Jiaxiang Wu,
Junyi Huang,
Qiang Liu,
Yong Chen,
Yuchun Li*,
Li Yang,
Qin Yin,
Zhenru Gao,
Shuangzhang Wu and
Xinxin Ren
College of Field Engineering, Army Engineering University of PLA, Nanjing, 210007, China. E-mail: liyuchunmail@163.com
First published on 8th January 2020
To investigate the influence of SiC and Al2O3 as additives on the mechanical response and reactive properties of Al/PTFE (aluminum/polytetrafluoroethylene) reactive composites, Al/SiC/PTFE and Al/Al2O3/PTFE samples with different component ratios were prepared for quasi-static compression and drop-weight tests. Al/Al2O3/PTFE samples with different particle sizes were prepared for simultaneous thermal analysis experiments. The stress–strain data, characteristic drop height and thermogravimetry-differential scanning calorimetry (TG-DSC) curves of the composites were recorded. The results show that the addition of SiC and Al2O3 significantly enhance the strength of Al/PTFE. The enhancing effect of SiC on the composite strength was stronger than that of Al2O3. The addition of SiC and Al2O3 contribute toward reducing the sensitivity of the composites, where the reducing effect of Al2O3 on Al/PTFE sensitivity was weaker than that of SiC. Nanoscale Al2O3 reacts with PTFE to form AlF3, and the reaction heat decreases dramatically with an increase in the Al2O3 particle size. The addition of nanoscale Al2O3 improves the reaction heat and energy density of the composites.
Al/PTFE is both a composite and energetic material, thus, the experimental research should not only focus on the study of its mechanical properties, but attention needs to be paid to the reaction characteristics of the materials. For the purpose of the successful application of Al/PTFE, it is necessary to ensure that Al/PTFE has enough strength to guarantee its safety during production, storage and explosive loading, meanwhile, it can also generate exothermic reactions while penetrating the target. Wang et al. 12 investigated the penetration enhancement behavior of an Al/PTFE double-layered linear shaped charge against thick steel targets. The experimental results and numerical simulations indicate that its penetration performance and reactive material mass entering the penetrated target strongly depended on the reactive liner thickness and standoff. And, the initiation delay time of Al/PTFE rose evidently with an increase in the reactive liner thickness. Feng et al.13,14 observed an intense reaction phenomenon of a Al/PTFE sample treated by a specific sintering process under quasi-static compression for the first time. Based on this discovery, the impact exerted by sintering temperature, component ratio and Al particle size on the quasi-static reaction of Al/PTFE were investigated. Wang et al.15 studied the effect of temperature on the mechanical properties and reactive behavior of Al/PTFE under quasi-static compression. Scanning electron microscopy results showed that the temperature played a very momentous role in the fracture mechanisms of PTFE. The material went through brittle–ductile transformation related to a temperature-induced phase transition of the PTFE matrix.
In recent years, extensive research has been conducted on the application of additives in reactive materials to tune the reactivity of composites.16,17 He et al.18 utilized a synthesized polydopamine binding layer to adjust the reactivity of nanoscale Al/PTFE, where it was found that the mixture of PTFE and nanoscale Al coated with polydopamine showed increased energy release and reduced sensitivity, and more importantly tunable reactivity. In order to improve the strength and density of materials, metal particles are also very common additives, such as W particles. Wang et al.19 investigated the mechanical behavior and impact insensitivity of Al/W/PTFE composites with different W percentage, and the results indicate that the strength under dynamic compression loading and insensitivity under impact loading of Al/W/PTFE composites show an increasing tendency with increased W content. Cai et al.20 and Herbold et al.21 carried out research on the influence of particle size on the mechanical properties, failure and shock behavior of Al/W/PTFE. The numerical results reveal that the strength of Al/W/PTFE decreased as the W particle size rose owing to the function of force chains. However, W cannot participate in the reaction and only acts as a mass carrier in the materials system, which leads to a decrease in the energy density of the materials.
