Thermal Degradation of Poly(acrylic acid) Containing Metal Nitrates and the Formation of YBa2Cu3O7x

STANISLAV DUBINSKY,1 YULIA LUMELSKY,1 GIDEON S. GRADER,2 GENNADY E. SHTER,2 MICHAEL S. SILVERSTEIN1
1 2

Department of Materials Engineering, TechnionIsrael Institute of Technology, Haifa 32000, Israel Department of Chemical Engineering, TechnionIsrael Institute of Technology, Haifa 32000, Israel

Received 28 July 2004; accepted 2 January 2005 DOI: 10.1002/polb.20405 Published online in Wiley InterScience (www.interscience.wiley.com).

The use of polymers containing metal salts as ceramic high-temperature superconductor (HTSC) precursors may provide a relatively simple and rapid method for producing materials that can take advantage of advanced polymer processing and then be pyrolyzed to HTSCs. The mechanisms of thermal degradation in these precursors, which have not been characterized, can be used to optimize the pyrolysis conditions for HTSC production. This article describes the degradation of a precursor based on poly (acrylic acid) (PAAc) containing yttrium, barium, and copper nitrates in the proportions needed for the formation of the HTSC YBa2Cu3O7x (YBCO). This article also describes the effects of the pyrolysis process on the resulting materials. The degradation of the precursor is a complex, multistage process. The presence of the metal ions and HNO3 reduces the thermal stability of PAAc and increases the degradation rate. The results indicate that the initial stages of the pyrolysis should be conducted in argon or nitrogen to inhibit BaCO3 formation and that the nal stages should be conducted in air/oxygen to enhance oxidation. Optimization of the pyrolysis conditions produces a YBCO lm with minimal contamiC 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 11681176, 2005 nation.  Keywords: FT-IR; poly(acrylic acid); pyrolysis; thermogravimetric analysis (TGA); YBa2Cu3O7x
ABSTRACT:

INTRODUCTION
The traditional methods of synthesizing ceramic high-temperature superconductors (HTSC) include milling and mixing the oxides, carbonates, oxalates, and/or nitrates of the appropriate metals. These methods can lead to macro- and microinhomogeneities and, consequently, to poor HTSC properties.1 The use of polymers containing metal salts as HTSC precursors may provide a relatively simple and rapid method for producing uniform HTSC thin lms and bers. PolyCorrespondence to: M. S. Silverstein (E-mail: michaels@ tx.technion.ac.il)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 43, 11681176 (2005)  C 2005 Wiley Periodicals, Inc.

mer/metal-ion complex formation can be used to produce a uniform dispersion of the metal ions and thus enhance HTSC formation.14 The polymer-based HTSC precursors can take advantage of advanced polymer processing such as microlithography, electrospinning, and ink-jet printing to produce complex structures that can then be pyrolyzed to HTSCs. HTSC microbridges have been produced with microlithography of an HTSC precursor based on a UV-sensitive polymer and metal nitrates.511 The mechanisms of thermal degradation in these polymer-based HTSC precursors have not been characterized. Thermoanalytical characterization of these precursors can be used to understand the mechanisms of degradation, and that knowledge can then be used to optimize the pyrolysis conditions

1168

THERMAL DEGRADATION OF POLY(ACRYLIC ACID)

1169

for the production of an HTSC with a minimal amount of undesired phases. The ionic structure of poly(acrylic acid) (PAAc), a UV-sensitive polymer, may complex with metal nitrates, potentially making it an appropriate polymer for an HTSC precursor. The combination of PAAc with yttrium nitrate (Y-N), barium nitrate (Ba-N), and copper nitrate (Cu-N) in a common solvent (water) could yield a precursor for the formation of the HTSC YBa2Cu3O7x (YBCO). The initial phase of this work focused on the thermal decomposition of PAAc in the presence of Cu-N. Previous research has shown that, of the various metal nitrates added, Cu-N has a dominant effect on the degradation process.1214 Adding Cu-N to PAAc yields a dramatic decrease in thermal stability. The degradation of PAAc containing Cu-N is a complex, multistage process that includes coppercatalyzed polymer chain scission and the formation of macroradicals that generate low-molecularweight organic compounds.14 This article describes complex formation in PAAc containing a mixture of Cu-N, Y-N, and Ba-N (where the ratio of Y/Ba/Cu atoms is 1/2/3), the degradation mechanisms involved, and the results of pyrolysis to an HTSC. The understanding of the degradation process gained is essential for the optimization of the pyrolysis conditions for HTSC formation.

