Difetti Inglese

Defects
Appendix 3 DEFECTS
All production processes are interlinked. Items carry with them a history from earlier processes which will influence their subsequent performance. In this sense, firing, being the last of a series of processes (edge grinding and polishing aside) and the one in which key physical, chemical and structural changes take place, highlights both earlier latent defects as well as those induced by firing itself. Being able to recognise a defect, at any stage of the production process, and knowing how to identify its causes are skills that are largely acquired by experience: they depend on extensive hands-on experience and a capacity to see the whole production line from raw material storage to sorting as a single organism and require both global and specific knowledge of the production plant and a truly wide-spectrum understanding of ceramics. Acquisition of such abilities is essential to the rapid elimination of production problems; identification of a defect and rapid deduction of its origin allows manufacturers to act fast through carefully targeted machine adjustments and thus limit the costs associated with product rejection or declassing. In general (especially on fired tiles), defects are of the following sort: structural: flatness, orthogonality, cracks, laminations surface: wrinkles, holes, bubbles, particles, flakes, crazing aesthetic: stains, shade or decoration defects process: defects associated more with the handling and flow of materials than the product itself - overlapping tiles, chipping, sticking, jamming etc. While any defect can usually be traced to a specific stage of the production process, it generally has a series of concomitant causes, which, beginning with the choice of raw materials, contribute to its emergence. A rough summary of how such causes are interlinked is given in the following table (tab.1).
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Applied Ceramic Technology
DE.ECT PREPARATION Black core Size
PRESSING
DRYING
GLAZING
.IRING
CAUSE Low grinding residue Incorrect particle size distribution (grinding residue) High H2O absorption Low Grinding too coarse, insufficient bending strength moisture Stains, cratering, specks Screening or iron removal errors Black core Pressure too high or not homogeneous Small side cracks Ejection too fast or imbalanced Size Incorrect filling Dimensional defects Incorrect press settings Low bending strength Low pressing force. Low moisture content Explosions at kiln inlet Pressing force too high, lamination Cracks Incorrect regulation, high temperature Explosions at kiln inlet Residual moisture content high, incorrect regulation Glaze defects Incorrect drier outlet temperature Soluble salt stains Unsuitable drying cycle Cracks Unsuitable temperatures, tiles knocked along line Explosions at kiln inlet Excessive wetting Cracks in middle of tile Unfired tile stored too long Stains, holes, cratering Incorrect application, glaze not aged correctly Planarity defects Poor glaze-body thermal expansion match Colour, surface defects Engobe of poor quality Side cracks Pre-heating too fast Side cracks cooling cracks Cooling too fast Explosions at kiln inlet High kiln inlet temperature Planarity defects Poor temperature control Black heart, glaze defects Unsuitable cycle, erroneous atmosphere Size Incorrect temperature distribution Surface stains Accumulations of glaze condensate Craters, holes etc. Preheating temperature too high
Tab. 1. Possible links between defect and production department.
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Defects
To help understand the causes and effects in the above table the following pages provide a more in-depth explanation of defects and how they correlate with the various stages of the production process. Defects associated with raw materials Defects attributable to the presence of impurities in the raw materials can be split into three main groups: Specks caused by the presence of impurities, usually particles of carbonacious minerals, pyrite, pyrolusite, carbon and mica. Specks caused by impurities absorbed during the manufacturing process such as particles of iron, drops of oil or grease or small fragments of rubber. More widespread defects caused by the presence of other kinds of impurities, such as organic matter and efflorescences. Carbonate particles (calcite and/or dolomite). With monoporosa products the presence of coarse particles of calcite and/or dolomite may lead to craters or holes. The larger the particles, the more extensive these defects. With single fire tiles, the defect depends not only on the presence and size of the such particles but also the melting point of the glaze. Those with low melting points tend to enhance the defect (fig. 1).
.ig. 1. Surface defect caused by coarse grains, degassing during firing.
The decomposition of minerals like calcite during firing is illustrated by the following reaction: CaCO3 > CaO+CO2
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This reaction occurs at approximately 800-900 C, depending on particle size. When particles are small, decomposition is complete and calcium oxide reacts with the other components to form calcium silicates or aluminosilicates (ghelenite, wollastonite, anorthite) of varying complexity. If, instead, particles are coarse, carbonate decomposition may be incomplete or, rather, the reaction of calcium with silica and alumina may remain incomplete. The post-firing presence of free calcium oxide may lead to expansion phenomena when the material comes into contact with moisture (expansion is caused by body components that have not reacted with CaO). The reaction is: CaO + H2O > Ca(OH)2 This phenomenon, where concentrated and localized, may form a hole of a very distinctive shape (fig. 2). When, instead, the defect is more generalized and diffused, latent tile expansion can cause adhesion failure of the tile after laying.
.ig. 2.
After grinding, it is possible to check for the presence of coarse calcite and/or dolomite particles by screening (e.g. via a 200 micron mesh) and then analysing the washed residue under a microscope. Adding a drop of diluted hydrochloric acid can also confirm the presence of carbonates. The exact nature of the particles can be determined precisely by analysing the area with an electron microprobe (SEM) or using more traditional chemical analyses. In this case, the exact nature of the elements in the agglomerate can be identified and the mineral can be identified. To eliminate or reduce the frequency and presence of such defects, it is good practice to minimize the percentage of calcite and/or dolomite particles larger than 120 microns. Using a suitable engobe as an interface between the tile body and the glaze may also be very effective.
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Defects
Pyrite particles Pyrite, an iron sulphide, may be present as an impurity in some types of clayey materials. The most probable defect associated with coarse particles of this mineral is specklike colouring of the body and/or glaze (fig. 3). The decomposition reaction of pyrite during firing is: 2.eS + 7/2 O2 > 2SO2 + .e2O3
.ig. 3.
Where thermal gradients are shallow, decomposition occurs between 400 and 500 C. Where, instead, firing cycles are rapid, and if there is insufficient oxygen in the firing atmosphere, oxidation remains incomplete and different reactions may occur. In both slow traditional firing and fast single-firing, the defects associated with the presence of coarse pyrite particles take the form of atypical coloured specks. If, in the case of fast firing, the oxidation reactions remain incomplete, or if the formed sulphur dioxide causes condensate inside the kiln, problems may be caused by the gas attacking the vitreous surface of the tiles (brightness loss). This problem does not, though, depend on the morphology (size) of the pyrite particles but the total amount of pyrite and conditions inside the kiln. As with carbonate particles, coarse particles of this mineral can be identified by washing the grinding residue left on a 80 mesh (approx. 180 micron) screen and analysing it. In most cases, this defect can be prevented by lowering the size of the pyrite particles to below 180 micron through use of suitable slip preparation sieves. As above, an intervening layer of engobe between tile body and glaze may be effective in solving the problem.
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Pyrolusite particles Pyrolusite (manganese dioxide) and goethite (iron hydroxide), when present as coarse grains, lead to the formation of spots on the surface of the glaze (fig. 4). As above, the particles can be identified with a microscope after screening and washing, again on a 80 mesh sieve. .inal results can, as with the above minerals, be improved by using suitable slip screening sieves (i.e. those able to separate 180 micron particles). A layer of engobe between tile body and glaze may be effective in reducing the severity and frequency of this problem.
.ig. 4.
Carbon particles Coarse particles of carbon in the post-grinding residue can cause concentrated specks similar to those caused by carbonates. These defects stem from combustion of the carbon during firing and the formation of CO2 or CO as per the following reactions: C + O > CO CO + O2 > CO2 .e2O3 + C > 2.eO + CO The carbon monoxide formed reduces the iron minerals in the composition and produces, together with silica and alumina, dark coloured glasses (fig. 5). In fast double firing, the defect may be arise from incomplete combustion of the largest carbon particles, which could finish burning during the second fire and so produce cratering or small dark holes. Identification of the carbon particles that cause the above defects involves washing and screening the grinding residue (at 230 mesh/63 micron) for consistency and then observing it under a microscope.
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Defects
.ig. 5.
An approximate weight percentage of carbon particles can be obtained via calcination of the residue after washing (after removal of carbonates by acid, e.g. CaCO3). If it is not possible to replace the raw materials that are the source of the defect, it may be better to grind it finer and sieve it through finer screens up to 120 mesh (2400 mesh/cm2 equal to 125 microns). An intervening layer of engobe between body and glaze may also be useful in limiting the problem. Specks caused by impurities absorbed during the manufacturing process Iron and/or iron oxide particles Iron and/or ferrous oxides can contaminate raw materials during extraction or during the subsequent mechanical handling. Body contamination is also possible during preparation processes and can occur in mills, storage silos, transfer elevators and cooling systems etc. The defect itself usually takes the form of a spot or agglomerate on the surface. A useful problem identification feature is the texture (softness or roughness) of both these defects. A metallic particle, partially dissolved in the glaze, with a surface that is rough to the touch, probably comes from the kiln cooling zone; a metallic particle enveloped in the body or glaze-body interlayer will definitely have other origins (fig. 6). If, after macroscopic analysis and evaluation of the different characteristics of the defect (position, colour, surface appearance) the causes are still unidentified, microscopic analysis of samples removed from the defective areas is carried out. Analysing the spot with an electron microprobe provides comprehensive information as to the chemical nature of the sample, without which it is virtually impossible to identify which part of the production cycle is responsible.
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.ig. 6.
However, attention should focus on the following: cleaning and tidiness (this can help identify contaminants) preventive maintenance preventive replacement of old plant components. Other impurities Other types of contaminant such as paint, grease, oil, wood or rubber particles can occur throughout the process (fig. 7). Where spray dried powders contain traces of unburned fuel (naphtha), the appearance of a defect, consisting of raised dots (some mm in diameter) over a certain area of the tile, is likely (fig. 8). This defect becomes more evident when fluxing glazes and firing cycles with very brief preheating times are used. As above, there are no general solutions to these problems, which will have to be analysed and the appropriate action taken.
.ig. 7.
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Defects
.ig. 8.
More widespread defects caused by the presence of other kinds of impurities, such as organic matter and soluble salts. Organic material Clayey materials may contain various percentages of organic matter up to 5% or more. When ceramic tiles with compositions containing a significant percentage of organic matter are fired, a dark centre known as black core may appear (fig. 9). In single fire floor (and wall) tiles this defect often occurs when very fast firing cycles or very high pressing pressures are used.
.ig. 9.
Silk-screen printing can augment the defect as it involves the use of organicbased vehicles (glycols or polyglycols), thus increasing the amount of organic matter. As stated above, black core problems depend both on the firing cycle and the characteristics of the raw materials. This chapter mainly focuses on how the problem is influenced by the nature of the raw materials and the impurities contained in them. The black core problem results in a multitude of effects: tile swelling (bubbles in the interior) pyroplastic deformation deterioration of the technical and aesthetic characteristics of glazes shade changes in the body and glaze.
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Tile swelling Depending on its severity the defect is either localised or present right across the tile (fig. 10). It mostly affects vitrified materials and is caused by the low temperature formation of vitreous phases in the body such as the reduction of ferric to ferrous oxide in red firing materials or surface melting, which prevents the escape of the gases that develop inside the piece (CO2 and CO), and areas of the surface are deformed.
.ig. 10.
If these organic materials oxidize prior to formation of the vitreous phase, the defect is not seen. With white firing materials, instead, where there is little iron in the body (< 1%), deformation is largely caused by the presence of gases (CO2 and CO) that are unable to escape because of melting at the surface (or the use of glazes with a low melting point). In addition to swelling, trapped gases inside the tile may form reduced phases close to the glaze surface grey or black in colour. Pyroplastic deformation Shows up as both tile geometry and flatness deformations of varying severity. As mentioned above, black core defects derive from the joint presence of a liquid phase and trapped gasses. It can also be said that in areas where black core appears the percentage of liquid phase is higher and viscosity is lower than in other areas of the tile. .or that reason, pyroplastic deformation occurs more often in vitrified products where porosity is lower than 3%. Deterioration of the technical and aesthetic characteristics of glazes A phenomenon that frequently accompanies black core is the appearance of a considerable quantity of gas bubbles in the glaze layer (fig. 11). This considerably reduces abrasion and stain resistance on account of widespread microporosity in the glaze and worsens pin holing. These gas bubbles are caused by gases (CO, CO2, H2) in the glaze layer that were generated by the oxidation reactions of organic matter originally present in the tile.
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Defects
.ig. 11.
Shade changes in the body and glaze Where the firing environment is not oxidising enough, the formation of black core may, in both floor and wall tiles, alter the colour of the product. Colour changes stem from the reduction of the iron oxide in the body composition, shifting the red shades, typical of this oxide, towards green or brown. With wall tiles containing a high percentage of calcium, however the colour changes from burnished orange to greenish beige. With single fire tiles the change in colour may stem from different degrees of oxidation of any copper, manganese and iron in the glazes, causing a shift towards duller shades. Dynamics of black core formation Black core defects are usually attributed to the presence of carbon residues from thermal decomposition of organic matter in the 300-800 C temperature range. Some researchers have suggested that it is the presence of reduced iron in the grey and black zones of the tile centre that characterizes the defect. Moreover, they have recently come to the conclusion that the components which cause black core are elements such as reduced carbon and iron oxides (.eO and .e3O4). The former is formed by pyrolysis of organic matter, the latter by reduction, mainly of the carbon, from .e2O3, present in the initial clay compositions. The chemical reactions, as well as the sequential dynamics of the black core formation are as follows: Loss of clay crystallization water Hydroxyl (OH) groups, which are freed at different temperatures depending on the kind of clayey mineral, can act as reducers.
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Thermal decomposition and reaction of organic materials As stated earlier, the organic matter dispersed in clays mainly consists of humic acids and carbon. When these materials are heated CO2 develops (below 500 C) as the molecule is split by the following reactions: R-COOH > RH + CO2 (g) R-OH > RH + H2O (g) where R-COOH R-OH RH g = = = = organic molecule with carboxyl functional group organic molecule with hydroxyl functional group product of the decomposition reaction gaseous substance.
