SOLUBLE SALTS IN MINERALS

In non-enamelled products such as bricks, tiles or extruded products in general, the presence of soluble salts is visible as efflorescences, that is to say as whitish salt deposits on the external surface of dried or baked products. The salts reach the surface after water evaporation and are deposited in the areas of greatest evaporation.
In the case of pressed floor tiles, soluble salts are deposited mainly along the edges andmay cause bubbles or local alterations of the enamel which lower the quality of the product.
This phenomenon can have a number of causes:

1. Salts that are naturally present in the argillaceous materials.

2. Salts present in the water used for grinding the paste, or for the enamel.

3. Salts that form during firing due to pyrite pyrolysis.

4. Salts that form on the pieces during firing owing to the presence of sulphur in the fuel used for the oven.

The phenomenon is perceptible to the eye when the total concentration of soluble salts is higher than 0.5% and, in general, the salts present are sodium, potassium, calcium and magnesium sulphates.
The formation of superficial salt deposits is affected by drying conditions and the following can be observed:

1. The phenomenon intensifies with an increase in ambient temperature.

2. The phenomenon intensifies with diminution of relative humidity.

Enamel alteration along the edges can be particularly intense in the double firing process and can be attributed to two causes:

1. Water absorbed by the ceramic object during the enamelling process carries back into solution any salts that may still be present after firing and the evaporation of these salts along the edges of the object leaves a local deposit of sodium, potassium, calcium and magnesium salts, which lead to a local alteration of enamel composition, which therefore becomes more brittle.

2. The decomposition of calcium and magnesium sulphates can be accelerated when the enamel has already passed softening temperature, due to the reaction of molten glass with these salts, causing the emission of gas which in turn leads to the formation of surface bubbles and craters.

In the case of porcelain gres, the concentration of salts along the edges leads to glassier and therefore also shinier areas.
The best solution for this phenomenon is to replace the materials affected by the presence of soluble salts, or, with sometimes unsatisfying results, to accelerate the heating process during drying in order to prevent water evaporation in particular points, thereby preventing the accumulation of salts. In the double firing process a drying agent can be useful at the end of the enamelling process.
In some cases, especially when the salts are present in water used for grinding, it can be useful to add a small percentage of barium carbonate to the paste, during grinding, in order to precipitate the sulphates.
The most common soluble salts present in materials used for ceramics are:

§ Calcium, magnesium sodium, potassium and aluminium sulphates.

§ Double sulphates of sodium-aluminium and potassium-aluminium.

§ Sodium and potassium carbonates.

§ Sodium and potassium chlorides

Other compounds have such low solubility that, for practical reasons, they can be

considered insoluble.

Highly soluble salts present in argillaceous materials

Salt Solubility g/l Decomposition temperature

CaCo3 0,015 In pastes it begins to separate into Ca and Co2 at approx. 800 C

CaSO4 2,09 Separates into CaO and SO3 between 1000 -1125 C

CaSO4 2H2O 2,41 Dehydration 140 – 150°C

Separates into CaO and SO3 between 1000 – 1125 C

CaMg(CO3)2 0,32 In pastes it begins to separate into Cao, MgO and Co2 at approx. 750 C

MgCl 542,5 Complete pyrolysis at 700 C

MgCO3 0,106 In pastes it begins to separate into MgO and Co2 at approx. 700 C

MgSO4 260,0 Begins to separate at approx. 750 C

Na2CO3 71,0 Melts at 851 C

NaCl 357,0 Complete pyrolysis at 700 C

Na2SO4 47,6 Decomposes between 650 and 700°C

K2CO3 1120,0 Melts at 891 C

KCl 347,0 Complete pyrolysis at 700 C

K2SO4 68,5 Decomposes between 500 and 600 C

Calcium sulphate is a very common soluble salt in argillaceous material and it can be seen on the above table that it is also the most harmful salt in enamelled products because its decomposition temperature, and resulting emission of gas, is to be found in the temperature interval at which most enamels sinter and mature.

Process for individuating soluble salts in clays.

1. Extraction of salts from material.

The finely dry-ground clay (<>

2. Separation of water containing salts.

The slip thus obtained is vacuum-filtered with 0.45 micron filters, or centrifuged, in order to separate out the water in which the salts are dissolved. The solution is brought to a known volume.

3. Chemical analysis of water.

The desired ions can be individuated within the solution (usually chlorides, sulphates, calcium, magnesium, sodium and potassium).
Various techniques can be used: colorimetry, atomic absorption spectrometer (AAS), plasma spectrometer (ICP), gravimetric analysis (precipitation of sulphates with barium chloride or of chlorides with Silver nitrate) or via dosing with EDTA.
Finally, the total quantity of soluble salts can be determined via gravimetric analysis by weighing the residue after evaporation of a known volume of water.

Quick definition of the presence of sulphate ions.

