Chuanhao Xua,
Chongwei An*ab,
Yanling Longa,
Qianbing Lia,
Hao Guoa,
Shuang Wanga and
Jingyu Wang*ab
aSchool of Environment and Safety Engineering, North University of China, Taiyuan, Shanxi 030051, P. R. China. E-mail: anchongwei@yeah.net; wjywjy67@163.com
bShanxi Engineering Technology Research Center for Ultrafine Powder, Taiyuan, Shanxi 030051, P. R. China
First published on 22nd October 2018
To explore a new manufacturing method in preparing energetic composites, an inkjet printing device possessing the ability of high precision and flexibility was utilized to deposit six 3,4-dinitrofurazanofuroxan (DNTF) and hexogen (RDX) based explosive inks. The printed quality, inner structure, printed density and crystal morphology of energetic composites were tested, as well as their thermal decomposition properties and detonation properties. The results indicate that inkjet printing provides a good formation uniformity for explosive inks. Interestingly, all energetic composites exhibit excellent printed density with all values higher than 90% theoretical maximum density (TMD). Meanwhile, the composite DNTF/RDX/EC/GAP (54/36/5/5) performs best, reaching 96.88% TMD, which has reached a new height in the three-dimensional printing of energetic composites. Further study manifests that there is no appearance of new material, and the stacking manner of rodlike structures in multilayer manufacturing is the key to achieving such an amazing result. The particles in the energetic composites are spherical with the size ranging from 500 nm to 2 μm and connect with each other closely in the matrix of binders. Moreover, the energetic composites that were directly deposited into wedge channels display a good capability in steadily detonating above the size of 1 × 0.32 mm.
At present, there are two charging methods used for loading explosive materials in MEMS safe-arm devices, including direct ink writing (DIW) and inkjet printing.2,3 With the precise stage platform and submillimeter nozzles, explosive materials can be loaded into grooves and holes in MEMS safe-arm devices through DIW and inkjet printing. Moreover, the nozzles and grooves don't contact with each other in the process of charging, which prevents contaminating other parts. Besides, the “wet charge” procedure, whose prepared form of explosive materials is inks during loading, improves the safety to a certain extent.
Nowadays, the commonly used technology is DIW, through which the colloidal suspensions of explosives are extruded out from nozzles and deposited into the channels or substrates to form specific shapes.2 To date, some researchers have made significant efforts in DIW and obtained great achievements,4–8 such as the CL-20 based EDF-11, which has been qualified by US army as a booster explosive.2 However, the development of inkjet printing in depositing explosive materials is relatively slow. Compared to DIW, inkjet printing is simpler for the only thing to do in the preparation of explosive ink is dissolve all desired ingredients into organic solvents. This “one-step, simple” method avoids the issues associated with particle agglomeration, growth, dispersion or clogging, and therefore attracts increasing attention to depositing and patterning energetic materials and energetic materials detection applications.9 For example, from 2011 to 2016, some scientists focused on the printing mechanism by using a DMP-2800 inkjet printer with the materials involving hexogen (RDX) and pentaerythrite tetranitrate (PETN).10,11 Unfortunately, the performances of limited printed samples were not tested due to the unreasonably slow printing speed which hinders the wide application of the inkjet printing technology.
To improve the speed, we have set up a low-cost inkjet printing device which consists of a three-axis platform and a piezoelectric-based nozzle. The assembled device can offer a higher printing speed of 3–10 ml h−1 than that of the reported inkjet printers.3 Based on it, the hexanitrohexaazaisowurtzitane (CL-20) based composite with high performance was printed in 2017.12 The density of samples was 1.7 g cm−3, reaching 86% of theoretical maximum density (TMD). However, the morphology of CL-20 changed to metastable state of β because of the addition of binders, which leads to some restrictions in application. In 2018, we printed the 3,4-dinitrofurazanofuroxan (DNTF) based composites, whose printed density achieved 1.785 g cm−3, 93.16% of TMD.13 In the field of explosive materials, for the same explosive, the strong detonation ability is mainly depended on the high charging density, which is chased in the manufacturing process. That result provided us with a direction in expanding the inkjet printing of explosive materials.