circulating air oven for 24 h, and then dried at 25 8C in a vacuum oven. The lm that formed on the Teon plate was ground with a mortar and pestle and then dried in a vacuum oven at 60 8C for 24 h to obtain a powder. A powder from the nitrate mixture was prepared in the same fashion. A precursor thin lm was prepared via spin-casting on SrTiO3 and drying for 2 h at 170 8C in a circulating air oven. This process was repeated ve times before pyrolysis to enhance the signal from X-ray diffraction (XRD). Characterization Simultaneous thermogravimetric analysis (TGA) and differential thermal analysis (DTA) in situ with TGA were performed from 25 to 1000 8C at 5 8C/min in either argon or air with 25-mg samples (92-16.18 thermogravimetric analyzer, Setaram). The differential thermogravimetry (DTG) thermograms were derived from the TGA results with the supplied software. An analysis of the pyrolytic exhaust gases was conducted with an online quadrupole mass spectrometer (Thermostar 200, Balzers Co.) synchronized with the TGA/DTA instrument. The TGA, DTG, DTA, and mass spectroscopy (MS) results are often combined into one gure with arbitrary units. The MS results for various species are also presented with arbitrary units and do not reect the relative amounts released for different species but rather how the amount released changes with temperature for a particular species. Differential scanning calorimetry (DSC) was used to expose the materials to high temperatures before Fourier transform infrared (FTIR) spectroscopy characterization. The samples were heated in the DSC cell to the desired temperature in either argon or dry air (4 mL/min) at 5 8C/min and then quickly cooled to room temperature (DSC-821 calorimeter, Mettler). The DSC samples were dry powders (46 mg) in an open aluminum pan, and an empty aluminum pan was used as the reference. The samples were then characterized by FTIR to observe the changes in molecular structure. FTIR spectra from 500 to 4000 cm1 at a resolution of 2 cm1 were taken in transmission with KBr pellets containing 1 wt % of the sample (Equinox 55, Bruker). XRD was employed for qualitative phase identication (PW 1840, Philips) with a Ni-ltered Cu Ka X-ray beam excited at 40 kV and 40 mA. Step scans were made with a 0.028 step and a 12-s exposure per step. The slight shift in the peak positions

EXPERIMENTAL
Materials The polymer was a commercial PAAc with a viscosity-average molecular weight of 450,000 (AldrichChemicalCo.).ThemetalnitrateswereY-N [yttrium nitrate pentahydrate, Y(NO3)35H2O, Aldrich], Ba-N[barium nitrate, Ba(NO3)2, Merck], and Cu-N[copper nitrate 2.5 hydrate, Cu(NO3)2 n]. The common solvent was 2.5H2O, Riedel-de Hae distilledwater.Allmaterialswereusedasreceived. Mixing The ratio of Y/Ba/Cu atoms was 1/2/3 in the mixture of nitrate salts [(Y,Ba,Cu)-N]. The HTSC precursor consisted of PAAc containing the nitrate mixture with a PAAc/(Y,Ba,Cu)-N mass ratio of 2/1 (termed 2/1 henceforth). The precursor solution was made by the addition of three parts of a 2% aqueous solution of the nitrate salts to two parts of a 6% aqueous PAAc solution. A precursor powder was prepared as follows: the precursor solution was cast onto a Teon plate, heated at 60 8C in a

1170

DUBINSKY ET AL.

found for some spectra originated from focusing problems associated with the small amounts of the sample in the grazing-angle goniometer. Scanning electron microscopy (SEM; XL30 SEM, Philips) and high-resolution scanning electron microscopy (HRSEM; LEO 982, Zeiss) were used to characterize the morphology of the ceramic after pyrolysis. X-ray energy-dispersive spectroscopy (EDS) with SEM was used for elemental analysis (LINK ISIS, Oxford Instruments).

