Color changes in roofing slates exposed to high temperatures

According to EN 12326-1, roofing slate is a material which do not need additional tests regarding to fire performance, since it is obvious that it doesn’t burn. However, different types of roofing slates submitted to high temperatures showed important changes in color and also in water absorption. This might be important for some cases like when reusing a material coming from a house burn, or if one wants to estimate the temperature of a fire affecting roofing slates. For that, I submitted 6 different types of roofing slates to a thermal ramp ranging from 100 to 900 °C. The changes in aspect and water absorption are related to the slate bulk compositon. The slate samples used were:

BRA: Shale from Minas Gerais, Brazil

ITL: Carbonate slate (>20% CaCO3) from Liguria, Italy

ECA: Slate from Valdeorras, Spain

VXE: Phyllite from Lugo, Spain

ALT: Schist from Alta, Norway

BUR: Burlington slate, United Kingdom

Fire resistance

Color changes for the selected slates (Y axis) along the increasing temperature (X axis, in °C)

In the figure is clearly seen how the color is changing to red tones in all the slates with the increasing temperature. This is a normal effect in all the rocks, high temperatures favor the iron oxidation. However, for the carbonate slate ITL, color tends to white tones, due to the carbonate alteration. Respect to water absorption, all the slates increases their values due to the development of cracks and detachments because of the thermal stress. Again, the slate ITL results are different, reaching close to 20% of water absorption due to the disappearing of carbonate at 600 °C. Anyway, the conditions of this experiment are exceptional, and will never be reached under normal conditions of use of the slate, so these results are merely illustrative.

Water absorption evolution with increasing temperature

Water absorption evolution with increasing temperature

 

Oxidation of iron sulphides in roofing slates

In previous posts I have discussed one of the main pathologies of the slate, the oxidation of iron sulfides. According to EN 12326, to determine the oxidizability of the slate is used the thermal cycle test, which consists on submerging in water for 7 hours the slates, and then put them in an oven at 110 ° c for 16 hours. These steps form one cycle. The essay consists of 20 cycles, which in practice means that the total development time is 4 weeks, at a rate of 5 cycles per week. It also requires facilities and dedicated staff during that time. At the end of the test, depending on the alteration of iron sulphides, a code is given to the slate, T1/T2/T3 code, being the most favorable case T1, and T3 less favorable.

There is a much faster, simpler and cheaper method of determining the oxidizability of the slate. For several years I have been working with pre-oxidations induced by Hydrogen Peroxide, H2O2. With this method, within 24 hours it is possible to know how oxidizable is a slate. The concentration of H2O2 used is similar to what is sold in pharmacies, 3% concentration. Slate tiles are immersed in H2O2 during 24 hours at room temperature (20-25 ° C). After that time, tiles are washed with water (distilled is better, to avoid leaving any traces when dry) and examined. In the picture you can see a plate of slate without attack (0a), attacked 24 h (1a), 48 (2a) and 72 (3a) h. Most of the oxidation occurs within the first 24 h.

05B_H2O2

This technique has some elements to consider. The first is the analysis of the slate. Personally I always use image analysis, for which first I scan the slates with a normal scanner, at a resolution of 300 dpi. As my scanner has a maximum scan area of ​​DIN A4 size, what I do is cut tiles to a size that fits well, eg 15 x 15 cm.

Once I have the images, I use a free program that works great, ImageJ. With this program I calculate the surface of the slate occupied by oxidations (pictures 0b, 1b, 2b and 3b), so that I have is a real numerical data, not the subjective assessment by an operator.

However, this method does not make much sense if it does not correlate with the levels of oxidation of EN 12326, T1, T2 and T3, which today are recognized and adopted by the slate sector. Oxidizability depends largely on the type of iron sulfide, so that neither can relate the oxidized area of the standard grades … nowadays.

This is one of the things I’m working on, the relationship between H2O2 attack and thermal cycling according to EN 12326.’s Solution shortly.

Roofing slate mineralogy – Part II

Secondary and accessory minerals

Secondary minerals

Formed during the metamorphic processes that originated the roofing slates. The most common secondary minerals in slates s.s. are iron sulphides (pyrite and pyrrhotite), carbonates (calcite and ankerite) and chloritoid. The iron sulfides are formed during the post-metamorphic processes. Some authors point out their origin as the remains of organic matter that could be contained in the slate matrix. Depending on the geological conditions and the ratio of iron (Fe) and sulfur (S), these iron sulfides may end up being different minerals with different potentials for oxidation.

