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Modelling of post-irradiation events in polymer gel dosimeters

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2001 Phys. Med. Biol. 46 2827
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INSTITUTE OF PHYSICS PUBLISHING

PHYSICS IN MEDICINE AND BIOLOGY

Phys. Med. Biol. 46 (2001) 28272839

PII: S0031-9155(01)22521-4

Modelling of post-irradiation events in polymer

gel dosimeters
J Back1,4
M Lepage1,5 , A K Whittaker2, L Rintoul3, S A
and C Baldock1,6
1 Centre for Medical, Health and Environmental Physics, Queensland University of Technology,
GPO Box 2434, Brisbane, Qld 4001, Australia
2 Centre for Magnetic Resonance, University of Queensland, Brisbane Qld 4072, Australia
3 Centre for Instrumental and Developmental Chemistry, Queensland University of Technology,
GPO Box 2434, Brisbane Qld 4001, Australia
4 Department of Radiation Physics, Lund University, Malmo University Hospital, SE-205 02
Malmo, Sweden

E-mail: c.baldock@qut.edu.au

Received 5 March 2001, in final form 6 August 2001

Published 5 October 2001
Online at stacks.iop.org/PMB/46/2827
Abstract
The nuclear magnetic resonance (NMR) spinspin relaxation time (T2) is
related to the radiation-dependent concentration of polymer formed in polymer
gel dosimeters manufactured from monomers in an aqueous gelatin matrix.
Changes in T2 with time post-irradiation have been reported in the literature
but their nature is not fully understood. We investigated those changes with time
after irradiation using FT-Raman spectroscopy and the precise determination of
T2 at high magnetic field in a polymer gel dosimeter. A model of fast exchange
of magnetization taking into account ongoing gelation and strengthening of
the gelatin matrix as well as the polymerization of the monomers with time is
presented. Published data on the changes of T2 in gelatin gels as a function of
post-manufacture time are used and fitted closely by the model presented. The
same set of parameters characterizing the variations of T2 in gelatin gels and the
increasing concentration of polymer determined from FT-Raman spectroscopy
are used successfully in the modelling of irradiated polymer gel dosimeters.
Minimal variations in T2 in an irradiated PAG dosimeter are observed after 13 h.

1. Introduction
Polymer gel dosimeters are typically composed of acrylic monomers dissolved in a hydrogel
matrix. In the most widely used polymer gel dosimeter (i.e. the polyacrylamide gel
5 Present address: Department of Diagnostic Radiology, School of Medicine, Yale University, 330 Cedar Street,

Fitkin B, New Haven, CT 06510, USA.

6 Author to whom correspondence should be addressed.

0031-9155/01/112827+13$30.00

2001 IOP Publishing Ltd

Printed in the UK

2827

2828

M Lepage et al

(PAG) dosimeter), the gelling agent is gelatin. Upon irradiation, the monomers undergo
a copolymerization reaction and the 1H-NMR properties of the dosimeter are changed
(Lepage et al 2001b). The production of solid polymer in the dosimeter causes a decrease in
the NMR spinspin relaxation time (T2) that can then be related to the absorbed radiation dose.
Initially, the observation of continuing changes in T2 post-irradiation was believed to arise
solely from a continuing polymerization reaction (Maryanski et al 1994, McJury et al 1999).
Changes with time in the properties of gelatin gels have been extensively studied (Djabourov
and Leblond 1987, Djabourov et al 1985, 1988, Maquet et al 1986, Normand et al 2000). Only
recently has it been recognized that these phenomena are also present in gelatin-based polymer
gel dosimeters (De Deene et al 2000). In a study of the gelation of gelatin gels, a continuous
decrease in T2 was observed until a quasi-steady state was obtained after approximately 30 h
(De Deene et al 2000). It was postulated that post-irradiation evolution of the PAG dosimeters
was due to both continuing polymerization as well as gelation. In that paper a qualitative
description of the processes was provided.
In PAG dosimeters, the relationship between T2 determined long after the absorbtion of
a radiation dose has been quantitatively described using a three-proton pool model for fast
exchange of magnetization (Lepage et al 2001b). FT-Raman spectroscopy was used in that
study to quantify the fraction of protons belonging to the polymer network as a function of the
absorbed dose, long after irradiation. In the present paper, we apply the same relaxation time
model to the evolution of T2 as a function of time and for different absorbed doses. Previously
published data for the changes in T2 in gelatin gels (De Deene et al 2000) are reanalysed.
In addition, an FT-Raman spectroscopy study of the continuing formation of copolymer
post-irradiation is presented. Taking both the variations originating from the gelatin matrix
and from the formation of the polymer network into account, the model is shown to fit closely
the evolution of T2 with time in PAG dosimeters. Continuing polymerization, ongoing gelation
and strengthening of the gelatin matrix are used to explain the experimental results.

