Casting Slip Control
Casting Slip Control
Casting Slip Control
Contents:
Introduction Slip Control Viscometer Measurement of Fluidity Measurement of Thixotropy Measurement of Slip Density Measurement of Baroid Permeability Control of Casting Slips Ageing of Casting Slips Casting Faults Practical Formulae Properties of Ceramic Materials Whiteware Faults and their Remedies Glossary of Terms 1 2 3 4 5 6 7 8 - 10 11 12 13 14 15 - 16 17
introduction
Almost all casting slips used in the production of traditional ceramic whitewares consist of plastic ball clay, kaolin, filler and flux in various proportions depending upon the application. The ball clay is the most difficult to disperse and is, therefore, normally processed and allowed to age prior to final casting slip preparation. Deflocculated casting slips with predictable, defined characteristics Chopped filter press cake Vacuum extrusions at working moisture contents c. 19-21% Crumble - aggregated body at about 10 - 12% moisture Dry mixed powders Noodles The form in which these bodies are supplied varies according to need and can include:
Shredded Blends - require deflocculating and the most processing and ageing prior to use
The other materials are then added to the aged ball clay slurry to form the casting slip with the required properties.
The manufacturers choice of form will depend on the manufacturing process, the availability of equipment, and the location of the factory.
For smaller or more specialised producers, such as FFC in sanitaryware, prepared bodies are readily available. Such prepared bodies contain the majority of raw materials necessary for the successful production of most forms of whiteware. The only other raw material requirements may be water and, in factories using the casting process, deflocculants.
Consistent behaviour of the ball clay and casting slips is vitally important in minimising day to day production problems. Such consistency is essential for the setting of factory production rates which achieve the most efficient and cost effective manufacture of the finished ware.
slip control
The most widely used method of casting slip control is based on the measurement of fluidity and thixotropy by means of the Gallenkamp Torsion Viscometer (GTV or TTV) (figure 1). Other instruments, e.g. the Brookfield Viscometer, Rheomat Viscometer or alternative methods, some of which are based on the use of a flow cup to measure fluid characteristics, may be used. An increasingly common method using the Brookfield Viscometer is the V60 test, designed to measure the build up of structure with time. The Gallenkamp instrument, however is widely available, simple to use, robust and relatively low in cost. The results it produces are quickly available and easy to interpret. Necessary adjustments can be made rapidly to casting slips and re-measurement of fluid characteristics takes only a few minutes.
the viscometer
Clamp
and suspended from its top end, with a metal cylinder attached to the lower end which is free to rotate with the wire (see Figure 2). When the cylinder is turned through 360 degrees and then allowed to unwind in a container of casting slip, the extent of its rotation is governed by the viscosity of the slip. A flywheel attached to the wire above the cylinder gives a more stable rotation. Hence the fluidity of the slip can be readily expressed in terms of degrees of rotation. Several sizes of torsion wire and cylinder are provided with each viscometer. For the control of casting slip, the most common sizes employed are the 30swg wire and the 11/16 cylinder or bob. Occasionally with certain types of slip, substitution of the 11/16 with the 1/4 cylinder will be necessary. Whichever wire size or cylinder is used, it is essential to level and adjust the instrument in order that the cylinder can freely rotate. This should be checked by ensuring that after rotation through 360 degrees in either direction, the overswing in air is within 3 degrees of a complete revolution.
