Self Healingpolymers

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Self-healing polymers: approaches of healing and their application
Article in Polymer Journal · March 2019

DOI: 10.15407/polymerj.41.01.004
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Self-healing polymers: approaches of healing and their
application
A.M. Fainleib, O.H. Purikova
Institute of Macromolecular Chemistry NAS of Ukraine

48, Kharkivske shose, Kyiv, 02160, Ukraine
Self-healing (S-H) polymers are a new class of smart materials with extended lifetimes that have the
capability to repair themselves when they are damaged without the need for detection or repair by
manual intervention of any kind. This paper reviews briefly the studies devoted to the development
and characterization of S-H polymeric materials. All relevant approaches in preparation of such
polymers can be devided into two groups: autonomic and non-autonomic. Autonomic healing are
fully self-contained and requiring no external intervention of any kind, however this method of self-
healing is also known as extrinsic because of presence of additional healing agent placed in reservoir
in polymer material. Autonomic healing can be further divided into sub-categories based on the self-
healing concept employed. The subcategories include: capsule systems and microvascular or fiber
network-based systems. Non-autonomic healing are partially self-contained; healing capability is
designed into the material, that is why this method is also named as intrinsic. But additional external
stimuli such as heat or UV-radiation is required for the healing to occur in this method. Intrinsic self-
healing polymer can be tailored to become chemically ‘sticky’ along break lines. Polymers can also
be designed to respond to a variety of different energetic conditions, e.g. specific electromagnetic
fields or bullet permeation. This paper also examines critically benefits and shortcomings of each
example of approaches proposed to prepare the S-H systems. Emerging self-healing technologies
designed to give polymeric materials the capability to arrest crack propagation at an early stage
thereby preventing catastrophic failures will go a long way in helping to increase the scope of
applications of these materials. Such techniques are very useful for repairing damage to satellites and
spacecraft caused by high-speed debris. Another attractive range of application of S-H polymers
observed in this review includes S-H coatings and adhesives. Finally, the challenges and research
opportunities are highlighted.
Key words: smart materials, self-healing polymers, polymer composites, adhesives, coatings.
Polymers and polymer composites have been widely constantly appearing.

used in tremendous engineering fields because of their Self-healing approaches.
advantages including light weight, good processibility, Mending, self-healing (S-H) of polymer and related
chemical stability in any atmospheric conditions, etc. composites were always on the top of the wish list of
However, long-term durability and reliability of polymeric researchers. Many concepts have been introduced for
materials are still problematic when they serve for struc- the healing of bulk polymers and their feasibility checked
tural application [1]. Exposure to harsh environment would [3]. A polymer displaying self-healing properties needs
easily lead to degradations of polymeric components. the ability to transform physical energy into a chemical
Comparatively, micro cracking is one of the fatal deterio- and/or physical response able to heal the damage – a
rations generated in service, which would bring about process which normally is not present in “conventional –
catastrophic failure of the materials and hence significantly non-self-healing” polymers [4]. The related approaches
shorten lifetimes of the structures. Since the damages deep are differently classified. Classifying usually considers
inside materials are difficult to be perceived and to repair whether or not the healing requires an external stimulus.
in particular, the materials had better to have the ability of When no external stimulus is required and healing agent
self-healing [2]. has to be preembedded then mending is termed as to au-
On the whole, researches in this field are still in the tonomic, whereas its triggering with additional treatment
infancy. More and more scientists and companies are in- when polymers are able to heal cracks by themselves (usu-
terested in different aspects of the topic. Innovative meas- ally heat) is called to non-autonomic [5]. Note that in both
ures and new knowledge of the related mechanisms are cases the healing agents are available in the bulk material
4 © 2019 A.M. Fainleib, O.H. Purikova

