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1.
A reliable simple method for prediction of the standard Gibbs energy of formation (ΔfGθ) of energetic compounds containing nitroaromatic, acyclic, and cyclic nitramine, nitrate ester, and nitroaliphatic compounds is introduced herein. The method is based on the contribution of elemental composition (ΔfGelemθ) and the correcting function for the presence of additive and non‐additive molecular fragments (ΔfGcorrθ). In presence of some molecular moieties, ΔfGcorrθ may increase or decrease the value of ΔfGelemθ, depending on the intermolecular interactions. The experimental root‐mean‐square error (RMSE) of the novel correlation (22.7 kJ mol−1) is quite good. For some energetic compounds, where the computed values of two complex models of the quantitative structure‐property relationship (QSPR) theory were available, the experimental RMSE developed by the new method is smaller than the values obtained by QSPR method.  相似文献   

2.
《Ceramics International》2017,43(11):8089-8097
Continuous tungsten carbide (WC) coatings were prepared on graphite flakes (Gf) by molten salt synthesis (MSS) technique using NaCl and KCl as reaction medium. The effect of reaction temperature, dwelling times and WO3/Gf molar ratio on the compositions and morphologies of resultant samples was investigated, and the related formation mechanism for the coatings was also discussed. The results show that continuous WC coatings can be prepared at 1100 °C for 60 min with a WO3/Gf molar ratio ranging from 1/15 to 1/5. These coatings exhibit homogeneous and crack free features, and their thickness increases with the increase of molar ratio. With the WO3/Gf molar ratio below or beyond the above range, discontinuous WC coatings or W/W2C/WC flake-like particles without graphite are obtained, respectively. The varied compositions of the samples obtained with different WO3/Gf molar ratio can be related to the detailed chemical reaction process between WO3 and Gf in the molten salts. A “template-growth” mechanism is proposed to explain the formation of WC coatings in the MSS process.  相似文献   

3.
Low‐melting paraffin wax was successfully used as a phlegmatizing agent to perform semi‐micro oxygen bomb calorimetry of spectroscopically pure samples of the sensitive explosive peroxides TATP and DADP. The energies of combustion (ΔcU) were measured and the standard enthalpies of formation (ΔfH°) were derived using the CODATA values for the standard enthalpies of formation of the combustion products. Whilst the measured ΔfH° of DADP (ΔfH°=−598.5 ± 39.7 kJ mol−1) could not be compared to any existing literature value, the measured ΔfH° value of TATP (ΔfH°=+151.4 ± 32.7 kJ mol−1) did not correlate well with the only existing experimental value and confirmed that TATP is an endothermic cyclic peroxide.  相似文献   

4.
Proton affinity of various “crown” ethers is discussed. Equations are given for simultaneous calculation of the complexation and the dissociation constants from conductivity data. pKf in 1.2-dichloroethane is 8.6 and 8.3, respectively, for the cis-syn-cis and the cis-anti-cis isomers of dicyclohexyl-18-CR-6, the most basic among the investigated “crown” ethers. pKf = 8.2 for the mixture of these isomers in acetonitrile (AN). The effect of water on pKf of “crown” ethers in aprotic solvents is discussed. It is suggested that a monohydrate of the “oxonium-crown” rather than a “hydronium-crown” may be formed. The proton binding capacity of “crown” ethers may be applied for extraction of acids and in catalysis. Dicyclohexyl-24-CR-8 has been found to be an equally effective extractant for HNO3 as the Dicyclohexyl-18-CR-6.  相似文献   

5.
A novel layered structure material, Pr3Si2C2, was synthesized at a low temperature of 850 °C using a molten salt approach for the first time, and subsequently used as the joining filler for carbon fibers reinforced SiC composites (Cf/SiC). A robust near-seamless Cf/SiC joint was successfully obtained at 1509 °C (Ti) for 30 s, while an ultrafast heating rate of 6000 °C/min was applied via electric field-assisted sintering technology. The near-seamless joining process was attributed to the newly precipitated SiC grains, which were densified well with the Cf/SiC matrix by liquid-assisted sintering. The liquid phase was in-situ formed by the eutectic reaction between Pr3Si2C2 and SiC. The shear strength of the near-seamless joint obtained at 1509 °C for 30 s was 17.6 ± 3.0 MPa. The failure occurred in the Cf/SiC matrix. The formation of near-seamless Cf/SiC joints dismisses the issues related to thermal mismatch between Cf/SiC matrices and traditional joining fillers.  相似文献   

6.

