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关晓鸽,李静,李彦峰等.亚甲基二硝基胍(BNGM)的热行为[J].含能材料,XXXX,XX(XX):653-658.

GUAN Xiao-ge,LI Jing,LI Yan-feng,et al.Thermal Behaviors of Bis(nitroguanidine)methane (BNGM)[J].Chinese Journal of Energetic Materials（Hanneng Cailiao）,XXXX,XX(XX):653-658.

亚甲基二硝基胍(BNGM)的热行为

  • 关晓鸽1

    机 构：西北大学化工学院，陕西 西安 710069

  • 李静1

    机 构：西北大学化工学院，陕西 西安 710069

  • 李彦峰1

    机 构：西北大学化工学院，陕西 西安 710069

  • 徐抗震1

    机 构：西北大学化工学院，陕西 西安 710069

    角 色：

  • 宋纪蓉1

    机 构：西北大学化工学院，陕西 西安 710069

  • 赵凤起2

    机 构：西安近代化学研究所，陕西 西安 710065

（1. 西北大学化工学院，陕西 西安 710069； 2. 西安近代化学研究所，陕西 西安 710065）

网络出版日期: 2018-05-08

Thermal Behaviors of Bis(nitroguanidine)methane (BNGM)

  • GUAN Xiao-ge1

    机 构：西北大学化工学院，陕西 西安 710069

  • LI Jing1

    机 构：西北大学化工学院，陕西 西安 710069

  • LI Yan-feng1

    机 构：西北大学化工学院，陕西 西安 710069

  • XU Kang-zhen1

    机 构：西北大学化工学院，陕西 西安 710069

    角 色：

  • SONG Ji-rong1

    机 构：西北大学化工学院，陕西 西安 710069

  • ZHAO Feng-qi2

    机 构：西安近代化学研究所，陕西 西安 710065

（1. School of Chemical Engineering, Northwest University, Xi′an 710069, China； 2. Xi′an Modern Chemistry Research Institute, Xi′an 710065, China）

Pubdate: 2018-05-08

    摘要

    为进一步评估亚甲基二硝基胍(BNGM)的热稳定性，采用差示扫描量热法(DSC)，微量热仪，热重-微分热重分析(TG／DTG)和撞击实验，研究了BNGM的热分解行为、比热容、绝热至爆时间,并测试了其撞击感度。结果表明： BNGM的热行为分为两个放热分解过程，10 ℃·min-1下两个分解过程的峰温分别为208.1 ℃和292.5 ℃，其自加速分解温度和热爆炸临界温度分别为189.6 ℃和190.9 ℃，298.15 K时摩尔热容为251.9 J·mol-1·K-1，估算绝热至爆时间约为280 s，撞击感度大于23.5 J，表明BNGM热稳定性良好。

    Abstract

    To further evaluate the thermal stability of bis(nitroguanidine)methane (BNGM) and explore its potential application as energetic material, the thermal behavior, specific heat capacity, adiabatic time-to-explosion and impact sensitivity of BNGM were studied by differential scanning calorimetry（DSC）, micro-DSC, thermogravimetry /differential thermogravimetry(TG/DTG) and impact experiment. Results show that the thermal behavior of BNGM can be divided into two exothermic decomposition processes. The peak temperatures of the two decomposition processes at a heating rate of 10 ℃·min-1 are 208.1 ℃ and 292.5 ℃, respectively. Its self‑accelerating decomposition temperature (TSADT) and critical temperature of thermal explosion (Tb) are 189.6 ℃ and 190.9 ℃, respectively. Its molar heat capacity at 298.15 K is 251.9 J·mol-1·K-1. Adiabatic time-to-explosion is estimated to be about 280 s. BNGM has a low impact sensitivity, which is higher than 23.5 J. The thermal stability of BNGM is good.

    GUAN Xiao-ge， LI Jing， LI Yan-feng， et al. Thermal Behaviors of Bis(nitroguanidine)methane (BNGM)[J]. Chinese Journal of Energetic Materials（Hanneng

    Cailiao）,2018,26(8):653-658.

    10.11943/CJEM.F001html/hncl/CJEM2017342/media/8ba85d47-4efc-490b-b1c1-caa0b93cce1b_image3.jpg

  • 1 Introduction

    1

    Compounds containing nitroxyl group (N—NO2) are of interest for practical use as energetic materials owing to their high energy density and nitrogen content [1,2,3,4]. Nitroguanidine (NG) is a simple nitroxyl compound. The effect of electron withdrawing of nitro group makes the lower electron density in the single carbon atom, so NG can behave as an active starting material in the reactions with nucleophilic reagents to get a series of NG-based energetic materials [5,6,7,8,9]. Because of the excellent property and low cost, NG has become an important moiety to design and synthesize other new high-nitrogen energetic materials [6,7,8,10,11,12].

