Organic Matter in Clays: Detailed

Overview
Section: Ceramic Tile, Subsection: General
Description
A detailed look at what materials contain organics, what its effects are in firing (e.g. black core),
what to do to deal with the problem and how to measure the amount of organics in a clay
material.

Article Text
Clays always contain organic material of various types and origins. In clays dating from more
recent eras we can find lignin and humic acids, in colloidal form and with notable ionic exchange
properties due to the functional groups -CH e –COOH present in their molecules. In clays of
older eras, carbonaceous and bituminous substances are more frequent, with few functional
groups capable of influencing colloidal and ionic exchange properties. Generally the calcareous
material is found in the form of lignite, in grains of variable dimensions that form agglomerates
or layers, or in the form of colloidal particles clinging to the crystals of argillaceous material. In
so-called “ball clays” the material in colloidal form can also be composed of humic acids which
facilitate the deflocculation process.

Combustion of organic substances occurs between 300 and 600°C and they decompose
entirely if the quantity of oxygen is sufficient for complete reaction development.

During the firing process of ceramic parts, the organic substances present in the clays can
cause the development of a central area (in the ceramic object) of a different color, varying from
black to yellow. This is known as the “black core”. This phenomenon is due to the thermal
decomposition of the organic material and to oxidation-reduction reactions of the inorganic
components. (1)(2).

Basically, whenever the quantity of organic substances is higher than a certain value or
whenever low permeability of the ceramic object does not permit complete combustion due to
lack of oxygen, carbon remains in the center of the matrix up to higher temperatures (where
these can cause reduction of the iron). The size of the black core depends on various factors,
such as temperature and firing cycle, forming method, porosity of the ceramic object and oven
atmosphere (3)(4).

The black core has no effect on the appearance of enameled objects if it does not cause
bubbles or craters. In fact, it increases the mechanic strength in that it creates a greater vitrified
cross section in the ceramic object. However, in the case of enameled tiles or porcelain tiles, the
black core, despite not damaging the enamel, can cause warpage (and quality reduction in the
final product). In the case of pressed floor tiles or those fired with rapid cycles, the phenomenon
can prove particularly damaging to enamels, and various methods are used in order to reduce
or eliminate it:

 Increase of the percentage of non-plastic materials in the composition.

 Addition of oxidants (MnO2 or nitrates).
 Increase of grinding residue.
 Reduction of residual humidity.
 Reduction of pressing force.
 Modification of the firing curve so as to increase time spent in the interval 250 – 600°C.
 Render oven atmosphere as oxidizing as possible.

The content of organic carbon in clays for ceramics can be identified and this is particularly
important if the transformations that take place in these substances during the production cycle
are to be studied, as well as their influence on the properties of intermediate and finished
products.

Normally the values found are in the following range:

Light firing clays 0.1 - 0.5 %

Red firing clays 0.1 - 1.0 %
Ball clays 0.1 - 3.5 %

The analytical techniques most commonly used in the ceramics sector for quantitative
determination of organic fractions are the following (see also description below):

 Walkley – Peech method (chemical oxidation).

 Tidy method (1)
 Infrared absorption and thermogravimetric analysis method (IRA/TG).
 Simultaneous thermal analysis method (TG7DTA).

Organic substances in some argillaceous materials according to

three different analytical methods (5)
Walkley
Peech IRA/TG TG (air)
Material Origin C% C% Weight
loss %
Kaolin Provins (France) 0.40 0.40 0.60
Kaolin Cornwall (U.K.) <0.10 0.13 <0.2
China clay S. Severa (Rome, 0.12 0.10 <0.2
Italy)
Illite - kaolin Gattinara (Vc, Italy) 0.10 0.12 0.4
clay
Illite - kaolin Escalaplano 1.04 0.95 0.9
clay (Cagliari, Italy)
Clay Westerwald 0.10 0.15 <0.2
(Germany)
 Clay Westerwald 0.30 0.14 <0.2
(Germany)
Ball clay Devon (U.K.) 2.98 2.93 3.2
Ball clay Devon (U.K.) 2.10 1.95 2.4
Illite - kaolin Monte S. Pietro (Bo, 0.25 0.12 <0.2
clay Italy)
Calcareous Codrignano (Ra, 0.70 1.70 0.6
clay Italy)