During the experiment of printing explosive ink, there is a process of recrystallization in which the solvent escapes from explosive inks. Compared to other methods, this process enables to easily produce uniform mixtures and even some new structures like co-crystals.14,15 Thus, the explosive inks including DNTF and other organic explosives will be interesting to survey. In this study, DNTF and RDX were selected as main explosives, while the ethyl cellulose (EC) and glycidyl azide polymer (GAP) were designed as binders. All components were dissolved into acetone to prepare particle-free explosive ink, which was deposited to produce energetic composite through inkjet printing devices. The properties of printed samples were tested and analysed.
To ensure the fast evaporation of solvent, aluminum plates which possesses a good thermal conductivity with the thickness of 1 mm were selected to be the substrates in the study. Prior to being used, the substrates were rinsed by deionized water (purchased from Shanxi YiFen Drink and Food Co. Ltd., Taiyuan, China) and then covered by ethanol (AR, produced by Tianjin Fuchen Chemical Reagents Factory, Tianjin, China) in ultrasonic cleaner for 15 minutes. Afterwards, the substrates were rinsed again by deionized water and dried in the oven at 50 °C for 20 minutes.
During the manufacturing, the shape of the final product was determined by the scheduled program in motion platform through which inks were deposited into the substrate and stacked layer-by-layer. The heat supplied by the temperature control platform offers the opportunity for solvent to escape from droplets printed in substrate. Built-in program in this study was a cubic whose length, width and layers were 50 mm, 7.5 mm and 400, respectively. The pulse controlling the volume of droplets was set as 0.3 ms in the study. The circulation in piezoelectric actuator and writing speed of the robot arm that determined the droplets space were set as 5.0 ms and 50 mm s−1, respectively. The distance between the nozzle and substrate was 3 mm so as to avoid the occurrence of satellites droplets. The pressure guaranteeing inks to stable transmit from syringe to nozzle was 0.05 MPa.
In order to prepare the explosive inks with printability, it is necessary to select proper solvent based on the solubility of solutes and evaporation rate. According to these two points, the acetone with the mass fraction of 84.72% was ultimately selected in the inks. The detailed formulations and their physical properties at 25 °C are summarized in Tables 1 and 2, respectively.
Formulations | DNTF | RDX | EC | GAP | Acetone |
---|---|---|---|---|---|
Ink-1 | 13.86 | 0 | 0.71 | 0.71 | 84.72 |
Ink-2 | 12.47 | 1.39 | 0.71 | 0.71 | 84.72 |
Ink-3 | 11.09 | 2.77 | 0.71 | 0.71 | 84.72 |
Ink-4 | 9.70 | 4.16 | 0.71 | 0.71 | 84.72 |
Ink-5 | 8.32 | 5.54 | 0.71 | 0.71 | 84.72 |
Ink-6 | 6.93 | 6.93 | 0.71 | 0.71 | 84.72 |
Formulations | ρ (kg m−3) | η (mPa s) | γ (mN m−1) |
---|---|---|---|
Ink-1 | 880 | 1.2 | 23.33 |
Ink-2 | 860 | 1.0 | 23.09 |
Ink-3 | 906 | 0.8 | 23.77 |
Ink-4 | 850 | 0.6 | 24.15 |
Ink-5 | 884 | 0.8 | 24.52 |
Ink-6 | 897 | 1.3 | 23.66 |
The Z values of inks from ink-1 to ink-6 are 36.94, 44.56, 58.01, 75.51, 58.2 and 35.44, respectively.
To evaluate the fluidic properties of inkjet inks, a dimensionless Fromm number Z, is defined as
(1) |
The images in Fig. 2 display the prepared particle-free explosive inks and their corresponding Z values, where the inks are clear and transparent without any visible particles. These inks can be stored in sealed glass bottles for several days at room temperature and kept stable without the appearance of turbid, crystallization and reduction of weight. The curve of Z values increases to the peak in ink-4, and finally reduces to the minimum in ink-6.