Tantalum is widely used in hip joint replacement and knee joint repair, but its clinical application is limited due to its poor biological activity and weak ability to promote new bone formation. Ca and Mg ions are thought to be involved in bone metabolism and play an important physiological role in the angiogenesis, growth, and mineralization of bone tissue. In this work, NaTaO3 films doped with Ca2+ and Mg2+ were prepared by hydrothermal synthesis and molten salt method. The doping amounts of Ca2+ doped at 450, 550, 650 and 750 °C were 0.59, 3.44, 32.75 and 29.88 at%, and that of Mg2+ doped at 300, 350, 400, 450, 500, 550 and 650 °C were 0.62, 1.03, 1.54, 20.12, 21.38, 14.37 and 0.74 at%, respectively. Ca2+ and Mg2+ are evenly incorporated into NaTaO3 and cause the change of crystal plane spacing without any significant changes of morphologies below 550 and 400 °C respectively. XPS shows that the cations are the A-site substitution of perovskite structure (ABO3). According to the morphology and composition analysis of Ca-incorporated samples and Mg-incorporated samples, the optimal preparation temperature of them is 550?°C and 400?°C, respectively. The results show that for “550?°C-Ca” and “400?°C-Mg” the hydrophilicity is 13.9° and 96.1°, the roughness is 114.3 and 54.3?nm, the doping ion concentration of Ca and Mg is 3.44 and 1.54 at%, and the 7-day ICP results is 69.8 and 1.4?ppm, respectively. In addition, cell proliferation experiments and cell morphology related to biological activity and osteogenic properties are discussed, and it is found that the performance of “550?°C-Ca” is better than “400?°C-Mg”. Ca2+–NaTaO3 is a promising implantable material that will be extensive used in bone implants, joint replacements and dental implants.

  相似文献   

7.
This paper presents the derivation of mathematical formulae for molecular and network parameters of branched step-growth polymerizations. Weight-average molecular weight, gel point, and weight fractions of soluble, pendant and elastically-effective material in a gel are derived. The direct “in-out” recursive analysis of Macosko and Miller is applied to four general step-growth polymerization systems. The method is introduced using the simple case of Af homopolymerization. Two new systems are then modeled; a homopolymerization of AfBg monomers with two types of reactive groups, and an Af+Bg+Ch terpolymerization. The fourth system presented is a general Af+Bg copolymerization of polydispersed reactants; we have partially analyzed this system before, but we give a new and complete presentation here to show the generality of the “in-out” analysis. We also survey some additional polymer systems that have been analyzed in the literature. Then, we discuss limitations of this modeling approach, the use of the models and their implementation in software. We give two numerical examples: a silicone rubber system and a segmented polyurethane network system. Appendices present the small amount of elementary probability theory and polymer distribution theory needed to support the analysis. This paper serves as an introduction to the “in-out” method; after reading this paper, the reader should be able to apply the “in-out” method to many step-growth polymer systems.  相似文献   

8.
In the previous work, we reported that the β-selectivity, morphology and tensile behavior of isotactic polypropylene (iPP) can be efficiently tuned by the combination of controlling the melt structure status (namely, creation ordered structure by tuning the fusion temperature Tf) and the addition of β-nucleation agent (β-NA, tradename WBG-II, concentration 0.01 wt%), which was called “Ordered Structure Effect” (OSE). This study further investigates the dynamic crystallization and melting behavior of β-iPP with a different melt structure status by differential scanning calorimentry (DSC) and non-isothermal crystallization kinetics. The results revealed that under all the cooling rates studied (2, 5, 10, 20 and 40 °C/min), the crystallization temperature on the cooling curves increased gradually with the decrease of Tf; meanwhile, when the Tf was in the temperature range of 168–186 °C where the OSE occurs (defined as Region II), the crystallization activation energy ΔE was found to be evidently lower, compared with that when the Tf was higher than 186 °C or lower than 168 °C. The results of the subsequent heating showed that the occurrence of the OSE can be observed at all the cooling rates studied; the location of the Region II was constant when the cooling rate varied. Low cooling rate encouraged the formation of more β-phase triggered by OSE. Moreover, the role of OSE on the β-α recrystallization was comparatively studied by tuning the end temperature of recooling (Tend) after held at Tf, and it was found that the OSE encouraged the formation of β-phase with high thermal stability at the low temperature part of Region II, while enhancing the β-crystal with relatively low thermal stability at the high temperature part of Region II.  相似文献   

