Intercalation of Graphite in the Ternary Systems C–HNO3–R (R = H2O, CH3COOH, H3PO4 , H2SO4)

The reactions between highly oriented pyrolytic graphite and HNO₃–R (R = H₂O, CH₃COOH, H₃PO₄, H₂SO₄) solutions were studied by x-ray diffraction and potentiometry. The results demonstrate that the nature of component R has a crucial effect on the intercalation process and phase composition of the reaction products. The ability to form ternary graphite intercalation compounds (GICs) depends on the acidity of R. It is shown that CH₃COOH, a weak protic Brönsted acid (pK = 4.76), does not form cointercalation compounds when graphite is treated chemically or electrochemically in HNO₃–CH₃COOH solutions. H₃PO₄, a weak Brönsted acid (pK = 2.12) forms ternary intercalation compounds. Stage II–IV ternary GICs with HNO₃ and H₃PO₄ (d _i = 8.05 Å) were for the first time synthesized and investigated. H₂SO₄, a strong Brönsted acid (pK = –2.8), forms stage I cointercalation compounds (I _c = 8.02 Å), independent of the HNO₃ content (5–95 wt %) of the oxidizing mixture. The potential of the HNO₃–H₂SO₄ solutions was found to be E _Ag/AgCl = 1.39 V, independent of the HNO₃ : H₂SO₄ ratio. The main relationships in the ternary systems were shown to be similar to those for the formation of binary GICs with acids. There is a perfect correlation between the redox potential of the HNO₃–R (R = H₂O, CH₃COOH, H₃PO₄, H₂SO₄) solutions and the stage index of the resulting GIC. The concentration ranges of GIC formation in nonaqueous HNO₃ solutions were extended substantially. The behavior of stage I–IV graphite nitrates in different solvents (H₂O, CH₃COOH, H₃PO₄, and H₂SO₄) was studied. Based on the experimental results, mechanisms of the processes in the systems studied were proposed.     

Fusion Diagrams in the \mathrm{BiBO}_{3}–\mathrm{YbBO}_{3} and \mathrm{Bi}_{4}\mathrm{B}_{2}\mathrm{O}_{9}–\mathrm{YbBO}_{3} Systems

A calculation model of the Gibbs energy of ternary oxide compounds from the binary components was used. Thermodynamic properties of \(\mathrm{Yb}_{2} \mathrm{O}_{3}\) – \(\mathrm{Bi}_{2}\mathrm{O}_{3}\) – \(\mathrm{B}_{2}\mathrm{O}_{3}\) ternary systems in the condensed state were calculated. Thermodynamic data of binary and ternary compounds were used to determine the stable sections. The probability of reactions between the corresponding components in the \(\mathrm{Yb}_{2} \mathrm{O}_{3}\) – \(\mathrm{Bi}_{2} \mathrm{O}_{3}\) – \(\mathrm{B}_{2} \mathrm{O}_{3}\) system was estimated. Fusibility diagrams of systems \(\mathrm{BiBO}_{3}\) – \(\mathrm{YbBO}_{3}\) and \(\mathrm{Bi}_{4} \mathrm{B}_{2} \mathrm{O}_{9}\) – \(\mathrm{YbBO}_{3}\) were studied by physical–chemical analysis. The isothermal section of the phase diagram of \(\mathrm{Yb}_{2} \mathrm{O}_{3}\) – \(\mathrm{Bi}_{2} \mathrm{O}_{3}\) – \(\mathrm{B}_{2} \mathrm{O}_{3}\) at 298 K is built, as well as the projection of the liquid surface of \(\mathrm{BiBO}_{3}\) – \(\mathrm{B}_{2} \mathrm{O}_{3}\) – \(\mathrm{YbBO}_{3}\) .     

In situ synthesis and properties of self-reinforced $$\hbox {Si}_{3} \hbox {N}_{4}\textendash \hbox {SiO}_{2}\textendash \hbox {Al}_{2} \hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3} \ (\hbox {La}_{2}\hbox {O}_{3}$$) glass–ceramic composites

