Effect and mechanism of reductive polyaniline on the stability of nitrocellulose

The search for new green and efficient stabilizers is of great importance for the stabilization of nitrocellulose(NC). This is due to the shortcomings of traditional stabilizers, such as high toxicity. In this study, reduced polyaniline(r-PANI), which has a similar functional structure to diphenylamine(DPA) but is non-toxic, was prepared from PANI based on the action with N_(2)H_(4) and NH_(3)-H_(2)O, and used for the first time as a potential stabilizer for NC. XPS, FTIR, Raman, and SEM were used to characterize the reduced chemical structure and surface morphology of r-PANI. In addition, the effect of r-PANI on the stabilization of NC was characterized using DSC, VST, isothermal TG, and MMC. Thermal weight loss was reduced by 83% and 68% and gas pressure release by 75% and 49% compared to pure NC and NC&3%DPA, respectively.FTIR and XPS were used to characterize the structural changes of r-PANI before and after reaction with NO_(2). The 1535 cm^(-1) and 1341 cm^(-1) of the FTIR and the 404.98 eV and 406.05 eV of the XPS showed that the -NO_(2) was generated by the absorption of NO_(2). Furthermore, the quantum chemical calculation showed that NO_(2) was directly immobilized on r-PANI by forming -NO_(2) in the neighboring position of the benzene ring.

Investigation on thermal characteristics and desensitization mechanism of improved step ladder-structured nitrocellulose

Nitrocellulose,or cellulose nitrate,has received considerable interest due to its various applications,such as propellants,coating agents and gas generators.However,its high mechanical sensitivity caused many accidents during its storage and usage in ammunition.In this work,two kinds of insensitive step ladderstructured nitrocellulose(LNC)with different nitrogen contents were synthesized.The products were characterized by FT-IR,Raman,XRD,SEM,elemental analysis,TGA,DSC,accelerating rate calorimeter analysis(ARC),and drop weight test to study their molecular structure,thermal characteristics and desensitization performance.Compared with raw nitrocellulose,LNC has a sharper exothermic peak in the DSC and ARC curves.The H50values of the two kinds of LNC increased from 25.76 to 30.01 cm for low nitrogen content and from 18.02 to 21.84 cm for high nitrogen content,respectively.The results show that the ladder-structure of LNC which provides regular molecular arrangement and a soft buffer made with polyethylene glycol could affect the energy releasing process of LNC and reduce the sensitivity of LNC.Insensitive LNC provides an alternative to be used as a binder in insensitive propellants formulation.

Synthesis,crystallographic characterization,and potential application of fullerene anisole derivatives as nitrocellulose stabilizer

A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose(NC)-based propellants.Single-crystal X-ray diffraction,nuclear magnetic resonance,highresolution mass spectrometry,Fourier transform infrared(FT-IR)spectroscopy,and UV-Vis spectroscopy were used to characterize the structures of the synthesized fullerene anisole derivative stabilizers.Methyl violet,differential scanning calorimetry test,isothermal weight loss,vacuum stability test,and adiabatic accelerated test were used to study their compatibility with NC and their ability to stabilize NC.The results show that the designed and synthesized novel fullerene anisole derivative stabilizer has good compatibility with NC,and their overall stabilizing effects on NC are better than those of the traditional stabilizers,diphenylamine(DPA),and N,N’-dimethyl-N,N’-diphenylurea(C2).The stabilizing effects was ranked as:3b>2d>2a>2c>C2>2b>DPA>NC.In addition,FT-IR analysis and electron spin resonance spectroscopy were applied to explore the stability mechanism of fullerene-based stabilizers to NC.The results reveal that the new fullerene stabilizer can adsorb and effectively eliminate the nitrogen oxide free radicals generated by NC degradation;therefore,it can forbid the autocatalytic degradation of NC and stabilize NC.

