Development of oxynitride glass-ceramics preparations and uses thereof

Abstract

A glass-ceramic material includes an oxynitride glass with a chemical formula Ca.sub.7Al.sub.14Si.sub.17OsN.sub.7 and zinc oxide. The zinc oxide is present in an amount of 8 to 16 percent by weight based on the total weight of the glass-ceramic material. The zinc oxide is doped in the oxynitride glass. The glass-ceramic material has one or more conductive channels having a length of 100 to 1000 m and a width of 0.5 to 10 m.

Claims

1. A glass-ceramic material, comprising: an oxynitride glass with a chemical formula Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7; and zinc oxide, wherein the zinc oxide is present in an amount of 8 to 16 percent by weight based on a total weight of the glass-ceramic material, wherein the zinc oxide is doped in the oxynitride glass, wherein the glass-ceramic material has one or more conductive channels having a length of 100 to 1000 m and a width of 0.5 to 10 m.

2. The glass-ceramic material of claim 1, wherein the one or more conductive channels have one or more distributary channels and the conductive channels form a conductive network.

3. The glass-ceramic material of claim 1, wherein the one or more conductive channels comprise voids having a length of 0.5 to 5 m and a width of 0.1 to 0.5 m.

4. The glass-ceramic material of claim 1, wherein the glass-ceramic material is made by a process comprising: heating a calcium oxide, an aluminum oxide, a silicon oxide, and a silicon nitride in an inert atmosphere to a temperature of 1500 to 1700 C. to form the oxynitride glass; grinding the oxynitride glass and adding zinc oxide to form a mixture; sintering the mixture at a pressure of 15 to 25 MPa and to a temperature of 500 to 1000 C. at a heating rate of 50 to 200 C./minute to form the glass-ceramic material; and polishing the glass-ceramic material.

5. The glass-ceramic material of claim 4, wherein the sintering is a spark plasma sintering process.

6. The glass-ceramic material of claim 1, wherein the glass-ceramic material has a density of 2.75 to 2.95 g cm.sup.3.

7. The glass-ceramic material of claim 1, wherein the glass-ceramic material has a thermal expansion of 4.5 to 5.0 ppm m.sup.1.

8. The glass-ceramic material of claim 1, wherein the glass-ceramic material has a thermal conductivity of 1.5 to 1.75 W m.sup.1 K.sup.1.

9. The glass-ceramic material of claim 1, wherein the glass-ceramic material has an atomic ratio of aluminum to aluminum and silicon of 0.4 to 0.5.

10. The glass-ceramic material of claim 1, wherein the glass-ceramic material further comprises europium.

11. The glass-ceramic material of claim 1, wherein the glass-ceramic material further comprises carbon nanotubes.

12. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 9 percent by weight zinc oxide and an activation energy of 0.6 to 0.8 eV.

13. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 15 percent by weight zinc oxide and an activation energy of 0.3 to 0.5 eV.

14. The glass-ceramic material of claim 11, wherein the glass-ceramic material has a DC conductivity value of 0.1 to 0.3 S/cm.

15. The glass-ceramic material of claim 1, wherein the conductive channels form a conductivity path that is an electron transfer path.

16. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 9 percent by weight zinc oxide and a hopping energy of 0.2 to 0.3 eV.

17. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 9 percent by weight zinc oxide and a structural disorder energy between jump sites of 0.8 to 1.0 eV.

18. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 15 percent by weight zinc oxide and a hopping energy of 0.1 to 0.2 eV.

19. The glass-ceramic material of claim 1, wherein the glass-ceramic material has 15 percent by weight zinc oxide and a structural disorder energy between jump sites of 0.4 to 0.6 eV.

20. The glass-ceramic material of claim 1, wherein the glass-ceramic material is conductive from 200 to 550 K.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) A more complete appreciation of this disclosure (including alternatives and/or variations thereof) and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:

(2) FIG. 1 is a flowchart depicting a method of forming a glass-ceramic material, according to certain embodiments.

(3) FIG. 2 depicts X-ray diffraction (XRD) patterns of glass (no Zn (0Zn)) and glass-ceramic materials (3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC), according to certain embodiments.

(4) FIG. 3A depicts a field emission scanning electron microscopy (FESEM) image of 0Zn at a scale of 20 m, according to certain embodiments.

(5) FIG. 3B depicts an FESEM image of 0Zn at a scale of 2 m, according to certain embodiments.

(6) FIG. 3C depicts an FESEM image of 3Zn at a scale of 100 m, according to certain embodiments.

(7) FIG. 3D depicts an FESEM image of 3Zn at a scale of 5 m, according to certain embodiments.

(8) FIG. 3E depicts an FESEM image of 6Zn at a scale of 100 m, according to certain embodiments.

(9) FIG. 3F depicts an FESEM image of 6Zn at a scale of 2 m, according to certain embodiments.

(10) FIG. 3G depicts an FESEM image of 9Zn at a scale of 100 m, according to certain embodiments.

(11) FIG. 3H depicts an FESEM image of 9Zn at a scale of 5 m, according to certain embodiments.

(12) FIG. 4A depicts an FESEM image of 15Zn at a scale of 100 m, according to certain embodiments.

(13) FIG. 4B depicts an FESEM image of 15Zn at a scale of 2 m, according to certain embodiments.

(14) FIG. 4C depicts an FESEM image of 15ZnC at a scale of 100 m, according to certain embodiments.

(15) FIG. 4D depicts an FESEM image of 15ZnC at a scale of 2 m, according to certain embodiments.

(16) FIG. 4E depicts an FESEM image of 15ZnC at a scale of 5 m, according to certain embodiments.

(17) FIG. 4F depicts an FESEM image of 15ZnC at a scale of 2 m, according to certain embodiments.

(18) FIG. 5 depicts infrared (IR) spectra of 0Zn, 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC, according to certain embodiments.

(19) FIG. 6A depicts an IR main band position against Al+Si content for 0Zn, 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC, according to certain embodiments.

(20) FIG. 6B depicts density dependence on Zn content for 0Zn, 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC, according to certain embodiments.

(21) FIG. 7 depicts AC conductivity versus temperature for 0Zn, 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC measured at 100 Hz at low- and high-temperature ranges, according to certain embodiments.

(22) FIG. 8A depicts AC conductivity spectra for exemplar temperatures with the Jonscher relation fit results obtained for low temperature measurements for 9Zn, according to certain embodiments.

(23) FIG. 8B depicts AC conductivity spectra for exemplar temperatures with the Jonscher relation fit results obtained for low temperature measurements for 15Zn, according to certain embodiments.

(24) FIG. 8C depicts AC conductivity spectra for exemplar temperatures with the Jonscher relation fit results obtained for high temperature measurements for 6Zn, according to certain embodiments.

(25) FIG. 8D depicts AC conductivity spectra for exemplar temperatures with the Jonscher relation fit results obtained for high temperature measurements for 9Zn, according to certain embodiments.

(26) FIG. 8E depicts AC conductivity spectra for exemplar temperatures with the Jonscher relation fit results obtained for high temperature measurements for 15Zn, according to certain embodiments.

(27) FIG. 9A depicts DC conductivity based on Jonscher power law (Eq. 1) as a function of temperature for 9Zn and 15Zn, according to certain embodiments.

(28) FIG. 9B depicts temperature dependence of the parameters from Eq. 1 for 9Zn and 15Zn, according to certain embodiments.

(29) FIG. 9C depicts DC conductivity for a low temperature range with the fitting of Eq. 2, according to certain embodiments.

(30) FIG. 9D depicts DC conductivity for a high temperature range with the fitting of Eq. 2, according to certain embodiments.

(31) FIG. 10A depicts electric modulus (M) versus frequency for exemplar temperatures for 0Zn, according to certain embodiments.

(32) FIG. 10B depicts electric modulus (M) versus frequency for exemplar temperatures for 3Zn, according to certain embodiments.

(33) FIG. 10C depicts electric modulus (M) versus frequency for exemplar temperatures for 6Zn, according to certain embodiments.

(34) FIG. 10D depicts variations of t as a function of temperature for 0Zn, 3Zn and 6Zn, according to certain embodiments.

DETAILED DESCRIPTION

(35) In the following description, it is understood that other embodiments may be utilized, and structural and operational changes may be made without departure from the scope of the present embodiments disclosed herein.

(36) Reference will now be made to specific embodiments or features, examples of which are illustrated in the accompanying drawings. In the drawings, whenever possible, corresponding or similar reference numerals will be used to designate identical or corresponding parts throughout the several views. Moreover, references to various elements described herein are made collectively or individually when there may be more than one element of the same type. However, such references are merely exemplary in nature. It may be noted that any reference to elements in the singular may also be constructed to relate to the plural and vice-versa without limiting the scope of the disclosure to the exact number or type of such elements unless set forth explicitly in the appended claims.