    Bis(nitroguanidine)methane (BNGM) was reported firstly by Yu et al[13] through the reaction of NG and formaldehyde. BNGM was considered as an important intermediate to synthesize other heterocyclic compounds because of the existence of C NNO2 and —NH2 groups. It is remarkable to note that when BNGM was treated with nitric acid/acetic anhydride, 2,4-dinitramino-1,5-dinitro-1,3,5-triazine was obtained [13,14,15,16]. Namely, the deammoniation cyclization and the nitration of cyclized product occurred simultaneously. 2,4-Dinitramino-1,5-dinitro-1,3,5-triazine is a nitrogen-rich explosive with slight positive oxygen balance. Unfortunately, its stability decreased obviously in comparison to that of BNGM. Containing two explosive groups ( C N—NO2) and possessing good thermal stability will make BNGM serve as an appropriate candidate of energetic materials.

    In this paper, we mainly report the thermal behavior, specific heat capacity and adiabatic time-to-explosion of BNGM, further estimating its thermal stability and exploring essential application values as an energetic material. The difference of thermal behavior between the parent material and BNGM is also discussed.

  • 2 Experimental

    2

  • 2.1 Synthesis

    2.1

    The parent materials were purchased from the trade, and formaldehyde was AR grade product. The purity of nitroguanidine was 98% and the concentration of hydrochloric acid was 38%. BNGM was prepared according to Ref [15] and the synthetic route of BNGM was showed in Scheme 1. 1H NMR (DMSO-d6, 500 MHz): 8.157, 4.597, 3.345. 13C NMR (DMSO-d6, 500 MHz): 159.532, 73.329. IR (KBr, ν/cm-1): 3319, 3180, 1586, 1542, 1367, 1252, 983, 719. Anal. calcd for C3H8N8O4 (%): C 16.36, H 3.64, N 50.91; Found: C 16.45, H 3.74, N 51.17.

    Scheme 1 Synthetic route of BNGM

  • 2.2 Experimental Measurements

    2.2

    The differential scanning calorimetry (DSC) experiments were performed using a DSC200 F3 (NETZSCH, Germany) apparatus under a nitrogen atmosphere with a flow rate of 80 mL·min-1. The heating rates were 5.0, 7.5, 10.0, 12.5 ℃·min-1 and 15.0 ℃·min-1 from ambient temperature to 350 ℃, respectively. The thermogravimetry/differential thermogravimetry (TG/DTG) experiment was determined using a SDT-Q600 apparatus (TA, USA) under a nitrogen atmosphere at the flow rate of 100 mL·min-1. The heating rate used was 10.0 ℃·min-1 from ambient temperature to 500 ℃. The specific heat capacity was determined using a Micro-DSCⅢ apparatus (SETARAM, France), and the sample mass was 196.9 mg. The heating rate used was 0.15 ℃·min-1 from 10 ℃ to 80 ℃. Energy of combustion was determined by IKA C5000 oxygen-bomb calorimeter (German) adiabatically. The calorimeter was calibrated with the standard substance benzoic acid having a purity of 99.99%, and the sample was tested with 6 times. The impact sensitivity was determined by using a ZBL-B impact sensitivity instrument (Nachcn, China). The mass of drop hammer was 2.0 kg, and the sample mass for test was 30 mg.

  • 3 Results and Discussion

    3

  • 3.1 Thermal Decomposition Behavior

    3.1

    Typical DSC and TG-DTG curves (Fig.

    html/hncl/CJEM2017342/alternativeImage/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-F002.jpg

    a. DSC

    html/hncl/CJEM2017342/alternativeImage/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-F003.jpg

    b. TG/DTG

    Fig. 1 Typical DSC curves of BNGM and NG and TG/DTG curves of BNGM at a heating rate of 10 ℃·min-1

    1) indicate that the thermal behavior of BNGM can be divided into two exothermal decomposition processes. The onset temperature, peak temperature and decomposition enthalpy at a heating rate of 10 ℃·min-1 are 205.7 ℃, 208.1 ℃ and 303.3 J·g-1 with a mass loss of about 32.2% for the first decomposition process, and 276.4 ℃, 292.5 ℃, 172.0 J·g-1 with a mass loss of about 31.7% for the second process, respectively. The final residue is about 25.4% at 400 ℃. The DSC curve of NG was also obtained, and there is an endothermic peak as a melting peak at 249.2 ℃. Subsequently, an intense exothermic process occurred at 254.5 ℃ for NG. It can be seen that the DSC curves of NG and BNGM are obviously different. Although BNGM possesses a good thermodynamic stability, it is lower than that of NG and the reason should be the new unstable —NH—CH2—NH— bond of BNGM molecule.