Bibliography
(1) E. W. Worrall, C. V. Green, The Organic matter in Ball Clays, Trans Brit. Cer. Soc. 52 p.58).
(2) A. Barba, A. Moreno, F. Negre, A. B,asco, Oxidation of black cores in firing, Tile and Brick
Int. 6 (1990) p. 17.
(3) X. Elias, The formation and consequences of black core in ceramica ware, Interceram 3
(1980) p. 380.
(4) H. M. M. Diz, B. Rand, I. B. Inwang, The effect of organic matter and electrolyte on the
rheological behaviour of ball clays, Br. Ceram Trans. 89 (1990) p. 124.
(5) A. Barba, F. Negre, M. J. Ortis, A Escardino, Oxidation of black core during the firing of
ceramic ware –3. Influence of the thickness of the piece and the composition of the black core,
Br. Ceram. Trans. 91 (1992) p. 36.
(6) M. Raimondo, P. Damasino, M. Dondi, Determinazione quantitativa del carbonio organico
nei materiali argillosi per uso ceramico: un confronto fra tre diversi metodi analitici, Ceramurgia
3 (1999) p. 179.

Walkley-Peech method (chemical oxidation)

This is an analytical procedure which allows for the quantitative evaluation of organic substance
content in an argillaceous material via chemical oxidation.

Principle
This method provides the percentage of organic carbon present in the material or the total
percentage of organic substances, using a suitable correction factor (1).
The organic substances are oxidized using potassium bichromate in a concentrated sulphuric
acid environment (at the temperature necessary for fast dilution of the acid). After a pre-
established time, the excess bichromate that has not reacted is identified by dosing with a
solution of Fe(2).

Apparatus and reactants

 25 ml flask (divisions of 0.05 ml).
 Potassium bichromate solution 1,000 N. Dissolve 49,035 g of K2Cr2O7, dried at 105°C,
in one litre of distilled water.
 Fe(2) solution 0.5 N. Pour 600 ml of distilled water and 15 ml of concentrated sulphuric
acid into a 1 litre flask. Add 200 g of Mohr salt [Fe(NH4)2(SO4)2• 6H2O] to bring up to 1
liter volume. The title of the solution is not stable (because Fe(2) changes to Fe(3)) and
should be examined for each series of analysis.
 Sulphuric diphenylamine solution (0.5 g in 50 ml concentrated sulphuric acid).
Procedure
Place a quantity of sample sieved at 150µm in a 500 ml flask.

Quantities:

500 g for samples containing more than 3% of organic substances

1,000 g for samples containing between 1 and 3% of organic substances
2,000 g for samples containing less than 1% of organic substances

The quantity is calculated so as to have at least 3 ml of unreacted bichromate after initial

oxidation.

Add 10 ml of the potassium bichromate at 1.0 N. Shake and add 20 ml of concentrated sulfuric
acid, letting it flow down the sides. Shake and leave to settle for 30 minutes. Add 200 ml of
distilled water.

At this point one proceeds to dosing of the excess bichromate by adding 5 ml of phosphoric acid
at 60%, 0.5 ml of diphenilamine indicator and finally the Fe(2) solution, until the color turns from
blue to green.

At the same time a blank test is carried out with 10 ml of bichromate, 20 ml of sulphuric acid and
200 ml of distilled water.

Calculation
Organic carbon % = 10 • (1 – T/S) • (0.39/P)

Where:
P = weight of sample
T = ml of Fe(2) solution used for dosing.
S = ml of Fe(2) solution used for the blank test.

If we presume that each equivalent of carbon is 77% oxidized, then the quantity of oxidated
carbon is given by: 10 • (1 – T/S) • (0.003/0.77).

In order to obtain the percentage of organic substances we must multiply the percentage of
organic carbon by the empirical factor of 1.72.

Notes
The percentage of organic substances as determined above could be higher than the actual
substances present due to interference by reducing oxides, such as manganese, and ferrous or
chloride compounds.

Generally if manganese oxides are present they exist in very low concentrations. Iron (2) oxide
can be oxidized by air exposure during drying whereas the interference of chlorides, which are
normally present in quantities less than 0.2%, can be eliminated by adding a few mercury
chloride crystals to the flask (before adding reactants).
The detection limit of this method is approx. 0.1% with good consistency (0.05%).

Bibliography
(1) Methods of Soils Analysis (Part 2), Soil Science Society of America, 1982

Infrared absorption and thermogravimetric analysis method (Ira/TG).

Analytical instrument procedure enabling the quantitative evaluation of organic substance
content in an argillaceous material. (1).

