[go: up one dir, main page]
Next Article in Journal
Eco-Friendly Concrete with Improved Properties and Structure, Modified with Banana Leaf Ash
Previous Article in Journal
Sustainable Polyamide Composites Reinforced with Nanocellulose via Melt Mixing Process
Previous Article in Special Issue
Synthesis of a New Composite Material Derived from Cherry Stones and Sodium Alginate—Application to the Adsorption of Methylene Blue from Aqueous Solution: Process Parameter Optimization, Kinetic Study, Equilibrium Isotherms, and Reusability
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
J. Compos. Sci.
Volume 8
Issue 10
10.3390/jcs8100420
jcs-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

The Impact of Activated Carbon–MexOy (Me = Bi, Mo, Zn) Additives on the Thermal Decomposition Kinetics of the Ammonium Nitrate–Magnesium–Nitrocellulose Composite

by
Zhanerke Yelemessova
*,
Ayan Yerken
,
Dana Zhaxlykova
and
Bagdatgul Milikhat
Institute of Combustion Problems, Almaty 050012, Kazakhstan
*
Author to whom correspondence should be addressed.
J. Compos. Sci. 2024, 8(10), 420; https://doi.org/10.3390/jcs8100420
Submission received: 5 August 2024 / Revised: 5 October 2024 / Accepted: 9 October 2024 / Published: 12 October 2024
(This article belongs to the Special Issue Theoretical and Computational Investigation on Composite Materials)
Browse Figures
Figure 1
<p>DSC curve of an AN–Mg–NC basic composite heated at <span class="html-italic">β</span> = 5 K/min.</p> "> Figure 2
<p>DSC curves of (<b>a</b>) AN–Mg–NC–AC; (<b>b</b>) AN–Mg–NC–AC–Bi<sub>2</sub>O<sub>3</sub>; (<b>c</b>) AN–Mg–NC–AC–MoO<sub>3</sub>; (<b>d</b>) AN–Mg–NC–AC–ZnO composites heated at <span class="html-italic">β</span> = 5 K/min.</p> "> Figure 3
<p>Kissinger plot of the basic AN–Mg–NC composite.</p> "> Figure 4
<p>Kissinger plot of the AN–Mg–NC–AC composite.</p> "> Figure 5
<p>Kissinger plot of the AN–Mg–NC–AC–Bi<sub>2</sub>O<sub>3</sub> composite.</p> "> Figure 6
<p>Kissinger plot of the AN–Mg–NC–AC–MoO<sub>3</sub> composite.</p> "> Figure 7
<p>Kissinger plot of the AN–Mg–NC–AC–ZnO composite.</p> ">
Versions Notes

Abstract

:
This research investigates the impact of additives such as activated carbon (AC) combined with metal oxides (Bi2O3, MoO3, and ZnO) on the thermal decomposition kinetics of ammonium nitrate (AN), magnesium (Mg), and nitrocellulose (NC) as a basic AN–Mg–NC composite. To study the thermal properties of the AN–Mg–NC composite with and without the AC–MexOy (Me = Bi, Mo, Zn) additive, a differential scanning calorimetry (DSC) analysis was conducted. The DSC results show that the AC–MexOy (Me = Bi, Mo, Zn) additive catalytically affects the basic AN–Mg–NC composite, lowering the peak decomposition temperature (Tmax) from 534.58 K (AN–Mg–NC) to 490.15 K (with the addition of AC), 490.76 K (with AC–Bi2O3), 492.17 K (with AC–MoO3), and 492.38 K (with AC–ZnO) at a heating rate of β equal to 5 K/min. Based on the DSC data, the activation energies (Ea) for the AN–Mg–NC, AN–Mg–NC–AC, and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, Zn) composites were determined using the Kissinger method. The results suggest that incorporating AC and AC–MexOy (Me = Bi, Mo, Zn) additives reduce the decomposition temperatures and activation energies of the basic AN–Mg–NC composite. Specifically, Ea decreased from 99.02 kJ/mol (for AN–Mg–NC) to 93.63 kJ/mol (with addition of AC), 91.45 kJ/mol (with AC–Bi2O3), 91.65 kJ/mol (with AC–MoO3), and 91.76 kJ/mol (with AC–ZnO). These findings underscore the potential of using AC–MexOy (Me = Bi, Mo, Zn) as a catalytic additive to enhance the performance of AN–Mg–NC-based energetic materials, increasing their efficiency and reliability for use in solid propellants.

