|
陶瓷釉及釉用原料中的氧化物
Al2O3 As2O3 B2O3 BaO BeO Bi2O3 C CaO CdO
CeO2 CoO CO2 Cr2O3 Cu2O CuO
F Fe2O3 FeO Free SiO2 H2O InO3 K2O KNaO LOI Li2O MgO MnO MnO2 MoO2 Na2O NiO
P2O5 PO4 PbO PrO2 Sb2O3 Se SnO2 SrO TiO2 Trace U2O8 V2O5 Y2O3 ZnO ZrO ZrO2
| 分子式 |
分子量 |
膨胀因子 |
熔点 |
性质 |
在釉中的作用 |
| B2B3 |
69.6 |
.031 |
577 |
Boric Oxide
(Sources: Borax Frits, Gerstley Borate/Colemanite, Boric Acid, Borax,
Ulexite)
-Boric oxide has no melting point, but a progressive softening and
melting range from 300-700C. The crystals begin to break down at 300C,
and a series of suboxides are produced with partial melting until full
fusion is reached at 700C. Boron glazes tend to have a fluid melt and
lower surface tension.
Some other borate minerals are:
NaBO2: Sodium monoborate or sodium metaborate
BO2H: Metaboric acid
Na2B4O7.4H2O (Na2O.2B2O3.4H2O): Kernite, rasorite
Ca4B10O19.7H2O (4CaO.5B2O3.7H2O): Pandermite
Mg6Cl2B14O26 (5MgO.7B2O3.MgCl2): Boracite
-The way in which boric oxide combines with oxides like calcia and soda
is not as well understood as other systems.
-Its low expansion makes it valuable in preventing crazing. However,
each glaze recipe tends to have an optimum amount above which the effect
is actually reversed and crazing can increase (10-14%). This effect is
due to the loss of elasticity associated with excess B2O3. Predicting
the expansion of high boron glazes can thus be misleading due to this
factor.
-Boric oxide is a unique oxide often not fully appreciated for all its
qualities. It reacts with whatever is available to behave as both the
'bones' and the 'blood' of glazes (acidic glass former and flux). In
some ways, it can thus be considered a low temperature equivalent of
silica. Because of its dual personality, technicians often are not sure
where to place it in the unity formula. If placed with the amphoterics,
where chemically it should go, it becomes difficult to relate the
formula to others that have no boric oxide.
-Like silica it does not crystallize on cooling unless significant
calcia is present to form calcium borate.
-Borax and Boracic Acid are both soluble and unsuitable sources for
glazes, but fine for frits.
-Boron has many advantages as a glass-forming oxide (although Gerstley
Borate, an important source, does have some consistency problems and can
flocculate a suspension). Borosilicate glazes have been the major
alternative to lead based formulations (melting as low as 750C), and
thus boron is critical to the ceramic industry. 'Pyrex' ware, for
example, is a low expansion high silica borosilicate glass. Boron glazes
are less fluid and this has been the major challenge in switching from
lead. While many users have increased firing temperatures to compensate,
this has not fully solved the 'healing' and bubble clearance problems.
-In low temperature glazes, it both substitutes for fluxes of
high-expansion, and for silica which cannot be present in large amounts.
-Boron's reactivity helps to form good clay-glaze interfacial zones that
inhibit crazing.
-The action of B2O3 depends upon the ratio of bases to silica existing
in the glaze before the addition. If the ratio is greater than 1:2, the
glaze will tend toward opalescence and crazing; if less toward clear and
transparent.
Toxicity of Boron:
The EPA Health Advisory Level for boron in drinking water is 0.6 ppm
(set primarily for water taste). The level for chronic harm from regular
exposure to boron is not well established. |
Glaze Color Low fire transparent glazes employing boron frits,
which have CaO and lack alumina, will have opalescent blue cloudy
effects from the formation of calcium borate crystals. These 'boron
blue' glazes work well visually on terra cotta bodies. These crystals do
not form well if there is adequate alumina to stiffen the melt. |
| ZnO |
81.4 |
.094 |
1800 |
Zinc Oxide
(Sources: Zinc Oxide)
-Together with PbO it is considered one of the metallic oxide fluxes.
-ZnO starts its fluxing action around 1000C (I.e. Bristol glazes)
whereas by itself ZnO does not melt until 1975C. However, ZnO is easily
changed to Zn metal by the action of CO and H2 in the reduction phase of
a gas-fired kiln (and possibly poorly ventilated electric kilns). Pure
Zn metal melts at 419C and then boils and vaporizes at 907C.
-It does take time for zinc to volatilize and meanwhile the it does
encourage the melting process to begin earlier, making it more vigorous.
However zinc metal in a more molten glaze is also more reduceable.
-ZnO is a low expansion secondary flux which is handy to prevent crazing
if used for, or instead of, high expansion fluxes.
-It improves elasticity and extends firing range.
-In moderate to high amounts it acts to produce mattes and crystalline
surfaces, especially if supersaturated (up to 0.8 molar) and cooled
slowly. However, these surfaces can be rough enough to cause cutlery
marking.
-Zinc can improve durability in some glazes.
-At low temperatures small amounts can have a marked effect on gloss and
melting, although at temperatures below Orton cone 03-02 it is not
normally an active flux.
-At middle temperatures, zinc can be used as a major flux in amounts to
5%.
-At higher oxidation temperatures it is valuable to provide a smooth
transition from sintered to melted stage.
-In certain mixtures it is very powerful, even in small amounts. The
melting power per unit added drops quickly as the amount used exceeds
5%.
-Zinc can have amphoteric qualities if it is used with boron.
-Zinc has a complicated color response. It can have harmful and helpful
effects on blues, browns, greens, pinks and is not recommended with
copper, iron, or chrome. |
Glaze Opacifier In larger amounts ZnO can produce opacity or
whiteness in glazes. It exhibits refractory properties and can
contribute to the development of a crystal mesh surface. |
| Al2O3 |
102 |
.063 |
2040 |
Al2O3 - Aluminum Oxide, Alumina
(Sources: Kaolin, Clays, Feldspar, Calcined Alumina, AluminaHydrate)
-Alumina has a very high melting temperature and alumina ceramics can
maintain up to 90% of their strength above 2000F. They are thus employed
in many refractory materials (I.e. Calcium Aluminate Cements have PCE's
above cone 35) and used to make parts that must withstand high
temperature.
-Alumina controls the flow of the glaze melt, preventing it from running
of the ware. It is thus called an intermediate oxide because it helps
build strong chemical links between fluxes and silica.
-Fired alumina ceramic parts can be harder than tungsten carbide or
zircon, two to four times as strong as electrical porcelain, and very
resistant to abrasion. Alumina is thus used in grinding media, cutting
tools, high temperature bearings, and a wide variety of mechanical
parts.
-Alumina is second in importance to silica and combines with silica and
basic fluxing oxides to prevent crystallization and give body and
chemical stability to a glaze.
-It is the prime source of durability in glazes. It increases melting
temperature, improves tensile strength, lowers expansion, and adds
hardness and resistance to chemical attack.
-Increasing it stiffens the melt and gives it stability over a wider
range of temperatures (although excessive amounts may tend to cause
crawling, pinholes, rough surfaces). The addition of alumina prevents
devitrification (crystallization) of glazes during cooling because the
stiffer melt resists free movement of molecules to form crystalline
structures. Thus crystalline glazes tend to have less than .1 molar
equivalents of Al2O3. The addition
of small amounts of CaO will help reduce the viscosity of a melt and
make it flow more freely.
-Calcined alumina does not work well in glazes or enamels as a source of
Al2O3, however, the hydrated form can be effective to matte a glaze if
it has a very fine particle size. If possible, kaolin or feldspar (and
nepheline syenite) are the best sources. Kaolin especially is ideal
because it is so important to other physical slurry properties (I.e.
Suspension, adhesion, and shrinkage control). If glaze batches are being
calculated from a source formula, it is normal to supply all possible
alumina from feldspar and kaolin until the alkali targets are met, then
furnish any additional alumina requirements with Bayer process alumina
hydrate.
Sometimes Bayer alumina is added where exceptional freedom fromiron is
needed.
-In most cases, the addition of alumina raises the melting temperature
of a glaze or glass. However, in some soda lime formulations, a small
alumina addition can decrease melting temperature.
-In glass, small amounts can reduce the coefficient of expansion,
increase tensile strength and surface tension, improve lustre, lengthen
working range, decrease devitrification, increase resistance to acid
attack. When substituting for silica, alumina makes the glass more
ductile and elastic.
-Alumina and boric acid are important constituents in all types of low
expansion glasses for chemical ware, cooking, and thermometers.
-Alumina (preferably in the calcined form) can be used in clay bodies as
an aggregate and filler in place of flint. This can increase the firing
range, decrease quartz inversion firing problems, and increase hardness
and whiteness in the fired body. However, alumina is much more expensive
than flint.
