Received: 28 September 2021

DOI: 10.1049/nde2.12032

REVIEW
- - Revised: 9 November 2021 Accepted: 9 December 2021

- IET Nanodielectrics

A review on the research progress and future development of

nano‐modified cellulose insulation paper

Chao Tang1,2 | Rui Chen1 | Jinzhu Zhang1,2 | Xiao Peng1 | Binghao Chen1 |
Liusheng Zhang1

1
College of Engineering and Technology, Southwest
University, Chongqing, China
2
International R & D Center for New Technologies
of Smart Grid and Equipment, Southwest University,
Chongqing, China
Correspondence
Chao Tang, College of Engineering and Technology,
Southwest University, Chongqing, China.
Email: swutc@swu.edu.cn
Funding information
National Nature Science Foundation of China,
Grant/Award Number: 51977179
Abstract
Focussing on the insulating material of power transformer—cellulose insulation paper,
this paper first introduces the basic characteristics and engineering application back-
ground of insulation paper. Then, the research progress of improving the mechanical
properties, thermal stability and electrical properties of insulation paper by nano modi-
fication in recent years is compared, and the promotion mechanism is analysed. In
addition, in practical engineering application, the oil–paper composite insulation system
composed of insulation paper and insulating oil is used for the internal insulation of oil
immersed transformer. Therefore, the influence of modified insulation paper on the
performance of oil–paper composite insulation system is analysed. Finally, the newly
reported new insulation paper is introduced, and the future development trend of
modification of traditional insulation paper is analysed.

KEYWORDS
ageing, composite materials, dielectric materials, electric strength, nanoparticles, paper

1 | INTRODUCTION increase of the transformer voltage class, the cellulose‐oil

Cellulose paper has a long history as an insulating material.
Natural cellulose has been used for preparing insulating paper as
early as the 1890s, and has been widely used in all kinds of elec-
trical equipment [1]. Even today, cellulose paper is still one kind of
important insulating material. According to the statistical trans-
former accident analysis, the insulation failure of transformers
accounts for the majority, among which the oil–paper insulation
failure is the main factor [2]. The reliability of power transformer
is essential to the whole society [3]. Oil–Paper insulation system
is the weakest point in transformers, and the service life of
insulating paper determines the service life of transformers.
Therefore, systematic research on insulating paper is necessary to
ensure the stable operation of power transformers.
1.1 | Properties of pure cellulose insulating
paper
The earliest insulating paper for transformers was made of
cotton cloth and paper coated or oil boiled. With the
composite insulation of kraft paper‐insulating oil appeared
in the 1920s [1]. Synthetic materials were firstly developed in
the 1950s and were also increasingly used in transformers.
The composite insulating paper made of cellulose and syn-
thetic material also has excellent performance. It has been
proved that the composite paper composed of cellulose
paper and polymer film has better dielectric properties
compared with pure cellulose paper [4].
The plant rich in cellulose is the main raw material for
producing cellulose insulating paper. Because of the high cel-
lulose content and long fibres of coniferous wood of the family
Pinaceae, the coniferous wood is often used to make insulating
paper [5]. Compared to composite insulating paper such as
Nomex insulating paper, natural cellulose insulating paper is
cheaper and greener with lower production cost. Because the
length of natural cellulose is long, the insulating paper made
from it has the advantages of high mechanical strength and
easy size control. The cellulose insulating paper has excellent
electrical performance and good compatibility with trans-
formers. The resistivity of sufficiently dried cellulose is on the
order of 1018 Ω/cm, while its dielectric strength is higher than

-
This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs License, which permits use and distribution in any medium, provided the
original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
© 2021 The Authors. IET Nanodielectrics published by John Wiley & Sons Ltd on behalf of The Institution of Engineering and Technology.

IET Nanodielectr. 2022;5:63–84. wileyonlinelibrary.com/journal/nde2 63


64
- TANG
that of most dielectrics, reaching the order of 2.5 million V/cm
[6]. Insulating paper and insulating cushion block are the main
insulating materials between winding turns and wire cakes, and
also play the roles of isolation and support. In addition, since
the insulating paper is wound on the copper conductor, good
mechanical properties are required.
Although cellulose insulating paper has many advantages,
during the long‐term operation of transformers, the insulation
paper is aged under the influence of several factors such as
temperature, electric field, moisture, oxygen and so on, and its
performance will change irreversibly. The decomposition of
cellulose is accompanied by the decrease of the degree of
polymerization, and various ageing products are formed in this
process. The mechanical and electrical properties of cellulose
insulating paper are gradually deteriorated, and the service life
of transformers will end with the deterioration of insulating
paper. Therefore, the development of pure cellulose insulating
paper is also limited.
1.2 | Engineering background
In recent years, with the start‐up of Chinese UHV transmission
project, the requirements for insulation of all kinds of power
equipment have also increased. Electrical performance of
insulating paper is an important index [7], which is directly
related to the insulation safety of power transformers. Ac-
cording to QB/T 3521, the breakdown strength of 500 kV
transformer turn‐to‐turn insulating paper shall be greater than
8.00 kV/mm at commercial power frequency. In addition,
ASTM D149, Standard Test Method for Dielectric Breakdown
Voltage and Dielectric Strength of Solid Electrical Insulating
Materials at Commercial Power Frequencies, imposes strict
requirements on insulating paper.
Operating temperature of transformers is higher than
normal temperature, and due to which thermal ageing insu-
lating paper will become brittle in high temperature environ-
ment for a long time, gradually losing its mechanical and
electrical properties [8]. According to the service life of insu-
lating paper, Technical Committee on Insulation Systems of
International Electrotechnical Commission divided the insu-
lating paper into nine grades according to heat resistance
performance: Y, A, E, B, F, H, C, N, and R, corresponding to
the limiting temperature of 90°C–250°C. The maximum tem-
perature resistance limit of natural cellulose insulating paper is
130°C, so it can be used as Class B insulating paper, while
Nomex paper can reach Class C.
The mechanical properties of insulating paper also cannot
be ignored, taking QB/T 3521 as an example, which specifies
the standard for the mechanical properties of turn‐to‐turn
insulating paper for 500 kV transformers. Similarly, ASTM
D828 has made corresponding requirements for tensile
properties of paper.
At present, cellulose insulating paper has the following
problems to be solved urgently: (1) Thermal stability of cel-
lulose insulating paper, which also determines the service life
of transformers [9]. The structure of cellulose will change
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
under high temperature, which will degrade the performance
of insulating paper, and may even cause falling off of cellulose
paper from winding, which will become impurities in insulating
oil of transformer, not only greatly affecting the insulation
performance of equipment, but also affecting the heat dissi-
pation of conductors. (2) Mechanical properties of cellulose
insulating paper, which are determined by hydrogen bond and
glycosidic bond connecting cellulose glucose monomer [10].
When the structure of cellulose is damaged, its mechanical
properties will decrease. Compared with other kinds of insu-
lating paper, cellulose insulating paper still has a certain gap in
this aspect. (3) Dielectric constant of cellulose insulating paper.
The electric field distribution of dielectric is inversely pro-
portional to its dielectric constant, and uneven electric field
distribution increases the possibility for breakdown of the
insulation system [11]. The dielectric constant of natural cel-
lulose at commercial power frequency is about 5.5 (20°C,
50 Hz). After the paper making process and fully impregnating
with mineral insulating oil, the dielectric constant of cellulose
insulating paper drops to about 4, but it is far from the
dielectric constant of 2.2 of insulating oil. [12, 13]. (4) Hy-
drophobicity of cellulose insulating paper. Due to the large
amount of polar groups such as –OH, –NH and C = O on the
surface of cellulose macromolecule chain constituting insu-
lating paper, cellulose molecule has strong hydrophilicity [14].
Moisture content is an important indicator of ageing state of
transformer [15]. Moisture will increase DC conductivity of
cellulose, thus accelerating its deterioration [16]. It has been
shown that the rate of hydrolytic ageing of cellulose doubles
for every 1% increase in moisture content [17].
1.3 | Nano‐modification technology
Nanomaterials are new materials which have special properties
different from bulk materials and can reach nanometre scale
(1–100 nm) at least in one dimension. T. J. Lewis originally
conceived the concept of nano‐dielectric in 1994 and pointed
out that the interface dielectric characteristics play an impor-
tant role in the breakdown performance of solid or liquid
dielectric materials [18]. In recent years, to improve material
performance with nano‐modification technology has become
one of research hotspots in the field of dielectric materials [19–
21]. Nanoparticles (NPs) are mainly introduced to enhance the
electrical and mechanical properties of insulating materials [22].
At present, there are two ways to study the properties of
NP‐modified cellulose insulating paper: one is to modify
insulating oil by NPs, and then to impregnate insulating paper
with insulating oil modified by NPs to modify insulating paper
indirectly; the other is to directly modify insulating paper with
NPs. NPs are added into insulating paper during the prepa-
ration, and then insulating paper is impregnated with insulating
oil to form oil‐paper mixed insulation system [23]. In the field
of electrical engineering, nano‐modification technology has
made great progress. Some scholars have successfully
improved the electrical and mechanical properties of insulating
paper by modifying insulating paper with nano‐TiO2,

TANG ET AL.
nano‐Al2O3 and nano‐SiO2, which effectively delays the ageing
process of insulating paper, and also explored the action
mechanism of NPs in insulating paper [24–27].
2 | RESEARCH PROGRESS OF
MODIFIED CELLULOSE INSULATING
PAPER
2.1 | Nano‐modification method
At present, there are many mature research studies on NP
modification in various fields. NPs modification of cellulose
insulating paper does not affect the chemical properties of
cellulose chains [28]. The nano‐modification methods mainly
include NP doping, radio frequency (RF) magnetron sputtering
and plasma‐enhanced chemical vapour deposition (PECVD).
2.1.1 | NP doping
The research of nano‐doped insulating paper mainly includes
preparing nano/cellulose composite by experiment and testing
its properties, and using molecular simulation technology to
analyse the properties of nano‐cellulose from a microscopic
point of view. At present, NPs used to modify cellulose insu-
lating paper mainly include carbon nanotubes, nano‐TiO2,
nano‐Al2O3, nano‐SiO2, etc. Figure 1a∼c represent the models
of nano‐TiO2, Nano‐Al2O3 and nano‐SiO2, respectively.
Due to the small size effect, surface effect and quantum
size effect, the molecular structure of NPs is bound, the trap
depth is deepened, and the properties of nano‐composite di-
electrics are changed. Literature [28] shows that when the size
of NPs is too large, the mechanical properties and deformation
resistance of insulating paper will be reduced. In addition, with
the increase of the size of NPs, the bond energy per unit
surface area of NPs and the cohesive energy density of the
system will decrease. Nano‐doping modification belongs to the
modification mode of doping NPs in vivo. The effect of in
vivo doping modification is closely related to the doping per-
centage of NPs and the dispersion degree of NPs, so
requirement of the process control is high, the modified model
is shown in Figure 2.
F I G U R E 1 Molecular models of common used nanoparticles.
(a) TiO2, (b) SiO2, (c) Al2O3
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
- 65
2.1.2 | RF magnetron sputtering method
RF sputtering is a technique in which targets are bombarded by
positive ions in radio frequency discharge plasma, and target
atoms are sputtered and deposited on the surface of grounded
substrate. It has been shown that Al2O3 functional films with
micro‐nano‐Structure prepared by RF reactive magnetron
sputtering on the surface of oil‐impregnated paperboard can
effectively inhibit the injection of space charges.
Compared with bulk doping modification, micro‐nano‐
Structure functional layer not only endows novel characteris-
tics on material surface or interface, but also maintains good
performance of material body, and can be used to design
micro‐nano‐Structure and composition of material surface or
interface according to function orientation. Therefore, RF
reactive magnetron sputtering method has outstanding ad-
vantages, mainly including controllable film thickness, good
repeatability, high film purity and strong bonding force be-
tween film layer and substrate [29].
2.1.3 | Plasma‐enhanced chemical vapour
deposition
PECVD technology is a method to deposit thin films on
substrates by chemical reaction of gaseous reaction precursors
containing components of thin films by plasma [30, 31].
Generally, PECVD generates plasma by glow discharge
under high‐frequency electrical field and high vacuum condi-
tions to realize rapid growth of dense thin film at relatively low
temperature [32], which has the advantages of strong film
adhesion, excellent coating property, low deposition tempera-
ture and marginal influence on the structure and physical
F I G U R E 2 Polyhedral oligomeric silsesquioxane modified cellulose
molecular model

