Biofriendly nanocomposite containers with inhibition properties for the protection of metallic surfaces

Abstract

An attempt to combine two ‘green’ compounds in nanocomposite microcontainers in order to increase protection properties of waterborne acryl-styrene copolymer (ASC) coatings has been made. N-lauroylsarcosine (NLS) served as a corrosion inhibitor, and linseed oil (LO) as a carrier-forming component. LO is compatible with this copolymer and can impart to the coating self-healing properties. For the evaluation of the protective performance, three types of coatings were compared. In the first two, NLS was introduced in the coating formulation in the forms of free powder and micro-containers filled with LO, correspondingly. The last one was a standard ASC coating without inhibitor at all. Low-carbon steel substrates were coated by these formulations by spraying and subjected subsequently to the neutral salt spray test according to DIN ISO 9227. Results of these tests as well as the data obtained by electrochemical study suggest that such containers can be used for the improvement of adhesion of ASC-based coatings to the substrate and for the enhancement of their protective performance upon integrity damage, whereas the barrier properties of intact coatings were decreased.

1. Introduction

Recently, a lot of research attention has been drawn to the development of biofriendly materials and approaches and to the replacement of toxic substances and synthetic pathways to the ‘greener’ ones. This trend is present in almost every industrial and scientific field, including protection against corrosion of metal substrates by painting compositions. Such a protection has always been a complex topic throughout the history because the effective maintenance has often involved the usage of harmful compounds. Corrosion inhibitors based on various heavy metals (chromium, lead, cadmium, etc.) have been used leading to carcinogenic or mutagenic subsequences, as some forms of such metals are toxic [1,2]. Almost all of these metals are included in the list of prohibited compounds [3], and the list is expanding further over the course of time. Some pathways have been suggested in order to replace hazardous chemicals [1,2,4]. One of the possible promising substituents is the N-lauroylsarcosine (NLS), which is the known corrosion inhibitor for the protection of iron, stainless steel, and other metallic compounds [5–7].

The usage of an inhibitor directly added into a coating formulation is assumed to be not efficient enough for a long period of time, because there is a relatively quick natural depletion of an inhibitor (by leaching, evaporation or degradation) caused by the surrounding medium (e.g. mechanical damage and subsequent impact by air and/or water). Otherwise stated, the removal rate of a corrosion inhibitor, r_c from a formulation follows first-order kinetics, i.e. r_c is directly proportional to the amount of an inhibitor present in the system at that time. Therefore, for increasing of the duration of inhibition activity, exponentially bigger amounts of the inhibitor are required [1].

The suggested mechanism to overcome this problem is a development of containers comprising a corrosion inhibitor with the controlled release rate of an active component. The second ingredient must be compatible with both NLS and a coating formulation. In particular, waterborne acryl-styrene copolymer (ASC) coating formulations were chosen, since they are widely used as well as eco-friendly, in general. However, this type of coating also has a substantial drawback, namely low corrosion resistance [8–11]. Utilization of such containers can help to overpass that issue and to increase the attractiveness for consumers. The advantage of such containers includes a limitation of the release of an inhibitor only to the case of a coating damage. Moreover, the flexible shell allows mixing of containers in the coating formulation and subsequent curing without breakage, therefore, saving an inhibitor inside.

In this work, we aimed to synthesize containers and investigate their efficiency. Containers comprise NLS and linseed oil (LO), serves as an auxiliary solvent for NLS and at the same time as a sealing agent. The outer layer consists of the polyvinyl alcohol (PVA) cross-linked by boric acid (BA). As a comparison, the direct application of the corrosion inhibitor by embedding both investigated samples into ASC coating formulations on the low-carbon steel substrates was made, followed by an examination of the corrosion by electrochemical and adhesion measurements of the final coatings. Corrosion inhibitor located within containers slowly diffuses through a coating, but the rate of this process is believed to be slow, thus providing the content of NLS on a sufficient level enabling the protection of the metal substrate in the case of a mechanical damage. In this situation, containers in the defected zone are also mechanically destroyed and an inhibitor is released quickly immediately starting to act. NLS forms a chelate complex comprised of a five-membered ring on the surface of bivalent metals (figure 1) [12]. The strong adsorption leads to a protective hydrophobic shield against the harmful impact of corrosive species on the metal surface.

Figure 1.

Five-membered ring which NLS forms with the metal (M) surface.

