ISBN: 978-1-4799-8903-4 2015 IEEE 11th International Conference on the Properties and Applications of Dielectric Materials (ICPADM)
Influence of Absorbed Moisture
on the Dielectric Properties of
Epoxy Resin Impregnated Paper Composites
Hongliang Zhang, Xin Ning, Hua Feng, Peng Liu, Chuang Wang, Zongren Peng
State Key Laboratory of Electrical Insulation and Power Equipment
Xi’an Jiaotong University
Xi’an, China
zhanghl-518@qq.com
Abstract—The absorbed moisture of epoxy resins (ER) and
epoxy resin impregnated paper (ERIP) composites have a great
influence on the insulation of ultra-high voltage direct current
(UHVDC) bushings. The ER and ERIP samples were prepared
according to a certain formulation. The moisture absorption
behaviors of ER and ERIP in deionized water were determined
by measuring periodically the change of weight. Through
comparing the absorption behaviors, it is found that ERIP
samples absorbed more moisture than ER samples, and the
moisture diffusion in ERIP samples can’t be described by one
dimensional Fickian or Langmuir-type model. The dielectric
spectra of ER and ERIP samples were measured over the
frequency range of 10-2 to 106 Hz at five different temperatures.
As measurement temperatures were below the glass transition
temperature of ER, the low frequency dispersion wasn’t observed
in dielectric spectra of ER and ERIP samples within absorbed
moisture in this work. The results show that the absorbed
moisture has a much greater influence on dielectric properties of
ERIP samples than ER samples. The absorbed moisture in ER
samples only slightly increases imaginary parts of relative
permittivity of ER samples and shift the spectra to right, while
the absorbed moisture greatly increase both real and imaginary
parts of relative permittivity of ERIP samples. The near-Debye
relaxations occurred in middle frequency ranges in ERIP
samples within absorbed moisture, which may be caused by
Maxwell-Wagner interfacial polarization or dipole polarization
of water molecular.
Keywords—moisture absorption; epoxy resin impregnated
paper; dielectric properties; bushing
I. INTRODUCTION
Bushings, as a device for carrying one or more high-voltage
conductors through a grounded barrier such as a wall or a metal
tank, are widely used in the power system. The epoxy resin
impregnated paper (ERIP) bushings, which represent the state-
of-the art technology, provide a list of significant advantages,
such as being fully dry, pressure-free, high temperature class,
partial discharge free, low dielectric loss, fire resistance,
outstanding mechanical properties [1]. Because of strong water
absorption capacity of paper, it is important to protect the
paper’s dry condition during the manufacturing. In the
manufacturing process of ERIP bushings, the ends of
978-1-4799-8903-4/15/$31.00 ©2015 IEEE
672
condenser core should be turned into a cone for grading
electrical fields. The turning process takes a long time to be
completed. During and after this process the condenser core
exposes in air in long time and moisture may diffuse into the
bushings. Carter and Kilber have pointed out that the water
absorption in epoxy resins (ER) doesn’t satisfy Fickian model,
as there are two types of water species in the epoxy matrix-
“mobile” and “bound” [2, 3]. T.pham Hong have found that
water absorption at interfaces between epoxy and fillers should
be consider in epoxy-glass-mica composites [4]. Water
absorbency of cellulose is much stronger than epoxy, so the
water absorption of cellulose in ERIP should be also
considered, as well as water absorption at interfaces between
epoxy and paper. However, it is not clear how moisture
diffuses in ERIP.
The absorbed moisture also has an influence on electrical
properties of epoxy resins and their composites. The quasi-dc
dielectric response was observed in epoxy resins within
absorbed moisture above glass transition temperature (Tg) [3].
In the flexible epoxy resins, absorbed moisture has an influence
on the space charge distribution in ER at high electric fields [5].
The low frequency dispersions were observed in dielectric
spectra of glass-mica-epoxy composites within absorbed
moisture [4].
In order to investigate the moisture absorption
characteristics in ERIP and its influence on the dielectric
properties of ERIP, the ER and ERIP samples are prepared, and
then the samples’ moisture absorption experiment are carried
out in deionized water. The dielectric spectra of ER and ERIP
samples within and without moisture are measured and the
dielectric properties are discussed.
