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.

Negative Thermal Expansion of (ZrMg)xY2-2xMo3O12 Ceramics with Low Hygroscopicity

(ZrMg)xY2-2xMo3O12(x=0.0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,and 1)ceramics have been synthesized to obtain less hygroscopicity and negative thermal expansion.With increasing the substitution of(ZrMg)^6+(ion radius 7.2×10^-11 m)for Y3+(ion radius 9×10^-11 m),the crystal water are reduced obviously.The linear thermal expansion coefficient is improved with increasing the content of(ZrMg)^6+.The material shows near zero thermal expansion(-0.12×10^-6 K^-1,430-870 K)with x=0.7.Meanwhile,ZrMgMo3O12 shows low non-hygroscopicity and negative thermal expansion,but low softening temperature.After substituting amount of Y^3+for(ZrMg)^6+in ZrMgMo3O12(x=0.8),the softening temperature increases remarkably(750 K to 830 K)and it presents near zero thermal expansion.

Insight into the behavior at the hygroscopicity and interface of the hydrophobic imidazolium-based ionic liquids

How to completely remove the water from ionic liquids(ILs)is difficult for researchers because of the hygroscopicity of ILs.In order to study the hygroscopicity of ILs,two kinds of ILs,1-Butyl-3-methylimidazolium hexafluorophosphate([Bmim][PF6])and 1-Butyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)([Bmim][NTf_(2)])were investigated by molecular dynamics simulations.Although[Bmim][PF6]and[Bmim][NTf_(2)]are hydrophobic,both of the ILs could absorb water molecules from the vapor.In this work,the process of absorbing water from the vapor phase was studied,and the water molecules could disperse into the IL.Aggregation was observed with increasing the water concentration.Although the absorbed water increases obviously,the amount of free water and small cluster in the ILs does not change significantly and always stays at a certain level.The amount of free water and small cluster in[Bmim][PF6]is more than that in[Bmim][NTf_(2)],which is consistent with their hydrophobicity.In addition,the liquid-vacuum and liquid–liquid interfaces of the ILs were simulated and analyzed in detail.The number density distribution and angle distribution indicated that[Bmim]+cations arrangement regularly at the IL-vacuum interface.The butyl chain point to the vacuum,while the imidazlium ring is close to the IL phase region and perpendicular to the interface.While at the IL-water interface,the cations and anions are disordered.

Surface modification of ammonium nitrate by coating with surfactant materials to reduce hygroscopicity

Ammonium nitrate(AN)is promising oxidizer in green propellants.In this work,the physical coating method was improved to modify the surface of ammonium nitrate particles with different surfactant materials to reduce hygroscopicity.Cetylalcohoi,stearic acid,stearyl alcohol,palmic acid,lauric acid,stearsmide,tetradecylamine,dodecylamine,and tetradecanol were used as coating surfactant agents.The hygroscopicity was tested for ammonium nitrate with and without coating.Fourier transform infrared(FTIR)and scanning electron microscopy(SEM)were used to characterize the surface of coated and uncoated ammonium nitrate.The mass ratio of coating layer and decline of absorption rate of ammonium nitrate coated by cetylalcohol were 1.00%,and 28.40%,respectively.The results indicate that coating with cetylalcohol surfactant have advantages over the other surfactants in term of low mass ratio of coating layer,and high decline of moisture absorption rate.Thus,cetylalcohol would be a promising coating surfactant material for ammonium nitrate.The idea and approach presented in this study have potential to made hydrophobic layer on the surface of particles to reduce hygroscopicity of AN,and also help the researcher to improving anti-hygroscopicity of ammonium salts.

Study on Improvement of Hygroscopicity of Magnesite-Bonded Wood Wool Panel

Magnesite-bonded wood wool panel(MWWP)is an inorganic-bonded panel product in which wood excelsior is bonded with magnesite.Lowering the hygroscopicity is one of the key measures to improve the quality of the panel.In this study,moisture absorption mechanism of MWWP and measures generally applied to lower its hygroscopicity were reviewed.Three methods were then experimented to improve the dimensional stability of the panel,including adjusting the molar ratio of raw materials,adding additives and optimizing the conditioning process.The results showed that satisfying dimensional stability could be achieved when the molar ratio of MgO to MgCl_(2) was 5:1,the No.2 composite additive(aluminum powder+NH_(4)H_(2)PO_(4)+ferric alum)was adopted and a constant temperature and humidity treatment was applied in the first stage of conditioning.