-Alumina hydrate promotes opacity in enamels and glazes by generating
gas bubbles in the glaze melt. |
Surface Modifier: - MATTE
The ratio of alumina to silica is mainly responsible for the degree of
matteness in glazes. In the absence of boron, ratios of less than 5:1
are generally quite matte; ratios of greater than 8:1 are usually glossy
in the absenceof high titania, zinc, magnesia or calcia (which cause
volatile melting or crystallization during freezing).Ratios of 1:18 are
possible, but certainly not typical. If a glaze remains matte when fired
higher, it is a true alumina matte.
Glaze Color: - COBALT BLUE Cobalt depends on presence of alumina or it
will fire pinkish. Chrome reds like alumina also.
Glaze Color: - PINK
Alumina is used in combination with chrome, manganese and cobalt to
achieve pink colors.
Surface Modifier: - CRYSTALLINE GLAZES
Since Alumina stiffens the glaze melt, it will prevent the growth of
crystals during cooling. Thus most highly crystalline glazes have very
little alumina. |
| As2O3 |
198 |
0 |
193 |
Arsenic Oxide
(Sources: Arsenic Oxide)
-Because of its oxidizing effect, it can be used as a fining agent to
clarify iron containing glass. It will also fade the color of manganese
and stabilize other colors (I.e. Light green).
-In pot glasses large quantities are used to reduce yellow coloration.
-Used in specialized enamels (I.e. Jewelry).
-Toxicity due to its vaporization on melting limits its use to tightly
controlled environments (sublimes 193C) |
Glaze Opacifier :Arsenic can be used as an opacifier in glazes,
although not as effectively as tin. |
| BaO |
153.3 |
.129 |
1923 |
Barium Oxide, Baria
(Sources: Barium Carbonate, Barium Sulfate, Baria)
-Baria is the heaviest of the divalent fluxing oxides and has some
properties at high temperatures that make it similar to what lead does
at low fire (I.e. Promotion of gloss).
-Together with CaO, SrO, and MgO it is considered one of the alkaline
earth group of oxides.
-Barium is most popular for the production of classic barium mattes.
These are dependent on adequate kiln temperatures and a slightly
reducing atmosphere to decompose the material to yield BaO.
-Barium gives unique color responses with certain oxides (I.e. With
copper it will give a marked blue compared with glazes fluxed with MgO,
SrO).
-BaO often contributes a high index of refraction and this can enhance
in-glaze colors.
-As a flux it can be very active in small amounts (not active at low
temperature). For example, in small percentages it can improve gloss,
mechanical strength, and acid resistance.
-Barium carbonate is very stable if not decomposed, and as such it will
remain unreacted in the glaze melt. In the stable carbonate form, it can
thus act as an opacifier and matting agent, especially in low
temperature glazes. Such are not true barium crystal mattes and are not
recommended because of the possibility of leaching and the ease with
which other oxides will opacify or produce a low fire matte (I.e. CaO,
MgO, Alumina, Zircon).
-Baria is more effective as a flux when associated with other fluxing
oxides with which it can combine (e.g. If fused in certain frit
formulations it can react readily in even low temperature glazes). It
can also form a strong eutectic with B2O3 to produce a glossy and runny
glaze.
-In larger amounts it becomes refractory and can produce dangerous
leachable glazes, since it does not fully combine to form insoluble
silicates. It is common to see glazes with more than 20% barium
carbonate, and at times, a 40-50% recipes are traded in the pottery
community. These are very likely not safe.
-Use with caution in functional ware! There is considerable controversy
concerning the safety of barium in glazes (I.e. If you see larger
amounts of barium in glazes labeled "Dry Matte" or "Stony
Matt", be very cautious). Like lead, it can be leached from the
surface (of improperly fired or formulated glazes) by acidic foods or
liquids. Government agencies have the power to level fines if ware is
found to be soluble.
-If possible, determine the reason for BaO in the recipe. The mechanism
may well be better accomplished by another oxide. For example, SrO and
CaO can both be employed to produce crystal mattes in saturation
(although a calcium matte will likely be coarser). K2O may produce a
better blue with copper or a brighter color.
-SrO has been promoted as a substitute for BaO and in some case this is
true. It has a lower disassociation temperature and reacts earlier and
is potentially able to produce a more perfect surface unmarred by the
bubbles and pits associated with higher temperature decomposition. Still
it is best to substitute BaO on a mechanism basis, choosing the best
alternate oxide or formula adjustment in each case.
-CaO will also produce crystal mattes when dominant in the RO group,
however, the texture will likely be coarser |
Surface Modifier: Baria is well known for its tendency to cause
the growth of a fine mesh of micro crystals to produce a silky matte
texture.
Glaze Color Barium glazes are well known for their ability to produce
matte turquoise colors with copper. While strontium is often used to
duplicate the matte texture of barium it does not have the same color
response. |
| BeO |
25.011 |
0 |
2650 |
Beryllium Oxide
(Sources: Beryl)
-Beryllium is a specialty oxide available as a pure material in a wide
variety of sizes and shapes.
-It is valuable for producing ceramics with high thermal conductivity,
particularly in the lower temperature ranges. Its thermal conductivity
is 400% more than that of dense alumina at high temperatures and even
greater at lower temperatures. Its thermal conductivity is dependent on
purity. For example 99.8% purity sees a 10-15% rise in conductivity.
-Has excellent dielectric properties.
-Has outstanding resistance to wetting and corrosion by many metals and
non-metals.
-It's mechanical properties are only slightly less than that of 95%
alumina ceramics.
-It has valuable nuclear properties including an exceptionally low
thermal neutron absorption cross section.
-Like alumina, it is readily metallized by thick and thin film
techniques |
|
| Bi2O3 |
466 |
0 |
820 |
Bismuth Oxide
(Sources: Bismuth Nitrate)
-Melts at 820-860C
-Bismuth oxide is derived from the ignition of bismuth nitrate which in
turn is obtained from the heavy metal bismuth, found in the US, Peru,
and Mexico. Bismuth is very similar to lead, however there is no
evidence that it is toxic. In fact, it is used in medicines taken orally
for stomach complaints.
-It has been used instead of lead oxide in amounts up to 50% in optical
glasses to improve durability and increase the specific gravitys and
refractive indexes. Arsenic is often used with it to prevent a tendency
toward grey coloration.
-Bismuth has also been used in low temperature frits and colors, as a
flux in conductive glazes, and in metal enamels.
-During the 1990's, industry has been under much pressure to discontinue
the use of lead compounds. Bismuth is a very effective substitute for
lead, providing the same high gloss, flow, 'healing' and 'bubble
clearance' characteristics, refractive index, surface tension,
viscosity, and resistance to 'aggressive' dishwasher detergents. Bismuth
melts lower than lead and thus glazes can be even more fluid.
-Bismuth is much more expensive than lead (glazes could be 3-4 times
more) and it does not provide the same gloss and durability in some
on-glaze cobalt blue and iron red colors. |
|
| C |
0 |
0 |
0 |
Carbon
(Sources: ball clays)
-C can be entered into an analysis to signify that LOI in a material is
carbonaceous matter that burns away during firing. Since it is lost
during firing, a weight of zero should be used during calculations so
there is no impact on the calculated formula or properties |
|
| CO2 |
0 |
0 |
0 |
Carbon Dioxide
-CO2 refers to the carbon in a material that burns away during firing.
It can be used in an analysis to make clear the nature of LOI
components. Since it is lost during firing, a weight of zero should be
used in calculations so that there is no impact on the calculated
formula or properties.
-CO2 is often produced when oxygen-hungry CO in the kiln chamber during
reduction firing (or incomplete oxidation) encounters compounds from
which it can rob an oxygen atom to form CO2 |
|
| CaO |
56.1 |
.148 |
2750 |
Calcia, Calcium Oxide, Quicklime
(Sources: Whiting, Wollastonite, Feldspar, Colemanite, Dolomite)
-Together with SrO, BaO, and MgO it is considered one the Alkaline Earth
group of oxides.
-Quicklime is pure calcia, but it reacts with water to produce calcium
hydroxide or slaked lime. Calcium oxide, on the other hand, is an
extremely stable compound.
-Calcium oxide is the principle flux in medium and high temperature
glazes, beginning its action around 1100C. It lacks usefulness in
high-fire bodies because its active fluxing action produces a body which
is too volatile (melting if slightly overfired).
-Calcia usually hardens a glaze and makes it more scratch and acid
resistant. This is especially so in alkaline and lead glazes. Its
expansion is intermediate.
-Calcia and silica alone will not melt even at high pottery
temperatures, but when soda and potash are added, calcia becomes very
active in both oxidation and reduction. Hardness, stability, and
expansion properties of silicates (of soda and potash) are almost always
improved with the addition of CaO.
-It is not effective below cone 4 as a flux in glazes but in small
amounts (less than 10%) it can dissolve in earthenware glaze melts
especially with lead, soda, potash) to add hardness and resistance to
leaching. In non-lead mixes it can also help reduce crazing. In larger
amounts, it encourages the growth of crystals which can give decorative
effects to glossy glazes and produce matteness (I.e. 30%).
-It reduces viscosity in glazes which have high silica, but if the melt
is too fluid, devitrification may take place.