though in very different forms. Healing agents may be in

reservoirs (capsules, capillaries) which break up upon
external mechanical damage thereby initiating the healing
reaction. When a catalyst is required, then it may be in-
corporated in the matrix polymer, available in one of the
healing components in non-active or latent form, and the
like. The chemical build up of the healing agent may mark-
edly differ from that of the matrix [6].
There are many papers in the literature related to the
self-healing materials [7]. They show that there is another
classification of self-healing methods based on the prop-
erty of material. This classification devides all methods
into intrinsic and extrinsic ones. The intrinsic self-heal-
ing composites the predominant molecular mechanisms
involved in the healing processes can be due to physical Fig. 1. Stages of self-healing mechanism: surface re-
interactions, and/or chemical interactions (for instance arrangement (a); surface approach (b); wetting (c);
thermally reversible reactions, hydrogen bonding, iono- diffusion (d); randomization (e) [4]
meric coupling, a dispersed meltable thermoplastic phase,
molecular diffusion, etc.). In the case of extrinsic self- interfaces, and provide an explanation for the functioning
healing composites, a healing agent has to be stored in principle of many self-healing concepts (Fig. 1), being
vessels and embedded into the polymeric matrix in ad- strongly related to molecular interdiffusion at or above
vance during the manufacture of the material. This cap- the Tg has been suggested [28]. At this temperature poly-
sule-based method was developed by White and co- mer segments are mobile enough to enable an efficient
workers [8–11]. As the cracks destroy the fragile vessels self-healing process. This relatively simple model is, in its
in which the healing agent is stored, this would be re- basic steps, applicable as a universal mechanism for near-
leased into the crack planes, due to capillary forces, and ly all self-healing concepts [29].
heal the cracks. In accordance with the types of contain- Healing by re-entanglement in amorphous polymers
ers these materials can be classified into different groups, was already performed in the 1980s, pioneered by the group
among which are: self-healing in terms of healant-loaded of Kausch [30, 31]. Interestingly, already at this time frac-
pipelines [7], self-healing in terms of healant-loaded mi- ture mechanical treatise was used to quantify the healing
crocapsules [7, 12], and self-healing in terms of vascular efficiency, which remained the dominant tool until now
materials [13–20] in which the healing agent is seques- [32]. Both amorphous and semicrystalline thermoplastics
tered in a network in the form of capillaries or hollow are often used for the toughening of thermosetting res-
channels [3, 21–25]. These chemical binder-based me- ins. The resulting morphology may be very different. Con-
thods change the material composition at the damage site sidering just the amount of the modifier the morphology
during healing and hence can be used to heal a damaged is varying between different disperse and continuous struc-
site in this material only once. tures. It is the right place to mention that a co-continuous
Intrinsic type of healing is used to heal, for example, morphology composed of thermoplastic and thermoset
thermoplastics by molecular re-entanglement processes. phases, is termed to as semi-interpenetrating polymer net-
As was mentioned, re-entanglements across the (broken) works (semi-IPNs). The preferred morphology for the pur-
surfaces of thermoplastics are typically triggered by heat. pose of toughening was micron-scale dispersion of the
The temperature, at least locally, should be higher than thermoplastic phase in the thermosetting matrix [33]. This
the glass (Tg) or melting temperature (Tm) depending is usually achieved with a thermoplastic content of less
whether the actual polymer is of amorphous or semicrys- than 15 wt.%. It is intuitive that this thermoplastic phase,
talline nature. This is also the basic principle of thermo- in whatever morphology present, may work for healing.
plastics welding. This means that an important aspect of One would expect that a semi-IPN structure results in a
intrinsic self-healing is the presence of a structure which better healing than a dispersed morphology [34–36].
is able to dynamically respond to an external stimulus This requirement can be easily met by poly(ε-caprol-
[26], enabling the restoration of the initial material proper- actone) (PCL) having a melting temperature of about 60 °C
ties. Due to their highly complex chain structure, poly- [37]. Moreover, PCL is a polyester that should have good
mers, in particular, are ideally suited to serve as molecules solubility in epoxy resin (EP). It is available commercially
for dynamic and thus self-healing properties. Thus, the in different molecular weights which is a further tool to
polymers are coupled to fast and efficient cross-linking control its dissolution in EP. In fact, PCL has been tried as
reactions [27]. toughening agent in EPs from the 2000s [38]. Attempts
A five-stage mechanism to unscramble the complexity were also made to control its reaction-induced phase sep-
of strength recovery at ruptured polymer/polymer aration through further additives, such as organo clay
5
[39]. Thermal mending of EP via thermoplastic PCL was self-healing composite. It is evident that a chemical bind-
first explored by Luo et al. [40]. The cited authors modi- er, once consumed, cannot be regenerated after the heal-
fied an aromatic amine-cured diglycidyl ether of bisphe- ing process is complete. In addition, the chemical binder-
nol A-based EP (DGEBA) with PCL, added up to 34.9 wt.%. based methods that use microcapsules and vascular net-
They revealed that the morphology above 15.5 wt.% PCL works for healing a damage require a minimum volume of
content consisted of a continuous PCL phase in which the binder filled in the hollow cavity to heal the material.
interconnected EP spheres are dispersed. As a conse- The microcapsules or vascular networks are practically
quence, the PCL phase may serve for thermal mending of obtrusive for use in thin polymer films such as wire-insu-
this high Tg EP that was proven, in fact. lation material in aerospace applications. So there is a
Another work was devoted to studying the thermally need to develop a self-healing technique for thin mem-
induced healing via reentanglement of molecules of the branes that can be repeatedly healed by the application
thermoplastic PCL phase formed by phase separation in of heat. It is anticipated that this composite material will
EP resins upon their curing [5]. PCL was dissolved in var- be useful as one of the layers of a wire-insulation com-
ious amounts in EPs initially exhibiting higher [EP(H)] and posite, inflatable membranes, and aerodynamic surfaces
lower Tg values [EP(L)] than the Tm of PCL. Healing was of microair-vehicles and in various aerospace applications.
triggered at 80 °C which was at about to far beyond the The airspace application of self-healing materials.
above transition temperatures. Note that the Tg of the EPs One of the biggest challenge facing materials scien-
varied with the EP/PCL compositions. Based on this study, tists is the idea to put in action self-healing composites in
it can be concluded, that the development of a bicontinu- aeronautic or in general aerospace applications. Epoxy
ous, semi-IPN-like structure in EP/PCL strongly contrib- resins are fast gaining ground as the preferred polymer to
utes to the thermally induced healing, also when per- be used as carbon fiber-reinforced materials to manufac-
formed repeatedly. ture large components being able to sustain aerodynamic
Thermal methods to heal a damage have been investi- loads. The introduction of these resins to the aeronautic
gated for structural polymers (mendable polymers or “men- industry was mainly driven by performance gains (better
domers”) [41–43]. The heat required for healing in men- design flexibility, no corrosion, easy production process,
domers is provided by a processes extrinsic to the materi- etc.) and most of all by weight reduction. This last aspect
al and at a time chosen by the damage detection method. is of relevance when considering issues related to the
In another thermal method, Kalista [44] uses an ionome- energy resources and supply, costs in service and air
ric polymer (Surlyn) to demonstrate autonomous self- pollution measures. This major advantage of the compos-
healing. In this work, heat generated during the damage ites, the lightness, is also obtained by saving and/or in-
event such as ballistic impact is harnessed to melt the creasing the material strength in such a way as to make
polymer at the damage location to heal the damage [45– traveling on aeroplanes more comfortable for the crew
48]. Smart Materials Research by Kalista [45], Kalista and and passengers in virtue of the possibility to slightly in-
Ward [46], and Varley and Vander Zwaag [47] demonstrates crease cabin pressures without increasing the structure
an interesting concept, it does not apply to damage oc- weight. Unfortunately, composites also possess some
curring in a material curing regular wear and tear. To ad- properties which reduce their advantage with respect to
vance the use of Surlyn in self-healing, Owen [49] devel- traditional metal alloys. One inherent shortcoming is the
oped a novel approach to mitigate this deficiency with poor impact damage resistance. Impact damage can be
Surlyn by dispersing magnetic particles in Surlyn. This due to several factors, such as unfavorable weather con-
method, while taking a step in the right direction, requires ditions, stones or rocks on the keel during landing, inci-
a large induction coil to heal the damage in the sample. In dental contact during maintenance, and bird strike. It may
addition to these methods, self-healing methods present- significantly affect the integrity of the composite struc-
ed in the review paper by Wu et al. [50], self-healing sen- ture of aircraft in service [56]. This process starts at the
sor skin [51], bioinspired methods developed by Trask et microscopic level with the formation of micro voids which
al. [13, 52], and recent work by White group [53] demon- then expand to generate deep micro cracks within the struc-
strate novel techniques for healing structural damages. ture [57]. Impact damage may lead to substantial matrix
Alongside these works, there has been a renewed interest micro cracking and delamination within the bulk of the
in thermoplastic polymers that use reversible ionic ag- composite, reducing the structural capability and leading
gregation to function as self-healing materials [54–55]. to premature failure, if it is not detected and repaired. Dam-
The current state-of-the-art in self-healing, with the age can also provide a route for the ingress of contami-
exception of some thermal and photochemical methods, nants into the structure [57]. The internal damage is diffi-
requires chemical modification to the structure and can- cult to detect and even more difficult to repair and, once it
not be healed at a damage site after one damage event. has developed, the integrity of the structure is greatly
While photochemical self-healing has proved to be able compromised. Restoration of the physico-mechanical prop-
to induce repeated healing of damages at the same dam- erties of such a material, once fractured, requires either
age site, it lacks the structural capabilities of a desired new covalent chemistry to generate additional cross-links,
6
or long periods of an nealing to enable thermal diffusion

