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Article

Influence of a Hydride-Forming Multi-Component Alloy on the Carbonization Behavior of Vulcanized Elastomer Composites

by
Mikhail Zadorozhnyy
1,2,*,
Ivan Savvotin
3,
Elena Berdonosova
3,
Semen Klyamkin
3,
Andrey Stepashkin
2,
Artem Korol
2 and
Vladislav Zadorozhnyy
2,*
1
Center for Project Activities of the Moscow Polytechnic University, Bolshaya Semenovskaya st., 2, Moscow 107023, Russia
2
Research Centre of Composite Materials, University of Science and Technology «MISIS», Leninsky prosp., 4, Moscow 119049, Russia
3
Department of Chemistry, Lomonosov Moscow State University, Leninskiye Gory, 1, Moscow 119991, Russia
*
Authors to whom correspondence should be addressed.
Metals 2022, 12(11), 1847; https://doi.org/10.3390/met12111847
Submission received: 31 August 2022 / Revised: 19 October 2022 / Accepted: 26 October 2022 / Published: 29 October 2022
Browse Figures
Versions Notes

Abstract

:
In this work, composites based on a hydride-forming fiber of a multi-principal-component (MPC) Ti20Zr20Nb20V20Hf20 alloy, carbosil, dicumylperoxide and nitrile butadiene rubber (NBR) matrix were obtained. The composites were prepared in a three-stage process including the mixing of elastomeric compounds via a rubber mixing mill and low-temperature vulcanization by heat pressing. Using dynamical mechanical analysis (DMA) and differential scanning calorimetry (DSC) the effect of the metallic filler on the process of carbonization of the composite elastomeric matrix was studied. The microstructure and gas separation properties of the resulting composites were also studied. The results showed that the filler content increase in the elastomeric matrix leads to a noticeable and gradual decrease in the activation energy of the carbonization process, reduces the temperature of this process, and accelerates the growth of the elastic modulus during carbonization. It was shown that the finely dispersed fiber of the MPC acts as an activation center for the process of thermal-oxidative degradation in the elastomeric matrix accompanying the onset of carbonization. The gas permeability values were found to be relatively low and no visible correlation with the MPC alloy content in the composite membrane was observed.

1. Introduction

Hydrogen is used as an environmentally friendly and efficient energy carrier [1,2]. The growing demand for high-quality hydrogen fuel is the driving force for the development of efficient purification technologies.
To improve the performance of hydrogen separation membranes, polymeric materials with high permeability but limited selectivity, or metal alloys, are often used. The main disadvantages of metallic, mainly palladium-based, membranes are high operating temperature and cost, in ability to be used for a wide range of gas mixtures, hydrogen-induced embrittlement phenomena, and surface poisoning with subsequent reduction in permeability of membrane [3]. One of the promising alternatives is the use of composite membrane materials consisting of a polymer matrix and a hydrogen-selective filler.
Hydride-forming metals and alloys are the most suitable for this latter purpose. Multi-principal-component alloys (MPCs) formed by five or more components in a close to equiatomic ratio have attracted special attention [4,5,6]. These alloys have excellent mechanical properties that can improve the durability of composite membranes. For some MPCs, high hydrogen absorption affinity was demonstrated [7,8,9,10,11,12,13,14,15,16]. Moreover, MPCs containing V group metals such as Nb, V, and Ta have enhanced low-temperature hydrogen permeability compared to palladium, which can be beneficial for membrane separation [17,18].
Fully- or partially-carbonized polymers based on various synthetic rubbers and phenolic resins (elastomer compositions) are very attractive candidates for a binder in metal-polymer composites [19,20,21,22,23,24,25,26]. Similar composites with carbon or silicon carbide fillers produced through a three-stage method (preparation of highly filled elastomeric compounds, vulcanization, and low-temperature carbonization) [27,28] demonstrated sufficiently high values of the tensile strength (Young’s modulus). In [29], composite materials based on carbonized elastomers showed high performance as bipolar plates for an all-vanadium redox flow battery, combining enhanced mechanical properties with zero electrolyte permeability.
The above features, as well as thermal and chemical durability, are crucial for gas separation membranes designed for use in industrial conditions. However, the presence of a dispersed metallic filler may affect the behavior of the initial elastomer during processing and the properties of the resulting composite.
In this work, we report on the synthesis and properties of elastomeric compositions filled with carbon and a multi-component alloy to develop new inexpensive composite membrane materials.

