ZHANG Rong-xian, ZHONG Xiao-sheng, LU Xiao-gang, KE Zhi-jiang,XU Jun，CHENG Jian, LIU Zu-liang

(1. School of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang 212013, China;2.Reading Academy, Nanjing University of Information Science & Technology, Nanjing 210044, China;3. Jiangsu Research Institute of High-Performance Alloy Material, Danyang 212300, China;4. School of Education Science and Technology, Zhejiang University of Technology, Hangzhou 310014, China;5. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China)

Synthesis, characterization and catalytic effect on thermal decomposition of AP: an eco-friendly energetic Bi(III) complex of ANPyO①

ZHANG Rong-xian1, ZHONG Xiao-sheng2, LU Xiao-gang1, KE Zhi-jiang1,XU Jun3，CHENG Jian4, LIU Zu-liang5

(1. School of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang 212013, China;2.Reading Academy, Nanjing University of Information Science & Technology, Nanjing 210044, China;3. Jiangsu Research Institute of High-Performance Alloy Material, Danyang 212300, China;4. School of Education Science and Technology, Zhejiang University of Technology, Hangzhou 310014, China;5. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China)

In this research, an eco-friendly, energetic Bi(III) complex of 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO) was synthesized and its structure was characterized by FTIR, elemental analyses and XPS measurements. Based on the results of structure analyses, we speculate that chemical constitution of the complex can be deduced as Bi(C5H4N5O5)3, and the ratio of Bi(III) and ANPyO is 1∶3. The central Bi(III) ion contributes its six empty orbitals to accommodate the long pair electrons from the imine N atoms and N→O O atoms from three different deprotonated ANPyO molecules. Impact sensitivity, friction sensitivity and shock wave sensitivity of Bi(III) complex of ANPyO are 220 cm, 36 kg and 5.8 mm, respectively. The thermal decomposition behavior of Bi(III) complex of ANPyO was studied by TG-DTG and DSC measurements. The thermal decomposition of the complex consists of one endothermic (320.6 ℃) and one exothermic (346.5 ℃) peaks in the temperature range of 50～450 ℃ with 31.2% residue. Meanwhile, the catalytic performance of the complex on the thermal decomposition of ammonium perchlorate (AP) was analyzed by TG-DTG and DSC analyses, the apparent activation energy and pre-exponential factor of pure AP and AP mixture in the low temperature decomposition stage and high temperature decomposition stage were calculated by Kissinger's formula as well. The results show that Bi(III) complex of ANPyO makes the exothermic peak temperatures and activation energy values of high temperature decomposition stage and low temperature decomposition stage for AP decrease by 63.6 ℃, 63.1 ℃, 23.1 kJ/mol and 61.5 kJ/mol, respectively, the apparent exothermic quantity for AP increase by 339.3 J/g, revealing that the complex has good catalytic effects on the thermal decomposition of AP.

energetic complex；ANPyO；sensitivity；thermal decomposition；catalytic effects

DIO:10.7673/J.ISSN.1006-2793.2017.04.009

0 Introduction

Highly energetic materials have received considerable attention due to their outstanding properties, such as high energy, high density, high heat resistance, and low sensitivity. Therefore, they can be used extensively in advanced conventional weapons, rocket propellants, demilitarization and industrial applications. There is tremendous interest in developing efficient methods to synthesize these molecules, and a well-known method was proposed to constitute the synthesis of 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO)[1]by Ritter and Licht in 1995. ANPyO is a realistic, high-performance energetic material which is thermally stable and insensitive to shock, spark and friction[2], with similar performance, stability and sensitivity to that of 2,4,6-triamino-1,3,5-trinitrobenzene (TATB). ANPyO belongs to a multi-amino, multi-nitro-heterocyclic N-oxide with structure units —N→O and —NH2. It may form stable complexes with a large number of metal ions similar to quinoxaline N1,N4-dioxide[3-4].

In accordance with previous studies on metal complexes of quinoxaline N1,N4-dioxide derivatives, we selected metals including Cu(II)[5], Co(III)[6], Fe(III)[6], Pb(II)[7]to construct novel ANPyO-based coordination compounds with similar structures to metal complexes of quinoxaline N1,N4-dioxide derivatives. As an interesting new family of energetic complexes, the metal complexes of ANPyO may be used in explosives, propellants and energetic catalysts due to their low sensitivity, high heat resistance, high energy and good catalytic performance on the thermal decomposition of ammonium perchlorate (AP)[5-7]. The asymmetric unit of these metal complexes comprises one central metal canon and two or three deprotonated ANPyO anions. Each central metal canon has a distorted octahedron, coordinated by nitrogen and oxygen from deprotonated ANPyO. This unique coordination mode that ligands direct coordinates with metal ions without additional anions or cations could stabilize entire molecular complexes.