66
- TANG
properties of the substrate. The energy of low‐temperature
plasma is higher than that of these chemical bonds, so it is
enough to break the molecular bonds on the polymer surface
and cause a series of physical and chemical reactions such as
etching, crosslinking, and grafting.
Compared with the latter two methods, the nano‐doping
method is more widely employed in the modification of
insulating materials, with more mature technology, more
thorough research and more completed theoretical system. In
the last 2 decades, a large number of scholars have prepared
excellent modified cellulose insulating paper materials by this
method, and have carried out extensive and deep research
studies on its mechanisms. This paper mainly summarizes the
progress of bulk‐doped modified cellulose insulating paper.
2.2 | Mechanical properties
2.2.1 | Introduction of background and
parameters
The determination of mechanical strength of insulating paper
is mainly carried out in accordance with the test methods for
paper tear and tensile strength mentioned in the current
standards such as ISO 1924‐1, ISO 1924‐2, GB/T 455, and
GB/T 12914. Tear and tensile strength are two main indexes to
reflect the mechanical properties of paper.
In recent years, there are two main ways to study the
properties of insulating paper: experiment and simulation. One
is performed through tensile strength test and analysis to
obtain insulating paper fracture resistance. The other is realized
by establishing the long chain model of cellulose of insulating
paper to measure the mechanical parameters such as bulk
modulus, shear modulus, elastic modulus, Poisson's ratio, and
Cauchy pressure, which can reflect the change of mechanical
properties of insulating paper.
2.2.2 | Comparative analysis of modification
effect of commonly used NPs
As mentioned above, in recent years, the modified particles
commonly used by researchers include nano‐Al2O3, nano‐
TiO2 and nano‐SiO2, and the performance of modified
insulating paper has also been greatly improved. This section
focuses on the improvement of mechanical properties of
modified insulating paper.
Nano‐Al2O3 modified insulating paper
In 2014, Liao Ruijin [25] et al. of Chongqing University in
China modified insulating paper by using nano‐Al2O3 treated
by KH570, and tested the tensile strength of the modified
insulating paper according to the constant speed stretching
method specified in GB/T 12914‐2008, and found that when
the content of Al2O3 was 1%, the tensile strength of insulating
paper increased by 14.13%, achieving the best effect. In 2015,
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
Zhang Song [33] also modified insulating paper with nano‐
Al2O3, which also confirmed the above conclusion. In addi-
tion, Zhang Song found that under 70°C–150°C, the bulk
modulus and shear modulus of the modified insulating paper
were improved, especially the optimal relative content of nano‐
Al2O3 was 1.3%t. In 2017, Liao Ruijin [34] et al. modified the
insulating paper with nano‐Al2O3 treated by KH550 on the
basis before, and found through tensile test that the tensile
strength of the modified insulating paper increased first and
then decreased with ageing time, but overall performance of
the modified insulating paper was better compared with the
unmodified insulating paper.
Nano‐TiO2 modified insulating paper
In 2014, Liao Ruijin [35] et al. modified insulating paper with
coupling agent KH570, and Lv Cheng [24] modified insulating
paper with coupling agent KH550. Through tensile test, it was
found that tensile strength did not fluctuate significantly when
the content of nano‐TiO2 was lower than 4%, while tensile
strength decreased significantly when the content of nano‐
TiO2 was greater than 4%. In 2019, Wang Chengjiang [36]
et al. of Three Gorges University in China analysed the change
of mechanical parameters of nano‐TiO2 modified insulating
paper by molecular simulation method, and observed that the
tensile modulus and Poisson's ratio of the modified insulating
paper were improved, the decrease was slower under high
temperature condition, the deformation resistance of the
modified insulating paper was increased, and the toughness
was improved. Meanwhile, the influence of NP size on me-
chanical parameters was studied, and it was found that the
smaller the particle size of nano‐TiO2, the smaller the tensile
modulus, Poisson's ratio and the Cauchy pressure, and the
overall mechanical properties of the insulating paper are
improved. In 2021, Liu [37] et al. also modified the insulating
paper with nano‐TiO2, and tested the tensile strength of the
modified insulating paper according to the constant speed
tensile method specified in GB/T 12914‐2008, and found that
the tensile strength of the modified insulating paper was much
lower than that of the unmodified insulating paper at the early
ageing stage. However, with the extension of ageing time, the
modified insulating paper exhibited excellent tensile resistance,
while the unmodified insulating paper almost lost the me-
chanical properties at the later ageing stage.
Nano‐SiO2 modified insulating paper
In 2017, Zhang [38] et al. of our research group continued to
study the effect of nano‐SiO2 content on mechanical proper-
ties of insulating paper, the model is shown in Figure 3. The
mechanical parameters of pure insulating paper (C0), insulating
paper with nano‐SiO2 (C1) and insulating paper with nano‐
SiO2 with surface saturation treatment (C2) are discussed.
The difference of mechanical parameters between C1 and C2 is
about 6% according to the data. Because C2 group is closer to
C0 group, the error between simulation model and actual
model can be reduced better. Therefore, using‐OH treatment
to unsaturated bond on the surface of nano‐SiO2 can improve
the performance of insulating paper. At the same time, it is
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 67

FIGURE 3 Spherical silica modified cellulose model

found that when the content of nano‐SiO2 is 5%, the elastic

modulus and shear modulus are the best.
In 2017, Hu Ting et al. [39] of Wuhan Nanrui Co., Ltd. of
Electric Power Research Institute of State Grid Corporation of
China modified the insulating paper with nano‐SiO2 surface
treated by aminopropyltriethoxysilane (APTES), and also
tested the tensile strength of the modified insulating paper
according to the constant speed tensile method specified in
GB/T 12914‐2008, the model is shown in Figure 4. It was
found that the tensile strength increased first and then
decreased with the increase of nano‐SiO2 content, and reached
the maximum when the content of nano‐SiO2 was 3%. FIGURE 4 Aminopropyltriethoxysilane surface treated nano‐SiO2
In 2018, Tang [40] et al. of our research group modified the
insulating paper with melamine‐grafted nano‐SiO2, the model
is shown in Figure 5. At the temperature of 650 K, the elastic good modification effect, and studied the effect of nano‐SiO2
modulus of the insulating paper modified by melamine‐grafted content on the mechanical properties of insulating paper by
nano‐SiO2 increased by 82.9% compared with unmodified means of molecular simulation, the model is shown in
insulating paper, and increased by 53.4% compared with the Figure 6. It was found that the maximum brittleness
insulating paper modified by nano‐SiO2. Under the influence improvement of insulating paper is achieved when SiO2 con-
of water content, increases were 22.5% and 7.8% respectively. tent was 3%, the mechanical property was improved most
In 2019, Wang [41] et al. of our research group studied the when SiO2 content was 12%, and the mechanical property of
differences in mechanical properties of insulating paper insulating paper decreased sharply when SiO2 content excee-
modified with KH550, KH560 and KH570‐grafted nano‐SiO2. ded 12.5%.
The mechanical parameters such as bulk modulus, shear
modulus, Poisson's ratio and elastic modulus were measured by
molecular simulation. The result showed that KH550‐grafted 2.2.3 | Other modification methods
nano‐SiO2 modified insulating paper showed the best me-
chanical properties, with the optimal anti‐deformation ability In addition to the above commonly used nano‐Al2O3, nano‐
and ductility. TiO2 and nano‐SiO2 to modify insulating paper, there are
In 2019, Wang Xiaobo [42] found that KH792‐grafted some other modification methods.
SiO2 modified insulating paper had better performance, and In 2001, S. J. Ferrito [44] of Cooper Power Systems Inc. in
the optimal graft density was 1.570. the United States used high‐temperature fibres to enhance the
In 2021, according to advantages and disadvantages of thermal ageing resistance of cellulose insulating paper, and
KH550 and KH792 reagents, Yang Lu [43] selected KH550‐ accelerated thermal ageing through severe overload cycles. It
grafted SiO2 modified insulating paper with lower price but was found that standard kraft paper had lost most of its

68
- TANG
FIGURE 5 Melamine‐grafted nano‐SiO2 insulating paper
FIGURE 6 KH550‐grafted SiO2 (3%) modified insulating paper
mechanical properties in the late ageing period, while insu-
lation paper modified with high‐temperature fibres still
retained a great deal of mechanical integrity.
In 2015, Qi Yixin et al. [45] of Wuhan University of
Technology in China modified insulating paper with modifiers
of KH550 and phenolic resin, and found that when phenolic
resin content was 20%, tensile strength of modified insulating
paper was 8.678 kN/m, elongation was 1.61%, and the
comprehensive performance was the best.
In 2016, Zhang et al. [46] of our research group modified
insulating paper with modified polysiloxane and grafted the
modified polysiloxane onto hydroxyl group connected with C6
atom of cellulose molecule by molecular simulation. They
found that when the content of polysiloxane was 6.5%, the
shear modulus, bulk modulus and Cauchy pressure of insu-
lating paper were improved, and the comprehensive effect of
mechanical properties was the best.
On this basis, in 2018, Wang [47] studied the performance
of polysiloxane modified insulating paper in micro‐water
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
environment, and found that due to the influence of poly-
siloxane the hydrogen bond network of cellulose chain would
not be damaged by its hydrophobicity, thus improving the
mechanical properties of insulating paper.
In 2021, Yang [48] et al. used polyhedral oligomeric
silsesquioxane (POSS) modified insulating paper to investi-
gate the optimum addition mass fraction of POSS. They
found that when the mass fraction of POSS was 3%, the
elastic modulus, shear modulus and bulk modulus pressure
of insulating paper were improved by 19.96%, 20.52% and
22.19%, respectively.
From the above references, it can be observed that it is
an advantageous means to improve the mechanical prop-
erties of insulating paper by modifying insulating paper
with NPs, which greatly improved compared with tradi-
tional physical and chemical modification methods. In this
section, Table 1 and Table A1 are obtained by summarizing
the data of the above materials, and the relevant parameters
are compared from the experimental and simulation point
of view, respectively. Therefore, if only the mechanical
properties of the modified insulating paper are considered,
the tensile strength of the insulating paper modified by
nano‐Al2O3 is increased by 14.13%. From the simulation
point of view, the mechanical parameters of insulating pa-
per modified by KH550‐grafted nano‐SiO2 showed the
maximum improvement and the elastic modulus, shear
modulus, bulk modulus, Cauchy pressure and Poisson's ratio
were improved by 16.1%, 96.1%, 37.5% and 24.6%,
respectively.
The mechanical properties of insulating paper can be
improved by using NPs, on the one hand, because there is a
certain force between NPs and fibre molecules after adding
NPs, which makes NPs bear some of the stress of the fibre
molecules; on the other hand, due to the existence of NPs,
the free motion of the fibre chain is restricted, so that the
strain of the fibre is greatly reduced. Mechanical parameters
such as elastic modulus are increased, the tensile strength
test results of insulating paper modified by different NPs are
shown in Table 1, and the simulation results are shown in
Table A1.

