Appropriate Supply of Ammonium Nitrogen and Ammonium Nitrate Reduces Cadmium Content in Rice Seedlings by Inhibiting Cadmium Uptake and Transport

Reasonable nitrogen(N) application is a promising strategy for reducing crop cadmium(Cd) toxicity. However, the specific form of N and the required amount that affect Cd tolerance and accumulation in rice remain unclear. This study explored the influence of different N-fertilizer forms(NH_(4)NO_(3), NH_4Cl, and KNO_(3)) and dosages on Cd tolerance and uptake in Cd-stressed N-sensitive and N-insensitive indica rice accessions. The results indicated that the Cd tolerance of N-sensitive indica accessions is more robust than that of N-insensitive ones. Furthermore, the shoot Cd content and Cd translocation rate in both N-sensitive and N-insensitive indica accessions decreased with an appropriate supply of NH_(4)NO_(3) and NH_4Cl, whereas they were comparable or slightly increased with increased KNO_(3). Unfortunately, we did not find significant and regular differences in Cd accumulation or translocation between N-sensitive and N-insensitive rice accessions. Consistent with the reduction of shoot Cd content, the addition of NH_(4)NO_(3) and NH_4Cl also inhibited the instantaneous root Cd^(2+) uptake. The expression changes of Cd transport-related genes under different N forms and dosages suggested that the decreased shoot Cd content, caused by the increased supply of NH_(4)NO_(3) and NH_4Cl, is likely achieved by reducing the transcription of OsNRAMP1 and OsIRT1. In summary, our findings reveal that an appropriate supply of NH_(4)NO_(3) and NH_4Cl could reduce Cd uptake and transport in rice seedlings, suggesting that rational N management could reduce the Cd risk in rice production.

Tailoring NH_(4)^(+)storage by regulating oxygen defect in ammonium vanadate

Defect engineering is an effective strategy for modifying the energy storage materials to improve their electrochemical performance.However,the impact of oxygen defect and its content on the electrochemical performances in the burgeoning aqueous NH_(4)^(+)storage field remains explored.Therefore,for the first time in this work,an oxygen-defective ammonium vanadate[(NH_(4))_(2)V_(10)O_(25)·8H_(2)O,denoted as Od-NHVO]with a novel 3D porous flower-like architecture was achieved via the reduction of thiourea in a mild reaction condition,which is a facile method that can realize the intention to regulate the oxygen defect content,with the capability of mass-production.The as-prepared Od_M-NHVO with moderate oxygen defect content can deliver a stable specific capacitance output(505 F g^(-1),252 mAh g^(-1)at 0.5 A g^(-1)with~80% capacitance retention after 10,000 cycles),which benefits from extra active sites,unimpeded NH_(4)^(+)-migration path and relatively high structure integrity.In contrast,low oxygen defect content will lead to the torpid electrochemical reaction kinetics while too high content of it will reduce the chargestorage capability and induce structural disintegration.The superior NH_(4)^(+)-storage behavior is achieved with the reversible intercalation/deintercalation process of NH_(4)^(+)accompanied by forming/breaking of hydrogen bond.As expected,the assembled flexible OdM-NHVO//PTCDI quasi-solid-state hybrid supercapacitor(FQSS HSC)also exhibits high areal capacitance,energy density and reliable flexibility.This work provides a new avenue for developing materials with oxygen-deficient structure for application in various aqueous non-metal cation storage systems.

Flame-retardant ammonium polyphosphate/MXene decorated carbon foam materials as polysulfide traps for fire-safe and stable lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries with high loading of flammable sulfur faces the challenges of electrochemical performance degradation owing to the shuttle effect and safety issues related to fire or explosion accidents.In this work,we report a three-dimensional(3D)conductive nitrogen-doped carbon foam supported electrostatic self-assembled MXene-ammonium polyphosphate(NCF-MXene-APP)layer as a heat-resistant,thermally-insulated,flame-retardant,and freestanding host for Li-S batteries with a facile and costeffective synthesis method.Consequently,through the use of NCF-MXene-APP hosts that strongly anchor polysulfides,the Li-S batteries demonstrate outstanding electrochemical properties,including a high initial discharge capacity of 1191.6 mA h g^(-1),excellent rate capacity of 755.0 mA h g^(-1)at 1 C,and long-term cycling stability with an extremely low-capacity decay rate of 0.12%per cycle at 2 C.More importantly,these batteries can continue to operate reliably under high temperature or flame attack conditions.Thus,this study provides valuable insights into the design of safe high-performance Li-S batteries.