2. Materials and methods

2.1. Gel preparation and irradiation
PAG dosimeters were manufactured from acrylamide (AA) and N,N
-methylene-bisacrylamide (BIS) (99+%, electrophoresis grade, Aldrich), gelatin (300 bloom, Aldrich) and
water (deionized). The monomers (AA and BIS) were dissolved in an aqueous gelatin matrix.
The proportions were AA 3%, BIS 3%, gelatin 5% and H2O 89%, all by weight. In the
manufacture process, gelatin was added to water at room temperature and left to soak for
10 min. The solution was then heated and maintained at a temperature of 45 C. AA and
BIS were subsequently added and magnetically stirred for typically 15 min until complete
dissolution was achieved. The solution was poured into glass vials having a teflon-lined
screw-top cap or into 5 mm NMR tubes sealed with epoxy resin and enclosed in heat-sealed
BarexTM pouches. After gelation of the solution, the monomers were assumed to be uniformly
dispersed throughout the gel. The PAGs were manufactured and sealed under a controlled N2
atmosphere inside a glove box. The concentration of oxygen in the glove box was monitored
with an oxygen meter (Quest Technologies, USA) and was maintained below 0.2%. No
inhibition of polymerization of the monomers could be detected at this level.
The PAGs were irradiated at 22 C in a Gammacell 200 (Atomic Energy Canada Limited)
delivering photons from 60Co. The dose rate had been calibrated as 0.27 Gy s1 (Baldock
et al 1999).

Post-irradiation events in polymer gel dosimeters

2829

2.2. Post-irradiation NMR spectroscopy

Sealed NMR tubes containing PAG dosimeter from the same batch were irradiated to 5 and
7 Gy, respectively. The 5 Gy sample was irradiated 150 min after manufacture and the 7 Gy
sample was irradiated 3 weeks after manufacture. The tubes were transferred to a Bruker
MSL-300 NMR spectrometer operating at 300 MHz within 10 min of -irradiation and the
variation in T2 monitored over a period of time extending up to 2000 min. The spectrometer
was equipped with a static 7 mm double resonance probe. The 90-pulse time for 1H NMR was
6 s, the spectrum width was 5 kHz and 8192 data points were acquired. T2 was determined
using the Carr-Purcell-Meiboom-Gill sequence. A single point was collected at the echo
maximum for 2048 echoes in a pulse train. The time between successive 180 pulses was set
to 600 s. The recycle delay was 5 s. T2-relaxation decays were collected every 20 min and
the standard uncertainty was 0.01 s.
2.3. Post-irradiation FT-Raman spectroscopy
Five vials filled with PAG dosimeter were irradiated from 2 to 10 Gy in steps of 2 Gy,
respectively. The samples were transported from the irradiation source to the FT-Raman
spectrometer within 30 min and scanned thereafter for 1500 min. The concentration of double
bonds from the monomers still remaining after the gel had absorbed a given radiation dose
was measured from the FT-Raman spectra (Baldock et al 1998). The FT-Raman spectrometer
(System 2000, Perkin-Elmer, Beaconsfield, UK) comprised a continuous wave Nd:YAG
laser emitting at 1064 nm. The scattered radiation was detected with an InGaAs solidstate detector. Four hundred scans at a resolution of 8 cm1 and laser power of 400 mW
were acquired for each sample. The time interval between successive acquisitions was
30 min.
3. Model for NMR relaxation, polymerization and gelation
3.1. Fast exchange of NMR magnetization
For systems for which the magnetization residing in all possible pools is in fast exchange, the
experimentally determined T2 (T2,exp) can be written as (Zimmerman and Brittin 1957)
1
T2,exp