TANG ET AL.
TABLE 1 Comparison of test results of tensile strength of insulating paper modified by different nanoparticles
Modified Test method of tensile
particle Graft reagent strength
Nano‐Al2O3 KH570 [25] GB/T 12914 Constant
speed
Nano‐Al2O3 Polyethylene glycol [33] drawing method
Nano‐TiO2 KH570 [35]
Nano‐TiO2 KH550 [24]
Nano‐SiO2 APTES [39]
Phenolic resin KH550 [45]
Abbreviation: APTES, aminopropyltriethoxysilane.
2.3 | Thermal stability
2.3.1 | Introduction of background and
parameters
The ageing of cellulose insulating paper materials determines
the service life of transformers, and at the same time, the
operating temperature of transformers determines the ageing
speed of insulating paper materials. If the oil‐immersed
transformer is under rated load, the transformer can operate
safely for 20–30 years under such conditions. However, if the
transformer is overloaded, the average temperature of winding
can be more than 60°C higher than the ambient temperature
during transformer operation, while the temperature of the
hottest point is more than 70°C higher than the ambient
temperature. The service life of the transformer will be seri-
ously shortened by the large increase of temperature [49–51].
Especially, a large number of UHV equipment has been put
into operation in recent years, and the improvement of voltage
level will have more stringent requirements on thermal stability
of insulating materials.
However, in recent years, NPs have been well applied in
the field of modifying the thermal stability of polymer insu-
lating materials, which can improve the thermal stability of
materials at high temperature. In the conventional method, the
thermal stability is studied by means of thermal ageing in the
laboratory. Generally, the thermal stability of cellulose insu-
lating paper can be judged by the degree of polymerization, as
well as the moisture content and acid value of insulating paper.
The radial distribution function (RDF), free volume, mean
square displacement (MSD), glass transition temperature and
interaction energy are often used to characterize the thermal
stability of cellulose in molecular simulations; a detailed
description of these parameters can be found in references
[52–55].
2.3.2 | Comparative analysis of experimental
modification effect
Now, there are extensive research studies on the thermal sta-
bility of cellulose insulating paper. Liao Ruijin [56] studied the
effect of dicyandiamide addition on the thermal stability of
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
- 69
Optimal content Change of tensile Percentage of tensile
of nanoparticles strength strength change
1% Increase 14.13%
‐ Decrease 2.36%
3% Basically unchanged 0
3% Basically unchanged 0
3% Increase ‐
20% Increase 7.35%
cellulose insulating paper, and conducted thermal ageing test in
a 130°C ageing box for 31 days. The results showed that
compared with insulating paper without addition, the ageing
resistance and thermal stability of insulating paper were
significantly improved after addition of dicyandiamide. At the
end of ageing, the polymerization degree of modified cellulose
insulating paper was 58% higher than that of unmodified pa-
per. Therefore, adding appropriate amount of dicyandiamide in
cellulose insulating paper could significantly improve its ther-
mal stability and ageing resistance. In addition, Liao Ruijin [57]
prepared composite insulating paper by adding appropriate
amount of montmorillonite to cellulose insulating paper, and
conducted thermal ageing test in a 110°C ageing box to study
the influence of montmorillonite on thermal ageing charac-
teristics of cellulose insulating paper. The research results
presented that compared with insulating paper without
montmorillonite, the insulating paper with montmorillonite, in
combination with amine compounds, could significantly
improve the thermal stability of cellulose insulating paper and
showed strong anti‐ageing property.
Zhang Song [33] conducted thermal ageing test on modi-
fied insulating paper and unmodified insulating paper con-
taining nano‐Al2O3 mass fraction of 1%, and carried out
accelerated thermal ageing test for 31 days in an ageing box at
130°C. The research results showed that at the end of ageing,
the polymerization degree of modified cellulose insulating
paper was 27.8% higher than that of unmodified paper. The
ageing trend of polymerization degree with time is shown in
Figure 7. Therefore, the nano‐modified insulating paper
exhibited better thermal stability.
Yan Shuiqiang [58] prepared composite insulating paper
with 2% mass fraction of nano‐Al2O3 doping and hand‐copied
sheets of ordinary insulating paper, immersed them in oil to
form oil‐paper composite insulating samples, and carried out
accelerated thermal ageing test in a 130°C ageing box. The
results showed that the electrical properties of nano‐Al2O3
composite insulating paper are better than that of ordinary
insulating paper at various ageing stages, and less ageing
products are produced.
In order to study the change of anti‐ageing capacity of
nano‐Al2O3 modified cellulose insulating paper, Mo Yang [59]
prepared hand sheets of nano‐Al2O3 modified cellulose
insulating paper (with the mass fraction of 2%) and ordinary

70
- TANG
F I G U R E 7 Relationship between polymerization degree of nano‐
Al2O3 modified insulating paper and heat ageing time [33]
cellulose insulating paper in laboratory, both of which were
vacuum impregnated with mineral oil as the comparative
research object. The results showed that the life index of oil‐
immersed insulating paper was increased by 20% after doping
nano‐Al2O3, with better anti‐ageing ability and longer elec-
trical life under the same electric field.
Tang Chao [40] prepared unmodified (C1), nano‐silica‐
SiO2 modified (CN) and melamine‐grafted nano‐SiO2 modi-
fied (CAN) cellulose insulating paper, and carried out accel-
erated thermal ageing test of three kinds of cellulose insulating
paper in an ageing oven at 130°C. The results showed that the
polymerization degree of CAN was 50% higher and that of CN
was 35.7% higher at the end of ageing compared with that of
the unmodified paper. The trend of polymerization degree
change with time is shown in Figure 8. Of the three kinds of
cellulose insulating paper, CAN presented the best thermal
stability.
Liu Daosheng [37] prepared nano‐TiO2 composite insu-
lating paper board with mass fraction of 5wt% and particle size
of 10 nm and ordinary insulating paper board, and carried out
thermal ageing test for 20 days in a 130°C ageing box. The
polymerization of the ordinary insulating paperboard
decreased from 1190 at the initial moment to 241 at 20 days of
ageing, while the polymerization of the nano‐TiO2 composite
insulating paperboard decreased from 1069 to 350. At the end
of ageing, the polymerization degree of modified cellulose
insulating paper was 45.2% higher than that of unmodified
paper, which indicated that nano‐TiO2 composite paper had
good anti‐ageing ability.
2.3.3 | Comparative analysis of modification
simulation
Zhang Song [46] grafted polysiloxane onto hydroxyl group
attached to C6 atom in cellulose chain to study its influence on
thermal stability of cellulose. The results showed that among
four models with 0%, 3.3%, 6.5% and 12.2 mass fraction of
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
F I G U R E 8 Relationship between degree of polymerization (DP) and
ageing time [40]
polysiloxane, respectively, the modified model with 6.5% mass
fraction of polysiloxane reached the best chain properties, and
the glass transition temperature of the modified model was
48 K higher than that of the unmodified cellulose model,
which indicated that the modification improved the thermal
stability of cellulose. In addition, Zhang Song [38] studied the
influence of nano‐SiO2 doped cellulose on its thermal stability
performance. Before doping nano‐SiO2 into cellulose, the
simulation parameters were calculated after treating the surface
unsaturated O atom with –H and the surface unsaturated sil-
icon atom with –OH. Compared with the unmodified model,
its free volume fraction decreased by about 6%, its glass
transition temperature increased by about 50 K, and the
thermal stability performance was significantly improved.
Tang Chao [40] established cellulose/water (C–H2O),
nano‐silica modified cellulose/water (CN–H2O) and melamine
grafted nano‐silica modified cellulose/water (CAN–H2O)
models by molecular simulation method, as shown in Figure 9.
The research results show that compared with C–H2O model,
the glass transition temperature of CAN–H2O model was
increased by 69 K, while that of CN–H2O model was increased
by 39 K. Among the three models, CAN–H2O model dis-
played the highest thermal stability.
Wang Xiaobo [47] adopted molecular simulation method
to compare and analyse the thermal stability of polysiloxane‐
grafted cellulose with moisture content of 3% in order to
improve the thermal stability of insulating paper cellulose in
micro‐water environment. The research results showed that
the glass transition temperature of grafted model is 60 K
higher than that of ungrafted model. The RDF and hydrogen
bond were analysed and calculated. Polysiloxane grafted insu-
lating paper cellulose could reduce the amount of hydrogen
bond formed between water molecule and cellulose chain, thus
reducing the damage of water molecules to cellulose chains.
Therefore, polysiloxane‐grafted insulating paper cellulose
improved the thermal stability in micro‐water environment.
Wang Lihan [41] studied the influence of three different
silane coupling agents grafted with nano‐silica on the thermal