9.
《Ceramics International》2022,48(7):9610-9620
Atmospheric plasma spraying (APS) was used to prepare three-layer environmental barrier coatings (EBCs) Si/Yb2SiO5/LaMgAl11O19 (LMA) on a SiCf/SiC substrate. Isothermal aging test of the specimens were performed between 1000 and 1360 °C for 500 h. The flexural strength of the specimens after isothermal aging was investigated. Microcracks and holes were observed in the as-sprayed EBCs because of the shock cooling during the APS process, but reduced after isothermal aging, and the EBCs became denser. At least 80.07% of the flexural strength of the SiCf/SiC substrate with EBCs was maintained after isothermal aging, but only 35.91% strength was maintained without EBCs. In particular, the retention ratio of flexural strength was 90.72% after isothermal aging at 1360 °C, despite a reaction between the layers of the EBCs. All the specimens with EBCs showed “pseudo-plastic” fracture, compared with the brittle fracture of specimens without EBCs.  相似文献   

10.
The NiPdPtAu-Cr filler alloy was proposed for joining Cf/SiC composites. The wettability on Cf/SiC composite was studied by the sessile drop method at 1200 °C for 30 min. Under the brazing condition of 1200 °C for 10 min, the Cf/SiC-Cf/SiC joint strength was only 51.7 MPa at room temperature. However, when used a Mo layer, the Cf/SiC-Mo-Cf/SiC joint strength was remarkably increased to 133.2 MPa at room temperature and 149.5 MPa at 900 °C, respectively. At the interface between Cf/SiC and Mo, Mo participated in interfacial reactions, with the formation of Cr3C2/Mo2C reaction layers at the Cf/SiC surface. The improvement in the joint strength should be mainly attributed to the formation of MoNiSi. The Cf/SiC-Mo joint strength was 86.9 MPa at room temperature and 73.7 MPa at 900 °C, respectively. After 10 cycles of thermal shock test at 900 °C the Cf/SiC-Mo joint strength of 71.6 MPa was still maintained.  相似文献   

11.
《Ceramics International》2023,49(1):565-570
Two novel low-εr Ca3Mg2CV2O12 (C = Si, Ti) ceramics with the garnet structure were synthesized by a traditional solid-state reaction method. Rietveld refinements based on XRD patterns show both the compounds crystallized into a cubic structure with the Ia-3d space group. Outstanding microwave dielectric properties (εr = 9.70, Q × f = 35,680 GHz, and τf = ?60.1 ppm/°C for Ca3Mg2SiV2O12 ceramic; εr = 11.70, Q × f = 48,530 GHz, and τf = ?43.7 ppm/°C for Ca3Mg2TiV2O12 ceramic) were obtained at 1240 °C and 1260 °C, respectively. The bond valence calculations reveal that Ca2+ at the A-site and Mg2+ at the B-site are slightly compressed, in combination with “rattling” Si4+ and “compressed” V5+ in the C-site of Ca3Mg2SiV2O12 compared to “rattling” V5+and “compressed” Ti4+ in Ca3Mg2TiV2O12, resulting in a negative deviation of ?7.16% for Ca3Mg2SiV2O12 and a positive value of 5.66% for Ca3Mg2TiV2O12 between the porosity corrected εr(Corr) (10.11 and 11.95) and theoretical εth (10.89 and 11.31) calculated by the C-M equation. The overall “rattling” effect in Ca3Mg2TiV2O12 results in a higher εr and a nearer to zero τf compared to Ca3Mg2SiV2O12. Besides, the Q × f values of Ca3Mg2CV2O12 (C = Si, Ti) ceramics were correlated with relative density and Raman mode (A1g).  相似文献   

12.
A carbothermal reduction reaction (CRR) approach was developed in this research to tailor the surface phase structure of the SiO2f/SiO2 composites with high chemical reactivity to replace the original inert surface. Results show that SiC can form after CRR treatments. For AgCuTi-SiO2f/SiO2 wetting interfaces, TiC and residual pyrolytic carbon layer can be found inside the reaction layer, which was the key, promoting the wettability of the AgCuTi-SiO2f/SiO2 system. The contact angle of the AgCuTi-SiO2f/SiO2 system dropped from 127° to 43° after the CRR treatments. The reliability of the bonded AgCuTi-SiO2f/SiO2 interface was also characterized by putting 3 different systems into comparison, i.e., the original AgCuTi-SiO2f/SiO2 system, the AgCuTi-SiO2f/SiO2 system with CRR treatments (SiC formation) and the AgCuTi-SiO2f/SiO2 system coated with powdered carbon (no SiC formation). The shear strength of the SiO2f/SiO2-AgCuTi-SiO2f/SiO2 system with CRR treatments was the highest, which was 3 times that of the other 2 brazing systems.  相似文献   

