**Ceramic Materials Based on Clay Minerals in Cultural Heritage Study**

Rodica-Mariana Ion, Radu-Claudiu Fierăscu, Sofia Teodorescu, Irina Fierăscu, Ioana-Raluca Bunghez, Daniela Ţurcanu-Caruţiu and Mihaela-Lucia Ion

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/61633

#### **Abstract**

The artifacts belonging to the ceramic heritage are mostly based on all clay types used by humans over the ages, because the sources of clays were easily available and people were interested to produce ceramics and pottery. This is the reason why the conservation of cultural heritage is of great concern. Ceramics (Greek κεράμιον Keramion) is a material obtained by shaping and firing clay. In the Romanian history, many ceramic pieces, of great diversity, have been discovered, and most of them are used in traditional house‐ holds. Ceramic materials based on clay minerals in cultural heritage (ceramic heritage) in‐ volve techniques of characterization of raw materials and ceramic objects based on clays, discovered in different archaeological sites, leading to some results about the production technology, provenance, authentication, and historical appartenance on Romanian terri‐ tory. The chemical composition of ancient ceramics and pigments decorating them, exca‐ vated from different Romanian archaeological sites, suggested a chemical composition of ceramic based on clay minerals (kaolinite, illite, and smectite), while the pigments be‐ longing to them contained red pigments (hematite or ocher), manganese oxides (brown pigments), and magnetite or carbon of vegetable origin (black-pigmented layers).

**Keywords:** Cultural heritage, clays, pottery, ceramics, Transylvania tiles

## **1. Introduction**

In ancient times, sources of clays were widely available, between them soils or surface sediments have been the proper sources for ceramics without further treatment, due to their natural mixture of plastic and nonplastic components [1]. Ceramics is an inorganic nonmetallic

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material obtained through thermal processing of natural raw materials at relatively high temperature [2]. The raw materials are clays with finely divided quartz (sand) (0.02–0.04 mm) and feldspar, responsible for the rheology along the thermal processing. Clay is a group of minerals in earth that is granular; plastic, when mixed with a little water; or hard and brittle, if combusted. The clay is composed of hydrated aluminum silicates, with the addition of an appreciable amount of other elements: magnesium, iron, calcium, and potassium [3,4]. The clays retain fluid water (liquid) (from pores between clay particle aggregates) at low temper‐ ature, molecular water from the surface of particles or crystallites at medium temperature, and, sometimes, neutral molecules (H2O) or ionic hydroxyl groups (OH<sup>−</sup> ) liberated at higher temperatures during thermal processing [5–7]. The production of ceramics was first imple‐ mented in the Neolithic period. The Greeks and Romans developed lime mortar cements, with a remarkable resistance, and some of these archaeological sites stand testimony to this day [8]. The Industrial Revolution of the eighteenth and nineteenth centuries registered significant improvements in the ceramic industry, while the twentieth century contributed to the scientific understanding of these materials. Conservation and restoration of cultural heritage has become one of the main concerns worldwide. In this respect, there is particular interest for investigations by nondestructive techniques some unique heritage ceramics for their subse‐ quent preservation and restoration. These nondestructive analytical methods are able to provide information on composition/chemical nature of cultural artifacts, selected parts and materials in order to elucidate their origin, state of degradation (surface and/or internal) objects as a result of exposure over a period to environmental conditions, and the effects/effectiveness of strategies to conservation/restoration during their implementation.

#### **1.1. Traditional ceramics**

The traditional ceramics involve those materials that are derived from common, naturally occurring raw materials such as clay minerals and quartz sand. The traditional ceramics is manufactured from naturally occurring raw materials: silicates—compounds based on silica (SiO2) and unmodified or chemically modified aluminosilicates (alumina [Al2O3] plus silica). In addition, the raw materials used in traditional ceramics could be classified into three groups: clay, silica, and feldspar [9].

Clay minerals such as kaolinite (Al2[Si2O5][OH]4) generated either by the weathering of igneous rocks under the influence of water, dissolved carbon dioxide, and organic acids, or from feldspar (KAlSi3O8) eroded from rocks such as granite and deposited in lake beds, which are aluminosilicates that contain sodium (Na), potassium (K), or calcium (Ca) with a composition from NaAlSi3O8 and KAlSi3O8 to CaAl2Si2O8. Feldspar acts as fluxing agents to reduce the melting temperatures of the aluminosilicate phases where they are subsequently transformed into clay [10]. Except feldspar, silica, as the second major ingredient in refractories, is usually added as quartz sand, sandstone, or flint pebbles [11]. The role of silica is either to maintain the shape during firing (as filler) or to improve the final mechanical properties.

The behavior of ceramics depends on its chemical, physical, and mechanical properties [7]. In the ancient ceramics, the main minerals are gehlenite (Ca2Al2SiO7), anorthite (CaAl2Si2O8), quartz (SiO2), belite (β-Ca2SiO4), and carbonates/calcite (CaCO3) and/or dolomite (CaMg(CO3)2). For ceramics with limestone as raw material, the fired products may also contain akermanite (Ca2MgSi2O7), gehlenite (Ca2(Al,Fe,Mg)(Si,Al)2O7), and Mg-silicates (e.g., diopside and CaMgSi2O6) [12,13].