RESULTS AND DISCUSSION

Pyrolysis of PAAc, Cu-N, Y-N, and Ba-N The degradation mechanism of PAAc includes dehydration, the formation of anhydride-type structures and their decarboxylation, chain scission, and depolymerization. There is no considerable difference between the pyrolysis of PAAc in argon and in air to about 340 8C. The combustive oxidation of the polymer in air, starting from 340 8C, ends in complete decomposition by 579 8C. The degradation in argon yields a carbonaceous residue and 15% residual mass.14 The results from the in-depth thermal analysis (TGA and DTG with contemporaneous DTA and MS, and DSC) of the nitrate salts are, in general, in good agreement with information in the literature. The melting points observed for Cu-N, Y-N, and Ba-N are 123, 106, and 550 8C, respectively.15 The pyrolysis of Cu-N consists of two main stages, dehydration and denitration, and proceeds more rapidly in air than in argon.14 The majority of the endothermic mass loss occurs between 150 and 250 8C. The residual mass of 33.6% corresponds to the formation CuO. The decomposition of Y-N in air involves four main stages. Between 150 and 300 8C, there are two endothermic dehydration and denitration stages from the formation of
Figure 1. Thermal analysis of the nitrate mixture (Y/Ba/Cu 1/2/3) in argon at 5 8C/min (mR residual mass).

Y(NO3)3 and Y(OH)(NO3)2 that account for about 50% of the mass loss.16,17 In addition, Y-N exhibits a signicant endothermic mass loss between 300 and 400 8C from the formation of YO(NO3) and a signicant endothermic mass loss between 400 and 600 8C. The residual mass of 58.5% corresponds to the formation of Y2O3.4,16 Ba-N is signicantly more stable than Cu-N and Y-N. There is a signicant endotherm connected with mass loss between 550 and 800 8C, and the residual mass of 58.5% corresponds to the formation of BaO.

Pyrolysis of the Nitrate Mixture (Y,Ba,Cu)-N The TGA, DTG, and DTA results from the decomposition of (Y,Ba,Cu)-N (a mixture of Y-N, Ba-N, and Cu-N with a Y/Ba/Cu atomic ratio of 1/2/3) in argon are presented in Figure 1. The MS of the H2O and N2O5 released during decomposition is

Table 1. Summary from the Thermal Analysis of the Nitrate Mixture (Y/Ba/Cu 1/2/3) in Argon and in Air TGA and DTG in Argon/Air Stage 1 2 3 4 5 Total Onset (8C) 25/25 186/187 244/243 312/310 500/473 DTG Peaks (8C) 197/201 274/271 650/661 Mass Loss (%) 6.8/7.6 16.2/14.9 10.3/11.1 9.7/10.1 15.4/14.9 58.4/58.6 DTA Peaks (8C) in Argon/Air Endo: 127/123 Endo: 200/206 Endo: 276/271 Endo: 575, 653/587, 664

THERMAL DEGRADATION OF POLY(ACRYLIC ACID)

1171

The origin of the carbon in BaCO3 is a contaminant in the nitrate mixture.14 The thermal analysis and MS results from the decomposition of (Y,Ba,Cu)-N in oxygen (not shown) are quite similar to those from the decomposition in argon in Figure 1. The summary of the decomposition process in air in Table 1 is almost identical to the summary of the decomposition process in argon. The end product, however, is quite different from that produced through pyrolysis in argon. The XRD results from the pyrolysis in oxygen (Fig. 2) indicate that there is less contamination (BaCuO2 and BaCO3) than from the pyrolysis in argon.

Pyrolysis of 2/1 PAAc/(Y,Ba,Cu)-N The TGA, DTG, and DTA results from the decomposition of 2/1 PAAc/(Y,Ba,Cu)-N in argon are presented in Figure 3. The MS results for various species released during decomposition are presented in Figure 4. The decomposition of 2/1 in argon also takes place in ve main stages, which are summarized in Table 2. There is a small amount of mass loss during the rst decomposition stage (25146 8C) involving the evaporation of physically absorbed water. For 2/1, however, there are no endothermic DTA melting peaks for Cu-N or Y-N. The lack of clear melting peaks provides a preliminary indication that complexes may have formed between the nitrates and PAAc. The second decomposition stage (146199 8C) involves a more signicant mass loss with the release of water, nitrogen oxides, and CO2. PAAc

Figure 2. XRD of 2/1 PAAc/(Y,Ba,Cu)-N after pyrolysis: nitrate mixture in Ar, nitrate mixture in O2, powder via R1, powder via R2a, and lm via R2b.

