Kinetics Evaluation of Passive Oxidation at High Temperature of Silicon Nitride Used in the Fabrication of Lightweight Metal Matrix Composites

In the present work, the passive oxidation kinetics of silicon nitride α-Si3N4 and (α+β)-Si3N4 powders at different temperatures from 1000 to 1200 °C were evaluated. Oxidation of these powders was carried out to improve wettability and pressureless infiltration of AZ91E Mg-alloy. The oxidation kinetic constant (kp) values and oxide layer depth were calculated. The oxidation kinetic constants kp, were 9.11e-16 and 6.35e-16 kg2/m4s and the oxidation depth were 4.25 nm and 3.69 nm, for α-Si3N4 and (α+β)-Si3N4, respectively. Furthermore, passive surface oxidation of silicon nitride was performed in order to achieve affinity between silicon nitride and AZ91E magnesium alloy. Therefore, the manufacture of AZ91E/Si3N4 magnesium matrix composite materials was successfully achieved by spontaneous infiltration process at a temperature of 800 °C. • Changes in passive oxidation kinetics of silicon nitride were identify by the β-Si3N4 presence in the Si3N4 powders. • The SiO2 amorphous coating produced by passive oxidation on the silicon nitride surface reduce the contact angle between Si3N4 and AZ91E magnesium alloy. • Passive oxidation of silicon nitride improves the wettability between Si3N4 and AZ91E magnesium alloy.


Introduction
Silicon nitride (Si 3 N 4 ) is considered one of the hardest advanced ceramic materials and is used in components subject to high temperatures and mechanical stress due to its very characteristic properties such as low coefficient of thermal expansion, high resistance to corrosion, high elastic modulus and excellent mechanical properties [1,2]. Silicon nitride is a potential candidate as a reinforcement for the manufacture of light composite materials by mixing it with magnesium alloys [3,4]. However, it has been shown that there is not a good affinity between silicon nitride and magnesium showing low wettability and promoting the formation of fragile phases such as MgAl 2 O 4 when magnesium interacts with the nitrogen in the system [5,6]. Few related systems have been achieved based on the use of techniques such as stir casting leading to magnesium matrix composite materials with low reinforcement content, in addition to exhaustive mixing control and the possibility of poor reinforcement distribution [7].
On the other hand, it is possible to increase the affinity of silicon nitride with alloys rich in magnesium due to the formation of SiO 2 on the surface of the Si 3 N 4 particles which reduces the contact angle between them. Silicon nitride, despite having a high chemical stability, it has been shown to decompose silicon nitride into silicon and nitrogen at temperatures above 1000 °C [8,9]. Passive oxidation of silicon nitride occurs if the surrounding atmosphere is rich in oxygen, with a well-established reaction: Where T is taken as the absolute temperature in kelvin (K). This kind of oxidation it is detected by gain mass in the (1) Si 3 N 4 (s) + 3O 2 (g) → 3SiO 2 (s) + 2N 2 (g) ΔG • = −1981 + 0.21T kJmol −1 silicon nitride due to the formation of a thin layer of SiO 2 and the release of nitrogen. Active oxidation, on the other hand, is the decomposition of silicon nitride into nitrogen and silicon monoxide according to the following reaction: This oxidation only occurs if the atmosphere contains a low partial pressure of oxygen, and it is detected by the mass lost after the oxidation process. The transition between the two types of oxidations is well studied and the possibility of a change from passive to active is almost impossible [8,10]. This type of surface treatment of silicon nitride has been studied since 1958 with the passivation surface treatment of silica by Wagner [11]. It has different purposes and application proposals like increasing the electrical properties of silica and the theoretical analysis about passive oxidation kinetics [12].
In this work it is proposed to perform and analyzed the oxidation behavior of two different silicon nitride powders through the measurement of parabolic constant rate and oxide layer depth of the SiO 2 layer. All this with the purpose to have enough oxidation of Si 3 N 4 powders to have good wettability between the Mg-alloy and the SiO 2 of the superficial layer of Si 3 N 4 powders. This analysis will give news results about oxidized silicon nitride systems and will propose an innovative application in the field of lightweight metal matrix composite (MMC) materials.