## **2. Background**

material obtained through thermal processing of natural raw materials at relatively high temperature [2]. The raw materials are clays with finely divided quartz (sand) (0.02–0.04 mm) and feldspar, responsible for the rheology along the thermal processing. Clay is a group of minerals in earth that is granular; plastic, when mixed with a little water; or hard and brittle, if combusted. The clay is composed of hydrated aluminum silicates, with the addition of an appreciable amount of other elements: magnesium, iron, calcium, and potassium [3,4]. The clays retain fluid water (liquid) (from pores between clay particle aggregates) at low temper‐ ature, molecular water from the surface of particles or crystallites at medium temperature,

temperatures during thermal processing [5–7]. The production of ceramics was first imple‐ mented in the Neolithic period. The Greeks and Romans developed lime mortar cements, with a remarkable resistance, and some of these archaeological sites stand testimony to this day [8]. The Industrial Revolution of the eighteenth and nineteenth centuries registered significant improvements in the ceramic industry, while the twentieth century contributed to the scientific understanding of these materials. Conservation and restoration of cultural heritage has become one of the main concerns worldwide. In this respect, there is particular interest for investigations by nondestructive techniques some unique heritage ceramics for their subse‐ quent preservation and restoration. These nondestructive analytical methods are able to provide information on composition/chemical nature of cultural artifacts, selected parts and materials in order to elucidate their origin, state of degradation (surface and/or internal) objects as a result of exposure over a period to environmental conditions, and the effects/effectiveness

The traditional ceramics involve those materials that are derived from common, naturally occurring raw materials such as clay minerals and quartz sand. The traditional ceramics is manufactured from naturally occurring raw materials: silicates—compounds based on silica (SiO2) and unmodified or chemically modified aluminosilicates (alumina [Al2O3] plus silica). In addition, the raw materials used in traditional ceramics could be classified into three groups:

Clay minerals such as kaolinite (Al2[Si2O5][OH]4) generated either by the weathering of igneous rocks under the influence of water, dissolved carbon dioxide, and organic acids, or from feldspar (KAlSi3O8) eroded from rocks such as granite and deposited in lake beds, which are aluminosilicates that contain sodium (Na), potassium (K), or calcium (Ca) with a composition from NaAlSi3O8 and KAlSi3O8 to CaAl2Si2O8. Feldspar acts as fluxing agents to reduce the melting temperatures of the aluminosilicate phases where they are subsequently transformed into clay [10]. Except feldspar, silica, as the second major ingredient in refractories, is usually added as quartz sand, sandstone, or flint pebbles [11]. The role of silica is either to maintain

The behavior of ceramics depends on its chemical, physical, and mechanical properties [7]. In the ancient ceramics, the main minerals are gehlenite (Ca2Al2SiO7), anorthite (CaAl2Si2O8), quartz (SiO2), belite (β-Ca2SiO4), and carbonates/calcite (CaCO3) and/or dolomite

the shape during firing (as filler) or to improve the final mechanical properties.

) liberated at higher

and, sometimes, neutral molecules (H2O) or ionic hydroxyl groups (OH<sup>−</sup>

160 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

of strategies to conservation/restoration during their implementation.

**1.1. Traditional ceramics**

clay, silica, and feldspar [9].

## **2.1. Romanian history of ceramics**

Ceramics, until the twentieth century, was essentially used for utilitarian purposes for ritual acts. At first, craftsmen did not know the potter's wheel, but they were very skilled at shaping and baking clay. Ceramic art painting in white, black and red, with models of great beauty and originality, was spread over a territory more extensive than present-day Romania and perfected for almost 2000 years [14]. The pottery techniques are extremely important for archaeologists as a source of results about cultural groups and their distribution areas. Through fragments of pottery, one can identify intercultural links or movements of populations in certain geographical areas [15]. For example, Romania's geographical region consists of Wallachia until Jiu Valley in Dobrogea, southwest Moldova and southeast Transylvania, and extending south to the Aegean Sea.

Some of the most relevant ceramic types specific to Romania are:


**Figure 1.** Cucuteni ceramics

For ancient ceramics, the methodological exact sciences have their beginning in the sixth decade of twentieth century, when it was widely used in X-ray diffraction (XRD) technique [18], investigation of thermal expansion [19], and optical microscopy ceramic artifact analysis [20]. In the next decade, new analytical methods such as Mössbauer spectroscopy [21], differential thermal analysis [22,23], and electron microscopy [24, 25] were explored. Through improvements in the investigation methods in the last decade of the twentieth century, the characterization of such ceramics reached impressive new levels [26–28]. The eighth decade of the twentieth century coincided with the development of some methods based on SEM that currently dominates the studies about pottery. The use of these methods allowed for a better understanding of structural changes due to the different types of clay burning at different temperatures [14], which allowed the extraction of information, enabling economic and social outline of the communities that produced these artifacts. At present, the world can identify and understand the most stages of the technological process of making ceramics in different chronological periods and in different cultures.

It is important to use modern chemical analysis, both nondestructive (which can be in some cases fully noninvasive) methods and destructive methods of modern microanalysis, for small samples analysis [29–32]. They may be extremely valuable in the provenance investigation of an object, the origin of the materials used for its manufacture, in determining its degradation state and, finally, to choose the most suitable methods of restoration and conservation, the type of materials for conservation, and also in monitoring the progress of conservation processes, or to identify the fake art objects [33]. The main aspects of ceramic characterization are classification, production technology, and provenance through specific techniques for chemical and mineralogical characterization: spectroscopic techniques (FT-IR, Raman, XRD, EDXRF, and ICP-AES) and thermoanalytical techniques [34].

## **2.2. Analytical techniques for investigation**

Modern chemical methods and measuring techniques can be used for archaeometric purposes. Some analytical techniques have been investigated with exemplification for different Roma‐ nian artifacts.