also included in Figure 1. The thermal decomposition of (Y,Ba,Cu)-N takes place in ve main stages, which are summarized in Table 1. In the rst stage (25186 8C) there is a DTA melting endotherm at 127 8C and a minor mass loss from dehydration. The second stage (186244 8C) exhibits a more signicant mass loss originating in the dehydration of Cu-N and Y-N and the denitration of Cu-N (MS, Figure 1). The Cu-N denitration reaches a maximum at about 275 8C, during the third stage (244 312 8C), and the Y-N denitration reaches a maximum at about 375 8C, during the fourth stage (312500 8C). The fth stage (from 500 8C) includes a Ba-N DTA melting endotherm at 575 8C followed by Ba-N denitration, which reaches a maximum at about 640 8C. The residual mass at 1000 8C is 41.6%. This residual mass corresponds to the residual mass calculated for the formation of YBa2Cu3O6.5 from the nitrate mixture. The XRD results from the nitrate mixture heated to 1000 8C in argon are shown in Figure 2. In addition to YBa2Cu3O7x, the pyrolyzed nitrate mixture contains some Y2BaCuO5 and BaCO3. One of the objectives of this research is to optimize the processing of the HTSC precursor to minimize the production of such contaminants.

Figure 3. Thermal analysis of 2/1 PAAc/(Y,Ba,Cu)-N in argon at 5 8C/min (mR residual mass).

1172

DUBINSKY ET AL.

Table 3. Assignments for the FTIR Bands Group Ketone C O stretch Ba-N: NO 3 asymmetric stretch Cu-N and Y-N: NO 3 stretch Ba-N: NO 3 symmetric stretch BaCO3 COO stretch C C COOH stretch Anhydride C O C stretch CH, CH2 stretch OH stretch Band (cm1) 1125 1169, 1240 1362 1385 1416 1433 1657 1670 1716 1760 28003100 3129

Figure 4. Mass spectra of 2/1 PAAc/(Y,Ba,Cu)-N during thermal analysis in argon at 5 8C/min.

has a glass-transition temperature (Tg) of 128 8C and, when it is heated above its Tg, acrylic acid is released.14 This second stage, with its DTG peak at 175 8C and exothermic DTA peak at 170 8C, involves anhydride formation, decarboxylation, and denitration. The exothermic DTA peak represents the oxidative degradation of the polymer catalyzed by the presence of the copper ion and the highly acidic nitrogen oxide species. The decomposition of PAAc and the nitrates with the evolution of H2O, CO2, CO, acrylic acid monomer, and nitrogen oxides continues during the third stage (199330 8C) with its DTG peaks at 262 and 279 8C. The most signicant mass loss, which is related to the degradation of the PAAc and the
Table 2. Summary from the Thermal Analysis of 2/1 PAAc/(Y,Ba,Cu)-N in Argon TGA and DTG DTG Peaks (8C) 175 262, 279 390 DTA Peaks (8C) Exo: 170 Exo: 382, 495 Exo: 845

Stage 1 2 3 4 5 Total

Onset (8C) 25 146 199 330 626

Mass Loss (%) 4.0 13.0 15.9 40.1 4.8 77.8

elimination of almost all the organic matter, occurs during the fourth stage (330390 8C). This degradation is characterized by a DTA exotherm at 382 8C and a DTG peak at 390 8C as well as a DTA exotherm at 495 8C associated with the release of acrylic acid. The nal stage of the decomposition (from 626 8C) involves a DTA exotherm at 845 8C, the release of CO and HNO3, and a minimal mass loss. This stage is associated with the decomposition of Ba-N, the most stable of the nitrates, and the decomposition of BaCO3. The pyrolysis of 2/1 in argon results in a residual mass of 22.3%. Previous results have shown that the pyrolysis of PAAc in argon yields a carbonaceous residue with a residual mass of 15%, and the pyrolysis of the nitrate mixture in argon yields a residual mass of 41.6%.14 Based on the pyrolysis of the components, the calculated residual mass for 2/1 is 24%. The actual residual mass is slightly smaller; this most likely indicates a slight decrease in the amount of carbonaceous residue. The band assignments in Table 3 used to interpret the FTIR spectra in Figure 5 were taken from the literature.10,1822 The as-cast 2/1 [Fig. 5(a)] exhibits a band at 1657 cm1 associated with the COO stretch from carboxylic groups that have formed a complex with metal cations. The as-cast 2/1 also exhibits a band at 1716 cm1 associated with the COOH stretch from carboxylic groups that have not formed a complex. This indicates that only some of the carboxyl groups are involved in complex formation. The bands at 1362 cm1 (the NO3 asymmetric stretch from Ba-N) and 1 1385 cm (the NO3 stretch from Cu-N and Y-N) reect the presence of the nitrates. The NO3 bands dominate the spectra from the as-cast 2/1 and from the 2/1 exposed to 150 8C [Fig. 5(b)], but these

