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Nuclear Instruments and Methods in Physics Research B 271 (2012) 4447

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Nuclear Instruments and Methods in Physics Research B


journal homepage: www.elsevier.com/locate/nimb

Effect of gamma irradiation on the optical properties of UHMWPE


(Ultra-high-molecular-weight-polyethylene) polymer
S.K. Raghuvanshi a,,, Bashir Ahmad a, Siddhartha a, A.K. Srivastava b, J.B.M. Krishna c, M.A. Wahab a
a

Department of Physics, Faculty of Natural Science, Jamia Millia Islamia, New Delhi 110025, India
Department of Applied Science, Sharda University, Plot No. 32-34, Knowledge Park-III, Greater Noida, Uttar Pradesh 201306, India
c
UGC-DAEF Consortium for Scientic Research, Kolkata Center, III/LB-8 Bidhannagar, Kolkata 700098, India
b

a r t i c l e

i n f o

Article history:
Received 1 September 2010
Received in revised form 11 September 2011
Available online 9 November 2011
Keywords:
UHMWPE
Gamma irradiation
UVVisible spectroscopy
Optical band gap
Carbon clusters

a b s t r a c t
The UVVisible absorption spectra of virgin and high dose gamma irradiated (up to 2000 kGy) UHMWPE
polymer have been studied by using UVVisible spectrophotometer (JASCO, V-570). The existence of the
peaks, their shifting and broadening as a result of gamma irradiation has been observed. In the present
work the Urbach energy is calculated by using Urbach edge method. Also the direct and indirect energy
band gap in virgin and gamma irradiated UHMWPE polymer has been calculated. The values of indirect
energy band gap have been found to be lower than the corresponding values of direct energy band gap. A
decrease in the optical energy band gap with increasing gamma irradiation has been discussed on the
basis of gamma-irradiation-induced modication in the UHMWPE polymer. The correlation between
optical energy band gap and the number of carbon atoms in a cluster with modied Taucs equation
has been discussed in this polymer. We have also observed the color formation which became more
and more prominent with increasing dose and at the highest dose the fully transparent sample became
completely opaque.
Looking at the trend of the absorption curve this polymer can be used as a very good dosimeter for the
gamma ray irradiation.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The importance of polymers having improved surface and bulk
properties has increased very rapidly during the last few decades
because of their low weight, low cost, easy processability and easy
fabrication of thick and thin samples, etc. UHMWPE (Ultra-highmolecular weight-polyethylene) is one among those having monomer CH2. The applications of UHMWPE lie in the eld of medicine, microelectronics, engineering, chemistry and the food
industry, etc. In fact, UHMWPE has excellent properties of biocompatibility, electrical insulation, high mechanical and chemical
resistance. UHMWPE has special application in the gliding part of
the mobile prosthesis, such as the hip and knee joints and the
hydraulic tubes of different conductive uids. These applications
require high mechanical resistance in order to answer to high
dynamical pressure loads and long-term mechanical performance
[1].
Now a days the irradiation of polymers is one of the important
elds for altering the polymer properties like electrical, optical,
chemical, mechanical, etc. signicantly [24]. The interaction of

Corresponding author. Tel.: +91 99 90564720; fax: +91 11 26981753.


E-mail address: sraghu06@gmail.com (S.K. Raghuvanshi).
0168-583X/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.nimb.2011.11.001

radiation with polymers destroys [5] the initial structure of the


polymers and leads to chain scission, chain aggregation, formation
of double bonds and molecular emission. As a consequence of this
the polymer properties are modied [5,6].
The knowledge of optical properties of polymers is needed in
the fabrication of LEDs, optical sensors, antireective coatings,
etc. This justies the need of studying the irradiation effects on
the optical properties of the polymers such as optical energy band
gap [7].
In the present work we have studied the behavior of optical energy band gap and Urbach energy with increasing gamma dose [8].
Also we have calculated the optical energy band gap of UHMWPE
polymer with increasing gamma dose (02000 kGy) [9]. The simultaneous existence of direct and indirect energy band gap in
UHMWPE polymer and the number of carbon atoms (N) in a cluster
are also reported [8].

2. Experimental details
UHMWPE polymer sheets of thickness 1 mm were brought from
Good Fellow UK (United Kingdom) and were used without any further treatment. The samples, of size (2  1) cm2 each, were irradiated at UGC-DAEF CSR, Kolkata Center by using 1.25 MeV gamma