(37) When describing the present disclosure, the terms used are to be construed in accordance with the following definitions, unless a context dictates otherwise.

(38) Embodiments of the present invention will now be described more fully hereinafter with reference to the accompanying drawings wherever applicable, in that some, but not all embodiments of the disclosure are shown.

(39) In the drawings, reference numerals designate identical or corresponding parts throughout the several views. Further, as used herein, the words a, an, and the like generally carry a meaning of one or more, unless stated otherwise.

(40) Furthermore, the terms approximately, approximate, about, and similar terms generally refer to ranges that include the identified value within a margin of 20%, 10%, or preferably 5%, and any values therebetween.

(41) As used herein, the term oxynitride glass(es) refers to materials formed by the replacement of oxygen atoms by nitrogen in silicate and aluminosilicate glasses in various M-SiON, M-SiAlON, and M-SiMgON systems, where M is a modifying cation such as Mg, Ca, Ba, Sc, Y, and rare earth lanthanides. Oxynitride glasses are silicate or aluminosilicate glasses in which oxygen atoms in the glass network are partially replaced by nitrogen atoms. As nitrogen increases, glass transition temperature, clastic modulus, viscosity, and hardness increase while a thermal expansion coefficient decreases. As used herein, an oxynitride glass may be those made of Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7.

(42) As used herein, the term spark plasma sintering (SPS) refers to a technique for consolidating powder materials by the application of pulsed direct current and axial pressure concurrently to achieve a bulk of a material at a fast rate. SPS also refers to a sintering technique that is used to synthesize glass ceramic materials. SPS is a sintering technique for the densification of ceramic matrix composites. SPS may use pulsed or unpulsed DC or AC current to directly pass current through a graphite die and a powder compact to form a product.

(43) As used herein, the samples may be glass or pristine glass without zinc oxide (0Zn) in Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7, zinc oxide-doped oxynitride glass, Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7, also referred as ceramic glasses, with doping such as 3Zn (3 wt. % ZnO), 6Zn (6 wt. % ZnO), 9Zn (9 wt. % ZnO), 15Zn (15 wt. % ZnO), and 15ZnC (15 wt. % ZnO doped with carbon nanotubes).

(44) As used herein, 0Zn is referred to as pristine glass or glass, while 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC are referred to as glass-ceramics comprising Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 doped with 3 wt. % ZnO, 6 wt. % ZnO, 9 wt. % ZnO, 15 wt. % ZnO, and 15 wt. % ZnO doped with carbon nanotubes, respectively.

(45) As used herein, .sub.DC denotes the frequency-independent direct current (DC) conductivity, and its dependance with frequency part of conductivity is denoted as (), given by Jonscher power law as in Eq. 1.

(46) As used herein, the parameters are calculated as per the equations shown in the examples and references therein.

(47) The present disclosure is intended to include all hydration states of a given compound or formula, unless otherwise noted or when heating a material.

(48) Unless otherwise noted, the present disclosure is intended to include all isotopes of atoms occurring in the glasses and ceramic glasses used herein. Isotopes include those atoms having the same atomic number but different mass numbers.

(49) Aspects of the present disclosure are directed to ZnO-doped Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 glass-ceramic materials prepared by a spark plasma sintering (SPS) technique. The effect of ZnO on microstructure, density, thermal conductivity, thermal expansion coefficient, and electrical properties are evaluated. Addition of ZnO to the glass or glass-ceramic materials has an impact on the electrical conductivity of the glass-ceramic materials and may find application in advanced engineering and energy storage.

(50) A glass-ceramic material is described. The glass ceramic material includes an oxynitride glass with a chemical formula Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7. Oxynitride glasses are types of silicates or aluminosilicates formed in two systems, and can occur in M-SiON, M1-M2-SiON, M-SiAlON, and M1-M2-SiAlON systems where M, M1, and M2 are modifying cations such as alkali metals (Li, Na, K), alkaline earth metals (Mg, Ca, Ba, Sr), Y, La, and rare earth lanthanides. Examples of the oxynitride glasses include, but not limited to, CaSiAlON, NaCaSiON, LaSiAlON, LiNaKBSiON, CeSiON, CeAlSiON, NaBSiON, LiSiAlON, BeSiAlON, MgSiAlON, SiAlON, LiMgSiAlON, CeMgSiAlON, MgBaSiAlON, YSiAlON, MnSiAlON, NdSiAlON, NaBAlPON, KSiON, Si-M-ON(where M is an alkaline earth metal), SiON, NaSiON, MgSiON, LaSiON, silicates (such as LiSiON and CaSiAlON), borates (such as NaBON), phosphates (such as LiPON, NaPON, KPON, and NaBaAlPON), a combination thereof, and the like.

(51) The oxynitride glass is doped with zinc oxide. In some embodiments, oxides that can be used as modifiers apart from zinc oxide include, but not limited to, B.sub.2O.sub.3, SiO.sub.2, GeO.sub.2, P.sub.2O.sub.5, V.sub.2O.sub.5, As.sub.2O.sub.3, Al.sub.2O.sub.3, Sb.sub.2O.sub.3, ZrO.sub.2, TiO.sub.2, PbO, Beo, ZnO, MgO, Li.sub.2O, BaO, CaO, Na.sub.2O, SrO, K.sub.2O, combinations thereof, and the like. In some embodiments, oxides that can be used as modifiers may be used in place of or in combination with zinc oxide (ZnO). In a preferred embodiment, the zinc oxide is present in an amount of 8 to 16 percent by weight (wt. %), preferably 1 to 20 wt. %, preferably 2 to 18 wt. %, preferably 3 to 15 wt. %, preferably 6 to 12 wt. %, and preferably 8 to 10 wt. % based on the total weight of the glass-ceramic material. In some embodiments, the zinc oxide has a weight percentage of about 3 wt. %, preferably about 6 wt. %, preferably about 9 wt. %, and preferably about 15 wt. % in the glass ceramic material. The zinc oxide is doped in the oxynitride glass. The glass-ceramic material has one or more conductive channels having a length of 100 to 1000 m, preferably 200 to 900 m, preferably 300 to 800 m, preferably 400 to 700 m, preferably 500 to 600 m and a width of 0.5 to 10 m, preferably 1 to 9 m, preferably 2 to 8 m, preferably 3 to 7 m, preferably 4 to 6 nm. In some embodiments, the glass-ceramic material includes carbon nanotubes. In some embodiments, the glass-ceramic material includes 2 to 20 wt. % carbon nanotubes, preferably 5 to 18 wt. % carbon nanotubes, preferably 8 to 17 wt. % carbon nanotubes, preferably 12 to 16 wt. % carbon nanotubes, and preferably about 15 wt. % carbon nanotubes based on the total weight of the glass-ceramic material.

(52) In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of calcium in the range of 1-10 at. %, preferably 2-9 at. %, preferably 3-8 at. %, more preferably 5-7.2 at. %, and yet more preferably about 6.6-7.2 at. %. In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of aluminum in the range of 10-20 at. %, preferably 11-18 at. %, more preferably 12-16 at. %, and yet more preferably about 13.2-15.9 at. %. In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of silica in the range of 10-20 at. %, preferably 11-18 at. %, preferably 12-16 at. %, more preferably 13-18 at. %, and yet more preferably about 15.9-17.5 at. %. In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of europium in the range of 0-0.2 at. %, preferably 0.05-0.15 at. %, more preferably 0.09-0.12 at. %, and yet more preferably about 0.1-0.11 at. %. In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of oxygen in the range of 50-60 at. %, preferably 52-58 at. %, more preferably 53-55 at. %, and yet more preferably about 53-53.6 at. %. In some embodiments, the glass-ceramic material has an atomic percentage (at. %) of nitrogen in the range of 1-10 at. %, preferably 2-9 at. %, preferably 3-8 at. %, more preferably 4-7.5 at. %, and yet more preferably about 6.6-7.2 at. %.