    Table 1 The values of T0, Te, Tp and kinetic parameters of the first decomposition process for BNGM

    β/ ℃·min-1T0 /℃Te/℃Tp / ℃-ΔHd/J·g-1EK / kJ·mol-1log(A /s-1)rKEO/kJ·mol-1rO
    5.0165.3200.1202.6225230.4023.300.9999226.690.9999
    7.5167.2203.4205.9251
    10.0169.8205.8208.1294
    12.5171.5207.6209.9250
    15.0172.8209.1211.5243

    E is the apparent activation energy. A is the pre-exponential constant. r is the linear correlation coefficient. Subscript K is data obtained by Kissinger′s method. Subscript O is data obtained by Ozawa′s method.

    In order to obtain the kinetic parameters (the apparent activation energy (E) and pre-exponential constant (A)) of the first exothermic decomposition process, a multiple heating method (Kissinger′s method [17] and Ozawa′s method [18]) was employed according to the data in Fig.2. The determined values of the beginning temperature (T0), extrapolated onset temperature (Te) and peak temperature (Tp) at different heating rates are listed in Table 1. The values of T00 and Te0 corresponding to heating rate β→0 obtained by Eq.(1) are 164.1 ℃ and 189.6 ℃[19].

    T ( 0 o r e ) i = T ( 00 o r e 0 ) + n β i + m β i 2 + p β i 3 , i = 1 - 5
    (1)

    where n , m and p are coefficients.

    The calculated values of kinetic parameters (E and A) are listed in Table 1. E obtained by Kissinger′s method is consistent with that by Ozawa′s method. The linear correlation coefficients(r) are all close to 1. So the results are credible.

    The self-accelerating decomposition temperature (TSADT) and critical temperature of thermal explosion (Tb) are two important parameters required in evaluation of their safe storage and process operations for energetic materials and then to evaluate the thermal stability. TSADT and Tb for BNGM are calculated as 189.6 ℃ and 190.9 ℃, respectively [19,20], indicating that the thermal stability of BNGM is good

    Fig. 2 DSC curves of BNGM at different heat rates

  • 3.2 Specific Heat Capacity

    3.2

    Figure 3 shows the determination result of specific heat capacity (cp) for BNGM, using a continuous specific heat capacity mode of apparatus. It can be seen that cp presents a good linear relationship with temperature in determined temperature range. Specific heat capacity equation is shown as:

    cp=0.1763+3.2461×10-3 T (285.0 K＜T＜350.0 K)(2)

    The specific heat capacity and molar heat capacity of BNGM are 1.15 J·g-1·K-1 and 251.9 J·mol-1·K-1 at 298.15 K, respectively

    Fig. 3 Determination results of the continuous specific

    heat capacity for BNGM

  • 3.3 Adiabatic Time-to-explosion

    3.3

    The adiabatic time-to-explosion is also an important parameter for evaluating the thermal stability of energetic materials and can be calculated by Eqs. (3) and (4) [19,21,22,23,24,25].

    c p d T d t = Q A e x p ( - E / R T ) f ( α )
    (3)
    α = ∫ T 0 T c p Q d T
    (4)

    where cp is the specific heat capacity, J·mol-1·K-1; T is the absolute temperature, K; Q is the exothermic values, J·mol-1; A is the pre-exponential factor, s-1; E is the apparent activation energy of the thermal decomposition reaction, J·mol-1; R is the gas constant, J·mol-1·K-1; f(α) is the most probable kinetic model function and α is the conversion degree.

    After integrating of Eq. (3), the adiabatic time-to-explosion equation can be obtained as:

    t = ∫ 0 t d t = ∫ T 0 T c p e x p ( E / R T ) Q A f ( α ) d T
    (5)

    where the limit of temperature integration is from T00 to Tb.

