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Incomplete combustion of Al in solid propellants can be effectively resolved by coating of an oxidizer at the microscale. In this paper, Al@CL-20 composites with polydopamine as the interfacial layer were prepared using this strategy. The structure, heat of reaction, thermal decomposition properties, and combustion performances of these composites under the effects of graphene oxide (GO) and graphene-based carbohydrazide complexes (GO-CHZ-M, M = Co2+, Ni2+) have been comprehensively investigated. The experimental results show that the heat of reaction of Al@CL-20 is 6482 J g-1, which is 561 J g-1 higher than that of the corresponding mechanical mixture. The presence of GO-CHZ-Co can further increase the heat of reaction of Al@CL-20 to 6729 J g-1 with a decreased activation energy by about 54.8%. Under the synergistic effect of interfacial control and GO-CHZ-M, the ignition delay time of Al@CL-20-Co decreases from 5.1 to 4.2 ms. Besides, the D50 of the combustion condensed products (CCPs) decreased from 5.62 to 4.33 µm, indicating the combustion efficiency of Al is greatly improved.
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The high gravimetric (58.74 kJ/g) and volumetric (137.45 kJ/cm3) heat values loaded in boron (B) offer significant potential for application in solid propellants and explosives. However, the high melting (2076 °C) and boiling (3927 °C) points of boron powder and the low melting point (450 °C) of oxidation products affect the energy performance and application of boron. Fluorine-containing polymers have high oxidation potential and excellent mechanical properties and can produce expectant gaseous products through the combustion reaction with boron oxide, but research examining the interaction between purified boron powder and fluoropolymers and the optimal selection of the fluoropolymer remains scarce. Herein, the binding energy between typical fluoropolymers [Viton, polyvinylidene fluoride, poly(vinylidene fluoride-co-chlorotrifluoroethylene), and vinylidene fluoride] and boron was calculated via molecular dynamics simulations, which shows that Viton is an appropriate candidate for coating boron powder. In the experiment, The Bw@Viton core-shell composites were prepared using Viton as the coating layer, and boron powder was pre-purified with acetonitrile. Its structure, thermal properties, ignition, and combustion characteristics were then characterized. The results revealed successful removal of the oxide layer, and the hydrophobicity was significantly improved after Viton coating. Purification and coating synergistically enhance the energy release of boron powder, and the composites demonstrated excellent thermal, ignition, and combustion performances. In particular, the heat of oxidation and heat of combustion were increased by 26.6 and 32.7%, respectively. The ignition delay time was reduced by 53.2% compared to raw boron. A prospective reaction mechanism between boron and Viton is thus proposed.
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Direct initiation of secondary explosives by a semiconductor laser is highly demanded, but it is challenging to exclude the use of sensitive primers. Most laser-sensitive energetic materials are usually mechanically sensitive. In order to reduce the mechanical sensitivity (MS) of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) while improving laser absorbance in the near-infrared band, spherical CL-20 composites (SCCs) embedded with nano aluminum (Al) powder and graphene-based catalyst (GO-CHZ-Co) were prepared by a spray drying method. These SCCs have been characterized comprehensively in terms of their morphologies, particle size distribution, laser absorbance, thermal decomposition behaviors, MS, and laser ignition properties. Results show that the maximum critical impact energy of SCCs was 3.8 J, which is 2.8 J higher than that of pristine ε-CL-20. The critical friction load was increased by at most 108 N compared to pristine CL-20. The absorbance has also been significantly increased up to almost 70% in the wavelength between 400 and 1400 nm, where the peak absorption is located in the region of 800-900 nm. In addition, the initial decomposition temperature (Ti) of SCCs is lower than that of pure CL-20, especially in the presence of GO-CHZ-Co. The apparent activation energy (Ea) for the decomposition of SCCs was largely dependent on the particle size of Al. Preliminary ignition tests indicate that the SCCs can be ignited successfully by a small-power laser.
