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Thermosetting polymer composites: Manufacturing and properties study

  • Malek Ali EMAIL logo
Published/Copyright: November 2, 2023
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Abstract

In the proposed study, TiC is used in different sizes (i.e., 70–150 nm and 200–250 μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) to reinforce the epoxy matrix. Micro- or nano-epoxy–TiC mixtures are poured into molds that have been prepared. The results obtained show a significant improvement in hardness, impact, creep, and tensile strength when the hard particles of nano- and micro-TiC are increased up to 20 wt%. This is due to the good dispersion of the TiC powder with minimal agglomeration and air bubbles. In addition, the results obtained show a decrease in hardness, impact, creep, and tensile strength when the ratio of the hard particles of nano- and micro-TiC is increased to 30 wt% due to agglomeration and air bubbles, which create a path for cracks to propagate. The results of the hardness, impact, creep, and tensile strength tests when 20 wt% nano-TiC composite specimens are used are 22.4, 67.55 J·m−2, 0.0132, and 34.7 MPa, respectively. These results show higher values than other composite specimens. A pin-on-disc wear testing process with various sliding lengths is used to analyze wear behavior. The maximum wear resistance of the 10 wt% of micro-epoxy–TiC composites is found at a load of 5 N and a 100 m sliding distance. Optical microscopy shows small scratches on the 10 wt% micro-epoxy–TiC composite specimens in comparison with the 10 wt% nano-epoxy–TiC composites at a load of 5 N and a 200 m sliding distance.

1 Introduction

It is known that there are different types of materials, such as polymeric, ceramic, and metal materials, and through these basic materials, composite materials (i.e., matrix and reinforcement) can be manufactured [16]. The replacement of traditional materials, such as aluminum and iron, with polymer composites produces light and cheap composites that are equivalent to the traditional materials in terms of mechanical properties [7]. For so long, the use of epoxy has been of great importance in many engineering applications, such as those in the automotive, aviation, and electronics industries [8]. Epoxy has been used enormously in engineering applications due to its low density, low viscosity, low cost, good adhesion to various substrates, high resistance to chemicals and corrosion, and relatively good thermal and mechanical properties that make it suitable as a matrix for improving the design process and products [9,10]. Reinforcements used in epoxy, such as natural fibers, glass fibers, and carbon fibers, have poor compatibility and often need surface treatment before distribution, which causes a costly manufacturing process [11]. Epoxy–TiC composites have been developed by many researchers because of the thermodynamic stability of TiC, along with its hardness and low density, which are imparted to the composite [12,13]. Generally, epoxy–TiC composites offer outstanding mechanical and tribological properties that depend on the ratios and particle size of TiC. Numerous studies on the impact of TiC ratios in epoxy composites on their mechanical characteristics and wear rate came to the conclusion that increasing TiC ratios up to a certain point in a specific size increases the composite’s mechanical characteristics, including hardness, impact, creep, and tensile strength. On the other hand, it was noted that the size of the TiC reinforcement affects the wear resistance in comparison with the unfilled composites [1416]. To better understand the synthesis and characterization of epoxy–TiC composites, the current work concentrates on the impact of TiC content ratios and sizes on the mechanical and tribological behavior of the composites. According to research on the selection of TiC to reinforce the epoxy, the effect of TiC on epoxy reinforcement has only been researched for a few mechanical tests and in a single size; however, in this study, epoxy reinforcement was done in nano and micro sizes of TiC, and the effect of the two sizes was compared on most mechanical tests [8,9,15,16,21].

2 Experimental setup

2.1 Raw mater

In order to synthesize micro- or nanoscale epoxy–TiC composites, the epoxy resin (produced by East Coast Resin Company) is used as a matrix (resin to hardener ratio was 2:1) with a low density (i.e., 1.22 g·ml) and low viscosity (i.e., 800 MPa.s). In this composite, the TiC reinforcement particles of different sizes (i.e., 70–150 nm and 200–250 μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) are used. Because titanium carbide has high wettability, hardness, wear resistance, and thermal stability, it is a suitable material for epoxy matrix reinforcement [17].