    In fact, the conversion degree (α) of energetic materials from the beginning thermal decomposition to thermal explosion in the adiabatic conditions is very small, and it is very difficult to obtain the most probable kinetic model function f(α) at the process. So, we separately used Power-low model, Reaction-order model, Avrami-Erofeev model and the above obtained kinetic model function to estimate the adiabatic time-to-explosion and supposed different rate orders (n) [19,26]. The calculation results are listed in Table 2

    Table 2 The calculation results of adiabatic time-to-explosion

    modelrate orderequationtime/s

    power-low

    model

    		1 f ( α ) = 1 272.2
    2 f ( α ) = 2 α 1 / 2 326.3
    3 f ( α ) = 3 α 2 / 3 291.5
    4 f ( α ) = 4 α 3 / 4 252.6

    reaction-order

    model

    		1 f ( α ) = 1 272.2
    2 f ( α ) = 1 - α 329.5
    3 f ( α ) = ( 1 - α ) 2 398.9

    avrami-erofeev

    model

    		1 f ( α ) = 1 - α 329.5
    2 f ( α ) = 2 ( 1 - α ) [ - l n 1 - α ] 1 / 2 376.8
    3 f ( α ) = 3 ( 1 - α ) [ - l n 1 - α ] 2 / 3 331.1
    4 f ( α ) = 4 ( 1 - α ) [ - l n 1 - α ] 3 / 4 285.0

    In the calculation of adiabatic time-to-explosion, the following data, T00 =437.25 K, Tb =464.05 K, EK =226.69 kJ·mol-1,AK =1023.30 s-1, cp =1.15 J·g-1·K-1, Q = 252.5 J·g-1 and R = 8.314 J·mol-1·K-1, are used.

    From Table 2, we can see that the calculation results exhibit some deviations and the decomposition model has big influence on the estimate of adiabatic time-to-explosion. From the whole results, we believe the adiabatic time-to-explosion of BNGM should be about 280 s. It is a relatively long time, and the result indicates that BNGM has a good thermal stability.

  • 3.4 Enthalpy of Combustion

    3.4

    The determination results of the energy of constant volume combustion are shown in Table 3, so the constant-volume combustion enthalpy for BNGM is (-10171.4±27.5 ) J·g-1.

    Table 3 Determination results of enthalpy of combustion at 298.15 K

    sampleNo.m / gΔT / K-ΔcU / J·g-1
    BNGM10.207470.206410292
    20.209320.205810170
    30.211180.207210153
    40.198800.195010115
    50.200400.197210154
    60.210510.206410144
    mean10171.4±27.5

    The standard molar enthalpy of combustion ( Δ c H m θ ) was referred to the energy of combustion change of the following idealized reaction formulas (a) and (b) at T = 298.15 K and pθ = 101.325 kPa. Under the ideal condition of sufficient oxygen, we believe that the oxidation product of nitro group is NO2 (g) and other N element would be oxidized to N2 (g).

    C 3 H 8 N 8 O 4 ( s ) + 5 O 2 ( g ) = 3 C O 2 ( g ) + 4 H 2 O ( l ) + 3 N 2 ( g ) + 2 N O 2 ( g )
    2 N O 2 ( g ) + 2 3 H 2 O ( l ) = 4 3 H N O 3 ( l ) + 2 3 N O ( g )

    Δ c H m θ can be derived from the standard molar enthalphy of combustion in accordance with equations (6) and (7).

    Δ c H m θ = Δ c U m θ + Δ n 1 R T + Δ n 2 R T
    (6)
    Δ n = ∑ n i ( p r o d u c t s , g ) - ∑ n i ( r e a c t a n t s , g )
    (7)

    where ∑ n i is the total molar amount of gases in products or reactants.

    The standard molar enthalpy of formation ( Δ f H m θ ) can be calculated by Hess′s law [27], according to the above thermochemical equations. For BNGM, the standard molar enthalpy of formation is:

    Δ f H m θ B N G M , s = 3 Δ f H m θ C O 2 , g + 10 3 Δ f H m θ H 2 O , l + 2 3 Δ f H m θ N O , g + 4 3 Δ f H m θ H N O 3 , l - Δ c H m θ B N G M , s
    (8)

    The standard molar enthalpies of formation for CO2 (g), H2O (l), HNO3 (l) and NO (g) are as follows: Δ f H m θ (CO2,g)=-(393.51±0.13) kJ·mol-1,

    Δ f H m θ (H2O,l)=-(285.83±0.04) kJ·mol-1,

    Δ f H m θ (HNO3,l)=-(174.10±0.8) kJ·mol-1,

    Δ f H m θ (NO,g) =(90.25±0.75) kJ·mol-1[28].