1. Introduction

Ammonium nitrate (AN) has recently attracted attention as an environmentally sustainable and chlorine-free oxidizer for solid propellants [1,2], despite facing some challenges associated with its polymorphic characteristics [3,4]. However, AN is limited by factors such as low ignitability, slow burning rate, and high hygroscopicity, which restrict its exclusive application in energetic materials (EMs) [5]. Several studies have focused on enhancing AN-based formulations by integrating organic compounds, metallic powders, and aqueous solutions [6,7]. Currently, researchers are investigating the impact of various additives, including metal oxides, on the combustion properties of AN-based composites to enhance their combustibility [8].
Recent research on magnesium (Mg) in EMs highlights its potential for enhancing reactivity and energy release. For example, Mg nanoparticles demonstrated exceptional reactivity due to enhanced vaporization and accelerated energy release kinetics [9]. In addition, composites of boron, aluminum, and magnesium (BAM) showed improved oxidation and heat release compared to boron alone [10]. In another research study, the interaction between magnesium and 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB) resulted in favorable, exothermic composite formation with increased sensitivity to impulse stimulus [11]. Moreover, surface modification of magnesium with silicon through non-thermal plasma processing significantly reduced ignition temperature, enhancing combustion kinetics [12]. These studies demonstrate the versatility of Mg in EMs, offering opportunities for improved performance through strategic design and the composition of nano-energetic materials with tunable energy release properties.
Nitrocellulose (NC) is an energetic polymer which is widely used in propellants and explosives [13]. As a binder, NC plays a crucial role in triple-base propellant formulations, influencing mechanical properties and energy content [14]. Recent research has focused on enhancing NC’s performance through various methods. Incorporating manganese oxide nanoparticles into NC matrices has shown promising results, increasing decomposition enthalpy by 150% and enhancing the reaction propagation index by 261% [15]. Another approach involves blending NC with polyurethane (PU) to create energetic binders for composite solid propellants, potentially overcoming the performance drawbacks of conventional PU binders [16]. These advancements in NC-based compositions offer improved energy performance and decomposition kinetics, making them suitable for various high-energy applications.
Activated carbon (AC) has emerged as a versatile material in energetic applications. It can be used as a substrate for novel energetic materials by confining the oxidizers within its nanopores, potentially enhancing detonation properties [17,18]. For example, AC impregnated with TiO2 nanoparticles has shown promise in capturing NOx released from degrading nitrocellulose, with over 60% efficiency under UV light irradiation [19]. When doped with cupric oxide (CuO) [20] or cobalt (II, III) oxide (Co3O4) [21], AC acts as a catalyst in energetic composites, significantly improving thermal decomposition and combustion performance. Recent developments in AC synthesis have focused on maximizing porosity, using cheap precursors, and controlling morphology to enhance its performance in energy-related applications [22,23].
Metal oxides play a crucial role in enhancing the performance of EMs. Recent research has explored the use of metal oxides in energetic materials, focusing on their potential to enhance performance and reactivity [24,25]. Nanoscale composites of aluminum with metal oxides such as MoO3, WO3, CuO, and Bi2O3 have shown promising results in terms of pressure output and propagation velocity [26]. The incorporation of nanoscale TiO2 particles into energetic composites has demonstrated significant improvements in burning rates [27].
This study aims to investigate the effects of activated carbon (AC), both independently and in conjunction with metal oxides—specifically bismuth oxide (Bi2O3), molybdenum trioxide (MoO3), and zinc oxide (ZnO)—as additives on the thermal decomposition kinetics of the ammonium nitrate–magnesium–nitrocellulose (AN–Mg–NC) composite. The Kissinger method provides a theoretical framework for developing efficient composites and analyzing the kinetics of decomposition reactions in various composite materials. This method was applied to the AN–Mg–NC, AN–Mg–NC–AC, and AN–Mg–NC–AC–MexOy (where Me = Bi, Mo, Zn) composites to calculate their activation energies based on differential scanning calorimetry (DSC) analysis results. By examining the synergistic interactions of these additives, this research seeks to enhance the understanding of the influence of metal oxides on the thermal decomposition kinetics of ammonium nitrate-based energetic materials (EMs). The findings of this study present an opportunity to advance the development of propellants by improving their efficiency and reliability for solid propellant applications, as well as for other applications that require precise control over combustion and ignition processes.

2. Materials and Methods

2.1. Materials

The ammonium nitrate (AN, NH4NO3, Sigma Aldrich (St. Louis, MO, USA), ACS reagent grade, ≥98%) was used in composites as an oxidizing agent. Magnesium (Mg, Sigma Aldrich (Taufkirchen, München, Germany), powder, ≥99%) with a particle size ranging from 0.06 to 0.30 mm was used as the fuel component. Nitrocellulose (NC, C6H8O5(NO2)2, Skylighted, Inc. (Round Hill, WV, USA) with a degree of nitration of 12% was served as an energetic polymer binder. The activated carbon (AC) was synthesized under controlled laboratory conditions and used as fuel component. Bismuth (III) oxide (Bi2O3, Sigma Aldrich (Taufkirchen, München, Germany), nano powder 90–210 nm, 99.8% trace metals basis), molybdenum (VI) oxide (MoO3, Sigma Aldrich (Taufkirchen, München, Germany), nano powder < 100 nm, 99.5% trace metals basis), and zinc oxide (ZnO, Sigma Aldrich (Taufkirchen, München, Germany), nano powder < 100 nm) were used as catalytic additives and mechanically integrated into the pores of the AC through planetary milling.
Activated carbon (AC) was derived from an agricultural byproduct—rice husk (RH), carbonized at the Laboratory of Energy-intensive Nanomaterials of the Institute of Combustion Problems (Almaty, Kazakhstan). The production process involved utilizing an iron reactor in an argon atmosphere, following the methodology outlined in [28]. After carbonization, the AC underwent immersion in a KOH solution to eliminate the by-product SiO2. Subsequently, the solution was decanted to remove the base, and the AC-containing material was activated at 400 °C in the reactor. The synthesized AC then underwent multiple washing cycles with distilled water (approximately 20 cycles) until reaching a pH of 7.0. These procedures resulted in the production of AC with a high specific surface area of roughly 1200 m2/g (determined through BET analysis) and an absorption capacity of around 300 mL/g (measured using methylene blue).

2.2. Equipment

The masses of all components were determined using an analytical balance “Shimadzu AY220” (Shimadzu Corporation, Kyoto, Japan). Thermal analysis of the prepared composites was conducted using the “NETZSCH DSC 204 F1” thermogravimetric analyzers to investigate the effects of AC–MexOy (Me = Bi, Mo, Zn) additives on the thermal decomposition kinetics of the basic AN–Mg–NC composition. This analysis also aimed to calculate the activation energies and assess the effectiveness of AC–MexOy (Me = Bi, Mo, Zn) as catalytic additives via the Kissinger method.