The quantity of total CO2 developed from a sample is assessed by subjecting it to a combustion
process and measuring the intensity of the infrared absorption bandwidth. The instrument
(LECO CS-225) is calibrated (ASTM E 1019) with a reference standard at a known CO2 value.

The instrument individuates total carbon content, i.e. also that present in carbonates (which
must therefore be subtracted from the measurement via individuation through thermogravimetric
analysis or calcimetry (2).

Thermogravimetric analysis for the individuation of carbon in carbonates can be carried out in
either exposure to air or in a carbon dioxide environment, in order to increase the characteristic
temperatures of calcite and dolomite decomposition and to reduce interference attributable to
deoxydrilation of the argillaceous materials (decomposition reactions are normally in the range
650-800 C but in a CO2 atmosphere they are pushed to higher temperatures where we don't
have any reaction of water elimination from structures of clays).

Individuation is carried out on a sample quantity of 0.1 g and the results are expressed as a
percentage on the weight of the sample. The detection limit is less than 0.1% of total C (total
carbon in the clay including carbonates) and the consistency of data varies between 0.05 and
0.1% of total °C. With the calcimetric method the detection limits (0.2%) and consistency of the
method (0.2 – 0.3%) are increased.

In the case of calcareous clays, it is also necessary to carry out a thermogravimetric test, with
consequent uncertainties in the interpretation of the TG curve in order to find the percentage of
carbonates, rendering the method slower and less precise than the Walkley-Peech method.

Bibliography
(1) W. Gruner, E. Grallath, Improvements in the combustion method for the determination of low
carbon contents in steel, Steel Research 66 (1995) p. 455.
(2) B. Fabbri, P. Gazzi, G. G. Zuffa, La determinazione della componente carbonatica delle
rocce, La Ceramica 3 (1974) p. 13.

Simultaneous thermal analysis method (TG7DTA).

Instrument analytical procedure allowing only for a semi-quantative evaluation of organic
substance content in an argillaceous material, as it is less sensitive and accurate that the
previous two methods.

Using thermogravimetric analysis, the variations in mass of an argillaceous material are

identified as it is subjected to a controlled temperature gradient.
The combustion of organic substances occurs in the interval 200 – 500°C and is associated with
an exothermic effect on the DTA curve.

At the same temperature interval, weight loss and endothermic effects occur, due to dehydrating
reactions in Fe, Al and Mn hydroxides which may be present.

In order to eliminate interference, thermogravimetric analysis in nitrogen atmosphere can be

carried out in order to define weight loss due to deoxydrilation reactions of the previous
elements (which is subtracted from total weight loss in the same thermal interval).

The two analyses are carried out with approx. 10 mg of sample at the thermal interval 100 –
500°C with a heat increase of 10°C/min. Detection limits and consistency of this method are
influenced by the difficulty in interpreting the TG curves; uncertainty amounts to approx. 0.2 –
0.3% of total organic substance weight.

Through weight loss in air between 100 and 500°C, as shown in the previous table, it is possible
only to obtain a semi-quantitative estimation of organic carbon if this is higher than 0.5%.

Remark
According to F. Q. Al Khalissi e W. E: Worral (Trans. Brit. Ceram. Soc., 8,1982,pag.145) organic
substances can be completely removed by treating the ground clay with water oxygenated at
30% vol. and heated for several hours at approx. 80 C.

Black Coring, Black Core

Black coring usually occurs during a reduction firing and is a result of fast firing and/or lack of
oxygen in the kiln between 700 and 900C (usually in the bisque firing). If body carbon fails to
oxidize to CO2 it steals oxygen from Fe2O3 (reducing it to FeO, a powerful flux.) This FeO will
then flux the body, sealing it and preventing the escape of remaining carbon in the body. This
produces the characteristic 'black core' you see on ware cross section. The more iron in a body,
the greater the risk of this problem if firing is not right. Once iron is reduced to it is very difficult
to reoxidize it back to Fe2O3.

Notwithstanding this, there will always be some degree of blackness (or gray) in the cross
section of reduction fired ware made from iron-bearing raw clays. This is a testament to
compromises of reduction firing. As long as it does not exhibit glass development and melting it
is likely OK.

Note that electric kilns can also produce this problem, depending on the carbon and iron content
of the clay, density of the pack, available airflow, and speed of the firing.