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In this paper, several binary and ternary metastable intermixed nanocomposites Al/CuO, Al/PVDF, CuO/PVDF, and Al/CuO/PVDF have been prepared by simple mechanical mixing and ball milling followed by spray drying methods. In this way, the interfacial structure could be well tuned and compared in terms of reactivity. The nonisothermal DSC curves results showed that the exothermic reaction of Al/CuO/PVDF could be divided into three steps. In addition, it has been shown that for the same formulation, the reaction efficiency, pressurization capacity, and thermal reactivity are greatly dependent on the interfacial structure. As a typical example, composite Al@PVDF/CuO, where Al is fully covered with PVDF, exhibited a higher energy release of 10.7 kJ·cm-3 and pressurization rates of 22.79 MPa·s-1·g-1. The reaction between Al and PVDF has been facilitated in both extent of reaction and efficiency due to their intimate contact. Based on the thermal analysis, condensed combustion product analysis, and gaseous phase identification, the mutual reaction mechanisms of Al/CuO/PVDF have been proposed. The most likely reactions that occurred at each stage of the reaction are summarized, providing insight into the complicated underlying mechanisms. It shows that the regulation of energy release rates and improved efficiency could be easily realized by predesigned interfacial structures.
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In this paper, the two-dimensional (2D) high nitrogen triaminoguanidine-glyoxal polymer (TAGP) has been used to dope hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) crystals using a microfluidic crystallization method. A series of constraint TAGP-doped RDX crystals using a microfluidic mixer (so-called controlled qy-RDX) with higher bulk density and better thermal stability have been obtained as a result of the granulometric gradation. The crystal structure and thermal reactivity properties of qy-RDX are largely affected by the mixing speed of the solvent and antisolvent. In particular, the bulk density of qy-RDX could be slightly changed in the range from 1.78 to 1.85 g cm-3 as a result of varied mixing states. The obtained qy-RDX crystals have better thermal stability than pristine RDX, showing a higher exothermic peak temperature and an endothermic peak temperature with a higher heat release. Ea for thermal decomposition of controlled qy-RDX is 105.3 kJ mol-1, which is 20 kJ mol-1 lower than that of pure RDX. The controlled qy-RDX samples with lower Ea followed the random 2D nucleation and nucleus growth (A2) model, whereas controlled qy-RDX with higher Ea (122.8 and 122.7 kJ mol-1) following some complex model between A2 and the random chain scission (L2) model.
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High-energy-density photosensitive pyrotechnics with good thermal stability have been in increasing demand in recent years. In this paper, graphene oxide (GO)-intercalated energetic coordination polymers (ECPs) are prepared with improved thermostability but great photosensitivity by using high nitrogen compounds azotetrazole (AT) and 5,5'-bistetrazole-1,1'-diolate dehydrate (BTO) as ligands. The decomposition activation energy (Ea) of Cu-AT has been increased from 135.7 to 151.9 kJ·mol-1 after intercalating 5 wt% GO, and in the meantime, the exothermic peak temperature (Tp) was increased by 12.6 °C. However, the decomposition Ea of Cu-BTO decreased under the effect of the same amount of GO with little effect on Tp. This confirms that GO has stabilization effects on the Cu-AT crystal, whereas the catalytic effects on Cu-BTO would dominate after dehydration with its crystal lattice collapse. Also, when the content of GO was 3%, the resultant GO0.03-Cu-AT exhibits a higher density (2.88 g·cm-3) and good thermostability (Tp = 293.7 °C). This ECP shows excellent low-energy laser ignition performance, which can be ignited with an energy of less than 1 mJ at a wavelength of 976 nm. Low-energy laser initiation is considered to be a safer but more reliable method than the traditional electrical-based ones.
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In this study, a 2D structured triaminoguanidine-glyoxal polymer with a high nitrogen content has been coordinated with metal ions to produce energetic metal complexes (TAGP-Ms) employed as energetic burn rate inhibitors. The metal ions (Ba2+, K+, and Ca2+) are elaborately selected based on their ability of suppressing the burn rate of composite propellants. The CL-20 crystals were intercalated with prepared TAGP-Ms materials via a solvent-antisolvent method for realization of the precise control on burning behaviors of studied propellants. The influence of TAGP-Ms inhibitors on thermal decomposition and combustion characteristics of high-energy composite propellants was evaluated using thermal analysis and a combustion diagnostic method. Results of TGA/DSC-FTIR measurements suggest that the thermal decomposition of CL-20-containing composite propellants was found to be constrained by varied degrees as a result of TAGP-Ms additions, in which the TAGP-K displays a stronger effect on suppressing the thermal decomposition of CL-20 compared with that of other TAGP-Ms. The FTIR spectra indicate that the primary gaseous phase products are composed of N2O, H2O, and CO2 in CL-20 decomposition, as well as by HCl, H2O, NO2, and N2O in the decomposition of AP for all studied composite propellants. The combustion characterizations show that the TAGP-K-containing composite propellant exhibits a significantly reduced rate of heat release but is associated with a higher flame radiation intensity increased by 4.2% compared with that of the reference propellant, which clearly implies that the TAGP-K is capable of suppressing the energy release rate while ensuring the high energetic features of propellants to be well maintained. Moreover, the burn rate pressure exponents are considerably decreased by â¼10% for the TAGP-K-containing propellants in comparison with those of propellants with the typical formulation, which strongly suggests that TGAP-Ms are promising candidates for tuning the combustion behaviors of composite propellants by influencing the decomposition processes of CL-20 and AP collectively.