#### **2.3. Methods and apparatus**

**Figure 1.** Cucuteni ceramics

chronological periods and in different cultures.

162 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

EDXRF, and ICP-AES) and thermoanalytical techniques [34].

For ancient ceramics, the methodological exact sciences have their beginning in the sixth decade of twentieth century, when it was widely used in X-ray diffraction (XRD) technique [18], investigation of thermal expansion [19], and optical microscopy ceramic artifact analysis [20]. In the next decade, new analytical methods such as Mössbauer spectroscopy [21], differential thermal analysis [22,23], and electron microscopy [24, 25] were explored. Through improvements in the investigation methods in the last decade of the twentieth century, the characterization of such ceramics reached impressive new levels [26–28]. The eighth decade of the twentieth century coincided with the development of some methods based on SEM that currently dominates the studies about pottery. The use of these methods allowed for a better understanding of structural changes due to the different types of clay burning at different temperatures [14], which allowed the extraction of information, enabling economic and social outline of the communities that produced these artifacts. At present, the world can identify and understand the most stages of the technological process of making ceramics in different

It is important to use modern chemical analysis, both nondestructive (which can be in some cases fully noninvasive) methods and destructive methods of modern microanalysis, for small samples analysis [29–32]. They may be extremely valuable in the provenance investigation of an object, the origin of the materials used for its manufacture, in determining its degradation state and, finally, to choose the most suitable methods of restoration and conservation, the type of materials for conservation, and also in monitoring the progress of conservation processes, or to identify the fake art objects [33]. The main aspects of ceramic characterization are classification, production technology, and provenance through specific techniques for chemical and mineralogical characterization: spectroscopic techniques (FT-IR, Raman, XRD, **Thermal analysis** presented in the following chapter helped in the characterization of pottery in order to conclude about the chemical and phase composition, and it was recorded with a Mettler 4000 TA, TG 50 analyzer system at a rate of 10°C min–1 in a static air atmosphere; PerkinElmer thermoanalyzer TG S-2; and DTA 1700 at a rate of 10°C min–1. A sample (15 mg) of finely ground stones were subjected to analysis in a Pt plate at a temperature range of 35– 1000 oC (10°C min–1). This concluded that the archaeological pottery was fired at relatively high temperatures.

**Energy-dispersive X-ray fluorescence (EDXRF)** analyses were performed with an PW4025 apparatus, type Minipal PANalytical, with a Si(PIN)-detector and an Rh tube with an accel‐ eration voltage of 30 kV. Due to varying surface structures and inhomogeneities in the surface composition of the samples, the analyses are usually performed on both sides of the objects and a mean value is calculated, when the analysis must be completely nondestructive. When possible, the sample is powdered, so a representative homogenous sample can be obtained. An XRF is known as the first powerful, commercial, fast, nondestructive, and relatively accurate technique for qualitative as well as semiquantitative chemical analysis.

**Inductively coupled plasma—atomic emission spectrometry (ICP–AES)** was used to quantify minor and trace elements. Detection limit for major elements is under the ppm level and the analytical precision calculated from replicate analysis is ±1%. For the ICP-AES measurements (usually with Varian equipments), the samples are finely powdered in an agate mortar and then mineralized with a microwave-assisted digestion oven with the use of highpressure closed Teflon PFA vessels (with a mixture of 5 ml HF 40% and 5 ml HNO3 65%) and pressure and temperature control. Multielement matrix-matched standards were used for the quantitative determinations.

**X-ray diffraction (XRD)** patterns were recorded on a DRON UM1 diffractometer, operating at 32 kV and 25 mA, using Co Kα radiation (1.79021 Å) with an iron filter. The diffractometer is connected to the PC, so the collected data can be analyzed and interpreted using either the dedicated program or other specific data analysis software.

**Fourier transform IR spectroscopy (FT-IR)** standard spectra were collected by using a PerkinElmer Spectrum GX spectrometer, for a range of 400–4000 scans and a spectral resolution of 4 cm–1. It was possible to use the drift accessory with the powdered pure substance, thereby allowing for a better and easier analysis.

**The Raman spectroscopy** analysis performed with **Raman spectra** has been recorded with a First Guard Raman apparatus, BaySpec with two wavelengths (1,064 and 785 nm). The Raman system includes a "superhead" optic fiber for noncontact measurements, with a 50× long working distance (LWD)-visible Olympus lens. The spectral data were processed with a software application dedicated to the file generation of Raman spectra. The spectral resolution was 3 cm–1. All the spectra were recorded in the 200–3,400 cm–1 domain.

## **3. Case studies**

### **3.1. Ceramics from Schneckenberg culture (sixteenth century), Dealul Melcilor, Braşov, Romania**

Sampling, reported in Table 1, was performed at the ruins of the Schneckenberg culture (sixteenth century), Dealul Melcilor, Braşov, Romania. Some examples of the investigated ceramic samples are shown in Figure 2.

**Figure 2.** Different ceramic samples

It is interesting that this region conserved many cultures (Vatina, Gârla Mare, Luciu de Sus, Wietenberg and Otomani). Eight differently fabricated contemporary pottery samples were selected for characterization, as shown in Table 1.