Exploring the hygroscopic behavior of highly energetic oxidizer ammonium dinitramide(ADN)at different temperatures and humidities using an innovative hygroscopic modeling

Ammonium dinitramide(ADN)is a new type of green energetic oxidizer with excellent energy density and low pollution combustion characteristics.However,the strong hygroscopicity has a significant impact on its practical application.To assist in the research on moisture-proof modification of ADN materials,an innovative hygroscopic modeling approach was proposed to evaluate the hygroscopicity of ADN at various temperatures and humidities.By investigating the diffusion coefficient of water molecules in molecular dynamics processes,a visual insight into the hygroscopic process of ADN was gained.Furthermore,analyzing the non-covalent interactions between ADN and water molecules,the hygroscopicity of ADN could be evaluated qualitatively and quantitatively.The energy analysis revealed that electrostatic forces play a dominant role in the process of water adsorption by ADN,whereas van der Waals forces impede it.As a whole,the simulation results show that ADN presents the following hygroscopic law:At temperatures ranging from 273 K to 373 K and relative humidity(RH)from 10%to 100%,the hygroscopicity of ADN generally shows an increasing trend with the rise in temperature and humidity based on the results of three simulations.According to the non-hygroscopic point(298 K,52%RH)of ADN obtained by experiment in the literature,a non-hygroscopic range of temperature and humidity for ADN can be depicted when the simulation results in relative hygroscopicity is less than or equal to 17%.This study can provide effective strategies for screening anti-hygroscopic modified materials of ADN.

Evaluating the biosignature potential of ammonium in Proterozoic red beds and implications for the search for life on Mars

Over the past two decades,it has become increasingly apparent that early Mars may once have been warmer,wetter and more habitable for microbial life than it is today,which has spurred discussions about potential biosignatures that may be preserved in Martian sediments.An impediment to this line of research is the pervasive oxidation of Mars’surface due to photochemical oxidants that have likely destroyed remnants of organic matter.Here,we investigate whether nitrogen(N)transferred from biomass to phyllosilicate minerals during diagenesis can be preserved in oxidized mudrocks.We investigate two sequences of terrestrial Proterozoic red beds,namely the Sibley Group(1.4 Ga)in Canada and the Stoer Group(1.2 Ga)in Scotland,and we find enrichments in authigenic N in the range of several tens of ppm in both units.The highest concentrations(ca.100 ppm on average)are found in the most desiccated red beds of the Stoer Group,concurrent with enrichments in potassium(K).We discuss similarities and differences between the two sets of rocks with regards to salinity,pH,biological productivity and K-metasomatism,and we conclude that the ideal mechanism for the preservation of biogenic N in red beds may be in-situ release of ammonium from microbial mats into the clay substrate,possibly facilitated by early diagenetic,biologically induced illitization.Illite and smectite have been observed on Mars,and experiments suggest that Martian waters contained moderate amounts of dissolved K.Hence,it is conceivable that a similar K and N enrichment process could have occurred as to what we document for the Proterozoic,preserving evidence of life that may have survived to the modern day.

Ash removal from inferior coal via ammonium fluoride roasting and simultaneous yield of white carbon black

The quality upgrading and deashing of inferior coal by chemical method still faces great challenges.The dangers of strong acid,strong alkali,waste water and exhaust gas as well as high cost limit its industrial production.This paper systematically investigates the ash reduction and desilicification of two typical inferior coal utilizing ammonium fluoride roasting method.Under the optimal conditions,for fat coal and gas coal,the deashing rates are 69.02%and 54.13%,and the desilicification rates are 92.64%and 90.27%,respectively.The molar dosage of ammonium fluoride remains consistent for both coals;however,the gas coal,characterized by a lower ash and silica content(less than half that of the fat coal),achieves optimum deashing effect at a reduced time and temperature.The majority of silicon in coal transforms into gaseous ammonium fluorosilicate,subsequently preparing nanoscale amorphous silica with a purity of 99.90%through ammonia precipitation.Most of the fluorine in deashed coal are assigned in inorganic minerals,suggesting the possibility of further fluorine and ash removal via flotation.This research provides a green and facile route to deash inferior coal and produce nano-scale white carbon black simultaneously.