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Aluminum hydride (AlH3) is a promising fuel component of solid propellant, but its stabilization is still challenging. Herein, surface functionalization of hydrophobic perfluoropolyether (PFPE) followed by ammonium perchlorate (AP) coating has been implemented. In particular, AlH3@PFPE@xAP (x = 10, 30, 50, or 64.21%) composites (AHFPs) were prepared by a spray-drying technique. The PFPE-functionalized AlH3 with a hydrophobic surface shows an increased water contact angle (WCA) from 51.87° to 113.54°. Compared with pure AlH3, the initial decomposition temperatures of AHFPs were increased by 17 °C, and the decomposition properties of AP in the AHFPs were also enhanced with significantly decreased peak temperature and fairly increased energy output. Moreover, the decomposition induction time of AHFPs-30% was improved by almost 1.82 times that of raw AlH3, which indicates that the coatings of PFPE and AP could improve the stability of AlH3. The maximum flame radiation intensity of AHFPs-30% was 21.6 × 103, which is almost 7.71 times that of pure AlH3 (2.8 × 103).
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There is an interactive effect between ammonium perchlorate (AP) and aluminum (Al) powder during the combustion process of composite solid propellants, but the mechanism of this effect is still lacking. Using quantum chemical methods, we investigated this mechanism from a molecular perspective. The interaction process between Al and AP was analyzed by comparing the chemical bond changes between the atoms during the reaction process of the Al/AP system and the AP unimolecular thermal decomposition system. The results show that Al atoms alter the reaction mechanism of AP thermal decomposition, significantly decreasing the activation energy of AP decomposition at high temperature but increasing that at low temperature. Meanwhile, the temperature-dependent rate constant of each basic reaction was calculated by transition state theory. The rate constants increase with temperature. Under high temperature and pressure, Al can increase the high-temperature decomposition rate of AP by up to 1-3 orders of magnitude.
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Boron powder is a kind of metal fuel with high gravimetric and volumetric calorific values, which has been widely used in military fields such as solid propellants, high-energy explosives, and pyrotechnics. However, the easily formed liquid oxide layer can adhere to the surface of boron powder and react with the hydroxyl (-OH) group of hydroxyl-terminated polybutadiene (HTPB) binder to form a gel layer that is detrimental to propellant processing and restricts the complete oxidation of boron powder. Therefore, to improve the combustion efficiency of boron powder, the ignition and combustion mechanisms of boron powder have been studied, and surface coating modification strategies have been developed by researchers worldwide, aiming to optimize the surface properties, improve the reaction activity, and promote the energy release of boron powder. In this review, recent studies on the ignition and combustion mechanisms of boron powder are discussed. Moreover, the reported boron powder coating materials are classified according to the chemical structure and reaction mechanism. Additionally, the mechanisms and characteristics of different coating materials are summarized, and the mechanism diagrams of fluoride and metal oxide are provided. Furthermore, promising directions for modification methods and the potential application prospects of boron powder are also proposed.