If heating continues, the resulting solid residue (coke-like coal) reacts vigorously between 500 and 700 C and produces a nuclei polycondensation reaction. Above 700 C the following reactions may occur: 2 (R-H) > R-R + H2(g) R-H > R + H2 (g) where R-H = is the result of the initial decomposition reactions R-R = is the result of the dehydrogenation reaction. The clayey materials are essentially aluminosilicates capable of initiating a catalysis which aids the pyrolysis reaction that occurs in the 400-500 C range. Hence the following reactions between carbon oxide produced by decomposition of the organic matter and any other available gases: C(s) + H2O (g) > CO (g) + H2 (g) CmH2m+2 > mC (s) + H2 (g) where CmH2m+2 = a hydrocarbon formed from the decomposition reactions s = solid material. Without oxygen, the steam generated by previous reactions may combine with hydrocarbons or the existing free carbon. Oxidation temperature and rate will depend on the type of carbon and on the organic matters in the clayey raw materials. As a consequence of the above reactions, when clayey mixtures containing organic impurities are progressively heated, first the clay crystallisation lattice water
344
Defects
and then, starting from 550-600 C, a mixture of gases made up of H2O, CO2, CO and H2 are released. Reduction of iron oxide Iron is usually contained in clayey materials as hematite (.e2O3) and less frequently as goethite [.eO (OH)], limonite or carbonate. Iron carbonate decomposes at 460 C as per the following reaction: .eCO3 (s) > .eO (s) + CO2 (g) At approximately 400 C iron hydroxide changes into ferric oxide, which is stable in an oxidizing atmosphere (assuming the partial pressure of oxygen to be higher than its decomposition pressure). Without oxygen, hematite can, instead, progressively decompose and lose oxygen: .e2O3> hematite .e3O4> magnetite .eO> wustite .e (7) metallic iron
On the other hand, .e2O3 iron oxide, with carbon oxide and hydrogen (CO and H2) can be reduced even further at temperatures above 550 C. Working conditions that help eliminate black core problems Back core problems can be reduced by: Avoiding the use of high percentages of raw materials (clays) containing organic substances and/or inorganic compounds such as (bivalent) .e. There is no clear-cut upper limit for these materials as development of black core depends on many factors (firing cycle, tile size and thickness, pressing pressure, type of glaze used). .ormulating compositions that give the ceramic tile sufficient permeability to improve oxidation reactions during the pre-heating phase. In this case too, coming up with specific solutions that aid the development of high permeability lattices and thus the escape of reaction gases is no easy task. Nevertheless, the production process must adopt all those measures, where compatible with other parameters, that help bring about this situation. Optimisation of the firing curve Last but not least come in-kiln firing conditions. With some materials the prevention of black core requires that the firing curve includes a zone of constant or slowly rising temperature between 300 and 700 C. This aids decomposition and oxidation and also facilitates outflow of gases before the glaze melts and traps them. Bear in mind that the above temperature ranges may shift depending on body characteristics and the glaze softening point.
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Modification of the kiln atmosphere in the pre-heating zone It has been demonstrated that increasing the partial pressure of oxygen in the pre-heating zone reduces or even eliminates black core; this can be done by increasing the volumes of primary combustion air being fed to the burners. Efflorescences Efflorescences are salt concentrations which appear on the surface of fired tiles when more than a certain percentage of soluble salts is present in the body. High concentrations are caused by migration of salty solutions through the porous lattice of the tile, causing their accumulation, over-saturation and precipitation in areas where water evaporation is fastest. Soluble salt concentrations remaining equal, the problem is more evident on tiles with more permeable bodies. Soluble salts have various origins: they may be an intrinsic element in the raw materials or form during firing as chemical reactions take place among the different components or between the latter and the combustion gases surrounding the tiles. Generally speaking, the soluble salts that cause efflorescences are already present in the clayey raw materials or originate from: gases produced by combustion (SO3) water used in production (sulphides, chlorides, nitrates). In addition to the most soluble sulphates and chlorides in the raw materials, even low-solubility sulphates such as Ca and Mg and others can cause efflorescences. Manufacturing defects attributable to the presence of soluble salts appear as yellow-brownish stains, holes or bubbles on the surface of the glaze or, in some cases, as detachments of the glaze from the body (fig. 12). Yellow-brownish staining may be caused by the presence of iron and manganese soluble salts.
.ig. 12.
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Defects
Sometimes the above defects also depend on: hygrometric state of the ambient air: high levels of humidity and high ambient temperatures tend to concentrate the salts on the perimeter or the corners of the tile. firing conditions: the in-kiln dynamics of air volumes and combustion air turnover are critical factors in eliminating/limiting aggression on the glaze. The importance of eliminating or minimising the raw materials containing these salts is self-evident. If this is not possible corrections may be attempted as follows: try to precipitate the soluble salts in the form of insoluble salts with double exchange reactions. In the case of sulphates the addition of barium carbonate during grinding may produce good results. Added amounts of these salts must be batched stoichiometrically vis--vis the percentages of the already present salts so as not to worsen the situation. in double firing: fire the biscuit at higher temperatures to aid fixing of SO3, Cl ions in the ceramic body (this can reduce efflorescence but sometimes worsen glaze defects). vice versa, reducing the biscuit firing temperature can, in some cases, increase its porosity. This greatly reduces glazed tile defects because, as the water evaporates, the soluble salts are concentrated inside the biscuit and do not affect the glaze surface. Problems attributable to the technological characteristics of the body A proper treatise of this complex subject is beyond the scope of this volume: problems associated with technological aspects of the body differ widely depending on the product (floor or wall tiles) and the employed technology (double or singlefiring). Nevertheless, the following pages summarise some of the more general concepts associated with the various product families below: A) White firing vitrified floor tiles B) Red firing vitrified floor tiles C) Porcelain floor tiles D) White firing porous wall tiles E) Red firing porous wall tiles. Product families A, B and C are generally obtained through single fire technology. .amilies, D and E can, instead, be produced using either double or single fire processes; the problems will differ. The most frequent problems affecting the different body types are:
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Body deflocculation problems Deflocculation difficulties, with all product families, may necessitate the use of higher percentages of water at the body grinding stage. Such problems may be caused by: the nature of the minerals in the clays very fine particle-size distribution of clayey particles organic materials (humic acids or other) in excessive percentages high percentages of soluble salts. Pressing problems Affecting all groups. While actual defects may be different their technological causes are generally similar: mineralogical origin of the clays making up the bodies excessively fine particle-size distribution of the clays or other minerals particles flat (two dimensional), acicular or fibrous plasticity or non-plasticity of the body causing: lamination or peeling low bending strength values dirty moulds. Lamination involves powder stratification, which prevents the release of the air contained in the powders themselves and therefore inhibits pressing performance. Low post-pressing bending strength results in frequent tile breakages in both double and single fire plants. Excessively dirty moulds result in costly cleaning-related stoppages, common with steel dies but relatively rare with rubber-lined or resin ones. Drying problems These differ depending on production technology (single or traditional double firing). However, their causes are generally to be found in: the nature of the clayey minerals the excessively fine particle-size distribution of the clays atypical behaviour of pressed tiles during the drying phase (high expansion and low bending strength). These aspects or conditions of the raw materials making up the body may lead to the following production problems: excessive shrinkage during drying low post-drying bending strength. The defect is more evident where single fire technology is used as the tile is exposed to more mechanical stress, especially on the glazing lines.
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Defects
Generally, the bending strength of a ceramic product after drying should be higher than 25 kg/cm2. Other defects are influenced by: drier management (drying curve) moisture content of tiles entering the drier hygrometric / general conditions of air. Problems associated with the nature of the raw materials that appear after firing Like much of the previous subject matter, an in-depth treatise of these problems would require a book in itself. The variables that depend on sintering or vitrification are many and their interaction is highly complex. Hence only a general description is given. Good vitrification or sintering of the body evidently depends on the quality of the raw materials, their ratios and reactivity among the different components (oxides). It is obvious the characteristics such as: high bending strengths low shrinkage product-compatible porosity wide firing range mainly depend on the origin of the raw materials and their reactivity. Low dimensional stability during the firing process is, without doubt, more frequent in vitrified materials (groups A, B, C) where dimensional variations are more evident. The associated problems are ones of geometry (orthogonality), dimensional variation, sides (squareness) etc. The narrower the firing range, the more evident the defects. While the origin of the problem may also lie in the production process (pressing, firing etc.), it is the nature of the raw materials (i.e. the organic content and clay particle size) and thus body composition that play the key role. The stability of a vitrifiable composition is, in fact, regulated by the extent of the vitreous flows being formed and their viscosity. It is known that white firing bodies have wider stability ranges than red firing ones because of the nature of the glasses being formed and their higher viscosity. The phenomena is highly complex and dependent on many interlinked chemical-physical factors. Body composition or, rather, the nature of the raw materials, has much influence on the severity of the defect. Other defects associated with raw materials a) Excessive drying shrinkage This usually causes several small edge cracks some 1 to 1.5 cm long, many usually appearing on each side. This defect is typical of many high-plasticity clays and generally appears because the low bending strength of the green product is unable
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to withstand the mechanical stress caused by shrinkage. .or most pressed tiles the dry shrinkage limit is around 0.25-0.30%. This defect may result from clays extracted from different parts of a quarry or from their insufficient homogenisation. Shrinkage can be checked via simple laboratory tests. b) Low green tile bending strength This defect tends to cause frequent breakages in both single and double fire products either when tiles are turned over or loaded into the rapid driers. However, the resulting unfired waste can be reintroduced into the mill and is fully recyclable. To obviate this problem bending strength should be no lower than 0.7-0.8 N/mm2. c) Low dried tile bending strength Causes frequent breakages at critical stress points on glazing and conveying lines. Dry bending strength should normally be no lower than 1.8-2.5 N/mm2. The defect has its origins in the clay percentage or low plasticity. d) Excessive free quartz An increase in the percentage of free quartz in a body formula increases its expansion coefficient, the alpha-beta inversion at 575 C and the corresponding mechanical stress. Dilatometric analysis will identify quartz variations. If the quartz does not react (and change into silicate) during firing, coolinginduced creep can also occur. e) Low fired bending strength Results in inferior finished product resistance and customer complaints of wastage during tile laying. Insufficient reaction and sintering of the clay and non-clay components in the body lie at the heart of this problem, which may arise because of changes in either percentage or particle size distribution. As with the above defects, routine checks on technological characteristics generally prevent this problem. Body preparation defects a) Insufficient grinding The effects of insufficient grinding differ depending on whether the body has a single component or is an actual compound. In the former case there is a slight change in surface appearance and reduced bending strength, in many cases only slight and difficult to detect. The latter case is a more serious affair, with coarser particles delaying important reactions (i.e. carbonate degassing).
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Defects
The usual outcome is that the tile falls outside required physical-mechanical tolerances. Prevention and correction of this defect generally involves checking slip sieving residues and, when possible, the particle size distribution pattern. b) Inconsistent moisture content in powders to be pressed This defect usually occurs when the powder to be pressed has not been mixed in draining it from the various silos or stored long enough for moisture content to homogenise throughout the silo. The phenomenon is more frequent in dry grinding processes. The first effect is a tendency towards lamination; green and dry bending strengths are also found to be inconsistent. With spray-dried powders the problem is less serious because the moisture is concentrated inside, not outside, the particles. Moisture control is usually performed on powders sampled from different points of the conveyor belt over a time span of approximately one minute. Differences in moisture content can be reduced by storing spray dried products for at least 24 hours and dry ground wetted ones for 36-40 hours. c) Excessive moisture content in powders to be pressed The first effect of excess moisture is that the powder tends to stick to the die, thus requiring more frequent mould cleaning. Note that in fast fire processes excess powder moisture causes, indirectly, black core. d) Low moisture content in powders to be pressed Low moisture content makes pressing more difficult and can lead to lamination and de-moulding problems. Note that powders with a low moisture content tend to have higher pressing expansion. This increased expansion results in greater friction against the die liners when the lower punch ejects the tile. It can also cause low green bending strength and subsequent breakage later on in production. e) Excessively fine particle size of the powder to be pressed Causes lamination defects as a result of the low bulk density of the powder and the considerable air that needs to be expelled. f) Excessively coarse particle size This gives a rough tile surface with a granular appearance. .urther troubles include frequent dirtying of the dies. g) Particle size separation Particularly seen in the production of porcelain tile, this problem occurs where particle segregation in the press hopper causes the outer die cavities to be filled with grains coarser than those in the inner cavities. The defect is extremely detrimental when various coloured powders are mixed (e.g. salt and pepper).
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Generally speaking, it is necessary to use spray-dried powders of uniform particle size distribution (in the 0.3-0.5 mm range). h) Encrustation lumps These appear because condensate forms in the storage silos, the elevators and the hoppers. As moisture content and density in these lumps differ from those in the rest of the powder, their firing behaviour is also different. In the most evident cases, small cracks form around the lump on account of shrinkage differences. In less evident cases small depressions form on the surface of the glaze because of lower absorption in the areas affected by the lumps. To eliminate the defect the powder is passed through finer mesh sieves prior to the press feed point and efforts are made to prevent the lumps forming in the first place. Pressing defects Dirty dies The problem shows up as surface defects on the just-pressed product and can remain after glazing and firing (fig. 13, left). The quality of the die surface is highly important as any wear-induced roughness causes powder to stick to the die more easily. Rubber-coated dies help prevent this problem and can drastically reduce the frequency with which cleaning needs to be carried out.
.ig. 13.
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Defects
Lamination The defect consists of foliated stratification of the material that can sometimes be seen only after glazing and firing (fig. 14).
.ig. 14.
It has several possible causes: 1) When the first entry speed of the punch is excessive and does not allow air to escape from the powder. 2) When the punch lifting time between the first and the second entry is too brief to allow escape of the air. 3) When die construction is erroneous and clearances (which should take into account the working temperature of the die) between the liners and punches are too narrow. Defects caused by ejection difficulties This defect usually appears as: cracks running from the sides to the middle of the tile, but without necessarily affecting the edges themselves (fig. 15). planarity defects. There are various causes: 1) The upper punch moves too fast during ejection. 2) The die liners are not properly tapered, thus preventing normal expansion of the piece. 3) The interval between the end of pressing and the beginning of ejection is too long. 4) Excessive mould wear. 5) Unsuitable back pattern. .lash on tile edges (residues compacted between liners and punch) This defect is generally observed at the end of the brushing and fettling opera353
tions carried out on the collecting station. It can occur on both the face and back of the tile. The cause lies in excessive mould wear. The flash that forms during pressing on the edges of the surface to be glazed is usually removed by brushes, while the larger flashes on the back of the tile are removed by scrapers. Small bits of flash sticking on the surface to be glazed can cause visual defects and selection losses (fig. 13, right). .illing defects Non-uniformity of filling depends on filler box regulation and causes different densities at different points on the tile usually detected by thickness checks and bulk density measurements with either a penetrometer or mercury densometer.
.ig. 15.