THERMAL DEGRADATION OF POLY(ACRYLIC ACID)

1173

Figure 6. Thermal analysis of 2/1 PAAc/(Y,Ba,Cu)-N in air at 5 8C/min (mR residual mass).

Figure 5. FTIR spectra of 2/1 PAAc/(Y,Ba,Cu)-N after exposure to high temperatures in argon: (a) as cast, (b) 150 8C, (c) 300 8C, (d) 380 8C, and (e) 500 8C.

decomposition of 2/1 in air takes place in four main stages, which are summarized in Table 4. The rst two stages are similar to those for the pyrolysis of 2/1 in argon. Physically absorbed water is released during the rst stage (25122 8C) with a small mass loss. The second stage (122254 8C), with a DTA exotherm and DTG peak at about 170 8C, involves anhydride formation, decarboxylation, and denitration. There is a more signicant mass loss in the second stage from the release of water, nitrogen oxides, CO2, acetone, and acrylic acid.

bands begin to lose their dominance after exposure to 300 8C [Fig. 5(c)]. There is a signicant decrease in the relative heights of the NO3 bands after exposure to 380 8C [Fig. 5(d)], at which the signicant mass loss of the fourth stage occurs. The band at 1416 cm1 (the NO3 symmetric stretch from Ba-N), however, still appears after exposure to 380 8C. The presence of bands associated with anhydrides, unsaturated compounds, and ketones in Figure 5(d) indicates that organic material is still present at 380 8C. After the heating of 2/1 to 500 8C, the band at 1433 cm1 reects the presence of BaCO3, and the band at 1362 cm1 reects the presence of Ba-N.10 The degradation of any BaCO3 formed during the pyrolysis of 2/1 explains the release of CO at 800 8C in Figure 4.13 The TGA, DTG, and DTA results from the decomposition of 2/1 PAAc/(Y,Ba,Cu)-N in air are presented in Figure 6. The relative amounts of the various species released during decomposition, taken from MS, are presented in Figure 7. The

Figure 7. Mass spectra of 2/1 PAAc/(Y,Ba,Cu)-N during thermal analysis in air at 5 8C/min.

1174

DUBINSKY ET AL.

Table 4. Summary from the Thermal Analysis of 2/1 PAAc/(Y,Ba,Cu)-N in Air TGA and DTG DTG Peaks (8C) 173 281, 363, 397 DTA Peaks (8C) Exo: 170 Exo: 359, 400

Onset Stage (8C) 1 2 3 4 Total 25 122 254 455

Mass Loss (%) 2.0 22.7 58.2 3.2 86.1

prominent band remaining after pyrolysis in air to 500 8C is the band associated with residual BaCO3.3,10,13 The presence of oxygen enhances the degradation of the polymer in air and, therefore, there is none of the carbonaceous residue seen after pyrolysis to 500 8C in argon. Formation of YBCO These results complement other results from the literature indicating that the initial stages of the pyrolysis process should take place in argon or nitrogen to suppress the formation of BaCO3.11,13 The nal stages in the pyrolysis process should take place in air or oxygen to completely decompose the organic compounds and to provide the oxygen needed for the formation of YBa2Cu3O7x. The rst pyrolysis process (route R1) consists of heating a 2/1 powder in argon from room temperature to 500 8C at a rate of 5 8C/min, heating in air from 500 to 950 8C at rate of 10 8C/min, holding in