Effect of inorganic salt on the thermal degradation of nitrocellulose and reaction mechanism of its mixture

In this study,to better understand the reaction mechanism between inorganic salts and nitrocellulose,CaCO_(3) and Li_(2)CO_(3) were evaluated with respect to their effects on the thermal degradation of NC in nitrogen atmosphere using TG/DSC at three different heating rates(2,5,10 K/min).The numerical relationship between activation energy(E)and conversion rate was obtained by FWO and KAS method,and it was discovered that CaCO_(3) could improve the thermal stability of NC.Activation energy values were calculated by Kissinger method,and it was found that NC that contain Li2CO3had the highest activation energy while NC containing CaCO3had the lowest E value.By combining the thermal analysis data with Malek method,the most probable mechanism model of thermal degradation is obtained as Sesták-Berggren model,which expression is f(α)=α^(m)(1-α)^(n).As a result of this study,there are certain guiding principles that can be applied to the pyrolysis reaction model and to the actual production process of nitrocellulose.

EFFECT OF CRYOGENIC AND HEATING TREATMENT ON THE SOLUTION PROPERTIES OF NITROCELLULOSE

The effect of cryogenic and heating treatment on the solution properties of rigid polymer nitrocellulose(NC)indilute tetrahydrofuran solution were studied with a sealed viscometer and a size exclusion chromatograph(SEC),respectively.The experimental results show that the relative viscosity of NC solution decreases after repeated freezing-thawing treatment.The decreased viscosity value of NC could not be restored but decreased further after the solution beingre-heated.The experimental results of SEC are fully consistent with that of viscosity measurements.It is believed that theeffect of two treatments on NC solution both causes the apparent hydrodynamic volume to decrease.But they are assumed tobe ascribed to different mechanisms.

ESTIMATION OF THE CRITICAL RATE OF TEMPERATURE INCREASE OF THERMAL EXPLOSION OF NITROCELLULOSE USING NON-ISOTHERMAL DSC

A method of estimating the critical rate of temperature increase of thermal explosion for the first orderautocatalytic decomposition reaction system using non-isothermal DSC is presented. Information is obtained on theincreasing rate of temperature in nitrocellulose containing 13.54% of nitrogen when the first order autocatalytic decomposition converts into thermal explosion.

Fullerene bisadduct stabilizers:The effect of different addition positions on inhibiting the autocatalytic decomposition of nitrocellulose absorbed nitroglycerin

To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose(NC)/nitroglycerine(NG),we synthesized N-(4-methoxy)phenylpyrrolidine-C_(60) and four different of bis(N-(4-methoxy)phenylpyrrolidine)-C_(60) compounds through Prato reaction.Their structures were characterized by UVevis,^(1)H NMR,^(13)C NMR,high-resolution mass spectroscopy,and single-crystal X-ray diffraction.Their stabilization effect to NC/NG were investigated using differential scanning calorimetry,methyl violet,vacuum stabilization effect,weight loss,and accelerating rate calorimeter tests.The results indicated these compounds had excellent stabilization effect to NC/NG.The stabilization effect of the fulleropyrrolidine bisadducts to NC/NG is significantly better than that of fulleropyrrolidine monoadduct and C_(60).Moreover,the position where pyrrolidine binds to fullerene in fulleropyrrolidine bisadducts is different,and its stabilization effect to NC is also different.The stabilization effect order of different bisadduct isomers to nitrocellulose is as follows:e-edge>trans-2>cis-2>trans-3.Electron paramagnetic resonance(EPR)and FT-IR were used to study the stabilization mechanism of fulleropyrrolidine derivatives to NC/NG.The EPR results also show that fulleropyrrolidine bisadducts with different addition sites have different abilities to absorb nitroxide,and their ability is better than that of the monoadduct and C_(60),which is consistent with the results of stabilization effect performance test.

