Proces charakterizace samoléčitelných materiálů

Valentino Nikolić1), Radek Polanský2)

KET – Katedra materiálů a technologií
Fakulta elektrotechnická
Západočeská univerzita v Plzni
1)
vnikolic@fel.zcu.cz 2)rpolansk@fel.zcu.cz

Characterization Process of Self-Healing Materials

Abstract – In any system's research and development activity, the outcome
verification is significant in further product improvement and development. In
general, that means acquainting with the behaviour of the product by simulating
operating conditions and observing in-situ occurred test sample deviation. In this
respect, the paper briefly describes the characterization process on the example of
a self-healing, highly stretchable supramolecular elastomer and provides a general
idea of how such materials can be validated for their use in electrical insulation
technology. In more detail, the paper summarises the capability of the material for
usage in promising electrical engineering applications, such as insulating cables,
rotating machines, electronic components, etc. Besides that, the paper deals with
the strategy of the testing process of self-healing samples, designing the
experiment, and applying self-healing characterization competencies.

Keywords – Self-healing materials; characterization; testing; validation methodology;

data evaluation.

I. INTRODUCTION
A general term, definition, classification and designing strategies for self-healing
materials are earlier illustrated by Nikolic and Polansky [1] in the literature survey
"Process of Self-healing in Materials Based on the Encapsulation Principle″. The
document gives a brief overview to the readers regarding new self-healing technologies
in electrical engineering. Ex alia parte, in the following, will be distinguished
terminologies with which this document deals. Therefore, verification, validation, and
characterization procedures define the scope of the product analysis and are scoped by
quality management of any product. Herein, the verification particularly means proving
that the product is developed rightly according to the defined specification, while
validation is proving that the right product is designed according to the operational
requirements. Despite that, characterization represents a testing process of subjected
product and its behaviour description under applied loads [2]. In this manner, the paper
engages samples specification, material structure characterization via Fourier transform
infrared spectroscopy (FTIR), characterization of the material in terms of thermal
properties, broadband dielectric spectroscopy (BDS), high voltage testing and optical
and visual inspection. Ergo, various parameters are also examined regarding self-
healing behaviour, for instance, stimulus sort, recovery grade, and the time of returning
material's structure to initial condition or either material's colouring. Overall,
considering the material's property in a pristine state and after applied stresses or loads
[3-4]. The presented results in the paper are related to the universally autonomous self-
healing elastomer with high stretchability, which was supplied by the Department of
Biochemical Engineering, School of Chemical Engineering and Technology, Tianjin
University in P. R. China [5].
 II. INITIAL STRUCTURAL ANALYSIS OF THE TESTED MATERIAL
For the characterization was used flat samples with dimensions approx. 20 mm ×
20 mm and an average thickness of 0.82 mm. The tested self-healing material is a very
soft and mechanically less resistant elastomer. It is necessary to note that inside the
samples are under the microscope visible impurities and fibres through the polymer
structure, and these impurities could slightly influence the analysed properties, see
Figure I. b), c), and d) [6].
The initial characterization of delivered samples was performed via Fourier
transform infrared spectroscopy (FTIR) using Nicolet 380 spectrometer (manufactured
by Thermo Scientific). The spectroscopy was used to analyse the chemical bonds
present in the tested samples. The measurement was performed in the ATR (Attenuated
Total Reflectance) mode. A comparison of the obtained spectrogram with the Thermo
Nicolet Sample Library proved the highest similarity of self-healing material with
polydimethylsiloxane (PDMS), which forms a significant part of the polymer's
composition [6]. A further description of the rest presented the material components can
be found in the paper "Universally autonomous self-healing elastomer with high
stretchability" by researchers Guo, H., Han, Y., Zhao, W. et al. [5].
Furthermore, simultaneous thermal analysis (STA) characterization was also used
as a standard diagnostic procedure at the beginning of the characterization process. The
STA provides information that helps to acquaint with temperature interval appropriately
and prevent any melting and subsequent degradation of the material during further
measurements. STA was made with the SDT Q600 analyser (manufactured by TA
Instruments) in the temperature ranges from room temperature to 700 °C with a heating
rate of 10 °C/min. Used tested sample was approximately 9 mg of weight, and the
measurement was carried out in the air atmosphere [6].
On the thermogram in Figure I a) is presented the temperature dependence of the
weight loss. The weight loss is obviously minor during the gradual heating with a
constant heating rate of about 200 °C. In the following, the tested sample's weight
decreases, which relates to the ongoing thermo-oxidation reactions. Although of
reached an elevated temperature of 700 °C, 25 % of weight residue is present. At the
temperature of about 307 °C, the temperature dependence of the heat flow is visible in
the thermogram related to the beginning of first significant thermooxidation process [6].
A rapid test of the sample's cutting and its subsequent healing confirmed the high
adhesion of the cut surface of both cut parts. It was observed the tendency to fast re-
bonding of chains and the self-healing process, Figure I, b), c) and d) [6].