2.2 Mold fabrication

To investigate the effect of various ratios and particle sizes of TiC composites on the mechanical properties, the hardness, impact, creep, and tensile tests were performed in accordance with the American Society for Testing and Materials (ASTM) standards E10-18, D6110, D2990, and D638 [18]. According to these standards, a milling machine was used to create the primary samples’ shapes with exact dimensions for each mechanical test in an aluminum mold that was 20 × 10 × 2 cm in size. The cavity of the hardness specimen is designed to have a rectangular shape, while the cavity of the wear specimen is designed to be cylindrical with a depth of 1 cm, according to the dimensions and internal shape of the pin-on-disc machine. To prepare the epoxy–TiC composite specimens for mechanical tests without defects, great care is needed to prepare the mold and cavities in terms of accuracy and smoothness of the cavity surfaces. To ensure that the composite specimens can be withdrawn from the cavities without being damaged, the surfaces and sidewalls of the cavities are polished and coated with numerous layers of wax.

2.3 Composites’ preparation and characterization

Epoxy–TiC composites with different sizes (i.e., 70–150 nm and 200–250 μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC were fabricated. To fabricate epoxy–TiC composites, epoxy resin and hardener should be combined at a ratio of 2:1. Using a small cardboard funnel and two different mixtures of epoxy that were made in the appropriate quantities to make the proper number of different samples, the nano-sized TiC powder was added to the first container and mixed with a mechanical stirrer, and the process was repeated for the second container with micro-TiC. The mixture is manually poured into the cavities of the mold using a tiny metal funnel that has a constant, extremely slow flow. Composite materials are cured at room temperature, as shown in Figure 1. Various shapes of composite materials can easily be removed from the cavities without damaging them. In general, the components are mixed and stirred slowly to avoid the formation of air bubbles in the epoxy resin. Any air bubbles trapped in the resin will be difficult to remove.

Figure 1 
                  Cured shapes of epoxy–TiC composite specimens.
Figure 1

Cured shapes of epoxy–TiC composite specimens.

Mechanical properties are tested and measured using GUNT 410, 600, and 300 machines, respectively. The hardness specimens had a rectangular shape, while the cavities of the wear specimens had cylindrical shape with a depth of 1 cm. The specimens for the mechanical testing (impact, creep, and tensile strength) were fabricated according to ASTM (D6110, D2990, and D638) sizes and dimensions for each mechanical test (Figure 1). In general, the mechanical test results and their standard deviation show how much variance there is from the average mechanical test findings. To eliminate inaccuracies caused by local heterogeneity, the result of any mechanical test is the average of the results of the four values of the test and is plotted in the results graphs of the mechanical tests. A 50 kg weight is applied to the Vickers hardness machine for 5 s.

In order to gauge a specimen’s wear resistance, a pin-on-disk machine is utilized (Figure 2). The test for wear resistance is conducted in dry sliding circumstances with typical air pressure, humidity, and temperatures. A DC motor with a 5 N load and a sliding speed of 500 rpm is applied. The specimen’s weight loss is observed at the end of each test using an electronic weighing machine with 0.01 mg accuracy. The pin is cleaned with acetone before being weighed with an electronic balance for each desired cycle.

Figure 2 
                  Pin-on-disc testing machine.
Figure 2

Pin-on-disc testing machine.

3 Results and discussions

3.1 Hardness test

In composite materials, mechanical behavior is determined by hardness measurement, which is frequently correlated positively with hardness [19,20]. Four indentions were taken for each specimen to obtain the average hardness value and an accurate result. Significant improvements in hardness, impact, creep, and tensile strength were noticed when hard particles of micro- or nano-TiC were increased up to 20 wt%. This is because of the good dispersion of the TiC powder with minimum agglomeration and air bubbles, as shown in Figure 3.

Figure 3 
                  50× OM image of the TiC powder dispersion (i.e., shining particles) for 20 wt% nano-epoxy–TiC composite specimens.
Figure 3

50× OM image of the TiC powder dispersion (i.e., shining particles) for 20 wt% nano-epoxy–TiC composite specimens.