2. Materials and Methods

Nitrile butadiene rubber (NBR) (BNKS-18AMN, JSC “Krasnoyarsk Synthetic Rubber Plant”, Krasnoyarsk, Russia), shungite filler (Carbosil T-20, TU 5716-004-75625634-2006, Ecochim LLC, Saint Petersburg, Russia) with an average particle size of 5 µm, and dicumyl peroxide with an average particle size of 3–5 µm were used as matrix components to obtain composite materials.
The multi-principal-component (MPC) alloy (composition: Ti20Zr20Nb20V20Hf20) with an average particle size of 5 µm was used as a filler material. MPC alloy was obtained from the high purity metal chips: Ti (99.5%), Zr (99.5%), Nb (99.95%), V (99.7%), and Hf (99.95%). Electron beam melting (EBM) combined with pendant drop melt extraction (PDME) was used to produce continuous and discrete MPC fibers. Vacuum installation with electron beam melting of the preformed material, previously synthesized by conventional arc melting, was carried out for the formation of rapidly quenched fibers. In the PDME method, the lower end of a vertical billet is melted to form a hanging drop of melt. The resulting drop is in contact with a rotating heat sink and, after solidification, is cut in the form of an isosceles triangle. As the heat sink rotates, the solidified material is removed from the melt in the form of fibers due to the action of centrifugal force. In addition, this leads to the formation of microcrystalline or amorphous structures due to ultrahigh melt cooling rates (up to 1 Ч 106 K/s) [30,31].
A rubber mixing mill (friction coefficient of 1:1.25) with a temperature of the drive and return rolls of 303 and 308 K, respectively, were employed for mixture preparation. Complete and uniform mixing of all components was achieved after 30 min of mill shaking.
All the resulting composite mixtures were cured and vulcanized by thermal pressing in air on a TECAP APVM-904 vulcanization press (OJSC “NITI-Tesar”, Saratov, Russia) between two steel plates (the dimensions of one plate were 180 mm Ч 180 mm Ч 30 mm) at a 433 K for 20 min at a pressure of 3.5 MPa.
The obtained vulcanized composites were mechanically cut to provide at least ten samples of each composition. The thickness of the resulting membranes was 200–400 µm, the length 3 cm, and the width 0.5 cm. The compositions of the four produced materials are shown in Table 1.
The determination of vulcanization characteristics was carried out at a temperature of 433 K using a rotorless shear rheometer MDR 3000 (Montech AG, Buchen, Germany). The torque reached an equilibrium value in the time interval of 18–18.5 min; therefore, curing modes of 160/20 min were chosen.
The carbonization process and the thermal stability of the composites were studied in the temperature range of 308–633 K by differential scanning calorimetry (DSC) in a NETZSCH DSC 204 F1 Phoenix (Netzsch Erich Netzsch GmbH & Co, Selb, Upper Franconia, Bavaria, Germany) (aluminum crucibles and argon atmosphere) at a heating rate of 10 K/min. Argon gas as a protective agent was used in the DSC measurements. The gas purity was 99.999%. The argon flow was 50 mL/min for the working space (block of crucibles) and 100 mL/min for the thermocouple.
The phase composition and crystal structure of the materials after vulcanization were analyzed via powder X-ray diffraction (PXRD) using a DRON diffractometer (Research and production enterprise “Bourevestnik”, Saint Petersburg, Russian Federation) with CoKб monochromatic radiation in the 2и range of 20–100°. The PXRD measurements were performed in a stepwise scanning mode (steps 0.1°, acquisition time 5 s) [32,33].
The microstructure of the obtained vulcanized composites was studied in a TESCAN VEGA Compact scanning electron microscope (TESCAN ORSAY HOLDING, Brno, Czech Republic) in SE mode with an accelerating voltage of 20 kV.
A dynamical mechanical analyzer (Q800, TA Instruments, New Castle, DE, USA) was used for simultaneous testing of inelastic (internal friction, Q−1) and elastic (elastic modulus, E’) properties. The measurements were carried out in air in the mode of an oscillating tensile load at 0.1% strain with oscillation frequencies of 1 Hz, 5 Hz, and 10 Hz in the temperature range 310–620 K with a heating rate of 2 K/min.
The DMA experiments allowed us to evaluate the activation energy, Ea, of the carbonization process, which consists of exothermic depolymerization or thermal-oxidative destruction at temperatures above 500 K [28]. Ea was calculated from the Arrhenius-type correlation between the frequency and the transition temperature corresponding to the maximum internal friction (Q–1) [16].
K = Ae−Ea/RT
where K is the rate constant (in our case frequency),
A is the pre-exponential factor,
Ea is the activation energy,
R is the universal gas constant,
T is the phase transition temperature (in our case: the temperature of the start of the carbonization process corresponding to the position of the internal friction peak for each frequency).
Experiments on gas permeability were carried out using an automatic barometric device (GKSS). The measurements were carried out for O2, H2, CO2, CH4, and H2 at (298 ± 1) K. Gas pressure was ≈1 atm.
The integral registration mode for measurements was used. The gas permeability of flat membranes was defined as the gas flow penetrating through the membrane for a given pressure difference:
P = J·l/Дp·A
where P is the membrane permeability coefficient,
J is the gas flow through the membrane,
Дp is the pressure difference on opposite sides of the membrane,
l is the membrane thickness,
A is the membrane area.
The ideal membrane selectivity, б, was calculated as the ratio of the individual permeability coefficient associated with two different gases.