Since the encapsulation approach for the creation of the self-healing coatings is not a novel topic, several works have been already published [13–17]. Moreover, LO was used as a core material that serves as well as a healing substance, and urea-formaldehyde [18] or phenol-formaldehyde [19] were used for the formation of an outer layer.

Specific difficulty consists of the fact that a lot of research has been dedicated to the investigation of drying of LO in coatings at the interface with the air [20–23], whereas in the present case the process is going on in the bulk of the dispersion medium at the oil/water interface. Thus, it creates an additional restriction to the penetration of oxygen towards the interface of oil droplets. An analysis of regularities of this process can serve as a basis for a future work.

2. Experimental section

(a). Material and methods

(i). Materials

Water dispersion of ASC ‘Lakroten E-244’ was purchased from LLC Orgchimprom, Russia.

PVA (M_w 9.000–10.000 g mol⁻¹, 80% hydrolysed), BA, LO, NLS with purity of 98%, NaNO₂, ethyl acetate, xylene, Co(II), Ce(III) and Ca(II) 2-ethylhexanoates, azobisisobutyronitrile (AIBN), 2,2,4-trimethyl-1,3-pentanediol (known also as commercial product Nexcoat 795) and hydrogen peroxide were purchased from Sigma-Aldrich, Germany.

Low-carbon steel substrates with dimensions 126.5 × 76.5 × 0.8 mm (sandblasted steel, DC 04 B, SA 2.5, 12.5 µm surface roughness) were purchased from Krueppel Gmbh, Germany.

(ii). Methods

Particle sizes

A Zeta Sizer Nano (Malvern Instruments, UK) at 25°C was used for the determination of particle sizes, polydispersity indices (PDI) and zeta-potential (ζ) values of synthesized containers. Their suspensions in MilliQ water with appropriate concentrations were used for these measurements. For the size distribution measurements, a backscattering mode with a detector position of 173° was applied. The results of three subsequent measurements with 15 runs in each were then averaged to obtain a final value. The ζ-potential values were automatically calculated from the data of electrophoretic mobility measurements using the Smoluchowski equation. Each value was found as an average from three sequential measurements.

Scanning electron microscopy

A Gemini Leo 1550 instrument at an operation voltage of 3 keV was used for the determination of precise capsule structures and sizes. Samples were prepared by placing aqueous suspensions onto a glass substrate, drying and subsequent gold sputtering.

Neutral salt spray test

Coated and scribed steel plates were subjected to a neutral salt spray (NSS) test in accordance with ISO 9227 (ASTM B117) (http://www.iso.org/iso/catalogue_detail.htm?csnumber=63543 (accessed on 11 February 2017)). To this end, the panels were set on special racks in a salt spray chamber CC450XP (Ascott, UK) with the total inner volume of 450 l and the following conditions causing the accelerated onset of a corrosion: 100% rh, T = 35°C, continuous spraying of a 5 wt% aqueous NaCl solution. The duration of the NSS test was 260 h. Such relatively short duration is explained by the low protective performance of the ASC coatings, which usually lasts only for 240 h. Every coating type was tested in triplicate. The delaminated coating was mechanically detached from rinsed and dried samples with a scratching tool according to DIN EN ISO 4628-8 (http://www.iso.org/iso/catalogue_detail.htm?csnumber=51942 (accessed on 11 Feb 2017)).

Electrical capacity

For the determination of the electrical capacity of coatings a two-electrode electrochemical cell (figure 2) was used. An electrochemical cell was prepared by gluing the hollow glass cylinder with an internal diameter of 3 cm to a coated metal plate. Therefore, the first working electrode is a disc made of stainless steel located in the electrolyte solution parallel to the cell bottom. The second one is a segment of the steel with a coating (surface area is 7.07 cm²) forming a glass cylinder bottom.

Figure 2.

Two-electrode electrochemical cell: (a) scheme, where 1, stainless steel disc (first electrode); 2, electrolyte solution; 3, glass cylinder; 4, coating; 5, steel plate (second electrode); 6, electrode contact; (b) photo of the real set-up. (Online version in colour.)

The cell was filled with 25 ml of electrolyte, 0.5 M NaCl solution. This system was considered as the total condenser with losses, where armature is the steel substrate and electrolyte, and dielectric spacer is a coating. One of the clips was connected to a contact corner of a steel substrate and another to a contact place on a stainless steel disc. The AC current with 1 kHz frequency was applied.

