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RO R2O3 RO2
CaO 1.3
MgO 0.2
ZnO 0.1
Again, notice in the above that oxides are grouped into three columns: the bases, acids, and amphoterics or
simply as the RO, R2O3, and RO2 oxides (where "R" is the element combining with oxygen). Actually, the ratio of R
to O is significant. The right column has the greatest oxygen component, the left has the least. Simplistically, we
can view these three groups as the silica:alumina:fluxes system. This latter convention is not really correct
because there are more glass builders than SiO2, other intermediates besides Al2O3, and the RO's do more than
just flux. But because this method evokes immediate recognition, let's use it anyway. Ancient potters referred to
these three as the blood, flesh, and bones of a glaze (not a bad way to think of it).
All formulas have a formula weight, that is, the total calculated weight for that mix of molecules. Atomic weights
are known (the appendix in many ceramic texts list them); so deriving the weight of one molecule of an oxide is a
matter of simple addition.
The following chart shows how oxide weights are derived and how a formula weight is calculated from an existing
formula.
Calculating the Formula Weight
-----------------------------------------------------------------
Atoms Num *wt Formula to
in of of Total Oxide Calculate
Oxide Oxide Each Atom Wt Wt Weight For
-----------------------------------------------------------------
K2O K 2 x 39.1 = 78.2
O 1 x 16 = 16 = 94.2 x 0.60 = 56.5
CaO Ca 1 x 40.1 = 40.1
O 1 x 16 = 16 = 56.1 x 1.30 = 72.9
MgO Mg 1 x 24.3 = 24.3
O 1 x 16 = 16 = 40.3 x 0.20 = 8.1
ZnO Zn 1 x 65.4 = 65.4
O 1 x 16 = 16 = 81.4 x 0.10 = 8.1
Al2O3 Al 2 x 26.9 = 53.8
O 3 x 16 = 48 =101.8 x 0.90 = 91.6
SiO2 Si 1 x 28.1 = 28.1
O 2 x 16 = 32 = 60.1 x 9.00 = 540.9
-----------------------------------------------------------------
*Data from Appendix of many textbooks Formula Wt 778.2
These weights are not grams; they are atomic weight units. They compare the weight of a molecule of the oxide
with an atom of hydrogen. CaO weighs 56.1 because Ca (calcium) weighs 40.1 and O (oxygen) weighs 16. This
means only that CaO is 56.1 times heavier than a single atom of benchmark hydrogen. Al2O3 (alumina oxide) is
102 times heavier; so for each weight unit it will yield fewer molecules than CaO.
The Unity Formula
The three column format of expressing a formula was first used by Hermann Seger and today it is still called the
"Seger Formula". Such formulas are normally ‘unified’, that is, all the numbers are scaled so that the RO column
totals one (if RO oxides are lacking the R2O3 column is unified). A formula thus said to be "unified on the fluxes"
or "set to RO unity". Unity formulas are ‘standard’ and can be compared.
The following chart takes the above formula (which had Al2O3 unity) and recalculates to 'flux unity'. The
expression "bring the fluxes to unity" means "make the fluxes add up to one".
Adjusting a Formula to Flux Unity
---------------------------------
Raw Unity
Oxides Formula Formula
---------------------------------
K2O 0.6 / 2.20 = 0.3
CaO 1.3 / 2.20 = 0.6
MgO 0.2 / 2.20 = 0.1
ZnO 0.1 / 2.20 = 0.0
----- -----
Flux total 2.2 1.0
Mole% is a calculation of the percentage of oxide molecules by number (an analysis compares their weights).
Here is the method used to convert a raw formula to a Mole% formula.
Raw Mole
Oxides Formula Percent
------------------------------------
K2O 0.6 / 12.1 x 100 = 5.0%
CaO 1.3 / 12.1 x 100 = 10.7
MgO 0.2 / 12.1 x 100 = 1.7
ZnO 0.1 / 12.1 x 100 = 0.8
Al2O3 0.9 / 12.1 x 100 = 7.4
SiO2 9.0 / 12.1 x 100 = 74.3
----- -----
Total 12.1 100.0
-----------------------------------
Mole% ignores LOI as do formulas, it just looks at the oxides that makeup the fired glass (you only need to
account for LOI when inserting materials into the MDT). The INSIGHT Advisor dialog contains a few examples of
target formulas from Richard Eppler and references are based on Mole%. These will give you a feel for how the
system is used.
The Percentage Analysis
An "analysis" compares oxides by the weights of their molecules, not the numbers of molecules. It is important to
note that an analysis comparison between two glazes can look quite different from a Mole% comparison since
oxide molecule weights differ greatly.
Consider this example:
25 Porcelain Body
If you are not sure of the difference between an analysis and formula yet, think of a can of mixed nuts. It
may contain cashews, brazils, peanuts, almonds and filberts. The label may specify the percentage of
each type of nut in the mix. A mixture of 30% peanuts has 30% peanuts by weight because the nut
company mixes by weight (they don't count individual nuts). Think of the label on the can of nuts as an
analysis. When you open the can you may be surprised to find many more peanuts than expected. This is
because peanuts are the smallest and therefore the lightest, so even though they make up only 30% by
weight, they may well outnumber all the others combined. If you actually sorted and counted them, the
resultant ratio would be like a formula. It would compare the nuts by number and the results would look
quite different.