3. Results and Discussion

The aim of this work was to evaluate the effect of hydride-forming MPC alloy Ti20Zr20Nb20V20Hf20 on the carbonization process of nitrile butadiene rubber (NBR) and gas transport performance of the resulting composite membranes.
As can be seen from the SEM images (Figure 1), the starting MPC alloy represents finely dispersed fibers with linear dimensions of thickness 90–100 µm and grain size 5–10 µm resulting from PDME processing. After mixing the fibers with polymer by rolling and subsequent vulcanization (sintering), a homogeneous composite structure was formed. Minor inclusions of MPC alloy can be found on the surface and the cross-section of the composite (Figure 1c,d).
The powder X-ray diffraction patterns of the starting materials and the produced various filled composites after vulcanization are shown in Figure 2.
The original nitrile butadiene rubber (NBR) has an amorphous structure with two pronounced amorphous halos (Figure 2a). X-ray phase analysis of Ti20Zr20Nb20V20Hf20 MPC alloy obtained by electron beam melting (PDME) (Figure 2b) revealed a single-phase cubic BCC structure of the Im3m space group. As was shown in our previous work [12], the similar alloy can absorb up to 1.6 wt.% of hydrogen, which indicates good potential in relation to hydrogen separation and storage.
XRD patterns of the composite samples mainly contain the reflections related to carbosil (Figure 2c–g). Weak characteristic peaks from the MPC alloy appear in a sample with an initial filler content of 6 g (C-6) (Figure 2e) and become clearly visible when MPC content reaches 12 g (C-12).
The main thermal transformations occur in the bulk NBR elastomeric matrix, as all the fillers used (MPC, Carbosil T-20, Ecochim LLC, Saint Petersburg, Russia) was originally produced at much higher temperatures and, therefore, are much more thermally stable. The DSC curves (Figure 3) show similar inflection starting at 533 K for all the various filled composites. These thermal effects are related to the onset of multi-stage consisting of (i) macromolecule destruction in the polymer matrix (mainly in the side chains), (ii) the formation and accumulation of free radicals, and (iii) the formation of the destruction products. The main stage of thermal destruction occurs above this temperature with a maximum exothermic yield at ~630 K. The intensive gas release (N2, H2O, O2, CO2, NO, CO, CH2O, CH4, and C2H4) at this temperature is usually attributed to ongoing chemical reactions of the destruction of nitrile groups and molecular chains in rubber macromolecules that leads to a significant loss of carbon affecting the composite density, hardness, and microstructure [28].
Figure 4 shows the temperature dependence of internal friction Q−1(T) for the composites (Table 1). It can be seen that all four composite samples exhibit a peak in the selected temperature range (450–630 K), which is responsible for the processes promoting carbonization. Temperatures of the internal friction maxima are in good agreement with the above DSC data (Figure 3) and are superimposed on the inflection temperature of 533 K.
The obtained peaks on the curve of dependence of internal friction on temperature Q−1(T) allowed us to determine the activation energy of the carbonization process using the Arrhenius-type correlation between the frequency and the transition temperature corresponding to the maximum internal friction (Q−1). The activation energy values obtained from the calculation are given in Table 2.
The calculated data suggest that an increase in the MPC alloy content in the elastomeric matrix from 0 to 12 g leads to a noticeable and linear decrease in the activation energy of the carbonization process. In this case, finely dispersed metallic fibers act as activation centers in the elastomeric matrix simplifying the process of carbonization.
The dependence of the elastic modulus on temperature E’(T) (Figure 5) also indicates a smoothly running carbonization process. For all frequencies (1 Hz, 5 Hz, and 10 Hz), we observe changes in the elastic modulus. A sharp increase in the elastic modulus begins at 500 K, which also coincides with the onset of the corresponding peaks of internal friction Q−1(T) (Figure 4) for all samples in the region of plastic transition.
In the process of heating above 493–513 K, thermal-oxidative degradation proceeds in the material, which is accompanied by the release of water, nitrogen, CO, CO2, and other gases [28]. At the same time, the macromolecular cross-linking by C-C bonding takes place at the active centers formed during destruction. The cross-linking affects the material rigidity. The carbonization mode was chosen in such a way that the rate of cross-linking processes exceeds the rate of thermal degradation processes.
It was also found that the temperature at which the elastic modulus increases depends on the MPC alloy content. For example, a sharp increase in the modulus begins already at 501 K for a sample with the highest MPC content of the alloy (12 g), but, the temperature at which the elastic modulus increases for the samples with 8 and 6 g of MPC alloy is about 504 K and 507 K, respectively. A similar relationship is obtained with the maximum modulus of elasticity. The highest value of the modulus is observed for the composite with the highest content (12 g) of MPC alloy (459–479 MPa), and the lowest value for the composite sample without any MPC alloy (271–283 MPa).
The observed dependences of the elastic modulus and the internal friction on temperature, E’(T) and Q−1(T), respectively, allow us to conclude that the MPC alloy addition simplifies and accelerates the carbonization process in the elastomeric NBR matrix. As a result, higher values of the modulus are reached in the composites with a higher content of the metallic filler.
Generally, polymeric materials soften with increasing temperature, and the elastic modulus decreases. However, in our case, the membrane material undergoes thermal aging and low-temperature carbonization during heating that affects significantly its characteristics. Due to the competitive processes of thermal-oxidative destruction and further cross-linking along the active centers formed during local acts of destruction, a change in the degree of cross-linking occurs, therefore in terms of physical properties, the material is closer to ceramic: the heat resistance and elastic modulus of the material increase significantly [28,34,35].
The experimental results on gas permeability of the produced composite membranes are presented in Table 3.
The obtained permeability values are quite low, and there is no significant difference between the four studied composites. It was assumed that the affinity of the original MPC alloy for hydrogen would contribute to higher permeability with respect to H2. The phenomenon observed in the experiment is probably due to the small volumetric content of the filler. In addition, the metallic particles can be subjected to surface oxidation in course of the composite processing, which hinders the metal-hydrogen interaction. Approaches to the prevention of passivation (e.g., coating of the filler particles with oxidation-resistant metal) or/and re-activation of the as-prepared composites (post-treatment with high-pressure hydrogen) are currently being developed. The results will be published as a separate article.

