................................................................. 137

Chapter IV – Raw materials for frits and glazes ...................................................... 139


Raw materials for melting of frits ..................................................................................... 139
Technological aspects of frits and glazes ........................................................................ 141
Standard raw materials and their influence on the characteristics of glass .......... 145
Types of frit ............................................................................................................................ 150
Classification of ceramic glazes .......................................................................................... 156
Traditional double-firing ...................................................................................................... 160
Fast double firing .................................................................................................................... 162
Porous single firing wall tiling ........................................................................................... 166
Silk-screen printing products .............................................................................................. 167
Single firing floor tiling ........................................................................................................ 169
Dry-application grains .......................................................................................................... 171

Chapter V – Physical and structural properties of ceramic raw materials .... 175
Particle size distribution ....................................................................................................... 176
How water influences ceramic systems............................................................................. 186

Chapter VI – Rheology: basic concepts ....................................................................... 191


Rheology of clays ................................................................................................................... 201
Mineralogy and rheology of clays .................................................................................... 202
Rheology of ceramic bodies ................................................................................................ 204
Influence of grinding water ................................................................................................ 205
The wet grinding process and spray drying of the ceramic bodies from
a rheological standpoint ........................................................................................................ 206
Rheological additives ............................................................................................................. 213
Inorganic deflocculants ......................................................................................................... 215
Organic deflocculants ............................................................................................................ 217
Main additive classes ............................................................................................................. 220
Ceramic spray drying bodies ............................................................................................... 221
Ceramic glazes ......................................................................................................................... 223
Glazes: non-rheological side effects ................................................................................... 227
Most commonly used additives ........................................................................................... 228

Chapter VII – The removal of water ............................................................................ 231


The water-clay system and how it affects moulding ..................................................... 231
Removing the water ............................................................................................................... 232

Chapter VIII – Description of ceramic products .................................................... 245


Interpreting the behaviour of ceramic bodies ................................................................ 248

Chapter IX – Wall tiles ...................................................................................................... 255


Aesthetic features ................................................................................................................... 258
Raw materials for bodies ....................................................................................................... 260
Characteristics of raw materials for bodies ..................................................................... 261
Plastic raw materials .............................................................................................................. 261
Complementary raw materials ............................................................................................ 263
Body composition ................................................................................................................... 263
Product features ...................................................................................................................... 265
Raw materials for glazes ....................................................................................................... 266
Basic technological parameters ........................................................................................... 270
Plant engineering solutions ................................................................................................. 280
Machines ................................................................................................................................... 282
Weighing systems .................................................................................................................. 283
Mills ........................................................................................................................................... 283
Spray driers .............................................................................................................................. 285
Presses ....................................................................................................................................... 285
Driers ......................................................................................................................................... 286
Glazing machines ................................................................................................................... 287
Kilns ........................................................................................................................................... 288
Sorting ....................................................................................................................................... 290
Handling and storage systems ............................................................................................ 290
Conclusions .............................................................................................................................. 290

Chapter X – Floor tiles ...................................................................................................... 293


The market ............................................................................................................................... 294
Product classification ............................................................................................................. 296
Technical features ................................................................................................................... 296
Aesthetic features ................................................................................................................... 298
Raw materials for bodies ....................................................................................................... 299
Body composition ................................................................................................................... 300
Raw materials for glazes ....................................................................................................... 303
Basic technological parameters ........................................................................................... 304
Plant engineering solutions ................................................................................................. 308
Machines ................................................................................................................................... 311

Chapter XI – Porcelain tiles ............................................................................................. 321


Technical characteristics ...................................................................................................... 322
Commercial specifications .................................................................................................... 323
Raw materials for bodies ....................................................................................................... 327
Compositions ........................................................................................................................... 329
Basic technological parameters ........................................................................................... 333
Production technology .......................................................................................................... 336
The production process ........................................................................................................ 336
Technical outlook ................................................................................................................... 345
Aesthetic outlook .................................................................................................................... 346
Conclusions .............................................................................................................................. 347

Chapter XII – Accessories and trims ............................................................................ 349


The market ............................................................................................................................... 350
Applied Ceramic Technology

Technology .............................................................................................................................. 352


Materials ................................................................................................................................... 356
Organisation ............................................................................................................................. 358
Trims ......................................................................................................................................... 358
Production line ........................................................................................................................ 360
Machines ................................................................................................................................... 365
The production process ........................................................................................................ 366
Decoration ................................................................................................................................ 366
Firing ......................................................................................................................................... 369
Sorting ....................................................................................................................................... 370
Cutting the material ............................................................................................................... 370

Appendix 1 – Standards ..................................................................................................... 373

Appendix 2 – Tables and figures .................................................................................... 379

Bibliography ........................................................................................................................... 443

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Introduction

TO THE READER

The creation of a systematic compendium providing information on ceramic production technolo-


gy, with a clear focus on pressed tiles, is something of challenge as readers of such a publication are
likely to come from a wide range of fields and backgrounds, spanning both the academic and
industrial.
Such a work might be thought of as an introductory manual providing descriptions of work cycles
and machines, leaving aside more detailed understanding of the relevant materials and problems
or, vice versa, as an in-depth text on technological procedures, the results of which are taken for
granted. Readers with a technical-scientific background would, perhaps, like to see information on
innovative and original scientific developments – or at least a collection of information that would
be unavailable in a more compact publication. On the other hand, readers with a technical-manu-
facturing background would be more interested in a troubleshooting manual to help them deal with
the day-to-day problems that affect production lines. The young technician – a newcomer to the
complexities of a production process about which he has learnt little or nothing during his academ-
ic studies – would probably require an overview packed with everything he needs to know about
what happens in the “factory”, from delivery of raw materials through to packaging of the fin-
ished product.
To say that this first volume (and the forthcoming Volume II, which illustrates the production
process), attempts to reconcile all these different needs is not as presumptuous as it might sound,
although to state that it has actually succeeded in doing so certainly would be. What has been made,
though, is a serious attempt to provide a succinct – yet in-depth – description of the production line
without ignoring the descriptive and scientific foundations of the topic in hand: the result is this
first volume which offers the reader an explanation of what happens during each individual stage
of the production cycle, placing emphasis on the importance of correctly defining the nature of the
raw materials, their significance in a ceramic body and the problems they can cause. An overview of
possible products as a function of their technological characteristics is also provided.
A brief introduction outlines the main subject areas, subsequently dealt with in more detail. Volume
II, instead, aims to clarify the technological aspects of the individual stages of the production cycle:
rather than providing a description of specific machines that would inevitably and quickly become
obsolete, such clarification aims to explain the purpose and work cycle of each machine as regards
the creation of the final product. A substantial part of the book is dedicated to explanations of the
defects that can arise at each stage of the production cycle and there is also a clear overview of the
correlation between finished tile defects and the stage of the production process in which such defect
was generated. This first volume, as mentioned above, largely focuses on the manufacture of pressed
tiles, yet the reader will also find facts and figures on other products and technologies where this
aids understanding of reaction mechanisms.
A detailed appendix of standards, tables and figures completes the volume.

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Applied Ceramic Technology

10
Introduction

INTRODUCTION

When speaking of CERAMIC TECHNOLOGY it is important to introduce a


few key definitions that will provide us with useful reference points later on. The
first thing that needs to be defined is exactly what the word CERAMIC refers to.

Just what is a ceramic material? While dozens of definitions are possible, it can
effectively be described as “any product, having a form, made up of non-metallic inor-
ganic raw materials (whether mineral or artificial), which, from an incoherent powdery
state, are transformed, via various processes, into a semi-finished item, which, through fir-
ing, becomes a solid object of partially crystalline and partially vitreous structure”.

Virtually all the transformations and/or mixings become permanent after firing.
When speaking of inorganic raw materials it is necessary to bear in mind the level
of abundance of the most common elements in the earth’s crust, as it will obviously
be convenient and advantageous to manufacture ceramic items using the most widely
available and economic raw materials.
Fig. 1 (below) shows that these essentially include silicon and aluminium oxides

Fig. 1. The most common elements in the earth’s crust (from Kingery: Introduction to Ceramics - Wi-
ley).

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Applied Ceramic Technology

having different Fe, Ca, Mg, Na and K contents: these are, effectively, the 7 most
common elements in nature and are always present in a ceramic body.

Observing the Periodic Table (Tab. 1),

PERIODIC TABLE

INERT
GASES

Atomic number
Chemical symbol
Atomic weight

it can be seen just how few ceramic-relevant elements there are (Al, Si, Ca, Mg, Fe,
Ti, Na e K). Even when the main constituents of glazes (e.g. Pb, Zn, Sn, Zr, Cr, Ni,
Cr, V, B etc.) are taken into account it is evident that the assortment of elements
characterising a TRADITIONAL CERAMIC material is a restricted one.

In keeping with the general, introductory nature of this chapter, it can be said
that, where these materials are concerned, the field of study is limited to products
normally made up of natural oxides such as:
– TILES.
– SANITARYWARE.
– TABLEWARE.
– BRICK.
– CERTAIN REFRACTORY ITEMS.

Another approach is required where SPECIAL or ADVANCED ceramic materi-


als – generally made up of non-oxides or special oxides – are concerned: bioceramic
items, electrical and technical porcelains, electronic industry ceramics, catalysts,
special refractory items etc.

12
Introduction

A better insight into the composition of a traditional ceramic material can be


attained by taking a look at a “standardised” tile body, bearing in mind that with the
appropriate modifications, similar observations can be made with regard to other
traditional ceramic materials. The base body, then, is generally made up of:
– CLAYEY MATERIALS, which provide the plasticity needed to obtain a defined
form. These include Al, Si and a proportion of Ca, Fe, Ti.
– FLUXING MATERIALS such as feldspars, nepheline etc., which, during firing,
produce vitreous phases that act as particle-particle adhesives and promote sol-
id-solid reactions; these contribute Na, K, Al and Si.
– OTHER MATERIALS such as talc, silica, pyrophyllite, CaCO3 etc. (the so-called
“INERT” MATERIALS), used to obtain a certain type of performance: these
largely contribute Ca, Mg and Si.
– ADDITIVES, largely employed to improve the rheology of aqueous solutions;
these may be inorganic or organic and only limited amounts (< 1%) are intro-
duced into the bodies.

In summing up the main effects of each chemical component in a tile body, we


can state that the presence of oxides confers:

Al2O3 refractory characteristics and plasticity (where associated


with the presence of clayey materials).
SiO2 structure, framework, including neo-formed phases.
Fe2O3 and TiO2 colour and, sometimes, fluxing properties.
CaO and MgO shrinkage control, via the formation of calcium and magne-
sium silicates.
K2O and Na2O fluxes which form vitreous phases.

Despite this description of the ceramic characteristics that the chemical compo-
sition confers on the bodies, it is a well known fact that chemical analysis of a
ceramic body or raw material is not in itself the most important aspect of product
characterisation: it can easily be demonstrated that products with greatly differing
performance and fields of use, such as low water-absorption floor tiles, sanitary-
ware items, bricks etc. all have very similar chemical composition.

The quantity of Ca and Mg is significant as these will influence shrinkage


during firing and subsequent water absorption. The higher the content of these
elements the lower the degree of shrinkage, because calcium and magnesium sil-
icates form; these increase in volume as temperature rises, thus opposing the shrink-
age caused by the collapse of the silicate phases. Fig. 2b provides an example of
the tertiary diagrams used to establish equilibrium between the various compo-
nents.
A good example of such behaviour is given in the subsequent tertiary diagrams
(Figs. 3-8), which show compositions for product types such as majolica (low-shrink-
age wall tiles), cottoforte (intermediate behaviour owing to high water absorption)
and gres (high shrinkage and low water absorption).

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Applied Ceramic Technology

Tab. 2a. Composition and characteristics of different body types.

14
Introduction

[Remember that, for a system in equilibrium, tertiary diagrams illustrate the composi-
tion of systems consisting of 3 components. They display the relative percentages account-
ed for by each component as shown in the diagram below (Fig. 2b): any point within the
triangular area of the diagram is effectively an intersection of the lines running parallel
to the sides of the triangle and the point at which these lines converge gives the percentage
values of the components in the system. The percentage content of component A is read
off on the left-hand side of the triangle, component B on its base and component C on its
right-hand side.
For example, in fig. 2b point P represents a system where component A accounts for 30%
of the material (point E), B accounts for 20% (point F) and C the remaining 50% (point
G)].

Fig. 2b. How to read off composition percentages on the axes of a tertiary diagram.

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Applied Ceramic Technology

Fig. 3. SiO2/Al2O3/Fe2O3 tertiary diagram showing the compositional fields for majolica, cottoforte
and red gres bodies (Vincenzini and Fiori, 1977, vol. 2).

G = red gres
C = cottoforte
M = majolica

Fig. 4. Fe2O3/Na2O + K2O/MgO + CaO tertiary diagram showing the compositional fields for ma-
jolica, cottoforte and red gres bodies (Vincenzini and Fiori, 1977, vol. 2).

16
Introduction

GBp = potassium white gres


GBs = sodium white gres

GR = red gres

Fig. 5. SiO2/Al2O3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O diagram showing the composition-
al fields for red gres and potassium and sodium white gres bodies (Fabbri and Fiori, 1983, vol. 1).

GBp = potassium white gres


GBs = sodium white gres

GR = red gres

Fig. 6. Al2O3/Na2O/K2 tertiary diagram showing the compositional fields for potassium and sodium
white gres and red gres (Fabbri and Fiori, 1983, vol. 1).

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Applied Ceramic Technology

GBp = potassium white gres


GBs = sodium white gres

GR = red gres

Fig. 7. Al2O3/Na2O + K2O/TiO2 + Fe2O3 + MgO + CaO2 tertiary diagram showing the composi-
tional fields for red gres and potassium and sodium white gres bodies (Fabbri and Fiori, 1983, vol. 1).

1 red gres clays


2 cottoforte clays
3 majolica clays

Fig. 8. SiO2/Al2O3 + TiO/Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram showing the compo-
sitional fields for majolica, cottoforte and red gres clays (Sandrolini and Palmonari, 1974, vol. 2).

18
Introduction

To provide an effective description of a raw material or a ceramic body and give


information on its technological behaviour it is much more convenient to make use
of mineralogical (or crystal) analysis and particle size analysis.
To understand the usefulness of these techniques it is necessary to bear in mind
how a clayey raw material acts within a body, giving it plasticity during the produc-
tion process. In relatively simple terms, it can be said that a clay is made up of an
association of tetrahedral SiO4 repetition units (T symbol) associated with octahe-
dral units having an Al(OH)6 base (O symbol) as illustrated in Figs. 9-10.

Oxygen
Silicon

Aluminium, Magnesium etc.

Silicon
Oxygen

Fig. 9. Phyllosilicate repetition units: SiO4-4 tet- Fig. 10. Two-dimensional projection of oc-
rahedrons and Al(OH)63- octahedrons. tahedral structural units.

These form two-dimensional particles, the distance between two identical struc-
tural repetition units varying as a function of the type of material, as illustrated in
Fig. 11.
The interlayer space between two particles, micelles or two strings of particles
etc. may, by way of this repetition unit arrangement, vary from a minimum of 2.7
(in kaolinite) to a maximum of 8 (in chlorites) or more Angstroms [1Å = 10-8 cm],
thus determining whether or not extraneous molecules or ions can infiltrate the
structure.

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(A) Na-montmorillonite
(B) Ca-montmorillonite

(A) Vermiculite
(B) Tri-octahedral chlorite

(A) Muscovite (B) Illite

Fig. 11. Examples of the different inter-lattice spacings that characterise clayey raw materials.

20
Introduction

Where water lies between the particles they are able to slide against each other
more easily (i.e. thus conferring plasticity).
Such spaces may also be occupied by fluxing ions such as Na+ and K+, which
modify the technological properties of the raw material.
For this reason it is highly important that the mineralogical nature of the clayey
contents of a body be known so that the advantages and disadvantages of their
employment can be identified: this information is obtained using X-ray diffractom-
etry (XRD) techniques.

In speaking of fluxing materials, mainly feldspars, an understanding of their


mineralogical nature is once again important as the formation temperature of the
vitreous phase and the viscosity of the formed glass correlate closely with the type
of feldspar: sodium feldspars (mineralogically defined as albite) have low melting
points and low molten material viscosity too, while potassium feldspars (microcline,
orthoclase, sanidine etc.) have high viscosity, which can help in the event of sizing
and sticking problems during firing. Furthermore, clear information as to the min-
eralogical nature of the individual raw materials of a body helps with the planning
of special characteristics, such as the formation of “eutectics” (i.e. special composi-
tions with lower melting points).

Particle size distribution is another key factor: it is obvious that the purpose of
forming and firing a semi-finished ceramic item is to obtain a product in which
solid-solid reactions have been activated and completed as far as possible. In this
regard results are greatly influenced by the contact surface area of the particles: a
greater contact surface area is more conducive to the heat-induced passage from
sintering to reaction to fusion (see Fig. 12).

Fig. 12. Schematic illustration of the sintering process.

While the clayey particles are themselves small, they need to be mixed with
particles of other appropriately sized materials so as to plug as many gaps as possi-
ble and thus obtain maximum density: this is achieved via proper combination of
several grain sizes.
Therefore, proper control of body particle size distribution cannot be achieved

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Applied Ceramic Technology

via simple sieve residue alone: checks should be run using appropriate instrumenta-
tion (X-ray or laser etc.) that takes into account the interaction principles between
the individual particles (diffraction, scattering etc.).

The production process

Whatever the employed ceramic body raw material selection method, the subse-
quent production process will invariably be as follows:
– IN-QUARRY selection, mining and quality control.
– PREPARATION of raw materials for mixing.
– BODY preparation via GRINDING.
– FORMING.
– DRYING.
– Additional procedures to add AESTHETIC value to the product.
– FIRING.
– SORTING, PACKAGING and STORAGE.

Each of these stages requires attention and must be planned and executed care-
fully: constant quality control is essential.
There follows a stage-by-stage summary of the most common tile manufactur-
ing processes:

BODY PREPARATION
CRUSHER dry Hammer mill
Pendulum mill
wet Alsing (ball) mill
Continuous mill
Fast agitating disperser

FORMING Dry pressing


Extrusion
Casting
Decoration with multiple press fillings
(where applicable)

DRYING by convection, slow or fast,


by radiation

AESTHETIC PROCEDURES generally glazing or special applications

FIRING Traditional (slow) or rapid: for both


Single firing (body+glaze)
Double firing (glaze on already-fired biscuit)

22
Introduction

The following flow-charts (Tab. 3-4) summarise the most common production
processes.

raw material
storage
raw material
storage ê
ê batching
batching
ê
ê
wet grinding
wet or dry grinding
í î
ê
spray drying continuous mill discontinuous mill
or wetting
ê î í
pressing
spray drying
ê
drying ê
pressing
ê
biscuit firing ê
ê drying

glazing ê
ê glazing
glaze firing
ê
ê firing
sorting
ê
sorting

Tab. 3-4. Different ceramic tile production processes.

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Applied Ceramic Technology

If every stage of the production process has been well planned, properly-made
tiles will exit the plant: yet the aesthetic and performance requisites required of
tiles in airport halls differ enormously from those intended for use in apartment
bathrooms or on industrial flooring. Hence the concept of tile classification, summed
up as follows.

Tiles are generally classified on the basis of:


– INTERNATIONAL STANDARDS mainly based on the type of production
process or water absorption of the fired
product.

and, even today


– COMMERCIAL TRADITIONS that still use old names such as Gres,
Majolica, Klinker etc.

The correct approach, of course, would be to take into consideration a complete


set of FIRED TILE TECHNOLOGICAL CHARACTERISTICS, the key ones
being:
– Intended use (floor/wall tile, indoor/outdoor).
– Water absorption, but also resistance to freezing/thawing cycles.
– Shrinkage.
– Bending strength.
– Resistance to abrasion and staining.
– Body colour.
– Slip resistance.

Comprehensive knowledge of all these parameters will lead to proper classifica-


tion of a ceramic tile, thus allowing it to be employed appropriately.
This concludes our “summary” as to the nature of the subject of this volume.
The following chapters feature more in-depth elucidation, indicating just what sort
of analysis methods can and should be used and offering a systematic description of
each raw material and its behaviour during the various stages of the production
process.

24
Introduction

Chapter I

IDENTIFICATION AND CHARACTERISATION


OF CERAMIC RAW MATERIALS

Many properties of clays and other ceramic raw materials depend on the type
and quantity of the various minerals that constitute them. The identification of
such minerals is therefore of primary importance. Yet clear-cut identification is
made difficult by the fact that ceramic raw materials rarely consist of pure, well
crystallised minerals: instead, several minerals are generally present in appreciable
quantities together with many other minor constituents. Given these circumstanc-
es, identification of the main phases can be difficult, especially where they are all
rather similar.
Sometimes, and this is often the case with clays, a mineral cannot be identified
without prior purification and separation. Furthermore, a single clay may contain
various minerals and is nearly always associated with significant quantities of quartz,
calcareous materials, micas and others.
Also, clayey minerals are made up of very small particles (dimensions as small as
100 Å, that is 10-6 cm, are frequent), making identification even more problematic.
Moreover, clayey raw materials are often characterised by isomorphic substitution,
created by the genesis conditions described in the following chapter.
In general, then, analysis methods used for the study of these raw materials
must allow for recognition of minerals of non-constant, often intermingled com-
position sometimes made up of extremely small particles. Since identification of a
mineral depends on its key characteristics, which must necessarily always be the
same independently of mine attitude and the surrounding environment, analytical
methods which make use of the univocal properties of the individual raw material
classes must be employed.

Such properties can be summed up as follows:


– properties dependent on the chemical nature of the material
– properties dependent on the crystalline aspect of the mineral
– properties dependent on the atomic or ionic arrangement in the crystalline struc-
ture
– properties dependent on chemical or physical modifications in the mineral caused
by external factors (e.g. enthalpy variations induced by heating or cooling).

Other practical methods for identification or estimation in raw material mineral


content exist: for example, when rheological properties such as plasticity, thixotro-
py etc. are particularly evident, this suggests the presence of certain clayey miner-
als. Similarly, magnetic properties can indicate the presence of ferromagnetic min-
erals etc.
While these methods normally provide an overall picture as to the characteris-

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tics of the predominant mineral in the mix, they do not identify its individual com-
ponents.

An accurate description of the analytical methods used in raw material mineral


content recognition is outside the scope of this publication. Nevertheless, there
follows an approximate list of the main techniques and the criteria on which they
are based because, in the following description of the individual mineral types, ref-
erence will frequently be made to characteristic analytical data.

Sampling

Good analysis, whatever the type, where effected on a sample made up of a


mix of base components, and especially where that mix is heterogeneous, will
require proper preliminary sampling; this allows the necessarily small quantity
of material used in analysis to represent what can amount to tons of raw materi-
als stored in the body preparation department of a ceramic company. The analy-
sed sample, then, must be representative of all the material in question, not just a
portion of it.
Beginning with the most general case (i.e. in-quarry sampling, for which there
exist specially developed standardised procedures), samples must be taken from var-
ious points and different depths along the extraction front; if the material appears
to be uniform, selection and conservation of a sample representing about 1% of the
total sample may be effected (following mixing and quartering of the taken sam-
ples). Where the material is less uniform up to 5% of the taken sample may have to
be selected in order to obtain a reasonably analysable sample.
The same procedure applies to shiploads or truckloads of loose material.
The selected preliminary sample is then homogenised further, then quartered
again via subsequent formation of flattened heaps and the taking of opposite quar-
ters, until a final coarse sample of some 10-12 Kg is obtained. This will be ground
and quartered again until a suitable sample of about 3 Kg is obtained. The latter
should have an average particle size distribution no greater than 0.5-2 mm and
should not be over-ground so as to prevent oxidation of components sensitive to
contact with air; for similar reasons, in-sample moisture content should not be com-
pletely eliminated during comminution and quartering, and should remain within
the 4-12% range so as to prevent alteration or loss of soluble salts. Final drying and
grinding will only be effected immediately prior to analysis as a function of the
requirements of the analysis itself. The type of comminution can be critical as
there is a risk of contamination from the grinding machines themselves – especially
where metallic – or seriously altering the structure of certain minerals (e.g. those
with a two-dimensional conformation).

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Identification and characterisation of ceramic raw materials

Chemical analysis

Determination of the type and quantity of each element in a sample is of great


interest to ceramists. Yet in itself, such analysis often carries little significance. The
presence or absence of certain elements in certain quantities may certainly help
determine behaviour during firing but rarely provides information on the “work-
ability” of the raw material in question (i.e. in grinding, spray drying, pressing,
drying) or its physical behaviour.
Nevertheless, properly performed elementary analysis is an exact science while
many other techniques for the analysis and determination of technological proper-
ties are marred by error and uncertainty. Furthermore, the combination of struc-
tural data with constituent data allows for semi-quantitative identification of the
minerals in the sample.
A whole host of chemical analysis techniques exist. In particular, modern in-
strumental techniques provide fast, accurate results, the precision of which largely
depends on proper selection and preparation of the sample, a must for the attain-
ment of complete homogenisation.
In chemically analysing any substance, results are normally expressed in oxides
and, as specifically regards ceramic body materials, the main 8 are as follows: silicon
dioxide (Silica SiO2), aluminum oxide (Alumina Al2O3), titanium dioxide TiO2, ferric
oxide Fe2O3, calcium oxide CaO, magnesium oxide MgO, sodium monoxide Na2O
and potassium oxide K2O.
Oxides volatile at 1000 °C (carbon dioxide or carbon monoxide, sulphur oxides
such as SO3 and SO2, together with water) are normally indicated as Loss of Igni-
tion (L.O.I.). Accurate analysis will rarely see these components account for 100%
of the sample as other elements – generally accounting for less than 1% – are al-
ways present in varying quantities. These include Barium, Strontium and other
transition metals such as Copper, Chromium, Manganese and Boron, Lithium etc.
This type of analysis, however, does not indicate how the various elements are
combined and this can lead to errors in their technological evaluation: to under-
stand this concept just consider the difference between a calcium oxide originating
from feldspar rather than lime, or sulphur oxides that fail to take into account the
presence of mineral sulphides (e.g. Pyrite).

Before beginning a chemical analysis, then, it is necessary to select the sample


carefully as per the above methods. Such samples will, after proper drying at tem-
peratures that do not alter the volatile substance content, normally have a weight
ranging from a few hundred milligrams up to 1-2 grams; subsequent grinding is
effected using high-efficiency milling machines that do not contaminate the sample.
Methods vary depending on the hardness of the sample, ranging from corundum
or, even better, agate pestle-and-mortar tools to micro-mills with special hard alloy
grinding media.
With the sample weighed (and this is the point at which errors can creep into the
entire analysis), a solubilisation method which allows complete homogenisation must
be decided on: the sample is usually dissolved in chemical reagents to obtain a ho-

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mogeneous liquid solution, or is solubilised in a molten state in a special glass with


the resultant solid solution being analysed.
Ceramic materials, unfortunately, being silicate, aluminate and oxide-based, are
difficult to solubilise. There exists a vast argument-specific literature indicating
hydrofluoric acid HF and other mineral acids, such as nitric acid, HNO3, hydrochlo-
ric acid HCl or sulphuric acid H2SO4 as appropriate hot liquid solubilisation agents
requiring, as might be expected, the use of special containers.
“Classical” wet-type chemical analysis involved complex, systematic treatment
of samples to separate individual components prior to analysis true and proper,
mainly effected using (lengthy and complex) gravimetric, colorimetric or complex
metric methods (necessarily preceded by accurate preliminary calibration). These
methods, while still valid today, have undoubtedly been superseded by the advent of
more sophisticated instrumentation capable of extracting immediate analytical re-
sults from both solubilised and untreated samples alike.
All instrumental information is ultimately influenced by the initial measurement
of the mass of the sample and its proper preparation, which, whatever the method,
must provide conditions that are as standardised and homogeneous as possible.
The main aggression and acid solubilisation methods effected on ceramic raw
materials are:
– Hot acid aggression in open containers using HCl, HNO3 and HClO4-based acid-
oxidant mixes: the need to break up the silicate matrix nearly always makes the
use of HF indispensable too, thus making it impossible to use standard borosil-
icate glass. The use of open containers together with high-temperature solu-
bilising acids aids the loss of volatile components.
– Hot acid aggression in closed containers (and thus at high pressure). These sys-
tems, now becoming more widespread owing to the rapidity of aggression and
dissolution, usually employ Teflon containers and programmable microwave heat-
ing systems.
– Alkaline fusion and subsequent acid solubilisation, normally with HCl. There
exists a vast range of alkaline fluxes, to be employed as a function of the desired
fusion temperature and process efficacy: in all cases, of course, there is the addi-
tion, via the flux, of at least one cation (an aspect difficult to quantify in the
unknown specimen). The most widely employed alkaline fluxes are NaKCO3,
NaOH, LiBO2 and Li2B4O7, with various salts being added as detachment agents
(Lithium halogenides or alkalines in general, mostly complexing agents etc. - see
table on following page).

Fusion may be manual or automatic, thus guaranteeing standardised conditions


(always in platinum or similar containers). The obtained glass can undergo instru-
mental analysis directly or can be accurately solubilised to provide, following prop-
er dilution, an analytic solution.

28
Identification and characterisation of ceramic raw materials

Melting temperatures of compounds used in fusion-type decomposition of materials.

Compound Compound Compound

(1) After decomposition and transformation of bisulphate in pyrosulphate K2S2O7.


(2) Normally introduced in the dihydrate form.
(3) Like PbO after decomposition and outflow of carbon dioxide at 315 °C.
(4) Like PbO after decomposition at 500 °C approx.

Whatever the employed instrumental technique, the preventive establishment


of various calibration curves will be required via the utilisation of standard solu-
tions or solids within the presumed analysis range for the new samples.

The main methods used in quantitative ceramic material chemical analysis are
based on interaction (of the fluorescent emittance, absorption or emission type) of
the sample with electromagnetic radiation. The main methods are:

X-RAY FLUORESCENCE (XRF), in which raw minerals or, preferably, miner-


als finely dispersed in an alkaline glass, are bombarded by high-frequency short
wavelength radiation. The energy in the radiation induces fluorescent emission owing
to the excitation of inner electrons in the orbitals of the elements; these sample-
emitted electrons are collected in a special detector. The generated signal is associ-
ated with the position of the sample or the detector itself so as to identify the
relative intensity of the signal that can be compared with a standard one.
These methods allow for easy quantification of medium-high atomic weight
elements as far as the lower Na - F limit. More recently, considerable efforts have

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been made to extend sufficiently repeatable element assessment as far as Boron


(Fig. 13).

ABSORPTION SPECTROSCOPY (AAS-GFAAS). This technique exploits the


energy absorption caused by the presence of atoms placed in the path of one or
more monochromatic radiation beams generated by special lamps: in practice the
solution to be analysed is injected into a flame, the temperature, geometry and com-
position of which ensures that the elements are present in atomic (not ionic) form
and provides maximum interaction with the incident radiation. To obtain more ac-
curate resolution it is sometimes possible to use fast induction heating as the atom-
isation energy source instead of a flame: this is effected in a tube made of graphite
or other suitable material in an inert gas flow. Under specific conditions this tech-
nique can even be used for direct analysis of easy-volatilisation solid samples; it is
also a technique that gives excellent analytical results for any metallic element and
can provide superb resolution, in the order of, depending on the element, fractions
of parts per million (Fig. 14).

INDUCTIVELY COUPLED PLASMA-ATOMIC EMISSION SPECTROSCO-


PY (ICP-AES). Similar to the previous technique, but measures interaction with
the incident radiation in terms of emission as opposed to absorption. In this case
the sample solution is atomised by the combined action of a standard high temper-
ature torch and application of a radio frequency source. With respect to absorption
systems, this technique is advantageous in that it is possible to effect sequential
analysis of each sample without having to modify the source. Detection limits for
each element are generally poorer, yet results are actually better with some ele-
ments. In any case it is possible to switch from p.p.m. to p.p.b. fairly easily (Fig. 15).

Other chemical analysis methods pertinent to the search for specific elements
(e.g. FLAME PHOTOMETRY in tracking down alkaline elements) do, of course,
exist, but a detailed account of these is beyond the scope of this book.
It is, instead, worthwhile pointing out that specific chemical tests can be used to
check for the presence of specific elements (carbon, sulphur, fluorine...) or anions
(CO32- carbonates, SO42- sulphates…): these employ analytical techniques that are
generally simple and efficacious and provide extremely important information for
evaluating the applicability of a raw material in a ceramic process.

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Identification and characterisation of ceramic raw materials

Fig. 13a.

Fig. 13-13a. Operating principle of X-ray fluorescence (XRF) chemical analysis.

Fig. 14. Operating principle of atomic absorption spectroscopy (AAS).

Optical Systems
Torch
Generator
(ICP)

Pump/
Nebuliser

SPECTROMERC

SPECTRO AS 300 SPECTROSONIC

Fig. 15. Operating principle of inductively coupled plas-


ma-atomic emission spectroscopy (ICP).

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Mineralogical (or crystallographic) analysis

This type of analysis allows the technician to check for the presence of individ-
ual crystal phases in a sample and thus trace its mineral composition, the evaluation
of which is of primary importance in defining the technological characteristics of
a raw material or the contribution it will make to a body.
A preliminary form of such mineralogical information is provided first by na-
ked-eye and then microscopic inspection under reflected, polarised and transmitted
light (on naked samples included in the resin): by combining the cited observations
with other optical properties (e.g. refractive index) it is possible to obtain good
discrimination and recognition results. In the mineralogical analysis of ceramic
materials the entire science of optical microscopy should be viewed as a branch in
its own respect consisting of numerous techniques (as illustrated by the abundant
literature) that achieved maximum diffusion between the 1940s and 60s.The most
widespread mineralogical analysis technique now in use is X-RAY DIFFRACTO-
METRY (XRD). This can be effected on individual crystals or, more commonly, on
powders (Fig. 16).
The incident X-radiation falling on the sample, properly filtered so as to confer
monochromaticity, interacts with the crystal lattice, giving rise to related diffrac-
tion images, via the equation Bragg nλ = 2dsinϑ, at the inter-lattice distance d of the
crystal as a function of the diffraction angle. Since a wide range of X-ray sources
can be used (the most common is provided by Ni-filtered Cu anticathodes emitting
CuKα = 1.541 Å only) it is correct to list every interaction set of a particular crystal
lattice with the list of the active lattice distances expressed in Angstroms (Å).
Indexes and data bases are available for all crystalline substances (PDF, see the
examples in tables 5 and 6). These are updated by an international controlling body.
This reference material allows recognition of crystal types in natural and artificial
samples, while recent software improvements now provide more modal manage-
ment of diffractometry data, providing quantitative evaluations with regard to the
presence of individual minerals.

Of course, when working with powders it is essential that the sample be high-
ly representative of the whole. There should be no preferential orientation, easily
caused by bi-directionally developed crystals: this is why preparation and laying
out of the sample are so important. Milling must be carried out as efficiently as
possible, taking care not to alter the structural characteristics of the sample, es-
pecially where clayey, so as to aid homogenisation of all the phases and ensure
casual orientation of all crystalline faces; where analysis with a spinning sample
holder is excluded (such equipment is usually unavailable), one must be reason-
ably certain that a strongly non-oriented sample has been prepared, even in the
concomitant presence of phases having different density and inappropriate crys-
tallographic habit, such as clays and micaceous materials having micelles of a
well-developed bi-directional form.

X-ray diffractometry analysis is a fairly routine procedure. It is relatively quick

32
Identification and characterisation of ceramic raw materials

Fig. 16. X-ray diffrac-


tometry analysis equip-
ment (left) and the oper-
ating principle on which
it is based (top).

and simple and, on sufficiently simple matrices, leads to fairly easy interpretation of
the gathered data, allowing moreover – through combination with the verified pres-
ence of certain crystal phases, attribution of a chemical formula and combination
with quantitative chemical analysis – so-called rational analysis of a raw material or
body (i.e. approximation of its composition expressed in standard minerals). It will
therefore be possible to evaluate a ceramic body not only in terms of its oxide-based
chemical composition, but also its mineralogical composition, expressed in Quartz,
Kaolinite, Illite, Calcite, Dolomite, Albite (Sodium feldspar), Microcline (Potassium
feldspar) etc. (see Fig. 17 for example).

Thermal analyses

As the heading suggests, there is more than one way of analysing samples via
the parameter variations that occur as a function of an increase (or decrease) in
temperature. Variations in weight, temperature, heat evolved or absorbed, dimen-
sions, gaseous substances emitted etc. can all be registered as a function of a partic-
ular temperature gradient. Each of these techniques has a corresponding type of
analysis, as listed below:

TGA (ThermoGravimetricAnalysis),

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Tab. 5. PDF chart containing crystallographic data for quartz (SiO2).

Tab. 6. PDF chart containing crystallographic data for kaolinite.

34
Identification and characterisation of ceramic raw materials

“Porous single firing, coloured body” dry grinding, pressing

Fig. 17. Example of body chart with rational XRF + XRD analysis.

DTA (DifferentialThermalAnalysis),
DSC (DifferentialScanningCalorimetry),
TMA (ThermoMechanicalAnalysis) or DIL (Dilatometry),
EGA (EvolvedGasAnalysis).

These types of analysis are not only an obvious method for observing and pre-
dicting the behaviour of an individual raw material or a body during drying, firing
or cooling: they are also an excellent aid in determining the mineralogical composi-
tion of a material, as the observed effects closely correlate with the crystalline struc-
ture and the phase transformations of various minerals. Since the presence of min-
erals and salts such as dolomite, carbonates, sulphates, sulphides and fluorides etc.
(Figs. 18-22) can be recognised, such analyses can also help identify chemical pa-
rameters.

The instrumentation used for thermal measurements essentially consists of a


measuring head (which houses the appropriate physical form of the sample and
transforms variations in such sample into amplifiable, manageable electrical sig-
nals) and a heating system. The latter generally uses electrical elements which must

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Fig. 18. Comparison between the most significant (appropriately schematised) DTA curves represent-
ing clayey minerals: A = kaolinite; B = metahalloysite; C = Na-montmorillonite; D = Ca-montmo-
rillonite; E = vermiculite; F = sepiolite; G = polygorskite.

Fig. 19. Differential Thermal Analysis (by G. Peco 1952).


C = kaolinite; Cr = cristobalite; H = halloysite; Q = quartz; I = illite; Ca = limestone; M = montmo-
rillonite. TG, DTG, DTA and ETA analysis on Hirshau kaolin (by E. Kaisersberger and C. Urso).

36
Identification and characterisation of ceramic raw materials

Fig. 20. Examples of dilatometric curves. Unfired samples undergo irreversible transformation (curve
a) and fired ones, in cooling, essentially return along the curve followed during heating (curve b).

be extremely stable, homogeneous and programmable so as to ensure perfect


repeatability of measurement.
It is often possible to combine several such analyses with just one instrument
(e.g. TGA + DTA, TGA + DSC, DTA + EGA or TGA +DTA + EGA), allowing
the user to obtain a wealth of information from just one measurement.
To provide the reader with a short summary of the operating principle be-
hind some of these instruments, there follows a description of those most com-
monly used in the ceramic industry, beginning with the dilatometer and simulta-
neous TGA + DTA analysis.

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Fig. 21. Dilatation-Shrinkage (DS) and Differential Thermal Analysis (DTA) of secondary minerals
(by G. Peco 1970) Ca = limestone; Q = quartz; Cr = cristobalite; F = feldspar.

Fig. 22. Dilatation-Shrinkage (DS) and Differential Thermal Analysis (DTA) of standard clayey
minerals (by G. Peco 1970). C = kaolinite; H = halloysite; M = montmorillonite; Mi = mica.

38
Identification and characterisation of ceramic raw materials

Dilatometric analysis measures the expansion and shrinkage of an appropriately


pre-formed sample, usually parallelepiped or cylinder-shaped, and approximately
10 (∅) x 35-45 mm in size (unfired, pre-fired or fired). Simultaneously, elongation
of the measuring system and support must be compensated for: the latter is usually
made of quartz, for measurements of up to 950-1000 °C, or alumina (up to 1350
°C) owing to their limited expansion.
The heat will obviously cause all the materials, especially the clayey ones, to
dilate and shrink as a function of that which occurs in their interior. More specifi-
cally, the loss of volatile components (especially water) induces a “collapse” of the
crystalline structure of the clays which is detected as intense shrinkage at specific
temperatures. It is therefore possible, by observing the contraction (or expansion)
characteristics over temperatures up to or even beyond the normal firing range, to
distinguish between free or combined waters in the lattice. It is also possible to
identify critical temperatures where structural alterations are occurring and the
speed of such changes. Transitions such as α to β quartz and α to β cristobalite and
other reactions both reversible and irreversible can be noted and their potential
influence on the heating processes during manufacture considered.
The dilatometric analysis of standard materials illustrated in figures 20-21-22,
is significantly representative of this possibility.
There is also another – and highly important – use for dilatometric measure-
ments effected on ceramic raw materials and bodies: the measurement of a tenden-
cy of a material to expand or shrink within a certain temperature interval (i.e. its
linear thermal expansion coefficient).
This is expressed by the following formula:

αT1-T2 = ∆L / (L0 × ∆T)

where α is the linear thermal expansion coefficient between T1 and T2, L0 is the
initial length of the sample and ∆L is the difference between LT1 and LT2. It is,
however, consolidated practice in a factory to use, instead, the cubic coefficient. This
is obtained by multiplying the linear coefficient obtained from dilatometric mea-
surements by 3, on the arbitrary assumption that the propensity towards dimen-
sional variation is the same in all directions.
This data is extremely important in evaluating compatibility between different
materials during heating and, more importantly, during cooling, where any tension
that has built up as a result of dilatometric incompatibility becomes permanent.
Firing of a glaze that has been applied to a ceramic body is a classic example (Fig.
23).

In the light of the above it is clear that there exists the opportunity or, rather,
the need, to effect a series of “fine” analytical checks on raw materials used in the
ceramic production process: most companies do not have the relevant instruments
and thus checks are generally outsourced to laboratories or external bodies with
the equipment for accurate examination.

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Fig. 23. Opposing effects of dilatometric incompatibility between glaze and body in the cooling part of
the cycle: case A αglaze > αbiscuit - case B αglaze < αbiscuit.

Fig. 24. Dilatometric apparatus.

40
Identification and characterisation of ceramic raw materials

However, in-company organisation of production checks will allow work to


be carried out with continuity and homogeneity and is thus of great impor-
tance.
The greater the accuracy and frequency of such checks, the greater the chanc-
es of promptly correcting errors or improper settings; the more punctual and
orderly the recording, interpretation and filing of such results, the easier it will
be to recommence and optimise the manufacture of a given product line at some
later date.

For these reasons, manufacturers would be advised to carry out the following
checks.

Plastic, semi-plastic and non-plastic raw materials

Determination of the characteristics of incoming material via measurement of:

Moisture content
Size and appearance
Residue
Carbonates
Reducing agents

Moisture content expressed in %


A sample of wet material is weighed (Pu), then dried to constant weight in a
laboratory drier at 110 °C for about 24 h. Its dry weight (Ps) is then measured. The
difference between the two weights divided by the weight of the wet sample multi-
plied by 100 gives the moisture content of the sample:

Pu - Ps
u% = _______ x 100
Pu

Appearance of incoming material


Form and dimensions (piece size) of the incoming material should be noted, as
should colour and all other key characteristics.

Sieve residues
One hundred grams of dry sample is weighed and treated in a laboratory agita-
tor for about 30 minutes with 300 ml of de-ionised water to which 1g of sodium
tripolyphosphate or sodium polyacrylate is added so that the particles are complete-
ly broken up and dispersed.
The slip is sieved at 1,000, 2,500 and 10,000 mesh/cm2 (180, 125 and 60 µm
screens).

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Fig. 25. Apparatus for determination of the various particle size distribution bands.

The residue obtained in the various sieves is dried to constant weight and then
weighed. The resulting values directly provide residue percentages for the various
mesh sizes.
With non-plastic raw materials it may be interesting to carry out dry measure-
ment by sieving about 200 g of dried material through a sieve column of appropri-
ate mesh sizes [e.g. 11(2,000) - 35(1,000) - 140(500) - 590(250) - 1,600(150) - 4,700(90)
and 9,500(63) mesh/cm2 (mm)].

Carbonate content expressed in % CaCO3


Measurement is carried out using a calcimeter (e.g. Pizzarelli or Dietrich-Fru-
hling). One gram of sample material dried at 110 °C is placed in the container.
Diluted hydrochloric acid (1:1) is introduced into the container via a tap.
If the material contains carbonates of any kind CO2 will be released, which, by
exerting a pressure proportional to the quantity of carbonates in the sample, low-
ers the water column in the graduated cylinder: from here, the percentage of car-
bonates in CaCO3 form contained in the raw material can be read off directly or
calculated. Once the released volume of CO2 and the absolute temperature are known,
the following calculation can be made:

% CO2 = 53621 × VCO2 (litres) / °K

42
Identification and characterisation of ceramic raw materials

Fig. 26. Apparatus for the determination of carbonate minerals (calcite and dolomite).

Assuming that CO2 has been generated by CaCO3 only: % CaCO3 =% CO2 . 2.273.

Determination of total reducing substances


Effected via RedOx back-titration.
Approximately 2 g of powder < 200 µm are transferred into a 400-500 ml bea-
ker to which 10 ml of a K2Cr2O7 1 N solution (49 g in one litre of distilled water)
and 10 ml of concentrated H2SO4 are added. The container is then hand-shaken for
about one minute, then left on a slow magnetic stirrer for 30 minutes (the colour
should remain yellow-orange: if it is green another 10 ml of dichromate is added).
Then add 10 ml of phosphoric acid 85% to complex the iron which is present
and dilute with 200-250 ml of distilled water; add approximately 2 ml of indicator
solution (0.16 g of diphenylaminosulphonate of Barium in 100 ml of distilled wa-
ter), and titrate with FeSO4 0.5 N (140 g in 200 ml in distilled water + 40 ml of
H2SO4 concentrate, made up to a litre and stored in a dark glass container) under
slow agitation. Becoming bluer and bluer, it will change to light green at the equiv-
alence point.
The obtained value should be corrected in line with the effective reducing oxide
ratio of the reagents, obtained by effecting the same titration without the sample.

Formula:
ml of reduced K2Cr2O7 × 0.69 (stoichiometric factor)
___________________________________________ = total reducers %
sample weight (g)

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Example:

“Blank control” test: 10.0 ml of K2Cr2O7 added, 21.5 ml of FeSO4 necessary for
end point without clay: correction factor = 0.465 (10/21.5).
Measurement test: 2.125 g of sample + 10 ml K2Cr2O7, 19.25 ml of FeSO4 nec-
essary for end point: 10 - (19.25 x 0.465) × 0.69 /2.125 = 0.34% total reducers.

This measurement essentially detects the organic substances in the sample, but
is also influenced by the presence of any reducing substance, especially mineral
sulphides such as Pyrite, Marcasite etc.

44
Identification and characterisation of ceramic raw materials

Chapter II

ROCKS

The rock cycle

An understanding of rocks may be achieved by classifying them according to


how they are formed, giving us:
Igneous rocks (intrusive and extrusive).
Sedimentary rocks.
Metamorphic rocks.

The term “rock” refers to a natural aggregate of one or more minerals. The term
“mineral” refers to a homogeneous natural solid with a well defined chemical com-
position and its own crystalline structure. The interconnected processes that lead
to rock formation constitute what is known as the “rock cycle”. The earth is essen-
tially made up of a series of concentric layers - the Crust, the Mantle and the Core.

Cross section of the Earth

Crust

Mantle

Molten
outer core

Solid
inner core

Fig. 27. Simplified cross-section of the Earth’s interior.

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A part of the mantle (the external part) is molten as a result of the high temper-
atures and pressures at such depths; if this part of the mantle shifts to areas where
temperature and pressure are lower (i.e. towards the earth’s crust) it may solidify,
thus giving rise to intrusive rock. Where the molten mass (MAGMA) reaches the
surface, it cools much more rapidly, giving rise to extrusive rocks.
Intrusive rocks may subsequently be brought to the surface by forces of tectonic
origin.
Degradation processes effected by both atmosphere and hydrosphere continu-
ally alter the surface of the earth’s crust: for example, erosion may dismantle
existing igneous rock of both intrusive and extrusive origin. Such “surface deg-
radation” gives rise to sedimentary rocks. Aqueous solutions can lead to precipi-
tation of salts or supply materials to organisms. allowing them to form shells or
skeletons. Granules produced by the erosion of pre-existing rock, salts separated
from solutions by the activity of organisms and salts which precipitate directly
from the solutions themselves give rise to an accumulation of sediments. The
latter are compressed and permeated by other layers forming above them and
thus undergo that transformation (DIAGENESIS) which leads to the formation
of sedimentary rocks. These continue to be buried by later deposits and are con-
sequently shifted to greater and greater depths. However, tectonic forces may
bring them back to the surface where they are again exposed to degradation. Al-
ternatively, movements in the earth’s crust may bury rocks (sedimentary, extru-
sive, intrusive) even deeper; beyond certain depths, the changes in pressure and
temperature cause profound modifications. This is where metamorphic rocks are
formed. Like the others, metamorphic rocks too can be brought to the surface and
subject to degradation, thus resulting in new layers of sedimentary rock. Alter-
natively, rocks may be carried to extreme depths (or close to very high tempera-
ture zones) where they melt and give rise to new magma of a composition differ-
ent from that of the original magma.

Volcano
Atmosphere

Sea

Plutons

Magma Sedimentary Rocks

Metamorphic Rocks

Fig. 28. The magma-rock-magma cycle.

46
Rocks

The mantle-fed magma can arrive at the surface rapidly via volcanoes (2) or
consolidate within the earths crust (1). In this case tectonic forces (3) may brings
plutons (igneous intrusions) to the surface where the atmosphere and hydrosphere
cause degradation (4). The eroded materials are carried away by rivers and streams
into depository basins (5). This is where accumulation begins (6), transforming the
sediments into sedimentary rock (7). These may be returned to the surface (8) where
the “destruction-accumulation” pattern begins anew, or may sink deeper (9) where
they are transformed into metamorphic rocks. Similarly, intrusive rocks (1) can be
transformed into metamorphic rocks (9) by variations in temperature and pressure.
If pressure and temperature conditions are particularly intense the metamorphic
rocks will fuse and give rise to new magma (11).
The black arrows indicate tectonic forces.

Magma

Magma is an essentially silicate, high temperature solution in a partially or total-


ly molten state. It also contains considerable quantities of volatile elements (i.e.
gases), which directly influence both the physical behaviour of the magma and its
composition. The most important of these are: water vapour, carbon dioxide (CO2),
carbon monoxide (CO), hydrogen, ammonia (NH3), hydrochloric acid (HCl), hydro-
gen sulphide (H2S), sulphur dioxide (SO2) and sulphuric trioxide (SO3); these gases
are part primary and part secondary (i.e. originally present in the magma or intro-
duced by contact between the magma and the overlying rock).
Cooling~consolidation of the magma forms magmatic (or igneous) rock. The
key characteristic of these rocks is that they are made up of crystals of varying size
and form, visible to the naked eye or with the aid of magnifying glasses or micro-
scopes. Rocks of magmatic origin are of a varying chemical and mineralogical struc-
ture in which the main components are quartz, feldspars (orthoclase and plagiocla-
se), micas (muscovite and biotite), amphiboles, pyroxenes and olivines.

Clays and rocks

Clays, materials of prime importance to the ceramic industry, are extremely var-
iable rocks made up of different minerals, generally of a silicate nature, sedimented
in the form of platelets, fibres, belts etc., and are, for the most part, associated with
other minerals of detrital origin that often play a key role.
Variety is vast, since the combinations of initial rock types, morphological and
climatic conditions, types of erosion and alteration, transport and sedimentation
conditions, state and duration of attitude are virtually incalculable.
To render the concept of genesis clearer, consider a rise or any zone exposed to
atmospheric agents: erosion is caused by the combined action of rain, wind and the
freeze-thaw cycle, resulting in material that accumulates in the form of soil or is
washed far away by surface waters, giving rise to sedimentary basins.

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Subsequently, through orogenetic or tectonic movements or simple accumula-


tion of successive layers, the accumulated materials will, over geological time
spans, form a hollow and consequently be subject to enormous pressures and pro-
found morphological modifications, being turned to stone. Then, that stone un-
dergoes diagenesis (that set of phenomena that modifies a sediment, giving rise
to greater coherency). At a more advanced stage of transformation there is cati-
onic substitution on the crystal lattices and further increases of pressure and
temperature may lead to further formation of new rock (metamorphism). Finally,
further orogenetic or tectonic movements may bring these completely modified
rocks to the surface.
In the processes of alteration and erosion of rock, then, tectonics play a key role,
causing a series of movements/displacements of rock formations and stratigraphic
units. Tangential forces cause corrugation while vertical movements result in the
formation of new hollows in which accumulation of sediments can once again be-
gin.

Primary rocks

Since characterisation and understanding of the clayey formations found in nat-


ural deposits within the earth’s crust are of enormous interest, it is worthwhile
providing an introduction to the primary rocks that give rise to them.

In the field of petrography there are three main rock categories:


• Consolidated rocks of magmatic origin
Also known as igneous rocks, these derive from solidification of volcanic mag-
ma, a process that occurs:
a) deep underground: plutonic or intrusive
b) on the surface: volcanic or effusive.
These two magmatic rock types respectively give rise to basalts and granites,
which rarely come together in hybrid form.

• Sedimentary rocks
Produced by the consolidation of sediments, solid particles suspended in fluids
(usually water) that transport them considerable distances from the site of erosion.
These particles settle from the fluid owing to their greater density. The complete
formation process, then, involves the alteration phase of the original materials fol-
lowed by erosion, transport and, finally, depositing, the final result of which is greatly
influenced by the size of the particles and the pressures/temperatures exerted on
the sedimentary layer by subsequent geological events in the zone, any intervening
chemical reaction etc.

Among the sedimentary rocks, the most common minerals are clays, quartz and
calcite; it is important to distinguish:
a) Detrital rocks (argillites, pelites, conglomerates…)

48
Rocks

b) Organogenic rocks (limestone, marble, dolomite…)


c) Precipitation-derived rocks (evaporites, chalk…).

It is also important to point out that further classification is often effected ac-
cording to dimensional criteria. Such criteria give rise to different classifications of
well defined terminology such as those illustrated in the table below:

ROCKS CONSTITUENTS mm

Coherent Incoherent

RUDITES GRAVELS Mass > 300


Blocks 64
Pebbles 4
Granules 2

ARENITES SANDS Very coarse 1


Coarse 0.500 (= 500 µm)
Medium 0.250 (250)
Fine 0.125 (125)
Very fine 0.063 (63)

LUTITES SILTS Coarse 0.0315 (31.5)


Medium 0.0156 (15.6)
Fine 0.0078 (7.8)
Very fine 0.0039 (3.9)
Clay particles < 4 µm

• Metamorphic rocks
These are formed by chemical-physical solid state reactions caused by shifts in
the earth’s crust, such as, for example, in the sinking of surface rock masses.
In general, the crystals of rocks formed in this way point in the direction of the
tensions and loads acting on them (e.g. schist); the temperature increase associated
with the geothermal gradient originating from increased proximity with the earth’s
mantle leads to dehydration of the original minerals (e.g. formation of potassium
feldspars from micas).

In following the origin and history of a clayey formation it is extremely impor-


tant to have an understanding of the type of rock making up the erosion basin and

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the sedimentation basin so as to better understand the mechanisms that form clayey
rocks.
At present the earth’s crust, on average, is thought to be as follows:

% by weight % by weight % by volume


(oxides) (elements) (elements)
O 46.7 92
SiO2 60 Si 27.7 0.8
Al2O3 15.5 Al 8.1 0.8
FeO + Fe2O3 7 Fe 5.1 0.7
CaO 5 Ca 3.6 1.6
Na2O 4 Na 2.7 1.5
K2O 3 K 2.6 2.1
MgO 3.5 Mg 2.1 0.6
TiO2 1 Ti 0.5 0.1
Others 1 Others 0.9

The minerals representative of this composition are not very numerous, and are
those that generally give rise to clays.

50
Rocks

Main minerals in the earth’s crust

– CALCIUM-SODIUM FELDSPARS (Plagioclases) 42%

Albite 0 - 10% An Na[AlSi3O8]


Oligoclase 10 - 30% An
Andesine 30 - 50% An
Labradorite 50 - 70% An
Bytownite 70 - 90% An
Anorthite 90 -100% An Ca[Al2Si2O8]

– POTASSIUM FELDSPARS 22%

Orthoclase, Microcline, Sanidine K[AlSi3O8]

– QUARTZ SiO2 18%

– PYROXINES 9%

Diopside (Ca,Mg)[Si2 O6]


Augite (Ca,Mg,Fe,Ti,Al)2 [(Si,Al)2 O6]

– AMPHIBOLES 6%

Hornblende, Biotite, Olivine

– MUSCOVITE KAl2[AlSi3O10](OH,F)2 3%

– FELDSPATHOIDS <1%

Leucite K[AlSi2O6]
Nepheline KNa3[AlSiO4]4

Clayey formations may, then, vary greatly in terms of composition, degree of


consolidation etc. It is thus necessary to classify them by grouping them together
according to:
– Cohesion and water content - thus differentiating plastic clays from lithificated
ones.

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– Composition - in such a way as to differentiate pure clays (made up of just one


clayey mineral) from carbonatic clays (known as marls) and sandy clays (contain-
ing quartz, SiO2) etc.

If the mineralogical composition of the clays and their stratigraphic distribu-


tion etc. are variable it is said that they belong to the group of the clastic or
hallogenetic rocks. If the clays are found at the (sedimentation) location where
they were formed they are known as residual, while they are defined as alloch-
thonous if they have been transported and excavated in some other area. In any
case, the problem of clayey rock classification is extremely complex, and is be-
yond the scope of this work. Yet examination of individual clayey minerals, and
the characteristics that they have in an industrial context is, as might be expected,
of extreme interest.

Structure of clayey minerals

Having provided a brief summary of clayey formations in relation to the other


rocks from which they are derived, we shall now take a look at just what they consist
of so as to obtain a better understanding of their genesis. Of particular interest is
structure, as it is this which determines their behaviour and differentiates them,
especially as regards their capacity to combine with water – a key factor in provid-
ing plasticity.

Here, an introduction to simplified silicate classification will be useful (i.e. the


ways in which repetitive tetrahedral SiO4 units are organised). Links are made be-
tween vertices only, with oxygen atoms forming bridges between silicon atoms, thus
giving rise to:
• Nesosilicates, made up of independent tetrahedrons.

• Sorosilicates, with two, three, four or six tetrahedrons, possibly in a closed loop
configuration.

52
Rocks

• Inosilicates, having chains of tetrahedrons linked by cations.

• Phyllosilicates, in which the union of three vertices of each tetrahedron with


another forms layers.

• Tectosilicates, where the tetrahedrons unite to form a 3-dimensional lattice.

As mentioned above, clayey minerals are generally alumino silicate hydrates of


varying complexity, consisting of lamellas that can slide against each other (phyllo-
silicates). The molecular structure of such minerals consists of the combination of
tetrahedral repetition units (coordination 4), with a silicon atom surrounded by 4
oxygen atoms, and octahedral repetition units (coordination 6) with an aluminum
atom – sometimes substituted by magnesium or iron – surrounded by 6 oxygen
atoms.
Among the most common elements in the earth’s crust, oxygen is undoubtedly
the most widespread and is one of the largest too:

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ION IONIC RADIUS (Å)


O 2- 1.3
Si 4+ 0.4
Al 3+ 0.6
Fe 3+ 0.7
Ti 2+ 0.6
Ca 2+ 1.0
Mg 2+ 0.8
Na + 1.0
K+ 1.3

Bearing in mind the ionic radius of oxygen and silicon (the second most wide-
spread element) it can be seen how this has the bulk to be at the centre of a compact,
regular polyhedron of minimum potential energy, with a coordination number of 4
(i.e. the tetrahedron [SiO4]4-).
The octahedral configuration with a coordination number of 6 is given by the
regular arrangement of the oxygen ions – or, more commonly, hydroxyls (OH-),
which have the same radius – around an Al3+ ion of a size suitable for containment
at the centre of such a structure.
Both silicon-based tetrahedrons and aluminium-based octahedrons can combine
together to form repetition units via apex-apex, edge-edge or face-face bonds, giv-
ing rise to different structural repetition units of various shape.
The combination of tetrahedral and octahedral structural units, arranged in reg-
ularly overlain layers with well-defined inter-layer distances, is also possible: those
distances are extremely important in determining the macroscopic characteristics
of individual clayey minerals.
The simplest configuration is the two-layer one, with alternation of units made
up of tetrahedral – linked 2-by-2 by an apex (Si2O5)2- – and octahedral layers (Fig-
ures 29 a and b show grouping of the kaolinite and montmorillonite).

(A) Halloysite
(B) Kaolinite

Fig. 29a. Example of possible structural arrangements in clays.

54
Rocks

(A) Na-montmorillonite
(B) Ca-montmorillonite

Fig. 29b. Possible structural arrangements of clays.

This can be described by the rough formula (OH)3Al2(OH)Si2O5, or, more appro-
priately, Al2O32SiO22H2O, which corresponds better with the chemical analysis, ex-
pressed in oxides. This molecule is electrically neutral (6 positive charges from the
aluminum + 8 positive silicon charges = 14 positive charges, saturated by the 4
negative charges of the OH- groups and 10 negative charges from the remaining 5
oxygens = 14 negative charges) and consists of particles around 1 µ thick, although
the finest may be smaller than 0.005 µ (i.e. the equivalent of 7 elementary sheets),
thus forming ionic crystals of varying size.
Clayey minerals of greater complexity may have octahedral layers interspersed
between tetrahedral layers, in 3-layer arrangements as is seen with talc and pyro-
phyllite; this structure is also seen in Illite (mica group), where the triple tetrahe-
dral/octahedral/tetrahedral layer is associated with another octahedral layer etc.
(Figs. 30-31).

(A) Vermiculite
(B) Tri-octahedral Chlorite

Fig. 30. Further examples of phyllosilicate conformations.

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(A) Muscovite
(B) Illite

Fig. 31. Further phyllosilicate conformation examples.

This way of organising different types of clayey sheet constitutes the most use-
ful distinctive criteria in classifying clayey mineral groups. The fact that there is,
between the sheets, a space large enough to allow the introduction of one or more
water molecules (inter-sheet or inter-layer water) gives rise to a further classifica-
tion, this time a technological one, as the presence of such water greatly influences
the capacity of these various layers to slide against each other and thus ultimately
determine the plasticity of the material.
It is thus possible to formulate a simplified classification of the main clayey ma-
terials:

Tetrahedrons/Octahedrons Mineral group Lattice space (Å)

Non-crystalline ALLOPHANES —

1/1 KAOLINITE (Nacrite, Dickite) 7.2

1/1 HALLOYSITE 7.2 - 10.1

2/1 PYROPHYLLITE – TALC 10

2/1 MICAS (ILLITE) variable

2/1 SMECTITES (Montmorillonite etc.) 10 - 21


VERMICULITE 10 - 14

2/1/1 CHLORITE 14.1

Within such groups, the nature and position of the substitutive cations consti-
tute a further classification criteria.

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Rocks

For example, substitution within an octahedral cavity is particularly significant,


as in the passage from kaolinite Al2Si2O5(OH)4 to a mineral of the serpentine group
Mg3Si2O5(OH)4.
These substitutions also determine the ionic exchange capacity of these materi-
als that will be discussed further on. Indeed, the electrical balance must be main-
tained, and this means that ions originating from the environment surrounding the
material can compensate for any charge deficit.
In this sense the different cations behave in a selective manner, effecting an or-
derly substitution as follows

Na+ < K+ < Ca++ < Mg++

which means that the calcium ion can replace the sodium ion more easily than
the reverse. This compensatory exchange effect may vary as a function of the ionic
charge of the solutions.
An enormous variety of exchanges can take place, even including in-tetrahedron
substitution of silicon with aluminum; thus, as a function of the ionic charge, com-
pensation processes are activated, mainly through the participation of K+ and Na+
ions that position themselves, via electrostatic attraction, on the basal faces of the
micelles. In the case of Illite, for example, substitution of aluminum with silicon
may take place in the octahedron and this weakens the total ionic charge of the
clayey micelle in which there was a charge imbalance of a sign opposite to that at
tetrahedral level: the K+ cations, then, are fixed less stably on the surfaces, but tend
to position themselves laterally, largely where there are discontinuities or fractures,
and this alters the characteristics of this clayey material even further.
The process occurs, in the same way, and especially as regards substitutions in
the octahedral layers, in smectite-type minerals. In these cases there is a general
decrease in ion-sheet and sheet-sheet binding forces, thus leading to a variable lat-
tice distance that consequently allows insertion of whole water molecules, with all
the resulting consequences.
Similar phenomena occur in the chlorites, but the inter-layer water is often re-
placed by Al(OH)3, Fe(OH)3 and, above all, Mg(OH)2.

Cationic exchange capacity (CEC), easily established using routine analytical tech-
niques, is an intensive measurement which provides a realistic image of just how
much these phenomena are present in a clayey mineral. It gives a measure of the
ease of cationic exchange in the structure of the mineral, via the introduction of
Na+ ions. Observing that:

Clayey mineral CEC (meq/100g)


Kaolinite 5 - 15
Illite 20 - 50
Montmorillonite 50 - 150

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it is evident how isomorph substitutions are more marked in complex structures


having several associated layers of elementary tetrahedral-octahedral elements.

Characteristics of the main clayey minerals

From the above it can be seen that it is possible to effect a more or less complete
characterisation of clays in general via the description of a few clayey minerals
(kaolinite, illite, montmorillonite and chlorites), although it should be born in mind
that polyphyllitic mixed layers often occur (e.g. Bravaisite, consistent in a mix of
Illite and Montmorillonite).

We shall now go on to examine the main characteristics of the individual classes


of clayey raw materials.

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Rocks

Chapter III

RAW MATERIALS FOR CERAMIC BODIES

Kaolinite

Origin of the term


Derives from the Chinese words “kau-ling”, meaning “high hill”, indicating the
province of Jianxgi, the place where this raw material was first extracted for ce-
ramic manufacturing purposes.

Mineralogical structure
The base element consists of a “tetrahedral sheet” in which each tetrahedron
consists of four oxygen atoms (each with two negative charges), positioned at its
apexes, and a silicon atom (with four positive charges) at its centre. This is associat-
ed with an “octahedral sheet” in which each octahedron consists of six OH- hydrox-
yl units (each carrying a negative charge) located at its apexes and a cation (usually
trivalent but also bivalent) at its centre. This base element is illustrated in Fig. 32.

Structure of kaolinite
according to Gruner

Elementary
kaolinite cell
Fig. 32.

