Physica C 451 (2007) 98106 www.elsevier.

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Preparation of YBa2Cu3O7x superconducting solutions and lms from alkoxide-based precursors using solgel method and investigation of their chemical reaction mechanisms
Ibrahim Halil Mutlu
b

a,*,1

, Hediye Acun a, Erdal Celik b, Hasan Turkmen

a Harran University, Faculty of Arts and Sciences, Department of Physics, 63200 Sanlurfa, Turkey Dokuz Eylul University, Engineering Faculty, Department of Metallurgical and Materials Engineering, Bornova, 35100 Izmir, Turkey c Harran University, Faculty of Arts and Sciences, Department of Chemistry, 63200 Sanlurfa, Turkey

Received 18 August 2006; accepted 31 October 2006

Abstract In the development of coated superconductors solgel technique has been widely used as an eective processing method, especially in making long-length wires and tapes. However, one drawback associated with the deposition of YBa2Cu3O7x and Gd2O3 buer layer on Ni tape is the adhesion characteristic at interfaces YBCOGd2O3 and Gd2O3NiO and NiONi substrate. In this paper, two strategies for adhesion enhancement of multilayered ceramic oxide coatings on Ni substrate were proposed: (1) formation of chemical bonds through surface condensation reactions, and development of ceramic networks through diusion of alkoxide precursors. The current research has focused on the fabrication and adhesion of YBCO coatings on buered Ni substrate using nine solutions prepared from Y, Ba and Cu alkoxides, solvent and chelating agent. Only two of YBCO solutions were successfully obtained while the rest of them were unsuccessful. Among these solutions we scrutinized chemical reaction mechanisms of a successful and an unsuccessful solution for comparison. How the chemical bonds and solubility were aected by the acids, base and solvents used in the solutions was demonstrated. It was shown that pH of the solution, homogeneity of the solution and gelation, steric aect of the chemicals in solgel solutions are signicant issues to obtain high quality superconducting YBCO thin lms. In addition, X-ray diraction (XRD) was used to analyze phase structure of YBCO and compare results of chemical reactions obtained by a chemdraw programme. Scanning electron microscope (SEM) studies was carried out to examine microstructures of YBCO lms produced from alkoxide precursors, solvent, chelating agent and modifying liquid chemical materials such as triethanolamine or ammonium hydroxide. It was found to be YBCO, Gd2O3, NiO and Ni phases in YBCO/Gd2O3/Ni sample from XRD analysis. That the solution prepared by using triethanolamine provided the best lm quality and adhesion was determined by chemical reactions and gelation behaviour in the solutions and SEM observations. 2006 Elsevier B.V. All rights reserved.
Keywords: Solgel; YBCO; Buer layer; Hydrolysis; Condensation; Microstructure; Adhesion

1. Introduction Recently, the research on large-scale superconductivity applications has been focused on YBa2Cu3Ox (YBCO) coated conductors. In the development of coated superconductors the solgel technique has been widely used as an
*

Corresponding author. E-mail address: mutlu@harran.edu.tr (I.H. Mutlu). Tel.: +90 414 3129919; fax: +90 414 3128144.

eective processing method, especially in making longlength wires and tapes. On both single crystal and buered metallic substrates, high critical current density has been obtained from the high-quality lm [1]. Nevertheless, in the development of precursor solution, pH of the solution, homogeneity of the solution and gelation, steric eect of the chemicals in solgel solutions are signicant issues to obtain high quality superconducting YBCO thin lms. In solgel technique, in order to produce superconducting lms with high critical current density (Jc) powder-based

0921-4534/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.physc.2006.10.010