The analysis format is best suited to showing how much of each individual oxide is in a mix. For example,
feldspars are used as a source of flux, although they also provide SiO2 and Al2O3 , so a buyer wants to know how
much flux each brand has. A percentage analysis figure shows this, whereas a formula figure does not. An
individual item can be extracted from an analysis (e.g. 10% K2O) and it is meaningful. However, an individual item
in a formula is only significant in the context of other amounts in that formula.
An analysis provides flexibility in allowing the inclusion of organics, water, and additives which are burned away
during firing. For example, if a material loses 10% weight on firing, we can just say LOI (Loss on Ignition) is 10%.
However, it would be difficult to express this 10% loss in a formula. Strictly speaking a formula cannot have an
LOI because it expresses the mix of oxides in a fired ceramic. It is no surprise then that the analysis has become
a standard used to express the make-up of raw glaze and clay materials on manufacturers data sheets.
You might have noticed that many, in fact most published analyses do not total exactly 100. There are a variety of
reasons for this. It is common for the LOI to be wrong because it does not include all of the volatile materials
(even moisture in the sample). Also, labs typically measure the amount of a specific group of oxides, others that
are not checked for are not included in the total (most raw materials, especially clays, contain trace amounts of
dozens of elements). The amounts of some oxide types are more difficult to quantify and their numbers are thus
not as accurate. The fact that companies do not attempt to account for every last half percent of material is
generally an admission that the science of practical inexpensive chemical analysis is not exact.
Some people are critical of the use of the formula because it can be very misleading in comparing amounts of a
specific oxide in different formulations. To illustrate, consider comparing a pure feldspar with a typical cone 6
transparent glaze recipe.
The formula on the lower right makes it appear that there is more than twice as much silica and three times as
much alumina in the feldspar. However in the analysis on the left there is only a little more silica and much less
than twice as much alumina. This all relates to the difference in weight of various oxide molecules (refer back to
the mixed nut analog used above to rationalize this). Another criticism of formulas in favor of the analysis is that
having 1% iron in a body or glaze makes more sense than, for example, 0.05 in the formula. There is a lot of merit
in this observation, and most technicians rationalize the effects of coloring and opacifying oxides in terms of their
percentage in the analysis, often not even considering them in formula comparisons. However these observations
are in no way an indication that formulas are useless. Formulas are very useful as long as you are comparing two
similar mixtures (e.g. two cone 6 glazes using similar materials).
Loss On Ignition (LOI)
The primary purpose of recipe calculations is to derive the formula for the glass that comes out of the kiln, from
the mix of recipe materials that go into the kiln. A fired glass has no organics or carbonates; so it always has zero
LOI. This means that LOI is never shown for a glaze formula and you will never need to worry about it for any
batch-to-formula or analysis calculations.
However, many raw materials that go into the kiln do lose weight during firing; so they are not sourcing as many
oxide molecules as a calculation might suggest. If a raw material loses weight on firing, it must be accounted for in
calculations. This weight loss could be illustrated with the child and his LEGO blocks already considered. While
disassembling existing structures to free up all blocks, he may discard a number that do not lend themselves to
inclusion in the intended project. You can think of LOI as being like the shells we throw away from a bag of nuts.
We compensate for anything lost during firing by increasing the formula weight. For example, 100 grams of kaolin
going into a kiln produces only 88 grams of oxides for glass making. By increasing the formula weight of the kaolin
by the correct amount, a full calculated oxide yield will result. By increasing the formula weight of the kaolin by the
correct amount, a full calculated oxide yield will result. The INSIGHT software stores a material's formula in its
MDT (materials database) exactly as you enter it. It requires a formula weight for each material; so when needed
it can calculate the material's LOI as the difference between the recorded weight and the actual sum of the
weights of the oxides in the formula. Since INSIGHT knows the LOI for each material in a recipe, it can calculate
the LOI of the raw recipe as a whole. This can be very useful. For example, if you are blending materials to create
a composite material that will be used in recipes, you need to know its LOI when you add it to INSIGHT’s
materials database.
If you have an analysis lacking an LOI figure or suspect the accuracy of the analysis delivered by a lab, then you
can weigh, fire, and weigh again to derive the LOI and compensate the analysis. There is a lesson in the INSIGHT
manual that demonstrates this.
Following is a method of applying a 5% measured LOI to an existing analysis. This is called "LOI Compensating
an Analysis".
LOI Compensating an Analysis
100 - 95 = 5 / 100 = 0.95
-------------------------------
K2O 7.3% x 0.95 = 6.9%
CaO 9.4% x 0.95 = 8.9%
MgO 1.0% x 0.95 = 1.0%
ZnO 1.0% x 0.95 = 1.0%
Al2O3 11.8% x 0.95 = 11.2%
SiO2 69.5% x 0.95 = 66.0%
LOI 0.05 5.0%
-------------------------------
100.0% 100.0%
If you would like to study the mathematics of ceramic calculations, you can download a spreadsheet with an
instruction booklet from the Digitalfire website. Versions are available for Lotus, Quattro, and Excel; for Windows,
DOS and Macintosh.
Authors
• Tony Hansen (Owner)