4. Conclusions

Composite membranes based on the hydride-forming fiber of the Ti20Zr20Nb20V20Hf20 MPC alloy, carboxyl, dicumyl peroxide, and NBR (rubber) were obtained by a three-stage method.
It was found that an increase in the metallic filler content in the elastomeric matrix leads to a gradual decrease in the activation energy of the carbonization process from 274 to 174 kJ/mol. Particles of a multicomponent alloy may act as activation centers in the elastomeric matrix simplifying carbonization and reducing the temperature of this process.
Using DMA and DSC methods, the temperature range of 500 to 620 K for internal friction peaks corresponding to the carbonization process was determined. In the area of the carbonization process, the maximum values of the elastic modulus were evaluated as 271–283, 319–334, 380–399, and 459–479 MPa for composites containing 0, 6, 8, and 12 g MPC, respectively.
Permeabilities of the obtained composite membranes with respect to H2, He, N2, Ar, CH4, and CO2 were measured by the barometric method. The results failed to show the expected positive effect of MPC filler on hydrogen selectivity due to possible surface oxidation of the metallic particles in the course of composite processing.

Author Contributions

Conceptualization, V.Z. and S.K.; methodology, A.S.; validation, A.K., M.Z. and V.Z.; formal analysis, I.S.; investigation, E.B.; writing—original draft preparation, M.Z.; writing—review and editing, S.K.; visualization, A.K.; supervision, S.K.; project administration, V.Z.; funding acquisition, V.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Ministry of Science and Higher Education of the Russian Federation in the framework of the federal academic leadership program Priority 2030 under the increase competitiveness program of NUST «MISiS» (grant number K1-2022-032). S.K., E.B. and I.S. acknowledges the Development program of the Interdisciplinary Scientific and Educational School of Lomonosov Moscow State University «The future of the planet and global environmental change», and was supported by the Ministry of Science and Higher Education of the Russian Federation, projects: AAAA-A16-116053110012-5 and 122012400186-9. M.Z. acknowledges the financial support from the Moscow Polytechnic University within the framework of the grant named after Pyotr Kapitsa. A.S. also acknowledges the financial support from the Ministry of science and higher education of Russia in the framework of state assignment, project number 0718-2020-0036.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Metals 12 01847 g001 550
Figure 1. SEM images of obtained fiber of the Ti20Zr20V20Nb20Hf20 alloy (a), structure of the fiber surface (b), surface of the composite C-12 (c), cross-sections of the composite C-12 (d), The arrows indicate the inclusions of MPC.
Figure 1. SEM images of obtained fiber of the Ti20Zr20V20Nb20Hf20 alloy (a), structure of the fiber surface (b), surface of the composite C-12 (c), cross-sections of the composite C-12 (d), The arrows indicate the inclusions of MPC.
Metals 12 01847 g001
Metals 12 01847 g002 550
Figure 2. X-ray diffraction patterns of the initial components NBR (a), MPC (b), Carbosil (c) and the obtained composites C-0 (d), C-6 (e), C-8 (f), C-12 (g).