2.3. Methods

2.3.1. Oxygen Balance Calculation

Oxygen Balance (OB), a frequently employed method in the evaluation of solid propellants, was used to determine the sufficiency of oxygen within a composite for the full oxidation of all component elements [29]. The assessment of OB functions as a predictive tool to ascertain whether a substance will undergo complete combustion or yield residual products. Table 1 provides the essential data for the subsequent oxygen balance calculation of the AN–Mg–NC and AN–Mg–NC–AC–MexOy (where Me = Bi, Mo, Zn) composites.
In the context of mixed multicomponent explosives, a calculation sequence is commonly employed to ascertain the quantity of each component present in 1 kg of the composition [30]. To calculate OB [31] of a composite containing various components such as ammonium nitrate (AN), magnesium (Mg), nitrocellulose (NC), activated carbon (AC), and metal oxides (Bi2O3, MoO3, and ZnO), specific steps need to be followed. These steps include the following: (a) Determining the molecular weights and oxygen content of each component; (b) Establishing the mass fractions (or masses) of each component in the compound. It is crucial to compute the molecular weight (MW) and the oxygen content contribution (Oxygen Content, OC) for each element.
The total oxygen content (OCtotal) of the composite component (mn) can be determined using Equation (1) and the information provided in Table 1:
OC total = m n 100 %   ×   OC n MW n
The total fuel content (FCtotal) of the composite component (mn) can be determined using Equation (2) and the information provided in Table 1:
FC total = ∑ m n 100 %
The oxygen balance (OB) calculation involves determining the total oxygen content and total fuel content in the AN–Mg–NC–AC–MexOy (Me = Bi, Mo, Zn) composite, followed by calculating the oxygen balance (OB) according to Equation (3):
OB   ( % ) = 1600 MW   OC total 1   kg − 2 × FC total 1   kg
Oxygen balance is essential for solid propellants as it assesses the availability of oxygen to completely oxidize all elements, such as carbon and hydrogen. Determining the OB is crucial in predicting whether a compound will undergo complete combustion or leave residues, thus, providing insights into its performance and safety attributes.

2.3.2. Activation Energy Calculations via the Kissinger Method

The Kissinger method is a widely used technique for calculating the activation energy (Ea) of a chemical reaction, particularly within the context of thermal analysis. This method involves utilizing the peak temperature derived from differential scanning calorimetry (DSC) analysis at different heating rates to ascertain Ea. Through the construction of a graph that plots the natural logarithm of the heating rate divided by the square of the peak temperature (Tmax) against the reciprocal of the peak temperature, a linear correlation can be established. As per the Kissinger equation, the slope of this line is directly proportional to Ea. This method offers a direct and dependable approach for evaluating the kinetic parameters of the thermal decomposition of the composites, eliminating the necessity of understanding the reaction mechanism.

3. Results

3.1. Oxygen Balance Calculations

The concept of oxygen balance (OB) is predominantly applied in the context of energetic materials to assess the potential for a composite to undergo full combustion or decomposition. To ensure the thorough oxidation of the AN–Mg–NC–AC–MexOy (where Me = Bi, Mo, Zn) components to their corresponding higher oxides (if any) during the combustion process, we calculated the OB for each composite sample according to Equations (1)–(3). The results of these calculations are presented in Table 2. The objective of conducting an OB calculation is to assess the stoichiometric equilibrium of oxygen in various composites, including AN–Mg–NC, AN–Mg–NC–AC and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, or Zn).
A positive oxygen balance, as illustrated in Table 2, across all composites signifies an oxygen surplus in the composite. This surplus can potentially improve combustion efficiency and mitigate the production of harmful by-products (for example, carbon monoxide (CO), soot, etc.).

3.2. Thermal Decomposition Characteristics from DSC Analysis

The thermal analysis method referred to as differential scanning calorimetry (DSC) offers a swift and efficient means of examining the thermal ignition properties of energetic materials (EMs). Each sample underwent DSC measurements three times to ensure reliability. Figure 1 illustrates the DSC curve obtained from the basic AN–Mg–NC composite when exposed to a heating rate of β = 5 K/min in a nitrogen atmosphere.
The decomposition of the AN–Mg–NC basic composite is depicted in Figure 1, showing a three-stage exothermic reaction. The maximum exothermic peak occurs at Tmax = 534.58 K, corresponding to the decomposition of AN, with a heat release of 4.7 mW/mg. Additionally, an initial minor heat absorption peak at ~420 K is likely associated with the polymorphic transition of AN, accompanied by an endothermic peak at ~475 K that could be attributed to water evaporation.
Figure 2 depicts the DSC curves derived from the AN–Mg–NC–AC and AN–Mg–NC–AC–MexOy (where Me = Bi, Mo, Zn) composites when subjected to heating at a rate of β = 5 K/min in a nitrogen environment.
Figure 2 illustrates the DSC curves for AN–Mg–NC–AC, AN–Mg–NC–Bi2O3, AN–Mg–NC–AC–MoO3, and AN–Mg–NC–AC–ZnO composites. The inclusion of AC (Figure 2a) significantly altered the thermal behavior of the AN–Mg–NC–AC composite. The second peak experiences a decrease to Tmax = 490.15 K (with a heat release of 5.1 mW/mg) in comparison with the basic AN–Mg–NC composite with Tmax = 534.58 K (with a heat release of 4.7 mW/mg).
The inclusion of the AC–Bi2O3 additive (Figure 2b) brought about a notable change in the thermal characteristics of the AN–Mg–NC composite. The second peak exhibited a reduction to Tmax = 490.76 K (accompanied by a heat release of 6.0 mW/mg) compared to the basic AN–Mg–NC composite, which had Tmax = 534.58 K and a heat release of 4.7 mW/mg.
The incorporation of the AC–MoO3 additive (Figure 2c) into the basic composite AN–Mg–NC leads to an accelerated decomposition rate of the AN–Mg–NC–AC–MoO3 composite. The decomposition temperature decreases to 492.17 K (accompanied by a heat release of 5.5 mW/mg) compared to 534.58 K for the initial AN–Mg–NC composite, with a heat release of 4.7 mW/mg.
The incorporation of the AC–ZnO additive (Figure 2d) into the basic composite AN–Mg–NC leads to an accelerated decomposition rate of the AN–Mg–NC–AC–ZnO composite. The decomposition temperature decreases to 492.38 K (accompanied by a heat release of 6.1 mW/mg) compared to 534.58 K for the initial AN–Mg–NC composite, which has a heat release of 4.7 mW/mg.
The absence of endothermic peaks, which are typically indicative of water evaporation, observed in Figure 2a–d, in contrast to the basic AN–Mg–NC composite presented in Figure 1, may be attributed to the adsorption characteristics of AC.
The DSC analysis demonstrates that the inclusion of different additives (AC–Bi2O3, AC–MoO3, and AC–ZnO) in the AN–Mg–NC composite significantly accelerates the decomposition process. This is evident from the decrease in decomposition temperature from 534.58 K to approximately 490–492 K. Furthermore, these additives amplify the heat release during decomposition, elevating it from 4.7 mW/mg to values between 5.5 and 6.1 mW/mg. This indicates that the additives facilitate quicker decomposition and contribute to a more exothermic reaction. Such enhancements could be advantageous for applications requiring controlled and efficient energy release.