Previous studies show little research on the properties of Al/PTFE after adding ceramic materials. As typical ceramic particles, SiC and Al2O3 possess the excellent characteristics of high hardness and outstanding wear resistance. Osborne et al.22,23 reported a pre-ignition reaction (PIR) phenomenon that was controlled by the fluorination of the Al particle passivation shell (Al2O3) when nano-Al/PTFE was heated over 400 °C. Consequently, it can be considered that SiC and Al2O3 can be used as additives to increase the energy density while improving the mechanical properties of the composites. Because the raw material ratio and particle size have great effects on the properties of materials, Al/SiC/PTFE and Al/Al2O3/PTFE samples with different component ratios were prepared for quasi-static compression and drop-weight tests. Considering that SiC cannot react with Al/PTFE, the thermal behavior of Al/SiC/PTFE was not investigated, only Al/Al2O3/PTFE samples with different particle sizes were prepared for simultaneous thermal analysis experiments. The influence of SiC and Al2O3 as additives on the mechanical response and reactive properties of Al/PTFE reactive composites were ascertained.
Type | Al/wt% | PTFE/wt% | Ceramic particles/wt% | TMD/g cm−3 |
---|---|---|---|---|
A | 26.0 | 74.0 | 0 | 2.31 |
B | 23.4 | 66.6 | 10 (SiC) | 2.38 |
C | 20.8 | 59.2 | 20 (SiC) | 2.45 |
D | 18.2 | 51.8 | 30 (SiC) | 2.52 |
E | 15.6 | 44.4 | 40 (SiC) | 2.59 |
F | 23.4 | 66.6 | 10 (Al2O3) | 2.41 |
G | 20.8 | 59.2 | 20 (Al2O3) | 2.52 |
H | 18.2 | 51.8 | 30 (Al2O3) | 2.63 |
I | 15.6 | 44.4 | 40 (Al2O3) | 2.74 |
For thermogravimetry-differential scanning calorimetry (TG-DSC) tests, Al (50 nm)/Al2O3 (30 nm)/PTFE, Al (1 μm)/Al2O3 (30 nm)/PTFE and Al (1 μm)/Al2O3 (1 μm)/PTFE were mixed according to the mass ratios 22/63/15%. To better understand the thermal reaction process of the composites, Al (50 nm)/PTFE, Al (1 μm)/PTFE, Al2O3 (30 nm)/PTFE and Al2O3 (1 μm)/PTFE were prepared as references with a mass ratio of 26/74%. All mixtures were sonicated in ethanol solution for 20 min via an ultrasonic mixing method to make even dispersed powders, then the mixtures were dried in a vacuum oven for 24 h at 60 °C.
For the purpose of examining the homogeneity of the prepared composites, sections of the samples before sintering were photographed using a Hitachi S-3400N II scanning electron microscope (SEM) to investigate the interior microstructures of the composites (Fig. 1). The geometry of the Al particles is spherical, while those of the SiC and Al2O3 are irregular. It can be found that Al, SiC and Al2O3 are uniformly distributed in the PTFE matrix, indicating that the initial powders were homogeneously mixed through the preparation process outlined. Arising from the applied tensile force when specimens were broken off, PTFE fibers could be easily observed in the microstructures of the specimens.
Fig. 1 Microstructures of the composites: (a) Al particles; (b) SiC particles; (c) Al2O3 particles; (d) type A; (e) type B; (f) type F. |
A drop-weight instrument was applied to investigate the sensitivity and impact-initiation characteristics of reactive composites. The apparatus has a drop mass of 10 kg, which falls from a variable height in the range of 0 to 156 cm. The samples were placed on an anvil and impacted directly using a free drop hammer. The impact sensitivities of the materials were calculated from the characteristic drop height (H50), at which specimens can have a 50% possibility to react.
The thermal behaviors of the Al/Al2O3/PTFE composites were studied using a TG/DSC simultaneous thermal analyzer. Samples with an average mass of 2.0 mg were loaded into the crucible and argon was used as the insured gas at a flow rate of 30 mL min−1 to prevent air from participating in the reaction. The device was programmed to heat the samples at a rate of 5 °C min−1, covering the temperature range of 25–1000 °C.
Fig. 3 shows the true stress–strain curves of Al/SiC/PTFE and Al/Al2O3/PTFE samples under quasi-static compression. The results presented are the average of three samples under identical conditions. It can be observed that all types of samples went through elastic and plastic deformation during compression. Strain hardening phenomenon occurred after the samples reached yield strength. The addition of SiC and Al2O3 had a significant influence on the stress–strain curves, and the effect was primarily reflected in the strain hardening stage.