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The tetrahedral unit thus has four non-saturated negative charges; the octahe-
dral unit is negative too with three (if the cation is trivalent) or four (if bivalent)
non-saturated charges.
In the kaolinitic base element the two sheets “bind” by substituting an OH– hy-
droxyl on each octahedron with the sharing of an oxygen atom (at the tetrahedron
apex) which had a free charge.
This anion is thus shared by a tetrahedron and two octahedrons in that each OH–
hydroxyl unit is balanced by the aluminum cations of two adjoining octahedrons.
With this coupling the kaolinite structure is electrically neutral. This structure can
be repeated (vertically) a great many times while maintaining the same distance
between equal, adjoining levels.
It is this “structural rigidity” that explains the non-expandability of the pre-
served lattice despite the weakness of the forces on which maintenance of the struc-
ture depends (Van der Waals and hydrogen links).

Chemical composition
Al2(X2O5)(OH)4
Where x is the element in the tetrahedral position (Si4+ and, as vicariant, Al3+
and Fe3+, which lead the structure to be deficient by one positive charge).

Theoretical composition
SiO2 = 46.54%; Al2O3 = 39.50%; H2O= 13.96%

Genesis and characteristics of deposits containing kaolinite


These deposits originate from the transformation of crystalline rock feldspars
which leads to simultaneous removal of the alkaline elements (sodium and potassi-
um).
In those rare cases that give rise to the formation of nearly-pure kaolin (usually
from feldspathic veins) it is milky white, has low plasticity, a greasy surface and
leaves a persistent whitish film on the skin when touched.
Usually, though, kaolinitic deposits are mixtures of kaolinite, quartz (resistant
to alteration and transformation phenomena) and feldspars (relics of an incomplete
aggression and transformation action); ferrous oxides (largely responsible for any
colouring of the material) and micas also have to be considered.
Kaolin deposits are generally primary in origin. This means that they exist where
the source rocks once existed and therefore have not been transported; secondary
deposits, instead, are those that have undergone removal and re-deposition in an
aqueous (usually lacustrine) environment.
These processes concentrate and select the finest particles, while, however, con-
taminating them with materials of organic vegetable origin (leaves, branches, roots,
carbonaceous elements).

It is important to remember the difference between deposits of kaolin (of poor


plasticity) and kaolinitic clays. The latter, of secondary origin, are characterised by
high plasticity (ball-clays); this is a consequence of natural particle size selection

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Raw materials for ceramic bodies

and the addition of plasticizing materials (vegetable and carbonaceous parts) that
sometimes blacken the raw material.

Location of main deposits and extraction techniques


The most important kaolin and kaolinitic clay deposits are found in England
(Devon and Cornwall), Germany (Westerwald and Bavaria in the districts of Wie-
sau-Tirschenreuth and HirschauSchnaittenbach), France (Brittany), Czechoslova-
kia (Karlovy Vary) and the USA (Georgia and South Carolina).
The oldest industrial method for the extraction of kaolinite from the source
rock involves the use of high-pressure water jets (monitors).
These are directed against the walls of the deposit so that the kaolinitic part is
removed, suspended in water.
That suspension is then classified by sedimentation and cyclones. This technique
was invented in Great Britain and is still used on British extraction sites where
suitable. As far as ball-clays are concerned, modern extraction methods have virtu-
ally eliminated underground mining in favour of open-cast methods with terraces
and ditches.
In Devon (England) the overburden is removed by bulldozers and scrapers, with
extraction being performed on banks varying in thickness from 3 to 6 m using
hydraulic excavators, draglines and bucket-wheel excavators.
Numerous beds of lignite may result in up to 50% of the removed material
being discarded as waste. Working conditions in the pits, together with the imper-
meable nature of the raw material in question, can lead to flooding, thus requiring
the use of high-capacity pumps to keep the extraction zones operative.
Extraction is highly selective everywhere: removal is preceded by systematic
core sampling and laboratory tests which provide the required pre-mining informa-
tion. The techniques adopted involve “terracing” methods that employ continuous-
operation hydraulic wheel dredges that feed a series of conveyor belts (covered to
protect them from rain).
These carry the clay to the storage areas. Alternatively, hydraulic excavators are
used to load trucks to take out the clay.

Mineralogical analysis of kaolinitic raw materials; standard behaviour and identifi-


cation
Identification via X-ray diffractometry (Fig. 33) essentially involves observation
of the basal plane diffractions.
The specific lattice distances are as follows: (plane 001) 7.18Å; (plane 020) 4.47Å;
(002) 3.57 Å; (003) 2.38 Å; (004) 1.78 Å. The diffraction pattern for CuKa radiation
gives peaks in the following angular positions: 12.51 (001), 20.90 (020), 25.0 (002),
51.11 (004).

The presence of certain chlorites can mask the presence of kaolinite owing to
coincidence of basal reflections at 12.50° (corresponding to 7.18 Å).
In this case any splitting that occurs in the reflection on the 002 plane must be
checked for, given that there exists a small difference between the lattice distance of

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disordered
kaolinite

Fig. 33. Example of a diffraction pattern for highly disordered kaolinite.

kaolinite (3.47Å) and chlorite (3.54Å) to which positioning of the peaks at 24.90
and 25.20 correspond respectively.
The DTA (Differential Thermal Analysis) diagram for kaolinite (Fig. 34) shows
a net endothermic peak at 580-600 °C, associated with the transformation of ka-
olinite in meta-kaolin with crystallisation water loss; at around 980 °C there is,
instead, a marked exothermic peak that is probably connected with the crystallisa-
tion of mullite or alumina (Fig. 35).
Thermogravimetric (TG) analysis shows a sharp weight loss at around 520~580
°C (i.e. when the crystallisation water is lost); no variations, instead, are observed
towards 980 °C, in that this particular exothermic reaction is caused by the libera-
tion of bond energy and not the removal of material.

Up to 450 °C, dilatometry (Figs. 36-37-38) is characterised by weak dilatation


(because of substantial alumina content). There then comes (beyond 550 °C) an
initial shrinkage phase associated with the elimination of the OH hydroxyls (this
extends towards 880 °C) followed by a second, more marked stage of contraction
associated with the start of sintering reactions.

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Raw materials for ceramic bodies

Fig. 34. DTA curves for several minerals in the kaolinite group.

Fig. 35. Mullite crystals formed by heating of kaolinite in a siliceous matrix (magnification x 37,000)
(by Kingery: Introduction to Ceramics - Wiley).

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Linear expansion (%)

Temperature °C

Fig. 36. Dilatometric curve for a high-purity kaolin sample, showing two abrupt contractions corre-
sponding to the dehydroxylation phase and the recrystallization reaction.

Fig. 37. Dilatometric curves for kaolins of increasing quartz content (from curve a to curve c); the
effect of the quartz gradually prevails over that of the kaolinite.

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Raw materials for ceramic bodies

Fig. 38. Dilation-Shrinkage of kaolinite-quartz mixes (by G. Peco 1970). (0, 12, 24, 36, 48% of
quartz).

The table below gives standard mineralogical analysis for some common kaoli-
nitic raw materials:

BALL CLAY 1 2 3 5 6
Kaolinitic Minerals 50 48 76 27 36
Micaceous Minerals 21 19 11 25 32
Montmorillonite Minerals – – – 4 –
Quartz 22 28 7 37 28
Feldspars – – – 5 4
Others 1 1 3 2 –
CHINA CLAY 7 8 9 11 12
Kaolinitic Minerals 85 80 79 92 87
Micaceous Minerals 14 16 15 – 2
Montmorillonite Minerals – – –
Quartz 3 4 1 2
Feldspars ~ 5 8
Others 2 – 1 1

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Technological characterisation of pressed kaolinitic materials


It is, of course, necessary to distinguish between ball-clay, china-clay and ka-
olins.
Ball clays are characterised by:
– fairly good (> 0.3%) post-pressing expansion
– excellent unfired bending strength (green > 12 and dried > 30Kg/cm2)
– at 1100 °C shrinkage varies from 2 to 4% while apparent porosity is 10~15%
– again at 1100 °C, bending strength may vary (from 100 to 200 Kg/cm2) as a
function of “impurities”, which, to varying degrees, aid sintering
– again at 1100 °C, the coefficient of cubical expansion may vary between 150 and
200 x10-7.

China clay, instead, has the following characteristics:


– greater post-pressing expansion
– poor bending strength of both green and dried product
– possible post-drying expansion
– at 1100 °C moderate dimensional contraction and high water absorption values
(15-20%) are observed; bending strength (< 150 Kg/cm2) and the coefficient of
cubical expansion (120-180.10-7) are low, once again depending on the quartz
content.
On the whole the material is highly refractory.

Finally, the kaolins are characterised by:


– considerable post-pressing expansion
– water absorption (at 1100 °C) between 20 and 25%
– very low modulus of rupture in bending (80-150 Kg/cm2)
– very low coefficient of cubical expansion, generally between 100 and 150.10-7.

Ceramic uses of raw materials not subject to purification or treatment


This largely concerns ball-clays which are generally employed in their natural
form, at most mixing them with various other types in order to supply users with
blends of stable ceramic performance.
Ball-clays are employed in vast range of ceramic products (sanitaryware, tiles,
pottery, ornaments etc.) where they act as plasticizing binders.
The percentages in which they are employed vary from product to product, and
also within the different compositions used to obtain the same type of finished arti-
cle. However, as a rough guide, the following quantities are generally employed:

Tiles (wall) 25-50


Tiles (floor) 25-75
Porcelain tile 30-40
Pottery (earthenware) 20-35
Sanitaryware 22-26

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Raw materials for ceramic bodies

In the field of frits and glazes kaolinitic materials, purified using wet techniques,
are used as components in mixes to be fritted (melted) and as a “plasticizing” addi-
tive during the grinding of frits.
Kaolins of lesser purity are employed in the manufacture of alumina refracto-
ries where they act as alumina carriers.
For some such products untreated kaolins contaminated by the presence of iron
may sometimes be used.
However, only a small percentage of the world’s total kaolin output is actually
employed in the ceramic industry: almost 90%, in fact, is channelled into the paper
industry where it is used as a filler or surface coating.
It is also used in minor quantities as:
– a filler for tyres and rubber
– a filler for paints
– a pharmaceutical support (pills)
– a cosmetic and toothpaste support
– a powdery insecticide support
– a fertiliser support.

Illite

Origin of the term


From the name of the American state of Illinois where the mineral was first
identified.

Mineralogical structure
Similar to that of the micas. The basic structural unit consists of two tetrahe-
dral “sheets” sandwiching an octahedral one (of trioctahedral form), as illustrated
in Fig. 39. It is virtually the same as the montmorillonite structure except that some
silicon cations are always substituted by aluminum to which potassium is added,
thus maintaining the electrical balance of the structure.
However, the potassium cation is attached securely and is not easily replaced as
happens with montmorillonite.
The structural differences between illite and mica lie in lesser substitution of
silicon with aluminum and, therefore, less potassium aggregation. Furthermore,
illite may contain interlayered water molecules.
In addition to the trioctahedral illites, others of dioctahedral form (a sheet of
tetrahedrons with a sheet of octahedrons) exist.
Alteration causes the latter types to turn into montmorillonite while the former
are transformed into vermiculite. The SiO2/Al2O3 ratio (taking into account substi-
tutions in the octahedral sheet) varies from 2 to 4; it is frequently 3. Glauconite
(ferroan illite), an illite of particular interest, is generated by alteration of the bi-
otite.

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Fig. 39. Crystallographic structure of illite.

Chemical composition
Illite is represented by the following formula:

Al2 (Si3AlO10) K (OH)2 - Kx

Yet it is not completely definable; aluminum substitutes the silicon less frequent-
ly and, as a consequence, less potassium is required.

Genesis and characteristics of deposits


Illite deposits are generally linked to the laying down of sediments. Of course,
deposits never consist exclusively of this mineral: it is generally found in associa-
tion with chlorite, montmorillonite, kaolinite, quartz, calcite, dolomite, etc.

Location of main deposits and extraction techniques


Historically, the ceramic industry’s main source of supply has been the illite-rich
clayey deposits located in the Apennine hills of the Italian region of Emilia.
Here lie the extensive “grey-blue” clay beds dating back to the Pliocene, the so-
called “Complesso Emiliano” made up of the marls of Montepiano (red and green
clays that go by the name of “red-beds”) and the Antognola series (marls and grey-
blue clays). The chemical make-up of such clayey rocks is illustrated in the tertiary
diagrams (Figs. 40-43) on the following pages.

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Raw materials for ceramic bodies

Illite-chlorite clays

Illite-kaolinite materials
German
English
French

Fig. 40. Al2O3/Na2O + K2O/TiO2 + Fe2O3 + MgO + CaO tertiary diagram showing composition-
al fields for red gres clays and the imported kaolinitic materials used in white gres (Fabbri & Fiori,
1985/7).

Illite-chlorite clays

Illite-kaolinite materials
German
English
French

Fig. 41. Na2O + K2O/Fe2O3 + TiO2 /MgO + CaO tertiary diagram showing compositional fields for
red gres clays and the imported kaolinitic materials used in white gres (Fabbri & Fiori, 1985/7).

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Illite-chlorite clays

Illite-kaolinite materials
German
English
French

Fig. 42. SiO2 /AlO3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram showing com-
positional fields for red gres clays and the imported kaolinitic materials used in white gres (Fabbri
& Fiori, 1985/7).

nepheline
Feldspars syenite

Feldspathic rocks

Quartz-feldspathic sands

Quartz sands

Fig. 43. SiO2/Al2O3/TiO2 + Fe2O3 + MgO + CaO + Na2O + K2O tertiary diagram illustrating the
compositional fields for complementary raw materials used in the production of gres (Fabbri & Fiori,
1985/7).

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Raw materials for ceramic bodies

Yet Italy is not Europe’s only source of illite: of particular renown are the Hun-
garian deposits of white illite associated with montmorillonite, the plastic Miocene
clay of Czechoslovakia, and the vast Ukrainian deposits of kaolinitic illite that pro-
ducers of porcelain tiles (also known as vitrified stoneware or referred to by its
Italian name gres porcellanato) have recently begun using. In the United States (Illi-
nois), the illite deposits for the production of expanded clay have been in use for
some time.
Extraction techniques in hilly areas consist of successive ripping and scraping
operations on terraces (usually more than 20 m wide and some tens of metres long).
These continue until deposits are exhausted. Alternatively, on slopes, high-power
bulldozers are used.
In semi-flat areas where the extraction zone provides more room for manoeuvre,
scrapers are preferred to bulldozers. This vehicle, as the name implies, “scrapes”
wide strips of terrain, funnelling the material inwards towards the machine: this
system provides excellent homogenisation of the raw material, a process aided by
the vehicle loading system.
Ripping and scraping has several points in its favour. Firstly, it allows work to
be carried out over a vast surface area, with large-scale transportation of material
resulting in low unit costs. Secondly, there is the advantage of flexibility: unsuit-
able extraction zones can be isolated and the same machines can be used for both
handling and treatment of the extracted clay (crumbling, homogenisation, dry-
ing).
This last sequence takes place in the quarry itself: a 15-20 cm thick layer of the
material is spread out and left in the sun for a full day, occasionally being churned
over to ensure proper uniformity of exposure to the sun’s rays.

Mineralogical analysis of illite raw materials; standard behaviour and identification


Identification via X-ray diffractometry essentially involves observation of basal
plane diffractions.
Characteristic reflections appear at 8.80, 17.80 and 26.70° 2ϑ, corresponding
to lattice distances of 10, 4.9 and 3.33 Å respectively. The illite-relevant DTA
diagram (Figs. 44-45) shows a first endothermic peak at around 140 °C (removal
of zeolite water) followed by a second peak towards 600 °C (hydroxyl elimina-
tion). Towards 900 °C formation of alkaline silica-aluminates takes place; where
calcium is present, calcium aluminates, calcium silicates (wollastonite) and calci-
um ferrites are also formed. These neo-formations are indicated by an exothermic
peak.
Thermogravimetric (TG) analysis highlights moderate weight losses, large-
ly concentrated where removal of zeolite water and hydroxyls reaches a maxi-
mum.
Dilatometry (Fig. 46) produces a steady gradient up to and beyond 600 °C, some-
times preceded by a hint of contraction at around 120-140 °C; from 600 °C to over
800 °C comes the typical “flattening out” of the curve (i.e. no dimensional variation)
followed by an almost vertical contraction as the dilatometer leverage system in-
duces plastic deformation of the sample.

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Temperature °C

Fig. 44. The DTA curve for illite is characterised by weak endothermic effects at temperatures which, in
other clayey minerals, cause much more intense reactions.

Temperature °C

Fig. 45. A typical DTA curve for muscovite and dioctahedral micas in general.

Standard semi-quantitative mineralogical analyses of the three Emilia Apennine


clay types (taken by way of example of such clayey rocks) are provided below:

Illite Chlorite Montmor. Kaol. Quartz Feldsp. Carb. Mica


1. xxx xx xxx x xx tr.
2. xxx xx x xxx x x tr.
3. xxx xx x x xx x tr. tr.

As can be seen, the mineralogical picture is a fairly constant one and, on the
whole the only significant differences concern carbonate content which swings
from a maximum of 20-23% in Pliocene and Pleistocene grey-blue clays to 13-

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Raw materials for ceramic bodies

Fig. 46. Dilatation-Shrinkage of illite-quartz mixes (by G. Peco 1970). (0, 12, 24, 36, 48% of quartz).

16% in those of the Antognola series and just 0-6% in the red-beds.
With regard to red-beds it should be pointed out that these sometimes have a
very high carbonate content (sometimes higher than 16%!).
A final observation concerns natural plasticity (i.e. that of the unground raw
material); clays of the Antognola series and especially red-beds have undergone
diagenesis processes which have partially or completely inhibited this typical prop-
erty of clayey materials.

Technological characterisation of pressed illite materials


Tiles formed from predominantly illite raw materials have the following charac-
teristics:
– normal post-pressing expansion
– good unfired bending strength (green and dried)
– around 1100 °C shrinkage varies from 5 to 8% with water absorption values in
the 0-5% range. Nevertheless, in the (frequent) event that these clays are accom-
panied by a substantial carbonate content (from 15 to 23%), dimensional varia-
tion switches from +1 to –1% while porosity falls between 22 and 15%

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– the bending strength of fired products is markedly influenced by the presence or


absence of carbonates: where they are present the material is significantly weak-
er (from 100 to 200 Kg/cm2) while where they are absent strengths of 200 Kg/
cm2 are exceeded with ease
– the coefficient of cubical expansion (at 1100 °C) generally falls within the 180-
225.10-7 range.

On the whole tiles obtained from these raw materials are readily vitrified. Car-
bonate-free tiles achieve complete vitrification at 1050-1080 °C, within very tight
palliers (ranges); carbonitic ones are slightly more refractory and become vitreous
beyond 1100 °C, collapsing suddenly with a total absence of pallier (a characteristic
of carbonates).
Where clays are rich in carbonates fired product colouring varies from salmon
pink to yellowy and greeny-yellow (at vitrification); other clays, instead, become
bright red at lower temperatures, switching to dark brown when liquid-state reac-
tions gain the upper hand.

Uses in different industries


“White” firing illite clays are employed in certain industries as an alternative to
kaolinite clays (e.g. as powdered supports or fillers).
Some “red firing” types are employed in the production of light expanded mate-
rials used by the construction industry: in this case they must contain substances
that make the (previously pelletized) material expand during firing, or low-cost ad-
ditives having this characteristic must be used.
Curiously, illite is also used to produce cat litter; oddly, a renowned Italian prod-
uct directory (Villavecchia) cites only this use and completely “forgets” to mention
that clay is also employed in ceramics.

Montmorillonite (smectite)

Origin of the term


From Montmorillon in France where this clayey mineral was first identified.
The term bentonite indicates rock largely composed of montmorillonite, character-
ised by enormous swelling when it comes into contact with water. The name comes
from Fort Benton in Wyoming, USA, the site of important deposits.
Smectite is a synonym for montmorillonite.

Mineralogical structure
The (trioctahedral) base structure is made up of two tetrahedral sheets enclos-
ing an octahedral one (see Fig. 47). Specifically, this is the structure of pyrophyllite.

Some members of the montmorillonite family derive from substitution of sili-


con with aluminum in the tetrahedrons and substitution of magnesium and biva-
lent iron in place of aluminum in the octahedrons.

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Raw materials for ceramic bodies

The mineral crystals of this group are bound by particularly weak forces. There
are no hydrogen bonds (as in kaolinite) in that there is no possibility of contact
between the octahedral and tetrahedral layers belonging to different base struc-
tures, because the former are “prisoners” inside the latter. The only links are the
Van der Waals weak forces: consequently, the insertion of water molecules is ex-
tremely easy, resulting in the crystalline structure “expanding” to nearly six times
its original volume. The greater reactivity of the montmorillonite family (with re-
spect to, for example, the kaolinite family) derives from the suitability of the inter-
nal faces that mark the boundary of each “base structure”, in that these elements are
easily separable. The property known as “isomorphic substitution” (i.e. the capacity
for replacement of a cation with another of a different charge) is also much evident.
If, for example, a trivalent (aluminum) ion replaces the (tetravalent) silicon of the
tetrahedrons, electrical equilibrium is only achieved following absorption of an ex-
ternal (mono or bivalent) cation; in this second case the number will be equal to
half the negative charges released by the isomorphic substitution.
The peculiar behaviour of montmorillonite is partly explained by the extremely
small size of its particles.
Then there is the significant diversity between the sodium and calcic montmo-

Fig. 47. Elementary montmorillonite cell.

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rillonites: the former are much more plastic with a much higher ionic exchange
capacity.
It is also fairly common to encounter mixed structures created by the association
of montmorillonite and illite (interlayers). These are formed owing to the similari-
ty of the two different mineral “sheets”.

Chemical composition
X2Y4O10 (OH)2

X = trivalent aluminum cation and bivalent magnesium substitute (octahedral


sheet) plus mono or bivalent cations that aggregate to the structure to balance non-
equilibrated electrical substitutions.

Y = tetravalent silicon cation and trivalent aluminum substitute (tetrahedral


sheet) plus mono or bivalent cations that aggregate to the structure to balance non-
equilibrated electrical substitutions.

Theoretical composition
SiO2 = 66.7%; Al2O3 = 28.3%; H2O = 5%

Genesis and characteristics of deposits


Many montmorillonite clays were formed by alteration of volcanic rocks (pyro-
clastic rock and volcanic breccia) such as: rhyolites, trachytes, dacites, andesites,
basalts and liparites. The bentonite of Wyoming derives from in situ alteration of
volcanic ash that was accumulated in a Cretaceous formation. Sedimentary genesis
is equally common. Sedimentary deposits of montmorillonites usually consist of
layers or lenses several metres thick; those of hydrothermal origin may have some-
what irregular forms that complicate extraction.

Mineralogical analysis of montmorillonite raw materials; standard behaviour and iden-


tification
Identification via X-ray diffractometry largely involves observation of basal
plane diffractions (Fig. 48). It is not uncommon for the extreme fineness of the
particles to cause difficulties during diffractometry testing; where conditions per-
mit analysis to be carried out, reflection is detected at 6-6.9° 2ϑ (corresponding to
a lattice distance of 12.5 Å), which shifts towards a lower angle in the event of
glycolation of the sample (4.8-5° 2ϑ) and collapses at 8.8° after being heated to
550 °C. Smectite, however, is often in interlaminated form associated with illite.
In this event the resulting reflection band is greatly widened around 7.2°, ex-
pands again at 4.8-5.2° and collapses, after heating to approximately 550 °C, at
about 8.8°.
The DTA diagram for montmorillonite shows two endothermic peaks at 180
°C and between 450 °C and 650 °C respectively. The first of these peaks is linked
to removal of interlayer water and the second to removal of the OH- hydroxyls
(see Figs. 49-50-51).

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Raw materials for ceramic bodies

-
-
1
1
-
1 1

Fig. 48. Diffractometry analysis of a montmorillonite (Q = quartz, M = montmorillonite).

Thermogravimetric (TG) analysis shows, in correlation with DTA endothermic


peaks, two weight losses at 180 °C and 450/650 °C respectively.
After an initially short tract of limited expansion, the dilatometric curve shows

Temperature °C

Fig. 49. DTA curve for montmorillonite; the low temperature dehydration peak (100-250 °C) is the
most intense and characteristic and its form varies greatly as a function of the interlayer cation: a) Ca-
montmorillonite; b) Na-montmorillonite. The other dioctahedral smectites (beidellite and montronite)
have curves similar to those of montmorillonite.

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Temperature °C

Fig. 50. Typical DTA curve for trioctahedral smectite minerals such as saponite.

Fig. 51. Some montmorillonite and vermiculite DTA curves.

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Raw materials for ceramic bodies

a first contraction towards 180 °C followed by further expansion (which reaches its
maximum towards 573 °C should the raw material also contain free quartz).
Towards 900 °C further contraction is induced by sample sintering reactions
and softening.

Location of main deposits and extraction techniques


In Europe, the most important extraction sites are in Great Britain (Surrey,
Somerset and Bedfordshire), France (Limousin), Germany (Bavaria), Hungary (Is-
tenmezb and in the Tokay hills), Italy (Sardinia and the island of Ponza), Czech-
oslovakia, the ex-USSR (Caucasus and Kazakhistan), Greece (islands of Milos
and Mikonos) and in the formerly Yugoslavian countries. The United States has
the well-known Cretaceous deposits of Wyoming (bentonite) and others situated
in Arizona, Oklahoma, Texas and Nevada. Other North American deposits are
found in Canada (Alberta and Manitoba) and Mexico (in the regions of Puebla
and Monterrey).
Substantial bentonite deposits are also to be found in South America (Argenti-
na), Asia (India and Japan) and South Africa.
Quarries opened on predominantly montmorillonite clayey deposits are general-
ly of the “open-cast” type. These are thus earth-moving operations employing tra-
ditional methods.
Nevertheless, workers at these sites often have to deal with the material’s ex-
tremely high plasticity and water take up. Having to handle a material with a water
content of 15 or 25% is not uncommon. Under such conditions the enormous plas-
ticity often puts bulldozers out of action as huge “mattresses” of material tend to
build up on their tracks. Hence it is often preferable to use hydraulic excavators or
dredgers.
The latter also allow for more selective extraction and the accurate mining of
wide strips of limited thickness.

Technological characterisation of pressed montmorillonite materials


Montmorillonite deposits are generally characterised by the substantial pres-
ence of highly plastic colloidal particles. Tiles made of raw materials having a sig-
nificant portion of minerals from the montmorillonite family have the following
characteristics:
– generally low post-pressing expansion (0.5%)
– very high unfired bending strength (green and dried)
– intense drying shrinkage (> 1%)
– on fired products obtained at temperatures as low as 1020 °C dimensional varia-
tion oscillates from 5 to 10% (shrinkage) while the corresponding porosity may
range from practically zero to more than 5%, depending on the degree of post-
sintering expansion. These values vary greatly as a function of alkaline ion con-
tent in the inter-lattice spaces
– again at 1020 °C, bending strength varies greatly (from 150 to 250 Kg/cm2)
depending on the degree of expansion.

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Ceramic uses
While the use of clayey raw materials containing montmorillonite in layers mixed
with illite is quite common (especially in the manufacture of tiles, bricks and pot-
tery), utilisation of almost exclusively montmorillonite materials is extremely lim-
ited owing to the characteristics listed in the preceding paragraph. It should be
pointed out that montmorillonite has a markedly negative effect on the rheological
properties of slips. Bentonite, when hydrated, swells enormously and takes on the
aspect of a colloidal gel.

In ceramics, pure montmorillonites are, in fact, only employed as plasticizing


additives, and even in this case they are never used in proportions of more than
5%.

Uses in other industries


Bentonite is, first and foremost, a key constituent in the sludge used in oil drill-
ing operations. This sludge carries the lithic material removed during drilling to
the surface. The use of a fluid that is more viscous than water is a great aid to such
drilling operations, as long as it can be pumped. Drillers generally prefer to use
sodium montmorillonite: the clay must be of high purity and free from any abrasive
(quartz) particles. Montmorillonite raw materials are also used in de-colouring; here,
the employed material, known as “fuller’s earth”, predominantly consists of mont-
morillonite, although there are plenty of such deposits where the predominant min-
eralogical type is attapulgite or halloysite.
Another interesting industrial application of montmorillonite is in the clarify-
ing of alcoholic beverages (wine, beer, liquors etc.). This operation involves the
coagulation and removal of the colloidal impurities in suspension. Montmorillonite
(the sodium form is preferred in this case) is added directly to the beverages and
(after agitation) then separated using filter presses.

Chlorite

Origin of the term


Derived from the Greek “cloros” (meaning “green”), this word was introduced
by Werner to define this mineral on account of its predominant colour, stemming
from a high reduced iron content.

Mineralogical structure
These are lamellar minerals having an aspect similar to that of mica.
The classic chlorite structure consists of an alternating association of a mica-
ceous-like “sheet” (where an Al3+ or Mg2+ octahedral plane is enclosed by two
hexagonal planes of silica tetrahedrons) with a brucite one (characterised by a
flat hexagonal lattice of silica tetrahedrons with a central cation) as illustrated in
Fig. 52.

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Raw materials for ceramic bodies

Most chlorite minerals have a trioctahedral structure, yet dioctahedral forms


have also been identified. Cases of degraded chlorites showing lattice expansion
have also been observed: such expansion is caused by a capacity to adsorb zeolite
water as a result of weathering of the brucite “sheet”.
The existence of chlorite-vermiculite and illite-chlorite interlaminates should
also be noted.

Chemical composition
The mineralogical structure is not original, but derives, rather, from those of the
two associated micaceous and brucite sheets.
Composition of the micaceous sheets is as follows:

X8Y6O10 (OH)4

where: X is due to Si4+ or Al3+


Y is due to Mg3+ or Fe3+

Fig. 52. Elementary chlorite cell.

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The brucite sheets, are instead, composed as follows:

X6 (OH)12

where: X is made up of Mg2+, Al3+ or Fe2+.

When, in the micaceous structure, an Si4+ replaces an Al3+, the resultant electri-
cal charge difference is balanced by an excess charge in the brucite sheet generated
by the replacement of Al3+ with Mg2+.
The theoretic formula of true chlorite (or leptochlorite) is as follows:

Mg3 (Mg3-x Alx) (Si4-x Alx) O10 (OH)8

Oscillation of the x value (which can vary from 1 to 2) and the nature of the
substituents lead to the formation of different varieties, such as bavalite (ferrous
chlorite), clinocore, penninite, prochlorite, etc.

Genesis and characteristics of deposits


Deposits containing chlorites largely originate form sedimentations of the ma-
rine variety.
Minerals in the chlorite family may derive directly from the source rock (detrital
minerals) in that they are quite stable or may have been formed at the expense of
silicates rich in Fe and Mg, such as biotite and amphiboles, in the presence of a weak
washing away process.
Deposits consisting mainly of chlorites have yet to be found.

Location of main deposits and extraction techniques


Some of the richest chlorite mineral deposits are to be found in the Apennine
mountains of Emilia (Italy).
The clayey part of such deposits, in fact, mostly consists of illite and, in decreas-
ing order, chlorites.
This is the so-called Complesso Emiliano, made up of:
– the Marls of Montepiano (red and green clays that go by the name of red-beds)
that some researchers believe to be transgressive on previous formations and
then dispersed by local orogeny phenomena
– the Antognola series (marls and grey-blue clays).

Mining techniques in hilly areas see the application of ripping and scraping
techniques on “terraces” which continues until the material is exhausted (such ter-
races are generally more than 20 m wide and some tens of metres long). On slopes
high-power bulldozers are generally used.
In semi-flat areas where the extraction zone is of considerable size, scrapers are
preferred to bulldozers.
This vehicle, as the name implies, “scrapes” long, wide strips of terrain, funnel-
ling the material inwards for collection.

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Raw materials for ceramic bodies

This system results in excellent homogenisation of the raw material, a process,


in fact, aided by the vehicle loading system.
Ripping and scraping has several other useful characteristics:
– it allows work to be carried out over a vast surface area, with large-scale trans-
portation of materials resulting in low unit costs
– flexibility: unsuitable extraction zones can be isolated
– the same machines can be used for both handling and treatment of the extracted
clay (crumbling, homogenisation, drying).

This last sequence takes place in a clearing within the quarry grounds; a 15-20
cm thick layer of the material is spread out and left in the sun for a full day,
occasionally being turned to ensure proper uniformity of exposure to the sun’s
rays.

Mineralogical composition of deposits containing chlorites


Identification via X-ray diffractometry (Fig. 53) essentially involves observation
of basal plane diffractions.
The characteristic angular reflections (for Cu Kα radiation) are detected at 6.2°,
12.5° and 25.1° 2ϑ, corresponding to lattice distances of 14.3, 7.1 and 3.54 Å.

The 12.5° diffraction corresponds to that of the 001 kaolinite plane which can
cause errors in interpretation. To prevent this inconvenience the analysis is repeat-
ed by preheating the sample to 550-600 °C. In this case the detected basal reflec-
tions are cancelled while those at 6.2° are reinforced.
DTA analysis (Fig. 54) of different chlorite types gives widely varying results; a
first endothermic peak is generally noted towards 400 °C when the hydroxyls of
the brucite sheet are removed. A second peak is seen between 600 and 800 °C: this
corresponds to removal of the hydroxyls from the micaceous sheet.

As would be expected, thermogravimetric (TG) analysis shows two correspond-


ing weight losses.
Dilatometry analysis of the unfired product fails to indicate the low temperature
weight loss caused by removal of the zeolite water (unless there is substantial alter-
ation of the structure).

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No. d(Å) hkl


0 12.5 001
-
1 2.59 202
2 2.56 201
-
3 2.45 203
4 2.39 202
-
5 2.26 204

10 15

Fig. 53. X-ray diffraction patterns for two different, randomly-oriented chlorite polytypes: a) and b)
illustrate how the two samples have significant, yet differentiated peaks with respect to the 001 basal
plane and illustrate evident variations as regards the diffraction planes marked 1, 2, 3, 4 and 5.

Temperature °C

Fig. 54. DTA curves for the chlorites group show evident endothermic and exothermic peaks (curve a);
as iron content increases (curve b) there is a gradual lowering of the temperature at which the exother-
mic reaction takes place.

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Raw materials for ceramic bodies

Standard semi-quantitative mineralogical analyses of the three Emilian Apen-


nine clay types are provided below:

Illite Chlorite Montmor. Kaol. Quartz Feldsp. Carb. Mica


1. xxx xx xxx x xx tr.
2. xxx xx x xxx x x tr.
3. xxx xx x x xx x tr. tr.
1. blue-grey Pliocene-Pleistocene clays
2. clays of the Antognola series
3. red-beds

Observation of typical chlorite behaviour is, as might be imagined, significantly


complicated by the constant presence of other clayey minerals.

Technological characterisation of pressed samples prepared with chlorite raw materials


In evaluating the behaviour of clays having a substantial chlorite mineral con-
tent we shall once again refer to the raw materials of the Emilia Apennines, al-
though this is done with some reserve since these minerals are primarily made up
of illite.
Characteristics are as follows:
– normal post-pressing expansion
– good unfired bending strength (green and dry)
– at around 1020 °C shrinkage is between 2-6% with water absorption values of
13-5%. Nevertheless, in the (frequent) event that these clays are accompanied by
substantial carbonate content (from 15 to 23%) shrinkage varies from +1 to –1%,
while porosity lies between 22 and 15%
– the presence of carbonates also has a strong influence on the bending strength
of the fired product; in the first case decidedly lower values (from 110 to 160
Kg/cm2) are recorded while in the second they can easily exceed 200 Kg/cm2
– linear expansion coefficients for fired materials (at 1020 °C) generally settle be-
tween 25 and 75.10-7 °C-1. In practice, this figure is expressed in cubed form,
generally for temperatures between 20 and 450 °C.

On the whole the tiles obtained from these raw materials are quite fusible. Those
without carbonates vitrify completely at 1050-1080 °C within a very tight range.
Carbonate ones are slightly more refractory and become vitreous beyond 1100
°C, shrinking suddenly (a characteristic of carbonates).
Post-firing colour ranges from salmon pink to yellowy to greenish-yellow (on
vitrification) where clays are carbonate-rich; others have much deeper hues of red
(at lower temperatures) and turn dark brown once liquid-state reactions gain the
upper hand.

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Ceramic uses
Once again, Italian clayey raw materials of a predominantly illite-chlorite
nature are considered. They are mainly applied in the ceramic industry as fol-
lows:
– grey-blue Pliocene-Pleistocene clays in high-porosity coloured bodies (majolica)
for glazed wall tiling
– grey clays of the Antognola series for medium-porosity coloured bodies (cot-
toforte) for glazed floor and wall tiles; unglazed “Tuscan cotto” type bodies
– red-beds for frost-proof or low-porosity (single firing) glazed/unglazed (red gres)
for residential, industrial and outdoor flooring.

Pliocene grey-blue clays (i.e. those with a higher degree of natural plasticity)
are widely used in the manufacture of rustic pottery (majolica), ornaments and in
the production of large extruded bricks (lug bricks and ceiling bricks).

Talc

Origin of the term


Derives from the Arabic word “talq”.

Mineralogical structure
Mineral of mica-like structure with an elementary “sheet” made up of two
hexagonal planes of silica tetrahedrons containing an Mg2+ octahedral plane (Fig.
55).

The basic structural element is neutral and highly stable.


Talc, because of its structure, may be considered as belonging to the family of
clayey minerals. It has a characteristic lamellar shale (talc schist) structure and is
“greasy” to the touch. There exists another variety of more massive structure known
as steatite.

Chemical composition
Talc is a magnesium acid metasilicate having the following formula:

Mg3Si4O10 (OH)2

As no vicariant substitution with cationic elements of insufficient charge is pos-


sible, there is no introduction of alkaline cations.
Nevertheless, talc rocks usually contain various impurities which affect their prop-
erties significantly.
Talc is generally about 50% silica, more than 30% magnesium and a little less
than 10% alumina.

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Raw materials for ceramic bodies

Fig. 55. Elementary talc cell.

Genesis and characteristics of deposits


Talc is of metamorphic or hydrothermal origin. In the latter case it is often
associated with dolomite and magnesite. This association provides the key to cor-
rect interpretation of the genesis of this mineral, brought about by reactions be-
tween acid hydrothermal solutions (rich in silica) and the two magnesium carbon-
ates.
Sometimes, instead, it is associated with ultrabasic rocks (such as olivine, am-
phiboles and augite), its origin lying (as with chlorite and serpentine) in their trans-
formation via metamorphic forces.
Deposits are often stromatolith in nature.
In the case of the most important Italian deposit (at Fontane in Val Germa-
nasca, Piedmont) there is just one large strip over 2 km long, ranging in depth
from 1 to 15 m: it lies sandwiched between gneiss, mica schists and limestones (at
the base) and mica schists and chloro schists (above).
The same band, however, also contains contaminants made up of dolomia, am-
phiboles and strips of wall rock.

Location of main deposits and extraction techniques


Deposits are found in many countries, the key ones being Germany (Gbpfers-
grUn and the Fichtelgeibirge hills), Italy (Piedmont, Lombardy and Sardinia), Aus-
tria, Spain (Region of Barcelona), France (the Saint Barthèlemy massif), Greece,
Finland, former USSR countries (Ural mountains), USA (New York, California,
Georgia, Montana, Texas, Virginia, etc.), Canada (Ontario), India, Korea, China
(Szekiang and Shantung) and South Africa.
Because of the above-cited stromatolith nature mine shafts need to be sunk to
avoid removal of enormous quantities of overburden. The tout-venant is put through
a sorting and grinding process that brings it within the particle size distribution
range required by users.

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Standard behaviour and identification


X-ray identification is based on observation of basal plane diffractions (Fig. 56).
The lattice distances 9.36 Å, 4.68 Å, 3.11 Å, 2.63 Å and 2.48 Å have correspond-
ing (Cu Kα radiation ) peaks at the following angular positions: 9.44°, 18.86°, 28.62°,
34.0° and 34.5 2ϑ.

Differential thermal analysis (DTA) of a pure talc shows just one endothermic
peak between 900 and 1000 °C, which marks the point at which the OH– hydroxyls
are removed.
In certain cases, the presence of chlorite and the loss of zeolite water are high-
lighted.
The corresponding TG analysis indicates marked weight loss. Dilatometry too
is often influenced by the presence of other minerals, especially chlorite, which causes
a net increase in dilatation between 600 and 800 °C.

4
4

9.36
3.11

4
4.68

4 4
4
4.57
2.48

4
2.63

28.62

18.86
34.5

34.0

9.44

Fig. 56. Diffractometry (XRD) analysis of talc (t = talc).

Utilization and technological characterisation


Talcs may contain a high percentage of ferrous hydroxides and can be used to
produce tiles. These minerals are usually characterised by post-pressing expansion,
and poor green/dried bending strength.
In firing (at 1020 °C) products show high absorption (greater than 25%), slight
dimensional expansion and are very fragile.
The coefficient of cubical expansion for fired materials (at 1020 °C) is very high
(270.10-7 °C-1).
During firing, talc (especially where it has a high degree of purity and a low iron
content) behaves more or less like an inert material up to about 1050 °C while at
higher temperatures it begins to participate in reactions, acting as a flux.

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Raw materials for ceramic bodies

Mass %

Temperaturs difference

Temperature °C

Fig. 57. Thermogravimetric (TG) analysis and DTA of talc.


Shrinkage

Temperature °C

Fig. 58. Dilatometry analysis of talc.

Given this behaviour, even small in-body percentages (2-5%) can make a use-
ful contribution by forming, with the alkali in the feldspars, eutectic mixes with
particularly low melting points. Such effects are often desirable in the manufac-
ture of compact materials with extremely low water absorption (e.g. porcelain
tiles).

Ceramic uses
The introduction of talc into ceramic bodies allows manufacturers to control
thermal expansion.
This dilatometric aspect is especially important in the manufacture of tiles.

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At lower temperatures (i.e. before the development of massive liquid-state reac-


tions) it is characterised by a high expansion coefficient which aids glaze-body match
and, therefore, acts as a carbonate substitute.
At higher temperatures, instead, talcs have the opposite effect and are intro-
duced to improve thermal shock resistance in ceramic products that sinter at these
temperatures.
Talc is introduced for specific reasons in a number of ceramic materials:
– Porous wall and floor tile bodies: in some cases talc may be used in quantities as
high as 40%. Talc-based formulations are commonly used in the USA owing to
the generally low cost of the material there. Not only do they aid dilatometric
match between glaze and body, they also significantly reduce moisture expan-
sion of the fired product caused by absorption of humidity and, therefore, the
risk of delayed crazing. Talc-rich bodies are particularly suitable for rapid firing
in that, while maintaining optimum general characteristics, they emit only min-
imum gas. Generalised utilisation, though, is complicated by the difficulty of
properly mixing small or very small quantities of talc into a body and, above all,
by costs.
– Faenza pottery: these are calcareous or calcareous-magnesium compositions in
which a part of the carbonates (from 10 to 15%) are replaced by talc. As a result
the unfired body is more workable and there are fewer breakages as a result of
thermal shock.
– Gres and vitrified single firing products: talc, when added in small percentages (gen-
erally no more than 5%) lowers firing temperatures and increases cycle speeds.
“White” body compositions tend to bleach (perhaps because magnesium ferrite
formations “kidnap” the iron). In this case, of course, talc of considerable purity
must be employed.
– Vitreous-china sanitaryware: added in small quantities (2-3%), talc improves ther-
mal shock resistance.
– Refractories: in the case of semi-silicate refractories, using talc (in quantities rang-
ing from 2 to 10%) improves resistance to thermal shock (but also causes a re-
duction in refractory) and increases the bending strength of the unfired prod-
uct. The use of talc is practically indispensable in the production of platelets
and support items which are often subject to extreme thermal gradients, espe-
cially where fast firing cycles or shuttle kilns are used. Their utilisation is limit-
ed by the formation of eutectics, which can markedly lower their refractory char-
acteristics.
– Electrical insulators: talc is the main raw material as these items are (after firing)
made up of cordierite (5 SiO2 . 2 Al2O3 . 2 MgO) and clinoenstatite (SiO2 . MgO).
Steatite is generally preferred for these products.
– Table pottery: confers translucency and makes the pieces tougher.
– Bricks: small additions of talc aid extrusion by acting as a lubricant.

Increased bending strength of both unfired and fired items is observed, as is a


reduction in firing loss.

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Raw materials for ceramic bodies

Talc is also used in the production of certain magnesium glazes, while in sani-
taryware manufacture it is “sprinkled” in the mould cavities to aid release (especial-
ly in the manufacture of large items).
Many of the above-cited uses require high-purity talc, except where used in
coloured tile body mixes.

Uses in other industries


Used as a filler in the paper, plastics and paint industries. Where of especially
high purity it is often used as an alternative to kaolin. One of its better-known uses
is as a support for deodorant powders in the cosmetics industry.

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“NON-PLASTIC” MATERIALS

Silica

Origin of the term


From the Latin word “Silex”, meaning “hard stone”.

Mineralogical structure
The base structure of silica consists of a tetrahedron with oxygen anions at its
apexes and a centrally-positioned silicon atom. A complete tetrahedron, then, has
four negative ions (Figs. 59-60-61).

Anhydrous silicon has three crystalline forms: quartz, trydimite and cristobalite
and a glassy amorphous (i.e. non-crystalline) one. Each main type has varieties that
are stable in particular temperature ranges.

Fig. 59. Structural arrangement of silica tetrahedrons in quartz (British Ceramic Society).

Fig. 60. Crystalline structure (A) and vitreous structure (B) (according to W.H. Zachariasen and B.E.
Warren).

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Raw materials for ceramic bodies

Fig. 61. Trydimite (a) and cristobalite (b) structures (Worral, Clays and Ceramic Raw Materials -
Elsevier).

The most important transformations take place at the following temperatures:


Quartz → Trydimite 870 °C
Quartz α → Quartz β 573°
Trydimite → Cristobalite 1470°
Trydimite α → Trydimite β 117/163°
Cristobalite α → Cristobalite β 220/ 270°

Fig. 62. Equilibrium diagram for silica, including the metastable portions (from Kingery, Introduction
to Ceramics - Wiley).

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Chemical formula
SiO2

Genesis and characteristics of deposits


Firstly, a distinction should be made between primary deposits (quartzites) and
those of volcanic origin (perlites).
Primary deposits appear under stromatolith form in pegmatites or schists or
in zones of contact with magnetic bodies (halos). These veins vary greatly in size
(from just a few centimetres to tens of metres). Of course, only the most substan-
tial ones are of interest as only these will make extraction economically worth-
while. The purest deposits are whitish in colour with a typically translucent ap-
pearance. The presence of impurities, though, leads to clusters of varying colour
(from pinkish to grey, from yellowish to brown). The term “sands” refers to clas-
tic, loose sediments made up of granules between 2 and 0.25 mm in size. These,
then, are relatively coarse, non-cemented sedimentary deposits homologous of
sandstones. The latter are rocks with an identical granulometric structure but are
distinguished by intense cementation which give them a lithic appearance and
consistency.
Sandy deposits may be of alluvial, lacustrine, marine or even wind-driven origin.
This is, of course, a reference to the depositary environment of the particles, as in
the first three cases sedimentation will naturally be preceded by fast-flowing water
transport.
Only a river or torrent in flood, in fact, is able to reach the speeds needed to
“sustain” and carry the coarse particles of which sand is made. Deposition in lakes
and seas always takes place close to the shore, that is, in the vicinity of estuaries
where the water slows down as it disperses into the lake/sea. In seabed sedimenta-
tion, remoulding is frequent: this phenomenon involves redistribution of sediments
by strong currents or tides. Fluvial depositions, instead, take place where there is a
fall-off in water speed: the classic case is that of the river delta, where the river is
also affected by the braking action of the tides or where the river reaches a plain
and begins to meander.
Smaller-scale accumulation is observed on the inner banks of river bends where
water travels much more slowly than on the outer section of the bend (because of
centrifugal force) where, instead, erosion takes place.
Different sedimentation conditions will, of course, determine differing particle-
size distribution of materials and the presence/absence of finer (clays) or coarser
(gravel) contaminants.
During transport, sedimentation and compaction, sandy deposits undergo a “ma-
turing” process largely induced by chemical-physical aggression. The latter cause
alteration, transformation and dissolution of the less stable mineralogical elements
and modify the texture of the particles (dimension, form, etc.).
Generally speaking, secondary silica deposits contain more non-quartzose im-
purities than primaries: such impurities often include micas, feldspars, oxides and
ferrous hydroxides, clayey materials and vegetable substances.

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Raw materials for ceramic bodies

Note, though, that the term “quartzites” also refers to high-purity sedimentary
quartz deposits with an extremely high degree of cementation and to metamorphic
deposits characterised by recrystallization of the original granules.
A last, more specific type of silica deposit concerns the diatomites. These are
sedimentary rocks mainly consisting of the siliceous shells of diatoms (tiny marine
algae), and are characterised by high porosity and friability.
Such deposits, where in fresh water, are known as fossil flours while sedimentary
deposits in marine environments are known as tripoli.

Location of main deposits and extraction techniques


Stromatolith deposits renowned for their purity are mined in Germany (Moun-
tains of Taunus Gebirge), Brazil (within Paleozoic formations), ex-Yugoslavia (Stru-
mica, Macedonia) and the USA (Connecticut).
Important European deposits of poorly cemented siliceous sediments are found
in France (Fontainebleau), Belgium (Region of Namur) and Germany.
Well-known, abundant, well-cemented siliceous deposits are found in many States
within the USA (mainly along the Appalachian chain and in the South Eastern
States), while some of the best-known European sites are located in England (Shef-
field), Germany (again in the Taunus mountains, in Turingia and in Silesia), France
(Brittany, Central Massif and Normandy).
Extraction techniques vary depending on the inherent characteristics of the
deposits. Stromatolith deposits can only be extracted with the aid of explosives:
tunnelling may sometimes be necessary too. In the most fortunate cases extraction
is effected via a series of controlled explosions across a wide extraction front. The
tout-venant is then transported to processing plants where separation of siliceous
and sterile fragments is effected. Sorting is often carried out manually on conveyor
belts: more recently, optical recognition systems have been experimented.
Explosives are also employed on metamorphic and sedimentary deposits with a
high degree of cementation. “Pre-mining” techniques (a series of small explosive
charges which shake the rock and fracture it internally) are sometimes employed,
thus paving the way for ripping and scraping operations.
Where the terrain contains poorly cemented sedimentary deposits, the material
can be extracted simply by using earth-moving machinery such as bulldozers, scrap-
ers and hydraulic excavators.

Standard behaviour and identification


Mineralogical identification via X-ray diffractometry essentially involves obser-
vation of basal plane diffractions.
The specific diffraction pattern (for Cu Kα radiation) shows peaks in the follow-
ing angular positions: 26.63 (corresponding to a lattice distance of 3.34 Å) and
20.84 (corresponding to 4.26 Å) (see Fig. 63).

Differential thermal (DTA) and thermogravimetric (TGA) analysis of an anhy-


drous silica show behaviour influenced only by thermal effects connected with the
restructuring that corresponds to phase transitions (Fig. 64).

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3.34
1

4.26
1
1 1
1.81

1
1
2.45
1
2.28
2.12

2.23
1.98

39.46

26.63
42.45

36.54

20.84
50.1

45.7

Fig. 63. Diffractometry (XRD) analysis of quartz (q = quartz).

heating cooling

Temperature °C

Fig. 64. Endothermic effect (during heating) and exothermic effect (during cooling) in a quartz sam-
ple; the thermal inertia of the system provokes a delay in the appearance of maximum intensity, both in
cooling and heating.

Dilatometry (Fig. 65) shows, during heating, a sharp increase at 573 °C. This
corresponds to the switch from quartz α to quartz β , which, as is known, is accom-
panied by a sharp increase in volume.

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Raw materials for ceramic bodies

The same phenomenon occurs even more markedly just beyond 220 °C, when
cristobalite (rarely present) passes from the α to the β form.

If, during cooling, not all the free silica has been “bound” by the neo-formation
of more complexly-structured minerals (e.g. wollastonite or mullite), the passage
from quartz α to quartz β is signalled by marked dimensional contraction.
This is a particularly critical moment in ceramic manufacturing as excessively
fast cooling can cause certain types of damage to the tile.

Industrial treatment of the tout-venant


Sands are generally purified and classified so as to obtain products having char-
acteristics suitable for their intended use.
Such processing plants differ according to the type of deposit and market re-
quirements.
The key stages in the treatment of sand are: washing with elimination of clayey
components, attrition (rubbing the particles to detach the contaminant surface film),
magnetic separation, grinding, flotation (chemical reactions with anionic or cationic
reagents) and leaching (where acids attack the contaminating elements).

Fig. 65. Dilatometric behaviour in various structural forms of silica (from: Worral, Clays and Ceramic
Raw Materials - Elsevier).

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With quartzites the main (and most costly) task is grinding of the rocky frag-
ments; this is followed by granulometric classification.
Magnetic separation systems can be used to remove some impurities. However,
the efficacy of these methods is frequently undermined by electrostatic charging of
the dust: as a result, the use of powerful magnetic fields may cause the loss of a
substantial portion of output.
Companies often mine crystalline deposits containing both quartz and feldspars.
In these cases treatment becomes a somewhat more complex affair, being designed
to separate the two mineralogical components as efficaciously as possible.
Note that some users of silica – such as the glass industry – demand materials of
highly specific particle size distribution.
Glass makers, in fact, require that all particles fall within the 0.1 - 0.8 mm
range.

Ceramic uses
Single fired tiles, whether white or red body, use only small quantities of sand
(maximum 10-15%).
With coloured bodies even low-purity sands (e.g. those with a substantial iron
content) can be used without any particular problems.
Often, compositions for “white” single firing products do not include the direct
introduction of siliceous sands: the same effect is attained by employing natural
mixes of feldspar, clay and quartz known as “partially kaolinized feldspars”.
Some porcelain tile formulas also make use of minimum percentages of siliceous
materials. The addition of silica to vitreous-china and porcelain bodies serves the
purpose of balancing the presence of SiO2 and alumina, thus providing the stoichi-
ometric ratios, which, in firing, lead to the formation of mullite.
In the tile industry the main aim is to “open up” the mixes to aid degassing of
any impurities (organic substances) in the raw materials and removal of water dur-
ing the drying process: a further positive effect is reduced contraction and deforma-
tion (during firing).
Another important aspect concerns particle size distribution and the (crystalline
or amorphous) state of the quartz particles. Ceramic companies tend to use already
ground powders so as to reduce body grinding times.
While natural silica deposits already consisting of very fine particles do exist
(pyroclastic and diatomite deposits), these materials, unfortunately, have extreme-
ly negative effects on the rheological properties of ceramic slips and cannot be
used.
Manufacturers of vitreous-china and porcelain sanitaryware require especially
pure siliceous materials.
Proportions used are generally in the order of 20-25%. Earthenware pottery
requires about 10-15%, while glazed white body wall tiles employ quantities in the
order of 10-20%.
Silica is also used in the production of acid refractories. Siliceous bricks are
manufactured starting with quartzites: these are ground to the required particle
size distribution, with just small percentages of binder being added.

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Raw materials for ceramic bodies

Semi-silicates require the introduction of about 10% alumina; fireclays are 30-
40% alumina, the remaining part consisting of quartz.
Diatomites are used for insulating bricks.
Silica is also used in the preparation of frits where it is introduced in quantities
of 20-40%; for the most part it is air classified, although certain formulations re-
quire (sometimes significant) quantities in fine sand form.

Uses in other fields


The main consumer of silica is the glass industry.
Required raw material specifications depend on the intended final product. For
instance, for standard (green) bottles sands containing even l% of Fe2O3 may be
used. For semi-whites tolerance drops to 0.2%.
Sheet glass will not withstand percentages above 0.3% while white glasses have
a tolerance of less than 0.013%.
Finally, makers of the most sophisticated (optical) glass require sands having a
maximum Fe2O3 content of 0.008%, while SiO2 must account for 99.5%. A very low
TiO2 content (less than 0.05%) is also highly important and chromium and cobalt
must be present in the order of just a few parts per million.
Silica is also extensively employed in the metallurgical industry (in special al-
loys).
Perlite, thanks to its superb thermo-acoustic insulation properties, is used as a
lightweight aggregate in the preparation of construction blocks.
Finally, diatomites are used in the production of highly efficient “filter beds”.

Feldspathic minerals

Origin of the term


The etymology of the terms defining the most common predominantly felds-
pathic rocks is as follows:
– feldspars: from the German “Feldspat” (“field spar”) where the term “spar” refers
to coarse crystals that break up according to their elementary forms
– nepheline: from the Greek “neféle” (cloud); refers to the decomposition that oc-
curs when treated with acid, forming a jelly-like “cloud”
– pegmatite: from the Greek “pegma”, meaning concretion
– aplite: from the Greek “haplois” (simple), a reference to its mineralogical compo-
sition
– felsite: from the German “felsbildend” meaning “rock-former”.

Mineralogical structure
The basic feldspar structure consists of a ring of four tetrahedral units (Fig.
66); potassic and sodium feldspars have three silicon tetrahedrons and one alumi-
num one while in calcic feldspars half the four tetrahedral units are silicon-based
and half aluminium-based.

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Potassium feldspar can appear in two crystalline forms: orthoclase (monoclinic)


and microcline (triclinic). Nepheline crystallises into a hexagonal system and has a
structure highly similar to that of trydimite (a silica allotrope stable between 870
and 1470 °C), from which it is only distinguished by the substitution of an Si4+ with
an Al3+: that substitution is accompanied by the introduction of Na+ and, to a much
lesser extent, K+, which ensures the electrical neutrality of the structure.

K
Fig. 66. Elementary feldspar cell.

The crystals appear as flattened hexagonal prisms and are stable at low temper-
atures.
Carnegieite is an allotrope form of nepheline, stable at high temperatures; it
derives, by way of a process analogous to that illustrated above, from cristobalite
(another allotrope form of silica). Note that nepheline is found together with alka-
line feldspars in rocks called nepheline syenites, characterised by a silica content
deficiency.

Chemical composition
The general chemical formula for feldspars is as follows:

X Y4 O8

where: X is generally made up of Na+, K+ or Ca2+


Y almost always represents Al3+ and Si4+, but is sometimes partially substi-
tuted by Fe3+.

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Raw materials for ceramic bodies

The three main feldspars have the following formulas:


– orthoclase (microcline or sanidine): K (AlSi3O8)
– albite Na (AlSi3O8)
– anorthite Ca (Al2Si2O8).

Note, however, that solid solutions between these three feldspars are frequent; in
particular, albite and anorthite form, at high temperature, a continuous series of
crystalline solutions that remain intact even after cooling (plagioclases). These go
by the following names (the albite/anorthite ratio is indicated in brackets):
– oligoclase (7/1)
– andesine (2/1)
– labradorite (1/2)
– bytownite (1/7).

Orthoclase often contains, in its solid solution form, substantial percentages of


albite.
Na and K feldspars theoretically consist of:

SiO2 Al 2O3 Na2O K2O


Na feldspar % 68.7 19.5 11.8 –
K feldspar % 64.8 18.3 – 16.9

The general formula for nepheline is, instead:

X4 (Al4Si4O16)

where X mostly consists of Na, with K accounting for no more than 1/3.

Theoretical nepheline is made up of: 41.5% SiO2, 35.2% Al2O3 , 17.5% Na2O and
5.8% K2O.

Genesis and characteristics of deposits


Feldspar, aplite, nepheline, pegmatite, felsite etc. deposits are of igneous origin
(i.e. originating from the solidification of magma fluid). There are, however, partial-
ly feldspathic deposits of sedimentary origin (sands and sandstones).
In plutonic deposits (i.e. those consolidated deep underground) feldspathic rocks
take a stromatolith form and are generally associated with quartz and muscovite.
Genesis of these veins is thought to be connected with magmatic segregations (rich
in alkalis) that stem from a particular chemical reaction or fusion and the recrystal-
lization induced by metamorphic phenomena.
For example, in the case of pegmatites (usually associated with granitoid intru-
sions) the development of large crystals (feldspars and mica) has led experts to
hypothesize low-viscosity solutions that have saturated fractures in pre-existent
rocks.

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Aplites, characterised by much more minute crystallisation are, instead, thought


to have been formed by solutions having higher viscosity, probably as a result of the
removal of a good part of the volatile substances, which would otherwise have kept
the solution more fluid and aided the development of phenocrysts.
For example, the bulk of English feldspathic materials used to come from the
region of St. Austell (Cornwall) where a granite rock (kaolinized to varying de-
grees) known as Cornish Stone emerges. The colour of the rock ranges from white
to red/purple to tan.
The partial kaolinization is thought to be the result of weathering that took
place between the Cretaceous and the Tertiary periods. The genesis of feldspars
found at Pinzolo (Trento, Italy) seems, instead, to be linked to stromatolith segre-
gation from magma. The aplite of Campiglia Marittima (Grosseto, Italy) consti-
tutes an example of (quartz-feldspathic) acid magmatic differentiation that has crys-
tallised in the absence of volatile substances. Nephelines (or, rather, nepheline syen-
ites) are plutonic rocks formed by the cooling of silica-poor fluids.
Felsites are eruptive rocks characterised by a micro or crypto-crystalline base
body with or without phenocrysts.
Sanidine (a variety deformed by the orthoclase) is, instead, found in recent volca-
nic rocks (i.e. magma consolidated on the surface) but rarely appears in concentra-
tions sufficient to make it economically interesting.
Feldspathic sandstones and feldspathic sand deposits are mined for their high
alkali content.
Both are the result of weathering and subsequent accumulation of acidic source
rock (granite, pegmatite and feldspathic metamorphites) in an aqueous environ-
ment (river deltas, lakes or shoreline marine areas). In such deposits the separation
of feldspars from other minerals (usually quartz and mica) has already occurred
naturally; unfortunately, though, transport has resulted in the addition of contam-
inants; a richness of clayey minerals or ferrous hydroxides and the presence of
strata where heavy minerals are concentrated is common.

Location of main deposits; extraction and concentration techniques


Feldspathic and pegmatite veins are mined all over the world. Some of the most
important are found in Scandinavia, the countries of the former USSR (Karelia,
Ukraine and the Kola peninsula), Turkey, Great Britain (Cornwall and the Isle of
Man), Italy (Pinzolo, Dervio and Vibo Valenzia), Germany (Oberfranken, Oberpfalz
and Hagenarf-Weidhaus), France (Perpignan), the ex-Yugoslavian nations (Mace-
donia), USA (North Carolina, Georgia, Connecticut and California), Greece (Mace-
donia), Canada (Ontario and Quebec), Mexico, Japan, India, South Africa and Aus-
tralia. Aplite deposits have been found in the USA (Virginia and North Carolina),
Japan, Italy (Campiglia Marittima) and Germany (Weidhaus and Lesslohe).
The most important nepheline syenite deposits are located in the ex-USSR na-
tions (Karelia, Siberia and the Kola peninsula), Canada (Quebec, Ontario and British
Columbia), Norway, Finland (Island of St. Jerndy), Brazil (Minas Gerais and San
Paolo) and the USA (Arkansas).
Given their compactness, the extraction of feldspathic and feldspathoid rocks

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Raw materials for ceramic bodies

generally requires the use of explosives. In the event of partial kaolinization explo-
sives may be limited to a pre-mining role, being used to “shatter” the deposit before
machinery is moved in to extract it.
However, machinery can sometimes be used to extract the material from such
deposits directly.
The tout-venant is sorted manually (e.g. as it passes along on a conveyor belt),
although more recently, automatic sorting systems using optical recognition tech-
nology have been employed.
After crushing, it is then sub-divided by particle size. Magnetic separators are
sometimes used: these easily retain the metallic particles that stem from wear on the
machinery itself, but have little effect on weakly magnetic materials such as biotite,
a common contaminant.
In this case, getting results means applying a more intense magnetic field, yet in
doing so there is a real risk of attracting useful rocky particles that were electrically
charged during grinding. Such contaminants can sometimes render the deposits
unusable; a well-known case regards the above-cited Cornish Stone, where deeper
and deeper extraction has transferred operations into less kaolinized areas that are
decidedly richer in fluorine minerals. As is known, fluorine is a source of severe
environmental pollution, so the rock cannot be used unless it is put through floata-
tion treatment.
This is so costly that the material has effectively been priced out of the market,
explaining why mining in this still-important deposit has been brought to a halt.
Concentration of alkali content via floatation is a widespread practice in the
USA.
This technique allows the quartz to be separated from the feldspar using various
chemical reagents, creating special foams that remove, in suspension, one of the
two minerals.
With sedimentary deposits (feldspathic sands and sandstones) the most common
treatment consists of washing (which removes the mainly clayey fine particles) fol-
lowed by drying in a rotary kiln.
Where the deposit is poorly cemented earth-moving machinery (bulldozers and
scrapers) can be used to extract it without any need for grinding. If not, explosives
are used in the mine, then crushers break up the fragments.

Mineralogical identification of Feldspars


Positioning of the characteristic diffractometry (Cu Kα radiation) peaks and
lattice distances for some feldspathic minerals are illustrated in the following table:

Albite:
Angular position of peaks = 27.86 - 23.52 - 13.84 - 24.16 - 22.04° 2ϑ
Lattice distances = 3.20 - 3.78 - 6.39 - 3.68 - 4.03 Å

Orthoclase:
Angular position of peaks = 27.70 - 29.94 - 26.82 - 23.54 - 21.14° 2ϑ
Lattice distances = 3.21 - 2.98 - 3.32 - 3.77 - 4.20 Å

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Nepheline
Angular position of peaks = 29.46 - 22.96 - 27.08 - 21.08 - 30.68° 2ϑ
Lattice distances = 3.03 - 3.87 - 3.29 - 4.21 - 2.91 Å

Leucite:
Angular position of peaks = 27.24 - 25.86 - 16.43 - 30.60 - 31.48° 2ϑ
Lattice distances = 3.27 - 3.44 - 5.39 - 2.92 - 2.84 Å

For albite, DTA readings give endothermic peaks between 820 and 900 °C, indi-
cating its allotropic transformation.
Analysis of oligoclase and labradorite gives analogous peaks between 780 and
820 °C.
With nepheline, thermal activity is observed towards 1250 °C as a result of the
mineral’s allotropic transformation. Since there are no matter-removing reactions,
TG analysis provides us with no information at all.
Dilatometry shows an absence of variation up to 1050 -1100 °C, after which the
start of contraction – which reaches its peak after 1100 °C – is observed.

Ceramic uses
Feldspathic materials are used extensively wherever manufacturers intend to
achieve a high degree of vitrification: for example, in porcelain tiles and light co-
loured low porosity products 25 to 55% is used.
In vitreous-china sanitaryware and porcelain feldspathic materials are introduced
in quantities ranging from 20 to 30% and from 17 to 37% respectively.
Such percentages, of course, not only change from composition to composi-
tion but also as a function of the alkali content of the feldspathic material being
added.
Producers select potassium or sodium feldspar according to the desired specifi-
cations of the final product: bear in mind that potassium feldspar is a less powerful
flux than sodium feldspar but provides manufacturers with a wider vitrification range
(Figs. 67-68).

Potassium materials are sometimes added to compositions intended to produce


medium-high porosity tiles; a classic example of this is feldspathic earthenware
(presently in decline).
Height

Fig. 67. Fusibility test sequence for the Alavus feldspar as revealed by a Leitz heating microscope
(softening point 1240 °C, melting point 1400 °C).

104
Raw materials for ceramic bodies

Fig. 68. Softening range of feldspathic fluxers identified by heating microscope (A softening point, B
melting point).