A review on surface coating strategies for anti-hygroscopic of high energy oxidizer ammonium dinitramide

Ammonium dinitramide(ADN),which has the advantages of high energy density,no halogen and low characteristic signal,is not only considered as a new high-energy oxidizer that is expected to replace the traditional oxidizer ammonium perchlorate(AP)in solid propellants,but also a good performance explosive in itself.However,due to the strong hygroscopicity of ADN,its application in solid propellants and explosives is greatly limited.Solving the hygroscopicity of ADN is the key to realize the wide application of ADN.In this paper,we systematically review the research progress of anti-hygroscopic strategies of ADN coating.The surface coating methods are focusing on solvent volatilization,solvent-non-solvent,melt crystallization and atomic layer deposition technology.The characteristics of the different methods are compared and analyzed,and the basis for the classification and selection of the coating materials are introduced in detail.In addition,the feasibility of material for surface coating of ADN is evaluated by several compatibility analysis methods.It is highly expected that the liquid phase method(solvent volatilization method,solvent-non-solvent method)would be the promising method for future ADN coating because of its effective,safety and facile operation.Furthermore,polymer materials,are the preferred coating materials due to their high viscosity,easy adhesion,good anti-hygroscopic effect,and heat resistance,which make ADN weak hygroscopicity,less sensitive,easier to preserve and good compatibility.

Simple preparation of C(CS)/g-C_(3)N_(4)/Co carbon aerogel and its catalytic performance for ammonium perchlorate

Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a catalytic center point.The carbon aerogel(C(CS)/g-C_(3)N_(4)/Co)with a three-dimensional network-like structure was prepared by assembling the three materials through experimental operations such as freeze-drying and high-temperature carbonization.It was demonstrated by scanning and transmission characterization that the CS in the carbon aerogel could provide more active sites for the cobalt nanoparticles,and the doping of graphite-phase carbon nitride as a template dispersed the cobalt nanoparticles and changed the conductivity of the CS.To investigate the catalytic effect of carbon aerogel on ammonium perchlorate(AP),it was investigated by differential thermal analyzer and TG thermal analysis.This carbon aerogel was very effective in catalyzing AP,and the 10 wt% content of the catalyst reduced the AP pyrolysis peak from 703.9 to 595.5 K.And to further investigate the synergistic effect of the three materials,further carbon aerogels such as C(CS)/Co,g-C_(3)N_(4)/Co were prepared and applied to catalyze AP,and the same ratio reduced the AP pyrolysis peak by 98.1℃ and 97.7℃.This result indicates a synergistic effect of the assembly of the three materials.

Influence of ammonium sulfate on the corrosion behavior of AZ31 magnesium alloy in chloride environment

Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform corrosion.Acceleration effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion process.The latter is demonstrated as the dominant factor with the results in unbuffered and buffered environments.The severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low frequency.Meanwhile,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.

Synchronous organic-inorganic co-intercalated ammonium vanadate cathode for advanced aqueous zinc-ion batteries

Vanadium-based cathode materials are attractive for aqueous zinc-ion batteries(AZIBs)owing to the high capacity from their open frameworks and multiple valences.However,the cycle stability and rate capability are still restricted by the low electrical conductivity and trapped diffusion kinetics.Here,we propose an organic-inorganic co-intercalation strategy to regulate the structure of ammonium vanadate(NH_(4)V_(4)O_(10),NVO).The introduction of Al^(3+)and polyaniline(PANI)induces the optimized layered structure and generation of urchin-like hierarchical construction(AP-NVO),based on heterogeneous nucleation and dissolution-recrystallization growth mechanism.Owing to these favorable features,the AP-NVO electrode delivers a desirable discharge capacity of 386 mA h g^(-1) at 1.0 A g^(-1),high-rate capability of 263 mA h g^(-1 )at 5.0 A g^(-1) and excellent cycling stability with 80.4%capacity retention over 2000 cycles at 5.0 A g^(-1).Such satisfactory electrochemical performance is believed to result from the enhanced reaction kinetics provided by the stable layered structure and a high intercalation pseudo-capacitance reaction.These results could provide enlightening insights into the design of layered vanadium oxide cathodematerials.