3.3. Kinetics via the Kissinger Method

The Kissinger method is widely used for determining the activation energy (Ea) of thermally stimulated processes investigated through techniques such as differential scanning calorimetry (DSC). The Ea determination can be conducted via the Kissinger method, which is based on the Arrhenius equation that elucidates the relationship between the rate of a chemical reaction and temperature. By plotting the natural logarithm of the heating rate divided by the square of the peak temperature against the reciprocal of the peak temperature, a linear correlation is established. The slope of this linear relationship, as per the Kissinger equation, is directly correlated to the activation energy. This approach simplifies the determination of kinetic parameters for thermal decomposition processes, providing a reliable and effective means to analyze reactions without necessitating an in-depth understanding of the reaction mechanism.
The Kissinger method uses the following formula to determine the activation energy (Equation (4)) [32]:
E a = − R d l n β T p 2 d T p − 1
β—heating rate (K/min); Tp—peak temperature (K) at which the reaction rate is maximum; Ea—activation energy (J/mol); R—universal gas constant (8.314 J/mol·K).
The kinetic parameters of the thermal decomposition of the basic AN–Mg–NC composite are outlined in Table 3.
The plot (Figure 3) effectively illustrates the application of the Kissinger method in determining the activation energy (Ea) for the reaction of the AN–Mg–NC composite. A linear regression line is fitted to the data points, representing the optimal fit line based on the least squares method. The negative slope of the line aligns with the Kissinger equation. The calculation based on the slope yields Ea of approximately 99.02 kJ/mol. The linear correlation and the derived Ea offer significant insights into the thermal decomposition kinetics of the composite material.
For the AN–Mg–NC–AC composite, the kinetic parameters of the thermal decomposition were calculated using the Kissinger method (Table 4).
The plot (Figure 4) successfully demonstrates the use of the Kissinger method to determine Ea for the reaction of the AN–Mg–NC–AC composite. The negative slope of the line is expected according to the Kissinger method. From the slope of the line, Ea was calculated to be approximately 93.63 kJ/mol. The linear relationship and the calculated Ea provide valuable insights into the thermal decomposition kinetics of the composite material.
For the AN–Mg–NC–AC–Bi2O3 composite, the kinetic parameters of the thermal decomposition were calculated using the Kissinger method (Table 5).
The plot (Figure 5) successfully demonstrates the use of the Kissinger method to determine Ea for the reaction of the AN–Mg–NC–AC–Bi2O3 composite. The negative slope of the line is expected according to the Kissinger method. From the slope of the line, Ea was calculated to be approximately 91.45 kJ/mol. The linear relationship and the calculated Ea provide valuable insights into the thermal decomposition kinetics of the composite material.
For the AN–Mg–NC–AC–MoO3 composite, the kinetic parameters of the thermal decomposition were calculated using the Kissinger method (Table 6).
Figure 6 demonstrates that the obtained data points exhibit a good linear relationship, which validates the use of the Kissinger method for calculating the activation energy (Ea). The negative slope obtained from the linear fit directly relates to Ea. The larger the absolute value of the slope, the higher the Ea. The consistency of the data points along the linear fit suggests reliable and reproducible measurements of Tmax and heating rates.
The Kissinger method provides a precise and efficient approach to calculating the Ea of the AN–Mg–NC–AC–MoO3 composite. The Ea derived from this plot is 91.65 kJ/mol, signifying a lower energy barrier that must be surpassed for the reaction to advance compared to the basic AN–Mg–NC composite, which has an activation energy of 99.02 kJ/mol.
The kinetic parameters of the thermal decomposition for the AN–Mg–NC–AC–ZnO composite, as determined through the Kissinger method, are outlined in Table 7.
Figure 7 demonstrates that the data points exhibit a good linear relationship, which validates the use of the Kissinger method for calculating the activation energy (Ea). The negative slope obtained from the linear fit directly relates to the Ea. The larger the absolute value of the slope, the higher the Ea. The consistency of the data points along the linear fit suggests reliable and reproducible measurements of Tmax and heating rates. The Kissinger plot provides a clear and effective way to determine the Ea of the AN–Mg–NC–AC–ZnO composite. Considering the total number of exothermic peaks identified through DSC analysis, the Ea for the AN–Mg–NC–AC–ZnO composite was determined to be 91.76 kJ/mol, indicating that the energy barrier that needs to be overcome for the reaction to proceed is lower than that of the basic AN–Mg–NC composite. The summary of the kinetic parameters of AN–Mg–NC and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, or Zn) and the comparison which was calculated using the Kissinger method are outlined in Table 8.
Table 8 presents a comparative analysis of the kinetic parameters related to the thermal decomposition of various ammonium nitrate (AN) and AN-based composites, as determined via the Kissinger method. The pure AN sample exhibits a range of Tmax values, indicating diversity in their respective thermal decomposition temperatures. The activation energy (Ea) demonstrates notable variation among the pure AN samples, implying discrepancies in their thermal stability, potentially influenced by impurities or distinct experimental conditions. The ln(β/(Tmax)2) values for pure AN are predominantly negative, a characteristic feature of substances with a high Ea, suggesting a pronounced temperature dependency of the reaction rate. In contrast, the Tmax value for the AN–Pyrite composite is notably higher (648.15 K) than that of pure AN, signifying that the presence of pyrite enhances the stability of AN, necessitating a higher temperature for decomposition. The Ea value for AN–Pyrite is comparable to that of pure AN, indicating that while pyrite enhances thermal stability, it does not significantly alter the energy barrier for the decomposition reaction.
In the current study, the thermal decomposition behavior of AN–Mg–NC and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, or Zn) composites was investigated. The results show that the Tmax values of these composites are typically lower than those of pure AN and AN–Pyrite. This suggests that the obtained composites decompose at lower temperatures, which could be advantageous for applications that require lower decomposition temperatures. Furthermore, the Ea values for these composites are generally lower than those for pure AN, indicating that the AC–MexOy additives aid in the decomposition process by reducing the energy barrier. Additionally, the values of ln(β/(Tmax)2) are less negative compared to pure AN, suggesting a decreased temperature dependency of the reaction rate and potentially a more controlled decomposition process.