of unbroken, linear polymer chains into the damage zone
[58]. Several non-destructive damage detection tech-
niques have been developed, including ultrasonics, in-
frared thermography, X-ray tomography, and computer-
ized vibro-thermography. This technology can help with
damage detection, but generally the repair entails strong
increases in the aircraft operating costs and, in addition,
sometimes the damage is not visible from outside. Fur- Fig. 2. Design of the first self-healing system relying
thermore, in a composite, the weave is characterized by on capsule-based concepts [12]
different directions in different parts, so repairing struc-
tural parts is very difficult. Many times the current tech- concepts have emerged in the scientific literature, for many
nology related to the repair methods, such as welding or systems a similar healing mechanism based on the ring-
patching, can be applied at the macroscopic level to either opening metathesis polymerization (ROMP) of the heal-
rejoin or reinforce damaged areas. However, these solu- ing agent was proposed [3, 59–71].
tions are not always useful, either as a result of in acces- Among the systems relying on capsule-based con-
sibility to the damaged area, or because they lead to chang- cepts, the initial self-healing epoxy system involves the
es in the strength of the material, producing inter-phase incorporation of a microencapsulated healing agent, di-
surfaces that can act as weak regions of lower mechanical cyclopentadiene (DCPD) and a dispersed solid catalyst,
performance. It has been shown, in fact, that the location bis(tricyclohexylphosphine)benzylidine ruthenium (IV)
of the weld remains the weakest point in the material, dichloride (called Grubbs’ catalyst) in an epoxy-amine
and thus the site for future damage to occur. An aircraft network [12] (Fig. 2).
with inherent self-healing and or protective abilities could The reaction that allows repair of a mechanically
help to significantly extend the inspection intervals, there- induced damage is based on the polymerization of the
by increasing aircraft availability. Alternatively, existing healing agent released through capillary action that is
inspection intervals could be maintained with significant- triggered by contact with the embedded catalyst, bond-
ly thinner structures, thereby saving airframe weight and ing the crack faces within the polymeric matrix. The effi-
hence reducing fuel burn, in-service cost, and the envi- ciency of the self-repair function, in terms of trigger, speed
ronmental impact. Recent studies have highlighted the and yield, is related to ROMP of the healing agent by
potential of self-healing polymer composites to be used appropriate catalysts. The healing agent is a microencap-
as single structural materials, and/or for sandwich struc- sulated liquid monomer that must have a long shelf life,
tures. The main difficulty in the development of these prompt deliverability, high reactivity, and low volume
smart materials is due to the nature of the composite used shrinkage upon polymerization [60]. The monomer most
as structural materials. In fact, the self-repair activity has often used as the healing agent for the manufacture of
to be highly efficient in a relatively rigid structure (with these first ingenious systems is DCPD [3, 60]. Moreover,
reduced mobility of the molecular segments). In addition, blends of DCPD/5-ethylidene-2-norbornene (DCPD/ENB)
most of the functionalities responsible for triggering self- or DCPD/ 5-norbornene-2carboxylic acid have also been
repair actions have to be active after the drastic condi- proposed [72]. Thermosetting auto-repair polymers, which
tions of curing cycles used in the field of aeronautic mate- have been proposed so far, include Grubbs’ first-genera-
rials. In fact, the high temperatures required in the cur- tion catalyst (G1) [3, 73–76]; and currently, the possibility
ing process deactivate many of the already available of applying other ruthenium catalysts, such as second-
self-repairing reactions. generation Grubbs’ catalyst (G2) and Hoveyda–Grubbs’
As was mentioned above, according to the ways of second generation catalyst (HG2), is under evaluation [73,
healing, polymer composites can be classified into two 77, 78]. However, this system has some drawbacks. The
categories: intrinsic ones and extrinsic. For structural ap- first one is the thermal stability of the ruthenium cata-
plications such as aeronautic materials, the extrinsic self- lysts inside the epoxy resin during the curing cycle [73,
healing systems are of great interest because they would 78], and the second is the impossibility of utilizing pri-
overcome the difficulties connected with damage diagno- mary amines as hardeners, since they can poison the cat-
sis, and allow the following appropriate interventions to alyst. At the high temperatures of the curing cycles sched-
be reduced. The first capsule-based self-healing system uled for epoxy formulations, thermolytic decomposition
for thermosetting materials was proposed by the team from can limit the usefulness of these ruthenium systems in
the University of Illinois [12]. The concept was based on self-healing composites based on epoxy resins. This is a
the introduction of a micro-encapsulated healing agent crucial aspect for self-healing systems in aeronautic ap-
and a suspended catalyst phase in an epoxy matrix. Since plications because, even if linked to the cost reduction
that time, advances have been made in the field following from a process aspect, resins have been developed with
this conceptual approach and, although alternative low temperature manufacturing (under 100 °C), yet the
7
problem of the material treatment at high temperature is up to 160 °C without deactivating the self-repair activity
currently under investigation. For aeronautic applications, of the formulated systems. Curing cycles currently used
it is also critical that the self-healing activity functions at in the aeronautic field for primary structures may reach
low working temperatures, which can reach values as temperatures up to 180 °C. Concerning this last require-
low as 50 °C. This issue is even harder to solve for space ment, recent works have shown very promising results
vehicles or satellites where extreme fluctuations of tem- when the self-healing formulation contains Hoveyda-
perature between -150 and +150 °C are also possible. Grubbs’ 1st generation catalyst rather than G1, G2 or HG2
Indeed, a very efficient aeronautic or aerospace self-heal- catalysts [83-87]. The thermal stability of each of the cat-
ing material needs to satisfy these two fundamental re- alysts G1, G2, and HG1 was evaluated under conditions
quirements: (i) chemical stability and high thermal sta- of actual use for applications in self-healing structural
bility of the self-healing components (catalysts and ves- systems. The catalyst was dispersed in the epoxy matrix
sels filled with healing agents), (ii) high healing efficien- in its solid state and both the epoxy precursor and the
cy at low temperature. composite were cured by two-stage curing cycle; after
Stability and Reactivity of Catalysts for Self-Healing which, the catalysts were extracted with chloroform from
Formulations.Wilson and coworkers have evaluated the the epoxy matrix (after the curing process at high temper-
reactivities of G1, G2 and HG2 catalysts with various mon- atures) and analyzed by 1H-NMR spectroscopy. It is ob-
omeric healing agents with a view toward improving the servable that Grubbs’ 1st generation and 2nd generation
self-healing performances in a variety of epoxy matrices catalysts are stable if the temperature of the second stage
[73]. In the same paper they have also evaluated the ther- of the curing cycle is up to 150 °C for 2 h; it is not possible
mal stability of these three catalysts embedded into the to formulate self-healing systems related to ROMP of the
epoxy matrices with the aim of studying their stability to healing agents when a curing temperature of 180 °C is
processing conditions during manufacturing conditions. scheduled. Epoxy self-healing systems containing HG1
Self-activated M1 samples (epoxy matrix EPON 828 can be processed even with a temperature of the second
cured with DETA) containing 1.5 wt.% of as-received cat- stage up to 180 °C.
alyst were prepared and subjected to customary curing Another issue related to the stability of self-healing
cycles [3, 61, 64, 67] followed by an additional post curing components is the instability of the catalysts embedded
at 125 °C for 4 h before fracture testing. This fracture test in epoxy formulations to primary amines, which repre-