Compositional evolution for mixed aerosols containing gluconic acid and typical nitrate and the effect of multiply factors on hygroscopicity

The aging process of atmospheric aerosols usually leads to a mixture of inorganic salts and organic compounds of anthropogenic origin.In organic compounds,polyhydroxy organic acids are important components,however,the study on composition and hygroscopic properties of the mixture containing inorganics and polyhydroxy organic acids is scanty.In this study,gluconic acid,the proxy of polyhydroxy organic acids,is mixed with the representative nitrate(Mg(NO_(3))_(2),Ca(NO_(3))_(2))to form aerosols.ATR-FTIR and optical microscopy are employed to study the component changes and hygroscopicity as a function of relative humidity.As relative humidity fluctuates,the FTIR-ATR spectra display that the internal mixed gluconic acid(CH_(2)(CH)_(4)(OH)_(5)COOH)and nitrate can react to release acidic gases,forming relevant gluconate and further affecting the hygroscopicity.The specific presentation is particles cannot be recovered to their original size after the dehydration-hydration process and there will be some disparities in GF for mixed particles.For the gluconic acid-Ca(NO_(3))_(2)/Mg(NO_(3))_(2)mixtures with molar ratios of 1:1,higher degree of reaction resulting in the production of large amounts of gluconate should be responsible to the lower hygroscopicity compared to ZSR model.For 1:2 gluconic acid-nitrate mixed systems(with higher nitrate content),the hygroscopicity of mixtures are higher than the ZSR prediction.A possible reason could be‘salt-promoting effect’on the organic fractions of the surplus inorganic salt in the mixture.These data can improve the chemical composition list evaluation,in turn hygroscopic properties and phase state of atmospheric aerosol,and then the climate effect.

Atmospheric Particle Hygroscopicity and the Influence by Oxidation State of Organic Aerosols in Urban Beijing

A hygroscopic tandem differentialmobility analyser(H-TDMA)was used to observe the sizeresolved hygroscopic characteristics of submicron particles in January and April 2018 in urban Beijing.The probability distribution of the hygroscopic growth factor(HGF-PDF)in winter and spring usually showed a bimodal pattern,with more hygroscopic mode(MH)being more dominant.The seasonal variation in particle hygroscopicity was related to the origin of air mass,which received polluted southerly air masses in spring and clean northwesterly air masses in winter.Particles showed stronger hygroscopic behaviour during heavy pollution episodes(HPEs)with elevated concentrations of secondary aerosols,especially higher mass fraction of nitrate,which were indicated using the PM2.5(particulate matter with diameter below 2.5μm)mass concentration normalised by CO mass concentration.The hygroscopic parameter(κ)values were calculated using H-TDMA(κhtdma)and chemical composition(κchem).The closure study showed thatκchem was overestimated in winter afternoon when compared withκhtdma,because the organic particle hygroscopic parameter(κorg)was overestimated in the calculations.It was influenced by the presence of a high concentration of hydrocarbon-like organic aerosol(HOA)with a weak water uptake ability.A positive relationship was observed betweenκorg and the ratio of oxygenated organic aerosol(OOA)and HOA,thereby indicating that the strong oxidation state enhanced the hygroscopicity of the particles.This study revealed the effect of local emission sources and secondary aerosol formation processes on particle hygroscopicity,which is of great significance for understanding the pollution formation mechanism in the North China Plain.

Aerosol Hygroscopicity during the Haze Red-Alert Period in December 2016 at a Rural Site of the North China Plain

A humidification system was deployed to measure aerosol hygroscopicity at a rural site of the North China Plain during the haze red-alert period 17–22 December 2016. The aerosol scattering coefficients under dry [relative humidity（RH） 〈 30%] and wet（RH in the range of 40%–85%） conditions were simultaneously measured at wavelengths of450, 550, and 700 nm. It is found that the aerosol scattering coefficient and backscattering coefficient increased by only 29% and 10%, respectively when RH went up from 40% to 80%, while the hemispheric backscatter fraction went down by 14%, implying that the aerosol hygroscopicity represented by the aerosol scattering enhancement factor f（RH） is relatively low and RH exerted little effects on the aerosol light scattering in this case. The scattering enhancement factors do not show significant differences at the three wavelengths, only with an approximate 2% variation, suggesting that the aerosol hygroscopicity is independent of the wavelength. Aerosol hygroscopicity is highly dependent on the aerosol chemical composition. When there is a large mass fraction of inorganics and a small mass fraction of organic matter, f（RH） reaches a high value. The fraction of NO3^- was strongly correlated with the aerosol scattering coefficient at RH = 80%, which suggests that NO3^- played an important role in aerosol hygroscopic growth during the heavy pollution period.