Feldspar is sometimes added to lower the expansion coefficient when other raw
materials tend to produce a biscuit with an excessively high coefficient that can,
after glazing, take on the convexity caused by excessive glaze compression.
Large quantities of (sodium or potassium) feldspar are also used in the produc-
tion of frits: here, percentages vary from 20 to 40%.
Nepheline can be used instead of feldspar, however, because of its expense (es-
pecially where consumers are far from its source) its application is limited to cir-
cumstances where its high fluxing properties are essential.

Applications in other industries


More than 50% of the world’s feldspathic materials are absorbed by the glass
industry.
However, this industry tends to use only materials with a high alkali and very
low iron content (depending on the type of glass being produced).
Therefore, floated feldspars, especially nepheline, are employed extensively.
The latter contribute massive quantities of sodium and alumina, allowing man-
ufacturers to produce a less viscous glass that is easier to shape.

Pyrophyllite

Origin of the term


Derives from the association of the Greek words “pyros” (fire) and “phyllon”
(leaf), probably owing to its tendency to “peel” when heated.

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Applied Ceramic Technology

Mineralogical structure
A clayey mineral with a mica-like base structure consisting of two hexagonal
layers of silica tetrahedrons containing an octahedral layer of Al3+ (see Fig. 69).
Like talc, the external surfaces of the particles are covered with the oxygen atoms
of the SiO4 “sheet”, while the hydroxyls are always in the interior, protected by the
two tetrahedral layers. This condition gives structural neutrality, considerable sta-
bility and chemical inertia.

Chemical composition
Al2Si4O10(OH)2

No vicariant substitution or alkaline/alkaline-earth cation introduction takes


place.

Genesis and characteristics of deposits


Pyrophyllite originates from metamorphic or hydrothermal processes. It is often
associated with sericite (a mineral which, in turn, derives from alteration of biotite).
A soft rock (hardness scale 1) of rather high specific weight (2.8), its smooth,
patinated surface makes it similar in appearance to talc.

Location of main deposits and extraction techniques


Relatively pure pyrophyllite beds are uncommon. Nevertheless, substantial de-
posits are mined in Japan, the countries of the former USSR (the pyrophyllitic schists
of the Urals), the USA (between the tuffs and breccias of North Carolina), Brazil
and South Africa.
The latter go by the name of “stumatites” and can be worked to obtain objects of
well-defined shape.

O
OH
AI
8.13Å
SI

Fig. 69. Elementary pyrophyllite cell.

106
Raw materials for ceramic bodies

The friability of the material allows it to be extracted using heavy-duty earth-


moving machinery (bulldozers, hydraulic excavators etc.). In South African depos-
its extraction is effected manually and with extreme care as the aim is to obtain
sizeable, intact fragments.

Standard identification behaviour


Diffractometry (see Fig. 70) identifies the mineral via observation of basal plane
diffractions.
The lattice distances of 9.19 Å, 4.59 Å and 3.04 Å correspond (where Cu Ka
radiation is employed) to peaks at 9.61°, 19.31° and 29.1° 2ϑ respectively.
Differential Thermal Analysis (DTA, see Fig. 71) shows an endothermic peak
between 640 and 850 °C (with a maximum at 690/780 °C) owing to loss of the OH–
hydroxyls. At the same temperatures a steep gradient is also observed on the Ther-
mogravimetric (TG) chart. In dilatometry analysis (Fig. 72) the mineral is charac-
terised by a highly intense expansion phase which begins at the allotropic transfor-
mation temperature of quartz and continues at an unchanged gradient up towards
750° and then less intensely until 850 °C. Inversion of this tendency is observed
beyond 950 °C.

Technological characterisation of pressed samples prepared with pyrophyllitic raw ma-


terials
This is a highly refractory material that recrystallizes in mullite (Al6Si2O13 –
rough formula or 3Al2O3 2SiO2 – oxide formula) and silica at around 1200 °C and
melts at around 1630 °C.
Tiles made with pyrophyllatic raw materials have the following characteristics:
– normal post-pressing expansion
– poor unfired bending strength (especially the dried product)
– intense drying expansion.

1
3.34

0
0
3.03

9.19

0
-
4.59

1
9.97

- + -
4.25

1 1+ 0 +
4.98

1
1.99

2.45

2.55
2.12

7.16
35.12

20.85

12.35
19.31
45.4

42.4

36.5

29.1

26.6

17.7

9.61
8.86

Fig. 70. Diffractometry analysis (XRD) of pyrophyllite (P = pyrophyllite, Q = quartz, M = musco-


vite, K = kaolinite).

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Applied Ceramic Technology

Fig. 71. Differential thermo-analysis (DTA) of pyrophyllite.

Fig. 72. Dilatometric analysis of pyrophyllite.

– on products fired at 1020 °C expansion is intense (3.3%) with water absorption


touching 27%. At 1200 °C no dimensional variations are observed and water
absorption is about 19%
– at 1020 °C bending strength is insubstantial; only at 1150 °C is a strength of 120
Kg/cm2 attained.

Ceramic uses
The highly refractory nature of pyrophyllite limits its range of applications.
There are few examples of it being used in the manufacture of white body wall tiles

108
Raw materials for ceramic bodies

or glazed floor tiles (as in Brazil, etc.). In such cases, it is used in extremely low
percentages.
Generally speaking, pyrophyllite lowers the expansion coefficient and limits fir-
ing shrinkage: it might, therefore, be used in the production of bodies that vitrify at
high temperature (floor tiles) yet show reduced shrinkage where fired at low tem-
peratures (wall tiles).
It is also used to produce tableware, as it gives the fired product a glossy appear-
ance. Its main use, however, is in the manufacture of refractories, insulation ceram-
ics and refractory crucibles.

Applications in other industries


An alternative to kaolin, it can be used as a rubber and plastics filler and a sup-
port for insecticides and paints.
In a category of its own, South African stumatite is used in the small-scale man-
ufacture of ornaments owing to its excellent pliability. The shaped pieces are fired
at 1300 °C without any shrinkage, thus yielding considerably hygroscopic manufac-
tured items.

Wollastonite

Origin of the term


Named in honour of the English mineralogical chemist W.H. Wollaston.

Mineralogical structure
Wollastonite has a sorosilicate structure where two silicon tetrahedrons connect
to form a pair sharing an oxygen ion (Fig. 73).
Usually of fibrous appearance (the crystals are needle-shaped or, sometimes,
tabular), this mineral has a specific weight of 2.9, scores 4.5-5 on the Mohs hard-
ness scale and is white in colour.

Fig. 73. Elementary wollastonite cell.

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The natural form, stable at ambient temperature, changes to allotropic pseudo-


wollastonite at 1125 °C).

Chemical composition
A calcium metasilicate with the following formula:

Ca SiO3

Theoretical wollastonite is as follows:

48.3% CaO + 51.7% SiO2

Genesis and characteristics of deposits


Although a fairly common mineral, economically viable extraction sites are few
and far between, usually being generated by contact between limestone and igneous
rock (contact metamorphism).
Wollastonite is usually found together with calcite, garnet (alkaline-earth alumi-
nosilicate), quartz, feldspars, granates, diopside, tremolite etc.
A closely-knit association between wollastonite and other minerals is often ob-
served, giving rise to intergrowth phenomena that makes (economically worthwhile)
separation of the mineral virtually impossible.
In the best-known deposit (Willsboro in New York State, USA) the lithologic
situation is characterised by bands of “Iskarn” (a contact-formed metamorphic rock
of hybrid mineralogy) mainly consisting of lime, magnesium and silica that lie
against anorthosites (feldspathic rock).
The wollastonite is extracted from the “Iskarn” via a crushing, classification and
floatation process (to concentrate the effectively usable mineral) and high-intensity
magnetic separation (to remove the garnet).
In the Lappeenranta deposit (in Finland) the ore beds lie in the contact zone
linking granite and carbonate rocks (limestone and dolomite). Veins of amphibolite
and pegmatite run though these rocks: granates are completely absent. The treat-
ment process consists a grinding sequence followed by floatation-type separation
of the wollastonite from the calcite and quartz and elimination of iron via magnetic
separation. Natural deposits of the pseudo-wollastonite formed by de-vitrification
of glasses is, though, rare.

Location of main deposits


The main extraction areas are in the USA (New York and California), Finland
(Lappeenranta), Mexico, Kenya, in the ex-USSR nations, India (Rajastan), South
Africa, Sudan, Spain, Japan, New Zealand and Yugoslavia (Serbia).

Synthetic wollastonite
Made from limestone and siliceous fireclay (a kaolinitic clay of disordered struc-
ture).

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Raw materials for ceramic bodies

Mineralogical composition of wollastonite rocks and standard behaviour


X-ray diffractometry (Fig. 74) identifies the mineral through observation of basal
plane diffractions.
Where Cu Kα radiation is used the lattice distances 3.83 Å, 3.51 Å, 3.31 Å, 3.08
Å and 2.97 Å correspond to the following angular positions of the peaks: 23.2, 25.3,
26.9, 23.5 and 30.0, 2ϑ.
Wollastonite is a highly stable mineral that shows no material loss or allotropic
transformation below 1000 °C: consequently, no information can be obtained from
DTA or TGA investigation.
Where, of course, there are fairly consistent proportions of other minerals their
specific thermal reactions can be observed. Dilatometric testing of unfired items
shows a progressive, linear reaction of shallow gradient; the curve flattens out be-
fore 1000 °C and the first signs of the contraction phase are observed at 1020 °C.

Technological characterisation of bodies containing predominantly wollastonite-type raw


materials
Tiles formed with (rough) wollastonite and an addition of 10% water have the
following characteristics:
– normal post-pressing expansion
– minimum unfired/dried bending strength
– no drying shrinkage
– minimum firing shrinkage at 1020 °C (0.3%)
– very low fired product bending strength until 1060 °C where it exceeds 110 Kg/
cm2.

Ceramic uses
Mainly used in the manufacture of floor and wall tiles.

7
1
3.83
3.31

7
7
3.51

7
2.97

7 7 7
3.08
2.55

7
2.30

7 7
2.72

77
2.34
1.91

2.16
2.18
41.69
47.4

41.3

39.1
38.4

35.1

32.9

30.0

29.5

26.9

25.3

23.2

Fig. 74. Diffractometry analysis (XRD) of wollastonite (Q = quartz, W = wollastonite).

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Used extensively in the USA and Scandinavia where this mineral is available
cheaply.
In single firing products the addition of wollastonite improves the bending
strength of the bodies, reduces firing shrinkage and speeds up kiln cycle times due
to the smoother thermal expansion characteristics of the body. In porcelain tiles it
is used as a bleaching agent.
On unfired items wollastonite acts (like sands) as a lean raw material while dur-
ing firing (beyond 980-1050 °C) it acts as a flux.
Cooling can be faster as the beta to alpha quartz inversion at around 570 °C is
much reduced.
The introduction of this mineral in ceramic compositions also gives dimension-
al uniformity and aids glaze-body match.
Further characteristics of ceramic bodies based on wollastonite include: low ther-
mal expansion, lustre, a smooth surface and minimum swelling.
Wollastonite is also an important component in frits (being used in quantities
ranging from 5 to 20%), particularly in those used to produce sanitaryware and fine
ceramics where it provides an improved melting range and increases lustre.
It is also introduced, albeit in very limited percentages, into certain refractory
compositions (e.g. saggers) where it is thought to improve thermal shock and im-
pact resistance.

Applications in other industries


Some 50-60% of the world’s wollastonite output is consumed by the ceramic
industry (bodies and frits), the remaining part being employed as a “filler” in the
plastics and glass industry.

Carbonates

Origin of the term


Calcite: from the Latin “calx” used by the Romans to indicate the CaO obtained
by roasting lime.
Dolomite: from the surname of the French chemist Dolomien who first distin-
guished it from limestone.
Aragonite: from the Spanish region of Aragona where the mineral was first
identified.

Nature and chemical composition


The main carbonate mineral deposits are made up of:
Limestones: CaCO3
Dolomites: CaMg (CO3)2
Magnesites: Mg CO3

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Raw materials for ceramic bodies

Crystalline structure
Different carbonate minerals crystallise into the following systems:
Limestones:
Calcite rhombohedral
Aragonite orthorhombic
Dolomite: rhombohedral
Magnesite: rhombohedral
Aragonite is irreversibly transformed into calcite at around 500 °C.

Genesis and characteristics of deposits


Limestone
Originates from (marine environment) chemical-type deposition of over-satu-
rated saline solutions and accumulation of (carbonate) minerals from dead marine
organisms.
Genesis is aided by warm water, a high ambient temperature, ventilation and low
water turnover (closed seas).
This sedimentary phase is followed by diagenesis during which the original con-
stituent fragments disappear and are replaced by recrystallized calcite.
Calcareous deposits often include impurities (clay, sand) that sedimented togeth-
er with the chemical precipitation and the organogenic accumulation.
Concentrations of impurities are often observed in the form of lateral and verti-
cal strips, and such contaminants (phosphates and sulphides) can sometimes render
the deposit worthless.

Dolomites
Similar to that of limestone; however, during diagenesis about half the Ca2+
cations are replaced by Mg2+ (present in the saturating marine solutions) giving rise
to regular stratification between the two carbonates.
The increased pressure that accompanies accumulation aids substitution in that
magnesium is smaller than calcium and is embedded more easily.

Magnesites
Genesis is identical to that of dolomite, the two minerals often being found to-
gether.
It can be said that magnesite represents the final stage in the substitution of
calcium with magnesium.
Both a crystalline and cryptocristalline type can be distinguished.
In the latter, genesis is thought to have its origins in the reactions between car-
bonate-rich water and magnesium-rich silicate rock.

Location of main deposits and extraction techniques


Limestone
Found just about everywhere. In Europe genesis mainly dates back to the Devo-
nian, Triassic, Jurassic, Cretaceous and Tertiary eras and has resulted in the forma-

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Applied Ceramic Technology

tion of important parts of some of the continent’s mountain chains (Alps, Apen-
nines, Carpathians etc.).
Some of the more recent deposits, such as those concentrated in North Africa
(Tuf) and the Caribbean (caliza arrecifal) have not undergone diagenesis and are
found in a semi-coherent state.
Although calcareous rocks are not particularly hard their extraction does re-
quire the use of explosives; the above-cited semi-coherent deposits can be extracted
with the aid of earth-moving machinery.

Dolomites
Dolomite deposits (which take their name from the famous Alpine chain, itself
named after the French scientist Dolomieu) are also common, their origins dating
back to the Silurian, Devonian, Triassic and Jurassic eras.
Like limestone, the extraction of dolomites requires the use of explosives.

Magnesites
The main big-crystal deposits are located in Austria, ex-USSR, Czechoslovakia,
Spain, Brazil, China, the USA, Canada and Australia.
Cryptocrystalline deposits are of stromatolith form and are contained in ser-
pentines and ultrabasic rocks.
Key deposits of this type are found in Greece (Macedonia), the ex-Yugoslavian
nations (Balkan region), Austria (Steinmarck), Turkey (Eskisehir), India, the USA,
countries formerly part of the USSR and Canada.

Standard behaviour and identification


Limestones
Diffractometry analysis (Cu Ka radiation) reveals peaks at the following angles:
29.3, 31.3, 35.9, 39.34, 43.08, 47.42, 2ϑ corresponding to lattice distances of 3.04,
2.85, 2.50, 2.29, 2.09, and 1.91 Å (see Fig. 75).
Differential thermal analysis (DTA) (Fig. 76) shows a marked endothermic peak
at 920 °C that corresponds with dissociation of the mineral and removal of the
carbon dioxide (CaCO3 → CaO+CO2).
At the same temperature TG analysis reveals a steep gradient owing to the weight
loss caused by removal of the CO2.

Dolomites
Diffractometric analysis (using Cu Ka radiation ) highlights the characteristic
peaks corresponding to lattice distances of 2.88, 2.67, 2.53, 2.40, 2.19 and 1.80 rel-
ative to the following angular values: 30.97, 33.51, 35.34, 37.39, 41.14, 50.57. 2ϑ.

DTA clearly shows how, as in the case of dolomite, dissociation takes place in
two separate stages, at 780 and 920 °C respectively.
Thermogravimetric (TG) analysis also highlights the removal of the carbon
dioxide at those temperatures. The mineral behaves as if it were a mix of calcium
carbonates and magnesium.

114
Raw materials for ceramic bodies

2.88
#

3.04
$ ## #
#
$$ #

2.29
2.19

1.91
$$$

1.87

2.09
1.80

$
1.78

2.50
#
2.40

$
2.53

#
2.67

2.85
44.93

30.97

29.33
50.57

41.16

37.39

35.34

33.51

49.42
47.42

43.08

39.34
51.1

35.9

31.3
Fig. 75. X-ray diffractometry analysis of dolomite (left.) and calcite (right).
(D = dolomite, C = calcite).

Temperature (°C)
Fig. 76. Differential thermal analysis curves for calcite (curve a) and dolomite (curve b) with in-air
decomposition.

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Magnesite
Differential thermal analysis (DTA) reveals an endothermic peak connected with
decomposition of the mineral and removal of the CO2 at a temperature ranging
from 400 to 650 °C. Correspondingly, thermogravimetric (TG) analysis reveals a
steep gradient in that zone.

Influence on pressed materials


Differences in technological behaviour between a carbonate-free clay and a clay
with carbonates (calcite and dolomite) are particularly marked during firing. Disso-
ciation and the release of carbon dioxide result in increased porosity and body ex-
pansion.
To illustrate this the firing data for two clays from the Emilia Apennines in Italy
is given below: one mix (B) is virtually carbonate-free while the other (A) has a
carbonate content of about 15% (both bodies have been dry-ground).

A B
Shrink. Water. Abs. Shrink. Water. Abs.
1095° 4.8 7.3 7.3 0
1055° 1.2 16.6 7.8 1.3
1010° 0.9 17.8 4.1 8.7
960° 0.9 18.0 2.2 11.4
910° 0.9 18.0 1.4 13.8
CaCO3 tot.% 15.0 2.0

Clay A is a classic cottoforte “composition” obtained from in-quarry mixing of a


highly carbonate clay (about 20%) with one that is virtually carbonate-free (the lat-
ter is type B).
It is important to note that the presence of carbonates tends to narrow the vitri-
fication range, hence it is essential that compositions for low-absorption (> 2%)
bodies do not contain more than 3-4% carbonate. This level of carbonate content
may be useful in removing organic substances contained in the clays, thus reducing
black core and swelling defects.

Ceramic uses
Limestones and dolomites are essential raw materials in the manufacture of low-
porosity, low-shrinkage ceramic items such as porous wall tiles and glazed single
fired tiles intended for both wall and floor (monoporosa).
Their inclusion (limited, though, to 20/22 and 14/16% respectively) allows bod-
ies of suitable absorption values (especially for glazing purposes) and almost zero
shrinkage (or with a maximum shrinkage of 0.5~0.6%) to be produced. This last
characteristic has, in the past, allowed high-stack firing technology to be used in
situations that would not be feasible if shrinkage were too high.

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Raw materials for ceramic bodies

In single firing wall tiles limestone and dolomite are used (as a natural calcare-
ous clay corrective) in CaCO3 percentages of up to 12-15%, giving the tiles, thanks
to the formation of calcium silicates and magnesium, low firing shrinkage (< 1%).
Their presence, however, complicates firing (especially pre-heating) of the glazes,
as heat-induced dissociation of the carbonates causes CO2 emissions which must
pass through the glaze without hindrance so as not to alter it and cause pin hole
defects (called de-gassing effects).
In this sense it is also possible to make modifications to porcelain tile bodies by
adding carbonates of pre-fixed particle size distribution to the slip or the powder,
thus obtaining a new body suitable for the production of quality wall tiles.
The presence of carbonates, then, generally leads to an increase in the expan-
sion coefficient, thus improving compatibility with the majority of commercially
available glazes.
Consequently, carbonates are used extensively in the manufacture of majolica
and earthenware.
Dolomite and magnesite are also used in the manufacture of basic refractory
items.
Carbonate-rich clays are usually used in the manufacture of extruded products.
At this point it is important to point out the importance of the so-called “coquinas”.
These are calcareous fragments sometimes larger than 1 cm. They derive from de-
posits of chemical origin, or sometimes originate from the shell fragments of long-
dead marine animals (bivalves, gastropods, brachiopods, etc.). In both cases, when-
ever raw materials containing these elements are extruded or dry-ground, prob-
lems can arise. With tiles, dimpled white-yellow spots appear on the body, leading
to pin-holing of the glaze.
In the case of bricks the “coquina” fragments, partially dehydrated after firing,
can re-expand as a result of re-hydration or re-absorption of atmospheric CO2: if
this happens after the product has been laid flaking and breakage will result, with
easily imaginable effects on the appearance of walls.

Applications in other industries


The bulk of limestone output is absorbed by cement and lime manufacturers.
For these products, a minimum magnesium content is a must. Recent years have
seen high-purity limestones steadily replace kaolin as paper fillers (largely for eco-
nomic reasons).
Magnesite, instead, is used as a filler in the manufacture of insulating materials
and as a support for fertilisers and chemical products.

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ACCESSORY MINERALS
PRESENT IN CERAMIC RAW MATERIALS

Halloysite

Origin of the term


The name halloysite was given to a Belgian rock first studied by Omalius
d’Halloy.

Mineralogical structure
A mineral from the kaolinite family, it associates a tetrahedral “sheet” with an
octahedral one that has the quality of being hydrous (dioctahedral) (Fig. 77).

The intervening layer of water molecules gives the “sheets” a certain “mobility”.
They thus tend to roll up into cylinders, as examination under an electron micro-
scope clearly shows.
This characteristic behaviour can be explained by examination of the differen-
tial tensions between the tetrahedral sheet and the octahedral one.

Fig. 77. Elementary kaolinite, halloysite and muscovite cells.

118
Raw materials for ceramic bodies

However, the attraction between the sheets is evidently higher than the differen-
tial tension: if the contrary were true the lattice itself would be destroyed.
The cylinders can, however, unroll and flatten out, turning into metalloysite,
characterised by lower water content and a lattice distance of 7.4 Å (against the
10.1 Å of halloysite).
Metalloysite loses its entire water layer at around 200 °C and irreversibly chang-
es into a kaolinite-like structure.
In passing from kaolinite to metalloysite to halloysite a progressive increase in
hydration is observed, accompanied by an increased degree of disorder of the lat-
tice.
It is interesting to note how crystal size in the various kaolinite-family minerals
depends on the degree of stability (and disorder) of the structure.
Note that the smaller particles belong to halloysite while the larger ones are
seen in kaolinite.

Chemical composition
Al2 (X2 O5) (OH)4 2H2O

X = element in a tetrahedral position (to all intents and purpose this is Si4+ only,
in that substitutions with vicariants such as Al3+ or Fe3+ are almost never observed:
as is known, the latter result in the structure lacking a positive charge).

Genesis and characterisation of deposits


Halloysite is a constituent of numerous clayey deposits. It appears as a compact,
whitish mass (where free from chromophore contaminants) or may be yellow or
pink. Of shiny appearance, like kaolinite, it is greasy to the touch. Nevertheless, it is
not uncommon for it to be found in conditions of high plasticity.
Halloysite is generally generated from volcanic source rocks (ranging from the
acid to the neutral) and volcanoclasts (pyroclastic rock and volcanic breccia).
Broadly speaking, the transformation of these source rocks is similar to that
which leads to the formation of kaolinite.
As in the latter, removal of alkalis (sodium and potassium) occurs, a process that
is completed in full only in certain cases.
Persistence of substantial quartz residues is not uncommon; associations with
kaolinite and the presence of cristobalite and alunite (hydrous potassic sulpho-alu-
minate) are often observed too.
Halloysite deposits may be primary (i.e. found at the location of the pre-existent
source rock) or secondary (i.e. where particles have been transported and re-depos-
ited in an aqueous environment).
The genesis of halloysite deposits can often be traced to hydrothermal alter-
ation.

Location of main deposits and extraction techniques


While quite common, halloysite is rarely the most important mineral in a de-
posit.

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Some American States (Utah, Nevada, Idaho, North Carolina and Georgia) have
particularly extensive extraction sites.
The most important European deposits are found in France (Dordoigne) while
minor deposits exist in Czechoslovakia and ex-Yugoslavia.
Quarries are generally of the open-cast type and employ standard earth-moving
machinery (bulldozers, scrapers, hydraulic excavators, etc.).

Mineralogical analysis of halloysite raw materials. Standard behaviour and identifica-


tion
Identification via X-ray diffractometry exclusively involves observation of basal
plane diffractions (see Fig. 78).
Correspondence charts showing lattice distances (d) and positioning of the peaks
(using Cu Kα radiation) for halloysite and metalloysite are given below:

HALLOYSITE

d = 7.20 Å 4.42 Å 3.56 Å


2ϑ = 12.20° 20.10° 24.95°

METALLOYSITE

d = 7.10 Å 4.42 Å 3.57 Å


2ϑ = 12.40° 20.10° 24.90°

Fig. 78. Diffractogram pattern for halloysite, characterised by an intense reflection at about 4.4 Å, often
stronger than the basal ones at 7.2-7.4 Å and about 3.6 Å, which are broad and asymmetric towards
lower angles.

120
Raw materials for ceramic bodies

The differential thermal analysis (DTA) diagram for halloysite reveals a charac-
teristic endothermic peak just before 200 °C associated with the loss of interlayer
water; at higher temperatures behaviour is similar to that of kaolinite. A new en-
dothermic peak starts at 450 °C as a consequence of removal of the OH- hydroxyls
while at around 980 °C, in connection with the crystallisation of mullite or alumina,
a distinct exothermic peak is observed.
Correspondingly, thermogravimetric (TG) analysis reveals a sharp weight loss
just before 200 °C and towards 450 °C, connected with removal of the inter-layer
water and the OH hydroxyls respectively.
No variation, of course, is noted at 980 °C as this exothermic reaction does not
involve the removal of material, just the freeing of bond energy.
Dilatometry analysis shows initial, weak dilatation balanced by evident shrink-
age just beyond 150 °C: this is caused by the removal of interlayer water.
Once this phase is complete shrinkage continues, albeit on a much shallower
gradient, until just beyond 450 °C when a new, marked contraction occurs (loss of
the OH- hydroxyls); that contraction persists towards 880 °C at which point sinter-
ing reactions take hold and steeper-gradient shrinkage is observed, with conse-
quent softening of the sample.

Technological characterisation of pressed halloysite materials


Tiles made of a predominantly halloysite raw material would have the following
characteristics:
– normal post-pressing expansion
– good unfired bending strength (green and dried)
– considerable drying shrinkage
– fired at 1100 °C, dimensional contraction is already considerable (3-8%) with an
apparent porosity of 20-25%
– at 1100 °C bending strength is generally in the 100-150 Kg/cm2 range
– the coefficient of cubical expansion (for samples fired at 1100 °C) is incredibly
low (even lower than 100.10-7 °C-1).

Note that intense drying shrinkage makes removal of the water a real problem
and that this operation often leads to the fracture of a substantial number of
pieces.

Ceramic uses
In practice, halloysite is rarely used in the manufacture of tiles whatever their
colour (usually a coarse halloysite is used in combination with other raw materi-
als); it is, in fact, best avoided as there are considerable complications at the dry-
ing stage.
It is sometimes employed in the manufacture of bricks (especially in the USA),
fire-bricks and refractories (bear in mind that this is, in any case, a raw material of
high alumina content).
The use of halloysite in these products is justified when the plasticity of the mix
needs to be increased.

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Finally, note that this material has rather peculiar rheological properties: conse-
quently, its use in products involving wet grinding of raw materials leads to poor
deflocculation of the body.
On the whole, then, utilisation of a halloysite raw material must be well con-
tained (within 5-20%): such percentages will allow for fairly generalised use (pot-
tery, porous and vitrified tiles).

Applications in other industries


In some fields it can be used as an alternative to kaolin; in particular, halloysite
can be used as a filler in the manufacture of paper, tyres and rubber.
Certain “Fuller’s earths”, well-known for their de-colouring power, have sub-
stantial percentages of halloysite. However, their main constituent is always mont-
morillonite.

Attapulgite, Sepiolite, Vermiculite

Origin of the term


Attapulgite: from Attapulgus (Georgia - USA), where the first identified sample
was found.
Sepiolite: owing to its similarity with the cuttlefish (sepia) bone. Also known as
“Meerschaunm”, a German word meaning “sea foam”.
Vermiculite: derives from the long, worm-like filaments generated by rapid heat-
ing.

Mineralogical structure
Attapulgite: this is a silicon inosilicate. The tetrahedron apexes alternately point
in opposing directions; this distribution is coordinated between the two chains in
the sense that apexes pointing towards the other chain will find, on the latter, a
specular situation.
Octahedrally coordinated Al3+ and Mg2+ cations lie between the apexes of the
tetrahedrons of these two chains.
The structure is completed by the introduction of OH- hydroxyls at the extrem-
ity of the octahedrally-arranged cations while the interstices are filled with water
molecules.
Sepiolite: again an inosilicate, very similar in structure to attapulgite, yet differs
in terms of the size of the platelets and the minimum possibility of cation substitu-
tion. Sepiolite platelets are 50% larger than attapulgite ones.
Vermiculite: a phyllosilicate, the structure of which consists of overlaying mica-
like silicon units; on the whole the construction has a well-defined negative charge
(as observed in chlorite minerals) balanced by the (hydrous) Mg ions inserted be-
tween the silicate layers. The magnesium may be substituted by other cations. Dio-
ctahedral and trioctahedral forms also exist. This mineral has the characteristic,
when heated rapidly, of swelling up to 50 times its initial size and giving rise to
worm-like elements.

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Chemical composition
Attapulgite: (Mg, Al)2 Si4O10(OH) . 4H2O

Sepiolite: Mg4Si6O15(OH)2 . 6H2O

where: X is usually made up of Mg2+


Vermiculite: Mg3-x (Al,Fe3+ , Fe2+ etc.) x (Si, Al, Fe3+)4O10(OH)2 Mg0.33 . 4H2O

The substitutions that lead to a deficit of valence are balanced by the insertion
of alkaline-earth cations.

Genesis and characteristics of deposits


Attapulgite and sepiolite originate from hydrothermal processes that have been
followed by transport and re-depositing. The raw material appears as a fibrous,
lamellar or spongy mass of considerable size.
Sepiolite not only alternates with limestone layers, but is also a filling in lime-
stone cavities. Colour ranges from white to light pink (where dry), changing to dark
pink or grey-brown when wet.
Water-free fragments tend to float on water until saturation causes them to sink.
The genesis of vermiculite, instead, can be traced to ultrabasic intrusions rich in
biotite and pyroxines and, sometimes, to dolomite rocks that have undergone hy-
drothermal or weathering-induced transformations.
This explains the presence of biotite “relics” in vermiculite deposits. The miner-
al generally ranges in colour from off-white to green and then brown and tends to
separate along fracture lines.

Location of main deposits


On the whole deposits of these clayey minerals are few and far between.
Sometimes attapulgite and sepiolite deposits constitute the upper part of refrac-
tory (kaolinitic) clay deposits as is the case at Sezanne (France).
Another attapulgite deposit, again in France, is found at Argenteuil.
The main European sepiolite deposit is located in the Spanish province of Valle-
cas where it consists of greyish layers several metres thick within a Tertiary evap-
oration basin.
The deposit at Synia (Tanzania) is particularly appreciated on account of its
lightness and the “closed porosity” of the extracted pieces. As for vermiculite, com-
mercially-mined deposits exist throughout the USA (Montana, Wyoming, Colo-
rado, Nevada, Arizona, North and South Carolina, Georgia and Texas) and in South
Africa (Transvaal). The mineral vermiculite is found in these deposits in percentag-
es ranging from 30 to 60%.

Standard behaviour and identification


Attapulgite
The curve produced by differential thermal analysis (DTA) is rather complex
and varies considerably as a function of the specific composition of the mineral

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being examined. Nevertheless, above 100 °C, there is a distinct endothermic peak
associated with the removal of zeolite water. This is followed by a second peak
(towards 600 °C) associated with evaporation of the OH- hydroxyls. Since these are
effectively weight losses they are also show up in TG analysis as the customary on-
diagram gradient increases.

Sepiolite
The DTA curve shows a first endothermic peak at around 150 °C (loss of inter-
layer water) and a second at 800 °C (removal of the OH- hydroxyls), while towards
850 °C a net endothermic peak caused by neo-crystallisation of enstatite (SiO2 .MgO)
and cristobalite (SiO2) is observed.

Vermiculite
Differential thermal analysis gives a marked endothermic peak at around 150 °C
with a lower endothermic effect at 180 °C; both refer to the removal of water mol-
ecules. At 550 °C, and more markedly at 850 °C, endothermic peaks associated with
hydroxyl removal are clearly observed (Fig. 81-82).
All the reactions involve removal of material and consequently show up on the
TG curve too.

Ceramic uses
Use in the ceramic industry is extremely limited. Attapulgite and sepiolite (min-
erals rich in magnesium) can be employed in the production of magnesium glazes.
The attapulgite of Argenteuil has been used in the manufacture of Sèvres porce-
lain. Sepiolite is introduced into compositions for porous tiles, insulation porcelains,
pottery and sanitaryware. Thanks to the noted porosity of its structure it may also
be used in the production of insulating refractory bricks.

Fig. 79. A typical X-ray diffractometry trace for vermiculite.

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sepiolite
quartz
potassium feldspar

Fig. 80. Example of a diffractogram for a sepiolite sample containing quartz and potassic feldspar
impurities.

Temperature °C

Fig. 81. DTA curves for vermiculite. The overall configuration of the endothermic effect at 100-250
°C is modelled mainly by the type of interlayer cation: A = magnesium; B = calcium, C = sodium.

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Fig. 82. DTA analysis of Palygorskites and Sepiolites.

Applications in other industries


Attapulgite and sepiolite are mainly employed as sludge in oil drilling opera-
tions. Attapulgite is also used to de-colour oils, as a support for fertilizers, in phar-
maceutical products, cosmetics and as a paper and paint filler.
Owing to the extreme lightness conferred by its high porosity, Synia sepiolite is,
oddly enough, used to manufacture tobacco pipes and various other items, their
surfaces being water-proofed by lining the pieces with Canada balsam. Vermiculite,
thanks to its enormous cation exchange capacity, is, instead, used to fix radioactive
elements in certain types of waste. It is also used in the manufacture of thermal
insulators.

Micas

These mainly concern another two phyllosilicates, as well as the already-seen


principle components of an illite-chlorite type, having the following compositions:

biotite: 6SiO2 Al2O3 . 6(Mg,Fe) O. K2 O. 2H2O


muscovite: 6SiO2 3Al2O3. K2O. 2H2O

Decomposition of these via a hydration process gives rise to sericite:

6SiO2 3Al2O3 . K2 O . 4H2 O

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Raw materials for ceramic bodies

The structure of these minerals is similar to that of illite; they consist, in fact,
of two layers of silicon tetrahedrons enclosing a layer of aluminum octahedrons.
Numerous substitutions come into play, creating electrical imbalances that are ad-
justed by the introduction of new ions.
Biotite (or ferroan mica) has a brown-blackish, shiny appearance and is a prime
constituent of granites, rocks “related” to feldspars: consequently, it is often en-
countered as a contaminant in mined feldspar deposits.
The presence of biotite, within certain limits, correlates with that of anorthite
(calcium feldspar). During alteration of the source rocks (weathering, contact meta-
morphism etc.) it can easily alter into sericite, and is thus found only rarely in sedi-
mentary rocks. Muscovite (or potassic mica) appears in the form of metallic-like,
hexagonally-shaped, shiny, flexible platelets that flake easily. These platelets can
become enormous (even over 1 metre), as seen in Indian deposits. Like biotite, it is
present in certain types of granite, alteration transforming it into illite; neverthe-
less, it is frequently found in sedimentary rocks (clays and sands), sometimes in
significant percentages (even over 10%).
Sericite appears as long flat greenish fragments or needles. In certain sedimenta-
ry rocks its lithoid, non-carbonate nature (as in certain sandstones) constitutes, to-
gether with the ferrous hydroxides, the cement that binds the various components.
Diffractometry analysis of biotite (using Cu Kα radiation) highlights the character-
istic lattice distances (10.1 Å, 3.37 Å, 2.66 Å, 2.45 Å, 2.18 Å) with corresponding
peaks at the following angles: 8.70, 26.42, 33.66 and 41.40° 2ϑ.
A similar analysis of muscovite gives peaks at 26.80, 8.86, 34, 88, 45, 50 and
29.82° corresponding to lattice distances of 3.32, 9.95, 2.57, 1.99 and 2.99 Å.

DTA of biotite yields a completely flat line up to 1000 °C, while the same test on
muscovite shows an endothermic peak between 800 and 950 °C corresponding to
removal of the OH- hydroxyls (Fig. 83).
Biotite constitutes a significant problem in certain feldspar deposits, where only
high-intensity magnetic separators can remove it. However, it is not uncommon for
the separators to attract feldspar and quartz particles that were electrically charged
during grinding. In such cases a choice usually has to be made between somewhat
partial separation of the biotite (resulting in commercialisation of a product that,
after firing, varies in colour from grey to blackish and is blemished by black dots) or
a consistent loss of useful material which the magnetic separators inevitably re-
move together with the mica.

When present in substantial percentages, muscovite too can cause serious diffi-
culties.
A well-known example of this problem is Cornish Stone, extraction of which
ceased because the deposit was steadily becoming more and more muscovite-rich.
While muscovite can be split from the other components by “winnowing” and
floatation, such processes are very expensive, thus pricing the material out of the
market, which automatically selects products unaffected by this problem that do
not necessitate separation systems.

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Fig. 83. DTA analysis of micas.

As mentioned above, muscovite is often encountered in sedimentary rocks; for


example, it is found in various clays of the Emilia Apennines (Italy), but in amounts
too small to cause any production problems.
The presence of mica in porous bodies (fired at temperatures of approximately
1000/1020 °C) is easily seen with the naked eye.
Mica is rich in potassium and, on vitrified bodies, acts as a fluxer and contrib-
utes to vitrification of the material.
Note that the lamellar structure of muscovite makes it difficult to grind, a
characteristic that is even more marked when “wet” grinding technology is em-
ployed.
This may lead to clogging as the slip is passed through the sieves. It is thus
advisable to use sieves that eliminate the trapped material efficiently.

Mineral hydroxides

Mainly the hydroxides of:


– aluminum: gibbsite (also known as hydrargillite) represented by the formula Al
(OH)3,
diaspore [AlO(OH)] and boehmite (Al2O3.H2O)
– iron: goethite (FeO. OH).

Aluminum hydroxides are the main constituents of bauxites.

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Raw materials for ceramic bodies

DTA and TGA analysis of the various minerals give the following dehydration
temperatures:
– gibbsite: from 240 to 380 °C
– diaspore: from 410 to 570 °C
– bohemite: from 450 to 580 °C
– goethite: starting from 250 °C.

Characterised by significant colloidal content, hydroxides can cause problems


during drying and preheating in that, containing high percentages of hydroxyls,
they can cause dimensional settling of the pieces.
Fig. 84 shows key diffractometric indices for several oxides and hydroxides. DTA
results for a predominantly diaspore rock are also given, showing net endothermic
peaks at 500 °C. (Figs. 84-85)

Soluble salts

This term refers to all those carbonates, sulphates and alkaline/alkaline-earth


chlorides soluble in water. This capacity varies enormously from mineral to miner-
al: values are sometimes so low (in the order of just a few parts per thousand) that
they are, to all intents and purposes, insoluble.
Table n. 7 gives in-water solubility for these minerals. The most important solu-
ble salts are:
– Ca, Mg, Na, K and Al sulphates
– Na-Al, K-Al double sulphates
– Ca, Na and K carbonates
– Na and K chlorides.

Among these, calcium carbonate (its definition as a soluble salt considered by


some to be improper) is present in all the clays used to produce porous bodies. Also
worth remembering is ferric sulphate, generated by oxidation of the sulphides (py-
rite and marcasite) as per the following reaction:

FeS + H2O + 7/2 O2 → FeSO4 + H2 SO4

The geological history of the earth shows that the formation of sedimentary
ceramic raw material deposits is closely linked to that of soluble salt minerals. The
presence of these minerals is caused by precipitation conditions in sea water at the
same time as fine particles from suspensions of continental origin are deposited.
Hence the presence of such mineral “contaminants” in clayey deposits of sedi-
mentary origin. Nevertheless it should not be forgotten that the (mostly lacustrine)
continental deposits also derive from the break-up of pre-existing rocks that may,
in turn, have been of sedimentary origin, thus allowing transfer of soluble salts
from one “generation” of rocks to the next.
Soluble salts show up in a variety of ways.

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Fig. 84. List of the main aluminum, manganese, and titanium oxide and/or ferrous hydroxide reflec-
tions in decreasing interplanar spacing order.

Fig. 85. DTA analysis of mineral hydroxides.

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Raw materials for ceramic bodies

Water solubility (in g/l)


CaCO3 0.013
CaCl2 595.0
Ca(OH)2 1.850
CaMg(CO3)2 0.320
CaSO4 2.090
CaSO4 . 2H2O 2.410
BaCO3 0.020
BaCl2 310.0
BaSO4 0.002
MgCO3 0.106
MgCl2 542.5
MgSO4 260.0
Mg(OH)2 0.009
Na2CO3 71.0
NaCl 357.0
Na2SO4 47.6
K2CO3 1120.0
KCl 347.0
K2SO4 68.5

Tab. 7. In-water solubility of certain salts.

Distribution may be widespread but so microscopic as to be undetectable with


the naked eye except in periods of drought when evaporation of impregnation wa-
ter leaves them on the surfaces of clayey deposits, resulting in a characteristic whit-
ish film.
Sometimes, consistent concentrations are observed in depressions in the ground
underlying the clayey formations: this is where rainwater – the salt “vehicle” – gath-
ers.
Circumstances sometimes cause macroscopic particles to form. It is not uncom-
mon for gypsum crystals even a few millimetres wide to be found, in their charac-
teristic lenticular, spearhead or prismatic form. This grouping also includes the
“coquinas” – rounded, lightly-coloured carbonate elements that are the bane of ex-
truded item manufacturers.
Here, we are in the field of (apparently) general or casual distribution that in-
volves one or more veins of a formation. Sometimes, instead, deposits are concen-
trated in layers just a few millimetres thick which follow sedimentation planes ex-
actly and separate two adjoining veins.
However, concentrations along fractures in the deposit are far more likely. These
stem from the dissolution and recrystallization caused by impregnation waters but
are probably also the consequence of diagenesis phenomena, at least as far as the
oldest clayey formations are concerned (those deposits have never undergone meta-
morphosis in that they would have been transformed into schists or shale).

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They assume many different forms, ranging from thinly-spread films of varying
consistency and hardness to protruding crystallisations, soft and fragile or compact
and tough.
As usual, differential thermal analysis (DTA) provides useful information as to
the exo and endothermic reactions that take place during heating. Gypsum (dihy-
drate calcium sulphate) shows a first endothermic peak at 140 °C (transformation
into a hemi-hydrate), a second, smaller one at 150 °C (transformation in anhydride)
and a tiny exothermic one at 350 °C indicating the change from soluble anhydride
to insoluble anhydride.
At 1125 °C the anhydride changes from type α to type β (small endothermic
peak) and dissociation of CaO from SO3 begins.
Pyrolysis of the chlorides, instead, is complete by 700 °C; the magnesium sul-
phate begins to disassociate towards 900 °C, while in the case of sodium sulphate
such reactions may persist beyond 1000 °C. It thus follows that neo-genesis of
alkaline sulphates and alkaline-earths is almost completely annulled in ceramic bodies
that sinter at temperatures above 1000 °C.
Finally, in the case of ferric sulphate, pyrolysis begins towards 170 °C, while in
magnesium sulphate it is only seen above 400 °C.
As regards its influence on slip rheology it can be stated that the presence of
dissociated sodium and potassium soluble salts aids deflocculation while calcium,
magnesium and even iron ones cause flocculation.
Thixotropy too depends on the surface properties of the colloidal particles of
clay and is significantly influenced by the electrolytes that act on alterations be-
tween the particles.
It is known that the quantity of alkaline chlorides is directly proportional to the
tendency towards formation of kaolinitic clay suspension gels and inversely pro-
portional in the case of slips consisting of montmorillonites. The presence of sol-
uble salts can thus produce opposing effects which depend on the clayey minerals
present.
The firing behaviour of the main soluble salts is characterised by pyrolysis, with
consequent elimination of the gaseous phase and dehydration phenomena. For ex-
ample, the loss of the gypsum water molecules occurs at low temperature, overlap-
ping water loss in expandable-lattice clayey minerals, thus contributing to total
shrinkage of the piece at the drying and preheating stage.
The consequences of the above-cited phenomena increase in significance as fir-
ing cycle times shorten.
Certain reactions, almost insignificant in traditional tunnel kiln cycles, cause
huge problems in the rapid and ultra-rapid cycles of single firing items, difficulties
that can often only be resolved by eliminating certain raw materials.
Where rapid cycles are employed a further complication is posed by the re-
sistance of the glaze, as it covers a body that has not been stabilised by a first
firing.
Pyrolysis reactions involving the removal of gas when the glaze has high fluid-
ity, or the employment of unsuitable glazes, give rise to small “craters” on the face
of the tile that damage the finished item irreparably.

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Raw materials for ceramic bodies

Single firing glazes will only let gas bubbles pass through where fusibility is
extremely high or extremely low; in the former case low-temperature fusibility al-
lows re-closure of craters opened up by bubbles breaking the surface.
In the latter, the glaze only fuses at high temperature and thus preserves an
earth-like porosity well into the firing process, allowing gas bubbles to pass through
without hindrance.
Some authors claim that soluble salts cause “black core” problems, yet the source
of such defects is actually the presence of non-mineral carbon and iron.
The main effect of soluble salts on unglazed fired pieces is the appearance of
efflorescence.
This term refers to deposits that settle on the surface of the biscuit (sometimes
on the dried product too) by way of the mineral salt precipitation that occurs under
saturation conditions.
This phenomenon, generally seen on bricks, but also on both pressed and ex-
truded tiles, only occurs when the ceramic body is porous enough to allow, within
its interior, migration of salt solutions.
On reaching the surface, these give rise to rapid water evaporation. The raw
material must, of course, have a relatively high content of such salts (and alkaline
oxides and lime) or they must form during firing by way of pyrolysis of the pyrite
or the presence of sulphur in the kiln fuel. The phenomenon is perceptible as soon
as fired products contain more than 0.5%.
Efflorescence is, in order of frequency (on dried and fired products), caused by
sodium sulphates, calcium, potassium and magnesium, the carbonates of these met-
als and chlorides and alkaline nitrates. On fired items sulpho-aluminates and alka-
line carbonates are also observed.
The formation of efflorescence is greatly influenced by factors affecting the move-
ment of saline solutions inside the fired bodies (dimensions and distribution of
pores) and the way in which water evaporation occurs: bear in mind that, under
certain circumstances, this takes place not on the surface but in the interior of the
ceramic body.
Where salts migrate to the surface of pressed tiles (generally seen on double
firing wall tiles) there may be an accumulation of alkali-containing salts in those
zones subject to greater heating during drying (i.e. tile edges).
The extreme consequence of this phenomenon, also caused by re-wetting of the
biscuit during glazing, is the alteration of the chemical composition of the glazes at
the edges of the tile via increased contribution of fusible salts; it makes this part of
the tile, already subject to greater interaction with the heat of the kiln, even more
sensitive to temperature variations and, on average, more fusible. This can lead to
the side of the tile having an overly-fused, clearer-coloured appearance generated
by air bubbles in the glaze.
A similar phenomenon generated by salt migration is seen on porcelain tiles.
This defect is generated by salts building up at the tile support points during dry-
ing, thus giving rise to zones with a greater post-firing vitreous phase content of
shinier appearance.
In both cases the problem can be resolved – in addition to attempting to elimi-

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nate salt-carrying raw materials – by making drastic changes to the drying cycle,
accelerating it to the limits of piece bending strength so as to aid high-speed water
evaporation and thus prevent migration and accumulation of salts on certain parts
of the tile.

Vegetable substances and reducers

Vegetable substances (some examples are given in Fig. 86) found in clayey raw
materials can be divided into two main groups: non-carbonized and carbonized
materials.

The former include roots, wood fragments, leaves and humic acids; these ele-
ments are largely present in recent deposits or those connected with the pedolith
layer, or occur simply as a result of incomplete clearing of vegetation prior to ex-
traction.

Fig. 86. Organic substances found in clays.

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Raw materials for ceramic bodies

These vegetable substances are normally eliminated during the firing process,
sometimes with the aid of oxidising substances specially added to the body: they
start combusting at around 250 °C and stop at approximately 450 °C.
The latter group – consisting of various types of carbon and generally found in
older geological formations – is considerably more stable. Normally immune to treat-
ment with oxidants, these materials will, during firing, burn away in the 300 to 600
°C range.
The presence of vegetable substances causes various difficulties in the produc-
tion of both single and double firing items.
In fast single firing – especially where cycles are less than an hour, iron minerals
are present (red body) and manufacturers aim to produce low-absorption bodies –
centrally-placed, black ellipsoidal stains (“black core”) can form and, in the most
serious cases, there is intense swelling. These result from incomplete combustion
of the organic substances, giving rise to graphitic carbon which blackens the ce-
ramic body, while the CO2 from the burnt part, unable to pass through the piece,
causes swelling.
Furthermore, where inorganic salts are present, Na2SO4 salts also form: these
contribute to the formation of vitreous phases, blackened or darkened by the pres-
ence of chromophore cations (e.g. Fe, Cu, Cr etc.).

Where mineral sulphides (e.g. iron or copper sulphides) are present complex
reactions take place, giving rise to combinations between the silica and sulphide
decomposition products (Fig. 87) and resulting in a black, highly fusible glaze.

Fig. 87. DTA analysis of mineral sulphides.

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FeS2 + O2 → FeS + SO2 [350 - 450 °C]


4FeS + 9O2 → 2Fe2O3 + 4SO3 [500 - 800]
2FeSO4 + ½O2 → Fe2O3 + 2SO3 [560 - 775]

The actual appearance of such phenomena will also depend on other factors
such as powder grain size and moisture content, pressing force, firing curves and
in-kiln atmosphere. Negative effects can be reduced by:
– introducing lean (non-plastic) raw materials into the composition (sands, lapilli,
chamotte)
– adding oxidants to the composition (MnO2, various nitrates)
– increasing the particle size of components and powders
– reducing the moisture content of the powders (but taking care not to unduly
lower the dry bending strength)
– lowering pressing pressure
– applying a more appropriate firing curve that makes the 250-600 °C interval last
as long as possible
– establishing an in-kiln atmosphere that is as oxidising as possible.

Sulphur and sulphides (alunite)

Certain feldspathic or clayey materials sometimes contain sulphurs which vary


in colour from whitish to yellow. These are generally raw materials of an origin
associated with volcanic areas. Materials of this type found in Lazio (central Italy)
are a classic example.
Sulphur gives rise to a number of problems: during firing it turns into sulphur
dioxide and corrodes the internal structure of the kiln: sulphur dioxide also gives
rise to problems of an environmental nature both inside and outside the plant.
Many of the clays used to manufacture tiles (e.g. those from the Emilia Apen-
nines in Italy) contain ferrous sulphides (pyrite and marcasite).
Pyrite causes formation of the classic “black dot”, that is, on-biscuit mini-craters
with a dark core, which, in turn, lead to specks in the glaze. The mechanism that
gives rise to this is thought to be linked to the random presence of pyrite crystals
close to the surface of the bodies. At a temperature of around 400 °C an oxidising
process transforms the sulphur in oxide with removal of the SO2: the chemical
process is accompanied by an increase in volume and causes “flaking” of the small
fragment covering the crystal, thus leading to mini-cratering.
Alunite is a hydrous potassium sulpho-aluminate defined by the following for-
mula:

K2O(Al2 O3)3 (SO3)4. 6H2O

This mineral is generated under hydrothermal conditions that often lead to the
kaolinization of feldspathic veins. That’s why it is usually found together with ka-
olin, as seen in the famous kaolinitic deposit of Djebel Debar (Algeria). Observation

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Raw materials for ceramic bodies

of a DTA chart for this material shows a first endothermic peak at 550 °C (water
loss) while a second (at 850 °C) indicates the removal of a good part of the sulphur
dioxide that accompanies the formation of alumina and potassium sulphate.
The exothermic peak visible just after 700 °C has yet to be fully understood. The
freeing of sulphur trioxide involves problems cited previously.

Vitreous materials

Found in clayey or sandy deposits when, during genesis, volcanic materials are
introduced at the same time as sedimentation of the water-suspended particles.
When small, such products may be transported (by wind) a long way from the
point of origin (i.e. from the volcanoes). The characteristic vitreous state of these
materials is unstable and tends to evolve towards the crystalline; however, it is a
transformation that requires an extremely long time to develop and reach comple-
tion. This explains why vitreous particles of this type are still found in sediments
that are not particularly recent (as with certain red-beds of the Emilia Apennines).
The presence of these materials gives rise to melting dark dots on the biscuit
surface; with certain glaze types, this problem can become more marked and lead to
production problems.

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Raw materials for ceramic bodies

Chapter IV

RAW MATERIALS FOR FRITS AND GLAZES

It is common to apply a surface coating to tiles which, when fired, produces a


vitreous layer that is hygienic, easily cleanable and provides aesthetic qualities. Bear-
ing this in mind, let us now take a look at the most common techniques and materi-
als used in such technology.
Firstly, it is important to define just what is meant by the term “frit” (a name for
a major component in most glazes.
A frit is obtained by melting a mixture of materials in either continuous (basin)
furnaces or intermittent (rotary) furnaces.
Glazes contain combinations of one or more frits with other additives to obtain
various effects to be described later.
The pre-melting or fritting of materials serves to produce an amorphous, homo-
geneous compound, free from any non-dissolved raw material residues or bubbles,
which, on subsequent grinding will become even more homogeneous.
Fritting aims to:
1) make certain components (boron derivatives, alkaline salts, lead derivatives) in-
soluble: these would otherwise dissolve during the grinding stage if used in
their raw state.
2) completely eliminate all organic impurities, thus removing all volatile compo-
nents via reactions that would otherwise occur during firing of the finished prod-
uct.
3) disperse certain impurities (of ferrous and/or metallic nature) evenly within the
mass: even where such impurities are present in very low percentages they can
still cause local defects. Melting ensures that these contaminant particles are
dispersed throughout the molten mass and incorporated in the composition, thus
eliminating defects such as iron, copper specking etc.
4) aid reactions at high temperatures (i.e. 1400 °C or more), forming vitreous com-
pounds that would otherwise develop at standard body firing temperatures.

Raw materials for melting of frits

In selecting raw materials for the production of ceramic frits the following crite-
ria must be taken into consideration:
– consistency of chemical composition over time
– consistency of particle size distribution over time
– low Fe and Cr content
– absence of difficult-to-melt minerals (kyanite and sillimanite) that, remaining in
the frit as unmolten elements, compromise its quality

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– last but not least, materials should be economically viable and readily avail-
able.

The most important and thus the most commonly used materials are:
– quartzes and sands
– sodium feldspars
– potassium feldspars
– boric acid
– pentahydrate borax
– colemanite (calcium borate)
– anhydrous borax (sodium borate)
– ulexite (sodium and calcium borate)
– calcium carbonate
– zirconium silicate
– zinc oxide
– barium carbonate
– dolomite
– kaolin.

In lesser quantities, the following products are also used:


– potassium nitrate
– sodium carbonate
– potassium carbonate
– magnesium carbonate
– titanium dioxide.

Such a variety of raw materials means there is a need to make basic choices in
terms of storage and handling solutions. It should be noted, in fact, that some of
the above-cited raw materials cannot be stored in silos (or, rather, not in a way that
is straightforward).
Moreover, materials such as barium carbonate, titanium dioxide and potassium
nitrate are not available in bulk.
Zinc oxide differs from other materials in that, in its light form, it cannot be
stored in, or, rather, extracted from, silos: consequently, it is now common practice
to employ so-called “heavy” zinc oxide, a material without any particular handling
problems.
Given the above difficulties and the simple fact that they are often utilised in
small quantities these raw materials are, then, generally stored in sacks rather than
silos, while others may be delivered in bulk by truck.
Information regarding the type of minerals from which these materials are ex-
tracted, refining processes and chemical/particle size distribution limits that make
these compounds suitable/unsuitable for fusion is given below (see p. 145).

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Raw materials for frits and glazes

Technological aspects of frits and glazes

Final ceramic surface coatings are, then, made up of thin vitreous layers. They
are applied in aqueous suspensions – obtained by water grinding the frit and any
other raw components in the composition – onto fired or dried unfired ceramic
bodies.
A certain glass type, known as “cristallina”, is, on some wall tiles, applied on
already glazed and decorated tiles to obtain brighter and deeper colour effects.
Another characteristic glaze is “maiolica”, highly opaque, usually applied thickly
to give a rich white and glossy tile surface. The glaze get its opacity from the frit
opacifier, usually, zirconium silicate.
There are also frits for specific, finely-targeted use, such as those employed in
monoporosa. In addition to opacity and brilliance, these must also have very high
softening points (1020-1050 °C) so as to favour emission of the gas (CO2) emitted
from the body during firing.
With glazes, instead, the diffusion of vitreous single firing products has meant
that, in addition to the concept of opacity other factors such as surface appearance
(matt, semi-matt) should be considered.
This chapter will deal first with the theoretical aspects of the nature of the
glass, and then provide a review of the different types of frit and, finally, glaze
compounds.

Glass formation and formulation mechanisms


All vitreous masses come from the fusion of various constituents (see Tab. 8):
– vitrifying agents
– fluxes
– stabilizers
– opacifiers
– de-vitrifying agents.

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Tab. 8.

The key physical characteristic of glasses is that they are isotropic while crys-
talline-structured solid bodies are known to be anisotropic.
In the past, this led to the belief that glasses were amorphous substances; how-
ever, recent studies by Zachariasen and Warren have established that the character-
istic tetrahedral coordination of silicon is maintained in glass too.
While these tetrahedrons are, in crystals, arranged as a strictly regular geomet-
ric construction, in glasses they are arranged chaotically, without periodicity or
symmetry.
So while we can speak of a glass lattice, it must be born in mind that this is a
disordered, contorted lattice essentially made up of silicon and oxygen.
Two-dimensional illustrations of the tetrahedral arrangement in crystal-type
silica and molten silica are shown in figures 88 and 89 respectively.
Like silica glass, common glass also features this irregular arrangement of tet-
rahedrons; moreover, in the latter the ions of the other constituent elements fill the
gaps left by the silicon and oxygen.
The bonds in the glass lattice are not all equivalent as they are in crystalline
lattices; consequently, the energy needed to break them apart is differentiated.
Thus, as temperature rises the level of thermo-agitation energy increases until a
level sufficient to break the weakest bonds is reached.
Continued raising of the temperature results in the gradual breakdown of the
lattice and the corresponding, progressive liquefaction of the glass.

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Raw materials for frits and glazes

Fig. 88. Crystalline structure. Fig. 89. Vitreous structure.

For every temperature, then, there is a corresponding glass structure that char-
acterises it. During solidification, as the temperature gradually falls, the glass re-
establishes the bonds and tends to take on the structural state associated with lower
energy levels. However, as the increase in viscosity around the transition point is
somewhat rapid, the internal state of the solidified glass corresponds to that of
higher temperatures. Consequently, structural instability arises: while this instabil-
ity necessarily tends to evolve it does so over a very long time interval (Tab. 9).

Anorhtite
Gehlenite
Sphene
Gahnite
Willemite
Cristobalite
Tridymite
Spodumene
Magnesium titanate
Wollastonite
Rutile
Cordierite
Forsterite
Enstatite
Diopside
Zirconium silicate
Zirconium oxide
Celsian
Leucite
Tab. 9. Some crystalline components in de-vitrified frits.

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The cations, which, in the oxide state, can be obtained in the vitreous state sim-
ply by heating – and are thus known as lattice-forming cations – are Si4+ and B3+.
While silicon forms apex-linked tetrahedrons, the coordination 3 boron forms
equilateral triangles at the centre of which lies the B3+ ion.
Since the silicon ion has four bonds, while the boron ion has just three, it can be
seen how boric glass is less viscous and thus more fusible.
The fluxing cations, also known as lattice modifiers, split the links between the
tetrahedrons once they are added in the oxide state:

O O O O
– O – Si – O – Si – O by introduction of Na2O O – Si – O O – Si – O
O O O Na Na O

These ions generally take up positions in the interstices between the siliceous
polyhedrons.
The greater the number of sodium ions introduced, the greater the number of
splits, and so on, thus diminishing the viscosity of the glass. Furthermore, the high
number of splits between the tetrahedrons ends up compromising the existence of
the vitreous state itself because the more freedom the tetrahedrons gain, the more
marked is their tendency to take on the regular structure of crystals and, conse-
quently, of devitrified glass (Tab. 9).

O O O O
– O – Si – O – Si – O by introduction of CaO O – Si – O O – Si – O
O O O Ca O

Stabilising cations are lattice modifiers too: unlike alkaline cations, which, be-
cause of their weak ionic potential are only loosely linked to the lattice and thus
easily removed, resulting in alteration of the glass, alkaline-earth cations have twice
as much ionic potential and therefore reinforce the lattice structure of the glass and
act as stabilisers.
The replacement of a modifier ion (Na) with another of higher electrical charge
(Ca), having more or less the same dimensions, causes:
– an increase in density, because the greater attractive force exerted on the adja-
cent oxygen ions gives rise to greater compactness
– an increased refractive index as a result of the increased density
– a reduction in electrical conductivity stemming from reduced mobility of the
cations, in turn caused by increased bond energy
– increased viscosity for the same above-cited reason.

It was previously affirmed that boron is a lattice-former, with a coordination


number of 3.
However, we know that it is never used as the sole vitrifying agent, while it is
used extensively in siliceous glasses.

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Raw materials for frits and glazes

Therefore in exclusively boric glasses the lattice is made up of equilateral trian-


gles, apex-connected by oxygen atoms which act as bridges; in silica-boric glasses,
instead, increasing quantities of B2O3 first lead to the formation of BO4 tetrahe-
drons (boron coordination switches from 3 to 4), giving rise to a structure analo-
gous to that of a strongly silica glass. When the B2O3 exceeds a certain threshold
the triangular structures characteristic of pure boric glass, rather than BO4 tetra-
hedrons, are formed.
Aluminum ions cannot, in themselves, be called lattice-formers; nevertheless,
studies of feldspars have shown that they can, in the presence of electropositive
ions, substitute the silicon ions, forming a corresponding number of tetrahedrons.
Aluminum may behave similarly in the glass and this reinforcement of the tetra-
hedrons makes the glass more viscous, more chemically resistant and the vitreous
state more stable.
This behaviour of aluminum means that a net distinction between lattice-form-
ing and lattice-modifying ions cannot be established. Under certain conditions even
the latter may exist as lattice-formers. Numerous examples of such dual behaviour
are provided by the coloured ions, depending on whether they exist as formers or
modifiers.
In this respect it can generally be stated (Dietzel) that cations having high coor-
dination strengths with respect to the oxygen anion (Tab. 10) behave as lattice-
formers (Si4+, B3+) while those with the lowest values act as lattice modifiers (Pb2+,
Ca2+, Ba2+, Li+, Na+, K+) and, finally, those that have intermediate values may per-
form both functions (Fe3+, Be2+, Mg2+, Ni2+, Zn2+, Co2+).

Standard raw materials and their influence on the characteristics


of glass

1 - Silica (SiO2)
Introduced in the form of quartz, quartz sands, feldspathic sands and feld-
spars.
Silica is the prime component of vitreous compositions as it has the property of
vitrifying under the effect of the fluxes within a very broad temperature range. The
fluxes or modifiers are: PbO, B2O3 , K2O, Na2O and Li2O. Glazes rich in silica are
highly resistant to chemical agents and are extremely hard. The higher the silica
content in a glaze the higher its firing temperature.

2 - Diboron Trioxide (B2O3)


Introduced as boric acid, sodium borax, colemanite.
Because of its vitrification properties, boron is, after silica, the most important
element. However, it cannot be used on its own as it would give rise to strongly
soluble glasses . It acts as a flux in silica glasses; indispensable in glasses that are
lead-free with low melting points; dissolves many colorants, confers glossiness,
reduces viscosity and lowers the expansion coefficient in those glasses to which it
is added.

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Degree Dissociation Coordination Strength


of oxidation energy of single bond
(Kcal/g.atom) (Kcal/g.atom)

LATTICE FORMERS

INTERMEDIATES

MODIFIERS

Tab. 10. Bond strengths calculated for certain oxides.

3 - Lead monoxide (PbO)


Lead monoxide gives glass:
– high fusibility
– an increased refractive index
– increased density
– increased glossiness.

However, lead glazes also have:


– low viscosity

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Raw materials for frits and glazes

– high toxicity, proportional to lead content and as a function of the form in which
the glass is bound
– high sensitivity to acid attack where oxide content exceeds a certain propor-
tion.

4 - Alkalis (K2O, Na2O, Li2O)


Introduced as nitrates, chlorides, carbonates or feldspars. Alkalis are lattice mod-
ifiers: their introduction weakens the lattice structure of the glass by lowering the
melting point.
The Na+ and K+ ions occupy positions in the interstices separating the tetrahe-
drons. The K+ ions, which are larger than the Na+ ions, form stronger bonds, thus
giving rise to the easy alterability of sodium glasses.
Highly sodium glasses are easily soluble. Alkalis generally increase glass expan-
sion coefficients, except for lithium, which, as it is highly fusible, can produce the
same results while being used in extremely low percentages (much lower than sodi-
um or potassium).
Alkali, especially lithium, give the glasses gloss; however, on their own they are
unable to constitute the entire basic part of a glass composition owing to a tenden-
cy towards devitrification and the solubility of the formed silicates.

5 - Calcium oxide (CaO)


Introduced in the form of calcium carbonate, dolomite, wollastonite, anorthite.
Calcium oxide is a stabiliser: added to an alkaline silicate it eliminates the alter-
ability of the glass.
On its own it would form silicates with a high melting point (above 1400 °C);
mixed with other silicates it gives rise to the formation of vitrified masses.
It is thus obvious that high percentages of this oxide would lead to devitrifica-
tion (matt CaO). Introduced in the right proportions (5-10% by oxide analysis), the
calcium not only gives stability but also improves bending strength and body-glaze
adhesion.
Also lowers viscosity in glasses fired at high temperature.

6 - Alumina (Al2O3)
Introduced as calcined alumina or alumina hydrate, feldspars, kaolin, corun-
dum.
In glazes in appropriate proportions (4-8%) it confers, in the case of low-temper-
ature glazes, the following:
– increased viscosity
– reduced tendency to de-vitrify (crystallization)
– increased bending strength
– reduced expansion coefficient
– increased resistance to acids
– improved opacity (introduced in high percentages in concordance with the glaze
firing temperature).