(53) In an embodiment, the zinc oxide has a weight percentage of 0 wt. % (0Zn) in the glass ceramic material and the glass ceramic material comprises about 7.2 at. % of calcium, about 14.4 at. % aluminum, about 17.5 at. % of silicon, 0 at. % zinc, about 0.1 at. % europium, about 53.6 at. % oxygen, and about 7.2 at. % nitrogen, based on a total atom count of the glass ceramic material. In an embodiment, the zinc oxide has a weight percentage of about 3 wt. % in the glass ceramic material and the glass ceramic material comprises about 7.1 at. % of calcium, about 14.2 at. % aluminum, about 17.2 at. % of silicon, about 0.8 at. % zinc, about 0.1 at. % europium, about 53.6 at. % oxygen, and about 7.1 at. % nitrogen, based on a total atom count of the glass ceramic material. In an embodiment, the zinc oxide has a weight percentage of about 6 wt. % in the glass ceramic material and the glass ceramic material comprises about 7 at. % of calcium, about 13.9 at. % aluminum, about 16.9 at. % of silicon, about 1.6 at. % zinc, about 0.1 at. % europium, about 53.5 at. % oxygen, and about 7 at. % nitrogen, based on a total atom count of the glass ceramic material. In an embodiment, the zinc oxide has a weight percentage of about 9 wt. % in the glass ceramic material and the glass ceramic material comprises about 6.8 at. % of calcium, about 13.7 at. % aluminum, about 16.6 at. % of silicon, about 2.4 at. % zinc, about 0.1 at. % europium, about 53.5 at. % oxygen, and about 6.8 at. % nitrogen, based on a total atom count of the glass ceramic material. In an embodiment, the zinc oxide has a weight percentage of about 15 wt. % in the glass ceramic material and the glass ceramic material comprises about 6.6 at. % of calcium, about 13.2 at. % aluminum, about 16 at. % of silicon, about 4.1 at. % zinc, about 0.1 at. % europium, about 53.3 at. % oxygen, and about 6.6 at. % nitrogen, based on a total atom count of the glass ceramic material. In another embodiment, the zinc oxide has a weight percentage of about 15 wt. % and the carbon nanotubes have a weight percentage of about 15 wt. % in the glass ceramic material and the glass ceramic material comprises about 6.6 at. % of calcium, about 13.1 at. % aluminum, about 15.9 at. % of silicon, about 4.1 at. % zinc, about 0.11 at. % europium, about 0.6 at. % carbon, about 53 at. % oxygen, and about 6.6 at. % nitrogen, based on a total atom count of the glass ceramic material.

(54) In some embodiments, the Al/(Al+Si) ratio in the glass-ceramic material is in the range of 0.2-1, preferably 0.25-0.9, preferably 0.3-0.8, preferably 0.35-0.7, preferably 0.4-0.6, more preferably 0.45-0.5, and yet more preferably about 0.45, and all ranges in between. In a preferred embodiment, the Al/(Al+Si) ratio in the glass-ceramic material is about 0.45.

(55) Referring to FIG. 1, a flowchart of a method 100 of preparing the glass-ceramic material is described. The order in which the method 100 is described is not intended to be construed as a limitation, and any number of the described method steps may be combined in any order to implement the method 100. Additionally, individual steps may be removed or skipped from the method 100 without departing from the spirit and scope of the present disclosure.

(56) At step 102, the method 100 includes heating a calcium oxide, an aluminum oxide, a silicon oxide, and a silicon nitride to a temperature of 1500 to 1700 C., preferably 1550 to 1690 C., more preferably 1600 to 1670 C., and yet more preferably about 1650 C., in an inert atmosphere to form a first mixture. Each of the calcium oxide, the aluminum oxide, the silicon oxide, and the silicon nitride have a purity of at least 99%, preferably at least 99.5%, and more preferably at least 99.9%. In some embodiments, the inert atmosphere may comprise helium, nitrogen, neon, argon, krypton, xenon, radon, and the like. In a preferred embodiment, the inert atmosphere is a nitrogen atmosphere.

(57) At step 104, the method includes grinding the oxynitride glass and adding zinc oxide to form a mixture. In some embodiments, grinding may occur manually, mechanically, and/or by any methods known in the art.

(58) At step 106, the method 100 includes sintering the mixture at a pressure of 15 to 25 MPa, preferably 16 to 24 MPa, preferably 17 to 23 MPa, preferably 18 to 22 MPa, more preferably 19 to 21 MPa, and yet more preferably about 20 MPa and to a temperature of 500 to 1000 C., preferably 600 to 975 C., preferably 700 to 950 C., preferably 800 to 925 C., more preferably 890 to 910 C., and yet more preferably about 900 C. at a heating rate of 50 to 200 C./minute, preferably 55 to 190 C./minute, preferably 60 to 180 C./minute, preferably 65 to 170 C./minute, preferably 70 to 160 C./minute, preferably 80 to 150 C./minute, preferably 85 to 140 C./minute, preferably 90 to 130 C./minute, preferably 93 to 120 C./minute, preferably 95 to 110 C./minute, more preferably 98 to 105 C./minute, and yet more preferably about 100 C./minute to form the glass-ceramic material. In some embodiments, the mixture is sintered by SPS. As used herein, spark plasma sintering (SPS), which is also known as field assisted sintering technique (FAST) or pulsed electric current sintering (PECS), is a sintering technique, in which the pulsed DC current directly passes through a graphite die, as well as the mixture, in case of conductive samples. Joule heating has been found to play a role in the densification of powder compacts, achieving near theoretical density at lower sintering temperatures than conventional sintering techniques. The heat generation is internal, in contrast to the conventional hot pressing, where external heating elements provide the heat. This facilitates a high heating or cooling rate, and the sintering process may be fast. The general speed of the process has the potential to densify powders/mixtures with nanosize or nanostructure while avoiding coarsening, which accompanies standard densification routes.

(59) The mixture is fed directly into a graphite die without a pre-compaction step (e.g., by vibration or applying suitable pressure). The graphite die has a thickness of about 10-30 mm, preferably 15-25 mm, and more preferably about 20 mm. The die containing the mixture may be placed directly in an SPS chamber or furnace, and spacers may be used, if necessary. In some embodiments, a thin graphite foil, preferably a graphite film/sheet, is used as a spacer between the mixture and the die to facilitate sample ejection after sintering, to reduce the friction between the die walls and the mixture, and to prevent punch wear. In some embodiments, the graphite sheet has a thickness of 0.2-0.4 mm, preferably 0.22-0.38 mm, preferably 0.24-0.36 mm, preferably 0.26-0.34 mm, preferably 0.28-0.32 mm, and preferably about 0.3 mm. In a preferred embodiment, the graphite sheet has a thickness of about 0.35 mm. In some embodiments, the SPS chamber is closed, and the sintering is carried out in an inert atmosphere, preferably an argon atmosphere, with a partial vacuum at a pressure of no higher than 100 MPa being applied in the chamber, preferably 10-100 MPa, preferably 15-95 MPa, preferably 20-90 MPa, preferably 25-85 MPa, preferably 30-80 MPa, preferably 35-75 MPa, preferably 40-70 MPa, preferably 45-65 MPa, preferably 50-60 MPa, and preferably about 55 MPa. In a preferred embodiment, the sintering is carried out with a constant uniaxial pressure of about 20 MPa. In some embodiments, the SPS heating occur for 2-20 minutes, preferably 5-15 minutes, and more preferably about 10 minutes. At step 108, the method 100 includes polishing the glass-ceramic material. The glass ceramic material is further ground on a diamond disk to remove a graphite film used in the SPS.

(60) The mixture may be contaminated with traces of graphite. This may be removed using SiC abrasives, preferably SiC papers of varying grit sizes from 120 to 1200, preferably 150 to 1100, preferably 200 to 1000, preferably 300 to 900, preferably 400 to 800, preferably 500 to 700, and preferably about 600. In some embodiments, the glass-ceramic material is further polished using a polishing cloth with a diamond paste solution down to about a 1 m finish.

(61) In an embodiment, the glass-ceramic material has one or more conductive channels having a length of 100 to 1000 m, preferably 150 to 950 m, preferably 200 to 900 m, preferably 250 to 850 m, preferably 300 to 700 m, preferably 350 to 650 m, preferably 400 to 600, preferably 450 to 500, and preferably about 500 m and a width of 0.5 to 10 m, preferably 1 to 9 m, preferably 2 to 8 m, preferably 3 to 7 m, preferably 4 to 6 m, and preferably about 5 m. In some embodiments, the one or more conductive channels comprise voids having a length of 0.5 to 5 m, preferably 1 to 4 m, and preferably 2 to 3 m and a width of 0.1 to 0.5 m, preferably 0.2 to 0.4 m, and preferably 0.25 to 0.3 m. In some embodiments, the conductive channels form a conductivity path that is an electron transfer path. In some embodiments, one or more conductive channels have one or more distributary channels, and the one or more conductive channels form a conductive network. In some embodiments, the one or more conductive channels may be straight, curved, in the form of a wave, and any other form known in the art. In some embodiments, the one or more distributary channels may be straight, curved, in the form of a wave, and any other form known in the art. In some embodiments, the one or more distributary channels may connect the one more conductive channels. In some embodiments, the one or more distributary channels are conductive.

(62) In some embodiments, the glass-ceramic material has a density of 2.75 to 2.95 g cm.sup.3, preferably 2.80 to 2.90 g cm.sup.3, and preferably about 2.85 g cm.sup.3. In some embodiments, the glass-ceramic material has a thermal expansion of 4.5 to 5.0 ppm m.sup.1, preferably 4.6 to 4.9 ppm m.sup.1, preferably 4.7 to 4.8 ppm m.sup.1, and preferably about 4.6 ppm m.sup.1. In some embodiments, the glass-ceramic material has a thermal conductivity of 1.5 to 1.75 W m.sup.1 K.sup.1, preferably 1.55 to 1.70 W m.sup.1 K.sup.1, and preferably 1.6 to 1.65 W m.sup.1 K.sup.1.