II. EXPERIMENTAL
A. Sample preparation
ER samples were manufactured using epoxy resin E51,
anhydride hardener (methyl hexahydrophthalic anhydride) and
catalyst (N, N-dimethyl benzyl amine). ERIP samples have the
same components with ER in addition to a monolayer flat
paper, which thickness is about 0.09 mm. The resin, hardener
and catalyst were mixed uniformly according to a certain
 ISBN: 978-1-4799-8903-4 2015 IEEE 11th International Conference on the Properties and Applications of Dielectric Materials (ICPADM)

formulation. Then the mixture was degassed at 55℃ for 1 h in According to the classical Fickian behavior, the diffusion
the vacuum oven. After being dried at 100 ℃ for 12 h in coefficient D can be determined as [4]:
vacuum oven, monolayer flat paper were sandwiched between
h 2 m2 − m1 2
the stainless steel molds. The mixture was poured into the D =π( ) ( ) (2)
molds in vacuum oven. After the vacuum casting process, ER 4m∞ t2 − t1
and ERIP samples were obtained. The thicknesses of samples
are about 0.69 mm. The samples’ Tg is about 140℃ measured Where m1, m2 are moisture absorption values (expressed as
by the differential scanning calorimeter DSC822e. percentages) at times t1 and t2, and h is the sample thickness. In
this work, h is 0.69 mm.
B. Moisture Absorption Experiment Using 0.64% and 3.13% respectively as values of ER’s and
All samples were kept in the vacuum oven at 100℃ in ERIP’s m∞ , D can be determined according to (2).
order to get the “dry” mass of the samples. The samples were
periodically weighed by a high precision balance (0.1 mg The Fick’s second law can be described as follows by [4]:
resolution). After 3 days, the samples showed no further mass
decrement. To confirm that the samples had been completely Dt 0.75
m = (1 − exp(−7.3( ) ) × m∞ (3)
dried, the drying time was extended to 7 days. h2
After drying, samples were immersed in deionized water at According to (2) and (3), the moisture diffusion curves
room temperature. Moisture absorption versus immersion time governed by Fick’s second law for ER and ERIP samples are
was monitored by weighing. Samples were periodically showed in Fig. 1. The value of moisture absorption of ERIP
removed from water, slightly wiped with clean napkins, and obviously deviates from the theoretical curve, as shown in Fig.
placed in a dish for 1 h at room temperature in order to remove 1. ERIP samples absorbed more moisture than theoretical value
the excess water remaining at surfaces and obtain stable calculated by Fick’s law, which indicates that the moisture
moisture content during measurements. diffusion in ERIP samples can’t be simply described by one
dimensional Fickian model.
In this work, the percentage of the weight change was used
to characterize the moisture absorption. The percentage of
weight change is determined as follows:
m(t) − m0
c(t) = × 100% (1)
m0
Where, m0 is the initial weight of the dry sample, m(t) is
the weight of sample recorded at time t.

C. Dielectric spectroscopy
The dielectric measurements were taken using Novol
control broadband dielectric spectrometer concept 80. Both
sides of the sample were sputtered with golden
electrodes ,which diameter Φ is 30 mm .The dielectric
properties of samples were measured respectively in the
frequency range of 10-2 Hz to 106 Hz at -40℃, -20℃,0℃, 50℃
and 100 ℃ . The dry samples were measured from highest
temperature 100 ℃ , in order to avoiding the influence of
moisture. The samples within moisture were measured from Fig. 1 Water absorption of ER and ERIP samples
the lowest temperature (-40℃), in order to retaining moisture
as much as possible during measurements. The variation of A slight deviation from a pure Fick’s law was also observed
absorbed moisture in samples is neglected during the dielectric for ER samples. The presence of mobile water and bound water
measurements. in the epoxy matrix is the reason of the derivation for ER
samples. The conversion between mobile water and bound
III. RESULTS AND DISCUSSION water causes the water absorption process in ER samples
cannot be described by the classical Fickian model, and should
A. Moisture Absorption Characteristics be described by Langmuir-type model [5]. The presence of
moisture status in epoxy resins has been confirmed by the
Fig. 1 shows the increase of weight percentage versus the experiments [6].
square root of time (t1/2) for ER and ERIP samples. With the
same thickness, ERIP absorbed more moisture than ER as The reasons of the derivation for ERIP samples are more
shown in Fig. 1. The moisture absorption of ER got saturated complicated than for ER samples. For ER samples, water
after 60 h, while the moisture absorption of ERIP hasn’t yet got enters predominantly through the flat surfaces. However, for
saturated after 78 days. ERIP samples, water can enter through the edge of paper in

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 ISBN: 978-1-4799-8903-4 2015 IEEE 11th International Conference on the Properties and Applications of Dielectric Materials (ICPADM)
addition to the flat surfaces. The water diffusion at interfaces
between epoxy resins and paper and in the cellulose of paper
should also be included in the water absorption model of ERIP.
It has been reported mostly that water absorption
characteristics in epoxy resins without or within fillers, but
study on water absorption in ERIP composites is rarely
reported. We will carry out a more detailed study on the water
absorption in ERIP composites in future.
B. Dielectric Properties
According to Jonscher’s universal relaxation law, in the
frequency region above any loss peaks, the imaginary part of
the permittivity should vary as [7]:
ε ′′ ∝ ω n −1 where 0 < n < 1
Different mechanism of dielectric responses can be
distinguished by the universal relaxation law.