An automatic instrument Fluke PM 6306-571 (Fluke Corporation, USA) was used for the determination of the electric capacity values. This instrument measures the component current (I) and component voltage (V) and calculates capacitance (C) with the help of following formula:

$$C=\frac{1}{\omega (1+(1/Q^2))\parallel X_{\mathrm{S}}},$$ 2.1

where ω is radial frequency; Q, quality factor, Q = X_S/R_S; X_S, equivalent series reactance; R_S, equivalent series resistance. The method for monitoring of capacitance applied in our work is a simplified version of electrochemical impedance spectroscopy (EIS) method when the measurements are conducted at a constant frequency. The realization of EIS is enough for the qualitative estimation of the degradation processes in the polymer coatings of interest [24]. Especially on the first stage of the coating failure, the resistance of an insulating coating cannot be measured with an appropriate certainty. Thus, over this stage, the capacitance changes can yield more important information about the coating state. Moreover, a rapid change of capacitance is usually observed in the final stage of the coating degradation where its fails completely and underfilm corrosion reactions start.

Adhesion measurements

Adhesion measurements were carried out in accordance to ISO 4624 (http://www.iso.org/iso/catalogue_detail.htm?csnumber=62351 (accessed on 11 February 2017)) with the help of a Neurtek KN-10 (NEURTEK S.A., Spain). The measurement bodies with 20 mm diameter were glued onto the prepared surfaces of the investigated plates and stored for 3 days. Then the measurement bodies were inserted in the equipment socket and detached. The force of the breaking off was determined automatically.

(b). Preparation of containers

The formation of containers is feasible because the NLS possesses an amphiphilic structure, so the hydrophobic dodecyl ‘tail’ can be located inside the dispersed LO phase, and hydrophilic amino acid ‘head’ of N-methyl glycine is disposed on the surface of the oil. While placed in the water medium, LO in containers serves as non-miscible colloidal depots which can be cross-linked. In general, while exposed to the air, LO undergoes the spontaneous chemical process of autoxidation followed by a polymerization [20]. The addition of auxiliary oxygen can be done by using peroxides, by bubbling of air through the reaction mixture or by improving the shell drying (usage of siccatives based on various metals). Moreover, other factors can also influence a polymerization reaction: using initiators along with sufficient temperature for its dissociation, ultrasound treatment, etc.

Initially, three various procedures were comparatively used in order to prepare containers. The first two were meant to enhance the polymerization process of LO. They include usage of siccatives (Co(II), Ce(III) and Ca(II) 2-ethylhexanoates) in different ratios along with bubbling of the air stream into the reaction mixture and application of initiator AIBN along with hydrogen peroxide for the auxiliary oxygen. A third approach consisted of two steps. In the first one, LO droplets were stabilized as an oil-in-water (o/w) emulsion by means of using PVA as an emulsion stabilizer. In the second step, the PVA-stabilized LO droplets were transferred into aqueous BA solution. Owing to the reaction between PVA and BA, the PVA located on the droplets interface became cross-linked and thus served as a flexible shell of containers [25], (http://www.rsc.org/education/eic/issues/2005_Jan/exhibition.asp (accessed on 11 February 2017)), [26,27]. After the syntheses, next the characterizations were made in order to determine the features of synthesized containers. Light microscopy and dynamic light scattering (DLS) were used for the detection of their sizes. Measurements of zeta-potential and storage of synthesized containers under standard ambient temperature and pressure (SATP) conditions were used for the determination of their stability in time. After the comparative analysis of the obtained data the third synthetic approach was selected as a working procedure for the further preparation of the containers.

NLS was dissolved in LO with the help of an ultrasound bath and heated up to 40°C during 5 min with the concentration of 10 wt% which is considered to be enough, as only tiny amounts of the inhibitor in the final coating is needed (e.g. the 0.018 wt% NLS concentration already showed high efficiency in model coating systems) [8]. The o/w emulsion (5 wt%) of the above-mentioned sarcosine containing LO in 2.5 wt% PVA aqueous solution was prepared by treatment with an ultrasonic horn (ultrasonic processor VCX 500 Sonics and Co., 500 W). The following conditions were applied: diameter of the tip area of the horn is 10 mm, pulse work regime with 20 s work time and 10 s rest time, 40% amplitude, total treatment duration is 3 min. The resulting dispersion (named ‘PVA sample’) was placed into a glycerol bath at 70°C for 48 h for the enhancement of the further polymerization process in LO. After this step, containers were concentrated in the upper layer with the help of centrifuge at 1000 r.p.m. for 60 min. Then the topmost layer saturated with containers was mixed with the 2 wt% BA water solution under mild stirring (named ‘PVA + BA sample’). The centrifugation of this sample was repeated once again at the same processing conditions as mentioned above. Finally, the upper concentrated part was gently stirred with 10 ml of acidic aqueous medium (pH ≈ 2).