Fig. 3 Pictures of samples in CT tests: (a) is the sample before test; (b–d) are the CT images of (a) in front view, in the angle of 45 degrees and in the angle of 90 degrees, respectively. |
As shown in Fig. 3a, the pale yellow composites with cuboid shape are fixed in plasticene. In CT images, if the samples have poor uniformity, different gray values will be exhibited and the darker points represent the higher density. The gray values in Fig. 3b as well as Fig. 3c and d are uniform without any obvious dark points nor any weak points. The differences between these Fig. 3 in image definition are probably ascribed to the distinction in thickness in which the thickness of tested sample in Fig. 3b is 0.5 mm, while in Fig. 3c is 7.5 mm.
In the field of energetic materials, density is a key parameter in affecting detonation properties. Given that the explosive ink is commonly applied in micro scale explosion chain, printed density should be as high as possible. To obtain the desired explosive effect along the initiation train, a density per unit volume greater than 90% of the TMD is generally required. In this study, the printed cubic was removed from substrate for printed density tests for five times, and the TMD of printed sample for each formulation was calculated by the volume plus method.23 The details are shown in Fig. 4, which displays values of printed density of samples. The curve of printed density increases at first and then decreases reaching the values 1.664, 1.683, 1.693, 1.72, 1.717 and 1.667 g cm−3. Thus, the corresponding stacking ratio that correlated to the printed density and TMD can be calculated as 91.55%, 93.19%, 94.31%, 96.41%, 96.88% and 94.64%, respectively.
Fig. 5 Cross section of printed samples of different formulations: (a) ink-1, (b) ink-2, (c) ink-3, (d) ink-4, (e) ink-5, (f) ink-6. The scale bar is 50 μm. |
Fig. 6 Images of Fig. 5 under a high magnification. The scale bar is 5 μm. |
With a higher magnification, Fig. 6a shows a dendritic structure with spherical particles connected closely at the end of branches in which clearer particles visible in all printed samples. The size of particles appeared is around 500 nm accompanied with an agglomerated lamellar structure. Compared with Fig. 6a, the particles appeared in other samples (Fig. 6b–f) are relatively larger with size ranging from 1 to 2 μm. Among the six patterns in Fig. 6b looks the most flat, while Fig. 6c–f display concave and convex shapes.
Compared with raw materials, the peak intensity of G1 in the six printed samples is gradually weakening, yet G2 and G3 is getting higher and higher. This phenomenon is attributed to the content reduction of DNTF and content accumulation of RDX. Moreover, all peak widths of printed samples in G1 as well as G2 and G3 are higher than those of raw materials, probably because of the refinement of DNTF and RDX particles.24 In the view of diffraction angles, there are no new peaks for printed samples in the image, illustrating that inkjet printing does not have any influence on the crystal form of main explosives. Meanwhile, it also testifies that for printed samples prepared in this study, there are not any new composites such as co-crystals during the inkjet printing.
To probe the forming mechanism, the printed sample of ink-5 was selected to conduct a further observation in which cross section and longitudinal section were prepared by randomly cutting method. As shown in Fig. 8a, there are numerous rodlike composites cluster in the longitudinal section. In a higher magnification (Fig. 8b and c), the diameters of rodlike composites ranging from 2 to 5 μm are comprised of spherical particles with the size staying around 2 μm. In the rod, particles are nearly aligning one-by-one and closely connecting with each other by binders.
Fig. 8 Cross section and longitudinal of the printed sample of ink-5 under different magnification: (a), (b) and (c) are 600, 2000 and 3000 times, respectively. |
In Fig. 9 (insets), the melting point and exothermic peak of raw DNTF are 107.51 °C and 279.12 °C, respectively, while the raw RDX are 206.76 °C and 237.87 °C. The images ranging from a to f in Fig. 9 exhibit the variation of thermal decomposition in which the values of melting points and exothermic peaks both decline. Moreover, there are exothermic phenomena in all curves with the exothermic peak ranging from 180 to 190 °C. Compared with raw DNTF, the melting points of six printed samples advance 1.13, 3.35, 3.48, 3.59, 4.12 and 4.52 °C, respectively. The different values of six printed samples and raw DNTF in exothermic peaks are −18.52, −32.08, −37.38, −38.88, −40.04 and −40.11 °C, respectively.