Pointer Cylinder
Direction of Rotation
Figure 2: The Gallenkamp Viscometer
measurement of fluidity
Before taking a measurement of fluidity, the viscometer cylinder must have been wound through 360 degrees in a clockwise direction. With the viscometer beaker in position under the viscometer, the flywheel pin is released hereby enabling the flywheel to rotate in an anticlockwise direction. The overswing indicated by the pointer on the flywheel against the graduated scale is recorded as a measurement of fluidity It is important to ensure that the sample of slip is thoroughly stirred immediately prior to the actual measurement. Samples taken from production blungers or arks should be stirred in the viscometer beaker for exactly one minute, immediately placed into the measuring position and a reading taken after 5 seconds (some allow 15 seconds before taking the reading; either way, it is critical that the time is kept constant to ensure consistent, reproducible results). It is also important to ensure that the cylinder is fully immersed in the slip being measured (see Figure 3). Figure 3: Viscometer cylinder fully immersed in slip
measurement of thixotropy
Thixotropy, or the tendency of an undisturbed slip to thicken with time, is an important property which has a marked the viscometer flywheel immediately after taking the fluidity reading, allowing the slip to stand undisturbed for either 60 or 90 seconds, and then re-measuring the overswing. Thixotropy is defined as the difference between the two readings. In some instances, a 5 or 6 minute thixotropy reading is also useful. It is important that the temperature of the above measurement is recorded as temperature can severely affect viscosity values. effect on casting performance. It is measured by rewinding
Fluidity Overswing
o
Thixotropy o Overswing
40 30 20
10
15
Days
The density of a casting slip must be kept within defined limits as variations will affect casting performance. A low density slip can result in the rapid saturation of plaster moulds and subsequent difficulties with second casts and mould drying. Conversely, high density slips can lead to casting and pouring difficulties if particle packing and fluidity parameters are not controlled well. The measurement of slip density is quite simple (Figure 5). A pre-weighed vessel is filled to a calibration mark of either 500ml or 1 litre and then weighed. The difference in weights represents the weight of a slip in a given volume. Density of casting slip is normally expressed in g/l or g/cm3 (equivalent to kg/l).
The introduction of pressure casting in the traditional ceramics industry has led to the emergence of new testing methods, one of which is Baroid Permeability. Originally developed to provide casting performance data for pressure casting slips, it has also been found useful for quickly comparing the performance of traditional casting slips. The Baroid Permeability equipment consists of a small pressure vessel with a pressure regulator situated at the top, a filter membrane (normally paper) at the bottom together with an outlet (see Figure 6). The system is filled with slip and then pressurised to a known pressure (usually 75 or 90 p.f.s.i.) or (0.52 or 0.62 Mpa) for a set time. At the end of the experiment, the filtrate collected is weighed, the slip is drained and the cake produced is either weighed or the thickness measured. There are several methods of interpreting the results, ranging from reporting the measured cake weight through to carrying out various calculations to achieve a permeability constant for the slip.
pressure regulator
Figure 7 illustrates typical deflocculation curves for a casting slip using in one case, sodium silicate and in the other, sodium carbonate. Sodium silicate tends to give high fluidity slips with low thixotropy, while sodium carbonate will give lower fluidity slips with higher thixotropy. It is normal practice to use these two reagents together as this offers the possibility of obtaining high fluidity slips with an appropriate degree of thixotropy. The reagents are mixed in a ratio which will give the most effective control over fluid properties for the given casting slip system. This ratio may vary from 1:1 silicate:carbonate up to 4:1, but 3:1 is usually considered to be normal. Processed clays and clay bodies have been developed that include deflocculant in the formulation so that only small additions of sodium silicate are required to the slip prior to casting.
360
Degrees Overswing
SODIUM CARBONATE
Thixotropy
Deflocculant %
9
Figure 7: Typical deflocculation curves for casting slip
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casting faults
It is possible to overcome most casting faults by adjusting the control values of the casting slip. The table below details most of the common faults encountered and suggests actions which may be taken to overcome these faults.