showed that the lower retention of healing performance sent an important class of curing agents for epoxy formu-
observed for HG2 catalyst was an unexpected result since lations. In order to formulate a self-healing aeronautic resin,
HG2 is a catalyst with impressive chemical stability and it should be taken into account that the final material must
recyclability [73, 79, 80], great functional group tolerance, have suitable mechanical properties which depend not
as well as greatly enhanced air and water stability [81]. In only on the curing cycles, but also on the chemical nature
a recent paper [78] Guadagno and coworker have shown of the epoxy formulations. In the choice of epoxy mixture,
critical issues in the use of epoxy precursors in conjunc- it is necessary to consider that the structure of the resin
tion with HG2 metathesis catalyst. However, an appropri- strongly governs its chemical and some of its physical
ate curing cycle of the self-healing mixture allows to carry properties. This, combined with the nature of hardener
out the curing process at high temperatures without de- agent, the functionality, the stoichiometry, and the curing
activating the self-repair activity. The HG2 catalyst showed cycle determines the final properties of the cured resin,
exceptional stability, even after a thermal treatment at 180 especially in terms of mechanical and thermal properties.
°C in air atmosphere. Generally, hardeners (curing agents) based on the prima-
Using FTIR spectroscopy to monitor the reactivity of ry amines give the best mechanical performance. Unfor-
the epoxy groups [82], the authors demonstrated the re- tunately, these amines can poison many of the catalysts
activity, at temperatures higher than 80 °C, of the HG2 active in ROMP of monomers used as healing agents. The
catalyst embedded inside the epoxy matrix with the ox- instability of ruthenium catalysts to primary amines can
irane rings and found compromised effectiveness in the be a significant drawback in the design of self-healing
activation of the ROMP. The same authors found a solu- polymers; for this reason it is fundamental to evaluate the
tion to preserve the catalytic activity of HG2 catalyst in- activity of the catalysts embedded inside the specific
side the epoxy matrix. The addition of a step in the curing epoxy formulation [3, 61, 88].
cycle, at a temperature at which the HG2 catalyst does not Healing Efficiency at Low Temperatures. In aircraft,
react in competition with the hardener (below 80 °C) al- the operating range may vary roughly from -50 to +60 °C,
lows the opening of all the oxirane rings, preserving its therefore the healing agent must be able to heal the mate-
catalytic activity in successive curing steps at higher tem- rial also at very low temperatures. Merle and coworkers in
peratures. In this way, the catalyst remains intact, and a recent patent proposed the use of 5-ethylidene-2-nor-
hence it is capable of subsequently performing its cata- bornene (ENB) as a healing agent active at low tempera-
lytic activity in the ROMP of healing agents. This strata- ture [89]. Guadagno et al. analyzed the ROMP of this heal-
gem allowed the obtaining of samples cured at temperatures ing agent using G1, G2 and HG1 catalysts. The obtained
8
Table. Reaction rate and yield of ROMP reaction of Epoxy resin (HG1 5% Mic 10%) T = 180 °C
DCPD and ENB with G1,G2 and HG1 catalysts 0,16
Virgin
Catalyst/monomer Temperature, Time, Yeld,
Test Healed
ratio °C min % 0,12
1 1:1000 G1/DCPD 25 15 34
Load, kN
2 1:1000 G1/DCPD 0 5 0
0,08
3 1:1000 G1/DCPD 10 30 0
1 1:1000 G1/ENB 25 0,5 100
2 1:1000 G1/ENB 0 13 100 0,04
3 1:1000 G1/ENB -10 60 17
4 1:1000 G1/ENB -20 1440 79
0
5 1:1000 G1/ENB -30 1440 74 0 0,5 1,0
6 1:1000 G1/ENB -40 1440 52 Displacement, mm
1 1:1000 G2/ENB 25 1 99 Fig. 3. Load–displacement curves for virgin and healed
2 1:1000 G2/ENB 0 50 100 epoxy sample (HG1 5% Mic 10%) cured up to 180 °C [92,
3 1:1000 G2/ENB -20 60 79 93]
4 1:1000 G2/ENB -30 1440 74
5 1:1000 G2/ENB -40 1440 43 acid (E/MAA) copolymer in which the MAA groups are
1 1:1000 HG1/ENB 25 0,5 96 partially neutralized with sodium ions. This sodium iono-
2 1:1000 HG1/ENB -20 1440 93 mer is chosen as the matrix of the self-healing composite
3 1:1000 HG1/ENB -40 1440 99 for its low melt temperature of 95 °C and previously dem-
4 1:1000 HG1/ENB -40 240 98 onstrated healing capabilities. Carbon fibers are selected
5 1:1000 HG1/ENB -50 450 99 as a heating element due to its low electrical resistance,
resistive heating property, and reinforcement properties.
results were compared with those obtained using the most Other properties, such as low density and high strength,
common healing agent (DCPD monomer) [84, 85, 90]. Ta- make this an attractive option over other heating elements.
ble 1 summarizes data from all the performed experiments. Carbon fiber bundles in the self-healing composite dem-
The self-healing functionality based on the metathe- onstrated in this work are arranged in a unidirectional
sis reaction of DCPD activated by the G1 catalyst deacti- pattern between two layers of Surlyn sheets (200 µm thick)
vates if the damage occurs at a temperature equal to or and melt-pressed into a composite. For testing and char-
lower than 10 °C. On the other hand, the metathesis reac- acterization, two configurations of carbon fiber in
tion activated by G1 and G2 catalysts with ENB is active Surlyn is fabricated for this work. In the first configura-
even at -40 °C. A comparison with DCPD data highlights tion, the carbon fibers are uniformly distributed in the
the advantages of ENB as healing agent. The yield reach- matrix. In the second configuration, bundles of carbon
es a value of 100% after a reaction time of 30 s at 25 °C, fibers are distributed throughout the sample with finite
compared to DCPD where the reaction yield is about 34% spacing between adjacent bundles. Each bundle contain-
after a reaction time of 15 min. In the case where HG1 is ing 1000 carbon fiber threads is used as a singular unit.
used as catalyst and ENB as healing agent, the metathe- The carbon fibers distributed in the composite are exposed
sis reaction is significantly active also at -50 °C, whereas at the two ends (or) internally connected to copper wires
with G1 and G2 activity is reduced already at -40 °C. The of the pressed sheet for electrical access. In order to
systems based on ENB as healing agent and HG1 as cat- achieve uniform resistive heating, the composite is pro-
alyst offer the most promising results. In fact, HG1 posed to be used as individually addressable coupons
showed a higher thermal stability and optimal reactivity that will be electrically heated by the healing circuit for
for ROMP at low temperatures. healing. In addition, the electrical resistance of the car-
The healing efficiency ç (calculated as the ratio be- bon fiber bundles in the coupons is kept to aminimum to
tween the critical fracture loads of the healed and virgin achieve faster heating and hence a quick healing response.
samples) was obtained from load–displacement curves The electrical resistance of the bundles measuring 20mm
using an already established procedure [91, 92]. The re- long is kept within 5–10Ω. These self-healing coupons
sults are shown in Fig. 3. The healing efficiency was found are targeted to be used as a healing layer.
to be about 91%. The results demonstrate the ability of the polymer
The following work deserves special interest in the matrix to come together and close the path of penetration
field of airspace application. The attractive self-healing of a medium-velocity projectile (≈ 229 m/s). Subsequent
material presented in the Sundaresan with co-authors heating of polymer using embedded carbon fibers
paper is a composite material prepared by embedding car- demonstrates the ability of the polymer to further heal
bon fibers in Surlyn 8940 (referred to as “Surlyn” from Smart Materials Research and close any damage from this
this point forward) [93]. Surlyn is an ethylene/methacrylic impact. The polymer matrix made out of Surlyn melts at
9
95 °C from the heat generated in the carbon fiber layer the catalyst and epoxy required about six steps which are
and heals any surface and through thickness damage in complicated and time-consuming.
the polymer matrix. The carbon fiber layer has low resist- From the important strategies used to fabricate smart
ance and hence requires 2–3 W of electrical power in a coatings with self-healing characteristics is employing of
20 mm × 10 mm panel to heal any damage in the polymer. polyurea formaldehyde (PUF) microcontainers with po-
The mathematical model developed in this work charac- lymerisable agents loaded in it in which the process of