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chemical materials are dissolved in solvents to form a solution. Starting organometallic compounds that are called precursors compose of metal or metalloid elements surrounded by dierent ligands [2]. Initially a solution of desired elements is prepared in solgel process and the solution is polymerized to form a gel structure. After this process, the gel lms are generally dried in the temperature range of 200 350 C to burn out carbon material which comes from the precursors, solvents and chelating agents and subsequently red to displace the organic components in the solgel [35]. Alkoxides and metal salts are precursors, which are usually used in solgel technique. Metal alkoxides are important precursors to produce solgel solutions. General formula of alkoxides is given by M(OR)n where R is an alkyl radical (CH3, C2H5, etc.) [6]. Precursors are dissolved in an appropriate organic solvent to obtain the solution in the solgel process. Solvents must be attentively chosen to obtain a solution with proper viscosity, pH and high concentration. Alkoxides tend to react with all hydroxyl composites resulting in the substitution of their alkoxy group. In solgel processing the rate of gelation of a given alkoxide was adjusted by using a proper solvent since alkoxides with various alkyl groups indicate various reactivities with water. The homogeneity of gel is very important and this can be provided by using chelating organic ligands in solution to control hydrolysis rate of reactive alkoxide. If dierent components possess dierent hydrolysis and condensation rates, gel inhomogenity may occur [7]. Gelation, the transition from a solution into a solid, includes the hydrolysis and condensation of alkoxides through which a polymeric product is formed. It may be possible to control the degree of gelation. In our initial attempts [4,8], we have successfully fabricated some solutions for producing YBCO superconducting lms by mixing Y, Ba and Cu alkoxide precursors with different solvents and chelating agents. In the present paper, a comparison of the solutions prepared by using dierent precursors, solvents and chelating agent was investigated. The

chemical reaction mechanisms of these solutions were compared depending on the reactions of the chemicals each other. The reason for adhesion problems was evaluated using chemical reactions which form on metallic Ni substrate. It was found that some gel lms which produced from YBCO solutions were not adhered on the substrate. Furthermore, YBCO lms produced on Gd2O3 buered Ni tape were analyzed by X-ray diraction (XRD) and followed by scanning electron microscopy (SEM) examination. 2. Experimental Prior to applying solgel derived YBCO on buered Ni tape, deformed Ni substrates were subjected treatment. The Ni substrates were initially cleaned and rinsed with acetone and then annealed at 1100 C for 10 min under H2Ar atmosphere in order obtain textured structure in Ni substrate. The substrates were rinsed again with acetone. YBCO thin lms were deposited on the buered Ni tapes from solutions derived from Y, Ba and Cu alkoxides, solvent and chelating agent using a reel-to-reel continuous solgel process. Before preparation of the solutions, the precursors were weighted out by using a standard balance. The Y, Ba and Cu compounds were dissolved in 100 ml round bottomed asks using solvents and chelating agents as listed in Table 1 and then stirred at room temperature for 24 h in fume hood. Moreover, triethanolamin was incorporated into some solutions as a modifying liquid. Finally, nine of variety YBCO solutions were prepared in transparent structure. After preparation of transparent solutions, pH values of the transparent solutions were measured to determine their acidic and basis characteristics using a standard pH meter with Mettler Tolede electrode. The hydrolysis and condensation processes of the solutions were evaluated by a chemdraw programme. The chemical reaction mechanisms of these solutions were compared depending on the reactions of the chemicals each other.

Table 1 YBCO solutions that have been prepared using solgel method Solutions YBCO (1) YBCO (2) YBCO (3) YBCO (4) YBCO (5) YBCO (6) YBCO (7) YBCO (8) YBCO (9) Used chemical materials Yttrium isopropoxide, barium 2-ethylhexanoate, copper-II-methoxide, glacial acetic acid, methanol, ethanol, triethanolamine Yttrium isopropoxide, barium pentanedionate, copper-II-methoxide, glacial acetic acid, methanol, ethanol, triethanolamine Yttrium acetate, barium acetate, copper acetate, triuoro acetic acid, acetic acid, water Yttrium isopropoxide, barium isopropoxide, copper isopropoxide, triuoro acetic acid, water, isopropanol, acetylacetone, sec-butanol Yttrium acetate, barium acetate, copper acetate, glacial acetic acid, acetic acid, water Yttrium 2-methoxy ethoxide, barium methoxide, copper acetate, glacial acetic acid, water, methanol, ammonium hydroxide Yttrium-II-methoxy ethoxide, copper acetate, glacial acetic acid, ammonium hydroxide, methanol, water, acetylacetone Yttrium isopropoxide, barium ethoxide, copper ethoxide, triuoro acetic acid, glacial acetic acid, ammonium hydroxide, sec-butanol Yttrium acetate, barium acetate, copper acetate, triuoro acetic acid, ammonium hydroxide, sec-butanol pH 5.56.5 5.56.5 4.55 3.54.5 4.24.7 67 6.57.2 4.55.3 44.5 Result Successful Successful Unsuccessful Unsuccessful Unsuccessful Unsuccessful Unsuccessful Unsuccessful Unsuccessful

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Fig. 1. A ow chart of a process for YBCO superconducting lm.