Fault
Description
Cause
Cure
poor filling
flabby casts
brittle casts
poor draining
wreathing
small uneven fringes on slip side of cast, e.g. slight raised crescent shapes small holes just below surface on mould side of cast piece
decrease deflocculant addition or decrease water addition increase water addition or increase deflocculant addition
pinholes
cracking
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practical formulae
% Solids of a Suspension:
% Solids =
x 100
Brongniarts Formula: Dry Weight = (Dry weight in kg/l) (litre wt - 1) x Solids SG Solids SG -1
Volume of Water needed to produce a Slip of Desired Solids : Volume = Dry Weight of Material x (100 - % Solids Required) % Solids Required
To Dilute 1 litre of Slip of Density A (kg/l): Volume of Water to Add = (Volume in litres) A-B B-1 A = Density of Slip B = Required Density
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alumina calcined bone ash boro-calcite kaolinite (china clay) kaolinite, calcined chromium oxide cobalt carbonate cobalt oxide copper carbonate copper oxide dolomite feldspar, potash
Al2O3 Ca3(PO4)2 2CaO.3B2O3.5H2O Al2O3.2SiO2.2H2O Al2O3.SiO2 Cr2O3 CoCO3 Co3O4 CuCO3 CuO CaCO3 MgCO3 K2O.Al2O3.6SiO2
101.9 310.3 412 258.1 222 152 118.9 241 123.6 79.57 184 556
Al2O3 CaO P2O3 CaO B2O3 Al2O3 SiO2 Al2O3 SiO2 Cr2O3 CoO CoO CuO CuO CaO MgO K2O Al2O3 SiO2 Na2O Al2O3 SiO2 SiO2 FeO TiO2 Fe2O3 Cr2O3 Fe2O3 Fe2O3 Fe2O3 Li2O MgO MnO MnO K2O Na2O Al2O3 SiO2 NiO Li2 Al2O3 SiO2 SiO2 TiO2 Na2O Na2O Na2O SiO2 Li2O Al2O3 SiO2 MgO SiO2 SnO2 TiO2 CaO CaO SiO2 ZnO ZrO2 ZrO2 SiO2
101.9 56 142 56 70 102 60 102 60 152 75 75 79.57 79.57 56 40 94 102 60 62 102 60 60 71-84 79.9 160 152 160 160 160 30 40.3 71 71 94 62 102 60 74.7 30 102 60 60 79.9 62 62 62 60 30 102 60 40.3 60 150.7 79.9 56 56 60 81.3 123.2 123.2 60
1.0 0.542 0.458 0.271 0.51 0.395 0.465 0.46 0.54 1.0 0.631 0.934 0.645 1.0 0.304 0.218 0.169 0.183 0.648 0.118 0.195 0.687 1.0 0.474 0.526 0.516 0.454 1.11 1.0 1.035 0.405 0.476 0.61 0.817 0.080 0.158 0.350 0.412 1.0 0.049 0.167 0.784 1.0 1.0 0.585 0.365 0.508 0.492 0.081 0.274 0.645 0.318 0.634 1.0 1.0 0.56 0.48 0.52 1.0 1.0 0.673 0.327
2050 1670
1770 (decomposes before melting) 1770 2070 decomposes to oxide 2800 decomposes to oxide 1149 decomposes to oxide 1200
2.52 2.6 5.04 6.07 3.6 - 4.0 6.4 2.9 2.5 - 2.6
feldspar, soda
Na2O.Al2O3.6SiO2
524
1170 approx.
2.6 approx.
flint ilmenite iron chromate iron oxide (ferrous oxide) iron oxide (ferric oxide) iron oxide (ferroso ferric oxide) lithium carbonate magnesium carbonate manganese carbonate manganese dioxide nepheline syenite
SiO2 FeO.TiO2 Fe2O3.Cr2O3 FeO Fe2O3 Fe3O4 Li2CO3 MgCO3 MnCO3 MnO2 K2O.3NA2O.4Al2O3 8SiO2 NiO Li2O.Al2O3 8SiO2 SiO2 TiO2 Na2 CO3 NaNO3 Na2SiO3 Li2O.Al2O3 4SiO2 3MgO.4SiO2.H2O SnO2 TiO2 CaCO3 CaSiO3 ZnO ZrO2 ZrSiO4
1650 - 1750
1800 aprox
1565 1538 618 decomposes to oxide at 350 decomposes to oxide loses oxygen at 535 1200 approx.