terizes the heating characteristics of Surlyn-carbon fiber self-healing was stimulus by a crack-induced splitting of
composites for two configurations of carbon fiber in the the embedded capsules [97]. Another drawback of the
polymer. Once the composite is heated and held near the approach with microcontainers using is that the healing
glass transition temperature of the polymer matrix, the procedure can proceed only once.
experiments show that a surface damage in the polymer A unique approach among the self-healing methods
can be healed completely. A new metric, referred to as which can be used for self-healing coatings is a thermo-
width-heal ratio that characterizes the melt flow around set/thermoplastic mixture that offers crack sealing capa-
the damage, has been developed to represent healing in city when the material is heated, and the thermoplastic is
the polymer. The experiments demonstrate the damage in able to diffuse across the crack boundary to repair the
the material can be completely healed (with a heal ratio material and restore its mechanical and structural integri-
(WHR) > 0.9) by heating the damaged area to the melt ty after being damaged. Such technology based on a poly-
temperature in less than 30 s. Thus, a composite material urethane wood coating system was successfully devel-
made from Surlyn and carbon fibers that can be used as oped by Ou R. et al. [98]. Thermoplastic healing agent
the self-healing layer for various aerospace applications. polycaprolactone (PCL) was used as self-healing phase
Self-Healing coatings. allowing to repair the material and restore its mechanical
The global problem of metals and alloys corrosion is a and structural integrity after being damaged. Moreover,
complicated challenge that has bothered mankind for many the nanoparticles can be added to the self-healing wood
years [94]. Polymer coating systems are classically ap- coating to enhance the mechanical properties, so there is
plied on a metal surface to provide a dense barrier against no loss of hardness and related mechanical properties
the corrosive species. They are also applied for wood due to the presence of the thermoplastic. The nanoparti-
surface. Surface scratches are generated which develop cles can be, but are not limited to the following: an orga-
micro-cracks, eventually leading to macroscopic damage no-modified clay, metal oxide, organo-modified metal ox-
that causes the coating to lose its aesthetic and protec- ide, graphene, and carbon nanotubes. Phase separation
tive functions. The use of a self-healing coating will in- of the thermoplastic PCL and the thermoset polyurethane
crease the operational life of coatings and eliminate the made of polyol and isocyanate occurs at the later stage of
need to frequently refinish damaged coatings. In addition polymerization. The pre-neutralized hot prepolymer/ther-
to tremendous cost savings, this results in significant moplastic (PCL) mixture was poured into water, resulting
energy savings from fabrication and application of the in an emulsion in the case of waterborn resin. The emul-
coating materials and conserves supplies of raw wood, sion is then coated on the wood and cured by drying for
an important natural resource. one hour at room temperature and aging at 60 °C for 4
Smart coatings are regarded as the coatings of the hours. Solvent born resin was thermally cured foolowed
future. The main purpose of smart coating is to integrate by UV curing. Such kind of self-healing polymer coatings
self-healing agents within the coating which lead to par- are able to recover the original finish to between 85 and 95
tial or full coating recovery from any impairment. Intro- % of the original gloss value, with only a brief application
duction of urea formaldehyde microcapsules incorporat- of heat.
ed with healing materials into the organic coating was Superhydrophobic surfaces were successfully fabri-
firstly disclosed by N. Sottol [95] who succeeds in this cated on solid wood by spray coating of perfluoroalkyl
field in the year 1993. Since that, many scientists worked methacrylic copolymer (PMC)/TiO2 nanocomposites onto
in this hot topic leading to a lot of successful attempts of polydimethylsiloxane (PDMS) pre-coated wood sub-
self-healing coatings. As a result three main mechanisms strates (Fig. 4) [99]. The coated surfaces exhibited excep-
for accomplishing self-healing properties i.e. intrinsic, tional repellency toward water as well as organic liquids
capsule and vascular strategies are commonly proposed. with low surface tensions such as ethylene glycol (with
Yang et al. have investigated good self-healing coat- contact angle 150°).The damaged surface from UV irradi-
ing systems using microencapsulated epoxy resin, with ation and sandpaper abrasion could restore its superhy-
excellent protective anti-corrosion coating and high ef- drophobicity by a simple heat treatment. Besides, with
fectiveness for steel substrate by incorporating micro- the incorporated TiO2 nanoparticles, the coated surface
capsules into paints [96]. The microcapsule shells with exhibited desirable photocatalytic efficiency in degrad-
rough morphology strengthen the bonding between paint ing organic contaminants and also showed enhanced
matrix and microcapsule. The drawback of this approach photostability with obviously inhibited discoloration dur-
is that the preparation of capsules and loading them with ing UV exposure. Such mechanically durable, self-healing
10
180
(a) (b)
Contact angle, °
120
60
0
30 40 20 50 60 70
Surface tension, mN m-1
Fig. 4. Top-view SEM images of Cross-sectional SEM image of the coated surface showing the profile of the dual-
layered coating (a). Contact angles of liquid droplets on the surface as a function of their surface tensions. The inset
shows various liquid droplets on the coated wood (b)
superhydrophobic wood surfaces with multi-functionali- even enhancement after being damaged in the cyclic com-
ties may open new avenues in the field of novel wood- pression and shearing tests, even though only 0.086 % of
based materials. the healing agents were embedded per sponge mass and
Another work reports an in situ fabrication of hyper- finely dispersed in it.
branched polyurethane (HPU) nanocomposites with dif- Polyurethanes and polyureas can also be applied for
ferent weight percentages of reduced graphene oxide-sil- designing intrinsically healable polymers as those poly-
ver-reduced carbon nanodot (RGO-Ag-RCD) nanohybrid mers featured hydrogen bonds. These weak bonds are
as nano-reinforcing material. The nanohybrid preparation highly dynamic and, thus, can be utilized for designing
was performed by a single one pot facile hydrothermal intrinsic self-healing materials. In particular, Leibler and
process. There was made an attempt to achieve the com- his group demonstrated the self-healing effects caused
bined attributes of toughness, shape memory, self-heal- by dynamic hydrogen bonds [102]. Furthermore, the
ing and self-cleaning properties of the in situ fabricated shape-memory effect of polyurethanes can be utilized to
starch modified HPU nanocomposites using different enhance the self-healing behaviors of polymers, which
weight % of the RGO-Ag-RCD nanohybrid [100]. has been described as shape-memory-assisted self heal-
In the next study, electrospun core-shell nanofibers ing. During thermal treatment or exposure to water, re-
containing healing agents are embedded into a three-di- versible reactions can be observed in which the isocy-
mensional bulk matrix in a simple versatile process. Two anate and its corresponding co-reactant are reformed.
types of the healing agents (resin monomer and cure) are Cheng and co-workers presented a poly(urea-ure-
encapsulated inside the nanofiber cores [101]. The core- thane) that was able to self-heal due to the reversibility of
shell fibers are encased in the macroscopic three-dimen-
sional bulky material. To achieve this goal, the electro-
spun core-shell fibers containing two components of
PDMS (either resin monomer or cure) are directly embed-
ded into an uncured PDMS bath and dispersed there, es-
sentially forming a monolithic composite. For the evalua-
tion of the self-healing features, the interfacial cohesion
energy is measured at the cut surface of such a material.
Namely, the bulk of the prepared self healing material is
entirely cut into two parts using a razor blade and then re-
adhered due to the self-curing process associated with
the released healing agents. The results reveal that the
self healing fiber network works and releases a sufficient
amount of resin monomer and cure at the cut surface to