Excessive pressure In the fast single fire process excessive pressure can cause black core. The particles are packed so tightly that the gas produced by the (sometimes incomplete) combustion of the organic substances is unable to escape. Glaze and glazing defects There follows a description of the most commonly encountered defects. Defects caused by the glaze a) Excessive or insufficient grinding Over-grinding has a negative effect on glazes with very high surface tension such as zircon whites where shrinkage causes cuts or cracks to appear on the glaze before melting. The effects of unusual particle size distribution are many. .or example, an overground rustic corundum glaze will have a non-vitrified surface on account of excessive refractoriness, while excessive grinding of a glaze to which zircon sand materials have been added also produces cracks that do not close during melting.
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Defects
Considerable changes in surface appearance aside, excessive grinding always produces a glaze of higher water absorption capacity, thus causing drying problems. When glaze grinding residue is too high (materials ground for a short time) the glaze is difficult to sieve and normally has low viscosity and settles easily. Problems can be avoided by screening and checking residue at all mills before the material is used in production. b) Lack of plasticity Plasticity, where it refers to a glaze, is an improper term, yet one widely used to indicate its capacity to adhere to a tile body. The problem is often difficult to detect on the green tile as it generally appears during the initial stages of firing, when the glaze first starts to shrink and then melt; because it does not stick to the body properly, it tends to crawl away from the body. In single-firing, adhesives of the C.M.C. type often need to be used. This adhesive is also useful in resolving glaze detachment problems in the double fire process. Plasticity can also be improved by using ball clays, kaolins (these can be added in percentages of 8-10%) and bentonites (up to maximum 2%). The above materials, in addition to exerting a plasticising action, also play an important role as suspension agents. Proper suspension is important in that it ensures consistent application density and prevents separation of the larger particles by settling. c) Poor firing stability Some glazes are highly unstable, sensitive to very small temperature or firing environment changes. This sensitivity often results in tiles of different shades. d) Excessive fusibility The origin of this problem lies in the composition of the glaze itself. Excess fusibility can cause surface bubbling (pin holes) at the tile sides or where the glaze layer is thinner. e) Incomplete frit melting A problem that clearly has its origins in the frit and normally causes two types of defect: 1) surface bubbles and other surface defects caused by the escape of gaseous products that have not fully decomposed during melting. 2) partial solubility of components that have not chemically bonded completely. It is thus important that the supplied frit be subject to in-factory quality control checks.
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Application defects a) Glaze detachment The fired tile has areas of varying size where the glaze has crawled away from the surface during firing. These zones are generally surrounded by a rounded, thickened border. Such glaze movements can sometimes appear on the sides or edges of the tile; in other cases they take the form of extensive, thickened slicks in the midst of unglazed zones or may appear as circular holes of varying dimensions. .actors in preventing this problem include the quantity of plastic material in the glaze, application thickness, glaze-body adhesion, low grinding times and the unfired strength of the glaze. b) Glaze shrinkage Tensions between ceramic body and glaze may generate small fractures in the latter. Subsequently, where the melted glaze is highly viscous, these fractures are not sealed; typical of majolica with a high zirconium silicate content, the problem is much less frequent in most lead compound glazes. Moreover, where melted glaze surface tension is high, the glaze shrinkage problem is proportionately high. Glaze shrinkage (by way of surface tension) is attributable to: improper type or quantity of plastic material inclusion of special components. The presence of materials such as zinc oxide, talc, magnesium carbonate, marble, aluminium hydrate, all characterised by extensive drying and firing shrinkage, may be the source of such defects. These materials hold significant quantities of water and influence glaze viscosity. Over-grinding Excessive grinding increases glaze shrinkage and causes loss of adhesion. Presence of soluble salts The use of frits or raw materials of marked solubility can lead to phenomena similar to those described earlier. The defect tends to appear when manufacturers use very fine-ground glazes that have been left in slip form for some time. Overlapping applications Glazes not normally subject to shrinkage may produce this problem when: the base glaze is dusty or prevents the subsequently applied glaze adhering properly. the second application re-wets the just-dried first layer and causes it to lift off the body. the two glazes are incompatible on account of surface tension and viscosity during firing.
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Defects
c) Interaction with production processes Note that these defects often have joint causes and may originate from a combination of several factors independent of the glaze in itself. Poor glaze-body match Incompatibility between body and glaze expansion coefficients can cause serious defects. During cooling molten glaze interacts with the body; if the thermal expansion coefficients of body and glaze differ considerably tensions may arise, causing cracks in the now hardened glaze (crazing-flaking). a) Crazing and flaking If the thermal expansion coefficient of the glaze is higher than that of the body, the glaze, as it cools below the transformation point, contracts to a relatively greater extent and thus stretches. If the resulting tension is higher than the modulus of elasticity of the glaze, breakage occurs. Known as crazing, this defect appears as hairline fractures. Vice versa (i.e. when, during cooling, the thermal expansion coefficient of the body is higher than that of the glaze), the glaze is compressed. This causes it to fracture into numerous flakes that detach from the tile along the fracture lines, hence the term flaking. .laking, nevertheless, is a relatively infrequent phenomenon as compression resistance is some ten times greater than tensile strength. Experience has shown that it is actually preferable to have glazes that are slightly compressed as this helps contain any increase in body volume caused by moisture absorption prior to, during and after laying. Quite often, crazing appears as a series of localised fractures of circular shape, mainly at the sides of the tile. b) Glaze-body interaction Also deserving of mention are the expansion phenomena caused by interaction between body and glaze. Acceptable reactivity between body, engobe and glaze is indispensable if they are to adhere to each other properly and avoid separation due to edge impact, more frequent with double fire than single fire tiles on account of their lower reactivity. Glazed surface defects Tile surface defects take a multitude of forms. They rarely have one clearly definable cause but generally stem from a number of interacting negative factors. These defects rarely affect the functionality of the tile but can seriously compromise its appearance.
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a) Pin holes on the glaze These are a frequent problem and one of the most difficult to eliminate characterised by post-firing minute holes, hollows or craters scattered across the surface in varying concentrations. The holes are created during firing by gaseous bubbles bursting through the surface tension of the molten glaze. Under certain conditions this phenomenon does not have any lasting effects as the molten glaze automatically flows back into the pit and neatly seals it. The key gas escape factors are viscosity and surface tension. Glaze viscosity at its maturing temperature is an important characteristic as it determines the capacity of the glaze to spread over the body and form a uniform layer. More fluid glazes allow more complete, faster evacuation of the gasses entrained in the vitreous mass. .iring conditions being equal, high viscosity glazes are far more susceptible to large-size pin holing. Surface tension also pays a key role: higher tensions tend to aid re-absorption of residual bubbles during cooling. Nature and formation of gaseous emissions a1) Defective fritting Some glaze constituents do not react perfectly during preparation of the frit (especially at the melting point) and thus retain a certain instability, re-interacting with the other constituents of the vitreous mass during the second fire and generating gas. .rit instability or heterogeneity is particularly deleterious in rapid firing cycles as the available reaction times during the second fire are very short indeed. Consequently, gasses may generate defects on the molten surface that do not disappear at the cooling stage. a2) Additions in the mill With rapid firing cycles and where materials need to be added to the mill, it is important not to use raw materials with degassing or reactivity characteristics that clash with firing duration and/or temperature. .ailure to observe this rule can lead to dot-like craters, holes and pin holes etc. a3) Over-firing Over-firing of the glaze can cause pin holing. Glazes with a high alkaline or boron oxide content are particularly susceptible to this defect. These oxides, in fact, tend to volatilise if over-fired, thus giving rise to the offending bubbles. a4) Salts These are usually sulphates and carbonates (especially soluble ones), which can originate from the body, the grinding water, the pigments, additives or the glaze itself, and can cause pin holing.
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Defects
Specks in the glaze may have accidental causes such as: Contamination of the glaze during the production cycle Air retention during application Imperfect drying Incomplete firing.
b) Depressions (dimples) Glossy glazes, especially zirconium whites, often have their surface appearance marred by evident dimples. Appearing as a shallow circular hollow, the defect is rarely more than 5-6 mm in diameter. Such imperfections may have their origins in frit grains of large particle size, usually the result of imperfect sieving. During melting these grains behave differently from the rest of the vitreous mass. On double fire tiles depressions may also be caused by significant variations of water absorption in the body. c) Relief grains Grains standing out from the surface of the glaze are frequently a consequence of contamination that occurs during the production process. The defect may also stem from an in-mill addition of zirconium silicate or other hard materials that have not been suitably ground. In this case the defect is characterised by easily visible, small, white, protruding specks. d) Loss of gloss or mattness .inished tiles sometimes lack the intended shine; instead, their glossiness varies from one part the tile to another. In other cases the problem appears as variations in intensity or shade of colour. Where a highly fusible glaze is applied on a particularly porous body (especially where the latter is highly siliceous) it can react so intensely with the body that nearly all of it is absorbed. This aesthetically weakens the vitreous phase in the glaze to the extent that the final appearance is significantly altered. Concentration of those non-vitreous, low-reactivity compounds in the glaze usually gives rise to opaque and matt surfaces. This defect is frequently accompanied by the appearance of numerous tiny holes on the surface of the glaze, giving it a sponge-like texture. We have seen how an excessive tendency toward volatilisation of the alkaline oxides can cause dots to form. Glazes sometimes have undissolved phases, usually made up of silica or oxides (calcium, barium, aluminium, magnesium, tin or chromium) as well as spinels. If these usually opalescent phases are present on the surface or just beneath it, the glaze may occasionally be characterised by pseudo-mattness. Devitrification is a rather complex process and often creates problems. Surfaces intended to be uniformly matt may have relatively glossy patches or, vice versa,
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glossy glazes may be marred by duller areas. Earlier on we stated that devitrification, while dependent on glaze composition, is also heavily influenced by the firing cycle and, even more so, the cooling pattern. Generally speaking, where manufacturers using conventional cycles intend to prevent devitrification, the ratio between the SiO2 and basic oxides in the glaze should be 3:1. Nevertheless, even where this ratio is maintained (and even where ratios theoretically more efficient in preventing devitrification are used) the problem can still arise. This is because not all basic oxides behave the same way. Excessive calcium, magnesium or zinc oxide contents are notorious causes of devitrification. Moreover, the behaviour of the various devitrifying oxides during cooling differs enormously. Alumina matt glazes, for instance, are highly sensitive to temperature differences at this stage. Hence these glazes or those with high ZnO, CaO or TiO2 contents have a tendency, under certain conditions, towards non-uniform surface mattness or glossiness. The most common scenario is where the matt finish varies from one tile to another, an occurrence largely due to variation of the firing curve in different sections of the kiln. Slower cooling, in fact, gives complete devitrification while higher firing temperatures can increase shininess. This explains why gloss, satin and matt glazes all appear sensitive to devitrification phenomena when firing cycles are unsuitable. Other phenomena are closely correlated with devitrification problems. One of the most common is found in single layer rapid firing kilns where the leading edge of the tile has a markedly different appearance compared to the rest of it; with matt or crystallised glazes it looks shiny or bubbled. While evidently connected to cooling especially direct cooling this defect stems from the extreme sensitivity of these glazes vis--vis variable cooling temperatures. In such cases the thermal inertia of the kiln walls or even the tile mass itself may be sufficient to cause that non-uniformity. Depending on circumstances, these differences can then give rise to an overly rapid increase in viscosity with consequent bubbling, lack of devitrification and the appearance of shiny areas on the tile. e) Sulphur The damaging effects of sulphates contained in the tile body, the raw materials, the grinding water or the sulphur compounds in kiln fumes give rise to a whole series of finished tile defects. The most common are opalescence, surface halos, pin holes, bubbling, devitrification and creasing (wrinkling) at the sides. These defects usually appear more frequently when highly alkaline compositions are used. The alkali are usually introduced into the glaze as frits. Nevertheless, when these frits are insufficiently rich in silica, boric oxide or alumina, or if they have a certain reactivity due to incomplete fritting, the alkali may remain open to attack by any sulphur oxides. Reactions of the above type (i.e. determined by sulphur in the composition or the kiln fumes) are also likely to occur during fritting, although tests have yet to confirm this hypothesis.