-Calcia is a moderate flux in the cone 5-6 range, but a very active one
at cone 10.
-High calcia glazes tend to have good (although sometimes unexpected)
color responses. For example, in oxidation iron glazes calcia likes to
form yellow crystalline compounds with the Fe2O3 producing a 'lime
matte'. Without the calcia, glossy brown glazes are the norm.
CaO is not found pure in nature but rather is contained in various
abundant minerals (I.e. Calcite, aragonite, limestone, marble) but vary
greatly in their purity (impurities usually include magnesia, iron,
alumina, silica, sulfur). Of these iron and sulfur are most troublesome
(I.e. Where clarity is important in glass). Lime minerals vary in the
degree of crystallization and cohesion of the crystalline mass and the
homogeneity of the matrix.
The term "lime" encompasses several different minerals and
manufactured products.
-The term "Whiting" traditionally refers to calcium carbonate
produced by the grinding of chalk from the cliffs of England, Belgium
and France. However this title also refers to any ground calcium
carbonate material (I.e. Those processed from marble and calcite ores).
-Ground limestone and calcined limestone (burned lime) are used in the
glass industry.
-Dolomite (magnesium carbonate) is a mineral which supplies some
magnesia in addition to its CaO complement. It is preferred in many
situations because it more readily fluxes and the magnesia imparts
desirable properties.
-Wollastonite is a calcium silicate which is more expensive than other
sources of calcium, but is used bodies, glaze, porcelains, enamels and
frits for its many superior properties.
See Calcium Carbonate, Whiting |
Surface Modifier:High molar amounts of calcia combined with
adequate silica and preferably lower alumina will form a calcium
silicate crystal matte (lime matte). The presence of zinc will increase
the size of crystals. |
| CdO |
128.41 |
0 |
1426 |
Cadmium Oxide
(Sources: Cadmium Sulfide, Cadmium Silicate)
-Cadmium oxide is insoluble in water and alkalis, but soluble in acids
and ammonium salts.
-Cadmium by itself does not produce color in a glaze, but when used in
combination with selenium it gives red; and with sulfur produces yellow.
Great care is required to maintain the correct slightly reducing
atmosphere during firing for the latter. |
Glaze Color Red enamels are made using cadmium-selenium-sulfur
mixes because this combination goes into solution readily during the
short firing period (copper compounds are too slow to dissolve).
Great care is required to maintain the correct slightly reducing
atmosphere during firing.
Glaze Color Cadmium is blended with uranium to produce yellow optical
glass and yellow enamels. For example, a yellow stain for enamels can be
made with 12% selenium, 64.5% cadmium sulfide, and 23.5% cadmium oxide. |
| CeO2 |
172 |
0 |
2800 |
Cerium Oxide
(Sources: Salts, nitrates, carbonates)
-Used in glass and optics for UV protection properties
-It does react with other elements (I.e. Ti) to make colors (I.e. Ce-Ti
yellow). |
Glaze Color In combination with titanium, cerium produces a
yellow glass.
Glaze Opacifier Used as an opacifier for special effects in the tile
industry; as a replacement for tin opacifier in porcelain enamel. |
| CoO |
74.92 |
0 |
2860 |
Cobalt Oxide
(Sources: Cobalt Oxide)
-Cobalt is a trace element in vegetables and an important vitamin (B12)
in stock raising. Cobalt metal is used in steel and chrome alloys.
-Cobalt is a powerful and stable colorant used in glass, glaze, enamel,
and even paint. As little as 2 PPM can produce a recognizable tint, thus
cobalt is often cut in a medium to make it easier to weigh and
distribute in a mix.
-It is not volatile even at 1400C.
-Various raw forms are available and all break down to cobaltous oxide (CoO),
which is the stable form that combines with the glass melt to produce
color. These include black stable cobalto-cobaltic oxide (cobaltosic
oxide) Co3O4, which has a 93% conversion ratio and decomposes to
liberate oxygen at 800C. Grey cobaltic oxide (Co2O3) is 90% CoO and
mauve cobalt carbonate (CoCO3) has 63% effective stain content. Cobalt
dioxide (CoO2) is not marketed for ceramics.
-Because cobalt is quite soluble in glaze melts, it has little or no
opacifying effect.
-Although cobalt has a high melting point, it is a powerful glaze flux,
dissolving readily in most glazes, especially alkaline and boron types.
This active nature causes it to diffuse, making it difficult to maintain
a clean edge on painted decoration, especially overglaze.
-It is very dependable under both oxidizing and reducing furnace
conditions, fast and slow firing.
-Cobalt is used in a wide array of decal inks, underglaze colors, body
stains, and colored glazes |
Glaze Color Cobalt is often calcined with alumina and lime for
soft underglaze colors. Stains often employ mixes of alumina, cobalt,
and zinc for softer blue colors.
Glaze Color Cobalt is used in combination with manganese and selenium to
mask excess yellow coloration (yellow plus blue gives green which is
masked by the pink of selenium).
Glaze Color Combinations with iron and manganese can give a slate blue.
Glaze Color With barium shades of blue-green are possible.
With magnesia the color range is from violet to lilac.
Glaze Color With chrome and manganese blue-black and black are common.
Glaze Color With chrome and copper, cobalt can yield tints from pure
cobalt blue, to greenish-blue, to the green of chromium. These effects
work best when silica is not too high and there is adequate alumina.
Glaze Color With SiO2 and B2O3 and high MgO, red, voilet, lavender, and
pinks can be made.
Glaze Color With SiO2 and B2O3 and high MgO, red, voilet, lavender, and
pinks can be made.
Glaze Color Cobalt is a classic and reliable blue colorant at all
temperatures and in most types of glazes. The shade of blue can,
however, be affected in many ways by the presence of different oxides.
Cobalt is powerful and often less than 1% will give strong color. If the
color needs to be toned down, additions of iron, titanium, rutile, and
nickel may work.
Glaze Color When cobalt occurs with manganese (I.e. 1-3% cobalt carb,
3-5% manganese carb), purples and violets can be made. Less cobalt will
lighten the color. This effect works well in magnesia glazes. In high
magnesia glazes, 1-2% cobalt alone will give purple. Add tin to move the
color toward lavender.
Glaze Color With adequate SiO2 and high MgO (0.4 molar), purple, voilet,
lavender, and pinks can be made using 1% or more CoO. Mimimizing boron,
alumina, and KNaO will help prevent it from turning blue. Note that the
high MgO will generally make the glaze matte and it could suffer some
ill effects associated with excessive MgO.
Glaze Color With MgO, SiO2, and B2O3, red, voilet, lavender, and pinks
can be made.
Glaze Color Cobalt is a classic and reliable blue colorant at all
temperatures and in most types of glazes. The shade of blue can,
however, be affected in many ways by the presence of different oxides.
Cobalt is powerful and often less than 1% will give strong color. If the
color needs to be toned down, additions of iron, titanium, rutile and
nickel may work. |
| Cr2O3 |
152 |
0 |
2265 |
Chrome Oxide
(Sources: Chrome Oxide, Potassium Dichromate)
-Amphoteric chrome oxide is the only stable oxide of chromium metal and
can be used at all temperatures to 1200C (after which it can volatilize
somewhat).
-Chromium is a 'fast' color, meaning it produces its characteristic
green in slow or fast and oxidizing or reducing firing. It is also used
in paints and dyes.
-Chromium is used in the glass industry to make green glass (up to 1%).
Antimony is sometimes used as a reducing agent to ensure an emerald
green.
-Chromium is not very soluble in glass and does not form silicates or
combine with fluxes readily unless compounds are finely ground and
dispersed and amounts are not excessive (1% will dissolve in most
glazes).
-Zircon opacifier 1-2% is often added to chrome glazes to stabilize them
and prevent brown edges. Amounts up to 3% in a glaze recipe gives
opacity and greyish green coloration.
-Chrome oxide can be used as a body stain in amounts to 5% to give grey-green.
-Drab chrome greens can be moved toward peacock green with the addition
of cobalt oxide (1% each gives bright color). This works in boron and
soda glazes.
-Chrome in zinc glazes tends to form brown zinc chromate.
-Because chrome reacts with normally inert tin to produce chrome-tin
pink colors whiting and alumina are usually used instead of tin to
lighten and clarify chrome green glazes.
-Chrome-tin pinks are much more consistent if the combination is
premelted (I.e. Commercial stain) and if the glaze is high in calcium or
strontium, and free of zinc. Strontium is most effective if a wide
firing range is desired (0.1-0.5% chrome, 4-10% tin).
-Chromium oxide is added to enamels for green where borax and zinc are
used to increase the brilliance of the color. However, chrome in ground
coat enamels tends to react with the metal to cause blistering. |
Properties
Glaze Color Drab chrome greens can be moved toward peacock green with
the addition of cobalt oxide (1% each gives bright color, some MgO
needed also). This works in zinc free boron and soda glazes.
Glaze Color Chrome in zinc glazes tends to form brown zinc chromate.
Glaze Color Chrome in high lead glazes forms yellow lead chromate. Zinc
and chrome tend to produce orange.