Si 3 N 4 Powders
The materials used for this study were silicon nitride powder with particle diameter range between 400 to 600 nm. Two different samples of silicon nitride were used and compared: α-Si 3 N 4 and (α+β)-Si 3 N 4 (≤ 99.9 % Toshiba Materials Co. JPN and Sigma Aldrich Co. USA, respectively).
The oxidation kinetics of silicon nitride was carried out by means of superficial passive oxidation through thermogravimetric analyses. A Setaram Setsys Evolution 16/18 thermobalance, with a precision up to 0.003 mg, was employed. About 20 mg of sample was used in an atmosphere of dry air with a partial pressure of 21.5 kPa. The oxidation experiments were carried out at temperatures between 1000 to 1200 °C to evaluate the kinetic oxidation behavior of silicon nitride.
The structural characterization of the silicon nitride powders before and after the passive oxidation was carried out by X-ray diffraction on a Bruker D8 Advance diffractometer. The samples were scanned at 2 theta angles from 10° to 90° with 0.020 increment and a step time of 0.6 s. The morphological characterization and oxidation distribution were carried out in a FEGSEM 7600F field emission scanning electron microscope (FE-SEM).

AZ91E Magnesium Alloy
The magnesium alloy used to evaluate the affinity between the oxidated surface of silicon nitride was AZ91E whose chemical composition in wt.% is Mg 90.65%, Al 8.64%, Zn 0.44%, Mn 0.15%, Si 0.14%. The structural characterization of the magnesium alloy (AZ91E) was performed by X-ray diffraction on a Bruker D8 Advance diffractometer. Phases distribution in the AZ91E alloy were analyzed through scanning electron microscope (SEM).

AZ91/Si 3 N 4 Composites
To evaluate the affinity and wettability between the previously oxidated silicon nitride and the magnesium alloy, porous compacts of silicon nitride powders were prepared and oxidized at 1200 °C for 30 minutes and then compacted at 90 MPa. The infiltration was performed at 800 °C for 15 minutes to obtain a full fill metal matrix composite AZ91E/Si 3 N 4 . The morphological characterization, homogeneity, and phase distribution through scanning electron microscope (SEM) were carried out. Moreover, reaction products of the composite were analyzed through energy dispersive spectroscopy (EDS). The mechanical and thermal evaluation were carried out by measurements of Vickers microhardness and the coefficient of thermal expansion (CTE). The microhardness was evaluated by a Micro Vickers Hardness optical testing machine, Mitutoyo. The load used was 100 gf, widely used for magnesium alloys. The CTE was measured by dilatometry in a DIL Linseis L75 under the following conditions. The heating was controlled by 25 °C per minute to 350 °C under ultra-high purity argon atmosphere. Figure 1 shows the X-Ray diffraction patterns of two kinds of Si 3 N 4 powders used to compare the kinetics behavior of the passive oxidation. Figure 1a shows X-Ray results for the high purity α-Si 3 N 4 (≤ 99.9 % Toshiba Materials Co. JPN) revealing only α-phase with the indexed card 04-005-5074. Figure 1b shows the (α+β)-Si 3 N 4 of high purity (≤ 99.9 % Sigma Aldrich Co. USA). The indexed cards of both phases (α+β) are 04-005-5074 and 04-007-2386, respectively.  Figure 2c and d show SEM images of the start (α+β)-Si 3 N 4 powders. The particle size distribution was homogeneous and the average particle size was ⁓600 nm for both types of silicon nitride.

Microstructural Characterization of Si 3 N 4 Powders
The transformation of the α-Si 3 N 4 to β-Si 3 N 4 phase occurs around 1300 to 1450 °C. However, the hexagonal structure continues to prevail, the only difference is that the interplanar distance in the c axis of the unit cell for α phase (5.618 Ȧ) is almost double compared with the β phase (2.90 Ȧ). At room temperature β-Si 3 N 4 is more stable than α-Si 3 N 4 and the transformation of the α-Si 3 N 4 to β-Si 3 N 4 is also an irreversible process, therefore β-Si 3 N 4 is a more commercial reagent [13].

Microstructural Characterization of AZ91 Alloy
Microstructural characterization of the AZ91E magnesium alloy was carried out by X-ray diffraction on a Bruker D8 Advance diffractometer. Figure 3a shows the X-ray pattern obtained, being the Mg 17 Al 12 the only intermetallic detected. Figure 3b confirms the phases present in the AZ91E alloy which were analyzed through scanning electron microscope (SEM) by energy dispersive spectroscopy (EDS).