TANG ET AL.
FIGURE 9 Melamine‐grafted nano‐silica modified cellulose/water
stability of cellulose insulating paper, and calculated the inter-
action energy and free volume fraction of different models. As
shown in Table A2, the interaction energy of modified models
of KH550, KH560 and KH570 increased 63.63 kcal/mol,
50.76 kcal/mol and 15.83 kcal/mol, respectively, compared
with the unmodified model. The improvement degree of
thermal stability of nano‐silica/cellulose composite was as
follows: KH550 > KH560 > KH570.
Liu Yubin [60] used molecular dynamics to study the in-
fluence of different nano‐TiO2 doping content on the thermal
stability of cellulose to explore the nano content with relatively
good doping effect, the model is shown in Figure 10. The
results showed that when the content of nano‐TiO2 was 3.2%–
3.6%, the glass transition temperature of the modified insu-
lating paper was increased by 105 K and the free volume
fraction was reduced by 3.2% compared with the cellulose
insulating paper without adding nano‐TiO2, which indicated
that the nano‐TiO2 doped with 3.2%–3.6% has a relatively
good enhancement effect on the thermal stability of cellulose
insulating paper.
Yang Lu [43] effectively improved the thermal stability of
nano‐SiO2/cellulose system by grafting KH550 onto nano‐
SiO2 and doping it into cellulose. For nano‐SiO2/cellulose
system grafted with KH550, 12.5% grafting density achieved
the best modification effect.
Yang Lu [48] also established a pure cellulose model and
1wt%, 2wt%, 3wt%, 4wt%, and 5wt% POSS modified cel-
lulose models to study their thermal stability. The results
showed that the modification effect of 3wt% POSS modified
model was relatively the best. Compared with pure fibre
model, its MSD decreased by 26.7% and free volume fraction
decreased by 4.9%. In addition, Yang Lu [61] studied the
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
- 71
FIGURE 10 Titanium dioxide (3.5%) modified cellulose
effect of methyl, phenyl and aminophenyl groups on the
thermal stability of POSS modified insulating paper; the
model is shown in Figure 11. Figure 11a∼d represent POSS‐
CH3, POSS‐NH2, POSS‐phenyl and POSS modified cellu-
lose, respectively. The results showed that the addition of
POSS derivatives could effectively improve the thermal sta-
bility of cellulose. Among the three POSS derivatives, ami-
nophenyl group had the best modification effect on POSS.
Compared with pure cellulose, the glass transition tempera-
ture increased by 71 K. The MSD at different temperatures
was calculated, and it was found that the MSD was signifi-
cantly reduced, as shown in Figure 12. Figure 12a shows the
MSD of the pure cellulose model, Figure 12b shows the
MSD of the aminophenyl silsesquioxane (OAPS) model so
aminophenyl group was relatively the most obvious for
improving the thermal stability of cellulose.
In conclusion, whether from the perspective of experi-
mental analysis or molecular simulation, the thermal stability
and anti‐ageing properties of cellulose insulating paper modi-
fied by the above NPs will be improved to a certain extent.
From experiments, the addition of dicyandiamide greatly im-
proves the thermal stability of cellulose insulating paper. At the
end of ageing, the polymerization degree of cellulose insulating
paper increases by 58% compared with that without addition.
In terms of molecular simulation, the enhancement effect of
different NPs modified cellulose on different parameters is
shown in Table 2.
The thermal stability of cellulose insulating paper can be
improved by modifying the cellulose insulating paper with
NPs. From the microscopic point of view, the added NPs will
fill a part of the voids of cellulose chain and reduce its free
volume, the simulation models of pure cellulose model and
NPs modified model are shown in Figure 13a and Figure 13b
(the blue part represents the free volume and the grey part
represents the occupied volume). Due to the size effect of
NPs, they are more tightly bound to cellulose molecules, thus
increasing entanglement between cellulose chains and making
cellulose chains more compact. Therefore, the motion space of
cellulose chain is reduced, and the chain movement of cellulose
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
72
- TANG ET AL.

chain is suppressed, which makes its thermal stability chain and their interaction with the cellulose chain, while
improved. The microscopic mechanism is shown in Figure 14. Figure 14b shows polymer chain segments boned to NP sur-
Figure 14a shows the local distribution of NPs in the cellulose face in interfacial region.

F I G U R E 1 1 Amino modified POSS modified cellulose. (a) POSS‐ F I G U R E 1 2 Mean square displacement of 200 ps for cellulose model.
CH3, (b) POSS‐NH2, (c) POSS‐phenyl, (d) POSS modified cellulose. POSS, (a) Pure cellulose model, (b) aminophenyl silsesquioxanea model
polyhedral oligomeric silsesquioxane

TABLE 2 Comparison of simulation results of insulating paper modified by different nanoparticles

Glass transition Free volume Interaction Mean square

Modified particles, content temperature fraction energy displacement
Zhang Song [46] Polysiloxane‐grafted cellulose, 6.5% 48K ↑ ‐ ‐ ‐

Zhang Song [38] Nano‐SiO2, 5% 50K ↑ 6% ↓ ‐ ‐

Tang Chao [40] Melamine‐grafted nano‐SiO2, 1.2% 69K ↑ ‐ ‐ ‐

Wang Xiaobo [47] Polysiloxane‐grafted cellulose, 6.5% in 60K ↑ ‐ ‐ ‐

micro‐aqueous environment

Wang Lihan [41] KH550‐grafted nano‐SiO2 ‐ 8.21% ↓ 63.63 ↑ kcal/mol ‐

Liu Yubin [60] Nano‐TiO2, 3.2%∼3.6% 105K ↑ 3.2% ↓ ‐ ‐

Yang Lu [48] POSS, 3% ‐ 4.9% ↓ ‐ 26.7% ↓

Yang Lu [61] OAPS 71K ↑ ‐ ‐ ‐

Abbreviations: OAPS, aminophenyl silsesquioxane; POSS, polyhedral oligomeric silsesquioxane.

 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 73

FIGURE 13 Molecular simulation of free volume change which reflects thermal stability. (a) Pure cellulose model, (b) nanoparticles modified model

F I G U R E 1 4 Free volume mechanism diagram. (a) The local distribution of nanoparticles in cellulose chains and the interactions between nanoparticles and
cellulose chains, (b) polymer chain segments boned to nanoparticle surface in interfacial region [62, 63]

2.4 | Electrical property
2.4.1 | Background and electrical parameters
The insulating properties of insulating oil can be recovered
through oil replacement, but the insulating paper cannot be
replaced during operation, so the service life of transformers is
determined by the performance of insulating paper to the
greatest extent [57]. Increasing voltage levels and miniaturiza-
tion of electrical equipment require higher insulation strength
of insulating medium. The traditional oil–paper composite
insulation has become increasingly difficult to meet the re-
quirements. Electrical characteristics of insulating paper refer
to the polarization, conductance, dielectric loss and breakdown
under the action of an electrical field, and its four basic pa-
rameters are insulation resistance, dielectric constant, dielectric
loss and breakdown strength [5, 64].
Insulation resistance
Insulation resistance refers to the resistance value of the insu-
lating material under the action of DC voltage, pressurized for a
long time, and so that the charging current and absorption
current on the line disappears, only leakage current flows
through the insulating material. The higher the electrical resis-
tance of insulating paper, the lower its carrier mobility, indicating
that the insulating paper itself has good insulating performance.

74
- TANG
Dielectric constant
Insulating paper is a kind of composite dielectric body made of
interwoven cellulose. The relative dielectric constant of pure
cellulose is about 5.5, while that of general oil‐impregnated
insulating paper is about 4.4. For dry insulating paper,
it consists of cellulose with large dielectric constant and air
with dielectric constant of 1; while for oil‐impregnated paper, it
is composed of cellulose and impregnate. In double‐layer
dielectric, the distribution of electric field is inversely propor-
tional to the dielectric constant, the insulating oil with low
dielectric constant bears higher electric field strength. But the
breakdown field strength of external insulating oil is lower than
that of insulating paper, so it is necessary to reduce the
dielectric constant of insulating paper, improve the electric
field distribution of insulation system and increase the break-
down voltage of oil‐paper composite insulation.
Dielectric loss
Dielectric loss refers to the energy lost due to polarization and
conductance of dielectric under the action of electric field, and
the degree of dielectric loss is measured by the dielectric loss
factor (tgδ). The primary loss of insulating paper is conduc-
tivity loss, which mainly comes from impurities. The amount of
loss depends not only on the number of impurities but also on
their chemical composition. For transformer insulating paper,
dielectric loss is a crucial index, and its dielectric loss factor
shall be less than 0.23 according to regulations [64]. The lost
energy will be converted into heat energy, which raises the
temperature of insulating paper. If the medium loss is too
large, the continuous high temperature will accelerate the
ageing and decomposition of insulating paper, which will
eventually lead to the decrease of insulating performance of
insulating paper until complete failure.
Breakdown strength
Breakdown strength refers to the highest electric field strength
that insulation material can withstand to avoid breakdown under
the action of an electrical field, which is usually expressed by the
ratio of the breakdown voltage value to the thickness of test
sample. The test process is to place the insulating paper between
the electrodes, apply a voltage and raise the voltage at a certain
rate. When the voltage borne by insulating paper exceeds a
certain level, the paper will be damaged and loss of insulation
performance occurs, which called the electrical breakdown
phenomenon. For insulating paper, the larger the breakdown
field strength, the higher the voltage it can withstand, and the
better the insulation performance. According to QB/T 3521, its
commercial power frequency breakdown strength shall not be
less than 8.00 kV/mm.
2.4.2 | Comparative analysis on effect of
commonly used NP modification
Liao Ruijin et al. [35] found that nano‐TiO2 could effectively
improve the power frequency breakdown field strength of
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
insulating paper. When the mass fraction of nano‐TiO2 was
3%, the breakdown field strength was 61.78 kV/mm, which
was 20.83% higher than that of blank sample. The dielectric
constant, dielectric loss and conductivity of insulating paper
decreased with the increase of nano‐TiO2 content, and reached
the minimum value when the mass fraction of nano‐TiO2 was
3%. Lv Cheng [24] found that the power frequency breakdown
field strength of modified insulating paper was the highest at
3% nano‐TiO2 content, which increased by 20.81%.
Hu Ting et al. [39] successfully prepared SiO2 composite
insulating paper under the conditions of nano‐SiO2 content of
3%, polyamide acid solid content of 20% and curing temper-
ature of 180°C. Compared with the insulating paper before
composite modification, tensile strength and electrical strength
were increased 34.81% and 105.97%, respectively. The research
results of Li Xin et al. [65] showed that a layer of nano‐SiO2/
polyimide modified layer was formed on the surface of insu-
lating paper, which filled the voids of surface fibres of insu-
lating paper to form composite insulation system, resulting in a
significant increase in the breakdown strength of the insulating
paper. Chen Jie et al. [66] studied that there was a SiO2
modified layer on the surface of insulating paper, and SiO2 had
high surface activity and surface energy. Charged particles
collided with SiO2 particles after obtaining electric field energy,
and then new charged particles were generated. In addition, the
newly generated charged particles had lower energy. Therefore,
the propagation of electron avalanche was delayed to some
extent, so the short‐term electric ageing resistance of insulating
paper was improved.
Liao Ruijin et al. [25] studied that the dielectric constant
and dielectric loss of insulating paper decreased with the in-
crease of nano‐Al2O3 content, and reached the minimum value
when the nano‐Al2O3 content was 1%. Under commercial
power frequency conditions, the dielectric constant decreased
from 2.71 to 2.21, which decreased by 18.45%. When the
content of nano‐Al2O3 was 1%, the power frequency break-
down field of insulating paper was 66.78 kV/mm, which was
12.75% higher than that of blank sample. Yan Shuiqiang et al.
[58] studied that the doping of nano‐Al2O3 can improve the
DC breakdown electric field strength of insulating paper to
some extent. The change trend of relative dielectric constant
and dielectric loss tangent was consistent with the change trend
of measuring frequency, that is, the change was very gentle in
high frequency region and increased rapidly with the decrease
of frequency in low frequency region. Mo Yang et al. [59]
found that after nano‐Al2O3 doping and modification, the
service life index of oil–paper insulation increased by about
20% under laboratory hand sheet comparison, with better
resistance to electric ageing and longer electrical life under the
same electric field. According to Li Yanqing et al. [67],
compared with blank oil‐immersed insulating paperboard,
under 15 kV/mm DC electric field strength, micro‐nano
Al2O3/poly tetra fluoroethylene (PTFE) composite functional
layer reduced the total space charge in the paperboard by 40%.
Liu Heqian et al. [68] pointed out that the conductivity of
modified paperboard decreased first and then increased with
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 75

the increase of nano‐doping ratio, and the minimum value becomes easier. Besides, as the temperature increases, carrier
existed when the nano‐doping proportion was 1.0%. thermal vibration intensifies and it is easier to cross the
It can be seen from the above that NPs have small particle binding barrier of neighbouring molecules and participate in
size and large specific surface area, so the use of NPs to modify conduction. Therefore, when the electrical field strength and
polymers within a certain content will not reduce but increase temperature rise, the conductivity of the modified paperboard
the mechanical properties of the material. According to the system increases and space charge injection intensifies,
comparison and analysis of the present research results, the Figure 15a shows the energy band structure model of
commercial power frequency breakdown field of TiO2 with 3%
mass fraction can be improved to 20.83%, and the initial
discharge voltage of partial discharge increased by 40.88%. The
DC breakdown voltage improved by 105.97% when the mass
fraction of SiO2 was 1%. The dielectric loss of Al2O3 added
with mass fraction of 2% reduced to 73.68% at most. See
Table 3 for statistics.