    The standard molar enthalpy of combustion ( Δ c H m θ ) and the standard molar enthalpy of formation ( Δ f H m θ ) were calculated as (-2238.53±6.04 )kJ·mol-1 and (-66.73±6.05 )kJ·mol-1 (T =298.15 K and pθ =101.325 kPa).

  • 3.5 Sensitivity

    3.5

    The test result indicates that impact sensitivity of BNGM is higher than 23.5 J. So, BNGM is relatively less sensitive. The sensitivity is close to that of parent material NG (>30 J), but much lower than that of RDX (7.4 J) [29].

  • 4 Conclusions

    4

    (1) The thermal decomposition behavior of BNGM presents two exothermic decomposition processes. The self-accelerating decomposition temperature (TSADT) and critical temperature of thermal explosion (Tb) are 189.6 ℃ and 190.9 ℃, respectively.

    (2) Specific heat capacity equation of BNGM is cp = 0.1763+3.2461×10-3T (285.0 K< T <350.0 K), and the molar heat capacity is 251.9 J·mol-1·K-1 at 298.15 K. Adiabatic time-to-explosion of BNGM is estimated to be about 280 s. The standard molar enthalpy of formation of BNGM is (-66.73±6.05) kJ·mol-1, and the impact sensitivity of BNGM is higher than 23.5 J. The thermal stability of BNGM is good.