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Defects
The amount of sulphuric and sulphurous oxide contained in the combustion fumes varies depending on firing conditions. Oxidising atmospheres, particularly during the initial stages of firing, tend to accentuate sulphuric oxide production. The concomitant presence of high quantities of water vapour (from removal of water from the tiles and decomposition of hydrates) can form sulphuric acid. This attacks any basic components of the glaze (especially lead, calcium, magnesium) not securely bonded to the silica or other acid components of the glaze. Sulphates extremely damaging as they do not decompose easily at high temperatures thus form. These salts generally tend to form thin films on the surface of the tile, giving rise to devitrified areas. When these compounds are concentrated (e.g. at the edges), creasing or bubbling occurs. The phenomena described thus far could be detrimental in rapid double firing. The influence of stains The introduction of colouring oxides can generate defects on the surface of the glaze after firing. Such phenomena can generally be traced to unsuitable or incomplete pigment preparation, or interaction of the latter with some glaze components. A description of the most common production plant problems follows. a) Volatilisation Some colouring oxides are subject to volatilisation phenomena, giving rise to numerous defects on the tile surface during firing. Chromium oxides, for example, are used extensively in ceramics on account of their excellent colouring power and relative stability. Nevertheless, pure chromium oxide has a strong tendency to generate halos because of the sheer intensity of its colouring power, despite the fact that its vapour pressure is low and its volatilisation ratio not particularly high. Halos can be eliminated via calcination and subsequent oxide washing. b) Calcination Calcination is a key phase in the pigment preparation, its purpose differing according to the raw materials in question and the final product type. Generally speaking, it can be said that, in its simplest form, calcination aims to decompose the constituent components of a colour at high temperature, causing them to release gas. If noncalcinated colours are used in glazes they inevitably cause numerous defects such as specks, bubbling, halos etc. Where combined with the formation of crystalline lattices, the calcination function is a much more complex one. These lattices are the product of well mixed raw materials; during calcination the latter give rise (with the aid of catalysts) to crystalline neo-structures inside which chromophore ions are present by way of ionic exchange. The calcination process can also be used to obtain solid oxide solutions with
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improved characteristics as regards the original, individual components. A typical example of this is calcination of chromium oxide and aluminium hydrate to obtain a solid solution of the two oxides; this improves stability and reduces volatilisation of the chromium, especially at high temperatures. c) Washing After calcination the colour may still contain a certain quantity of salts subject to volatilisation. To eliminate these the finely ground oxide is washed, using water and additives that aid leaching of the soluble compounds. In the above-described case washing removes that part of the chromium oxide which would otherwise fail to enter into formation of the solid solution and would be water-soluble, its diffusion subsequently causing halos. Washing is also indispensable when calcination aims to create a crystalline structure and uses excess amounts of catalyst and chromophore salts. The production of zirconates is a classic example. With, for instance, turquoise zirconate, the process begins with zirconium oxide, quartz, vanadium pentoxide and catalysing agents. At the end of calcination the crystalline zircon lattice forms, with ionic diffusion of vanadium ions. This is usually achieved by introducing an excess of vanadium pentoxide. This, together with the catalysts only, needs to be washed out after calcination. If the catalysts are not removed they can reduce the colouring power of the oxide and, because they are usually soluble salts, can cause the relevant defects when added to the glazes as described above. Equally detrimental are vanadium salts that have failed to bond inside the lattice. As vanadium is a powerful fluxing agent, concentration of its salts during drying generates aggregation zones; when fired, the latter have different fusibility characteristics compared to the surrounding vitreous mass. Hence glazes with a high percentage of colours containing vanadium salts may be damaged by post-firing dimples and non-uniform colour. If the surface is screen printed reactivity is accentuated and some zones may be poorly coloured. d) Reactions with contaminants While colouring oxides generally have a certain inertia vis--vis the glazes in which they are dispersed, their sensitivity to the chemical composition of the glaze is far from negligible. This tends to highlight defects caused by colours reacting with glaze components or, more frequently, contaminants. The behaviour of red-pink oxides with a SnO2 - CaO - SiO2 - Cr2O3 composition is a classic example. These oxides are extremely sensitive to reduction. The presence of reducing contaminants such as carbon, iron or other metallic particles can cause alterations to the colouring lattice; the chromium chromophore ion is separated from the crystalline matrix by the reducers, thus freeing the tin oxide contained in the lattice. Consequently, the contaminated area is completely de-coloured. The surface of the finished tile is thus dotted with small white specks caused by the opacifying action of the tin oxide. Where the contaminant particle is quite large a dark spot appears at the centre
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Defects
of the affected zone. These defects are usually caused by inefficient removal of iron from the glaze. Use of magnets and the addition, in small percentages, of oxidants such as cerium oxide usually resolve the problem. Glaze application defects a) Drops falling on tiles One of the most evident and frequent defects where glaze is applied in disc or spray gun booths, it is caused by the fall of drops of glaze condensate; these can form at any point on the inner wall of the booth, often because the air exhaust suction is insufficient and the pulverised glaze thus condenses on its inner walls. The defect can occur even where pressure is very low. Likewise, with discs, the defect may be caused by condensate forming directly in the disc unit because of imperfect atomisation. The problems may also be caused by incorrect positioning of the protective screens, which, instead of channelling the glaze, allow it to splash and form drops that inevitably fall onto transiting tiles. Vibration transferred to the booth by other items of machinery contributes to the problem. Wet drops can generally be reduced or eliminated by increasing suction rates and by keeping all exhaust ducts and filters clean so as to maintain efficiency. b) Glaze clots (dry agglomerates) Clots, like drops, are caused by anomalous booth exhaust rates. Glaze settles on the inner surface of the booth and forms clots that subsequently detach from the wall and fall onto the surface of the transiting tiles. The defect appears when exhaust rates are excessive and the glaze hitting the walls tends to dry and encrust. Glazes with a high percentage of plastic components are particularly susceptible to drying, especially where applied at high density. Engobes, owing to their high plastic component, also tend to cause this defect. Vibration obviously accentuates this inconvenience as it shakes the crust off the wall. The simplest way to prevent this problem is to wash the booths according to a suitable schedule. Excessive suction or vibration, should, of course, also be eliminated. c) Stripes and waves with waterfall and bell units Stripes originate from imperfect sieving of the glaze and can appear as imperceptible lines or scratches or even unglazed streaks. In the first case the defect will probably escape the attention of glazing line inspectors and only become noticeable on the finished product; in the second case the defect is evident and the tile is rejected immediately. The cause is usually a clot or grain that has formed in the orifice, thus modifying glaze flow at that particular point or even blocking it altogether. In the latter case a tear is seen in the waterfall or veil.
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This defect can be eliminated, or at least limited, by properly sieving the glaze on the feed line and that recycled from recovery trays. Glaze containers should also be covered to ensure no contaminants get in. A similar problem is waves on the glaze surface, straight with the waterfalls and slightly curved with bell units. They may be-caused by: low glaze density or viscosity drop speed too high for tile transit speed glazing machine frame or floor vibration. Air bubbles in the glaze tear the veil and cause oval-shaped voids. With highly plastic glazes washing needs to be carried out at least twice a day to eliminate the crusts that form on ducts and sieves. d) Irregular disc application Applying the glaze by atomising it with centrifugal discs is perhaps the most commonly used technique in ceramics. Unfortunately this equipment is often troublesome, especially with larger tiles. To begin with, glaze application on the right and left hand sides of the tile is asymmetrical, a problem usually resolved by using two sets of discs that rotate in opposite directions, each applying 50% of the required glaze. Another defect caused by the discs, especially on large tiles, is the appearance of so-called stripes, caused by the glaze being deposited in alternating strips of different thickness. These problems generally stem from poor balancing of the disc unit, thus causing it to oscillate rhythmically and produce stripes. This explains the trend towards discs of smaller diameter and precision disc machining to ensure fine-tuned balance. Glazing machine manufacturers are currently engaged in intensive research activities aimed at solving both streak and droplet problems. .ollowing the recent shift towards very large tiles with smooth, uniform surfaces, waterfall and bell units are making something of a comeback as they do not produce the above problems and in any case produce smoother surfaces than disc units. e) Non-uniform cup application This application device is almost no longer used but certain problems/solutions may be relevant to other devices. The main defects caused by this type of application unit are: 1) More glaze is deposited on edges parallel to the direction of transit than elsewhere. especially on large tiles. The problem can be resolved by increasing cup rotation speed or increasing the clearance between cup and tiles. 2) Excess glaze is deposited on one side parallel to the direction of transit. In this case the manufacturer should check that the cup axis is perpendicular and that both cup and tile are horizontal. The cup also needs to be centred over the tile flow perfectly, and glaze feed should also be perfectly central.
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Defects
3) If a low density glaze is used less glaze may be deposited on the leading and trailing edges of the tile. To get round this problem the tiles can be arranged as a continuous carpet under the cup drop device. 4) Slightly arched streaks may be noticed crosswise to the direction of tile transit. This usually occurs either because the cup is not perfectly centred or because tile transit speed is excessive with respect to cup rotation speed. Decreasing transit speed or increasing cup rotation speed and adjusting weight usually solves the problem, although this does slightly alter the shape of the drop. 5) Drops parallel to tile motion. Mainly caused by too acute an angle of on-tile drop impact; reducing rotation speed, lifting the cup or inserting diaphragms along the drop fall trajectory usually resolves the problem. 6) If preparation glazes with intense colours are used or silk-screen printing is carried out prior to application of a very liquid glaze (scorza), application should be carried out at considerable distances so that it dries well and avoids any contamination of the glaze used for the cup. Moreover, consistent application of the glazed requires that absorption be kept constant before it is actually applied. f) Glaze on back of tile (dirtying) This defect is caused by glaze sticking to the support items (refractory slabs, rollers etc.). Problems can stem from incorrect adjustment of a waterfall orifice or bell (excessively fluid glaze, low tile conveying speed, violent fall of the glaze etc.) or may be associated with the application method itself, as with cup glazing where cloudy effects require very low density glazes. Where the problem depends on the glaze application method, the glaze can be removed from the back of the tile by brushes. Cleaning of fast single firing products is particularly difficult because using dry wire brushes wears the still soft tile and wet brushes cause water absorption. In this case engobes are applied after glazing to form a refractory layer between roller and tile (applications of water repellent before glazing are rarely used). This problem can drastically reduce the output capacity of a fast single firing plant. Not only that, it can also raise maintenance costs considerably on account of high roller replacement rates. g) Inefficient side fettling or cleaning Very frequent with both single firing and double firing. The problem is generally caused by incorrect adjustment of guides and fettling devices, or because the glaze is not yet dry enough. The defect can also damage the entire length of the tile side where fettlers are improperly regulated. Guides should have only a limited piece alignment effect and should be angled so as to only contact the bottom edges of the tiles. Lining the guides with Teflon generally gives good results: Teflon has waterrepellent properties and limits glaze adhesion.
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h) Glaze removal on unfired tiles Tiles may often collide with one another as they pass through the glazing line; these knocks tend to detach or chip the glaze and the defect then shows up during firing as glaze shrinkage. The situation is critical where gap-free tile carpets form (i.e. when the tiles bunch up as conveyor speeds slow). Generally speaking, this occurs before the silk-screen printing machines and before the single layer kiln loading or line compensators. Glaze detachment problems can at least partially be solved by augmenting bodyglaze adhesion with glues while mechanical impacts can be reduced by minimising speed differences from one conveyor section to the next. i) Shade differences caused by non-uniform glaze weight Inconsistent glaze weight/spread performance give rise to differences in colour and surface appearance, thus making sorting necessary. Such differences do not, in themselves, necessarily constitute defects. However, incorrect sorting does constitute a defect, and an excessive number of shades makes proper sorting extremely difficult. Shade differences that originate on the glazing line may be caused by variations in glaze density, absorption, body temperature or partial clogging of the glaze ducts. Density can be kept constant by checking it at fixed intervals; a density check is also compulsory whenever new glaze is added to the feed tank. Glaze application weight needs to be closely monitored when absorption time changes. Partial clogging of the glaze ducts is especially frequent in nozzles and holed tubes. Such problems are best prevented by proper sieving of the glaze and scheduled washing of the equipment and ducts through which it flows. l) Too much/little water This affects density and thus causes some of the defects described above. Note that too little water, especially with disc glazing, leads to a very grainy, rough surface of poor spreading performance during firing. The outcome is a glaze with a hammered look. Vice versa, an excessive amount of water causes small craters; cuts on the edges may also be noticed, especially where multiple glaze coats are applied. This inconvenience is particularly frequent in on-glaze flame effects, because the spray gun colour requires a perfectly dry attachment base. On a wet surface it tends to move and produce the above-mentioned defects. Another technique often affected by excessive amounts of water is waterfall washing after application of repellent and glaze, thus resulting in high water quantities being absorbed by the biscuit.
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Defects
Decoration defects Recent years have seen intense development of screen printing techniques, with associated ink preparation problems and difficulties in finding suitable vehicles for machines that have very different operating principles. A whole subset of defects is linked to these difficulties. The main ones, for flat screen printing, are: a) White line on tile side closest to worker This defect is caused by the lack of screen printing paste on the side of the tile closest to the operator and parallel to the direction of tile transport. The screen can be cleaned but the defect often reappears just a few tiles later. If paste residue is within the proper range and no dry areas are observed on the screen, proceed as follows: Check that the screen is not too close to the tile Check that the squeegee is aligned properly Check that tile height is aligned with belt support guide Check for proper squeegee pressure. b) White line on tile on side opposite worker (as above) Check that the home position of the squeegee is high enough; it must not press the screen against the tile edge when the tile exits (if it does adjust the shuttle cam) Check synchronism of movement between belt and shuttle. c) Accumulation of glaze at corners This defect is usually caused by an excessive screen-tile gap. Check that the tile is properly aligned between belt and support guide Lower the screen over the corner where inconsistent accumulation is observed. d) Pattern/motif not centred properly Check that the screen is positioned and secured properly Check that the belts grip the piece firmly. e) Tile sticks to screen Check fixative application is working properly Check height of screen above tile. N.B. Above-tile screen clearance is usually set to 4-5 mm but this can vary as a function of: Screen tension Screen fabric Screen printing paste viscosity.
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f) Screen breaks and/or splits This usually occurs over tile edges or corners and is caused by: Excessive on-screen squeegee pressure Excessive glaze residue Screen with poorly catalysed gelatine (emulsion). A well made screen usually has a working life of some 2000-2500 m2 (depending on tile size). Firing defects with effects on the glaze a) Temperature differences Usually associated with tunnel kilns, but can easily occur on other kiln types. The result is differences in tile shade or, sometimes, variations in glaze surfaces. The problem is a serious one because it causes almost imperceptible shade differences between adjoining tiles. This makes sorting particularly difficult. b) Lack of oxidation This does not mean that ambient air in the kiln is completely reducing, but, rather, that there is not enough excess kiln air to ensure so-called scrubbing (air washing). Hence fume passage zones form, often sufficiently concentrated to cause a defect; this generally consists of eggshell or bubbles on tile corners. There may also be zones where the air stagnates and is full of glaze vapours. This nearly always causes surface opacity, sometimes accompanied by pinholes. In both cases the defect can be corrected by increasing air turbulence and volumes, thus increasing stack exhaust rates and, consequently, air intake. c) Incorrect fume flow Normally appears as surface opacity and can degenerate into eggshell. Originates from improperly regulated pressures that cause some of the fumes from firing zones to follow the tiles towards the outlet instead of immediately being drawn towards the stack. When these tiles cool, condensate can deposit on the surface of the still molten glaze and thus be incorporated in it. This problem can be controlled by: increasing the air aspirated towards the stack increasing counter-flow fume speed to stack increasing the volume of direct cooling air. d) Over/Under-firing of glazes Excess and insufficient firing often generate similar outcomes (as with fusible and refractory glazes); the former generates an outer cordon characterised by bubbles or other defects while the latter can lead to the formation of matt or hammered-looking surfaces.
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Defects
With floor tile glazes, the matter may be more complex as it is not always possible to establish whether the tile has been fired too much or too little. .or a single firing glaze with a high percentage of added coarse material and a highly fusible vitreous base, for example, excessive firing can cause separation of the added material, (which remains on the surface) from the glaze (absorbed by the body). The result is a rough, hard surface, that initially brings to mind an under-firing defect. In such cases a good understanding of glaze types and firing behaviour is required. e) Cycles too fast or too slow for the glazes Like bodies, glazes may also be affected by fast firing cycles; these can stop the glass maturing or halt development of desired colour and/or texture. With simple glazes like transparent or zircon white frits, a hammered appearance may be noticed because the glaze has no time to spread properly. .loor tile glazes nearly always maintain the same surface area as when they are unfired; when disc-applied they are consequently never smooth enough. Despite the cost, manufacturers usually prefer to correct these defects by increasing glaze meltability rather than extend firing cycles. The latest bell application techniques give green materials a smoother surface without manufacturers having to use the fluxing agents that, in fast single firing, affect the geometry of the body. Eggshell and opacity often occur especially with highly fusible glazes on the edges because of sublimation of components that are then missing from the composition of the glaze itself. Since the cycle cannot be shortened, the amplitude of the firing curve is reduced and the duration of maximum temperature is limited.