A ow chart of the process for preparing YBCO superconducting lms on the Gd2O3 buered Ni tape substrates via solgel technique has been given in Fig. 1 and published elsewhere in details [8]. X-ray diraction (XRD) pattern of the YBCO superconducting lms on the Gd2O3 buered Ni tape was determined by means of a Philips diractometer with a Cu Ka irradiation (wavelength, k = 0.15418 nm). The surface topography of YBCO thin lms was examined by using the ESEM (PGT Princeton Gamma-Tech 540). 3. Results and discussion 3.1. Chemical reactions of the solutions Solgel precursors undergo chemical reaction with solvents and the other species present in the solution. One of the most ecient models used to predict those reactions is the partial charge model. Various atomic or molecular groups called ligands can bind to a complex C or cation M (metal) either directly or by substituting another ligand. The mechanism of the transformation depends on the partial charge of the dierent atoms in the species. Those with a negative partial charge are nucleophilic, and those with a positive charge are electrophilic. Similarly, in a substitution reaction, the new ligands with the highest partial charge is the nucleophile while the group in the metal complex with the highest positive charge is the leaving group [6].

In solgel processing, when Y, Ba and Cu alkoxides are used they are often dissolved in an aqueous medium. The Y, Ba and Cu alkoxides dissociate into their ions which disperse in the solution as cations and anions. In this case, these anions are sometimes considered as impurities; they must be eliminated in order to produce pure YBCO as an oxide ceramic thin lm. However, they can also be invaluable in channeling the chemical transformations within the solution. In any case, the ions rst solvate with the water molecules, a reaction due to polar nature of the solvent. As a consequence, the cations are entrapped by a number of water molecules which constitutes, since they are the rst neighbors, the rst salvation shell. There is also a second shell of water molecules beyond this rst solvatation shell. Here, the solvatation of anions is not important as the one of cations that is responsible for the hydrolysis of the precursors, a complex chemical transformation leading to the formation of oxide superconducting materials [6]. According to the transformation reaction mechanisms, the use of acetic acid in solutions prevents the constitution of a colloidal gel and promotes that of a polymeric gel. The main role of acetic acid is to decrease the hydrolysis rate, thus making the precipitation of hydroxides more dicult. In the solution, acetic acid produces a complex with alkoxides and this complex is not immediately hydrolyzed. The pH value of the solution was adjusted by using a base [3,6]. Triethanolamine and ammonium hydroxide have been used as bases for YBCO solutions. It is clear from Table 1 that the solutions, which was used triethanolamine deposited on the ceramic metal oxide buered Ni tape substrate, were generally the best one. After heat treatment and partial oxygen diffusion on quality of these superconductor lms were measured and published elsewhere [4,8]. Due to the fact that triethanolamine is a soft steric strain base, we have preferred to use in our experiments and fabricated the textured buer layers and YBCO superconducting lms [5,9]. Ammonium hydroxide is not steric strain base; it quickly reacts with metal hydroxides. The solution, whose ammonium hydroxide is used, is not regularly coated on substrate [2]. The results obtained from the solutions were investigated according to their chemical reaction mechanisms of YBCO (1) and YBCO (8) as follows. 3.1.1. YBCO (1) The pH values of the rst solution were in the range of 56.5 and this solution has been deposited on the buered substrate. Triethanolamine was used in this solution and the pH value of solution was appropriate for solgel processing [8]. Triethanolamine, which is steric strain base, unreacts in the solution and only adjusts the pH of the solution. Hydrolysis reaction of this solution was controlled by using suitable acid, base and solvent. Chemical reaction occurs between OH ions on the ceramic surface and MOH groups form in the solution before gelation [2]. After this chemical reaction successfully occurs MO M bonds provide gelation form. Generally speaking, we have four steps such as formation of carboxylates,

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hydrolysis of acetates, condensation, adjusting of pH and formation of buer layers and YBCO lm surface from solution preparation to lm formation. 3.1.1.1. Formation of carboxylates. Barium acetate forms by reacting barium 2-ethylhexanoate precursor with glacial acetic acid, methanol and ethanol according to the following equation:

3.1.1.2. Hydrolysis of acetates. Hydrolysis is the deprotonation of a solvated metal cation; it consists in the loss of a proton by one or more of the water molecules that surrounds the metal M in the rst solvatation shell. As a consequence, the aquo ligand molecule, H2O that is bonded to the metal is either transformed into an hydroxo ligand OH, if only one proton leaves, or into oxo ligand, O2, if two protons detaches. Hydrolysis of barium acetate