The third and fourth stages of the pyrolysis of 2/1 in air are signicantly different from the pyrolysis in argon. These differences are most obvious in the DTA results and in the mass spectra. The third stage (254455 8C) is characterized by signicant exotherms. There is a broad exotherm, extending from 300 to 450 8C with a peak at 400 8C, upon which a narrow exotherm with a peak at 359 8C is superposed. TGA and DTG indicate a moderate mass loss rate before and after a rapid mass loss at 363 8C, which corresponds to the narrow DTA peak. MS follows the same pattern: H2O and CO2 exhibit a broad peak in the third stage upon which is superposed a narrow peak at about 360 8C. The nitrogen oxides, acetone, acrylic acid, and larger PAAc decomposition fragments [mass-to-charge ratio (m/z) 50] only exhibit a narrow peak at about 360 8C. There is a relatively small amount of mass lost in the fourth stage (from 455 8C). The residual mass from the pyrolysis of 2/1 in air is 14.0%. The pyrolysis of PAAc in air yielded no residual mass.14 Based on the residual mass of 41.4% from the pyrolysis of the nitrate mixture in air, the calculated residual mass for 2/1 is 13.8%, close to the experimental results. This indicates that there is no carbonaceous residue remaining after the pyrolysis of 2/1 in air. The FTIR spectrum of 2/1 pyrolyzed in air to 150 8C [Fig. 8(a)] is similar to that of 2/1 pyrolyzed in argon to the same temperature. However, the FTIR spectrum of 2/1 pyrolyzed to 300 8C in air [Fig. 8(b)], which is in the third stage, is somewhat different from the spectrum after pyrolysis to 300 8C in argon. Both the bands associated with organic groups and the bands associated with NO3 lose their prominence after pyrolysis in air. The disappearance of NO3 and organic material is even more evident after pyrolysis in air to 380 8C, beyond the narrow exotherm in Figure 6. The only

Figure 8. FTIR spectra of 2/1 PAAc/(Y,Ba,Cu)-N after exposure to high temperatures in air: (a) as cast, (b) 150 8C, (c) 300 8C, (d) 380 8C, and (e) 500 8C.

THERMAL DEGRADATION OF POLY(ACRYLIC ACID)

1175

holding at 450 8C for 3 h, and cooling to room temperature at 3 8C/min, all in oxygen. Applying this process (R2) to precursors based on PAAc yields a signicant reduction in the amount of contaminants, as shown in Figure 2. There is only a very small amount of BaCuO2 in the powder pyrolyzed with R2a and relatively small amounts of BaCuO2 and Y2Cu2O5 in the lm from 2/1 pyrolyzed with R2b. Sintering the YBCO lm at 950 8C for 3 h (R2b) produces a relatively dense lm with some pyramidal contaminant grains of BaCO3 [see pyramids in Fig. 9(b) from EDS].

CONCLUSIONS
The thermal decomposition of an HTSC precursor based on PAAc and the ceramic material formed after precursor pyrolysis have been investigated. The degradation of the precursor is a complex, multistage process that is described here in detail for the rst time. The thermal decomposition of 2/1 takes place in ve stages in argon and four stages in air. The presence of the metal ions and HNO3 reduces PAAc thermal stability and increases the rate of degradation. The degradation in argon includes the release of nitrogen oxides and CO, anhydride formation, anhydride decarboxylation, carbonization, and BaCO3 formation. The relatively high residual mass indicates the presence of a carbonaceous residue reecting incomplete PAAc oxidation. The degradation in air is similar to the degradation in argon during the rst two stages. The third and fourth stages, from about 250 8C, involve rapid oxidation. These results indicate that the pyrolysis of the HTSC precursor should initially take place in argon or nitrogen to inhibit BaCO3 formation and then in air/oxygen to enhance oxidation. Optimized pyrolysis conditions produce a dense YBCO lm with a relatively small amount of contamination.
The authors gratefully acknowledge the partial support of the GermanIsraeli Foundation and helpful discussions with I. von Lampe. This research was supported in part by a joint grant from the Center for Adsorption in Science of the Israeli Ministry of Immigrant Adsorption and the Committee for Planning and Budgeting of the Council for Higher Education under the framework of the KAMEA program.

