Beruflich Dokumente
Kultur Dokumente
Journal
Lei Ying, Changgui Lin,, Qiuhua Nie, Zhuobin Li, Yinsheng Xu, Feifei Chen, and Shixun Dai,
The School of Information Science and Engineering, Ningbo University, Ningbo 315211, China
The School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China
I.
Introduction
II.
Experimental
J. Heocontributing editor
Manuscript No. 30209. Received August 21, 2011; approved January 18, 2012.
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April 2012
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Fourier Infrared spectrophotometer (Thermo Nicolet Corporation, Madison, WI) in the mid-IR region ranging from
2.5 to 16 lm, respectively. Crystals in glassy matrix were
observed by a scanning electric microscope (SEM) and the
marks and cracks made by indentation were observed with
optical microscope (VHX-1000E; Keyence Corporation,
Osaka, Japan). XRD data were collected using a D8
Advance X-Ray diractometer (Voltage 36 kV, current
20 mA, Cu Ka; Bruker AXS, Madison, WI). Raman spectra
were conducted at room temperature using back (180) scattering conguration by Laser Co-focal Raman Spectrometer
(Renishaw, inVia) with excitation wavelength of 488 nm. The
resolution in the frequencies is 0.5 cm1. Vickers microindenter (Everone MH-3, Everone Enterprises. Ltd., Shanghai,
China) was used to obtain hardness with a charge of 100 g
for 5 s. All the characteristics were averaged over measurement on 10 indentations per sample.
III.
(a)
(b)
(c)
(d)
Cut-o
edge (1 nm)
Base
20 h
40 h
60 h
90 h
120 h
637
643
825
1027
1273
1608
Density,
(0.002 gcm3)
3.595
3.671
3.794
3.790
3.732
3.867
Hardness, Hv
(2 Kgmm2)
177
175
180
186
194
193
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(a)
(b)
(a)
(b)
April 2012
1323
b
T2c
Ec
RK0
ln
RTc
Ec
(1)
Fig. 8.
First (In2S3)
Second (Sb2S3)
Third (GeS2)
Ec (kJmol1)
K0 (s1)
K295C (s1)
152.30
155.34
160.84
6.8 9 1012
1.1 9 1012
0.5 9 1012
3.49 9 103
2.68 9 103
2.63 9 103
Fig. 7. DSC curves of the 54GeS236Sb2S310In2S3 glasses heattreated at 295C for dierent heating rates from 1C/min to 20C/
min.
Table II.
Tg ( 1C)
Tx ( 1C)
1
5
10
15
20
265
281
283
284
286
339
370
377
384
389
Fig. 9. DSC curves of the 54GeS236Sb2S310In2S3 glasses heattreated at 295C for dierent durations.
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(a)
(b)
(c)
Fig. 10. Schematic illustration of In2S3, Sb2S3,and GeS2 crystallization processes in a glass matrix: (a) precursor glass, (b) In2S3 nuclei
formation, and (c) glass ceramics.
lized than Sb2S3 and GeS2 at 295C. Hence, the crystallization rate constant K should be considered. In general, the
crystallization rate constant K increases exponentially with
temperature indicating that the crystallization is a thermally
activated process. It can be computed with Ec and K0, and
mathematically expressed as:
Ec
K K0 exp
RT
IV.
(2)
Conclusion
In this work, we demonstrate that reproducible glass ceramics were obtained from 54GeS236Sb2S310In2S3 chalcogenide glass. The obtained glass-ceramics are highly transparent
in the mid-IR region. In addition, the crystallization behaviors of the In2S3, Sb2S3, and GeS2 phase have been systematically investigated by XRD, Raman, and DSC analysis. Based
on the results, the evolution of the three CPs for the crystallized bulk indicates that the precipitation of In2S3 and Sb2S3
crystal phase are responsible for the rst and the second CP,
and that of GeS2 phase for the third one in DSC curves. The
lower value of activation energy Ec and higher value of crystallization rate constant K for the rst CP illustrates the
much easier crystallization mechanism of In2S3. These results
allowed us to deduce that the [S3InSInS3] units are specied to possible nearest-neighbor conguration of In-related
units, which are demixed from the network backbone.
Acknowledgments
This work is partially supported by Natural Science Foundation of China
(Grant No. 61108057), Zhejiang Provincial Natural Science Foundation of
China (Grant Nos. R1101263 and Y4110322), Program for Innovative
Research Team in Ningbo City (Grant No. 2009B21007), Natural Science
Foundation of Ningbo City (Grant No. 2011A610091), Program for New Century Excellent Talents in University (Grant No. NCET-10-0976), and the outstanding Dissertation Engagement Foundation of Graduate School of Ningbo
University (Grant No. PY20100010).In addition, it was also sponsored by K.
C. Wong Magna Fund in Ningbo University.
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