Passive Oxidation of Si 3 N 4 Powders
Passive oxidation experiments were performed at different temperatures from 1000 to 1200 °C to evaluate the oxidation kinetics. The first oxidation experiment was performed at 1000 °C with a heating control of 7 °C per minute. Figure 4 shows the comparative of mass gain rate between α-Si 3 N 4 and (α+β)-Si 3 N 4 with a similar behavior under 1000 °C. It can be observed that the passive oxidation reaction starts at about 690 °C even though the literature indicates that the temperature at which passive oxidation begins is at about 1000 °C in an atmosphere of dry air [8]. Moreover, some authors mention that the temperature can vary from 600 to 950 °C when the oxygen concentration is increased in the oxidizing atmosphere [9,14,15]. The present results indicate that the passive oxidation below 1000 °C is negligible. Thus, it was decided to increase the heating rate to 30 °C/ min up to 1200 °C.
According to Hou et al. [16], the passive oxidation occurs from the surface of the particle towards the nucleus, first transforming the superficial layers into SiO 2 and with an intact nucleus of silicon nitride. Yang et al. [9], also mentioned that a time of 30 minutes at 1200 °C is enough for the particle to be completely oxidized. The superficial passive oxidation of silicon nitride can be observed as translucent zones on the surface of the particles and can also be identified by the slight formation of necks between particles due to oxidation. The kinetic oxidation analyses of powders of α-Si 3 N 4 and (α+β)-Si 3 N 4 were carried out at 1200 °C for 5 hours. Figure 5 shows the morphological comparison between α-Si 3 N 4 and (α+β)-Si 3 N 4 oxidized powders. The morphological analysis by SEM reveals that α-Si 3 N 4 and (α+β)-Si 3 N 4 do not present relevant changes in terms of morphology, but they do in terms of particle size distribution because of sintering of particles due to passive oxidation. On the other hand, the α-Si 3 N 4 promotes nucleation and slow fine-grain growth in the crystallized proportion of SiO 2 . β-Si 3 N 4 phase tends to promote coarse grain growth and the formation of defects in the interface with SiO 2 [17]. In Fig. 5, the necks formation between particles is evident and can be considered as a sintering process. The formation of necks between particles can improve densification as occurs with Al 2 O 3 , Y 2 O 3 and MgO which are used to promote the formation of a glassy phase used in some sintering processes [8,18]. Figure 6 shows the crystallographic comparison between α-Si 3 N 4 and (α+β)-Si 3 N 4 before and after 5-hour oxidation. Regarding the structural analysis ( Fig. 6a and  b), no changes were identified despite knowing that the surface is composed of amorphous SiO 2 . The formation of SiO 2 promotes sintering and densification of particles. There is evidence of the crystallization of SiO 2 which favors the formation of microcracks at the interface [17]; although another work mentions that crystallization occurs at 870 °C and SiO 2 transforms from α-quartz to α-tridymite [9]. In this work, evidence of crystallization greater than 5% by weight was not found and, therefore, it was not identified by the X-ray diffraction technique. On the other hand, the kinetic data reported by other authors are limited to obtaining the kinetic oxidation constant k p and the activation energy E. Moreover, no evidence was found in the literature about kinetic oxidation studies of β-phase silicon nitride on its influence in passive oxidation. Passive oxidation on silicon nitride has been mainly focused on obtaining a surface layer that facilitates the fluidity of Si 3 N 4 slurries or promoting the formation of other phases such as Si 2 N 2 O [8,19]. Therefore, there are mostly comparative studies between (α) and (β) silicon nitride that described the grain growth of the SiO 2 phase [17]. Even though, it has been demonstrated [20] that the formation of Si 2 N 2 O does not occur unless a secondary treatment is given to Si 3 N 4 . In this work, evidence confirms that passive oxidation of silicon nitride improves the wettability with magnesium alloys. Figure 7 shows the thermogravimetric results for α-Si 3 N 4 and (α+β)-Si 3 N 4 . It can be observed that the influence of β-phase is null during heating process. The amount of β-phase has more impact in the oxidation process at a given temperature. Because the β-phase of Si 3 N 4 is more stable than the α-phase; once it is formed, it can no longer be transformed into α-phase [13]. This implies that the amount of β-phase in the system reduces the oxidation kinetics. Due to the difficulty of quantifying the β-phase content, experiments cannot be carried out by changing the β-phase content in the system. Further experiments are required to better observe the β-phase dependence on the oxidation process as literature shows that silicon nitride is treated indifferently; regardless the amount of Si 3 N 4 phase in the system [16].
As has been observed in Fig. 5, there are no important changes on the surface in terms of morphology. However,  4.86% and 2.87% mass gain, respectively. The findings has not been reported in a most recent review on the subject [8]. Being data that has been omitted over time, it is possible to obtain the parabolic oxidation rate constant and the surface reaction depth [21,22].
To perform the kinetic calculations, the specific surface areas for α-Si 3 N 4 and (α+β)-Si 3 N 4 were obtained as 12.629 and 8.598 m 2 /g, respectively. Surface area measurements were obtained using a QuantaChrome surface area analyzer. For the case of the parabolic oxidation rate constant, k p , the following equation was used [21]: Where W 2 is the mass gain per unit area squared, expressed in g 2 /m 4 , k p is the kinetic oxidation constant, expressed in kg 2 /m 4 s and t is time. The k p is obtained from the slope by plotting W 2 versus time. On the other hand, for the calculation of the oxidation depth, equation (5) may be applied [22].
Where d is the depth in (nm) of the oxidized layer, %W is the mass gain rate, S is the surface area of the material in (nm 2 /g), ρ is the density of the material, M(r) is the molecular mass of Si 3 N 4 and M(p) is the molecular mass of SiO 2 . For the thermogravimetric analyses, the initial sample mass for α-Si 3 N 4 and (α+β)-Si 3 N 4 powders were 22.64 and 23.31 mg, respectively. Figure 8 shows the oxidation kinetic constants obtained by the slope of the plot W 2 versus time from the α-Si 3 N 4 and (α+β)-Si 3 N 4 thermogravimetric results. The oxidation kinetic constant achieved for α-Si 3 N 4 was 9.11x10 -16 kg 2 / m 4 s and a Pearson R of 0.9889. The same procedure was carried out for (α+β)-Si 3 N 4 powders obtaining an oxidation kinetic constant of 6.35x10 -16 kg 2 /m 4 s. These results indicate a strong dependence of the kinetic oxidation constant with temperature when compared with the other values in the literature. For example, at temperatures in the range of 1823 to 1923 K, Hirai et al. [23] found a higher kinetic constant, when working with α-Si 3 N 4 manufactured by CVD, whose values are between 5.83x10 -11 and 2.22x10 -10 kg 2 /m 4 s. Similar values are reported by Ogbuji and Fox [12,24] who calculated the kinetic constants being in the range from 1.75x10 -12 to 2.44x10 -11 kg 2 /m 4 s at the same temperature range. Moreover, Butt et al. [25] reported kinetic constants between 5.86x10 -25 to 1.71x10 -22 kg 2 /m 4 s at 973 and 1173 K, respectively. For temperature ranges close to this work like the results obtained by Franz et al. [26] at 1273 and 1533 K, the kinetic constants are between 3.4x10 -18 and 1.6x10 -17 kg 2 / (3)