Clay minerals, as the main material for production of ceramics and pottery, show some characteristic reactions—dehydroxylation, decomposition, transformation—during the firing (heating effects, 20–800°C), and several steps for reconstruction of former production condi‐ tions are identified, knowing that the temperature at which ancient ceramics and pottery were fired varies over a wide range (600–800°C) depending on the type of clay used. Thermogravi‐ metric (TG) analysis and differential thermogravimetric (DTG) analysis are very important characterization methods used for the control of the reaction process and of the properties of the materials obtained [35–38]. The presence of some minerals is related to the ceramics firing process, giving information about the manufacture technology of the pottery. For a firing temperature higher than 900°C (observed for all the analyzed samples), a certain conclusion had been reached that the glazed ceramics was usually fired at temperatures ranging from


900°C to 950°C, mostly due to the reaction between quartz and carbonates when the temper‐ ature reaches 900°C.

#### **Table 1.** The ceramic samples analyzed

working distance (LWD)-visible Olympus lens. The spectral data were processed with a software application dedicated to the file generation of Raman spectra. The spectral resolution

**3.1. Ceramics from Schneckenberg culture (sixteenth century), Dealul Melcilor, Braşov,**

Sampling, reported in Table 1, was performed at the ruins of the Schneckenberg culture (sixteenth century), Dealul Melcilor, Braşov, Romania. Some examples of the investigated

It is interesting that this region conserved many cultures (Vatina, Gârla Mare, Luciu de Sus, Wietenberg and Otomani). Eight differently fabricated contemporary pottery samples were

Clay minerals, as the main material for production of ceramics and pottery, show some characteristic reactions—dehydroxylation, decomposition, transformation—during the firing (heating effects, 20–800°C), and several steps for reconstruction of former production condi‐ tions are identified, knowing that the temperature at which ancient ceramics and pottery were fired varies over a wide range (600–800°C) depending on the type of clay used. Thermogravi‐ metric (TG) analysis and differential thermogravimetric (DTG) analysis are very important characterization methods used for the control of the reaction process and of the properties of the materials obtained [35–38]. The presence of some minerals is related to the ceramics firing process, giving information about the manufacture technology of the pottery. For a firing temperature higher than 900°C (observed for all the analyzed samples), a certain conclusion had been reached that the glazed ceramics was usually fired at temperatures ranging from

was 3 cm–1. All the spectra were recorded in the 200–3,400 cm–1 domain.

**3. Case studies**

ceramic samples are shown in Figure 2.

164 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Figure 2.** Different ceramic samples

selected for characterization, as shown in Table 1.

**Romania**

Thermal analysis enables detection of exothermic and endothermic peaks (effects due to gain/ loss of enthalpy) occurring in the sample when undergoing controlled heating and compares to an inert reference material [39–46]. The endothermic peak around 100°C is due to moisture water, whereas those appearing at about 200–250°C are attributed to "bound" water, or to "hydrated" interlayer cations (as in swelling clay minerals). The TG/DTG diagrams for different colored ceramics are shown in Figure 3.

Figure 4 shows the TG/DTG diagram for the Transylvania tile ceramics.

Some effects have been observed as follows:


In both cases, an abrupt increase in weight starts immediately at room temperature and lasts up to 200°C. To our knowledge, such thermoanalytical behavior of pottery samples has never been observed previously.

Usually, the ceramic heritage contains mostly the following clay types: kaolinites (kaolinite, dickite, nacrite, and halloysite), illites (illite, hydrous micas, phengite, glauconite, and cela‐ donite), smectites (montmorillonite, beidellite, and saponite), vermiculites, and palygorskite (palygorskite and sepiolite). Some minerals, such as kaolinite, illite, and smectite, show strong endothermic peaks (in the range 550–650°C (higher for chlorite)), and some endothermic peaks are at 840°C (single peak)—for calcite and dublets at 780°C and 860°C—for dolomite. They are

**Figure 3.** Thermal analyses of colored ceramics

**Figure 4.** Thermal analyses of tile ceramics

due to the escape of CO during the breakdown of their structure (other carbonates are unusual in ancient ceramic materials). The presence of these characteristic thermal effects indicates that the primary minerals survived the firing processes required to destroy the structure of the minerals. The DTA curves of salts are complex, and their interpretation needs familiar experience with the technique, and also information from other analytic techniques, such as XRD, XRF, ICP-AES, FT-IR [48], micro-chemical tests, and microanalyses (scanning electron microscopy and energy-dispersive X-ray microanalysis (SEM-EDX)).

The X-ray diffraction, as one of the most important techniques for potteries analysis, led to the identification of the following mineral phases: quartz, kaolinite, illite, gibbsite, goethite, feldspar, and mixed layers (smectite/illite). The presence of illite peak in X-ray diffraction patterns indicates the presence of calcite, too. We observe that quartz, kaolinite, and K-feldspar are common elements. These are basic constituents of the original clay matrix.

From profile of the DTG curves, the clays could be classified as Ca-rich and Ca-poor raw clays. **Ca-poor ceramics** include quartz, feldspar, and micas.

For them some processes could be observed:


**Figure 5.** XRD diagram for tile (F1) and ceramics (green (F2) and brown (F3))

due to the escape of CO during the breakdown of their structure (other carbonates are unusual in ancient ceramic materials). The presence of these characteristic thermal effects indicates that the primary minerals survived the firing processes required to destroy the structure of the minerals. The DTA curves of salts are complex, and their interpretation needs familiar

**Figure 3.** Thermal analyses of colored ceramics

166 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Figure 4.** Thermal analyses of tile ceramics

**The Ca-rich ceramics** (with CaO content >5%) include kaolinite, illite, and chlorite. They show peaks at about 640°C, where clay minerals decompose. The samples present very low firing temperatures (740°C), and CaO has an important role in the transformation process of the ceramic matrix. The red bricks show extensive vitrification with iron oxide phases dispersed almost homogeneously in the vitreous matrix (allocated to large hematite crystals surrounded by lemonite) [55]. In the ceramics with higher percentage of CaO, calcium aluminosilicate microcrystalline is obtained, simultaneously with a color difference, due to the trapping of iron in the augite lattice [56]. A denser, less porous, and more durable ceramics is observed for the red bricks, mostly due to a higher vitrification.