The mechanical property parameters of all types of samples under quasi-static compression calculated based on the stress–strain data are listed in Table 2. The yield strengths and compressive strengths of the Al/SiC/PTFE and Al/Al2O3/PTFE samples are compared in Fig. 3. As can be seen, with an increase in the SiC content, the yield strength of the Al/SiC/PTFE samples shows an upward trend, reaching a maximum value of 38.52 MPa for a SiC content of 40 wt%. The yield strengths and compressive strengths of the Al/Al2O3/PTFE samples first increase and then subsequently decrease as the Al2O3 content increases, which means that an excess of Al2O3 destroys the continuity of the PTFE matrix, resulting in the reduction of the strength of the composites. In addition, the yield curves of the Al/SiC/PTFE samples are always above those of the Al/Al2O3/PTFE samples, as shown in Fig. 4, indicating that the enhancing effect that SiC has on the material strength is stronger than that of Al2O3 in the case of the same ceramic particle content.
Type | Yield strength/MPa | Elastic modulus/MPa | Hardening modulus/MPa | Compressive strength/MPa | Failure Strain |
---|---|---|---|---|---|
A | 20.49 | 342.64 | 29.75 | 77.81 | 1.48 |
B | 25.87 | 401.74 | 39.28 | 91.35 | 1.46 |
C | 28.03 | 441.25 | 45.79 | 87.56 | 1.26 |
D | 34.84 | 518.61 | 34.65 | 83.54 | 1.22 |
E | 38.52 | 539.57 | 23.98 | 79.91 | 1.21 |
F | 25.26 | 373.48 | 35.31 | 84.09 | 1.48 |
G | 27.68 | 429.34 | 35.82 | 93.33 | 1.46 |
H | 31.63 | 468.55 | 24.59 | 85.71 | 1.44 |
I | 28.38 | 420.53 | 16.22 | 64.48 | 1.49 |
Fig. 5 shows the states of the morphologies of the Al/SiC/PTFE and Al/Al2O3/PTFE samples after quasi-static compression. It can be seen that the most internally development cracks formed during the failure of the type A specimen, where with an increase in the SiC and Al2O3 content, the number of internal cracks decreased correspondingly. Therefore, the addition of SiC and Al2O3 effectively inhibit the formation of cracks, resulting in a significant strength increase of the Al/PTFE composites. Fig. 5(f) presents the internal failure morphology of the type A sample cross section. The sample became evidently brittle with typical shear fractures along the 45° planes (the direction of the maximum shear stress in an axially loaded bar).
(1) |
The experimental data of the type A, B, C and D samples were recorded according to the “up-and-down technique” and the results are presented in Fig. 6. From eqn (1), the H50 values of all of the types of samples were calculated. Fig. 7 depicts the curves of the H50 values vs. the ceramic particle fractions of the Al/SiC/PTFE and Al/Al2O3/PTFE samples. The data show that the sample without ceramic particles has the lowest H50 and is the most sensitive. The H50 increased monotonously with an increase in the ceramic particle content, implying that adding ceramic particles to Al/PTFE contributes towards reducing the sensitivity of the reactive composites, but that the degree of influence is different. The effect of Al2O3 on the reduction of Al/PTFE sensitivity was weaker than that of SiC. According to the mechanism of hot-spot formation at the crack tip of Al/PTFE proposed by Feng26 et al., with the addition of ceramic particles, the content of Al/PTFE involved in the reaction decreased, and the hot-spot area formed during the drop impact process was reduced, leading to a diminishing of the composite sensitivity. The difference between SiC and Al2O3 in reducing the sensitivity of the composites can be mainly attributed to the addition of SiC, which improves the thermal conductivity of the system, while Al2O3 changes the reaction pathway. Besides this, all types of samples reacted under drop hammer impact. Combined with the unreacted phenomena under quasi-static compression, it can be concluded that the composites showed different mechanical response and reactive properties under different strain rates, showing that a strain rate effect exists.