M(r) M(p) − M(r)
1 m 4 s. This corroborates the impact of temperature on the passive oxidation of silicon nitride.
The results of the oxidation depth, as well as the kinetic constants are shown in Table 1.
As observed in Fig. 8, the slope of the curves of (α+β)-Si 3 N 4 is lower which is likely due to the content of β-phase in the Si 3 N 4 powders, this observation has not been fully studied in the past. The present results, based on thermogravimetric analyses, are in contradiction to the work of Backhaus-Ricoult et al. [17] who mentioned that the β-phase content increases the oxidation kinetics. As shown in Fig. 7 for short times of passive oxidation seems that β-phase increases the kinetic oxidation, but it changes for long periods of time. Since it is well known that the β-phase is more stable, monocrystalline, and defectfree structure, the present results suggest that presence of β-phase decreases the oxidation rate as compared to α-Si 3 N 4 alone. It is well known that the first passive oxidation behavior occurs in the superficial layer of the silicon nitride particles [16], then the kinetic behavior change due to other factors such as SiO 2 crystallization, micro-cracking generated by crystallization, SiO 2 allotropic changes, SiO 2 grain growth modes and even the possible formation of Si 2 N 2 O, some of these phenomena are described  for some authors. Backhaus-Ricoult et al. [17], also mentioned that the content of β-phase promotes a high density of defects in the oxidized interface and the formation of Sionite-type silicon oxynitride Si 2 N 2 O, because the oxidation mechanism is due to the decomposition of Si 3 N 4 and the formation of amorphous SiO 2 , a devitrification and crystallization of SiO 2 begins in the form of cristobalite that increases with the nitrogen content trapped during the decomposition of Si 3 N 4 . The cristobalite is easily formed at temperatures around 1300 °C. Authors such as Narushima et al. [10] mention that the presence of Si 2 N 2 O decreases the oxidation kinetics, since it is a phase formed between the Si 3 N 4 and SiO 2 layers; Si 2 N 2 O phase also limits the diffusion of oxygen through the interface. There is no evidence of the formation of defects between the crystallized SiO 2 grains for α-Si 3 N 4 . Trapped nitrogen is the one that plays the most important role during cristobalite grain growth and in its particle size distribution. In general terms, the β-phase promotes grain growth to large grains, which promotes the formation of defects as porosities and the formation of silicon oxynitride. In case of the α-phase, it promotes the nucleation of new grains with slow growth and fine grain size, avoiding the formation of defects and the formation of additional phases [17]. The present kinetic results were compared with other systems that have already been studied. Table 2 shows a comparison of the oxidation kinetic constants for different Si 3 N 4 systems studied. As aforementioned no oxidation kinetic studies have been made taking into account the type of phase present in silicon nitride.