Figure I. a) STA results and fast self-healing test: b) before sample cutting, c) after sample
cutting, and d) - after occurred healing process [6]

III. ANALYSIS OF DIELECTRIC PROPERTIES

Broadband dielectric spectroscopy (BDS) is a standard diagnostic tool in electrical
engineering that determines a material's relative permittivity and other dielectric
parameters. The real part of the complex relative permittivity for chosen frequencies is
known as dielectric constant, ε', while the imaginary part is loss factor, ε″. The
Analyzer Alpha A (manufactured by Novocontrol Technologies) with an active ZGS
electrode system (cylindrical electrodes with a diameter of 20 mm) was used for BDS.
The temperature interval was from -70 °C to 60 °C, with the sequence 25 °C → -70 °C
→ 60 °C → 25 °C, where the cooling was carried out by using liquid nitrogen. Whereas
Figure II a) presents the electrode system, Figures II b) and c) present dependencies of
dielectric constant and loss factor in the frequency range from 0.1 Hz to 1 MHz, and the
temperature ranges from -70 °C to 60 °C, respectively. It can be concluded from these
graphs that for the mentioned frequency and temperature ranges, dielectric constant
values are within limits for a common polymer insulating material. Despite that, it can
also be noticed that, especially at elevated measured temperatures, e.g., 50 °C, the loss
factor values are higher than usual for the dielectric's application. In the frequency-
temperature dependence graph of the loss factor, the polarisation transition can be
assessed that at low frequencies and higher temperatures increase the conductivity of
the tested self-healing material [6].

Figure II. a) BDS electrode system, and dependencies of temperature ranging from
-70 °C to 60 °C in the frequency range from 0.1 Hz to 1 MHz versus b) dielectric
constant and c) loss factor [6]

High voltage (HV) testing was performed to measure electrical strength (dynamic
method with a voltage increase rate of 0.5 kV/sec.). The behaviour of material was
observed during the AC voltage test (frequency of 50 Hz). A laboratory system
consisting of a power supply unit (HighVolt, type LM30) with a control transformer, a
control unit (HighVolt, type SM4) and a high voltage part was used for the
measurement. It is evident from Figure III that the effects of material degradation
caused by sudden breakdown are significant. Darker structures and a rounded
depression prove an essential effect of increasing the temperature and melting the
material around the electrodes. More minor cracks and more significant light gaps
between darker regions indicate shrinkage of the material in the highest stress (visible
blackening). A liquid phase of the material, which filled the formed conductive channel
and other cracks, was also detected in breakdown after the testing [6].

Figure III. HV breakdown process (one-minute dynamic test) [6]

 IV. CONCLUSION
Based on the performed tests and the evaluated analyses, the tested self-healing
material could be used as an electrically insulating material primarily in low-
temperature applications without the exposition to long-term mechanical stresses. A
proposal for improving the material should be advanced thermal stability, increased
stiffness, and reduced flammability for the usage in standard electro-insulating
applications [6]. Nevertheless of the obtained results, observing the nature of self-
healing material is always something that fascinates every researcher, especially
considering that the tested material is the latest state of the art in today's material
technology. Furthermore, it should be emphasized the impression of the self-healing
ability of this material. In electrical engineering, the main focus is on promising
materials with electrical insulation properties for insulating cables, rotating machines,
electronic components, etc. These are primarily polymers, withstanding the highest
possible electrical resistivity (at least more than 10E13) and the highest electrical
strength values. For the mentioned application in electrical engineering, the relative
permittivity values shall be in the order of units and loss factor lower than 0.01, ideally
0.001 - 0.01.

ACKNOWLEDGMENT
This paper was supported by an internal project to support student scientific
conferences SVK1-2021-005 and the Student Grant Agency of the University of West
Bohemia, grant No. SGS-2021-003 "Materials, technologies and diagnostics in
electrical engineering". The authors also thank Jing Yang from the Department of
Biochemical Engineering, Tianjin University, for providing the testing material.

LITERATURE
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