45

S.K. Raghuvanshi et al. / Nuclear Instruments and Methods in Physics Research B 271 (2012) 4447

radiation source of 60Co in the high vacuum (2  106 Torr) radiation chamber (in the form of cylindrical chamber of 14 cm length
and 10 cm diameter with dose rate 4 kGy/h and source strength
74 GBq). One sample was kept as virgin for reference and the other
four samples were exposed so as to achieve the doses of 500, 1000,
1500 and 2000 kGy respectively.
Monte Carlo calculations of absorbed dose in air and UHMWPE
were performed with MCNP5 (Monte Carlo N-Particle Transport
Code) software [10]. This software can be used for neutron, photon,
electron, or coupled neutron/photon/electron transport. For photons, the code takes into account the coherent and incoherent scattering, the possibility of uorescent emission after photoelectric
absorption, absorption in pair production with local emission of
annihilation radiation and bremsstrahlung. Results of Monte Carlo
calculations were always given per one emitted particle; here it
was absorbed dose in MeV/g per one emitted photon.
MCNP-4B energy deposition tally-f6 was used for dose calculation in air and UHMWPE with the dimensions (2  1  0.1) cm3
under irradiation with gamma radiation source 60Co. This isotope
emits two gamma rays at 1.332 and 1.173 MeV, respectively. A
PC version of MCNP5 was run on PC AMD Pentium II X4 3 GHz
4 GB computer. Statistical uncertainty less than 5% was used as
output criteria in calculations, which led to tracking more than
108 photons and up to more than 100 min of CPU time for each
simulation. Absorbed doses in the air and UHMWPE were obtained
as 2.7044 E-07 and 3.07229E-07 MeV/g per one emitted photon,
respectively, and their ratio is 0.88.
The UVVisible absorption spectra of virgin and high dose
gamma irradiated UHMWPE polymer have been studied by using
UVVisible spectrophotometer (JASCO, V-570) in the wavelength
range of 190900 nm. All the spectra were recorded by mounting
the samples in the integrating sphere assembly attached with the
spectrophotometer, keeping air as reference.

caused by the formation of extended systems of conjugate bonds


i.e. possible formation of carbon clusters [8]. The absorption bands
are associated to the electronic p ? p transitions. This type of
transitions occur in the unsaturated centers of the molecules i.e.
in compounds containing double or triple bonds and also in aromatics. The excitation of p electron requires smaller energy and
hence, transition of this type occurs at longer wavelength.
The optical absorption coefcient (a) was calculated from the
absorbance (A) by using the following formula [11]

av

A
l


I0
where l is the sample thickness in cm and A is dened as A log I ,
where I0 and I are the intensity of the incident and transmitted
beams, respectively.
3.2. Urbach energy
The absorption coefcient near the band edge for non-crystalline materials shows an exponential dependence on the photon energy (hm) which follows the Urbach formula [12]
hv

av a0 expEu

where a0 is a constant, Eu is an energy which is interpreted as the


width of the tail of localized states in the forbidden band gap, m is
the frequency of radiation and h is the Plancks constant. The origin
of Eu is considered as thermal vibrations in the lattice [13]. The logarithm of the absorption coefcient a(m) was plotted as a function of
the photon energy (hm) for virgin and gamma irradiated UHMWPE

0kGy
500kGy
1000kGy
1500kGy
2000kGy

3.5
3.0
2.5

3.1. Study of optical behavior

2.0

d c

-1

ln() (cm )

3. Result and discussion

'a'
'b'
'c'
'd'
'e'

The UVVisible absorption spectra of virgin and gamma irradiated (5002000 kGy) UHMWPE polymer samples are presented in
Fig. 1. The recorded spectra show a shift of absorption edge towards longer wavelength with increasing gamma dose. The broadening of absorption peak with increasing gamma dose is observed
in the spectra (Fig. 1). This behavior is generally interpreted as

1.5
1.0
0.5

Absorption (log( I0/I))

0.0

0kGy
500kGy
1000kGy
1500kGy
2000kGy

'a'
'b'
'c'
'd'
'e'

-0.5
1.5

2.0

2.5

3.0

3.5

h (eV)
Fig. 2. The dependence of natural logarithm of a on photon energy (hm) for virgin
and gamma irradiated UHMWPE polymer.

a b

c d e

Table 1
Urbach energy, energy band gap (direct and indirect) and carbon atoms in a cluster in
virgin and gamma irradiated UHMWPE polymer.

0
400

500

600

700

800

Wavelength (nm)
Fig. 1. UVVisible spectra of virgin and gamma irradiated UHMWPE polymer.

Gamma-radiation
dose (kGy)

Urbachs
energy (meV)

Energy band gap


(eV)

Carbon atoms
(N) in a cluster

Direct

Indirect

Direct

Indirect

0
500
1000
1500
2000

70.8
38.0
39.1
41.2
51.0

3.21
3.10
2.84
2.74
2.61

3.1
2.87
2.28
2.14
2.06

6
6
6
7
7

6
6
8
9
9

46

S.K. Raghuvanshi et al. / Nuclear Instruments and Methods in Physics Research B 271 (2012) 4447

Fig. 3. Color formation in UHMWPE polymer samples. The samples are arranged in the increasing order of doses (0, 5  102, 1  103, 1.5  103 and 2  103 kGy) from left to
right.