It is important to know whether containers can retain the entire initial amount of NLS after their addition to the aqueous medium or some part of the inhibitor is dissolved in this medium. Some sources suggest that solubility of NLS in water medium is low, namely 0.5 g l⁻¹ at 25°C at pH value of 4.2 (http://echa.europa.eu/registration-dossier/-/registered-dossier/5710/4/9 (accessed on 11 February 2017)). However, with the increasing pH it is assumed that the solubility of NLS as an amino acid is also increasing [28]. Considering that ASC coating formulation has a basic pH value (7.0–9.0), one has to be aware of an undesirable leakage of the NLS into the outer medium. That is why synthesized containers were concentrated in an aqueous medium with low pH.

After the centrifugation step of both ‘PVA sample’ and ‘PVA + BA sample’ solutions, the gravimetrical studies were performed, i.e. two samples of these saturated solutions were placed in the oven at 50°C until complete drying of the liquid phase. Thus, knowing initial mass and mass after evaporation, the content of the sarcosine-in-oil in the saturated solutions was calculated. The concentration of containers was equalled to approx. 10 wt%.

(c). Preparation of metal plates and coating procedure

For the preparation of every sample, the 3 wt% 2,2,4-trimethyl-1,3-pentanediol (served as coalescent) and 2 wt% of 15 wt% NaNO₂ (in turn, as an inhibitor of atmospheric corrosion), aqueous solution were introduced prior to the deposition in ASC formulations, followed by the addition of a calculated amount of corrosion inhibitor in the corresponding form (free powdered or encapsulated), and all dispersions were thoroughly stirred. After this step, mixtures were left to stay for 90 min before coating. Metal plates were cleaned by means of ultrasound bath treatment during 15 min with successive utilization of ethyl acetate and xylene as cleaning solvents.

Deposition was done with a pneumatic spray gun set-up with the nozzle diameter 1.4 ÷ 1.6 mm and processing pressure 4 to 5 bars in three successive steps with the intermediate drying for 30 min. The thickness of each wet layer was about 60 µm, and considering the content of the non-volatile part of the acryl-styrene coating in the order of 50%, the total thickness of the dry layer was supposed to be in the range of 90 µm. However, additional water added together with containers dispersion before the coating led to the reduction of the final values of thicknesses. The dry film thicknesses (DFT) were measured afterwards by means of a coating thickness gauge, Surfix^® Pro S (Phynix GmbH, Germany).

After the application, the plates freshly coated by ASC emulsions were conditioned for 24 h under the SATP conditions and afterwards were cured in an accelerated fashion at 80°C for 3 h.

Before testing in the salt spray chamber, the cut edges and back surfaces of the cured plates were protected using a transparent Scotch tape. Then, in the middle part of each plate a vertical scribe with the length of 100 ± 5 mm and width of 1 mm was made with the help of a scribing device, ScratchMaster 3000 (mtv messtechnik oHG, Germany), with the scribing tool according to Sikkens.

3. Results and discussion

(a). Characterization of containers

In order to see how the addition of BA affected the containers, both ‘PVA sample’ and ‘PVA + BA sample’ were investigated. Corresponding data are summarized in table 1. As can be seen from the table, the addition of BA did not lead to any prominent change. However, the decrease of deviation values in zeta-potential measurement along with the slight decrease of ζ-potential values can be noted as a stabilization step.

Table 1.

Summarized data on PVA and PVA-BA samples.

sample	pHa	ζ-potential (mV)	deviation (mV)	conductivity (mS cm−1)	particle size (nm)	PDI
PVA	3.7	−14	13	0.088	179	0.17
PVA + BA	3.7	−16	6	0.065	173	0.13

^apH measurements were conducted in the freshly prepared dispersions (5 wt%), whereas all others on diluted (1 wt%) dispersions.