(63) In some embodiments, the glass-ceramic material has 9 percent by weight zinc oxide and an activation energy of 0.6 to 0.8 eV, preferably 0.65 to 0.75 eV, more preferably 0.68 to 0.7 eV, and yet more preferably about 0.69 eV. In some embodiments, the glass-ceramic material has 15 percent by weight zinc oxide and an activation energy of 0.3 to 0.5 eV, preferably 0.35 to 0.45 eV, more preferably 0.41 to 0.43 eV, and yet more preferably about 0.42 eV. In some embodiments, the glass-ceramic material has a DC conductivity value of 0.1 to 0.3 S/cm, preferably 0.15 to 0.25 S/cm, more preferably 0.19 to 0.21 S/cm, and yet more preferably about 0.2 S/cm. In some embodiments, the glass-ceramic material has 9 percent by weight zinc oxide and a hopping energy of 0.2 to 0.3 eV, preferably 0.22 to 0.26 eV, more preferably 0.23 to 0.25 eV, and yet more preferably about 0.24 eV. In some embodiments, the glass-ceramic material has 9 percent by weight zinc oxide and a structural disorder energy between jump sites of 0.8 to 1.0 eV, preferably 0.85 to 0.95 eV, more preferably 0.89 to 0.91 eV, and yet more preferably about 0.9 eV. In some embodiments, wherein the glass-ceramic material has 15 percent by weight zinc oxide and a hopping energy of 0.1 to 0.2 eV, preferably 0.12 to 0.18 eV, more preferably 0.15 to 0.17 eV, and yet more preferably about 0.16 eV. In some embodiments, wherein the glass-ceramic material has 15 percent by weight zinc oxide and a structural disorder energy between jump sites of 0.4 to 0.6 eV, preferably 0.45 to 0.55, more preferably 0.51 to 0.53 eV, and yet more preferably about 0.52 eV. In some embodiments, the glass-ceramic material is conductive from 200 to 550 K, preferably 250 to 500 K, preferably 300 to 450 K, and preferably 350 to 400 K.

(64) The glass or the glass-ceramic material of the present disclosure may be used in smart devices, electronic devices, electrical appliances, home appliances, kitchen wares, and the like.

EXAMPLES

(65) The following examples demonstrate a glass-ceramic material, as described herein. The examples are provided solely for illustration and are not to be construed as limitations of the present disclosure, as many variations are possible without departing from the spirit and scope of the present disclosure.

Example 1: Materials

(66) The Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 (at. %) based oxynitride glass was prepared using high-purity (99.9%) oxides of CaO, (Alfa Aesar GmbH & Co), Al.sub.2O.sub.3 (ChemPur GmbH), SiO.sub.2 (ABCR GmbH & Co), and Si.sub.3N.sub.4 (99% ChemPur GmbH) as a source of nitrogen.

Example 2: Synthesis of Zinc Oxide Doped Calcium-Aluminosilicate Oxynitride Glass-Ceramics

(67) A precursor mixture was placed in an Nb crucible and heated in a nitrogen atmosphere up to the final temperature of 1650 C. The glass composition was obtained by electron microprobe analysis (EMPA) with a JEOL 8500F instrument operating at 12 kV and 30 nA. ZnO was added to the re-grinded glass matrix prior to the spark plasma sintering (SPS) (HP D5, FCT Systems, Frankenblick, Germany). 5 grams (g) of Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 glass powder was mixed with 3, 6, 9, and 15 wt. % of ZnO. Additionally, 15 wt. % carbon nanotubes (CNT) were doped with 15 wt. % ZnO and 5 grams of Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 glass powder. A trace amount (0.05 g) of Eu.sub.2O.sub.3 was also added to each sample as a nucleation agent. The details about the sintering process and sample IDs are listed in Table 1. The IDs of samples are correlated with the added wt. % of ZnO, respectively: 0Zn, 3Zn, 6Zn, 9Zn, 15Zn, 15ZnC.

(68) A mixture of ZnO and Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 powder was poured into a 20 mm graphite die. A constant uniaxial pressure of 20 MPa was applied at room temperature before sintering at 900 C. (just below the pristine glass transition temperature, 940 C.). The heating rate was 100 C./min, and the soaking time was 10 minutes. The sintering process was performed in a vacuum with an initial pressure of 510.sup.2 mbar [Irshad, H. M. et al., Effect of Ni content and Al.sub.2O.sub.3 particle size on the thermal and mechanical properties of Al.sub.2O.sub.3/Ni composites prepared by spark plasma sintering, Int J Refract Hard Met., 2018, 76, 25-32; and Hakeem, A. S. et al., Synthesis and characterization of alkaline earth and rare earth doped sialon Ceramics by spark plasma sintering, Int J Refract Hard Met., 2021, 97, which are incorporated herein by references in their entireties] Synthesized glass-ceramics disks, approximately 20 mm in diameter and 5 mm thick, were produced. Further synthesis and characterization details are given in references [Ali, S. et al., Issues associated with the development of transparent oxynitride glasses, Ceram. Int., 2015, 41, 3345-3354; Ali, S. and Jonson, B., Glasses in the BaSiON System, J. Am. Ceram. Soc., 2011, 94, 2912-2917; Sharafat, A. and Bo, J., Compositional effects on the properties of high nitrogen content alkaline-earth silicon oxynitride glasses, AE=Mg, Ca, Sr, Ba, J. Eur. Ceram. Soc., 2011, 31, 611-618; Sharafat, A. et al., Formation and properties of nitrogen-rich strontium silicon oxynitride glasses, J. Mater. Sci., 2009, 44, 664-670; and Sharafat, A. et al., Glass-forming region in the CaSiON system using CaH.sub.2 as Ca source, J. Eur. Ceram. Soc., 2008, 28, 2659-2664, which are incorporated herein by references in their entireties]. During the spark plasma sintering (SPS) process, a contamination layer formed on the sample surfaces due to the graphite sheet used. This layer was eliminated using SiC abrasive paper with grit sizes ranging from 120 to 1200. For microstructure analyses, a final polishing step was carried out using diamond polishing down to 1 m finish. Unlike conventional sintering techniques, the SPS process generates heat by passing a high-pulsed direct current through a graphite die and the sample to be sintered.

(69) Six glass-ceramic composites were synthesized using the spark plasma technique. Detailed compositional information is delineated in Table 1. The incorporation of ZnO and Eu.sub.2O.sub.3 was confirmed using SEM-EDX analysis. The ratios of Al/Si and Ca/(Al+Si) within each composition exhibit consistency, attaining values of 0.82 and 0.23, respectively. FIGS. 3A-3H and FIGS. 4A-4F show the morphology of the synthesized samples.

(70) TABLE-US-00001 TABLE 1 Sample designation, wt. % of ZnO doped, and SPS synthesis temperature and pressure ZnO doped Synthesized Pressure ID (wt. %) temperature ( C.) (MPa) G 0 NA NA 0Zn 0 900 20 3Zn 3 900 20 6Zn 6 900 20 9Zn 9 900 20 15Zn 15 600 18 15ZnC 15 600 18

Example 3: Characterization Study Using X-Ray Diffraction (XRD) Spectroscopy

(71) The physical properties, such as phase composition, crystal structure, and orientation of powder, solid, and liquid samples, were analyzed by XRD spectroscopy. The amorphous/crystalline nature of the pristine Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 sample and glass-ceramics after melting and sintering with the SPS process, respectively, were verified by powder X-ray diffraction, using a Panalytical Xpert PRO MPD diffractometer and Cu(K.sub.) radiation (=154.1 m). Microstructure observations were conducted using an optical microscope (DSX510, Olympus, Japan) and a scanning electron microscope (JSM-7000F, JEOL, Japan with Schottky-type FEG) equipped with an energy-dispersive X-ray spectrometer (EDS detector, Oxford Instruments, UK). The scanning electron microscope (SEM) was operated at acceleration voltages of 15 kV, and specimen images were captured in backscattered electron mode. The samples were analyzed using XRD (2/min from 10 to 100). Results of XRD and SEM analysis support that increasing the amount of Zn increases the crystallinity in the glass matrix.

(72) The structure of the samples was examined using the XRD technique, and the obtained diffractograms after normalization are presented in FIG. 2. The initial oxynitride glass G, Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 (not shown), and comparative sample 0Zn exhibit a characteristic amorphous halo observed in glasses. ZnO-doped samples 3Zn, 6Zn, 9Zn, 15Zn, and 15ZnC display amorphous halos and sharp reflections, indicating the presence of different crystalline phases. The intensities and widths of these reflections vary with the ZnO content in the glass matrix. ZnO is also observed as a separated crystal in XRD analysis.