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Firing defects Tile bursts in the pre-kiln (explosions) Abrupt evaporation of water can cause tiles to explode. The problem originates from excessive water content, be it residual after drying/glazing or reabsorbed during green tile storage. .iring with water contents above 2% is inadmissible; if necessary, drying should be extended. As a guideline, drying temperatures in the 250-300 C range are appropriate. However, such a degree of caution is only required in critical situations: pre-kiln temperatures are usually in the order of 350500 C. To contain temperatures, which rise significantly when gaps appear in production, the air intakes in the pre-kiln channel (through which the fan draws ambient air) can be opened. The occasional explosions of just-glazed tiles with a high concentration of stratified water just below the glaze is not particularly significant here, nor is the bursting of pieces with de-airing defects (flaking or peeling). Breakage during preheating Characterised by fracture lines with ragged edges running from the outer zones of the tile towards its centre; the glaze tends to penetrate the fracture and round its edges (fig. 16). Breakage is caused by the cracking that occurs when edges heat up and shrink faster than the rest of the tile. Single fire breakages of this sort are relatively rare and are usually associated with extreme thermal gradients. The problem may also appear as cracks some 20-30 mm long; these are nearly always multiple and never appear at the corners. They tend to occur at points on the kiln cross-section where temperature increases occur first. The critical range lies between 700 and 900 C. Very hot flames under the rollers are the most common cause. Reducing the temperature of the first/second under-roller burner set by 20-30 C usually resolves the problem; increasing air flow towards the burners also helps as this cools the flame.
.ig. 16.
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Small, almost imperceptible cracks can also appear on lower tile edges at the sides of the kiln load. These are usually the forerunner of much more evident cracking during cooling. Pre-heating breakages can also occur at around 800-900 C because the load comes into direct contact with cold air. This happens when burners have been shut down or when rollers have been removed and apertures inadvertently left open. To all intents and purposes these are actually cooling breakages on already-stiff pieces that have just passed through a critical temperature range. Preheating damage may also take the form of multiple, tightly packed, short cracks on the upper edges (fig. 17), sometimes almost covered by the glaze. This defect sometimes involves the leading edge only (i.e. the part of the tile most exposed to the flow of gasses towards the stack).
.ig. 17.
The problem lies in preheating gradients that are too steep for pieces already made susceptible to such defects by sharp or ragged, poorly compacted edges, high stratified moisture contents beneath the glaze and low body plasticity. Worn press punches can also contribute to the problem, as can intense kiln reagulation for concave deformation at the preheating stage. Broken corners can also occur during preheating; the line of fracture often gives the detached corner a characteristic pistol shape (fig. 18). The point at which this defect occurs can be identified simply by inspecting the bottom of the firing channel: a heap of broken pieces usually indicates where the trouble lies. Lowering temperature a few tens of degrees usually solves the problem. Increasing air flow to the burners may also help as this cools the flame. The broken pieces must be dropped to the kiln hearth through a trap to stop them obstructing the load.
.ig. 18.
371
Other defects also characterised by ragged fracture lines and rounded edge glaze are often mistaken for preheating faults; their true cause, however, is generally found upstream from the firing process. a) Long, curving, occasional cracks occurring randomly across the load (fig. 19).
.ig. 19.
Caused by mechanical stress: crucial checkpoints include screen printing, row accumulation units, conveyors in general and unfired tile box loading/unloading units. b) Cracks some 10-30 mm long at the corners, occurring randomly across the load. Usually caused by inter-tile collisions during row formation. An accumulation of shards and corner chippings on the floor usually identifies the critical conveyor point. c) Cracks in the glaze, parallel to one or more sides of the tile (fig. 20). d) Similarly, fissures may form inside the piece, again parallel to the sides (fig. 21). Caused at the pressing stage during ejection of the piece from the die cavity. e) Slightly divaricated cracks some 20-30 mm long, not localized at any particular point of the kiln cross-section. Their emergence depends on how long the unfired tiles have been stored. Often seen together with the longitudinal fissures described in d) (fig. 22).
.ig. 20.
372
Defects
.ig. 21.
.ig. 22.
The origin lies in longitudinal breakage that occurs during ejection from the die; excess water applied during glazing stratifies in the longitudinal fissure and cracks on the glazed surface then appear during the initial stages of preheating. f) Small cracks on the glazed surface, often so small as to be confused with pin holes or on-glaze depressions (fig. 23). The cause lies in defective ejection from the press die cavity or, more frequently, application of excess water during glazing.
.ig. 23.
g) So-called chicken claw crack (fig. 24). If the crack does not go all the way through the tile it is most likely the result of a de-airing fault at the pressing stage (e.g. lamination). Vice versa, where the crack
373
.ig. 24.
penetrates the full thickness of the tile, it may have been caused by an impact received from below during conveying: for example a pulley with an overly small belt will jolt against the underside of the tile as it passes over. h) Laminations causing detachment or even explosion of large plaques from the surface of the body and consequent crumbling of the piece (fig. 25).
.ig. 25.
This stems from poor de-airing during pressing. i) Cracks that look just like the preheating cracks described earlier (fig. 16). Where they can all be traced to the same press cavity, the real cause lies in pressing. Such defects do not correlate with any particular part of the kiln load but are generally found on the same area of each tile. Check that the die cavity and/or punch are in good condition. Similar cracks can also be produced at the drying stage: they do not appear on any particular zone of the kiln load but they are consistently localised on a specific zone of the drier load. In this case the cracks can often be highlighted at the drier outlet with liquid colorants (e.g. kerosene). In second fire, complete tile breakage can occur; where this is at random across the load and seen to intensify at certain moments, it is attributable to existing lesions in the body that compromise resistance to the tensions generated during preheating.
374
Defects
Cooling breakage (or cooling cracks) This damage originates from excessive tensions generated by non-uniform dimensional variations. It is usually associated with the very high cooling ratios that accompany the inversion of quartz at about 573 C and results in markedly different temperatures from one area of the tile to another. Damage risk is higher where the body contains significant quantities of free quartz, tiles are thick and large, and cooling cycles are rapid. Rapid cooling gradients or changes in gradient caused by discontinuous tile feed also increase the likelihood of damage. The cracks themselves tend to be curved with sharp, clear-cut edges, as with broken glass. .issures are never open and are, in fact, often difficult to spot without a coloured liquid; they always run from the outer edge of the tile towards its centre. In non-porous products the fracture has a smooth, shiny, conchoid look. Tapping the tile produces a dull, muffled noise. Cooling is a three-stage process and takes place in three different kiln sections. Initial RAPID COOLING lowers piece temperature to 650-700 C. Subsequent SLOW COOLING gradually cools tiles to at least 550-500 C. A third .INAL COOLING stage cools them to the point where they can be handled at the kiln outlet. Any attempt to correct cooling problems should take into account the following: 1 Temperatures detected by thermocouples in the firing kiln are much lower than the actual temperature of the moving tiles. 2 Pieces at the outsides of the load cool down much faster than pieces in its middle: this difference is accentuated by steep cooling gradients. 3 Temperatures at the sides of the tile are lower than in its middle; this difference, accentuated by steeper cooling gradients, is the true cause of tile breakage. 4 Barriers (chicanes) separating firing and cooling zones must be intact; efficient zone separation is essential for stable regulation of both firing and cooling. Identifying the point of tile failure If cooling breakages occur repeatedly in specific zones of the load and specific situations the manufacturer is provided with useful information on the regulation error being made. a) Breakages are localised at one or both extremities of the roller conveyor. This indicates that damage is occurring in rapid cooling, which is either too intense or extended. Correction involves raising the in-zone temperature and closing off one or more blowers so that each tile spends less time directly under the air jets. Reducing the stack aperture and thus increasing hot air intake can also help. A further measure consists of closing the first heat diffuser segment in slow cooling.
375
The above-roller thermocouple in the fast cooling zone usually gives a temperature reading of around 570-600 C, temperatures being lower where cycles are faster. Tiles exiting rapid cooling can be checked for proper temperature with the aid of a portable thermocouple; this is inserted inside the last roller of the zone. A reading of 600-620 C is ideal. b) Breakages are mainly localised at the centre of the kiln. Indicative of problems at the start of the final cooling zone: centrally positioned tiles cool more slowly and may pass under final cooling jets before their temperature has dropped below 573 C. The problem can be corrected by enhancing cooling performance in the first two cooling stages and/or delaying final cooling. The dissipators should be opened wider. A moderate increase in stack draught is also useful, as is reduced hot air intake (especially the initial intake) and closure of the initial cold air blower in final cooling. The temperature of the last thermocouple in the slow cooling zone should be around 480-500 C. c) Breakages occur on the first tiles to enter the kiln after a significant gap in product flow and persist for several minutes. Gaps cause cooling temperatures to drop: a reduction of just 50-70 C can cause problems. Check that, with the air modulation valve in the rapid cooling section closed, the blowers are not excessively pressurised. It may be necessary to reduce heat exchanger efficiency by partially opening the by-pass valve. Check the slow cooling section and make sure the heat dissipator modulating valve closes completely when temperature drops. Generally speaking, it is best to modify kiln volumes by aspirating large volumes of hot air. Check that the thermoregulators in rapid and slow cooling are working properly. d) Breakages occur after significant load gaps, not on the first tiles but those following on some minutes after. The problem is usually transitory. As per c). It is especially important to limit maximum air pressure in rapid cooling. Crazing Similar in aspect but very different in origin and nature, crazing is often confused with cooling cracks. It takes the form of sharp-edged fracturing of the glaze only and often shows up only with the aid of marker dyes or certain lighting conditions.
376
Defects Crazing is not necessarily evident at the kiln outlet either; it can appear at a much later stage during long-term de-tensioning, or during re-hydration of the hygroscopic body. Crazing fracture patterns are highly distinctive: lines do not necessarily run from edge to middle and tile edges are often unmarred. The cause of crazing lies not in cooling errors but a poor glaze-body expansion match that stretches the glaze. Tests can be carried out by putting samples through repeated autoclave cycles according to a specific protocol. A more empirical way of identifying susceptibility to crazing is to lay tiles with cement: if the glaze-body match is incorrect crazing will appear. However, the test can take a long time and is not well controlled. Uniformity of shrinkage over the kiln cross-section Attainment of uniform firing is especially difficult where kilns have wide inlets and are used to produce large tiles. The extent of shrinkage and, more importantly, the body vitrification range, are crucial in highlighting the effects of even small temperature differences across the firing channel. Temperature differences can be quantified and pinpointed by measuring pieces pressed in the same die cavity and fired in different load positions (all tiles must be oriented the same way with respect to the press outlet). After marking the tiles to indicate their position (fig. 26) all the right and then all the left side pieces are compared.
R I G H T
L E F T
D: 449,7
S: 450,1
D: 449,6
S: 450,0
D: 449,6
S: 450,0
D: 449,8
S: 450,2
D: 450,1
S: 450,5
Fig. 26. An example is evaluated as follows: +0.2 mm on left side of kiln with respect to middle tile +0.5 mm on right side of kiln with respect to middle tile. An indistinct comparison between right and left sides includes pressing errors (0.4 mm on right-hand side of piece). When checking the tile dimensions comparisons should be made between tiles all across the kiln section and care should be taken to note any effect resulting from pressing errors which overlap with firing variations.
377
a) The most frequent occurrence is larger tiles in the cooler areas nearer to the outside edges of the kiln cross-section. Several causes combine to create the problem (fig. 27):
.ig. 27.
378
Defects
.lame temperature at the nozzle is lower than further away where combustion is complete. Re-circulation of colder ambient air on account of the Venturi effect generated by flame speed. .umes move more slowly near the walls than in the middle of the channel because of friction (flow towards chimney). Stronger irradiation of centre of the load by perpendicular walls. Outward dispersion of roller heat by conduction. Aspiration of cold air via improperly plugged roller seats in the firing zone. Low-speed cold air blow movement, especially above rollers. The problem can be corrected on several fronts (fig. 28).
.ig. 28.
Kiln pressure (see relevant paragraph) must be positive in the firing zone (at roller height) so as to prevent cold air infiltration; however, pressure should not be too high. Insertion of one or more deflectors at the beginning and inside the firing zone diverts more fumes towards the tiles near the walls. Using a suitable number of burners with semi-radial dispersion above and below the rollers is a tried and tested system that compensates for colder flame areas near burner nozzles and any intake of colder ambient air. To fine-tune, air can be dosed to the burners to modify flame temperature and length. .lame deflector screens can also be positioned in front of firing zone burners beneath the rollers (fig. 29). b) Irregular shrinkage across the cross-section (known as candy paper). Characterised by shorter tile sides 60-70 cm from the walls and longer ones adjacent to them (fig. 30). Here, despite the similarities with case a), erroneous flame geometry (especially on burners above the rollers) is usually the culprit. Considerable modifications to
379
.ig. 29.
.ig. 30.
flame speed and geometry are usually required. An easy and often effective solution is to shut down a burner in those sets that markedly influence size; alternatively, the flow of burner air can be modified. c) Other, differently configured, irregularities can also occur; depending on the situation, their solution may require use of the above solutions or even their direct opposites. Glaze brilliance and shade In terms of shine, satin effects, opacity, spread and shade the final outcome of glazing essentially depends on the high temperature firing stage. Higher temperatures or extended firing time results in more compact vitrification of the glaze and thus improves shine. Longer times at relatively lower temperatures give a satin look and better (flatter) spread. Much, of course, depends on the nature of the glaze, the limitations of which are inevitably highlighted by pin holes and micro-bubbles if temperatures are too high. The appearance of satiny effects (clouding of the glaze at certain points of the load) indicates a combustion defect on one or more burners in the high temperature zone; a check on (and possible increase in) the flow of combustion air is generally required. Shade changes across the load are the result of temperature gradients. Lustre
380
Defects
applications, for instance, are particularly sensitive to overheating and can easily vanish. Where strongly reactive colouring oxides are used (iron, selenium etc.), longer firing is known to disturb colour development. Hence iron oxide veers towards green where firing lasts longer and red where firing is shorter and sharper. Pin holes - holes - bubbles in the glaze These are caused by small gas bubbles that expand in the glaze and burst, leaving a small crater on the surface. Gas bubbles have numerous causes. Sectioning a defective tile and taking a close look at its interior can provide valuable information. Using a magnifying glass or pocket microscope, it is good practice to observe the glaze along the line of fracture, paying special attention to the nature of the trapped bubbles. Bubbles are very small, densely packed and close to the surface. This defect stems from very low melting viscosity or over-firing, causing the glaze to boil. Generally attributable to overly hot flames on the last above-roller burners or, more simply, too high a firing temperature (fig. 31).