In figure 3, the SEM image on the basis of the PVA 5 wt% emulsion is shown. Sizes of containers are in a range of hundreds of nanometres, and this is in accordance with the DLS results. The observed spherical and spheroidal shapes evidence that micro-objects shells are either soft or have a gel-like nature.

Figure 3.

SEM image of sample prepared on the basis of 5 wt% oil in PVA solution emulsion.

(b). Neutral salt spray test and adhesion measurements

There were three series consisted of 10 plates each for the deposition of every type of coatings. The joint information about the series is combined in table 2.

Table 2.

Explanation and properties of the series.

series number	composition of the coating	NLS concentration on the dry coating (wt%)	DFT (µm)	adhesion (MPa)
series I	pure ASC coating	0	97.7	3.3
series II	dispersion of free pure NLS in ASC	0.1	96.2	2.9
series III	concentrated dispersion of containers with NLS in the ASC	0.1	55.2	3.2

Coated metal plates were withdrawn from the NSS chamber after 260 h of the exposition time, and corrosion as well as delamination on the scribe were determined semi-quantitatively. The corresponding photographs are presented in figure 4. In the case when no inhibitor was added into coating formulation (figure 4a, series I), the interface has the most damaged outlook; the coating can be easily removed by even low mechanical impact, on some samples the complete removal was observed, i.e. the overall adhesion to the metal surface is very low. Areas on the scribe are rusted on the level of 85–90%; moreover, rust places are visible in the vicinity of the scribe. For the samples from series II (figure 4b), the delamination of coatings is lower, areas on the scribe are rusted on the level of 55–60%. Almost no rust is visible in the vicinity of the scribe. Coatings can be removed from the surface, but it requires the application of a higher force than in the previous case. Regarding series III plates (figure 4c), the overall picture is of the same rate as in series II samples (areas on the scribe are rusted on the level of 60–65%). The delamination of the coating near the scribe is essentially less pronounced; however, some merged areas of delamination occurred there caused by bubbles. The adhesion in this case is the highest. One has to apply a quite strong force upon scratching in order to remove the coating from the surface. Noteworthy, samples in last series have mean thicknesses that are approximately 43% lower than in the Series I and II (table 2). Therefore, one can assume that by increasing the thickness to the same range, the blistering, delamination and bubbles interference on the coating would be even smaller.

Figure 4.

Photographs of metal plates with coatings after the NSS test: (a) series I; (b) series II and (c) series III.

The quantitative degree of the delamination was determined according to the DIN EN ISO 4628-8. For series I and II, average values are close, correspondingly 27 ± 4 and 27 ± 5 mm, whereas for series III the value is lower 16 ± 6 mm.

Comprehensive overview of different types of protective systems effectively acting against corrosion of various metal substrates is given in [17]. Here, not only corrosion protective coatings with embedded core-shell morphology capsules with inhibitors showed superior protective performance but also other types micro- and nanocontainers were found to be efficient for the incorporation in anticorrosive coatings. Efficiency of used core-shell systems for the self-healing of coatings was also presented quite recently by Szabo et al. [18].

It is known that an incorporation of even the smallest objects (such as oil droplets or inhibitor powder) into the coating can often lead to the decrease of its barrier properties [29]. On the contrary, the distribution of an inhibitor on the molecular level (under precondition of the absence of side chemical reactions with other coating components) does not disturb the integrity of a coating. The NLS added in the powdered form to the ASC dispersion with basic pH was completely dissolved. In the case of employment of containers there are places where oil droplets concentrated in the matrix of a coating. Since both NLS and fatty acids of LO are soluble in the water medium, a penetration of water towards the matrix is possible. NLS then goes away ensuing an increase in electric capacity (see §3.3) and a lowering of barrier properties. He & Shi [13] did not investigate the changes in barrier properties of anticorrosive primer caused by the addition of cage-like microcontainers filled with repairing agent because of their use immediately on the substrate surface. On the other hand, upon damage, the EIS results for the coating with incorporated microcontainers confirmed improved protection performance compared with the standard coating.

