表面活性剂改善RDX在EA低共熔物体系中的分散性研究

通过 RDX临界表面张力以及硝酸铵 (AN) -乙二胺二硝酸盐 (EDD)低共熔液 (EA)的表面张力测定 ,研究了表面活性剂对 AN-EDD低共熔液在 RDX表面的润湿吸附性。表面活性剂降低了 AN- EDD低共熔液的表面张力 ,使其能在 RDX晶体表面铺展吸附 ,从而提高了 AN- EDD- RDX炸药的装药密度     

Miscibility windows in ternary polymer blends of a polyester,polymethacrylate and poly(styrene‐co‐acrylonitrile)

Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (T_g) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry     

硝酸铵AN_Ⅳ?AN_Ⅲ相变机制与改性添加剂研究进展

对硝酸铵AN_Ⅳ?AN_Ⅲ相变机制进行介绍,并对不同种类硝酸铵改性添加剂的效果及作用机制进行分析,涉及改性剂种类包括无机盐、聚合物、表面活性剂。3种类型添加剂均能够不同程度的改善硝酸铵AN_Ⅳ?AN_Ⅲ的相变温度,起到抑制相变并减轻硝酸铵结块程度的作用,同时被改性的硝酸铵的膨胀率、堆积密度、抗压强度等物性也会发生不同程度的变化。并介绍水含量对硝酸铵相变和结块的影响,随水含量增加,硝酸铵相变点降低,结块严重,因此应控制硝酸铵的水含量。     

Graft copolymerization of acrylonitrile onto Cassia tora gum with ceric ammonium nitrate–nitric acid as a redox initiator

The graft copolymerization of acrylonitrile (AN) onto Cassia tora gum (CTG) was carried out in an aqueous medium with a ceric ammonium nitrate (CAN)–nitric acid initiation system. The percentage grafting and percentage grafting efficiency were determined as functions of the concentrations of CAN, nitric acid, AN, and CTG and the polymerization temperature and time. The results are discussed, and a reaction mechanism is proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 129–136, 2003     

Determination of Urea Nitrate and Guanidine Nitrate Vapor Pressures by Isothermal Thermogravimetry

Since the bombing of Pan Am Flight 103 over Lockerbie, Scotland in 1988, detection of military explosives has received much attention. Only in the last few years has detection of improvised explosives become a priority. Many detection methods require that the particulate or vapor be available. Elsewhere we have reported the vapor pressures of peroxide explosives triacetone triperoxide (TATP), diacetone diperoxide (DADP), and 2,4,6‐trinitrotoluene (TNT). Herein we examine the vapor signatures of the nitrate salts of urea and guanidine (UN and GN, respectively), and compare them to ammonium nitrate (AN) and TATP using an isothermal thermo‐gravimetric method. The vapor signatures of the nitrate salts are assumed to be the vapor pressures of the neutral parent base and nitric acid. Studies were performed at elevated temperatures (80–120 °C for UN, 205–225 °C for GN, 100–160 °C for AN, and 40–59 °C for TATP), enthalpies of sublimation calculated and vapor pressures extrapolated to room temperature. Reported vapor pressure values (in Pa) are as follows: GN ≪UN <AN ≪TATP 2.66×10⁻¹⁸ 3.94×10⁻⁵ 5.98×10⁻⁴ 24.8     

Condensed Phase Behavior in the Combustion of Ammonium Dinitramide

This paper reports on the thermal and combustion behaviors of ammonium dinitramide (ADN). The thermal behavior is measured by a pressure thermogravimetric analysis (TGA) at pressures below 8 MPa. The burning rates of pure ADN and ADN/ammonium nitrate (AN) mixtures are measured in the range 0.2–12 MPa, and the burning temperature profiles are obtained using thermocouples with diameters of 5 and 25 μm. This report mainly focuses on the condensed‐phase behavior in the vicinity of a burning surface. The temperature profiles are complicated because the ADN decomposition and AN dissociation compete during the condensed phase, and the bubbles of the decomposition gas and gas‐phase flame also affect the surface temperature. AN addition helps to understand the effects of AN during the condensed phase, and it was shown that the burning temperature rises to the critical temperature of AN. Based on these experimental results, the pressure dependency of the burning rates is also discussed.     

