# Investigation of Structural Formation of Starting Composition 2245 in the Bi-Pb-Sr-Ca-Cu-O System Superconductors

Authors: Ashoka Nukkanahalli Venkataswamy; George Thomas Chirayil; Srinivasan Kannaiyan
Journal: Journal of Solid State Physics
 (2014)

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## Abstract

Structural formation of Bi1.65Pb0.35Sr2Ca4Cu5Oy (2245 phase) superconducting compound was investigated by preparing the sample in a new matrix route. The phases formed at different intervals of heat treatment are monitored by X-ray diffraction studies. Bi-2212 phase was found to be the predominant phase till 20 hours of sintering at 850°C after which Bi-2223 phase was found to be the major phase. Traces of Ca2PbO4 were also noticed along with 2212 and 2223 phases. For the first time, the highest TC onset of 127 K with maximum superconducting volume fraction was observed for the sample sintered at 850°C for 30 hours in this preparation. Further sintering is found to deteriorate the TC onset value of the sample. There was no signature of the formation of 2234 or 2245 phase in this synthesis.


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## Body

## 1. Introduction

The bismuth system superconductors are generally represented by the formula Bi2Sr2Can−1CunO2n+4 with critical temperature (TC) values around 10 K, 80 K, and 110 K for n=1,2, and 3, respectively [1, 2]. Among the above, n=2 member, namely, Bi2Sr2Ca1Cu2O8 (2212), is found to be the most stable one. Preparation of n=3 member, Bi2Sr2Ca2Cu3O10 (2223), as a single phase is extremely difficult because of the intergrowth of low TC 2212 phase with 2223 phase. Many research groups have tried to synthesize 2223 compound as a single phase [3–8]. The addition of lead to the superconducting Bi-Sr-Ca-Cu-O compounds leading to the formation of 2223 phase has been reported by Wang et al. [5]. Shi et al. [6] have tried to synthesize 2223 phase by heating an off stoichiometric starting composition with excess Ca and Cu. Sastry et al. [7] have tried the matrix method to obtain a single phase 2223 compound with a TC  120 K. Though there were many attempts made to synthesize n=4 (2234) and n=5 (2245) members [9, 10], no conclusive evidence is available on the structure and TC  values of the above phases. In this paper we report the results of our attempt to synthesize the 2245 phase by solid state reaction method.


## 2. Materials and Methods

The sample Bi1.65Pb0.35Sr2Ca4Cu5Oy was prepared by solid state reaction method as the combinations of two matrices M1 and M2 (M1 = Bi1.65Pb0.35Sr2Cu3Ox and M2 = 2Ca2CuO3). High purity (99.9%) Bi2O3, PbO, SrCO3, CaCO3, and CuO powders were used as starting materials. The powders with the molar ratio of [Bi] : [Pb] : [Sr] : [Cu] = 1.65 : 0.35 : 2 : 3 (matrix M1) and [Ca] : [Cu] = 4 : 2 (matrix M2) were separately prepared by thoroughly mixing the components for about an hour using an agate mortar and pestle. The final mixtures in powder form were kept in two alumina crucibles and calcined at 810°C for 16 hours in a tubular furnace. The calcined powders were reground and pressed into pellets of about 10 mm in diameter and 2 to 3 mm in thickness under a pressure of 5 tons/cm2. These pellets of matrices M1 and M2 were sintered at 835°C for 40 hours with two intermediate grindings and pelletisation and then furnace cooled to room temperature. One pellet of each sample was used for experimental measurements such as X-ray diffraction (XRD), SEM, and EDAX.The two matrix samples M1 and M2 were mixed stoichiometrically into M12 sample of composition Bi1.65Pb0.35Sr2Ca4Cu5Oy. The samples were well ground and mixed thoroughly into a fine powder. It is pressed into pellets of 10 mm diameter and 2 to 3 mm thick. These pellets were kept in a crucible and pulled along the axis of the tubular furnace at the rate of 1 cm per minute. The constant temperature region of the furnace was maintained at 900°C and it took about 40 minutes to pull the samples from one end to the other end of the furnace. The temperature profile along the axis of the tubular furnace is shown in Figure 1. Though a slight melting was observed on the surface of the pellets, all the pellets could be separated. These pellets were further sintered in air at 850°C for varying durations of 5 hours, 10 hours, and 15 hours, removing one pellet at the end of each interval after furnace cooling. The remaining pellets were ground, repelletised, and sintered at 850°C and one pellet each was removed as before at the end of total of 20 hours, 25 hours, 30 hours, and 40 hours, respectively. The removed pellets were labelled as M12 (A, B, C, D, E, F, and G), respectively. For comparison, one more sample of the same composition was prepared by the usual solid state reaction route in which all the constituent compounds are mixed initially and calcined at 810°C for 20 hours, followed by sintering at 835°C for 45 hours with one intermediate grinding and pelletisation. This sample is labelled as P 2245.Figure 1
Temperature profile of the tubular furnace.One part of each pellet was cut, powdered, and used for X-ray diffraction, scanning electron microscopy (SEM), and energy dispersive X-ray analysis (EDAX) measurements. Another piece of the pellet was used forTC measurement. The TC of the sample was determined by self-inductance method. A Colpitts oscillator and a frequency counter along with a liquid nitrogen cryostat were used for the purpose. The temperature of the sample was recorded using a calibrated chromel-alumel thermocouple with an accuracy of ±1°C. The TC of the samples were also confirmed by resistance measurement using the conventional four-probe method.