In figure 5, the photographs of samples after adhesion measurements are shown. All the samples demonstrated well-expressed adhesive failure with almost no residual coating on the substrate. This finding is important and means that the introduction of the inhibitor in both free and encapsulated states does not influence the mechanical integrity of the cured coating and, therefore, its cohesion strength. The quantitative results for all series are also quite similar with only small reduction for the series II (table 2). However, it is important to mention the thickness difference between series and its possible influence on the results. The thin layer of coatings in series III is sufficient for provision of the same adhesion as approximately 43% thicker film based on the same composition (series I). As follows from modern studies of the effect of the coating thickness on the interfacial strength [30], with the increase of adhesive thickness, the interfacial strengths decrease and approach asymptotically a constant value typical for the strength of bulk adhesive material. On the other hand, for thicknesses in the range of 100 µm, the adhesion strength of ASC-based coatings should remain on the constant level. This is in accordance with data obtained in this work showing that adhesion is not disturbed by the presence of microcontainers incorporated in the coating matrix (table 2).

Figure 5.

Photographs of metal plates with coatings after adhesion test: (a) series I; (b) series II and (c) series III.

(c). Electrochemical measurements

Chronograms of electric capacities of all ‘painted metal-electrolyte’ systems are given in figure 6. The introduction of NLS powder almost does not affect barrier properties of initial ASC dispersion. When an encapsulated inhibitor is added in the system, the barrier properties of coatings decrease significantly, as electric capacity values are increasing. The thinner the thickness of the spacer (applied coating in this case), the more active the corrosion influence.

Figure 6.

Averaged chronograms of electric capacity for: (a) series I; (b) series II; (c) series III and (d) averaged and normalized values for all series. The lines are guides for the eyes.

In figure 6c, the jumps of values of electric capacities starting in the time range from 450 to 750 h are a natural consequence of the gradual deterioration of the coating layer and of the drop of its barrier properties. The rate of this process is higher when the dissolution of fatty acids of LO takes place. As mentioned in §3.2, the corresponding development of empty voids in the coating occurs, followed by a gradual filling of them with the electrolyte solution from the electrochemical cell. Moreover, the steep increase of electric capacity values in series III after 500 h is related to the smaller coating thickness.

As thicknesses between all series are different, the normalization was done in order to directly compare electric capacity values (figure 6d). This normalization, however, does not reflect the degradation kinetics for the coatings with different thicknesses, since the water penetration possesses faster kinetics. Calculations of averaged and normalized values of electric capacity, C_reduced were made with the following formula:

$$C_{\mathrm{reduced}}=\frac{h_{\mathrm{real}}}{h_{\mathrm{set}}}{C}_{\mathrm{real}},$$ 3.1

where h_real, real value of plate thickness; h_set, predetermined thickness value of 70 µm and C_real, real value of electric capacity.

After the 1000 h of electrochemical tests, the glass cylinders were removed. Two samples from each series with general trend were selected and corresponding photos of metal plates with coatings are shown in figure 7.

Figure 7.

Photographs of metal plates with coatings after electrochemical test: (a) series I; (b) series II and (c) series III.

The appearance of rusted places where the cylinders were located confirms the quantitative data. The most vivid colour has plates from series III.

4. Conclusion

The following conclusions can be drawn: the incorporation of containers in the coatings does not disturb its adhesion to the substrate and decrease delamination at corrosion tests (NSS). On the other hand, the dilution of the coating formulation by suspension of containers leads to the reduction of the coating thickness and to the decrease of its barrier properties.

The collected data allow the prediction that the coating with the enhanced corrosion protection performance could be designed as a two-layered system with an optimal combination of the primer layer filled with inhibitor containers and a topcoat made of pure ASC formulation. In this case, both a decrease of delamination and an increase in barrier properties should be expected.

Data accessibility

The ISO links are given in the References section.

Authors' contribution

T.R.V. carried out the synthesis part and NSS test experiment, participated in data acquisition, analysis and interpretation, participated in the design of the study and drafted the manuscript; V.E.K. carried out the electrochemical and adhesion measurements; participated in data acquisition, analysis and interpretation; P.V.G. carried out the electrochemical and adhesion measurements; participated in data acquisition; S.N.S. participated in data analysis and interpretation, coordinated the study; D.O.G. carried out the NSS test experiment, participated in data analysis and interpretation, conceived of the study, designed the study, coordinated the study and helped draft the manuscript. All authors gave final approval for publication.

Competing interests

We have no competing interest.

Funding

T.R.V. thanks the joint ‘Nikolai Lobachevsky’ program (no. 91547081) between DAAD and Republic of Tatarstan, Russia for the financial support.