5.2 - 5.3 5.0 - 5.5 2.1 3.04 3.6 4.7 - 5.0 2.5 - 2.6
nickel oxide petalite quartz rutile sodium carbonate sodium nitrate sodium silicate spodumene
6.6 - 6.8 2.4 - 2.5 1470 1600 852 310 1080 2.65 4.2 2.5 2.27 2.4 2.6
talc tin oxide titanium oxide whiting wollastonite zinc oxide zirconium oxide
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2.5 - 2.8 1127 1600 decomposes to oxide at 825 1540 1800 2700 2550 6.6 - 6.9 3.8 2.7 - 2.9 2.7 - 2.9 5.6 5.5 4.56
zirconium silicate
Appearance
pinholes in glaze after firing
Cause
gas evolution from body and/ or glaze during firing: under-firing of body air trapped in clay over-application and over-firing of underglaze colours soluble salts excessive whiting in the glaze under-firing of the glaze over-firing of the glaze giving rise to volatilisation sulphur gases present in kiln atmosphere reacting with glaze: sulphates in body sulphur present in kiln gases gaseous materials being provided during firing: glaze not fully matured glaze/ body over-fired glaze and body are not fully compatible glaze rubbed or knocked off before firing
Suggested Remedies
fire body to recommended firing temperature wedge plastic clay thoroughly reduce application of underglaze colours add barium carbonate (0.1 - 0.25%) to body to precipitate soluble salts reduce whiting in glaze fire glaze to recommended firing temperature reduce firing temperature of glaze ventilate kiln as soon as possible fire biscuit ware to temperature high enough to liberate sulphur
sulphuring
blistering
fire more slowly and/or soak at top temperature reduce length of firing/ soak and/or drop temperature change the body/ glaze combination
knocked glaze
handle more carefully and only when completely dry add a binder to the glaze (1% gum, starch or sodium carboxymethyl cellulose) avoid placing new pots in glaze firing too close to kiln bricks or new props do not fire biscuit ware in the same firing as glost ware ensure pots do not touch in glaze fire wipe off glaze from base of pots use bat wash or placing powder ensure all tools and containers are free from rust ensure pots are free of loose material before dipping sieve glaze regularly experiment with an alternative glaze add clay to pigment reduce firing temperature fire at lower temperature use an alternative glaze
starved glaze
dull patches
glaze volatiles are sucked away from the surface by porous kiln furniture
stuck ware
pots touching during glaze firing or too soft a glaze flowing down onto the shelf contamination - often from too many rusty tools or from loose particles of biscuit ware and applied decoration dropping onto glaze during dipping high solubility of the colouring oxide to the colouring glaze
specking
dark specks
blurring
firing away
over-firing underglaze chrome tin pink may fade with glazes high in Boric Acid too thick an application of underglaze decoration too thin an application of glaze over the cobalt devitrification usually due to under-firing thermal expansion of colour not matching that of underlying glaze aggravated if colour applied to very stiff porcelain type glazes gold applied too thinly excessive use of thinners ware not properly cleaned too much lustre applied fired too quickly after application
ironing
matt colours
matt texture
apply another layer use less thinners and apply thicker clean with warm water and detergent apply more thinly allow to dry completely before firing
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Appearance
bubbles from within body during firing
Cause
expansion of body produced by pressure build-up of gase trapped in a partially fused mass: over-firing or irregular firing carbon trapped within vitreous body body too high in fluxes presence of impurities in clay or glaze: particles or plaster from mould surface sulphates and/or carbonates present in mould body rapid or uneven drying of clay ware clay of poor plasticity blunt turning tools firing body too fast up to 300oC overworking of clay during making excessive handling of ware before firing oil, grease, dust, etc. on ware before glazing cracking of glaze layer during drying and before firing excessive colloidal matter (clay) present in the glaze soluble salts present in the body over-application of the glaze mismatch of glaze and body thermal expansions (body should have higher expansion to maintain the glaze under compression) glaze applied too thickly moisture expansion of the body under-firing of body or glaze
Suggested Remedies