Sulphates are generally present as calcium sulphate and this element can be present also as a carbonate or as an exchangeable cation.
The addition of sodium silicate as deflocculant can cause the following reactions:

1. Ca (Clay-OH)₂ + Na₂SiO₃ = Na clay-OH + CaSiO₃

2. CaCO₃ + Na₂SiO₃ = Na₂CO₃ + CaSiO₃

3. CaSO₄ + Na₂SiO₃ = Na₂SO₄ + CaSiO₃

Reaction 1 provokes an increase in deflocculation and calcium is precipitated as an insoluble salt (CaSiO3).
Reaction 2 causes the formation of a deflocculant salt (Na2CO3) and calcium is precipitated as an insoluble salt (CaSiO3).
Reaction 3 causes the formation of an insoluble salt (CaSiO3) and a soluble salt (Na2SO4) which acts as flocculant.
It is possible to individuate the presence of sulphates without extraction and filtering of the soluble salts.
Method:

§ Prepare a suspension 1:1 of clay with distilled water. For example 500 g of clay in 500 ml of water.

§ Add sodium silicate until sufficient fluidity is obtained and shake for 10 minutes.

§ Measure viscosity. Add BaCO3 in small doses. For example 100 mg at a time per 500 g

of clay.

§ Mix for 15 minutes each time and measure viscosity.

If viscosity increases, no sulphate ions are present.
If viscosity decreases, sulphate ions are present.

Individuation of sulphates via precipitation.

The analysis consists in slow addition of a diluted solution of barium chloride to the heated and slightly acidified solution containing the salts.
The following reaction takes place:

Ba₂+ + SO₄= = BaSO₄

BaSo4 is a low solubility salt (circa 3mg/l) and is separated by filtration, washed with water, calcined at approx. 800°C and then weighed.
The low solubility of barium sulphate is further lowered in presence of a slight excess of Ba2+, but slightly increased in presence of H+ ions, via the following reaction:

H⁺ + SO4⁼ = HSO₄^-

Despite this, precipitation is carried out in a slightly acidic solution in order to reduce contamination of the precipitate and in order to encourage the formation of larger and more easily filtered crystals. In an acidic environment, moreover, the formation of carbonate, chromate and barium phosphate can be avoided.
BaSO4 tends to co-precipitate other salts which may be present, such as Ba(NO3)2 and Ba(ClO3)2 by forming mixed crystals. Chlorates and nitrates, if present, need therefore to be removed beforehand.
Ions such as Ca²⁺, Al³⁺, Cr³⁺ and Fe³⁺ also interfere by co-precipitating BaSO₄ isomorphous sulphates.
One should remove these ions first, and also use highly diluted solutions.
During calcination, the carbon derived from partial combustion of the filter paper can reduce the sulphate to sulphur at temperatures below 600°C, according to the following reaction:

BaSO₄ + 4C = BaS + 4CO

Combustion of the filter paper should be avoided.
Calcination takes place at approx. 900 C, keeping the crucible in a tilted position so as to guarantee good air circulation, thereby oxidising into sulphate any sulphur that may be present. At higher temperatures, sulphate cracking takes place.
If the calcination residue is of a greyish colour, this indicates the presence of carbon, in which case it should be left to cool before adding 1 or 2 drops of concentrated sulphuric acid, before repeating calcination, so as to transform any sulphur into sulphate, according to the following reaction:

BaS + H₂SO₄ = BaSO₄ + H₂S

This method is also useful for individuating barium and other cations such as Pb2+ and Sr2+. These two cations have higher solubility, which can be reduced in hydro-alcoholic solution.

Individuation of sulphates via dosing.

Sulphates can be individuated via dosing, with a standard solution of BaCl2, using tetrahydroxyquinone as internal indicator.
Method

§ Transfer 25ml of solution into a 250ml flask and create slight acidity using a N/100

solution of chloric acid with phenolphthalein as indicator.

§ Add 25ml of isopropylic alcohol, which aids quick precipitation during dosing.

§ Add 0.2 g of tetrahydroxyquinone. The colour should tend towards yellow.

§ Dose with a standard solution of BaCl2 until the colour tends towards pink.

§ Calculate the percentage of sulphates (SO4=) in the water using the ratio 208,27 (BaCl2): 96 (SO4--).

Individuation of chlorides.

The classic method is dosing using Mohr salt.
The solution is dosed with a solution of Silver nitrate, in the presence of potassium chromate as indicator.
The method is based on the relative solubilities of silver chloride and silver chromate. Silver chloride is white, whereas Silver chromate is bright red, and the final stage of dosing takes place when a slight excess of silver nitrate leads to the formation of chromate.
Method:

Transfer 50ml of solution into a 250ml flask and add 1ml of potassium chromate solution at 5%.

Dose with a N/50 solution of silver nitrate until the red colour disappears.

Calculate the percentage of chlorides using the ratio 170 (AgNO₃) : 35,5 (Cl^-).