facilitate self-healing. In addition, chopped into short fil-
aments core-shell fibers were embedded into highly po-
rous sponge-like media. After a mechanical damage in
Fig. 5. Schematic representation of the reversible
compression or shearing fatigue, this sponge-like materi-
reaction of the sterically hindered amine with an
al also revealed restoration of stiffness due to the released
isocyanate-functionalized polymer [106]
self-healing. The sponges revealed a 100% recovery and
11
the dynamic urea bonds [103]. Nevertheless, the investi- design strategy may serve as a versatile method for poly-
gated substances were soft materials with poor mechani- mers to prepare strong and efficient SHAs.
cal properties (a Young’smodulus of ca. 1MPa at room Urea–formaldehyde capsules were synthesized in mi-
temperature). The follow-up study by the same authors cro and nano sizes, containing linseed oil, and were incor-
described an improvement in the mechanical properties porated through epoxy coatings applied on C-steel
by using a denser polymer network, which could be com- panels. [109]. The smaller microcapsules created higher
pletely depolymerized under thermal treatment, resulting self-healing performance for the coating matrix. The con-
in the formation of the educts [104]. Consequently, re- centration of the embedded microcapsules affected the
mendability as well as recyclability of the polymer net- self-healing capability samples containing 15 wt.% micro-
work was possible. However, this behavior was associat- capsules showed higher corrosion resistance. Nano/mi-
ed with the nearly complete depolymerization of the net- cro capsules improved the self-healing performance, wet
work and, thus, a partial decrease in the mechanical integ- adhesion and corrosion resistivity rather than micro ones.
rity of the material. Besides creation of self-healing ability, the capsule em-
Martin D Hager and co-authors investigated the re- bedment also reduced the permeability of water through
versibility of dynamic poly(methacrylate) systems the film. Nevertheless, added microcapsules as well as
crosslinked with dynamic urea moieties (PMA-U) and their increasing their concentration reduced the adhesion
corresponding self-healing properties (Fig. 5) [105]. A ster- strength of the epoxy coating. Despite of this, the reduc-
ically hindered amine is utilized during polymerization due ing of synthesized capsule size (by means of ultrasonic
to its ability to open urea bonds during thermal treatment. energy application and/or higher agitation rate) could
The polymer network is obtained after a simple photopo- compensate the adhesion weakening. That is why nano
lymerization procedure. The tensile testing featured ex- samples were the preferred choice.
cellent mechanical properties (E-moduli between 0.34 and Another attractive branch of self-healing adhesives is
0.97 GPa). However, according to the bulk-healing tests covalently reversible chemical cross-link based on chem-
the healing efficiency based on the maximal stress values ical bonds that can be broken by external influences, mainly
was 50 %. IR- and Raman spectrocopies as well as DSC heat or radiation energy. The most studied covalently ther-
investigations of model compound showed that the urea mo-reversible systems are based on the Diels-Alder (DA)
bonds opened during thermal treatment at 100 °C, prov- reaction, probably because it ensures fast kinetics and a
ing the reversibility of the urea bonds. Nevertheless, at high number of recycles with little, if any, degradation
much higher temperatures (150 °C), slight bond opening between 50 and 200 °C.
was also observed for synthesized PMA-U polymers. Among the many chemical groups able to react via
Complete opening of the bonds of these polymers would DA mechanism the most investigated ones involve furan
have resulted in an enormous loss in the mechanical per- as diene and maleimide as dienophile. The reason for this
formance. resides probably in the fast kinetics, which renders them
One other example of a self-healing material with a attractive for potential industrial application.
high E-modulus (up to 4.55 GPa) was described by Wudl Self-healing coatings based on reversible polymer
and co-workers, who utilized a highly crosslinked poly- network systems can be used to actively heal a local dam-
mer network (E-modulus: 3 GPa) [106, 107]. The authors age by application of an external stimulus, breaking the
reported a healing efficiency of ~ 50 % even under nearly reversible covalent bonds. The self-healing principle is
complete depolymerization of the network owing to ther- based on the reversible Diels–Alder equilibrium reaction
mally reversible DA cross-links. between furan and maleimide functional groups (Fig. 6)
Self-healing adhesives. [110–112].
Self-healing adhesives (SHAs) are materials with re- Increasing the temperature shifts the reaction equilib-
markable practical potential for long-term adhesion. How- rium toward the breaking of the reversible bonds, destroy-
ever, reports are extremely limited because it is difficult to ing the network structure and allowing the sustained dam-
meet high strength and efficient self-healing properties. age to be healed. Upon cooling, the reversible bonds are
Tang with co-authors in their study have introduced formed again and the polymer network structure is re-
alternating rigid and flexible segments in the dynamic stored.
quaternization cross-links of poly(1,2,3-triazolium) vitrim-
er (VPTA) adhesives [108]. In consequence, the VPTA
adhesive demonstrates particularly high adhesive strength
of 23.7 MPa, compared to the reported SHAs (≤7.5 MPa).
The adhesive joints of VPTA can self-heal after complete-
ly broken for 20 times, while maintaining strengths all
above 10 MPa, which is rarely reported. Furthermore, this
adhesive also exhibits excellent solvent resistance, high Fig. 6. Thermoreversible Diels–Alder equilibrium
durability, and good creep resistance. The structural reaction between furan and maleimide
12
The Diels–Alder polymer networks reported by Wudl healing can heal scratches or damages on the metallic
and co-workers depolymerized completely during thermal surfaces within a micro to millimeter scale range.
treatment, resulting in a very mobile phase and, conse- Some of the main issues related to self-healing materi-
quently, in efficient self-healing behavior [107]. However, als for aerospace applications have been also analyzed.
during depolymerization and formation of the educts, the In particular, the attention has been focused on the devel-
mechanical integrity was partially lost. opment of self-healing materials to reduce the effect of
Conclusions. the impact damage (mechanical stress, etc.) on the struc-
Self-healing materials are able to repair themselves tural integrity of the material. For aeronautic applications,
when damaged, either autonomously or in response to self-healing is not an alternative to the usual repair main-
external stimuli, and have potential to prolong the lifetime tenance, but rather it is for repairing at the early stage of
of materials. This article highlights the state of the art of matrix microcracking and/or in the initial stage of delami-
self-healing materials for application as coatings and ad- nation. Materials for aeronautic application are processed
hesives. Different methodologies of self-healing have been in very drastic conditions of temperatures. Furthermore,
presented. the operating temperature of the final materials ranges
Extending the working life of the different structural between -50 and +60 °C. Therefore the self-healing func-
and industrial metallic surfaces could be depending on tionality must be assured at temperatures over this wide
the fabrication of novel self-healing protective smart-coat- range.
ings which able to repair scratches and eliminate the cor- Acknowlegments. This work was fulfilled in the frame
rosion. The importance of this category of coating that it of the AERO-UA project “Strategic and Targeted Sup-
can deal with respond to any internal or external stimulus port for Europe-Ukraine Collaboration in Aviation Re-
and initiate the healing process. This makes the smart search”, funded by the European Commission under
coatings very attractive materials for protection from cor- Horizon 2020 Programme for Research and Innovation,
rosion especially in the places hard-to-reach. The self- Grant Agreement No 724034.
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couplings. Polemeros: Ciencia e Tecnologia, 2005, 15, no. 2: Íàä³éøëà äî ðåäàêö³¿ 10 âåðåñíÿ 2018 ð.
Ñàìîçàë³êîâóâàí³ ïîë³ìåðè: ï³äõîäè çàë³êîâóâàííÿ òà ¿õ çàñòîñóâàííÿ