## 3. Results and Discussion

The X-ray diffraction patterns of the matrices M1 and M2 are shown in Figure 2. The XRD of matrix M1 indicates almost a single phase compound and is indexed in an orthorhombic cell with cell parameters a=5.387 Å, b=5.301 Å, and c=24.574 Å. The XRD pattern is similar to the one obtained by Sinclair et al. [11]. Two peaks of unreacted CuO were also identified in the XRD pattern of M1. All the peaks in the XRD pattern of matrix M2 (except one small peak at 2θ=38.74° due to CuO) were indexed in an orthorhombic cell with cell parameters a=12.247 Å, b=3.780 Å, and c=3.259 Å. This pattern is similar to that of pure Ca2CuO3 compound identified with the ICDD XRD file (34-0282) as reported by Breuer et al. [12].Figure 2
X-ray diffractogram of matrices M1 and M2.The XRD pattern of samples M12 (A, B, C, and D) is indicated in Figure 3. The XRD pattern shows that majority of the peaks belong to 2212 phase (marked as L). Three peaks of Ca2PbO4 at 2θ = 17.62°, 31.06°, and 32.08° have also been identified in B, C, and D patterns. It can be noted that peaks due to 2223 phase (marked as H) gradually develop as the duration of heat treatment is increased. The analysis of XRD pattern of the samples M12 (E, F, and G) (Figure 4) has shown an increase in cell parameter values and has been indexed in a tetragonal structure with a≈b≈5.4 Å and c≈37.2 Å. These peaks are due to the 2223 phase which has formed when the duration of heat treatment exceeded 20 hours at 850°C. Figure 5 shows the XRD pattern of the sample P2245. Except for three peaks at 2θ = 17.62°, 31.06°, and 32.08° of Ca2PbO4 all peaks are identified with that of 2223 phase. The lattice parameters of all the samples calculated from XRD data are given in Table 1.Table 1
Heating profile and results of X-ray diffraction analysis of samples.
Sample name
History of heat treatment
a
Å
b
Å
c
Å
Cell volume (×10−30) m3
Grain size (in nm)
Temperature (°C)
Duration (hours)
M1
835
42
5.387
5.301
24.574
701.747
40.116
M2
835
42
12.247
3.780
3.259
150.871
74.570
M12 A
850
5
5.393
5.421
30.788
900.200
61.139
M12 B
850
10
5.389
5.395
30.767
894.580
75.690
M12 C
850
15
5.392
5.365
30.874
893.198
61.137
M12 D
850
20
5.401
5.391
30.775
896.255
72.250
M12 E
850
25
5.404
5.396
37.253
1086.570
63.580
M12 F
850
30
5.398
5.402
37.220
1085.335
58.870
M12 G
850
40
5.390
5.415
37.216
1086.217
44.170
P 2245
835
45
5.423
5.407
37.003
1085.008
68.814Figure 3
X-ray diffractogram of samples M12 (A, B, C, and D).Figure 4
X-ray diffractogram of samples M12 (D, E, F, and G).Figure 5
X-ray diffractogram of sample P 2245.The scanning electron microscope (SEM) images and superimposed EDAX spectra of samples M1 and M2 are represented in Figure 6. The EDAX spectra are in conformity with the atomic weight percentage of constituent elements as per the stoichiometry. As evident, SEM images reveal a granular and porous surface. The average grain size is calculated from XRD data using Scherrer formula, t=0.89λ/Bcos⁡θB, where t is the grain size, λ is the wavelength of the X-rays, θB is the Bragg angle, and B is the full width at half maximum (FWHM). SEM images of samples M12 (E, F, and G) and P 2245 are indicated in Figure 7. The variation of average grain size with duration of heating is shown in Figure 8. The mean value of grain size is found to be about 60 nm.Figure 6
SEM and EDAX images of the samples M1 and M2.Figure 7
SEM images of the samples M12 (E, F, and G) and P 2245.Figure 8