C2H5 CHCH2CH2CH2CH 3 O Ba O C CH3CH2CH2CH2CH C2H5 O C O 2CH3COOH - 2CH3CH2CH2CH2CHCOOH C2H5 H3C O O Ba C O C O CH3

Barium 2-ethylhexanoate

Barium Acetate

Similarly, yttrium acetate and copper acetate are respectively formed by reacting yttrium isopropoxide and copper (II) methoxide precursors with glacial acetic acid, methanol and ethanol according to the following equations:

occurs according to Eq. (4). In addition hydrolysis reactions of copper acetate and yttrium acetate occur in the solution according to Eqs. (5) and (6). During their hydro-

CH3 C OCH3 3 CH3COOH Y H3CO OCH3 - 3CH3OH H3C C O O O Y O C CH3 O O

Yttrium isopropoxide
OCH3 Cu -2 CH3OH OCH3 H3C C O O 2 CH3COOH O Cu O C

Yttrium Acetate
CH3

Copper (II) Methoxide

Copper Acetate

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lysis, an hydroxo ligand (OH) replace an alkoxy group (OR).

to form a polynuclear complexes consisting of two metal atoms. Such a reaction, also called condensation, can,

C2H5 CHCH2CH2CH2CH3 O Ba O O C CH3CH2CH2CH2CH C2H5 Hydrolysis - CH 3CH2CH2CH2CHCOOH - CH3COOH C2H5 OH Ba O O C CH3CH2CH2CH2CH C2H5 Hydrolysis HO Ba OH O Hydrolysis C H3C O Ba OH Hydrolysis C O CH3COOH - CH 3CH2CH2CH2CHCOOH C2H5 H3C O C Ba O O CH3 C O

O O C H3C Cu O

CH3 C O Hydrolysis O C H3C

CH3 C O

OH OH Cu O Hydrolysis Cu + OH 2CH 3COOH

O H3C C O O Y

O Hydrolysis O C CH3 H3C C

OH O Y O O O C CH3 Hydrolysis OH Hydrolysis O H3C C O Y OH

OH HO Y OH + 3CH3COOH

3.1.1.3. Condensation. Two mononuclear complexes of M, each comprising only one metal atom M, can react with one another in a polymerization reaction in order

depending on the metal and if the conditions are right, keep on going so as to produce bigger polynuclear species as shown:

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OH Ceramic M OH + HO Ba OH HO Cu O Ba OH + HO Y OH

-H2O Ceramic M O Ba OH OH + H2O HO Cu O Ba O Y OH

3.1.1.4. Adjusting of pH value. Triethanolamine was used to adjust the pH values of the solution. The pH values of the solution were measured to be in the range of 5.56.5, which is good in this application. As mentioned before, due to the fact that triethanolamine is a soft steric strain base, it is better to form homogeneous, continuous, textured thin lms on Ni tapes. Its reaction is given as

more than nine solutions (Table 1) but we only discussed the best and the worst solutions here. 3.1.2.1. Formation of carboxylates. As explained before, barium acetate forms by reacting barium 2-ethylhexanoate precursor with triuoro acetic acid and sec-butanol according to Eq. (9). By the same token, yttrium acetate and cop-

CH2CH2OH :N HOH2CH2C + CH3COOH CH2CH2OH

CH2CH2OH + N+ CH2CH2OH HOH2CH2C H

CH3COO-

Triethanol amine

3.1.1.5. Formation of metal oxides and coated metal surface. YBCO/buer layer/metal conguration is demonstrated in Fig. 2. It is clear that this lm has smooth surface owing to no aking o. The strong bonding between YBCO and buer layer can be seen from Fig. 2.

per acetate are respectively formed by reacting yttrium isopropoxide and copper (II) methoxide precursors with triuoro acetic acid and sec-butanol according to the following equations:
OCH2CH3 Ba 2 CH3COOH -2CH3CH2OH OCH2CH3 H3C
CH3 C OCH3 3CH3COOH Y H3CO OCH3 - 3CH3OH H3C C O O O Y O C CH3 O O