4. Discussion

This study aimed to investigate the impact of activated carbon (AC) in conjunction with different metal oxides (Bi2O3, MoO3, and ZnO) on the thermal decomposition kinetics of the basic AN–Mg–NC composite via the Kissinger method. The results offer convincing proof of the catalytic effectiveness of these additives in altering the thermal properties of the composite, thereby holding substantial implications for the advancement of sophisticated energetic materials.
The thermal properties of the AN–Mg–NC composite with and without the AC–MexOy (Me = Bi, Mo, Zn) additives were evaluated using differential scanning calorimetry (DSC) analysis. The incorporation of AC–MexOy additives led to a notable reduction in the decomposition peak temperature, as revealed by the DSC data. This significant decline in decomposition temperature highlights the catalytic function of these additives in improving the thermal reactivity of the basic composite.
The activation energies (Ea) for the decomposition reactions, determined via the Kissinger method, indicate a decrease in Ea for the composites incorporating the AC–MexOy additives. This decline in Ea suggests a more efficient decomposition process, facilitated by the catalytic influence of the additives. The observed thermal behavior can be explained by the catalytic mechanism resulting from the synergistic effects between AC and MexOy. The high surface area of AC facilitates the dispersion of metal oxides, which serve as catalytic sites. The metal oxide (MexOy) promotes electron transfer processes, reducing the energy barriers for bond dissociation in the AN–Mg–NC composite.
The improved thermal characteristics of the AN–Mg–NC–AC–MexOy composites have important implications for the advancement of energetic materials. The reduced decomposition temperatures and activation energies indicate that these composites may attain increased burning rates and enhanced performance, which are crucial for their application in solid propellants. The results indicate that AC–MexOy additives have the potential to customize the thermal properties of energetic materials, thereby boosting their effectiveness and dependability.
While this study has offered valuable insights into the catalytic effects of AC–MexOy additives, additional research is required to comprehend the underlying mechanisms and to optimize the additive compositions for specific applications. Future studies could explore the impacts of varying ratios of activated carbon to metal oxides, along with exploring the potential advantages of using alternative metal oxides. Furthermore, it is imperative to examine the long-term stability and compatibility of these additives with other constituents in energetic formulations.

5. Conclusions

This study presents a conclusive demonstration of the substantial catalytic impact achieved by the incorporation of activated carbon (AC) in conjunction with metal oxides (Bi2O3, MoO3, or ZnO) on the thermal decomposition kinetics of the basic AN–Mg–NC composite. Through a comprehensive analysis involving the DSC technique and the application of the Kissinger method, it was observed that the introduction of AC–MexOy (Me = Bi, Mo, Zn) significantly reduces the decomposition peak temperature (Tmax) and lowers the activation energy (Ea) of the composites. The DSC results revealed a decrease in the peak decomposition temperature from 534.58 K (for AN–Mg–NC) to 490.15 K (with AC), 490.76 K (with AC–Bi2O3), 492.17 K (with AC–MoO3), and 492.38 K (with AC–ZnO), underscoring the catalytic efficacy of the additives. Furthermore, the Ea values decreased from 99.02 kJ/mol for the basic composite to approximately 93.63, 91.45, 91.65, and 91.76 kJ/mol with the inclusion of AC, AC–Bi2O3, AC–MoO3, and AC–ZnO, respectively.
From a scientific standpoint, these catalytic effects can be attributed to the ability of AC–MexOy (Me = Bi, Mo, Zn) additives to facilitate the more efficient breakdown of chemical bonds in the basic AN–Mg–NC composite. Activated carbon provides a substantial surface area for interactions, while metal oxides serve as active sites for catalysis. These sites likely enhance electron transfer processes and lower the energy barriers for the decomposition reactions, resulting in decreased decomposition temperatures and reduced activation energies. The synergistic interaction between activated carbon and metal oxides accelerates the thermal decomposition process, making the energetic material more reactive and efficient.
The obtained results highlight the potential of AC–MexOy additives to significantly improve the performance, efficiency, and reliability of AN-based energetic materials, making them highly suitable for advanced solid propellant applications. The enhanced thermal properties and reduced activation energies suggest that these composites can achieve higher burning rates and superior overall performance, which are essential factors in the development of effective and reliable solid propellants.

Author Contributions

Conceptualization, Z.Y.; methodology, Z.Y.; software, A.Y.; validation, Z.Y. and D.Z.; formal analysis, Z.Y.; investigation, Z.Y., A.Y. and D.Z.; resources, Z.Y.; data curation, Z.Y., A.Y. and B.M.; writing—original draft preparation, Z.Y.; writing—review and editing, Z.Y.; visualization, Z.Y.; supervision, Z.Y.; project administration, Z.Y.; funding acquisition, Z.Y. All authors have read and agreed to the published version of the manuscript.

Funding

This research is funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan, grant numbers AP13268793 and AP22784194.