Determination of Fe - S proportions of iron sulphides in several roofing slates. The two most common minerals are pyrite and pyrrhotite

Determination of Fe – S proportions of iron sulphides in several roofing slates. The two most common minerals are pyrite and pyrrhotite

On the other hand, the carbonates are normally deposited occupying the empty spaces and voids that could be in the rock matrix. The chloritoid is formed perpendicular to the slaty cleavage. This mineral appears only in some types of slates with a high content of magnesium (Mg) and a slightly higher metamorphic grade than the average of slates s.s.

From the point of view of quality, iron sulfides and carbonates play a decisive role, since they are alterable minerals. Their appearance is undesirable. The chloritoid may cause fissility problems, since it grows perpendicular to the slaty cleavage, hindering the correct elaboration of the tiles.

Accessory minerals

They are found in quantities below 5%. The most common are tourmaline, rutile-leucoxene, zircon, monazite and organic matter. They have no importance for the quality of the board, since they are not alterable, with exception of the organic matter. This can be found under the form of graphite, small fragments of between 5 and 30 microns, which are opaque seen to the microscope. It can become very abundant in localized areas of a quarry and is often linked to iron sulfides. Organic matter also undergoes oxidative processes, although do not causes color changes. Its alteration leads the pH to decrease, acidifying the medium and greatly accelerating the oxidation rate of the iron sulfides. Sometimes the accumulation of organic matter can be seen on the surface of the slate, forming what the miners call “burnt slate“. This slate is not usable to make plates, and it should be discarded.

1. Chloritoid crystal in a Galician slate, Spain<br />2. Small chloritoids in a slate from Arouca, Portugal<br />3. Turmaline fragment in a slate from Monte Rande, Galicia, Spain<br />4. Monazite in a slate from Puente de Domingo Flórez, León, Spain<br />5. Small black and rounded fragments of organic matter in a shale from Minas Gerais, Brazil<br />6. The upper half of the image corresponds to an exceptional accumulation of organic matter, known as “burn slate”

1. Chloritoid crystal in a Galician slate, Spain
2. Small chloritoids in a slate from Arouca, Portugal
3. Turmaline fragment in a slate from Monte Rande, Galicia, Spain
4. Monazite in a slate from Puente de Domingo Flórez, León, Spain
5. Small black and rounded fragments of organic matter in a shale from Minas Gerais, Brazil
6. The upper half of the image corresponds to an exceptional accumulation of organic matter, known as “burnt slate”

Pathologies – part III

Acting against oxidation

Above all, it must be remembered that oxidation is a purely aesthetic defect, which does not involve the loss of the roof waterproofing. Only in exceptional cases, where the size of the iron sulphide is greater than the plate thickness, the oxidation can break it.

Up: Lateral view of a slate tile, in which the thickness of the iron sulphides is lower than the thickness of the tile itselfDown: The thickness of the iron sulphides is now higher that the thickness of the tile, breaking it when the oxidation develops

Up: Lateral view of a slate tile, in which the thickness of the iron sulphides is lower than the thickness of the tile itself
Down: The thickness of the iron sulphides is now higher that the thickness of the tile, breaking it when the oxidation develops

It is also necessary to know the susceptibility of the slate to oxidation. An experienced technician will have no problem recognizing the existence, abundance and types of iron sulphides present, so it is possible to estimate the oxidizability of a slate variety quite rightly. Also, preoxidation treatments with H2O2 can be very illustrative, although the attack conditions must be carefully checked for no erroneous results.

In recent years there have been proposed two types of oxidation treatments, application of chemical products and passivation of the iron sulphides. The application of chemicals products is done in huge treatment stations located in the same slate producing factory. These products have several disadvantages to be considered, during the application stage and with the effective protection they can give to the slate. Still, there are already slate producing companies applying this type of products, albeit in a restricted way.