Solidification Behavior of the Hydrazine Nitrate‐Nitroguanidine Eutectic System

In an attempt to better understand the properties of energetic eutectic materials, the eutectic mixture of hydrazine nitrate (HN) and nitroguanidine (NQ) was prepared by a melt crystallization method. The melting temperature and fusion enthalpy of the pure components and the eutectic were determined using differential scanning calorimetry. The structure of the HN‐NQ title compound was characterized by infrared spectroscopy (IR), X‐ray diffraction (XRD), and scanning electron microscopy. Thermodynamic functions such as excess Gibb’s energy, excess enthalpy, and excess entropy of the title mixture were calculated using activity coefficient data. The intermolecular interactions of different molar ratios of the HN‐NQ eutectic were determined by density functional theory (DFT) methods. The results of the excess thermodynamic functions and computer simulations indicate that the eutectic is not a mechanical mixture. IR spectroscopic and XRD studies confirm that there is some interaction between the components during the formation of the eutectic mixture. Moreover, the microstructure of the eutectic mixture at a molar ratio of 3 : 2 was more uniform than others, which was proved by DFT calculations. The Jackson’s roughness parameter was found to be greater than 2, suggesting a faceted, irregular morphology. These results could pave a way for further investigation of the energetic eutectic system aiming to supersede TNT.     

Preparation of bi‐continuous poly(acrylonitrile‐co‐methyl acrylate) microporous membranes by a thermally induced phase separation method

Poly(acrylonitrile‐co‐methyl acrylate) [P(AN‐MA)] flat microfiltration membranes were successfully prepared via the thermally induced phase separation (TIPS) method, by using low polar caprolactam (CPL) and methoxypolyethylene glycol 550 (MPEG 550) as the mixed diluent. In this work, P(AN‐MA) membranes exhibit bi‐continuous networks, porous surfaces, high porosity, and big pore size, when membrane fabricated from a high MPEG 550 content, low P(AN‐MA) concentration, and small cooling rate, it can be dry state preservation and do not need to be impregnated by any solvent. When the ternary system was composed of 15 wt % P(AN‐MA), 12.5 wt % CPL, and 87.5 wt % MPEG 550, formed at 25 °C air bath, membrane has the highest water flux of 4420 L m^?2 h^?1. The obtained P(AN‐AN) membrane displays a high carbonic black ink rejection ranging from 83.7 to 98.5 wt %. Moreover, P(AN‐MA) polymer not only retains the advantages of PAN but also reduces the polar component from 16.2 to 10.77 MPa^0.5. It can be used membrane matrix to obtain pore structure and excellent mechanical property membrane via TIPS. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46173.     

Permeation and Separation Characteristics of Acetic Acid‐Water Mixtures by Pervaporation through Acrylonitrile and Hydroxy Ethyl Methacrylate Grafted Poly(vinyl alcohol) Membrane

Abstract

In this study, acrylonitrile (AN) and hydroxyl ethyl methacrylate (HEMA) were grafted onto poly(vinyl alcohol) (PVA) using cerium (IV) ammonium nitrate as initiator at 30°C. The graft copolymer was characterized using the Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The grafted PVA membranes (PVA‐g‐AN/HEMA) were prepared by a casting method, and used in the separation of acetic acid‐water mixtures by pervaporation. The effects of the membrane thickness, operating temperature, and feed composition on the permeation rate and separation factor for acetic acid‐water mixtures were studied. Depending on the membrane thickness, the temperature and feed composition PVA‐g‐AN/HEMA membranes gave separation factors 2.26–14.60 and permeation rates of 0.18–2.07 kg/m²h. It was also determined that grafted membranes gave lower permeation rates and greater separation factors than PVA membranes. Diffusion coefficients of acetic acid‐water mixtures were calculated from permeation rate values. The Arrhenius activation parameters were calculated for the 20 wt.% acetic acid content in the feed using the permeation rate and the diffusion data obtained at between 25–50°C.     