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The quantity of Al2O3 introduced into a glaze increases or decreases in propor-


tion to the firing temperature. Quantities will thus be higher in matt or satin-finish
glazes and lower in high-gloss glazes.
The quantity of Al2O3 introduced into a glaze also depends on its particle size
distribution. As the particles become finer the percentage that can be introduced
drops, while larger particles allow the introduction of higher quantities.
Since it is an amphoteric substance this oxide has the capacity to combine as
much with silica as with basic oxides. It is thus the most efficient of the stabilis-
ers.

7 - Barium oxide (BaO)


Normally utilised by introducing barium carbonate (BaCO3) into the composi-
tion. This oxide increases density and refraction, thus giving the glaze shine. It is
also an excellent flux in the fusion of silicate glasses, a property that, in part, allows
it to substitute lead oxide effectively; it is, however, highly toxic.
Where present in significant percentages (over 0.3% in molecular equivalents),
this oxide hardens glazes and induces de-vitrification. A barium glaze melts much
more rapidly than a calcium one and is less viscous too.

8 - Magnesium oxide (MgO)


Introduced by means of dolomite, magnesium carbonate and talc.
Magnesium oxide behaves in glasses in much the same way as calcium oxide.
The only difference is that it gives rise to more viscous glasses. It cannot be used in
overly high percentages as it would otherwise raise the firing temperature of the
glass. The magnesium reduces the expansion coefficient yet heightens the surface
tension of the glass.

9 - Zinc oxide (ZnO)


In acid glazes with a high alumina content, zinc oxide plays a fluxing role.
Depending on the percentage used, this oxide has a range of effects:
a) in low percentages: increases the brightness of glasses and colours except for
greens and blues; together with alumina it improves the opacity and whiteness
of the glazes as long as CaO content is low: in the absence of B2O3 it reduces the
expansion coefficient.
b) in high percentages: devitrifies from the vitreous mass, giving the glaze surface a
characteristic matt finish, brought out where the glaze is basic.
c) in very high percentages: crystallizes and individual crystals made up of ZnO
silicates separate. Glasses rich in this oxide are extremely vulnerable to acid
aggression.

10 - Titanium dioxide (TiO2)


Titanium dioxide improves chemical resistance and offsets crazing. This last ef-
fect immediately becomes apparent even where only small percentages of the oxide
are employed and remains steady even as percentages increase.

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Raw materials for frits and glazes

Adding TiO2 colours the glass: even at just 2% yellowing is observed. Simulta-
neously the surface of the finishing glaze takes on a matt appearance, becoming
hard and coarse as oxide percentages increase.
It has opacifying properties that improve in the absence of B2O3 and especially
where the glass composition is rich in Al2O3 and added in the mill; under these
conditions the colour fades.
These characteristics are particularly evident if TiO2 is introduced into the glass
as anatase, while, where introduced as rutile, it loses its de-vitrifying characteristics
until, in high percentages at high firing temperatures, it gives rise to needle-shaped
crystals.
Crystallisation occurs mainly in high-fusibility glasses.

11 - Stannic dioxide (SnO2)


Although a superb opacifier even at low percentages (6-10%) it is rarely used
owing to its high cost.
The opacity stems from suspension of the oxide in the vitreous mass as finely
dispersed particles. Its opacifying potential thus depends on the purity of the
oxide, the fineness of its particles and the nature of the vitreous mass to which it
is added.
Alkalines and boron may prove detrimental to good opacification of this oxide.
The tin is best introduced into the mill during grinding stage and not in frit melting.

12 - Zirconium dioxide (ZrO2)


Used in the form of zirconium silicates of varying particle size distribution. An
excellent opacifier (not quite as efficient as stannic oxide but much more economic)
and undoubtedly the one preferred by industry.
High percentages of this oxide raise the firing temperature of the glass into
which it is introduced. Zirconium silicates lend themselves as opacifiers in all glaze
types firing between 940 and 1300 °C.
Only a part of the introduced zirconium silicates combines with other compo-
nents, the majority remaining as it is.
The part that combines heightens the crazing resistance of the glaze. Zirconium
also has the property of being a colour stabiliser. Calcium and/or barium oxide (no
more than 0.2 molecular equivalents) help the zirconium improve opacification as
do zinc and alumina.
Three different types of zirconium silicate are commercially available: these large-
ly differ in terms of particle size distribution:
– micronized zirconium silicates (very fine)
– zirconium silicate powder (coarser)
– zirconium silicate sand (very coarse).

The most commonly used glaze opacifiers are micronized products, while pow-
ders are used in frit melting and sands are used as hardeners or fillers. Low firing
temperature glazes, opacifiers with zirconates, often have non-smooth surfaces, un-
doubtedly in relation to their highly viscous nature.

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Table 11 provides an overview of the mineral types allowing the introduction


of different oxides.
Table 12, instead, shows the most significant ceramic oxide parameters. Such
parameters are:
– molecular weight
– surface tension
– expansion coefficient.

Types of frit

As seen, the term “frit” is commonly used to indicate, in industrial production


processes, a vitreous mix cooled suddenly in water.

TABLE SUMMARIZING THE COMMONEST MATERIALS FOR


THE GLASSES AND GLAZES COMPOSITIONS
Oxides Used raw materials
SiO2 Quartz, Feldspars,
Quartz, Feldspars, China-clays
China-clays, Zirconium Silicates
B2O3 Boric acid*, Borax*, Colemanite
PbO Minium, Litharge
Na2O Feldspars, Borax*, Na2CO3, NaCl*
K2O Feldspars, KNO3*
Li
LiOO
2 2
Feldspars, Li2CO3
CaO Wollastonite, CaCO
Wollastonite, CaCO3
, Feldspars,
, Feldspars,
3
Dolomite
Dolomite, Colemanite
BaO BaCO3
MgO MgCO3, Talc, Dolomite
Al2O3 Al2O3, Al(OH)3, China-clays, Feldspars
ZnO Zinc oxide
SnO2 Tin oxide
TiO2 Titanium oxide, Rutile sand
ZrO2 Zirconium silicates, Zirconium oxide
* materials soluble in
materials soluble in HH22O,
O,therefore
thereforeusable
usableininfusion
frit
melting
only only

Tab. 11.

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Raw materials for frits and glazes

TABLE SUMMARIZING THE CHARACTERISTICS OF THE MAIN CERAMIC


OXIDES
Oxides Molecular Superficial Expansion coefficient x10-7
weight tension

ENGLISH WINKELN MAYER


TURNER SCHOTT HAVAS
SiO2 60.1 3.4 0.15 0.8 0.8
B2O3 69.6 0.8 -1.98 0.1 0.1
PbO 223.2 1.2 3.18 3 4.2
Na2O 62 1.5 12.96 10 10
K2O 94.2 0.1 11.7 8.5 8.5
Li2O 29.9 4.6 - - -
CaO 56.1 4.8 4.89 5 5
BaO 153.4 3.7 5.2 3 3
MgO 40.3 6.6 1.35 0.1 0.1
Al2O3 101.9 6.2 0.52 5 5
ZnO 81.4 4.7 0.21 1.8 2.1
SnO2 150.7 - - 2

TiO2 80.1 3 - - 4.1


ZrO2 123.2 4.1 0.69 - 2.1
SrO 103.6 - - -

CoO 75 4.5 - - 4.4


Fe2O3 159.7 4.5 - - 4
MnO2 86.9 4.5 - - 2.2
CuO 79.6 - - 2.2

Tab. 12.

Frits are used as bases in finishing glazes and in low-temperature glazes to ren-
der the components insoluble.
The market offers a wide range of frits having different fusibility, glossing, opaci-
fication and matting performance specifications.
They can be grouped as follows:

1 - Glossy transparent frits


a - for traditional double firing (a slow glost cycle)
Characterised by low temperature fusibility. They are made up of a high per-

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centage of SiO2 (50-60%) and a low percentage of fluxing elements (20-25%, in-
cluding Na2 O-K2 O-PbO-B2O3).
The rest of the composition consists of stabilisers (Al2O3-ZnO-CaO-BaO-MgO),
almost always accounting for only very limited percentages (max 7-9%).
These frits are mainly used in the preparation of transparent glazes although
they are occasionally employed in low percentages in certain glazes fired at low
temperature.
At temperatures above 1100 °C these are employed – albeit in low percentages
– in the preparation of almost all glazes so as to improve vitrification and confer
fusibility.

b - for fast double firing


Frits used in fast double firing are substantially different from the previous types
in order to provide the thermal specifications needed in the much faster firing cy-
cles. The need to “mature” the glass in just a few minutes has led to the formulation
of entirely new glasses.
More specifically, the silica-boron-alkali-alkaline-earth ratios have been changed.
Figure 90 illustrates the modifications to oxide content needed to make frits suit-
able for rapid firing.

c - for monoporosa
For porous fast single firing technology, the frit will have a radically different
composition on account of specific needs of the bodies, which generally have a high
carbonate content (8-14%).
This has thus resulted in the development and fine-tuning of frits with high
melting points that soften above 950 °C so as to allow complete emission of the
carbon dioxide formed during decomposition of the calcite and/or dolomite.
Examination under a heating microscope must show such frits to have a very
high softening point together with a sphere point close to that of the previously
described frit.
To satisfy these requisites and aid/trigger this “eutectic” fusion it has been nec-
essary to increase CaO, ZnO, MgO and BaO oxide content (with respect to double
firing).
At the same time the percentage of fluxing oxides has been reduced. The
goal was to produce “fast” frits (i.e. capable of melting suddenly at high temper-
ature).

2 - Glossy opaque viscous frits (known as “zirconium whites” or “majolicas”)


a - for traditional double firing
The only difference between these and the frits in the previous grouping is
that they are opacified. In terms of characteristics and composition they are iden-
tical.

Opacification is achieved with the aid of zirconium silicate, introduced into the
composition in quantities ranging from 8 to 14%.

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Raw materials for frits and glazes

Na2O → decrease

N
K2O → increase

Na2O+K2O → decrease

CaO → increase

ZnO → increase

BaO → increase

MgO → increase

B2O3 → decrease

SiO2 → decrease

Fig. 90. Oxide content changes to adapt frits to fast firing.

These frits are mainly used in the preparation of glossy white glazes of both the
high and low-temperature firing type.
Of course, in glazes fired at high temperature the percentage of frit diminishes
considerably in favour of the raw materials. In the preparation of glazes other than
glossy whites these frits are used only occasionally.

b - for fast double firing


Essentially the same as glossy transparent frits. Here too, rapid firing requires
substantial modifications to formulation in order to make the fusibility compatible
with rapid firing.
The expansion coefficients for white, opacified and transparent frits suitable for
fast double firing are slightly higher than those used in traditional double firing
(linear coefficients range from about 60 to 70 × 10-7).

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c - for porous single firing


Apart from the utilisation of zirconium silicate, the concepts expressed above
for the glossy frits apply.

3 - Matt frits (CaO-ZnO-TiO2)


a - for traditional double firing
This group includes all those frits where a component added in large quanti-
ties to the appropriate vitreous base shows clear devitrification characteristics.
The devitrifying elements are: calcium, barium, zinc and titanium.
The first two normally de-vitrify in alkaline-boric vitreous bases while the
zinc and titanium devitrify in lead bases.
Calcium and barium matts are normally lead-free; these frits are also viscous
and opaque.
Zinc matt frits are, instead, slightly fusible, leaded (PbO 25-30%) and semi-
opaque.
Titanium matt frits are also slightly fusible, leaded, covering (opacified) and
are always yellowish in colour.
Normally used in the preparation of matt glazes or as correctives in other, not
necessarily matt glazes.
In many cases it is preferable to introduce ZnO-CaO-BaO-TiO2 in the frit as
opposed to using the respective raw materials. This is to avoid the use of hygro-
scopic raw materials (ZnO) or those rich in volatile substances such as the CO2
contained in carbonates (CaCO3-BaCO3).

b - for fast double firing


These frits differ substantially from their traditional firing “cousins” in that while
with the just-cited technology it was possible to employ formulas with high per-
centages of free alumina and zirconium, this is not possible in rapid firing.

c - for porous single firing


No substantial formulation differences exist between these frits and those suitable
for fast double firing, except for high lead content (>10%), not used in single firing.

4 - Glossy, transparent medium fusibility frits


These differ from crystalline viscous frits in that they are more fusible.
The silica percentage, in fact, drops to 35-50% while the quantity of fluxing
elements (Na2O-K2O-PbO-B2O3-Li2O) increases until it accounts for 30-40%.
These frits are extensively employed in the preparation of virtually all glazes
fired at low temperature.
They are also occasionally used in low percentages in the preparation of
several special glazes that fire at high temperatures (e.g. “leather” and “pearled”
glazes).

The widespread use of these frits stems from their fusibility which favours in-
mill introduction of high quantities of raw material and devitrification of all the

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Raw materials for frits and glazes

matting elements. In this way a range of glazes with significant technical and
aesthetic differences can be obtained simply by using just one frit and varying in-
mill addition.

5 - Fluxing frits (leaded and lead-free)


These frits feature high fusibility, hence the “fluxing” tag.
Depending on the employed fusible element, they may be leaded (lead silicates)
or lead-free (boric-alkaline or alkaline-boric fluxes).
In some glazes these frits are used, in small percentages, as correctives, the aim
being to add the fusible elements that would otherwise be impossible to introduce
as raw materials in that they are water soluble (alkali and boron) or toxic (lead).
The frits belonging to this group are used extensively in reagent silk-screen
colours, in certain preparation bases and in some spray gun flame effects.
Use of these frits diminishes rapidly as glaze firing temperatures rise and at
high temperatures is abandoned altogether.
Lead borosilicate fluxers and lithium lead-free fluxes belong to this group. Note
that the lead borosilicates include “Monoboron” and “Lustre” (blue) frits, the ap-
proximate composition of which are illustrated below:

MONOBORON: PbO 68-70%


B2O3 15-20%
SiO2 10-15%

LUSTRE: PbO 40-45%


B2O3 18-20%
SiO2 33-38%

In addition to high fusibility, these frits are characterised by strong reactivity,


which shows up as a marked tendency to attack and penetrate the bodies and all the
glazes that come into contact with them during firing.
These frits are used only in certain reactive glazes fired at low temperatures and
are always introduced into the glaze in very small percentages (except for special
“torn”, “stone” and “streaked” glazes).
Their use in the preparation of particularly reactive silk-screen colours is, in-
stead, widespread.
Where glazes and colours are fired at high temperatures these frits are used
rarely, if at all.

6 - Frits coloured on fusion


These frits differ from those in the preceding groups only in that they are co-
loured.
In fact, were it not for the colouring they could quite easily be classified within
groups 2 and 3.
The usual colouring elements are iron, cobalt, manganese, copper, cadmium and
selenium.

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Cadmium and selenium frits are used on their own to obtain the respective glaz-
es, unable to be produced in any other form.
Coloured frits are only used to obtain certain coloured transparents or to intro-
duce colorants in a stabilised form in flame or disc applications.
Tables 13 and 14 show approximate compositions and key characteristics of the
most commonly used frits in traditional/fast double firing and monoporosa tech-
nology (i.e. transparent, glossy and matt white).

Classification of ceramic glazes

A great many tile types – produced using a wide range of technologies –


exist.
Depending on that technology, glazes will have specific characteristics, their chem-
ical make-up and physical parameters varying greatly.
There are also a series of type-based requisites dictated by the market. The var-
ious commercial tile types require, in fact, “specialised” glazes to produce the de-
sired aesthetic effect.
Highly specific production technologies often correspond to well-defined, diver-
sified commercial types.
However, glazes that can satisfy several production technologies are much sought
after.
For clarity we shall illustrate the double classification system, which shows the
correlation with both the production technology and the aesthetic needs of the
marketed products (Fig. 91).
Production technologies have, over the years, evolved as a function of that equi-
librium which involves all the factors typical of industry in general.
These include:
– technology renewal and relative amortization costs
– competitive benefits in terms of quality and aesthetics
– benefits in terms of potential added value and output
– general/economic conditions in the factory
– general state of the economy.

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Raw materials for frits and glazes

GROUP 2 GROUP 3 GROUP 4

ELEMENTS A B C A B C A B C

alkali 8 6 4 8 7 5 1

MgO 1 1 2

CaO 3 8 12 3 6 9 5 40 40

BaO 3 3

ZnO 1 10 11 1 6 13 28

PbO 4 15 11 11

Al2O3 8 8 9 6 7 6 1

B2O3 19 6 3 15 11 5 10 6 6

SiO2 58 54 60 58 52 52 40 43 43

ZrO2 9 11 8

TiO2

Firing T 970 1040 1110 970 1040 1110 970 1040 1110

Softening T 890 950 1020 920 940 1040 750 1100 1100

Semi-sph. T 1160 1150 1120 1240 1210 1140 1000 1150 1150

Firing cycle 10h 40min. 50min. 10h 40min. 50min. 10h 40min. 50min.

Frit kiln T 1350 1450 1470 1350 1450 1520 1300 1350 1350

CT CR CM BT BR BM MT MR MM

Group 2 glossy transparent frits

Group 3 glossy opaque frits

Group 4 matt frits

A used for traditional double-firing

B used for fast double-firing

C used for monoporosa

Tab. 13. Composition and characteristics of the most common frits.

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Applied Ceramic Technology

GROUP 5 GROUP 6 GROUP 7 GROUP 8

ELEMENTS A B C D E F G H I

alkali 3-7 10-15 0-2 6-10 2-4

CaO 3-6 2-10 16-20

BaO 0-2

ZnO 3-6 0-5 20-30 2-4

PbO 30-40 65 75 85 69 45 25-35 0-5 25-35

Al2O3 2-4 0-2 2-5 2-4

B2O3 5-10 20-30 20 20 2-4 6-12 30-40

SiO2 40-50 35 25 15 40-50 11 35 35-55 50-60 30-40

ZrO2 0-5

TiO2 7-10

Group 5 glossy transparent frits at average fusibility *

Group 6 (lead and leadfree) fluxes *

Group 7 reactive fluxes *

Group 8 frits coloured on fusion

A bisilicate

B rocaille

C monosilicate

D leadfree flux

E monoboron

F lustre glaze

G ZnO matt

H CaO matt

I TiO2 matt

(* Use limited to low-temperature firing)


Tab. 14. General characteristics of frits.

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Raw materials for frits and glazes

Õ zirconium white glaze

TRADITIONAL alkaline transparent


DOUBLE-FIRING Õ
frit

Õ engobe Ô
FAST DOUBLE-
FIRING

Õ matt Ô

POROUS SIGLE-
FIRING
glazes for silk-screen
Õ Ô
printing

particular glazes Ô

waxy glazes Ô

VITRIFIED
SINGLE-FIRING
majolica glazes Ô

glazes with rustic and


Ô
antique effects

cotto-like glazes Ô

crystalline glazes Ô

technical glazes Ô

Fig. 91. Types of market-available glazes correlated with product-specific needs.

These factors have given rise to the present-day situation where different tech-
nologies are used to produce commercially overlapping products. Such technologies
include:
– traditional double firing
– fast double firing
– porous single firing (monoporosa)
– vitrified single firing.

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Applied Ceramic Technology

Each of these technologies, which can themselves be split into sub-groups, re-
quires glazes of specific chemical-physical characteristics.

Traditional double firing

This technology – virtually the only one up until the 1960s – involved dry ground
and pressed bodies fired in tunnel kilns at around 1000-1150 °C in a 15-30 hr cycle.
The obtained ceramic biscuit, known as cottoforte, was characterised by high water
absorption and porosity.
This was sent on to the glazing line and then fired again at around 950 °C to
1050 °C in a further 12-hr cycle. Until just a few decades ago virtually all commer-
cially available tiles – glossy, matt, rustic and surface-effects glaze – were produced
this way.
To avoid giving an out-of-date classification of double firing glazes, note that
the glazes now employed in nearly all double firing operations are the following:

Glossy zirconium white


A white glaze almost entirely consisting of the characteristic frit, it has a high
viscosity which gives mirror-like, covering surfaces.
Plastic raw materials such as selected high quality white clays and/or kaolins
are added in percentages varying from 3 to 10% so that grinding provides stable
slips that do not settle quickly.
Aqueous suspensions of this type, mostly made up of vitreous particles, often
require a 0.01% - 0.3% addition of ionic systems, which, acting on the electrolytic
characteristics of the vehicle (water), modify the rheology of the slip. Depending
on requirements, they can also exert a suspending or fluidising action (increase or
reduction of slip viscosity) to make application easier.
A zirconium white should be selected mainly on the basis of the firing condi-
tions dictated by the available technology.
It is good practice to use whites having a sphere point close to maximum kiln
firing temperature, in that the thermal change rate in kilns of this type allows us to
hypothesize very low product inertias.
No special preheating behaviour is required in that the body is inert. Linear
expansion coefficients must fall between 55 and 60 × 10-7 °C-1 to maintain glaze
compression and prevent crazing in the more challenging areas of product use.

Transparent glaze
This product is normally used to manufacture tiles with a transparent, deep-
glaze look.
The application sequence usually involves a layer of engobe made up of frits of
the zirconium white and/or transparent alkaline type to which feldspar raw materi-
als, zirconium silicates (to improve covering), clays and kaolins (to adjust rheology)
may be added on top of which the glaze is applied.
In addition to these components, double firing engobes may also contain other

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Raw materials for frits and glazes

frits having specific functions: as fluxes to improve anchoring to the body, or special
frits to increase the expansion coefficient of the layer of glaze in order to prevent
excessive tile convexity.
After the engobe the transparent glaze may be applied directly or there may be
an intervening second layer of glaze which regulates the fusibility between them.
Then the film of true transparent glaze is applied.
Silk-screen printing can be before or after the transparent layer to obtain a deep
or surface effect.
Chemical-physical parameters are the same as those for zirconium whites, ex-
cept for the absence of zirconium silicate which gives the finishing glaze a transpar-
ent appearance.
Any introduction of additives is effected as with zirconium whites. In quantita-
tive terms it should be born in mind that the engobes and semi-glazes usually have
different viscosity characteristics from those of whites and transparents in that
they have a higher plastic raw material content (clays and kaolins).

Matt glazes
These cover a decidedly smaller wall tile market share (10-20%) than glossy
glazes. They are formulated as a function of devitrification with the development
of a matt surface.
Devitrification is generally caused by an excess of calcium or zinc. In this firing
technology both alumina and zirconia can also be used as they contribute to the
creation of a matt surface in addition to conferring their other typical characteris-
tics.
Zinc, titanium, calcium, barium and magnesium oxides matt by crystallisation
while aluminum oxide and sometimes zirconium silicate matt by hardening.
Glazes matted with zinc and titanium oxides normally consist of a fusible vitre-
ous base and tend to be leaded.
Aesthetically, they are an imperfect white, tending to grey where zinc is present
and yellow where titanium is included.
Glazes matted with alkaline-earth oxides are always white in colour and are nor-
mally highly viscous. Glazes matted by hardening always consist of fusible vitreous
bases (see frit group 4) thoroughly hardened with alumina, corundum and zirconi-
um silicate.
When the matting element is alumina or corundum, satin-finish glazes are ob-
tained while, with zirconium silicate as a matting element, stone-like glazes are
obtained.
Low-temperature matt glazes (ZnO-CaO) are directly made with the relative
frits (see frit group 6) in high percentages: at higher firing temperatures, raw mate-
rials added to the mill are used.
One of the most frequent problems is a varying degree of matt across the kiln
cross-section. In some cases partially glossy tiles are produced where in-kiln burn-
ers are too close to the product and create microclimates unfavourable for devitrifi-
cation.
Matt surfaces are also influenced by in-kiln cooling conditions. Gradual cooling,

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in certain cases, aids development of devitrification. The final aesthetic effect is


provided by the successive applications of silk-screen products having chromatic or
gloss-matt contrast effects.

Engobes
These are applied before the glazes and have a wide range of functions.
For example, engobes can homogenise the degree of water absorption in subse-
quent applications.
They are thus able to reduce the dimples caused by inconstant absorption across
the surface of the body.
Engobes also have the function of slowing down water absorption, thus pre-
venting the formation of air bubbles in successive applications. Ceramic functions
include the slowing down and, above all, splitting up of the gas bubbles that rise up
from the body during firing because of pyrite, hematite or chalcopyrite (“coquina”)
clusters in impure bodies. A further function is that of isolating the colour of the
body, covering the base and thus making subsequent use of coloured transparent
glazes or coloured preparation bases possible without any interference with the
(often dark) body colour.
Note also that engobes aid adhesion to the body without there being any prob-
lems of aggression with the latter and they also modify the average expansion
coefficient of the vitreous state so as to avoid the problems cited earlier. Perfect
calibration of all these chemical and rheological parameters with the optimum use
of frits and raw materials is thus highly important.
Today, more knowledge and skill is required for proper formulation of engobes
than glazes themselves.
The normally-used frits belong to the category of glossy whites, alkaline trans-
parents, fluxes (used to a lesser extent) to aid adhesion and special high-expansion
frits (to modify the dilatometric characteristics of the system). Overall percentages
vary from 40% to 80%. Raw materials used to complete formulation – all of which
must be high quality – include: zirconium (for covering performance), good quality
feldspars and quartzes and plastic raw materials (for rheology) such as clays and
kaolins. In this case very good fluidisation is required to ensure a good on-product
spread during application.

Fast double firing

Note that this technology was largely developed to reduce the high production
costs associated with traditional double firing; that goal was achieved by introduc-
ing a whole series of automation and firing technology changes that have since
gone on to characterise the entire ceramic industry.
Employment of new kiln construction materials with low thermal inertia and
the adoption of single layer roller systems (thus doing away with the need for sup-
ports) allowed manufacturers to develop firing cycles (min. 25 minutes ~ max. 60
minutes) according to product size without failure of the ceramic body. Costs thus

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Raw materials for frits and glazes

fell on all fronts – but glaze suppliers were forced to reformulate their entire range
of products.

Zirconium whites
These glazes, even when used in a fast double firing context, continue to consist
of at least 90% frit. However, the base frit making up these glazes has been substan-
tially modified to adapt thermal characteristics to the much faster firing cycles. As
regards the other technological aspects it can be said that the concepts expressed in
the description of traditional double firing zirconium whites remain valid. Remem-
ber that it is, here, more difficult to attain high opacity owing to the difficulty in
achieving a good degree of glaze maturation. Applying an increased percentage of
zirconium and balancing out its refractory effect with increased boron and alkali
content fails to provide good results in that it can cause partial solubility of the frit.

Alkaline transparent glazes


Essentially the same as zirconium whites. However, fast firing requires substan-
tial formulation changes to make product fusibility compatible with short firing times.
To ensure that the glaze spreads properly, it is good practice not to economise on the
gram weight of the glaze itself or that of the engobe. Use of high quality raw
materials in the transparent glaze guarantees results exempt from any partial opal-
escence or accentuated straw-yellow colouring even where thickness is high.

Matt glazes
Like the above glazes, these too differ substantially from the corresponding tradi-
tional double firing products. Observations as to the required modifications largely
correspond to those given in previous sections.
There is no progression in passing from a glossy surface to a matt one: the switch
from satin-finish surfaces to gypsum-like ones takes place without any intermediate
values. Experience teaches us that the best way of obtaining devitrified surfaces is
to use calcium – even in very high percentages – introduced in the form of wollas-
tonite or to use specific frits.
Introducing calcium as a carbonate or as a dolomite is, instead, inadvisable, in
that CO2 bubbles produced by thermal decomposition may be trapped. Zinc is also
capable of giving very soft matt surfaces, but obtaining a glaze that remains inert in
the face of chemical aggression is virtually impossible where this oxide is present in
substantial percentages. Fluidity should be better than it is with traditional double
firing glazes. It is possible to have both opacified and transparent products although
control of crazing is more difficult on the latter. Application of an engobe is nor-
mally required.

Engobes
Fast double firing employs higher-expansion engobes to ensure flatness or slight
convexity of the tiles: therefore more use is made of special high-expansion frits.
The remaining parameters are similar to those of traditional double firing en-
gobes.

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Applied Ceramic Technology

Special glazes
A whole range of wall tile glazes that were extremely successful in the past have
now lost ground in terms of commercial potential to white and semi-transparent
glazed products. A brief list of these follows below (Fig. 92).

Waxy glazes
Semi-covering glazes of average fusibility. Normally formulated with semi-flux-
es to which small percentages of zirconium, zinc, etc. are added. These were used
with coloured preparation bases and applied using techniques that led to uneven
thickness.
They are now mainly used in single firing and are currently making a weak
comeback in both traditional and rapid double firing.
Consequently, their composition is generally as follows:
– medium-fusibility vitreous base: type 4 frits or a mix of group 1 (A and B) and
group 5 frits

waxy glazes

streaked glazes

torn glazes

iridescent

GLAZES
PARTICULAR flaked glazes
FOR
DOUBLE-FIRING

glazes with rustic


effects

pearled glazes

crystalized glazes

leather glazes

Fig. 92. Different types of glazes once used in double firing (from the 60s to the 80s).

164
Raw materials for frits and glazes

– slightly opacified with zirconium silicate (4-8%)


– slightly matted with TiO2-ZnO-SnO2.

Streaked and torn glazes


These glazes have almost all disappeared from the technological-commercial
scene. They were characterised by floating refractory “islands” usually made of
zirconium which came to rest above the normally leaded fusible part, thus creating
wide, irregular far-apart grooves in torn glazes and fine, closely-bunched furrows
in streaked ones.
These glazes are obtained by saturating highly fusible vitreous, reactive bases
with high percentages of zirconium silicates, almost exclusively at low firing tem-
peratures.
To improve or enhance the torn effect a thin film of a fusible preparation base
should be applied under these glazes.

Iridescent glazes
Glazes containing special components that give surface iridescence. Used rarely.
The iridescence was obtained from boric vapour fallout (using leaded frits with a
high percentage of boric oxide known as “blue frits”) or by using specific heavy
metal oxides such as V, Bi, Mo, W.

Flaked glazes
Highly fusible glazes made up of special oxides (such as that of cerium) which
tend to generate split-ups and produce an effect where white flakes are immersed in
the transparent glaze. Used rarely, as they tend to craze.

Rustic-effect glazes
These glazes are currently regaining ground in the wall tile business while in
the flooring sector they are already used extensively. They contain hard raw mate-
rials of large particle size such as zircon sands and corundums which give the tiles
a rustic appearance.
All those glazes having varyingly fusible vitreous bases strongly hardened with
coarse materials can be classified in this group. These materials (various sands and
corundums) are normally introduced into the composition at the end of grinding.

Pearled glazes
Glazes having a soft surface and slightly gloss-matt nuances that evoke the ap-
pearance of a pearl. These are normally leaded and opacified with oxides (e.g. stan-
nic oxide). Not used on today’s market.
These could be categorized as matt glazes, but since they have rather unique
composition and reactivity characteristics they deserve a separate description.
A fusible vitreous base forms the necessary starting point for the production of
this glaze (see group 5 frits for low firing temperatures). This base is then opacified
with micronized zirconium silicate in medium-low percentages and then matted
with the oxide mix (ZnO-TiO2-SnO2).

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Leathery glazes
Glazes resembling worked leather in terms of texture and colour. Normally of
leaded formulation, they are rich in stannic oxide, zirconium silicate, and contain a
little titanium dioxide. Colouring is provided by an orange pigment, accompanied
by ferrous oxide. These were often applied on markedly leather-coloured bases and
used flame effects to improve the overall chromatic effect. Used extensively until
just a few years ago they have now all but disappeared, although they are still used
in specific niches of the wall tile industry.

Aventurines
Glasses characterised by minute crystals in suspension (Fe-Cr-Cu), made highly
fusible by a lead monoxide and/or alkaline-boric compound-based composition.
Crystallization occurs by saturation (during firing) of these finishing glazes on the
part of an oxide and relative separation of the latter during cooling.

Preparation bases
Made up of strongly-coloured, varyingly fusible finishing glazes. Never used on
their own but always beneath other glazes.

Porous single firing wall tiling

This technology stemmed from appreciation of the technological benefits that


came with the advent of single firing vitrified products. The goal (achieved in full)
was to obtain products that would enjoy the cost-cutting benefits associated with a
single body+glaze firing sequence while maintaining the characteristics required
of wall tiling: low weight per m2, limited thickness, well-controlled sizing and flat-
ness, aesthetic results on a par with double firing.
Bodies consist of a mix of typical carbonate clays, or white firing clays mixed
with calcite, quartz and feldspathoids.
Once dried and glazed, single-stage firing takes place. Firing temperatures gen-
erally oscillate between 1060 °C and 1120 °C (depending on whether the body is red
or white) while firing cycles last from 30 to 50 minutes depending on tile size.

Zirconium whites
With respect to fast double firing formulations it became necessary to increase
percentages of oxides such as CaO, ZnO, MgO and BaO in order to promote and
trigger this “eutectic” fusion. At the same time percentages of fluxing oxides such
as alkalis and boric oxide were reduced.
The aim is to have “rapid” frits that melt suddenly at high temperatures. The
same concept is equally valid for the alkaline transparent frits. As regards other
characteristics the observations made for fast double firing apply.
Rheological aspects require, in addition to fluidisers, the introduction of 0.3% of
CMC (carboxymethyl cellulose) to help bind the unfired glaze to the body. Without
the CMC adhesion during preheating would be insufficient.

166
Raw materials for frits and glazes

At present, low-viscosity CMCs are employed to reduce – or even eliminate – the


need for fluidisers.

Alkaline transparent frits


The same concepts expressed in the above paragraph apply. In this case too a
percentage of CMC (0.2-0.4%) is added to the suspension.

Matt glazes
Formulations differ little from those used in rapid double firing. The additives
used in the whites and transparents are applicable here too.

Engobes
In this case too, the observations made vis-à-vis fast double firing apply. Perhaps
more so than in other cases (i.e. fast and traditional double firing), much attention
needs to be paid to viscosity.
Appropriate percentages of fluidising materials (0.05-0.3%) are, in fact, added to
the engobes because they are formulated using percentages of clay and glaze weights
higher than those used in fast double firing.

Silk-screen printing products

Nearly all wall tiling products, whether they employ zirconium white, alkaline
transparent or matt glazes, employ silk-screen or rotary decorating techniques to
meet aesthetic demand. A specific series of glazes has thus been developed for this
purpose.
The glazes in question are dispersed with short or medium-chain polyglycols to
give pastes just the right viscosity and simultaneously ensure decomposition of the
polyglycols themselves in the first stage of preheating, thus avoiding interference
at the glaze softening phase. The most frequently used glazes are the following (see
Fig. 93).

Range of colours
These are coloured glazes and coloured transparent frits that can be applied
under various conditions.
To obtain neutral effects alkaline transparent bases are generally used.
For slightly deeper effects the use of semi-fluxing materials is preferred.
Subsequent definition of matrix parameters refers to the number of threads
per cm.
Silk-screen printing matrices are generally made with nylon, polyester or, in
special cases, steel fabric.

Highly-covering white glazes


Formulated with leaded bases that have been opacified with ceric oxide and stan-
nic or zirconium oxide. The matrix fabric mesh varies from 45 to 75.

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range of colours

highly-covering white
glazes

alkaline transparent frits

white relief glazes


SILK-SCREEN PRINTING
GLAZES
FOR
ALL TECHNOLOGIES
heavy glazes

lustre glazes

iridescent glazes

reactive glazes

Fig. 93. Glaze types most frequently used as screen printing bases (all production technologies).

Alkaline transparent glazes


Used for gloss-matt effects. The matrix fabric mesh ranges from 21 to 77.

White relief glazes


Formulated using zirconium whites with the addition of opacifying raw materi-
als: zirconium, zinc, tin. Fabrics with a low number of threads per cm2 are used.
Their use in third-firing is currently popular.

Heavy glazes
Used for incision effects on zirconium white or transparent glazes. Formulated
with vanadium frits or bases with high PbO percentages. Printing is usually effect-
ed with matrices having 51-77 threads per cm2.

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Raw materials for frits and glazes

Lustre glazes
Formulated with alkaline bases to which tungstic oxide or metallic tungsten are
added. Can also be formulated with special cerium frits. Matrices with 45-100 threads
per cm2 are used.

Iridescent glazes
Formulated with boric bases or heavy metals such as molybdenum, bismuth,
vanadium. Matrices with 21-45 threads per cm are used.

Reactive glazes
Used under the glaze (not just in screen printing) to obtain a mixing effect with
the overlying glaze during firing. Of high fusibility and applied using matrices hav-
ing 18-45 threads per cm.

Single firing floor tiling

This is currently the most widespread floor tile production technology. In the
Sassuolo area this technology was largely based on the use of local dry or wet-
ground red clays for the higher quality products. Red bodies were then replaced by
wet-ground, spray-dried ones and, more recently, these have, in part, been replaced
by stoneware or porcelain.
Over the years the technology has been refined to provide products of ever-
more sophisticated aesthetics and ever-better quality. Glazing is effected on a hot
body after treatment in a drier (80-120 °C).
It is essential to glaze the tile while it is hot enough to evaporate the water in the
glaze suspension and thus aid drying.
The addition of carboxymethyl cellulose in the glaze suspension is indispens-
able in ensuring proper adhesion of the glaze-body interlayer during preheating.
Light coloured bodies are generally fired at a temperature of around 1160-1220
°C with cycles lasting 35-55 minutes.
Red bodies are generally fired at temperatures of around 1120-1130 °C with
cycle times similar to those cited above. Finally, high-porosity red bodies are fired at
1080-1100 °C with firing cycles of 30 to 50 minutes.
Descriptions of the most commonly used single firing floor tile glazes are given
below.

Waxy glazes
Refers to a category of glazes – used extensively in single firing – of a silky matt
appearance. Their covering capacity lies midway between that of a white and a
transparent.
Sometimes, completely transparent products are also defined as waxy (but only
in single firing).
Fusibility is always medium-to-high and under-glaze decorations or applications
may be applied. Above-glaze applications are generally limited to silk-screen deco-

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ration only. CMC is added to these glazes to improve on-body adhesion. Formula-
tion generally makes use of averagely leaded frits.
The added raw materials, which make up 10-30% of the glaze are: zirconium
silicates, zinc and stannic oxides, feldspars, wollastonite, clays and kaolins.

Opacified white glossy glazes


These differ markedly from their double firing counterparts. Generally formu-
lated using frits with a high calcium or zirconium content and very low levels of
lead. Added raw materials generally consist of micronized zirconium silicates, clays
and kaolins. These glazes can be applied immediately after the engobe and before
application of other glazes (waxy, crystalline etc.). Decoration is always performed
on top of the glaze. Application is generally of the disc type.

Rustic-effect glazes
In recent years this category has become extremely diversified. These glazes
generally have non-gloss surfaces, are soft to the touch and opaque to reflection of
light or rough and strongly satined. They may also be gypsum-like and markedly
opaque. Formulation varies widely. The employed frits are of the semi-fluxing type,
such as, for example, disilicates, accompanied by various other frits. Added raw ma-
terials too constitute a highly varied group, ranging from corundums and sands to
confer hardness and coarseness to zinc oxide, tin and wollastonite for softness (cal-
cium is also introduced as carbonate and/or dolomite). Feldspars and nephelines
are also employed to give the glazes glassiness and clays and kaolins to regulate
rheology.
Zirconium silicate is used in low percentages. Covering capacity is highly vari-
able and depends on the need to utilise highly elaborate (and often under-glaze)
applications. Items produced with these glazes are commercially referred to as rus-
tic. Such products may require up to 15 successive applications that involve disc
application, brushing, airbrushing, washing with water, air-jet blowing and dry ap-
plications. The resulting aesthetics are superbly sophisticated, especially when one
bears in mind that pre-structured bodies can extend decorative opportunities even
further.

“Cotto” glazes
These glazes were created to imitate classic, unglazed cotto. They have since
been diversified into a range of products to meet more specific aesthetic needs such
as rustic cottos etc.
Composition largely falls into line with that of the rustic glazes, yet a wider
range of colours is available. These products are normally off-shade and matched
with rustics to obtain floors that fall within the extensive “rustic” category. Applica-
tion is as described for rustics.

Crystallised glazes
Currently regaining lost ground after a prolonged absence from the market.
Formulated using fluxing frits and high percentages of titanium dioxide. The

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Raw materials for frits and glazes

above-cited oxide crystallizes during firing under the form of rutile. The use of
coloured bases gives rise to “deep-colour effect” products. The greatest inconve-
niences stem from the level of crystallization which is difficult to keep constant.
Modern fast firing processes should aid uniformity of firing across the entire kiln
cross-section.

Engobes
These serve the same purposes described for the other technologies. Formulated
with a high percentage of clayey raw materials and kaolins.

Coloured bases
May be formulated with fluxing frits coloured on fusion, mixes made with high
percentages of pigments and colorant oxides such as ferrous and manganese ox-
ide.
These coloured bases are used to obtain special under-glaze effects by way of
their reactivity with the overlying glazes.
The applied glaze layer can also be brushed to concentrate the colour in struc-
tured body cavities, thus creating highly interesting deep-colour effects.

Matt glazes
These glazes are formulated using frits of high calcium, zinc and/or magnesium
content. Semi-fluxing frits are sometimes used too, while zirconium silicate, wollas-
tonite and plastic materials are added in the mill.
Matt glazes are generally applied using the disc method.

Technical glazes
These glazes feature excellent abrasion resistance and porosity both on the
surface and inside the vitreous mass. Generally formulated using hard raw mate-
rials such as corundums. Special frits that give rise to devitrification-type crystal-
lisation during firing are sometimes used too (glass-ceramic). Application begins
with a specific white base followed by fairly thick (e.g. 12-thread) silk-screen print-
ing that provides the product with marked technical characteristics. Improvement
of on-product aesthetics is achieved via widespread utilisation of coloured silk-
screen printing products applied between the base and the thick “technical” glaze
layer.

Dry-application grains

Dry application techniques have come a long way over the last few years: these
were originally conceived to meet both the continually evolving aesthetic demand
and satisfy a pressing need within the ceramic industry to reduce the environmental
impact of glaze application and preparation.
It should be born in mind that the grinding and wet application of glazes
generates substantial quantities of by-products (i.e. ceramic sludge) which need

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to be disposed of in compliance with standards. The cost of doing so is high and


results are not always satisfactory. Dry glazing, on the other hand, does not involve
any grinding (which, as we shall see, is carried out “dry” or wet by the glaze manu-
facturer). Glazing thus requires no vehicle and does not produce any sludge.
Dry glazing products have so far enjoyed extensive success in single firing floor
items and have evolved to form the three main categories that simultaneously exist
on today’s market.
Initially unsatisfactory attempts made in the 70s which consisted of dry-apply-
ing standard glazes in powdered form were followed by the first proper products
known as frit grains. These products are made via controlled crushing of the
frits (described in greater depth further on). The resulting grains are put through
particle size selection, the out-of-range part being rejected. Frit grains have been
– and still are – used extensively on numerous commercial tile types ranging
from the glossy to semi-glossy and even the “technical”. Application begins with
an initial wet-applied base glaze followed by drop-application of the dry grains.
If the manufacturer has the forethought to apply the grains while the underly-
ing glaze is still damp (i.e. has not yet dried) the grains adhere to the tile surface
extremely well.
Nevertheless, producers often prefer to apply a glue suspension over the grains to
prevent them being detached by in-kiln air flow. An alternative to the glue suspen-
sion solution is application of a further layer of glaze: this improves adhesion and
can also yield certain aesthetic effects (interpenetration or transparency).
Frit grains can also be used on a base that has been coated with a high viscosity
glue beforehand using silk-screen printing techniques. Of course, the grains only
“stick” where the glue has been applied and even a weak air flow will carry the rest
away: a whole range of effects can be obtained this way.
One of the main problems with frit grains is that of “unmelted particles”. These
are foreign bodies which sometimes exist in miniscule percentages within the frit.
The nature of this “contamination” often varies. It may consist of small quartz
grains or pieces of refractory material that have detached from the melting kiln
lining.
The presence of mixed unmelted particles in the grains frequently generates dots
on the surface of the finished tile.
Last but not least, note that the particle size distribution range of these grains
lies between 0.15 and 0.6 mm.
A second type of grain – sintered grains – was subsequently launched on the
market. These are produced from a ground, dried glaze that is then treated so as to
form agglomerates obtained by way of extrusion or pelletization. The agglomerates
are then put through a 24-hr heat treatment in discontinuous or fast kilns similar to
those used for the tiles themselves.
Temperature must reach the glaze softening point so that well-vitrified agglom-
erates of good consistency form. These agglomerates are then crushed repeatedly
to produce the grains.

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Raw materials for frits and glazes

The final stage consists of particle size selection. These grains offer a series of
advantages with respect to frit grains. The first is the total absence of infusions in
that sintered grains are produced with ground glazes. A second advantage lies in the
possibility of using just about any type of composition, an alternative unavailable
where frits are used “as they come”.
The particle size range for these sintered grains spans from 0.18 to 1.5 mm. While
sintered grains cost much more than frit grains their use is justified by the excellent
aesthetic effects they produce.
The third mainline grain group takes the name of pelletized grains.
These are produced from ground, dried glazes that are pelletized and hardened
with chemical additives. Once again, proper particle sizing is essential, the typical
range spanning from 0.18 to 3 mm. Used on all tile types, these grains provide a
range of advantages with respect to their sintered cousins, not least of which is the
lower cost. The use of additives acting as binders may cause degassing problems
(especially where firing conditions are borderline and products are already loaded
with other organic substances that have to be decomposed).

Glossy white
Used on the market in all three above-described types. The frit grain is usually
produced in a less fusible form while sintered and pelletized grains use high-fusibility,
generally leaded white glazes opacified with zirconium, tin, zinc.

Transparent glaze
Here too, the most commonly used products are highly fusible. Suitable for types
that require the grains to melt until the product spreads completely. In other cases
tiles with only partial grain fusion are produced.

White matt
This product is difficult to use in pelletized form in that it is harder to eliminate
the adhesive degassing problems. As a frit grain there are often persistent infusion-
related problems.
Another generalized problem is that it is difficult to obtain flat surfaces without
using zinc (albeit in small percentages) as a devitrifying agent.
Remember that in these cases zinc often lays the tile surface open to attack by
acid.

Special grains
These include glazes with lustre effects (those obtained from the frit being es-
pecially effective), crystallized effects and deep-colour transparent effects (sintered
grains are in a league of their own here).
Note that it is also possible to mix different grain types (even where they belong
to different families) and production techniques, thus multiplying the range of ce-
ramic and chromatic effects. It should, however, be born in mind that particle size
differences must be limited otherwise separation and layering will occur during both
storage and application.

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Technical grains
Usually of very fine particle size, these are frit or pelletized grains. Applied on
specific base glazes in very thin layers. Made from frits belonging to the “technical”
family, they thus feature excellent abrasion resistance and good compactness even
inside the vitreous mass. Capable of passing even the ISO 10545/7 Class V test.
Fig. 94 provides an overview of grain types, showing how they split into the
three main production technologies.

FRIT GRAINS PELLETIZED GRAINS SINTERED GRAINS

SPECIAL TECHNICAL WHITE GLOSSY TRANSPARENT WHITE MATT


GRAINS GRAINS GLAZE FRIT GLAZE

LUSTRE
GLAZE

COLOURED
TRANSPARENT
FRIT

CRYSTALLIZED
GLAZE

Fig. 94. Various types of grain.

174
Raw materials for frits and glazes

Chapter V

PHYSICAL AND STRUCTURAL PROPERTIES


OF CERAMIC RAW MATERIALS

Many properties of raw materials, whether fired or unfired, correlate with their
chemical or mineralogical composition.
Yet other parameters, such as size and shape of particles, their arrangement and
the way they come into contact with each other – the very structure of the ceramic
body – are equally important. Such factors strongly influence the chemical and physi-
cal changes that take place in the presence of the energy input associated with
firing.
For this reason, most ceramic materials need to be broken down to a size that
will optimise subsequent production processes: this goal can be achieved via a series
of methods, collectively known as COMMINUTION.

A comminution process consists of applying energy to particles until they


break or separate to form smaller particles: the reactivity of individual particles,
of course, will vary as a function of compression and abrasion resistance, hard-
ness, elasticity and the nature of the particle as dictated by the type of deposit,
how it is fractured and the whole geological history behind it (pressure, tempera-
ture) etc.
Without entering into an in-depth description of the principles behind the grind-
ing process (a subject that will be dealt with in Volume 2), let us examine the main
means of comminution.
– Crushing or compression of particles, between the very hard surfaces in the cru-
shing or milling machine. In theory, the effectiveness of this comminution pro-
cess varies as a function of the compression resistance of the ceramic material,
yet the irregular shape of the particles also considerably influences the forces
that shatter them. Crushing generally yields relatively uniform sized particles
and little powder.
– Grinding of particles, in which comminution occurs by rubbing and shattering
the particles against each other and use of fixed or mobile grinding media, resul-
ting in gradual reduction of average particle size and simultaneous production
of finer powder and a correspondingly wider particle size distribution.
– Impact fracturing, instead, involves new comminution principles: force is applied
on particle edges/corners and thus works efficiently along the “fissure” lines in
the particles themselves. Breakage usually occurs along the natural lines of we-
akness of the structure (associated with the mineralogical nature of the mate-
rial) or where different minerals meet.

Generally speaking, raw material comminution machines (to be described in


greater depth in Volume 2) employ a combination of the above-described principles.

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The main problem is the sharp drop in grinding efficiency that occurs as the par-
ticles get smaller.
It is thus common practice to employ return-feed screening systems that filter
out already-ground material as soon as it forms.

Particle size distribution

A raw material made up of particles of different size and shape may be defined
as a particulate system: size distribution of the grains in such a system is enor-
mously important, yet very difficult to measure.
Were they perfectly spherical, it would be easy to sort them via dimensional or
gravimetric selection (assuming constant sphere density): yet with a clayey system
the matter is somewhat more complex, making it difficult to define exactly what is
meant by the word “particle”.
While it has already been described how a clay is made up of extremely small
particles (micelles), it is also a known fact that these micelles, in the ceramic bodies
and raw materials themselves, are aggregated and agglomerated, thus making them
difficult to isolate in their free form.
Particles produced by grinding clays, then, will essentially be made up of many
small agglomerates of irregular form and variable surface/peripheral charge, thus
influencing behaviour in aqueous suspensions and during firing.
The first problem, then, in attempting to measure the dimensions of ceramic
particles and their distribution, is to decide whether to concentrate on the dimen-
sions of the individual particles or, vice versa, the agglomerates.
Similarly, the choice of pre-analysis dispersion systems will be decisive, as these
could break down the agglomerates/particles or even cause further agglomeration:
particle size analysis on a material dispersed in water with rheological additives
gives results that differ substantially from measurements made on the same powder
in its dry state.
Further complications are found in the enormous variety of granulometric sizes
within a ceramic body, especially where it has been dry-ground: however, even wet-
ground materials contain particles ranging in size from just a few tenths of a µm, to
tens of mm, and there is no instrumentation capable of providing adequate accu-
racy over such a wide range.
Finally, the particles of a ground ceramic material, especially where clayey, are
far from spherical, often plate-like.
These particles are mixed in with other materials that break down to form par-
ticles that, while spherical, are of greatly differing density.
Nevertheless, use of statistical evaluation and particle shape correction equa-
tions, which give spherical-equivalent diameters, makes it possible to effect reliable
particle size distribution measurements of solids in a suspension (usually in an aque-
ous solution) so as to evaluate the behaviour of the combinations during grinding,
forming, drying and firing.

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Physical and structural properties of ceramic raw materials

The main dimensional classification methods are listed in the following table,
which orders the methods according to minimum and maximum detectable particle
size.

Method Detection interval (µm)

Sieving > 50
Micro-sieving/filtration 0.2 - 50

Optical microscope 25 - 2500


SEM - Electronic microscope 0.5 - 1000
AFM - Atomic force microscope 0.001 - 5

Sedimentation 1 - 50
Elutriation 2 - 50
Centrifugation 0.05 - 5

X-ray dispersion 0.05 - 100


Laser diffraction 0.05 - 200

Gas permeability 0.1 - 300

Powder classification is always expressed as per national standards on the basis


of equivalent sieve classification, according to ISO (international), BS (British), UNI
(Italian), DIN (German) or NF (French) values. However, the MESH ASTM classi-
fication (USA) is used extensively all over the world and the equivalent sizes are
given on the following page:

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Mesh A.S.T.M. Micrometer (µm) Mesh / cm2


5 4000 3
6 3350 4
7 2800 6
8 2360 9
10 2000 11
12 1700 14
14 1400 19
16 1180 26
18 1000 35
20 850 50
25 710 75
30 600 100
35 500 140
40 425 200
45 355 270
50 300 380
60 250 590
80 180 1100
100 150 1600
120 125 2400
170 90 4700
200 75 6200
230 63 9500
270 53 12350
325 45 18200
400 38 26000

The above table highlights the limitations of sieving methods, their use being
confined to rather approximate discrimination: on the other hand, hydrodynamic
methods, long used for finer resolutions, are complex and lengthy (especially so for
very fine particles). The best compromise is to use short wavelength incident radia-
tion (X or laser) interaction instruments through the application of modifications
to Stoke’s law.
This is expressed by the following equation:
2 (ρ - ρ ) g r 2
1 2
V= ____________________


where V, the speed of a falling particle in cm/sec, is obtained from the values:
η viscosity of the suspension medium [water = 0.013 (10 °C), 0.010 (20 °C), 0.008
(30 °C) poises].
ρ1 density of the particle
ρ2 density of the suspension medium
g gravitational acceleration (981 cm/sec)
r radius of the particle, assumed to be spherical (cm).

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Physical and structural properties of ceramic raw materials

At constant temperature, where all constant parameters are known and the sedi-
mentation speed of a set of particles is measured, it will be possible to calculate the
average dimensions of the particles themselves.
By applying Stoke’s equation values to a particle with a density of approximately
2.5 g/cm3 and a diameter of 1 mm, it can be deduced that it will drop through water
at 20 °C, in the absence of any interaction with the water itself, at just under 1.2
cm/hour. The appropriate practical modifications to the equation, as a function of a
real particle, reduces this speed to about 0.3 cm/hr, thus giving a clear idea of just
how long hydrometric particle size analysis can take where a sedimentation of at
least 20 cm (and thus a wait of some 64 hours) is required.

Whichever system is used, particle size distribution can be represented by two


graphs (see Fig. 95): an actual % greater or less than a particular size or a cumula-
tive % against a logarithmic scaled size on the x axis.

Industrial production involves a series of particle size distribution tests designed


to ensure the desired outcome: it is, in fact, necessary to:
a) check the dimensions of the raw materials destined for grinding so as to optimi-
se control of the process itself.
b) remove coarse (sieve-retained) materials resistant to the grinding process, elimi-
nating them or recycling them back into the grinding process.

Fig. 95. Example of differential and cumulative particle size distribution curve.

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c) run a series of checks, with appropriate sieving, so as to ensure smooth opera-


tion of the spray drier pumps, the spray drier, the presses, and the glaze/engo-
be/silk-screen application stations along the production line.

All this is essentially based on a “no larger than…” principle through use of
appropriate sieves.
At this point it is important to highlight, with particular reference to grinding
(and homogenisation), the influence of variations in particle size both throughout
the process and on final product characteristics and classification.
The understanding and control of particle size is essential to ensure optimum
body texture and homogeneity and the required porosity, specific weight, modulus
of rupture.
The texture of the material is strongly influenced by the type and degree of
grinding. This is because grinding alters the size and shape of the individual grains
and causes variations in the way in which they associate, thus influencing particle
“packability” and final density.
Various studies on maximum attainable packing density have been carried out
with regard to both spherical particle systems with no particle deformation and
for isomorph sphere systems: these studies have yielded an ideal distribution that
gives rise to two possible solutions: “open packing” with spheres arranged by
cubic symmetry, where empty gaps account for 48% of the entire occupied vol-
ume and “closed” tetrahedral-symmetry packing with gaps accounting for just
26% of total volume.
Of course, systems featuring mixtures of different, always-spherical grains will
give rise to ever-more complicated theoretical models which optimise use of space
enormously: for example, a tri-modal system based on appropriately calibrated
spheres (having an assumed diameter ratio of 50:8:1) of large (62% by volume),
medium (24%) and small (9%) size will, in theory, fill the space very efficiently,
leaving an air-gap residue of just 5% (62 + 24 + 9 + 5 = 100%).

While the individual particles in a ceramic body are generally angular rather
than spherical – the above-explained general principle may be taken – except where
particles are particularly elongated in one direction – as being applicable, albeit
inexactly as there are many other inconveniences linked to the fact that the irregu-
lar shape of the particles stops them sliding against each other.
On the other hand, that irregularity will, statistically, give rise to the real possi-
bility of forming more extensive areas of tighter agglomeration and, all in all,
lowering average porosity.
In general, grinding processes that involve initial impact crushing followed by
abrasive comminution (as in an Alsing-type ball mill), give optimum yields in terms
of attainable density, especially where the treated materials are of different hard-
ness and density: this thus permits the co-presence of relatively coarse particles
(feldspars, quartz etc.) and others of smaller and smaller particle size distribution
(e.g. clays).
Clearly, a particle size control system consisting of just one simple sieving (so-

180
Physical and structural properties of ceramic raw materials

called sieve residue) serves only to establish whether production activities com-
pleted thus far have remained within operational parameters. Fig. 96 shows two
bodies (the particle size distribution curves of which are illustrated) with an identi-
cal residue of about 2% at 63 µm: yet they clearly differ substantially in terms of
particle size composition, with body A having a Gaussian distribution around 15
µm, and body B having bimodal distribution centred around 0.6 µm, with an aver-
age dimension of about 9 µm.

Slip sample “A” (AVG. DIAMETER = 15.3 MICRONS)

Particle Size (Microns)

Slip sample “B” (AVG. DIAMETER = 9.1 MICRONS)

Particle Size (Microns)

Fig. 96. Particle size distribution analysis of two bodies having same residue but different particle size
distribution.

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The technological behaviour of the two bodies, which seem identical in the light
of residue-only analysis will actually be radically different, as B is much more
compactable than A.
The “unpackability” of ground raw materials and the forces applied during the
forming process (pressing, extrusion…) make the production of a ceramic body
without any empty spaces at all virtually impossible, no matter how accurate selec-
tion and particle size distribution may be.
All ceramic materials, except for some glasses, have pores or empty spaces: the
porosity of a material is, then, defined by the quantity of air it contains. In scientific
literature there are six different kinds of porosity (see Fig. 97):

Fig. 97. Different types of porosity. From: Grimshaw, Chemistry and Physics of Clays-Benn.

a) closed pores
b) capillary canals connecting closed pores
c) blind pores
d) interconnected pores
e) open or “ink bottle” pores
f) micropores (so small they prevent entry of water or any other liquids).

There are two types of closed pore: those formed by pressing the semi-finished
item and those originating from open pores that are sealed by material that melts or
forms during firing.
In both cases, but mostly the latter, closed pores are full of air, water vapour,
SO2, CO2 or CO, or even O2.
When a ceramic body is heated, the pressure inside the pore increases and
exerts considerable force on the surrounding solid material: this can cause fissur-
ing, lamination and even explosions as long as the material remains rigid (low
temperature), but when the latter starts to soften at temperatures close to and

182
Physical and structural properties of ceramic raw materials

beyond the vitrification point, the pressure exerted by the enclosed gas may cause
expansion of the material itself and create bubbles which, in turn, form new
macroscopic pores.
Dimples or “pin-hole” defects seen on fired glazes often stem from closed pores
too: these are formed by carbonates, sulphates and other pyrolysis-affected com-
pounds that emit gas at high temperatures: if this occurs when the glasses in the
glaze are about to become plastic the glaze will block the escape and elimination of
such gases.
Open pores (i.e. those connected to the exterior by capillary channels of varying
length and width) may be formed by the original particle packing configuration,
elimination of water vapour during drying or the initial stages of firing, elimina-
tion of gas during firing, micro-structural alterations in the pieces during drying
etc. The presence of such pores is closely tied to the size of the body particles and
how they are packed.
In general, since fluids (rainwater with regard to freezing resistance and inks,
oils etc. for staining and cleaning parameters) can enter and exit open pores, it is
preferable for a fired product to have open pores of either a very large average
diameter (>300 µm, to allow easy evacuation of water or introduction of deter-
gent solutions) or a very small one (<40 µm, the smaller the better) so as to make
fluid entry difficult and prevent any water contained therein from freezing as a
result of extremely strong capillary forces: it thus follows that materials with a
substantial amount of medium-size open pores (from 40 to 300 µm) remain at
risk.

Such a wide range of scenarios makes it possible to measure two different body
parameters: total porosity and apparent porosity.
The true (or real) porosity of a body is the ratio of all (open and closed) empty
space volumes to total volume, while the much more frequently-used apparent po-
rosity parameter is defined as the ratio between the volume of water the body can
absorb under certain conditions (during prolonged boiling or vacuum treatment)
and the total volume of the piece.
Such porosities will clearly be influenced by the dimensions, shape and packing
of the particles, the chemical nature of the materials making up the body, and the
technological treatment applied to materials during production: an often-underesti-
mated parameter is the intrinsic porosity of the individual particles.
As stated in the introduction, depending on their mineralogical formation, clays
possess widely differing structures with interlayer spaces ranging from 5 to 20 or
more Å; in this respect they differ greatly, of course, from quartz or other compact
material particles.
For this reason a clay-based body containing large quantities of sands and feld-
spars, especially where the latter are of suitable particle size, will be less porous
than that of a predominantly clayey body.
In addition to these morphological features, body texture and particle size distri-
bution will play an important role in physical and chemical reactivity during firing,
as will be illustrated further on.

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Any particle size variation, in fact, will have an influence on the specific surface
area of the powders and an immediate influence on the inter-particle surfaces, sharply
increasing that reactivity surface area, which, via solid-solid or solid-viscous liquid
reactions (high-temperature ceramic bodies), is of primary importance for proper
sintering.
The example in Fig. 98 shows a ceramic body matrix made up of relatively coarse
feldspar (F) and quartz (Q) particles contained in a brick-like framework of clayey
particles:

Fig. 98. Progressive fusion-reaction hypothesis.

The sintering process begins at the particle contact points, where the fluxing
action of the feldspars first acts (the black dots in the far left drawing).
Following initial reactivity, which tends to involve the smaller particles in closer
contact with the fluxing agents, a liquid phase forms: this goes on to involve, par-
tially, the surrounding clayey structure.
During the process, and especially during cooling, crystalline neo-phases form
and reinforce the sintering phenomena in the mass.

The importance of particle size distribution in ceramic manufacturing is not


just limited to the need for proper grinding: there must also be proper control of
the powder agglomerates sent on to the pressing department.
As seen in the introduction, ceramic technology allows us to form ceramic tiles
by pressing powders of low moisture content (3-6%).
Such powders may be produced by dry grinding (i.e. with dense, irregularly-
shaped and often sharp-edged solid particles), followed by appropriate addition of
water, or wet processing followed generally by spray drying that produces (some-
times hollow) smooth spherical particles which can agglomerate.
In both cases it is essential that powders flow smoothly from the silo to the press
feeder without segregation and fill the press cavity as evenly as possible: they must
therefore be properly granulated.
Particle size distribution of granules is extremely important in attaining a post-
pressing “green” tile that is compacted evenly all over and free from defects.
The differences between dry and wet ground powders will be dealt with in depth
in Volume II of this work.

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Physical and structural properties of ceramic raw materials

In both the former case (particle size distribution either natural or induced by
raw material grinding) and the latter (particle size distribution of semi-finished
items), it is essential to evaluate the relative amount of the different granule classes
so as to obtain the best possible mix and optimum compaction.

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HOW WATER INFLUENCES CERAMIC SYSTEMS

Water plays a vital role in ceramics. Most ceramic raw materials are sedimentary
in nature and thus formed in an aqueous environment.
Many key minerals are of secondary origin, created by water-induced weather-
ing of primary rock.
Furthermore, water is added at most stages of the ceramic production process
to aid completion of shaped semi-finished items.
Although water has a significant effect on any type of raw material, it plays a
particularly important role in clays owing to the already-described structural char-
acteristics: these include inter-particle spaces and electrostatic charges that allow
intense interaction with the water molecules, which, because oxygen and hydrogen
have different electronic affinities, may be seen as small dipoles with a partial nega-
tive charge on the
Hδ+
O and a partial positive charge on the H δ-O < δ+.
H
When water is mixed in with the powders in quantities equal to approximately
one fifth the weight of the powder itself, plastic bodies are obtained. Where that
proportion rises to between a third and a half, suspensions of extremely differenti-
ated rheological characteristics result: given the dimensions of the clayey particles,
these may be considered and treated as colloidal suspensions.
Given the complex nature of water these “basic” interlayer electrostatic interac-
tions are accompanied by others dependent on structural or chemical irregularities,
generally influencing the surface of the particles:
a) distorted ionic groupings
b) broken surface bonds, unsaturated bonds, sliding or crumbling planes
c) cations of unsaturated charge, or cations which create charge defects in the crys-
tal lattice etc. If a basal plane of the crystal lattice is theoretically in electrical
equilibrium and the surface, vice versa, has a excess/insufficient charge (gener-
ally caused by the high number of oxygen2- atoms in the ceramic material), a
fracture will greatly disturb that equilibrium, causing different attraction/repul-
sion scenarios involving the water molecules (Fig. 99).

In general, though, the particle surfaces are deemed to be sufficiently charged to


attract at least one layer of water (see Fig. 100), which remains attached by a strong
electrostatic bond and differs from free water in that it is denser (like ice): this first
layer of molecules, oriented according to the attraction of the particle on the di-
pole, is known as a “double electric layer” and has been studied and characterised
extensively. It varies in thickness from approximately 7 to 60 Å.

In-depth analysis of double layer interactions is outside the scope of this pub-
lication. Many experts interpret it as a sort of molecular condenser, the (zeta)
potential of which can be calculated by studying variations in the potential en-
ergy of the system (see Fig. 101). Here we shall simply examine the macroscopic

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Physical and structural properties of ceramic raw materials

Fig. 99. Kaolinite crystals with positive and negative edge charges (A and B respectively), defloccula-
tion (C), edge-to-face flocculation (D), face-to-face flocculation (E), flocculated Ca clay (F), deflocculat-
ed clay -Na (G).

free water

free water

bound
water

Fig. 100. Distribution of charges and water, free and bound, around clay particles in suspension. The
cross-hatched area in the middle is the clayey core.

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variations caused by disturbance of these electrostatic interactions at molecular


level.

Before examining these variations in more detail it is worthwhile highlighting a


parameter often neglected in academic works but of great importance in industrial
practice: time. That is, the contact time between water and the ceramic material.
It is a factor on which the completion of many reactions depends: such reactions
can have an enormous influence on the final characteristics of the suspension to be
spray-dried or cast, the body to be extruded or the semi-dry powder to be pressed.
The time factor involves both physical and chemical changes. These range from
the degree of hydration significantly influencing the plastic properties to the solu-
tion of substances present. The latter can result in the freeing of ions, alteration of
pH or aiding the oxidation of cations in iron and sulphides.

Another important – yet often neglected – alteration of significant macroscopic


implications is the emission of hydration heat, which, in clayey raw materials may
vary from 0.1 to more than 600 calories per gram yet is generally negligible in
other ceramic raw materials (0.0015 c/g for quartz, 0.04 for Feldspars).