reduce firing temperature fire more slowly reduce flux content of body and/or grog to open up body
blow out
cratering in body
avoid possible contamination: remove any plaster plucked away from mould surface use more refined clays
cracking
cracks in ware
dry more slowly (invert mugs, jugs or bowls when of sufficient strength) increase plasticity of clay use sharper turning tools slow down initial firing rate (2-4 hours) reduce handling time during making minimise handling of ware before glazing keep biscuit ware clean handle dipped ware very carefully, reduce clay content of glaze add barium carbonate (0.1-0.25%) to precipitate soluble salts reduce glaze application
crawling
bare unglazed patches on surface of the whiteware, glaze ruckled into small islands
crazing
devitrification glossy glazes appearing matt milky appearance of transparent glaze (often bluish-pink over terracotta bodies) precipitation taking place during cooling of glazes appearance of small crystals on surface of glaze (calcium, zinc, silicates etc) milky precipitate (calcium borate) too rapid heating and/or cooling of body especially around 573oC and 220oC (silica inversion temperatures) body too high in silica large variations in wall thick ness or article giving rise to thermal gradients over-firing of body glaze under excessive compression migration of solube salts to surface of body on drying or firing giving rise to poor adhesion of glaze
increase body expansion: fire body to higher temperature soak body for longer at peak temperature increase silica content of body reduce glaze expansion add silica or china clay to glaze use Borax frit of lower expansion reduce glaze thickness reduce porosity of body cool more quickly down to 700oC (ie while the glaze is still semi-molten reduce lime content of the glaze add china clay to glaze use low solubility glaze instead of leadless glaze fire and cool the body more slowly through temperature ranges at which silica inversions take place reduce silica content of the body give careful consideration in design reduce firing temperature of the body open up by addition of grog
dunting splitting of ceramic ware due to silica inversion (when glaze has run into crack: dunting has occurred during heating cycle; crack with sharp edge: dunting has occurred during cooling cycle) glaze lifting away from body (occurs mainly on edges of post such as cup rims and handles)
peeling
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reduce body expansion: reduce firing temperature reduce body soaking period increase glaze expansion: add high expansion alkaline frit reduce silica and/or alumina content of glaze add barium carbonate (0.1 - 0.25%) to body to precipitate soluble salts sponge rims and handles of clay ware before biscuit firing
glossary of terms
Ark Tank in which clay slip is agitated and/or stored Grog Ground refractory materials used as a raw material to improve working proper ties in refractories, terracotta, stoneware, FFC sanitaryware and similar products
Blunger Tank with mixer for the production of clay slips or slurries
Reagent Body, Ceramic Workable mixture of clays and non-plastic materials with properties suitable for firing, from which ceramic products are made A reactive chemical e.g. a deflocculant
Thermal Expansion Reversible or permanent change in the dimensions of a body due to heat
Casting Slips Ceramic bodies mixed with water and deflocculant to form a slurry Thixotropy Property of a suspension to increase in viscosity upon standing, due to a build up of structure within it, which can then be destroyed by agitation
Deflocculant Reagent used to disperse agglomerates to achieve fluid slips at higher density
Viscosity Dunting Cracking in fired ceramics which have undergone uneven heating or cooling Is the measurement of a fluids resistance to flow
Vitrification Fettling The removal of rough edges, mould marks and irregularites from unfired ceramic ware, usually through abrasion, scraping or cutting Progressive reduction in a bodys porosity due to heat treatment and fusion, during which a glassy or non-crystalline material is formed
Volatilisation Conversion of a chemical substance from a solid/liquid state to a gas through the application of heat or a reduction in pressure
Frit Melted glass, quenched in air or water to produce small friable particles which are milled for use in porcelain enamels, fritted glazes and frit chinaware
Wreathing Slight raised crescent shape on the inside wall of slip-cast ware
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