Bismuth compounds have been widely used in clinics due to their effectiveness and low toxicity in treating a variety of microbial infections, as well as their anti-cancer and radio-therapeutic properties[8-10]. Moreover, they show excellent catalytic performance in the thermal decomposition of double-base (DB) propellants due to their modifying effects on lead compounds. In recent years, bismuth compounds have been used as eco-friendly ballistic modifiers[11-15]. They do not produce blue smoke during combustion, and are therefore useful in lead and mercury minimum-signature propellants[16].

This study developed a new strategy for the synthesis and characterization of Bi(III) complex of ANPyO (Bi-ANPyO). The sensitivity, thermal decomposition behavior and catalytic performance of Bi-ANPyO were also studied and discussed.

1 Experiment

1.1 Materials and instruments

All chemicals used were analytical grade, and purchased from commercial sources without further purification. FTIR spectra were recorded on a Nicolet-10 infrared spectrometer as KBr pellets with absorption in cm-1. Elemental analysis was performed on a Vario EL III instrument (Elmentar Analysen Systeme GmbH, Germany). XPS was performed with an American Thermo ESCALAB 250 electron spectrometer using Al Kαradiation.

DSC studies were performed on a DSC823e METTLER TOLEDO with heating rates of 10 K/min, respectively. TG-DTG analysis was conducted on TGA/SDTA851eMETTLER TOLEDO with a heating rate of 10 K/min, in a flow of dry oxygen-free nitrogen at 30 ml/min.

The friction sensitivity was measured by applying a Julius Peter apparatus following the BAM method[17]. Impact sensitivity was determined with the Bruceton method on the standard fall hammer apparatus, and the compacted sample was hit with a 2.5 kg drop hammer on the apparatus[18]. Shock sensitivity was determined by a designed shock sensitivity apparatus[19].

1.2 Synthesis

1.2.1 Synthesis of ANPyO

ANPyO was prepared according to the literature[1]. Anal. Calcd.(%):C,27.89; H, 2.32; N, 32.54. Found: C, 27.77; H, 2.35; N, 32.75.

1.2.2 Synthesis of Bi-ANPyO

BiCl3(0.315 g, 1.0 mmol) was added into a solution of ANPyO (0.215 g, 1.0 mmol) in ethanol (20 ml) at 80 ℃ for 2 h, then cooled to room temperature and filtered, washed with ethanol and dried in air. An orange-yellow solid powder (0.24 g) was formed in a 85.56% yield (based on ANPyO). Anal. Calcd.(%):C, 21.15;H, 1.41;N, 24.67. Found: C, 21.18; H, 1.45; N, 24.15.

2 Results and discussion

2.1 Chemistry

Elemental analysis(%) of Bi(III) complex of ANPyO: Calcd: C, 21.15; H, 1.41; N, 24.67. Found: C, 21.18; H, 1.45; N, 24.15.The chemical constitution of Bi-ANPyO can be deduced as Bi(C5H4N5O5)3.

The FTIR spectra curves of ANPyO and its Bi(III) complex were illustrated in Fig.1. The main vibration bands relative to coordination for the ANPyO and its Bi(III) complex were shown in Table 1.

The FTIR spectra of the Bi-ANPyO (Fig.1) show a similar pattern to those previously reported for metal complexes in the family of quinoxaline N1,N4-dioxide[3-4]. Both strong bands corresponding toVas(NH2) andVs(NH2) of the amino group of 2-position, locates for the ANPyO in the 3448 cm-1and 3283 cm-1region, disappears after coordination. Only one band (V(NH) of medium intensity with 3369 cm-1is observed, in agreement with the presence of a secondary amine.Vas(NH2) andVs(NH2) of the amino group of the 6-position, locates for the ANPyO in the 3448 cm-1and 3283 cm-1region turns to medium after coordination without a significant displacement. The strongV(N→O) stretching mode, locates 1325 cm-1for the ANPyO, also turns to medium after coordination without a significant displacement. As previously reported[3-4], this behavior might support coordination of the ANPyO to Bi(III) through the N→O group and the deprotonated amino group.

Table 1 Main FTIR bands of ANPyO and its Bi(III) complex

V:stretching;Vas:asymmetric stretching;Vs:symmetric stretching;s:strong;m:medium.