O O C Ba O

CH3 C O

3.1.2. YBCO (8) In this solution, triuoro acetic acid, glacial acetic acid and ammonium hydroxide were used and inhomogeneous gel was obtained, which has pH of 4.55.3. When these results are compared with the best solution (YBCO1), the pH value of this solution is lower than that of YBCO (8) inasmuch as appropriate base was not used. Therefore, hydrolysis rate of alkoxides was not properly controlled. Ammonium hydroxide reacts with metal hydroxide on substrate on the grounds that ammonium hydroxide is not a steric strain base. As a result, MNM bonds partly establish instead of MOM bonds [9]. In this solution, inhomogeneous gelation occurs before bonding between the hydrolyzed precursor and the substrate. Consequently, ammonium hydroxide gives rise to solution uncoated ceramic layer. Film quality of these solutions can be understood which is mostly porosity and air bubbles and some part of lms aked o or uncoated region exists on the substrates. It can be said that in this work, we investigated

10

OCH2CH3 Cu OCH2CH3 H3C 2CH3COOH -2CH3CH2OH C O Cu

CH3 C O

11

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3.1.2.2. Hydrolysis of acetates. Hydrolysis of barium acetate occurs according to Eq. (12). Apart from hydrolysis of barium acetate, hydrolysis reactions of yttrium acetate and copper acetate occur in the solution according to Eqs. (13) and (14). During their hydrolysis, an hydroxo ligand (OH) replace an alkoxy group (OR).
H3C C O O Ba O O C CH3 Hydrolysis O C CH3 HO Ba O Hydrolysi s

YBCO phase with dierent orientations such as (1 0 0), (1 0 3), (2 1 3) and (3 0 3) was determined from XRD analysis. Besides, Gd2O3, NiO and Ni phases were found owing to buer layer and substrate. NiO formed during production process of YBCO at 500 C for 4 h under oxygen owing.

Ba HO OH

+ 2CH3COOH

12

CH3 C O O H3C C O O Y O C CH3 Hydrolysis OH Hydrolysis HO Y OH

CH3 C Hydrolysis O H3C O C Cu Hydrolysis Cu O OH OH + 2CH 3COOH OH

O Hydrolysis H3C C

OH O Y O O O C CH3

13

OH + 3CH3COOH H3C C

O Y O OH

O O C H3C Cu O

14

3.1.2.3. Condensation. The following reactions are possible at condensation step of YBCO (8) solution as shown in Fig. 3. Because condensation reaction does not regularly form, YBCO lms are ake o. Therefore, adhesion of YBCO to the buered substrate is not good in YBCO (8) solution. There is no regular condensation reaction on account of ammonium hydroxide. As a result of this, MNM bonds are partly established instead of MOM bonds in YBCO (8) solution. 3.2. Phase structure Fig. 4 shows XRD pattern of YBCO/Gd2O3/NiO/Ni architectured tape after annealing process of YBCO.

3.3. Microstructure Our previous works [4,8,9] pointed out that porosity, coating thickness, and cracks in solgel dipped coatings depend on the structure and content of molecular precursor as well as the relative rates of condensation and evaporation during coating process. In addition, viscosity, withdrawal speed, surface tension and contact angle with substrate are very important factors. These factors inuence surface morphology, structure and mechanical properties of coatings. Depending on these factors, YBCO formation can be explained. Film quality strongly depends on solution preparation. Fig. 5 depicts SEM micrographs of YBCO lms prepared from the YBCO (1) to YBCO (8) solutions.

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O O Y O Cu

O Cu O

O Cu O

O Ba O

O Ba

O YBCO

O O M O O O M O M O O M

O M O O M O

O M O O M O METAL

O M O O M O

O M O O M O

O Ceramic Oxide O n

Metal Oxide n

Fig. 2. YBCO/buer layers/metal conguration, which was prepared from YBCO (1) solution, after gelation and heat treatment processes.

Fig. 4. XRD pattern of YBCO/Gd2O3/NiO/Ni architectured tape after annealing process of YBCO at 500 C for 4 h under oxygen owing. Y-123 represents YBa2Cu3O7x (YBCO) superconducting phase.