10

0kGy
500kGy
1000kGy
1500kGy
2000kGy

'a'
'b'
'c'
'd'
'e'

e d
c

1/2

-1

(cm eV)

1/2

( h)

polymer samples as shown in Fig. 2. The value of Urbach energy (Eu)


was calculated by taking the reciprocal of the slopes of the linear
portion in the lower photon energy region of these curves. The calculated value of Urbach energy for virgin and gamma irradiated
UHMWPE polymer samples are presented in Table 1. The decrease
in Urbachs energy may be due to the decrease in the crystalline
nature of the polymer.
Upon irradiation, the transparent UHMWPE polymer became
yellow and the degree of yellowness was found to be increased
with increasing gamma irradiation dose. The optical photograph
of the polymer samples are shown in Fig. 3. The samples are
arranged in increasing order of doses (0, 5  102, 1  103,
1.5  103 and 2  103 kGy) from left to right.

3.3. Determination of direct and indirect energy band gap


The relation given in Eq. (2) was rst proposed by Urbach [12]
to describe the absorption edge in alkali halide crystals. Also, this
relation has been found to hold for many amorphous materials.
Eq. (2) has been modied to a more general form by Mott and
Davies [14].

ahv

Bhv  Eg n
hv

'a'
'b'
'c'
'd'
'e'

2.5

3.0

3.5

h (eV)
Fig. 5. Plots for indirect energy band gap (eV) in virgin and gamma irradiated
UHMWPE polymer.

of photon energy (hm) respectively [7,1519] taking into account


the linear portion of the fundamental absorption edge of the UV
Visible spectra (curves ae in Fig. 1). Such plots are shown in
Figs. 4 and 5 respectively. From the intercept of the best t lines
on hm axis, direct and indirect energy band gaps were calculated
for virgin and gamma irradiated UHMWPE polymer samples and
the results are presented in Table 1. This, in turn, clearly indicates
the simultaneous existence of direct and indirect energy band gap
in UHMWPE polymer with decreasing tendency at higher gamma
dose. Furthermore, the values of indirect energy band gap are
found to be lower than the corresponding values of direct energy
band gap. To the best of our knowledge simultaneous existence
of indirect as well as direct band gap in UHMWPE polymer has
not yet been reported although such a coexistence of direct and
indirect band gap have been observed in other materials [7,8,15
19].
3.4. Carbon atoms in a cluster

The number of carbon atoms (N) in a cluster is correlated to the


optical energy band gap (Eg) determined with the modied Taucs
equation [11].

b a

( h) (cm-1 eV)2

0kGy
500kGy
1000kGy
1500kGy
2000kGy

10000

2.0

where hm is the energy of the incident photons, Eg is the value of the


optical energy gap between the valence band and conduction band,
and n is power, which characterizes the electronic transition,
whether it is direct or indirect during the absorption process in
the K-space. Specially n is 2, 3, 1/2, 3/2, for indirect allowed and
indirect forbidden, direct allowed and direct forbidden transitions,
respectively. The factor B depends on the transition probability
and can be assumed to be constant within the optical frequency
range.
From the UVVisible spectra, the direct and indirect optical energy band gap of virgin and gamma irradiated UHMWPE polymer
samples were calculated. For the determination of direct and indirect energy band gap, (ahm)2 and (ahm)1/2 were plotted as a function
15000

5000

2bp
Eg

where 2b is the band structure energy of a pair of adjacent p sites


and b is taken to be 2.9 eV as it is associated with p ? p optical
transitions in C@C structure. The results are presented in Table 1.

2.0

2.5

3.0

3.5

h (eV)
Fig. 4. Plots for direct energy band gap (eV) in virgin and gamma irradiated
UHMWPE polymer.

4. Conclusion
In the present study of virgin and gamma irradiated UHMWPE
polymer samples, the values of the optical band gap (Eg), and
Urbach energy (Eu) were calculated using the UVVisible

S.K. Raghuvanshi et al. / Nuclear Instruments and Methods in Physics Research B 271 (2012) 4447

spectroscopy analysis. The observed fact indicates that the values


of indirect energy band gap are lower than the corresponding values of direct energy band gap in virgin as well as in gamma irradiated UHMWPE polymer. The analysis also indicates that the energy
band gap (Eg) decreases with increasing gamma irradiation dose.
One can also conclude that the cluster size (number of carbon
atoms (N) per conjugated length) increases with increasing absorbed dose of gamma irradiation. The formation of yellow color
was observed due to irradiation which became more and more
prominent with increasing dose of gamma irradiation and at the
highest dose the sample became completely opaque while the virgin sample was fully transparent. The formation of color may be
due to the creation of V-centers (color center) due to gamma
irradiation.
From the present study of gamma ray irradiation effect on this
polymer we have concluded that this polymer can be used as a
very good dosimeter for the gamma ray irradiation.
Acknowledgements
The authors are thankful to Dr. A.K. Sinha, Director, UGC-DAEF
Consortium for Scientic Research, Kolkata Center, for his help in
getting the samples irradiated. We are also thankful to Dr. A.K.
Saha for his kind help.

47

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