The chemical composition of Bi-ANPyO can be further confirmed by XPS measurement. As shown in Fig.2(a), in which discloses the presence of C, N, O and Bi, respectively. XPS spectrum of Bi-ANPyO also exhibits six peaks at 679.2, 465.7, 442.3, 164.7, 160.8 and 24.9 eV, corresponding to Bi4p3, Bi4d3, Bi4d5, Bi4f5, Bi4f7 and Bi5d5 spin-orbit of Bi-ANPyO, respectively, which confirm the formation of bismuth. The presence bismuth can be further confirmed by N 1s and O 1s XPS spectrums of Bi-ANPyO in Fig.2(c) and Fig.2(d), respectively, in which the characteristic peaks are close to 398.2 (Bi-N) and 529.9 (Bi-O) eV. This confirms the formation of Bi-N and Bi-O bonds in the molecular structure of Bi-ANPyO. From Fig.2(b), C 1s XPS spectrum of Bi-ANPyO shows four types of carbon with different chemical states observed, which appear at 283.5(C—H), 284.3(CC), 284.8(C—N) and 286.4 eV(CN), respectively. Fig.2(c) and Fig.2(d) also exhibit the N 1s and O 1s XPS spectrums of Bi-ANPyO, six types of nitrogen and three types of oxygen with different chemical states observed, which appear at 398.2(N—Bi), 398.7(N—H), 401.1(N—C, NC), 404.2(N—O, N→O), 406.0(N—O, NO2), 529.9(O—Bi), 531.2(O—N, N→O) and 533.8 eV(O—N, NO2), respectively. The above results are in agreement with the chemical composition of Bi-ANPyO that we speculated, which are close to the our early study about Co(III) complex of ANPyO.

The elemental analysis, FTIR and XPS measurements and analyses of Bi-ANPyO might indicate that the central Bi(III) ion contributes its six empty orbitals to accommodate the long pair electrons from the imine N atoms and N→O O atoms from three different deprotonated ANPyO molecules.

2.2 Sensitivity

In order to study the stability and hazardous nature of the Bi-ANPyO, we tested the sensitivity properties of the ANPyO and its Bi(III) complex, and compared this with that of TATB and Co(III), Fe(III) complexes of ANPyO. The results were shown in Table 2.

ANPyO belongs to a multi-amino, multi-nitro-heterocyclic compound with the molecular structure of symmetry. The intramolecular, intermolecular hydrogen bonds are formed by the amino and nitro groups[20]. The molecular structure of ANPyO is planar, which is similar to the structure of graphite. When the ANPyO is stimulated by the external energy, the energy can flow in the entire planar, reducing the energy stimulus on the single ANPyO molecule. At the same time, the planar structure is similar to graphite, and can be used as a boundary lubricant. It can effectively reduce friction between interfaces and particles, as well as the probability of hot spot occurrence. This is the main reason for the lower sensitivity of ANPyO. In addition, the π-electron conjugated effect and the amino donor effect are also responsible for the low sensitivity of ANPyO.

Table 2 Sensitivity test results of ANPyO and its Bi(III) complex

CompoundImpactsensitivity/cmFrictionsensitivity/kgshocksensitivity/mmANPyO252365.6Bi(ANPyO)3220365.8Fe(AN-PyO)3272365.8Co(AN-PyO)3276365.8TATB320364.5

When ANPyO forms energetic complexes with metals, i.e., Co(III), Fe(III), Pb(II), the crystal structure of the energetic complexes relative to ANPyO experienced two alterations. On one hand, when the crystal structure of the energetic complexes went from the ANPyO plane layered structure to the three-dimensional network structure, the intermolecular hydrogen bonds became weak. This is not condutive to reducing sensitivity of the energetic complexes. On the other hand, the unique coordination mode of the ANPyO direct coordinate with metals without additional anion or cation stabilizing the entire molecular complex. This helps to reduce the sensitivity of the energetic complexes. The sensitivity of the energetic complexes changes in the relative ANPyO depending on the combined results of two aspects. Our early study shows that Co(III), Fe(III) complexes of ANPyO exhibit lower sensitivity compared to that of ANPyO. From the analysis above, we deduce that the form of coordinate bonds and chelation might be the main reasons for the lower sensitivity in the Co(III) and Fe(III) complexes. As shown in Table 2, the impact sensitivity, friction sensitivity and shock wave sensitivity of Bi-ANPyO are 220 cm,36 kg and 5.8 mm, respectively. This clearly indicates that the sensitivity of Bi-ANPyO increases slightly compared to that of ANPyO. From the above analysis, we deduce that the form of Bi(III) might be the main reasons for the higher sensitivity in the Bi-ANPyO.