Data Availability Statement

The data presented in this study is available upon request from the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Remissa, I.; Jabri, H.; Hairch, Y.; Toshtay, K.; Atamanov, M.; Azat, S.; Amrousse, R. Propulsion Systems, Propellants, Green Propulsion Subsystems and their Applications: A Review. Eurasian Chem.-Technol. J. 2023, 25, 3–19. [Google Scholar] [CrossRef]
  2. Jos, J.; Mathew, S. Ammonium Nitrate as an Eco–Friendly Oxidizer for Composite Solid Propellants: Promises and Challenges. Crit. Rev. Solid State Mater. Sci. 2016, 42, 470–498. [Google Scholar] [CrossRef]
  3. Yelemessova, Z.K.; Imangazy, A.M.; Tulepov, M.I.; Mansurov, Z.A. Energetic Metal–organic frameworks: Thermal behaviors and combustion of nickel oxide (II) based on activated carbon compositions. J. Eng. Phys. Thermophys. 2021, 94, 804–811. [Google Scholar] [CrossRef]
  4. Kamunur, K.; Jandosov, J.M.; Abdulkarimova, R.G.; Hori, K.; Yelemessova, Z.K. Combustion study of different transitional metal oxide based on AN/MgAl composites gas generators. Eurasian Chem.-Technol. J. 2017, 19, 341. [Google Scholar] [CrossRef]
  5. Yang, M.; Chen, X.; Wang, Y.; Yuan, B.; Niu, Y.; Zhang, Y.; Liao, R.; Zhang, Z. Comparative evaluation of thermal decomposition behavior and thermal stability of powdered ammonium nitrate under different atmosphere conditions. J. Hazard. Mater. 2017, 337, 10–19. [Google Scholar] [CrossRef] [PubMed]
  6. Boukeciat, H.; Tarchoun, A.F.; Trache, D.; Abdelaziz, A.; Ahmed Hamada, R.; Bouhantala, A.; Bousstila, C.; Hanafi, S.; Dourari, M.; Klapötke, T.M. Towards Investigating the Effect of Ammonium Nitrate on the Characteristics and Thermal Decomposition Behavior of Energetic Double Base NC/DEGDN Composite. Materials 2022, 15, 8138. [Google Scholar] [CrossRef]
  7. Sinditskii, V.P.; Egorshev, V.Y.; Levshenkov, A.I.; Serushkin, V.V. Ammonium nitrate: Combustion mechanism and the role of Additives. Propellants Explos. Pyrotech. 2005, 30, 269–280. [Google Scholar] [CrossRef]
  8. Ketegenov, T.; Nadirov, R.; Teltayev, B.; Milikhat, B.; Kalmuratova, B.; Keiichi, H.; Kamunur, K. The Effect of CuO on the Thermal Behavior and Combustion Features of Pyrotechnic Compositions with AN/MgAl. Sustainability 2024, 16, 1488. [Google Scholar] [CrossRef]
  9. Ghildiyal, P.; Biswas, P.; Herrera, S.; Xu, F.; Alibay, Z.; Wang, Y.; Wang, H.; Abbaschian, R.; Zachariah, M.R. Vaporization-Controlled Energy Release Mechanisms Underlying the Exceptional Reactivity of Magnesium Nanoparticles. ACS Appl. Mater. Interfaces 2022, 14, 17164–17174. [Google Scholar] [CrossRef]
  10. Agarwal, P.P.K.; Matsoukas, T. Synthesis and Oxidation Chemistry of Highly Energetic Boron/Aluminum/Magnesium Composites. FirePhysChem 2023, 3, 173–178. [Google Scholar] [CrossRef]
  11. Türker, L. 1,3,5-Triamino-2,4,6-trinitrobenzene and Magnesium Interaction-A DFT Treatment. Earthline J. Chem. Sci. 2021, 5, 175–190. [Google Scholar] [CrossRef]
  12. Wagner, B.; Ghildiyal, P.; Biswas, P.; Chowdhury, M.; Zachariah, M.R.; Mangolini, L. In-Flight Synthesis of Core–Shell Mg/Si–SiOx Particles with Greatly Reduced Ignition Temperature. Adv. Funct. Mater. 2023, 33, 2212805. [Google Scholar] [CrossRef]
  13. Touidjine, S.; Boulkadid, K.M.; Trache, D.; Belkhiri, S.; Mezroua, A. Preparation and Characterization of Polyurethane/Nitrocellulose Blends as Binder for Composite Solid Propellants. Propellants Explos. Pyrotech. 2021, 47, e202000340. [Google Scholar] [CrossRef]
  14. Sanghavi, R.R.; Pillai, A.G.S.; Velapure, S.P.; Singh, A. Studies on Different Types of Nitrocellulose in Triple Base Gun Propellant Formulations. J. Energ. Mater. 2003, 21, 87–95. [Google Scholar] [CrossRef]
  15. Elbasuney, S.; Yehia, M.; Ismael, S.; Saleh, A.; Fahd, A.; El-Shaer, Y. Nitrocellulose catalyzed with nanothermite particles: Advanced energetic nanocomposite with superior decomposition kinetics. J. Energ. Mater. 2021, 41, 550–565. [Google Scholar] [CrossRef]
  16. Touidjine, S.; Karim Boulkadid, M.; Trache, D.; Belkhiri, S.; Mezroua, A.; Islam Aleg, M.; Belkebiche, A. Preparation of ammonium nitrate-based solid composite propellants supplemented with polyurethane/nitrocellulose blends binder and their thermal decomposition behavior. Def. Technol. 2021, 18, 2023–2033. [Google Scholar] [CrossRef]
  17. Van Riet, R.; Amayuelas, E.; Lodewyckx, P.; Lefebvre, M.H.; Ania, C.O. Novel opportunities for nanoporous carbons as energetic materials. Carbon 2020, 164, 129–132. [Google Scholar] [CrossRef]
  18. Lesbayev, B.; Rakhymzhan, N.; Ustayeva, G.; Maral, Y.; Atamanov, M.; Auyelkhankyzy, M.; Zhamash, A. Preparation of Nanoporous Carbon from Rice Husk with Improved Textural Characteristics for Hydrogen Sorption. J. Compos. Sci. 2024, 8, 74. [Google Scholar] [CrossRef]
  19. Bouriche, R.; Tazibet, S.; Boutillara, Y.; Melouki, R.; Benaliouche, F.; Boucheffa, Y. Characterization of Titanium (IV) Oxide Nanoparticles Loaded onto Activated Carbon for the Adsorption of Nitrogen Oxides Produced from the Degradation of Nitrocellulose. Anal. Lett. 2020, 54, 1929–1942. [Google Scholar] [CrossRef]