Reductive recovery of manganese from low-grade manganese dioxide ore using toxic nitrocellulose acid wastewater as reductant

The hydrometallurgical strategy of extracting Mn from low-grade Mn ores has attracted attention for the production of electrolytic manganese metal(EMM). In this work, the reductive dissolution of low-grade Mn O2 ores using toxic nitrocellulose acidic wastewater(NAW) as a reductant was investigated for the first time. Under the optimized conditions of an Mn O2 ore dosage of 100 g·L-1, an ore particle size of-200 mesh, concentrated H2 SO4-to-NAW volume ratio of 0.12, reaction temperature of 90°C, stirring speed at 160 r·min-1, and a contact time of 120 min, the reductive leaching efficiency of Mn and the total organic carbon(TOC) removal efficiency of NAW reached 97.4% and 98.5%, respectively. The residual TOC of 31.6 mg·L-1 did not adversely affect the preparation of EMM. The current process offers a feasible route for the concurrent realization of the reductive leaching of Mn and the treatment of toxic wastewater via a simple one-step process.

Preparation of ammonium nitrate-based solid composite propellants supplemented with polyurethane/nitrocellulose blends binder and their thermal decomposition behavior

To improve the performance of solid composite propellants(SCPs)supplemented with ammonium nitrate(AN)as an oxidizer,the incorporation of energetic ingredients such as explosives,energetic binders or catalysts is a common effective approach.For this purpose,polyurethane(PU),a typical inert binder,was mixed with nitrocellulose(NC)as an energetic polymer.Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared.The prepared formulations were characterized using Fourier transform infrared spectroscopy(FTIR),RAMAN spectroscopy,X-ray diffraction(XRD),electron densimetry,thermogravimetric(TG)analysis,and differential scanning calorimetry(DSC).A kinetic study was then performed using the iterative KissingerAkahira-Sunose(It-KAS),Flynn-Wall-Ozawa(It-FWO),and non-linear Vyazovkin integral with compensation effect(VYA/CE)methods.The theoretical performances,such as theoretical specific impulse,adiabatic flame temperature,and ideal exhaust gaseous species,were also determined using the NASA Lewis Code,Chemical Equilibrium with Application(CEA).Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants.According to density tests,the density of the propellant increases as the nitrocellulose component increases.According to the thermal analysis and kinetics study,the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants.Based on the theoretical study,increasing the amount of NC in the propellant increased the specific impulse and,as a result,the overall performance.

Theoretical Studies on the Relationship Between the Structure and Property of Cellulose and Nitrocellulose——Nitration Activity and Mechanism

Many derivatives of industrially useful cellulose have hydroxyls of the anhydroglucose(AHG) units uncompletely substituted. Since each AHG unit of a cellulose molecule is a trihydric alcohol,consisted of one primary(position 6) and two secondary hydroxyl groups(positions 2 and 3), the distribution of substituents in these trihydric alcohol units could be different for different derivatives. The

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Impact factors of the degradation of bisphenol A by nitrocellulose membrane under illumination

Nitrocellulose membrane(NCM)can produce hydroxyl radicals under illumination,which promotes the oxidative degradation of organic pollutants.In this paper,NCM was used to oxidize bisphenol A(BPA)under simulated sunlight.The effects of p H,temperature,light intensity,anion and cation on the degradation of BPA were analyzed.The photodegradation process of BPA was discussed.The optimal photolysis rate was 0.031 min^(-)1 when the temperature was 30°C,the light intensity was 2.67×10^4 Lux,and the p H value was 9.0.The alkaline environment,temperature and light intensity can promote the photodegradation of BPA.Except for nitrate ions,anions and cations can inhibit the photodegradation of BPA.Compared with cations,anions have a greater inhibitory effect on BPA degradation.The degradation products of BPA by NCM were analyzed by gas chromatographic/mass.This study may provide useful information for the BPA degradation by NCM in complex water samples.

Fabrication and thermal decomposition of glycidyl azide polymer modified nitrocellulose double base propellants

Glycidyl azide polymer （GAP） with the advantages of non-volatility and excellent thermal stability is a candidate as a re- placement for nitroglycerine （NG） in a double base propellant. The GAP-NC double base propellants were formulated with GAP and nitrocellulose （NC） fibers. Tensile test and SEM characterization indicated that GAP-NC propellants had a homoge- neous structure. Thermogravimetric analysis of GAP-NC propellants revealed that the onset decomposition temperature reached a high level ranging from 192.9 to 194.6 ℃, which indicated that the substitution of NG with GAP contributed to the safe storage and process operations for double base propellant. The result analysis of decomposition products of GAP-NC propellants showed that the main gas decomposition products of the propellants were NO, NO〉 CO, CO2, NH3, CH4, HCN, N2 CH20 and C2H40. The thermal decomposition process of the specimens was proposed.