Î.Ì. Ôàéíëåéá, Î.Ã. Ïóð³êîâà
²íñòèòóò õ³ì³¿ âèñîêîìîëåêóëÿðíèõ ñïîëóê ÍÀÍ Óêðà¿íè,

48, Õàðê³âñüêå øîñå, Êè¿â, 02160, Óêðà¿íà
Â îãëÿä³ ñòèñëî ðîçãëÿíóò³ äîñë³äæåííÿ, ïðèñâÿ÷åí³ ðîçðîáö³ òà õàðàêòåðèñòèö³ ïîë³ìåðíèõ

ñàìîçàë³êîâóâàíèõ ìàòåð³àë³â (Self-healing, S-H) ç òðèâàëèì òåðì³íîì ñëóæáè, ÿê³ çäàòí³
ñàìîñò³éíî â³äíîâëþâàòèñü ïðè ïîøêîäæåíí³ áåç äîäàòêîâîãî âèÿâëåííÿ öüîãî ïîøêîäæåííÿ
òà çîâí³øíüîãî ìåõàí³÷íîãî âòðó÷àííÿ. Óñ³ â³äîì³ ï³äõîäè ñàìîçàë³êîâóâàííÿ äëÿ ïîë³ìåð³â
ìîæíà ðîçä³ëèòè íà äâ³ ãðóïè: àâòîíîìí³ òà íåàâòîíîìí³. Àâòîíîìíå çàë³êîâóâàííÿ ñàìîñò³éíå
³ íå âèìàãàº í³ÿêîãî çîâí³øíüîãî âòðó÷àííÿ, õî÷à â ë³òåðàòóð³ öåé ìåòîä òàêîæ íàçèâàþòü
çîâí³øí³ì (extrinsic). Öå ïîâ’ÿçàíî ç íàÿâí³ñòþ â ìàòåð³àë³ äîäàòêîâîãî çàë³êîâóþ÷îãî àãåíòà,
ÿêèé ðîçì³ùåíî â ðåçåðâóàðàõ. Çàëåæíî â³ä êîíöåïö³¿ ñàìîâ³äíîâëåííÿ àâòîíîìíèé ï³äõ³ä ìîæíà
ðîçä³ëèòè íà ï³äãðóïè, à ñàìå: êàïñóëüíèõ ñèñòåì ³ ñèñòåì ì³êðîâàñêóëÿðíèõ àáî âîëîêîííèõ
ñ³òîê. Íåàâòîíîìíå çàë³êîâóâàííÿ ÷àñòêîâå; çàë³êîâóþ÷ó çäàòí³ñòü çàêëàäåíî â ìàòåð³àë, òîìó
öåé òèï çàë³êîâóâàííÿ ùå íàçèâàþòü âíóòð³øí³ì (intrinsic), àëå íåîáõ³äí³ äîäàòêîâ³ çîâí³øí³
ôàêòîðè âïëèâó, òàê³ ÿê òåïëî àáî óëüòðàô³îëåòîâå âèïðîì³íþâàííÿ. Êð³ì òîãî, ïîë³ìåðè
âíóòð³øíüîãî ñàìîçàë³êîâóâàííÿ ìîæóòü áóòè ñòâîðåí³ òàêèì ÷èíîì, ùîá áóòè õ³ì³÷íî “ëèïêèì”
ïî ë³í³ÿõ ðîçðèâó, àáî â³äïîâ³äàòè ð³çíèì åíåðãåòè÷íèì óìîâàì, íàïðèêëàä, áóòè ÷óòëèâèìè äî
ä³¿ åëåêòðîìàãí³òíîãî ïîëÿ àáî ïðîíèêíåííÿ êóë³. Êðèòè÷íî ðîçãëÿíóòî ïåðåâàãè òà íåäîë³êè
êîæíîãî ç ï³äõîä³â, çàïðîïîíîâàíèõ äëÿ ñòâîðåííÿ S-H ïîë³ìåðíèõ ñèñòåì. Íîâ³ òåõíîëîã³¿
ñàìîâ³äíîâëåííÿ, ðîçðîáëåí³ ç ìåòîþ íàäàííÿ ïîë³ìåðíèì ìàòåð³àëàì çäàòíîñò³ çóïèíÿòè
ðîçïîâñþäæåííÿ òð³ùèí íà ðàíí³õ ñòàä³ÿõ, çàïîá³ãàþòü êàòàñòðîô³÷íîìó ïîøêîäæåííþ öèõ
ìàòåð³àë³â ³ äîïîìîæóòü çíà÷íî ïîøèðèòè ñôåðè çàñòîñóâàííÿ öèõ ìàòåð³àë³â. Òàê³ òåõíîëîã³¿
ïåðñïåêòèâí³ äëÿ ñòâîðåííÿ ñóïóòíèê³â ³ êîñì³÷íèõ àïàðàò³â ç ôóíêö³ºþ çàë³êîâóâàííÿ
ïîøêîäæåíü, ÿê³ âèêëèêàí³ âèñîêîøâèäê³ñíèìè êîñì³÷íèìè óëàìêàìè. ²íøîþ ïåðñïåêòèâíîþ
ãàëóççþ çàñòîñóâàííÿ S-H ïîë³ìåð³â, ðîçãëÿíóòîþ â öüîìó îãëÿä³, º ñòâîðåííÿ S-H ïîêðèòò³â òà
àäãåçèâ³â. Êð³ì òîãî, âèñâ³òëþþòüñÿ ïðîáëåìè òà ïåðñïåêòèâè äîñë³äæåíü.
Êëþ÷îâ³ ñëîâà: «ðîçóìí³» ìàòåð³àëè, ñàìîçàë³êîâóâàí³ ïîë³ìåðè, ïîë³ìåðí³ êîìïîçèòè, àäãåçèâè, ïîêðèòòÿ.
17
Ñàìîçàëå÷èâàþùèåñÿ ïîëèìåðû: ïîäõîäû çàëå÷èâàíèÿ è èõ ïðèìåíåíèå