fH
i
T2,i

(1)

where the fraction of protons in the ith proton pool is fiH having an apparent T2 of T2,i. The
apparent T2 values result from the intrinsic rate of spinspin relaxation in each proton pool (i.e.
in absence of exchange with other pools) and from a contribution of magnetization exchange
with other proton pools. This model has been used successfully to describe the changes
of T2 as a function of the absorbed dose long after irradiation in PAG dosimeters (Lepage
et al 2001a, 2001b). Three proton pools corresponding to free and quasi-free protons (denoted
as mobile, mob), a growing polyacrylamide network (poly) and a gelatin matrix (gela) were
required:
1
T2,exp

H
H
H
fpoly
fgela
fmob
+
+
.
T2,mob T2,poly T2,gela

(2)

The fraction of mobile protons initially contains the protons from water and the monomers.
The latter are gradually transferred to the polymer pool on irradiation. The fraction of protons

2830

M Lepage et al

in the gelatin pool is kept constant. The concentration of monomers remaining long after
absorption of a given dose, and hence the concentration of polymer, was determined using
FT-Raman spectroscopy. Note that this model is an alternative to the more conventional model
including bound or hydration water protons (Koenig and Schillinger 1969). The existence
of bound water has been disputed from the thermal analysis of p(HEMA) hydrogels with an
adiabatic calorimeter (Roorda et al 1988). An equivalence between the two models could be
achieved if it were considered that some water protons were instead included in the gelatin or
the polymer pool. However, this remains an open question that is beyond the scope of this
work. As it will be shown, the simple model of equation (2) provides a good description of
the events taking place in a polymer gel dosimeter post-irradiation.
3.2. Kinetics of gelation
The evolution with time of the NMR spectra of diluted solutions of -gelatin chains has
been investigated (Finer et al 1975). The only change in the spectra during gelation was a
mono-exponential decrease in the intensity of the high-resolution (or mobile gelatin)
component. The time constant for this decrease extracted from their data is approximately
93 min at 15 C. The authors proposed that this time constant described the transition from
single -gelatin molecules in random-coil conformation to nucleated random coils. This
was supposed to be followed by a rapid transition to rigid collagen-like triple helices, which
could then slowly reorganize to more ordered configurations. This is in agreement with the
suggestion that a continuous breaking and remaking of junction zones could lead to a slow
reorganization of gelatin gels (Rees 1969).
The subsequent observation of a progressive decrease in T2 in gelatin gels after
manufacture was taken as evidence that protons are progressively incorporated into a rigid
structure (Maquet et al 1986). In addition, an increase in shear modulus was reported to
result from the formation and reorganization of triple helices, proceeding towards a stable
equilibrium (Djabourov and Leblond 1987). In the latter study, results for the changes in
T2 as a function of time were explained using the ZimmermanBrittin formalism, where
three different water pools were considered. However, the evolution of T2 with time was
not quantitatively modelled. A direct relationship was established between 1/T2 and the
helix content, derived from optical rotation measurements, for a gelatin concentration of
21%.
The gelation kinetics of gelatin was recently studied for samples with controlled molecular
weight distributions and at different temperatures during gelation (Normand et al 2000). In
all cases, the elastic modulus was observed to increase linearly with the logarithm of time
for the time interval between 1 and 100 h. The time constant for this process extracted
from their data, for a 6.66% gelatin gel at 20 C, is 445 min. The extension of existing
crosslinks (defined as the formation of segments of intermolecular triple helix (Normand
et al 2000)) within the gelatin matrix, rather than the formation of new crosslinks, has been
invoked to explain the observation. This means that a large proportion of gelatin molecules
have already reached the nucleated coil conformation and proceed towards the formation
and/or the reorganization of triple helices, thereby increasing the elastic modulus. A small
amount of new crosslinks cannot, however, be ruled out. Since an increase in gel strength can
be expected to lead to more immobilized gelatin molecules, a lower T2,gela can therefore be
expected.
In the model of fast exchange of magnetization used here, we consider that all water
protons are included in one mobile proton pool. As mentioned earlier, considering that some
water protons instead belong to the gelatin or the polymer pool would be consistent with