The dielectric responses of ER samples are shown in a log-
log plot in Fig. 2.
(a) Dry epoxy resins
(b) Epoxy resins for mass uptake 0.4 %
Fig. 2 Real (solid markers) and imaginary (open markers) parts of the relative
permittivity of epoxy resins
ε', The real part of the permittivity remains almost constant
over the whole frequency ranges, and increases slightly in
magnitude as the temperature increases in both dry and wet ER
samples. ε' of wet ER samples is slightly larger than one of dry
samples. At the same frequency, ε'', the imaginary part of the
permittivity, of wet ER samples is larger than in dry samples.
As the temperature increases, a strong rise of loss at low
frequencies occurs in both dry and wet ER samples. These
observations above suggest that ionic dc conduction is the
dominant in ER samples at low frequencies and high
temperature. The absorbed moisture shifts the spectra to the
right, which is similar with the effect of temperature. In the wet
samples, loss peaks appear in the middle frequency range,
which are most obvious at 100 ℃. The same loss peak can’t be
(4) observed in dry ER samples. The loss peak may be related to
the absorption moisture in ER samples, which needs further
investigation to ascertain.
The low frequency dispersion which has been reported by
Dodd in [3, 8] didn’t be observed in this work, because highest
temperature at which measurements are carried out, is lower
than Tg (140℃) of the ER samples in this work. The dielectric
responses in Fig. 2 are β processes. To distinguish the
responses of dipolar and charge-carrier in β processes, it is
better to study on responses in time domain, as suggested in [7].
This work will be carried out in future.
The dielectric responses of ERIP samples are shown in a
log-log plot in Fig. 3. At low frequencies and high temperature,
a strong rise of loss also occurs for dry ERIP samples.
Compared with the Fig. 2 (a), the responses of dry ERIP
samples in Fig. 3 (a) show that the rise of loss become larger
at low frequencies and high temperature than in ER. This
indicates that paper increases the conductivity of ERIP
samples. The spectra of dry ERIP measured in this work are
also β processes.
The dielectric responses of wet ERIP samples are obviously
different from the formers. The increases of ε'' are obvious
which are mainly caused by the moisture absorption. The
narrow loss peak occurs at all temperatures, and the increasing
of temperature shift the spectra to the right. At the loss peak, ε'
decreases as the frequency increases. The spectra in middle
frequency ranges in Fig. 3 (b) are near the Debye relaxation,
which may be caused by Maxwell-Wagner interfacial
polarization or dipole polarization of H2O. At low frequencies
and high temperature, a strong rise of loss also occurs in wet
ERIP samples. However, ε'' looks discontinuous at 50℃ and
100℃, the slopes of which are greater than formers. It is
unclear whether the discontinuity was caused by measurement
interferences or macrostructure’s mutations in samples. It
needs to investigate in future work. The low frequency
dispersion doesn’t occur in wet ERIP samples in this work,
which was observed in wet glass-mica-epoxy composites in [4].
This may mean that the moisture absorption in ERIP is
different with in glass-mica-epoxy composites. In the latter,
mica and glass do not absorb water, and water diffuses in the
epoxy and interface regions. However, in ERIP samples, water
can diffuse in epoxy, paper, and interface regions between
epoxy and paper.
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 ISBN: 978-1-4799-8903-4 2015 IEEE 11th International Conference on the Properties and Applications of Dielectric Materials (ICPADM)
(a) Dry epoxy resin impregnated paper
(b) Epoxy resin impregnated paper for mass uptake 2.73 %
Fig. 3 Real (solid markers) and imaginary (open markers) parts of the relative
permittivity of epoxy resin impregnated paper
IV. CONCLUSIONS
ERIP samples absorbed more moisture than ER samples,
which are mainly caused by the easy-absorbent property of
paper. The moisture absorption in ER and ERIP samples can’t
be described by the classical Fickian model. The moisture
diffusion model in ERIP samples is more complicated than in
ER samples.
675
As measurement temperatures were below the Tg of epoxy
resins in this work, the low frequency dispersion didn’t occur
in dielectric spectra of ER and ERIP samples. The absorbed
moisture has a much greater influence on dielectric properties
of ERIP samples. The absorbed moisture in ER samples only
slightly increases ε'' of ER samples and shift the spectra to
right, while the absorbed moisture greatly increase ε' and ε'' of
ERIP samples. The near-Debye relaxations occurred in middle
frequency ranges in ERIP samples, which may be caused by
by Maxwell-Wagner interfacial polarization or dipole
polarization of water molecular.
ACKNOWLEDGMENT
The authors thank the support of The National High
Technology Research and Development Program (863
Program) of China (2014AA051801）.
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