13.
The present investigation is concerned with the development of a new iterative method permitting, for a Fickian sorption of a binary liquid mixture in thin polymer sheets, the simultaneous determination of the self‐diffusion coefficients of the components of the mixture, and their uptake fractions at equilibrium. The approach is based on a new equation describing a parallel Fickian sorption of the components of the mixture into thin polymer sheets. The procedure was tested with ideal and Monte Carlo simulated data. The method, applied to ideal simulated data that corresponded to various values of D1, D2 and f, perfectly extracted the desired parameters. The application of the method to Monte Carlo simulated data revealed that this method is fairly applicable even when the simulated data are considerably obscured by “noise”. Finally, the proposed method was successfully applied to the experimental data concerning the sorption kinetics of ethanol–water mixture (75 vol % in EtOH) at 37°C in thin polymeric sheets of triethyleneglycol dimethacrylate (TEGDMA). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

14.
《Polymer》2007,48(1):382-392
Nucleation mechanism of polymers was studied by means of small angle X-ray scattering (SAXS) by improving our two previous studies. The first one showed first direct SAXS observation of nucleation of polyethylene (PE). The second one reported how “size distribution f(N,t)” of nuclei of nano-meter size (nano-nuclei) evolves with time (t), where N is number of “repeating unit” in a nucleus. Unfortunately the f(N,t) was obtained by incorrect analysis of SAXS intensity (IX), i.e., too simple one-dimensional (1D) nucleus was assumed to analyze the IX. In this paper, we determined simultaneously correct f(N,t) and “two-dimensional (2D) shape” of nano-nucleus. From this it is clarified that nano-nucleus shows significant fluctuation in size and shape and repeats frequent generation and disappearance, which corresponds to the conclusion that the end surface free energy of the nano-nucleus (σe(nano)) is 1/5 times as large as that of macroscopic crystal (σe(macro)). f(N,t) decreased with increase of N. f(N,t) increased and saturated with increase of t.  相似文献   

15.
Our recent work on the consequences of multispherule cluster aggregate (CA) formation and deposition-rates on much larger solid targets has emphasized the decisive role of “momentum-shielding” in determining aggregate “mobility” compared to N isolated spherules in the same gaseous environment—an effect analogous to the drag-reduction advantages experienced by birds electing to move “in formation.” The extent of “momentum shielding” is conveniently quantified via a dimensionless function: Smom(N;Kn1, aggregate structure), which facilitates predicting the deposition-rate consequences of aggregation in aerosol flow systems when the cluster deposition mechanism is dominated by either: (i) isothermal convective-diffusion (C-D), (ii) thermophoresis (T-P) or: (iii) inertial impaction (I-I). Significantly, isothermal C-D was found to be the only transport-mechanism leading to aggregation-induced reductions in spherule deposition rates on large targets (cf. isolated spherules present at the same mainstream spherule volume fraction). However, we demonstrate here that, for aggregate deposition on sufficiently small solid targets—e.g., fibrous filter elements with diameters of O(10 μm)—even these reductions, which exceed one decade for N = O(103), can be overcome by the mechanism of “direct-interception” (D-I) associated with nonzero effective aggregate size, without the need to invoke either inertial impaction or thermophoresis. This is especially true for Diffusion-Limited (i.e., “open”) CAs (with Df = 1.8) at gas pressures such that the constituent spherules are near the continuum (Kn1 << 1) limit. Our present analysis and numerical illustrations exploit the fact that direct-interception is expected to play a negligible role for the capture of individual (dense) nanospherules (perhaps comparable in size to the prevailing gas molecule mean-free-path) but the underlying theory, exploited, extended, and illustrated here, was developed with the help of initial capture rate experimental data for much larger diameter (but unaggregated) aerosols on single filter fibers in low Re crossflow. With such small diameter targets, we demonstrate that this “interception” augmentation for large CAs can occur even for the limiting case of rcp Df = 3 aggregates, before the expected onset of CA-inertial effects–i.e., StkN << Stkcrit, where, for Re = O(1), Stkcrit is also O(1). A simple method is also presented for predicting interception-modified spherule deposition rates in the presence of log-normal type aggregate size distributions.