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    查找原文
    参考文献 2
    RuanH W, LingY F, WangG X, et al. Synthesis and characterization of 2-nitro-2-azaadamantane-4,8-diyl dinitrate[J]. Chinese Journal of Energetic Material（Hanneng Cailiao）, 2016, 24(6): 544-549.
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    查找原文
    参考文献 4
    ChavezD E, ParrishD A. Synthesis and characterization of 1-nitroguanyl-3-nitro-5-amino-1,2,4-triazole[J]. Propellants, Explosives, Pyrotechnics, 2012, 37(5): 536-539.
    查找原文
    参考文献 5
    ShuklaM K, WangJ, SeiterJ.Understanding the fate of insensitive munitions compounds: computational study on adsorption of nitroguanidine (NQ) and 1,1-diamino-2,2-dinitroethylene (FOX-7) on pristine and Al-hydroxylated α-alumina surfaces[J]. The Journal of Physical Chemistry C, 2017, 121(21): 11560-11567.
    查找原文
    参考文献 6
    MetelkinaE L.2-Nitroguanidine derivatives: X. synthesis and nitration of 4-nitriminotetrahydro-1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their substituted derivatives[J]. Russian Journal of Organic Chemistry, 2007, 43(10): 1447-1450.
    查找原文
    参考文献 7
    ChavezD E, HiskeyM A, GilardiR D. Novel high-nitrogen materials based on nitroguanyl-substituted tetrazines[J]. Organic Letters, 2004, 6(17): 2889-2991.
    查找原文
    参考文献 8
    FuQ J, ZhuC H, FuX Y. On the synthesis, structure and properties of spiro-nitramines and spiro-nitrosamines[J]. Acta Armamentarii, 1992, 1(1): 28-35.
    查找原文
    参考文献 9
    ZhangQ H, HeC L, YinP, et al. Insensitive nitrogen-rich materials incorporating the nitroguanidyl functionality[J]. Chemistry-An Asian Journal, 2014, 9(1): 212-217.
    查找原文
    参考文献 10
    LiY X, WangJ L, WangY H, et al. A novel synthetic method of 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine (NNHT)[J]. Chinese Journal of Organic Chemistry, 2011, 31(2): 256-259.
    查找原文
    参考文献 11
    JiaoS X, LiT, QiS Z. Synthesis of 2-nitroiminimidazolidine[J]. Hebei Chemical Industry, 2002(6): 40.
    查找原文
    参考文献 12
    KonyM, DagleyI J. Synthesis of oetahydro-2,5-bis(nitroimino)imidazo[4,5-d] imidazole[J]. Heterocycles, 1994, 38(3): 595-600.
    查找原文
    参考文献 13
    YuY Z, SuZ, DuanB R, et al.Synthesis of polynitro compounds from nitroguanidine[J]. Propellants, Explosives, Pyrotechnics, 1989, 14(4): 150-152.
    查找原文
    参考文献 14
    LiJ K, ZhouC, YangW, et al. Synthesis and characterization of 2,4-dinitrimino-1,5-dinitrohexahydro-1,3,5-triazine[J]. Chinese Journal of Spectroscopy Laboratory, 2012, 29(4): 2540-2542.
    查找原文
    参考文献 15
    ZhouC, WangB Z, HuoH, et al. A novel energetic material hydrazinium 3,5-dinitroamino-1,2,4-triazole: synthesis and properties[J]. Chinese Journal of Energetic Materials（Hanneng Cailiao）, 2014, 22(4): 576-578.
    查找原文
    参考文献 16
    LiY F, ZhaiL J, XuK Z, et al. Thermal behaviors of a novel nitrogen-rich energetic compound hydrazinium 3,5-dinitroamino-1,2,4-triazole[J]. Journal of Thermal Analysis Calorimetry, 2016, 126(3): 1-7.
    查找原文
    参考文献 17
    KissingerH E.Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706.
    查找原文
    参考文献 18
    OzawaT.A method of analying thermogravimetric data[J]. Bulletin of the Chemical Society of Japan, 1965, 38(11): 1881-1886.
    查找原文
    参考文献 19
    HuR Z, GaoS L, ZhaoF Q, et al. Thermal Analysis Kinetics (2th)[M]. Beijing: Science Press, 2008.
    查找原文
    参考文献 20
    ZhangT L, HuR Z, XieY, et al.The estimation of critical temperatures of thermal explosion for energetic materials using non-isothermal DSC[J]. Thermochimica Acta, 1994, 244(244): 171-176.
    查找原文
    参考文献 21
    SmithL C.An approximate solution of the adiabatic explosion problem[J]. Thermochimica Acta, 1975, 13(1): 1-6.
    查找原文
    参考文献 22
    XuK Z, SongJ R, ZhaoF Q, et al.Thermal behavior, specific heat capacity and adiabatic time-to-explosion of G(FOX-7)[J]. Journal of Hazardous Materials, 2008, 158(2-3): 333-339.
    查找原文
    参考文献 23
    XuK Z, SongJ R, ZhaoF Q, et al.Non-isothermal decomposition kinetics, specific heat capacity and adiabatic time-to-explosion of a novel high energy material: 1-amino-1-methylamino-2,2-dinitroethylene (AMFOX-7)[J]. Journal of the Chinese Chemical Society, 2009, 56(3): 524-531.
    查找原文
    参考文献 24
    MaH X, YanB, LiZ N, et al.Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to explosion of NTO·DNDZ[J]. Journal of Hazardous Materials, 2009, 169(1-3): 1068-1073.
    查找原文
    参考文献 25
    XuK Z, ChenY S, WangM, et al.Synthesis and thermal behavior of 4,5-dihydroxyl-2-(dinitromethylene)-imidazolidine (DDNI)[J]. Journal of Thermal Analysis and Calorimetry, 2011, 105(1): 293-300.
    查找原文
    参考文献 26
    VyzovkinS, BurnhamA K, CriadoJ M, et al.ICTKA kinetics committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1-2): 1-19.
    查找原文
    参考文献 27
    AtkinsP, PaulaJ D.Atkins′ Physical Chemistry (7th)[M], Beijing: High Education Press, 2006.
    查找原文
    参考文献 28
    DavidR L.Handbook of chemistry and physics[M].Boca Raton, FL： CRC Press, 2003.
    查找原文
    参考文献 29
    ZhouT H, LiY F, XuK Z, et al.The new role of 1,1-diamino-2,2-dinitroethylene (FOX-7): two unexpected reactions[J]. New Journal of Chemistry, 2017, 41(1): 168-176.
    查找原文

  • 基本信息

    DOI: 10.11943/CJEM

    中图分类号: TJ55；O65

    文献标识码: A

    引用信息

    关晓鸽,李静,李彦峰等.亚甲基二硝基胍(BNGM)的热行为[J].含能材料,XXXX,XX(XX):653-658.GUAN Xiao-ge,LI Jing,LI Yan-feng,et al.Thermal Behaviors of Bis(nitroguanidine)methane (BNGM)[J].Chinese Journal of Energetic Materials（Hanneng Cailiao）,XXXX,XX(XX):653-658.