2.4.3 | Mechanism of electrical performance

improvement
Effect of nano‐doping on energy band structure of modified
paperboard
As the ratio of nano‐doping increases, the spacing between
adjacent NPs decreases. When the distance between two
NPs is large, the potential energy curves are isolated from
each other, and the potential barrier between them is high
and wide. When the NPs are close to each other, they are
subjected to the interaction potential field, so the width of
the forbidden band decreases, and the width and height of
the barrier formed also decrease [69]. At this time, carriers
can jump to the conduction band of the system by means
of traps provided by NPs, and then cross or pass through
the barrier through tunnelling effect, so the conductivity of
modified paperboard increases.
When DC electric field is applied, the band structure in F I G U R E 1 5 Energy band structure model of modified paperboard
the system will shift, which leads to the reduction of the under high electrical field strength. (a) Band structure model of unmodified
binding barrier which carriers need to cross and the transition paperboard, (b) Energy band structure model of modified paperboard [12]

TABLE 3 Improvement results of electrical properties of insulating paper modified by different nanoparticles

Results
Nanoparticle Commercial power frequency Initial discharge DC breakdown
modification Author Mass fraction breakdown voltage voltage Dielectric loss voltage
TiO2 Liao Ruijin [35] 3% 20.83% ↑ ‐ ‐ ‐
Lv Cheng [24] 3% 20.81% ↑ 40.88% ↑ ‐ 37.52% ↑

SiO2 Hu Ting [39] 3% 105.97% ↑ ‐ ‐ ‐

Li Xin [65] 3% 105.97% ↑ ‐ ‐ ‐
Chen Jie [66] 3% 34.% ↑ ‐ ‐ ‐

Al2O3 Liao Ruijin [25] 1% 12.75% ↑ ‐ 18.45% ↓ ‐

Yan Shuiqiang [58] 2% 13.66% ↑ ‐ 73.68% ↓ 8.33% ↑
Mo Yang [59] 2% ‐ ‐ 20.% ↓ ‐
Liao Ruijin [25] 1% 12.75% ↑ ‐ ‐ ‐
Li Yanqing [67] Coating 15.% ↑ ‐ ‐ ‐
Liu H [68] 2.5% 14.39% ↑ ‐ 31.91% ↓ 6.63% ↑

76
- TANG
unmodified paperboard, while Figure 15b shows the energy
band structure model of modified paperboard.
Effect of trap characteristics on dielectric properties of
modified paperboard
The essence of trap is the localized state in the band gap which
binds charges. In the nano‐modified paperboard system, the
trap will be formed by the branch chain and end group, folding
and breaking of chains, as well as impurities and lattice defects
of NPs in cellulose, having significant influence on charge
transport and storage, ageing and breakdown characteristics of
composite dielectrics [70, 71]. When the ratio of nano‐doping
is low, the probability of the NPs contacting with cellulose is
small, so the interface volume increases obviously and the
number of traps increases accordingly. With increased nano‐
doping ratio, the spacing between NPs becomes smaller, and
the conductive layers of adjacent NPs may overlap or even
merge with each other, as shown in Figure 16. Meanwhile, the
contact probability between NPs and cellulose increases. The
combination of branched unbonded atoms and lattice defects
will consume a certain amount of traps, and the adsorption
effect of the limiting layer on cellulose branches will be
enhanced, which also leads to the decrease of relative dielectric
constant and dielectric loss factor of modified paperboard [68].
3 | RESEARCH PROGRESS ON OIL‐
PAPER COMPOSITE SYSTEMS OF
MODIFIED INSULATING PAPER
3.1 | Background
The internal insulation of oil‐immersed transformers is an oil–
paper composite insulation system composed of insulating
paper and insulating oil. The insulating ability of oil–paper
composite insulation is a decisive factor which determines
whether the oil‐immersed transformer can operate normally.
The insulating property of such a composite insulating struc-
ture changes due to the change of the properties of insulating
paper or insulating oil.
The relative dielectric constant of pure cellulose is about
5.5, while that of general oil‐impregnated insulating paper is
about 4.4. Because the inside of insulating paper is not
completely tight and there are a large number of voids, the
introduction of insulating oil makes these voids filled with
insulating oil. The relative dielectric constant of insulating oil is
F I G U R E 1 6 Charge distribution around an isolated particle and that
around an adjacent particles with overlapped interaction area
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
much lower than that of pure cellulose, so the relative dielectric
constant of the whole oil‐immersed insulating paper decreases.
The decrease of relative dielectric constant of insulating paper
makes the distribution of electrical field in oil‐paper composite
systems more reasonable, reduces the electrical field strength in
the insulating oil, and improves the reliability of oil‐paper
composite insulation systems. At the same time, oil‐paper
composite insulation can improve the distribution of space
charge inside insulating paper, making the electrical field dis-
tribution more uniform inside insulating paper, and change the
number of electric charge traps inside insulating paper, which
can effectively improve the insulating property of insulating
paper.
Therefore, it is not enough to only pay attention to the
performance improvement of insulating paper, but also study
the impact of modified insulating paper on the performance of
oil‐paper composite insulation systems.
3.2 | Study on performance of existing oil‐
paper mixed insulation systems
Up to now, most researches on the modification of oil‐paper
insulation systems have been done on the following NPs: (1)
Titanium dioxide (TiO2); (2) Silica (SiO2); (3) Alumina (Al2O3).
Ying Yupeng et al. [72] studied the influence rule of tita-
nium dioxide NPs on the DC breakdown strength of oil‐paper
composites, and analysed the action mechanism of NPs, and
their main conclusions are as follows: the concentration of
NPs, the combination mode of oil‐paper and the morphology
of NPs all affected the DC breakdown strength of oil‐paper
composites, and the breakdown of oil‐paper composites had
polarity effect. With the increase of the concentration of
spherical particles, the breakdown voltage of oil–paper com-
posites increased first and then decreased. The best modifi-
cation effect was obtained at 0.02 g/L. When the adding
concentration was 0.02 g/L, the voltage distribution in the oil
was almost identical with that in the paper during the boosting
process, so the breakdown voltages of the positive and negative
poles were also the highest, which were 22.5% and 3.6% higher
than those of pure oil–paper composites.
To study the insulating properties of nano‐TiO2 modified
insulating paper, Liao Ruijin [35] et al. prepared insulating
paper handsheets containing different mass fractions of nano‐
TiO2 in laboratory, and tested the properties of insulating
paper after oil immersion in vacuum. The results showed that
within a certain mass percentage of nano‐TiO2, the commer-
cial power frequency breakdown field strength of the modified
insulating paper was greatly improved, for example, when the
mass fraction of nano‐TiO2 was 3%, the power frequency
breakdown field strength was increased by 20.83%. The
dielectric constant, dielectric loss and conductivity of the
insulating paper decreased with the increase of nano‐TiO2
content within 3%. Liao Ruijin's team also studied the effect of
nano‐TiO2 addition on the tensile strength of insulating paper
and found the tensile strength of insulating paper did not
decrease, but slightly increased, and the dispersibility decreased
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 77

with the increase of nano‐TiO2 mass fraction. However, when

the mass fraction of nano‐TiO2 reached 4%, the tensile
strength of insulating paper dropped dramatically and the
dispersibility increased sharply.
Li Xu [26] of our research group studied the addition of
silica NPs (GNPs) to meta‐aramid insulating paper after 3‐
aminopropyl triethoxysilane grafting modification. The
addition of GNPs improved the thermal stability of amor-
phous region in the modified insulating paper. The addition
of GNPs weakens the chain movement of MPIA fibres,
thus increasing the thermal stability of MPIA fibres. On the
other hand, it fills up the original large gaps, so that
cohesive energy density increases, playing a role similar to
adhesive. The addition of GNPs also weakens the diffusion
of water, acid and gas in MPIA fibres, thus decreasing the
influence of these substances on the thermal stability of
aramid fibres, which further improves the thermal stability
of aramid insulating paper, and delays the ageing process of
F I G U R E 1 7 Molecular model of amine compounds. (a) Melamine,
oil impregnated aramid insulating paper. (b) dicyandiamide, (c) polyacrylamide
The team of Liao Ruijin [25] modified the oil‐immersed
insulating paper with nano‐Al2O3. When the content of
nano‐Al2O3 was 1%, the insulation performance and me- is the relative optimum concentration in the papers, with the
chanical performance of the oil‐immersed insulating paper best improvement of electrical, mechanical and thermal sta-
were significantly improved. The influence of nano‐Al2O3 bility performance. It can be seen from the above studies that
on the electrical performance of oil‐paper insulation sys- the electrical performance, thermal stability and mechanical
tems was also studied by the group of Liao Ruijin [73], properties of transformer oil‐paper insulation systems are
and they explained the mechanism from the perspective of improved for nano‐modified insulating paper.
space charges. Their research results showed that the per-
formance of nano‐Al2O3 modified oil‐impregnated paper
was the comprehensive result of agglomeration effect and 3.3 | Mechanism analysis
interface effect. For oil‐impregnated insulating paper with
low mass fraction of NP doping, the agglomeration phe- The mechanism can be summarized as follows:
nomenon was weak, the interface effect was dominant and
the overall performance was improved. However, the cel- (1) Electrical performance: The introduction of NPs greatly
lulose structure of the modified paper with higher mass increases the number of shallow traps in the oil‐paper
fraction of NPs was destroyed by nano‐agglomerates, so composite insulation system and reduces the number
the overall properties of the modified paper decreased, so of deep traps. The breakdown of nano‐modified oil‐
that the volume resistivity and breakdown field strength paper composites occurs first in the oil‐impregnated
increased first and then decreased with the increase of the paper, while the breakdown of pure oil‐paper compos-
mass fraction of NPs. ites occurs first in the oil gap and leads to the overall
Liang Ningchuan [74] studied the effect of amine com- breakdown. With the increase of the number of shallow
pound modified insulating paper on the oil‐paper insulating traps, the energy of carriers such as electrons is
system, the amine compound model is shown in Figure 17. consumed by constantly getting into and out of traps, so
According to the study, amine compound (2.25wt% melamine, they cannot develop into the effective discharging elec-
0.75wt% dicyandiamide, and polyacrylamide and 0.2wt% trons, which improves the breakdown performance,
polyacrylamide) had the best anti‐ageing performance for partial discharge and initial discharge voltage of nano‐
insulating paper, but it accelerated the deterioration of insu- modified insulating paper
lating oil and increased of CO2 concentration in oil. At the (2) Thermal stability: A large number of hydrogen bonds are
same time, Liang Ningchuan [75] also studied the performance formed between NPs and cellulose of insulating paper, and
of amine compound and nano‐Al2O3 composite modified the formation of these hydrogen bonds enhances the
insulating paper, and found that the composite modification interaction between NPs and cellulose. Under the influ-
further improved the heat ageing resistance of insulating paper, ence of NPs, the chain motion of cellulose is weakened
and at the same time improved the adverse impact of amine and the thermal stability is enhanced. The introduction of
compound on insulating oil. NPs and the existence of oil gaps weaken the diffusion of
Table 4 shows the percentage of the performance water, acid and gas in the insulating paper, thus reducing
improvement of commonly used NP‐modified insulating pa- the influence of these substances on the thermal stability
per in oil–paper insulation systems. The content of NPs listed of cellulose, which further improves the thermal stability