In-situ-grown \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\)-reinforced \(\hbox {SiO}_{2}\textendash \hbox {Al}_{2}\hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) self-reinforced glass–ceramic composites were obtained without any \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) seed crystal. These composites with different compositions were prepared in a nitrogen atmosphere for comparison of phase transformation and mechanical properties. The results showed that \(\hbox {SiO}_{2}\textendash \hbox {Al}_{2}\hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) glass can effectively promote \(\upalpha \)- to \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) phase transformation. The crystallized \(\hbox {Y}_{2}\hbox {Si}_{2}\hbox {O}_{7}\textendash \hbox {La}_{4.67}\hbox {Si}_{3}\hbox {O}_{13}\) phases with a high melting point significantly benefited the high-temperature mechanical properties of the composites. The \(\hbox {Si}_{3}\hbox {N}_{4}\textendash \hbox {SiO}_{2}\textendash \hbox {Al}_{2} \hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) glass–ceramic composites exhibit excellent mechanical properties compared with unreinforced glass–ceramic matrix, which is undoubtedly attributed to the elongated \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) grains. These glass–ceramic \(\hbox {Si}_{3}\hbox {N}_{4}\) composites with excellent comprehensive properties might be a promising material for high-temperature applications.     

Radiative Properties of Ceramic $$\hbox {Al}_{2}\hbox {O}_{3}$$, AlN and $$\hbox {Si}_{3}\hbox {N}_{4}$$Si3N4—II: Modeling

In Part I of this study (Cheng et al. in Int J Thermophys 37: 62, 2016), the reflectance and transmittance of dense ceramic plates were measured at wavelengths from 0.4 \(\upmu \hbox {m}\) to about 20 \(\upmu \hbox {m}\). The samples of \(\hbox {Al}_{2}\hbox {O}_{3}\) and AlN are semitransparent in the wavelength region from 0.4 \(\upmu \hbox {m}\) to about 7 \(\upmu \hbox {m}\), where volume scattering dominates the absorption and scattering behaviors. On the other hand, the \(\hbox {Si}_{3}\hbox {N}_{4}\) plate is opaque in the whole wavelength region. In the mid-infrared region, all samples show phonon vibration bands and surface reflection appears to be strong. The present study focuses on modeling the radiative properties and uses an inverse method to obtain the scattering and absorption coefficients of \(\hbox {Al}_{2}\hbox {O}_{3}\) and AlN in the semitransparent region from the measured directional-hemispherical reflectance and transmittance. The scattering coefficient is also predicted using Mie theory for comparison. The Lorentz oscillator model is applied to fit the reflectance spectra of AlN and \(\hbox {Si}_{3}\hbox {N}_{4}\) from 1.6 \(\upmu \hbox {m}\) to 20 \(\upmu \hbox {m}\) in order to obtain their optical constants. It is found that the phonon modes for \(\hbox {Si}_{3}\hbox {N}_{4}\) are much stronger in the polycrystalline sample studied here than in amorphous films reported previously.     

Microwave dielectrics: solid solution,ordering and microwave dielectric properties of $$(1{-}x)\hbox {Ba}(\hbox {Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}{-}x\hbox {Ba(Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}$$ ceramics

The effect of Ba(\(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) phase on structure and dielectric properties of \(\hbox {Ba(Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}\) was studied by synthesizing \((1{-}x)\hbox {Ba(Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}{-}x\hbox {Ba}(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) (\(x = 0\), 0.005, 0.01 and 0.02) ceramics. Superlattice reflections due to 1:2 ordering appear as low as \(1000^{\circ }\hbox {C}\). \(\hbox {Ba}(\hbox {Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}\) forms solid solution with \(\hbox {Ba}(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) for all ‘x’ values studied until \(1350^{\circ }\hbox {C}\). Ordering was confirmed by powder X-ray diffraction pattern, Raman study and HRTEM. Ceramic pucks can be sintered to density \({>}92\%\) of theoretical density. Temperature and frequency-stable dielectric constant and nearly zero dielectric loss (tan \(\delta \)) were observed at low frequencies (20 MHz). The sintered samples exhibit dielectric constant (\(\varepsilon _{\mathrm{r}})\) between 30 and 32, high quality factor between 37000 and 74000 GHz and temperature coefficient of resonant frequency (\(\tau _{\mathrm{f}})\) between 21 and \(24\hbox { ppm }^{\circ }\hbox {C}^{-1}\).     

Crystal Structure of An(VI) Complexes with Succinate Anions, [PuO2(C4H4O4)(H2O)] and Cs2[(AnO2)2(C4H4O4)3]·H2O (An = U,Np, Pu)

Radiochemistry - Actinide(VI) complexes with succinate anions [PuO2(succ)(H2O)] and Cs2[(AnO2)2(succ)3]·H2O (An = U, Np, Pu), where succ = [C4H4O4]2 ?, were synthesized and studied by...     