.ig. 31.
Bubbles observed in body of glaze only; bubbles that are forming, incomplete or touching the body are not observed (fig. 32).
.ig. 32.
Indicative of high melting viscosity or low quality glaze containing impurities. May also indicate a glaze preparation (milling) or application (bubbling) error. The problem cannot be solved by adjusting the kiln. This defect also occurs when glaze is applied to an excessively hot body, thus causing water vapour to form between body, engobe and glaze.
381
In addition to those in the glaze, other bubbles are seen to be forming in the body and rising off it (fig. 33).
.ig. 33.
The most likely cause in this case is incomplete degassing prior to glaze softening: black core, especially if it is stratified near the glaze or takes the form of specks scattered through the body. carbonate degassing problems, an eventuality more or less limited to monoporosa products: the defects are larger than pin holes and the underlying engobe is frequently exposed. pyrite degassing with SO2 emission: in this case the tiles need to be held at 10401050 C for several minutes (frequently solved by fine sieving of the body slip). Confirmation that degassing is involved in the pin holing problem is usually provided by a simple double fire test: some unglazed pieces are sampled at the drier outlet and then fired to fully degas them. They are then passed through the glazing stations, ensuring that each inter-station time lapse is long enough to let water be absorbed or evaporate. The samples are then re-fired: absence of bubbles in the glaze confirms that body degassing was the cause. There may also be larger holes in the glaze. These have various causes: late degassing of body carbonates, especially where their particles are quite coarse. In this event the 920-980 C firing time needs to be extended. Body grinding and composition must be checked. thin, compacted flakes of body, especially from the sides of the die box, work their way into the tile body or flakes/powder stick to its surface at the time of ejection from the press: in the kiln this causes micro-peeling. The only solution is to ensure that dies are kept clean by suction/blower devices. Pin holes, holes and bubbles in the glaze may also be caused by defects in the glaze or its application: grinding and sieving viscosity and rheology CMC deterioration incompatible glaze-engobe melting points
382
Defects
high screen print stickiness compromises adhesion of glaze to underlying engobe or body glazing on excessively hot body inadequate spacing between glazing units poor glaze-body adhesion overlaying of incompatible glazes. In some cases extending the firing time towards 500-600 C may be useful; it will, in any case, be necessary to eliminate the cause of the problem by correcting glaze and glazing technology. Degassing All ceramic bodies lose a considerable amount of weight during firing. Mainly by the loss of residual process water and the water in the clays. The rest is attributable to gasses and vapours produced by the combustion of organic contaminants, the decomposition of carbonates (especially CaCO3) and sulphur compounds etc. Gas generation occurs during preheating, a stage that ends with the formation of the first vitreous phases, which rapidly reduce permeability. This generally occurs at 980-1000 C in single fire operations and around 1100 C with porcelain tiles. High temperatures also generate vapours (fluorine, chlorine etc.); while they do not necessarily cause product defects, they often attack the refractory and steel parts of the kiln structure. Other vapours released by the glaze (lead, boron compounds etc.) can easily condense on the kiln walls and roof, resulting in the fall of droplets and damage to transiting tiles. The theory behind degassing is a simple one: the aim is to raise the material to a temperature at which gasses and vapours develop as quickly as possible and then hold the temperature for as long as it takes for all the gasses to escape. The best temperature is the highest possible (but, of course, still below the body and glaze vitrification point). Degassing problems depend on several factors: composition, purity and particle size of raw materials thickness, density and moisture content of pressed tile fusibility of glaze and frit characteristics and quantities of screen printing inks and their media (vehicles). The prevailing opinion is that a richly oxygenated preheating environment aids degassing; this is true only in part and in any case needs further explanation. .or instance, the flow of exiting gas may stop ambient oxygen penetrating the piece. However, it is true that burners fed with excess air supply all the required energy and high volumes at low temperature: this makes overheating and thus early development of the vitreous phase and reduced permeability less likely.
383
Similarly, good fume draught is helpful. The first degassing benefit is not the draught-induced vacuum, which might erroneously be thought of as sucking the gases out of the tile, but the considerable quantities of hot volumes drawn in from the firing zone; these allow a reduction in gas flow to the pre-heating burners (and thus lower flame temperatures). Degassing in double fire processes Since the biscuit has already been fired once the second fire is usually free from degassing problems. Nevertheless, problems may arise with biscuits that have been put through rapid firing cycles and then left on hold for some time after application of the glaze. The problem may be caused by water (from glaze, or absorbed by hygroscopy) reacting with calcium oxide (CaO) residues left over from the first fire (in longterm storage it could transform into CaCO3 again). The resulting defects take the form of evident, foamy bubbles and bare sections of body, often confused with glaze adhesion problems. In this event it is good practice to extend the preheating time below 550-950 C both by easing the temperature gradient and slowing the cycle. Black core This defect has already been dealt with in the section on defects associated with raw materials (see Appendix 3: Defects, Organic material). It takes the form of a halo, ranging in colour from yellow-green to grey or black, in the tile interior. The problem can also appear as simple black specks dispersed throughout the body. Black core is caused by incomplete combustion of organic residues in the body or by subtraction of oxygen from iron oxides: in any case, it is always a reduction phenomenon. Black core would not, in itself, constitute a problem (often normal in extruded products) were it not associated with other defects such as: pin holes and bubbles in the glaze glaze porosity and its stain resistance differently shaded halos and spots appearance of back pattern on the face of the tile dimensional and planarity defects. The most suitable firing range for elimination of black core generally lies between 880 and 960 C. While the bulk of good quality glazes have a softening point of around 980-1000 C, note that a few low-fluxing glazes seal pores at just 680-700 C; where the latter are used the firing cycle will need to be slowed down considerably. High-temperature glazes and bodies allow preheating to be extended towards 1100 C. No less important than optimal temperature is duration of exposure to effective degassing temperatures. Maximum efficiency is obtained by keeping temperatures high at the start of preheating and low in the approach to the firing zone:
384
Defects
here, it may be useful to blow air through switched off burners (taking care not to generate significant temperature differences above and below the rollers as these can change tile planarity). Good degassing requires abundant volumes, both from the firing and cooling zones and the burners. Hence any cooling adjustment that exhausts a lot of hot air (cooling stack) is to be avoided. Degassing problems also raise energy costs. The use of more refined raw materials and tile technology should thus be attentively evaluated. Black core can appear as: a localised halo in the core of the tile or as scattered specks (fig. 34) an under-glaze halo that fades towards the centre of the tile (fig. 35). Glaze reaches its softening point too quickly and prevents degassing of the body.
.ig. 34.
.ig. 35.
A localised halo at the core of the tile that fades towards the glaze (fig. 36).
.ig. 36.
385
High temperature preheating time too brief or under-roller temperature at end of preheating is too high. Halos limited to areas of lenticular cross-section (fig. 37).
.ig. 37.
Highlights non-uniform pressed piece density caused by a die filling defect or accumulation of fine powder. Where intensity is low the defect can generally be resolved by holding the optimum degassing temperature long enough. Rather than halos, there may be evident swelling of small, circumscribed areas. Such cases are generally sporadic (see fig. 38).
.ig. 38.
The intensity of the phenomenon means that it cannot be resolved via kiln adjustment. Swelling is usually caused by drops of machine oil, carbon particles formed by poor spray drier combustion or other body contaminants (even very wet or high density grains). Planarity defects Precise diagnosis of planarity problems requires in-depth observation of the defects. Deformation profiles, small differences between one area of the load and another, variations caused by specific events and circumstances and links with other problems are all, in the light of product characteristics, essential if a reasonable hypothesis is to be developed and then tested. Planarity defects are not necessarily caused by malfunctioning or incorrectly adjusted kilns; more properly, it should be said that the kiln is often unable to eliminate errors that occurred upstream from it. A poor dilatometric (thermal expan386
Defects
sion) match between body, glaze and engobe is a frequent cause; alternatively, the problem may be associated with heterogeneous tile density or the low structural strength of very molten, very thin or specially shaped pieces. However, that is certainly not to say that proper kiln adjustment never solves the problem: it often does. Sometimes it merely attenuates the defect and sometimes it has no effect at all: in any case, close collaboration between kiln operators and technologists is essential if an effective plan of action is to be developed. Controlling tile planarity largely involves control of the consequences of linear shrinkage during firing. Imagine a tile cross-section: if the face of the tile is subject to higher temperatures than the back then it will shrink more, causing the tile to bend and become concave; vice versa, if the underside of the tile is exposed to more heat, the back of the tile contracts more and makes the tile convex. Only a small area of a convex/concave tile actually rests on the rollers. Once the body reaches its softening point, the unsupported part of the tile, tends to collapse under its own weight: this secondary deformation works in the opposite direction to the initial one caused by temperature differences. Because it takes time for the tile to soften and collapse, this secondary effect takes place at the same time as the curvature effects of thermal expansions occur at the beginning-middle of the firing zone. Because the edges of the tile heat up faster than the middle, an appreciable temperature difference during the brief final firing stage can accentuate concavity or convexity at the corners. Planarity problems can also result from non-uniform cooling of tile face and back: this changes both the moment in which the glaze locks to the body and influences the relationship between glaze and thermal body expansion. Smooth, clean, straight rollers are essential for orderly in-kiln movement of tiles and the prevention of mechanically-induced warping and planarity deformations. There follows a description of the most common planarity defects. Downturned corners All four tile corners droop (usually the outermost 3 cm or so); the rest of the surface is essentially flat or slightly convex (fig. 39). The defect is distributed throughout the load and is constant; deformation is slightly reduced at the ends of the loaded tiles (head and tail). Corrections should be made in the final firing zone by raising temperature above the roller plane and reducing temperature below it. Diagnosis should be effected with care as it is easy to confuse this defect with others, different in nature, that are similar at first glance but quite different when observed more closely (figs. 40-41).
387
.ig. 39.
.ig. 40.
.ig. 41.
Upturned corners All the tile corners are upturned (outermost 3 cm); the rest of the surface is essentially flat or slightly concave (fig. 42).
.ig. 42.
The defect is distributed evenly throughout the load and is constant; deformation is slightly reduced at the ends of the loaded tiles. Corrections should be made in the final firing zone, where it will be necessary to lower the temperature above the roller plane and increase temperature below it. Diagnosis requires caution as it is easy to confuse this defect with others, different in nature, that are similar at first glance (figs. 43-44).
388
Defects
.ig. 43.
.ig. 44.
Convexity Homogeneous downward bending of all tiles, with similar deformation profiles on all four sides (fig. 45).
.ig. 45.
One of the most frequent and difficult planarity problems as the defect stems from glaze-body expansion incompatibility. .actors such as engobe, glaze-body thickness ratio, tile density, tile size, degree of vitrification, back pattern and others all influence this problem. The temperature curve in itself rarely causes convexity: only a central-final firing zone characterised by higher below-roller temperatures is capable of doing this. However, this is not to say that kiln adjustment cannot provide solutions; in many cases results are rather good. Nevertheless not all products respond to adjustment the same way, hence the need to distinguish between different product types. .or instance, with single fire floor tile we can hypothesise: a) Correction in Rapid Cooling Zone Below-roller direct blowing is intensified at the start of rapid cooling. This reduces convexity throughout the piece, especially on sides parallel to the rollers. By cooling the body earlier the latter contracts before the glaze locks and opposes it. This difference between sides parallel to the rollers and those at right angles to them may be explained by the fact that they undergo different cooling processes. Parallel sides (leading and trailing tile sides) are cooled all in one go
389
while sides at right angles to them are cooled from one end to the other as the tile advances (fig. 46).
.ig. 46.
Meaningful correction results can only be achieved with properly designed final cooling zones: there should be a fair concentration of blowers beneath the roller planes, especially in the first section, and each blower must have a certain output rate; it should also be possible to shut off corresponding above-roller blowers. Additionally, more hot air can be aspirated into the cooling area; this air stratifies above the rollers and keeps the glaze hot for longer, thus delaying its attachment to the body. Removing the rollers immediately above the bottom blowers also helps. Avoid overly dense packing of tiles in rapid cooling (i.e. maintain space between lines). Similar results are also attainable with unglazed porcelain tiles, especially large ones. However, no discernable advantages have been observed with porous products (monoporosa, biscuit, glazed double firing). Considerable temperature differences (hot tiles on top of the rollers and cold air under) can cause evident roller deformation. This, in turn, generates asymmetry and overlapping of tiles. The only way out of this quandary is to use specially designed rollers with high heat transmission coefficients. b) Correction in the .iring Zone Takes the form of a firing curve structured to give higher below-roller temperatures in the initial section, from 1050 C to just beyond peak temperature. The difference is usually 20-30 C, but may require peaks of 50-60 C. Convexity correction is always slightly more marked on sides at right angles to the rollers than on those parallel to them (fig. 47).
.ig. 47.
The dynamics of correction may be illustrated as follows: Stage 1 Higher temperatures beneath the roller cause the bottom of the tile to shrink faster than the top: the piece thus becomes convex (fig. 48).
390
Defects
- t
SHRINKAGE + SHRINKAGE
+ t .ig. 48.
As the tile shrinks it also becomes soft. Stage 2 In passing from one roller to another the convex tile rests on its leading and trailing edges (black areas): the central section is suspended (fig. 49).
Convex tile rests on leading and trailing edges only (black area).
.ig. 49.
The whole of the weight rests on the points of contact (fig. 50).
~8cm
SHRINKAGE + SHRINKAGE
Support zones
.ig. 50.
Gravity causes the tile to flex and droop. Stage 3 .iring continues: the face of the tile is now exposed to temperatures and shrinkages similar to those on the back, thus causing concavity (fig. 51).
= t
= SHRINKAGE
= t .ig. 51.
391
Sides parallel to the rollers are rather more uniformly supported (or suspended) and anti-convexity correction is visibly modest. Over-correction can produce a defect characterised by upturned leading and trailing edges affecting sections some 8 cm long (fig. 52)
~8 cm
~8 cm
.ig. 52.
or the priest hat deformation (fig. 53).
.ig. 53.
