Owing to the crystalline lattice particularly reach in cavities, zeolites are lightweight ceramic materials. The crystalline lattice of zeolites consists of a three-dimensional aluminosilicate network composed of SiO

1. Zeolite structure

Zeolites are ceramics with a hybrid ionic-covalent structure and, owing to the crystalline lattice particularly reach in cavities, they are lightweight materials. The crystalline lattice of zeolites consists of a three-dimensional aluminosilicate network composed of SiO

₄

and AlO

₄ tetrahedra connected together by the oxygen atoms. Since negative charges are present in the aluminosilicate framework, extra-framework cations are required for the material electroneutrality condition. Monovalent metal cations are located close to the aluminum atoms in order to balance their negative charges, while bivalent metal cations are positioned halfway between two neighboring negatively charged sites. In particular, the extra-framework ions, typically present in nature-made zeolites, are alkali (K

tetrahedra connected together by the oxygen atoms^[1][2]. Since negative charges are present in the aluminosilicate framework, extra-framework cations are required for the material electroneutrality condition. Monovalent metal cations are located close to the aluminum atoms in order to balance their negative charges, while bivalent metal cations are positioned halfway between two neighboring negatively charged sites. In particular, the extra-framework ions, typically present in nature-made zeolites, are alkali (K

⁺

, Na

⁺

) and alkaline-earth (Ca

²⁺

, Mg

²⁺

) metal cations. Since mineral zeolites have mostly aluminous nature, i.e., they are characterized by a low value of the Si/Al ratio, which usually ranges from 4 to 7, a large amount of charge-balancing metal cations is contained. Many natural zeolites also contain iron, which causes a reddish coloration of the mineral. Iron can be present both in the covalent framework (isomorph substitution of silicon, like in the aluminum case) and/or in the extra-framework, as charge-balancing cations (ferric cations, Fe

³⁺

).

Zeolites are microporous crystalline materials due to the presence of large and small reticular cavities (α and β cages, respectively). These cages are connected to each other to form regular arrays of channels. As visible in Figure 1, the silica and alumina tetrahedra, connected together by shared oxygen atoms, give rise in clinoptilolite to three types of channels that are organized in form of a two-dimensional array. In particular, the A-type (openings: 3.1–7.5 Å) and B-type (openings: 3.6–4.6 Å) channels are parallel to each other and parallel to the c-axis, while the C-type channels (openings: 2.8–4.7 Å), which are parallel to the a-axis, perpendicularly intersect the A and B channels.

Zeolites are microporous crystalline materials due to the presence of large and small reticular cavities (α and β cages, respectively). These cages are connected to each other to form regular arrays of channels. As visible in Figure 1, the silica and alumina tetrahedra, connected together by shared oxygen atoms, give rise in a very common zeolite type named clinoptilolite to three types of channels that are organized in form of a two-dimensional array. In particular, the A-type (openings: 3.1–7.5 Å) and B-type (openings: 3.6–4.6 Å) channels are parallel to each other and parallel to the c-axis, while the C-type channels (openings: 2.8–4.7 Å), which are parallel to the a-axis, perpendicularly intersect the A and B channels.

Fig. 1 - Schematic representation of the channels structure in clinoptilolite crystals.

Extra-framework cations and adsorbed water molecules are located inside these channels, both close to the aluminum atoms. Owing to the strong electrostatic interaction (Coulomb’s forces) acting between the extra-framework cations and the negatively charged aluminum atoms, these cations practically do not move under the effect of an electric field at room temperature. Actually, the negative charge is not wholly localized on the aluminum atoms, but it is spread by the mesomeric effect on a ‘nucleophilic area’, including the aluminum atom and the four neighboring oxygen atoms. Differently, at high temperatures, cations with a low charge density (i.e., K⁺ or Na⁺) have enough energy for hopping among neighboring empty nucleophilic areas. Empty nucleophilic areas are contained in the zeolite framework because of the bivalent cations, the presence of which leaves a number of locally unbalanced negative sites in the covalent crystal. Such electric behaviour of zeolite is potentially useful for a number of devices activated by temperature (e.g., thermal switches, thermistors, temperature sensors, etc.).

2. Electrical conductivity of zeolite

2.1 Vučelić conduction model

Zeolites have unique physical properties resulting from their unusual chemical structure. Vučelić defined the extraordinary crystalline structure of zeolite as a ‘reverse’ metallic lattice^[13]. According to the electrical conduction model proposed by Vučelić in 1977^[24][35], only those extra-framework charges capable of moving in the ‘free ionic conduction zones’, i.e., the free cationic conduction bands located exactly in the middle of crystal channels, can promote electrical transport trough the ceramic material. Indeed, ions at the centers of cavities are effective carriers of current since they move through the zeolite crystal with only minimal activation energy. This interesting model proposed by Vučelić constitutes an analogous depiction of the behavior of electrons in a fixed cationic electromagnetic field and their electrical conduction mechanism. Therefore, Vučelić has conformed zeolites to the commonly adopted representation of electrical transport in metallic crystal structures.