À.Ì. Ôàéíëåéá, Î.Ã. Ïóðèêîâà
Èíñòèòóò õèìèè âûñîêîìîëåêóëÿðíûõ ñîåäèíåíèé ÍÀÍ Óêðàèíû,

Õàðüêîâñêîå øîññå, 48, 02160 Êèåâ, Óêðàèíà
Â ýòîì îáçîðå êðàòêî ðàññìîòðåíû èññëåäîâàíèÿ, ïîñâÿùåííûå ðàçðàáîòêå è õàðàêòåðèñòèêå

ïîëèìåðíûõ ñàìîçàëå÷èâàþùèõñÿ (Self-healing, S-H) ìàòåðèàëîâ ñ äëèòåëüíûì òåðìèíîì
ñëóæáû, êîòîðûå ñïîñîáíû ñàìîñòîÿòåëüíî âîññòàíàâëèâàòüñÿ ïðè ïîâðåæäåíèè áåç
äîïîëíèòåëüíîãî âûÿâëåíèÿ ýòîãî ïîâðåæäåíèÿ è âíåøíåãî ìåõàíè÷åñêîãî âìåøàòåëüñòâà.
Âñå èçâåñòíûå ïîäõîäû ñàìîçàëå÷èâàíèÿ äëÿ ïîëèìåðîâ ìîæíî ðàçäåëèòü íà äâå ãðóïïû:
àâòîíîìíûå è íåàâòîíîìíûå. Àâòîíîìíîå ñàìîçàëå÷èâàíèå ÿâëÿåòñÿ ñàìîñòîÿòåëüíûì è íå
òðåáóåò íèêàêîãî âíåøíåãî âìåøàòåëüñòâà, õîòÿ â ëèòåðàòóðå ýòîò ìåòîä òàêæå íàçûâàþò
âíåøíèì (extrinsic). Ýòî ñâÿçàíî ñ íàëè÷èåì â ìàòåðèàëå äîïîëíèòåëüíîãî çàëå÷èâàþùåãî
àãåíòà, ïîìåùåííîãî â ðåçåðâóàðû. Â çàâèñèìîñòè îò êîíöåïöèè ñàìîçàëå÷èâàíèÿ àâòîíîìíûé
ïîäõîä ìîæíî ðàçäåëèòü íà ïîäãðóïïû, à èìåííî: êàïñóëüíûå ñèñòåìû è ñèñòåìû
ìèêðîâàñêóëÿðíûõ èëè âîëîêîííûõ ñåòåé. Íåàâòîíîìíîå çàëå÷èâàíèå ÿâëÿåòñÿ ÷àñòè÷íûì;
çàëå÷èâàþùàÿ ñïîñîáíîñòü çàëîæåíà â ìàòåðèàë, ïîýòîìó ýòîò òèï çàëå÷èâàíèÿ åùå íàçûâàþò
âíóòðåííèì (intrinsic), îäíàêî íåîáõîäèìû äîïîëíèòåëüíûå âíåøíèå ôàêòîðû âîçäåéñòâèÿ,
òàêèå êàê òåïëî èëè óëüòðàôèîëåòîâîå èçëó÷åíèå. Êðîìå òîãî, ïîëèìåðû âíóòðåííåãî
ñàìîçàëå÷èâàíèÿ ìîãóò áûòü ñîçäàíû òàêèì îáðàçîì, ÷òîáû áûòü õèìè÷åñêè “ëèïêèìè” ïî
ëèíèÿì ðàçðûâà, èëè áûòü ÷óâñòâèòåëüíûìè ê ðàçëè÷íûì ýíåðãåòè÷åñêèì óñëîâèÿì, íàïðèìåð,
âîçäåéñòâèþ ýëåêòðîìàãíèòíîãî ïîëÿ èëè ïðîíèêíîâåíèþ ïóëè. Êðèòè÷åñêè ðàññìîòðåíû
ïðåèìóùåñòâà è íåäîñòàòêè êàæäîãî èç ïîäõîäîâ, ïðåäëîæåííûõ äëÿ ñîçäàíèÿ ïîëèìåðíûõ
ñèñòåì S-H. Íîâûå òåõíîëîãèè ñàìîâîññòàíîâëåíèÿ, ðàçðàáîòàííûå ñ öåëüþ ñîçäàíèÿ ïîëèìåðíûõ
ìàòåðèàëîâ ñî ñïîñîáíîñòüþ îñòàíàâëèâàòü ðàñïðîñòðàíåíèå òðåùèí íà ðàííèõ ñòàäèÿõ,
ïðåäîòâðàùàþò êàòàñòðîôè÷åñêîå ïîâðåæäåíèå òàêèõ ìàòåðèàëîâ è ïîìîãóò çíà÷èòåëüíî
ðàñøèðèòü ñôåðû èñïîëüçîâàíèÿ ýòèõ ìàòåðèàëîâ. Ðàññìîòðåííûå òåõíîëîãèè S-H ÿâëÿþòñÿ
ïåðñïåêòèâíûìè äëÿ ñîçäàíèÿ ñïóòíèêîâ è êîñìè÷åñêèõ àïïàðàòîâ ñ ôóíêöèåé
ñàìîâîññòàíîâëåíèÿ ïîâðåæäåíèé, âûçâàííûõ âûñîêîñêîðîñòíûìè êîñìè÷åñêèìè îáëîìêàìè.
Äðóãîé ïåðñïåêòèâíîé îòðàñëüþ ïðèìåíåíèÿ S-H ïîëèìåðîâ, ðàññìîòðåííîé â ýòîì îáçîðå,
ÿâëÿåòñÿ ñîçäàíèå S-H ïîêðûòèé è àäãåçèâîâ. Êðîìå òîãî, îñâåùåíû ïðîáëåìû è âîçìîæíîñòè
èññëåäîâàíèé â îáëàñòè ñîçäàíèÿ S-H ìàòåðèàëîâ.
Êëþ÷åâûå ñëîâà: «ðàçóìíûå» ìàòåðèàëû, ñàìîçàëå÷èâàþùèåñÿ ïîëèìåðû, ïîëèìåðíûå êîìïîçèòû, àäãåçèâû,

ïîêðûòèÿ.
18
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Self-healing polymers: approaches of healing and their application

Article in Polymer Journal · March 2019

PhD Thesis View project

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Institute of Macromolecular Chemistry NAS of Ukraine

Polymers and polymer composites have been widely constantly appearing.

4 © 2019 A.M. Fainleib, O.H. Purikova

though in very different forms. Healing agents may be in

or long periods of an nealing to enable thermal diffusion

materials: a review of recent developments. Progress in Polymer no. 8: 743–753. https://doi.org/10.1016/S1359-835X(03)00138-

polymer syntheses based on furan/maleimide reversible 95–101. https://doi.org/10.1590/S0104-14282005000200007

Ñàìîçàë³êîâóâàí³ ïîë³ìåðè: ï³äõîäè çàë³êîâóâàííÿ òà ¿õ çàñòîñóâàííÿ

²íñòèòóò õ³ì³¿ âèñîêîìîëåêóëÿðíèõ ñïîëóê ÍÀÍ Óêðà¿íè,

Â îãëÿä³ ñòèñëî ðîçãëÿíóò³ äîñë³äæåííÿ, ïðèñâÿ÷åí³ ðîçðîáö³ òà õàðàêòåðèñòèö³ ïîë³ìåðíèõ

Ñàìîçàëå÷èâàþùèåñÿ ïîëèìåðû: ïîäõîäû çàëå÷èâàíèÿ è èõ ïðèìåíåíèå

Èíñòèòóò õèìèè âûñîêîìîëåêóëÿðíûõ ñîåäèíåíèé ÍÀÍ Óêðàèíû,

Â ýòîì îáçîðå êðàòêî ðàññìîòðåíû èññëåäîâàíèÿ, ïîñâÿùåííûå ðàçðàáîòêå è õàðàêòåðèñòèêå

Êëþ÷åâûå ñëîâà: «ðàçóìíûå» ìàòåðèàëû, ñàìîçàëå÷èâàþùèåñÿ ïîëèìåðû, ïîëèìåðíûå êîìïîçèòû, àäãåçèâû,

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