Structure and electrical properties of polysilicon films doped with ammonium tetraborate tetrahydrate

Here,p-type polysilicon films are fabricated by ex-situ doping method with ammonium tetraborate tetrahydrate(ATT)as the boron source,named ATT-pPoly.The effects of ATT on the properties of polysilicon films are comprehensively analyzed.The Raman spectra reveal that the ATT-pPoly film is composed of grain boundary and crystalline regions.The preferred orientation is the(111)direction.The grain size increases from 16−23 nm to 21−47 nm,by~70%on average.Comparing with other reported films,Hall measurements reveal that the ATT-pPoly film has a higher carrier concentration(>10^(20)cm^(−3))and higher carrier mobility(>30 cm2/(V·s)).The superior properties of the ATT-pPoly film are attributed to the heavy doping and improved grain size.Heavy doping property is proved by the mean sheet resistance(Rsheet,m)and distribution profile.The R_(sheet,m)decreases by more than 30%,and it can be further decreased by 90%if the annealing temperature or duration is increased.The boron concentration of ATT-pPoly film annealed at 950℃ for 45 min is~3×10^(20)cm^(−3),and the distribution is nearly the same,except near the surface.Besides,the standard deviation coefficient(σ)of Rsheet,m is less than 5.0%,which verifies the excellent uniformity of ATT-pPoly film.

Micro-aluminum powder with bi-or tri-component alloy coating as a promising catalyst:Boosting pyrolysis and combustion of ammonium perchlorate

A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.

Biobased Furfurylated Poplar Wood for Flame-Retardant Modification with Boric Acid and Ammonium Dihydrogen Phosphate

Furfurylated wood exhibits excellent dimensional stability and corrosion resistance,making it a promising material for constructing buildings,but it is highly flammable.Herein,flame-retardant furfurylated poplar wood was produced via a two-step process utilizing boric acid(BA)and ammonium dihydrogen phosphate(ADP)as flame-retardant components,and biomass-derived furfuryl alcohol(FA)as a modifier.The acidity of BA and ADP allowed them to catalyze the polymerization of FA,which formed a cross-linked network that immobilized BA and ADP inside the wood.The addition of BA/ADP substantially delayed the time to ignition from 10 to 385 s and reduced the total heat release and total smoke release by 58.75%and 77.31%,respectively.Analysis of the pyrolysis process showed that the decomposition products of BA and ADP protected the underlying furfurylated wood and diluted combustible gases.This method significantly improved the fire retardancy and smokeless properties of furfurylated wood,providing promising prospects for its application as an engineering material.

Humic Acid Effects on Reducing Corn Leaf Burn Caused by Foliar Spray of Urea-Ammonium Nitrate at Different Humic Acid/Urea-Ammonium Nitrate Ratios

Technologies for reducing corn leaf burn caused by foliar spray of urea-ammonium nitrate (UAN) during the early growing season are limited. A field experiment was carried out to evaluate the effects of humic acid on corn leaf burn caused by foliar spray of undiluted UAN solution on corn canopy at Jackson, TN in 2018. Thirteen treatments of the mixtures of UAN and humic acid were evaluated at V6 of corn with different UAN application rates and different UAN/humic acid ratios. Leaf burn during 1 2, 3, 4, 5, 6, 7, and 14 days after UAN foliar spray significantly differed between with or without humic acid addition. The addition of humic acid to UAN significantly reduced leaf burn at each UAN application rate (15, 25, and 35 gal/acre). The reduction of leaf burn was enhanced as the humic acid/UAN ratio went up from 10% to 30%. Leaf burn due to foliar application of UAN became severer with higher UAN rates. The linear regression of leaf burn 14 days after application with humic acid/UAN ratio was highly significant and negative. However, the linear regression of leaf burn 14 days after application with the UAN application rate was highly significant and positive. In conclusion, adding humic acid to foliar-applied UAN is beneficial for reducing corn leaf burn during the early growing season.