Melting of hydrogels containing ammonium nitrate

The fusion of hydrogels containing ammonium nitrate (AN) has been investigated by differential scanning calorimetry (DSC). The polymers used were guar and xanthan gums as well as synthetic polyacrylamide polymers. Water in hydrogels could be classified into three types labeled as ordinary water (hump of the melting peak), intermediate water (broad component of the peak), and bound nonfreezing water (without any phase transition). The temperature of fusion of intermediate water was about 10° to 35°C lower than that of ordinary water. Intermediate and bound water was found in all the gels studied, whereas ordinary water existed mainly in mixtures with total water content higher than 62%. The presence, type, and concentration of a crosslinker had no effect on the amount of bound water in hydrogels containing AN. In such mixtures the amount of nonfreezing water increased with the polymer concentration as well with the AN proportion relative to water and represented in some cases up to 27% of the gel. Cold-crystallization was observed in all cases (except xanthan) and was probably initiated by AN or the crosslinking agent.     

The comparative effect of a mixed urea,ammonium nitrate,ammonium sulphate granular formulation on the efficiency of N recovery by perennial ryegrass

The¹⁵N isotope was used to study the mode of action of individual nitrogen sources in a 30% urea:30% ammonium nitrate: 10% ammonium sulphate:30% filler (w/w) granular fertilizer for perennial ryegrass in a greenhouse pot experiment. The fertilizer consisted of two types of granules, one containing 80% urea and 20% filler and the second containing 48% ammonium nitrate (AN), 16% ammonium sulphate (AS) and 36% filler. In addition the effect of dolomite compared with silica as the filler was investigated on nitrogen recovery from the 30:30:10:30 formulation.Dolomite adversely affected the recovery of nitrate N from the system and evidence suggested that MgCO₃ was the active component. Granules containing dolomite resulted in a lower dry-matter yield than those containing silica, however the difference was not significant as nitrate contributed only 20% of the N in the formulation. AN gave the greatest DM yield and urea the lowest with AS being intermediate. The¹⁵N budget in shoots, roots and soil indicated that only 65% of the N from urea was recovered at the end of the experiment compared with 86% for AN and 91% for AS. The dry-matter yield of the 30:30:10:30 formulation using silica as the filler was intermediate between urea and AN; however, the apparent N recovery was significantly higher than expected from the sum of the individual components. The use of¹⁵N labelling indicated that using separate granules for ammonium N and urea the recovery of urea was improved by 11% in the triple N mixture when both AN and AS were present in the second granule compared to the recovery on its own. The enhanced recovery of urea appeared to be a function of AN and AS acting together as neither source in double combination with urea had any effect on urea N recovery.Urea enhanced the recovery of nitrate N by 10% but decreased the recovery of AS by 6% (in the 30:30:10:30 formulation) in comparison with the single sources on their own. The results indicate that interactions can occur between N sources even when they are physically separated by being in different granules.     

The comparative effects of ammonium nitrate,urea or a combined ammonium nitrate/urea granular fertilizer on the efficiency of nitrogen recovery by perennial ryegrass

The comparative effects of ammonium nitrate (AN), urea or a combined 1:1 (w/w) AN/urea granular fertilizer with two different fillers (CaCO₃ or silica) were investigated on the efficiency of dry matter production and¹⁵N recovery by perennial ryegrass grown in pots under controlled environmental conditions.There was no significant difference between CaCO₃ and silica as the filler and therefore no indication that the presence of CaCO₃ in the pellet enhanced N loss from urea. Ammonium nitrate was the most efficient N source and urea the least efficient in terms of all the parameters studied. The¹⁵N budget in shoots, roots and soil indicated that only 60% of the nitrogen from urea was recovered at the end of the experiment compared with 95% for AN. However, the % recovery of¹⁵N from urea was increased by 17% in the presence of AN whereas the % recovery of AN was decreased by 19% in the presence of urea. The combined 1:1 (w/w) AN/urea source therefore gave intermediate yields between AN and urea alone. The results indicate that an interaction occurred between AN and urea in the granule.     

AN EXTRACTION STUDY OF LANTHANIDE NITRATO COMPLEXES THE ADOGEN-464NO3- NH4NO3SYSTEM.