**Figure 6.** (a) XRF spectra of the analyzed samples. (b) XRF spectra of the analyzed samples: a break was inserted in order to observe the variation of the elements; the color codes are the same as for Figure 6 a. (c) XRF spectra of the analyzed samples: the intensity scale was modified in order to observe the variation of the minor elements; the color codes are the same as for Figure 6 a.

Quartz, feldspar, white mica, biotite-like mica, iron oxides, and calcite are the main phases present, but the archaic ceramics contain smaller amounts of detrital feldspar. Also, ilmenite, sphene, zircon, rutile, spinel, epidote, apatite, and monazite have been identified by EDXRF (Figure 6 a,b,c) and SEM in some samples [57]. Cs and Rb concentrations are influenced by the presence of K-feldspar and mica (Cs and Rb are substitute for K). This observation, coupled with their low K2O and Na2O content and high Al2O3 content, suggests that during the preparation of the raw materials, the potters production followed a procedure, probably "levigation," separating the less fine nonplastic particles such as K-feldspar and albite. Th and Sc are considered as proper sensors for ancient ceramics provenance due their insolubility and their reduced effects on metamorphism, weathering, and diagenesis [58,59].

in the augite lattice [56]. A denser, less porous, and more durable ceramics is observed for the

2 4 6 8 10 12 14 16

2 4 6 8 10 12 14 16

2 4 6 8 10 12 14 16

Energy (keV)

(c)

**Figure 6.** (a) XRF spectra of the analyzed samples. (b) XRF spectra of the analyzed samples: a break was inserted in order to observe the variation of the elements; the color codes are the same as for Figure 6 a. (c) XRF spectra of the analyzed samples: the intensity scale was modified in order to observe the variation of the minor elements; the color

Cu Zn

Cu Zn

Energy (keV)

(b)

FeK

FeK

FeK

Cu Zn

Energy (keV)

(a)

FeK

FeK

CaK

Ti V Cr Mn

CaK

Ti V

CaK

Ti

V Cr Mn

CaK

K

Cr

Mn

K

FeK

PbL

PbL

PbL

PbL

PbL PbL

 White ceramic Brown ceramic Red ceramic Light grey ceramic Dark grey ceramic Transilvania tile Black ceramic

PbL

PbL

PbL

red bricks, mostly due to a higher vitrification.

168 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

Intensity (a.u.)

0

0

Na

Al

1000

2000

Intensity (a.u.)

codes are the same as for Figure 6 a.

3000

4000

Si S Rh

2000

4000

Intensity (a.u.)

Na Al Si

S

K

Rh

CaK

Na Al Si S

Rh Cl

CaK


**Table 2.** Major and trace elements ICP-AES analytical results for ancient ceramics and raw material sample (in wt.% and ppm)

The presence of certain chemical elements in the composition of ceramic samples and in the composition of the enamel can provide interesting data on the types of materials used in the medieval period. Some of these elements are found in the recipes used in painting [60–64]. The fact that the composition was found in zirconia ceramics is proof of the use of bentonite as raw material [15,33].

The degradation of the ceramic parts can be explained by the presence of potassium. Depend‐ ing on environmental conditions, potassium becomes potassium hydroxide by artifact drying and then potassium carbonate by reacting with CO2 from the atmosphere. The presence of KOH makes the area around the vessel to become alkaline, this being responsible for corrosion layer present only in enamel. This is the reason that it should be kept in a controlled humid environment to prevent the subsequent artifacts degradation [30].


**Table 3.** Chemical composition of artifacts detected by XRF and XRD

From Tables 2 and 3, similarities for different tempers can be observed, as a proof that most samples fall close, but the ceramic fragment containing sand and feldspar are less similar.

SiO2 and Al2O3 together comprise more than 50 wt.% of the ceramic chemical composition. The alkali oxides (K2O, Na2O, CaO, and MgO) constitute together less than 5 wt.% and Fe2O3 reaches 10 wt.% on average. A high H2O value (10 wt.% on average) is observed, which is too high for burned ceramic material. The Al2O3 and H2O contents explain the great abundance of clay-derived minerals, and confirm the abundance of partial dehydroxylation of clay material derived from kaolinite (main mineral of the ceramics) [65].

The chemical and mineralogical data, as well as textural aspects, conclude that the main raw material for ceramic elaboration comes from fine-grained clay quartz-rich material. Some important conclusions could be reached:

**•** When SiO2 concentration is high, the sample contains quartz sand.

medieval period. Some of these elements are found in the recipes used in painting [60–64]. The fact that the composition was found in zirconia ceramics is proof of the use of bentonite as raw

The degradation of the ceramic parts can be explained by the presence of potassium. Depend‐ ing on environmental conditions, potassium becomes potassium hydroxide by artifact drying and then potassium carbonate by reacting with CO2 from the atmosphere. The presence of KOH makes the area around the vessel to become alkaline, this being responsible for corrosion layer present only in enamel. This is the reason that it should be kept in a controlled humid