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Energetic materials are a special class of energy materials composed of C, H, O, and N. Their safety always deteriorates with increasing energy. Regulating the properties of energetic materials to meet application requirements is one of the focuses of research in this field. Energetic metal-organic frameworks (EMOFs) are good candidates as primary explosives to replace lead azide (LA) and other explosives containing toxic metal elements. However, safety remains the biggest concern in applications. In this paper, crystal morphology modulation of EMOF was carried out by stepwise coordination of metal ions and energetic ligands on surfaces of graphene oxide (GO) and amino-functionalized graphene oxide (AGO). Two energetic composite materials, Cu-AFTO@GO and Cu-AFTO@AGO, were successfully synthesized and also the EMOF (Cu-AFTO). The structures and morphologies of these materials were fully characterized. The thermal decomposition behaviors, mechanical sensitivity, and electrostatic discharge sensitivity were investigated in detail. The electric ignition ability of EMOF and two composite materials was tested. This study shows that it is possible to reduce the diameter of EMOF crystals from hundreds of microns to tens of nanometers by a stepwise coordination method. The high electrical conductivity and sensitivity-reducing effect of GO and/or AGO allow the nanosized EMOF crystals to have a lower ignition threshold and lower sensitivity.
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The thermochemical ablation of insulation material caused by slag deposition in solid rocket motors has increasingly attracted researchers' attention. Understanding the ablation mechanism and the ability to calculate reaction kinetics parameters determine the height of the thermal protection design for advanced solid rocket motors. In this work, the interaction of the Al2O3-C system is determined through static ablation experiments. Using X-ray diffraction, HSC thermodynamic software, and a thermogravimetric analyser, the carbon thermal reduction of alumina is analysed and the reaction mechanism and physical model are obtained. Isothermal experiments at 1700-1850 °C and mathematical analysis provide the kinetic parameters of the overall and step-by-step reactions. The results show that the overall reaction of the Al2O3-C system involves three steps. The overall reaction kinetics are described by the contracting area model R2 with apparent activation and frequency factors estimated as 254.5 kJ mol-1 and 5.5 × 106 min-1, respectively. The distribution reaction kinetics of steps 1 and 2 are described by the first-order chemical reaction control model (F1) and that of step 3 is described by the one-dimensional diffusion control model (D1). The corresponding activation energies are 107.9 kJ mol-1, 240.3 kJ mol-1, and 567.5 kJ mol-1, and frequency factors are 625.94 min-1, 8.3 × 105 min-1, and 1.6 × 1014 min-1, respectively.
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The thermal behavior, decomposition kinetics and mechanisms of 1-amino-1-(tetrazol-5-yldiazenyl) guanidine (tetrazene) and 2-(tetrazol-5-yldiazenyl) guanidine (MTX-1) have been investigated using DSC, TG techniques, and quantum chemical calculations. It has been found that MTX-1 is much more stable than tetrazene and MTX-1, and both of them decompose in three steps with different kinetic parameters. Tetrazene is melted-dehydrated at 128.4 °C with a heat absorption of 50 J g(-1) and then it starts to decompose at around 118.6 °C with a peak temperature of 126.3 °C covered by a heat release of 1037 J g(-1) at a heating rate of 1.0 °C min(-1), while MTX-1 starts at 167.7 °C with a main peak of 191.1 °C covered by a heat change of 1829 J g(-1) under the same conditions. The activation energy is almost the same for their first decomposition steps (225 kJ mol(-1)), which are controlled by a three dimensional nucleation and growth model (A3). The mechanisms of the rate-limiting steps are supported by quantum chemical calculations. They could undergo a similar rate-limiting chemical process producing 1H-tetrazole and N2 for both cases, while the former also produces aminocyanamide and the latter produces cyanamide.
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Low sensitivity octahydro-1,3,4,7-tetranitro-1,3,5,7-tetrazocine (HMX) has garnered significant attention from researchers due to its reduced shock sensitivity. However, the crystallization process poses challenges due to the high solidity and viscosity of the metastable α phase. Despite efforts to address this with additional energy sources like ultrasonic irradiation, prolonged exposure duration often results in small particle sizes, hindering the production of HMX with a consistent particle size distribution, thus limiting its applicability. To overcome these challenges, a method combining ultrasonic irradiation and trace H+ additive was proposed and investigated for their impact on the polymorphic transformation of HMX. The H+ additive was found to modify barriers, thus there was a lack of competitive driving force for the nucleation or growth of the metastable α form, thereby shortening the transformation pathway and duration. Moreover, the H+ additive significantly accelerated the nucleation rate of the ß form (67.7 orders of magnitude faster with 0.10 wt H+) and the growth rate of ß form HMX (5.8 orders of magnitude faster with 0.10 wt H+). While H+ additive alone was insufficient to induce spontaneous nucleation of the ß form, combining it with short-duration ultrasonic irradiation further promoted ß nucleation and shortened the polymorphic transformation duration (almost 20 orders of magnitude shorter). This rational approach led to effective control of the transformation process. The resulting low sensitivity HMX crystals exhibited varying mean sizes ranging from 20 to 340 µm, with purity exceeding 99.6 %, an apparent density greater than 1.8994 g/cm3, and few internal defects, fully meeting the requirements of low-sensitivity HMX, thus significantly expanding its potential applications. Our study sheds light on the mechanisms governing HMX polymorphic transformation in the presence of additives and ultrasonic irradiation, offering guidance for the rational control of this complex transformation.