Theoretical studies on structure-property relationships of cellulose and nitrocellulose I.Conformation,stability and conductivity

The banding and electronic structures of a series of long-chain macromolecules of cellu- lose,2-,3-,6-mononitrocellulose,2,3-,2,6-,3,6-dinitrocellulose and trinitrocellulose as well as their structural units(i.e.single-,double-or three-ring systems)have been calculated by both the EH and CNDO/2 methods.The increase of molecular total energies is consistent with the decrease of their stabilities at the three conformations of gg,gt and tg.The Mulliken bond order of O—NO_2 bond is the samllest in each molecule at any of the three conformations,which indicates that this bond is the weakest,and supports the view of initial homolytic cleavage of O—NO_2 bond on slow thermal decomposition.The band gap at the edge of the first Brillouin zone far surpasses 5 eV for cellu- lose,and is less than 3 eV for mono-,di-,and trinitrocellulose.The results show that cellulose is a typical insulator,as we know,and it can be predicted that nitrocellulose has electric conductivity similar to that of semiconductor.

Nitration of Wood Cellulose in HNO_3/Organic Solvent Medium

A steam explosion pretreatment at various severities was applied to pure wood cellulose; the influences of steam pretreatment on the morphological structure, the hydrophilic property and viscosity-average molecular weight of cellulose were evaluated. The nitration of steam-exploded cellulose was carried out in the nitrating agent medium （HNOa/organic solvent）. The performance indexes of nitrocellulose, prepared from original and steam exploded samples, were determined by using the polarized optical microscope. The results show that after pretreatment the reactivity of the three hydroxyl groups in anhydroglucose unit of cellulose is improved, and the nitrogen content and the uniformity of NC from steam exploded cellulose observably increas.

Stereoselective Synthesis of Nontethered trans-4 Bis(aziridino)[60]fullerene Derivatives

Comprehensive Summary,The stereoselective preparation of fullerene bis-adducts through nontethered methods remains difficult due to the significant amount of regioisomers produced.The trans-4 aziridino[60]fullerenes,C_(60)(NC_(6)H_(4)R)n(n=1 or 2,R=OMe,OEt,OBu),were selectively synthesized even without a catalyst by reacting octabromofullerene with the corresponding aniline.Nuclear magnetic resonance spectroscopy,UV-vis spectroscopy,and X-ray structural analysis provided convincing characterization of the compounds.A possible reaction process was proposed to clarify the synthesis of highly regioselective trans-4-bisaziridino[60]fullerenes.The possible application of these aziridino[60]fullerene derivatives as propellant stabilizers was also explored.

Climatic significance of δD time series in tree rings from Tianmu Mountain

Based on cross-dating tree ring age from Tianmu Mountain, Zhejiang Province, theδD of each tree ring nitrocellulose was measured and then theδ D annual time series was established. Using meteorological data from Tianmu Mountain Observatory, the responds ofδ D of tree ring to climatic factors were analyzed. The results suggest that theδ D time series of the tree ring correlates well with climatic conditions, primarily with precipitation of the second half of each year, average annual air temperature and average annual maximum air temperature. The reconstructed maximum winter air temperature by theδ D of tree ring is in good correlation with local instrumental data. The low-frequency variations of reconstructed mean maximum air temperature of the winter in Tianmu Mountain corroborate with the temperature change in a large special scale. Tianmu Mountain is located in winter monsoon sensitive zone, thus the influence of winter temperature on tree growth is quite obvious. The results in this paper suggest thatδ D of tree ring is an effective proxy for winter temperature in non-limited regions.