Higher above-roller temperatures in the final firing and/or maximum temperature zone may also prove useful, possibly involving shutdown of burners below the rollers. Excessive correction in this sense can, however, produce the priest hat effect and produce upturned corners (fig. 54).
.ig. 54.
Concavity Homogeneous upward curving of all tiles with similar deformation profiles on all four sides (fig. 55).
392
Defects
.ig. 55.
A somewhat rare defect: if it were caused by an erroneous glaze-body expansion match the glaze would be stretched and crazing would result. Concave deformation is often transitory in nature, being caused by accidental kiln shutdown or macroscopic errors in the firing curve. Correction at the start of the firing zone Takes the form of a firing curve structured to give higher above-roller temperatures in the first section, from 1050 C to just beyond peak temperature. The temperature difference may be as high as 50-60 C. The resultant correction is spread uniformly over the four sides. The dynamics of concavity correction are similar to those for convexity. Stage 1 Higher temperatures above the roller plane cause the face of the tile to shrink sooner than the back: the piece thus becomes concave (fig. 56).
+ T
.ig. 56.
- T
Shrinkage is accompanied by softening. Stage 2 In passing from one roller to another, the concave tile rests on its middle; the remaining peripheral areas are suspended (fig. 57).
Constantly suspended part of tile (black areas)
.ig. 57.
393
The whole weight of the tile is supported on the central part in contact with the rollers (fig. 58).
Suspended areas
.ig. 58.
As the suspended areas press down the tile tends to flex and flatten out (fig. 59).
+ shrinkage % shrinkage %
.ig. 59.
Stage 3 .iring continues: the back of the tile is now exposed to temperatures and shrinkages similar to those on the face, thus causing convexity (fig. 60).
= T
= shrinkage %
= T
.ig. 60.
Exaggerated corrective action can produce a central asymmetric hump between the leading and trailing edges (fig. 61) (i.e. only central part of tile is convex).
.ig. 61.
Correction at the end of firing Higher below-roller temperatures in final firing and in the maximum temperature range are also useful; this may involve the shutdown of burners above the rollers.
394
Defects
Excessive correction in this sense can, however, produce deformation (fig. 62).
downturned edges
roller effect (porpoising) .ig. 62.
Correction in the rapid cooling zone Concentrating blown air above the rollers at the start of the zone is useful. Maximum efficiency is obtained by pointing the blowers not at the tiles but towards the kiln roof and bunching the tile rows as close together as possible by decreasing rapid cooling zone roller speed. This accelerates hardening/locking of the glaze, thus increasing the effect of glaze-body thermal expansion coefficient differences. Roller effect A classic single-fire defect (fig. 63).
8 cm
3 cm
.ig. 63.
The defect only involves the sides of the tile at right angles to the rollers; the two sides parallel to them are perfectly straight or only slightly convex. A central area, generally flat or slightly concave, is bracketed by evidently upwardly bent strips, some 8 cm wide, on the leading and trailing edges. The last 3 cm of those strips curve downwards.
395
This deformation has a number of possible causes: 1. Below-roller heating in the firing zone (or at least in its central and final section) is excessive. The piece thus becomes convex on account of relatively more intense underside shrinkage; as the tile advances only its leading and trailing edges are supported by the rollers (fig. 64).
.ig. 64.
The now decidedly soft piece is unable to sustain its own weight and the central section of the tile collapses. If this is the case deformation is resolved by increasing temperature above the rollers and decreasing temperature to the same extent below them: correction should begin at the end of the firing zone and then retreat back towards its beginning. 2. Greater below-roller heating at the start of the firing zone causes relatively greater shrinkage of the tile underside, thus making it convex (fig. 65).
- T + T
.ig. 65.
SHRINKAGE
Shrinking is accompanied by softening. Because only the leading and trailing edges of the tile rest on the rollers the piece deforms as described in the CONVEXITY paragraph and on exiting the kiln will be concave, but with a tighter radius over the outermost 8 cm of the leading and trailing edges (fig. 66). Such defects are easily confused with others (CONCAVITY or UPTURNED CORNERS) and often erroneously corrected by increasing below-roller temperatures in the final firing zone (fig. 67).
8 cm
8 cm
.ig. 66.
396
Defects
3 cm
.ig. 67.
Because the tiles remain in this section for only a short period correction influences the corners only, thus causing the outermost 3 cm of the leading and trailing edges to become convex. In this event deformation can be resolved by: .IRST: increasing the temperature above the rollers at the end of the firing zone and then lowering it to the same extent below them. The resulting deformation is as illustrated in fig. 66. THEN: increasing the temperature above the rollers at the start of the firing zone and lowering it to the same extent below them. 3. There is a somewhat rarer third scenario, limited to products fired at very high temperatures. Known also as the ROLLER E..ECT, it is fairly evident but has gentler curves (fig. 68).
.ig. 68.
Solving this sort of problem requires an altogether different kind of approach. Temperatures below the rollers need to be increased considerably and temperatures above them reduced: this needs to be done from the beginning of firing onwards and inevitably involves an intermediate priest hat stage. Priest hat .requently observed where glaze and body expansion coefficients are significantly different (i.e. mainly with glossy glazes and grains, especially where applied thickly, in monoporosa and floor tile). Characterised by a central convex area with a peak at the geometric centre of the tile and upturned extremities, particularly over the last 3-4 cm at right angles to the rollers (fig. 69).
397
.ig. 69.
Where the defect is mild the ends appear flattened. The radius of the central, convex curve remains unchanged (fig. 70).
.ig. 70.
Priest hat can also be caused by an attempt to resolve convexity (by increasing above-roller temperatures at the end or in the central section of the firing zone). In this event bringing the temperature differences back within more acceptable limits and applying a more suitable anti-convexity stratagem will usually suffice. May also be caused by excess temperatures below the rollers in the initial firing zone. There are two possible approaches: bring temperature differences back within more acceptable limits. force the existing adjustment by increasing the temperature differential, extending it into the central firing zone and, if necessary, into the final firing zone with higher below rollers temperatures. Note that where such adjustment is performed on products without any particular expansion match problems, the end result is the roller effect (fig. 71).
which represents the exact opposite of priest hat
.ig. 71.
Where priest hat develops at the start of firing there often follows asymmetric warping caused by irregular feed, pieces bumping into each other and overlapping. These secondary deformations tend to mask the priest hat itself and can delay its identification. Problem solving thus needs to be prioritised: first priest hat, then warping. Given their associations, the two are often eliminated simultaneously.
398
Defects
Asymmetric deformation or warping Irregular deformation, mostly occurring on sides at right angles to the rollers and corresponding to specific positions on the load (fig. 72).
.ig. 72.
The appearance of tiles like those in the illustrations should be taken as a warning sign that the rollers need cleaning: this is, in any case, always the first measure that needs to be taken. This defect always stems from tiles which are not lying flat on the rollers. There are two possible causes: 1. Evident heat-induced tile deformation destabilises the tiles, causing them to pitch, roll and rotate around their centre and advance or retreat with respect to the other tiles in the row (fig. 73).
.ig. 73.
They thus tend to overrun the inter-tile gap (spacer) and bump into each other or overlap. The best approach is to adjust the temperature curve and eliminate or attenuate the differences that caused tile deformation in the first place. 2. The quality and characteristics of rollers in the firing zone. Ceramic rollers, now commonplace, must meet certain dimensional requisites (inter-roller gap, temperature range, load bearing capacity, geometric uniformity) and have certain qualitative characteristics (hot bending strength, modulus of elasticity etc.). Observation of any kiln shows that rollers flex constantly under the weight of the tiles. However, because load density is never fully homogeneous or continuous, gaps between rows and poor tile alignment sometimes allow rollers to straighten out momentarily.
399
It thus follows that where properly arranged, aligned, straight tiles jump from a flexed or bent roller to a straight one and vice versa, asymmetric non-identical deformations can result. The problem is intensified by worn, dirty rollers and the random mixing of rollers of different quality. Solutions: Adjust tile feed density so as to minimise inter-row gaps: a compact load makes it harder for individual tiles to leave the formation and thus re-arrange it. Depending on planarity priorities, use temperature settings that prevent concavity in preheating, and avoid tiles moving around and becoming disordered or out of line. Use specially shaped rollers that are thicker in the middle: these correct and compensate for the arch-shaped rows that stem from relatively higher speeds at the sides of the kiln. A number of these rollers, properly distributed, can improve the situation considerably. In the rapid cooling zone, the beginning of which is especially critical, the often evident roller deformation produced by temperature differences between the heated part of the load and the simultaneously cooled part can be disastrous. The solution lies in reducing roller blowing to a minimum. Stability and reliability can also be increased by using rollers of high thermal conductivity (in silicon carbide or blends of silicon carbide and refractory) that deform little if at all. Sometimes, the only answer is to replace a number of rollers with others of better quality, especially in the firing zone (less bending under load). Such defects have no easy diagnosis or solution. The best approach is to analyse the situation from several angles and apply a blend of possible solutions. Other deformations regard only porcelain tile manufacture. Well-defined strips that droop at the leading and trailing ends (fig. 74) is one such example. This problem is more frequent with thin, highly vitrified products.
.ig. 74.
This defect is caused by intense softening and inter-roller distance: as the tile passes from one roller to the next, overhanging portions droop under their own weight. The only solution is to drastically reduce below-roller temperature at the end of the firing zone; this may involve shutdown of some burners and/or use of blown air. Vitrification is affected only slightly. A wide variety of evident, widespread warping is more likely to be seen on double
400
Defects
filling products (even where pressing results seem good); the problem, however, is also seen with traditional die filling. Rapid cooling, with abundant quantities of air blown through above-roller tubes only, sometimes provides an effective solution. Directing air jets upwards and compacting the load by slowing down roller speeds increases the effectiveness of this adjustment. Nevertheless, in other cases it may be useful to use only blowers below the rollers and direct the jets upwards at the tiles. Hard and fast rules are elusive and manufacturers will need to evaluate problems and take action on a case by case basis. Monoporosa The complexities of the monoporosa firing process have yet to be fully understood and are still a cause of much debate. However, attentive observation in a variety of situations has already produced a wealth of experience that allows the monoporosa technician to solve at least the most common problems. Convex planarity (Monoporosa) Convex planarity occurs during cooling. It is particularly evident during the allotropic quartz conversion at around 573 C. This phenomenon is easily observed by removing a tile via an inspection hatch near the rapid cooling zone: hold the piece with a pair of tongs and it bends before your eyes. The extent of deformation largely depends on the tensions generated by the different expansion coefficients of body, glaze and engobe, their relative thickness, the extent of back pattern protrusion, pressed tile density, ambient moisture content and tile ageing etc. The role played by individual parameters varies from product to product. .ig. 75 shows how expansion varies over the firing range. It goes without saying that quality tiles are only obtained where such parameters are optimised. As long as tile design error remains within reasonable limits there are several ways of nullifying it via kiln adjustment. Bear in mind that the porous nature of the body leads to absorption of atmospheric moisture and, consequently, moisture expansion. If that expansion overstretches the glaze the end result is crazing. Hence reasonable error means that the tile body must still contract more than the glaze during cooling, thus ensuring that latter is compressed, albeit minimally, under all circumstances. Because porous bodies can expand on absorbing moisture, the tile must leave the kiln with its glaze under sufficient compression so that it always remains so throughout the life of the tile. Otherwise crazing results when the glaze comes under tension.
401
EXPANSION %
C .ig. 75.
Correction in Preheating The term PREHEATING usually refers to the low temperature zone in which degassing occurs, as opposed to the high temperature zone where melting, shrinkage and thus planarity control take place. With monoporosa that distinction is no longer applicable because, between 920 and 1020 C calcium carbonate decomposes and generates considerable CO2 outflow and, at the same time, the most important expansion event of the entire firing process takes place. Anti-convexity measures generally involve application of higher temperatures below the rollers, a measure that is most effective from 950 C onwards. Similar measures are often taken at lower preheating temperatures; rarely successful on their own, they do provide considerable benefits in conjunction with other adjustments. Planarity differences on sides parallel to the rollers are minimal, if they exist at all. No substantial differences in results have been observed by increasing/decreasing burner air volumes or increasing/decreasing flame speed. However, a gradual approach towards 950-960 C has proved moderately beneficial. Under such temperature conditions direct in-kiln observation shows that the convex tiles pitch on the rollers (fig. 76).
.ig. 76.
402
Defects
Excessive temperature differences above and below the rollers can cause unacceptable deformities; if they are excessive the tile will be deformed at the kiln outlet as illustrated in fig. 77:
.ig. 77.
Temperature differences between above and below-roller areas may be extended as far as the 1000-1080 C range. In this case marked concavity will probably be observed on sides parallel to the rollers and the trailing edge is always more concave than the leading edge (fig. 78): the reason for this is not yet known.
.ig. 78.
Immediately after CONVEX deformation the tile becomes visibly concave, a 3040 mm strip all the way round the perimeter of the tile appearing raised; the middle of the tile is affected to a far lesser extent. Correction in firing Anti-convexity action here generally involves application of higher temperatures above the rollers, a measure that essentially becomes effective after 1100 C. Temperature differences between the upper and lower kiln areas are in the order of 5-30 C. Results are fairly uniform over the four sides of the tile but a little less so over the load cross-section. Applying these temperature differences influences the part of shrinkage produced by high temperature sintering (fig. 79):
403
EXPANSION %
.ig. 79.
As with floor tiles, the top of the tile receives more heat and shrinks more, thus making the piece concave (fig. 80):
+ Temperature + Shrinkage
Temperature Shrinkage .ig. 80.
Excessive temperature differences between the above and below-roller areas thus causes exiting tiles to have the defect illustrated in fig. 81.
.ig. 81.
Correction at the end of the firing zone The tail end of the firing zone (usually the last 2-4 m and, more rarely, the last 6 m) provides excellent convexity correction opportunities; results are usually homogeneous, within the required limits, and do not generate the deformation seen in fig. 82.
404
Defects
.ig. 82.
Correction usually involves shutting down pairs of burners (left-right) below the rollers, 1-4 or at most 6, and then feeding large volumes of air through them (up to 40-50 m3/h). Rather than following the logic of temperature difference = shrinking difference, this correction attenuates the effect of the body expansion on the relatively lower glaze expansion, thus delaying the moment in which the glaze adheres to the body. With the body incandescent (over 1100 C) and the glaze molten (i.e. liquid), cooling of the body from beneath is begun in advance. The body starts to contract as per its expansion curve and the liquid glaze follows it without offering any resistance. Correction ends when the glaze stiffens (cools) and starts to follow its own expansion curve. This technique allows a part of body expansion to occur before glaze adhesion, the practical equivalent of a better glaze-body expansion match. It is not, of course, a system that allows for any increase in glaze heating (i.e. no increase in above-roller temperature allowed). If this were the case the higher temperature = greater shrinkage rule would apply, resulting in the deformation illustrated below (fig. 83).