Zeta potential:

e = charge
D = dielectric constant
d = distance between rigid and diffuse layer

rigid diffuse
layer layer
potential
resultant
R = repulsion

distance
A = attraction

Weak double layer: R weak à attraction prevails à flocculation


Strong double layer: R intense à repulsion prevails à deflocculation

Fig. 101. Attraction and repulsion potentials in a radial direction starting from the surface of a grain
dispersed in a solution.

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Physical and structural properties of ceramic raw materials

As regards aqueous suspensions of ceramic bodies, the main events which need
to be controlled and guided are flocculation and its opposite, deflocculation. In the
former, rapid sedimentation of “flaky” particle aggregates of greater density easily
separated from the system are created from within a homogeneous in-water particle
suspension. In the latter attempts are made, vice versa, to aid dispersion of aggre-
gates using appropriate additives, thus obtaining particles that remain in suspen-
sion for long periods even in the absence of agitation. This last characteristic is, of
course, particularly sought after in the wet grinding of clayey bodies.
Both effects are the result of disturbing the solid-water electrical particle layers:
flocculation is usually caused by the introduction of small – and therefore high
charge-density – bi or tri-valent cations; these can seriously alter the electrostatic
equilibrium of the suspension. Deflocculation, instead, is generally achieved by adding
organic or inorganic polymeric molecules that “isolate” the particles from each other
by separating them on account of their structural characteristics. Here too, the
presence of appropriate cations (Na+, NH+) that alter the equilibrium of the double
layer aids the effectiveness of the additive.
Because ceramic particles are negatively charged, they easily attract positively
charged cations. The tendency of cations to be adsorbed has been shown, for the
most common, to be: H+ > Al3+ > Ba2+ > Sr2+ > Ca2+ > Mg2+ > NH4+ > K+ >Na+ >
Li+, so the useful cations, such as sodium and potassium, have little chance to act.
The effect (which will depend on the ratio of their charge and volume) may be used
to vary the electrical characteristics of a suspension or by adding excess to act on
the exchange equilibrium

(CLAYn-. Xm+) + Ym+ ⇔ (CLAYn-. Ym+) + Xm+

where X and Y are the different cations.

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Physical and structural properties of ceramic raw materials

Chapter VI

RHEOLOGY: BASIC CONCEPTS

The word “RHEOLOGY” is a relatively recent addition to the vocabulary of


ceramics: yet it concerns problems that the ceramist has to deal with all too fre-
quently.
Rheology – from the Greek words “reo” meaning “flow”, and “logo” meaning
“study” – is, then, the study of flow. This includes flow in both solids (e.g. the rheol-
ogy of powders) and fluids (e.g. the rheology of slips or even gases). Such matters
are of enormous interest to the ceramist, as they are of relevance at nearly every
stage of the production cycle, especially during the wet grinding of bodies and
glazes and during on-tile application of the glazes.

One of the biggest challenges facing the ceramic technician is translating that
colourful jargon surrounding the practical aspects of rheological phenomena into
more rigorous terminology.
Remarks such as “the glaze flows like oil”, “it’s bubbly”, “it’s settled and hard-
ened in the tank”, “it’s thinned out too much”, “the mill’s jammed” and “the slip
has frozen” are all common factory floor comments. These empirical expressions
actually reflect considerable knowledge of how rheological factors affect the pro-
duction process. Yet it is a knowledge that has been built up on a trial and error
basis and which, to a large extent, has not been rationalised in a way that allows it
to be transmitted.
Nevertheless, the ceramic industry continued to rely on this rather uncertain
wealth of knowledge for years, and it has to be said that production processes
were, by and large, kept under control; when production cycles were slower and
product change-overs less frequent, this level of understanding was more than
good enough.
Now, though, with the advent of new technologies and the fast-changing flurry
of products and glazes there is no longer time to build up an empirical understand-
ing of events.
Instead, the glaze or body slip must comply with precise production standards,
defined according to standardised units of measure.

Let us begin by shedding some light on the concept of viscosity. This term has
become a part of everyday vocabulary and is now mentally associated with a greater
or lesser ease of flow.
To arrive at an exact definition it is first necessary to define the exact physical
measurement one is referring to.
A rather crude definition of viscosity might be the effort needed to make a fluid
attain a certain speed.

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The first thing is to clarify that one cannot refer to the speed of a moving fluid as
if it were a racing car.
If that were the case then all the fluid, like all the components of the car, would
be moving in exactly the same way.
For example, we can talk about the speed of a drop of water as it falls into an
empty glass: the entire drop moves with respect to the sides of the glass and thus its
speed is defined by the ratio between distance covered and time taken – as with the
racing car.
Yet a fluid flowing in a tube is subject to quite a different set of conditions: the
part of the fluid in contact with the wall of the tube moves much more slowly than
the fluid in its middle. The absolute speed of a fluid molecule thus differs according
to its position inside the tube, reaching a maximum in the centre and a minimum up
against the walls.
In shifting from the wall to the centre, then, speed increases constantly; this is
because none of the molecules are free to move in the same way as a car on the race
track or the drop falling into the glass.
They are, instead, obstructed by the other molecules in the fluid as a result of
internal friction.
The wider the tube the easier it is for the fluid to flow because the particles in the
central zone are less affected by friction than those up against the walls. Or, in tubes
of equal diameter, the lower the friction between the molecules of the fluid the
higher the speed of the fluid in the central position.

Velocity gradient
To define viscosity we need to know all the parameters affecting it. One of these
is the velocity gradient. If, in a certain zone of a moving fluid mass we measure
maximum speed (vmax), and in another the minimum (Vmin) and then the distance
separating the two points at which the measurements were taken (l), we obtain a
gradient value valid for the moment of measurement. The difference between the
two speeds divided by the distance is defined as the “velocity gradient” and is indi-
cated by D:

D = Velocity gradient = (Vmax - Vmin)/ l

As we have seen, this value is directly affected by the degree of friction within
the fluid. If, all conditions being equal, a fluid has a high velocity gradient this
indicates that its molecules generate low-level internal friction. The physical di-
mensions of D are:

v [LT -1]
D= ___ = _______ = [T –1] = reciprocal seconds
L [L]

This is the inverse of a time. Reference is always made to the velocity gradient
expressed in reciprocal seconds.

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Rheology: basic concepts

Shear stress
The second element affecting viscosity is the “stress” the fluid is subject to.
Let us go back to our example of the tube for a moment: tube diameter and in-
fluid friction remaining equal, it can intuitively be seen that increasing pressure
increases the velocity gradient (i.e. the fluid will flow faster).
However, the concept of pressure, as a description of the stress to which the
fluid is subject, is inadequate in that it is not necessarily connected with flow.
In a closed system there is no flow at all, whatever the applied pressure. This is
because pressure is the ratio between a force and a surface perpendicular to the force
itself and does not necessarily generate movement.
Example: a concrete block resting on a floor generates a pressure defined as
force per unit of surface area. Getting the block to move requires considerable force,
but such force must be applied parallel to the floor, not perpendicular to it. At a
certain point, once the applied force reaches a certain threshold, the block will start
moving along the surface of the floor.
The force needed to start the block moving will be considerable as cohesive forces
that bind two objects in contact when at standstill need to be overcome: such mo-
tion-opposing forces, which tend to “stick” two immobile objects together, are de-
fined as static friction.
In mechanics the ratio between the orthogonal forces acting on the two surfaces
in contact, when movement begins, is defined as the coefficient of static friction, µ
(mu).
Note that, since the coefficient of friction is an intrinsic characteristic of the two
surfaces in contact, surface area is non-influential: both forces act on the same sur-
face even though they are orthogonal.
When the body, still subject to the pressure of its own weight, finally starts
moving, a traction force needs to be applied: this will be proportional to speed and
surface roughness.
This applied stress, like the above-mentioned static friction, is needed to over-
come the forces generated by dynamic friction (generally lower than static fric-
tion).

Of course, one cannot speak of friction between two surfaces subject to orthogonal
forces where fluids in motion are concerned: the relevant concept in this case is
internal friction, and thus the only significant value when studying the flow of a
fluid is the force applied tangentially to the unit of surface.
This is defined as “shear stress” and is indicated by the Greek letter τ (tau) and is
measured as a pressure:

Ft [LMT-2]
τ= ___ = ________ = [L-1 MT-2] = N / m2 = Pascal
A [L ]
2

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Viscosity
Referring to the above measurements it can be said that applying a force to a
certain area of a fluid mass to keep it moving causes the fluid to respond by gener-
ating shear stresses that result in different zone-to-zone speeds.
Within the mass, then, a velocity gradient is created. Its value depends on the
internal friction of the fluid, a factor closely related to its viscosity.
Viscosity is defined as the ratio between the shear stress and the velocity gradi-
ent. It is indicated by the Greek letter η (eta) and has the dimensions of a pressure
over time:

τ [L-1MT-2]
η= ____ = _________ = [L-1 MT-1] = Ns/m2 = 10 Poises
[T ]
-1
[T ]
-1

This essential formula tells us that viscosity is directly proportional to the shear
stress needed to obtain a given velocity gradient in the fluid.
On the basis of the units of measure adopted for D and τ, viscosity is usually
defined as:

η = pascals per second

This however, is too large for many practical applications, so a sub-multiple is


preferred:

millipascals per second = mPa . s = centipoises = cP

Other methods of defining viscosity are to be found in more specialist litera-


ture.
In the context of ceramics, then, viscosity varies enormously, spanning from
just a few centipoises in the case of disc or spray gun-applied glazes to hundreds of
centipoises for bell-applied ones or slips prior to spray drying.
The range of velocity gradients to which ceramic suspensions are subject is
even wider, extending from tens of reciprocal seconds in slow-stir tanks to hun-
dreds of reciprocal seconds in pumps and several thousand inside nozzles.
Glazes may be subject to large and sudden variations in the velocity gradient:
final on-tile flows, in fact, starting from a situation that varies widely depending on
the type of applicator, always end with a zero velocity gradient.
At first glance such a wide velocity gradient interval is no cause for concern in
that once the viscosity η of our glaze suspension is defined it should be possible to
forecast its behaviour whatever the flow situation.

Unfortunately, this is true only in a minority of cases of ideal or Newtonian


viscosity where the ratio between shear stress and velocity gradient remains con-
stant for any velocity gradient value.
In these few fortunate cases (e.g. Vaseline oil), the behaviour of the fluid can be

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Rheology: basic concepts

fully described by the value η as it remains constant whatever the flow speed and
depends on temperature only.
A graph showing τ (shear stress) values against variations in D (velocity gradi-
ent) gives us the line illustrated in Fig. 102.

This way of illustrating rheological behaviour, generally defined as a “rheogram”,


is extremely useful.
Viscosity is represented by the ratio between the two quantities, that is, the angle
of the line (i.e. the tangent of the angle α). The greater the angle the higher the
viscosity.
Predicting behaviour in fluids like this is easy: it will continue to flow at decreas-
ing speeds as shear stress decreases and will stop flowing altogether when shear
stress is completely eliminated.
Example: oil spilt on a floor seems to spread forever. While flow speed depends
on the viscosity of the oil, flow will continue until the shear stress produced by the
hydrostatic pressure (determined by the level of the liquid) is counterbalanced by
surface tension. Since oil has very low surface tension the “slick” will spread a long
way.

Yield point
Experience teaches us that ceramic suspensions are decidedly non-Newtonian.
In attempting to define those divergences from ideal behaviour that significantly
affect the technological cycle, it should first be pointed out that one of the most
important aspects of such a suspension is that it will often start flowing only when
applied shear stress exceeds a certain threshold.
Similarly, if it is already moving, it will only stop doing so once shear stress
drops back below that threshold.
Returning momentarily to the example of the concrete block resting on a floor,
there is a clear analogy with the tangential force needed to shift the block. The level
of such force depends on friction.
Getting back to the flow of fluids (i.e. rheology), this threshold value is defined
as the yield-point. This is an initial shear stress indicated by τ0 (tau zero) and is
measured in pascals.
Where a fluid has a yield point and flow only begins at a threshold level of shear
stress, the velocity gradient remains zero until the τ0 level is reached as in the graph
in Fig. 103. This important characteristic is common in ceramic fluids where flow
stops though still subject to shear stress.
It is this parameter that determines the spread of disc-applied glazes, the form
of the droplets in the droplet method, the thickness of the dipped glaze or the
thickness of glaze applied to a vertical surface before it starts to run.

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Fig. 102. Standard rheogram for Newtonian-type fluid where the following relationship applies:
τ
η = _____ = tan α.
D

Fig. 103. Rheogram for a fluid with an initial yield point τ0 (Bingham plastic).

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Rheology: basic concepts

The importance of time


Certain types of non-ideal rheological behaviour are important in ceramics
because of both their practical importance in industrial processes and the fact
that they sometimes give rise to quite striking phenomena.
For instance, it is known that ceramic suspensions, especially those with con-
siderable percentages of clays, can become rigid if left undisturbed for a time and
then turn fluid when agitated. This characteristic is particularly evident in the
bentonites.
The latter, in fact, are used in the oil industry to seal drilling wells: the well is
filled with an easily pumpable slip that, when left undisturbed, hardens to form an
efficient plug.
The advantage of this system is that the well can be reactivated simply by
directing a water jet into it, thus agitating the bentonite and returning it to its
fluid state.
This property stems from the fact that, at standstill, the structure of the fluid
changes as a function of time: three-dimensional bonds form between the par-
ticles, making the structure rigid.
These bonds are destroyed by the application of shear stress and need time to
reform once the fluid is again motionless. Hence viscosity changes as a function
of time.
While most body or glaze slips behave this way, time-dependent viscosity is
not generally a problem as it occurs at very low flow rates and ceramic suspen-
sions are usually stirred constantly at much higher velocity gradients.
Note that the key difference regarding the yield point is that its effects are seen
as soon as the fluid drops below a given shear stress value; whilst this is indepen-
dent of time the viscosity of such suspensions will still be time dependent.
The difference is that the yield point remains a characteristic of the fluid even
when it is agitated, while, if the fluidity is also time-dependent, the τ0 value can
increase drastically if the fluid remains at standstill. This poses a problem as to
how the yield point is measured.
Since ceramic suspensions are also time-dependent, it is necessary – before
constructing the rheogram – to subject the suspension to the highest possible
velocity gradient for a period long enough to destroy all the structures that may
have formed; then the velocity gradient is brought to the minimum D and τ is
measured to produce the τ rheogram as D varies.
As might be expected, where time-dependence is absent the D/τ rheogram
will, as D values are increased and then decreased, turn back along the same path
to give a single curve valid for both the “outward” and “return” scenarios.
Where, instead, behaviour is time-dependent the rheogram obtained by de-
creasing D is different from the increasing one.
The only way of measuring time-dependence in itself is to take viscosity mea-
surements as a function of time while keeping the D value of the sample con-
stant, thus constructing a rheogram.

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In constantly-stirred suspensions this measurement is of little interest: how-


ever, if the extent of the time-dependence is abnormal it can cause difficulties in the
production process.
For example, the suspension may thicken so quickly as to make mill emptying
slow or impossible, or the viscosity of the suspension may increase steadily even as
it is slowly stirred.
In this last case the slip can be unloaded, pumped and sieved easily enough but as
soon as it is introduced into the tank it tends to “freeze” because the agitator turns
too slowly to prevent bonds forming in the fluid.
Without the addition of fluidizers the situation can soon become critical and the
contents of the tank thicken so much that only the area actually swept by the agita-
tor paddles remains fluid.
Unfortunately, at this point the addition of fluidizers becomes awkward as they
can no longer be distributed efficiently.
The best solution is to dilute the fluidizer in water and add it to the slip slowly,
employing a pump to create a top-to-bottom return flow within the tank contents.
It may take a while to completely homogenise the fluid and more solid parts of the
suspension.

Thixotropy
A third type of rheological behaviour frequently encountered in ceramics is thix-
otropy which, if excessive, can cause difficulties.
This is a tendency that leads some suspensions to change their rheological
behaviour as a function of the yield stress they have previously been subject to.
The most common scenario is that in which viscosity is lower where the fluid
comes from a situation of higher stress, and is often when a yield point exists.
In practice a graph illustrating τ and D for initially higher and then lower veloc-
ity gradients (D) yields a rheogram with hysteresis (Fig. 104).

This hysteresis effect is defined as “thixotropy”; however, a unit of measure that


allows for absolute evaluation does not exist.
The only way of estimating the phenomenon is to take a series of measurements
at higher and higher and then lower and lower velocity gradients and then trace a
graph of the results.
Thixotropy is represented by the area enclosed by the curve. It is evident that
the obtained values will depend on measuring procedures: the use of standardised
procedures is thus essential if one is to obtain results that can then be compared.
Since, in ceramic suspensions, this effect is always linked to the presence of a
yield point and a certain time-dependence, it is highly advisable to use the same
procedures at all times.
This allows that type of thixotropy which is most damaging (i.e. that which
remains after the suspension has been stressed at maximum velocity) to be high-
lighted.

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Rheology: basic concepts

(a) thixotropic behaviour (b) antithixotropic behaviour


(e.g. kaolin suspensions in H2O) (e.g. magnesium hydroxide in H2O)

(c) rheopexic behaviour (d) antirheopexic behaviour


(e.g. vanadium oxide in H2O)

(e) thixo-rheopexic behaviour (f) antirheopexic-antithixotropic


behaviour

(g) thixo-antithixotropic behaviour (h) antirheo-rheopexic behaviour

Fig. 104. Rheograms showing hysteresis and corresponding definitions of the behaviour that produces
them.

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From an application point of view, interest generally focuses on evaluating the


behaviour of fluids subject to high stress levels and which progressively slow to a
halt (e.g. a droplet launched from a disc).
The most relevant tract of the rheogram (Fig. 104) is thus the one showing
the decreasing velocity gradient, which, with glazes, is often perfectly linear. The
rheological behaviour of the suspension can thus efficiently be described in terms
of plastic viscosity and yield point.
If thixotropy is excessive, application problems can arise, especially where low
viscosity and a certain yield point are required.
Thixotropy hinders the control of viscosity because it varies depending on
how the suspension is agitated.
This particular rheological effect is generally caused by in-suspension particles
of a shape that leads them to align according to direction of flow (e.g. like plate-
lets, sticks or filaments).
As the velocity gradient steadily increases the initially disordered particles
gradually align. When the velocity gradient is subsequently lowered, the align-
ment remains and the fluid flows more easily.
Thixotropy is always undesirable, yet can largely be ignored. However, certain
circumstances will require efforts to minimise it.
As explained, thixotropic behaviour is linked to the geometry of the particles
in the suspension and it is clayey minerals, in fact, that have the dimensional char-
acteristics most likely to trigger it.

If a glaze is excessively thixotropic it is good practice to modify clayey compo-


nent ratios, trying out different types of clay if need be.
Should the thixotropic behaviour of a body be excessive it is, instead, neces-
sary to modify the deflocculant, perhaps using components with a synergetic ef-
fect.

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Rheology: basic concepts

Rheology of clays

The rheological behaviour of clay slips generally characterises them as non-


Newtonian systems. More specifically, they can be classified as plastic and
pseudoplastic fluids of the thixotropic type. Note that the same clay may behave
in either a plastic or pseudoplastic manner depending on the percentage of solid
in the slip, as will be illustrated further on.
Depending on the industrial application in question, such effects may be posi-
tive or negative. In ceramics the presence of thixotropy and yield points linked to
plastic behaviour are undesirable.
However, it should be pointed out that, given the technological cycle of clay
slip production, effects are limited except in sieving and where the slip is left in
the storage tank for a lengthy period.
From the information provided in preceding chapters it should be fairly clear
which chemical-physical parameters control rheology of clays. In particular, it
can be said that all those factors directly influencing the zeta potential – especially
cationic exchange, contact surface area between liquid and solid (which depends
on particle size distribution of the clays) and the in-clay presence of soluble salts,
especially sulphates and calcium salts – are of primary importance. The effect of
the above factors on the rheology of the clays can be controlled in a number of
ways: the simplest is to vary the percentage of clay in the slip. Alternatively, the
quantity and type of deflocculant can be adjusted or the grinding process can be
modified.
While the role played by grinding in determining the rheological qualities of
a slip is one of the lesser known aspects in ceramics, it is probably one of the most
important factors in the rheology of systems.
Grinding (especially its duration) directly influences system particle size dis-
tribution and slip temperature. In practice we could determine the rheological
characteristics of a slip by adjusting grinding, bearing in mind that the longer
the mix is ground the greater the solubility of the salts, the greater the contact
area between water and solids and, consequently, the higher the level of cationic
exchange.
This normally leads to decreased system fluidity and an increase of apparent
viscosity, accentuation of thixotropy and the appearance or increase of a yield
point.
These effects are enhanced even further as temperature rises when grinding
times are increased. Temperature increase plays two roles: the first directly influ-
ences the rheology of the system in a generally negative manner, in that tempera-
tures of > 60 °C are reached (as with porcelain tiles), while the second aids the
kinetics of salt dissolution and cationic exchange, leading to the above effects.
The percentage of clay in a slip causes rapid and often obvious changes in the
rheology of the slip itself: to this end note that all clayey systems feature some
degree of thixotropy, seen more as the percentage of solid increases.

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A water-clay system can also be controlled via the use of deflocculants: the
same ceramic material deflocculated with different percentages of sodium tripoly-
phosphate (STPP) will show significant system rheology differences, with the ap-
pearance of a yield point and accentuation of hysteresis.
Less favourable rheological conditions reign with higher tripolyphosphate per-
centages, indicative of an over-deflocculation that causes incorrect system fluidi-
zation.
Analogous situations arise when the type of deflocculant is changed.
Given our present level of understanding it can be said that the phosphates
(especially tripolyphosphates) tend to give good results right across the known
range of clays by providing sufficient control of system thixotropy. Silicates yield
good results with clays that are lean or of high kaolin content, but control of
thixotropy is more difficult than with phosphates.
Organic products are generally good dispersants and stabilizers but are less
efficient in controlling apparent viscosity. As regards the ratio between
deflocculants, the yield point and plastic viscosity in water-clay systems, little
information is available. This is particularly so in industrial-type systems, owing
to the difficulty of discriminating between the various factors that influence the
two parameters above.

Mineralogy and rheology of clays

The most common clayey minerals in clays used by the ceramic industry are
kaolin, illite, the smectites (montmorillonite, nontronite) and chlorites.
The rheological characteristics of a clay thus depend on the type and quantity
of clayey minerals it contains, though they cannot neatly be summed as a function
of their in-clay percentages. This is because of the already-cited presence of ac-
cessory minerals, which can be important in defining the rheological characteris-
tics of a clay.
There follows a brief description of the rheological characteristics of the above-
cited minerals: however these observations refer to the minerals in their pure
state, while for clays used in industry other parameters influence.

Kaolin: of a mineralogical structure that precludes the presence of interlayer


water. No cation exchange capacity. There are usually no soluble salts as kaolins
are normally very pure.
These factors result in non-plastic rheological behaviour. Consequently no yield
points are observed except where rheological conditions are particularly
unfavourable (e.g. high concentrations, unsuitable deflocculants, extensive grind-
ing-though among the various clayey minerals, kaolin is the one least affected by
grinding).

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Rheology: basic concepts

The pH of kaolins normally falls between 5 and 6, allowing for optimum


deflocculation with sodium silicates, sodium carbonate or, under very favourable
conditions, sodium hydrate: products that shift system pH from 7 to 9.
Of coarse, phosphates and organic salts also have an optimum effect on the
water-kaolin system, while the use of acid pH products is to be excluded.
Whilst the above observations apply to pure kaolins, they nevertheless remain
largely valid for both white and red kaolinitic clays as long as contamination of
the system by soluble salts or clayey minerals of a different nature is limited.

Illites: as illites of a purity comparable to that of kaolins do not exist, one can
only reason in terms of clayey systems containing varying percentages of illites.
This fact, taking into account that rheological characteristics cannot neatly
relate to the percentage of minerals present and the difficulties in determining
the percentages of such minerals with accuracy, shows how difficult it is to inter-
pret the rheological characteristics of an illite clay.
Let us evaluate, for example, an illite-kaolinitic clay in which other minerals
and impurities are assumed to be absent.
In this case, compared to a kaolin, all other conditions being equal, there is an
increase in the plastic behaviour of the system, with more accentuated thixotropy
and greater apparent viscosity.
On the other hand, comparing an illite-montmorillonite to a montmorillonite
clay, the apparent viscosity, yield point and thixotropy of the system will be lower,
but compared to an illite-kaolinite clay they will on average be higher.
All in all it can be said that illite is a clayey mineral having rheological charac-
teristics less desirable than those of kaolin as there is the appearance of a yield
point and thixotropy.
Certain grinding conditions emphasise these characteristics as illite is more
sensitive to grinding than kaolinite. The most effective deflocculants are tripoly-
phosphate and sodium metasilicate, while products that act on pH only, such as
carbonate and sodium hydrate, are of limited use. This is because the natural pH
of illite is less acid than kaolin.
The above observations will obviously require modification where minerals of
a different nature predominate in the illite clay system.

Montmorillonite: from a rheological viewpoint this mineral is without doubt the


worst, at least as far as the clay slips used in ceramics are concerned. In other
industries, however (e.g. as a sludge in oil drilling), it is actually prized on account
of those characteristics. Montmorillonite is characterised by high thixotropy and
a particularly marked yield point, features that correspond with plastic behaviour
of the slip.

Both plastic and apparent viscosity are high even where the percentage of solids
is low. A certain differentiation in the behaviour of these clayey minerals is ob-

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served as a function of the type of cations in the layers. There are, roughly speak-
ing, three main types of montmorillonite: acid, sodium and calcium. The acids are
montmorillonites obtained by treating natural minerals generally extracted as so-
dium or calcium montmorillonite.
Generally speaking, the acids are extremely difficult to deflocculate, unless
deflocculants that raise pH sharply are used. On the other hand the sodiums are the
easiest to deflocculate and can be fluidized with STPP and polyacrylates.
Calcium montmorillonite is the mineral commonly found in clays for ceramic
use; it is more difficult to deflocculate than the sodium type and generally requires
phosphate or polyacrylate-based mixes. In any case, use of this mineral must be
tightly controlled and it is good practice to limit quantities to no more than 6% in
lean bodies and 4% in plastic bodies.

Chlorites: with respect to the above-described minerals, defining the rheological


characteristics of a chlorite is extremely problematical. This is because chlorite,
while one of the most common clayey minerals, is – given its genesis – always
accompanied by illite or smectite.
It is thus extremely difficult to discriminate between the rheological behaviour
of these minerals and chlorite. One can only affirm that, given the structure and
mineralogical similarities, the presence of chlorite in a clay is generally to the det-
riment of rheological characteristics with the appearance of thixotropy and the
presence of a yield point.

In concluding this brief analysis of the rheological characteristics of clays, it


should be underlined that only laboratory tests can provide accurate knowledge as
to the rheological behaviour of a clay.
Mineralogical and chemical data only allows us to hypothesize general behavioural
rules useful for evaluation on the basis of the mineralogical characteristics of the
clays: yet such rules will always be approximate in nature.

Rheology of ceramic bodies

Ceramic bodies are essentially made up of a plastic clayey fraction, a “hard”


quartzose (inert)/feldspathic (fluxing) fraction and limited quantities of chamotte,
carbonates, recycled materials and sludge, colorant oxides and opacifiers. The ap-
propriately batched set of raw materials is loaded into a mill with the required
quantities of water and deflocculant and ground to a pre-determined residue.
Since the clayey fraction spans a particle size distribution range below that of
normally required residues it is simply broken up or dispersed to its fine phase,
while the harder elements are subject to a true grinding action by impact and roll-
ing.

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Rheology: basic concepts

On the basis of the mineralogical and chemical composition of a body, we can


hazard a rough rheological classification of the components as follows:
a) colloidal clayey fraction, the effects of which were discussed in the previous
chapter.
b) inert or fluxing materials virtually insoluble in water, such as feldspars, quar-
tz, zirconium silicate, alumina... etc.
c) soluble materials in appreciable quantities: alkaline salts and earth-alkalines
contained in the raw materials and in any additives in the form of waste,
sludge.

Non-plastic insoluble products only act on slip rheology as “number of par-


ticles per unit of volume” or by crowding the system with particles having a high
specific surface area (which increases enormously as particle size reduces).
Their effect is largely that of corpuscles which, from a chemical-physical view-
point, are substantially inert, yet active in a rheological sense in that they occupy
a space already crowded with masses and electrical charges; they therefore oppose
a certain resistance to layer flow and influence rheological properties.
As already seen, soluble ions can approximately be divided into flocculating
ions (small and highly charged) such as Ca2+, Mg2+, Fe2+, Fe3+, Al3+, Zn2+ and other
cations such as Na+, K+ and, less frequently NH+4, as well as the anions: sulphates,
chlorides, carbonates and bicarbonates and borates. They may come from clays,
sludges and, above all, grinding water.
The importance and effect of the flocculating ions is easily understood: they
contribute to a reduction of the zeta potential between the micelles by reducing
their repulsive forces.
Somewhat less obvious is the rheological relevance of the other ions, which
can be explained as follows: overcrowding of charges, and thus a decisive increase
in the total ionic strength of the aqueous phase, has a negative influence on the
zeta potential and obstructs the exchange processes. The presence of the other
ions is, then, a hindrance to deflocculation even where the concentration of true
flocculating ions is relatively low.
With regard to the relative importance of the three main ceramic body compo-
nents, it can certainly be stated – from a rheological standpoint at least – that the
plastic clayey fraction plays the lead role in slip behaviour, although the influence
of soluble salts is often decisive.
The effect of the non-plastic inert materials, in comparison to that of the other
two components, is decidedly secondary.

Influence of grinding water

Lab tests using de-ionised water have confirmed that soluble ion slips prepared
with de-ionised water show much better viscosity than all the others prepared with

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potable or industrial water (other variables remaining equal) for reasons already
cited (presence of flocculating ions, high total ionic charge).

Furthermore, ceramic body grinding water is often the worst in the whole fac-
tory, containing runoff and waste from other departments (i.e. glazes, various or-
ganic substances and so on). However, even “clean” water recovered from waste
beneficiation can contain small quantities of flocculants (ferric chloride, aluminum
chloride, lime, polyacrylamides) and can have worse effects – from a rheological
viewpoint – than untreated waste water.
A further grinding water factor is pH: as already mentioned, there is an optimum
deflocculation pH range (normally 8 to 9). Water with pH values outside this range
will make the whole process more difficult.
From these observations it can be concluded that periodic inspection of the grind-
ing water may be useful, if not necessary. Rather than a true chemical analysis,
which would be difficult to carry out inside most ceramic production plants, it might
be preferable to run the following tests as they can be completed quickly and do not
require the use of costly equipment:
a) pH: using a pH-meter. The importance of pH is cited in the preceding para-
graphs.
b) electrical conductivity: using a conductimeter (simple hand-held versions are
available), giving an approximate idea of total ionic concentration.
c) total hardness: determined by titration, measures the quantity of flocculating
ions (Ca2+ and Mg2+).
d) COD (Chemical Oxygen Demand): a measure of the oxidizable organic substan-
ces in the water. This assessment, while more complex than the others, is done
by titration.

Periodic and frequent control of these parameters will provide sufficient (but
incomplete) grinding water quality data, allowing correlations to be drawn between
changes in such parameters and any worsening of the rheological characteristics
of the slips. It also allows, albeit in an entirely empirical fashion, the establishment
of a “good water” range outside which action needs to be taken (e.g. dilution with
non-recycled water).

The wet grinding process and spray drying


of the ceramic bodies from a rheological standpoint

The entire process can be summarised as follows:


a) batching of main and auxiliary raw materials, water, deflocculant and loading of
mills.
b) homogenisation of the mass inside the mill as it starts to rotate.

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Rheology: basic concepts

This part of the process is practically ineffective in terms of grinding, and is of


extremely variable duration.
c) true grinding: this stage reduces solid particle size and “adjusts” the particle size
distribution curve, shifting it towards lower and lower values.
d) unloading of mills.
e) screening of the slip using a series of vibrating sieves.
f) in-tank slow-stir storage.
h) transfer into smaller service tanks, high-pressure pumping and spray drying.

During the settling and homogenisation stage, characterised by extremely vari-


able density, the deflocculant dissolves (where this has been introduced in a solid
state) or is, in any case, dispersed within the aqueous phase.
The efficiency of this first stage often determines the outcome of the entire
grinding process, and the development of negative phenomena at this stage can
have long-lasting effects, sometimes causing serious unloading problems or low
grinding effectiveness.
“Jamming” of mills, observed in systems with a high plastic material content, is
a classic example.
The rotary movement creates compact spheroidal masses (“blocks”) of greatly
differing size, which in worst-case scenarios actually envelop the grinding me-
dia: these generally consist of clay or other materials lined with layers of plas-
tic clay.
Where they are small they tend to float on the suspension; sometimes, instead,
they “snowball”, gathering up solids as they roll and when grinding is over they
have to be broken up mechanically.
The result is that the “jammed” material is not ground and final residue is abnor-
mally high.
Exactly why this happens is not clear, although the poor “wettability” of certain
raw materials, overly irregular loading (sometimes causing stratification) and the
accumulation of deflocculant in only certain zones (thus delaying its dispersing
action) are all thought to be contributing factors.
The appearance of such phenomena can be prevented by introducing or improv-
ing pre-mixing of all the body components, adding water simultaneously with the
raw materials during mill charging and, above all, using deflocculants that are al-
ready in solution and/or dissolved in the grinding water. If this line of action fails
to resolve the problem then the trouble may lie with the grinding media, in which
case the load will need to be reviewed in terms of quality, quantity and media size
distribution.
A combination of these actions will shorten this initial phase and rapidly bring
the system to a degree of homogenisation that renders the action of the grinding
media effective, thus reducing the total grinding time.

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As soon as a sufficiently homogeneous, constant-density slip is formed the rheo-


logical characteristics of the system take on more significance. At this point the slip
may be described, by and large, as an unstable, pseudoplastic, thixotropic suspen-
sion with a yield point.
In an analysis of the grinding process true and proper, variations in viscosity
and residue (taken as an index of particle size fineness) are illustrated in the graph
in Fig. 105.

Grinding residue (curve A) decreases and finally stabilises: extending the grind-
ing time beyond this point yields no advantages whatsoever and merely wears the
grinding media. Viscosity, instead, initially declines sharply, stabilises during a sec-
ondary variable-duration phase and then recovers over the final phase as grinding
continues.
This behaviour can be explained as follows. The initial falloff in viscosity is
caused by the action of the deflocculant; the constant-viscosity phase is linked to
the fact that the clayey portion, which is more involved in the interactions with the
deflocculant, is already, at this point, in a homogeneous system of a particle size
distribution well below that set by the residue; the final increase is a result of vari-
ous factors:

Viscosity
Residue

time
Fig. 105. Changes in viscosity and residue during wet grinding.

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Rheology: basic concepts

a) particle size reduction of the inert fraction causes a higher concentration of


particles of higher specific surface area.
b) system temperature may increase beyond the optimal range (40-50 °C).
c) grinding time, temperature and physical-mechanical stress can lead to partial
deterioration of the deflocculant or have a negative effect on exchange mechani-
sms.

At this stage of the process, where the system is subject to continuous and in-
tense shear stresses, viscosity is the most important factor: it must be low enough to
allow proper movement of the grinding media but not so low as to cause their rapid
wear, which would result in poor grinding efficiency. This is particularly true where
high-density grinding media are used.
Some examples of viscous grinding have, in fact, led to a reduction in overall
grinding times.
Unloading difficulties can effectively be resolved by adding small quantities of
deflocculant (generally 10-20% of the total quantity) a few minutes before the end
of grinding: this lowers the yield point and results in smooth slip outflow. High-
efficiency liquid deflocculants and automatic or semi-automatic dosing systems make
the task considerably easier.
Emptying or unloading the mills normally takes from 15 minutes to 1 hour; the
slip is subject to low shear stress and factors such as yield point and thixotropy
count for more than viscosity in itself.
It is at this stage that thixotropic slips with a high yield point tend to take on a
pseudo-solid structure (in jargon, they are said to “ice” or “gel”), forming a surface
crust and leaving significant quantities of residue on the grinding media and the
mill lining, thus making unloading tasks long and difficult.
It is interesting to note how this effect is never seen while the slip is kept mov-
ing, yet increases progressively under standstill or slow-flow conditions.
Systems which, at the end of grinding, reach and exceed 70-80 °C are a case
aside; in addition to having higher viscosity, these often form surface crusts because
of the increase in local density induced by water evaporation. Note also that exces-
sive end-of-grinding temperatures are not only useless (or detrimental) as regards
the rheological characteristics of the slip: they also imply wasteful use of energy
and may be indicative of problems or irregularities in grinding media size and/or
the ratio between the latter and the mill load.
Sieving is sometimes an integral part of unloading or is sometimes carried out
afterwards. It will be fast where yield points are low since an important trend is
towards finer mesh sizes to maximise the removal of potentially damaging impuri-
ties.

Sieving is often the slowest part of the entire production process. Consequently,
a number or series of sieves are used.

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At this point the body slip goes into holding tanks with low-speed agitation.
Holding times vary greatly depending on the size of the plant, ranging from 6-8
hours to 12-15 days.
Under these conditions (very low shear stresses and extended duration) time-
dependent phenomena such as thixotropy become crucial, especially where tanks
are full and there are nearly-still areas of slip.
Consequently, the formation of surface “crusts” – often a tell-tale sign of im-
pending “gelling” or “thickening” of the entire mass – are sometimes observed:
this event is known and feared by all ceramists, as it is the forerunner of a whole
series of difficulties. To recover from this problem pre-diluted liquid deflocculant
is added but it may take time to disperse throughout the tank.
Ceramic suspensions have inherently poor stability and should not be held for
prolonged periods unnecessarily.
Where unloading and sieving problems or thixotropy-related in-tank viscosity
increases occur continuously and frequently an in-depth rheological analysis and
review of the entire process may well be needed.
This chapter does not aspire to give a precise, exhaustive explanation of (or
easy solutions to) problems that often stem from a host of concurrent factors. It
does, however, intend to scrutinise the various factors contributing to the rheo-
logical characterisation of a body slip and provide guidelines that allow produc-
ers to predict (if not prevent) the phenomena and take effective countermea-
sures:

Increased viscosity and other phenomena may be attributable to:


1) raw materials
2) grinding water
3) additives
4) deflocculants
5) particle size distribution.

On closer analysis, we can state:


1) An increase in viscosity and plastic behaviour may be attributable to changes,
in a plastic sense, in one or more raw materials (mostly the clayey ones); the
more frequently the raw materials are topped up, the more probable this beco-
mes. Variations in the moisture content of the clayey components can also lead
to changes in viscosity, yet such changes are always accompanied by easily
recognisable increases in slip density. If, instead, the mineralogical and/or che-
mical composition of some of the body components has altered, identifying
the “guilty” party will be extremely difficult without the aid of accurate che-
mical and diffractometry analyses, and even these sometimes fail to clarify the
problem. These plastic increases can sometimes be identified through repeated
measuring of unfired bending load or shrinkage on both unfired and fired pie-
ces. The only way to prevent the problem is to run accurate rheological tests

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Rheology: basic concepts

on the raw materials at the same time as the usual technological ones (absorp-
tion, shrinkage, firing colour, presence of carbonates etc.).
The same phenomena occurs when errors in formulation, weighing and so on
result in combinations overly-rich in plastic components being fed into the
mills.

2) Variation in the composition of the water (see preceding pages).

3.A) Addition (or increase) of plasticizers or glues. Any introduction/changes to


quantity of such products in a body must always be preceded by laboratory
tests.

3.B) Addition of sludge, glazes and recycled materials from glazing plants: once
again, laboratory testing is essential.

3.C) Addition (or increase) of exhausted lime from kiln filters. As calcium ions
cause flocculation in slips, dosing must be calibrated with care. With respect
to lime-free loads extra deflocculant must be added according to the quantity
of lime that has been introduced: in the most difficult cases this ranges from
50 to 100%, and has led some companies to abandon the use of recovered
lime in grinding altogether as it is anti-economic with respect to other solu-
tions (e.g. assistance from specialised companies).

4.A) Drop in the percentage of deflocculant caused by erroneous dosing.

4.B) Drop in percentage of deflocculant as the latter itself absorbs the water. A
fairly rare phenomenon that is usually easily visible to the naked eye.

4.C) Wrong type of deflocculant (supplier error).


Identification of this cause is fairly easy in that the difficulties coincide with
change-overs in the product being used.

5.A) Variation in particle size distribution in that there is an increase in the fine or
super-fine fraction owing to an extended grinding time (drop in residue). A
marked increase in grinding time generally leads to increased viscosity.

5.B) Like 5.A but brought about by the addition/increase of very fine recycled
dust or unfired scrap. In these cases too it is highly advisable to effect lab
tests before making any definitive changes.

The stocked and sieved slip is pumped to the spray drier at a pressure of a few
tens of atmospheres (on average about 30 Atm) using piston pumps.

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From a rheological viewpoint this is perhaps the least understood stage of the
entire process, as the physical stress the system is subject to is virtually impos-
sible to reproduce using laboratory instruments. On the whole though, it seems
safe to state that the system, where subject to very high yield stress, behaves in a
Newtonian manner in a laminar fluxing situation, at least as far as the nozzle
outlet where, aided mechanically, it rapidly transforms into a disordered “cloud”
to form the droplets that, following interaction with heat, will become spray-dried
grains.
If this fails to happen (or happens too late) the jets released from the nozzles
are projected and build up on the inner surface of the chamber, which if left can
seriously affect the performance of the drier.
Density, viscosity and other rheological parameters undoubtedly influence the
quality of the spray-dried product, but correlations between these parameters are
difficult and individual experiments are necessary in each case.

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Rheology: basic concepts

Rheological additives

The main rheological additives are given in the table below:

ADDITIVES FOR DEFLOCCULATION


INORGANIC ORGANIC
Na2CO3 Humic acids

Na2O. nSiO2 Tannins

Polymeric phosphates (NaPO3)6 Derivatives of acrylic acid


CH2=CHCOOH

Na5P3O10

BaCO3 Derivates of oxalic acid (COOH


|
COOH)

In everyday language, the term deflocculant refers to a substance which, when


added to an aqueous suspension of dispersed colloidal powders, causes greater flu-
idity of the suspension, diminishing its apparent viscosity.
Deflocculant is a synonym for fluidizer and merely correlates the deflocculation
process with a decrease in viscosity, neglecting its function as a dispersant and a
preventer of the rapid aggregation that would cause precipitation of the solid par-
ticles suspended in the water.
Deflocculants are compounds which impede flocculation by way of a higher zeta
potential and a relative increase in the repelling forces between the particles.
A good dispersing action creates very high zeta potentials, thus giving minimum
viscosity.
It follows, then, that the term “deflocculant” includes both the basic concept of
dispersion and that of fluidization.

A dispersant is that prevailing fluid phase into which the non-mixable solid or
liquid fractions are dispersed (such fractions thus represent the dispersed phase). In
most applications the dispersant is water.

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Deflocculation is that process in which the solid colloidal particles in the dispers-
ant fluid (e.g. a slip) move away from each other yet remain in suspension because of
the repelling electrostatic action that the deflocculant substance induces (by increas-
ing their zeta potential).
A fluidizer is a substance capable of making a fluid flow more smoothly (i.e.
lowering its viscosity). It is the exact opposite of a thickener, an agent that in-
creases the consistency of a fluid mass.
A deflocculant is a substance which, when added in small quantities to a fluid
mass, is capable of preventing agglomeration of the colloidal particles and thus
their precipitation. Since this effect can be achieved via dispersion (i.e. by addition
of the fluid phase) the two can easily be confused; while it is certainly true that a
deflocculant also acts as a fluidizer, it is not necessarily true that all fluidizers are
also deflocculants. The fundamental mechanisms that explain the deflocculating
action may be explained as follows:
l. shifting of the pH towards basic values by introducing OH- ions into the H2O-
solid system via an addition of monovalent bases or basic electrolytes which, by
hydrolysis, give OH- ions (an excess causes over-deflocculation).
2. substitution of other cations constituting the positive side of the diffused double
layer with Na+, K+, Li+, NH4+.
3. an increase in the negative charge on the clayey particles by adsorption of cer-
tain types of anion (adsorption is preferential for anions of higher valence with
a strong electric field).
4. increase in the total negative charge of the solid-liquid system, assuming a non-
ionic colloid carrying a negative charge.
5. addition of a “shielding” colloid that shields the suspended particles from the
action of flocculants.
6. elimination of any flocculants:
– by precipitation of the flocculating ion

Na2CO3 + Ca2+ → CaCO3 ↓ + 2 Na+


BaCO3 + Ca2+ → CaCO3 ↓ + Ba2+
BaCO3 + SO42- → BaSO4 ↓ + CO32-

– via formation of coordination complexes


[XA]B where X = flocculating cation (Ca2+, Fe3+)
(Polyphosphates).

The most complex deflocculants act via a combination of the above-described


mechanisms.
Deflocculants may be inorganic or organic. Inorganic deflocculants are electro-
lytes (monovalent bases, basic electrolytes, carbonates, silicates and sodium phos-
phates).
Organic deflocculants may or may not be electrolytes. Whether organic or inor-
ganic deflocculants are used, it is necessary to take into consideration not only their

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Rheology: basic concepts

undesirable side effects, but also the effect they have on the dehydration rate, plas-
ticity and bending strength of the body.
The influence of the deflocculant on thixotropy and its effects during the down-
stream forming phase (adhesion to dies, chemical aggression on mould) must also
be evaluated.
Inorganic deflocculants are more sensitive to the nature and the quantity of ions
already present in the suspension, are not eliminated during the drying and firing
phase and do not generally have any thixotropic effects.
Concentrations being equal, organic deflocculants are more effective, less sensi-
tive to interference from other ions and have greater stabilising power. They volatilise
during firing, are usually thixotropic and are more expensive.
Choosing the right deflocculant is a case-by-case affair and will necessarily in-
volve practical tests.
The most complex problems can be resolved by using compatible mixes of or-
ganic and inorganic substances that provide good synergic performance.

Inorganic deflocculants

• Na2CO3

Clay Ca2+ + Na2CO3 → Clay Na+ + CaCO3↓


Ca(HCO3)2 + Na2CO3 → CaCO3 ↓ + 2NaOH + 2CO2

These fundamental reactions make sodium carbonate an excellent deflocculant:


the more Ca2+ is present the better the effect. The property of precipitating the
calcium, while advantageous for the purposes of deflocculation, is, for example, some-
what less so as regards the life of the plaster casting moulds.

CaSO4 + Na2CO3 → CaCO3 ↓ + Na2SO4

The aggression of the salt Na2SO4 lowers deflocculating power and damages the
plaster.
Na2CO3 , which melts at 850 °C, increases plasticity and the dry bending strength
of bodies but reduces the drying rate.

• Na2O - n SiO2

The sodium silicate, which hydrolyses easily with an alkaline reaction (pH > 11)
gives Na+ and OH- by separating the colloidal silica

Na20 - n SiO2+ H2O → n SiO2 + 2Na+ + 2OH-

The silicate is not as aggressive towards the plaster as the carbonate and has
binding properties. Where sulphates are present its deflocculating power is reduced.

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The mix:
Na2CO3 + Na2O - n SiO2

has the advantage of acting in a good four of the six ways described in the
preceding paragraph (namely 1, 2, 5 and 6). It thus has a higher deflocculating
power and results in fewer defects being caused by the aggression of Na2CO3. These
are stable solutions that let gelatinous silica separate. Additions usually fall in the
0.2-0.6% range (by weight).

• Phosphates, Polyphosphates
Those with the most remarkable deflocculating power are sodium
hexamethaphosphate (NaPO3)6 and the polyphosphates, especially sodium tripoly-
phosphate (Na5P3O10).
The mechanism exploits the fact that the phosphoric anion is one of the anions
that is preferentially adsorbed by the clay particle, increasing its negative charge.
The consequent increase in the zeta potential makes a key contribution to a greater
dispersant effect. They are also capable of seizing flocculating ions to form coordi-
nation complexes.
An example is provided by hexamethaphosphoric acid (H6P6O18) which, with the
Ca2+, Mg2+, Fe3+ ions forms complex compounds of the following type:

[CaP6O18]4-, [Ca2P6O18]2-

The considerable deflocculating power of sodium hexamethaphosphate can be


attributed to the action of the Na+ cation, the strong anionic adsorption and the
seizing of the flocculating cations. The polyphosphates behave in a similar fashion:
some of the most interesting of these are:
Na5P3O10 (sodium tripolyphosphate) in alkaline oxide
Mn+2 Pn O3n+1 is the general formula with M = monovalent metal
If n = 1 M3PO4 (orthophosphates)
If n = 2 M4P2O7 (pyrophosphates)
If n = 3 M5P3O10 (tripolyphosphates)
If n = 4 M6P4O13 (tetrapolyphosphates)
For n > 4 vitreous-structure mixes form.
These compounds too seize the flocculating cations under the form of complexes.
The polyphosphates have a chain-like structure and have many uses; even where
dosed at < 0.4% they are still effective as dispersants on clayey materials.
Deflocculating suspensions with polyphosphates break down over time and in-
crease their viscosity when heated.

• BaCO3

The presence of SO4= obstructs the processes of deflocculation (reduction of

216
Rheology: basic concepts

the zeta potential) especially in the presence of the ideal flocculant Ca2+, Mg2+, Fe3+
etc.
This is because the SO4= anion (unlike other anions such as the phosphoric one)
is easily adsorbed by the clayey particle even in substitution of the OH- ions. This
happens even if SO4= is present in the form of a strong electrolyte (e.g. Na2SO4):
other strong electrolytes such as NaCl act similarly.
The ideal thing is thus to remove the SO4= groups.
As mentioned above Na2CO3 reacts with the sulphates (e.g. CaSO4) and CaCO3
precipitate forms, removing the Ca2+ flocculating cation, but failing to eliminate the
SO4= anions which always remain (like Na2SO4 soluble in H2O) even where silicates
or sodium phosphates are present:

CaSO4 + Na2SiO3 → CaSiO3 + Na2SO4


3CaSO4+ 2Na3PO4 → Ca3 (PO4)2 + 2Na2SO4

To make Na2SO4 insoluble it is necessary to add barium compounds:

Na2SO4 + BaCO3 → BaSO4 ↓ + Na2CO3 ↓

The latter acts as a deflocculant. In place of BaCO3 (almost insoluble), soluble


BaCl2 could be employed, but this is only possible via stoichiometric dosing of the
sulphates present in the materials to be deflocculated in that the excess Ba2+ ion acts
as a dangerous flocculant. Hence BaCO3 is preferred on account of its limited solu-
bility.
BaCO3 should be added before the deflocculants in quantities ranging from 0.02
to 0.1%.

Organic deflocculants

Organic deflocculants are also electrolytes or polyelectrolytes in the form of


sodium salts and act according to the mechanisms described in the inorganic
deflocculants section. Their anion has a colloidal property and aids the deflocculating
power of the various compounds.

• Humic acids and derivatives


Extracted from humus, peat and lignites, these are oxycarboxylic acids of high
molecular complexity with furanic rings and different functional units with the fol-
lowing properties: negative radical of a colloidal nature, solubility in alkalis even if
diluted, insolubility of their salts with bi or trivalent metals.
It is believed that humic acids wrap up the clay particles to form a clayey-humic
compound, thus inhibiting the action of the flocculating cations, and so involving
other mechanisms.
Just how much the protective sheath that wraps up the mineral particle disturbs
the action of the typically deflocculating Na+ is, however, unknown.

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The colloidal clay-humic acid mix is very stable and thus difficult to disperse. A
commercially available humate-based deflocculant has been obtained by treating
the lignite with soda.

• Tannin compounds
Tannins of a colloidal nature and those of vegetable origin such as the humic
acids (used in tanning processes owing to their insolubility and because they pre-
vent the leather gelatine from rotting), have deflocculating properties.
The “prototypes” are tannic acid and gallatannic acid (a mix of glucose and gal-
lic acid esters), the latter belonging to the vast group of the phenolic acids, organic
compounds having a molecule that simultaneously houses more than one carboxylic
group and one or more phenolic hydroxyls.

From this compound for the elimination of CO2, pyrogallic acid is obtained. The
alkaline salts of such compounds (sodium tannate, sodium gallate, pyrogallates) are
all good deflocculants on a par with the humic derivatives. It has been hypothesized
that the tannin molecules are adsorbed at the surface of the dispersed particles with
the aromatic part protruding into the dispersant. This would alter the exterior of
the particles with variations in hydration and consequent lowering of viscosity.

• Acrylic derivatives
Derived from acrylic acid CH2 = CHCOOH, with an acid force greater than that
of acetic acid, CH3 COOH.
Na+ ed NH4+ salts can easily be obtained via substitution of H+.
Acrylic acid gives rise to a wide range of polymers with which it is possible to
form acrylic resins, important groups of thermoplastic resins. Furthermore, the
double ethylenic bond is another “point” capable of reacting. Also of interest are
compounds of the CH2 = CHCOOR type where

R = metal, alkyl
If R = CH3 (acrylic ester)
If R = C2 H5 (polyester)
Others of importance are: CH2 = CHCH acrylonitrile
CH2 = CHNH, acrylamide

Acrylic acid and its derivatives polymerise easily under the action of heat, light
and peroxides (benzoyl), giving rise to (polyanionic) polyacrylic acids with the corre-
sponding polyelectrolytes, the polyacrylic derivatives, polyesters, polyacrylnitriles etc.

COOR CN
| |
- CH2- CH - CH2 - CH - CH - CH2 - CH - CH2 -
| |
COOR CN

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Rheology: basic concepts

Polyacrylic acid dissolves fairly slowly in water and its alkaline salts are easily
soluble. Polyesters and polyacrylnitriles are insoluble.
It should be noted how certain electrolytes obtained by way of a partial alkaline
hydrolysis of the polyacrylnitrile have considerable aggregating power. Others are
effective dispersants.
The length of the chain is fundamental. Those of greater molecular mass act as
flocculants.
Polyacrylates are electrolytes and perform their deflocculating action according
to the rules typical of the deflocculant; the polymer anion is easily adsorbable by the
clayey particles, thus guaranteeing an exceptional dispersant action and excellent
stability over time.
Acrylic deflocculants appear to be better than traditional ones (silicate, carbon-
ate, NaOH, polyphosphates), seeming less sensitive to overdeflocculation and inter-
fering cations.
Their thermo-plastic nature, however, can make their employment difficult. Fig.
106 compares acrylic deflocculants with other deflocculants such as silicate and
sodium tripolyphosphate which alter the viscosity of a slip as a function of the
quantity introduced.

Polypropylate Na
Brookfield viscosity (epoises)

Acrylic RLP/4

Acrylic R727/S

Acrylic R747

Percentage of deflocculant

Fig. 106. Comparison of how various deflocculants, applied in different percentages, affect the viscosity
of a white tile body (by G. Malandrino).

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A powdery product consisting of a compatible mixture of organic and inorganic


fluidizers in quantities ranging from 0.16 to 0.22% is known to confer better bend-
ing strengths than those obtained with standard deflocculants such as NaTPP, one
of the most effective fluidizers for inorganic suspensions available.
It is, however, overly sensitive to small variations in water content and thus a
mixture of organic deflocculants having optimum ionicity characteristics so as to
obtain maximum stability of the dispersion has been proposed.

• Ammonium derivatives
Substituting NH3 (ammonia) with one or more organic radicals gives methy-
lamine (RNH4) and diethylamine etc. The amines are basic substances which disso-
ciate in water. Aliphatic amines are more dissociated in aqueous solutions than NH3
and are thus more basic. Aromatic amines are less basic.
Many substances such as ethyl amine, diethylamine, polyvinylammine and pip-
eridine are good deflocculants but are used only rarely.

• Oxalates
COOH
These derive from oxalic acid | which is quite a strong acid and can form
COOH
complex salts. Sodium and ammonium oxalate are used little as deflocculants: these
are both soluble in water, unlike the other oxalates which are insoluble.
Sodium and ammonium oxalate have the property of making the Ca2+ precipi-
tate completely. The oxalate anion may also be adsorbed by the surface of the clay
particles. These compounds are also used together with others having a higher
deflocculating power.

• Other substances
Other deflocculating substances worth remembering are the sodium salts of the
polymerised alchil-naphtalen-sulphonic (pH 8-10,5) acids, lithium citrate and the
sodium derivatives of carboxymethyl cellulose (CMC), an electrolyte with colloidal
anion (Fig. 107).

The CMC anion is irreversibly adsorbed at the surface of the mineral particles,
thus increasing their negative charge and dispersion capacity. The smaller the de-
gree of polymerisation, the greater the observed deflocculating effect.
CMC is used in ceramics as a binder while, however, bearing in minds its
deflocculating properties.

Main additive classes

Effects, advantages and disadvantages of practical use. Side effects


So far, then, we have seen that a correct rheological approach with regard to the

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Rheology: basic concepts

Cellulose

Caboxymethyl cellulose

Fig. 107. Cellulose and carboxymethyl cellulose (CMC) structural formula.

aqueous suspension systems used in ceramics is of great importance and the main
operative mechanisms of rheological additives have been illustrated.
As seen, rheological additives are used because it is necessary to work with aque-
ous suspensions of a high solid content; yet we must be able to modify and/or
maintain precise characteristics of viscosity, plasticity, thixotropy etc. vis-à-vis the
manner in which the solution will subsequently be used.
For this reason various classes of rheological additives have been defined as a
function of the role they play in the preparation and control of clayey bodies and
glazes.

Ceramic spray drying bodies

While costly, the technological process of wet-grinding raw materials in Alsing


ball mills and then spray drying the obtained slip is the best because it produces
bodies that are homogeneous, impurity-free and with the optimum granulometric
characteristics required for subsequent pressing and firing in rapid-cycle kilns.
This set of processes involves an enormous quantity of water (30-40% of the total
mass, reduced to 5-7% during spray drying). The use of rheological additives, which
in ceramics means deflocculants or fluidizers, is thus essentially linked to the need to
operate with as low a percentage of water as possible without compromising the
viscosity, plasticity etc. that will make emptying of the mills, in-tank holding, slow
stirring, sieving, pumping and spray drying practical. The criteria are thus economic-
productive: a reduction in the water content, other conditions remaining equal, re-
sults in a lower volume of water to be evaporated and greater plant productivity.

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Of coarse, the whole process also depends on other factors such as the grinding
time and the cost/performance ratio of the deflocculant.

The main body deflocculants, then, are:


1) sodium carbonate
2) sodium silicate
3) various sodium polyphosphates
4) natural organic compounds (humic acids and humates, tannins, ligninsulphona-
tes...)
5) synthetic organic compounds (polyacrylates, polymethacrylates and derivatives).

Already described in the preceding paragraphs, we shall now summarise their


main characteristics.

Sodium bicarbonate – used only rarely in spray drying bodies and only in those
bodies with very low plastic clayey fraction content (white body double firing) be-
cause of its low fluidizing effect.

Sodium silicate – a colloidal protector often used, for example, in sanitaryware


casting slips, together with sodium carbonate which shifts the calcium from the slip.
The effect of the sodium silicate is to “coat” the clayey micelles in mixes without
polyvalent ions; it is thus highly suitable for slips without organic colloidal-protec-
tors (i.e. those containing low-plasticity clays).

Natural organic products – used only very rarely.

Polyphosphates and polyacrylates – used extensively, especially sodium tripoly-


phosphate. Evaluating which product (or products) is the best is somewhat difficult.
In any case it is good practice to effect comparative industrial and laboratory tests
for each individual body, which has its own specific characteristics.

Side effects
Common to all deflocculants – not just those used in ceramic bodies – is the
phenomenon of over-deflocculation. This is an increase in apparent viscosity caused
by an excess of deflocculant. Organic products, where introduced into bodies where
a situation of compromise or risk already exists, tend to emphasize those “black
core” reduction phenomena caused by poor permeability or problems connected
with a firing curve that is unsuitable for oxidation. This tendency is much less marked
in synthetic products.

Another effect (this time a positive one) sometimes observed, although not yet
fully understood, is a possible increase in the unfired strength of the pressed items.
This is mainly connected with silicates or sodium polyphosphates.

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Rheology: basic concepts

Ceramic glazes

As seen, in the ceramic industry the use of rheological additives is not so much
governed by economic-productive aspects as by the absolute need to work with
suspensions having certain chemical-physical properties that are suitable for on-tile
application and compatible with different application technologies which often in-
volve machines with extremely different operating principles.
In this case, rather than sub-dividing the most commonly employed additives on
the basis of characterisation, they have been classified according to the effects they
produce:

RHEOLOGICAL ADDITIVES FOR GLAZES: 1) Deflocculants


2) Suspension agents
3) Glues (binders)

1) Deflocculants – the main effect these have on a glaze slip is to lower its appar-
ent viscosity. These products can be added at the grinding stage or on the glazing
line (the latter being suitable for liquid or easily soluble products only).
The main product classes are the already-seen ones of the sodium polyphosphates
(tripoly, tetrapoly...), the sodium or ammonia derivatives of polyacrylic or
polymetacrylic acid or copolymers of more complex structure.
The advantages of high density grinding (i.e. with a high percentage of solid)
are as follows:
– reduction of grinding times
– greater uniformity of particle size distribution
– better reproducibility
– greater versatility in subsequent applications.

These additives are used in varying percentages, depending on the efficiency of the
product and the desired effect: generally, percentages range from 0.03% to 0.4%.
Additions along the production line are mainly to correct viscosity to the specifica-
tion required by the application machinery and the aesthetic effects instantaneously.
Another (positive) effect sometimes observed, the mechanism of which has yet
to be fully understood, is a possible increase in the unfired strength of the glaze,
largely connected with utilisation of silicates and sodium polyphosphates.

Side effects
Can be summed up as follows:
a) glaze dries more slowly
b) improved spreading, especially with disc application
c) slower short-term sedimentation rates
d) formation of extremely tenacious sediments (or “cementing”) in the medium and
long term
e) reduced plasticity and thixotropy in high-density glaze suspensions where bell
application systems are used.

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Overdosing effects
a) viscosity too low and flow excessive: may cause irregular application (e.g. accu-
mulation at sides)
b) overdeflocculation.

SUSPENSION AGENTS form another category of rheological additive. These


act by way of electrostatic effects on the inter-atomic or inter-molecular bonds
where soluble salts in polar solvents (water) are concerned, or by increasing viscos-
ity (CMC) or the colloidal load in suspension. In any case, they have the effect of
reducing sedimentation rate: this, in turn, depends on a complex series of factors
such as the specific weight and particle size distribution of the suspended solids, the
density and viscosity of the slip and the presence of colloids.

The most commonly used products are:


– sodium chloride
– electrolyte mixes in solution
– cellulose derivatives (high-viscosity CMC)
– bentonite clays
– colloidal silica.

The final group of additives is the glues (binders). Certain glues are used in ceram-
ics as glaze adhesives. There are various types: methylcellulose, ether and ester
starches etc. Undoubtedly the most commonly used glues are the carboxymethyl
celluloses (CMC).
Use is made of their properties as binders, in that they improve the cohesion of
the unfired glaze particles and the adhesion of the latter to the tile body, as evapo-
ration regulators (they slow down evaporation of the liquid phase), and they im-
prove the spreading characteristics of the glazes.
Rheological effects strictly depend on the type of CMC used: a rough classifica-
tion, based on the viscosity of the solutions at 2%, can be made as follows:
low-viscosity CMC (between 5 and 50 mpa.s approx., where mpa.s = milli pascal ×
second)
medium-viscosity CMC (between 100 and 1000 mpa.s approx.)
high-viscosity CMC (between 1000 and 10,000 mpa.s and beyond)
The corresponding rheological effects, at standard usage percentages of 0.1-
0.6%, are:
– low-viscosity CMC – causes a slight drop in viscosity in the suspension and
tends to lead to “cementing”
– medium-viscosity CMC – limited effect on viscosity and a light suspending ef-
fect
– high-viscosity CMC – causes an increase in viscosity and has a high suspending
effect. Overdosing, of course, causes excessive increase in viscosity, extended
drying times, irregular absorption of the glaze by the body.

Some interesting rheological examples are given in Figs. 108-113.

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Rheology: basic concepts

Fig. 108. Rheological behaviour of a bell-applied double firing glaze: high viscosity (indicated by
graph gradient), zero yield point. (Curve obtained after stressing the fluid at the maximum value of D
for 1 minute).

without additive

Fig. 109. Effect of adding small quantities of sodium tripolyphosphate (NaTPP) and carboxymethyl
cellulose (CMC) to a glaze with high yield point. (Curve obtained after stressing the fluid at the maxi-
mum value of D for 1 minute).

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without additive

Fig. 110. Effect of adding high molecular weight CMC to a low-viscosity glaze. (Curve obtained after
stressing the fluid at the maximum value of D for 1 minute).

Fig. 111. Rheological behaviour of a disc-applied glaze. (Curve obtained after stressing the fluid at the
maximum value of D for 1 minute).

Kaolin

Without additive

Fig. 112. Effect of adding kaolin and bentonite to a glaze suspension.

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Rheology: basic concepts

Fig. 113. Effects on rheological properties of increasing the apparent density of a glaze: as density
increases there is a marked increase of all parameters: viscosity (gradient), thixotropy (area of hyster-
esis), yield point (shift from origin).

Glazes: non-rheological side effects

Effects of a non-rheological nature are linked to the presence of:


a) polyphosphates
b) sodium
c) chlorine
d) soluble salts
e) other non-volatile inorganic products (SiO2 , Al2 O3 ...)
f) various organic substances.

The effects may be catalogued as follows:


a) During firing the polyphosphates lead to the formation of P2O5 glasses, insolu-
ble in SiO2-based glasses: this may lead to the formation of micro-bubbles and
black specks.
b) The sodium becomes a part of the glasses, exerting a certain fluxing action and
giving rise to over-firing “pin holes”.
c) Thermal decomposition of chlorides may lead to formation of gaseous chlorine
which damages the rollers, metal parts and the kiln lining because of corrosive
condensation. Gaseous chlorine is also environmentally harmful.
d) Soluble salts give rise to the phenomenon of migration towards the tile sides,
especially during drying: localised staining, marking, pin-holing and bubbling
may result.
e) Any inorganic compound which is non-volatile at firing temperature becomes
part of the finishing glaze, thus contributing – to varying degrees – to the mo-
dification of its composition and alteration of its fusibility and surface aspect.

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f) Organic substances decompose under the effects of heating, giving rise to gase-
ous substances which exit via the glazed surface. If there is poor compatibility
between the quantity and quality of the organic substances and the firing cycle
there may be degassing and black speck problems.

The presence of certain organic products (starches, CMC and other cellulose
derivatives) also causes biological decomposition via micro-organisms (moulds, bac-
teria). This mostly occurs in solution. The main effect in a glaze slip is loss of
adhesive power, which immediately translates into pin-holing, dimples right across
the surface, and then micro-fractures and fissures on the sides.
This problem occurs with glazes containing CMC applied some few days after
grinding.
In truth, though, it should be noted that the rheological additives form only a
tiny proportion of total chemical auxiliaries, represented by silk-screen printing
products. The latter, in fact, are the main cause of fume filter clogging and in-
creased COD in waste waters etc.

Most commonly used additives

As far as the BODIES are concerned there is a widespread tendency for produc-
ers to use low-cost additives, even where they are less effective. Producers also tend
to invest little in new product research.
The most widely used product class is that of the fluidizer-deflocculant
polyphosphates. In particular, sodium tripolyphosphate is used extensively in quan-
tities of 0.2 - 0.4% (by dry raw material weight).