Solid-liquid phase equilibrium for the system ammonium polyphosphate-urea ammonium nitrate-potassium chloride-water at 273.2 K

Based on the dynamic method,a quaternary system of ammonium polyphosphate (APP)-urea ammonium nitrate (UAN,CO(NH_(2))_(2)-NH_(4)NO_(3))-potassium chloride (KCl)-H_(2)O and its subsystems (APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O and APP-KCl-H_(2)O) were systematically investigated at the temperature of 273.2 K.Each ternary phase diagram contains one invariant point and three crystallization regions.The crystallization regions are:(1)(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7)and ((NH_(4))_(3)HP_(2)O_(7)+(NH_(4))_(4)P_(2)O_(7)) for APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram;(2) KCl,KNO_(3)and(KCl+KNO_(3)) for KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O diagram and (3)(NH_(4))_(3)HP_(2)O_(7),KCl and((NH_(4))_(3)HP_(2)O_(7)+KCl) for APP-KCl-H_(2)O diagram.The quaternary phase diagram of APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-KCl-H_(2)O has no quaternary invariant point but includes four solid phase crystallization regions,i.e.,(NH_(4))_(3)HP_(2)O_(7),(NH_(4))_(4)P_(2)O_(7),KNO_(3)and KCl,in which the KNO_(3)region occupies the largest area.The maximum total nutrient content (N+P_(2)O_(5)+K_(2)O) existing as ionic forms in the APP-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,KCl-[CO(NH_(2))_(2)-NH_(4)NO_(3)]-H_(2)O,APP-KCl-H_(2)O and quaternary systems is 44.70%,32.86%,45.56%and 46.23%(mass),respectively,indicating that the maximum nutrient content can be reached using raw materials of the corresponding systems to prepare liquid fertilizer.In the quaternary system,the content of NH_(4)~+-N ascends with the increase of the total nutrient content,while the contents of NO_(3)^(-)-N and CO(NH_(2))_(2)-N increase with elevated total N.This work can help optimize the operating parameters for the production,storage and transportation of liquid fertilizers.

Activation mechanism of ammonium oxalate with pyrite in the lime system and its response to flotation separation of pyrite from arsenopyrite

The activation properties of ammonium oxalate on the flotation of pyrite and arsenopyrite in the lime system were studied in this work.Single mineral flotation tests showed that the ammonium oxalate strongly activated pyrite in high alkalinity and high Ca^(2+)system,whereas arsenopyrite was almost unaffected.In mineral mixtures tests,the recovery difference between pyrite and arsenopyrite after adding ammonium oxalate is more than 85%.After ammonium oxalate and ethyl xanthate treatment,the hydrophobicity of pyrite increased significantly,and the contact angle increased from 66.62°to 75.15°and then to 81.21°.After ammonium oxalate treatment,the amount of ethyl xanthate adsorption on the pyrite surface significantly increased and was much greater than that on the arsenopyrite surface.Zeta potential measurements showed that after activation by ammonium oxalate,there was a shift in the zeta potential of pyrite to more negative values by adding xanthate.X-ray photoelectron spectroscopy test showed that after ammonium oxalate treatment,the O 1s content on the surface of pyrite decreased from 44.03%to 26.18%,and the S 2p content increased from 14.01%to 27.26%,which confirmed that the ammonium oxalatetreated pyrite surface was more hydrophobic than the untreated surface.Therefore,ammonium oxalate may be used as a selective activator of pyrite in the lime system,which achieves an efficient flotation separation of S-As sulfide ores under high alkalinity and high Ca2+concentration conditions.

A review on the high energy oxidizer ammonium dinitramide:Its synthesis,thermal decomposition,hygroscopicity,and application in energetic materials

Ammonium dinitramide(ADN)is considered as a potential substitute for ammonium perchlorate in energetic materials due to its high density,positive oxygen balance,and halogen-free characteristics.However,its application has been severely limited because of its strong hygroscopicity,difficult storage,and incompatibility with isocyanate curing agents.In order to better bloom the advantages of the highly energetic and environment-friendly ADN in the fields of energetic materials,an in-depth analysis of the current situation and discussion of key research points are particularly important.In this paper,a detailed overview on the synthesis,thermal decomposition,hygroscopic mechanism,and antihygroscopicity of ADN has been discussed,its application in powdes and explosives are also presented,and its future research directions are proposed.