Figure 2. X-ray diffraction patterns of the initial components NBR (a), MPC (b), Carbosil (c) and the obtained composites C-0 (d), C-6 (e), C-8 (f), C-12 (g).
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Metals 12 01847 g003 550
Figure 3. DSC curves of the obtained composites.
Figure 3. DSC curves of the obtained composites.
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Metals 12 01847 g004 550
Figure 4. Dependence of internal friction on temperature Q−1(T) obtained at frequencies (1, 5, and 10 Hz) for various filled composites.
Figure 4. Dependence of internal friction on temperature Q−1(T) obtained at frequencies (1, 5, and 10 Hz) for various filled composites.
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Metals 12 01847 g005 550
Figure 5. Dependence of the elastic modulus on temperature E’(T) obtained at various frequencies (1, 5, and 10 Hz) and for differently filled composites.
Figure 5. Dependence of the elastic modulus on temperature E’(T) obtained at various frequencies (1, 5, and 10 Hz) and for differently filled composites.
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Table
Table 1. Designations and components for the four obtained composite materials.
Table 1. Designations and components for the four obtained composite materials.
DesignationContent of the Mixture Components (g)
NBRCarbosilDicumyl PeroxideMPC Ti20Zr20Nb20V20Hf20
C-01001001-
C-610010016
C-810010018
C-12100100112
Table
Table 2. Calculated activation energy values of the carbonization process for differently filled composites.
Table 2. Calculated activation energy values of the carbonization process for differently filled composites.
Sample Nameѓ, HzT, KQ−1Ea, kJ/mol
C-01527 ± 10.086274 ± 2
5522 ± 10.072
10519 ± 10.069
C-61523 ± 10.089241 ± 2
5518 ± 10.076
10517 ± 10.072
C-81528 ± 10.085224 ± 2
5522 ± 10.072
10521 ± 10.068
C-121525 ± 10.090174 ± 2
5520 ± 10.076
10519 ± 10.072
Table
Table 3. Gas permeability of the obtained composite membranes.
Table 3. Gas permeability of the obtained composite membranes.
Sample NamePermeability Coefficient, Barrer *
N2CO2HeCH4ArH2
C-00.711.14.51.31.45.6
C-60.59.73.51.01.15.0
C-80.812.65.32.21.67.0
C-12-9.54.5-1.45.9
* 1 barrer = 10−10 cm3 (normal test conditions)*cm/s/cm2/cmHg).
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Zadorozhnyy, M.; Savvotin, I.; Berdonosova, E.; Klyamkin, S.; Stepashkin, A.; Korol, A.; Zadorozhnyy, V. Influence of a Hydride-Forming Multi-Component Alloy on the Carbonization Behavior of Vulcanized Elastomer Composites. Metals 2022, 12, 1847. https://doi.org/10.3390/met12111847

AMA Style

Zadorozhnyy M, Savvotin I, Berdonosova E, Klyamkin S, Stepashkin A, Korol A, Zadorozhnyy V. Influence of a Hydride-Forming Multi-Component Alloy on the Carbonization Behavior of Vulcanized Elastomer Composites. Metals. 2022; 12(11):1847. https://doi.org/10.3390/met12111847

Chicago/Turabian Style

Zadorozhnyy, Mikhail, Ivan Savvotin, Elena Berdonosova, Semen Klyamkin, Andrey Stepashkin, Artem Korol, and Vladislav Zadorozhnyy. 2022. "Influence of a Hydride-Forming Multi-Component Alloy on the Carbonization Behavior of Vulcanized Elastomer Composites" Metals 12, no. 11: 1847. https://doi.org/10.3390/met12111847

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