Synthesis of Ternary Intercalation Compounds in the Graphite–HNO3–R (R = H2SO4 , H3PO4 , CH3COOH) Systems

The reactions of stage II–IV graphite nitrates with concentrated H₂SO₄, H₃PO₄, and CH₃COOH were studied at graphite : acid weight ratios from 3 : 1 to 1 : 1. The results demonstrate that the reactions in question follow different paths. In the graphite nitrate–H₂SO₄system, the reaction decreases the stage index and yields a ternary graphite intercalation compound. The contents of intercalated HNO₃and H₂SO₄are controlled by the amount of H₂SO₄and the stage index of the parent graphite nitrate. The reaction between graphite nitrate and H₃PO₄leads to partial replacement of HNO₃by H₃PO₄, increasing the identity period without changes in the stage index. The results for the graphite nitrate–CH₃COOH system provide no direct evidence for the formation of an intercalation compound with HNO₃and CH₃COOH. It is shown that varying the nature and amount of the second intercalate species opens up possibilities for preparing oxidized graphite with controlled physicochemical properties.     

Synthesis and crystal structure of a new Np(V) oxalate, Na4(NpO2)2(C2O4)3·6H2O

A new oxalate complex, Na₄(NpO₂)₂(C₂O₄)₃·6H₂O, with the Np:C₂O₄ ratio of 2:3 was synthesized and studied by single crystal X-ray diffraction. In the crystal, the NpO ₂ ⁺ cations and oxalate anions are bound in open networks [(NpO₂)₂(C₂O₄)₃] _n ^4n- parallel to the bc plane. The Na(1) cations are accommodated in large voids of the neptunyl oxalate networks with the formation of crimped mixed-cation layers of the composition [Na₂(NpO₂)₂(C₂O₄)₃] _n ^2n- . The negative charge of the layers is compensated by the Na(2) cations arranged between the layers. The Np atoms have a pentagonal bipyramidal coordination surrounding with the equatorial plane formed by the oxygen atoms of three oxalate anions. The structure contains tridentate-bridging and tetradentate-bridging oxalate anions.     

Synthesis and structure of Cs3[UO2(CH3COO)3]2(NCS)·H2O

The compound Cs₃[UO₂(CH₃COO)₃]₂(NCS)·H₂O (I) was synthesized and studied by IR spectroscopy and single crystal X-ray diffraction. Compound I crystallizes in the monoclinic system with the following unit cell parameters: a = 7.8286(9), b = 19.892(2), c = 20.050(2) Å, β = 94.527(2)°, space group P2₁/c, Z = 4, R = 0.0387. The uranium-containing structural units in crystals of I are mononuclear complexes [UO₂(CH₃COO)₃]^? belonging to crystal-chemical group AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?) of uranyl complexes.     

Complexes with substituted 2,5-dihydroxy-p-benzoquinones: The inclusion compounds [Y(H2O)3]2 (C6Cl2O4)3·6.6H2O and [Y(H2O)3]2 (C6Br2O4)3·6H2O

Single crystal of [Y(H₂O)₃]₂ (C₆Br₂O₄)₃·6H₂O and [Y(H₂O)₃]₂ (C₆Cl₂O₄)₃·6.6H₂O were grown in aqueous silicagel. The compounds are in principle isostructural. In Y chloranilate one additional water site is occupied as verified by X-ray single crystal structure analysis. Y³⁺ is nine-coordinated by three water molecules and six oxygen atoms of the bischelating (C₆X₂O₄)²⁻ ions (XCl, Br). The coordination polyhedron is an only slightly distorted tri-capped trigonal prism. The connection of Y³⁺ with the dianions leads to infinite, corrugated layers. The layer stacking yields cage-like cavities in which water molecules are accomodated. Hydrogen bonds interlink adjacent layers. Further hydrogen bonds involve the entrapped water molecules. DSC measurements indicated a complicated dehydration process which caused right at the start destruction of the single crystals.     

Influence of hydrothermal treatment on the microstructure and oxidation resistance of a Zn4B2O7·H2O (4ZnO·B2O3·H2O) coating for C/C composites

Antioxidant modification for C/C composites by in situ hydrothermal synthesise at 140 °C of a 4ZnO·B₂O₃·H₂O crystallite coating has been successfully achieved. The influence of hydrothermal time on the phase composition, microstructure of the as-prepared Zn₄B₂O₇·H₂O (4ZnO·B₂O₃·H₂O), and its antioxidant modification for C/C composites were investigated. Samples were characterised by XRD, SEM, isothermal oxidation test and TG-DSC. Results show that, 4ZnO·B₂O₃·H₂O crystalline coating is achieved on the surface of C/C composites after the hydrothermal treatment at 140 °C for time in the range of 2–12 h. A smooth and crack-free 4ZnO·B₂O₃·H₂O layer can be obtained when the hydrothermal time reaches 8 h. Isothermal oxidation test demonstrates that the oxidation resistance of C/C composites is improved. The as-modified composites exhibit only 1.52 g·cm^?2 weight loss after oxidation at 600 °C for 15 h, while the non-modified one shows a 6.57 g·cm^?2 weight loss after only 10 h oxidation. For the uncoated C/C composite the oxidation rate is approximately linear with time (non-protective oxidation), thus at 15 h exposure one can estimate the mass loss to be 6.57 g·cm^?2 after 10 h for direct comparison with the coated samples.     