Hygroscopicity of particles generated from photooxidation of α-pinene under diferent oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of α-pinene/NOx with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer （TDMA） in terms of hygroscopic growth factor （Gf）, with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols （SOA） formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor （ACSM） and matrix factorization （PMF） method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.

Hygroscopicity of ambient submicron particles in urban Hangzhou,China

In this study,hygroscopicity of size-segregated ambient submicron particles in urban Hangzhou was studied from 28th December 2009 to 18th January 2010,using a hygroscopicity-tandem differential mobility analyzer(H-TDMA).The submicron particles in Hangzhou showed a minor hygroscopic growth at 73%relative humidity(RH),and then grew significantly between 77%and 82%RH.Monomodal distribution accounted for 90%for 30 nm particles,17%for 50 nm particles,and less than 7%for particles larger than 50 nm at 82%RH.Deconvolution of the bimodal distribution indicated a less hygroscopic group and a more hygroscopic group,with the fraction of the more hygroscopic group increasing with the initial dry particle size and then remaining almost constant for accumulation mode particles.Our results imply that submicron particles in urban Hangzhou were almost entirely externally mixed,and the hygroscopic properties of ambient particles in urban Hangzhou were mainly a function of their size and chemical composition.

Hygroscopicity measurement of sodium carbonate,β-alanine and internally mixed β-alanine/Na2CO3 particles by ATR-FTIR

Water-uptakes of pure sodium carbonate(Na2CO3),pureβ-alanine and internally mixedβ-alanine/Na2CO3 aerosol particles with different mole ratios are first monitored using attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR)technique.For pure Na2CO3 aerosol particles,combining the absorptions at 877 and 1422 cm-1 with abrupt water loss shows the efflorescence relative humidity(ERH)of 62.9%–51.9%.Upon humidifying,solid Na2CO3 firstly absorbs water to from Na2CO3·H2O crystal at 72.0%RH and then deliquesces at 84.5%RH(DRH).As for pureβ-alanine particles,the crystallization takes place in the range of 42.4%–33.2%RH and becomes droplets at^88.2%RH.Whenβ-alanine is mixed with Na2CO3 at various mole ratios,it shows no efflorescence of Na2CO3 whenβ-alanine to Na2CO3 mole ratio(OIR)is 2:1.For 1:1 and 1:2β-alanine/Na2CO3 aerosols,the ERHs of Na2CO3 are 51.8%–42.3%and 57.1%–42.3%,respectively.Whileβ-alanine crystal appears from 62.7%RH for 2:1 and 59.4%RH for both 1:1 and 1:2 particles and lasts to driest state.On hydration,the DRH is 44.7%–75.2%for Na2CO3 with the OIR of 1:1 and 44.7%–69.0%for 1:2 mixture,and those of β-alanine are 74.8% for 2:1 mixture and 68.9%for two others.After the first dehumidification–humidification,all the water contents decrease despite of constituent fraction.And at^92%RH,the remaining water contents are 92%,89%and 82%at^92%RH,corresponding to OIR of 2:1,1:1 and 1:2 mixed system,respectively.

Water uptake of multicomponent organic mixtures and their influence on hygroscopicity of inorganic salts

The hygroscopic behaviors of atmospherically relevant multicomponent water soluble organic compounds（WSOCs） and their effects on ammonium sulfate（AS） and sodium chloride were investigated using a hygroscopicity tandem differential mobility analyzer（HTDMA） in the relative humidity（RH） range of 5%–90%. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model（E-AIM） and Zdanovskii–Stokes–Robinson（ZSR） method. The equal mass multicomponent WSOCs mixture containing levoglucosan, succinic acid, phthalic acid and humic acid showed gradual water uptake without obvious phase change over the whole RH range. It was found that the organic content played an important role in the water uptake of mixed particles.When organic content was dominant in the mixture（75%）, the measured hygroscopic growth was higher than predictions from the E-AIM or ZSR relation, especially under high RH conditions. For mass fractions of organics not larger than 50%, the hygroscopic growth of mixtures was in good agreement with model predictions. The influence of interactions between inorganic and organic components on the hygroscopicity of mixed particles was related to the salt type and organic content. These results could contribute to understanding of the hygroscopic behaviors of multicomponent aerosol particles.