2.3 Thermal decomposition behavior

DSC and TG-DTG measurements were conducted to identify the thermal behavior of Bi(III) complex of ANPyO. DSC and TG-DTG curves of Bi(III) complex of ANPyO under the linear heating rate of 10 K/min were shown in Fig.3 and Fig.4.

As shown in Fig.3, the thermal decomposition of the Bi(III) complex is divided into three stages. The first step is a slow weight loss process, with 26.2% mass loss from the initial mass in the temperature range of 264.9～331.4 ℃, which reaches the largest rate at 313.6 ℃. Corresponding to the DSC curve of the Bi(III) complex, which shows that there is one endothermic peak in the first step, within the range of 259.6～330.5 ℃.This is the endothermic decomposition process, with an endothermic peak of 320.6 ℃. The second step is a fast weight loss process, with 25.1% mass loss from the initial mass in the temperature range of 331.4～402.3 ℃, which reaches the largest rate at 350.9 ℃. Corresponding to the DSC curve of the Bi(III) complex, which shows that there is one exothermic peak in the second step, with the range of 330.5～364.5 ℃. A sharp exothermic peak is shown in the DSC curve with a peak temperature of 346.5 ℃. The third step is a slow weight loss process with 17.5% mass loss from the initial mass in the temperature range of 402.3～518.2 ℃, which reaches the largest rate at 467.2 ℃. The DSC curve of the Bi(III) complex shows that there is no obvious change in the third step. The mass fraction of the final residue is 31.2%, calculating that the final decomposition product might be Bi2O3.

2.4 Catalytic effects on the thermal decomposition of AP

2.4.1 TG-DSC analyses

AP is the common oxidizer in composite solid propellants, and its thermal decomposition characteristics greatly influence the combustion behavior of solid propellants[21-22]. In order to provide theoretical support to further performance studies combustion catalysts, this study explore how the Bi(III) complex of ANPyO promotes thermal decomposition of AP. The catalytic performance of the complex on the thermal decomposition of AP was analyzed by TG-DTG and DSC measurements, and the results were shown in Fig.5, Fig.6 and Fig.7 (complex and AP were mixed at a mass ratio of 5∶95).

Results of the TG-DTG measurements of pure AP and AP with 5% Bi(III) complex of ANPyO were shown in Fig.5 and Fig.6, respectively. As shown in Fig.5, the thermal decomposition of pure AP occurs in two weight loss steps. The 21% weight loss at low temperature(264.3～345.1℃) is attributed to the partial decomposition of AP. The 79% weight loss at high temperature(345.1～409.7℃) is caused by the complete decomposition of the intermediate to volatile products. The TG-DTG curves for the thermal decomposition of AP in the presence of Bi(III) complexes of ANPyO are shown in Fig.6. As shown in Fig.6, there are noticeable changes in the decomposition pattern. The thermal decomposition of AP catalyzed by Bi(III) complex of ANPyO contains only one step, corresponding to 98.5% weight loss. AP is completely decomposed at the lower temperature in a shorter time.

The DSC curves for pure AP and AP in the presence of Bi(III) complex of ANPyO were also shown in Fig.7. The endothermic peak at 242.3 ℃ is due to a crystallographic transition. The exothermic peaks at 332.2 ℃ and 432.5 ℃ in Fig.7 are attributed to the low-temperature decomposition (LTD) process and the high-temperature decomposition (HTD) process of AP, corresponding to the two weight loss steps. The DSC curve of AP in the presence of Bi(III) complexes of ANPyO shows that the Bi(III) complex of ANPyO additive has no effects on the crystallographic transition temperature, but leading to significant changes in the decomposition pattern.

The exothermic band of the system of the Bi(III) complex of ANPyO with AP had one broad peak and two flat peaks, suggesting a complicated mechanism of decomposition. The HTD peak of the mixture system (368.9 ℃) is 63.6 ℃, which is lower than of pure AP. The LTD peak of the mixture system (269.1 ℃) is 63.1 ℃, which is lower than of pure AP. Furthermore, the decomposition heat of the mixture systems (825.6 J/g) is 339.3 J/g higher than the corresponding value of pure AP.