Thermodynamic Analysis of the AZ91E/Si 3 N 4 System
Attempts have been made to use silicon nitride for the manufacture of metal matrix composite materials with high reinforcement contents, without favorable results using the pressureless infiltration technique [6]. This is due to the low wettability and high contact angle formed between the liquid magnesium and the silicon nitride. Some authors [5,6] even mention that the interaction between magnesium and nitrogen to form Mg 3 N 2 leads to the formation of brittle phases such as the MgAl 2 O 4 spinel. Also, it is possible that Si 3 N 4 reacts with Al to form AlN. Figure 9 shows a thermodynamic analysis of the AZ91E/Si 3 N 4 system for the possible reactions among the system components.

Mechanical Properties of the AZ91E/Si 3 N 4 System
It has been found that some magnesium alloys by the addition of silicon nitride, in low percentages, improve certain mechanical properties such as hardness, elastic modulus, toughness, tensile strength, and the failure strain; most of these composites are fabricated by stir casting [3,4]. In this work, some mechanical properties of the Mg-AZ91/ Si 3 N 4 composite were predicted, such as elastic modulus and hardness, which directly depend on reinforcement content. Mechanical properties such as the Young's modulus can be roughly predicted with models such as the mixture rule [32], the Halpin-Tsai model [33] and the Hashin & Shtrickman model [34]. The rule of mixture is the simplest model. Halpin-Tsai model is a mathematical model for the prediction of elasticity of composite material based on the geometry and orientation of the reinforcement and the elastic properties of the reinforcement and matrix. Hashin and Shtrickman model is based in the aspect ratio of the particles mainly. Figure 10a shows a graphic of the calculated elastic modulus using these models, giving values between 100 and 200 GPa for 50 wt.% of reinforcement. This is more than 100% higher as compared to the 45 GPa for monolithic alloy [35]. Figure 10b shows a graphic of the calculated hardness using the above cited models, giving values between 1042 and 1120 HV.