Bloating and Black Coring

[A brief analysis of a complicated problem]

Bloating occurs when the firing cycle does not match the clay being fired. The symptom is a void created in the walls of the
the remedy does not lie with the clay: it is the firing that needs to be adjusted. We can generate some guidelines for adjusti
firing based on an understanding of the chemical processes that lead to bloating.

Why do pots bloat? In the simplest terms, it is because gases are formed in the body that cannot escape. With no place to
expand while still inside the pot and generate the voids called bloats. So where do these gases come from, and why can't t
escape?

The gases are generated from carbon and sulfur in the clay components of the body. As a natural part of the weathering an
deposit of clay particles, organic materials containing carbon and sulfur settle throughout the clays we mine and use for mo
ceramics. When these organic materials reach temperatures ranging from 1290° to 1650° Fahrenheit, they combine with ox
form gases, escape the clay body through the pores, and exhaust from the kiln. Under optimal conditions, all of the organic
expelled from the clay through this process during the bisque firing. However, it is possible to leave carbon and sulfur in the
under the following two circumstances.

First, the bisque firing can be too fast. Not only must the firing go to or beyond 1650°, but it must allow enough time for the
maximum quantity of carbon to burn out. The process is not instantaneous; it takes time for all the carbons and sulfurs to c
with oxygen, and it takes time for the subsequent gases to work their way out of the body.

Second, the atmosphere in the bisque kiln can be oxygen poor. If this is the case, some of the organics will remain in the b
because they can find no oxygen with which to combine. We see this phenomenon in both gas and electric kilns. In electric
with poor ventilation and tightly packed ware, the organics in the clay quickly combine with what little oxygen is available, a
is no means for new oxygen to get to the pots. Gas kilns have good ventilation, but that does not mean that oxygen is avail
too much reduction is used in the 1290° to 1650° range, the atmosphere will be oxygen poor and carbon and sulfur will be
behind.

Once the organics have been left in the body, they are likely to bloat in the glaze firing. As the glaze begins to melt, and the
glaze interface becomes vitreous, it forms a barrier. The left-over carbon and sulfur combine with the oxygen in the kiln, bu
now non-porous surface prevents the escape of these gases. With nowhere to go, the gases form "bubbles" or bloating wit
walls of the fired objects.

These problems are compounded in iron-bearing clay bodies. In low-iron bodies, gases contend only with the clay-glaze in
In iron-bearing bodies, early reduction causes the formation of "black glass" (reduced iron and silicate) within the body. Thi
glass is a powerful flux which becomes active at 1650° F. As temperatures rise, the black glass throughout the body gets s
The net effect is that the body becomes better at trapping the gases at the same time that its softness makes it less capabl
resist the expansion of the gases! This sequence of events results in bloating as the body reaches its normal maturing tem

Unfortunately, we may not know that the carbon or sulfur remain in the body after glaze or bisque firing. Sometimes, improp
fast-fired bisque may exhibit a pink cast on the surface, which, if broken open will often reveal black coring. Black coring is
evidence of trapped organics in the form of a layer of black visible just beneath the surface of the piece. The layer of black
in a "bloat" in a glaze-fired piece, or it may just be a black layer beneath the surface of the glaze. It is even possible for the
coring to exist throughout the fired clay body. Black coring will be present in glaze fired pieces where organics have been tr
Black coring can explain existing bloats, or it can warn us that the firing process is prone to create bloats even if none have
appeared.

With this understanding of the bloating phenomenon, how can it be prevented? It is as simple as eliminating the causes:

1. Fire slowly enough 1290° to 1650° F to give the carbon and sulfur in the body time to combine with oxygen and wo
way out of the clay body. The burnout process must be done slowly and completely before the glaze begins to mel
2. Provide an oxygen rich atmosphere. In electric kilns, use plenty of ventilation in the bisque fire. If your kilns are den
loaded, use a downdraft kiln vent. In gas kilns, keep the kiln in oxidation from 1290° to 1650° F.
3. When using iron-bearing clay bodies, fire up to 1950° F in complete oxidation to allow for proper and complete burn
the organics; then, if desired, begin the reduction process.
The above information offers a brief sketch of how to prevent bloating. Different clay bodies require different treatment as c
vary in their organic content. The following are a few of the many sources for additional information on bloating and proper
Time spent improving firing techniques is money in the bank!

 The Potter's Dictionary of Materials & Techniques by Frank and Janet Hamer
 Ceramic Science for the Potter by W. G. Lawrence
 Ceramic Faults & Their Remedies by Harry Fraser
 The Art of Firing by Nils Lou