Post-irradiation events in polymer gel dosimeters

2831

models using bound water populations. The apparent T2,gela becomes time-dependent to take
into account the changes in the gelatin matrix. Ongoing gelation is also considered. This
H is initially mobile and eventually nucleates and
means that a small fraction of the final fgela
forms a triple helix. Newly formed crosslinks are then able to reorganize (and thus strengthen)
with time. The same overall idea has been previously applied by Djabourov et al (1985).
Normand et al (2000) have recently studied the well-known temperature sensitivity of
gelatin gels. They reported that the gel strength decreased with an increase in the gelation
temperature. However, the kinetics of gelation was found to be only slightly dependent on
the gelation temperature within the range 520 C . In the study of De Deene et al (2000), the
gelation temperature was constant but the manufacture temperature was varied. In consequence
for their samples, it is reasonable to expect that the kinetics of gelation will be constant but
that the parameter T2,gela, indicative of the gel strength as argued below, may be affected by
the manufacture temperature.

3.3. Evolution of the copolymerization reaction

A study of the kinetics of the chemically initiated polymerization of AA and BIS in water
has been reported (Gelfi and Righetti 1981). The absorbance of light at 600 nm for an initial
solution of AA 4.25% and BIS 0.75% was characterized by an initial plateau followed by
a decrease consistent with the rapid formation of precipitated polymer particles. The initial
absence of change reflects the fact that the gelation point had not been reached. After this initial
plateau, we found that the decrease in absorbance they published could be empirically fitted
with a two-exponential function having time constants of 1 and 6 min. When increasing the
proportion of BIS, these authors found that the rate of polymerization decreased dramatically,
so the time constants for the decrease in absorbance are getting longer. Consequently,
significantly higher time constants are expected for the present samples containing 3% of
AA and 3% of BIS.

4. Results and discussion

4.1. Evolution of the gelatin matrix
An experimental study of the stability of PAG dosimeters has been published recently
(De Deene et al 2000). The reproducibility in the manufacture of gelatin gels and the effect
of temperature during manufacture was investigated. The values of T2,exp from this study are
reproduced in figure 1. The upper panel demonstrates the reproducibility in the manufacture
of a 6% gelatin gel at 50 C. The lower panel shows the effect of varying the temperature
during manufacture of a 6% gelatin gel.
Our proposed model for gelation was applied to these data and the results are shown in
figure 1 as solid curves. Using an MRI scanner with the same magnetic field (1.5 T) as that
used by De Deene et al (2000), it was previously determined that T2,mob was 3.0 s (Lepage et al
2001a, 2001b). The relevant parameters relating to the instantaneous concentration of gelatin
and the changes in gelatin strength were adjusted to provide best fits to the data. However,
since the gelation temperature was the same for all samples, it is required that the parameters
related to the kinetics of gelatin are kept constant.
The values of the fitting parameters found to provide the best description of the data of
De Deene et als results are now detailed. Ninety-four percent of the total gelatin proton
fraction was considered as gelled when the gel began to set, the time which defines the origin