Magnetic measurements,Raman and infrared spectra of metal–ligand complex derived from $$\hbox {CoCl}_{2}\cdot \hbox {6H}_{2}\hbox {O}$$ and 2-benzoyl pyridine

Nanocrystalline complex of \(\hbox {CoCl}_{2}\cdot 6\hbox {H}_{2}\hbox {O}{-}2\)-benzoyl pyridine is prepared by chemical route. Each component of the desired complex is identified by analysing the X-ray diffractograms. Energy-dispersive X-ray analysis (EDX) data confirmed the presence of the desired elements of the sample. Theoretical optimized structure of the complex was derived using ab initio density functional level of theory (DFT) method of calculation. The average nanocrystallite size estimated from the XRD data is \(\sim \)43 nm. Static magnetic property of the complex is studied in the temperature range from 300 K down to 14 K. The estimated magnetic moment of the complex is high when compared to that of the free ion magnetic moment of \(\hbox {Co}^{2+}\) and this is attributed to the less effect of the crystal field acting on the ion in the organic complex due to which orbital moments are not fully quenched. The magnetic property of the complex is also remarkably enhanced compared to that of the diamagnetic 2-benzoyl pyridine which may be suitable for applications in devices. FTIR and Raman spectra of the ligand, 2-benzoyl pyridine and the synthesized complex are recorded at room temperature, which not only confirm the presence of each phase in the complex, but some interesting results are also extracted from the analyses of different Raman active modes of the complex.     

Synthesis and characterization of a new organic sulphate, [2,3-(CH3)2C6H3NH3]HSO4·H2O

Crystals of a new hybrid compound C₈H₁₂N⁺, HSO₄^?·H₂O were synthesized in aqueous solution and characterized by X-ray diffraction and IR absorption spectroscopy. This compound crystallizes in the orthorhombic non-centrosymmetrical space group P2₁2₁2₁ and an unit cell with a = 5.74(2) Å, b = 9.17(2) Å, c = 21.34(4) Å, V = 1124(6) Å³, and Z = 4. Its crystal structure is a packing of alternated inorganic and organic layers parallel to (a,b) planes. The different components are connected by a bi-dimensional network of strong OH…O and NH…O hydrogen bonds. Then, in order to detect phase transitions and watch changes in the conductivity behaviour, investigations by DTA–TG and differential scanning calorimetry (DSC) and electrical conductivity measurements were carried out.     

Al(H2PO4)3/Al2O3复合硬质材料吸湿改性研究

磷酸二氢铝、磷酸铬铝等无机材料作为高温粘结剂具有固化收缩率低、高强度、耐高温等优点,被广泛应用于冶金、化工以及航天航空领域,但其可吸收空气中的水蒸汽,从而降低材料的强度和完整性.为减少无机高温粘结剂在大气环境下的吸湿量,以有机聚合物聚醚砜、无机添加剂氧化锆粉、热辐射屏蔽剂金粉制备出一种具有耐高温、低导热、热辐射屏蔽的复合密封材料,并将其应用在Al(H2PO4)3/Al2O3复合硬质材料的吸湿改性中.通过对比改性前后样品的扫描电镜图、吸湿率曲线,测试复合密封材料对基体材料吸湿性能的改性效果,并为研究喷涂密封材料对基体材料隔热、强度等性能的影响,进一步分析改性前后样品导热系数、弯曲强度的变化.结果表明,聚醚砜可在基体材料表面形成致密的密封膜,不仅可以隔绝空气中的水蒸汽,使吸湿率最高下降68.39％,还可以提升材料的弯曲强度.同时,金粉的添加可以形成辐射屏蔽层,从而降低材料的高温热导率.     

