水菱钇型碳酸钕的形成及聚甘油脂肪酸酯对结晶的影响

Amorphous Neodymium carbonate was prepared by the precipitation reaction of neodymium chloride with ammonium bicarbonate in solution, and then aged at 60 ℃ to form crystalline neodymium carbonate. The feed molar ratio of n_(NH4HCO3)/n_(NdCl3 was 2.5, and the precipitation was carried out with or without addition of polyglyceryl fatty acid ester (PGFAE). The phase type and morphology of crystalline neodymium carbonates were examined by XRD and SEM, and the effect of PGFAE on the crystallization speed was investigated by volume change in deposit layer and in situ pH determination. The content of neodymium and chloride in crystals was analyzed, and the crystallization reaction or crystal growth characteristics were discussed. It was found that all the crystalline neodymium carbonates were tengerite type, and contained less crystalline water and chloride than that of lanthanite type neodymium carbonate crystallized at room temperature, which is beneficial to the production of neodymium carbonate with higher neodymium and lower chloride content. The addition of PGFAE not only could eliminate the foam formed during precipitation, but also could shorten crystallization time, and form large radiative-like shape conglomeration by the irregulative linkage of one dimension needle crystals. It is also suggested that the morphology and the chloride content of neodymium carbonate were dependent on the structure and crystal growth characteristics.     

碳酸氢铵与氯化钇反应及结晶产物的组成和晶相类型

The relationships of crystal type, crystallization speed, purity, grain size and shape of rare earth carbonate with precipitation and crystallization conditions are very important for the production of rare earth carbonate with high efficiency, high quality and low cost. It is necessary for us for further understand the crystallization process mechanism and the factors effect on the crystallization. In the present paper, the crystallization characteristic, composition and crystal phase type of yttrium carbonates or ammonium yttrium carbonates precipitated from yttrium chloride solution using ammonium bicarbonate as precipitant were determined by chemical analysis, X-ray powder diffraction and the pH situ-determination. It was found that the crystal phase type was dominated by the feed molar ratio of ammonium bicarbonate to yttrium chloride, and the crystallization speed and the crystal composition were also influenced by temperature, feed manner and aging period etc. When precipitating and aging under lower temperature, crystallization is easy to take place in the high feed molar ratio zone, and when increasing tempera-ture, crystallization will take place both in lower and higher feed molar ratio zones. The results show that spherical yttrium carbonate with tengerite type crystal phase can be formed within the temperature 30～70℃ when feed molar ratio of ammonium bicarbonate to yttrium chloride is less than 4, and that a rhombus flake crystal, which possesses the composition of ammonium yttrium quasi-double carbonate and a new XRD pattern, is formed when the feed molar ratio is over 4. Their compositions can be represented as (NH₄)_aY(CO₃)_b(OH)_c·nH₂O, a< 1, 1< b< 2, c=3+a-2b. A fine crystal of ammonium yttrium double carbonate with the formula of (NH₄)Y(CO₃)₂·H₂O can also be obtained as using an enough amount of ammonium bicarbonate and aging enough time.     

含氟体系中DDR型分子筛的合成

DDR (Deca-dodecasil 3R) zeolite was synthesized hydrothermally in fluoride medium. The effects of synthesis conditions including the amount of KF, different fluoride sources and seeds on crystallization of DDR zeolite were investigated. The as-synthesized DDR zeolite samples were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results demonstrated that DDR crystallization was strongly affected by n_KF/n_SiO2, fluoride sources and seeds. Pure DDR zeolite could be successfully obtained in n_KF/n_SiO2 range of 0.5～1 after 9 days of hydrothermal synthesis. The synthesis time was reduced to 1 day by adding small amount of seeds with yield approaching 100%.     

结晶碳酸钕的水热合成、外观形貌及其组成

Crystalline neodymium carbonates were prepared by treating the amorphous precipitate formed from the reaction between neodymium chloride and ammonium bicarbonate under hydrothermal condition. Their composition, morphology and crystal phase were identified by means of elemental analysis, SEM and XRD. It was found that Nd₂(CO₃)₃·2.5H₂O with tengerite-type structure and sheet morphology was obtained when the feed molar ratio(FMR=n_(NH4)2CO2/n_NdCl3)was 2 or 1.8 and hydrothermally treated at 150 ℃ for 12h. However, orthogonal NdOHCO₃ particles agglomerated with long rod crystals were formed when lowering FMR to 1.5 under the same hydrothermal condition. Phase transformation from tengerite-type Nd₂(CO₃)₃·2.5H₂O to orthogonal NdOHCO₃ was occurred when increasing hydrothermal temperature or prolonging hydrothermal time, which is beneficial to the preparation of neodymium hydroxyl-carbonate with neodymium oxide content higher than 70%.     