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2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is one of the high-energy oxidants, but has limited application due to its high sensitivity. In this work, polyvinylidene fluoride (PVDF) was used as a co-oxidizer, which is expected to increase the safety of CL-20. One kind of novel graphene-based carbohydrazide complex (GCCo and GCNi) was employed to modify the properties of dual-oxidant CL-20@PVDF composites by the spray drying method and compared with traditional nanocarbon materials (CNTs and GO). The properties of these composites were investigated using the TGA/DSC technique and impact test. The results show that GCCo and GCNi could increase the activation energy (Ea) of CL-20@PVDF composites, and change the physical model of CL-20@PVDF, which followed the random chain scission model and then the first-order reaction model. In addition, these nanocarbon materials could reduce the impact sensitivity of CL-20@PVDF by their unique structure. Besides that, a dual-oxidant CL-20@PVDF system was used to improve the combustion property of Boron. GCCo and GCNi with the synergetic effect could increase the flame temperature and control the burn rate of CL-20@PVDF@B compared with CNTs and GO. The energetic nanocarbon catalyst-modified oxidant provides a facile method for stabilizing high-energy but sensitive materials to broaden their application.
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The combustion efficiency of Al plays a critical role in the combustion of high-energy aluminum-based solid propellants. For traditional formulations, the Al powders are dispersed in the binder matrix, leading to limited contact with the oxidizers and hence usually insufficient combustion and higher values of the pressure exponent. In this paper, various core-shell structural Al/oxidizer composites such as Al@HMX, Al@AP, and AP@Al have been prepared by a spray-drying technique based on which solid propellants with precise interfacial control between Al particles and oxidizers were realized. Compared to the control sample, the modified propellants have a greater heat of explosion of 5890 J g-1 (15% higher) and a reduced ignition delay time of 58 ms (65% decrease). Without changing the content of components, the burn rates of propellants can be easily modulated by tuning the interfacial contact of Al and oxidizers, where it varies in a wide range of 4.56-5.79 mm s-1 at the same pressure of 1 MPa. After introducing Al/oxidizer composites, the lowest pressure exponent of 0.19 within 1-15 MPa could be achieved by using Al@HMX and AP@Al composites. The agglomeration of Al was also inhibited by using Al/oxidizer composites, and the mechanism can be interpreted by using a classical "pocket" model. Moreover, the improved combustion efficiency of the solid propellants was verified by a noticeable reduction in the unreacted Al content.
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Aluminum hydride (AlH3) has attracted much attention due to its potential to replace aluminum (Al) as a novel energetic material in solid propellants. In this research, ammonium perchlorate (AP) and perfluoropolyether (PFPE) as functionalized coatings and a combination of acoustic resonance and spray drying technology have been employed to prepare AlH3@Al@AP (AHAPs) and AlH3@Al@AP@PFPE (AHAPs-F) energetic composite particles. The formulations of composite propellants and modified AlH3 particles were designed and fabricated. Their thermal reactivity, reaction heat, density, vacuum stability, combustion performance, and condensed combustion products (CCPs) have been systematically investigated. The results show that the solid propellants containing AHAPs (SP13) and AHAPs-F (SP14) composites can significantly enhance the reactivity and energy output compared to conventional solid propellants with the mechanical mixture Al/AlH3 (SP12). In particular, the total heat releases of SP13 and SP14 are almost 1.2 and 1.7 times higher than those of conventional ones (SP12, 1442 J g-1), respectively. Among the AlH3-based propellants, SP14 propellants exhibit the highest reaction heat of 5887 J g-1, the most intensive flame radiation of 31.4 × 103, and the highest combustion wave temperature of 2495 °C. Moreover, the particle size distribution of CCPs from SP14 propellants is much narrower and smaller than that of SP12, resulting in higher combustion efficiency.