  20. Atamanov, M.; Yelemessova, Z.; Imangazy, A.; Kamunur, K.; Lesbayev, B.; Mansurov, Z.; Yue, T.; Shen, R.; Yan, Q.-L. The catalytic effect of CuO-doped activated carbon on thermal decomposition and combustion of AN/Mg/NC composite. J. Phys. Chem. C 2019, 123, 22941–22948. [Google Scholar] [CrossRef]
  21. Yelemessova, Z.; Kydyrbekova, S.; Yerken, A. Thermal Characteristics Enhancement of AN/Mg/NC Composite Using Activated Carbon/Cobalt Oxide as Highly Effective Catalytic Additive. J. Compos. Sci. 2023, 7, 471. [Google Scholar] [CrossRef]
  22. Sevilla, M.; Mokaya, R. Energy storage applications of activated carbons: Supercapacitors and hydrogen storage. Energy Environ. Sci. 2014, 7, 1250–1280. [Google Scholar] [CrossRef]
  23. Imangazy, A.; Smagulova, G.; Kaidar, B.; Mansurov, Z.; Kerimkulova, A.; Umbetkaliev, K.; Zakhidov, A.; Vorobyev, P.; Jumadilov, T. Compositional Fibers Based on Coal Tar Mesophase Pitch Obtained by Electrospinning Method. Chem. Chem. Technol. 2021, 15, 403–407. [Google Scholar] [CrossRef]
  24. Shi, W.; Wang, X.; Xu, J.; Guan, Z.; Jiang, Q.; Zhang, W.; Yu, C.; Song, C.; Chen, J. Enhancing the energy release performance of nanothermites through metal oxides free oxygen and pores. J. Chem. Eng. 2023, 481, 148483. [Google Scholar] [CrossRef]
  25. Vorobyev, P.; Mikhailovskaya, T.; Yugay, O.; Serebryanskaya, A.; Chukhno, N.; Imangazy, A. Catalytic Oxidation of 4-Methylpyridine on Modified Vanadium Oxide Catalysts. Iran. J. Chem. Chem. Eng. 2018, 37, 81–89. [Google Scholar] [CrossRef]
  26. Sanders, V.E.; Asay, B.W.; Foley, T.J.; Tappan, B.C.; Pacheco, A.N.; Son, S.F. Reaction Propagation of Four Nanoscale Energetic Composites (Al/MoO3, Al/WO3, Al/CuO, and Bi2O3). J. Propuls. Power 2007, 23, 707–714. [Google Scholar] [CrossRef]
  27. Reid, D.L.; Kreitz, K.R.; Stephens, M.A.; King, J.E.S.; Nachimuthu, P.; Petersen, E.L.; Seal, S. Development of Highly Active Titania-Based Nanoparticles for Energetic Materials. J. Phys. Chem. C 2011, 115, 10412–10418. [Google Scholar] [CrossRef]
  28. Jandosov, J.M.; Shabanova, T.A.; Shamalov, M.E.; Beisenbaev, M.A.; Mansurov, Z.A. Production of Carbon Material with a High Specific Surface Area and Research of Synthesis Products. Combust. Plasmochem. 2010, 8, 257–261. (In Russian) [Google Scholar]
  29. Nadirashvili, M.; Tsulukidze, G. Regulation of oxygen balance in the process of synthesis of explosives. Def. Sci. 2023, 2, 29–34. [Google Scholar] [CrossRef]
  30. Televnyi, I.; Kapliuk, O.; Kirdeiand, L.; Spodin, A. On Calculation of Oxygen Balance of Multicomponent Thermobaric Explosive Substance. St. Sci. Res. Inst. Arm. Mil. Equip. Test. Cert. 2021, 9, 145–151. [Google Scholar] [CrossRef]
  31. Stine, J.R. On predicting properties of explosives—Detonation velocity. J. Energ. Mater. 1990, 8, 41–73. [Google Scholar] [CrossRef]
  32. Trache, D.; Maggi, F.; Palmucci, I.; DeLuca, L.T. Thermal behavior and decomposition kinetics of composite solid propellants in the presence of amide burning rate suppressants. J. Therm. Anal. Calorim. 2018, 132, 1601–1615. [Google Scholar] [CrossRef]
  33. Dave, P.N.; Sirach, R. Comparative Study of the Thermal Decomposition of Ammonium Nitrate in the Presence of Nano Copper Ferrite Additive. Mater. Adv. 2023, 4, 6665–6672. [Google Scholar] [CrossRef]
  34. Gunawan, R.; Zhang, D. Thermal stability and kinetics of decomposition of ammonium nitrate in the presence of pyrite. J. Hazard. Mater. 2009, 165, 751–758. [Google Scholar] [CrossRef]
Jcs 08 00420 g001
Figure 1. DSC curve of an AN–Mg–NC basic composite heated at β = 5 K/min.
Figure 1. DSC curve of an AN–Mg–NC basic composite heated at β = 5 K/min.
Jcs 08 00420 g001
Jcs 08 00420 g002
Figure 2. DSC curves of (a) AN–Mg–NC–AC; (b) AN–Mg–NC–AC–Bi2O3; (c) AN–Mg–NC–AC–MoO3; (d) AN–Mg–NC–AC–ZnO composites heated at β = 5 K/min.
Figure 2. DSC curves of (a) AN–Mg–NC–AC; (b) AN–Mg–NC–AC–Bi2O3; (c) AN–Mg–NC–AC–MoO3; (d) AN–Mg–NC–AC–ZnO composites heated at β = 5 K/min.
Jcs 08 00420 g002
Jcs 08 00420 g003
Figure 3. Kissinger plot of the basic AN–Mg–NC composite.
Figure 3. Kissinger plot of the basic AN–Mg–NC composite.
Jcs 08 00420 g003
Jcs 08 00420 g004
Figure 4. Kissinger plot of the AN–Mg–NC–AC composite.
Figure 4. Kissinger plot of the AN–Mg–NC–AC composite.
Jcs 08 00420 g004
Jcs 08 00420 g005
Figure 5. Kissinger plot of the AN–Mg–NC–AC–Bi2O3 composite.
Figure 5. Kissinger plot of the AN–Mg–NC–AC–Bi2O3 composite.
Jcs 08 00420 g005
Jcs 08 00420 g006
Figure 6. Kissinger plot of the AN–Mg–NC–AC–MoO3 composite.
Figure 6. Kissinger plot of the AN–Mg–NC–AC–MoO3 composite.
Jcs 08 00420 g006
Jcs 08 00420 g007
Figure 7. Kissinger plot of the AN–Mg–NC–AC–ZnO composite.
Figure 7. Kissinger plot of the AN–Mg–NC–AC–ZnO composite.
Jcs 08 00420 g007