78
- TANG
TABLE 4 Relative optimum values of performance improvement of commonly used nanoparticle modified insulating paper in oil‐paper insulation systems
Average
nanoparticle Test object
Nanoparticles size (nm) (paper/nanoparticles)
TiO2 [35] 30 Softwood pulp board imported
from Russia/Shanghai
Maikun Chemical
Co., Ltd.
Al2O3 [25, 73] 30 Russia imported softwood pulp/ 1%
Shanghai Maikun Chemical
Co., Ltd.
SiO2 [26] 35 ‐ 1wt%
of insulating paper, and delays the ageing process of oil‐
immersed insulating paper
(3) Mechanical performance: NPs can be a bridge between
fibres at the gap. The NPs and cellulose have relatively
good binding energy. At the same time, NPs are in contact
with both insulating paper and insulating oil. The existence
of oil gaps can play the role of shock absorption and
buffering, thus improving the mechanical performance of
insulating paper
It can be seen from the existing research results that
insulating paper modified with different NPs can all improve
the performance of oil‐paper composite insulation systems. It
can be seen from the above sections and Table 4 that boron
nitride (h‐BN) showed the most significant increase of the AC/
DC breakdown voltage of oil–paper composite insulation
systems, with AC breakdown voltage increase of 34% and DC
breakdown voltage increase of 21%; the initial voltage of
partial discharge was increased by 19.93% by nano‐TiO2.
Among several commonly used NPs, nano‐Al2O3 displayed
the most remarkable effect on tensile strength of insulating
paper, up to 14.13%. For the thermal stability of insulating
paper in oil–paper composite insulation systems, the intro-
duction of nano‐SiO2 greatly improved the thermal stability of
insulating paper.
4 | RECENT PROGRESS AND FUTURE
PROSPECTS
4.1 | New types of insulating paper
Kangliyuan Technology (Tianjin) Co., Ltd. disclosed the
structure and production process of NMN insulating paper
[76]. In this invention, inorganic ceramic fibre paper and pol-
yoxadiazole polyester fibre insulating paper are added on the
traditional NMN insulating paper. The inorganic ceramic fibre
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
Nanoparticle Mechanical Thermal
content Electrical properties properties stability
3% Commercial power frequency break- Slight increase in ‐
down field strength was increased tensile
by 20.83%, strength
Partial discharge initiation voltage
increased by 19.93%,
Breakdown voltage increased by
17.68%
Power frequency breakdown field Tensile strength ‐
strength increased by 12.75%, increased by
Dielectric constant decreased by 14.13%
18.45%
‐ Tensile strength Thermal
increased by stability
4.9% greatly was
improved
paper has strong impregnability, which keeps the NMN insu-
lating paper fibre wet after dipping paint, which improves the
insulation and chemical stability. The polyoxadiazole polyester
fibre insulating paper has extremely high heat resistance, and
its heat resistance grade reaches H (180°). Besides, it has
extremely strong mechanical strength and electrical strength,
thus improving the heat resistance and mechanical strength of
NMN insulating paper.
Henan Jinzhi New Insulation Materials Co., Ltd. dis-
closed a new type of high‐strength insulating paper [77]. It
relates to the technical field of insulating paper, including
the insulating paper body, which is composed of meta‐
aromatic polyphthalamide fibres, steel wires, a first cutting
groove and polyester film layers. A steel wire is embedded
in the inner middle portion of the meta‐aromatic poly-
phthalamide fibre, and a first cutting groove is provided on
the outside of the steel wire. Active carbon fibre layers are
installed at the inner upper and lower sides of the meta‐
aromatic polyphthalamide fibre, and a sponge layer is fixed
on the side of the active carbon fibre layer far from the
centre line of the meta‐aromatic polyphthalamide fibre. A
first polyester film layer is embedded on the outside of the
insulating paper body.
Liu Qiankun invented a preparation method of high tem-
perature resistant polysulfone‐based composite insulating pa-
per [78]. The invention uses polysulfone resin as the base
material to prepare high temperature resistant polysulfone‐
based composite insulating paper, wherein the polysulfone
resin can obtain superior thermal oxygen stability due to its low
polarity, two phenyl rings adjacent to the sulfone group form a
conjugated diphenol structure so that the molecular chain has
good rigidity, and the main chain of the polysulfone resin
neither contains isopropylidene group, which can affect heat
resistance, nor biphenyl group, which can make the molecular
chain excessively rigid, so that the polysulfone resin retains
good oxygen resistance and thermal stability of the polysulfone
polymer.
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 79

The mechanical strength, electrical strength and heat will undergo chemical reaction when the bond is broken during
resistance of cellulose insulating paper have been improved to operation to restore the dense linking state of insulating paper
a certain extent by modifying the chemical structure of inner fibres, thus recovering its mechanical and electrical properties
fibre layer of cellulose insulating paper. to a certain extent, which increases the reliability of equipment
operation [17].
At present, researchers have made preliminary research
4.2 | Hydrophobic insulating paper results on self‐repair of cellulose [81, 82]. By combining mo-
lecular simulation with modern composite analysis and syn-
At the beginning of the 20th century, some scholars have thesis technology, a new type of natural cellulose insulating
realized the influence of moisture on insulating paper [79]. A paper with high performance has been prepared by functional
large number of studies have shown that when the water molecular design and modification of natural cellulose, which
content in cellulose insulating paper increased from 0.3% to can reduce dielectric constant and improve its long‐term heat
4%, the ageing rate of insulating paper would increase by 12–
45 times [80].
Our research group used polytetrafluoroethylene PTFE
NPs, fluorocarbon surfactant ST‐110 and fluorinated alkyl
silane to prepare aqueous solution coating, the preparation
process is shown in Figure 18. The waterborne coating is
applied on insulating paper by special process, which can
produce good hydrophobic and oleophobic properties, the
coating has long‐term high temperature durability and good
acid‐alkali resistance, and the stability test results are shown in
Figure 19.

4.3 | Insulating paper with self‐repairing

hydrophobic coating

Because it is difficult to replace cellulose insulating paper

during the operation of the equipment, the service life of the
insulating paper determines the service life of the equipment.
After self‐repairing modification of cellulose insulating paper,
the reversible (non‐) covalent bond inside the insulating paper FIGURE 19 Stability test for hydrophobic coated insulating paper

FIGURE 18 Preparation process


80
- TANG
resistance and mechanical properties while realizing self‐
repairing and hydrophobic features of cellulose insulating
paper.
The super‐hydrophobic coatings of our research group
have certain self‐repairing ability to both chemical and
physical damages. The scanning electron microscope (SEM)
image of coated insulating paper is shown in Figure 20.
Figure 20a is a SEM image of the original sample,
Figure 20b,c show the self‐repairing process of the coated
insulating paper. It can be seen from the abraded insulating
paper fibres in Figure 20b that some coating substances are
damaged and the surface roughness is between the original
insulating paper and the coated insulating paper, but there
are still hydrophobic NPs which provide certain hydropho-
bic features. After heating repair, the hydrophobic molecules
migrate to the surface under the guidance of heat action,
and the roughness of the surface increases obviously, which
proves the self‐repair of hydrophobic function under heat-
ing. After experiments, our research group preliminarily
concluded that the insulating paper prepared had better self‐
repairing and hydrophobic properties, and the more detailed
research results will be presented in future papers.
4.4 | Future prospects
It can be seen from the existing research results that insulating
paper modified with different NPs can improve all kinds of
properties of oil‐paper composite insulation systems, but the
number of production steps has increased and production
costs have risen. In Nano doping, some properties of di-
electrics, such as dielectric constant and dielectric loss,
conductive properties, material micro morphology, depth of
traps, and so on, have limitations and poor repeatability of
characterization and test results, as well as their own irregularity
or even contradiction due to the dispersion of NPs and the
instability of agglomeration structure. In addition, the interface
composed of surface is complex and changeable. This specu-
lation that the existence of the interface region between NPs
and matrix can improve the properties of materials is still
artificial [83]. In addition, NPs are also found to be relatively
FIGURE 20 Scanning electron microscope (SEM) image of coated insulating paper. (a) Original sample, (b) abrasion injury sample, (c) self‐healing sample
after heating
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
expensive in themselves, for example, h‐BNs. Besides, it is also
important to consider whether the NPs can be effectively filled
in cellulose during the addition of NPs. The oil–paper insu-
lation system is a holistic system, and the influence of adding
NPs on the insulating oil needs further study. Excessive im-
purities may form ‘small bridges’ in the insulating oil, which
will increase the possibility of breakdown of the insulating
paper. Finally, it is worth mentioning that the mechanism of
the property improvements of insulating paper due to NPs also
needs to be further explored.
With the increase of operation voltage levels and system
capacities, due to the restriction of transportation and field
installation conditions as well as economic and technical in-
dicators, various motors tend to be miniaturized, enlarged in
capacity and diversified for operating environment. In order to
meet the requirements of electrical insulation materials, it is of
great significance to develop and study new insulating paper.
The future development trend of insulating paper primarily
includes the following aspects:
The structure, interface, and space‐time multi‐level effects
of nano‐dielectric materials.
The nano‐dielectric phenomenon is a mesoscopic phe-
nomenon between the macroscopic matter and the micro-
scopic atomic scale. Its research requires a comprehensive
application of traditional dielectric theory and microscopic
quantum theory. Inside nano‐dielectric, the size of the filler and
the distance between the fillers are in the nanometre range, and
the filler will interact chemically and physically with the poly-
mer matrix, resulting in mesoscopic properties that are neither
atomic nor macroscopic. Nano‐scale dielectric phenomena not
only involve electrical and electronic insulating media, but also
micro‐dielectric behaviour in sensing and functional dielectrics,
non‐linear optical dielectrics, and bio‐dielectrics. Many excel-
lent properties of nano‐dielectrics are considered to be related
to the interface structure and behaviour.
(1) The study of nano‐scale dielectric phenomena is helpful to
understand the microstructure mechanism corresponding
to the macro‐dielectric properties of polymer/inorganic
nanocomposite dielectrics, and it is possible to greatly
improve the insulation quality of power equipment and