Copyright © 2018 American Association for Aerosol Research  相似文献   


16.
Ca3-xMg1+xLiV3O12 (0 ≤ x ≤ 1) ceramics with cubic-garnet-structure were synthesized by the solid-phase reaction. The replacement of Ca2+ with the smaller Mg2+ exerted an increasingly strong “rattling” effect at the A-site of Ca3-xMg1+xLiV3O12. With increased Mg2+, εr increased from 10.5 ± 0.1 to 15.4 ± 0.1 and εcorr increased from 11.0 ± 0.1 to 16.0 ± 0.1, whereas the theoretical εth decreased from 12.0 ± 0.1 to 10.5 ± 0.1. εcorr was higher than εth due to the “rattling” effect. The enhanced “rattling” effect caused τf to increase rapidly from –64.1 ± 1.0 ppm/°C to +267.2 ± 1.0 ppm/°C. With increased x, Q × f decreased from 74,700 ± 500 GHz to 15,370 ± 500 GHz, due to the decreased packing fraction, increased FWHM of the A1g modes, and enhanced “rattling” effect. Additionally, the chemical compatibility between Ca2.75Mg1.25LiV3O12 and Ag electrodes was confirmed, indicating this material’s potential for LTCC.  相似文献   

17.
Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γd s and γd l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γd s was determined to be 71.5 mJ/m2, and its temperature dependence was 0.36 mJ m?2 K?1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γd s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γd s and d(γd s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.  相似文献   

18.
The glass transition in argon at a high cooling rate is simulated. At a temperature of 50 K (considerably below the melting temperature T f = 83.8 K), the fluctuation volume fraction reaches the constant value f g ? 0.03–0.05, which is close in the order of magnitude to the criterion for the glass transition in liquids f g = const 0.02–0.03 within the excited state model. At this temperature, the second maximum of the radial distribution function is split as a result of the glass transition at the temperature T g = 50 K. The approximate empirical “two-thirds” rule T g = (2/3)T f is reasonably satisfied for argon. The data obtained are interpreted in the framework of the excited state model.  相似文献   

19.
In order to further improve the tribological performance of glass fiber reinforced epoxy (GF/EP) composites, highly flexible, binder‐free, molybdenum trioxide MoO3 nanobelt/graphene oxide (GO) film (f‐MoO3‐GO) is prepared by a hydrothermal method. Herein, f‐MoO3‐GO is adopted to modify GF/EP composites prepared through the vacuum‐assisted resin transfer molding method. The neat GF/EP and MoO3‐GO modified GF/EP composites are also fabricated for comparison. The tribological performance is performed using a ball‐on‐disc (“steel‐on‐polymer”) configuration under a dry sliding condition. The coefficient of friction is reduced from 0.61 for neat GF/EP composites down to 0.23 for f‐MoO3‐GO modified GF/EP (f‐MoO3‐GO/GF/EP) composites and the anti‐wear performance is improved by more than four times. The worn surface morphological observation for the composite samples is used to explain the possible wear micro‐mechanisms. The wear reducing effect of the f‐MoO3‐GO/GF/EP composites can be assigned to the increased self‐lubricating effect of f‐MoO3‐GO. With the combined advantageous properties of the used individual components, these unique composites can be used for many other applications.  相似文献   

20.
Dimensions of conical dies were found to have a significant influence on thermal, morphological, orientation, ultradrawing, and dynamic mechanical properties of the as‐prepared and/or drawn ultrahigh molecular weight polyethylene (UHMWPE) fiber specimens prepared in this study. Many demarcated “micro‐fibrils” were found paralleling to fiber direction of the as‐prepared UHMWPE fiber specimens. The percentage crystallinity, melting temperatures, orientation factor (fo) and achievable draw ratio (Dra) values of each as‐prepared UHMWPE fiber specimen prepared at a fixed length of outlet land reach a maximum value, as the entry angles of the conical die approach the optimum value at 75°. The maximum fo and Dra values obtained for each F2075‐y as‐prepared fiber series specimens prepared using the optimum entry angle reach another maximum value as their length of outlet land approach the optimum value of 6.5 mm. The ultimate tensile strengths and moduli of the drawn UHMWPE fibers prepared at the optimum entry angle and length of outlet land are significantly higher than those of fibers prepared at other conditions but stretched to the same draw ratio. Possible reasons accounting for the above interesting properties were discussed in this study. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers  相似文献   

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