IGC反气相色谱法分析氧化铝包覆碳酸钙二元复合物表面能的研究

Spindly calcium carbonate coated with AlOOH has been successfully prepared by bubbling carbonization method. SEM and XRD analysis results suggested an amorphous filiform the coating layer of AlOOH. Inverse gas chromatography (IGC) analysis indicated that γ_s^D, the London component of surface energy of calcium carbonate increased after being coated with AlOOH, especially when with the coating weight quantity of 4%. And the reduction of the γ_s^D value with the ascending column temperature became more obvious along with the increase of the coating weight quantity, which might be due to the desorption of water from the surface. In addition, the surface acid- alkali capacity of calcium carbonate also increased after coating.     

改变枸橼酸和EDTA抗衡阳离子对草酸钙结石抑制作用的体外模拟

The effects of counterions of citric acid and EDTA on the crystallization of calcium oxalate (CaO_x) were in-vestigated in silica gel with a double diffusion technique. The ability of inhibiting the growth and aggregation of CaO_x crystal and the ability of inducing formation of COD follows： potassium citrate 》 sodium citrate >citric acid. Na₂EDTA had a stronger ability to inhibit the aggregation of CaO_x crystals than that of EDTA， but a weaker ability to inhibit nucleation and growth of CaO_x crystals. Since COM exhibits a greater degree of attachment to renal tubule cells in culture compared with COD， that is， COD is easy to be expelled from the body along with the urine. So both inducing formation of COD and inhibiting growth and aggregation of CaO_x crystal can decrease the probability of urinary stones. These results have positive significance in the prevention and cure of urinary stones clinically.     

纳米Mn-Zn铁氧体的制备和研究

Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe₂(SO₄)₃, ZnSO₄·7H₂O, MnSO₄·H₂O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15～25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn_1-xZn_xFe₂O₄ was also discussed. The lattice of nanosize Mn_1-xZn_xFe₂O₄ decreases with x increasing; and its value deviated the standard lattice (a₀) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of Mn_xZn_1-xFe₂O₄ with x increasing was studied: nanosize Mn_xZn_1-xFe₂O₄ particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe₂O₄ samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn²⁺, Zn²⁺ and Fe³⁺) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.     

反相微乳液法合成SrTiO3纳米棒

SrTiO₃ nanorods were synthesized in cetanyl trimethyl ammonium bromide (CTAB) reverse microemulsion containing CTAB, n-hexanol, n-octane and water with Ba(OH)₂ as reactants. The effects of different conditions such as ω₀ [ω₀=n_H2O/ n_CTAB], aging time and the concentration of reactants on the formation of the nanorods were studied. Transmission electron microscope (TEM), electron diffraction (ED) and X-ray diffraction(XRD)were used to characterize the morphology and the structure of the synthesized nanorods. The results show that SrTiO₃ nanorods with a length of 260～2 000 nm and a diameter of 50～100 nm belonging to single crystal are single cubic system. The molar ratio of Sr to Ti of products is 1.0 as determinded by ICP.     

氢氧化锌合苯甲酸层状化合物的水热合成与表征

The organic-inorganic layered compound zinc hydroxide-benzoic acid with basal spacing of 1.92 nm was synthesized hydrothermally using amorphous Zn(OH)₂ and benzoic acid at the reaction temperature of 90～130 ℃, the molar ratio of C₆H₅COOH/Zn(Containing 6 mmol of Zn) of 0.4～0.6, 20 mL H₂O and the reaction time of 6 h. The character, structure, particle morphology and chemical composition of the layered compound were characterized by means of XRD, TG-DTA, SEM, TEM and elemental analysis. The results indicate that the layered compound is of plate-like morphology and that with the temperature raising of hydrothermal synthesis, the particle of plate-like piece becomes smaller. The chemical formula of the layered compound could be written as Zn(OH)_2-y·(C₆H₅COO)_y·0.3H₂O, 0.36≤y≤0.54.     