ABSTRACT

Extraction of lanthanides and yttrium was studied in the interval of ammonium nitrate concentrations from 1 to 10M, and of Adogen-464 nitrate concentrations from 0·00039 to 0·39M. From the aqueous phase separation factor and from the published stability constant for Eu, stability constants for 1:1 complexes of La, Nd, Gd, Ho, Tm, Lu and Y have been determined, at 1M ammonium nitrate concentration. It was found that stability constant decreases from 2·7 for La to 2·3 for Lu. It has been shown that in the interval of Adogen-464 nitrate concentrations employed, lanthanides from La to Nd appear in the organic phase as 1:5 complexes, whereas lanthanides heavier than Nd appear also as 1:4 complexes. Relative values (with regard to lanthanum) of Gibbs energy, enthalpy (from the temperature effect) and entropy for formation of 1:5 complexes,and the position of yttrium within lanthanides have been determined. It is concluded from the experimental data that the extracted 1:4 and 1:5 complexes are of the inner sphere type, with nitrate ions acting as bidentate ligands, and that the contribution from covalency to bonding is the same in the aquo ion and in the 1:5 nitrato complex.     

Structures and properties of thermoregulated acrylonitrile–methyl acrylate sheet containing microphase change materials

A series of melt processable poly(acrylonitrile–methyl acrylate) copolymers with a feeding ratio of 85/15 mol% (abbreviated as 85/15 AN/MA below) containing 0–25 wt% of microencapsulated phase change materials (micro‐PCMs) were synthesized by aqueous precipitation polymerization. The number average sequence lengths (NASLs) and tacticity of 85/15 AN/MA were determined using ¹³C‐NMR. The results showed that the NASL of contiguous AN sequences is 10.00 and the tacticity is atactic with approximately 51% m and 49% r diads (the relative orientation of two adjacent cyanogroup). 85/15 AN/MA containing various contents of micro‐PCMs were processed into sheets in melt condition at 210°C and 20 MPa. The structures and properties of the copolymers and sheets containing micro‐PCMs were studied by using Fourier transform infrared spectroscopy, nuclear magnetic resonance (¹H‐NMR), scanning electron microscopy, differential scanning calorimetry, gel permeation chromatography, X‐ray diffraction, and dynamic mechanical analysis. The composition of AN/MA copolymer agreed well with its monomer feed ratio. The melting enthalpy of the sheets containing 25 wt% of micro‐PCMs was approximately 25 J/g, which increased steadily as the micro‐PCMs content increased. The modulus of the sheets decreased with the micro‐PCMs content increased. The glass transition temperature (T_g) of the sheets was in the range of 79.7–81.7°C, which also increased with the micro‐PCMs content increasing. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

几种添加剂对硝酸铵热稳定性的影响

利用差示扫描量热法(DSC)研究了添加剂作用下硝酸铵(AN)的晶型转变和热分解规律．探索了添加剂对提高AN常温安定性和高温热活性的途径和机理。结果表明．几种有机添加剂在常温条件下削弱了AN的晶变热效应，对AN具有晶型稳定作用．加入木粉、棉纤维、H3PO4、KCl、K2Cr2O7使AN放热温度提前。释能突发性增强，能够促进AN在高温条件下的热分解。     

Azeotropy in terpolymerization of 2-pyrimidyl acrylamide with different alkyl acrylates and acrylonitrile

2-Pyrimidyl acrylamide monomer (2PA) has been prepared by the reaction of 2-amino pyrimidine with acrylolyl chloride in the presence of triethylamine as catalyst. Its structure was confirmed by IR and ¹H NMR spectroscopy. Ternary copolymerizations of 2-pyrimidyl acrylamide monomer (2PA) with methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BuA) and acrylonitrile (AN) were carried out in THF at 65°C in the presence of a free radical initiator. Experimental terpolymerization data agree well with calculations based on the Alfrey–Goldfinger equation. The determination of unitary, binary and ternary azeotropies of the various systems studied were easily handled by a computer. The ternary azeotropic compositions for 2PA–MA–AN and 2PA–MMA–AN were 32.20:17.5:50.30 and 13.54:52.64:33.82mol%, respectively. Pseudo-azeotropic regions were identified where the deviation between feed and polymer composition is very small.     