2832

M Lepage et al

0.94

Gelatin 6%, 64 MHz

0.92
Heated at 50C
during manufacture
Tube 1
Tube 2
Tube 3
Tube 4

T2 (s)

0.90
0.88
0.86
0.84
0.82
0
0.98

500

1000

1500

2000

2500

3000

Gelatin 6%, 64 MHz

0.96
Maximum manufacture
temperature
40C
50C
60C
70C
80C
90C

0.94

T2 (s)

0.92
0.90
0.88
0.86
0.84
0.82
0

500

1000

1500

2000

2500

3000

TIME (mins)
Figure 1. Experimentally determined T2 (T2,exp) from 6% gelatin gels (reproduced from De Deene
et al (2000)). The upper panel shows the reproducibility for four different preparations of the gel
at a temperature of 50 C (tubes 14). The lower panel shows T2,exp for different manufacture
temperatures. The solid curves are derived from the model and only the final T2,gela value is
changed.

of the post-manufacture time scale. The remaining 6% of gelatin molecules, which are still
contributing to the mobile proton pool, underwent continuing gelation (i.e. the formation of
new crosslinks) with a time constant of 700 min. This process is slower than the reorganization
of the triple helices and involves only a small proportion of the gelatin molecules. It is possible
therefore that this effect is superimposed on the overall increase of optical rotation and is
therefore unnoticed in those optical experiments (Djabourov and Leblond 1987). However, in

Post-irradiation events in polymer gel dosimeters

2833

the present paper, the consideration of this small effect proved to be important to the quality
of the fits obtained.
We now examine the parameters representing the increase in gelatin strength. The value of
T2,gela for newly gelled gelatin molecules was initially 17% higher than its final value (table 1).
The precise explanation for this change in T2,gela must be related to the geometrical
conformation change of the triple helices and/or the extension or the lengthening of crosslinks,
but further work would be necessary to elucidate this. The value of T2,gela then decreases
exponentially, in accordance with the previously observed linear increase in gel strength with
the logarithm of time (Normand et al 2000). The time constant found in the present paper
(340 min) is 25% lower than the time constant of 445 min for the change in elastic modulus
of a 6.66% gelatin gel at 20 C between 1 and 30 h post-gelation, as extracted from the work
of Normand et al (2000). Differences of 10% were obtained in the same work for their
different gelatin samples studied at 10 C (upper panel in figure 1). The small discrepancy
could therefore be due to different gelatin batches and/or a different temperature during the
manufacture and/or the measurement procedure. Since it can be assumed that the dynamics
of plasticized swollen gelatin will be comparable to those of a rubbery polymer, we can
make comparisons between our gelatin results and those of rubbers for which a theory exists
(Gotlib et al 1976). It has been found that in the high-temperature limit (well above the glasstransition temperature) T2 of rubbery polymers decreases in a regular manner with increased
crosslink density. This supports the apparent inverse proportionality between T2,gela and the
elastic modulus of gelatin, a theory (Gotlib et al 1976) based on the calculation of the scaled
dipolar interaction for anisotropic motion of chain segments in a Kuhn chain (Kuhn and Grun
1942). A Kuhn chain replaces the detailed polymer by an equivalent chain of segments,
each consisting of a number of monomer units. Their work shows that T2 is proportional to
the rigid-lattice T2 multiplied by a constant z, the number of statistical segments between
junction points which constrain the motion of the chain. Although many assumptions are used
in developing the full theory, it has been tested with success a number of times in the literature
(Fry and Lind 1988, Litvinov et al 1998).
Table 1. T2,gela used in the model for different temperatures of gel manufacture. All values in ms
0.2 ms.