2.1 Theoretical treatment

The electrical properties of zeolites mainly depend on the contained monovalent metal ions (Me⁺) because they are less strongly held by the negatively charged lattice and can easily migrate between two neighboring negative sites through the free ionic conduction zones. In mMore detailgenerally, the electrical conductivity of clinoptilolite, σ(T), depends only on the following three factors: (i) charge of the electrical carriers: Ze⁻, where e⁻ is the elementary charge (e⁻ = 1.602 10⁻¹⁹ C); (ii) concentration of the electrical carriers: [Me^Z+]; and (iii) mobility of the electrical carriers: μ, according to the following physical law: σ(T) = Σ_i[Z_i∙e⁻∙[Me^z+]_i∙μ_i], where the sum is formally extended to all extra-framework cations present in the substance. However, for thea clinoptilolite-K,Ca sample, potassium ions located in the super-cages are almost exclusively involved in the migration under an applied sinusoidal field. Indeed, the contribution of Ca²⁺ cations is negligible because they have an electrical charge larger than K⁺ and are present in the clinoptilolite sample at a lower concentration. (iIn addition, iron does not participate in the electrical transport mechanism because it is mostly located in the framework, isomorphous substitution, just like in the case of aluminum atoms, while its ionic form (Fe³⁺) has a very large electrical charge and stably adheres to the crystal framework). Finally, it is possible to approximately write:

σ(T)=e^-·[K⁺]*·μ_K+

where [K⁺]* is the molar concentration of the excited K⁺ cations present in the system at T temperature. Each K⁺ ion is located in a potential well (the ‘nucleophilic area’), the walls of which are represented by the four negatively charged oxygen atoms located close to the aluminum atom. The concentration of excited K⁺ present at a zeolite cage/channel center is a temperature-dependent quantity; indeed, [K⁺]* increases with increasing temperature, thus determining an increase in the zeolite electrical conductivity. In particular, the dependence of [K⁺]* on temperature is given by the following expression:

[K⁺]* =[K⁺]_tot/(1+exp(ΔG°/RT))

3. NTC-devices based on zeolite

Materials adequate for fabricating NTC devices (e.g., a thermal switch capable of turning on reversibly by heating) must have quite a low electrical conductivity at service temperature (e.g., room temperature) and show significant/rapid change in such a value with increasesing in temperature. This device type could be based on zeolites; however, for showing this special electrical behaviour, the Si/Al atomic ratio is a critical parameter and it needs to have a convenient value because zeolite electrical conductivity strictly depends on it. Among the natural zeolite types, clinoptilolite mineral seems to be the best choice for this application because it has an intermediate value of Si/Al atomic ratio, which is capable of guaranteeing electrical insolation at room temperature and a significant electrical conductivity increase with heating (good electrical conductor at high temperature). Indeed, the Si/Al atomic ratio typically ranges from 3.5 to 7 in natural zeolites, and it falls close to 5 for clinoptilolite mineral. In addition, this natural zeolite possesses a number of further useful characteristics that are strictly needed for fabricating inexpensive, stable, and robust devices. For example, clinoptilolite is one of the most common types of natural zeolite, widely available on the market at a very low cost. This material is non-toxic and biocompatible. In addition, differently from other nature-made zeolites, clinoptilolite has good thermal stability (in a wet environment also) and excellent mechanical proprieties for a natural ceramics material, due to the highly compact organization of lamellar crystals in its inner structure. These unique physical/chemical characteristics allow to use clinoptilolite for fabricating ver robust functional devices that are adequate for an industrial exploitation.

In order to verify the NTC-potentialities of zeolites, a naturobust functional devices that are very adequate for an inal clinoptilolite sample has been electrically characterized under the application of thermal pulses. As visible in Figure 2a, the application of a thermal pulse to this monolithic sample promptly generated an electrical micro-current in it. This micro-current grew very quickly with the increase in time after turning on the lamp. During the successive cooling step in air (i.e., turning off the incandescent lamp), the micro-current intensity readily decreased until it reached its starting value, negligibly. The resulting current intensity peak had quite an asymmetric profile because the process of sample cooling in air was slower than the previous heating process. In particular, the heating step followed a linear behavior (see inset in Figure 2b) with a slope of (13.8 ± 0.1) µA/s, while the cooling step followed a hyperbole law. Figure 2b shows the sample behavior under repeated heating/cooling cycles; as visible, four repeated cycles were unable to modify the electric behavior of these NTC materials. The higher value of current intensity that is usually recorded during the first heating step (see Figure 2b) probably represents a hysteresis in the electrical behavior of the dehydrated clinoptilolite sample. Indeed, before electrical characterization, the ceramic samples were only mildly dehydrated by using well-activated silica gel (activation conditions: 5 h at 150 °C under vacuum) and some water molecules (i.e., loosely-bound water) were still present inside the clinoptilolite channels. According to the Vučelić model of the ‘free ionic conduction zone’, these residual water molecules which are adsorbed on the surface of channel walls promote the electrical transport in the material. Differently, water molecules are mostly removed from the sample during the first heating step that takes place at quite high temperatures; therefore, the sample’s electrical conductivity results reduce in all the successive heating cycles of the electrical test, as shown in Figure 2b.

Figure 2. Temporal evolution of effective current intensity in the clinoptilolite sample with the turning on/off of the heat source (a) and NTC material behavior under repeated thermal pulses (b). Linearity of the temporal current intensity behavior is shown in the inset.

4. Conclusions

In conclusion, the clinoptilolite mineral is an electrically conductive material (strial exploitationingle charge carrier ionic conductor), and its impedance value has shown a strict dependence on temperature. In particular, surface impedance of clinoptilolite changes readily, substantially, linearly, and reversibly with heating in the temperature range of 25–120°C and above. This electrical performance allows us to suggest the use of NTC devices based on this zeolite type for AC electronic circuits applications as an alternative to traditional semiconductor-based devices.

In conclusion, the clinoptilolite mineral is an electrically conductive material (single charge carrier ionic conductor), and its impedance value has shown a strict dependence on temperature. In particular, surface impedance of clinoptilolite changes readily, substantially, linearly, and reversibly with heating in the temperature range of 25–120°C and above. This electrical performance allows us to suggest the use of NTC devices based on this zeolite type for AC electronic circuits applications as an alternative to traditional semiconductor-based devices.

This entry is adapted from the peer-reviewed paper 10.3390/ceramics7020029