These salts exert an excellent chelating (“sequestering”) action on the polyva-


lent ions in the solution and their action is immediate and effective. Another impor-
tant advantage is the completely inorganic nature of the salt, which is unaffected by
pyrolitic phenomena during firing that can have undesirable effects on the ceramic
body (e.g. localised reductions where pieces have low permeability, “black core” etc.
and discharge emissions - condensation, fume depuration etc.).
Polyphosphates require a well-defined pH range in suspension, which they them-
selves help determine. This should be between 8 and 9, outside of which they are no
longer as effective because of changes in the electrostatic forces between the par-
ticles in suspension.
The main disadvantages of these additives are that they decay rapidly and soon
lose effectiveness. Furthermore, the rather difficult in-water solubility of sodium
tripolyphosphate may create non-homogeneous fluidity inside the mill.
The polyacrylates are another frequently used class of product; these are gener-
ally sodium or ammonia-based and have an extremely intense deflocculating action,
especially where added after grinding.

These are normally used in percentages of around 0.1%. Since they are perfectly

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Rheology: basic concepts

soluble (the products are commercialised in solution), their action is always well
distributed and stable over time.
The main disadvantages, though, are high costs and the fact that the polyacrylic
chain breaks up if added during grinding, thus reducing effectiveness. Further-
more, as they are organic compounds they are less suitable for addition to the body
as they produce, by pyrolysis, damaging reducer compounds and ammonia (or, gen-
erally, nitrogen-containing) salts which makes the lime in purification units mal-
odorous. If dosage is excessive their effects are irreversible but an increase of so-
dium and/or ammonium may create undesired effects.
Other additives which have been used or tested in a production context are hu-
mates etc., applied in percentages varying from 0.1 to 0.2%; while considered to be
highly active, they have very slow reaction times owing to their low solubility. This
can create serious problems at the mill before they are effective. While generally
inexpensive, these additives contain high percentages of carbon, with all its pos-
sible consequences.
Sodium silicate has the advantage of being very low cost, but its effectiveness is
not generalised and it does not exert a truly deflocculating action.
Overdosing can cause serious problems, and optimisation curves are very nar-
row indeed.

We shall now take a look at the additives used in the preparation of GLAZES. In
general it can be said that double firing glazes do not require any particular addi-
tives (sometimes suspension agents are used), single firing glazes always feature the
addition of glues and sometimes suspension agents, while monoporosa glazes gen-
erally require the addition of glue, fluidizer and sometimes a suspension agent.
Particle size distribution of the glaze itself (and thus mill load and grinding
media) plays a key role in glaze rheology as does solubility of the frits, which can
place cations of enormous rheological interference in the solution, with consequent
aging problems.
The fluidizers used in actual industrial production belong to the same categories
as those used in bodies.

One of the already-mentioned suspending electrostatic-action ionic compounds


is sodium chloride, normally used at 0.1-0.3%, which gives the glaze more “body”
and increases its viscosity. This prevents “dry dips” occurring as the glaze tends to
yield water more slowly. While its low cost is highly advantageous it should be
pointed out that the salt can tend to migrate to the sides of the tile, thus making the
unfired glaze layer more fragile (lateral scratches). It is hygroscopic and less effec-
tive than other similar-action salts, such as barium chloride, which also sequesters
undesired anions highly effectively.

There also exist specially produced combined-action salt mixtures with very
good storage properties.
Excessive dosing of these products results in excessive viscosity increases with
deleterious in-tank (“ricotta”) effects.

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Other often-used additives include clays and kaolins, normally introduced in


quantities of 2-4%. These aid application as they increase viscosity. In monoporosa
it is necessary to keep the frit grains separated, therefore the above-mentioned clays
are added as they carry finer particles which work their way in between the grains.
Adding excessive quantities of clays interferes with the quality of the opaque
and/or gloss aspect of the finished product.
Other special additives such as ethylendiaminictetracetic acid (EDTA) salts,
tetramethylammonia salts, various complexing agents etc. have no practical indus-
trial use, although their effects are studied and they are occasionally tested in an
industrial setting.

Summing up: optimum rheological characteristics in a ceramic body or glaze


suspension can be said to depend largely, for ceramic bodies, on the type and quan-
tity of the clayey materials, the employed grinding technology and accurate control
of additive optimisation curves.
With glazes, optimum rheological characteristics greatly depend on the applica-
tion method, the formulation of the glaze itself, the solid/liquid ratio and the qual-
ity/quantity of the additives used.

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Rheology: basic concepts

Chapter VII

THE REMOVAL OF WATER

The water-clay system and how it affects moulding

Plasticity allows a ceramic body to be moulded into a shape that will subse-
quently be fixed during firing. This plastic state may be seen as an intermediate
condition in which the material is neither a solid nor a viscous liquid.
Applying pressure to a liquid causes it to flow according to the limitations and
specifications described in the preceding chapters, yet applying pressure to a solid
generates no appreciable changes until the ultimate load is exceeded and the piece
breaks.
A body with plastic properties behaves in an intermediate manner, as is evident
in the case of extruded materials prepared from bodies with a high water content:
outflow speed is proportional to applied pressure and continues as long as that pres-
sure is applied, yet the material maintains its shape and cannot therefore be consid-
ered a liquid.
With “dry” pressed ceramic materials (with a moisture content of about 3-6%)
the body does not have plastic properties as such; nevertheless the mineralogical
composition of the components and water content are essential for good pressing
results. The very structure of the clayey minerals – crystallised “strips” separated
by well-defined gaps – allows the lattice sheets to slide against each other when the
interlayer water acts as a lubricant.
Plasticity in these semi-plastic systems depends, then, on the formation of a
film of water around each individual grain of material. The thickness of that
layer is crucial: if it is excessive a second layer of free water – which does not
interact with solid particles or cations in fracture zones – forms, generating a
different type of flow that is actually detrimental to the plasticity of the system.
On the other hand, insufficient quantities of water will cause the particles to touch
each other, generating attrition and destroying any plastic properties. System plas-
ticity thus depends on a certain equilibrium which, in turn, depends on water
content and wettable surface area.
The thickness of the film of water enveloping the clayey particles when plastic-
ity is at its height, while difficult to calculate, has been defined (for an applied pres-
sure of 8 Kg/cm2) as:

China Clay 2100 Å (1Å = 10-8 cm)


Ball Clay 2400
Bentonite 3400
Brick clay 3100
Clayey soils 700

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This “ideal” value can be significantly altered by innumerable factors, which, one
way or another, change the state of disturbance and electrostatic interaction be-
tween the water and the clayey particles. Such factors include:
– water content
– particle size distribution
– size, shape and structure of particles
– particle composition
– aggregation
– surface area and intermolecular attraction
– the effects of additives (including natural additives such as salts dispersed in the
raw materials)
– particle orientation.

Leaving aside an in-depth examination of the many methods used to measure


the plasticity of a ceramic system (most of which apply to extruded products), it
should be pointed out that a good indication of plasticity can be obtained from the
bending strength of the pressed material (green or dry). Thus a body with good
plastic qualities results in better pressing, higher compaction, higher apparent den-
sity and, finally, a higher bending strength (consequently, it will also be more diffi-
cult to dry).
Because of the low water content the pressing process is unable to bring about
all those preferential particle alignment phenomena seen in extruded products. The
compaction mechanism during pressing will largely be influenced by proper size
distribution of the particles and their extreme smallness, which allows almost all
the gaps to be filled: furthermore, the film of water lying between the particles
must have a consistency that sticks the latter together, thus aiding, among other
things, subsequent sintering reactions during firing.
It is also important that the material does not stick to the mould surfaces as a
result of one-way re-absorption of the film of water eliminated from the body at
the ceramic-metal or ceramic-rubber interface.
In particularly clay-rich bodies orientation phenomena may occur, with wa-
ter separating out onto planes perpendicular to the direction of pressing and
causing lamination, a possible cause of problems during drying or in-kiln pre-
firing.
Optimisation of these compaction processes through the use of isostatic presses
or punches is described in the chapter on ceramic products.

Removing the water

Water added to raw materials for refinement (e.g. production of pure kaolins),
purification or grinding purposes must subsequently be reduced to allow moul-
ding.

232
The removal of water

There are several methods:


– sedimentation (e.g. sludge clarification)
– centrifugal separation (little used in ceramics)
– filtration (e.g. filter-pressing in the manufacture of sanitaryware or tableware)
– electro-osmosis (e.g. in some types of glazing)
– evaporation (usually spray drying)
– selective absorption, on solid vehicles that absorb more water.

Independently of the need to eliminate water from a ceramic material suspen-


sions, in wet grinding, where the spray is slip-dried (see Vol. II on ceramic products)
– undoubtedly the process that removes the greatest quantity of water – it is impor-
tant that the production process leaves a certain amount of water in the body to
lubricate the particles during moulding and, because of the applied forces, produces
the preliminary, partial inter-particle adhesion that aids subsequent sintering pro-
cesses.
Extruded products are formed in a highly plastic state and thus the pre-forming
residual water content is necessarily high (15-25% by weight).
However, in so-called dry pressing – the most common tile production technique
– required water content varies as a function of required plasticity and is generally
much lower at just 3-6%.
Nevertheless, even this water will have to be eliminated, together with that ab-
sorbed by the pieces during decoration and glazing, before the tile enters the kiln.
Hence pre-firing drying is necessary.
Even though the amount of water to be evaporated is rather modest, the drying
phase is an extremely delicate one because of the ease with which fatal mechanical
stress can affect the still-inconsistent material.
Water, like all liquids (and, to a lesser extent, solids), has a tendency to become
gaseous, thus absorbing energy. Vapour emission does not continue indefinitely:
when the vapour reaches saturation point it ceases. An equilibrium is thus estab-
lished between the number of molecules that evaporate and the number of vapour
molecules that re-liquefy: this equilibrium corresponds to a certain pressure known
as saturated water vapour pressure. Water vapour pressure rises as temperature
rises.
When, as temperature increases, vapour pressure equals atmospheric pressure,
boiling occurs (i.e. the vapour escapes not just from the surface of the liquid but
from its interior too, forming bubbles).
Boiling point diminishes with pressure and every substance, at a certain tem-
perature, has its vapour pressure. Water (see Fig. 114) has a saturated vapour pres-
sure of 1 Atm at 100 °C.
The energies in play, then, taking into account that which is absorbed during the
liquid-vapour transformation phase, are often underestimated.

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Water vapour pressure

Atm p 105 Pa
Temperature °C
Fig. 114. Saturated water vapour pressure at different temperatures.

For example:

(1) Energy needed to increase the temperature of 80 g of clay containing 20 g


of H2O from 20 °C to 100 °C, eliminating the water by evaporation:

20 g H2O from 20 a 100 °C: m. Cs. ∆T = 20. 1. 80 = 1,600 calories


evaporate 20 g. H2O: m. L = 20. 540 = 10,800
80 g clay from 20 a 100 °C: m. Cs. ∆T = 80.0.2.80 = 1,280
________
13,680 calories

(2) Energy needed to increase the temperature of 80 g of clay from 100 °C to


1000 °C.

80 g of clay from 100 to 1000 °C: m. Cs. ∆T = 80. 0.2. 900 = 14,400 calories

Cs = specific heat (1 for H2O, 0.2 for clay)


L = latent evaporation heat

The above example illustrates that in a production process such as extrusion,


drying, although generally considered to be energetically modest, actually absorbs
almost as much heat as the firing process.

Drying can essentially be seen as a process conditioned by three factors:

234
The removal of water

Drying rate

time

Fig. 115. Variation of drying speed against time (according to Y.H. Perry, from A.G. Verduch).
Drying rate

Moisture

Fig. 116. Variation of drying speed against moisture content (according to Y.H. Perry, from A.G.
Verduch).

– the “drying power” of the work area, relative humidity, air speed
– forces acting at capillary level
– shrinkage caused by loss of moisture.

The drying process, then, involves transfer of heat from the surrounding envi-
ronment to the ceramic body and the simultaneous movement of water vapour in
the opposite direction. The heat (energy) needed for the former may reach the piece
via convection, radiation or conduction: normally, all three are involved.

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Applied Ceramic Technology

The most common effect of drying (by hot air convection) can be described by
the sequence:
– transfer of heat from air to piece
– transformation of water from liquid to vapour
– removal of vapour from surface of piece
– transport of liquid water from piece interior to the surface.

When surface evaporation speed exceeds internal capillary transfer capacity an-
other drying phase begins during which the evaporation front moves inside the
piece itself.
All this is usually represented by the classic description of a convection-type
drying process for porous and hygroscopic materials, according to a curve split into
at least three phases that are governed by different drying speed gradients at differ-
ent depths.

During the first drying phase water evaporation occurs as per the laws that gov-
ern evaporation from a body of water such as a lake, where a constant surface area
is in contact with an air flow of constant temperature and relative humidity: drying
speed is thus constant too.
During the second stage, drying speed decreases rapidly as the volume of water
evaporating from the surface has to be drawn from the interior of the piece by
capillary action: the rapidity with which this takes place will depend on the extent
to which the piece is heated and its dimensional variations (which influence the
vapour pressure of the fluid and thus its transfer speed).
As the evaporation front moves deeper and deeper into the piece, drying speed
falls as capillary resistance to diffusion increases: this resistance, of course, is in-
versely proportional to the size of the capillary ducts themselves. The smaller the
average diameter of the capillary the higher the resistance (according to the func-
tion x = k √ rt, where x is the speed of diffusion of the liquid, r is the capillary
radius, t is time and k is a constant that takes into account the surface tension and
viscosity of the liquid according to Poiseuille’s law).
As a rough guide, vapour pressure values for water as a function of capillary
diameter are given in the following table:

Radius (mm) Vapour pressure


5 10-5 0.1
7 10-5 0.2
12 10-5 0.4
48 10-5 0.8
105 10-5 0.9
209 10-5 0.95
558 10-5 0.98
1070 10-5 ≅ 10mm 0.99

236
The removal of water

According to Norton, the diffusion of water in the interior of the ceramic piece
is, then, a function of various parameters

dV k (U2 - U1) p
___ = ___________ dV/dt = flow rate of water through the piece
dt dη
U1-U2 = difference in moisture content between core
and surface
p = permeability of the ceramic body
d = distance from surface of interior point U2
η = water viscosity

in which the most representative variable of the choice of raw materials, techno-
logical process and characteristics of the ceramic piece is undoubtedly p (perme-
ability), greatly affected by particle size, plasticity and compaction etc.

Clays and ceramic bodies subject to drying, then, undergo consistent modifica-
tions in terms of shrinkage and weight loss caused by the evaporation of water.
Barellatographic analysis, employed to see just how these variations progress, yields
Bigot curves which illustrate the behaviour of the material in terms of shrinkage/
weight loss at a constant T, or other curves derived from these.
The drying process revealed by the barellatograph corresponds to theoretical
models put forward by Bourry (see Figs. 117 and 118). These diagrams represent
the percentages of body (by volume) occupied by clay, water and pores as a function
of drying time.
The ABC curve illustrates shrinkage: at time T1, for example, a body with an
initial volume of 100 consists of up of 56% clay + 15% water + 8% pores, and has
undergone a shrinkage of 21%.

Such curves, initially developed for extrusion technologies employing very slow
drying cycles (at ambient temperature and relative humidity), can also be traced –
making the appropriate modifications – for products of low water content subject
to extremely fast, high-temperature drying cycles.
As seen, one of the most significant factors affecting evaporation during the
drying of ceramic materials is the surface area of the material to be dried, which
influences the permeability of the material itself. Evaporation speed is also influ-
enced by hygrometric parameters in the drying area: a flow of dryer or completely
dry air is particularly effective in increasing evaporation during the first stage of
drying, while its influence will decrease at the capillary transfer stage as surface
evaporation comes to an end.
Once the critical humidity point is reached (point of inflection on Bigot curve),
the ceramic body assumes an almost-definitive consistency and rigidity and adapts
to tension less easily.
As shrinkage in the first stages of drying is much more marked than in subse-
quent stages, the resulting tension may lead to differential shrinkage, deformation

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Kaolin Montmorillonite

Shrinkage
Shrinkage

Water Pores
Volume (%)

Volume (%)
Water Pores

Clay
Clay

Hours Hours

Fig. 117. Drying or Bourry diagram for a kaolin and a montmorillonite.

Shrinkage

Water Pores
Volume (%)

Clay

Hours

Fig. 118. Bourry drying diagram.

238
The removal of water

or crazing when an excessive humidity gradient exists between the interior and
exterior of the ceramic body. The distribution of water around the particles and
the way in which the latter gather closer together as drying progresses are illus-
trated in the diagrams in Fig. 119.

The differing orientation of the clayey particles and the presence of differently
sized particles of other “hard” materials has, then, an enormous influence on dry-
ing. For example, clayey structures with a “playing card castle” configuration dry
faster than those arranged as a “deck of cards”. This is because the latter are more
compact and oppose greater resistance to evaporation.

Figure A – Before the start of drying the indi- Figure B – As soon as the surface water has evapo-
vidual particles are separated by a thin film of rated and water starts being drawn from the in-
water (grey area). terior by capillarity, the particles begin moving
and may start coming into contact with each other.

Figure C – Even after the second drying stage Figure D – In the final stages of drying tem-
significant quantities of water still remain be- peratures must exceed boiling point to remove any
tween the particles, in the pores. residue. At this point there is a partial collapse of
the particle structure.

Fig. 119. Structural rearrangements during following drying.

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Applied Ceramic Technology

Illustrating, then, what happens during the removal of water in terms of its
interaction with solid particles as opposed to its position in the piece, it can be said
that drying removes the water in pores or interstices, water adsorbed on the surface
of the mineral (especially clayey) particles or water introduced into their structural
interlayer.
None of these “types” of water form part of the crystalline structure of the
clayey minerals.
The drying (and plastic) properties of clays are mainly determined by the size
and shape of particles, by composition and structure, ionic exchange capacity,
exchangeable types of ion and, finally, by their current state of hydration. To
these intrinsic qualities must be added extrinsic ones such as spatial relations
between the particles, pore size and interstice size distribution, degree of com-
paction etc.
The water surrendered at modest temperatures – that which is neither part of
the crystalline structure nor attributable to the OH- hydroxyls in the composition
(the so-called “chemical water” expelled between 500 and 800 °C) – can be divided
into three categories:
– water in the pores, on the surface and at the edges of the particles
– interlayer water, between elementary clayey sheets (e.g. in smectites)
– water in structural channels (e.g. in zeolites).

Eliminating water of the first category requires low yet constant energy as seen
in Fig. 115 and thus relatively low temperatures (even ambient temperatures will do
where relative humidity is low). Temperatures in excess of 100 °C are used to accel-
erate the process and increase the thermal gradient between the interior and exte-
rior of the piece.
On the other hand, waters of the second and third category are eliminated with
lesser or greater difficulty as a function of various other parameters closely tied to
the texture and compaction of the materials. Interactions between clay and water
depend, in fact, on the physical and chemical reactivity of the surface of the clayey
mineral, where oxygen, hydroxyls and – in the fracture zones – other elements are
present; the distribution of these active sites determines the surface activity of the
clayey minerals (exchange capacity, ionic selectivity...); specific surface charge, sur-
face area and pH also play an important role.
Clayey minerals are not perfect crystals. On the one hand, they always have frac-
tured edges and consequent bond breaks that remain unsaturated. On the other
hand isomorphic atomic substitutions bring cations of different oxidation states
into play; these alter the natural electro-neutral structure of the crystal. These
factors, then, cause the solid particles to behave as if they were large, weakly (mostly
negatively) charged insoluble ions, as isomorph substitutions of insufficient charge
are more common.

These charged particles are, then, distributed in contact with and within the wa-
ter, which is, of course, “impure” (i.e. exempt from ionic charges due to saline
solubilisations).

240
The removal of water

All this contributes to further alteration of the structural arrangement of the


material and complication of water bonding phenomena. Consequently, the drying
release mechanism becomes more complex.

Thus far, we have examined concepts that regard drying by convection. Drying
processes that use only conduction are few and have little relevance here owing to
the poor thermal conductivity of ceramic materials. Yet the drying possibilities
offered by radiation are, instead, certainly worth a brief look as they offer the op-
tion of a more selective kind of drying that acts almost only on the water actually
contained in the piece.
These systems can accelerate the drying process significantly and are extremely
energy-efficient, using electromagnetic radiation at the infrared (IR) and micro-
wave (MW) wavelengths (see Fig. 120).

In both cases, since the majority of water in the piece is contained in its inner-
most layers and ceramic materials are virtually radiation-transparent, heating takes
place from within.
This is because it is the water which first transforms the radiation energy into
heat energy.
Of course, this also aids evacuation of vapour because, unlike convection heat-
ing, surface porosity is unaffected by structural shrinkages (except, perhaps, at the
end of drying). Infrared driers exploit the fact that water has an almost unitary
absorbance factor (0.92) for radiation of wavelength λ = 2.8 µm, and a still-excel-
lent absorbance factor (0.91) at λ = 5.95 µm (see Fig. 121).

At these wavelengths air is completely transparent and its presence becomes


irrelevant: yet in the context of drying, the fact that it does not heat up is a negative
one.
The water vapour generated by selective heating inside the piece is a negative
factor too, as it absorbs part of the incident radiation.
The ceramic body, depending on its composition, colour and degree of compac-
tion, will absorb a varying amount of the incident radiation and generally tends to
heat up.
These systems, which reached a peak of “popularity” in the 80s, have proved
highly successful, reducing drying times from the once standard 40-45 minutes to
12-15 minutes.
The main problem with such radiation systems is that power levels limit pen-
etration capacity, thus making it difficult to use them with particularly thick prod-
ucts where the bulk of the energy is absorbed by the surface of the piece.
However, no penetration problems exist where hyper-frequency 2450 MHz (122
mm) microwave radiation is used: this acts selectively on the water molecules thanks
to the selective absorption caused by the high dielectric constant of water, which
has a decidedly dipolar molecule.

The main obstacles to its use, especially in Italy, lie in the high cost of electricity

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Applied Ceramic Technology

Fig. 120. The electromagnetic spectrum.

(such hyper-frequency radiation cannot be generated from any other source) and
the difficulty of controlling the drying process effectively, as it tends to be too
rapid, thus causing the pieces to break. Moreover, the working life of microwave
generators (magnetrons) is relatively limited and their maintenance is somewhat
costly.

A description of the most commonly used drying systems employed by the ce-
ramic industry is given in the relevant section of Volume II of this work, which

242
The removal of water

Fig. 121. IR absorption of water as a function of wavelength.

focuses more on the ceramic products themselves. That section will also examine
the most important technological parameters for proper control of the drying pro-
cess, namely:
– temperature distribution
– contact surface area
– airflow
– vapour extraction.

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244
Description of ceramic products

Chapter VIII

DESCRIPTION OF CERAMIC PRODUCTS

Although we have now clarified the main characteristics of the individual raw
materials and stated how they are selected, combined and prepared, we have yet to
provide information on the most suitable combinations and mixtures for the pro-
duction of ceramic tiles, which cover a wide range of technological characteristics.
In fact, depending on the context in which they are used, tiles must have good-to-
excellent load, abrasion and stain resistance (floor tiles) or, where they are to form
regular geometric patterns, need to be sized extremely accurately (wall tiles). Tiles
may sometimes be laid outdoors where they are subject to freeze/thaw cycles or
extremes of heat and humidity where different absorption and long term reactivity
to water or humidity are required.
These characteristics are listed in the International Standards contained in the
Appendices at the end of this volume.
Two of the most important final properties required of a tile, whether glazed or
unglazed, are bending strength and good dimensional characteristics (size and flat-
ness), as illustrated in Fig. 122. Yet these properties, with limits and tolerances that
depend on the intended type of product, are not in themselves sufficient to define
the formulation of a good body.
There are, in fact, plenty of other conditions that need to be satisfied, such as: a
plasticity sufficient for moulding and unfired handling purposes, the ability to dry

PRIME
OTHER NECESSARY GOALS
GOALS
FINAL TILE DURING FINAL TILE
PROPERTIES MANUFACTURING PROCESS PROPERTIES
Unfired bending

Ease of drying

of black core

Good glaze
Rapid firing
Sizing and

expansion
Absence

moisture
Bending
strength

strength
flatness

Limited
cycles

match

Composition
Grinding
Pressing
Firing

Fig. 122. Factors determining ceramic tile body quality.

245
Applied Ceramic Technology

the material properly (and perhaps very rapidly), suitability for the firing process
etc.
Should manufacturers fail to meet these conditions the final product may suffer
from defects such as lamination, cracking, incompatibility with the glazed surface,
black core, post-expansion and so on.
Going back for a moment to bending strength, it should be pointed out that
products must meet minimum strengths as defined by relevant standards (Fig. 123);
to this end the ISO standard requires that not only Modulus of Rupture (MOR) but
also Breaking Strength be measured so as to ensure product bending strength inde-
pendent of thickness and size.
While, in fact, MOR is an intensive measurement that characterises the quality
of one material with respect to another, effective breaking strength indicates the
working behaviour of the specific piece.
To illustrate: a thin vitrified product has in any case a very high modulus, yet
the effective breaking load might actually be less than that of a standard-thick-
ness wall tile.
Another example that highlights the difference is the behaviour of unfired tiles
of identical thickness but differing sizes (e.g. 20 × 20 cm and 50 × 50 cm tiles): their
modulus will, of course, be the same, but the effective breaking load (and thus resis-
tance to stress on the production line) in the bending strength test will be much
lower for the larger tile.

This explains why finished product bending strength requisites set by Interna-
tional Standards establish minimum Modulus of Rupture from 15 N/mm2 (wall
tiles - class B III) up to 35 N/mm2 (stoneware - class B Ia), while minimum breaking
strength values range from 60 to 130 Kg.
MOR (kg/cm2)

Fig. 123. Bending strength requisites according to ISO standards (1 kg per cm2 ~ 0.1 N/mm2).

246
Description of ceramic products

Meeting these requisites is fairly easy, in that the same body can be used for more
than one product class; yet things become a little trickier when all the key proper-
ties of the tile are taken into consideration.

Above all, body behaviour during vitrification needs to be examined (Fig. 124):
vitrification curves (shrinkage and water absorption as a function of maximum fir-
ing temperature) for different product types [red (R) and white (B) body wall tile,
red (R) and white (B) body floor tile, porcelain tile (P)] show just how great the
differences can be.
% WA

wall red
wall white
floor red
floor white
porcelain tile

Fig. 124. Vitrification curves.

Wall tile bodies have high porosity within a fairly wide range at low-temperature
and then vitrify too rapidly to be used as flooring. A body intended for total vitrifi-
cation (water absorption = 0), such as stoneware, has, unlike standard glazed floor
tile bodies, wider stability at low porosities.
Such behaviour needs to be understood not only for production process
optimisation but can also be explained, forecast and modified as a function of the
chemical-physical characteristics of raw materials and body formulations.
As with porosity, shrinkage curves highlight an enormous diversity of behaviour
between the various bodies (Fig. 125).
The graph shows that white bodies are generally more stable than red, which are
more clayey and have a less balanced composition, in both vitreous and porous com-
positions.
As far as porous products (typical of wall tiling) are concerned, note the limited
shrinkage (< 1%) at low firing temperatures: this was once deemed necessary to
ensure maximum size uniformity.
Bending strength (Fig. 126) is, then, for the most part linked to processes that
take place during sintering.

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Applied Ceramic Technology

Shrinkage %

wall red
wall white
floor red
floor white
porcelain tile

Fig. 125. Shrinkage curves.


Bending strength

wall red
wall white
floor red
floor white
porcelain tile

Fig. 126. Bending strength curves.

Consequently higher strengths are seen for the red bodies. which tend to be
more vitreous, except for porcelain tiles, the composition of which is specifically
intended to develop the glassy phases.

Interpreting the behaviour of ceramic bodies

So far only those macroscopic factors that are usually monitored and controlled
during the production process have been considered. It is, though, possible to make
a more in-depth analysis of the structural modifications that take place in the mate-

248
Description of ceramic products

rials (especially during firing), thus allowing us to observe the root causes of the
phenomena illustrated above.
This more detailed examination highlights even sharper differences between the
compositional and behavioural differences of porous and vitrified bodies.
Starting with the former (Fig. 127), it can be seen how wall tile bodies are
characterised by an abundance of calcium and/or magnesium in the form of car-
bonates that decompose at temperatures above 800 °C, freeing the corresponding
oxides.
These oxides subsequently react with the rest of the ceramic matrix to form (at
relatively low temperatures) new crystalline compounds, Ca and Mg silica-alumi-
nates that provide a certain firing stability and develop bending strength before
giving rise to an uncontrollable fusion.
The numerous crystallines that can be created by a CaO - Al2 O3 - SiO2 system
are shown in the tertiary diagram in Fig. 128. Note the formation of gehlenite,
pseudo-wollastonite and anorthite, which, together, can lead to marked lowering
of melting points, thus fuelling further reactions via the formation of liquid
phases.

The following table (Fig. 129) shows some of the properties of the crystalline
compounds already in both the original compositions and the neo-formed composi-

% WA
Shrinkage
MOR

Decomposition
Degassing through glaze
of carbonates Presence
Tendency towards post-expansion
of free CaO
Increased bending strength
Dimensional stability
Increased shrinkage
Formation of Deformation
crystalline phases:
Gehlenite Uncontrolled
Uncontrolled
Diopside formation
formation of
of
Wollastonite glassy
glass phases
Anorthite phase

Fig. 127. Wall tiles: the symbols correspond to A.A. (water absorption), MOR (bending strength) and
shrinkage.

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Applied Ceramic Technology

Fig. 128. Tertiary diagram for calcium silica-aluminates.

Compound (10-7/°C) T (°C)


fusion

Quartz

Albite

Orthoclase

Anorthite

Gehlenite

p-Wollastonite

Diopside

Forsterite

Spinel

Mullite

Fig. 129. Expansion coefficients and melting points for crystalline compounds existing or formed in the
bodies.

250
Description of ceramic products

tions (i.e. those formed during firing); these take part in the firing process and influ-
ence the final structural properties of the products. Note the generally high expan-
sion coefficients of the new compounds containing calcium and magnesium which
serve to inhibit shrinkage.

Theoretical melting points for pure compounds are, however, very high and their
formation from solid-solid or solid-liquid reactions is thus difficult: therefore the
percentages detected in fired products (especially where rapid firing cycles are used)
are generally low.
This is particularly true for mullite, which is unlikely to form even at very high
maximum firing temperatures. XRD analysis of fired wall tile powders (Fig. 130)
still show, however, significant traces of crystallinity of starting minerals, espe-
cially quartz, and partial formation of neo-phases (e.g. Diopside).

Where a composition has an incorrect balance of components of poor particle


size distribution the firing cycle may be too fast to allow stable crystalline phases to
develop. Though this structure may be frozen in a meta stable phase it will still
survive for the lifetime of the product.
If, for example, we consider the formation mechanisms of a vitrified product,
based on the fluxing action of sodium and potassium compounds, it can be seen
that, compared to wall tiles based on calcium-magnesium systems, reaction tem-
peratures shift to a higher level: the low-temperature mechanical characteristics of
vitrified products are therefore generally poorer than porous ones.

Fig. 130. X-ray diffraction analysis of wall tile body (Q= quartz, C= neo-formed comp.).

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Applied Ceramic Technology

Moreover, intermediate neo-formed compounds that start developing in an as-


yet insufficiently bonded matrix result in under-fired vitreous bodies that tend to
have higher moisture expansion than porous wall tiles. Consequently they are un-
suitable for use as wall tiles, even where there are no particular final product shrink-
age – and thus size – requirements.
The expansion curve for an unfired vitreous body (Fig. 131) highlights, in addi-
tion to the α - β quartz transition, a relatively gradual vitrification process: opti-
mum firing temperature is clearly identifiable via the derivative of the expansion/
shrinkage curve which peaks where the shrinkage is fastest. At this temperature
vitrification takes place extremely quickly: use of higher temperatures not only
wastes energy but can also give rise to less dense structures owing to the onset of
expansion (Fig. 132).

The Na2O - K2O - Al2O3 - SiO2 tertiary diagram (Fig. 133) for sodium silicates,
potassium silicates and silica, shows how, in certain compositional fields, the devel-
opment of a liquid phase at decidedly low temperatures is possible (1118 °C for
sodium feldspar, 1150 °C for potassium feldspar). The tertiary diagrams refer, of
course, to systems in thermodynamic equilibrium and do not provide any informa-
tion on reaction speeds and necessary vitrification time which, especially in fast
firing cycles, must be brief.

Fig. 131. Expansion curve for a wall tile body.

252
Description of ceramic products

Absorption
Shrinkage
MOR

Phase transformations:
Metakaolin-spinel
Partial crystallite destruction Increased bending strength
(albite, orthoclase, quartz) Increased frost resistance,
Reduced permeability, shrinkage
Formation of
Deformation
glassy phase
Increased bending strength
Formation of new
crystallites (mullite)

Fig. 132. Totally vitrifiable bodies (for symbols Absorption and MOR see fig. 127).

Fig. 133. Tertiary diagram for sodium-potassium feldspars.

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Applied Ceramic Technology

However, the reaction speeds of solid state compounds depends greatly on the
available surface area and, therefore, particle-size distribution. Completion of a crys-
talline solid particle reaction is unlikely inside a ceramic body. Yet it is possible for
reactions, mostly of the “cementing” type, to take place between the individual grains
aided by imperfections in the crystalline lattices and impurities, which, even in small
quantities can act as catalysts or give rise to low-fluxing eutectics (the same quan-
tity of material, at a density of, for example, 2.5 g/cm3, has a reaction area of 24
cm2/g where its average particle diameter is 1 mm; if this size is reduced to 50 µm,
the reaction area increases to 480 cm2/g).

Taking into consideration all the above factors and arguments and, most impor-
tantly, production needs, plant limitations, market demand, the availability of suit-
able raw materials and their cost, producers need to decide which type of ceramic
tile to manufacture. There are, in essence, three main product classes:

WALL TILES FLOOR TILES

PORCELAIN TILES

ACCESSORIES AND TRIMS

254
Description of ceramic products

Chapter IX

WALL TILES

Introduction
Tiles were one of the earliest man-made “technological” materials.
From the very start they provided hygiene and fulfilled artistic and decorative
functions as well.
One of the oldest examples of glazed tiling is to be found on the Ishtar gate of
the Babylonian king Nebuchadnezzar II (575 B.C.), a restored version of which is
now on show in the Pergamon museum of Berlin.
Then there are the palaces of Nimroud and Khosabab, those of Cyrus, Darius,
Xerxes, several monuments in India, China and Turkey. The ceramic tile, then, has
been with us throughout nearly all human history.
In Italy, tiles were first manufactured during the Middle Ages, absorbing Arab
and other influences.
From these tentative beginnings came modern ceramics with its well-defined,
standardised products such as majolica, cottoforte, earthenware, gres, etc.
In Italy, the ceramics industry took off in the post-war reconstruction period of
the 1950s, with the manufacture of red gres and majolica and the advent of
“cottoforte”, a classic Italian product made using double firing techniques. It was
also during the 50s that ceramics was transformed from a network of small-scale
workshops into a true industry.
The technical dynamism of the industry proved decisive in promoting continu-
ous evolution of processes and materials.
The result was a shift from traditional double firing to fast double/single firing.
Tiles also became larger and their aesthetic/decorative effects were constantly up-
graded.
Most of these developments have taken place over the last twenty years, stem-
ming from experience in single fired floor tile products.
During the ’70-80s the fast firing process, as far as wall tiles were concerned,
focussed almost entirely on glazed tiles and was initially a simplification of tradi-
tional tunnel firing systems using refractory saggers on cars.
Later, during the energy crisis at the beginning of the ’80s the single firing
process was developed and adopted for porous body tiles too.
Single and double fast firing technology quickly became commonplace all over
the globe. Its spread has been (and is) dependent on a number of factors: local
levels of technical and professional skill, energy costs, labour costs and cultural
traits.

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Applied Ceramic Technology

The market
Figure 134 compares the evolution of the Italian market for double firing and
monoporosa wall tiles from 1990 to 1998. Note the slight fall off in double firing
output in 1993, followed by a more positive trend which lasted until 1998, stabilis-
ing at about 85 million m2 in the period 1996-97-98.
Monoporosa, however, showed a constant upward trend from 1991 onwards,
reaching a peak of 48 million m2 in 1995. The graph in Figure 135 shows percent-
ages of output accounted for by single and double firing respectively against the
total quantity of wall tiles.

Product classification
General wall tile classification includes products obtained by both double and
single firing.
International ISO UNI EN 13006 classifies ceramic tiles into several groups on
the basis of their forming method and finished product water absorption (see Fig.
137).
On the basis of current ISO 13006 standards, porous wall tiles are included in
the group

B III Absorption > 10%

Fig. 134. Evolution of Italian monoporosa and double firing output from 1991 to 1998 (millions of
square metres – source: Ceramic World Review n. 32/99).

256
Wall tiles

Fig. 135. Percentage of total wall tile out-


put accounted for by single and double firing
products (source: Ceramic World Review n.
32/99). Note: the term double firing includes
all materials obtained with two fires wheth-
er fast or traditional).

Fig. 136. Shows output increases in percent-


age terms for both double firing and mo-
noporosa with respect to 1991.

Water absorption
Shaping

GROUP Old EN GROUP Old EN GROUP Old EN GROUP Old EN


I IIA IIB III
≤ 3% 3% - 6% 6% - 10% > 10%

extrusion GROUP EN 121 GROUP EN 186/1 GROUP EN 187/1 GROUP EN 188


A1 AIIa1 AIIb1 AIII

GROUP EN 186/2 GROUP EN 187/2


AIIa2 AIIb2

GROUP
dry pressing BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
≤ 0.5% BIIa BIIb BIII

GROUP
BIb
Bib
0.5% - 3%

Fig. 137. Classification of tiles according to ISO 13006.

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Technical features
Wall tiles generally have the following characteristics:
– high dimensional stability during firing, with almost no shrinkage (less than
1%)
– porosity between 13% and 18% (expressed as percentage of water absorbed)
– MOR between 200 and 250 kg/cm2.

These properties are only indicative, mainly helping us to classify the product
from a commercial viewpoint that takes into account its field of use.
The specifications provided for under ISO 10545.1 - 17, group BIII, include the
dimensional, physical and ceramic properties of the products.
Fig. 138 charts these last two, without taking size into account.
For more realistic comparison purposes the table shows, in addition to the values
defined by the standards, some characteristics of products actually available on the
market.
Any description of wall tiles must necessarily include the types and characteris-
tics of the glazes used in the new fast firing technologies. It should also be observed
that, as far as surface aesthetics (i.e. glazes) are concerned, the use of such technolo-
gies has neither modified nor materially improved the final results, since aesthetic
quality was already very high. Transparent (crystalline) glasses and opaque glazes
(mainly white), both of which are glossy, remain the most popular glaze bases to
this day.
While glazes have evolved to suit different firing technologies (traditional, dou-
ble fast, monoporosa), their technical performance in terms of resistance to stain-
ing, chemical agents and abrasion have remained largely unchanged. In the case of
white and crystalline glazes, the limitations – and the potential – provided by the
new technologies have required new frit and glaze formulations, with a shift from
“viscous low-fluxing” materials to “high-fluxing” compounds with eutectic melting.
This evolution in composition has affected both double fast firing and monoporosa
glazes.

Aesthetic features

Size
During the ’60-70s, traditional firing processes mainly offered 15 × 15 and 20 ×
20 cm tiles. With the introduction of fast double firing and porous single firing
(monoporosa), tile size increased to 25 × 33, 33 × 45 and in certain cases 40 × 60 cm
– and beyond.
The most common sizes, however, are those in the middle of the range: 20 × 20,
20 × 25, 25 × 33 cm etc.
Large tile production is much more limited but now increasing rapidly, such tiles
no longer being seen as just niche products. Such large tiles generally require sin-

258
Wall tiles

FEATURES STANDARD MAXIMUM STANDARD- REAL VALUE


PRESCRIBED VALUE OF MARKETED PRODUCTS

WATER ASSORBATION ISO 10545.3 >10 ,< 20% - min. 9% 13 - 18%

MODULUS OF RUPTURE (MOR)* ISO 10545.4 12 - 15 N/mm2 > 20 N/mm2


BREAKING STRENGTH* ISO 10545.4 min 600 - min 200 N min 700 - min 300 N
ABRASION RESISTANCE** ISO 10545.6/.7 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER
EXPANSION COEFFICIENT ISO 10545.8 TEST AVAILABLE 6,5 - 7,5 . 10 -6
THERMAL SHOCK RESISTANCE ISO 10545.9 TEST AVAILABLE CONFORME

MOISTURE EXPANSION ISO 10545.10 TEST AVAILABLE < 0.06 mm/mt


CRAZING RESISTANCE ISO 10545.11 REQUIRED MEETS SPECIFICATIONS
FROST RESISTANCE ISO 10545.12 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER
RESISTANCE TO HOUSEHOLD CHEMICALS ISO 10545.13 CLASS GB min CLASS GB min
RESISTANCE TO ACIDS AND ALKALIS ISO 10545.13 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER

RESISTANCE TO STAINING ISO 10545.14 CLASS 3 min CLASS 3 min


Pb AND Cd LEACHING ISO 10545.15 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER
COLOUR DIFFERENCE ISO 10545.16 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER
FRICTION COEFFICIENT** ISO 10545.17 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER

Standards 10545.1 and 10545.2 are not shown in the table owing to limited space. Nevertheless, the reader is reminded that they
contain sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (< 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving.
For more detailed information see UNI publications (Italy).

Fig. 138. Technical characteristics of porous wall tiles according to ISO standards.

gle-layer kilns and the advanced automation/ handling systems now available on
new fast-firing plants.

Trims
Special pieces, considered complementary to standard tile production, have gained
much ground in recent years. These pieces feature relief work obtained by pressing
(inserts, festoons, bull-nose pieces etc.). Production of such items is generally
outsourced to other companies and they are made using a glazing process followed
by decoration and third firing.
Moreover, there is also an increasing demand, especially in American and Asian
countries, for trims acting as a “technical complement”: these are used to finish
outside or inside corners or frame the perimeter of a tile-covered surface. Generally
speaking, these pieces are obtained using presses of limited power and special dies.
They are normally double-fired. In most cases, biscuit pieces are covered with stand-
ard glazes.

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Applied Ceramic Technology

Surface appearance
Traditionally, wall tiles have always been glossy. Consequently, glazes are gener-
ally transparent (crystalline) or opaque (basically white), rarely matt.
In the ’60-70s, in traditional firing, frits with a high content of lead, boron and
cerium were used to obtain such decorative effects as “torn”, “reactive”, “mother-of-
pearl”, etc.
From a ceramic viewpoint, the effects were fascinating, yet their resistance to
abrasion and chemical aggression was very limited. The adoption of new formula-
tions and the partial replacement of lead with other fluxes has now provided manu-
facturers with crystallines and glazes on a par with their predecessors but better
suited to the new technologies.
Recently, the influence of developments in architecture and interior design has
given rise to new effects known as “antiqued”, which mimic aged plaster, chalky
surfaces, etc. and are sometimes highlighted by special elements built into the tile,
such as structured surfaces or intentional chipping around the edge.
The bulk of production, though, still uses glossy-effect glazes, enriched by decors
that take their cue from natural stones such as marble and breccia etc.

Raw materials for bodies

General features
In recent years wall tile compositions have evolved considerably, mainly to adapt
to fast firing cycles where body and glaze are fired together.
With monoporosa there may be interference between the degassing of certain
raw materials in the biscuit and the molten glass: this can lead to surface defects on
the glaze.
The key factors in the evolution of body compositions – from those suited to
traditional firing, then fast double firing and finally porous single firing – have
been:
– reduction of clayey material percentages
– introduction of higher percentages of fillers and complementary raw materials
(feldspars, feldspathic sands, quartz)
– limitation of minerals which give off gaseous phases at high firing temperatures
(calcite and/or dolomite), especially in monoporosa.

In pursuing these goals it has been possible to employ tried and tested materials
by changing the quantitative composition.
In the case of monoporosa, it is preferable to use raw materials with a high
degree of purity and a fine particle size distribution.
Generally speaking, finished wall cladding products must have a high degree of
size stability.

260
Wall tiles

The formation of crystalline compounds, such as wollastonite, gehlenite, anorthite


and diopside, not only guarantees that stability: they also condition and stabilise
other features, such as post-expansion and expansion coefficient, etc.

Characteristics of raw materials for bodies

According to commercial classification, wall tiles can be divided into “red” and
“white”. In both cases, the raw materials are of two basic types:
– clayey materials
– complementary materials (feldspars, feldspathic sands, quartzes, calcites).

Figure 139 shows the chemical-physical features of the raw materials most com-
monly used in bodies for both fast double firing and monoporosa.
Some notes about the overall nature and mineralogical features of these materi-
als follow.

Plastic raw materials

Marl-carbonitic clays: mineralogical associations may be of the illite-chlorite or


sometimes illite-kaolinitic type (the latter in lesser quantities). The quantity of cal-
cite in the clayey matrix varies and is sometimes considerable. These clays give the
body plasticity. Generally speaking, after firing they take on a beige-orange colour
due to the presence of ferrous minerals.
Vitrifiable plastic red firing clays: almost entirely carbonate-free. Clayey minerals
may be associated with illite-chlorite types.
Their function is to confer plasticity on the system, making it possible to achieve
good breaking load values on green, dry and fired pieces too, since they are gener-
ally vitrifying materials.
Ball-clays: generally white firing. The clayey matrix is of a kaolin type, with
little illite. Particle size distribution is generally fine, so good plastic behaviour can
be expected. Post-firing bending strength and porosity are extremely good.
Kaolin-type china-clays: behaviour is generally refractory; the limited plasticity is
basically due to the intrinsic particle size distribution of the material.
Carbonitic and/or vitrifiable clays are evidently used to achieve a beige-orange
biscuit, whereas ball-clays and china-clays are used for white biscuits.

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Applied Ceramic Technology

1 1 2 3 4
3
4 2

3
1
2

3
1
2

Key: A - semi-plastic clays, B – plastic clays, C – plastic clays, D – kaolinit-


1 ic clays, E – feldspathic sands, F – quartz, G – calcium carbonate.
3
2

3
PHYSICAL FEATURES A B C D

1
2 BREAKING LOAD BEFORE DRYING kg/cm2 6/8 8/10 10/15 4/6
4
BREAKING LOAD AFTER DRYING kg/cm2 15/20 20/30 25/40 10/15
3 4
1
FIRING AT 1100 °C A B C D
2
POROSITY % 8/12 2/6 5/10 15/20
12
SHRINKAGE % 2/3 4/6 3/5 2/4

3 BREAKING LOAD AFTER FIRING kg/cm2 180/200 200/300 200/300 80/120

Fig. 139. Chemical and physical characteristics of different raw materials suitable for the production
of porous products, especially monoporosa for indoor tiles.

262
Wall tiles

Complementary raw materials

Feldspathic sands, feldspars and quartz: introduced into the composition as fillers
and/or sandy non-plastic materials to facilitate effusion of the volatile compounds
which escape during firing. Potassium feldspars are preferred as they are less reac-
tive than the sodium kind.
Feldspars also help lower the overall expansion coefficient of the ceramic body.
Quartz also plays a key role in adjusting the expansion coefficient (the latter in-
creases proportionally to the quantity present).
Given the rather coarse particle size distribution and the fast firing cycle, reac-
tivity of free quartz against alkaline-earth oxides (CaO and MgO) is thought to be
limited.
Calcite and/or dolomite: fundamental materials for wall tile bodies. In-body per-
centages range from 8% to 15%.
Their natural and post-grinding particle size distribution is particularly impor-
tant. In fact, very fine particle size distributions favour both decarbonation reac-
tions and, at a later stage, synthesis reactions with “residuals” of the clayey materi-
als (especially amorphous silica), thus allowing formation of transparent neo-formed
compounds (over 900 °C).
Of special importance are the kinetics of decarbonation and thus the kinetics of
gas (CO2) emission before “softening” of the surface glass (glaze) takes place.
The evolution and completion of synthesis reactions between silica, alkaline-
earth oxides and alumina play a key role in defining the physical and mechanical
features of the ceramic piece after firing (bending strength, expansion coefficient,
etc.).
It is evident that the quantitative ratio of clayey materials, calcite, feldspars,
quartz etc. depend on the intrinsic mineralogical nature and particle size distribu-
tion of the clays.
As a rough guide, Fig. 140 illustrates both a monoporosa (red and white fired
colour) and a fast double firing composition.

Body composition

As stated above, wall tiles can be obtained by double or single firing, and always
using fast cycles. Furthermore, body composition may aim to produce white or red
firing products. The latter mainly consist of varyingly carbonatic clays with a high
iron content. Other components may include feldspathic sands, feldspars, quartzites
and – if necessary – calcites and/or dolomites.
White firing bodies, on the other hand, use more balanced mixes of light col-
oured clays, calcite, feldspathic sands and quartz.
The most significant difference between white and red compositions lies in the
quantity and typology of clay used, whereas the most significant percentage differ-
ence between double and single-fired bodies is that the former may have high per-

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Applied Ceramic Technology

Fig. 140. Possible compositions for porous single firing (red and white) and double firing bodies.

centages of calcite and/or dolomite, even as high as 15-18% and, in certain cases,
raw materials with a slightly lower degree of purity may be used.
Figure 141 shows examples of different body compositions for porous single
firing and fast double firing, red and white firing respectively. In addition to com-
pound formulations (i.e. formulations obtained by mixing raw materials), the chart
also shows a clay-only body formulation.
This kind of composition is used more frequently in the case of fast red double
firing and is quite widespread in zones which have access to “mixed” clayey materi-
als which already include the various complementary minerals. Figure 141 also
shows the (CaO-MgO) - SiO2 - Al2O3 tertiary diagram for the formulations in the
previous figure. Three specific body compositions are highlighted; two of them are

264
Wall tiles

TIPOLOGIA - TYPOLOGY SiO2 Al2O3 TiO2 Fe2O3 CaO MgO K2O Na2O P.F.
Monoporosa 65.38 12.89 0.29 0.53 7.00 1.26 0.72 0.19 11.69
Monoporosa 61.42 14.08 1.18 1.22 7.40 0.99 2.06 0.17 10.96
Monoporosa rossa - Red monoporosa 56.10 15.12 0.91 3.79 7.80 1.40 1.25 0.90 12.89
Monoporosa rossa - Red monoporosa 54.76 15.98 0.90 4.88 8.10 0.77 2.37 0.99 11.31
Monoporosa rossa - Red monoporosa 65.99 18.9 0.70 3.04 0.80 0.56 1.72 4.67 3.62
Monoporosa 60.26 16.34 0.76 1.16 7.60 0.42 2.23 0.59 10.78
Monoporosa 69.36 12.30 0.50 0.59 5.70 0.29 3.47 0.23 7.37
Bicottura - double fired 60.31 13.40 0.57 1.95 9.35 0.31 1.17 0.25 12.82
Bicottura - double fired 61.29 11.45 0.68 2.85 5.92 2.61 2.39 2.03 10.76
Bicottura - double fired 59.37 11.58 0.63 4.56 5.78 3.13 2.49 2.04 10.44
Bicottura - double fired 63.12 12.68 0.52 4.51 6.06 0.79 2.71 0.42 8.51
Bicottura - double fired 65.80 13.77 0.89 1.56 5.82 0.6 1.41 1.86 8.29

CaO+MgO

Fast firing
Bicottura - Fast firing
Monoporosa
Monoporosa
Monoporosa rossa - Red monoporosa
Red monoporosa

SiO2 Al2O3
CD.0110
Fig. 141. Composition areas in the (CaO+MgO) - SiO2 - Al2O3 tertiary system relevant to the above-
described body composition for monoporosa and fast double firing.

for white and red monoporosa, whereas the third is a special combination obtained
only with double firing clayey material.

Product features

The final features of a ceramic wall tile are heavily influenced by newly formed
compounds which develop during firing.
These are created by the reactivity of calcium and magnesium oxides which
originate, respectively, from the destruction of the calcite and/or dolomite lattices
during firing, with the silica and alumina originating from the destruction of the

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Applied Ceramic Technology

clayey lattice. These newly formed compounds are gehlenite, diopside, anorthite
and wollastonite.
Features such as bending strength, expansion coefficient, moisture expansion
etc. depend on the quantity and quality of these compounds.
In fast firing cycles the tendency towards synthesis of new compounds, start-
ing with phases of varying reactivity, largely depends on the natural particle size
distribution of the materials and the degree of grinding that follows.
The pattern of decomposition and synthesis reactions which take place during
fast firing of a monoporosa body is shown in Figure 142: this diagram shows the
dynamics of original mineral decomposition and the formation of new compounds.

Figure 143 shows X-ray diffraction patterns for different firing temperatures.
Note that at 900 °C dolomite has almost entirely disappeared, yet the first crystal-
lisation embryos – attributable to diopside and gehlenite – have appeared. The
latter tend to increase up to a temperature of 1140 °C.

Raw materials for glazes

The most frequently used glazes are glossy, either transparent (crystalline) or
opaque (basically white).
These glazes use different frits depending on how they are to be used (i.e.
traditional or fast double firing or monoporosa).
Frits generally account for 90-95% of the glaze.
Small quantities (5-10%) of plastic materials such as china and ball clay, as
well as organic additives which adjust rheological features and adhesion to the
biscuit are used too.

Traditional double firing


Initially (in the ’60 and ’70s), these glazes used frits with a high lead content,
such as lead silicates, and boron.
Gradually, these fluxes were replaced by others of alkali and alkaline-boron
type.
Opaque glazes had the same glassy matrix as transparent ones, plus a zirconium
silicate content of between 8% and 12%. The softening point of these frits was very
low (750-850 °C), whereas the firing temperature was around 950 °C.

Fast double firing


Glazes suitable for the 30-50 minute firing cycles used in this technology have
very short glass maturing times (2-4 minutes). Therefore the frits have moderate
softening points and low melting viscosity at maximum firing temperature (about
1050-1100 °C).

266
Wall tiles

Fig. 142. Firing decomposition/synthesis reactions for a monoporosa body.

*103
1.50 1.50

1140°C
1100°C
0.75 0.75

900°C

*103 650°C
3.50 0.00 0.00
22.00 32.00 42.00 52.00

1.75 1140°C
1100°C

900°C

0.00 650°C
2.00 22.00 42.00 62.00 2θ

Fig. 143. Monoporosa body XRD analysis at different firing temperatures.

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Applied Ceramic Technology

To achieve these goals, alkaline-boron fluxes are used in most cases. To further
optimise viscosity at peak firing temperature, the latest frits include high quanti-
ties of CaO and ZnO in their formulation, mainly at the expense of Na oxide.

Monoporosa
The need for carbonate minerals in wall tile body compounds (useful for intro-
ducing calcium and magnesium oxide) has resulted in considerable technological
problems in finding appropriate glazes for porous single firing.
Gas (CO2) emissions from the calcite and/or dolomite within a temperature
range of 750-950 °C (the maturing zone of traditional glazes) was one of the
main problems in perfecting this process.
The need for glaze softening temperatures higher than 950 °C made it neces-
sary to use new high-temperature fluxing formulations, based on eutectic melting
compounds.
This was made possible by reducing the quantity of oxides such as B2O3 and
Na2O and introducing CaO, MgO, ZnO and K2O as active elements in order to
bring about high temperature “eutectic fusion”.
To clarify this behaviour, Figure 144 shows heating microscope softening graphs
for two frit samples “A” and “B”. Sample “A” is a glaze for traditional double firing
which softens about 60-70 °C earlier than “B”. Sample “A” is clearly unsuited to
porous single firing because of its tendency to seal the surface too soon, trapping
gases in the body.
Figure 144 also shows the different chemical compositions for frits “A” and “B”,
used in traditional double firing and in porous single firing respectively.

Besides softening points, other important factors useful in defining the firing
behaviour of a monoporosa frit include: surface tension and hot viscosity of the
glaze.
Low surface tension helps to eliminate any gas bubbles in the glaze during
firing.
Low hot viscosity values, on the other hand, favour better glaze application
and also improve the smooth covering of the surfaces it comes into contact with
(engobe and/or body).
In addition to reactivity with the engobe and/or the body, glaze expansion
coefficient is also of great importance. A good expansion match with body and
engobe is essential to control tile curvature.

Engobes
An engobe is a partially glassy composition usually applied on the body. It is
virtually indispensable on monoporosa products and certainly advisable on dou-
ble firing ones and serves the following purposes:
– inhibits any reactions of the glaze with chromophore impurities in the body

268
Wall tiles

A B
A
SiO2 55/56 53/55
Al2O3 7/8 8/9
20°C 840°C 960°C 1050°C 1260°C B 2O 3 12/13 8/9
CaO 2/3 7/9
MgO 0.5/1.5 2/4
Na2O 6.5/7.5 -
K2 O 2/3 3/5
B
ZnO 1/2 9/10
20°C 940°C 1020°C 1060°C 1210°C ZrO2 8/9 5/6

Fig. 144. Softening graphs under “Leitz” heating microscope: two frit samples of different softening
points.

– improves the expansion match between body and glaze


– cuts applied glaze costs, as its use makes it possible to apply lower glaze wei-
ghts.

The engobes normally used for monoporosa and double fast firing consist of a
percentage of frits (30-40%), ball-clays, zirconium silicate and sometimes feldspar
and quartz. The specific functions of each component may be summarised as fol-
lows:
– the frits help to make the glassy matrix
– the ball-clays provide the required plasticity
– zirconium silicate improves the degree of whiteness
– quartz and feldspar help control not only the fusibility of the mix, but also its
expansion coefficient.

The final features of a monoporosa engobe are:


– no appreciable glassy phase is developed until 1000 °C: chemical inertia prevails
before such temperature
– high degree of whiteness (covering power)
– waterproofing against any coloured solutions which may enter from the back of
the tile when in service (no staining)
– adhesion to the fired body and formation of an important intermediate layer
between body and glaze.

Figure 145 shows two macro photographs which highlight how the engobe re-
duces contamination by any impurities present in the biscuit.

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Applied Ceramic Technology

Fig. 145. Macro photographs showing how the engobe reduces contamination by any impurities inside
the body.

Basic technological parameters

The final properties and appearance of the product not only depend on the chemi-
cal and mineralogical nature of its raw material components but also on the practi-
cal as well as the technical requirements demanded by the various processes in the
production cycle.
a - Grinding
b - Spray drying
c - Pressing
d - Drying
e - Biscuit firing
f - Glazing
g - Monoporosa firing
h - Glaze firing

a - Grinding
The purpose of grinding is to reduce the size and homogenise the incoming raw
materials until a final, constant particle size distribution is attained.
With porous single firing bodies, the extent of raw material grinding, together
with other chemical and physical factors, may affect the extent to which carbonates
break down during firing and hence appreciably influence the temperature at which
gas (CO2) is emitted. The degree of grinding can also influence the reactivity of the
components being fired, and the degree to which newly formed compounds are
created.

Considerable reactivity favours the formation of these compounds and helps


improve the mechanical properties of the fired material. The graph in Figure 146

270
Wall tiles

Grinding residue

_____ Breaking load after firing (kg/cm2) .......... Calcite precentage in the grinding residue (%)

Fig. 146. Changes in fired breaking load (left scale) relative to the percentage of calcite in the grinding
residue (right scale).

illustrates variations in fired breaking load (kg/cm2) in fired materials made from
compositions with different residues after grinding.
The same graph also shows the percentage of CaCO3 in the residue, again for
the same compositions: post-grinding residue, in the case of compound bodies for
either monoporosa or double firing, is generally around 4-6% (at 63 microns - 230
mesh). In the case of red firing bodies, which mainly consist of clayey materials,
this value can be as low as 3-4%.

b - Spray drying
The purpose of this process is to evaporate a part of the water contained in the
slip while forming spheroid particles.
The particle size distribution of a wall tile body is not so different from that of
any other spray-dried body (i.e. single-fired floor tiles, porcelain etc.).
The graph in Figure 147 illustrates the similarity of the typical particle size
bands for monoporosa and double firing bodies.
Note that there is a concentration in both of around 70 to 80% in the 425-180
micron range.

c - Pressing
The purpose of pressing is to obtain the greatest possible green tile powder
density that is compatible with the “black core” or degassing problems which may
arise during firing.
Applying different pressing forces will, of course, result in pressed pieces of
different bulk densities and thus different shrinkage and porosity values too.

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Applied Ceramic Technology

Double firing

Single-fired wall tiles

Microns

Microns Single-fired Fast-double


wall tiles firing
> 600 2% 2%
600-425 13% 13%
425-300 13% 14%
300-250 44% 50%
250-180 14% 13%
180-125 9% 7%
< 125 6% 2%

Fig. 147. Estimated variations in particle size distributions of monoporosa and fast double firing
bodies (spray-dried).

In the case of porous products, green bulk density variations do not involve
substantial shrinkage changes because shrinkage values for these products are in
any case very low (less than 1%).
High bulk density values (more than 2.1-2.2 g/cm3) can make the escape of gas
from the body more difficult during firing, and may cause “boiling” problems on the
glaze (monoporosa).
Bulk density differences within an individual pressed piece (e.g. powder loading
errors) can give rise to areas of porosity values that cause glaze application and
absorption problems.
The graph in Figure 148 shows the range of bulk dry density within which frits
having different softening points should not suffer from de-gassing problems.
The graphs also show the generally accepted production threshold values (shaded
area).
Specific moulding pressures for compound wall tile bodies are generally around
200-250 kg/cm2; for red firing bodies, which tend to be more plastic, pressure may
be less, even as low as 150 kg/cm2.

272
Wall tiles

Frit softening points (°C)


Moulding (kg/cm2)

1.83 1.91 1.93 1.97 1.99


Dried apparent density (gr/cm3)

Fig. 148. Relationship between dry bulk density ranges within which frits with different softening
points should not have degassing problems (shaded area).

d - Drying
This is an apparently simple stage, since the physical phenomena that accom-
pany the evaporation of residual humidity in the body (4-7%) are sufficiently un-
derstood and easily controlled.
During this phase, as residual moisture evaporates, the bending strength of the
ceramic piece increases because the particles move closer together and develop
stronger bonds.
In single firing products bending strength must be high: to withstand the me-
chanical stress of silk-screen printing. MOR must be no less than 25 kg/cm2.
With modern day drying cycles it is good practice to keep dimensional shifts
during drying within a shrinkage range of 0-0.3% so as to prevent cracking on the
faces or edges of the tiles.

e - Biscuit firing
Firing curves and kiln temperatures must permit and aid the development of
reactions between the various components so that the desired fired properties (po-
rosity, bending strength, expansion coefficient etc.) can be obtained.
It should be evident at this point that the sintering reactions of a ceramic mass
depend on the chemical and physical nature of the body, the degree of grinding, the
bulk density of the pressed material, and, finally, on the firing temperature (the
graph in Fig. 149 shows how unfired bulk density affects porosity and shrinkage
values.

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Applied Ceramic Technology

The graph in Figure 150 highlights the thermal expansion coefficient of sam-
ples fired at different temperatures. In both cases the data refers to a red firing body
composition.

f - Glazing
With wall tiles, the most commonly marketed products belong to the: transpar-
ent crystalline and opacified glossy white glazes.
Today’s market demands a wide range of finishes, including rustic and antique
effects.
This trend, deeply rooted in the floor tile industry, is also beginning to take hold
in the wall tile market, though to a far lesser extent.
The most common glaze application devices are the “bell” units.
These allow producers to achieve smooth, mirror-like surfaces by passing the
unfired or fired tile through a continuous curtain of glaze of constant thickness
and flow rate.
In order to optimise application and prevent problems related to the glazing of
unfired tiles (monoporosa) there is now a tendency to reduce the quantity of water
in glaze slips as far as possible.
The rheological behaviour of such suspensions is often far from ideal and takes
on characteristics which tend towards a plastic and often thixotropic condition. In
the case of bell applications, optimum rheological performance in a traditional stand-
ard glaze will be provided by high density, very low yield point, constant viscosity
and very low thixotropy values.

Bulk
Bulkdensity
densityafter drying
after drying
(gr/cm ))
(gr/cm 33

1,83 1,91 1,93 1,97 1,99


Assorbimento d'acqua

0,00 20
Water absorption

0,20
absorption
Contrazione

15
Shrinkage
Shrinkage

0,40
0,60 10
Water

0,80
5
1,00
1,20 0

Fig. 149. Influence of post-drying bulk density on water absorption (porosity) and fired contrac-
tion.

274
Wall tiles

400
350
300
(30+400°C)
3 Alpha

250
200
150
100

CD.0106
50
0
650 750 850 950 1050 1100 1150
Firing
Temperatura di temperature
cottura - Firing (°C)
temperature (°C)
Fig. 150. Thermal expansion coefficients of body samples fired at different temperatures.

Figure 151 shows two rheograms for slips of different density.


The diagram shows the variation of the speed gradient D (1/s) as a function of
shear stress τ (Pa).

Table 13 shows rheological parameters such as viscosity, thixotropy and yield


point in different glaze suspensions.
In order to minimise problems associated with the use of very high viscosity
glazes, the “bell unit” has recently undergone significant changes:
– elimination of the vibrating sieve
– replacement of trapezoid tank with a double chamber funnel
– elimination of the adjustment valve in the final part of the overflow device.

The purpose of these modifications is to minimize the development of air bub-


bles and scratches (bell lines).
Glaze water is absorbed into the biscuit during glazing depending on the capil-
larity of the body.
This facilitates adhesion to the biscuit and influences glaze spread and glaze
drying time.
There is thus a need to control the rate of absorption of the biscuit, a property
which depends on its basic composition, the extent to which it is fired and the den-
sity and viscosity of the glaze.
In monoporosa glazing the process variables to be controlled are many, and tol-
erances for the following are narrower:
– rheological characteristics of the glaze
– application equipment performance
– post-drying tile features (bending strength, residual moisture and tile tempera-
ture).

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τ [Pa]
Tau
300

NR 1 H2O 27.0%
200

100

NR 2 H2O 28.5%

0
0 100 200 300 D [1 / s]

Figure 151. Variations in the speed gradient D (1/s) as a function of shear stress t (Pa) for glaze
suspensions of different densities.

Another important aspect is screening and magneting of the glazes. Highly effi-
cient circular vibrating screens are now used almost universally.
There are three types of magnet but their efficiency depends on the flow rate
and density of the glaze:
– cylindrical metal bars
– beehive-shaped
– rollers.

Glaze suspension Viscosity Yield point Thixotropy


(cPoise) (mPa sec) (Pa/sec cm3)
Engobe 198 4.5 92.3
Engobe 175 3.0 145.7
White glaze 367 2.5 109.4
Transparent 327 2.5 44.0

Tab. 13. Rheological characteristics such as viscosity, yield point and thixotropy for different glaze
suspensions (values indicative only).