Figure 9. Micrographs of 2/1 PAAc/(Y,Ba,Cu)-N after pyrolysis: (a) SEM image of a powder via R1; (b) HRSEM image of a lm via R2b.

air at 950 8C for 10 min, and cooling in air to ambient temperature. This process yields YBCO that contained some contaminant phases (BaCO3 and Y2O3), as shown in the XRD results in Figure 2. Several different types of crystals can be seen in the SEM micrographs in Figure 9(a) of the material after pyrolysis of a 2/1 powder with R1. EDS analysis of the darker grains [P1 in Figure 9(a)] indicates that they are contaminant phases, whereas EDS analysis of the lighter akes [P2 in Figure 9(a)] indicates that they are YBCO. The optimized pyrolysis process developed for producing YBCO from precursors based on m-cresol formaldehyde resin is more complex.23 This process involves heating from 25 to 450 8C at 5 8C/min, holding at 450 8C for 2 h, and heating to 700 8C at 5 8C/min, all in nitrogen. The process then involves heating to 950 8C at 10 8C/min, holding at 950 8C for either 1.5 h (route R2a, used for powders) or 3 h (route R2b, used for lms spun on SrTiO3 substrates), cooling to 450 8C at 3 8C/min,

REFERENCES AND NOTES

1. Pomogailo, A. D.; Savostynov, V. S.; Dzardimalieva, G. I.; Dubovitskii, A. V.; Ponomaryev, A. N. Izv Akad Nauk Ser Khim 1995, 6, 1096.

1176

DUBINSKY ET AL.

2. Chien, J. C. W.; Gong, B. M.; Madsen, J. M.; Hallock, R. B. Phys Rev B: Condensed Matter and Materials Physics 1988, 38, 11853. 3. Naka, K.; Tachiyama, V.; Ohki, A.; Maeda, S. J Polym Sci Part A: Polym Chem 1996, 34, 1003. 4. Jergel, M.; Chromik, S.; Strbik, V.; Smatko, V.; Hanic, F.; Plesch, G.; Buchta, S.; Valtyniova, S. Supercond Sci Technol 1992, 5, 225. 5. von Lampe, I.; Gotze, S.; Zygalsky, F. J Low Temp Phys 1996, 105, 1289. 6. von Lampe, I.; Bruckner, A.; Gotze, S. Angew Makromol Chem 1997, 25, 157. 7. von Lampe, I.; Schmalstieg, A.; Gotze, S.; Muller, J. P.; Zygalsky, F.; Lorkowski, H. J.; Matalla, M. J Mater Sci Lett 1997, 16, 16. 8. Zygalsky, F.; von Lampe, I.; Gotze, S. Appl Supercond 1998, 6, 795. 9. von Lampe, I.; Zygalsky, F.; Hinrichsen, G. Phys C: Supercond 2000, 341, 2381. 10. von Lampe, I.; Schultze, D.; Zygalsky, F. Polym Degrad Stab 2001, 73, 87. 11. von Lampe, I.; Schultze, D.; Zygalsky, F.; Silverstein, M. S. Polym Degrad Stab 2003, 81, 57. 12. Silverstein, M. S.; Najary, Y.; Grader, G. S.; Shter, G. E. J Polym Sci Part B: Polym Phys 2004, 42, 1023.

13. Silverstein, M. S.; Najary, Y.; Lumelski, Y.; von Lampe, I.; Grader, G. S.; Shter, G. E. Polymer 2004, 45, 937. 14. Dubinsky, S.; Grader, G. S.; Shter, G. E.; Silverstein, M. S. Polym Degrad Stab 2004, 86, 171. 15. Lide, D. R. CRC Handbook of Chemistry and Physics, 75th ed.; CRC: New York, 1994. 16. Hamdy, M. I.; Hussein, G. A. M. Powder Technol 1996, 87, 87. 17. Hussein, G. A. M. Thermochim Acta 1994, 244, 139. 18. McGaugh, M. C.; Kottle, S. J Polym Sci Part B: Polym Lett 1967, 5, 817. 19. Cardenas, G.; Munoz, C.; Carbacho, H. Eur Polym J 2000, 36, 1091. 20. Colthup, N. B.; Daly, L. H. Introduction to Infrared and Raman Spectroscopy, 3rd ed.; Academic: New York, 1990. 21. Rojas, R. M.; Kovacheva, D.; Petrov, K. Chem Mater 1999, 11, 3263. 22. Cseri, T.; Bekassy, S.; Kenessey, G.; Liptay, G.; Figueras, F. Thermochim Acta 1996, 288, 137. 23. Lumelsky, Y. The Degradation of Novolak Containing Metal Nitrates and the Formation of YBCO. M.Sc. Thesis, Technion, Haifa, Israel, April 2004.