Glaze Color Chrome is a constituent in almost all black oxidation
colors. It is used up to 40% in Cr-Co-Fe blacks and as high as 65% in
Cu-Cr blacks.
Glaze Color Chrome and tin are a widely used combination to produce
pinks in zinc free glazes with at least 10% CaO and low MgO (alkaline
glazes work well). Many stains are based on this system and typically
have around 20-30 times as much tin oxide as chrome oxide. Tin would
typically be around 4-5%.
Glaze Color Chrome in high lead glazes forms yellow lead chromate.
Alkalies are recommended in the base glaze. Added zinc can extend the
range to orange.
In other types of glazes, less than 0.5% chrome oxide will give
yellowish or yellow green tints.
Glaze Color Chrome is a classic green colorant for recipes in oxidation
and reduction at all temperatures. However, the shades it produces can
be opaque, dull, and uninteresting. In the presence of CaO, the color
moves toward grass green.
Glaze Color Below 950C in high lead, low alumina glazes, chrome will
produce reds to oranges, often with a crystalline surface. The addition
of soda will move the color toward yellow.
Glaze Color Chrome-tin pinks move toward purple in glazes with
significant boron. One glaze with 3.3 SiO2, 0.27 Al2O3, 0.2 B2O3, 0.15
Li2O, 0.5 CaO, 0.1 MgO, 0.15 Na2O employed 5% tin oxide, 0.6% cobalt
carbonate, 0.17% chrome oxide giving a good purple at cone 6. |
| Cu2O |
143 |
0 |
1230 |
Cuprous Oxide
(Sources: Red Copper Oxide)
See Cupric Oxide
-Reduction firing reduces normal CuO copper oxide to Cu2O to produce
bright red coloration in the reaction:
2CuO + CO -> Cu2O + CO2
-Bright red colors are usually achieved with very small amounts of
copper (I.e. .5%).
-If larger amounts of copper are present, the reaction could precipitate
very tiny copper metal particles (colloidal copper) in the glaze melt to
yield a red color (I.e. Flamb?or sang-de-boeuf).
-Copper luster can be produced by oxidation firing at low temperature
glaze (950C) with heavy reduction cooling to leave a metallic layer of
copper on the surface. 2-8% copper is required and cooling should be
done in 15 minute cycles of reduction, interspersed with intervals where
the atmosphere is allowed to clear. This can be carried out in cooling
electric kilns by creating reduction through the introduction of
flammable materials. |
Properties
Glaze Color Copper is well-known for it ability to produce blood-red and
fire-red colors in steady reduction atmosphere firings where CuO is
altered to Cu2O. See example copper red recipes in RECIPE area.
Bright red colors are usually achieved with very small amounts of copper
(I.e. 0.2-0.5%) in a low alumina base with at least .4 molar equivalents
of CaO and plenty of the alkalis. Tin oxide will enhance color. Use of
silicon carbide in oxidation (2%) can produce red.
Glaze Color The use of boron in a copper red reduction glaze will give a
purple hue.
The following formula produces good purple at cone 10: BaO 0.1, CaO 0.5,
MgO 0.1, KNaO 0.2, ZnO 0.1, B2O3 0.15, Al2O3 0.2, SiO2 3.0.
Glaze Color In copper red glazes, barium additions in a high feldspar
base will produce turquoise to deep blue depending on how much copper is
added.
Glaze Color Large amounts of copper in a glaze give metallic and even
graphite effects.
Glaze Color Fluoride, when used with copper, can produce blue green
colors. |
| CuO |
79.54 |
0 |
1148 |
Cupric Oxide
(Sources: Black Copper Oxide)
-Decomposes at 1026C
-Copper can be produced from many different raw materials, the main
being black tenorite (CuO), deep red cuprite (Cu2O), bright green
malachite (CuCO3.Cu(OH)2), and bright blue azurite (2CuCO3.Cu(OH)2).
-Under normal oxidizing conditions the CuO molecule remains unchanged
and produces clear green colors in glazes.
-CaO is unlikely to affect the color of copper in a glaze.
-Copper is well-known for it ability to produce blood-red and fire-red
colors in reduction atmosphere firings where it is altered to Cu2O (see
Cu2O).
-Purple copper reduction glazes are the result of a mixture of copper in
its green oxidized form and red reduced forms. This effect appears most
frequently in high lime glazes or where early stages of firing are
oxidizing or latter stages are light or neutral.
-The shade of copper greens can vary with firing rate and soaking
changes. The best colors are generally obtained with fast firing and
little soaking.
-Copper is an active flux and may increase melt fluidity and may
increase crazing because of its high thermal expansion.
-Crystalline glazes can be attractive when done with copper.
-In the enameling industry, copper is used in combination with small
quantities of cobalt, manganese, or nickel in making black where the
black is produced in the smelter.
-Copper and titanium can produce beautiful blotching and specking
effects. Pure copper metal filings can make an extremely potent specking
material in reduction firing for both bodies and glazes.
-Generally additions of copper to a glaze will reduce crazing (if
supplied in adequate amounts; beyond 1 or 2 percent).
Note: When added to low lead solubility glazes copper can cause the
solubility of the lead to be greatly increased. Copper can have similar
effects in other types of glazes at other temperatures also. If an
overnight soak in vinegar or acid changes glaze appearance, be careful. |
Properties
Glaze Color Under normal oxidizing conditions CuO produces clear green
colors in most glazes. The shade of green depends not only on the amount
but also on other oxides present (I.e. Lead in larger amounts will
enhance and darken the green, the presence of alkalies or high boron
will shift it toward blue).
Copper in calcium/magnesium glazes gives a green very different from
that produced with lead.
Glaze Color Combinations of CuO with tin or zircon will give turquoise
or blue-greens when the glaze is alkaline (high KNaO) and low alumina.
Look for a frit with this profile for best results. Glazes of this type
often craze.
Glaze Color Copper in a barium/zinc/sodium glaze gives a blue. Color can
also be enhanced by lithia.
Tin and copper can produce turquoise to robin's egg blue.
Glaze Color 7% copper in glossy oxidation glazes can produce striking
metallic green colors.
Glaze Color Combinations of CuO with tin or zircon will give turquoise
or blue-greens when the glaze is alkaline (high KNaO) and low alumina.
Look for a frit with this profile for best results. Glazes of this type
often craze.
Glaze Color K2O can turn a copper glaze yellowish. If Na2O or PbO are
present, K2O should not exceed 0.15 equivalent. |
| F |
19 |
0 |
0 |
Fluorine
-Fluorine gas is given off during firing of some materials like Cornwall
Stone and fluorspar. F is often listed separately in analyses from
manufacturers (not included in general LOI) because of its hazardous
nature during firing. |
|
| Fe2O3 |
160 |
.125 |
1565 |
Ferric Oxide, Ferrosic Oxide, Iron
(Sources: Iron Oxide, Stained Clays, many others)
-Iron compounds are the most common coloring agent in ceramics. On one
hand, they are nuisance impurities where they stain an otherwise white
clay or glaze or where they muddy an otherwise bright color. At the same
time, iron exhibits so many personalities with different kiln
atmospheres, temperatures, and firing cycles and with different glaze
chemistries that it is among the most exciting of all materials.
-Chemically, iron is amphoteric like alumina. Fe2O3 generally behaves as
a refractory antiflux material in a glaze melt, combining with alkalis.
Oxidation iron-red glazes, for example, can have very low alumina
contents yet do not run off ware because the iron acts like alumina to
stabilize and stiffen the melt. However these glazes likely will have
somewhat reduced durability.
-In glazes low in flux it can behave as an alkali, combining with
silica.
-Fe2O3 is very affected by a reducing atmosphere where it can act as a
flux in both bodies and glazes at high temperatures. Its fluxing action
in reduction is quite remarkable and can be demonstrated using a line
blend in a clear glaze. Higher amounts of iron exhibit dramatically
increased fluidity (see FeO for more info).
-Fe2O3 is the most natural state of iron oxide where it is combined with
the maximum amount of oxygen. In oxidation firing it remains in this
form to typically produce amber to yellow up to 4% in glazes (especially
with lead and calcia), tans around 6% and browns in greater amounts. In
the 20% range, matteness is typical. However, once it reduces to FeO and
immediately begins fluxing and forming a glass, it is difficult to
reoxidize. Since the breakdown of carbon or sulfur compounds in body and
glaze so easily reduces iron, a slow and very thoroughly oxidizing
atmosphere is critical through the 700-900C range to assure that all the
iron remains in its antiflux oxidized form.
-Most glazes will dissolve more iron in the melt than they can
incorporate in the cooled glass. Thus extra iron precipitates out during
cooling to form crystals. This behavior is true both in oxidation and
reduction. For example, a typical mid-temperature fluid oxidation glaze
of 8-10% iron will freeze black with fine yellow crystals. Lower
temperature glaze with their high flux content can dissolve more iron
(I.e. Aventurine).
-Zinc can produce unpleasant colors with iron.