Effects of water solubility of acrylonitrile on vinylidene chloride/acrylonitrile/styrene suspension polymerization

The water solubility of acrylonitrile (AN) and its effects on vinylidene chloride/acrylonitrile/styrene (VDC/AN/St) suspension copolymerization were investigated in this study. It shows that the VDC/St ratio and the presence of suspending agent have no obvious influences on AN phase partition between the monomer and aqueous phases, whereas the water solubility of AN increases as temperature increases. Polymerization in the aqueous phase occurs extensively with azobis(isobutyronitrile) (AIBN) as initiator, whereas with lauryl peroxide (LPO) as initiator, polymerization in the aqueous phase is negligible. Theoretical analysis and experimental results indicate that transport of the monomer molecule is possible during polymerization. Both VDC and AN transfer from the monomer phase to the aqueous phase when AIBN is used as initiator. AN transfers from the aqueous phase to the monomer phase for the polymerization system initiated by LPO. Sodium nitrite (NaNO₂), but not sodium sulfide (Na₂S), can be used to effectively inhibit polymerization in water and exerts less influence on the polymerization in the monomer phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1431–1438, 2001     

Thermally‐induced phase transformations in Na0.5Bi0.5TiO3–KNbO3 ceramics

The structures and functional properties of Na_0.5Bi_0.5TiO₃–xKNbO₃ (NBT‐xKN) solid solutions, with x in the range from 0.01 to 0.09, were investigated using a combination of high‐resolution synchrotron X‐ray powder diffraction (SXPD) and ferroelectric property measurements. For low KN contents, an irreversible transformation from cubic to rhombohedral phases was observed after the application of a high electric field, indicating that the polar nanoregions (PNRs) in the unpoled state can be transformed into metastable long‐range ordered ferroelectric domains in the poled state. In contrast, the near‐cubic phase of the unpoled ceramics was found to be remarkably stable and was retained on cooling to a temperature of ?175°C. Upon heating, the field‐induced metastable ferroelectric rhombohedral phase transformed back to the nanopolar cubic state at the structural transformation temperature, T_ST, which was determined as approximately 225°C and 125°C for KN contents of 3% and 5% respectively. For the field‐induced rhombohedral phase in the poled specimens, the pseudo‐cubic lattice parameter, a_p, exhibited an anomalous reduction while the inter‐axial angle increased towards a value of 90° on heating, resulting in an overall increase in volume. The observed structural changes were correlated with the results of temperature‐dependent dielectric, ferroelectric and depolarization measurements, enabling the construction of a phase diagram to define the stable regions of the different ferroelectric phases as a function of composition and temperature.     

Properties of ASA/SAN/NBR ternary blends: effect of AN content in NBR

Abstract

Nitrile–butadiene rubbers (NBRs) with different acrylonitrile (AN) contents were used to toughen acrylonitrile–styrene–acrylic terpolymer/styrene–acrylonitrile copolymer (ASA/SAN) blends. The properties of the ASA/SAN/NBR ternary blends were investigated via dynamic mechanical analysis, heat distortion temperature, Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). The effects of AN content in NBR on physical properties, heat resistance and morphology of the ternary blends were studied. Heat distortion temperature of the blends decreased with increasing AN content of NBR. The impact strength reached the maximum value when 20 phr NBR with 26 wt-%AN content was added. Images (SEM) were in accordance with results of mechanical properties.     

Thermal Decomposition of Energetic Materials 56. On the fast thermolysis mechanism of ammonium nitrate and its mixtures with mangnesium and carbon

Fast thermolysis studies of ammonium nitrate (AN) and its mixtures with magnesium and activated charcoal have been carried out by the Fourier transform infrared spectroscopy/temperature profiling technique. When subjected to rapid heating (ca. 80°C/s), AN Sublimes/decomposes around 300°. Sublimation dominates at ambient pressures. The IR-active products of decomposition are NH₃, NO₂, N₂O and H₂O. Reaction schemes accounting for the products are proposed which involve proton transfer leading to NH₃ by the decomposition products of HNO₃. The decomposition of AN is significantly enhanced when AN is mixed with magnesium powder or charcoal, and occurs at as low a temperature as 135°C. Whereas NH₃ is the major product of decomposition of AN Mg mixtures, no NH₃ is observed from AN C mixtures. The results are explained by the reaction of HNO₃ and NH₃ with Mg or C.