Figure 4 displays the average hardness values for composites with various TiC particle sizes and ratios. It is observed that all nano-epoxy–TiC specimens have higher hardness values in comparison with the micro-epoxy–TiC specimens at the same wt% of TiC. It was also discovered that the highest average hardness for nano-epoxy–TiC composite specimens was 22.4 for 20 wt%. The low hardness of the micro specimens is due to several reasons, such as porosity on the surface and the possibility of deposition of coarse TiC particles in the lower region of the composites [21]. In fact, the hardness values depend on the degree of distribution of TiC particles through the epoxy matrix and are certainly affected by the agglomeration of TiC particles in the specimens. It should be noted that if the agglomeration of TiC particles is concentrated on one side of the specimen, the other side will be harder. However, a uniform distribution of the TiC particles in the specimens would produce the highest value of hardness. In other words, the agglomeration of TiC particles in the specimens causes the absence of an epoxy matrix between the TiC particles, which in turn decreases the hardness values. When the hardness test is performed, the Vickers indenter directly presses on the composite surface.

Figure 4 
                  Average hardness for epoxy–TiC composites with various sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC.
Figure 4

Average hardness for epoxy–TiC composites with various sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC.

In addition, the indentation size depends on the number of TiC particles and the strength of their adhesion to the epoxy matrix. In the case of TiC particle agglomeration and the absence of an epoxy matrix, the bonding between the adjacent TiC particles becomes weak, which makes it easy to dent the surface. Increasing air bubbles on the composite surface would cause a decrease in hardness as well. In addition, the state of the surface being examined is crucial in establishing the hardness rating. As demonstrated in Figure 5, a perfect indention with a symmetrical size on both the horizontal and vertical axes of the indention form requires a smooth, flat surface. If the surface is not flat and smooth, a clear indention cannot be obtained, and both the horizontal and vertical axes of the length of the indention are not symmetrical, as shown in Figure 6.

Figure 5 
                  OM image of symmetrical indentation on the surface of epoxy–TiC specimens.
Figure 5

OM image of symmetrical indentation on the surface of epoxy–TiC specimens.

Figure 6 
                  OM image of non-symmetrical indentation on the surface of epoxy–TiC specimens.
Figure 6

OM image of non-symmetrical indentation on the surface of epoxy–TiC specimens.

3.2 Impact test

Shock resistance is an important property of epoxy–TiC composites that is used in some mechanical applications that need to withstand sudden shocks. In general, material toughness is directly proportional to the amount of TiC reinforcement, as shown in Figure 7. In fact, there is an upper limit to increase the toughness of the material when the reinforcement content is increased.

Figure 7 
                  Impact strength of epoxy–TiC composites with different sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC.
Figure 7

Impact strength of epoxy–TiC composites with different sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC.

From Figure 8, it is noted that all nano-epoxy–TiC specimens have higher toughness values in comparison with the micro-epoxy–TiC specimens with equivalent reinforcement content. With the addition of 20 wt% of nano- or micro-TiC, the composite’s toughness increases significantly to 53.86 and 67.55 J·mm−2, respectively. In general, the dispersion of nano-fillers is better than that of micro-fillers, which leads to stronger interfacial adhesion between matrix and fillers [22]. Because nano-epoxy-TiC composites have a higher resistance to fracture propagation, there is a difference in toughness between the two types of specimens. This is because of the increase in stress transfer between nano-TiC and matrix, adhesion between nano-TiC and matrix, and dispersion of nano-TiC. With the increase of TiC to 30 wt%, the toughness of nano- or micro-epoxy–TiC specimens becomes 50.73 and 63.34 J·mm−2, respectively. The decrease in toughness is due to the decrease in crack propagation resistance that is affected by the porosity percentage and agglomerations, as shown in Figure 8.

Figure 8 
                  OM with 50× of (a) agglomerated TiC particles, and (b) air bubbles in 30 wt% nano-epoxy–TiC composite specimens.
Figure 8

OM with 50× of (a) agglomerated TiC particles, and (b) air bubbles in 30 wt% nano-epoxy–TiC composite specimens.