-Titanium and rutile modify iron and can give some striking variegated
effects. For example, a popular middle temperature pottery glaze employs
4% tin, iron, and rutile in a clear base to give a highly variegated
gloss brown. Another popular cone 6 glaze uses 85% Albany slip, 11%
lithium, and 4% tin to produce an attractive gloss brown with striations
and flow lines similar to classic lead glaze effects.
-While many iron-stained clays are reddish in color, high iron clays can
also be blackish, grey, brown and deep brown, pinkish, greenish and
yellowish or maroon. Some can be quite light in color yet fire to a
brown or red color. 6-7% iron is considered a high-iron clay, but some
stained clay-like materials can have 20% or more iron. A typical ivory
colored oxidation firing body has 1-2% iron oxide.
-Low temperature earthenwares can exhibit a wide range of iron red
colors, depending on the firing temperature. Typically, low fired
materials burn to a light orange. As temperature is increased this
darkens to light red, then dark red, and finally to brown. The
transition from red to brown is often very sudden, occurring across a
narrow temperature range. Thus the working temperature should be
sufficiently above or below this range to avoid radical color changes
associated with kiln variations.
-Fe3O4 is an intermediate form of iron which is brown in color and
exhibits intermediate properties. Fe3O4 can either be a mix of FeO and
Fe2O3 resulting from an incomplete conversion from one type to the
other, or it can be a completely different mineral form of iron known as
magnetic iron oxide from the ore magnetite. The latter is a hard
crystalline material of use in producing specking in bodies and glazes.
-Generally additions of iron oxide to a glaze will reduce crazing (if
supplied in adequate amounts; beyond 1 or 2 percent). |
Glaze Color In reduction glazes Fe2O3 tends to fire bluish or
turquoise to apple green with high soda (boric oxide may enhance). 0.5%
iron with K2O may give delicate blue to blue green.
Glaze Color
Glaze Color Fe2O3 tends to fire yellowish with calcia and in alkaline
glazes straw yellow to yellow brown.
In reduction, 3-4% iron with 0.4 BaO, 0.15 KNaO, 0.25 CaO, 0.2 MgO, 0.3
Al2O3, 1.7 SiO2 and 15-20% zircon opacifier will produce a yellow
opaque.
Glaze Color Low fire lead, potash and soda glazes encourage reddish
colors with iron. Should be barium free. |
| FeO |
81.8 |
0 |
1420 |
Ferrous Oxide
(Sources: Black Iron Oxide)
-Fe2O3 is easy to reduce to the FeO state with a light reduction firing
as follows:
Fe2O3 + CO2 -> 2FeO + CO2
-Some suppliers quote iron in its reduced form as part of a materials
formula.
-In clays and glazes, firing in reducing conditions, or with clays
containing significant organic matter, the Fe2O3 converts to FeO as
early as 900C. FeO is a very powerful flux. Once iron has been reduced
and becomes active in glass forming, it is difficult to reoxidize it
again. For this reason, reduction firings for iron effects should be
light throughout to reduce the iron early before glaze melt and fired
slowly through the 250-500C range to provide adequate time for organics
to burn away. A period of clearing in oxidation at the end of a firing
does not affect the color of iron in the molten glass.
-FeO is so active as a flux that it can often be introduced by
substituting for other fluxes like lead and calcium oxide.
-Most glazes will dissolve more iron in the melt than they can
incorporate in the cooled glass. Thus extra iron precipitates out during
cooling to form crystals. This behavior is true of oxidation but doubly
so of reduction. For example, a typical high-temperature fluid glaze
with 15% iron will freeze to a sparkling rust colored mesh of crystals.
-Many popular iron glazes and slips for pottery are based on clays
highly stained with iron. For example, Albany slip was used for many
years to produce a wide variety of glazes which exploited its unique
blend of high iron, low melting point, moderate plasticity, low thermal
expansion, low cost and unique character. For example, using Alberta
Slip (an Albany substitute) one can make a tenmoku glaze with 90%
Alberta slip and a little added iron and feldspar.
-If clay is not allowed to oxidize thoroughly through the 700-900C range
during firing, carbon present within will rob the Fe2O3 of its oxygen
and escape as CO2 leaving the FeO as an active flux within the body to
break it down from within. This is called black coring.
-Iron bearing clays fire much darker in reduction than oxidation. In
addition, reduction fired iron bodies experience sudden color changes
from red or tan to dark brown across a narrow temperature range
characteristic to each formulation. Classic iron reduction mottled
effects are created by firing to the transition point where color is
just changing producing light and dark patching of color as the darker
color invades the surface.
-In reduction firings it can produce greens and blues (I.e. Celadons),
and yellows and maroons (I.e. Mustard, oatmeal glazes). In higher
amounts it saturates to produce crystalline deep brown and black effects
(I.e. Tenmoku 10-13% and kaki 13%+).
-Iron pyrite and similar minerals often contaminate stonewares and
fireclays; and they are responsible for the popular speckling effects in
reduction fired stonewares. |
Glaze Color A typical high-temperature fluid reduction glaze
with 15% iron will freeze to a sparkling rust colored mesh of crystals.
Alkaline glazes work best. Barium can impede this effect.
Glaze Color Saturated reduction iron glazes normally firing to black in
reduction will move toward brown if alumina is high, toward blue if
alumina is low.
Glaze Color The presence of phosphorous pentoxide, lithia and soda also
encourage blue in both normal and saturation conditions in reduction
firing.
Iron glazes will move toward blue if alumina is low.
Glaze Color When 1-5% iron is used in a transparent reduction glaze
which has some calcia and potash (barium also helps) celadon glazes are
produced. 'Celadon' glazes are glossy shades of green which exhibit
depth of color due to suspended micro-bubbles in the glass.
Glaze Color Classic reduction black-breaking-to-brown tenmoku glazes are
made with 8-12% iron.
Glaze Color See Green Celadon. |
| Free SiO2 |
60.1 |
.035 |
1710 |
Free SiO2
(Sources: clays, feldspars)
-Some analyses quote two types of SiO2. This is a recognition that SiO2
in a material often exists by itself as particles of quartz or in
combination with other oxides in minerals like NaAlSi3O8, KAlSi3O8,
CaAl2Si2O8, CaHPO4, MgSiO3, FeSiO3, MnSiO3, etc. |
|
| H2O |
0 |
0 |
0 |
Water
(Sources: clays, hydrated minerals)
-Some suppliers will quote moisture or water in a material's analysis.
Many materials are hydrated. An example is calcium sulfate. When it is
heated past a certain point, the chemically bound water is expelled,
converting the material into one of different chemistry.
-Chemical water in materials burns away during firing and so it has no
impact on the fired chemistry. Since it is lost during firing, a weight
of zero should be used if included in calculations |
|
| InO3 |
277.64 |
0 |
0 |
Indium Oxide
-An n-type semiconductor used as a resistive element in integrated
circuits.
-Used in certain stain formulations |
|
| K2O |
94.2 |
.331 |
750 |
Potassium Oxide
(Sources: Potash Feldspar, Cornwall Stone, Nepheline Syenite, Frits in
low fire glazes)
-Together with sodium and lithium oxides, it is classified as one of the
Alkaline group. Colored glazes whose flux portion is alkaline-dominated
tend to be visually intense, especially if the alumina is low.
-K2O is considered together with sodium, since it almost always occurs
together with sodium and contributes very similar properties. When taken
together the two are often labeled KNaO.
-It is an important auxiliary flux in high temperature glazes.
-It is a heavy oxide and in general hosts the brightest colors of all
fluxes except for lead. It is usually preferred even to soda for a more
brilliant glaze and longer firing range. The best colored glazes are
thus made with K2O-PbO-SiO2 predominant formulas.
-Considered a very stable and predictable oxide.
-Relatively high expansion tends to contribute to crazing in higher
amounts, but not quite as bad as sodium. Thus high alkali glazes almost
always craze. If the color depends on this (I.e. Copper blue), then it
may be necessary to adjust the body to eliminate crazing since a
reduction of the alkalis to reduce crazing will mean a loss of color.
-The alkalis can increase lead solubility. |
Glaze Color Reduction tenmoku black-rust glazes with 8-10% iron
work well in high potash glazes. |
| KNaO |
78.1 |
.359 |
0 |
Potassium/Sodium Oxides
(Sources: Feldspars)
This pseudo-oxide is provided for in cases where a manufacturers data
sheet groups K2O and Na2O together. The weight and expansion are an
average of the two. |
|
| LOI |
0 |
0 |
0 |
Loss on Ignition
-The LOI summarizes the components within a raw material that burn away
or products of decomposition that are lost as gases during firing. Some
companies separate the different components of weight lost during firing
as C, H2O, SO3, etc. A formula weight of zero should be used in each
oxide of this type so there is no impact on fired formula calculations.
-Note that if a material contains a volatile in its analysis that you
would like to enter into the analysis and have it treated like an LOI,
and if that item is not contained in the OXIDES database, you can
manually key an "L" in the status column of the analysis to
force FORESIGHT to accept it as an LOI type material.