    稿件历史

    网刊发布 : 2018-05-08
    收稿日期 : 2017-10-25
    修回日期 : 2017-12-18

    • 关晓鸽

    机 构：西北大学化工学院，陕西 西安 710069

    李静

    机 构：西北大学化工学院，陕西 西安 710069

    李彦峰

    机 构：西北大学化工学院，陕西 西安 710069

    徐抗震

    机 构：西北大学化工学院，陕西 西安 710069

    角 色：

    宋纪蓉

    机 构：西北大学化工学院，陕西 西安 710069

    赵凤起

    机 构：西安近代化学研究所，陕西 西安 710065
    html/hncl/CJEM2017342/alternativeImage/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-F002.jpg
    html/hncl/CJEM2017342/alternativeImage/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-F003.jpg
    β/ ℃·min-1T0 /℃Te/℃Tp / ℃-ΔHd/J·g-1EK / kJ·mol-1log(A /s-1)rKEO/kJ·mol-1rO
    5.0165.3200.1202.6225230.4023.300.9999226.690.9999
    7.5167.2203.4205.9251
    10.0169.8205.8208.1294
    12.5171.5207.6209.9250
    15.0172.8209.1211.5243
    html/hncl/CJEM2017342/media/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-image004.png
    html/hncl/CJEM2017342/alternativeImage/8ba85d47-4efc-490b-b1c1-caa0b93cce1b-F005.jpg
    modelrate orderequationtime/s

    power-low

    model

    		1 f ( α ) = 1 272.2
    2 f ( α ) = 2 α 1 / 2 326.3
    3 f ( α ) = 3 α 2 / 3 291.5
    4 f ( α ) = 4 α 3 / 4 252.6

    reaction-order

    model

    		1 f ( α ) = 1 272.2
    2 f ( α ) = 1 - α 329.5
    3 f ( α ) = ( 1 - α ) 2 398.9

    avrami-erofeev

    model

    		1 f ( α ) = 1 - α 329.5
    2 f ( α ) = 2 ( 1 - α ) [ - l n 1 - α ] 1 / 2 376.8
    3 f ( α ) = 3 ( 1 - α ) [ - l n 1 - α ] 2 / 3 331.1
    4 f ( α ) = 4 ( 1 - α ) [ - l n 1 - α ] 3 / 4 285.0
    sampleNo.m / gΔT / K-ΔcU / J·g-1
    BNGM10.207470.206410292
    20.209320.205810170
    30.211180.207210153
    40.198800.195010115
    50.200400.197210154
    60.210510.206410144
    mean10171.4±27.5

    -- a.

    Fig. 1 Typical DSC curves of BNGM and NG and TG/DTG curves of BNGM at a heating rate of 10 ℃·min-1 -- a.

    -- b.

    Fig. 1 Typical DSC curves of BNGM and NG and TG/DTG curves of BNGM at a heating rate of 10 ℃·min-1 -- b.

    image /

    无注解

    无注解

    E is the apparent activation energy. A is the pre-exponential constant. r is the linear correlation coefficient. Subscript K is data obtained by Kissinger′s method. Subscript O is data obtained by Ozawa′s method.

    无注解

    无注解

    In the calculation of adiabatic time-to-explosion, the following data, T00 =437.25 K, Tb =464.05 K, EK =226.69 kJ·mol-1,AK =1023.30 s-1, cp =1.15 J·g-1·K-1, Q = 252.5 J·g-1 and R = 8.314 J·mol-1·K-1, are used.

    无注解

  • 参考文献

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      Li Y F, Wang M J, Xu K Z, et al.Thermal behaviors of 1-amino-2-nitroguanidine[J]. Chinese Journal of Energetic Material（Hanneng Cailiao）, 2016, 24(9): 848-852.

    • 4

      Chavez D E, Parrish D A. Synthesis and characterization of 1-nitroguanyl-3-nitro-5-amino-1,2,4-triazole[J]. Propellants, Explosives, Pyrotechnics, 2012, 37(5): 536-539.

    • 5

      Shukla M K, Wang J, Seiter J.Understanding the fate of insensitive munitions compounds: computational study on adsorption of nitroguanidine (NQ) and 1,1-diamino-2,2-dinitroethylene (FOX-7) on pristine and Al-hydroxylated α-alumina surfaces[J]. The Journal of Physical Chemistry C, 2017, 121(21): 11560-11567.

    • 6

      Metelkina E L.2-Nitroguanidine derivatives: X. synthesis and nitration of 4-nitriminotetrahydro-1,3,5-oxadiazine and 2-nitriminohexahydro-1,3,5-triazine and their substituted derivatives[J]. Russian Journal of Organic Chemistry, 2007, 43(10): 1447-1450.

    • 7

      Chavez D E, Hiskey M A, Gilardi R D. Novel high-nitrogen materials based on nitroguanyl-substituted tetrazines[J]. Organic Letters, 2004, 6(17): 2889-2991.

    • 8

      Fu Q J, Zhu C H, Fu X Y. On the synthesis, structure and properties of spiro-nitramines and spiro-nitrosamines[J]. Acta Armamentarii, 1992, 1(1): 28-35.