Table 1. The initial data for oxygen balance calculation.
Table 1. The initial data for oxygen balance calculation.
Composite Components (n)Mass Ratio (mn)Molecular Weight (MW, g/mol)Oxygen Content (OC, g/mol)
Ammonium nitrate (NH4NO3)80%80.048.0
Magnesium (Mg)5% (10% *)24.30.0
Nitrocellulose (NC)5% (10% *)297.0112.0
Additive (n)
Activated Carbon (AC)5%12.00.0
Bismuth (III) oxide (Bi2O3)5%465.948.0
Molybdenum (VI) oxide (MoO3)5%143.948.0
Zinc oxide (ZnO)5%81.416.0
* For oxygen balance calculation of the basic AN–Mg–NC composite.
Table 2. The calculated total oxygen content (OCtotal), total fuel content (FCtotal), and oxygen balance (OB) for AN–Mg–NC, AN–Mg–NC–AC and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, Zn) composites based on 1 kg of the material.
Table 2. The calculated total oxygen content (OCtotal), total fuel content (FCtotal), and oxygen balance (OB) for AN–Mg–NC, AN–Mg–NC–AC and AN–Mg–NC–AC–MexOy (Me = Bi, Mo, Zn) composites based on 1 kg of the material.
CompositeTotal Oxygen Content (OCtotal, kg)Total Fuel Content (FCtotal)Oxygen Balance (OB)
AN–Mg–NC0.5170.162+3.27%
AN–Mg–NC–AC0.4990.150+3.95%
AN–Mg–NC–AC–Bi2O30.5040.150+3.14%
AN–Mg–NC–AC–MoO30.5150.150+4.61%
AN–Mg–NC–AC–ZnO0.5080.150+3.94%
Table 3. Detailed results of the activation energy (Ea) calculation for the basic AN–Mg–NC composite using the Kissinger method.
Table 3. Detailed results of the activation energy (Ea) calculation for the basic AN–Mg–NC composite using the Kissinger method.
Tmax, K1/TmaxHeating Rate (β), K/minln (β/(Tmax)2)
534.580.001875−12.37
549.200.0018210−12.34
556.200.0018015−12.32
567.710.0017620−12.30
From Kissinger Plot
Slope:−11,910.06
Intercept:11.36
Ea:99.02 kJ/mol
Table 4. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC composite using the Kissinger method.
Table 4. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC composite using the Kissinger method.
Tmax, K1/Tmax (K−1)Heating Rate (β), K/minln (β/(Tmax)2)
490.150.002045−10.78
512.170.0019710−10.17
514.120.0019415−9.77
522.180.0019120−9.52
From Kissinger Plot
Slope:−9818.63
Intercept:9.21
Ea:93.63 kJ/mol
Table 5. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–Bi2O3 composite using the Kissinger method.
Table 5. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–Bi2O3 composite using the Kissinger method.
Tmax, K1/Tmax (K−1)Heating Rate (β), K/minln (β/(Tmax)2)
490.760.0020385−10.78
511.590.00197410−10.17
513.820.00194615−9.77
518.330.00192920−9.59
From Kissinger Plot
Slope:−10,001.74
Intercept:11.58
Ea:91.45 kJ/mol
Table 6. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–MoO3 composite using the Kissinger method.
Table 6. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–MoO3 composite using the Kissinger method.
Tmax, K1/TmaxHeating Rate (β), K/minln (β/(Tmax)2)
492.170.0020325−10.78
511.600.00196710−10.17
515.720.00193915−9.78
520.630.00192120−9.51
From Kissinger Plot
Slope:−10,023.35
Intercept:11.55
Ea:91.65 kJ/mol
Table 7. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–ZnO composite using the Kissinger method.
Table 7. Detailed results of the activation energy (Ea) calculation for the AN–Mg–NC–AC–ZnO composite using the Kissinger method.
Tmax, K1/TmaxHeating Rate (β), K/minln (β/(Tmax)2)
492.380.0020315−10.77
510.990.00196610−10.11
516.230.00193715−9.78
521.110.00191920−9.51
From Kissinger Plot
Slope:−10,038.08
Intercept:11.58
Ea:91.76 kJ/mol
Table 8. Data summary of the kinetic parameters estimated using the Kissinger method at a heating rate of 5 K/min.
Table 8. Data summary of the kinetic parameters estimated using the Kissinger method at a heating rate of 5 K/min.
CompositeTmax, K (β = 5 K/min)ln (β/(Tmax)2)Ea, kJ/molReference
Pure AN543.00−10.98155.80[33]
AN–Pyrite648.15−12.25101.80[34]
AN–Mg–NC534.58−12.3799.02Current study
AN–Mg–NC–AC–Bi2O3490.76−10.7891.45Current study
AN–Mg–NC–AC–MoO3492.17−10.7691.65Current study
AN–Mg–NC–AC–ZnO492.38−10.7791.76Current study
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Yelemessova, Z.; Yerken, A.; Zhaxlykova, D.; Milikhat, B. The Impact of Activated Carbon–MexOy (Me = Bi, Mo, Zn) Additives on the Thermal Decomposition Kinetics of the Ammonium Nitrate–Magnesium–Nitrocellulose Composite. J. Compos. Sci. 2024, 8, 420. https://doi.org/10.3390/jcs8100420

AMA Style

Yelemessova Z, Yerken A, Zhaxlykova D, Milikhat B. The Impact of Activated Carbon–MexOy (Me = Bi, Mo, Zn) Additives on the Thermal Decomposition Kinetics of the Ammonium Nitrate–Magnesium–Nitrocellulose Composite. Journal of Composites Science. 2024; 8(10):420. https://doi.org/10.3390/jcs8100420

Chicago/Turabian Style

Yelemessova, Zhanerke, Ayan Yerken, Dana Zhaxlykova, and Bagdatgul Milikhat. 2024. "The Impact of Activated Carbon–MexOy (Me = Bi, Mo, Zn) Additives on the Thermal Decomposition Kinetics of the Ammonium Nitrate–Magnesium–Nitrocellulose Composite" Journal of Composites Science 8, no. 10: 420. https://doi.org/10.3390/jcs8100420

Article Metrics

Back to TopTop