-A material's formula weight is equal to the sum of the weight of the
oxides in its formula divided by 100-LOI divided by 100 |
|
| Li2O |
29.8 |
.068 |
1000 |
Lithium Oxide, Lithia
(Sources: Lithium Carbonate, Lithium Feldspar I.e. Spodumene)
-Lithium is the lightest, smallest, and most reactive flux. Adding small
amounts by weight introduces disproportionately large amounts to the
glaze formula.
-Together with boron and sodium, it acts as a melter at lower
temperatures. Together with sodium and potassium oxides, it is
classified as one of the Alkaline group.
-Lithium Carbonate, its main source, has a very low melting point and is
a very active and powerful flux. It is typically used in smaller amounts
to improve fluidity, uniformity, and reduce maturing times.
-High cost limits its use in larger amounts, but in small amounts it
acts as a powerful auxiliary alkaline flux with welcome thermal
expansion lowering effects.
-1% additions can increase glaze gloss to a marked degree and slightly
greater amounts (3%) can reduce melting temperature by several cones and
affect surface tension of the melt.
-Calculated expansion projections tend to break down with all but low
additions of lithium to glazes (less than 5%). Its contribution in
nonlinear, especially in high sodium and potassium glazes. Often high
lithium glazes appear to shiver whereas the calculated expansion does
not indicate a sufficiently low expansion. It is known that molten
lithia is mobile (diffuses into the surrounding matrix because of its
small ionic radius and low charge). It can also diffuse into the body
and create a low expansion glaze interface. One theory proposes that
glazes with more than about 5 mol% Li2O could develop a lithium-rich
interface (this could be coupled with a lithium-deficient upper glaze
layer). The result could be crystallization of a spodumene layer thereby
introducing its inversion and associated sudden expansion at 1082 C
during cooling.
-Lithia gives the most intense colors in low alumina in high alkali
glazes.
-The alkalis can increase lead solubility.
-Its expansion is much lower than soda or potash, and it is used to
produce special low-expansion bodies and glazes which are resistant to
heat-shock. When used as a substitute for sodium and potassium oxides,
it produces glazes of lower expansion.
-It can promote textural effects in the glaze surface.
-In some systems small additions of lithium will react with quartz
during firing and can eliminate the alpha-beta quartz transition in the
cooling cycle.
-Lithia promotes devitrifaction in glass systems |
Glaze Color Lithia can produce blue effects with copper.
Glaze Color Lithia can produce pinks and warm blues with cobalt.
Surface Modifier Lithia contributes to mottled and flow effects when
used in small amounts (-1%). |
| MgO |
40.3 |
.026 |
2800 |
Magnesium Oxide, Magnesia
(Sources: Talc, Dolomite, Magnesium Carbonate)
-Together with SrO, BaO and CaO it is considered one the Alkaline Earth
group of oxides.
-Like CaO, MgO is refractory at lower temperatures, so much so that it
can be used to increase opacity, as a matting agent (I.e. Magnesium
carbonate), and as a check to glaze fluidity in a manner similar to
alumina (I.e. To prevent devitrification, that is, the tendency to
produce crystalline surfaces). When mixed with CaO, it is not as
refractory.
-It can act as a catalyst in low temperature bodies assisting in the
conversion of quartz to higher expansion cristobalite which reduces
crazing.
-In high temperature glazes it acts as a flux (beginning action about
1170C) producing viscous melts of high surface tension and opaque and
matte glazes. Like CaO, its melting action drastically accelerates at
high temperatures.
-The surface tension of MgO-containing melts is less of a problem in
reduction.
-Zircon and Magnesia melt at 2800C making them the highest melting
oxides. Remarkably, MgO readily forms eutectics with other oxides to
melt at surprisingly low temperatures.
-It is valuable for its lower expansion and crazing resistance. When
introduced into a glaze it should preferentially replace calcia, baria,
and zinc before the alkalis to maintain surface character. Adding too
much will generally move the surface texture toward matte or dry.
-MgO is a light oxide and generally is a poor choice for glazes to host
bright colors. However, it does work well in earthtone and pastel
glazes, especially in high temperature reduction firing. Likewise, it
may be harmful to some under-glaze colors.
-Does not volatilize. |
Surface Modifier Magnesia is well known for the pleasant vellum
'fatty matte' and 'hares fur' tactile and visual effects that it
produces around 1200C, especially in reduction firing (dolomite matte).
However, it can produce matte effects at all temperatures. |
| MnO |
70.9 |
.05 |
1650 |
Manganous Oxide
(Sources: Manganese Dioxide)
-Manganese monoxide exists only above 1080C where the dioxide form
disassociates to release its oxygen.
-Manganese is a colorant using in bodies and glazes, producing blacks,
browns, and purples.
-Manganese is a constituent in many igneous rocks, and thus occurs in
many clays weathered from these parent rocks. In most cases it is a very
minor oxide, but does occur in much greater amounts in some slip and
highly stained materials. It is thus a color contributor in many
traditional and historic slip glazes.
-Smaller amounts are easily dissolved in most glaze melts; however,
around the 5% threshold, the manganese will precipitate and crystallize.
In large amounts in a glaze (I.e. 20%), metallic surfaces are likely.
-Above 1080C, half of the oxygen disassociates to produce MnO, a flux
which immediately reacts with silica to produce violet colors in the
absence of alumina, browns in its presence. Manganese browns have a
different, often more pleasant character than iron browns.
-High temperature glazes well above 1080C can use large amounts of
manganese to produce very metallic bronze-like surfaces. Manganese
dioxide by itself can be used and will fuse well, even running down the
ware.
-Manganous oxide is unaffected by reduction, but is normally considered,
at its best, in oxidation slips and glazes above 1200C.
-Manganese fuses and dissolves very well above 1200C in oxidation. Like
iron, it will dissolve to a greater extent in a hotter melt. This means
that if more than about 4% MnO is used, the oversupply will precipitate
on cooling leaving a network of crystals in a manner similar to iron in
high fire reduction. Speed of cooling, glaze fluidity, and amount of
manganese will all affect the results. |
Glaze Color In glazes below 1080C, it can give coffee color
browns when used with tin and dull browns in lead and low alkaline
glazes.
Glaze Color Very pleasing tan-brown reduction fired glazes can be
achieved with 5% manganese dioxide in reduction. |
| MnO2 |
86.9 |
.05 |
1080 |
Manganese Dioxide
(Sources: Manganese Dioxide)
-Manganese dioxide exists only below 1080C, above which the dioxide form
disassociates to release its oxygen (see MnO for more information).
-Manganese is a colorant using in bodies and glazes, producing blacks,
browns, and purples.
-Manganese is a constituent in many igneous rocks, and thus occurs in
many clays weathered from these parent rocks. In most cases it is a very
minor oxide, but does occur in much greater amounts in some slip and
highly stained materials. It is thus a color contributor in many
traditional and historic slip glazes.
-Smaller amounts are easily dissolved in most glaze melts, however,
around the 5% threshold, the manganese will precipitate and crystallize.
In large amounts in a glaze (I.e. 20%), metallic surfaces are likely.
-In glazes below 1080C, it can give coffee color browns when used with
tin. |
Glaze Color Purple colors can be produced in glazes of high
alkali (KNaO) and low alumina, especially in combinations with cobalt
(look for a frit with this profile for best results).
Glaze Color Manganese and cobalt mixture produce black. Iron can also be
used. For example, a mix of 8 iron, 4 manganese, and 0.5 cobalt make a
raw black stain. |
| MoO2 |
143.94 |
.094 |
780 |
Molybdic Oxide, Disulfide, Trioxide
-In glazes, glasses, and bodies, small amounts (-0.2%) act as a wetting
agent during the melt phase. It lowers surface tension dramatically.
This can encourage the development of crystals in crystalline glazes.
Moly can give an iridescent quality to crystals and lustres.
-Also used in enamels as an adherence promoter and in some stains.
-It oxidizes quickly above 800F |
|
| Na2O |
62 |
.387 |
800 |
Sodium Oxide, Soda
(Sources: Feldspar, Nepheline Syenite, Sodium Frits in low fire glazes)
-Soda is a slightly more powerful flux than potassium. Together with
potassium and lithium oxides, it is classified as one of the Alkaline
group.
-It has high expansion and will promote crazing in glazes lacking silica
or alumina.
-Sodium can begin to volatilize at high temperatures.
-It decreases tensile strength and elasticity compared to other common
bases.
-Gives strong color responses to copper, cobalt, and iron, but the color
can come at the expense of glaze fit and excessive fluidity because high
soda is required. High alkali glazes definitely tend to craze. If the
color depends on this (I.e. Copper blue) then it may be necessary to
adjust the body to eliminate crazing since a reduction of the alkalis to
reduce crazing will mean a loss of color.
-Soda works well with boric oxide (and also lithia and potassium) in low
temperature lead-free glazes.
-Low alumina in high alkali glazes give the most intense colors.
-The alkalis can increase lead solubility. |
Glaze Color Copper red reduction glazes are best in
formulations with high alkali. The presence of boron can give a more
pleasant red.