The Coiling of Split Dandelion Scape Induced by Cell Hygroscopicity

It is of great significance to study the water absorption and expansion of cells,which are essential for the growth and life regulation of plants,not only for understanding the complex life phenomena of plants,but also for the manufacture of biomimetic materials.The main purpose of this study is to shed light on the mechanism of a novel coiling phenomenon of the split dandelion scape soaked in water and the high concentration mannitol solution.We discovered that the difference between water absorption/dehydration capacities of inner cells and lateral cells of the split dandelion scape generates asymmetric expansion/contraction between inner and lateral layers,resulting two opposite coiled patterns.Analogous to the deformable hypothesis of the thermal expansion model,the water absorption-induced cell expansion model was proposed to explain the coiling process of the split dandelion scape.Both the simulation and experimental results revealed that the coiling of dandelion scape is strongly depended on the response of cells to the stimulation of the solution environment.Showing considerable potential load bearing capacity of plants,the coiling phenomenon can be an inspiration to the designs of soft robots and bionic sensors for humidity control.

Hygroscopicity and optical properties of alkylaminium sulfates

The hygroscopicity and optical properties of alkylaminium sulfates （AASs） were investigated using a hygroscopicity tandem differential mobility analyzer coupled to a cavity ring-down spectrometer and a nephelometer. AAS particles do not exhibit a deliquescence phenomenon and show a monotonic increase in diameter as the relative humidity （RH） ascends. Hygroscopic growth factors （GFs） for 40, 100 and 150 nm alkylaminium sulfate particles do not show an apparent Kelvin effect when RH is less than 45%, whereas GFs of the salt aerosols increase with initial particle size when RH is higher than 45%. Calculation using the Zdanovskii-Stokes-Robinson mixing rule suggests that hygroscopic growth of triethylaminium sulfate-ammonium sulfate mixtures is non-deliquescent, occurring at very low RH, implying that the displacement of ammonia by amine will significantly enhance the hygroscopicity of （NH4）2SO4 aerosols. In addition, light extinction of AAS particles is a combined effect of both scattering and absorption under dry conditions, but is dominated by scattering under wet conditions.

Synthesis,Characterization and Water Absorption Analysis of Highly Hygroscopic Bio-based Co-polyamides 56/66

This study aims to develop highly hygroscopic bio-based co-polyamides(CPs)by melt co-polycondensation of polyamide(PA)56 salt and PA66 salt with varying molar fractions.The functional groups and the chemical structure of the prepared samples were determined by Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(^(1)H-NMR)spectroscopy.The relative viscosity was determined with an Ubbelohde viscometer.The melting behavior and the thermal stability of CPs were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Furthermore,the water absorption behavior of CP hot-pressed film was studied.The results reveal that the melting point,the crystallization temperature and the crystallinity of CPs firstly decrease and then increase with the molar fraction of PA66 in CPs.The copolymerization of PA56 with PA66 leads to an obvious increase in water absorption.The CPs with PA66 molar fraction of 50%possess a high saturated water absorption rate of 17.6%,compared to 11.6%for pure PA56 and 7.8%for pure PA66.

Recent Progress of Aerosol Light-scattering Enhancement Factor Studies in China

Assessment of the radiative forcing of aerosols in models still lacks sufficient input data for aerosol hygroscopicity. The light scattering enhancement factor [ f(RH, λ)] is a crucial parameter for describing aerosol hygroscopic growth properties.In this paper, we provide a survey of f(RH, λ) studies in China for the past seven years, including instrument developments of humidified nephelometers, ambient f(RH, λ) measurements in China, f(RH, λ) parameterization schemes, and f(RH, λ)applications in aerosol measurements. Comparisons of different f(RH, λ) parameterizations are carried out to check their performance in China using field measurement datasets. We also summary the parameterization schemes for predicting f(RH, λ)with aerosol chemical compositions. The recently developed methods to observe other aerosol properties using f(RH, λ)measurements, such as calculating the aerosol hygroscopicity parameter, cloud condensation nuclei number concentration,aerosol liquid water content, and aerosol asymmetry factor, are introduced. Suggestions for further research on f(RH, λ) in China are given.