3.3 Creep test

Creep is the gradual deformation due to a constant load on composites [23]. Most materials are affected by different degrees of creep. This also depends on the properties of the material, the applied load, and the load time. Rigidity, high impact strength, and low creep rate are required in many mechanical applications, and this calls for improving thermoplastic composites to become suitable for metal replacement. The elasticity of the composite increases the creep rate. The composite elastic properties depend on the matrix and reinforcement elasticity effects. Creep rate is also greatly affected by temperature, stress level, and humidity. Therefore, it is important to study the creep properties of cross-linked epoxy resin in detail. Initially, after applying a load on the composite specimens, the creep rate would be relatively high. In the secondary creep stage, the creep speeds up to a steady pace. Later, before the fracture stage, the creep rate rises once more. As the TiC particles increase, the matrix brittleness increases, which reduces the elongation and break value. Figure 9 shows the elongation values at the break value of nano-epoxy–TiC composites with 10, 20, and 30 wt% of TiC that were 0.0139, 0.0124, and 0.0144, respectively. On the other hand, micro-epoxy–TiC composites with 0, 10, 20, and 30 wt% of TiC were 0.0153, 0.0148, 0.0132, and 0.0161, respectively. Brittle materials such as epoxy polymers usually fail with relatively low stress values [24]. The elongation at break values continues to decrease, starting from 0 to 20 wt% nano- or micro-epoxy–TiC composites, because these ratios restrict the mobility of the epoxy matrix and increase the composite’s brittleness. From the elongation values shown in Figure 10, it is noted that the elongation at the break value increases for 30 wt% nano- or micro-epoxy–TiC composite specimens. This increase in elongation is due to more air bubbles and agglomerated TiC particles at this ratio in the composite. The applied load of 25 N contributed to an increase in the width of each resulting crack and air bubble, which led to an increase in the longitudinal dimension of the specimens. Thus, the creep resistance was low and the elongation was high at this ratio.

Figure 9 
                  Elongation at the break for epoxy–TiC composites with various sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC with a load of 25 N for 60 min.
Figure 9

Elongation at the break for epoxy–TiC composites with various sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC with a load of 25 N for 60 min.

Figure 10 
                  Tensile strength for different sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC in the epoxy–TiC composites.
Figure 10

Tensile strength for different sizes (i.e., nm and μm) and different ratios (e.g., 0, 10, 20, and 30 wt%) of TiC in the epoxy–TiC composites.

TiC and epoxy’s excellent interfacial adhesion enhances creep resistance by streamlining the transfer process that causes failure delay [25]. Nano-epoxy–TiC composites exhibit higher creep resistance in comparison with micro-epoxy–TiC composites. This is because micro-TiC composites have weak adhesion forces with the matrix. In addition, coarse TiC particles produce larger air bubbles during composite fabrication, which lead to many large cracks [26]. Rapid brittle failure usually occurs at low temperatures and high strain rates. Sometimes individual debonding leads to a fast, brittle fracture through the matrix. If loads are applied at high temperatures and low strain rates, the cracks will propagate by debonding. At extremely low stresses, cracks propagate slowly through the matrix. Crack propagation through agglomerated TiC or voids is less energy-consuming, which reduces toughness and creep resistance [27].