    • 9

      Zhang Q H, He C L, Yin P, et al. Insensitive nitrogen-rich materials incorporating the nitroguanidyl functionality[J]. Chemistry-An Asian Journal, 2014, 9(1): 212-217.

    • 10

      Li Y X, Wang J L, Wang Y H, et al. A novel synthetic method of 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine (NNHT)[J]. Chinese Journal of Organic Chemistry, 2011, 31(2): 256-259.

    • 11

      Jiao S X, Li T, Qi S Z. Synthesis of 2-nitroiminimidazolidine[J]. Hebei Chemical Industry, 2002(6): 40.

    • 12

      Kony M, Dagley I J. Synthesis of oetahydro-2,5-bis(nitroimino)imidazo[4,5-d] imidazole[J]. Heterocycles, 1994, 38(3): 595-600.

    • 13

      Yu Y Z, Su Z, Duan B R, et al.Synthesis of polynitro compounds from nitroguanidine[J]. Propellants, Explosives, Pyrotechnics, 1989, 14(4): 150-152.

    • 14

      Li J K, Zhou C, Yang W, et al. Synthesis and characterization of 2,4-dinitrimino-1,5-dinitrohexahydro-1,3,5-triazine[J]. Chinese Journal of Spectroscopy Laboratory, 2012, 29(4): 2540-2542.

    • 15

      Zhou C, Wang B Z, Huo H, et al. A novel energetic material hydrazinium 3,5-dinitroamino-1,2,4-triazole: synthesis and properties[J]. Chinese Journal of Energetic Materials（Hanneng Cailiao）, 2014, 22(4): 576-578.

    • 16

      Li Y F, Zhai L J, Xu K Z, et al. Thermal behaviors of a novel nitrogen-rich energetic compound hydrazinium 3,5-dinitroamino-1,2,4-triazole[J]. Journal of Thermal Analysis Calorimetry, 2016, 126(3): 1-7.

    • 17

      Kissinger H E.Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706.

    • 18

      Ozawa T.A method of analying thermogravimetric data[J]. Bulletin of the Chemical Society of Japan, 1965, 38(11): 1881-1886.

    • 19

      Hu R Z, Gao S L, Zhao F Q, et al. Thermal Analysis Kinetics (2th)[M]. Beijing: Science Press, 2008.

    • 20

      Zhang T L, Hu R Z, Xie Y, et al.The estimation of critical temperatures of thermal explosion for energetic materials using non-isothermal DSC[J]. Thermochimica Acta, 1994, 244(244): 171-176.

    • 21

      Smith L C.An approximate solution of the adiabatic explosion problem[J]. Thermochimica Acta, 1975, 13(1): 1-6.

    • 22

      Xu K Z, Song J R, Zhao F Q, et al.Thermal behavior, specific heat capacity and adiabatic time-to-explosion of G(FOX-7)[J]. Journal of Hazardous Materials, 2008, 158(2-3): 333-339.

    • 23

      Xu K Z, Song J R, Zhao F Q, et al.Non-isothermal decomposition kinetics, specific heat capacity and adiabatic time-to-explosion of a novel high energy material: 1-amino-1-methylamino-2,2-dinitroethylene (AMFOX-7)[J]. Journal of the Chinese Chemical Society, 2009, 56(3): 524-531.

    • 24

      Ma H X, Yan B, Li Z N, et al.Preparation, non-isothermal decomposition kinetics, heat capacity and adiabatic time-to explosion of NTO·DNDZ[J]. Journal of Hazardous Materials, 2009, 169(1-3): 1068-1073.

    • 25

      Xu K Z, Chen Y S, Wang M, et al.Synthesis and thermal behavior of 4,5-dihydroxyl-2-(dinitromethylene)-imidazolidine (DDNI)[J]. Journal of Thermal Analysis and Calorimetry, 2011, 105(1): 293-300.

    • 26

      Vyzovkin S, Burnham A K, Criado J M, et al.ICTKA kinetics committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1-2): 1-19.

    • 27

      Atkins P, Paula J D.Atkins′ Physical Chemistry (7th)[M], Beijing: High Education Press, 2006.

    • 28

      David R L.Handbook of chemistry and physics[M].Boca Raton, FL： CRC Press, 2003.

    • 29

      Zhou T H, Li Y F, Xu K Z, et al.The new role of 1,1-diamino-2,2-dinitroethylene (FOX-7): two unexpected reactions[J]. New Journal of Chemistry, 2017, 41(1): 168-176.

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