**Piesa/element Green paint Blue paint White paint Ceramics** Na2O — 3 4.2 — MgO 2 — 2.1 2.9 Al2O3 20.2 18.5 24.2 17.6 SiO2 30.2 36.9 36 52.6 SO3 12.1 — — 0.63 Cl 5.46 3.4 5.79 2.1 K2O 2.23 3.89 1.67 3.45 CaO 2.16 2.2 3.27 9.66 TiO2 1.29 1.21 1.63 0.985 V2O5 0.02 0.03 0.03 — Cr2O3 0.04 0.05 0.041 0.04 MnO 0.043 0.04 0.079 0.22 Fe2O3 1.53 2.17 1.96 9.17 Co3O4 0.070 0.24 0.02 0.069 NiO 0.1 0.36 0.02 — CuO 0.047 0.064 0.042 0.02 As2O3 0.03 0.35 —- — PbO 22.3 36.9 18.7 0.17 ZnO — — 0.03

From Tables 2 and 3, similarities for different tempers can be observed, as a proof that most samples fall close, but the ceramic fragment containing sand and feldspar are less similar.

SiO2 and Al2O3 together comprise more than 50 wt.% of the ceramic chemical composition. The alkali oxides (K2O, Na2O, CaO, and MgO) constitute together less than 5 wt.% and Fe2O3

environment to prevent the subsequent artifacts degradation [30].

170 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Table 3.** Chemical composition of artifacts detected by XRF and XRD

material [15,33].


### **3.2. Archaeometric investigation of medieval polychrome glazed pottery**

The composition and origin of the tile sample taken from the Medieval Customs archaeological site, Bran region, Braşov County, dating back to the seventeenth and the eighteenth centuries, have been used at first for ceramic composition for making ceramics and for the composition of paints used to decorate this tile. The chemical composition of ancient pigments is an important criterion for the identification of pottery preservation, decoration, and technology used. The study was focused on red, brown, and black pigments from a pre-Roman pottery a Transylvania tile, Figure 7 [67].

#### **Figure 7.** Transylvania tile

#### *3.2.1. Historical aspects*

It seems like ancient tiles appeared in Germany around 1300. The tiles were more advantageous than open fireplace due to storage of warmth and for elimination of smoke in the room. Their use is common in our country and quickly spread throughout Europe, thanks to their advan‐ tages. The oldest tile known to us dates from the early fifteenth century. These are unglazed and they represent biblical scenes, mythological strange mermaids with fish or snake tail and wing, real or fantastic animals, pictures knighthood, geometrical, and floral motifs. The tiles could be glazed and polychrome painted with cobalt blue, green, yellow, and brown pigmentbased enamel. Besides functionality, tiles were always meticulously decorated in relief. They had to be not only stove plates, but beautiful objects, providing protection and comfort family space. We have too few studies about the representations that appear on Transylvania tiles, how they were chosen, who were favorite reasons, motivations, and their symbolism elections. It is interesting to follow the trail forms and reasons in the European recurrence in different cultures. It seems that often the choice of decoration for tiles was linked to beliefs and rituals apotropaic, popular superstitions. In this respect, chimney, hearth were considered passage‐ ways, as well as threshold or window. Transitional spaces were exposed to evil spirits, evil eye, magic outside. And inside the house, the stove was considered a dangerous object, which could cause fire and smoke poisoning of the occupants of the house. Hence the need for home care through icons and symbols apotropaic fireplace [68]. An analysis of the compositions of the Roman ceramics reveals that the latter tend to have lower concentrations in Cs, Rb, K2O, Na2O, and CaO and higher in Al2O3.

## *3.2.2. Ceramics support*

of paints used to decorate this tile. The chemical composition of ancient pigments is an important criterion for the identification of pottery preservation, decoration, and technology used. The study was focused on red, brown, and black pigments from a pre-Roman pottery—

It seems like ancient tiles appeared in Germany around 1300. The tiles were more advantageous than open fireplace due to storage of warmth and for elimination of smoke in the room. Their use is common in our country and quickly spread throughout Europe, thanks to their advan‐ tages. The oldest tile known to us dates from the early fifteenth century. These are unglazed and they represent biblical scenes, mythological strange mermaids with fish or snake tail and wing, real or fantastic animals, pictures knighthood, geometrical, and floral motifs. The tiles could be glazed and polychrome painted with cobalt blue, green, yellow, and brown pigmentbased enamel. Besides functionality, tiles were always meticulously decorated in relief. They had to be not only stove plates, but beautiful objects, providing protection and comfort family space. We have too few studies about the representations that appear on Transylvania tiles, how they were chosen, who were favorite reasons, motivations, and their symbolism elections. It is interesting to follow the trail forms and reasons in the European recurrence in different cultures. It seems that often the choice of decoration for tiles was linked to beliefs and rituals apotropaic, popular superstitions. In this respect, chimney, hearth were considered passage‐ ways, as well as threshold or window. Transitional spaces were exposed to evil spirits, evil eye, magic outside. And inside the house, the stove was considered a dangerous object, which could cause fire and smoke poisoning of the occupants of the house. Hence the need for home care through icons and symbols apotropaic fireplace [68]. An analysis of the compositions of the Roman ceramics reveals that the latter tend to have lower concentrations in Cs, Rb, K2O,

a Transylvania tile, Figure 7 [67].

172 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Figure 7.** Transylvania tile

*3.2.1. Historical aspects*

Na2O, and CaO and higher in Al2O3.