Adsorption characteristics of Pb(Ⅱ)ions on sulfidized hemimorphite surface under ammonium sulfate system

In this work,the effect of ammonium sulfate on the adsorption characteristics of low-concentration Pb(Ⅱ)ions on the sulfidized hemimorphite surface was comprehensively investigated.The results showed that ammonium sulfate could increase the maximum recovery of hemimorphite from 69.42%to 88.24%under a low concentration of Pb(Ⅱ)ions.On the hemimorphite surface pretreated with ammonium sulfate,the adsorption of Pb(Ⅱ)ions was enhanced and the main species of Pb adsorbed was changed from Pb―O/OH to PbS.This was due to the larger amount of ZnS providing more effective adsorption sites for Pb components to generate Pb S.Meanwhile,the intensity of ZnS decreased with the formation of PbS,demonstrating that ZnS was covered by PbS which formed later on the mineral surface.It was beneficial for the adsorption of butyl xanthate on the hemimorphite surface to form more hydrophobic substances.As a result,ammonium sulfate played a crucial role in realizing the efficient recovery of hemimorphite.

Studies on ammonium dinitramide and 3,4-diaminofurazan cocrystal for tuning the hygroscopicity

Ammonium dinitramide(ADN)is a promising oxidizer with high energy characteristic,which is a relatively new environmentally friendly oxidizer without halogens and carbon elements.However,ADN has high hygroscopicity when exposed to high humidity air,restricting its applications on the solid propellants.In this paper,a novel energetic cocrystal composed of ammonium dinitramide and 3,4-diaminofurazan(DAF)was proposed and successfully synthesized by antisolvent crystallization method,and the properties of the cocrystal were systematically investigated by analytical characterization and theoretical simulation calculations.The formation of the cocrystal was confirmed by powder X-ray diffraction,differential scanning calorimetry,scanning electron microscopy,infrared spectroscopy and Raman spectroscopy,indicating that the synthesized product was a cocrystal.Through theoretical studies,the ADN/DAF cocrystal structure was predicted,and the powder X-ray diffraction,morphology,water sorption capacity of ADN/DAF cocrystal were calculated,which was consistent with experimental phenomena.The results showed that newly prepared cocrystal of ADN/DAF had lower hygroscopicity compared to pure ADN,and the water sorption capacity was reduced from 15.35%to 7.90%.This may be due to the formation of N-H…O medium-strength hydrogen bonds between the ammonium ion of ADN and the O atom of DAF in the cocrystal,which prevents the binding of water molecules in the air and ammonium ions and reduces the probability of ADN binding to water molecules,leading to the reduction of cocrystal hygroscopicity.The newly prepared energetic cocrystal can provide theoretical and technical guidance for the study of the anti-hygroscopicity of ADN and advance the practical application of ADN.

Wettability alteration of organo-vermiculites induced by layer charge and tailored bis-N-heterocyclic quaternary ammonium salts

Wettability is an important surface property that deserves to further explore the factors on its alteration.Series of bis-N-heterocyclic quaternary ammonium salts with different spacer length and N-heterocyclic headgroups(morpholinium(BMMB,BMMD and BMMH),piperidinium(BPMH)and piperazinium(BMPMH))have been synthesized and employed for altering the wettability of vermiculite and its derivates(Vts)treated by Li^(+)-saturated heating method.The results of X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),thermogravimetric analysis(TG-DTG),scanning electron microscopy(SEM)and N_(2)adsorption/desorption isotherms indicate that all of the bis-N-heterocyclic quaternary ammonium salts have been successfully inserted into the vermiculite layers,leading to the organic monolayer.The results of capillary rise tests combined with Lipophilic to Hydrophilic Ratio(LHR)values unveil the wettability alteration of the organo-Vts.As the layer charge decreases,the hydrophilicity of the organo-Vts gradually increases,which is probably caused by the decline in binding sites.As the result of the change in spacer length of modifier,the wetting properties of morpholinium-based organo-Vts change in order of BMMD-Vts>BMMH-Vts>BMMB-Vts,and difference in N-heterocyclic headgroups leads to the sequence of wettability:BMPMH-Vts>BPMH-Vts>BMMH-Vts.Layer charge of Vt,spacer length and the type of the N-heterocyclic headgroup of modifier have the synergistic effect on the regulation of the wettability.