Grain size versus duration of heating.The normalised frequency (f/fRT, where fRT is room temperature frequency) of Colpitts oscillator versus temperature plots of the samples after different durations of heat treatment is represented in Figure 9. The normalised resistance (R/RRT, where RRT is the resistance at room temperature) versus temperature graph of selected samples is shown in Figure 10. Table 2 shows the TC values and identified phases in the prepared samples. The superconducting signature is observed in the sample only after 15 hours of sintering at 850°C. The volume fraction of the superconducting phase gradually increases with increase in the duration of heat treatment which is evident from the steeper transitions (Figure 9, M12 C and D). The major phase present in the sample after 20 hours of heating is 2212 phase. The sample heated for 25 hours at 850°C shows a two-step transition, one around 125 K (2223 phase) and another at around 105 K (2212 phase). The corresponding XRD pattern (Figure 4, M12E) confirms this observation. The maximum value of TC onset (127 K) was observed for the sample heated for 30 hours (Figure 9, M12F). The sample heated for 40 hours shows the TC onset at 125 K but the volume fraction of the superconducting phase has decreased drastically which is evident from the relatively smaller change in frequency. The XRD pattern of this sample (Figure 4, M12G) also shows two peaks at 2θ = 27.8° and 28.1°, respectively, which are identified with that of Bi2O3. Therefore, it is inferred that prolonged heating up to 40 hours has resulted in some Bi2O3 coming out of the structure and hence the decrease in volume fraction of the superconducting phase. The TC  values measured by four-probe method also shows similar values which are tabulated in Table 2.Table 2
T
C values and identified phases in the samples.
Sample
Sintering at 850°C  (hours)
Phases identified   from XRD
Colpitts oscillator
Four-probe
T
C onset (K)
T
C (K)
T
C onset (K)
T
C zero (K)
M12 A
5
2212, 2223, Ca2PbO4
M12 B
10
2212,2223, Ca2PbO4
M12 C
15
2212, 2223, Ca2PbO4
110
—
—
—
M12 D
20
2212, 2223, Ca2PbO4
120
—
—
—
M12 E
25
2223, 2212, Ca2PbO4
124
107
125, 111
95
M12 F
30
2223, 2212, Ca2PbO4
127
110
127, 115
105
M12 G
40
2223, 2212, Ca2PbO4, Bi2O3
122
100
121
105
P 2245
45
2223, 2212
119
100
120
100Figure 9
Normalised frequencies versus temperature curves of samples.Figure 10
Normalised resistance versus temperature curves of the selected samples.TheTC  value of cuprate superconductors is known to vary with oxygen stoichiometry and is found to be a maximum for an optimum value of oxygen content. This can be manifested in terms of partial change of the valence state of copper from Cu2+ to Cu3+ in the Bi system superconductors [13–16].


## 4. Conclusions

We synthesised Bi1.65Pb0.35Sr2Ca4Cu5Oy superconductor by the matrix method with a new sintering cycle. The sample was initially heated at a comparatively high temperature of 900°C for a short duration followed by sintering at 850°C for different durations. The formation of the different phases as a function of duration of heat treatment was monitored. The X-ray diffraction analysis of the prepared samples revealed the presence of predominantly 2212 phase when sintered at 850°C for 20 hours. Further sintering at the same temperature for 25 hours, 30 hours, and 40 hours, respectively, resulted in the formation of the 2223 phase as the major component. But after 40 hours of sintering, Bi2O3 was noticed to be coming out of the structure. The highest TC onset value (127 K) with maximum superconducting volume fraction was found for the sample sintered at 850°C for 30 hours. The presence of Ca2PbO4 is noticed in all samples which are preheated at 900°C. No traces of 2234 or 2245 phase were noticed under the above preparation conditions.



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*Source: 716032-2014-09-15.xml*