Ceramic is a type of kaolin as hydrated aluminum silicate double, feldspar formed by the decomposition of igneous rocks and by the action of carbonic acid and water, under pressure, and subjected to high temperatures. The clays are some of the most common rocks from the earth, with smaller grains of 0.002 mm, composed of a complex mixture of clay minerals: kaolinite, illite, montmorillonite, etc. These are aluminum and magnesium silicate hydrate, made from altered feldspar and other silicates. They add muscovite, feldspar, heavy minerals (zircon, ilmenite, rutile, magnetite, garnets, etc.), fragments of shells, and other sulfide minerals as diagenetic, glauconite, calcite, and very fine particles of minerals from rock unspoiled page of complex colloidal silicate, hydrated, and the remnants of organic substances. The chemical composition of clays varies by minerals they contain. Ceramic clays and semi-acid clays are used in brick masonry construction, terracotta tiles, or cement. Semi-acid clays have a content of approximately 30%. Al2O3 can be used for the extraction of alumina in the synthesis process; and strong base and basic clays (refractory clays) are used in the manufacture of refractory chamotte for the manufacture of fine ceramics. Clays always contain a greater or lesser amount of impurities, which reduce refractoriness [69].

#### *3.2.3. Pigments for glazed tile*

For aesthetic and for a consistent colored ceramic, pigments are used with metallic oxides and different salts. Pigments vary from green to blue-green to blue. They can be used as dyes in clay bodies and glazes, directly or mixed with water. The coating is constituted of lead-alkali glass with the addition of copper or iron ions as coloring agents.

The presence of the oxides is vital. For example, chrome oxide gives green color, but it may fume or volatilize. If tin is present in a white or pastel glaze, the chrome reacts with the tin to create a pink coloration. If zinc oxide is present in the glaze, a dirty-brown color will be obtained. For green color, cobalt-zinc-alumina-chromite blue-green pigment system could be used, where varying the amounts of cobalt and chrome oxides produces a green ceramic color. Many pigments have mineral origin with different colors; for example, ocher: red and yellow; cinnabar: bright red; azurite: blue; malachite: green; lime: white; carbonized bone: black. As organic pigments red madder and murex shell purple are used, and as binding media, egg, casein, and wax.

The chemical compositions of the ancient ceramics and pigments used are shown in Table 4.

Except all these techniques, FT-IR has been used for ceramic composition identification, including the assignment on the basis of the typical wavenumbers of the contributions to the FTIR absorbance spectra of minerals given in the Sadtler database "Minerals and Clays" [70]. Making a distinction of clays present in the samples was also a difficult task: the contribution centered at ~1033 cm–1 can be attributed both to illite and montmorillonite. Montmorillonite is visible at the peak from ~615 cm-1, while the band centered at ~1,633 cm–1 could be attributed to illite spectrum. Montmorillonite could be derived from hydrolysis process occurring during the burial period of the findings [71]. Calcite, as clearly shown by the FT-IR spectrum in which the large band centered at about 1444 cm–1 and the contribution at about 870 cm-1, typical of this mineral, is present. The absorptions from the main quartz phase (Si–O) could also be easily identified in the FTIR spectrum of ceramics and pigments used for glaze (Figure 8; 1163, 1083, 798, 778, 695, 514 cm –1) [72]. The several intense bands in the range 800–550 cm–1 (725, 646, 584 cm–1) are characteristic of the metal–oxygen vibrations in the ceramic samples [73]. However, additionally the characteristic carbonate (calcite phase) vibrations at 1795, 1430, 876, 713 cm– <sup>1</sup> [74] and M–O vibrations at 725, 685, 642,580, 531 cm–1 could also be determined. Characteristic Si–O, C–O, and M–O stretchings could be easily identified in all FT-IR spectra. Broadbands between 3700–3000 cm–1 can be assigned to the adsorbed water (or water of crystallization) and O–H vibrations of glazed pottery. This could be associated with specific surface properties of pottery, which stimulate adsorption of moisture from atmosphere at ambient conditions.


**Table 4.** Chemical composition of the Transylvania tile

The Raman spectra collected have to be compared with those obtained previously from reference materials. Published libraries of spectra are now widely available in the literature on historical pigments [75,76], enamel and glazing pigments [77], modern synthetic pigments [78], modern inks [79], gums, waxes, varnishes, resins and other binders of historical and archaeo‐ logical importance [80,89], minerals [70,90,91], and plant fibers [92]. As already mentioned, Raman scattering is a very weak phenomenon that requires an intense monochromatic light source to generate a readily detectable effect. Also, the use of lasers has allowed a wider choice of excitation lines, with wavelengths ranging from 351.1 nm to 1064 nm. In Raman spectra, the hematite (α-Fe2O3) bands are identified at 613 (s); 408 (s); 227 (m); 204 (w) cm–1, whereas 663 cm–1 band indicates the presence of magnetite (Fe3O4) [94]. The 1329cm–1 band is also assigned to hematite. When the sample has been produced in an oxidizing atmosphere, the most important indicator is the hematite [90,93]. If magnetite is present, this is an indicator of its incomplete phase transformation into hematite [91].

The Raman spectrum of the tile ceramic is shown in Figure 9. The representative Raman band for beta-quartz is located at 462 cm–1, while the medium intense 507cm–1 band is assigned to albite (Na-feldspar). Specific bands appear here: 462, 401, 356 cm–1, all being attributed to quartz. The band from 506 cm–1 together with the shoulder around 600 cm-1 indicates the presence of hematite. All these are more pronounced for not-glazed face (red colored spec‐ trum). The broadband around 1350–1500cm–1 is due to amorphous carbon, 461 cm–1 band is assigned to β-quartz. Also, in the Raman spectrum of the ceramic supports, the medium intense —550 cm–1—band reveals the presence of hematite, as shown in Figure 10.