Fabrication of AZ91/Si 3 N 4 Composites by Infiltration Technique
Fabrication of AZ91E/Si 3 N 4 composites by several techniques has been carried out but with very low reinforcement content. The low reinforcement content is related to the low wettability between magnesium and silicon nitride [3,4,7]. Therefore, magnesium matrix composite materials are limited to manufacturing processes such as stir casting, squeeze casting, ultrasonic vibration, twin roll casting, shear compaction processing, powder metallurgy, in-situ reaction synthesis, mechanical alloying and even spray forming. In addition, processes such as stir casting have some disadvantages like the possibility of obtaining an heterogeneous distribution of the reinforcement particles, segregation, unwanted inclusions, and even porosity [36]. However, magnesium alloys in manufacturing processes for MMC such as pressureless infiltration is little considered in most recent reviews [36][37][38]. Pressureless infiltration is one of the most complete manufacturing processes for MMC due to the ease in changing composition of the alloy and reinforcement, also, it is one of the most economical processes, in addition to not requiring machining due to its near-net shaping property. Pressureless infiltration process is made possible by the passive oxidation of silicon nitride, due to the formation of SiO 2 on the surface of the particles. Is well known that the contact angle between SiO 2 and Mg is around 56° [39], promoting wettability between the oxidized Si 3 N 4 particles and the magnesium alloy AZ91E.   Figure 11 shows the micrographs and chemical mappings of AZ91E/Si 3 N 4 compound manufactured by pressureless infiltration. The infiltration was carried out at 800 °C for 15 min, obtaining a complete infiltration of the alloy in the porous Si 3 N 4 preform made with the powders previously oxidized for 30 min at 1200 °C. Complete infiltration by gravity (Fig. 11a-f) and by capillarity (Fig. 11g-l) were obtained due to the good wettability between the alloy and the SiO 2 of the superficial layer of Si 3 N 4 powders. The compounds were manufactured in a 50-50% volume ratio, but with the advantage that this process facilitates the variation in reinforcement content.
The passive oxidation treatment becomes novel for the system AZ91/Si 3 N 4 when it comes to magnesium matrix composite materials due that it improves the wettability and enables the pressureless infiltration process. However, there is only evidence of being used in alloys rich in titanium such as Mg-Ti-C and Mg-Ti-B reinforced with B 4 C [36], or in the alloy AZ91E reinforced with AlN [40]. In the latter, the predominant limitation is temperature since it is only feasible to infiltrate at 900 °C, which is a high temperature for magnesium alloys due to its volatility and flammability.
The production of AZ91E/Si 3 N 4 Mg-matrix composites is still under development and there are conditions to improve in addition to many possible application areas. Regarding the microhardness of the composite material and the combination of properties of the 65 Hv AZ91E alloy and the 1450 Hv silicon nitride leaves a wide range of hardness. The composite has a hardness in the range from 550 to 700 Hv. In the case of the coefficient of thermal expansion, this was reduced from 26x10 -6 K -1 for magnesium alloys to 13.63x10 -6 K -1 for the AZ91E/ Si 3 N 4 composite measured by dilatometry. The reduction is due to the addition of silicon nitride which is 3.5x10 -6 K -1 .
The magnesium metal matrix composites can reduce the weight in automotive and aerospace industry [41] in addition to reduce CO 2 emissions; and in the case of electric vehicles, their autonomy is increased [42]. The reduction on costs and manufacturing step processes increase the possible  implementation of this kind of materials in the automotive industry [41]. Moreover, magnesium alloys are also capable of reducing weight in military vehicles and increase the ballistic impact resistance, however, their mechanical properties are limited [43,44]. With the help of passive oxidized silicon nitride as a reinforcement, the mechanical properties of magnesium alloys can be improved for the above applications by means AZ91E/Si 3 N 4 composites by pressureless infiltration.

Conclusions
• Oxidation kinetics of silicon nitride (α-Si 3 N 4 ) and (α+β)-Si 3 N 4 powders were evaluated at temperatures from 1000 to 1200 °C. Passive oxidation of silicon nitride was applied in order to achieve wettability between Si 3 N 4 and AZ91E Mg-alloy. • The oxidation kinetic constants k p at 1200 °C for 5 h were 9.11e -16 and 6.35e -16 kg 2 /m 4 s, for Si 3 N 4 (α) and Si 3 N 4 (α+β), respectively. • Oxidation depths of 4.25 nm and 3.69 nm were achieved at 1200 °C for 5 h for α-Si 3 N 4 and (α+β)-Si 3 N 4 , respectively. • AZ91/Si 3 N 4 composites were successfully produced by pressureless infiltration process at temperature of 800 °C for 15 minutes. Which it is indicative that oxidation of Si 3 N 4 surface was enough to achieve wettability between Si 3 N 4 and Mg-alloy (AZ91E).
• A complete infiltration by gravity and by capillarity were obtained due to the good wettability between the Mg-alloy and the SiO 2 of the superficial layer of Si 3 N 4 powders. • The compounds were fabricated with 50% volume reinforcement with the premise that this process enables the variation in reinforcement content. Funding This work was supported by the Coordinación de la Investigación Científica-UMSNH

Data Availability
The datasets analyzed and generated during the present study are fully included in the results of this paper declared by the authors.

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