3.4 Tensile test

Through previous studies by a number of researchers, it was confirmed that adding nano-TiC particles to polymers, including epoxy, has a significant effect on most mechanical properties, including tensile strength [28,29,30,31]. In general, most of the mechanical properties of composites are mostly influenced by the characteristics of the composite components (i.e., matrix and reinforcement). Furthermore, mechanical properties depend on each of the following factors: (i) degree of adhesion between reinforcements and matrix; (ii) dispersion of the reinforcements through the matrix; and (iii) pores produced during the manufacturing process. Thus, any weakness or defect in the aforementioned factors leads to a decrease in the values of composites’ mechanical properties. Brittle materials, such as epoxy polymers, usually fail with relatively low stress values [32]. The effect of TiC with different sizes (i.e., 70–150 nm and 200–250 μm) and ratios (e.g., 0, 10, 20, and 30 wt%) on the values of tensile strength is illustrated in Figure 10. It is clear that the presence of TiC particles, whether in nano- or micro-scale, enhances the tensile strength of the epoxy matrix. The increase in epoxy–TiC composites’ tensile strength is expected because the tensile strength of TiC is about 258 MPa. In addition, the homogeneous dispersion with strong adhesion of the hard nano-TiC particles in the matrix enhances the tensile strength due to the increased resistance propagation of microcracks. The addition of 20 wt% nano- or micro-TiC particles give a remarkable increase in tensile strength. Nano-epoxy–TiC composites exhibit higher tensile strength in comparison with micro-epoxy–TiC composites because of the weak adhesion between TiC and matrix, as well as coarse TiC particles that produce larger air bubbles during composite fabrication, which leads to more microcracks. The tensile strengths of nano-epoxy–TiC composites with 10, 20, and 30 wt% of TiC were 29.88, 34.7, and 27.14 MPa, respectively. On the other hand, micro-epoxy–TiC composites with 10, 20, and 30 wt% of TiC were 27.63, 30.85, and 26.2 MPa, respectively. Using a nano- or microscale, minimal strength was achieved. Low stress transfer in 30 wt% TiC can be attributed to the creation of fractures surrounding agglomerated TiC particles and air bubbles, which also explains the decrease in tensile strength. One or more of the following factors usually causes the formation of cracks, even under low loads:

  1. Poor dispersion of TiC particles throughout the matrix.

  2. Poor adhesion between TiC and epoxy.

  3. Formation of air bubbles in the matrix.

  4. Agglomeration of TiC particles in the epoxy matrix.

Since epoxy is a brittle material, the addition of TiC particles increases the epoxy’s brittleness. This is evident by the smooth and flat fractures of epoxy–TiC composite. The fractures were discovered to be perpendicular to the applied stress direction, as shown in Figure 11.

Figure 11 
                  A fractured tensile specimen for different sizes and different ratios of TiC in the epoxy–TiC composites.
Figure 11

A fractured tensile specimen for different sizes and different ratios of TiC in the epoxy–TiC composites.

3.5 Pin-on-disc wear test

The addition of hard ceramic TiC particles in nano- or microscale enhances the removal resistance of the epoxy matrix, as shown in Figures 12 and 13. The factors affecting composites’ wear resistance depend on the kind of matrix material, the type of reinforcement, the manufacturing process, the surface roughness, the sliding speed, the load, and the type of friction (i.e., dry or lubricated) [33,34,35].

Figure 12 
                  Weight loss for nano-epoxy–TiC composites with various wt% ratios of nano-TiC particles.
Figure 12

Weight loss for nano-epoxy–TiC composites with various wt% ratios of nano-TiC particles.

Figure 13 
                  Weight loss for micro-epoxy–TiC composites with various wt% ratios of micro-TiC particles.
Figure 13

Weight loss for micro-epoxy–TiC composites with various wt% ratios of micro-TiC particles.