2.4.2 Non-isothermal reaction kinetics

Kinetic parameters of the overall decomposition processes of pure AP[23]and AP in the presence of Bi(III) complex of ANPyO, calculated by the Kissinger's method[24], were given in Table 3. Specifically, for pure AP (Table 3), the calculated activation energies (Ek) of the LTD and HTD are 173.9 and 185.6 kJ/mol, respectively. However, in the presence of the Bi(III) complex of ANPyO additive, theEkof the AP decomposition in the LTD and HTD processes considerably decreases to 112.4 and 162.5 kJ/mol, respectively. The above results indicate that Bi(III) complex of ANPyO not only influences the primary dissociation of AP, but also accelerates the completely decomposition of AP. Clearly, Bi(III) complex of ANPyO exhibits a better catalytic activity on AP, which is consistent with the TG-DSC results. Furthermore, as shown in Table 3, Bi(III) complex of ANPyO significantly increases the overall heat in the HTD and LTD processes during the decomposition of AP.

It can be inferred that the Bi(III) complex of ANPyO decomposes and releases a large amount of heat itself. This enhances the total heat of the mixture, as well as the formation of Bi2O3at the nano-sized level on the AP surface[23], which may contribute to its catalytic effect on the thermal decomposition of AP. Obviously, AP decomposition is accelerated in the presence of the Bi(III) complex of ANPyO.

Table 3 Kinetic parameters of pure AP and AP mixtures in LTD and HTD processes calculated by the Kissinger's method

3 Conclusions

In conclusion, this study demonstrate a facile strategy to prepare for an energetic Bi(III) complex of ANPyO, and characterize its structure with FTIR spectroscopy, elemental and XPS analyses. The complex formula is Bi(C5H4N5O5)3. Tests on impact sensitivity, friction sensitivity and shock wave sensitivity of the complex reveal that the complex is slightly more sensitive to mechanical stimuli than ANPyO. TG-DTG and DSC analyses show that the thermal decomposition of the complex consists one endothermic and one exothermic peaks in the temperature range of 50～450 ℃ with 31.2% residue. TG-DTG and DSC analyses show that the complex exhibits good catalytic effects on the thermal decomposition of AP.

Acknowledgements

We gratefully acknowledge the financial support from Nanjing University of Science and Technology and Xi'an Modern Chemistry Research Institute. This work is supported by Five-Year (2011～2015) Pre-research Project (NO.62201070102) and Doctoral Innovation Program Foundation of Jiangsu Province (CXLX12 0646).

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(編輯：薛永利)

ANPyO Bi(III)含能配合物的合成、表征、熱分解行為及其對高氯酸銨熱分解的催化作用

張蓉仙1，鐘笑笙2，陸小剛1，柯志江1， 徐 駿3，成 健4，劉祖亮5

(1.江蘇大學 化學化工學院，鎮(zhèn)江 212013；2.南京信息工程大學 雷丁學院，南京 210044；3.江蘇高性能合金材料研究院，丹江 212300；4.浙江工業(yè)大學 安全科學與工程系，杭州 310014；5.南京理工大學 化工學院，南京 210094)

合成了2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO) Bi(III)含能配合物，采用FTIR、元素分析和XPS光電子能譜表征了含能配合物的結構。根據(jù)結構表征結果推測，ANPyO Bi(III)含能配合物的分子式為Bi(C5H4N5O5)3，金屬離子與配體的配比為1∶3。其中，可能的配位方式為：每個配體ANPyO 2-位的氨基脫去一個氫原子，分別以NH和N→O結構單元中N原子和O原子與Bi(III)形成配位鍵。ANPyO Bi(III)含能配合物的撞擊感度、摩擦感度和沖擊波感分別為220 cm、36 kg和5.8 mm。采用TG-DTG和DSC測試考察了ANPyO Bi(III)含能配合物的熱分解行為，配合物在50～450 ℃范圍內(nèi)熱分解過程由一個吸熱熔融峰和分解放熱峰組成，相應的峰溫分別為320.6 ℃和346.5 ℃，配合物熱分解剩余殘渣量為31.2%。同時，考察了配合物對高氯酸銨熱分解的催化作用，并采用Kissinger法對純AP和AP混合物熱分解過程低溫分解階段和高溫分解階段的表觀活化能和指前因子進行了計算。結果表明，ANPyO Bi(III)含能配合物可使高氯酸銨高溫分解階段和低溫分解階段的峰溫提前63.6 ℃和63.1 ℃，表觀活化能降低23.1 kJ/mol和61.5 kJ/mol，表觀分解熱增加339.3 J/g?？砂l(fā)現(xiàn)，ANPyO Bi(III)含能配合物對AP的熱分解具有顯著的催化作用。

含能配合物；ANPyO；感度；熱分解行為；催化作用

date：2015-12-25；Revised date：2016-10-09。

V512 Document Code:A Article ID:1006-2793(2017)04-0448-08

Biography：Zhang Rong-xian(1966—),female, doctor, specialty: The flow field and thermal structure of solid rocket motor。E-mail：rong@ujs.edu.cn