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This mini-review summarizes the seminal exploration of aqueous supramolecular chemistry of crown ether macrocycles. In history, most research of crown ethers were focusing on their supramolecular chemistry in organic phase or in gas phase. In sharp contrast, the recent research evidently reveal that crown ethers are very suitable for studying abroad range of the properties and applications of water interactions, from: high water-solubility, control of Hofmeister series, "structural water", and supramolecular adhesives. Key studies revealing more details about the properties of water and aqueous solutions are highlighted.
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Herein, we propose a highly sensitive wireless rehabilitation training ball with a piezoresistive sensor array for patients with Parkinson's disease (PD). The piezoresistive material is a low percolation threshold conductive hydrogel which is formed with polypyrrole (PPy) nanofibers (NFs) as a conductive filler derived from a polydopamine (PDA) template. The proton acid doping effect and molecular template of PDA are essential for endowing PPy NFs with a high aspect ratio, leading to a low percolation threshold (â¼0.78 vol %) and a low Young's 004Dodulus of 37.69 kPa and hence easy deformation. The piezoresistive sensor exhibited a static and dynamic stability of 10,000 s and 15,000 cycle times, respectively. This stability could be attributed to the increased hydrophilicity of conductive fillers, enhancing the interfacial strength between the conductive filler and the matrix. The interaction between the PDA-PPy NFs and the hydrogel matrix endows the hydrogel with toughness and ensures the stability of the device. Additionally, the microdome structure of the conductive hydrogel, produced by hot screen-imprinting, dramatically improves the sensitivity of the piezoresistive sensor (â¼856.14 kPa-1). The microdome conductive hydrogel can distinguish a subtle pressure of 15.40 Pa compared to the control hydrogel without a microstructure. The highly sensitive piezoresistive sensor has the potential to monitor the hand-grip force, which is not well controlled by patients with PD. The rehabilitation training ball assembled with a sensor array on the surface and a wireless chip for communication inside is built and used to monitor the pressure in real time through the WeChat applet. Thus, this work has significantly broadened the application of hydrogel-based flexible piezoresistive sensors for human activity monitoring, which provides a promising strategy to realize next-generation electronics.
Assuntos
Nanofibras , Polímeros , Condutividade Elétrica , Humanos , Hidrogéis/química , PirróisRESUMO
To improve the condensed-phase reaction rate of ε-CL-20, polydopamine (PDA)-nickel complex-coated multiwalled carbon nanotubes (CNTs) have been prepared and used as combustion catalysts. The PDA-Ni complex has been prepared and in situ coprecipitated with ε-CL-20 by an antisolvent crystallization process in its dimethyl sulfoxide (DMSO) solution. It has been shown that crystalline CL-20 composites included with PDA-Ni complexes are polygon-shaped with a smooth surface and an average diameter of 10-15 µm, whereas it is 140 µm for raw ε-CL-20 crystals. The catalytic reactivity of the complex on thermolysis of CL-20 has been investigated using the differential scanning calorimetry (DSC) and thermogravimetry (TG)-coupled Fourier transform infrared (FT-IR) spectroscopy technique. It has been found that CNT@PDA-Ni complexes have catalytic effects on the decomposition of ε-CL-20 by decreasing/shifting of the exothermic peak from T p = 240.1 to 238.7 °C. The FT-IR spectra of CL-20 decomposition products under the effect of the catalyst predominantly show peaks at 1274, 1644 and 1596, 1912, 2265, and 1956-1800 cm-1, indicating the presence of fragments with N2O, NO2, NO, HNCO, and NO/CO, respectively. The change in the ε-CL-20 decomposition mechanism should be attributed to the catalytic action of CNT, decreasing the formation of NO2. Also, under the effect of the carbon-based catalyst, the HNCO formation was detected at another temperature in comparison with raw CL-20, with peak absorption at 224.1 vs 232.3 °C and the evolution was completed at 250.8 vs 246.2 °C, respectively.