(73) Microstructure observations are depicted in FIG. 3A and FIG. 3B. The FESEM images of the 0Zn sample show a homogeneous topography of glass (FIG. 3A and FIG. 3B). Even a marginal addition of ZnO causes an alteration in the topography of the samples. Samples doped with ZnO exhibit inhomogeneities with elongated and narrow shapes, resembling paths. In the 3Zn sample, the apparent inhomogeneities accumulated in the form of paths are discontinuous and short (FIG. 3C). Upon closer examination, it is observed that the inhomogeneities lack a pronounced longitudinal orientation (FIG. 3D). A higher ZnO content causes an increase in the amount of inhomogeneities observed in both the 6Zn (FIG. 3E) and 9Zn (FIG. 3G) samples, which begin to form longer and more continuous paths. The continuity and longitudinality of the tracks are also visible at higher magnification for both samples (FIG. 3F and FIG. 3H for 6Zn and 9Zn, respectively).

(74) Upon doping with a higher amount of ZnO, no large differences in topography are visible for the 15Zn sample (FIGS. 4A and 4B) compared to the 9Zn sample; however, the simultaneous addition of carbon nanotubes and ZnO does affects the topography of the 15ZnC sample (FIGS. 4C-4F). In addition to a visible increase in the number of longitudinal inhomogeneities, thickening of the longitudinal inhomogeneities is also observed. Additionally, darker clusters derived from carbon nanotubes are visible (FIGS. 4E and 4F). Energy dispersive X-ray (EDX) microanalysis is a technique of elemental analysis associated with electron microscopy based on the generation of characteristic X-rays that reveal the presence of elements in the specimens [Scimeca, M. et al., Energy Dispersive X-ray (EDX) microanalysis: A powerful tool in biomedical research and diagnosis, Eur. J. Histochem., 2018, 62, 1, 2841, which is incorporated herein by reference in its entirety]. EDX analysis showed that the visible paths are well-conductive and are composed mostly of Zn and Eu. The remaining matrix surrounding the visible paths is a good dielectric consisting mainly of Si, Al, and Ca. O, N, and Eu are uniformly distributed throughout the sample.

(75) Based on the FESEM-EDX images, the phases that best matched the visible reflections were determined. For the 3Zn sample, two low-intensity reflections were associated with crystalline phases: SiO.sub.2 (reference code: 01-079-1914, ICSD collection code: 067125) and ZnAl.sub.2O.sub.4 [Hazen, R. M. et al., High-pressure crystal chemistry and amorphization of -quartz, Solid State Communications, 1989, 72, 507-511, which is incorporated herein by reference in its entirety] (reference code: 01-074-1138, ICSD collection code: 026856). For the 6Zn sample, an additional reflection related to ZnO (reference code: 01-079-0208, ICSD collection code: 065122) appears, but the ZnAl.sub.2O.sub.4 phase still dominates [Albertsson, J. et al., Atomic displacement, anharmonic thermal vibration, expansivity and pyroelectric coefficient thermal dependences in ZnO, Acta Crystallographica Section B, 1989, 45, 34-40, which is incorporated herein by reference in its entirety]. For higher ZnO dopant contents, the ZnO crystalline phase begins to dominate. The addition of carbon nanotubes changes the structure of the 15ZnC sample, in which a new crystal phase Ca.sub.2Al.sub.2SiO.sub.7 (reference code: 01-074-1607, ICSD collection code: 027427) [Korczak, P. and Raaz, F., Anz. Oesterr. Akad. Wiss., Math.-Naturwiss. Kl., 1967, 104, 383, which is incorporated herein by reference in its entirety] was observed. Additionally, a higher content of the ZnAl.sub.2O.sub.4 phase can be noticed.

Example 4: Infrared Spectroscopy of Glass and Ceramic Glasses

(76) Structure measurements using infrared (IR) spectroscopy were conducted utilizing a Frontier FTIR spectrometer from PerkinElmer. Samples for analysis were prepared by milling and compressing a mixture of the sample and KBr powders. The spectra were collected within the 400-4000 cm.sup.1 range, with a resolution of 4 cm.sup.1, averaging 64 scans. To facilitate a more accurate qualitative comparison, the displayed spectra were normalized to their maximum range in the mid-infrared region and underwent background correction. The estimated error in the infrared band position is 2 cm.sup.1.

(77) In the case of silicate glasses, the addition of aluminum is a glass-forming ingredient, not as a glass-modifying ingredient. This is true when the aluminum content is close to the silica content, as observed in the synthesized samples (Al/(Al+Si) ratio0.45). Additionally, aluminum and silicon have comparable masses and ionic ratios, which facilitates their vibrational coupling, which can be observed in IR spectra [Hwa, L.-G. et al., Infrared and Raman spectra of calcium alumino-silicate glasses, J. Non-Cryst. Solids., 1998, 238, 193-197; and Okuno, M. et al., Structure of SiO.sub.2Al.sub.2O.sub.3 glasses: Combined X-ray diffraction, IR and Raman studies, J. Non-Cryst. Solids., 2005, 351, 1032-1038, which are incorporated herein by references in their entireties]. The Al/Si ratio is similar throughout the glass-ceramic samples; therefore, the changes observed in the structure are correlated with the ZnO addition and lower Al+Si content. The effect of ZnO content on the structural properties of Al.sub.2O.sub.3SiO.sub.2 glass is observable because ZnO can act as a network modifier or network-forming agent, depending on its concentration. The introduction of Zn.sup.2+ cations into the glass may cause the breakage of bridge bonds, which may lead to the formation of non-bridging oxygens (NBO).

(78) FIG. 5 depicts IR spectra of the glass-ceramic materials. The materials exhibit rounded curves, characteristic of amorphous materials. In 0Zn, the dominant asymmetric band appears at 969 cm.sup.1 with a shoulder at 1150 cm.sup.1. The strongest high-frequency band and its envelope are attributed to SiO band vibrations in Q.sup.2 units (silicate tetrahedra with two non-bridging oxygen) and the Q.sup.4 units, respectively [Ali, S. et al., A novel approach for processing CaAlSiON glass-ceramics by spark plasma sintering: Mechanical and electrical properties, J. Eur. Ceram. Soc., 2022, 42, 96-104; and Kamitsos, E. I. et al., Vibrational study of the role of trivalent ions in sodium trisilicate glass, J. Non-Cryst. Solids., 1994, 171, 31-45, which are incorporated herein by references in their entireties]. The next distinct band appears at 692 cm.sup.1 and can be correlated with the network-substituted AlO.sub.4 polyhedra including condensed alumina octahedra or isolated alumina tetrahedra within the network of calcium aluminosilicate glass [Hwa, L.-G. et al., Infrared and Raman spectra of calcium alumino-silicate glasses, J. Non-Cryst. Solids., 1998, 238, 193-197; Okuno, M. et al., Combined X-ray diffraction, IR and Raman studies, J. Non-Cryst. Solids., 2005, 351, 1032-1038; and Kamitsos, E. I. et al., Vibrational study of the role of trivalent ions in sodium trisilicate glass, J. Non-Cryst. Solids., 1994, 171, 31-45, which are incorporated herein by references in their entireties]. The last visible band at 462 cm.sup.1 may be associated with the bending modes of bridging oxygen (BO) in the SiOSi and OSiO glass [Fondeur, F. and Mitchell, B. S., Infrared studies of preparation effects in calcium aluminate glasses, Journal of Non-Crystalline Solids, 1998, 224, 184-190; and Videau, J. J. et al., Structural approach of sialon glasses: M-SiAlON, J. Eur. Ceram. Soc., 1997, 17, 1955-1961, which are incorporated herein by references in their entireties]. The high-frequency band shifts towards lower frequencies as the ZnO content increases and the total Si and Al content decreases, compared to that observed in the 0Zn reference sample (FIG. 6A). In the 15ZnC sample containing CNT, in which the Si+Al content is slightly lower than in the 15Zn sample, the positions of the dominant band and the band at 930 cm.sup.1 are the most shifted in the spectra. This phenomenon is attributed to the gradual change in the SiO stretching frequency or the superposition of discrete bands arising from the Si(OAl).sub.x unit, where x is the number of aluminate tetrahedra adjacent to the silicate tetrahedron [Fondeur, F. and Mitchell, B. S., Infrared studies of preparation effects in calcium aluminate glasses, Journal of Non-Crystalline Solids, 1998, 224, 184-190; and Videau, J. J. et al., Structural approach of sialon glasses: M-SiAlON, J. Eur. Ceram. Soc., 1997, 17, 1955-1961, which are incorporated herein by references in their entireties]. Due to the consistent Al/Si ratio in the materials, the first situation of the gradual change in the SiO stretching frequency may be more likely. The shift of the main band to lower frequencies may be attributed to the progressive depolymerization of the silicate-aluminate network as a consequence of the Zn content increase. A new shoulder appears near 1037 cm.sup.1 with the gradual addition of at least 6 wt. % ZnO, which suggests the presence of Q.sup.3 units (silicate tetrahedra with one non-bridging oxygen) and an increase in the polymerization of glass network; however, the bands within the region of 800-1200 cm.sup.1 may be also attributed to ZnO.sub.4 stretching vibrations [Rashid, S. S. A. et al., Comprehensive study on effect of sintering temperature on the physical, structural and optical properties of Er3+ doped ZnO-GSLS glasses, Results in Physics, 2017, 7, 2224-2231, which is incorporated herein by reference in its entirety]. A band at 670 cm.sup.1 in samples with a higher ZnO content may also be correlated with the ZnOSi bending vibrations [Zaid, M. H. M. et al., Comprehensive study on compositional dependence of optical band gap in zinc soda lime silica glass system for optoelectronic applications, Journal of Non-Crystalline Solids, 2016, 449, 107-112; and Khalil, E. M. A. et al., Infrared absorption spectra of transition metals-doped soda lime silica glasses, Physica B: Condensed Matter, 2010, 405, 1294-1300, which are incorporated herein by references in their entireties] and the bands within the range of 400-460 cm.sup.1 may also correspond to the ZnO stretching vibrational bond in ZnO.sub.4 tetrahedral structures [Effendy, N. et al., Characterization and optical properties of erbium oxide doped ZnO SLS glass for potential optical and optoelectronic materials, Materials Express, 2017, 7, 59-65; Cui, H. et al., Nanoparticle Synthesis of Willemite Doped with Cobalt Ions (Co.sub.0.05Zn.sub.1.95SiO.sub.4) by an Epoxide-Assisted Sol-Gel Method, Chemistry of Materials, 2005, 17, 5562-5566, which are incorporated herein by references in their entireties]. In 15ZnC, the small bands around 580-600 cm.sup.1 may be due to ZnO symmetric stretching vibration [Zaid, M. H. M. et al., Synthesis and characterization of low cost willemite based glass-ceramic for opto-electronic applications, Journal of Materials Science: Materials in Electronics, 2016, 27, 11158-11167, which is incorporated herein by reference in its entirety]. Simultaneous changes in the relative intensity of the mentioned bands with increasing ZnO content for 9Zn, 15Zn, and 15ZnC indicate their relationship.