T2,gela

Tube 1
50 C

Tube 2
50 C

Tube 3
50 C

Tube 4
50 C

Tmax
40 C

Tmax
50 C

Tmax
60 C

Tmax
70 C

Tmax
80 C

Tmax
90 C

57.0

58.1

57.2

57.8

56.5

56.8

58.0

57.4

59.4

61.7

The parameters described were hereafter kept constant, except for the final value of T2,gela
(table 1) which was expected to change for different temperatures, and were used to model the
curves shown in figure 1. It can be seen that the model closely fits all experimental data. The
model includes only two proton pools, i.e., a gelatin pool and a mobile pool. This is a simpler
alternative to the model proposed by Maquet et al (1986) which includes three different water
pools.
The values of the fraction of gelatin protons as a function of post-manufacture time and
for T2,gela as a function of the post-gelation time for tube 2 (from De Deene et al (2000)) are
shown in figure 2. The post-gelation time is defined as the time after which a new chain is
formed. Therefore, for 94% of the total gelatin proton fraction, the post-manufacture time and
the post-gelation time are the same. The remaining 6% of gelatin protons undergo gelation at
a given post-manufacture time and this sets the origin of their post-gelation time.

2834

M Lepage et al

POST-GELATION TIME (mins)

0

500

1000 1500 2000 2500 3000

MODEL DATA FOR

6% GELATIN GEL

68

5.10

5.05
66

64
4.95
62

fgelaH (%)

T2,gela (ms)

5.00

4.90

4.85

60

4.80
58
0

500

1000 1500 2000 2500 3000

POST-MANUFACTURE TIME (mins)



H
and apparent T2 for the gelatin pool (T2,gela) as
Figure 2. Fraction of gelatin protons fgela
computed from the theoretical model.

The expected overall increase of T2,gela with increasing temperature can be noted in
table 1. However, no further quantitative conclusions on the values of T2,gela with manufacture
temperature can be drawn from this experiment since the samples have not been heated to a
single temperature for a constant time (De Deene et al 2000).
4.2. Post-irradiation changes in PAG dosimeters
The parameters describing the kinetics of gelation of gelatin determined in section 4.1 are
used here in an analysis of the time evolution of relaxation times in PAG dosimeters. The
fraction of gelatin protons was calculated for a PAG dosimeter containing 3% AA, 3% BIS,
5% gelatin and 89% H2O. The value of T2,gela for this system was found to be 48 ms at 64
MHz and 35 ms at 300 MHz in a previous publication (Lepage et al 2001a). The slightly
lower T2,gela of 48 ms compared to those extracted from the results of De Deene et al (2000)
may simply be due to the amount of time for which the gelatin was heated during manufacture
or due to a difference in gelatin strength, not unexpected for different batches of gelatin. The
kinetic parameters obtained from the modelling of T2,exp for the 6% gelatin gels are used for
PAG dosimeters containing 5% gelatin. This follows the finding of Normand et al (2000) that
the ratio of the kinetic constant of crosslink formation and crosslink melting does not change
significantly with a small increase in gelatin concentration.