TANG ET AL.
power electronic devices, and open up the new field of
application of dielectrics
(2) Develop insulating paper with high dielectric and me-
chanical performance. The level of working field strength
is an indication of whether the insulation structure of
electrical products is advanced or not. China is further
strengthening the development and industrialization of
new insulating paper for high electrical field
(3) Develop insulating paper with high heat resistance. Heat‐
resistant insulating material is one of the key develop-
ment directions of modern insulating material products.
According to China's national conditions, the directions
will be strengthening the popularization and application of
existing F, and H grade insulation materials, exploring its
new uses, and developing new F and H grade heat‐
resistant fibre paper with moderate price on this basis
(4) Develop high environmental performance and energy‐
saving insulating paper. It is a cross‐century task to
develop low, pollution‐free and resource‐protected insu-
lating materials with high environmental performance in
their production and application for China and abroad
ACK NO W LE DG E MEN T S
This work was supported by the National Nature Science
Foundation of China [Project No. 51977179].
CO NF L ICT O F I NT E R ES T
All authors have declare that: (i) no support, financial or
otherwise, has been received from any organization that may
have an interest in the submitted work; (ii) there are no other
relationships or activities that could appear to have influenced
the submitted work & quot;
P ERM ISSIO N T O RE PRO D U CE M AT E RI A L S
F ROM OTH E R SO U R CE S
Yes, the referenced figures and tables have been licenced.
DA TA AVA IL AB I L I T Y S TAT EM E NT
All data included in this study are available upon request by
contact with the corresponding author.
O RC ID
Chao Tang https://orcid.org/0000-0002-5572-2671
REFE R ENC ES
1. Prevost, T.A., Oommen, T.V.: Cellulose insulation in oil‐filled power
transformers: Part I ‐ history and development. IEEE Electr. Insul. Mag.
22(1), 28–35 (2006)
2. Chen, S.: Analysis of transformer common accidents and anti‐accident
measures. Master’s thesis, School of Electrical and Electronics Engi-
neering, China (2012)
3. Morsalin, S., et al.: Diagnostic challenges in dielectric loss assessment and
interpretation: a review. IET Sci. Meas. Technol. 13(6), 767–782 (2019)
4. Tanaka, T., Yongming, C.: Technical level of oil impregnated insulation in
Japan. Insul. Mater. 6(12), 42–46 (1985)
5. Lv, J., Zhan, H., Jin, H.: Power transformer insulation paper: its prop-
erties and insulation aging. China Pulp Pap. 27(05), 54–58 (2008)
6. Kohman, G.T.: Cellulose as an insulating material. Ind. Eng. 31(7),
807–817 (1939)
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
- 81
7. Hu, Z.: Insulating material technology. Chemical Industry Press (2005)
8. Liu, C., et al.: Development and application of insulating paper. In: 2017
China Special Paper Technology Exchange Conference and the 12th
Annual Meeting of Special Paper Committee, Zhejiang, China, pp. 79–90.
(2017)
9. State Grid Corporation of China: Q/GDW 1168—2013 Test code for
condition based maintenance of power transmission and transformation
equipment. China Electric Power Press (2014)
10. Wang, Y., Kang, Y.: Study on thermal aging test of insulating paper in
transformer. Electr. Technol. 4(8), 23–25 (2018)
11. Huaqiang, L., et al.: The DC breakdown of mineral insulating oil and oil‐
pressboard. In: 2013 Annual Report Conference on Electrical Insulation
and Dielectric Phenomena, Shenzhen, China, pp. 929–931. (October
2013)
12. Liu, H., et al.: Analysis of dielectric characteristics of nano‐Al2O3
modified insulation pressboard. Proc. CSEE. 37(14), 4246–4253 (2017)
13. Liao, R., et al.: Experiments research on the influence of copper on
thermal aging of transformer oil. High Volt. Eng. 36(5), 1090–1095
(2010)
14. Tang, L.: Cellulose Science. CSPM Press (1996)
15. Zhang, M., et al.: Measurement of dielectric response of transformer
moisture content. IET Sci. Meas. Technol. 12(5), 594–602 (2018)
16. Suleiman, A.A., et al.: Moisture effect on conductivity of kraft paper
immersed in power transformer vegetable‐based insulation oils. IET
Gener. Transm. Distrib. 11(9), 2269–2274 (2017)
17. Zhu, M., et al.: Simulation of diffusion of moisture in insulation paper
and the affect on mechanical properties of the paper. Trans. China
Electrotech. Soc. 30(10), 338–345 (2015)
18. Li, D., Jia, D.: Progress and application of polymer/inorganic nano-
composites. Polym. Mater. Sci. Eng. 19(4), 22–26 (2003)
19. Zhang, D., et al.: Industry applications of nanotechnology in high
performance insulation composites. Sci. Sin. Chim. 6(8), 725–743
(2013)
20. Hou, X.: Interface design and performance of epoxy resin‐based/carbon
fiber composites. Master’s thesis, School of Materials Science and En-
gineering Nanchang Hangkong University, China (2019)
21. Choudhary, S., Sengwa, R.J.: Morphological, structural, dielectric and
electrical properties of PEO–ZnO nanodielectric films. J. Polym. Res.
24(3), 1–12 (2017)
22. Nazir, M.T., et al.: Dielectric and thermal properties of micro/nano
boron nitride co‐filled EPDM composites for high‐voltage insulation.
Micro & Nano Lett. 14(2), 150–153 (2019)
23. Zhang, S.: The micromechanism on the doping modification of nano
SiO2 to the oil‐immersed cellulose insulating paper. Master’s thesis,
Southwest University, China (2018)
24. Lv, C.: Studies on the preparation and properties of cellulose insulation
paper modified by nano‐TiO2. PhD thesis, Chongqing University, China
(2014)
25. Liao, R., et al.: Insulating properties of insulation paper modified by
nano‐Al2O3 for power transformer. J. Electr. Power Sci. Technol. 29(1),
3–7 (2014)
26. Li, X.: The thermal stability improvement mechanism of MPIA insu-
lating paper modified by nano‐SiO2 surface‐grafted via APTS. Master’s
thesis, Southwest University, China (2018)
27. Wang, Qi, et al.: Effect of TiO2 nanoparticles on surface discharge
characteristics of transformer oil impregnated pressboard. Insul. Mater.
48(8), 36–40 (2015)
28. Liao, R., et al.: Quantum chemistry study on mechanism of antithermal
ageing performance of thermally upgraded insulation papers. Proc.
CSEE. 33(25), 196–203 (2013)
29. Ge, Y., et al.: Effects of TiO2 nanoparticles on streamer propagation at
the surface of oil‐impregnated insulation paper. IEEE Trans. Plasma Sci.
46(7), 2491–2496 (2018)
30. Tang, C., et al.: Molecular dynamics simulations of the effect of shape
and size of SiO2 nanoparticle dopants on insulation paper cellulose. AIP
Adv. 6(12), 125106 (2016)
31. Langmuir, I.: Oscillations in ionized gases. Proc. Natl. Acad. Sci. 14,
627–637 (1928)