Example 5: Density, Thermal Conductivity, and Thermal Expansion of Glass and Glass Ceramics

(79) Densities were measured using Archimedes method on the glass and glass ceramics using water at 22 C. with (H.sub.2O)=0.998 g/cm.sup.3. Thermal conductivity was assessed using a thermal conductivity analyzer (C-THERM-TCi, Canada). The thermal conductivity of the specimens was measured at room temperature by applying transient but constant heat to the sample via a one-sided interfacial heat reflector sensor. To investigate thermal expansion, the Mettler Toledo instrument (TMA/SDTA-LF/1100) was employed to measure the coefficients of expansion of the synthesised samples at room temperature in the air environment. Smooth-surfaced samples were cut into cubes approximately 444 mm in size for the thermal expansion measurements.

(80) Measured densities for the pristine glass and glass-ceramics are given in Table 2. As shown in FIG. 6B, the density values vary between 2.75 and 2.93 g/cm.sup.3 and increase with increasing Zn content. The increase in density with the increase in Zn content may be attributed to the large atomic weight of the Zn atom. The data also show that pristine glass, doped with Zn and carbon nanotubes (CNT) (15ZnC) exhibits a low density that may be correlated with the low density of carbon nanotubes. Thermal conductivity, varying between 1.52 and 1.72 W.Math.m.sup.1.Math.K.sup.1, depends on the ZnO content (see Table 2). Thermal conductivity of materials is influenced by both their micro- and macrostructure. Crystals with long-range order generally exhibit higher thermal conductivity compared to their amorphous counterparts [Kittel, C., Interpretation of the Thermal Conductivity of Glasses, Physical Review, 1949, 75, 972-974; and Pertermann, M. et al., Transport properties of low-sanidine single-crystals, glasses and melts at high temperature, Contributions to Mineralogy and Petrology, 2008, 155, 689-702, which are incorporated herein by references in their entireties]. Long-range order facilitates propagation of vibrational modes. Thermal conductivity of glass decreases when the network structure is depolymerized. This decrease depends on both the types of network-forming cations (Si, B, Al) and modifying cations (alkali and alkaline earth metals) [Hiroshima, Y. et al., Thermal conductivity of mixed alkali silicate glasses at low temperature, J. Non-Cryst. Solids., 2008, 354, 341-344; Kim, Y. et al., The effect of borate and silicate structure on thermal conductivity in the molten Na.sub.2OB.sub.2O.sub.3SiO.sub.2 system, J. Non-Cryst. Solids., 2015, 415, 1-8; and Kim, Y. and Morita, K., Temperature dependence and cation effects in the thermal conductivity of glassy and molten alkali borates, J Non Cryst Solids., 2017, 471, 187-194, which are incorporated herein by references in their entireties]. In crystalline materials, grain boundaries lower macro-scale thermal conductivity due to phonon-phonon scattering [Sood, A. et al., Direct Visualization of Thermal Conductivity Suppression Due to Enhanced Phonon Scattering Near Individual Grain Boundaries, Nano Letters, 2018, 18, 3466-3472, which is incorporated herein by reference in its entirety]. Molecular dynamic simulations have indicated thermal conductivity of silica glass increases with a higher fraction of incorporated crystalline nano-threads and nano-plates [Kim, H. et al., Theoretical study of the thermal conductivity of silica glass-crystal composites, J. Am. Ceram. Soc., 2023, 106, 977-987, which is incorporated herein by reference in its entireties]. Similarly, incorporating crystalline MnO.sub.2 and Fe.sub.2O.sub.3 into cathode ray tube glass through powder sintering enhances thermal conductivity compared to melt-quenched counterparts with similar compositions [stergaard, M. B. et al., Influence of foaming agents on solid thermal conductivity of foam glasses prepared from CRT panel glass, J. Non-Cryst. Solids., 2017, 465, 59-64, which is incorporated herein by reference in its entirety]. Thermal expansion values (a) are given in Table 2, ranging between 6.4 and 4.5 ppm/m, and decreasing with increasing the ZnO content in the glass-ceramics. The 15ZnC sample doped with carbon nanotubes has also the lowest thermal expansion coefficient of 4.5 ppm/m. Thermal expansion values of glass-ceramic materials are influenced by the presence of voids and the breaking of bonds between constituents of the composite [Irshad, H. M. et al., Effect of Ni content and Al.sub.2O.sub.3 particle size on the thermal and mechanical properties of Al.sub.2O.sub.3/Ni composites prepared by spark plasma sintering, Int J Refract Hard Met., 2018, 76, 25-32, which is incorporated herein by reference in its entirety]. Glass-ceramics have lower thermal expansion value than ordinary glasses [Lunkenheimer, P. et al., Thermal expansion and the glass transition, Nature Physics, 2023, 19, 694-699, which is incorporated herein by reference in its entirety], due to the crystallization process reducing the amorphous (non-crystalline) content in the material, leading to a more stable and less expansive structure.

(81) TABLE-US-00002 TABLE 2 Details about sample composition, density (), thermal expansion (), and thermal conductivity (k) measured at room temperature (ppm/ k (W/ ID Composition (at. %) (g/cm.sup.3) m) m.sup.1 .Math. K.sup.1) G Ca.sub.7Al.sub.14Si.sub.17O.sub.52N.sub.7 2.748 6.4 NA 0Zn Ca.sub.7.2Al.sub.14.4Si.sub.17.5Eu.sub.0.1O.sub.53.6N.sub.7.2 2.747 5.2 1.52 3Zn Ca.sub.7.1Al.sub.14.2Si.sub.17.2Zn.sub.0.8Eu.sub.0.1O.sub.53.6N.sub.7.1 2.782 4.9 1.52 6Zn Ca.sub.7Al.sub.13.9Si.sub.16.9Zn.sub.1.6Eu.sub.0.1O.sub.53.5N.sub.7 2.832 4.8 1.54 9Zn Ca.sub.6.8Al.sub.13.7Si.sub.16.6Zn.sub.2.4Eu.sub.0.1O.sub.53.5N.sub.6.8 2.840 4.8 1.54 15Zn Ca.sub.6.6Al.sub.13.2Si.sub.16Zn.sub.4.1Eu.sub.0.1O.sub.53.3N.sub.6.6 2.937 4.6 1.72 15ZnC Ca.sub.6.6Al.sub.13.1Si.sub.15.9Zn.sub.4.1Eu.sub.0.11C.sub.0.6O.sub.53N.sub.6.6 2.682 4.5 NA

Example 6: Electrical Behavior of Glass and Glass Ceramics

(82) The electrical properties of samples were studied by the impedance spectroscopy method. Complex impedance measurements were performed using a Novocontrol Concept 40 broadband dielectric spectrometer Alpha-A, equipped with ZG4 dielectric interface in a frequency range from 10 mHz to 1 MHz and over a temperature range of 153 K to 623 K. A 1 Vrms AC voltage was applied in constant voltage mode. The temperature was incremented in steps of 10 K. Low-temperature measurements (153-473 K) were conducted in a nitrogen atmosphere using Quatro Cryosystem temperature-controlling system, while high-temperature measurements (373-623 K) were carried out in an air atmosphere using a high-temperature Novotherm HT 1600. The measurements involved multiple heating and cooling cycles in both the low- and high-temperature ranges. Gold electrodes were deposited via vacuum evaporation onto the polished, parallel surfaces of circular samples for electrical measurements.