In this study, four explosive inks including ink-1, ink-2, ink-4 and ink-6 were chosen to explore the rule of main explosives changes under different contents. The optical images of printed samples are shown in Fig. 10a in which flaxen and uniform composites are situated in the channels in aluminum substrates. Then, the substrates were covered by aluminum plates and initiated using 8# electric detonator in the cylindroid charges. After detonation, the aluminum plates can be seen in Fig. 10b in which the width of channels greatly increases with the obvious propagated traces of the shock wave. Based on the explosion trace, the critical size of detonation can be calculated by formula
(2) |
In Fig. 10b, for four printed samples of explosive inks, B can be seen and their values are 2.33, 3.39, 4.39 and 10.55 mm, respectively. Combined with the known A and C, whose values are 100 and 3 mm, respectively, the dc can be obtained by formula (2), and the values are 0.07, 0.102, 0.132 and 0.317 mm, corresponding to the composites of ink-1, ink-2, ink-4 and ink-6.
In density, all printed samples exhibit an amazing stacking ratio which exceeds 90% TMD. Interestingly, the composites of ink-5 including DNTF/RDX/EC/GAP (54/36/5/5) peak among six samples and reach 96.88% TMD. In the field of 3DP for explosive materials, the ratio between actual density and TMD of solidified products in suspended explosive and particle-free explosive inks ranges from 86% to 95%, indicating that the prepared energetic composites have reached a new height.2,5,8,12,13 In further studies, there are no new peaks in XRD curves, which excludes the emergence of new structures in explosive crystals like co-crystals. Moreover, different from the prepared CL-20 based composite in our previous work in which obvious layers trace exhibited in cross section, the DNTF/RDX based printed samples of ink-5 display stronger connection properties between layers based on the rodlike structure formed. These results confirm the forming mechanism of high density, namely, the stacking manner of printed materials plays a key role in determining printed quality.
The composites possessing binary explosives perform better than the single one in printed density though the crystal density of RDX is lower than that of DNTF. In the view of inner structure, there are some printing traces left in the printed samples of ink-1 (without RDX, Fig. 5a), ink-2 (Fig. 5b) and ink-3 (Fig. 5c), where stratified structures are visible along with some holes. However, with the increasing content of RDX, this phenomenon is gradually disappearing. This effect, then, is hypothesized to be caused by a combination of effects including (a) the increasing saturation of explosive inks involving RDX, which is the result of poor solubility of RDX in acetone, and (b) the intermolecular forces between RDX and DNTF particles. In manufacturing, it will be easier for the explosive inks including RDX to approach saturation and precipitate in the thermal field. Due to the fact that the higher content of RDX for explosive inks will precipitate faster and the evaporation process of solvent will become shorter, then, there is not enough time left for filling air when ink droplets reach the solidified composite in the upper layer, resulting in a dense appearance. Moreover, there are interactions between DNTF and RDX during forming composites in which intermolecular forces affect the arrangement of particles. When the weight ratio between DNTF and RDX in the composite is 6:4, namely the printed samples of ink-5, the intermolecular forces may reach the maximum, leading to an amazing result.
For the printed samples of ink-1, the reduction of exothermic peak temperature in Fig. 9 may be attributed to the addition of EC because of the inexistence of energetic structure. This speculation has also been proved in other researcher's study in which GAP and DNTF had a good compatibility.19 Compared with curve a (Fig. 9), the advanced exothermic peaks from b to f are more obvious, which is ascribed to the addition of RDX. As shown in curves from b to f, the melting point of RDX does not appear at 206.76 °C, which indicates that RDX decomposes slowly in the liquid DNTF. The decomposition products obtained further accelerate the decomposition of DNTF.28 These results imply that the printed energetic composites containing RDX possess a higher activity in the thermal sensitivity.
In the critical size of detonation, the minimum value of composites formed by ink-1 is mainly attributed to the reduction of the particle size and the lower critical diameter of detonation of DNTF. As the particle sizes are similar, the main reason for the growth of dc with the increasing content of RDX among other three samples, lies in the difference between DNTF and RDX themselves in critical diameter.29 Meanwhile, it can be speculated that the critical sizes of detonation for energetic composites of ink-3 and ink-5 are mostly lower than those of ink-6. Thus, all energetic composites prepared in this study can provide a steady detonation above the charge size of 1 × 0.32 mm, which contributes to the application in micro scale channels and conforms to the trend of smart weapon systems.
This journal is © The Royal Society of Chemistry 2018 |