Glaze Color Oxidation copper blues work best in high alkaline, low
alumina glazes. Increasing copper to 4-6% will move color toward
turquoise. |
| NiO |
74.7 |
0 |
1453 |
Nickel Oxide
(Sources: Nickel Oxide)
Most often used to modify and soften the color of other metallic oxides
and thus small amounts are normally employed.
It is not normally used in low fire glazes due to the refractory nature
of nickel oxide powder. Glazes that are already matte or immature will
thus be made more dry by the addition of nickel.
Since nickel is used in smaller amounts, flashing from other glazed ware
and the chemistry of the glaze can have an effect on ware color. |
Glaze Color Nickel with zinc oxide can produce steel blues.
With larger amounts of zinc, lavender blue can be made.
Glaze Color Nickel with calcium can produce tan.
Glaze Color Nickel with barium can produce brown. In high sodium glazes
it can fire brown also.
Glaze Color Nickel in lead glazes tends to produce grey colors.
Glaze Color Nickel can produce pinks in high potash or lead glazes.
Glaze Color In lithium glazes nickel can produce yellow.
Glaze Color In the presence of high MgO, nickel can produce greens. Zinc
is also helpful to develop color. |
| P2O5 |
141.9 |
0 |
580 |
Phosphorus Pentoxide
(Sources: Bone Ash, Wood and Plant Ash)
-Phosphorus along with calcium is an essential element in plant and
animal growth, thus its principal source is organic ash (I.e. Calcined
cattle bones).
-Phosphoric oxide is normally present in only trace amounts in ceramic
materials.
-It can act as a melter in middle to high fire, but its power per unit
added drops drastically beyond 5% additions.
-Small amounts can produce colloidal opacity as in Chinese chun glazes.
The depth of Sung glazes is attributed to phosphorus.
-P2O5 is a glass network former like boric oxide and silicon dioxide.
Phosphoric glass tends to show as a bluish flush in glazes. It is not in
any way a substitute for silica and does not enter the silica chain, but
remains as a separate colloidal presence in the silicate matrix.
-Phosphorus can vitrify porcelains without softening and is the key to
translucency in bone china.
-Phosphate ions are added to glaze frits as a color control agent during
the melting of titania opacified frits.
-P2O5 is known to influence the rate of nucleation and/or
crystallization in Li2O and MgO low expansion glaze systems.
-P2O5 combined with certain oxides of iron forms colorless compounds.
This suggests that P2O5 could be used to allow the use of less pure
materials in glazes and glass.
-Phosphorite mineral Ca3(PO4)2 and Apatite 3Ca3(PO4)2 Ca(Cl,F)2 are the
parent rocks of phosphate fertilizers. The latter can thus be used to
introduce phosphorus into glazes and frits. |
Surface Modifier Phosphorus can produce variegated and mottling
effects in glazes (especially low fire) when used in small amounts (e.g.
Up to 2%). Bone ash is a source. |
| PO4 |
94.969 |
0 |
0 |
Phosphorus Oxide
(Sources: Bone Ash)
Phosphates in this form are contained in bone ash and tricalcium
phosphate type materials |
|
| PbO |
223.2 |
.053 |
888 |
Lead Oxide
(Sources: Lead Frits, Litharge)
-Together with ZnO, PbO is considered one of the Metallic oxide fluxes.
-Reacts easily with silica to form low melting lead silicates of high
gloss and deep character. Lead is very easy to use. It is the heaviest
oxide and produces incredible colors and surface characteristics. Lead
also has 'blemish healing' and flow characteristics that are unmatched.
Lead glazes tend to have high resistance to chipping. In addition, lead
is a 'forgiving material' that tends to hide imperfections on the
finished fired surface. Lead glazes have been demanded for fine China
for many years, although substitutes have been developed.
-Lead carbonate, a favorite source is highly pure and has a very fine
particle size. It also promotes good suspension in raw glazes as well as
rapid fusion.
-Lead promotes low expansion, a long firing range, and it decreases
viscosity and tendency to devitrify.
-Lead is often used in combination with boric oxide which improves
crazing problems and resistance to chemical attack.
-Problems include toxic nature of many forms, volatilization, and loss
of gloss during higher firing; dimming of brilliance after long use, and
less abrasion resistance. Note that even leaded frits can produce glazes
which are soluble if the formulation is faulty or firing is wrong.
Lead Safety:
Public and industry attitudes toward lead have shifted in the past few
years, and finally most potters and companies are realizing that the
narrow parameters within which lead can be used safely (or perceived to
be used safely) are just too difficult to work within. Public paranoia
is common even though, for example, there are no known cases of lead
related illness in the US for domestic manufactured ware.
Inhalation exposure to lead is considered to be significant if the
amount of lead in the air is more than half the lead-in-air standard
I.e.. >0.075 mg/m3 over an 8 hour working day. Concentration in the
human body is significant if it exceeds 40 micrograms/100ml of blood.
The US FDA (Food and Drug Administration) has been a driving force in
the move to eliminate lead worldwide. European standards (I.e. (European
Community Directive 1984) are less stringent and will be modified to
allow export to the US. The Compliance Policy Guide adopted by the FDA
in 1992 reduces allowable limits dramatically. It is based on the
standard 4% acetic acid text as follows:
Category, Samples, Lead Release (micrograms/ml), Pre 92, Current
--------------------------------------------------
Flatware, 6, 7.0, 3.0
Small Hollowware, 1, 5.0, 2.0
*Cups and Mugs, 1, 5.0, 0.5
Large Hollowware, 1, 2.5, 1.0
*Pitchers, 1, 2.5, 0.5
*New category
The US Consumer Product Safety Commission and the Environmental
Protection Agency has also issued voluntary standards.
In the early 90's, industry has been in a compliance mode, adopting
quality assurance standards and formulation expertise (I.e. BS 5270, ISO
9000) to meet the challenge and increase credibility. However,
environmental concerns and political pressure are forcing the industry
to eliminate lead completely or face a total ban. The sectors which most
depend on lead are bone china, vitrified hotelware, feldspathic
porcelains, and earthenware.
International industry leaders (Corning, Lennox, Mikasa, Noritake,
Pfaltzgraff, Royal Doulton, Villeryoy & Boch, Wedgewood) have formed
the Coalition for Safe Ceramic Ware to represent the interests of the
industry. Only companies with good reputations for producing quality
ware are eligible for membership. The CSC called for the reduction of
lead limits and was instrumental in the FDA's revisions in Apr 1992. The
CSC has continued to develop and apply quality and design control
standards which individual members must document and validate with
sampling programs. In addition, the CSC has published material to help
consumers assure that tableware products are safe to use.
CSC has also taken on the challenge of educating the public as to what
it sees as inappropriate. Examples are California's Proposition 65 which
requires that consumers be warned if lead levels are more than one-one
thousandth of the level at which there is observable effect on human
health. For example, a restaurant must warn its patrons with signage.
Lead levels of this nature are difficult to measure with test equipment |
|
| PrO2 |
172.9 |
0 |
0 |
Praseodymium Oxide
(Sources: Stains)
-Used for lemon yellow stains in combination with zircon. These stains
are not as powerful as antimony or vanadium but are flexible.
-PrO2 can be used in reduction firing, even at high temperatures.
-While it is toxic, it is not as dangerous to use as either vanadium or
antimony.
-Different glaze chemistries can produce brighter yellow coloration.
-PrO2 glazes do not tolerate contamination of other coloring oxides
well. |
|
| Sb2O3 |
291.6 |
0 |
630 |
Antimony Oxide
(Sources: Antimony Oxide, Antimony Sulfide)
-Antimony oxide is used as an opacifier in low fire glazes and porcelain
enamel (mainly leadless but it has been replaced to an extent by
titania). Antimony is easily reducible; thus an oxidizing agent like
potassium nitrate may be required to prevent it from going into solution
and losing its opacifying power and affecting color.
-It is not useful in glazes over cone 1 due to volatilization.
-Antimony can be used as a yellow body stain in combination with rutile
or titanium.
-Antimony will bleach the surface of low fire red-burning clay to a buff
color to produce variegated coloration.
-The glass industry uses antimony as a decolorizing and fining agent to
clarify glasses and as a stabilizing agent in the production of emerald
green glass. |
Glaze Opacifier Antimony works to a limited extent as an
opacifier to cone 1.
Glaze Color It can give a yellowish color if the glaze contains lead,
this is a result of the precipitation of yellow lead antimonate (known
as Naples yellow). |
| Se |
111.2 |
0 |
217 |
Selenium
(Sources: Element itself, sodium selenite, barium selenite)
-Semi-metallic element of the sulfur group. Its main value as a colorant
depends on a reduction or mildly oxidizing atmosphere to maintain its
metallic state.
-With cobalt it is a good decolorizer for glass because it produces a
pink which is close to complementary of iron green thus canceling it
out.
-Used as a colorant in making rose and ruby glass.