(83) AC conductivity was studied at low-temperature (LT) and high-temperature (HT) regions under nitrogen and air atmospheres, respectively, and during heating and cooling. FIG. 7 displays temperature dependence of the samples at 100 Hz. AC conductivity mostly increases with an increase in temperature, which is observed for thermally activated conduction mechanisms like electron or ion hopping. For the 0Zn sample, the conductivity values are the lowest and were measurable only in the high temperature range above 373 K. The conduction process in this sample may result from the jumping of oxygen vacancies due to no other element being able to move in the glass aluminum-silicate matrix. Ca.sup.2+ ions are usually strongly bound to the glass network, but there is a possibility that a small amount of the Ca.sup.2+ ions move with oxygen vacancies. Adding a small amount of ZnO (3 wt. %) increases the conductivity by about one order of magnitude; therefore, it is possible to measure the AC conductivity at lower temperature ranges to 273 K for sample 3Zn. In the 3Zn sample, ZnO added in small amounts acts as a modifier in the glass lattice. The increase in ZnO increases the number of ions modifying the mobile lattice (Zn.sup.2+) in the glass and may also affect the content of oxygen vacancies; therefore, the conductivity increases. The increase in ZnO content in 6Zn also affects the conductivity. The ZnO in 6Zn is observed as a separated crystal in XRD, as SEM supports the presence of longer and more connected paths rich in Zn. In 6Zn, the conductivity exhibits measurable values (above 10.sup.12 S cm.sup.1) throughout the measured temperature range (from 153 K). The contribution to conductivity may have the free electron transport, which can occur in the crystalline ZnO phase. 9Zn exhibits AC conductivity values one order of magnitude higher than 6Zn. The conductivity values for 15Zn are in good agreement with sample 9Zn. The conductivity results from the content of crystalline ZnO. Electron conduction paths are more continuous and there are more electrons that are able to be transferred. Discrepancy in the conductivity measurement results observed for low-temperature measurements in nitrogen and high-temperature measurements in air for the last two samples (9Zn and 15Zn) may be correlated to the different electrodes used during the measurements: gold for low temperatures and platinum for high temperatures. The trend is changing, which may suggest that the conduction process is influenced by unlimited access to oxygen, which has a lowering effect at high temperatures (temperatures 373-423 K). This effect was not as pronounced in the case of samples with lower ZnO content. There is a possibility that in the 6Zn sample, the dominant conduction mechanism at low temperatures is electron transfer, and at high temperatures the access to oxygen changes the conduction mechanism to ionic. The sum of all processes occurring in the sample is obtained, the slower process dominates. This is why a decrease in conductivity is observed. Another explanation is that air relaxes the samples' structure due to the materials being synthesized in a vacuum during the manufacturing process; therefore, redox processes may occur, and the oxygen content in the sample may change. The structure in glass (0Zn) and 3Zn remains unchanged even after cooling after melting. 6Zn has a small amount of crystallinity; however, in ceramics produced in a vacuum, certain relaxation or oxidation processes may occur upon first contact with oxygen and simultaneous heating.

(84) FIG. 7 shows the AC conductivity spectra for exemplar temperatures measured for 3Zn, 6Zn, 9Zn, and 15Zn at low and/or high temperatures. The conductivity increases with frequency over the entire temperature range for the 6Zn sample. A frequency-independent area is not visible. The content of crystalline ZnO is not high enough to create continuous conduction paths. Additionally, part of Zn is involved in the formation of ZnAl.sub.2O.sub.4 crystals, which are not semiconductors. The conduction paths on 6Zn are discontinuous, hence the observation of only AC conductivity and no DC conductivity at measured frequency and temperature ranges. Similar behavior is found for 3Zn and 0Zn. In the 9Zn sample, the content of crystalline ZnO is high enough to form continuous conduction paths; therefore, there is a part of the DC conductivity distinct from the low-frequency region. The DC conductivity part is visible from a temperature of 233 K up to the temperature limit of 513 K. The DC conductivity increases its frequency range with increasing temperature and becomes dominant for high-temperature measurements compared to the AC part. For 15Zn, the DC conductivity dominates even at a low temperature range.

(85) The Jonscher power law, Eq. 1, was used to estimate DC conductivity values and other conduction parameters [Jonscher, A. K., The universal dielectric response, Nature, 1977, 267, 673-679; and Andrew, K. J., Dielectric relaxation in solids, Journal of Physics D: Applied Physics, 1991, 32, R57, which are incorporated herein by references in their entireties]
()=.sub.DC(T)+A(T).sup.S(T)(Eq. 1)

(86) The term () represents the frequency-dependent real part of conductivity, while DC denotes the frequency-independent direct current (DC) conductivity. A is a coefficient, and s is an exponent that depends on both temperature and material characteristics. A.sup.s accounts for alternating current (AC) dispersion [Jonscher, A. K., The universal dielectric response, Nature, 1977, 267, 673-679, which is incorporated herein by reference in its entirety]. Results of the fit are shown in FIGS. 8A-8E. There is good agreement of conductivity data with Eq. 1. DC conductivity values were determined based on the fitting results for 9Zn and 15Zn for the low- and high-temperature ranges and are summarized in FIG. 9A. DC conductivity increases with temperature for both samples, with 9Zn showing lower values in the low-temperature range (four orders of magnitude) than 15Zn in the high temperature range (over two orders of magnitude). Changes in direct current conductivity observed for the temperature dependence in both samples for the low and high temperature range are of different natures. For low temperatures, the conductivities do not obey Arrhenius' law, suggesting that their activation energy varies with temperature (FIG. 9C). Schnakenberg presented a theoretical model describing this behavior of electronic conductivity. According to the model of the nonadiabatic polaron hopping regime, the activation energy of conductivity varies with temperature, and the temperature dependence of DC conductivity takes the form of Eq. 2 [Schnakenberg, J., Polaronic Impurity Hopping Conduction, physica status solidi (b), 1968, 28, 623-633, which is incorporated herein by reference in its entirety]:

(87) $\begin{array}{cc}=\frac{A}{T}\sqrt{\sin h\left(\frac{h}{\mathrm{kT}}\right)}{\exp }^{-\frac{4W_H}{h}\tan h\frac{h}{4\mathrm{kT}}}{\exp }^{-\frac{W_D}{\mathrm{kT}}}& \left(\mathrm{Eq}.2\right)\end{array}$

(88) A is a constant, k is Boltzmann's constant, is the phonon frequency, W.sub.H is the hopping energy, and W.sub.D is the structural disorder energy between the jump sites. The W.sub.H energy, also called the polaron binding energy, describes the depth of the potential well, and the W.sub.D energy is correlated with the strain energy [Sen, S. and Ghosh, A., Semiconducting properties of magnesium vanadate glasses, Journal of Applied Physics, 1999, 86, 2078-2082, which is incorporated herein by reference in its entirety]. The total activation energy needed to move an electron somewhere else includes both parts. Eq. 2 was used to fit the DC conductivity data in FIG. 9C and obtained a good agreement. Based on the obtained fitting results, it can be concluded that the energy of jump and structural disorder is lower for the 15Zn sample than for the 9Zn sample; however, the W.sub.H values are similar, indicating the same electronic conduction mechanism. This suggests that zinc ions form conductive paths in the crystalline ZnO phase, which is an electron semiconductor. In such situations, conduction takes place primarily in crystallites. For the 15Zn sample, which contains more ZnO than 9Zn, the distance between adjacent crystallites is smaller, hence the lower jump energy. Additionally, in the 9Zn sample, some Zn ions are involved in the non-conducting crystal phases of ZnAl.sub.2O.sub.4, and there is more dielectric matrix around the conductive phase, hence the higher disorder energy. At higher temperatures, activation energy stabilizes to a constant value, as shown in FIG. 9D. In this case, the application of the Schnakenberg equation did not give good results, so the Arrhenius equation (Eq. 3) was used, which also describes the electrical conductivity of semiconductors:

(89) $\begin{array}{cc}{}_{\mathrm{DC}}T={}_0{e}^{-\frac{E_A}{\mathrm{kT}}}& \left(\mathrm{Eq}.3\right)\end{array}$

(90) .sub.0 represents the conductivity pre-exponential factor and E.sub.A represents the activation energy associated with the long-range diffusion of mobile charge. The estimated values of E.sub.A obtained from the fitting using Eq. 3 is seen in FIG. 9D. The activation energy for the DC process is still low, which suggests the dominance of electronic conductivity even at high temperatures, especially in the 15Zn sample. In the high temperature region, the activation energy, W, resulting from electron-lattice interactions and static disorder, can be described by relation Eq. 4.