In situ DRIFTS study of hygroscopic behavior of mineral aerosol

In situ diffusion reflectance infrared Fourier transform spectroscopy was used to study the water adsorption on mineral oxides （SiO2, a-Al2O3, MgO, Fe2O3, TiO2）. The results showed that all the water adsorption isotherms were well fitted with the Brunauer-Emmett-Teller （BET）-Ⅲ type equation, with the calculated monolayers occurring at 24%-30% relative humidity. It showed that about 1-5 layers of water adsorbed on oxides surfaces in ambient relative humidity （20%-90%）. The measured deliquescence relative humidity of NaCl was （74 ± 1）%, which demonstrated that DRIFTS is a useful method for the study the hygroscopic behavior of mineral dust. In addition, the limits of DRIPTS were also discussed.

Preparation of Triethylene Glycol Maleate and Its Effect on Plasticization of Oxidized Starch

A plasticizer triethylene glycol maleate（TEG-MA） was synthesized. The dominated monoester of moderate hydrophobicity with apparent oil-water partition coefficient of 0.042 in the product was confirmed by acid value determination, HPLC and FTIR. Its plasticizing effect on oxidized starch was manifested by crystallization, aging behaviour, moisture absorption, and mechanical performance. X-ray diffraction data showed that the relative crystallinity of the plasticized starch decreased. Both the crystal and the crystallinity of starch films were rarely changed in aging. Moisture absorption relied on the ester content and relative humidity. The elongation at break increased significantly with plasticizer content more than 10% in the matrix.

Production of Wood Fibers from Thermally Treated Wood

The reduction of the hygroscopicity of wood fibers was investigated through a Thermal Treatment(TT)on wood chips performed before the defibering process.The TT and defibering tests were both carried out on a continuous pilot at semi-industrial scale.The thermal treatment study of wood chips,equivalent to a low temperature pyrolysis,was achieved for four conditions(280°C–320°C)for a duration of 10 min.Mass quantification of solids,condensables and gases(FTIR)at the outcome of the thermal treatment allowed to achieve the mass balances for each condition.The increase of the reactor temperature from 280°C to 320°C leads to a lower solid yield(94%–82%)while gaseous(1%–3.8%)and condensable(3%–11%)products increase significantly.Thermally treated wood samples were afterwards successfully defibered in different conditions to produce suitable fibers for insulation panel production.The aim of the study is also to evaluate the effects of the TT on the lowering of energy consumption necessary for the defibering process while producing good quality fibers.Energy consumption during defibering process shows a significant decrease with the increase the TT severity.Fiber morphology is affected by TT and the morphological quality of the fibers decreases as TT severity increases.The mass percentage of dust was also quantified as a quality marker of produced fibers.Measurements of equilibrium moisture(at 20°C and 65%RH)of the different materials(wood chips before and after TT,produced fibers)show a significant effect of the TT on wood chips hygroscopicity(8.2%for untreated wood to 4.1%for TT at 320°C).However,the effect of the TT on the hygroscopicity reduction of thermally treated wood fibers is drastically less significant due to breaking of the wood structure during defibering process.

Study on the Factors to Influence Dynamic Heat - moisture Comfort of Summer Clothing Fabrics

In this paper, the factors to influence the dynamic heat - moisture comfort of summer clothing fabrics have been studied. It is pointed out that, when the wind speed outside is high, or the air permeability is very good, the sweat of human body will evaporate mainly through turbulent diffusion. Because of the rapid sweat evaporation, human body will feel cold, and then, the difference in temperature and humidity of the micro - climatic section will be very slight. On the contrary, when the wind speed outside is slow or the air permeability is unsatisfactory, the sweat of human body will evaporate mainly through molecular diffusion, and in this case, the humidity of the micro - climatic section will be depended on the hygroscopicity of the fabric, that’ s to say, the better the hygroscopicity, the lower the humidity. It is difficult for pure wool fabric to loss heat because of its giving out much heat during the course of moisture - absorption in the initial stages of sweating. For pure polyester fabric,