-Used in some special purpose stains. |
Glaze Color Used in making red glazes with cadmium for low
fire. Lead enhances the coloration. |
| SnO2 |
150.7 |
.02 |
1127 |
Tin Oxide, Stannic Oxide
(Sources: Tin Oxide powder)
-The fully oxidized state of tin metal. It is a very white powder of low
density. Although tin metal melts at a very low temperature, the oxide
form is stable to cone 1150.
-Tin oxide is used primarily as an opacifier in amounts of 5-15% in all
types of glazes for many centuries. The amount required varies according
to the glaze composition and temperature. The mechanism of the opacity
depends on the white tin particles being in suspension in the molten
glass. At higher temperatures, these particles will start to dissolve
and opacity will begin to be compromised.
-Like zirconium oxide, larger amounts of tin in lower temperature glazes
have a refractory effect, stiffening the melt and increasing the
incidence of pinholing and crawling.
-Tin white is considered a softer white than that produced by the very
popular and much cheaper zirconium opacifiers.
-One peril with tin is that it reacts very strongly with minute amounts
of chrome to produce pink colors. If volatile chromium is flashing in
the kiln atmosphere from other glazes, the white color will be lost.
-Other opacifiers include zirconium oxide (gives a harsher glassy
white), calcium phosphate (problems with off-coloring to greys), cerium
oxide (restricted to low temperatures), antimony (dissolves in some
glazes and gives yellows with lead), and titanium dioxide (discolors if
any iron oxide is present). |
Glaze Opacifier Tin is an effective opacifier to transform
transparent glazes to white. The quality of color tends to be a
'soft-bluish white' compared to harsher effects with other oxides. |
| SrO |
103.6 |
.13 |
2430 |
Strontium Oxide, Strontia
(Sources: Strontium Carbonate)
-Together with CaO, BaO, and MgO it is considered one the Alkaline Earth
group of oxides.
-Does not break down till 1090C (cone 02) so it is not useful as a glaze
flux below this temperature. SrO must thus be employed in frit form
below 1090C to be effective.
-It has an expansion akin to CaO and a similar decomposition behavior.
-Strontium compounds have not been widely used because of their more
limited availability, although the value of this oxide has long been
known.
-It is very useful at lower temperatures (I.e. Cone 1) for high gloss,
craze resistant glazes which develop a good interface with the clay
body. The interface development is thought to occur due to the
mixed-oxide effect (bodies do not normally contain SrO).
-Strontium is important because of its non-hazardous, non-poisonous
nature. With it, glazes of all temperatures can be made free of lead and
barium (in spite of its different expansion, it can be a viable
substitute for small proportions of lead).
-Even though it has a very high melting temperature, SrO is an effective
flux above 650C when interacting with other oxides (provided it is added
in fritted form).
-Like CaO and ZnO, it forms a crystal matte surface on cooling if
dominant in the RO group. Conversely, a diversity of fluxing oxides
associated with SrO will reduce crystallization.
-SrO has been used with success as a substitute for lead oxide in glazes
using smaller amounts. Glossy glazes melting as low as cone 01 without
any zinc are possible (long soaking periods may be necessary). Like
lead, strontium develops vivid colors.
-Small additions of SrO can improve the surface of viscous high fire
zirconium glazes.
-If BaO is replaced in whole or in part with SrO, glazes can develop
better interface and have a lower expansion. However, they may also be
less elastic than those formed by Ba and this could lead to fit problems
where body and glaze are not closely compatible. SrO has a different
color response to copper and cobalt; it has a lower expansion, and is a
little more powerful at fluxing.
-The lower temperature decomposition of SrCO3 potentially produces an
earlier reaction of SrO giving the melt more time to clear of bubbles
and pits. |
Surface Modifier Like calcia and baria, it will produce a fine
crystalline mesh to give attractive satin matte surfaces. |
| TiO2 |
79.9 |
.144 |
1830 |
Titanium Dioxide, Titania
(Sources: Titanium Dioxide, Rutile)
-Titania is a complex material because it opacifies, variegates, and
crystallizes glazes. It also modifies existing colors from metals like
Cr, Mn, Fe, Co, Ni, Cu.
-In amounts below 1% titania can dissolve completely in a glaze melt. In
slightly greater amounts it can give a bluish-white flush to transparent
glazes (depending on their amount of alumina).
-Above 2% it begins to significantly alter the glaze surface and light
reflectance properties through the creation of minute crystals. This
crystal mechanism gives soft colors and pleasant opacity, and breaks up
and mottles the surface. In the 2-6% range, it increasingly variegates
the glaze surface. Many potters add titania to their glazes or paint on
overglaze titania washes for this purpose.
-Large amounts (10-15%) will tend to produce an opaque and matte surface
if the glaze is not overfired. They will also subdue color and can add
sparkle to the surface. As much as 25% can be absorbed by some lead
glazes. Up to 0.8 molar can be used to effect crystal melts in glossy
glazes.
-Although titania will form a glass by itself, it is not highly soluble
in silica melts. However, it is considered by some as a glass former in
certain circumstances since it can stiffen the melt and stabilize the
fired glass against leaching (I.e. It is used in lead frits to lessen
the solubility of the lead).
-Titania can act as a modifier and within a narrow range it will combine
with fluxes to make a glass. It can also act in a flux-like way in very
high silica melts.
-Minute amounts (I.e. 0.1%) can be used to intensify and stabilize
colors (I.e. Iron can be altered to produce yellow and orange). It can
alter and intensify existing color and opacity in a glaze. Titania can
be reduced to produce colors in keeping with the elements present. If
highly reduced it can yield a red, with iron the color could be yellow,
brown or green. Other combinations can yield blues, greens, yellows.
Titania is oxygen-hungry and will quickly oxidize from its reduced state
if given the chance.
-Glazes containing titania are phototropic and can change color slightly
by the action of light. They can also be thermotropic in that they can
change color (I.e. Toward yellow) when heated.
-Some have chosen to treat TiO2 as an 'inert' with respect to the
chemistry of the glaze. However, a phase diagram of Al2O3 and TiO2 shows
a eutectic at 80% Al2O3 at 1705C demonstrating that TiO2 does 'react'
with the second most important ceramic oxide.
-TiO2 is considered an impurity in ball clays and kaolins used to make
porcelain because it can react with any iron present to form rutile
crystals which detrimentally affect body color and tranlucency. |
Glaze Opacifier Titanium can be used as an opacifier. |
| Trace |
0 |
0 |
0 |
Trace Elements
Use this item to group trace elements together in an analysis. It should
be defined with a weight of zero to ignore them in any formula
calculations. |
|
| U2O8 |
842 |
0 |
2176 |
Uranium Oxide
(Sources: Uranium Oxide)
A colorant which can be used in amounts to 15% to achieve or modify
yellows, reds, and oranges. Although this form of uranium is said to be
less radioactive, the use of any form of uranium is considered dangerous
by most authorities.
Other oxides of uranium are also available. |
Glaze Color It is possible to achieve reds in lead silicate
glazes low in alumina and having no boric oxide. Zinc is also helpful to
develop the color.
Glaze Color Yellow is the usual oxidation color for uranium modified
glazes. The presence of CaO and ZnO are beneficial. |
| V2O5 |
181.9 |
0 |
690 |
Vanadium Pentoxide
(Sources: Vanadium Oxide)
An acidic metallic oxide which produces yellow coloration in amounts to
10%. Its color in generally weak, but can be strengthened when fritted
with tin and zirconia. Although yellows can be prepared with antimony,
vanadium is stable at higher temperatures.
The most vibrant color is obtained in leaded glazes.
Also a strong flux.
Another form, Vanadium Trioxide (V2O3) also exists and is alkaline in
nature. |
Glaze Color A classic yellow colorant. |
| Y2O3 |
225.81 |
0 |
2585 |
Yttrium Oxide
-Used in electrical conducting ceramics, refractories, insulators,
glass, and stains.
-Used with Sc, La, Cs oxides in TiO2 bodies for better control of
properties than possible with alkaline earths.
-With ZrO2 it make good high temperature refractories. |
|
| ZrO |
107.2 |
.02 |
0 |
Zirconium Oxide, Zirconia
(Sources: Zircon opacifiers, Zirconium silicate)
See ZrO2
Zirconia has an inversion with an associated 3% expansion/contraction. |
Surface Modifier ZrO can produce patterns of minute darker and
lighter areas in an otherwise drab glaze surface. Significant amounts
are needed (e.g. Up to 15%).
Glaze Color Zircon is used in stains to stabilize colors. |
| ZrO2 |
123.2 |
.02 |
2700 |
Zirconium Dioxide
(Sources: Zircon opacifiers, Zirconium silicate)
-Zirconium oxide is an extremely refractory material and its metallic
form likewise melts very high, the highest of all oxides except MgO.
-It is primarily used as an opacifier in glazes with properties similar
to tin oxide. Tin is about twice as effective in producing opacity. The
opacifying effects of zirconium are a product of its ability to form a
second crystal phase. |
Glaze Opacifier Zirconium is an effective opacifier, especially
in the Zirconium Silicate form. Parent materials of finer particle size
are more effective.
In lead glazes a cream tint is likely. Glazes high in boron or alkalis,
or low in alumina and silica may not opacify well. |
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