Experimental roof with tiles of slate treated with different products and treatments

Experimental roof with tiles of slate treated with different products and treatments

The other type of treatment involves selectively attacking the iron sulphides, weathering first their surface and then coating them with an inert mineral crust that protects against the environmental conditions. This method is effective in theory, and it has not been developed for practical use yet, so its real effectiveness can´t be known.

As a general recommendation, against oxidation on the roof, we should act calmly, first weighing the extent and type of damage, and then considering the possibility of changing the affected tiles. Each case is different, and not always the oxidized tiles are negative. In restoration of historic monuments it is common to search for oxidized tiles to replace the originals. Also in modern buildings, rusted slate offers new attractive textures and colors.

Portugal2007 (84)

Further reading:

Passivation techniques to prevent corrosion of iron sulphides in roofing slates

Oxidación de sulfuros en pizarra ornamental: tratamientos protectores con siloxanos

Protocolo de valoración de la efectividad de productos protectores de pizarra para cubiertas

Sealant composition for roofing slate

Pathologies – part II

Oxidation

Iron oxidation consists of the change of Fe2+ to Fe3+, by the gain of an electron. In roofing slates, most important iron minerals are iron sulphides, being the most abundant pyrite (FeS2), which is oxidized in the presence of oxygen according to the reaction:

FeS2 + O2 –> Fe2+ + 2SO2-4 + H+

The oxidation of these iron sulfides is favored by acid urban environments and coastal areas, where sea salts favor oxidation reactions.

However, not all the iron sulfides oxidize in the same way. There are several types of iron sulfides, such as pyrite, pyrrhotite, marcasite, arsenopyrite, etc, being the two firsts the most abundant by far. Each iron sulphide has a different structure. Thus, the oxidation susceptibility depends on the strength of this mineral structure. For example, pyrrhotite has a poorly ordered hexagonal structure, being more vulnerable to oxidation than the pyrite cubic structure. In real world, most oxidations developed in roofing slates are due to pyrrhotite, so it is very important to distinguish between these two minerals, since the oxidability of the slate depends on it.

Finally, the occurrence of organic matter in the slate favors the oxidation, due to the increase of acidity during its decomposition.

1 - Pyrrhotite, brown color, with not recognized shape. 2 - Pyrrhotite partially oxidized together with an inclusion of organic matter. 3 – Pyrrhotited fossil of a bivalve. 4 - Cubic pyrite crystal. 5 - Cubic pyrite crystals forming aggregates called framboids. 6 - Footprint of a disappeared cubic crystal of pyrite oxidized.

1 – Pyrrhotite, brown color, with not recognized shape. 2 – Pyrrhotite partially oxidized together with an inclusion of organic matter. 3 – Pyrrhotited fossil of a bivalve. 4 – Cubic pyrite crystal. 5 – Cubic pyrite crystals forming aggregates called framboids. 6 – Footprint of a disappeared cubic crystal of pyrite oxidized.

Further reading: Determination of iron sulphides in roofing slates from the north west of Spain

Pathologies – part I

Pathologies in roofing slates

The pathologies formed in slate roofs are mainly due to the presence of potentially unstable minerals (iron sulfides, carbonates and organic matter). These minerals may become altered by the effect of environmental agents, once the slate roof is finished. The pathologies are mainly associated with oxidation and gypsification processes of the cited mineral phases.

The oxidation is generated when the iron sulfides which may contain the slate became weathered, forming iron oxides. This forms reddish rust marks on the surface of slate tiles. This is mainly an aesthetic defect, as only rarely slate tiles disintegrate due to oxidation. However, it is the main fact in volume of complaints from slate customers (Figure 01). The presence of tiny fragments of organic matter may favor the oxidation processes.

Fig01

Customers complaints by volume of monetary costs

The gypsification occurs when the carbonates react with the environmental SO2, forming gypsum. In this case, gypsum has larger size than carbonates, so a swelling may occur within the slate tile, causing it to disintegrate. Despite this, the incidence that this pathology in the customer complaints is significantly lower than oxidation, maybe since it is not as striking (Figure 01).

There are also other characteristic pathologies and minor defects but also must be taken into account.

Following the criteria dictated by ICOMOS, defects and pathologies found in roofing slates can be classified into 3 groups (Table 01).

Most common  pathologies in roofing slates

Most common pathologies in roofing slates

Further reading: Standard tests for the characterization of roofing slate pathologies