**Figure 8.** FT-IR spectra of the pigments

this mineral, is present. The absorptions from the main quartz phase (Si–O) could also be easily identified in the FTIR spectrum of ceramics and pigments used for glaze (Figure 8; 1163, 1083, 798, 778, 695, 514 cm –1) [72]. The several intense bands in the range 800–550 cm–1 (725, 646, 584 cm–1) are characteristic of the metal–oxygen vibrations in the ceramic samples [73]. However, additionally the characteristic carbonate (calcite phase) vibrations at 1795, 1430, 876, 713 cm– <sup>1</sup> [74] and M–O vibrations at 725, 685, 642,580, 531 cm–1 could also be determined. Characteristic Si–O, C–O, and M–O stretchings could be easily identified in all FT-IR spectra. Broadbands between 3700–3000 cm–1 can be assigned to the adsorbed water (or water of crystallization) and O–H vibrations of glazed pottery. This could be associated with specific surface properties of pottery, which stimulate adsorption of moisture from atmosphere at ambient conditions.

174 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Compound Green pigment Blue pigment White pigment Ceramic** Na2O — 3 4.2 — MgO 2 — 2.1 2.9 Al2O3 20.2 18.5 24.2 17.6 SiO2 30.2 36.9 36 52.6 SO3 12.1 — — 0.63 Cl 5.46 3.4 5.79 2.1 K2O 2.23 3.89 1.67 3.45 CaO 2.16 2.2 3.27 9.66 TiO2 1.29 1.21 1.63 0.985 V2O5 0.02 0.03 0.03 — Cr2O3 0.04 0.05 0.041 0.04 MnO 0.043 0.04 0.079 0.22 Fe2O3 1.53 2.17 1.96 9.17 Co3O4 0.070 0.24 0.02 0.069 NiO 0.1 0.36 0.02 — CuO 0.047 0.064 0.042 0.02 As2O3 0.03 0.35 — — PbO 22.3 36.9 18.7 0.17 ZnO — — 0.03

The Raman spectra collected have to be compared with those obtained previously from reference materials. Published libraries of spectra are now widely available in the literature on historical pigments [75,76], enamel and glazing pigments [77], modern synthetic pigments [78],

**Table 4.** Chemical composition of the Transylvania tile

**Figure 9.** FT-IR and RAMAN spectra of calcite

**Figure 10.** FT-IR and RAMAN spectra of the ceramic tile

#### **4. Conclusions**

Many ceramic pieces known as ceramic heritage have been discovered, characterized by specific techniques of characterization either for raw materials or ceramic objects based on clays, discovered in different archaeological sites, leading to some results about the production technology, provenance, authentication, and historical appartenance. The chemical composi‐ tion of ancient ceramics and pigments decorating them, excavated from different Romanian archaeological sites, suggested a chemical composition of ceramic based on clay minerals (kaolinite, illite, and smectite), while the pigments belonging to them contain hematite or ocher (a red pigment), manganese oxides (brown pigments), and magnetite or carbon of vegetable origin (black-pigmented layers).

## **Acknowledgements**

This paper received the financial support of the projects: PN 09.09.03.07, PNII 222/2012 and PNII project 261/2014.

## **Author details**

**Figure 9.** FT-IR and RAMAN spectra of calcite

176 Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

**Figure 10.** FT-IR and RAMAN spectra of the ceramic tile

Many ceramic pieces known as ceramic heritage have been discovered, characterized by specific techniques of characterization either for raw materials or ceramic objects based on clays, discovered in different archaeological sites, leading to some results about the production technology, provenance, authentication, and historical appartenance. The chemical composi‐

**4. Conclusions**

Rodica-Mariana Ion1,2\*, Radu-Claudiu Fierăscu<sup>1</sup> , Sofia Teodorescu3 , Irina Fierăscu<sup>1</sup> , Ioana-Raluca Bunghez1 , Daniela Ţurcanu-Caruţiu<sup>4</sup> and Mihaela-Lucia Ion5

\*Address all correspondence to: rodica\_ion2000@yahoo.co.uk

1 ICECHIM, Nanomedicine Research Group, Bucharest, Romania

2 Valahia University, Nanomaterials Research Center, Târgovişte, Romania

3 Valahia University, Multidisciplinary Science and Technology Research Institute of Vala‐ hia University of Târgoviste - ICSTM, Târgovişte, Romania

4 Ovidius University, Art Faculty, Constanţa, Romania

5 Valahia University, History Faculty, Târgovişte, Romania

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## *Edited by Gustavo Morari do Nascimento*

This book presents the state-of-the-art results of characterization of clays, clay minerals and ceramic materials based on clay minerals. The main goal of this work is to contribute to the rationalization of some important results obtained in the open area of clays and clay materials characterization. Moreover, this book also provides a comprehensive account on polymer and biopolymer-clay nanocomposites, use of clay as adsorption materials for industrial pollutants, ceramic materials in cultural heritage and physical-chemistry aspects of clay and clay minerals aqueous dispersions. This book will be beneficial for students, teachers and researchers of many areas who are interested to expand their knowledge about clays and its derivates in the fields of Nanotechnology, Biotechnology, Environmental Science, Industrial Remediation, Cultural Heritage, etc.

Photo by Givaga / DollarPhotoClub

Clays, Clay Minerals and Ceramic Materials Based on Clay Minerals

Clays, Clay Minerals and

Ceramic Materials Based on

Clay Minerals

*Edited by Gustavo Morari do Nascimento*