Synthesis of Double Uranyl Phthalates of the M4[(UO2)4(μ3-O)2(C6H4C2O4)4] ⋅ nH2O Type with M = NH4, K, and Cs. Crystal Structure of K4[(UO2)4O2(C6H4C2O4)4] ⋅ 3H2O

Double U(VI) phthalates with NH ₄ ⁺ , K⁺, and Cs⁺ ions in the outer sphere were synthesized. The X-ray phase analysis shows that their structures are similar. Single crystals were prepared and the structure of K₄[(UO₂)₄(μ₃-O)₂(C₆H₄C₂O₄)₄] ? 3H₂O was solved. In the [(UO₂)₄O₂(C₆H₄C₂O₄)₄]^4? anions forming the main structural motif, each bridging oxygen atom μ₃-O combines one pentagonal and two hexagonal bipyramids, which, in turn, are combined in centrosymmetrical tetramers. The phthalate ions have coordination capacity equal to 3; each ligand coordinates U(1) in the bidentate fashion via one carboxy group and U(2) in the bidentate fashion to form a planar seven-membered chelate ring.     

Facile one-step synthesis of Fe5(PO4)4(OH)3 · 2H2O hollow octahedra and their application for DNA separation

A simple one-step process has been used to synthesize novel Fe₅(PO₄)₄(OH)₃?·?2H₂O hollow octahedra in a mixed solvent of diethylene glycol (DEG) and H₂O. The x-¹ray diffraction (XRD) and scanning electron microscopy (SEM) have been provided for the characterizations of the nanostructures. The shape of the as-obtained products could be controlled by adjusting the volume ratio of DEG and H₂O in the solvothermal process. The possible formation mechanism was proposed based² on nucleation and the Ostwald ripening process as well as the soft-template function of DEG. In addition, the study herein demonstrated that the hollow octahedra exhibit excellent capability for the adsorption of salmon sperm DNA and would have great application potentials in DNA separation.     

Crystal structure of a double Np(V) ammonium propionate, NH4[(NpO2)3(C2H5COO)4(H2O)]·3H2O

The structure of NH₄[(NpO₂)₃(C₂H₅COO)₄(H₂O)]·3H₂O was studied by single crystal X-ray diffraction. The single crystals were prepared by hydrothermal synthesis. In the structure, there are three crystallographically independent Np atoms with different equatorial surrounding. All of them have CN 7; the coordination polyhedron is a distorted pentagonal bipyramid. Each NpO ₂ ⁺ cation is bonded to four other cations, acting simultaneously as a bidentate ligand and a coordination center for two other dioxocations. The cation-cation interactions result in formation of trigonal-hexagonal cationic networks.     

Novel self-assembled decavanadate clusters forming 1D molecular chains and 2D molecular arrays: [HMTA-H···H2O][HMTA-CH2OH][H3V10O28{Na(H2O)4}]·4H2O and [Na2(H2O)10] [H3V10O28 {Na(H2O)2}]·3H2O

Two novel materials, [HMTA-H··H₂O] [HMTA-CH₂OH] [H₃V₁₀O₂₈[Na(H₂O)₄}]·4H₂O, 1 and [Na₂(H₂O)₁₀][H₃V₁₀O₂₈[Na(H₂O)₂}]·3H₂O, 2 containing decavanadate clusters interconnected through hydrated sodium cations forming 1D molecular chains and 2D molecular arrays have been self-assembled from acidified, aqueous vanadate solution in the presence of organic bases, hexamethylenetetramine and 1,3,5-triazine respectively.     

Complexes with substituted 2,5-dihydroxy-p-benzoquinones: AE[C6(C2H5)2O4]·3H2O (AE=Ca,Sr, Ba)

Single crystals of AE[C₆(C₂H₅)₂O₄]·3H₂O belonging to space group P2₁2₁2₁ were grown in aqueous silicagel (AE=Ca, Sr) and in aqueous solution (AE=Ba), respectively. AE²⁺ is coordinated by four oxygen atoms of two bis-chelating [C₆(C₂H₅)₂O₄]²⁻ ions, thus forming infinite, corrugated chains extending along [010]. The coordination polyhedron is completed by additional water molecules. The coordination sphere is different for the three different AE²⁺ ions yielding CN increasing from Ca²⁺ to Ba²⁺. The principle features of the crystal structure, however, remain unchanged. Adjacent chains are interlinked by hydrogen bonds between water molecules of the coordination sphere and the oxygen atoms of the [C₆(C₂H₅)₂O₄]²⁻ ion.     

完全γ部图Kγ(t)的{C3,C2k}-强制分解

本文研究完全多部图的强制圈分解的存在性问题,得到了完全r部图Kr(t)的3圈和2k圈{C2,C2k}-强制分解存在时t与r的4种可能关系,特别地,给出了k=2,3时t与r满足这些关系之一为强制分解存在的充分条件。