BaO-Al2O3-B2O3系密封玻璃的结构与性质

The BaO-Al₂O₃-B₂O₃ glasses manufactured for solid oxide fuel cell(SOFC) sealing were studied. The effect of different n_BaO/n_B2O3 on crystal, thermal properties, density and infrared spectra of this system has been discussed. The results show that the trends of crystallization, glass transformation temperature, dilatometric softening temperature and density increase with n_BaO/n_B2O3 values. But a typical property deviation occurs when n_BaO/n_B2O3 is 0.875, and its coefficient of thermal expansion has the maximum at this point. The changes of properties can attribute to the conversion of boron from tetrahedral coordination to trigonal, breakage of the local glass network and interaction between the network modifiers. These can be proved by infrared spectra of glasses. Thermal properties of some studied samples are suitable for the sealing of SOFC using Sm doped ceria electrolyte and operating at 400～600 ℃.     

Physico-chemical properties of Chitosan films

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.     

Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by¹³C and ¹⁵N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.     

Aqueous p-nitrotoluene oxidation induced with direct glow discharge plasma

A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe²⁺ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH ₄ ⁺ , NO ₃ ⁻ and CO₂. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.     

Catalytic air oxidation of manganese in synthetic waters

An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially at high values of pH and concentration. The reaction was found to be first order with respect to Mn²⁺ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment plant of Corum Municipality.     

Zur Kenntnis der Reaktionsfähigkeit des Thiomorpholins und alkylsubstituierter Thiomorpholine, 4. Mitt.

Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).

Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.     

Beiträge zur Chemie der Pyrrolpigmente, 39. Mitt.: Ein Kraftfeldmodell zur konformationsanalytischen Untersuchung von Gallenfarbstoffen

A force field model was designed with respect to the special needs of bile pigments. It is parametrized and tested using partial structures of bile pigments as well as an integral pigment; the solution structures of the molecules were previously deduced using independent experimental methods.

38. Mitt::Falk, H., Schlederer, T., Wolshann, P., Mh. Chem.112, 199 (1981).     

Präparation und röntgenographische Untersuchung eines neuen Kupfer-Oxoaluminats: Cu2Al4O7

Solid state reaction of CuO and Al₂O₃ with a flux of PbO about 930°C and reaction time of 8d gives the new compound Cu₂Al₄O₇. The red single crystals were examined by energydispersive microanalysis and X-ray diffraction methods. Cu₂Al₄O₇ has cubic symmetry, space group ,a=908.0 pm. The typical coordination of Cu⁺ (CN=6 and CN=12) and the interstitial arrangement of the AlO₄-tetrahedra are discussed with respect to related compounds.

     

Hydrazyl,Nitronyl-, and imino-nitroxides: Synthesis,properties and reaction with nitric oxide and nitrogen dioxide

Ten novel and stable free radicals of nitronyl-, imino-nitroxide and hydrazyl type compounds were synthesized and their physico-chemical properties investigated. UV-Vis and ESR spectroscopic data, as well as the lipophilicities and specific hydrophobic areas of the compounds are compiled. The reaction of these radical compounds with nitric oxide and nitrogen dioxide was also investigated. The radicals synthesized, show selectivity in their reaction with these nitric oxides, depending on their structure (nitronyl-nitroxide radicals react with NO, while hydrazyl radicals react with NO₂). The processes are easily monitored by UV-Vis or ESR spectroscopy.     

Kinetische und thermodynamische Untersuchungen im System AgCl-LiCl-NaCl

In the ternary system silver chloride-lithium chloride-sodium chloride the kinetics of the galvanic deposition of silver on graphite electrodes was investigated as well as its dissolution without current in the molten salt saturated with chlorine gas.In addition the emf-values were measured in the temperature range between 923 K and 1,173 K by means of, the formation cell graphite/Ag(s)/AgCl(l)–LiCl(l)–NaCl(l)/Cl₂ graphite From these data the partial molar free excessGibbs energies were calculated. Using the equation for a multicomponent system as suggested byRedlich-Kister ¹ G _AgCl ^E values were obtained by a non-linear fitting process, where the fit was performed for all investigated temperatures and over the entire concentration range in the ternary system. With the parameters obtained the partial and integral excess valuesG _i ^E ,G ^E ,H _i ^E ,H ^E ,S _i ^E andS ^E were calculated.

     

A kinetic method for <Emphasis Type="Italic">para</Emphasis>-nitrophenol determination based on its inhibitory effect on the catalatic reaction of catalase

The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction: in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10⁻⁵–2.5·10⁻⁵ mol/L and the detection limit was 3·10⁻⁶ mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed.