TiO2 (Titanium Dioxide, Titania)

Family: Glass
Weight: 79.900
Expansion: 0.144
Fusion: 1830C

(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.

Properties
 Fusion - 1870C
Titanium can be used as an opacifier.

 Glaze Color - Red

In high fire matte glazes, iron oxide and titanium can produce red colors.

 Glaze Opacifier - White

Additions of 5-10% titanium to many types of glazes produces yellow and light
tan coloration, the surface effect is usually crystalline in nature. Lead greatly
enhances the yellow at low temperatures.

 Glaze Opacifier - Off-white

Titania in significant amounts (+5%) will almost always contribute to a glaze
opacity of mottled and variegated character.

 Surface Modifier - Variegation

Titania is a classic addition to produce mottled and variegated effects in all sorts
of glazes. The more you use the greater the effect (up to 10%).
ZnO (Zinc Oxide)
Family: Flux
Weight: 81.400
Expansion: 0.094
Fusion: 1800C

(Sources: Zinc Oxide)

-Together with PbO it is considered one of the metallic oxide fluxes. In smalls amounts
zinc helps in the development of glossy and brilliant surfaces the way lead did.

-ZnO starts its fluxing action around 1000C (i.e. bristol glazes) whereas by itself ZnO
does not melt until 1975C. It is a late and vigorous melter for low fire glazes and thus
useful in fast fire applications.

-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 it does encourage the melting
process to begin earlier in stoneware applications, 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 so that glazes which might
otherwise craze or shiver will fit.

-ZnO can extend 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. In others it can reduce resistance to acid
attack.

-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. Zinc is common in fast fire glazes.

-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.

Properties
 Fusion - 1800C
From The Oxide Handbook

 Glaze Opacifier - White/Off-White

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.

Linked Articles
 Unwanted Crystallization in a Cone 6 Glaze
Someone is having a problem with a cone 6 glaze going glossy and crystallizing,
this article rationalizes the problem in terms of chemistry

MgO (Magnesium Oxide, Magnesia)

Family Flux
Weight 40.300
COLE - Co-efficient of Linear Expansion 0.026

Notes
-Together with SrO, BaO and CaO it is one of the Alkaline Earth group of oxides. It has a
cubic crystal structure.
-Like CaO, MgO is refractory at lower temperatures, so much so that it can be used to
increase opacity, to perform as a matting agent (i.e. magnesium carbonate), and act as a
check to glaze fluidity in a manner similar to alumina (e.g. to prevent devitrification or
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 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.

Mechanisms

 Glaze Matteness - Fatty Matte

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). The mechanism is phase separation of the suddenly melting
MgO, but MgO can also produce matte effects at lower temperatures as a
refractory melt-stiffening additive.

MnO (Manganous Oxide)

Family Colorant
Weight 70.900
COLE - Co-efficient of Linear Expansion 0.050
Notes
-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.

Mechanisms

 Glaze Color - Brown

Very pleasing tan-brown reduction fired glazes can be achieved with 5%

manganese dioxide in reduction.

 Glaze Color - Brown

 In glazes below 1080C, manganese can give coffee color browns when used with
tin and dull browns in lead and low alkaline glazes. The presence of alumina
assures brown (if it is lacking colors will be violet).

MnO2 (Manganese Dioxide)

Family Colorant
Weight 86.900
COLE - Co-efficient of Linear Expansion 0.050

Notes
-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.

Mechanisms

 Glaze Color - Black

Manganese and cobalt mixture produce black. Iron can also be used. For example,
a mix of 8 iron, 4 manganese dioxide and 0.5 cobalt make a raw black stain.

 Glaze Color - Purple, Violet

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).
SiO2 (Silicon Dioxide, Silica)
Family Glass
Weight 60.100
COLE - Co-efficient of Linear Expansion 0.035

Notes
-The principle, and often only glass forming oxide in glaze. Normally comprises more
than 60% of most glazes and 70% of clays. Special purpose formulations which lack
silica often compromise structural stability and strength.

-Adjust this in relation to fluxes to regulate melting temperature and gloss.

-Increase it at the expense of B2O3 to make glaze harder, more durable, and brilliant.
Boric oxide and silica can be interchanged to glaze melting temperature.

-Decreasing SiO2 increases the melt fluidity; increasing it raises the melting temperature,
increases acid resistance, lowers expansion, increases hardness and gloss, and increases
devitrification.

-It is normal to use as much as possible in any glaze to keep expansion low, to prevent
crazing, and enhance body/glaze fired strength. Note, however, that in certain boracic and
feldspathic compositions it can increase crazing so that other low expansion oxides may
be needed to reduce glaze expansion.

-With boron and alumina, it has the lowest expansion of all oxides.

-In clay bodies, flint mineral particles act as a filler and behave as an aggregate, while
SiO2 in feldspar, kaolin, ball clay, etc., participates directly in the chemical reactions
taking place to build silicate glasses. Thus the particle size of the parent material is often
important in determining whether contributed silica affects the chemistry and/or
mineralogy or acts as an aggregate.

Mechanisms

 Glaze Matteness - High Alumina

Low silica high alumina glazes produce matte effects. The silica:alumina molar
ratio is considered a good indicator of this type of matteness. A ratio of 5:1 is
matte; 10:1 is glossy. The high alumina stiffens the glaze melt preventing it from
solidifying to a flat surface.