Post-irradiation events in polymer gel dosimeters

2835

The decrease in intensity with time of the peaks in the FT-Raman spectra associated with
the vinyl groups of the two monomers (AA and BIS) was found to be adequately described by
a two-exponential function. Similarly the data of Gelfi and Righetti (1981) can be fitted to a
two-exponential function, although in their case a plateau could be observed before the decay
in monomer concentration. The initial slow rate of polymerization occurs prior to gelation
of the system. The two-exponential decay in monomer concentration could be due to two
possible reasons. First, there may be regions of different densities within the precipitating
polymer network, as was observed for materials having lower BIS content by small angle x-ray
scattering (Cohen et al 1992). It would be expected that the rate of diffusion of the monomers
within these two regions will be different, but that in each region the polymerization reaction
would follow first-order kinetics. The overall rate of disappearance of monomers would
therefore be described by the sum of two exponential decays. Second, a first-order process
assumes that the radical concentration is constant (steady-state condition) and sufficient to
initiate polymerization until all the monomers have reacted. Given that all the free radicals
from water react quickly, one must consider the concentration of growing macroradicals. It
was established that these macroradicals precipitate during the polymerization reaction and
hence become less accessible to the unreacted monomers (Lepage et al 2001a). The effective
or accessible radical concentration thus decreases with time, and the result is a second-order
decrease in monomer concentration. Although the analytical solution to this problem cannot be
derived simply, the overall form of the decay would be similar to a two-exponential function.
It is likely that either or both of these mechanisms contribute to the observed kinetics of
monomer reaction, and thus there is no need to invoke the participation of supposed radicals
trapped on gelatin sites.
In all cases examined in the present study, the decrease in concentrations of AA and BIS
was described by a two-exponential function. However, large variations in the time constants
and the relative amplitudes of the short and long decay components were observed. The
short time constant varied from 20 to 46 min while the long one varied from 170 to 500 min.
These time constants are longer than those of Gelfi and Righetti (1981), as expected from
the much larger BIS concentration in the present samples. We have suggested elsewhere that
an increase in BIS concentration leads to more rapid precipitation of growing macroradicals,
leading to a lower polymerization rate (Lepage et al 2001a). This has the effect of making
it more difficult for monomers remaining in solution to diffuse to the macroradical and
participate in the propagation reaction, leading to polymerization extending to unusually
long periods (Chapiro 1962). Alternatively, the lower polymerization rate may partly arise
from the presence of gelatin. An increasing gelatin concentration can lead to either increased
scavenging of initiator fragments or increased chain transfer reactions to gelatin molecules or
both (Lepage et al 2001a).


H
formed in the 7 Gy sample as a function of time,
The fraction of polymer fpoly
determined from the decrease in monomer concentration using FT-Raman spectroscopy, is
shown in figure 3. Scatter in the experimental data can be observed, and is believed to be due
to temporal variations in the laser power and increasing opacity of the samples with time. The
decay time constants obtained for the decay of the monomers were 21 10 and 273 21 min
for this sample. In the model, decay constants of 30 and 200 min were found to give the best
fit to the results presented below. The fraction of polymer calculated using the latter decay
constants is shown as a solid curve in figure 3.
The values of T2,exp at 300 MHz for the two PAG dosimeters irradiated at 5 and 7 Gy,
respectively, are shown in figure 4. It is apparent that T2,exp varies rapidly in the first 500 min.
This observation is in agreement with the results of De Deene et al (2000) but is in sharp

2836

M Lepage et al

3.2

fpolyH (%)

2.8

3% AA, 3% BIS,
5% gelatin, 89% H2O

2.4

Model
FT-Raman

2.0

1.6

1.2

500

1000 1500 2000 2500 3000

POST-IRRADIATION TIME (mins)



H
Figure 3. Variation in the fraction of polymer protons fpoly
for PAG dosimeters ( ) with
H
time. fpoly is taken as the difference between 1 and the fraction of monomers left in the PAG, as
determined from FT-Raman spectroscopy. The curve (solid) used in the theoretical model is also
shown.

contrast with those of McJury et al (1999) who reported a saturation of R2 (1/T2) only after
approximately 18 000 min.
The fraction of monomers remaining in the PAG dosimeter depends upon the absorbed
dose and can be quantified using FT-Raman spectroscopy (Lepage et al 2001a). The
H along with the variations in T
corresponding final fpoly
2,exp arising from the ongoing gelation
and change in conformation in gelatin were included in the model. The value of T2,mob was set
to 3.0 s as determined previously (Lepage et al 2001b). The apparent T2 of the polymer pool
(T2,poly) was fixed at 14.5 ms, a value that has been used previously for the same formulation
of PAG dosimeters (Lepage et al 2001a).
The output of the model is shown as solid curves passing through the data points in figure 4.
Of relevance to the stability of PAG dosimeters, it can be concluded that T2,poly is constant with
time, suggesting that the polymer morphology and topology does not change over the course
of these experiments. This means that the additional polymer material formed with time has
the same general structure as that formed at short times, but that the overall conversion to
polymer increases with time.
The importance of considering the changes in the gelatin matrix in the analysis of the
time evolution of the relaxation times can be judged from a comparison of the results for
the samples irradiated at different times after manufacture. The 5 Gy sample was irradiated
150 min after manufacture while the 7 Gy sample was irradiated 20 days later, where the
variations in the gelatin matrix can be neglected. For comparison, the output of the model for