82
- TANG
32. Zhang, H., Chen, Q.: Recent progress of non‐thermal plasma material
surface treatment and functionalization. Acta Phys. Sin. 70(9), 095203
(2021)
33. Zhang, S., Tang, C., Chen, G.: The influence and mechanism of nano
Al2O3 to the thermal stability of cellulose insulation paper (in Chinese).
Sci. Sin. Tech. 44(11), 1167–1179 (2015)
34. Liao, R., He, L., Lv, Y.: Influence of nano‐Al2O3 on properties of oil‐
paper insulation during thermal aging process. Trans. China Electro-
tech. Soc. 32(15), 207–215 (2017)
35. Liao, R., Lv, C., Wu, W.: Insulating property of insulation paper modified
by nano‐TiO2. High Volt. Eng. 40(7), 1932–1939 (2014)
36. Wang, C., et al.: Molecular simulation of the influence of TiO2 particle
size on the strength and thermal stability of cellulose. J. Atom. Mol. Phys.
36(6), 969–975 (2019)
37. Liu, D., et al.: Thermal aging effect on properties of pure and doped
nano‐TiO2 cellulose pressboard. IEEE Trans. Dielectr. Electr. Insul.
28(1), 133–141 (2021)
38. Zhang, S., et al.: Thermal stability and dielectric properties of nano‐SiO2‐
doped cellulose. Appl. Phys. Lett. 111(1), 1–4 (2017)
39. Hu, T., et al.: Preparation of nano‐SiO2 composite modified insulation
paper. Insul. Mater. 50(6), 22–26 (2017)
40. Tang, C., et al.: Enhanced mechanical properties and thermal stability of
cellulose insulation paper achieved by doping with melamine‐grafted
nano‐SiO2. Cellulose. 25(6), 1–15 (2018)
41. Wang, L., et al.: Molecular dynamics simulation on the thermodynamic
properties of insulating paper cellulose modified by silane coupling agent
grafted nano‐SiO2. AIP Adv. 9(12), 1–7 (2019)
42. Wang, X.: The microscopic mechanism research of cellulose insulating
paper modified by nano‐SiO2 surface‐modified via silane coupling agent.
Master’s thesis, Southwest University, China (2019)
43. Yang, L., et al.: Influence of KH550 grafting density on surface of nano‐
SiO2 on mechanical properties and thermal stability of modified cellulose
insulating paper. Insul. Mater. 54(1), 25–30 (2021)
44. Ferrito, S.J., Stegehuis, R.L.: Thermal endurance of high temperature
fiber reinforced cellulose insulation. In: 16th International Conference
and Exhibition on Electricity Distribution. Amsterdam, Netherlands
(2001)
45. Qi, Y., et al.: Preparation of modified insulating paper and its short‐term
heat resistance analysis. Insul. Mater. 48(9), 25–28+33 (2015)
46. Zhang, S., et al.: Improvement of thermal stability of insulation paper
cellulose by modified polysiloxane grafting. Appl. Phys. Lett. 109(17), 1–4
(2016)
47. Wang, X., et al.: Thermal stability improvement of polysiloxane‐grafted
insulating paper cellulose in micro‐water environment. AIP Adv. 8(10),
1–9 (2018)
48. Yang, L., et al.: Insulating paper cellulose with high mechanical perfor-
mance and low polarizability: the effect of doping concentration on
polyhedral oligomeric silsesquioxanes‐modified cellulose. Adv. Eng.
Mater. 23(8), 2100022 (2021)
49. Lin, Y., et al.: Kinetics and mechanism of cellulose pyrolysis. J. Phys.
Chem. C. 113(43), 20097–20107 (2009)
50. Antal, M.J., Várhegyi, G., Jakab, E.: Cellulose pyrolysis kinetics: revisited.
Ind. Eng. Chem. Res. 37(4), 1267–1275 (1998)
51. Antal, M.J., Mok, W.S.L.: The pathways and kinetics of cellulose pyrolysis
revisited. Abstr. Pap. Am. Chem. Soc. 188(8), 39–46 (1984)
52. Liu, X., Luo, D.: The concept and discussion of the radial distribution
function. J. Liaocheng Teachers Univ. 15(1), 48–49+85 (2002)
53. Yang, T.: Molecular dynamics study on the impact of temperature and
electric field on the microscopic properties of oil‐immersed insulation
paper. Master’s thesis, Chongqing University, China (2013)
54. Wang, Y., et al.: Glass transition in amorphous region of transformer
insulation paper by molecular dynamics. High Volt. Eng. 38(5),
1199–1206 (2012)
55. Fu, Y.Z., et al.: Molecular dynamics simulation on binding energies and
mechanical properties of HTPB and different crystal faces of Al. Acta
Phys. Chim. Sin. 25(1), 187–190 (2009)
56. Liao, R., et al.: Preparation of a dicyandiamide‐contained novel insu-
lation paper and an experiment on the thermal aging characteristics of
25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
ET AL.
relevant oil‐paper insulations. J. Chongqing Univ. 694(3), 198–208
(2013)
57. Liao, R., et al.: Preparation and thermal aging properties of montmo-
rillonite modified thermally‐upgraded paper. Trans. China Electrotech.
Soc. 30(1), 220–227 (2015)
58. Yan, S., et al.: Influence of nano‐Al2O3 on electrical properties of insu-
lation paper under thermal aging. Trans. China Electrotech. Soc. 32(11),
225–232 (2017)
59. Mo, Y., et al.: Influence and mechanism of doped nano‐Al_2O_3 on
electrical life of cellulose insulating paper. Trans. China Electrotech. Soc.
33(19), 4618–4626 (2018)
60. Liu, Y.: Molecular simulation study on the influence of Nano‐TiO2
doping on the microscopic properties of insulating paper. Master’s
thesis, China Three Gorges University, China (2020)
61. Yang, L., et al.: Cellulose insulation paper with high thermal stability and
low polarizability: influence of different substituents on POSS modified
cellulose insulating paper. Cellulose. 28(10), 6023–6033 (2021)
62. Li, S., et al.: Influence of hydrostatic pressure on dielectric properties of
polyethylene/aluminum oxide nanocomposites. IEEE Trans. Dielectr.
Electr. Insul. 21(21), 519–528 (2014)
63. Du, B., Su, J., Han, T.: Compressive stress dependence of electrical tree
growth characteristics in EPDM. IEEE Trans. Dielectr. Electr. Insul.
25(1), 13–20 (2018)
64. Wang, S.: Transformer insulating materials. Transformer. 39(11), 31–34
(2002)
65. Li, X., et al.: Effect of SiO2 composite modification on breakdown
voltage of insulating paper. Chem. Eng. Equip, (3), 8–10 (2018)
66. Chen, J., Zhu, L.: Study on the mechanical and electrical aging properties
of nano‐SiO2 modified insulating paper. Synthet. Mat. Aging Appl. 49(6),
52–54 (2020)
67. Li, Y., et al.: Fabrication of the micro/nano‐structure Al2O3/PTFE
composite functional film on the surface of insulation pressboard and its
effect on space charge injection. Trans. China Electrotech. Soc. 35(18),
3960–3971 (2020)
68. Liu, H.: Study on the dielectric properties of nano SiC and Al2O3
modified insulation pressboard. PhD thesis, Harbin University of Science
and Technology, China (2018)
69. Gu, F., et al.: The influence of polymerization degree of dispersing agent
on the power properties of nano alumina. J. Funct. Mater. 2(36), 318–320
(2005)
70. Shengtao, L., et al.: Short‐term breakdown and long‐term failure in
nanodielectrics: a review. IEEE Trans. Dielectr. Electr. Insul. 17(5),
1523–1535 (2010)
71. Liao, R., et al.: Numerical calculation of the trap depth for space chargein
polymer insulators. Insul. Mater. 39(6), 51–54 (2006)
72. Ying, Y.: Influence of nanoparticles on DC breakdown strength of oil‐
paper composite insulation. Mater’s thesis, North China Electric Power
University, China (2020)
73. Liao, R., et al.: Effects of nano‐Al2O3 on space charge behavior and trap
energy distribution characteristics of insulation paper. High Volt. Eng.
45(3), 681–690 (2019)
74. Liang, N., et al.: Influence of amine compounds on the thermal stability
of paper‐oil insulation. Polymers. 10(8), 1–11 (2018)
75. Liang, N.: The research of preparation and properties of novel thermal‐
resistant insulating paper based on amine compounds and nano‐alumina.
PhD thesis, Chongqing University, China (2018)
76. Sun, Z.H., et al.: Structure and production process of NMN insulation
paper. CN110682615A[P]. (China Patent) (2020)
77. Dong, J.S.: New high‐strength insulation paper. CN210886764U[P].
(China Patent) (2020)
78. Liu, Q.K.: Method for preparing high temperature poly sulfone group
composite insulation paper. CN110735355A[P]. (China Patent) (2020)
79. Liao, R., et al.: Molecular dynamics simulation on the hydrophilicity of
physical modification cellulose insulating materials. High Volt. Eng. 39(1),
1–7 (2013)
80. Tang, C., et al.: Experimental analyses and molecular simulation of the
thermal aging of transformer insulation paper. IEEE Trans. Dielectr.
Electr. Insul. 22(6), 3608–3616 (2016)
 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
TANG ET AL.
- 83

81. Abbaspoor, S., Ashrafi, A., Salehi, M.: Cathodic disbonding of self‐
healing composite coatings: effect of ethyl cellulose micro/nano- How to cite this article: Tang, C., et al.: A review
capsules. Corrosion Eng. Sci. Technol, 1–9 (2021) on the research progress and future development of
82. Yang, X., et al.: Highly efficient self‐healable and dual responsive nano‐modified cellulose insulation paper. IET
cellulose‐based hydrogels for controlled release and 3D cell culture. Adv. Nanodielectr. 5(2), 63–84 (2022). https://doi.org/10.
Funct. Mater. 27(40), 1–10 (2017)
83. Lei, Q., Li, S.: Several important issues and thinking about engineering
1049/nde2.12032
dielectrics. High Volt. Eng. 56(7), 2473–2480 (2015)

APPEN DIC E S

T A B L E A1 Comparison of simulation results of insulating paper modified by different nanoparticles

Simulation
Modified experiment
particle conditions Modulus of elasticity Shear modulus Bulk modulus Poisson's ratio Cauchy pressure
Nano‐Al2O3 Temperature 23.07% increase with First increase, then Same trend as left Same trend as left Negative value
[33] 70°C–150°C temperature decrease and then becomes positive
variation decrease, but value compared to
overall higher unmodified model
thanunmodified
model

Nano‐TiO2 [36] Particle size Decrease with Decrease with Same trend as left Increase with particle Decrease with
change increasing particle increasing particle size increasing particle
size size size

Nano‐SiO2 [38] Whether the Increase of nano‐SiO2 24.35% increase of ‐ ‐ ‐

surface of modified insulating nano‐SiO2
SiO2 is paper after modified insulating
unsaturated unsaturated paper after
treatment unsaturated
treatment

Melamine Effect of Decrease with Decrease with ‐ ‐ ‐

grafted temperature increasing increasing
nano‐SiO2 and temperature, temperature,
[40] moisture 82.9% higher at 94.4% higher at
650 K 650 K

Nano‐SiO2 [41] Different Increase 16.1% with Increase 96.1% with ‐ Increase 37.5% with 24.6% with KH550,
grafting KH550, 2.91% KH550, 54.3% KH550, 8.2% with 2.01% with
reagents: with KH560, and with KH560, and KH560, and 1% KH560, 18.5%
KH550, 11.4% with 81.8% with with KH570 with KH570
KH560, KH570 KH570
KH570

Modified Mass fraction When the mass When the mass When the mass When the mass When the mass
polysiloxane change of fraction of fraction of fraction of fraction of fraction of
[46] modified polysiloxane is polysiloxane is polysiloxane is polysiloxane is polysiloxane is
polysiloxane 6.5%, the optimal 6.5%, the optimal 6.5%, the optimal 6.5%, the optimal 6.5%, the optimal
effect is achieved, effect is achieved, effect is achieved, effect is achieved, effect is achieved,
with an increase of with an increase of with an increase of with an increase of with an increase of
24.7% 6.38% 9.01% 3.03%. 47.73%

POSS [48] Modified Improve 19.96% at Increase 20.52% at Increase 22.19% at Basically unchanged Basically unchanged
insulating POSS content of POSS content of POSS content of
paper 3wt% 3wt% 3wt%

Abbreviation: POSS, polyhedral oligomeric silsesquioxane.

 25143255, 2022, 2, Downloaded from https://ietresearch.onlinelibrary.wiley.com/doi/10.1049/nde2.12032 by National Institutes Of Health Malaysia, Wiley Online Library on [31/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
84
- TANG ET AL.

T A B L E A2 Comparison of experimental results of insulating paper modified by different nanoparticles

Percent increase
Ageing Ageing in degree of
Modified particle and content Sample temperature time polymerization
Liao Ruijin [56] Dicyandiamide Homemade in laboratory, raw material is pure 130°C 31 days 58%
sulphate wood pulp imported from Russia
for quantitative analysis

Liao Ruijin [57] Montmorillonite (dicyandiamide, melamine, Home made in laboratory, raw material is pure 110°C 120 days 15% (tensile
polyacrylamide (mass ratio: 6: 6: 1) Joint sulphate wood pulp imported from Russia strength)
action)

Zhang Song Nano‐Al2O3, 1% Home made in laboratory with thickness of 130°C 31 days 27.8%
[33] 0.1 mm, the raw material is coniferous wood
pulp imported from Russia

Yan Shuiqiang Nano‐Al2O3, 2% Home made in laboratory, thickness: 0.12 mm, 130°C 31 days 15.7%
[58] raw material is unbleached softwood kraft
pulp imported from Russia

Tang Chao [40] Melamine grafted nano‐SiO2, 1.2% Home made in laboratory 130°C 31 days 50%

Tang Chao [40] Nano‐SiO2, 5% Home made in laboratory 130°C 31 days 35.7%
3
Liu Daosheng Nano‐TiO2, 5% Home made in laboratory, density: 1.15 g/cm , 130°C 20 days 45.2%
[37] thickness: 1 mm, raw materials are provided
by Nantong Zhongling Electric Power
Technology Co., Ltd, China