Since the solution prepared by using triethanolamine as a modiying liquid chemical material exhibits good gelation behaviour, namely regular hydrolysis and condensation reactions as explained before, crack-free, pinholefree, continuous and homogeneous YBCO lms were

fabricated on the Gd2O3 buered Ni tape using the reel-toreel solgel technique (see Fig. 5a). As oppose to YBCO (1), the solution prepared by using ammonium hydroxide exhibits bad gelation behaviour as shown in Fig. 3. Cracks,

NH4OH

:NH3

H2O

Ba HO

+ :NH3 OH HO

Ba

+ H2O NH2

Cu HO OH

+ :NH3

Cu HO

+ H2O NH2

Ba HO NH2

OH Y HO OH

Ba HO

Cu + NH2 HO OH

OH Ba HO N H Y OH + H2O HO Ba N H Cu OH + H2O

OH HO Y OH + NH3 HO Cu Ba + OH HO OH

HO H2N Y OH + H2O Cu HO O Ba

+ H2O OH

Fig. 3. Condensation reactions of YBCO (8) prepared from yttrium isopropoxide, barium ethoxide, copper ethoxide, triuoro acetic acid, glacial acetic acid, sec-butanol and ammonium hydroxide.

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Fig. 5. SEM micrographs of YBCO lms prepared from the YBCO (1) and YBCO (8) solutions.

pinholes and heterogeneous YBCO lms were obtained on the Gd2O3 buered Ni tape using the reel-to-reel solgel technique (Fig. 5b). In this application, chemical reactions in solutions or gelation characteristics inform us about further processes, which include drying, heat treatment and annealing, thin lm quality as well as better adhesion. Also note that adhesion is an important mechanism that depends on mechanical interlocking, electrostatic attraction, physical adsorption, chemical bonding, and weak boundary layers. All of the factors aecting adhesion are porosity, micro and macro cracks, residual stresses, and coating parameters. Upon examining the SEM micrographs from the point of view, YBCO (1) lm is much better than YBCO (8) as lm quality and adhesion. 4. Conclusion In summary, an ideal YBCO solution preparation for proper chemical reactions, gelation, lm quality and adhesion can be summarized as follows: (1) Transparent and homogeneous solutions directly inuence chemical reactions, gelation characteristics and lm quality with preparing pH values in the range of 5.56.5 as an ideal solution. (2) Due to the fact that selection of the base is very important for good gelation, steric strain base such as triethanolamine should be used to adjust pH of the solution. The other bases that are not steric strain are unsuitable to prepare good gelation. In the case of these bases, MOM bonds partly occur, in addition the other bonds such as MNM occurred. (3) YBCO, Gd2O3, NiO and Ni phases were determined from XRD analysis.

(4) In as much as lm quality strongly depends on solution preparation, crack-free, pinhole-free, continuous and homogeneous YBCO lms were fabricated on the Gd2O3 buered Ni tape from the solution prepared by using triethanolamine as a modifying liquid chemical material using the reel-to-reel solgel. In addition, YBCO (1) lm has better adhesion than that of YBCO (8).

Acknowledgements The authors thank B.R. Goddard at National High Magnetic Field Laboratory (USA) for his assistance in SEM pictures, and Dr. Y.S. Hascicek and M. Tomsic at CEO, IEMM Inc. and Hyper Tech Inc. (USA) for providing the chemical materials and rolled Ni tapes. References
[1] B. Zhao, H.B. Yao, K. Shi, Z.H. Han, Y.L. Xu, D.L. Shi, Physica C: Superconductivity 386 (2003) 348. [2] C.W. Turner, Ceramic Bulletin 70 (1991) 1487. [3] C.J. Brinker, G.W. Scherer, SolGel Science: The Physics and Chemistry of SolGel Processing, Academic Press, San Diego, 1990, p. 2. [4] I.H. Mutlu, E. Celik, M.K. Ramazanoglu, Y. Akin, Y.S. Hascicek, IEEE Transactions on Applied Superconductivity 10 (2000) 1154. [5] E. Celik, Y. Yamada, I. Hirabayashi, Y. Shiohara, Materials Science and Engineering B 110 (2004) 94. [6] A.C. Pierre, in: L. Klein (Ed.), Introduction to SolGel Processing, Kluwer Academic Publishers, 1997, p. 11. [7] G. Yi, M. Sayer, Ceramic Bulletin 70 (1991) 1173. [8] I.H. Mutlu, Z. Aslanoglu, M.I. El-Kawni, E. Celik, H. Okuyucu, Y. Akin, W. Sigmund, Y.S. Hascicek, Advances in Cryogenic Engineering 48 (2002) 589. [9] E. Celik, I.H. Mutlu, Y.S. Hascicek, IEEE Transaction on Applied Superconductivity 10 (2000) 1341.