Post-irradiation events in polymer gel dosimeters

2837

PAG dosimeter
300 MHz
0.38

5 Gy
7 Gy
Gelation
included
not included

T2 (s)

0.36

0.38

0.34

0.36
0.34
0.32

0.32

0.30
0.28
10

100

1000

0.30

0.28

500

1000 1500 2000 2500 3000

POST-IRRADIATION TIME (mins)

Figure 4. Post-irradiation variation in T2,exp with time in PAG dosimeters, measured at 300 MHz.
The two samples were irradiated to 5 and 7 Gy, respectively. Both the effects of ongoing gelation
and strengthening of the gelatin matrix and the polymerization of the monomers are included in the
model. The calculations for the 5 Gy sample when the changes in the gelatin matrix are neglected
are also shown (dashed curves). The difference is more clearly seen in the inset where the time is
plotted on a logarithmic scale.

the 5 Gy sample, ignoring the variations in the gelatin matrix, has been added to figure 4. It
can be immediately seen that neglecting the changes in the gelatin matrix leads to a poorer fit
to the experimental data. The fit to the 7 Gy data appears superior than the fit to the 5 Gy data.
This is due to the changes in gelatin which are present in the latter but absent in the former.
Our parameters were derived from the study of De Deene et al (2000) who used a different
batch of gelatin. Although the magnitude of the changes in T2,exp arising from the variations

2838

M Lepage et al

in the gelatin matrix is smaller than those arising from the polymerization reaction, these must
be taken into account to describe the system fully.
5. Conclusions
A theoretical model of the time dependence of the NMR relaxation in PAG dosimeters has
been presented and validated using experimental results from different techniques. The model
assumes fast exchange of magnetization between three different proton pools. The mobile
pool initially contains the protons from water, the monomers and ungelled gelatin molecules.
The polymer proton pool is initially empty and is gradually filled as a polyacrylamide network
is formed. The formation of polymer is characterized by two time constants derived from
results of FT-Raman spectroscopy measurements. The gelatin pool also evolves with time,
initially containing 94% of all gelatin protons, the remaining 6% being added with time as
ongoing gelation proceeds. The parameter T2,gela depends on the inverse of the gelatin matrix
strength, which increases with time. The kinetic parameters for the gelation of gelatin gels
were extracted from the results published by De Deene et al (2000) on the changes in T2 in
different gelatin gels obtained from a clinical MRI scanner.
Finally, the changes in T2 with time were monitored using an NMR spectrometer operating
at 300 MHz, and were modelled using the information described above. While the details of
the exchange of magnetization between the pools cannot be ascertained from this work, an
excellent agreement was found between the simple model used and the experimental results.
Since the study of De Deene et al (2000) was performed on a different batch of gelatin, the
model may be generally applicable to polymer gel dosimeters.
From a practical point of view, the conclusions from De Deene et al (2000) are
corroborated. Minimal variations in T2 in an irradiated PAG dosimeter are observed after
13 h. This is in sharp contrast with the conclusions of McJury et al (1999). Further, it
becomes apparent that imaging calibration vials and a phantom at different times a short time
after irradiation could lead not only to an absolute error in the dose calibration but also to
distortions in dose distributions.
Acknowledgments
We thank Y De Deene for kindly providing us with the experimental data of figure 1. The

support of Southern X-Ray Clinics and the Wesley Research Institute are acknowledged. SAJB
acknowledges the support from The Swedish Foundation for International Cooperation in
Research and Higher Education (STINT).
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