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Wall tiles

g - Monoporosa firing
This is a very important stage of production, since all the reactions which deter-
mine the features of the final product take place here.
Monoporosa firing dynamics are special, since the body mass contains carbon-
ates and must be compatible with glaze characteristics.
The glaze must behave “eutecticly”, have certain refractory characteristics and
be fairly gas-permeable up to temperatures in the 950-1030 °C range after which it
must melt suddenly.
The critical parts of the firing curve and the technical explanations of them are
highlighted in Fig. 152.
The initial part of the curve up to 800 °C (A) coincides with the pre-heating
phase of the material and the destruction of the clayey materials.
In part (B), between 800 and 900 °C, the carbonates start to decompose and
CO2 escapes. It is essential that the glaze maintain a certain porosity during this
stage to aid gas emission.
In part (C), between 900 and 1100 °C, synthesis reactions between alkaline-
earth oxides (CaO, MgO), generated by decomposition of carbonates, take place
and residual amorphous phases appear due to the disintegration of the clays.
The development of these neo-formed compounds is essential in adjusting and
defining the physical and mechanical features of the product.

Monoporosa Temp.
Tile

Upper zone ...... Upper zone


Temperature °C

Lower zone

Tile

Lower zone

Firing time min.

Fig. 152. Simplified firing temperature graph illustrating basic firing aspects of monoporosa mate-
rials:
A: destruction of clayish minerals
B: total expulsion of gas (CO2)
C: neo-formed compounds begin to appear
D: stabilization of neo-formed crystalline compounds and complete melting of glaze
E: fast tile cooling.

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Sintering of the body is completed in the maximum temperature zone (D):


simultaneously, spreading and melting of the glaze are optimised.
Zone (E) coincides with the fast cooling phase of the glass down to 600 °C.
A slow cooling phase follows, in order to limit the stress generated by trans-
formation of the free quartz, still present in the fired body.
The three lines of the graph illustrate tile temperature and in-kiln tempera-
tures above and below the rollers.
Different temperature gradients between the upper and lower surfaces of the
tile can, within certain limits, condition and control its curvature.
This is done by exploiting the expansion/shrinkage features of the material to
induce stresses on the upper and lower tile surfaces.

h - Glaze (or glost) firing


In double firing two kinds of frits, which might be classified as “traditional”
and “eutectic composition”, are generally used.
Firing of both these frits will require curves and temperatures different from
those for monoporosa in order to allow the glass to melt properly.
The traditional frits will need temperatures of around 1020-1050 °C and the
eutectic or monoporosa type frits around 1080-1120 °C.
In both cases, maximum temperature is maintained for a few minutes so as to
aid glaze spread and enhance glossiness.
Whatever kind of frit is used, firing is followed by fast cooling down to 600 °C.
Once this temperature has been reached, the subsequent drop to 500 °C must
be very slow in order to prevent stress induced by transformation of the quartz
(cooling cracks).
Firing cycles last from 30' to 50' depending on tile size.
Figure 153 shows firing curves for biscuit and glaze.

Finished product features


The graph in Fig. 154 aims to provide a clearer picture of overall wall tile
characteristics, illustrating variations in bending strength, shrinkage and water
absorption over various temperature ranges.
The same graph also shows the final parameters at the optimum firing tem-
perature.

278
Wall tiles

Glaze firing curve

Biscuit firing curve


Temperature °C

DOUBLE FIRING

Firing time min.

Fig. 153. Glazed tile and biscuit firing curves (double firing).

CD.0112

<
MOR modulus of rupture (kg/cm2)

>

=
Shrinkage (%)
Water Abs. (%)
Porosity

?
>

=
<

Firing temp. (°C)

Fig. 154. Variations in MOR, shrinkage and porosity for bodies fired at different temperatures. The
significance of the different shaded areas is number-coded (4 refers to the most frequently used industri-
al firing temperatures for these materials).

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Plant engineering solutions

The dynamism of the ceramic industry has been decisive in the ongoing evolu-
tion of production processes.
The ’70s saw significant technological-engineering developments, with a change-
over from traditional tunnel kilns to modern processes with roller kilns and fast
firing cycles.
Adoption of such technologies involved completely new layouts and the huge
increase in automation led to significant cuts in production costs. Significant devel-
opments in each stage of the production process continued to be made throughout
the 80s too.
These included:
– widespread use of wet discontinuous grinding
– introduction of spray drying
– increased use of hydraulic presses
– adoption of fast driers
– increased use of roller kilns.

The introduction of fast firing processes for wall tiles was neither as immediate
nor as far-reaching as it was for floor tiles. Traditional firing technology, with the
plant engineering and automation solutions available at that time, not to mention
the aesthetic quality of the then-produced tiles, was still to some extent irreplace-
able.
However, the advent of so-called “high-temperature fluxing eutectic glazes” ac-
celerated technological developments, since the surfaces attainable with these glazes
were – and still are – of high aesthetic quality and comparable to, if not better than,
traditional ones.
The ’90s thus saw a boom in monoporosa and fast double firing processes, result-
ing in manufacturing improvements and lower industrial costs.
Today’s production plants offer various levels of sophistication, depending on
their degree of automation and type of control systems.
The factors influencing the degree of sophistication of a new plant are:
– local levels of technology and general education
– plant size
– required plant flexibility.

Figure 155 shows flow diagrams for monoporosa and fast double firing, and
highlights the various processing phases (assuming use of continuous grinding,
increasingly popular even in small and medium-size plants).
Note that with monoporosa the material can be stored after glazing and firing
and can also be sent directly from the kiln outlet to the sorting area. In the case of
double firing, storage of the biscuit and the glazed tiles takes place in specially
designated areas.

280
Wall tiles

Fig. 155. Flow diagram for monoporosa and double firing processes with modern plants featuring
continuous grinding.

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Tiles are moulded in hydraulic presses, dried in fast automatic driers, put through
fast firing cycles in roller kilns and sorted using almost entirely automated machin-
ery.
Modern electronics has made it possible to automate the movement of green
and fired tile cars completely using wire and laser-guided systems.
The effects of such rapid technological-engineering developments are evident
and may be summarised as follows:
– increased operator productivity
– decrease in surface area occupied by plant
– lower unit industrial costs.

Figure 156 shows the lay-out for a fast double firing wall tile plant.

1 2 4 6

3a 3b
CD.0109

Fig. 156. General plant lay-out for the fast double firing manufacture of about 8000 m3/day of wall
tiles.
Key: 1. Body batching and preparation - 2. Pressing - 3a. Body firing area -
3b. Glazed tile firing area - 4. Glazed and fired product storage -
5. Glazing department - 6. Sorting.

Machines

A brief description of the main machines used in a typical wall tile production
plant follows.
Other machines and production processes involving dry grinding and powder
re-granulation, which can also be used to produce wall tiles, will not be dealt with
here.
Dry preparation can be used in double firing where body compositions rich in
clayey materials (or materials with very similar morphological features) are avail-
able.
Production of monoporosa using dry grinding is less widespread and is gener-
ally more difficult.

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Wall tiles

Weighing systems

Batching is performed using machinery and equipment of varying levels of au-


tomation.
With discontinuous grinding, batching of raw materials may be carried out us-
ing traditional mechanical leverage systems, or more sophisticated systems involv-
ing individual weighing hoppers mounted on load cells.
Continuous grinding generally features a microprocessor-controlled on-belt con-
tinuous weighing system.
The batched mix is temporarily stored in a pre-loading silo, from where it is fed
into the continuous mill.
In certain cases, where the clay has appropriate features, pre-dispersion of a part
of the clayey materials can be effected. In this event, the clay suspension, which
already includes the fluidizer (totally or in part), can either be sent, after proper
batching, to the mill inlet or can be added to the rest of the body after it leaves the
mill.

Mills

Wet grinding of the body may be performed using either a continuous or dis-
continuous process: selecting the most appropriate one depends on a number of
factors, such as:
– plant size
– professional qualifications of work force
– characteristics of raw materials.

As mentioned above, continuous grinding is becoming increasingly widespread.


The advantages it provides may be categorised as:
– technological
– technical-managerial
– economic.

From a technological viewpoint, the most immediate advantages are:


– greater consistency of slip characteristics
– increased density
– improved rheological features.

From a technical-organizational point of view, plant management becomes more


rational, while from an economic standpoint continuous grinding implies not only
direct labour savings but indirect energy savings too as less water evaporation is

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required in the spray drier: this is because it is possible to work with slips having a
greater solid content than would be possible with discontinuous grinding.
To clarify, a brief description of the constructive and functional differences fol-
lows.
Discontinuous mills are cylinder-shaped and made of very thick sheet metal.
They have material loading-unloading ports and their interior is lined with various
materials, such as silica, alubit® (sintered alumina) or rubber; the grinding media
may be made of silica or alubit®.
The drive unit may be fitted with a static frequency converter and PLC control
logic so as to allow, where necessary, variations in mill rotation speed even during
the grinding cycle itself in order to optimise power consumption and productiv-
ity.
The continuous mill also consists of a cylindrical steel structure. The cylinder
interior is divided into two or three grinding chambers, separated by one or two
bulkheads. Hatches that open outwards are provided for inspection and mainte-
nance purposes.
The inside of the mill is lined with specially shaped wear-resistant rubber de-
signed to provide maximum grinding efficiency. Once again, grinding media may be
silica or alubit®.
In discontinuous grinding the properly batched load is introduced into the mill
together with the preset quantity of water and fluidizer.
Once grinding is over and the residue has been checked, the slip is screened and
unloaded into storage tanks.
In continuous grinding, instead, the mix is introduced into the mill without in-
terruption by various loading systems. The raw materials and the deflocculant are
pre-mixed with the watery suspension containing the screening residues.
At the mill outlet, the slip is classified first with a wide-mesh screen, then with a
battery of finer screens to sort the material more efficiently. The screen residue is
returned to the mill together with the pre-batched water, while the slip is delivered
to a holding tank equipped with an agitator from where it can be sent directly to the
spray drier.
Should the physical characteristics of the materials be satisfactory (naturally
low residue values), a part of the clays (and, if needed, the green scrap) can be
dissolved in a turbine mixer without being introduced into the mill.
Alternatively, the clayey raw materials may be put through a preliminary
disintegrator after which they are ground in the mill together with other body
components.
This option is especially appropriate where bodies have a high proportion of
very plastic clays with relatively high natural moisture content (above 15-20%).

284
Wall tiles

Spray driers

Spray drying evaporates nearly all the water contained in the slip. Water con-
tent is reduced to percentages of around 4 to 7% by spray drying.
The slip is injected upwards from the bottom of the drier through variously
sized nozzles situated on a ring mounted at the centre of the cylinder: these noz-
zles are fed by high pressure pumps (25-30 bar).
Simultaneously, hot air flows downwards from the top of the cylinder and is
distributed tangentially, the counter-flow with the slip resulting in heat exchange.

The spray drier may be seen as the “final digester” of dirty wash water, sludge
and all the powders generated during the production process as it batches them
into the slip systematically.
To ensure compliance with environmental standards, the spray drier can also
be provided with dry or wet filters to capture particularly fine dust which would
otherwise be dispersed with the steam coming out of the chimney.
Where appropriate, the spray drier can be powered by co-generation systems
so as to reduce running costs.
The spray drier, then, transforms the “slip” into a powder of controlled parti-
cle size and humidity which is then conveyed, via conveyor belts, to the storage
silos.

Presses

This stage of the process is a very important aspect of ceramic production


technology. Normally, the aim is to obtain the highest green tile density that is
compatible with degassing and “black core” problems.
The pressures generally used for these products are in the 250 ±50 Kg/cm2
range.
The currently available hydraulic presses are especially suitable for large tiles.
They provide high mechanical/ceramic reliability and cut power consumption to
a minimum.
In addition to the actual “press”, key accessories such as the powder filler box
and the mould need to be taken into account. The former feed the powders into
the moulds and ensure that their cavities are loaded homogeneously.
The dies generally used to form the tile are of the entering-punch kind and are
normally rubber-lined to cut down the frequency with which they need to be
cleaned.
The punch may be of the traditional (rigid) type or the so-called “isostatic”
kind, which allows the user to optimise pressing homogeneity and hence obtain
uniform bulk density values over the entire tile.

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Hydraulic press.

This last requirement is met not only by the above-mentioned isostatic punches:
special feeding devices which ensure uniform powder distribution in the die are
also used.

Driers

Drying, which eliminates the residual moisture from the just-pressed tiles, is
performed on either vertical or horizontal driers.
The tiles exiting the presses are transferred on roller conveyors.
Vertical driers consist of a load-bearing structure made of steel sections with
insulation panelling.
The tiles are laid out on racks (consisting of revolving roller shelves) which are
hinged on the links of a chain system that supports them and moves them through
the drying channels.
Internal ducts feed hot air to the drying area and cold air to the cooling area via
a series of manually adjusted dampers. Heat is provided by air-flow (in-vein) burn-
ers which can run on liquid and/or gas fuels.
Horizontal driers consist of metal modules with insulating panels and insulated
exterior piping for air re-circulation.

286
Wall tiles

Vertical rapid drier.

The tiles run through the whole length of the drier on a speed-adjustable roller
conveyor. The machine consists of a series of identical modules, each one with its
own independent thermo-hygrometric and ventilation air flow characteristics. Each
zone has its own hot air generators too.
Normally, the final section of the machine is designed to stabilise the tempera-
ture of the outgoing pieces.
With vertical driers, the drying cycle lasts 35-70 minutes; with horizontal
driers, cycles can be speeded up to 6-20 minutes. In both cases, however, the dura-
tion of the cycle depends on the type of body and the size and thickness of the
pieces.
With monoporosa, a uniform tile temperature at the drier outlet is essential.
Since vertical driers have high thermal inertia, they keep the surface temperature of
the outgoing tiles within minimal tolerances even in the event of frequent produc-
tion line (glazing) stoppages.

Glazing machines

The glazing lines used for monoporosa and double firing products are essen-
tially the same, except for a few complementary devices such as the fettlers (the
type depends on whether the tiles are fired or dried). Monoporosa glazing lines are

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generally longer. As seen, the majority of wall tiles have smooth, mirror-like sur-
faces. The most suitable engobe/glaze application devices for this sort of finish are
“bell units”.
Special “airless” atomisation systems have also become increasingly widespread:
these provide even distribution of water, fixing agents and engobe. Where “an-
tique” or rustic effects are desired, repeated application tasks such as flashing, brush-
ing, dry application, etc. will be required in addition to the traditional disc or bell
curtain glazing systems.
Glazing machine manufacturers have responded to such requirements with ma-
chinery that provides high-quality aesthetics. Note also that in order to obtain a
proper degree of flexibility on glazing lines there should be numerous application
stations and all the relevant equipment useful for rapid product change-over. This
inevitably implies very long glazing lines which have, over the years, maintained
the same basic structural and functional features.
Moving on to decoration, the wide range of print types and patterns currently
in demand means that both flat and rotary screen machines are used. Rotary ma-
chines are increasingly used because they are fast and require little monitoring and
maintenance.
There are several kinds of rotary silk-screen printing machines, the main differ-
ences lying in the printing technique. Those deserving of special mention are the
tampo-print and lithographic decor machines and others employing more sophisti-
cated decor techniques, such as the incave-graphic method which uses hollowed
silicon rollers carrying the decor image.
Glazing line automation concepts are evolving steadily. This has led to the avail-
ability of: devices for dynamic applied glaze weight control, PLC units to manage
drive speed via inverters, etc.
However, the extreme automation now seen at just about every stage of the
production process has yet to appear in the glazing department as personnel still
play an essential, priority role.

Kilns

The ’70s saw the industry start switching from slow to fast firing: hence all
stages of the firing process have been reviewed accordingly, as fast firing has cre-
ated new technological opportunities.
Today, an extensive knowledge of raw materials, the nature of the bodies, the
composition of engobes and glazes as well as the wealth of acquired experience
have all resulted in the simplification and standardisation of this phase too.
Ever-more complex, sophisticated kilns and equipment now make it possible to
achieve a degree of temperature adjustment and control which, even just a few
years ago, would have been unthinkable.

288
Wall tiles

Single layer kiln.

Kiln cross-sections have increased and combustion systems have been improved,
providing constant, uniform temperature over the entire kiln cross-section.
Burner lay-out and number, of course, differ in the double firing and monoporosa
kilns. The burners and their combustion chambers are normally sized so as to pro-
vide high combustion flame speeds and low per-unit thermal potential.
In addition to high speed burners, today’s technology provides other burner
types which allow the user to “fluctuate” the flame over the kiln cross-section and
adjust flame power, cyclical flow and duration. This optimises the way in which
the heat is distributed over the tiles, especially at “critical” points of the firing
curve.
The burner unit – generally constituting the combustion chamber – may be made
either of refractory rammed material or silicon carbide. The latter gives better heat
resistance at maximum firing temperatures and also provides greater resistance to
thermal shock.
Tile conveyance rollers are a key feature on modern kilns. These may be made of
ceramic or metal; each kiln zone is fitted with specific roller types suited to that
particular stage of the firing cycle.
Adoption of rapid single or multi-layer firing has facilitated tile handling, fa-
voured production of large tiles and increased production flexibility.
A high degree of flexibility in determining and setting firing curves, together
with maintenance of firing conditions, is ensured by microprocessor control sys-
tems which keep temperatures within very narrow tolerances.
Computers provide high levels of kiln automation and also allow the user to
monitor and store the process data.

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Sorting

Although sorting does not affect product features, it is a delicate stage in the
production cycle.
Here too, automation is pervasive, covering everything up to boxing and
palletizing.
Tile geometry (flatness) can be checked by electronic and/or camera systems
which then send the product to specific outlet points.
The number of outlets depends on classification logic and product flatness/shad-
ing criteria.
Normally, there are seven outlet positions (two shades and three sorting classes).
In highly automated installations the operator need only analyse aesthetic defects
and code the tiles to define their class.

Handling and storage systems

In addition to the traditional metal trolley tile handling and storage systems
where the trolleys are pushed along tracks by rigid push and transfer bars, handling
and storage installations with automatic drive vehicles are becoming increasingly
widespread.
In double firing, biscuit storage systems consist of wide racks. The tiles are then
picked up by devices provided with suction cups which transfer them to the glazing
line.
Other solutions feature tile stacking “platforms”. Tiles are then sent on to the
glazing lines via trolleys which move along flat trackless surfaces, guided by a floor-
embedded wire or laser beam system.
The same AGV (wire-guided) or LGV (laser-guided) systems can be used in
single firing to move the trolleys carrying both the green and fired tiles.
In both cases, a computerised control station monitors all transport system han-
dling, effecting real-time monitoring of production flows to and from the tile stor-
age area.

Conclusions

Porous single firing and fast double firing, following initial teething problems,
have undoubtedly resulted in technical and aesthetic achievements which are com-
parable – and certainly superior to – those of traditional double firing.
Today, monoporosa and fast double firing may be seen as two complementary
technologies, and only an in-depth assessment of the technical, economical, cul-
tural and environmental aspects facing the manufacturer will allow selection of the
most appropriate plant.

290
Wall tiles

Although the decorative features achieved to date have been excellent (they would
have been unimaginable just 10 years ago), research – both technical and graphic –
is likely to result in even more exciting results.
Larger tiles and surface effects which realistically resemble marble and breccia
will allow ceramic products to compete with natural materials on an almost even
footing, as many now have technical properties superior to their natural equiva-
lents.

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292
Description of ceramic products

Chapter X

FLOOR TILES

Foreword
Simple brick-like cotto tiles have been used as paving for so many centuries that it
is impossible to establish exactly when they first appeared.
Painted and glazed natural-coloured terracotta, and decorated paving tiles are,
however, thought to have appeared in the 11th century AD. From then on, up to the
20th century, floor tile production in Italy was very limited, largely being under-
taken by craftsmen working for wealthy clients.
The acceleration of development that was to transform Italian ceramics into a
true industry took place at the beginning of the 1950s, when cottoforte first came on
the market; this classically Italian product was made using traditional double firing
techniques, and had features which made it ideal for paving.
Two other key technological developments were made during the ’50s: the auto-
matic press and the tunnel kiln.
Increasing market demand combined with these two innovations transformed
craftsmen’s workshops into true industrial companies.
During the ’60s fast firing plants appeared. These introduced single firing tech-
nology, thus paving the way for the use of highly automated continuous production
systems.
In simple terms “single firing” means a production system in which the tile body
and the on-tile glazes are fired together in a single operation. It became widely
established around the mid-70s.
The ceramic industry of the ’70s and ’80s was dominated by three highly impor-
tant factors:
– Automation
– Fast firing
– The energy crisis.

The introduction of single firing, with the use of fast firing cycles, was to lead
to substantial changes, especially as regards firing technology and kiln construc-
tion.
Innovation was certainly not limited to firing: changes occurred throughout the
production cycle, especially in tile handling.
Tunnel kilns, which conveyed stacked tiles on wheeled cars, were abandoned in
favour of roller kilns where the tiles were supported by refractory plates. The latter
developed into present-day kiln versions where tiles are moved by rollers directly
without the need for an intervening support.

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The same period also saw modernisation of the kiln structure and improved
reliability, with greatly improved firing performance and much enhanced control of
thermodynamic parameters.
Thermodynamic notions vis-à-vis the new roller kilns were entirely different
from those applied to tunnel kilns.
New ideas concerning fast tile firing were based on the theoretical models devel-
oped by Prof. Korac, and with roller kilns these ideas were soon adopted on an
industrial scale.
These models identified the single layer kiln as the one with the lowest specific
consumption too.
In the context of the ’70s energy crisis, then, this new technology was also to
spread fast on account of its economic benefits.
Yet the success of vitrified single firing products was not just related to energy
savings: there were other plus factors, such as simplification of the glazing system,
the opportunity to produce large tiles, the adoption of advanced automation sys-
tems.
The introduction onto the market of vitrified single firing products meant that
consumers could enjoy greatly improved physical and mechanical features but with-
out having to compromise on aesthetic content.
This combination of technical quality and aesthetic content plus lower manufac-
turing costs has, then, made floor tiles extremely popular.

The market

Figure 157 shows the evolution of vitrified single firing tile output in Italy from
1990 to 1998.
This data is compared with porcelain tile output over the same period.

Note that the slight fall off in output in 1991 and 1992 was followed by a con-
stantly upward trend that lasted until 1996.
Over the same period, porcelain tiles gained ground constantly.
The following graph (Fig. 158) shows changes in the percentages of output
accounted for by vitrified single firing tiles and porcelain tiles as from 1990. Fig.
159, however, shows annual output increases for these two products.

294
Floor tiles

Fig. 157. Comparison of Italian vitrified single firing tile output and porcelain tile output from 1991
to 1998 (the porcelain tile figures for 1997-1998 include 27 and 70 million m2 of glazed porcelain
tiles respectively).

Fig. 158. Percentages of total floor tile out-


put accounted for by vitrified single firing
and porcelain tiles, 1991-1998.

Fig. 159. Annual output variations for vitrified single firing tiles and porcelain tiles (variations on
1991 output levels).

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Product classification

The term “vitrified single fired tile” is self-explanatory. It refers to a tile body
with a “compact” mass (“grès” in Italian), although international standards define
different degrees of porosity, expressed as water absorption, for different classes of
materials (see Figure 160).
The classification below is based on ISO 13006 standards which distinguish prod-
ucts according to their degree of porosity:

Note that some products included in the BIb family are totally frost-proof.

Water absorption
Shaping

GROUP Old EN GROUP Old EN GROUP Old EN GROUP Old EN


I IIA IIB III
≤ 3% 3% - 6% 6% - 10% > 10%

extrusion GROUP EN 121 GROUP EN 186/1 GROUP EN 187/1 GROUP EN 188


A1 AIIa1 AIIb1 AIII

GROUP EN 186/2 GROUP EN 187/2


AIIa2 AIIb2

GROUP
dry pressing BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
≤ 0.5% BIIa BIIb BIII

GROUP
BIb
Bib
0.5% - 3%

Fig. 160. Classification of floor tiles according to ISO-EN 13006 standards.

Technical features

Table 14 summarises the main features of the materials belonging to the various
families (specifications required by UNI EN ISO 10545-1/17 standards).

296
B I b ( H2O = 0.5 - 3 %) B II a ( H2O = 3 - 6 %) B II b ( H2O = 6 - 10 % )

FEATURES STANDARD STANDARD-PRESCRIBED VALUE STANDARD-PRESCRIBED VALUE STANDARD-PRESCRIBED VALUE

WATER ABSORPTION ISO 10545.3 > 0.5, < 3% (max. 3.3 %) > 3 , < 6 % (max. 6.5%) > 6, < 10 % (max. 11 %)

2 2
MODULUS OF RUPTURE (MOR)* ISO 10545.4 30 N/mm (min 27) > 22 N/mm (min. 20) > 18 N/mm2 (min. 16)

BREAKING STRENGTH* ISO 10545.4 min 1100 - min 700 N min 1000 - min 600 N min 800 - min 500 N

3 3
a) DEEP ABRASION RESISTANCE** ISO 10545.6 a) max. 175 mm a) 345 mm a) 540 mm3

b) SURFACE ABRASION RESISTANCE** ISO 10545.7 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER

EXPANSION COEFFICIENT ISO 10545.8 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE

THERMAL SHOCK RESISTANCE ISO 10545.9 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE

MOISTURE EXPANSION ISO 10545.10 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE

297
CRAZING RESISTANCE ISO 10545.11 REQUIRED ** REQUIRED ** REQUIRED **
Floor tiles

FROST RESISTANCE ISO 10545.12 REQUIRED FOR SUB-ZERO EXTERNAL USE SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER

RESISTANCE TO HOUSEHOLD CHEMICALS ISO 10545.13 CLASS GB min - UB min *** CLASS GB min - UB min *** CLASS GB min - UB min ***

RESISTANCE TO ACIDS AND ALKALIS ISO 10545.13 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER

RESISTANCE TO STAINING I SO 10545.14 CLASS 3 min **** CLASS 3 min **** CLASS 3 min ****

Tab. 14. Floor tile technical characteristics according to ISO standards.


COLOUR DIFFERENCE ISO 10545.16 TEST AVAILABLE TEST AVAILABLE TEST AVAILABLE

FRICTION COEFFICIENT** ISO 10545.17 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER

Standards 10545.1 and 10545.2 regard sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (≥ 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving
*** Unglazed products
**** Glazed products
For more detailed information see UNI publications (Italy).
Applied Ceramic Technology

The table clearly shows why these materials, capable of withstanding heavy wear
and mechanical stress, are especially suited for use as floor tiles.
In the context of single firing floor tiles, glazes assume enormous importance
and should be seen as an integral part of the tile itself.
Since the advent of vitrified single firing, glazes have gone through several stages
of development.
The first glazes repeated the features of products obtained by traditional firing.
Later, during the ’80s and early ’90s, marked changes in the technical characteristics
of the body led to the development of new glazes (grains, sintered and devitrified
materials).
These were generally applied using a mixture of dry and wet techniques. The
resulting products were of a rather simple appearance based on combination of
colours and sizes; technical aspects took precedence over aesthetic ones.
The trend over the last few years has been towards glazed surfaces with a
natural stone look.
Especially popular are surfaces with an aged (or “antique“) appearance. Sum-
ming up, it can be said that the evolution – and optimisation – of technical fea-
tures has made excellent aesthetic results available to all.
In terms of abrasion resistance most tiles of this kind are “Class 4”, with some
“Class 5”, as per test methods defined in ISO 10545-7.
With regard to body features, there is an increasing, though not generalised,
tendency for porosimetrical parameters to approach those of porcelain tiles (i.e.
water absorption values around 1%).
This trend towards emulation of porcelain tiles is slowly shifting single firing
products out of their traditional water absorption range (3% < WA < 6%) into
the BI UNI EN 176 class.

Aesthetic features

Size
Much of the production over the last few years has focussed on square, aver-
age-size tiles.
In 1996, Italian production of the 30 × 30 cm size accounted for about 40-45%
of total output.
Rectangular sizes took a far less significant share of the market.

Surface appearance
Recently, there has been an increasing trend, especially in Italy, towards tiles
with an “antique” or stone-like appearance (matt satined surfaces). Such finishes
are achieved through use of specifically developed glazes and structural-type mor-
phological operations on the tile surface and perimeter.
Attaining such results requires quite complicated glazing lines consisting of

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Floor tiles

various application devices/systems such as discs, spray-guns, screen printing ma-


chines, brushes, etc.
Where glossy glazes are used they sometimes have a printed matt relief effect
to increase their abrasion resistance.
Recently, innovative new tile types with a very high aesthetic content have
appeared: these require especially sophisticated and complex production technol-
ogy.
For example, excellent special effects can be obtained by applying powder or
grained glazes (generally dry-applied) and then polishing after firing. These tech-
niques provide highly attractive marble or breccia-like finishes.

Raw materials for bodies

General features
According to one kind of commercial classification, bodies suitable for the manu-
facture of vitrified single firing floor tiles can be divided into “red” and “white”.
In both cases, raw materials are of two basic types:
– clayey materials
– complementary materials (feldspars, feldspathic sands, quartzes, calcites).

In red bodies, the clayey materials include illitic-chloritic and illitic-kaolinitic


clays.
In white bodies, the ball-clay or china-clay types, of illitic-kaolinitic or kaolinitic
nature respectively, predominate.
Complementary raw materials include minerals with fluxing and/or inert fea-
tures: such as feldspathoids, feldspars, feldspathic sands and quartz. The quantita-
tive ratio between clayey, fluxing and quartz materials will, of course, depend on
the intrinsic mineralogical nature of the clays, on particle size distribution and
the characteristics of the fluxes.
White bodies are themselves subdivided into “potassium” and “sodium” types
according to the prevalence of these oxides in their formulation.
Figure 161 shows the chemical and physical characteristics of different raw
materials suitable for white and red single firing tiles.
Summing up the functions of the components: the ball and red clays provide
plasticity and bending strength to the unfired tiles.
The china-clay types are of secondary importance in determining green tile
characteristics, yet play a key role in controlling vitrification on fired tiles on
account of their high alumina content.
Feldspars, feldspathoids, feldspathic sands are fluxing elements; their melting
characteristics help make the materials denser during firing.
Quartz balances the above, since it adjusts their viscosity and conditions shrink-
age during firing.

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Applied Ceramic Technology

3 1 2 3
2 1

3
2 1

3
2 1

3
Key: A - plastic clay; B - semi-plastic white clays (china clay); C - red
2 1 vitrifiable clays; D - potassium feldspars; E - sodium feldspar; F - feld-
spathic sands; G - quartz.

3 PHYSICAL FEATURES A B C

2 1 BREAKING LOAD BEFORE DRYING kg/cm2 8/10 6/8 10/25

BREAKING LOAD AFTER DRYING kg/cm2 20/30 15/20 30/40

3
2
1 FIRING AT 1100 °C A B C

POROSITY % 5/10 15/20 2/6


2 3
SHRINKAGE % 3/5 2/4 4/6

1
BREAKING LOAD AFTER FIRING kg/cm2 180/250 80/120 200/300

Fig. 161. Vitrified single fired tiles: chemical-physical characteristics of various raw materials (single
firing technology). The lowest percentages (0.5-1.0%) are shown in the table only as they will not show
up on the graph.

Body composition

Unlike white, red bodies mainly consist of clays with a high iron content and
small percentages of complementary materials such as feldspars and quartzites.
White-firing bodies, on the other hand, are more diversified and feature a bet-
ter balance of raw materials that includes iron-free clays, feldspars, feldspathoids,
quartz.

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Floor tiles

Figure 162 shows, as an example, two compositions for white and red bodies
respectively.
White bodies, due to the inherent nature of their raw materials, have wider and
more stable size and absorption ranges than red ones because of their higher alumina
and lower ferric oxide content, and have very different vitrification characteristics
(see Fig. 163).
The increase in linear shrinkage and the decrease in water absorption develop
less gradually and at lower temperatures in red gres compared to white gres. The
red develops more liquid phase of lower viscosity from the illitic materials. This is
particularly true in the case of red bodies consisting mainly of clayey minerals (75-
80%).
Where red clays are mixed with feldspars and quartz, firing behaviour (varia-
tions in shrinkage and porosity) is closer to that of light-coloured bodies.
Figure 164 shows composition areas occupied by various formulations inside the
Al2O3 - SiO2 - Alkali tertiary diagram, while Figure 165 shows the areas which can
be derived from the same compositions (A = Feldspathoids, B = Quartzes, C = Clay
minerals).
In particular, the diagrams show six light-coloured body compositions of which
three have predominantly sodium fluxing agents (Ws) and three predominantly
potassium fluxing agents (Wp), together with four red vitrified single firing compo-
sitions.

Argille rosse greificabili Red vitrifiable clays 70 - 80 %


Feldspatoidi Feldspathoids 15 - 20 %
Quarzo Quartz 10 - 20 %

Fig. 162. Body compositions for red and white vitrified tiles.

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Applied Ceramic Technology

<
<

= <
=
=

Fig. 163. Vitrification curves for white and red-firing bodies.

TYPE SiO2 Al2O3 TiO2 Fe2O3 CaO MgO K2O Na2O P.F.
Ws 67.93 18.70 1.15 1.51 1.35 0.35 1.20 3.44 4.49
Ws 66.80 18.09 1.50 1.96 1.42 0.38 1.50 3.36 5.46
Ws 66.35 21.33 0.76 1.22 0.68 0.40 1.76 3.18 4.50
R 68.00 15.85 0.53 4.56 0.36 0.46 3.00 1.91 4.81
R 66.37 16.00 1.07 4.79 0.98 0.96 2.91 1.52 5.70
R 68.30 17.15 0.53 3.04 0.54 0.54 2.80 1.73 5.65
R 65.35 15.60 0.76 4.25 1.15 1.55 3.33 1.63 6.15
Wp 66.75 19.95 0.48 1.71 0.57 0.51 5.00 1.80 3.66
Wp 67.03 18.00 0.54 1.52 0.67 0.95 4.00 1.55 5.78
Wp 66.18 18.80 0.54 1.52 0.67 0.95 4.37 1.30 5.78
Wp 67.54 18.76 0.71 1.06 0.57 0.48 4.37 1.30 5.50

SiO2 Al2O3

1 Wpp
GB
Ws = white
GB sbody with sodium
2 Wss
GB = gres grosso
R = red body grosso
Gr = gres
3 3 R
Gr 2
2 3 1
1 Wp =p white
GB = gresbodygrosso
with potassium
CD.0064

Alcali
Alkali Al2O3

CD.0063 Na2O K2O

Fig. 164. Composition areas for various body formulations within the Al2O3-SiO2-Alkali tertiary sys-
tem.

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Floor tiles

Fig. 165. Composition areas of red and white single firing bodies related to mineralogical components.

Raw materials for glazes

The physical properties of glazes, such as resistance to wear, acids and alkalis,
ultimately determine where such products can be used.
This is why research into new kinds of glass with innovative physical-mechani-
cal and chemical properties is ongoing.
Glaze properties basically depend on the raw materials used in their formulation
and on firing temperature.
Formulation is based on the use of different kinds of frit (medium and high
viscosity) in varying proportions; nowadays eutectic-melting frits (calcium and zinc)
are used too.
Other natural and synthetic materials are introduced into the glazes together
with the frits, depending on the exact “texture” and glaze properties the manufac-
turer is aiming at.
Some of these non-fritted components, such as feldspars, nepheline and zinc
oxide form, together with the frits, the vitreous matrix of the glaze.
Others, such as zirconium sand and corundum, are partly dissolved inside the
glass and help improve abrasion resistance, or else work as opacifiers (zirconium
silicate) or matting agents (alumina oxide).
Other glaze components include:
– Anatase (titanium dioxide). Not only a matting agent: it also has positive effects
on the mechanical and chemical properties of the glass.
– Wollastonite, calcium and magnesium carbonate. Minerals with an alkaline-ear-
th base which act as matting agents and help form the vitreous matrix.

One of the most important features of a glaze is its expansion coefficient, which
must match that of the body so as to control the final tile curvature.

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Applied Ceramic Technology

Basic technological parameters

The final features of a product depend not only on the chemical and mineralogi-
cal nature of the raw materials, but on the technical conditions during the produc-
tion process and these two factors will be inter-related particularly in the following
areas:
a - Grinding
b - Spray drying
c - Pressing
d - Drying
e - Glazing
f - Firing

a - Grinding
The purpose of grinding is to reduce the size of the raw materials to a final,
constant required particle size.
With vitrified bodies, the degree of grinding of the raw material, together with
other chemical and physical factors, may affect the degree of vitrification and thus
influence shrinkage and porosity values.
The graph in Figure 166 shows variations in shrinkage of a given composition
against grinding residues over a range of temperatures.
Generally speaking, post-grinding residue, for compound vitrified bodies, is
around 7-10% (63 microns-230 mesh). In the case of red bodies, mainly consisting
of clayey materials, this value may drop to 4-6%.

b - Spray drying
The purpose of this process is to evaporate a part of the water contained in the
slip while forming spherical particles. Such particles are of a similar size in all types
of ceramic tile body.
Fig. 167 illustrates particle size distribution for a single-fired body. Note that
some 70-80% of particles are grouped in the 180-425 micron range.

304
Floor tiles

Fig. 166. Fired shrinkage as a function of grinding residue variations (checked with a 63-micron
screen).

50%

40%

30%

20%

10%

0%
600 425 300 250 180 125 63
microns

Microns Vitrified single fired tiles


> 600 1%
600-425 9%
425-300 10%
300-250 42%
250-180 17%
180-125 14%
< 125 7%

Fig. 167. Particle size distribution of a spray-dried vitrified single firing tile powder.

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c - Pressing
Pressing aims to achieve the greatest possible green tile powder density that is
compatible with the “black core” or degassing problems which may arise during
firing.
Applying different pressing forces will, of course, result in pieces of different
bulk densities and thus different shrinkage and porosity values too.
The graphs in Figures 168-169 highlight variations in these two parameters
as a function of moulding pressure and firing temperature for a white body. In
white bodies specific moulding pressure is around 250-300 kg/cm2 (white). For
red bodies, which tend to be more plastic, pressure may be lower, around 200 Kg/
cm2.

d - Drying
This is an apparently simple operation, since the physical phenomena which take
place during the evaporation of residual body moisture (4-7%) are understood and
easily controlled.
Note, however, that extremely kaolinitic bodies do tend to expand after drying,
resulting in low unfired bending strength.
Where drying is too fast this may lead to cracks on the tiles. With today’s cycles,
post-drying expansion should be a maximum of 0.3% or 0.4% and may even be
negative. Dried piece bending strength should be at least 25 kg/cm2.

e - Glazing
The catalogues of today’s ceramic companies feature countless types of glazes.
Generally, however, they all belong to one of the following families:
– glossy
– matt (devitrified)
– rustic.

These products are obtained by layering different glazes using dry and wet ap-
plication techniques.
“Wet” techniques require special devices such as discs, spray-guns and silk-screen
printing machines. With “dry” materials (grains and agglomerates) powder applica-
tors are used.
The use of so many kinds of glaze requires a very flexible production plant,
especially on the glazing lines themselves. Furthermore, each application and the
numerous kinds of glaze which overlap on the same product have very different
features, thus necessitating different know-how and skills for each product.
Some floor tiles require only simple disc applications where the glaze is ap-
plied in minimal quantities (up to 500 g/m2), while others require complex proce-
dures (up to 20 different applications) involving applied glaze weights of up to 3
kg/m2.
These glazes may be both wet (density of 1.2 - 2.0 kg/l) and dry applied (highly

306
Floor tiles

Fig. 168. Fired shrinkage and water absorption as a function of specific moulding pressure.

Fig. 169. How green bulk density influences post-firing shrinkage and water absorption.

307
Applied Ceramic Technology

variable particle size distribution). It is often necessary to apply binders and other
organic products.
The green body is therefore subject to considerable stress and must be able to
absorb considerable quantities of water without bending beyond a certain limit, as
this would compromise silk-screen printing operations.

f - Firing
Optimum firing curves allow fusion reactions and crystallisation to take place on
the various body and glaze components.
These reactions help produce the required absorption and shrinkage goals, while
improving the technical features and the finish of the glazed surface.
The vitrification conditions of a ceramic mass evidently depend not only on the
chemical and physical nature of body but also on the extent of grinding, the bulk
density of the pressed material and on maximum firing temperature.
Fig. 169 shows the influence of green tile bulk density on fired shrinkage and
porosity of a red vitreous body.
To evaluate the characteristics of a body, it is very important to define its size
stability and change in porosity (if any) where firing is performed using different
temperature cycles and/or gradients.
Figure 170 highlights variations in breaking load (MOR), shrinkage and water
absorption at different temperature intervals for a typical vitrified single firing body.
The same graph also identifies the physical-mechanical characteristics relative
to optimum firing temperature.

Plant engineering solutions

The dynamism of the ceramic industry has been decisive in the ongoing evolu-
tion of the production process.
The ’70s saw significant technological-engineering developments, accompanied
by a shift from double firing to single firing production processes. Adoption of such
technology, which uses roller kilns and rapid firing cycles, involved completely new
layouts.
Shortened firing times and single/multi-layer roller kilns led to huge increases
in automation while cutting production costs significantly. Important developments
in each stage of the production process continued to be made throughout the 80s
too.
These included:
– widespread use of wet discontinuous grinding with Alsing mills
– introduction of spray drying
– increased use of hydraulic presses
– adoption of fast driers
– increased use of roller kilns.

308
Floor tiles

<
?

>

>
=
=
<

Fig. 170. Variations in physical-mechanical characteristics at different temperatures. The significance


of the different shaded areas is number-coded (4 refers to the most frequently used industrial firing
temperatures for these materials).

The ’90s witnessed further refinement of these production processes, leading to


increased output capacity and lower maintenance costs thanks to technological in-
novation and massive use of automation.
The same period also saw marked improvements in tile finish and decoration as
a result of fast-changing market demand.
Today’s production plants offer various levels of sophistication, depending
on their degree of automation and type of control systems (department super-
visor).
The main factors to assess in deciding the level of sophistication of a new plant
are generally the following:
– local levels of technology and general education
– plant size
– required plant flexibility.

The flow chart in Figure 171 illustrates the various stages of the vitrified single
firing process.
Continuous grinding – now becoming more widespread even in small and me-
dium-size plants – is followed by pressing with high-tonnage hydraulic presses,

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Applied Ceramic Technology

Fig. 171. Vitrified single firing process block diagram for a modern plant (with continuous or discon-
tinuous grinding).

310
Floor tiles

drying with fast automatic (both vertical and horizontal) driers and fast firing using
roller kilns.
The sorting department uses almost entirely automated machinery.
Electronic control systems now allow full automation of green and fired tile
handling, with storage cars being wire or laser-guided.
The effects of such rapid technological-engineering developments are evident
and may be summarised as follows:
– increased operator productivity
– decrease in surface area occupied by plant
– lower unit costs.

An analysis of the various stages of the production process shows that it is


possible to store the material after glazing.
The material can also be sent directly from the kiln outlet to the sorting line.
Figure 172 shows the lay-out for of modern plant using continuous grinding
technology.

1a 1b 4 6
5

2
3

CD.0075
Fig. 172. Lay-out for production of vitrified single firing floor tiles. 1a. Body preparation; 1b. Glaze
preparation; 2. Pressing and drying dept.; 3. Glazing dept.; 4. Unfired/fired tile storage area; 5. Fir-
ing dept.; 6. Sorting dept.

Machines

A brief description of the main machines – such as wet grinding mills and spray
driers – used in a typical single firing production plant follows.
Although other machines and production processes (involving dry grinding and
powder re-granulation) can be used to produce floor tiles, they are much less com-
monplace and will not be dealt with here.

Weighing systems
Batching may be performed using machinery and equipment of varying levels
of automation.
With discontinuous grinding, batching of raw materials may be carried out
using traditional mechanical leverage systems, or more sophisticated systems

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Applied Ceramic Technology

involving individual weighing boxes with deformable load cells.


Continuous grinding generally features a microprocessor-controlled on-belt con-
tinuous weighing system. The batched mix is temporarily stored in a pre-loading
silo, from where it is fed into the continuous mill.
In certain cases, where the clay has appropriate features, pre-dispersion of a part
of the clayey materials can be effected. In this event, the clayey suspension, which
already includes the fluidizer (totally or in part), can either be added, after proper
batching, to the mill or can be placed in storage tanks for future mixing with the
milled slip.

Mills
Selecting either a continuous or discontinuous process depends on a number of
factors, such as:
– plant size
– professional qualifications of work force
– characteristics of raw materials.

Continuous grinding is becoming increasingly widespread as it offers techno-


logical, technical-organizational and economic advantages.

From a technological viewpoint, the most immediate advantages are:


– greater consistency of slip characteristics
– increased density
– improved rheological features.

From a technical-organizational point of view, plant management becomes more


rational, while from an economic standpoint continuous grinding implies not only
direct labour savings but indirect energy savings too as less water needs to be evapo-
rated in the spray drier from the higher density slip compared to that from discon-
tinuous mills.
To clarify these points, a brief description of the constructive and functional
differences follows.
Discontinuous mills are cylinder-shaped and made of very thick sheet metal.
They have material loading-unloading ports and their interior is lined with various
materials, such as alubit® (sintered alumina), rubber or – rarely – silica; the grinding
media may be made of silica or alubit®.
The drive unit may be fitted with a static frequency converter and PLC control
logic so as to allow, where necessary, variations in mill rotation speed even during
the grinding cycle itself in order to optimise power consumption and productiv-
ity.
The continuous mill also consists of a cylindrical steel structure. The cylinder
interior is divided into two or three grinding chambers, separated by one or two
bulkheads (separating plates).

312
Floor tiles

Grinding department with continuous mill.

Even more modern continuous mills do not have dividing separation plates but
control the flow of material through them with spiral lifters built into the rubber
linings. Hatches that open outwards are provided for inspection and maintenance
purposes and for replenishing the grinding media.
The inside of the mill is lined with specially shaped wear-resistant rubber de-
signed to provide maximum grinding efficiency. Once again, grinding media may be
made of silica or alubit®.
In discontinuous grinding the properly batched load is introduced into the mill
together with the preset quantity of water and fluidizer.
Once grinding is over and the residue has been checked, the slip is screened and
unloaded into storage tanks.
In continuous grinding, instead, the mix is introduced into the mill by various
loading systems.
The raw materials and the deflocculant – pre-mixed with the watery suspension
containing the screening residues – are introduced together.
At the mill outlet, the slip is sieved first through a wide-mesh screen, then with
a battery of finer screens to classify the material more efficiently. The screening
residue is returned to the mill together with the pre-batched water, while the slip is
delivered to a holding tank equipped with an agitator from where it can be pumped
to the spray drier.
Should the physical characteristics of the materials be satisfactory (low residue
values), a part of the clays (and, if need be, the green scrap) can be dispersed in a
turbo-mixer without being introduced into the mill.
Alternatively, the clayey raw materials may be pre-dispersed after which they are
ground in the mill together with other body components.
This option is particularly appropriate where bodies have a considerably high

313
Applied Ceramic Technology

proportion of very plastic clays with relatively high natural moisture content (above
15-20%).

Spray drying
Spray drying evaporates nearly all the water in the slip leaving a powder con-
taining just 4-7% moisture.
The slip is injected upwards from the bottom of the drier via nozzles of various
size situated on a ring placed at the centre of the cylinder: these nozzles are fed by
high pressure pumps (25-30 bar).
Simultaneously, hot air flows downwards from the top of the cylinder and is
distributed tangentially.
The counter-flow of the hot air and the atomised droplets of slip results in heat
exchange.
The spray drier may also be seen as the “final consumer” of dirty wash water,
sludge and all the powders generated during the production process.
To ensure compliance with environmental standards, the spray drier can also be
provided with dry or wet filters to separate and collect particularly fine dust which
would otherwise be dispersed with the steam coming out of the chimney.
Where appropriate, the spray drier can be powered by co-generation systems so
as to reduce running costs.
The spray drier, then, transforms the semi-finished “slip” into a powder of con-
trolled particle size and humidity which is then conveyed, via conveyor belts, to the
storage silos.

Presses
This stage of the process is a very important aspect of ceramic production tech-
nology. Normally, the aim is to obtain the highest green tile density that is compat-
ible with degassing and “black core” problems.
Moulding pressures used for these products generally fall within the 200 - 350
Kg/cm2 range or may be higher still.
Today’s hydraulic presses are highly developed and given the available pressing
power, they are also ideal for the production of large tiles.
High mechanical/ceramic reliability and greatly reduced power absorption pro-
vide further benefits.
In addition to the actual “press”, accessories such as the die and powder filler box
play a key role.
Most of the dies used to form vitrified single fired tiles are of the entering
punch type and are normally rubber-lined so as to cut down the frequency with
which they need to be cleaned. Rubber is also used to obtain “structured” surface
effects.
The punch may be of the traditional “rigid” or more innovative “isostatic” type.
The latter allows optimisation of pressing homogeneity and thus ensures uniform
bulk density right across the tile.

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Floor tiles

Hydraulic press.

This is an important concept because, with vitrified single firing floor tiles, not
only pressing power but homogeneous loading of the powders inside the die cavity
is essential.
Proper loading is normally achieved by using “alveolar” grating (grid) as op-
posed to the more traditional “slatted” ones.
Imperfect loading can lead to incorrect tile geometry (orthogonality and square-
ness). Such problems can be resolved using special powder feeders or, as mentioned
above, “isostatic” punches, which have proved highly successful in reducing geom-
etry defects of the finished tiles subject to shrinkage.

Driers
Drying, which eliminates the residual moisture from the just-pressed tiles, is
performed on either vertical or horizontal driers.
The tiles exiting the presses are transferred on roller conveyors to the driers.

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Press cavity powder feeding device (note the alveolar grating).

Vertical driers consist of a load-bearing structure made of steel sections with insu-
lated panelling.
The tiles are laid out on racks (consisting of revolving roller shelves) which are
hinged on the links of a chain system that supports them and moves them through
the drying channels.
Internal ducts feed hot air to the drying area and cold air to the cooling area via
a series of manually adjusted dampers. Heat is provided by air-flow burners which
can run on liquid and/or gas fuels.
Horizontal driers consist of metal modules with insulating panels and insulated
exterior piping for air re-circulation.
The tiles run through the whole length of the drier on a speed-adjustable roller
conveyor having one or more levels.
The drier consists of a series of identical modules, each one with its own inde-
pendent thermo-hygrometric and ventilation air flow characteristics. Each zone has
its own hot air generators too.
Normally, the final section of the machine is designed to stabilise the tempera-
ture of the outgoing pieces.
With vertical driers, the drying cycle lasts 35-70 minutes; with horizontal
driers, cycles can be speeded up to 6-20 minutes. In both cases, however, the
duration of the cycle depends on the type of body and the size and thickness of
the pieces.

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Floor tiles

Three-layer horizontal roller drier.

Glazing machines
The world tile market has become an increasingly sophisticated and diversified
one, requiring machines and equipment capable of producing a wide range of glaz-
ing and decoration applications.
Glazing machine manufacturers have responded to this demand with machinery
that provides superb aesthetic effects yet still relies to a large extent on the manual
skills inherent in all glazing operations.
Note also that in order to obtain a proper degree of flexibility on glazing lines
there should be numerous application stations and all the relevant equipment use-
ful for rapid product change-over. This inevitably implies very long glazing lines
which have, over the years, maintained the same basic structural and functional
features.
Where “antique” or rustic effects are desired, repeated application tasks such as
flashing, brushing, dry application, etc. will be required.
Where glossy finishes are required the engobe and glaze are best applied using
“bell units”.
There is also an increasing trend towards the use of spray-gun devices that
evenly distribute water, fixing agents and (airless) engobe over the tile surface.
Moving on to decoration, the wide range of print types and patterns currently
in demand means that both flat and rotary screen machines are used. Rotary ma-
chines are increasingly popular because they are fast and require little monitoring
and maintenance.

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Applied Ceramic Technology

Several kinds of rotary silk-screen printing machines exist, the main differences
lying in the printing technique. Those deserving of special mention are the tampo-
print and lithographic decor machines and others employing more sophisticated
techniques, such as the incave-graphic method which uses hollowed silicon rollers
carrying the decor image.
Glazing line automation concepts are also evolving steadily. This has led to the
availability of: devices for the dynamic control of the applied glaze weight, PLC
units to manage drive speed via inverters, etc.
However, the extreme automation now seen at just about every stage of the
production process has yet to appear in the glazing department as personnel still
play an essential, priority role.

Kilns
The ’70s saw the industry start switching from slow to fast firing: hence all
stages of the firing process have been reviewed accordingly, as fast firing has led to
the development of new technologies.
Today, an extensive knowledge of raw materials, the nature of the bodies, the
composition of engobes and glazes as well as the wealth of acquired experience
have resulted in the simplification and standardisation of this phase too.
Ever-more complex, sophisticated kilns and equipment now make it possible to
achieve a degree of temperature adjustment and control which, even just a few
years ago, would have been unthinkable.
Kiln widths have increased and combustion systems have been improved, pro-
viding constant, uniform temperature over the entire kiln cross-section. The burn-
ers and their combustion chambers are normally sized so as to provide high com-
bustion flame speeds and low per-unit thermal potential. In addition to high speed
burners, today’s technology provides other burners which allow the user to “fluctu-
ate” the flame over the kiln cross-section and adjust flame power, cyclical flow and
duration.
This optimises the way in which the heat is distributed over the materials to be
fired, especially at “critical” points of the firing curve.
The burner unit – generally constituting the combustion chamber – may be made
either of refractory rammed material or silicon carbide. The latter gives the unit
better heat resistance at maximum firing temperatures and also provides greater
resistance to thermal shock.
Tile conveyance rollers are a key feature on modern kilns. These may be made of
ceramic or metal; each kiln zone is fitted with specific roller types suited to that
particular stage of the firing cycle.
Adoption of rapid single or multi-layer firing has facilitated tile handling, fa-
voured production of large tiles and increased production flexibility.
Firing temperatures and cycles generally fall within the 1100-1200 °C and 35-
60' ranges respectively, depending on the nature of the ceramic materials and the
size of the tiles.
Fig. 173 shows two firing curves. The first is generally suitable for standard

318
Floor tiles

Single-layer high temperature roller kiln.

white bodies, while the second is designed for bodies sensitive to “black core” prob-
lems.
A high degree of flexibility in determining and setting firing curves, not to
mention maintenance of firing conditions, is ensured by microprocessor control
systems which keep temperatures within very narrow tolerances. Computers pro-
vide high levels of kiln automation and also allow the user to monitor and store the
process data.

Fig. 173. Typical firing curves for standard vitrified single firing floor tile bodies and those sensitive to
“black core”.

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Sorting
Although sorting does not affect product features, it is an important stage in the
production cycle. In this area too, automation is pervasive, covering everything up
to boxing and palletizing. Tile geometry (size and flatness) can be checked by elec-
tronic and/or camera systems which then send the product to specific outlet points.
In highly automated installations the operator need only analyse aesthetic defects
and code the tiles to define their class.

Handling and storage systems


In addition to traditional metal trolley tile handling and storage systems where
the trolleys are pushed along tracks by rigid push and transfer bars, handling and
storage with automatically guided vehicles is becoming increasingly widespread. In
these systems the trolleys are transported by the vehicles along flat trackless sur-
faces, guided by a floor-embedded wire or laser beam system. In both cases, a com-
puterised control station monitors the entire handling system, effecting real-time
monitoring of production flows to and from the tile storage area.

Conclusions
After twenty years of continuous technological development, today’s single fired
floor tiles are products of superb technical and aesthetic quality.
However, research continues and there is still room for innovation and improve-
ment. Technical and structural tile properties already go far beyond the standards
required by the construction industry; tile finish and decor can also successfully
compete with anything offered by other natural or artificial materials. Last but not
least, ceramic floor tiles remain inexpensive and enjoy excellent market competi-
tiveness.

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Description of ceramic products

Chapter XI

PORCELAIN TILES

Foreword
Porcelain tiles (also known as fine porcelain tiles, fully vitrified stoneware or
sometimes referred to by the Italian gres porcellanato) have excellent technical char-
acteristics, featuring exceptionally good bending strength and water absorptions
often lower than 0.1%.
In the context of the ceramic tile industry, porcelain tiles have gained ground
rapidly, from a very small share of the market and a limited range of applications to
an ever-increasing level of demand and wider fields of use.
While, in the past, this product was of interest largely on account of its techni-
cal characteristics, its refined aesthetic potential has now ensured its success in more
sophisticated market segments, accompanied by a marked increase in output.
Yet porcelain tiles are not exactly new. While their origins lie in now-obsolete
production technologies, development can be attributed to the introduction of in-
novative chemical-mineralogical compositions suitable for use with modern tech-
nologies such as high pressure moulding, recently developed decoration techniques
and, of course, fast firing - even on large tiles.
This chapter provides a general overview of the porcelain tile market, techno-
logical aspects, the different stages of the production cycle and the outlook for the
future.

Market
Note that in the early ’80s just 8 million m2 of porcelain tiles were produced,
accounting for just 2% of Italian ceramic tile output. By the year 2000 that figure
had jumped to 300 million m2, some 40% of all Italian output. Fig. 174 illustrates
this extraordinary escalation. The increase in output can be explained by the fact
that these tiles are appreciated not only in Italy and Europe but all over the world
(60% of Italian porcelain tiles are exported).
Global porcelain tile production capacity is currently estimated at around 700
million m2/year (accurate figures are difficult to obtain as there is a lack of informa-
tion with regard to China, which has a huge industry, and new producers are ap-
pearing all the time the world over). Production involves 265 companies, 100 of
which are Italian.
The key producer nations are China with about 80 plants, Spain with 22, Taiwan
with 20, France and Germany with 7, Malaysia with 7, Thailand, Indonesia and
India with 5.
Bringing up the rear are Portugal, Poland, the Czech and Slovak Republics, Tur-
key, South Korea, Japan, the Philippines, Sri Lanka, Argentina, the USA, Venezuela
and Morocco, each having just a few or only one production plant.

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Italian sales Export Output

Output

Fig.174. Production and sales data for Italian porcelain tiles from 1991 to 1998 (In 1997 and 1998
glazed porcelain tiles accounted for 24,750,000 and 70,322,000 m2 respectively).

Technical characteristics

The word “porcelain” is well known as a description of fine, prestigious ceramic


ware.
It is used here to emphasise tiles of high specification having an extremely com-
pact mass of crystal phases in the vitreous matrix.
Fig. 175 shows product classification according to ISO 13006.
These standards place porcelain tiles in Group BIa, which incorporates vitrified
materials characterized by porosity values lower than 0.5% (expressed as water ab-
sorption).
Actually, industrially produced tiles have a porosity much lower than that re-
quired by the standards, generally less than 0.1%.
Such tiles are ideal for flooring as they are extremely resistant to all kinds of
wear on account of their hardness.

322
Porcelain tiles

Water absorption
Shaping

GROUP Old EN GROUP Old EN GROUP Old EN GROUP Old EN


I IIA IIB III
≤ 3% 3% - 6% 6% - 10% > 10%

A GROUP EN 121 GROUP EN 186/1 GROUP EN 187/1 GROUP EN 188


extrusion A1 AIIa1 AIIb1 AIII

GROUP EN 186/2 GROUP EN 187/2


AIIa2 AIIb2

GROUP
B BIa EN 176 GROUP EN 177 GROUP EN 178 GROUP EN 159
dry pressing ≤ 0.5% BIIa BIIb BIII

GROUP
BIb
Bib
0.5% - 3%

Fig. 175. Classification of porcelain tiles according to ISO 13006.

Moreover, they are highly resistant to frost, chemicals and stains and have ex-
ceptional bending and compression strength etc.
Tab. 15 illustrates their main characteristics, comparing standard-permitted mini-
mum values with real values observed on marketed products.
Other aspects which should not be underrated are their antistatic and hy-
gienic properties, making them ideal for computer rooms, hospitals and operat-
ing rooms.

Commercial specifications

Size
Over the last ten years some 90% of Italian output has been accounted for by
medium size tiles.
More specifically, 60% can be attributed to the 30 × 30 cm and 33 × 33 cm sizes,
with 40 × 40 cm tiles accounting for just 10%.
In addition to these standard sizes, there are other products which range from
the very large (e.g. 60 × 120 up to 120 × 180 cm) to the very small (accessories and
trims).
Moreover, porcelain tile producers have recently begun to offer product ranges
which coordinate square and rectangular tiles, especially on “rustic” product
lines.

Categories of use
The combination of technical and aesthetic aspects determines the suitability of
the final product for a specific use.
Fig. 176 illustrates different fields of application for different types of glazed

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FEATURES STANDARD STANDARD-PRESCRIBED ACTUAL PRODUCT VALUES

WATER ABSORPTION ISO 10545.3 ≤ 0,5 % < 0,1 %

MODULUS OF RUPTURE (MOR)* ISO 10545.4 > 35 N/mm (min 32)


2
> 50 N/mm2

BREAKING STRENGTH* ISO 10545.4 min 1300 - min 700 N min 1500 - min 2000 N

a) DEEP ABRASION RESISTANCE*** ISO 10545.6 < 175 mm 2


< 150 mm2

b) SURFACE ABRASION RESISTANCE** ISO 10545.7 SPECIFIED BY THE MANUFACTURER SPECIFIED BY THE MANUFACTURER

EXPANSION COEFFICIENT ISO 10545.8 TEST DISPONIBILE ~ 7 x 10 -6

THERMAL SHOCK RESISTANCE ISO 10545.9 TEST AVAILABLE NO CHANGES

MOISTURE EXPANSION ISO 10545.10 TEST AVAILABLE TEST AVAILABLE

CRAZING RESISTANCE ISO 10545.11 REQUIRED REQUIRED

FROST RESISTANCE ISO 10545.12 REQUIRED NO VISIBLE EFFECT

RESISTANCE TO HOUSEHOLD CHEMICALS ISO 10545.13 Class GB min Class GB min

RESISTANCE TO ACIDS AND ALKALIS ISO 10545.13 TEST AVAILABLE SPECIFIED

RESISTANCE TO STAINING ISO 10545.14 Class 3 min Class 3 min

Pb AND Cd LEACHING ISO 10545.15 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER

COLOUR DIFFERENCE ISO 10545.16 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER

FRICTION COEFFICIENT ISO 10545.17 TEST AVAILABLE SPECIFIED BY THE MANUFACTURER

Standards 10545.1 and 10545.2 are not shown in the table owing to limited space. Nevertheless, the reader is reminded that they
refer to sample acceptance methods and size and surface quality characteristics.
* Depending on thickness (< 7.5 mm ≥ greater than 7.5 mm)
** To be effected only where used as paving
*** Unglazed products
For more detailed information see UNI publications (Italy).

Tab. 15. Porcelain tiles according to ISO BIa standards. Standard-required values and actual product
values are shown.

Large porcelain tile.

324
Porcelain tiles

Aesthetical characteristics
Requisiti estetici Stoneware
Glossy Gres ceramico

Brillante

Light comm. Medium comm. Heavy comm. Industrial use


Comm. residenziale Comm. leggero Comm. intensivo Industriale
Ordinary mat. Special mat.

mat Mat speciale


Technical characteristics
Caratteristiche tecniche

Klinker

Resistance Aesthetics
Resistenza Estetica

CD.0023

Fig. 176. Surface characteristics related to fields of application. Note that porcelain tiles, previously
confined to industrial uses, are now used extensively in the heavy commercial field and have gained a
foothold in the medium commercial field.

and unglazed tile, namely: light commercial, medium commercial, heavy commer-
cial and industrial.
The y-axis indicates technical and aesthetic values while the x-axis illustrates
the increasing bending strength and resistance to wear corresponding to a decrease
in aesthetic appearance.
Note that porcelain tiles, originally confined to an industrial context, now oc-
cupy a significant share of the heavy commercial field and, thanks to their much-
improved aesthetic properties, the medium commercial field too.

Research has led to the creation of new, innovative tile types which maintain the
above technical characteristics. This has resulted in marked product differentiation
and the spread of porcelain tiles into areas traditionally occupied by tiles of high
aesthetic value.
There follows a general overview of these relatively new commercial types, in-
cluding those which have been on the market for some time.

a) Plain tiles
The simplest products from an aesthetic viewpoint. Pastel shades dominate. Pol-
ished plain tiles are often used in shopping malls. Obtained from spray-dried pow-
ders of uniform colour.

b) Granito (salt and pepper)


Obtained from a combination of differently coloured spray-dried powders, re-

325
Applied Ceramic Technology

sulting in the so-called “salt and pepper” effect. The base body colour is often white
or another light colour.

c) Marble effect (veined or streaked) tiles


Produced using mixtures of coloured powders (spray-dried, or sometimes mi-
cronized powders obtained from further grinding of spray-dried powders). These
are distributed at random inside the press mould cavity by special feed systems,
giving rise to marble-like (or “veined”) or shaded finishes, often polished to improve
the veined effect.

d) Macro granito
Obtained from spray-dried powder mixes with a 10-50% of a large grain con-
tent. The latter are produced via dry or wet regranulation of spray-dried or mi-
cronized powders of single or multiple colour. The tile surface background colour
is similar to that of granito or marble effect products, thus highlighting the grains
to give a natural stone-like appearance. These products normally feature a polished
finish.

Example of marble effect porcelain tile.

e) Tiles decorated with soluble salts and glazes


Obtained by silk-screen printing or spraying (disc, spray-gun) glazes or solu-
tions containing chromophore salts (Fe, Cr, Co, V, Mn, etc.) onto white or superwhite
unfired or biscuit fired bodies. High-grade, innovative aesthetics result. Usually pol-
ished.

326
Porcelain tiles

f) Glazed rustic tiles (flashed/screen-printed tiles)


Produced with base or recycled bodies and pressed with dies having structured
surfaces. Finishing involves the flashing or silk-screen printing of small amounts
of glaze and/or soluble salts. Surface brushing may complete the process. Special
surface effects mimic the natural ageing caused by time and wear, thus making these
tiles competitive with more traditional products like cotto.
Fig. 177 illustrates some of these tile types. Their aesthetic properties – rustics
excepted – are generally enhanced by total or partial smoothing and polishing.
Ongoing product differentiation has allowed – and continues to allow – porce-
lain tiles to penetrate new markets where they have become a viable substitute for
natural materials and glazed ceramic tiles. Fig. 178 shows market shares for the
above-cited tile types at the end of the 1990s and highlights their short and me-
dium-term growth.

Fig. 177. Various kinds of porcelain tile.

Raw materials for bodies

The raw materials used in porcelain tile body compositions can be divided into
several mineral groups, each with its own specific function: the clayey raw materials
confer plasticity, while complementary non-plastic materials include fluxing miner-
als or those with a structural function.
The former include minerals of illitic-kaolinitic or montmorillonitic origin. These
have plastic characteristics that vary as a function of mineralogical structure and
particle size distribution. Fluxing minerals include feldspars and feldspathoids, talc,

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Applied Ceramic Technology

Tinte
Plain Unite
colours
Event Tint

Granito
Granito
Granite

Marble effect
Variegato
Shaded
(veined)

Macrograniti
Macro granito
Macrogranite

Rustici
Rustics
Rustics

Decorati
Decorated
Decorated
0 5 10 15 20 25 30 35 40

% over total production

Fig. 178. Expected development trends for different types of porcelain tile.

eurites, pegmatites, while quartz and generally quartzites – the most refractory
ones – have a structural function.
All components must have low concentrations of colouring oxides (e.g. Fe2O3
and TiO2) to prevent “contamination” of natural body colour.
Quantitative body component ratios depend on the mineralogical nature and
particle size distribution of the clays and, finally, on the reactivity of the latter with
the fluxing minerals.
Fig. 179 provides an overview of the chemical and physical characteristics of
porcelain tile compositions/products.
The PLASTIC CLAY (B) provides the green tile plastic properties needed dur-
ing pressing and confers the required post-drying bending strength.
The CHINA CLAY (A) complements the unfired properties of the plastic clay,
yet is also essential in increasing the alumina content of the body. Feldspar (or
possibly a small quantity of talc) acts as a flux at standard firing temperatures
(1200-1230 °C).
Quartz, where it participates in the melting of the feldspars, helps balance vis-
cosity and the vitreous flows; where it does not, it constitutes the base matrix of the
crystal phase in the finished product, together with a small quantity of mullite,
generated by decomposition of the china-clays.