Fig. 6 The drop-weight test data points of selected samples: (a) type A; (b) type B; (c) type C; (d) type D. |
Fig. 7 The H50 values of the Al/SiC/PTFE and Al/Al2O3/PTFE samples as a function of the ceramic particle fraction. |
Al particle size | No. | Onset temperature/°C | Peak temperature/°C | End temperature/°C | Heat release/J g−1 |
---|---|---|---|---|---|
1 μm | Endo-peak-A | 321.9 | 340.8 | 354.8 | −3.78 |
Endo-peak-B | 508.9 | 570.0 | 589.8 | −32.59 | |
Exo-peak-C | 598.1 | 599.1 | 606.8 | 0.93 | |
Endo-peak-D | 648.7 | 658.8 | 670.2 | −7.42 | |
50 nm | Endo-peak-A | 329.3 | 341.1 | 352.2 | −3.99 |
Exo-peak-B | 485.6 | 508.5 | 523.8 | 4.58 | |
Exo-peak-C | 536.4 | 581.3 | 594.3 | 146.42 | |
Endo-peak-D | 640.1 | 649.5 | 661.2 | −3.68 |
As can be seen from Fig. 8(a), there are three endothermic peaks and one exothermic peak in the DSC curve of the Al (1 μm)/PTFE sample in the process of heating to 800 °C. It can be seen that the endothermic peak A is the melting endothermic peak of the PTFE matrix and the endothermic peak D is the melting endothermic peak of the residual Al powder due to there being no obvious changes in the peaks. The endothermic peak B starts at 508.9 °C, accompanied by the reduction of the sample mass, indicating the formation of gases, which can be considered a product of the decomposition of PTFE. The exothermic peak C starts at 598.1 °C and is thought to be a result of the exothermic reaction between the Al and the decomposition product of PTFE. According to Fig. 8(b), it can be seen that there are two endothermic peaks and two exothermic peaks in the DSC curve of the Al (50 nm)/PTFE sample. Only the properties of peak B changed when compared with the data shown in Fig. 8(a), peak B is endothermic in Fig. 8(a), whereas it is exothermic in Fig. 8(b). The exothermic peak B starts at 485.6 °C and ends at 523.8 °C, and the reaction heat is 4.58 J g−1 as a result of the pre-ignition reaction between nanoscale Al and PTFE during heating. The Al2O3 layer on the surface of the Al particles reacted with the fluoride ions produced by the condensing of PTFE to form the catalyst AlF3 in the unstable β-phase.21 The reaction heat exceeded the heat absorbed by the decomposition of PTFE. Therefore, an exothermic peak B appeared in Fig. 8(b). Besides this, since the specific surface area of the 1 μm Al particles (2.22 m2 g−1) was significantly smaller than that of the 50 nm Al particles (44.44 m2 g−1), the Al2O3 layer, which participates in the pre-ignition reaction, was correspondingly reduced, and the pre-ignition reaction energy was smaller than the PTFE decomposition absorption energy, leading to the appearance of the endothermic peak B, as shown in Fig. 8(a). In addition, as listed in Table 3, the reaction heat of Al (50 nm)/PTFE was as high as 146.42 J g−1, while that of Al (1 μm)/PTFE was only 0.93 J g−1, which demonstrates that the reaction between the nanoscale Al particles and PTFE was more intense than that of microscale Al particles. Levitas et al.27–29 believed that this was attributed to the unique melt-dispersion mechanism (MDM) of nanoscale Al particles.
Pantoya et al.33 studied the influence of alumina passivation on nano-Al/PTFE reactions and the DSC curves as a function of temperature for Al2O3/PTFE mixtures with Al2O3 according to particle size were measured and the results are shown in Fig. 10. Combined with the phenomenon that the larger the Al2O3 particle size, the smaller the area of the exothermic peak, it can be inferred that only nanoscale Al2O3 reacts with PTFE, and that the reaction heat decreases with an increase in the Al2O3 particle size.
(1) In quasi-static compression tests, because SiC and Al2O3 can effectively inhibit the formation of cracks during compression, the addition of SiC and Al2O3 can significantly enhance the strength of Al/PTFE. The enhancing effect of SiC on the composite strength was stronger than that of Al2O3.
(2) In drop-weight tests, adding ceramic particles to Al/PTFE contributes towards reducing the sensitivity of the reactive composites, and the reducing effect of Al2O3 on the Al/PTFE sensitivity was weaker than that of SiC.
(3) Nanoscale Al2O3 reacts with PTFE to form AlF3, and the reaction heat decreased dramatically with an increase in the Al2O3 particle size. The addition of nanoscale Al2O3 improved the reaction heat and energy density of the composites.
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