As shown in Figure 13, it is clear that the weight loss of pure epoxy increases with the increase in sliding distance due to the brittle nature of the pure epoxy in addition to the small actual contact area between the specimen and the rotating disc. At the beginning, the specimen surface, which lies opposite the disc, consists of peaks and valleys. As the friction progresses, the burrs are flattened, resulting in an increase in the actual contact area. In addition, the rate of weight loss from the matrix is increased by the direct friction of the entire specimen surface. When the sliding distance increased from 100 to 200 m, a certain amount of epoxy matrix was eroded, and many micro-fractures occurred in the matrix. Therefore, a very thick layer was removed from some areas as well. Moreover, many sharp grooves and scratches appeared on the worn surfaces, as shown in Figure 14a. This caused an increase in overall wear loss. By further increasing the sliding distance from 200 to 300 m, the epoxy matrix broke into small pieces and spread between the two friction surfaces. This caused further damage and epoxy material loss from the specimen surface. In general, strong surface adhesion between the TiC matrix and the epoxy, in addition to the uniform distribution of the hard TiC particles, improves and strengthens the epoxy bonds between the TiC particles, which in turn reduce wear and increase hardness. Thus, it can be inferred that pure epoxy has low wear resistance in comparison with epoxy–TiC specimens. It is clear from Figures 12 and 13 that the weight loss for all specimens with different sizes (i.e., 70–150 nm and 200–250 μm) and ratios (e.g., 0, 10, 20, and 30 wt%) of TiC particles increases when the sliding distance increases. This is due to the release of large amounts of epoxy and TiC particles from the composite surface caused by the abrasive paper during the rubbing process. In addition, it is clear from Figures 12 and 13 that the weight loss of micro-epoxy–TiC composites is lower than that of pure epoxy and nano-epoxy–TiC composites. Furthermore, the weight loss values increase as TiC content increases due to the agglomerated TiC particles pulled out of the matrix, which act as an abrasive medium at the rubbed contact surfaces. The lowest weight loss was for the 10 wt% micro-epoxy–TiC due to the larger TiC particles that are located more deeply in the tested surface where they cannot be easily released from the composite’s surface. The micro debris of TiC is, in fact, removed from the system without getting caught between the contact surfaces, which prevents further damage on both surfaces as shown in Figure 14b. Nano-TiC particles on the friction surface are scraped off of the composites’ surface and become caught between the contact surfaces. This leads to further harm on both surfaces, as shown in Figure 14c. The surface has very minor ridges and dings (Figure 14b), whereas the worn surfaces (Figure 14c) have many scratches and sharp grooves for the same reasons previously mentioned in detail.

Figure 14 
                  OM image of worn surface for: (a) epoxy matrix, (b) 10 wt% micro-epoxy–TiC composite, and (c) 10 wt% nano-epoxy–TiC composite at a load of 5 N and 200 m sliding distance.
Figure 14

OM image of worn surface for: (a) epoxy matrix, (b) 10 wt% micro-epoxy–TiC composite, and (c) 10 wt% nano-epoxy–TiC composite at a load of 5 N and 200 m sliding distance.

4 Conclusions

In order to synthesize nano- or micro-epoxy–TiC composites, the epoxy resin was used as a matrix with a low density of 1.22 g·ml and a low viscosity of 800 MPa·s, whereas the reinforcement particles were TiC with different sizes (70–150 nm and 200–250 μm) and ratios (e.g., 0, 10, 20, and 30 wt%). Mixtures of nano- or micro-epoxy–TiC were poured into prepared molds, and mechanical and tribological tests were performed for the nano- and micro-epoxy–TiC composites. Mechanical properties (i.e., hardness, impact, creep, and tensile strength) were improved when hard particles of nano- or micro-TiC were increased up to 20 wt% due to the good dispersion of the TiC powder with minimum agglomeration and air bubbles. On the other hand, mechanical properties values decreased for 30 wt% nano- or micro-epoxy–TiC composites due to agglomeration, the absence of epoxy matrix between the TiC particles, and air bubbles. The nano-TiC specimens with 20 wt% exhibited higher values for hardness, impact, creep, and tensile strength in comparison with other composite specimens. The hardness, impact, creep, and tensile strength for the 20 wt% nano-TiC specimens were 22.4, 67.55 J·m−2, 0.0132, and 34.7 MPa, respectively. The maximum wear resistance was recorded for 10 wt% of micro-epoxy–TiC composites at a load of 5 N and a 100 m sliding distance, because the micro-TiC particles were deeply located in the composites. While the optical microscopy (OM) for the 10 wt% micro-epoxy–TiC composite showed relatively few surface ridges and scratches, the OM for pure epoxy showed a very thin layer lost from some sections of the specimen with grooves and scratches on the worn surfaces in comparison with the 10 wt% nano-epoxy–TiC composite at a load of 5 N and a 200 m sliding distance.

  1. Funding information: The author states no funding involved.

  2. Author contributions: The author has accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The author states no conflict of interest.

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Received: 2023-05-26
Revised: 2023-08-18
Accepted: 2023-09-19
Published Online: 2023-11-02

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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