328
Porcelain tiles

3 1 2 3 4
1
2

4
1

3 2

3
1

4 2 Key: A - Semi plastic white clay; B - Plastic white clay; C - Sodium feldspar; D -
Quartz; E - Talc.

2 3
PHISICAL FEATURES A B
1
BREKING LOAD BEFORE DRYING Kg/cm2 4/6 8/10

DRY BREAKING LOAD AFTER DRYING Kg/cm2 10/15 20/30

1
3 2 FIRING TO 1100 °C A B

POROSITY % 10/12 3/6

SHRINKAGE % 5/7 4/6

BREAKING LOAD AFTER FIRING Kg/cm2 120/150 250/350

Fig. 179 - Chemical and physical characteristics of raw materials used in porcelain tile production.
The table indicates the Na feldspar, yet K feldspar or mixes of the two may also be used. The lowest
percentages (0.5-1.0%) are shown in the table only as they will not show up on the graph.

Compositions

Porcelain tiles have evolved from the material known as chemical stoneware.
This was once used to produce small (5 × 5 cm, 10 × 10 cm) tiles, using now-
obsolete technologies.
The adoption of modern compositions, roller kilns and modern, high power,
high precision hydraulic presses have resulted in progressive improvement of tech-
nological product characteristics and yielded the benefits of reliability provided by
fast firing.
Fig. 180 compares a traditional chemical stoneware composition (item 1: firing
temperature about 1200-1220 °C and firing cycles of 30-50 hours) and a present-

329
Applied Ceramic Technology

day fast firing composition (item 2: temperature of 1200-1230 °C and cycles of 50-
70 min.).
The structures of the fired materials are similar in both, but in the slow firing
one there is high mullite content and no microporosities (closed or open pores),
thus conferring very high stain resistance.
Nearly zero porosity and the formation of mullite crystals can mainly be attrib-
uted to the extended firing time, which aids sintering and hardening.
The porcelain tile composition shown in fig. 180 (item 2) is typical of a so-called
base body.
For tiles decorated with soluble salts a very white (so-called superwhite) body is
preferred to bring out the intensity and nuances of the colours.
Other raw materials such as zirconium silicate, anhydrous alumina etc. are thus
used to augment whiteness; where these refractory raw materials are introduced
they partially replace quartz.
To clarify the above concepts Fig. 181 gives a chemical analysis of several base
and superwhite bodies as well as a ceramic stoneware body once used with tunnel
kilns.
The SiO2-Al2O3-(K2O+Na2O) tertiary diagram for these compositions is also
given.
These values should only be taken as a rough guide as there is a tolerance for
each in relation to the type of oxide in question.

D A = CHINA CLAY 35/45 %


A B = PLASTIC CLAY 12/18 %
1
C C = FELDSPAR 27/32 %
B
D = QUARTZ 12/18 %

E A = CHINA CLAY 12/18 %


D A
B = PLASTIC CLAY 27/32 %
2 C B
C = FELDSPAR 42/48 %
D = QUARTZ 5/10 %
E = TALC 0/3 %
CD.0025

Fig. 180. Possible porcelain tile compositions using the raw materials described above. 1) Standard
porcelain tile composition for traditional processing cycles (temperature of 1200-1220 °C and cycles of
30-50 hours). 2) Composition for fast cycles (temperature of 1200-1230 °C and cycles of 50-70 min-
utes).

330
Porcelain tiles

40 0 Body components 1 2 3 4 5
SiO2 65 67 71 68 64

K2
Al2O3 24 21.0 18 18 21

O
30 10
3
2O

K 2O 1.5 1.7 1.8 1.4 2.9

-N
1
Al

Na2O 3.0 4.5 4.0 3.5 3.9

a2O
20 2 5 20
4
3 CaO + MgO 0.1 0.8 0.9 0.7 0.7
Fe2O3 + TiO2 0.3 0.8 0.9 0.6 1.0
10 30 ZrO2 - - - 4.4 3.1
90 80 70 60
P.F. 6.1 4.2 3.4 3.4 3.4
SiO2 CD.0027

Fig. 181. SiO2-Al2O3-(K2O + Na2O) tertiary diagram illustrating the following body compositions: 1.
Chemical stoneware (tunnel kiln firing) 2-3. Porcelain tile (base bodies) 4-5. Porcelain tile (superwhite
bodies).

a) Spray-dried powders
Spray-dried powder particle size distribution is largely the same as with other
tile types.
The table below shows particle size distribution for a standard body.

Size range Sieve


(µm) residue (%)

> 600 1%
600 - 425 9%
425 - 300 10%
300 - 250 42%
250 - 180 17%
180 - 125 14%
< 125 7%

b) Regranulated powders
Regranulation consists of increasing grain sizes from 0.1-0.8 mm (spray-dried
powders) to 2-8 mm, depending on the specific process:

– Dry regranulation system:


Grains are very compact, they have the same moisture content as the spray-
dried powders they are made from and they consist of sharp-edged flakes. Grain
size is around 2-6 mm and specific weight 1.2-1.4 g/cm3.

– Wet regranulation system:


Grains are rounded and 1-8 mm in diameter and can be plain or multi-coloured
depending on the number of coloured slips used.
Under certain conditions the grains may have a high moisture content (>12%),
making it advisable to dry them before screening and pressing; optimum grain mois-

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Applied Ceramic Technology

ture content is near to that of spray-dried powder. Specific weight is usually higher
than in spray-dried powders (1.15-1.30 g/cm3).
Whether dry or wet compacted, the percentage of grains added to the basic
spray-dried powders is generally lower than 25% to prevent the risk of subsequent
pressing problems.
The machines and techniques used to produce the grains will be described in
“Plant engineering solutions” further on.

c) Micronized powders
For certain tile types (e.g. marble effect tiles) it may be necessary to use superfine
(micronized) powders which generally have a particle size distribution of less than
200 µm.
These are obtained by crushing the spray-dried powders even further.
Despite the handling and storage problems associated with micronized powders,
where mixed with spray-dried powders they give tile finishes of superb aesthetic
quality.

Example of porcelain tiles obtained with micronized powder.

332
Porcelain tiles

Auxiliary materials for decoration


Soluble salt decoration techniques provide an original finish by using colouring
solutions (or silk-screen pastes) applied on both dried and biscuit-fired bodies (al-
though the latter has largely been abandoned).
The last few years have seen the ceramic industry channel significant resources
into the development and use of new colouring salts. Consequently, know-how has
been increased and aesthetic quality and product personalization potential have been
significantly improved.
These are not simple inorganic salts but organo-metallic complexes, each with a
different chemical nature that depends on the relevant metal, ranging from tar-
trates and oxalates to gluconates.
They provide colouring and brilliance on a par with colouring oxides normally
used for glaze compositions.
The salts are applied by silk-screen units, in disc booths or, more rarely, by spray-
gun.
Combinations of soluble salt application techniques may also be used: the salts
are first applied in a paste thickened with the appropriate additives and followed by
a disc-applied liquid solution.
Materials decorated with soluble salts are partially or fully polished to give shiny
mirror-like surfaces.
The last few years have also seen rapid diffusion of techniques in which semi-
finished products (dry-pelleted materials, glaze or body flakes, glaze powder) are
used to decorate the product directly on the press.
Such techniques are already widespread and are likely to become even more so as
semi-finished materials become ever-more refined and the on-press equipment ever-
more sophisticated.

Basic technological parameters

Final product features depend not only on the chemical and mineralogical nature
of the raw materials, but on the technological parameters used during the produc-
tion process too.

a) Degree of grinding: to aid vitrification and hardening during firing, the ground
slip residue on 230 mesh must be very low, in the 0.5 - 1% range (average parti-
cle diameters of 15 - 20 microns). Such fineness helps to increase the specific
surface area of the particles in the ceramic mass and therefore their firing reac-
tivity.

b) Unfired density: the aim of pressing is to achieve the greatest possible green tile
density that is compatible with the “black core” or degassing problems which can
arise during firing. Standard moulding pressures (350-450 kg/cm2) give pressed
tile densities of 1.95-2.00 g/cm3.

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Applied Ceramic Technology

With macro granito higher pressing pressures (up to 600 kg/cm2) are needed to
compensate for the unavoidable variations in the bulk density of the grains.

c) Firing cycle and temperature: it is in this final phase that the results of grinding
and pressing are seen. Here, the key parameters are temperature and cycle time:
these must be carefully evaluated if the goal of a vitrified material of very low
porosity is to be achieved. On average, fast firing of porcelain tiles requires cycles
of 50-70 minutes and firing temperatures of about 1200-1230 °C.

Note that the above parameters must be evaluated as a whole because the inter-
action and combined effects of simultaneous variations in one or more of them
must be considered as illustrated in Fig. 182.
With coloured bodies it is very important to obtain a good vitrification curve
“balance” vis-à-vis the various compositions; added pigments, in fact, can modify
the tendency of the body to vitrify and shift the optimum firing point (see Fig. 183),
sometimes making it necessary to modify the composition.
Fig. 184, instead, shows changes in bending strength, firing shrinkage and water
absorption as a function of firing temperature.
Finished product properties (virtually zero water absorption, very high bending
strength, exceptional deep scratch resistance and excellent resistance to staining)
are influenced both by the choice of raw materials and the conditions prevailing at
the batching, grinding, pressing, drying and firing stages.
Pr
es
se
ure

dp
rat

rod
pe

uc
tem

td
en
ing

sit
Fir

yg
r/c
m
3

Residue %

Fig. 182. Diagram showing how the degree of grinding, unfired bulk density and firing temperature
influence tile vitrification.

334
Porcelain tiles

Shrinkage
(%)

Fig. 183. Vitrification curves for bodies coloured with different pigments or colouring oxides. In this
example the balance of the different curves may be regarded as satisfactory.

<

>

=
= >

<

Fig. 184. Diagram illustrating changes in bending strength, shrinkage and water absorption for differ-
ent firing temperatures.

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Applied Ceramic Technology

Production technology

Compared to other kinds of ceramic tile, porcelain tiles involve some techno-
logical and engineering aspects that are unique:
– the slip colouring process, common to all porcelain tile output
– batching and mixing of the coloured powders needed for the granitos
– production of grains and their combination with powders of different density
for the manufacture of macro granitos
– distribution of the coloured powders directly in the press cavity (veined pro-
ducts)
– formulation, application and drying of colouring solutions for decorated pro-
ducts.

The block diagram in Fig. 185 gives a general overview of the different stages
of the porcelain tile production process, while Fig. 186 illustrates how flows relate
to the different tile types.
Manufacturers of plain tiles will, of course, have the most straightforward pro-
duction plant set-ups.
Where granitos are manufactured the plant becomes more complex on account
of the batching and mixing of differently coloured and/or treated powders.
Macrogranitos require further changes to the powder granulation process and
also involve handling of separation phenomena which can appear when the grains
are mixed with the spray-dried powders.
Whilst the diagram shows the application of colour onto unfired tiles it could
also be applied to prefired or inertised tiles.
Fig. 187 gives an example of a versatile production plant lay out, arranged for
all the above products, glazed or decorated; each area identifies a department.

The production process

Batching
Depending on the degree of plant complexity and the type of grinding pro-
cess (discontinuous or continuous), batching may feature various levels of auto-
mation.
With discontinuous grinding, batching of raw materials may be carried out us-
ing traditional mechanical leverage systems, or more sophisticated systems involv-
ing individual weighing hoppers with load cells.
Continuous grinding generally features a microprocessor-controlled continuous
weighing system.
The batched mix is stored in a pre-loading silo, from where it is fed into the mill
continuously after mixing of the raw materials and the deflocculant with the aque-
ous suspension containing re-circulated sieve residue.

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Porcelain tiles

POWDER STORAGE

UNFIRED STORAGE

Fig. 185. Block diagram showing flows related to the production of different product types.

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Plain colour

Granito

Veined-shaded

Decorated

Rustics

Macrogranito

Fig. 186. Block diagram showing possible production flows for various porcelain tile types.

In certain cases, producers pre disperse part of the clayey materials (usually the
finer, more plastic part) and sometimes the unfired base body scrap too.
This gives a clayey suspension that can be added to the mill or sent further
downstream where it is mixed with the slip produced by the mill itself.

Grinding
Continuous mills, generally used to obtain the base slip (white body), are becom-
ing more and more common in porcelain tile production plants too.
A series of sieves are installed at the mill outlet. The first of these is designed to
separate any coarse solid particles (e.g. grinding media residue) while the others
have a more technological function, screening the slip to be spray-dried.
The sieving residue is recycled into the mill.

Body colouring
Base bodies can be coloured by the discontinuous addition of concentrated syr-
ups (the term “syrup” refers to a coloured slip with a high concentration of pig-
ments). These suspensions are ground in task-specific mills or by continuously
batching and mixing the syrups themselves using devices for the measurement and
regulation of flow (by volume or mass).

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Porcelain tiles

2
4 6
1 5

CD.0032

Fig. 187. Lay-out for manufacture of porcelain granito, macro granito and decorated tiles.
Key: 1. - Body preparation area; 2. - Pressing and drying dept.; 3. - Glazing dept.; 4. - Unfired/fired
tile storage; 5. - Firing dept.; 6. - Sorting dept.

Volumetric delivery systems batch concentrated syrups held in tanks (each con-
taining just one colour) and allow producers to adjust the delivery rate according to
the desired degree of concentration.
Massic batching units, instead, use density measurements to dose liquid semi-
finished products. Electronic batching control systems ensure accurate setting and
monitoring of the mixing process.

Spray drying
The size of a spray drying department largely depends on the tile type and the
number of spray-dried powder colours required.
Although spray drying is theoretically the same for all ceramic products, the
complexity of the powder mix (dependent on aesthetic and commercial goals) de-
termines the required number of tanks and silos and the number and production
potential of the spray driers.
Furthermore, where regranulation processes are required there will be a need
for extra grain storage silos.
Leaving aside micronized powders and grains (used in veined and macro granito
respectively), optimum particle size distribution for base bodies and colours used to
manufacture granitos is actually very similar to that seen in the manufacture of
other types of tile.

Regranulation of spray-dried powders


In most cases, the semi-finished product used to obtain the agglomerate is the
spray-dried powder. The main industrial methods for the production of the granu-
late are:
– dry regranulation
The spray-dried powders are dry compacted by pelletizers which produce ag-
glomerates that can then be crushed and screened to meet particle size distribution
requirements.

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Storage silos.

– wet regranulation
Agglomeration is effected by spraying the slips (which may be differently coloured)
onto a mass of powder agitated by rotary stirrers. The process simultaneously gives
rise to agglomeration and colouring.

Batching and mixing of semi-finished products (spray-dried powders - large grains)


A key aspect of macro granito production is batching of the powders and grains;
batching is effected by belt feeders placed at the outlet of the respective storage
silos.
As with the raw materials, these devices are equipped with load-cells and encod-
ers to monitor conveyor speed.
An electronic batching control system stores the formulas and controls and ad-
justs delivery rate settings.
The batched and mixed powders are then conveyed to the mixed product silos or
directly into the press feed hoppers.

Pressing
Extreme compaction gives rise to a high density tile structure which limits shrink-
age and greatly reduces the porosity of the fired product. However, the specific
moulding pressure (normally in the order of 350-450 kg/cm2) must be such that

340
Porcelain tiles

the resulting pressed tile density still allows oxidation of organic substances and
escape of the gases produced during firing.
Another essential factor is homogeneity of powder loading inside the press cavi-
ties. The physical nature of some mixtures, such as those consisting of both spray-
dried powders and grains, can vary substantially, thus making pressing somewhat
problematic.
To ensure optimum cavity filling press fillers can be fitted with an alveolar float-
ing grating. These devices allow manufacturers to limit in-cavity filling variations,
resulting in fewer surface defects (shaded lines, differences in colour tone etc.) and
dimensional variations. In recent years the resolution of such geometrical defects
has been significantly aided by the introduction of isostatic moulds.

Hydraulic press.

Drying
The drying of porcelain tiles does not involve any particular difficulties as drier
operating conditions and drying cycles are very similar to those used in the manu-
facture of other sorts of tile.
Where tiles are to be decorated with soluble salts it is essential that they have
bending strengths that support the pressure of silk-screen printing (25-30 kg/
cm2).
Driers may be vertical or horizontal: from a technological point of view these
are essentially the same. Drying cycles in vertical driers generally range from 45 to
65 minutes, depending on tile size and thickness (the bigger and thicker the tile, the
longer the cycle).

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On horizontal driers cycles fall within the 15-30 minute range, once again de-
pending on tile dimensions.
Where soluble salts are applied on glazing lines it is essential that the tem-
perature at the drier exit be stabilised so that the salt spreads uniformly through
the tile.
If this is not so problems of heterogeneous colour tone will probably arise,
becoming especially evident after the tile has been polished.

Decoration
The technology concerning the use of soluble salts is relatively new and some-
times complex.
Steady product evolution and increasing demand for ever-more sophisticated
tiles has seen the number of special glazing lines equipped for this purpose grow
rapidly.
Such lines vary in length from 30 to 80 m depending on the complexity of the
product, which in the simplest cases need just 1 or 2 silk-screen printings compared
to 3 or 4 silk-screen printings plus disc or spray-gun applications in the more com-
plex ones.
The key factors affecting the outcome of glazing are:
– body temperature: affects the diffusion of the saline solution through the tile
– application type and method: the quantities of colouring salts or glazes to be
used largely depend on the application method (disc, silk-screen printing,
spray-gun), as each one has its specific characteristics and properties. Note
that with silk-screen paste decoration the salt takes much longer to penetrate
the body
– applied quantity: the amount of colouring salt determines the intensity of the
colour, as does the quantity of solvent, which affects the depth of impregna-
tion.

Drying and stabilization of the impregnated tiles


Once the salt has been applied on the unfired or biscuit-fired body, it can be
stabilized in a number of ways: by special driers on the production line or naturally
in a dedicated area of the department.

Firing
As already said, firing aims to achieve vitrification (nearly zero water absorp-
tion) of the mass and dimensional stability. The most important factors are:
– reactivity among the body components
– the degree of slip grinding
– moulding pressure
– firing temperature and cycle time.

Optimum sintering in completely vitrified tiles depends on the reactivity of the


clayey components and the synergic vitrification action developed by the feldspars
and the gradually forming vitreous phase.

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Porcelain tiles

The complex destruction reaction of the clayey lattices, which starts with the
vitreous flows and continues until a compact structure is formed, is controlled by
the heat energy supplied during firing.
Other factors, such as slip grinding and pressed tile density, affect the kinetics of
the reaction (i.e. its rate).
The heat energy responsible for the inter-component reactions is defined by the
firing curve (fig. 188); this is designed to supply a quantity of energy that allows
reactions to take place gradually without affecting tile geometry.
Firing cycles currently used for porcelain tiles range from just 45 minutes for
the smallest, thinnest tiles (e.g. 20 × 20 cm, 7 mm thick) to 90 minutes for the
largest, thickest ones (e.g. 60 × 60 cm, 12 mm).
Cycles may stretch to 120-160 minutes where outsize tiles in the order of 100 ×
200 cm are produced.
Maximum firing temperatures range from 1180 to 1240 °C. The exact tempera-
ture will depend on body composition, the extent of slip grinding, the compactness
of the pressed powders etc.
Recently developed roller kilns – specially designed for high temperatures – em-
ploy sophisticated microprocessor control systems which allow manufacturers to
maintain accurate control over firing conditions and thus keep temperatures within
very narrow tolerances.
High power computers and dedicated software let the user display real-time pro-
duction data, firing conditions and work parameters: where required, these can be
printed.

Fig. 188. Example of firing curve for porcelain tiles.

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Single-layer high temperature roller kiln.

Sorting
Although sorting – selection and sub-division of tiles according to the market’s
quality requirements – does not affect the characteristics of the finished product it
is an important part of the production process.
Tile sorting is an essential tool in defining company image: hence sorting crite-
ria must be evaluated with great care.

Polishing and squaring


Polishing of extremely hard porcelain tile surfaces results in mirror-like finishes
of high aesthetic quality.

The various stages of industrial polishing may be summed up as follows:


a) polishing
Tiles are generally wet polished after being sorted and selected by flatness and
straightness of edge. The machines consist of a series of stations with oscillating
rotary heads containing blocks of abrasive material.

The polishing phase is divided into:


– surface levelling: using diamond-tipped tools, the purpose of this operation is to
eliminate any small differences in flatness and even out tile thickness
– surface grinding: effected with coarse silicon carbide based abrasives. Similar to

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Porcelain tiles

Tile flatness control device.

Finished product sorting line.

surface levelling, this operation makes the tile as flat as possible and eliminates
any scratches or surface imperfections
– polishing: this represents the first stage of finishing and involves progressive
reduction of surface roughness through the use of a series of abrasives of de-
creasing coarseness
– finishing: the surface is treated with finer and finer abrasives to produce the final
mirror-like finish.

Once the above process has been completed, squaring and bevelling machines
can be used to finish the edges of the tiles.
Theoretical polishing line feed rates may be as high as 8 m/min, but in practice
work rates are conditioned by tile size and sorting methods: where sorting is manual,
speeds are unlikely to exceed 4 m/min.

b) squaring and bevelling


Specially designed wet milling machines fitted with squaring and bevelling
chucks holding diamond-tipped heads are used: up to 1-2 mm of material may be
removed.
Since edge squaring allows manufacturers to produce tiles of a uniform size it is
sometimes done on all the tiles exiting the kiln whether they are to be polished or
not.

Technical outlook

The technical characteristics of porcelain tiles – consisting of very hard crystal


phases and sintered at high temperature – are undoubtedly the very best that ce-
ramics has to offer.
Further technical development aimed at improving performance may seem, from
a commercial viewpoint, superfluous. From a technical viewpoint, though, it should

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be pointed out that even a multiphase ceramic material has intrinsic microporosity
owing to the impossibility of filling the empty gaps between the solid crystal par-
ticles and the surrounding glass phase, even after a long firing cycle.
Even porcelain tiles feature such microporosity, albeit at minimum levels: unless
controlled carefully, this could lead to problems of surface cleanliness.

In general, open porosity values are very low (about 0.1% in terms of water
absorption and 0.5% in terms of mercury porosimetry) and so the tile surface tends
to resist staining well.
Internal closed porosity, instead, is estimated at 6%, with pore sizes ranging
from 1 to 10 microns; this porosity is exposed during polishing where about 0.5-1
mm of surface material is removed.
There are several ways (some of which have already been widely adopted) to
reduce the effects, or the incidence of residual microporosity itself, on product per-
formance.
On the question of microporosity, it has been demonstrated that penetration of
staining agents and their removal are linked to pore size and diameter. Relatively
large open pores will obviously make the product easier to clean, but to the detri-
ment of the visual aspect of the surface.
Vice versa, very small pores solve the problem in advance, as they block any
intrusion of foreign matter; as part of their product enhancement efforts, manufac-
turers thus prefer this “small pore” approach.
Appropriate adjustments to work parameters can also provide significant in-
creases in tile density. For example:
– by increasing the specific surface area of body components, particularly the har-
der ones (quartz and feldspars). Controlled via the milling process
– by increasing powder compaction with higher moulding pressure
– by using more reactive fluxes compatible with the chemical-physical stability of
the bodies and their tendency towards pyroplastic deformation.

Through application of these and other solutions manufacturers are steadily


succeeding in raising porcelain tile quality even higher.

Aesthetic outlook

In the light of current (2000) output trends, porcelain tile aesthetics will inevita-
bly continue to evolve, widening the range of decorative effects – a key factor in the
success of the product – even further.
New products playing a key role in this aesthetic diversification are the already-
cited macro granitos, tiles decorated with soluble salts, veined tiles, structured rus-
tic products decorated with soluble salt flashing and other techniques such as brush-
ing. Then there are those obtained using mixed application techniques (silk-screen
printing, pelletized glazes and the use of soluble salts on both structured and flat
surfaces).

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Porcelain tiles

With some product types, polishing provides surfaces that closely resemble marble
and natural granite.
This ongoing aesthetic progress can only raise the “added value” of porcelain
tiles even further, and is likely to lead to their use on the residential market and as
outdoor wall cladding through the application of tiles as large as – or even larger
than – 100 × 200 cm.

Conclusions

It is logical to assume that advances in decoration will also allow porcelain tiles
to capture a significant share of the high quality wall tile market (indoor and out-
door tiles for public buildings, shopping malls etc.).
From a technical viewpoint the results already obtained are excellent. Now, to-
gether with the evolution of decoration devices (on the press itself or along the
production line), the industry is steadily creating a well balanced product capable
of competing with “natural” materials.
Further improvements to productivity are likely to be achieved by making
organisational changes to body preparation departments, where the production of
high-quality, versatile “base bodies” will probably become more common, allowing
manufacturers to make modifications, using additives, to the bodies in the slip tanks
or the mills themselves.

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348
Description of ceramic products

Chapter XII

ACCESSORIES AND TRIMS

“Accessories and Trims” form a vast “high added value” product category that
consists of tiles decorated in second (single firing tiles), third and fourth firing,
mosaics, strip and border tiles and other elements that can be matched with both
wall and floor tiles.
The accessories and trims industry is, then, closely tied to standard tile manufac-
turing. It consists of companies that actually produce these complementary prod-
ucts and others that perform specific tasks separate from the actual ceramic side of
manufacturing (cutting, polishing, on-mesh gluing etc.).
Even today, accessories and trims are often referred to as “third fired” products.
This is because, back in the mid-70s when the industry largely consisted of small
family concerns, finished tiles were usually hand decorated (mostly with floral mo-
tifs); since the bulk of output consisted of double firing wall tiles this hand-painted
decoration was subsequently third fired.
Over the last twenty years things have changed somewhat: aesthetics have im-
proved immeasurably and output has rocketed. These changes have affected not only
“decoration” (trims included) but also “accessories” such as strip and skirting tiles.

Some examples of accessories and trims.

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A continuously expanding market for wall and floor tiles – now key elements in
furnishing – has significantly accelerated growth in the accessories and trims in-
dustry, to the extent that some of the original “third firing” workshops are now
modern industrial concerns of key importance.

This evolution has also stimulated the development of complementary pro-


duction processes, which tile manufacturers often prefer to outsource; this has
resulted in the appearance of a whole host of small companies specialising in
tasks such as porcelain tile polishing, border and insert cutting and mosaic mesh
mounting.
This new production scenario has not only allowed manufacturers to respond
quickly to fast-changing aesthetic demand – it also allows them to forecast that
demand and even influence future trends.
Such results have largely been achieved thanks to effective teamwork between
the R&D divisions of the ceramic accessories and trims companies themselves and
ceramic colour producers, the former focussing on aesthetics and graphics, the lat-
ter on glazes and coloured pigments.
A further boost has come from the producers of ceramic manufacturing machin-
ery. Recent developments have allowed technology and automation already tested
with standard tiles to be transferred to the accessories and trims sector.

The market

The accessories and trims market is closely tied to the wall and floor tile market:
tile companies, in fact, usually offer customers a line of “decorated items” (borders,
strips, inserts and trims) specially made by external accessory manufacturers to
match their own ‘plain” tiles.
In recent years the main accessory producers have activated direct-to-market
distribution, providing the final user with a greatly increased selection of plain
and decorated items and thus allowing him to engage in true product personalisa-
tion.
Market potential is continually on the increase, as accessories and trims con-
sumption is to some extent dictated by “fashion” – a concept once confined to the
clothing market.
In Italy alone some 120 companies employ over 3000 workers (late ’90s), gener-
ating total sales of over e 250 million; 9% of companies (11) employ over 100
people and may thus be considered small-medium plants rather than just work-
shops.
Yet attaining reliable output figures for individual items is virtually impossible
owing to the vastness of the product range.

From a quantitative viewpoint, the accessories and trims market is inevitably


linked not only to tile consumption but demand in the construction industry.

350
Accessories and trims

Different ceramic accessory and trim types (from Fashion tile, Gruppo Editoriale Faenza Editrice).

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A brief summary of the various types of accessory might be:


– Materials obtained by subsequent working of the finished tile and a 2nd, 3rd or 4th
firing.
– Elements or pieces obtained by pressing them while plastic and/or by extrusion.
– Elements or trims obtained by dry pressing.
– Elements or pieces complementary to wall tiling (borders, bullnose tiles, strips
etc.).
– Composites of small pieces sometimes of different materials such as marble or
travertine etc. glued onto paper or mesh in the form of particular designs for use
as borders or friezes.
– Trims assembled from several components (e.g. steps, edging).
– Trims obtained from on-mesh assembly of elements cut with a water-jet (e.g.
round or elliptical multi-piece “mosaic” patterns).
– Trims obtained with special techniques such as laser engraving and sculpting,
chemical attack, lapping, partial polishing etc.

At least 50% of output is accounted for by the first item on the list (i.e. tiles
produced in 2nd, 3rd and 4th firing).

Technology

In the mid 70s the accessories and trims industry essentially consisted of small
workshops: decoration in the form of hand painting of simple motifs or application
of decals was largely manual, with second-grade tiles often being recovered for
these purposes.
The decorated tiles were then fired in muffle kilns, which had limited holding
capacity and relatively long firing cycles.
Since then two key innovations have been introduced into the decorating depart-
ment, both regarding the initial phase of operations: automated silk-screen printers
have replaced the hand-held brush while roller kilns have greatly modified factory
layouts and increased cycle flexibility.
The whole decorating process has thus become very similar to the glazing/fir-
ing sequence used to produce the tiles themselves, although manual ability is still
important in ensuring accurate application.
Tile decorators may no longer need any particular drawing or painting skills,
but they must be able to position the printing screens, batch the colours and moni-
tor the process in general.

Moreover, the introduction of computerised graphics has revolutionised deco-


ration by increasing the opportunities for artistic expression while drastically re-
ducing the time needed for new product introduction.
No important innovations are forecast for the immediate future.

352
Accessories and trims

Instruments for chromatic graphic settings (from Fashion Tile, Gruppo Editoriale Faenza Editrice).

Today, accessories and trims still involve a degree of craftsmanship, thus pre-
cluding the introduction of massive automation (which is not justified by the small
production runs).
Nevertheless, given the keenly competitive nature of the accessory and trim mar-
ket and the fact that both machinery and glaze/colour manufacturers dedicate sig-
nificant resources to it, it seems reasonable to expect further improvements in the
future.
Technologically, then, the industry has moved on from manual or carbon-dust-
ing techniques followed by hand painting, to the application of decals, ever-more
numerous and complex silk-screen printings and the dry application of pigment
grains, glazes or glasses.
Recent years have also seen the perfection of cutting and assembly techniques
for composite trims and huge improvements in polishing.
The current trend is towards personalised “relief ” decoration: this effect, attain-
able via the employment of complex on-press systems, acquires particular aesthetic
value in 3rd firing by combining 2-3 silk-screen colour coatings with the application
of highly transparent grains (vetrosa).

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The latter are mixed with glues and starches, the low expansion coefficient
and chemical nature of which allow application of very thick layers, thus provid-
ing double firing, single firing and porcelain tiles with a substantial degree of
relief.
“Vetrosa” are generally layered: a first “pressed” layer is compacted onto the tile
and a second silk-screen layer and a third layer are sprinkled over the entire tile so
as to consolidate the decoration.
Second firing decoration is also increasingly used on porcelain tiles: silk-screen
machines apply powders on the fired tile which then has a fast re-firing cycle (960-
980 °C).
These decorations, often polished, are specially designed to provide not only
excellent aesthetic properties but also a high degree of hardness and abrasion
resistance. This is achieved by mixing compositions that, when combined with
industrial frits, lead to the formation of glass ceramics (partially recrystallised
glasses).
At this point a few words should be said about lapping, a technology often used
to enhance aesthetics. Lapping involves a technique that, even where glazes of a
particular hardness and gloss are applied on perfectly flat tiles, allows the user
(through use of carefully selected abrasives) to partially polish the glaze without

Products featuring polished relief glaze decoration (from Fashion tile, Gruppo Editoriale Faenza
Editrice).

354
Accessories and trims

Lapped and semi-lapped ceramic accessories (from Fash-


ion tile, Gruppo Editoriale Faenza Editrice).

actually removing any surface layers and therefore without exposing any closed
pores in the glaze itself.

The above techniques, then, allow manufacturers to produce a vast range of


effects that realistically simulate marble and other natural stones using “waxed” or
“antique” effects.
Moreover, aesthetic potential can be heightened by matching differently shaped
pieces (that have been cut by water jet) to form intricate compositions.

The water jet technique, used extensively in the porcelain tile sector, allows manu-
facturers to produce myriad geometric forms, from the very simple to the very com-
plex: very high pressure water jets carrying abrasive sands have proved to be highly
effective in cutting the hard, compact ceramic while numerical control devices pro-
vide pinpoint accuracy.
Attractive, highly detailed compositions, pre-assembled on paper or mesh, some-
times using marble or cotto inserts shaped by diamond-tipped tools, can thus be
created. The resulting design opportunities are innumerable.
Another key development in the decoration of accessories and trims is the Four
Colour (or Quadro) system. This is essentially an evolution of silk-screen printing
in which four prime colours are overlapped to obtain any other desired colour: used
in conjunction with computerised graphics, manufacturers can produce high-defini-

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Mesh-mounted trims produced using the water jet tech-


nique (from Fashion tile, Gruppo Editoriale Faenza
Editrice).

tion photographic quality images with excellent colour separation. Four colour print-
ing requires more precise alignment at the moment of application than with stand-
ard silk-screen printing: consequently, the latest machines feature electronic piece
alignment.

Materials

The decorative materials used with accessories and trims can be split into:
– Ceramic colours and pigments.
– Precious metals and lustres.
– Ceramic glazes (relief and non-relief).
– “Vetrosa” grains or glass pastes.
– Metallic-like colours.
– Solvents, suspending agents, printing and painting media.

The ceramic colours used to decorate accessories are similar to those used on
tiles: they largely consist of frits, ceramic pigments and various inorganic raw ma-
terials (mainly oxides) which are mixed and ground to obtain a fine powder (gener-
ally < 30 µm).
Depending on the decoration technique and the specific requisites of the final,

356
Accessories and trims

decorated, fired product, one of the following three kinds of ceramic colour will be
used:
– On-glaze colours: applied on the already-glazed, fired tile; this is then re-fired
between 700 and 950 °C, the exact temperature depending on the firing cycle
which causes the colours to melt and combine with the glaze surface underne-
ath.
– In-glaze colours: these penetrate the glaze during firing. Used extensively in
tableware and porcelain decoration, highly resistant to chemical aggression and
abrasion.
– Under-glaze colours: normally applied beneath a layer of transparent or semi-
transparent glaze, diffusing into the latter during firing.

Ceramic colours are usually supplied in powder form and thus need to be sus-
pended in appropriate liquids so that they can be applied on the tile; such vehicles
generally consist of glycols or organic polyglycols that burn away during firing.
For porcelain tiles a decoration technique has been developed in which the ap-
plied metal organic pigments penetrate the dried unfired or fired tile. Their effects
can be further enhanced after firing by polishing.
Colours for third firing applications are normally pre-mixed by the supplier,
who may also provide the correct fluxes to suit the firing cycles. Where the sup-
plier provides the bases small quantities of pigments can be added to adjust their
shade.

Third firing decoration often makes use of precious metals and lustres. Lustres
are semi-finished items similar to lacquers, made up of organo-metallic compounds
with a precious metal base combined with resins that form a film once fired on glass,
majolica or porcelain.
Lustres produce very thin, intensely coloured films, often no thicker than the
wavelength of the incident light.
The resulting luminous interference and reflection phenomena produce attrac-
tive, highly glossy, iridescent effects. Lustres are classified according to tone, which
depends on precious metal content, and the type of effect (e.g. crackled, veined,
iridescent, pearl).
Metal preparations involve the use of organic compounds with a precious metal
base; these are combined with other organo-metallic fluxes to aid adhesion and with
resins to produce films.
When applied on a smooth substrate they form, after firing, a very thin yet highly
reflective metallic film.
The resulting colours depend on the combination of precious metals: bright
golds (red-yellows consisting of Au), yellow golds (yellow-green, consisting of
an Au/Ag alloy), platinums (white gold, Au/Pt alloy) or palladiums (white gold,
Au/Pd alloy).
Introducing small quantities of matting agent produces a similar effect but with
a matt finish. A whole series of intermediate burnished finishes can be obtained by
introducing special additives.

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There are also other products which can be sprinkled onto the piece: these are
obtained from gold leaf and precipitated gold powder. They are extensively used in
the production of high quality decals.

Organisation

Accessory and trim production enterprises must be flexible and capable of re-
sponding to the needs of their client companies (i.e. tile manufacturers) quickly, as
the market often forces the latter to operate on a just-in-time basis.
That flexibility has largely been attained thanks to the advent of roller kilns,
which, because they are much more compact and have much faster firing cycles than
traditional systems, are far better suited to the production of small lots.
Flexibility has also been enhanced by the increased number of small sub-suppli-
ers performing so-called intermediate processes (silk-screen printing) or comple-
mentary tasks (cutting, mesh mounting, decal application etc.).
In certain manufacturing areas these enterprises form an important part of the
local economy.
Another, equally important factor is logistics, an aspect that has changed consid-
erably over recent years: in an industry in which the handling of materials is cru-
cial, the refinement of logistics management techniques and the appearance of lo-
gistics specialists – virtually unheard of in ceramics until just a few years ago – has
proved inevitable.
It seems reasonable to assume that, in the near future, increasing market pres-
sures will make logistics a key aspect of every stage of the product life-cycle, from
the supply of raw materials to post-sales assistance.
Providing a realistic Italy-wide picture of the accessory-trim output situation is
virtually impossible. Accessories, trims etc. play an increasingly important auxil-
iary role in top-of-the-range tiles, and represent a fast-expanding area of strategic
importance (the last few years have seen consistent annual growth rates of around
12%).
What’s more, there is a whole host of small and very small businesses which are
difficult to categorise as they are often small workshops or even family concerns
focussing on tasks such as hand painting, silk-screen decoration, cutting, bevelling,
gluing and polishing.
Accessory manufacturers (who are in direct contact with big industrial clients
and thus play a key role in this market) now outsource an increasing amount of
work to these enterprises.

Trims

Trims are ceramic products generally used to enclose or “finish” a geometrically


and spatially complex ceramic lay out.
The number of pieces that can be utilised is limited only by the producer’s im-

358
Accessories and trims

agination, as today’s highly personalised tile layouts clearly demonstrate; however,


producers do need to offer a minimum number of different pieces so as to cope with
the majority of laying situations.
There are four main types of trim, each reflecting a particular geometric con-
figuration in the laying area and each including a wide range of products specially
designed to line such configurations, taking into account the need to cover both
internal and external corners. The following table offers only a brief overview of
the most common trims (a complete list would run into the hundreds). As a rule
factories need to be organised so they can produce about 30 different trim types per
tile size.

Several types of trim.

Use of trims is especially widespread in the United States and other Anglo-
Saxon countries; the relative narrowness of the overall tile market dictates rather
scant total output.

In quantitative terms output can generally be calculated as being 15-18% of


total matchable product output.
Most of these (50-70% approx.) are flat, rectangular or square, with one rounded

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MAIN TRIM FAMILIES


1) Skirting complements
both terminal : cove base
and consecutives: normal cove

2) 90° angles between two surfaces, EXTERNAL

3) 90° angles between three surfaces, INTERNAL AND EXTERNAL

4) End pieces and countertops

Some commonly used trims.

edge. This explains why, despite the fact that there are over 160 different types of
trim, so few of them are produced in numbers that justify the installation of auto-
mated machinery.
For further information on the terminology, nomenclature and classification of
these products the reader should consult the relevant trim production standards
(see bibliography).

Production line

An explanation of how a trims production line should be organised is best begun


with the following observations:

360
Accessories and trims

a) single and double firing trims


All trims can be produced using single firing techniques: the choice of technology
largely depends on logistical concerns.
Note that pieces of a size or geometry that require manual fettling (edge scraping)
are easier to handle if fired.
Another point in favour of double firing is that it is more suitable for small lots: a
large amount of fired material can be produced and then glazed and re-fired when
required.
Where instead, production is more continuous and product size/geometry is more
standardised, single firing is a more logical choice.

b) piece handling
Another key factor is the conveying system: while most pieces can be conveyed
normally along a standard production line there are many others which require the
use of refractory supports, racks and plates. However, as the latter generally in-
volve only a relatively small portion of output, an alternative to manual handling
– especially on the glazing line – is difficult to justify.

c) porous or vitrified material


Beyond the obvious technological aspects, the need to produce porous or vitrified
pieces also has important plant engineering implications: for example, a porous trim
glazing line will require bell or waterfall systems while vitrified products will re-
quire the use of disc booths.
In firing increased vitrification will require the use of refractory supports, items
that are unnecessary where the same product has higher absorption.

The main features of a trim production line are illustrated in the flow sheet in
Fig. 189 and the plant layout diagram in Fig. 190.

A brief description of the various stages of the production process follows.

Body preparation
Generally the body is the same as that used for standard tile production (both
porous and vitrified products).
This does not, however, mean that bodies are always spray dried the same way:
with trims spray-drying should aim to produce coarser grains with as low a “fine”
content as possible (maximum 3% at < 200 micron). Moisture content will gener-
ally be higher too (up to 6.5-7%).
This coarser, “wetter” spray-dried product makes the powders more plastic, thus
reducing the density differences created in the piece during pressing.

Pressing
Regularly shaped pieces can be produced using the standard single firing proc-
ess. In this instance the presses are those used for the traditional formats, equipped
with normally-raised moulds or shaped dies.

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More geometrically complex pieces must be produced outside the main line us-
ing manual-ejection presses.
Keeping the moulds clean can sometimes be a problem on account of the
higher moisture content of the powders and the frequent use of fluidisers and
release agents (special sprays or even diesel fuel). Moulds are generally lined
with rubber.

PRESS
PRESSES
e.g. PH 690
e.g. PH 120
whit automatic collection,
fettling, brushing

Manual
Drier
fettling and
rack loading
on refractory
plate
Chamber
drier
Glazing

Manual Support change


glazing and clean

Storage Biscuit storage


Firing
on racks

Firing

Single firing cycle

Double firing cycle

Fig. 189. Trim production flow sheet.

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Accessories and trims

1 – Feeder
2 - Brusher
FUME TREATMENT UNIT
3 - Blower
4 - Water spray
5 - Drive unit
6 - Silk-screen printing
7 - Double disc booth

STORAGE AREA
8 - Conveyor
9 - Bell unit
10 - Glaze stirrer
11 - Spray gun
12 - Scraper unit
13 - Turntable
14 - Single disc booth
15 - Aligner +
straightener
16 - Row former
17 - Aut. KPT4 line
unloader
18 - Aut. KPT5 line
unloader
19 - Press
20 - Aut. KPT2 line
loader
21 - Tile aligner
22 - Roller pre-kiln
drier
23 - Automatic roller
unit
24 - FL 29.4/1600 gas
kiln
25 - Bar cooler
26 - Modular roller unit
27 - Tunnel drier
28 - Glazing station
(optional)
29 - FL 14.7 kiln
(optional)
30 - Press with auto.
unload. (optional)
31 - Complete cutting
line (optional)

Fig. 190. Trim production plant layout.

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Fettling (or edge scraping)


Post-pressing brushing and fettling is a delicate stage of the production proc-
ess. It must be suitable for all types of piece and should be automated where
pieces are flat.
Scrapers, grinding wheels or shaped brushes that can be changed quickly are
normally used.

Drying
A standard fast single layer drier is generally used.
Where geometry allows, the pieces are run through the machine directly on
the rollers; where more irregular they are conveyed in special containers or on
refractory or metal plates.
Where piece thickness varies considerably (with the accompanying risk of ex-
cessive stress) a shuttle drier may be more appropriate.

Glazing
Together with fettling this is the most delicate stage of the process and the list
of potential problems is a long one.
Most difficulties stem from the need to apply a similar thickness of glaze on
differently oriented surfaces.
Glazing may be single or double-row and use bell, waterfall or disc application
systems.
The piece is sometimes tilted (vertically and transversely) when under the ap-
plicator to optimise glazing of curved surfaces.
As at the press outlet, piece-specific scraping and deburring systems are in-
stalled.
Where pieces are of particularly complex geometry they are glazed manually
on lines characterised by versatility and flexibility.
The trims are normally placed on trays or directly on the conveyor belts. In
any case they must arrive at the glazing zone under pre set temperature condi-
tions so as to limit variations in shade.
Glazes should generally be of high thixotropy so that they “freeze” as soon as
they come into contact with the piece.
This reduces the risk of bare patches or glaze build-up on non-horizontal sur-
faces: it also helps stop “lumps” of glaze forming at the edges of inclined surfaces,
an inconvenience that requires fettling.

Storage
Given the highly discontinuous nature of production a loading-unloading stor-
age system should be installed at both the drier and glazing line outlets.

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Accessories and trims

Firing
Regularly shaped pieces may be fired directly on the rollers using the same
firing cycles employed for standard production.
Others of more complex geometry will require separate piece-specific firing
sessions.
Kiln unloading and sorting are normally done manually, with a first quality
yield comparable to that of standard production for simple pieces and about 10-
15% less for more complex items.

Machines

While the manufacture of accessories and trims is still, to some extent, a craft-
like operation, industrial development has been rapid over recent years.
Although the introduction of modern technologies and materials have yielded
products with innovative aesthetic characteristics, this situation has obviously had
(and has) an effect on the originality and “hand made” nature of the individual
pieces.
The range of accessory and trim products is vast: some may be porous, others
partially or totally vitrified (e.g. porcelain tile accessories) and they may be pro-
duced using different technologies (e.g. double or single firing).
A perhaps even more important aspect concerns the configuration of the piece
(i.e. tile, border, bullnose tiles, pencil tiles etc.).
Such a heterogeneous range of products, then, clearly entails a wide range of
plant engineering solutions, an exhaustive description of which is beyond the
scope of this book.
The very nature of the materials (e.g. pieces pressed in a semi-plastic state to
obtain relief effects) calls for a high percentage of manual work and working
conditions are very different from those adopted for other, more standardised ce-
ramic accessories.
However, increased automation and, consequently, improved handling, has paved
the way for innovative plant layouts that reduce the need for manual labour. The
end result has been a huge fall in production costs.
The advent of fast firing has radically modified “third firing” (i.e. ceramic ac-
cessory) production criteria, yet it should be pointed out that its adoption was
neither immediate nor widespread and there are still items for which it cannot be
used (the appropriateness of fast firing ultimately depends on the configuration
and nature of the body).
The degree of sophistication of a third firing plant, then, essentially depends
on the characteristics and the “individuality” of the pieces.
Some manufacturing operations require hybrid layouts that feature a combina-
tion of both industrial and craft-like aspects (i.e. a high degree of automation and
a high degree of manual work).

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The flow diagram in Fig. 191 shows a typical production sequence for third
firing products. It is only intended as a rough guide in that it refers to one specific
product.
For example, flow charts illustrating the production scenario for bullnose tiles,
pencil tiles or pieces pressed in a semi-plastic state would be very different.
As illustrated in Fig. 190, the tiles, after being fired and unloaded from the
kiln, are stored on special racks (should further silk-screen applications or manual
decoration be required) and then re-introduced into the production cycle and re-
fired according to parameters compatible with the new decoration.
Fig. 192 shows a typical layout for the manufacture of tiles with third firing
technology.

The production process

The following section only deals with those processes peculiar to second, third
and fourth firing technology, leaving aside more global matters such as body grind-
ing, pressing, drying glazing and firing.

Decoration

While tile decoration in second, third and fourth firing processes can be done
manually, producers generally use, where possible, silk-screen printing machines:
their level of sophistication depends on the configuration of the piece and the
overall number of pieces to be decorated.
Manual decoration and silk-screen printing may be complemented by the ap-
plication of decals, for which a wide range of automatic machines is available.
Whatever the decorative task, it is preferable to brush the piece before starting.
The market offers a wide range of silk-screen machines, from traditional mod-
els to more modern ones that allow printing to be effected parallel or perpendicu-
lar to the conveyor.
Together, the above machines form decorating lines of varying complexity;
furthermore, the application of electronic logic can provide producers with accu-
rate line feed systems.

Relief effects can be obtained on tiles and multi-tile compositions with dry-
ground grains (Fig. 193) for which the market offers a wide range of application
machines. Production lines may also need to be equipped with compensers.
Depending on how much space is available for the various silk-screen print-
ing/glazing stages, the compenser may be equipped with an autonomous forced-
draught heating system.
Decorated pieces are generally stored on automatic rack systems which can

366
Accessories and trims

THIRD FIRING FLOW CHART

Fired product storage Raw material storage

Line loader Glaze formulation

Brushers and blowers Glaze weighing and mixing

Water sprays Grinding

Disc-type glaze applicator Refining and screening

Fixative spray Lab tests

1st silk-screen printing Finished glaze storage

Spray gun fixing

Storage and control of finished


2nd silk-screen printing
screens

Fixative spray Screen preparation

3rd silk-screen printing

Mobile spray gun

Line unloader

Glazed product storage

Manual finish (where required) Manual silk-screen printing

Kiln loading Manual sponge decoration

Firing Manual brush decoration

Sorting

Quality control

Packaging and palletization

Finished product shipment

Fig. 191. Flow diagram illustrating tile production with third firing technology (standard production).

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Fig. 192. Generalised layout for production of tiles with third firing technology.

368
Accessories and trims

have drive systems consisting of two inverter-controlled mechanical transfer


arms.
The production line may be made up of a complete plant for closed-circuit
silk-screen printing (Fig. 194), itself consisting of a loader-unloader and racks
connected to the decorating machines by a conveyor.

Firing

Except for very thick pieces and trims with variable thickness, tiles decorated
in second, third and fourth firing are fired in single-layer kilns with cycles appro-
priate to the particular decoration (i.e. gold, platinum or glass grains). A complex
piece could therefore require several different cycles.

These successive firing cycles, even at lower temperatures, may alter the prod-
uct shade. It is therefore essential to inspect the tile for any such changes before
each successive firing: should this problem arise testing will be required to find
more suitable firing temperatures and cycles.

Fig. 193. Screen printing machines for the application of dry ground grains (Kemac).

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Fig. 194. Closed-circuit silk-screen printing machine for the production of trims in third firing (Kemac).

Sorting

Tiles are normally sorted at the kiln exit or stored on racks and sorted later.
These products are normally sorted manually.

Recently, semi-automatic sorting systems have been introduced. The choice of


manual or semi-automatic sorting system will depend on the type and concept of
production plant logic and, above all, on the type of material being produced.

Cutting the material

Given the vast range of ceramic accessories and the relative production diffi-
culties, the spread of cutting technology – already used extensively with stone
products – has been rapid. Cutting machines allow manufacturers to reduce stand-
ard tiles to a whole range of sub-sizes which can then be used as borders or strips,
cornices, mosaic elements etc.

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Accessories and trims

These machines cut the ceramic material continuously and generally have tile
conveyance mechanisms featuring variable-speed drives. They also feature verti-
cal and transverse adjustment and allow fast change-over of the diamond-edged
cutting wheels.

Ceramic accessories and trims – and the machines used to produce them – play
a key role in today’s ceramic industry. An exhaustive analysis of such a vast argu-
ment is beyond the scope of this book and this chapter, like the preceding ones on
wall, floor and porcelain tiles, is intended only as a basic introduction.

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372
Floor tiles

Appendix 1

STANDARDS

In July 2000 Italy adopted unified international ceramic tile standards, as drawn
up by ISO between August 1985 and July 1992.
To a large extent, these reflect the contents of the widely applied UNI-EN stan-
dards, yet it should be observed that substantial modifications have been made to
ceramic product classification and test methods. Furthermore, new technological
parameters have been introduced.

With regard to tile classification, the most important innovation is the sub-divi-
sion of the first water absorption class (≤ 3 %) for pressed products into two sub-
groups: the first of these is BIa, which includes tiles with water absorption of ≤
0.5%. This new system allows for easier, more accurate product classification.

Technological tests have been modified as follows:


• NEW TESTS:
– Friction or attrition coefficient
– Impact resistance (resilience)
– Breaking load
– Colour tone
– Pb and Cd leaching on glazed products.

• VARIATIONS:
– Moisture expansion and stain resistance (glazed and unglazed products)
– Agents for resistance to chemical attacks at low and high concentration
– Elimination of the Mohs hardness test (ex EN 101).

A complete version of the new ISO standards would amount to more than 100
pages. Owing to limited space and commercial copyright reasons there follows just
a brief summary of the various tile classes, the test methods and a table comparing
the “old” UNI-EN standards.

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ISO 13006 – PRODUCTS and main characteristics


GROUP A I (ex EN 121)
Extruded tiles with WA ≤ 3 %
– MOR increased from > 20 to 23 N/mm2
– Deep abrasion reduced from 300 to 275 mm3 max.

GROUP A IIa part 1 (ex EN 186-1)


Extruded tiles with 3 < WA ≤ 6 %

GROUP A IIa part 2 (ex EN 186-2)


Extruded tiles with 3 < WA ≤ 6 %
– MOR increased from > 10 to 13 N/mm2

GROUP A IIb part 1 (ex EN 187-1)


Extruded tiles with 6 < WA ≤ 10 %

GROUP A IIb part 2 (ex EN 187-2)


Extruded tiles with 6 < WA ≤ 10 %
– MOR increased from < 8 to 9 N/mm2

GROUP A III (ex EN 188)


Extruded tiles with WA > 10 %
______________________________________________

GROUP B Ia (ex EN 176)


Pressed tiles with WA ≤ 0.5 %
– MOR increased from 27 to 35 N/mm2
– Deep abrasion reduced from 205 to 175 mm3 max.

GROUP B Ib (ex EN 176)


Pressed tiles with 0.5 < WA ≤ 3 %
– MOR increased from <27 to 30 N/mm2
– Deep abrasion reduced from 205 to 175 mm3 max.

GROUP B IIa (ex EN 177)


Pressed tiles with 3 < WA ≤ 6 %

GROUP B IIb (ex EN 178)


Pressed tiles with 6 < WA ≤ 10 %

GROUP B III (ex EN 159)


Pressed tiles with WA > 10 %

374
Standards

ISO 10545 – TEST METHODS

• ISO 10545.1 Sampling and acceptance criteria ex EN 163

• ISO 10545.2 Surface size and quality ex EN 98

• ISO 10545.3 Water absorption and apparent porosity,

relative apparent density ex EN 99

• ISO 10545.4 MOR and breaking load New

• ISO 10545.5 Impact resistance via measurement

of coefficient of restitution New

• ISO 10545.6 Deep abrasion resistance (unglazed tiles) ex EN 102

• ISO 10545.7 Surface abrasion resistance (glazed tiles) ex EN 154

• ISO 10545.8 Coefficient of linear thermal expansion ex EN 103

• ISO 10545.9 Resistance to thermal shock ex EN 104

• ISO 10545.10 Moisture expansion ex EN 155

• ISO 10545.11 Crazing resistance (glazed tiles) ex EN 105

• ISO 10545.12 Frost resistance ex EN 202

• ISO 10545.13 Resistance to household chemicals ex EN 106,122

• ISO 10545.14 Stain resistance ex EN 106

• ISO 10545.15 Leaching of Cadmium and Lead from glazed tiles New

• ISO 10545.16 Colour differences New

• ISO 10545.17 Friction (attrition) coefficient New

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Brief comparison of test methods

TEST Number EN STANDARD Part ISO 10545


(EN) (ISO) standard
Dimensions and surface 98 same as ISO 2 same as EN
quality
Water absorption 99 boiling method only 3 uses boiling method to assign
group (as EN) but also
measurement of porosities (this is
carried out under vacuum)
Bending strength 100 measurement of F and σ 4 measurement of F and (the s in
EN) and measurement of a load
that takes into account surface
area of piece (defined as Σ).
Mohs hardness 101 1 – 10 on Mohs scale inexistent inexistent
Deep abrasion 102 Meas. of lengths and 6 same as EN
resistance volumes erased
Linear thermal 103 same as ISO 8 same as EN
expansion
Thermal shock 104 test with and without 9 test with and without immersion in
immersion in water water, heating temp. changed to
(temp. 15 and 105 °C) 145 °C.

Crazing resistance 105 1 hour to reach 5 Atm 11 1 hour to reach 5 Atm and 2 hours
and 1 hour holding holding

Chemical resistance 106 immersion solutions and 13 immersion solutions and test times
(unglazed) times different from ISO different from EN

Chemical resistance 122 chemical solutions and 13 Harshness of attack depends on


(unglazed) times different from ISO utilisation and degree of resistance
offered by material

Abrasion resistance 154 classes from 1 to 4 7 classes from 1 to 5 with stain test
(glazed) compulsory for class 5

Moisture expansion with 155 Same as ISO 10 same as EN


boiling water
Frost resistance 202 50 cycles from +15 °C to 12 100 cycles from +5 °C to –5 °C.
–15 °C cycles are faster and tile wetting
method is different

Impact resistance - - 5 coefficient of restitution of the


material is measured and impact
damage is evaluated by visual
inspection
Stain resistance 122 K permanganate and 14 chrome green in light oil, iodine in
methylene blue for 24 alcohol solution, olive oil for 24 hrs
hours on glazed on glazed and unglazed products:
products: cleaning with gradually more vigorous 5-stage
water and neutral cleaning.
detergent

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Standards

Pb and Cd leaching - - 15 As per loss test for tableware

Measuring colour - - 16 effected with colorimeter (as per


differences ASTM method)

Measuring friction - - 17 - measurement of angle of


coefficient slippage (as per DIN 51130)
- dynamic attrition measurement
(as per BCRA)
- measurement of static attrition
(as per ASTM but with different
weights and sliding elements)

Material classification 87 - 4 categories in Group B 13006 - 5 categories in Group B (dust


(dust pressed tiles) pressed tiles) (group BIa with AA
- 6 categories in Group A >0.5% in introduced)
(extruded tiles) - 6 categories in Group A
(extruded tiles)

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378
Description of ceramic products

Appendix 2

TABLES AND FIGURES (source: Italy)


Table 1. CLASSIFICATION OF PRESSED MANUFACTS

379
Table 2. PERIODIC TABLE

INERT
GASES

Atomic number
Chemical symbol
Atomic weight

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Tables and figures

Table 3. ATOMIC WEIGHTS TABLE


Based on carbon -12

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Table 4. WRITING AND PRONUNCIATION

382
Tables and figures

Table 5. MATHEMATICAL TABLES


Squares, cubes, roots, inverses, logarithms, perimeter and circles area

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Table 6. MATHEMATICAL TABLES


Numerical common factors

384
Tables and figures

Table 7. MATHEMATICAL TABLES


Plane figures area

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Table 8. MATHEMATICAL TABLES


Conversion factors

386
Tables and figures

Table 9. MATHEMATICAL TABLES


Conversion factors

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Table 10. MATHEMATICAL TABLES


Physical quantities and units of measure

388
Tables and figures

Table 11. MATHEMATICAL TABLES


Si-Units of the international system

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Table 12. MATHEMATICAL TABLES


Metering units conversion factors

390
Table 13/1. TABLE OF MATERIALS MOST COMMONLY EMPLOYED IN CERAMIC INDUSTRY

391
Tables and figures
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Table 13/2.

392
Tables and figures
Table 13/3.

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Table 13/4.

394
Tables and figures
Table 13/5.

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Table 13/6.

396
Tables and figures
Table 13/7.

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Table 13/8.

398
Tables and figures
Table 13/9.

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Table 13/10.

400
Tables and figures

Table 14. SOLID BODIES SPECIFIC WEIGHTS (in kg/dm3)

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Table 15. SPECIFIC WEIGHTS, ANGLES AND FRICTION COEFFICIENT OF SOME


INCOHERENT MATERIALS

402
Tables and figures

Table 16. LINEAR EXPANSION ON 1 M-LENGTH FOR HEATING FROM 0° TO 100 °C

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Table 17. COEFFICIENT OF CUBIC EXPANSION RELEVANT TO DIFFERENT SOLIDS

404
Tables and figures

Table 18. MELTING POINTS OF SOME COMPOUNDS AND MINERALS

Table 19. HARDNESS COMPARATION TABLE

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Table 20. CHEMICAL-PHISICAL PROPERTIES OF CERAMIC PRODUCTS


SUITABLE FOR MILLS (LININGS AND GRINDING MEDIA)

optimum optimum optimum optimum


optimum optimum optimum optimum

406
Tables and figures

Table 21. LOAD FORMULAE OF SACMI MADE MILLS

A) BODY
1) For table 22A and 22D use the following formula:
Kg dry material to charge = 0.55 × Vu × d × y/100
2) For tables 22B and 22C use the following:
Kg dry material to charge = 0.67 × Vu × d × y/100
where:
Vu = working volume of the mill (with lining) in litres
d = slip density
y = % dry matter in the slip
0.55 – 0.67 = mill load coefficient with silica or alubit grinding media.

B) GLAZE
1) For porcelain grinding media use the following formula:
Kg dry glaze to charge = 0.345 × Vu × d × y/100
2) For table 22C use instead:
Kg dry glaze to charge = 0.455 × Vu × d × y/100
where:
Vu = working volume of the mill (with lining) in litres
d = glaze density at the outlet (generally l.7) in kg/l
y = % dry in the glaze (generally 67%)
0.455 = mill load coefficient with alubit grinding media.

407
Table 22a. MILL LOADING
Lining: Silica - Grinding media: Silica

408
Table 22b. MILL LOADING
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Lining: Rubber - Grinding media: Alubit


Table 22c. MILL LOADING
Lining: Alubit - Grinding media: Alubit

409
Tables and figures

Table 22d. MILL LOADING


Lining: Rubber - Grinding media: Silica
Table 22e.

Specific consumption in dry kg/ton of ground body


Product type
Lin. ALUBIT Lin. ALUBIT Lin. RUBBER Lin. RUBBER
Pebbles ALUBIT Pebbles SILICE Pebbles ALUBIT Pebbles SILICE

A) Monoporosa, double firing, white body


1.5-2.5 2-4 1.5-3 3-4
single fired vitrified tile

B) Red body single firing vitrified tile 0.6-1 0.8-1.6 0.6-1.2 1.2-1.6

C) Porcelain tile 2.5-3.5 - 2.5-3.5 3-4

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Tables and figures

Table 23. VISCOSITY CONVERSION TABLE

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Table 24. TABLE OF COMPARISON BETWEEN THE INTERNATIONAL STANDARD


OF THE SCREENS

412
Tables and figures

Table 25. SPECIFIC WEIGHT - CONTENT OF WATER - CONTENT OF SOLID MATTER

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Table 26. EQUIVALENCES BETWEEN BAUMÈ DEGREES AND SPECIFIC


WEIGHTS OF HEAVIER THAN WATER LIQUIDS

414
Tables and figures

Table 27. MAIN COMBUSTION REACTIONS

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Table 28. SEGER CONES

416
Tables and figures

Table 29. WATER HARDNESS

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Table 30. SURFACE TENSION OF FRITS AND GLAZES

418
Tables and figures

Table 31. COEFFICIENTS OF VISCOSITY

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Table 32. OPACIFIERS AND SUBSTANCES WICH CONCUR TO OPACIFICATION

420
Tables and figures

Table 33. NATURAL DYES: METAL SALTS OR OXIDES

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Table 34. ARTIFICIAL AND SYNTHETIC PIGMENTS

Red Si-Zr-Fe

422
Tables and figures

Table 35a. SILK SCREEN PRINTING FABRIC SPECIFICATIONS


Nylon fabric

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Segue Table 35a.

424
Tables and figures

Table 35b. SILK SCREEN PRINTING FABRIC SPECIFICATIONS


Polyester fabric

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Segue Table 35b.

426
Tables and figures

Table 35c. SILK SCREEN PRINTING FABRIC SPECIFICATIONS


Steel fabrics

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The tertiary diagrams and graphs on the following pages illustrate the reactions between the various
oxides and compounds that take place during firing. The graphs are numbered 1-19 to make consulta-
tion easier.

Fig. 1.

Fig. 2.

428
Tables and figures

Fig. 3.

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Fig. 4.

430
Tables and figures

Fig. 5.

Fig. 6.

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Fig. 7.

432
Tables and figures

Fig. 8.

Fig. 9.

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Fig. 10.

Fig. 11.

434
Tables and figures

Fig. 12.

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Fig. 13.

436
Tables and figures

Fig. 14.

Fig. 15.

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Fig. 16.

438
Tables and figures

Fig. 17.

439
Applied Ceramic Technology

Fig. 18.

440
Tables and figures

Fig. 19.

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Applied Ceramic Technology

442
Standards

BIBLIOGRAPHY

For a greater understanding of ceramics and more detailed information the reader
is referred to the following works:

• Kingery, Bowen e Uhlmann – “Introduction to Ceramics”


Wiley-Interscience (1975)

• Grimshaw – “The Chemistry and Physics of Clays and Other related Materials”
Benn Ltd (1981)

• Singer, Singer – “Industrial Ceramics”


Chapmann & Hall (1975)

• Jouenne – “Traité de Céramiques et Matériaux Minéraux”


Editions Septima (1975)

• Sigg – “Les Produits de Terre Cuite”


Editions Septima (1991)

• Handle – “Brick and Tile Making”


Bauverlag (1992)

• Parmelee – “Ceramic Glazes”


Cahners Book (1978)

• Hench – “Characterization of Ceramics”


Dekker Publ. (1985)

• Materie prime per fritte e smalti


Centro Ceramico Bologna

• Tozzi – “Smalti Ceramici”


Gruppo Editoriale Faenza Editrice (1992)

• Fiori, Fabbri, Ravaglioli – “Materie prime ceramiche”


Gruppo Editoriale Faenza Editrice (1989) 3 voll.

• Peco – “I Prodotti Ceramici”


Marzorati (1991) 2 voll.

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Applied Ceramic Technology

• Emiliani – “Tecnologia Ceramica”


Gruppo Editoriale Faenza Editrice (1998)

• Galassi e Pozzi – “La Reologia dei Materiali Ceramici Tradizionali”


Gruppo Editoriale Faenza Editrice (1994)

• Soc. Ceramica Italiana – “Reologia Ceramica Applicata”


Distr. da Faenza Ed. (1984)

• Soc. Ceramica Italiana – “Il reparto Controllo e Sviluppo”


Distr. da Faenza Ed. (1982)

• S. Caillerre – S. Henin – “Minéralogie des argiles”


Masson & Cie

444
Introduction

445
Printed September 2002
by Tipografia Moderna of Ravenna
for Editrice La Mandragora of Imola