(91) $\begin{array}{cc}W=W_H+\frac{W_D}{2},T>\frac{{}_D}{2}& \left(\mathrm{Eq}.4\right)\end{array}$

(92) .sub.D is a Debye temperature which can be estimated from the relation .sub.D=h/k, where h is the Plank's constant [Mott, N. F., Conduction in glasses containing transition metal ions, Journal of Non-Crystalline Solids, 1968, 1, 1-17; and Emin, D., Small polarons, Physics Today, 1982, 35, 34-40, which are incorporated herein by references in their entireties]. The W values were calculated based on the Schnakenberg relation fitting results and obtained values of 0.69 eV for the 9Zn sample and 0.42 eV for the 15Zn sample. When comparing the estimated activation energy with the energy obtained from high temperature data, a slight overestimation can be observed. The differences in the activation energy and a change in the temperature behavior of conduction suggest a change in the conduction process from non-adiabatic polaron hopping to another [Wjcik, N. A. et al., Mechanism of hopping conduction in BeFeAlTeO semiconducting glasses and glass-ceramics, Journal of Materials Science, 2022, 57, 1633-1647, which is incorporated herein by reference in its entirety]. Mott's single-phonon approach to small polaron hopping states that the activation energy at high temperatures should stabilize at a constant value. Differences in conductivity at low and high temperatures and as a result of oxygen access may be caused by varying participation of optical and acoustic phonons. Electrons interact strongly with the lattice, so their hopping is strongly related to lattice distortions caused by optical and acoustic phonons. The participation of the mentioned phonons changes with temperature changes. At high temperatures, optical phonons contribute mainly to conduction. In the middle-temperature range, both optical and acoustic phonons contribute to electron hopping, and at low temperatures, optical phonons are frozen [Okoczuk, P. et al., Increasing the conductivity of V.sub.2O.sub.5TeO.sub.2 glass by crystallization: structure and charge transfer studies, Journal of Materials Science, 2023, 58, 8700-8719, which is incorporated herein by reference in its entirety]. The electron-phonon coupling can also be dependent on oxygen access and be different for different modes [Slusarenko, V. et al., Temperature Dependence of the Oxygen Absorption Band in ZnTe:O, physica status solidi (b), 1990, 161, 897-906; and Varshney, D. et al., Interpretation of Resistivity of Nd.sub.1.85Ce.sub.0.15CuO.sub.4: Electron-Phonon Mechanism, Journal of Superconductivity, 2002, 15, 535-538, which are incorporated herein by references in their entireties].

(93) Based on the Jonscher power law (Eq. 1), exponents for 9Zn and 15Zn were estimated at low and high temperatures. FIG. 9B shows the obtained s values as a function of temperature. The exponent s can be useful in predicting the conduction mechanism in glass-ceramics. For both samples, the s parameter ranges from 0.6 to 0.72. In 9Zn it slightly decreases with increasing temperature, while in sample 15Zn the behavior is opposite, but the changes are small. By comparing the values of the exponent s and its temperature behavior with the models [Elliott, S. R. et al., The diffusion-controlled relaxation model for ionic transport in glasses, Philosophical Magazine B, 1989, 60, 777-792, which is incorporated herein by reference in its entirety], it is observed that the conduction process may result from an overlap of the polaron tunneling mechanism and quantum mechanical tunneling between semiconductor ZnO crystallites in glass-ceramics.

(94) The inset in FIG. 9A depicts conductivity behavior of 15ZnC containing carbon nanotubes. The conductivity is DC for the range of frequency and temperature tested (153 to 473 K). Conductivity values are high and amount to 0.2 S cm.sup.1. This is a value for a good semiconductor, caused by the addition of carbon nanotubes, which have high electrical conductivity. In a CNT, each carbon atom is bonded to 3 other carbon atoms, and each atom has 1 free valence electron available for electrical conduction. This makes carbon nanotubes excellent conductors, and, at the nanoscale, some nanotubes have up to five times greater electrical conductivity than copper [Winiewska, P. et al., Rubber wastes recycling for developing advanced polymer composites: A warm handshake with sustainability, Journal of Cleaner Production, 2023, 427, 139010; and Lekawa-Raus, A. et al., Electrical Properties of Carbon Nanotube Based Fibers and Their Future Use in Electrical Wiring, Advanced Functional Materials, 2014, 24, 3661-3682, which are incorporated herein by references in their entireties]. Adding a small amount (15 wt. %) of carbon nanotubes in a ZnO-doped semiconductor increases electrical conductivity.

(95) DC conductivity was not able to be determined for 0Zn, 3Zn, and 6Zn. Instead, behavior of the modulus parameter was analyzed to compare them. Electrical modulus formalism is employed to investigate the electrical relaxation mechanism in ion-conducting materials [Mtioui, O. et al., Thermal behavior and dielectric and vibrational studies of Cs.sub.2(HAsO.sub.4)0.32(SO.sub.4)0.68.Math.Te(OH).sub.6, Ionics, 2015, 21, 411-420, which is incorporated herein by reference in its entirety]. An advantage of this approach is that it suppresses the effects of electrode polarization. The electrical modulus can be mathematically represented as follows: M*=M+jM [Soares, B. G. et al., Dielectric behavior of polyaniline synthesized by different techniques, European Polymer Journal, 2006, 42, 676-686, which is incorporated herein by reference in its entirety]. FIGS. 10A-10C depicts the imaginary part of electric modulus (M) as a function of frequency for different temperatures for samples 0Zn, 3Zn, and 6Zn, respectively. The plots exhibit a relaxation peak. As the temperature increases, the peak shifts towards higher frequencies. The asymmetry observed in the broadening of the peak indicates a range of relaxation times with varying time constants, which is indicative of non-Debye-type relaxation in the materials. The position of peak frequency, f.sub.max, was determined for each temperature and converted to relaxation time, . The dependence between and temperature is illustrated in FIG. 10D. The dependence may be described by the Arrhenius law, as described by equation 5:

(96) $\begin{array}{cc}={}_0{e}^{-\frac{E_A}{\mathrm{kT}}}& \left(\mathrm{Eq}.5\right)\end{array}$

(97) .sub.0 is a pre-exponential factor and E.sub.A is the activation energy for the relaxation process. The estimated activation energy values exceeded 1 eV, suggesting a conduction process resulting from ion hopping. The conduction process may be due to the hop of oxygen vacancies. Doping with ZnO decreases the relaxation time and the activation energy, suggesting the creation of more oxygen vacancies or the presence of an additional conduction process.

(98) CaAlSiON glass-ceramics with varying ZnO contents were synthesized via spark plasma sintering. Zn-containing samples exhibited an increase in crystalline phases with higher in ZnO content. Doping with ZnO influenced material properties, such as density and thermal expansion values. Addition of ZnO to the glass or glass-ceramic materials impacts electrical conductivity. Dopant quantity affects the electrical properties. Glass-ceramic materials with a minimum 9 wt. % ZnO showed measurable DC conductivity. AC conductivity analysis using the Jonscher relation and DC conductivity values aligned with the Schnakenberg model for low temperatures and the Arrhenius equation for high temperatures. A transition from oxygen ion dominance to electron transfer is observed with increasing ZnO content, along with the formation of continuous conduction paths. This suggests a complex interplay of factors influencing the electrical properties of these materials. Conductivity in glass without ZnO and glass-ceramics with a small amount of ZnO is governed largely by the transfer of oxygen ions with a minor contribution to electronic conductivity. This suggests that the movement of ions, particularly oxygen ions, plays a role in the conductivity of these materials. As the content of ZnO increases, continuous conduction paths are formed between ZnO crystallites. With the increasing content of ZnO, the conductivity shifts from being largely dominated by the transfer of oxygen ions to being largely dominated by electron transfer. This shift indicates a change in the dominant mechanism of conductivity in the material as ZnO content increases.

(99) Numerous modifications and variations of the present disclosure are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the disclosure may be practiced otherwise than as specifically described herein.