.ig. 83.
An identical technique can be applied with floor tiles, but later, during rapid cooling. Non-uniform planarity across the kiln load in monoporosa Less efficient anti-convexity correction near the kiln walls is a common problem: the more marked the corrective adjustments the more evident this drop in efficiency becomes. This is explained by the fact that, in preheating, temperature differences between the above and below-roller areas are attenuated by the empty spaces that form near the walls (between tile load and wall) and, in the above-roller part of the firing zone, by the fact that it is physically impossible for the burners to heat the
405
area near the walls in exactly the same way as they heat the central zone. The sum of these two phenomena thus reduces correction efficiency. Solutions a) .airly high kiln pressures should always be maintained; ideal firing zone pressures at burner level in the above-roller part of the firing zone are around 0.3-0.4 mm (water column). Note that this pressure must be generated by damping the exhaust fume flow, not by limiting hot air intake in the cooling zone. In other words, the solution works if there is an albeit modest flow from firing to cooling, not vice versa. b) Appropriate use of the chicanes fitted on the roof can improve matters; these need to be in good condition and no higher than 80-100 mm. It is essential that high temperature zones where higher above-roller temperatures have been set be defined by lowered chicanes. Conversely, any transverse walls below the rollers at the start of or inside the firing zone need to be eliminated. c) Installing semi-radial burner units above the rollers in the firing zone also helps; these must be arranged and adjusted so as not to compromise glazing results. d) Generally speaking, gradual rapid cooling settings, with blowers emitting no more air than is strictly necessary, are to be preferred. The above also applies to double fire processes (first fire and second glost fire). Non-uniform planarity over time (Monoporosa) Small planarity variations caused by small or difficult-to-monitor changes in production parameters and/or raw materials are, over a period of hours and days, quite normal: for the kiln operator, the resultant corrections are all in a days work. Macro alterations at the front of a load following a gap in production are an altogether different matter. The alterations that take place in an empty kiln (or, more correctly, one in which the carpet of tiles that physically separates the above and below-roller zones is absent) are easily understood. The burners under the rollers produce more heat than usual and the ones above them less. The newly introduced load thus enters a kiln in which energy distribution has been radically altered and effects on planarity are inevitable. Active adjustment of specific burner gas flow valves has been seen to reduce deformation, the downside being that the problem then seems to last longer. It is, perhaps, best to accept this inconvenience as inevitable, leaving gas modulation valves to operate freely, keeping deformation within as narrow a time span as possible; rejection of the first 10-20 rows following a significant gap in production is also routine practice. If post-gap tile deformation persists well beyond those first 10-20 rows, thermoregulator and gas modulating valve reaction times need to be speeded up.
406
Defects
Non-uniformity of size across the load cross-section in monoporosa While monoporosa is characterised by firing shrinkages of around 1%, heterogeneous shrinkages of considerable magnitude are far from rare, especially with large tiles. As with floor tiles, the defect takes the form of increased size at the sides of the kiln load. However, the dynamics behind the defect are quite different: with floor tiles the root cause is lower temperatures near the firing zone walls. With monoporosa, instead, the problem lies in overly-fast heating of the load sides within the 950-1000 C range, during the fast contraction that correlates with carbonate decomposition, and the way in which expansion and shrinkage overlap and interfere with each other (fig. 84).
temperature expansion temperature + shrinkage + Edge shrinkage is obstructed by expansion of the centre: = the edge shrinks less than it should
SHRINKAGE
EXPANSION
EXPANSION
Edge expansion is boosted by greater residual expansion of centre = the edge remains larger.
.ig. 84.
There is no clear-cut solution to this problem. Experience has shown that spacing the tile rows apart helps as it homogenises the gap situation at the sides of the load. This evens out the size variation by bringing all the tiles towards the larger end of the range. Some success has also been obtained by adjusting pre-heating burners to reduce temperatures at the load sides. Surer results, however, are to be had by reducing temperatures beneath the rollers, especially in the 950-1000 C range (if planarity control so allows).
407
It has yet to be understood why size defects are a constant with certain body formulations and completely absent with others (fig. 85).
.ig. 85.
Comparison of expansion curves for problematic and problem-free bodies highlights that: The problem is common where bodies have a high percentage of calcium carbonate. Size problems exist where the contraction associated with carbonate decomposition is more marked. .urther, marked expansion following carbonate decomposition is decidedly negative. Production contamination Cases vary considerably and tracing the cause of the defect is no easy task. Analysis of the circumstances under which the phenomenon is more marked, frequency and distribution across the load, glaze depth at which contamination is found, size, shape and colour all provide useful clues. A small microscope will prove indispensable. In-kiln contamination may be sub-divided into the following groups. a) Vitreous contamination b) Ceramic contamination c) .errous metal contamination d) Non-ferrous metal contamination e) Carbon contamination. Note that a contaminant particle produced by the kiln can never sink below the thickness of the glaze. Its exact position is found by sectioning the tile and examining the cross-section under the microscope. Contamination by grinding wheels, welding machines and debris near the production line during assembly and maintenance work is an altogether different matter.
408
Defects
a) Vitreous contamination Appears as round blotches (drops) of considerable size (1-40 mm in diameter), mostly yellow, green or brown. The phenomenon initially appears occasionally and then becomes more frequent with each passing day. Increases in intensity following significant gaps in the tile feed and substantial variations in the final preheating zone. Dependent on the presence of strong contaminants (mainly lead and boron) in glazes and frits. The vapour from the frits condenses on the roof and walls of the kiln at temperatures between 850 and 1000 C. Excessive accumulation or lower viscosity caused by high temperatures causes it to drip onto the material in transit: the blotches have an evidently vitreous appearance. Note that condensate formation cannot be prevented by kiln adjustment: significantly increasing flow rates gives some improvement, but the practical benefits are limited and the resultant increase in energy consumption is considerable. When vitreous contamination begins to compromise sorting yield, the roof must be cleaned. The rate of condensate accumulation is sometimes high and frequent cooling of the kiln for cleaning purposes (done by chiselling and scraping) is infeasible. The alternative is to raise temperature (by 100-150 degrees C) in the 900-1000 degree C area for about 2 hours. This sharply decreases viscosity of the condensate, causing it to run off in large quantities. Needless to say, the underlying rollers must be protected from the inevitable fouling and must thus be removed beforehand. However, if the rollers are in poor condition removal is inadvisable: in this event they should be protected by a ballast (i.e. unglazed tiles) and the rollers should be moved backward and forward for the entire cleaning period. Be careful to switch the forward/backward movement on and off frequently enough to prevent activation of the relevant safety device that shuts off the gas valves. To facilitate the increase in temperature, keep the final cooling fan running and, if effective, stop the hot air suction fan. Monitor the kiln carefully, especially the inlet where, because of the increase in pressure, there is a risk of damage (photocells, cables, rubber rollers etc.). In any event, cleaning the roof by raising temperature is an expedient that should be used sparingly. In the long run, repeated heating can compromise insulation because the refractory material becomes impregnated (note that the refractory must be cleaned with the kiln cold and that impregnation reduces cleaning efficiency). In the long run, the only proper solution to the condensate problem is an intelligent selection of compatible glazes. Condensates of a powdery aspect may also be observed at low temperatures in the pre-kiln and in preheating. Here, roof and walls can be cleaned with a jet of compressed air passed through a metal tube: the latter is inserted through the side wall hatches under the roof. Combining water with compressed air provides a more efficient car-wash spray clean. Kiln cooling and roller extraction are unnecessary. b) Ceramic contamination Ceramic contamination appears as a relatively glossy, small, rounded dark spot, perceptible when scratched with a fingernail.
409
Observation with a microscope reveals an aggregate-like aspect typical of ceramic material and no halo: cavities are absent. This is the fine dust that accumulates as dunes anywhere there is turbulence and then detaches as small flakes because of excessive accumulation, vibration or thermo-dimensional variations. .lakes may also be produced by overly compact loads (tiles pitching against each other as they move over the rollers). Always keep the area around the kiln clean to prevent circulation of dust, bearing in mind that the kiln interior is a low pressure area in which air currents from all directions converge; this is because large volumes are aspirated by fans and discharged from the chimneys and because of ascending currents produced by the hot mass of the kiln. Installing good filters at the combustion air and rapid cooling fan inlets is an effective preventive measure; these filters must be kept scrupulously clean. The kiln areas involved in this problem are: Kiln inlet Loading machine structures and guards above the tiles, where dust collects. Blowing of the material, especially where autonomous fans are used: fit fans with filters and periodically clean blower tubes. Pre-kiln Kiln inlet door, above the load: brush and vacuum-clean. Roof, fume outlets and walls above the roller plane should be cleaned with compressed air (via a metal tube inserted through special hatches). Edges of the ambient air intake in the roof at the end of the pre-kiln: brush and vacuum-clean. Burner Only burners above the roller plane are involved. However, those below the rollers still require regular cleaning to ensure their efficiency. Sand the heater and electrodes and blow with compressed air. Clean burner casing with compressed air, tap the air valve and the flex hose fitting and clean with compressed air. Rapid cooling Where contamination originates here it is rigid or just partly molten, rough to the touch and always on the surface. Clean the blowers periodically: blow air through them simply by detaching the flex hose from one side and knock them to detach contamination. Blow air through the air regulation valve and the flex hose. Directing the below-roller blowers downwards can lift dust and waste which inevitably settles on the back of the tiles. However, such contamination ends immediately after the blowers are re-oriented. In rare cases, and only in double fire operations, the unscraped, under-tile flash
410
Defects
produced by presses with worn punches tears off during the rapid cooling phase and falls onto the still soft glaze. This type of contamination takes the form of fragments of elongated shape with ragged edges sticking to the still molten glaze. Debris from exploded tiles and the waste produced when workers walk over the kiln roof or adjust the chicanes and tube valves can also cause problems (but only occasionally). Blowing in final cooling is never a source of contamination as this area of the kiln is already a long way from any molten glaze. c) .errous metal contamination Appears as a black speck characterized by a small brown ring around a black nucleus, clearly visible with the microscope; quite frequent but very rarely produced by the kiln. To identify the cause section the tile and identify where the problem lies. If the contamination is produced by the kiln, the defect will always be superficial and poorly amalgamated with the glaze. Possible sources of contamination: The kiln inlet door (above the rollers) and the piping above it. .ume outlets in the kiln, especially where the system is subject to frequent power failures that cause formation and stagnation of acid condensate and moisture. Rub down and brush the door. Pierce the piping insulation at several points and tap with a hammer and chisel so that any unstable encrusting breaks off. The rare event of oxidation inside the rapid cooling piping should be monitored by placing special filters at the consumption points and inspecting pipes internally. It is inadvisable to direct the above-roller blowers at tiles directly as contamination does not sink into the glaze and remains very rough to the touch. d) Non-ferrous metal contamination Shows up well under microscopic observation on account of its glossy crystalline appearance, reminiscent of cast iron fragments, and the absence of the brown ring produced by partial oxidation of the iron. Possible sources of contamination include all the exposed stainless steel and refractory parts in the firing channel above the load and therefore: .ibre plate anchors in the pre-kiln roof. Generally small particles which include body and condensate, these increase markedly in intensity and density in post-gap loads as a consequence of the increase in pre-kiln temperature. Clean with compressed air, using a metal tube inserted through the doors. As soon as the kiln cools brush thoroughly.
411
Burners Particularly heavy duty working conditions can cause the heater to overheat and deteriorate or wear out. Contamination produced in this manner is then put into circulation by the fast flame. Contaminant particles are always small and round, their frequency and diffusion remaining constant and uniform. The same applies to excessively long starting electrodes: in this case shortening the electrodes, thus eliminating the part that shows signs of carbonisation, usually suffices. Rapid cooling blowers These produce very small powder-like black specks; contamination increases sharply following gaps in tile feed. These metal specks remain on the surface of the tiles and are rough to the touch. Contamination is caused by deterioration of the blowers above the roller surface, usually the 2 or 3 closest to the firing section. Blower deterioration is caused by overheating of the steel: where cooling is poorly adjusted deterioration can happen quickly. Regulate rapid cooling so as to ensure minimum blower cooling when the blown air modulation valve is open to minimum: set pressure no lower than 10 mm approx (water column). Under no circumstances should rapid cooling fan be stopped during the transitory phases of kiln heating or when there are gaps in the load. Avoid exposing blowers to fumes in the firing section by adjusting chicane height between firing and cooling accordingly: inspect chicanes regularly to make sure they are intact. Avoid cooling settings that suck firing fumes towards the rapid cooling zone. If blower degradation is within reasonable limits, detaching the flexible pipe from one side and blowing out the accumulated waste will suffice. .or more pronounced degradation, remove the blowers, brush them and knock them. Beyond a certain limit, especially if blowers are evidently deformed, their replacement becomes absolutely necessary. Lining those blowers most at risk with ceramic fibre prevents contamination with waste produced on the surface exposed to the firing channel. Today, silicon carbide blowers are often used. While costly, this material avoids the above problems. Blower tubes made of refractory alumino-silicates can be broken by thermal shock: when breakage occurs jamming of the tiles is inevitably involved. Heat exchanger Only rarely a source of contamination, usually because of the care and attention involved in its design. This type of contamination can easily be identified by the shape of the metal flakes: lamellar with sharp edges. In this event it is necessary to brush down the exchanger (with the kiln cold, of course).
412
Defects
e) Carbon contamination Infrequent and limited to cases where use of fuels such as L.P.G. or liquid fuels results in poor combustion and thus formation of carbon in the burners. Appears as small black specks, opaque and ringless (without halo). Regular cleaning of the burners is essential, as is monitoring and correction of air-fuel regulation.
413
Printed September 2002 by Tipografia Moderna di Ravenna for Editrice La Mandragora of Imola

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Defects

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DE.ECT PREPARATION Black core Size

Tab. 1. Possible links between defect and production department.

.ig. 1. Surface defect caused by coarse grains, degassing during firing.

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or the priest hat deformation (fig. 53).

Constantly suspended part of tile (black areas)

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roller effect (porpoising) .ig. 62.

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Temperature Shrinkage .ig. 80.

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