Periodic precipitation of cobalt(II) oxinate

The conditions for obtaining periodic precipitation of cobalt(II) oxinate in agar-agar gel are investigated. The dependence of the nature of periodic precipitation on the concentrations of inner and outer electrolytes is studied in detail. The spacing law of Jablczynski and the time law of Morse and Pierce are verified in this system. The dependence of velocity constant (K) and the spacing coefficient (p) on the concentrations of inner and outer electrolytes has been studied. The velocity constant shows a nonlinear variation with the concentrations of the inner and outer electrolytes. The spacing coefficient (p) is inversely proportional to the concentrations of the inner and outer electrolytes. According to Shouji Shinohara's revised flocculation theory, the flocculation values are computed. The dependence of the flocculation value on the concentrations of the outer and inner electrolytes is studied.     

Mossbauer Spectroscopic Study of 57Co-Labelled Cobalt(II) Bisoxine Dihydrate

The chemical states of ⁵⁷Fe atoms in ⁵⁷Co-labelled cobalt(II) oxinate and in iron(II) oxinate have been studied by means of Mössbauer spectroscopy. Consquently the trivalent charge state of iron atom was found in ⁵⁷Co-labelled hydrated cobalt(II) oxinate, and remarkable difference in Mössbauer parameters of ferrous ion in ⁵¹Co-labelled cobalt(II) oxinate and iron(II) oxinate complexes are observed.     

Sorption of Cobalt on Modified Silica Gel Materials

Various silica gel materials were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzod-18-crown-6 (DB18C6). The degree of functionalization of the covalently attached molecule was calculated from C, H, N analysis and ranged between 0.270 and 0.552 mmol/g (for sorbents with imidazole) and between 0.043 and 0.062 mmol/g (for sorbents with DA18C6 and DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.050 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter <40 Å was used too. Change of pore diameters of silica gel support to larger pores should have a positive influence on access of cobalt ion to sorption centers to increase of sorption capacity of sorbents. The sorption kinetics of cobalt and the influence of cobalt concentration, pH of various kinds of silica gel matrix with immobilized imidazole group in static conditions on sorption were measured. The sorption of cobalt in various conditions (pH, contact time of phases) with constant liquid-solid ratio (V/m = 50 ml/g) was studied. The distribution coefficients ranged between 200 and 50 000 ml/g (for imidazole), 85 and 120 ml/g (for DB18C6) and between 230 and 500 ml/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. Protons significantly competes to sorption of cobalt in acidic solutions. The influence of presence of other heavy or toxic metals (Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was investigated. Sorption of cobalt decreases in order Hg > Cu > Cd > Zn, Fe > Mn > Al, Cr. The presence of sodium and potassium ions at concentration 0.05 mol/l significantly influences on the sorption of cobalt with sorbent with immobilized DB18C6 functional group.     

DSC analysis of phase transformations during precipitation hardening in Al–Zn–Mg alloy (7020)

The hardening of the Al–Zn–Mg alloys during ageing process is based on very complex phase transformations. In order to contribute to the comprehension of these phenomena, we proceed to study the phase transformations of 7020 alloy using differential scanning calorimetry and X-ray diffraction analysis. The results confirm the formation of hardening phase GP zones, intermediate hardening metastable phase η′ and the equilibrium phase η. The calorimetric and X-ray diffraction results are in good agreement and confirm the successive precipitation/dissolution sequence. The dissolution of the precipitates is accompanied by the increase in the crystallographic lattice parameter due to the increase in solid solution concentration and by the softening of the material. On the contrary, the precipitation produces a lower concentration of the Zn/Mg solutes in the Al matrix, which generates a decrease in the lattice parameter value. These precipitates produce the hardening of the alloy. The sequence of phase formation and dissolution explains the evolution of the 7020 hardness as a function of the ageing temperature.

     

Hydrophobic Effects of o-Phenanthroline and 2,2′-Bipyridine on Adsorption of Metal(II) Ions onto Silica Gel Surface

The effects of o-phenanthroline and 2,2′-bipyridine on the adsorption of metal(II) (Fe, Co, Ni and Cu) ions onto silica gel surface have been studied. The adsorption is expressed in terms of the measured concentrations of both metal and ligand at equilibrium. Each adsorption of the four metal ions is increased with the presence of the ligands. In addition, adsorption increases slowly with pH at low pH values and then increases rapidly up to near the pK_a value of silica gel (≈6.5). The adsorption of each metal ion at low pH is increased with increased ligand concentration. However, at high pH the adsorptions of Fe(II) and Cu(II) are decreased with increased ligand concentration whereas the adsorptions of Co(II) and Ni(II) are always increased. At low pH values the ligand to metal ratio adsorbed on the silica gel surface is ca. 3:1 while at high pH values it is 1:1, 2:1, and 3:1, corresponding to the initial ligand to metal ion concentration ratio. The addition of ethanol to the phenanthroline-SiO₂ solution results in a decrease in the adsorption of phenanthroline. The effect of ethanol is also observed in the Fe(II)-phenanthroline-SiO₂ system. The behavior of the adsorption is interpreted qualitatively by hydrophobic expulsion, the formation of surface complexes, and electrostatic interaction. It is concluded that hydrophobic expulsion plays an important role in the adsorption of metal ions in the presence of hydrophobic ligands on silica gel surface.     

Liquid Phase Hydrogenolysis of Biomass‐derived Lactate to 1,2‐Propanediol over Silica Supported Cobalt Nanocatalyst

Liquid phase hydrogenolysis of ethyl lactate to 1,2‐propanediol was performed over silica supporting cobalt catalysts prepared by two different methods: precipitation‐gel (PG) technique and deposition‐precipitation (DP) procedure. The cobalt species (Co₃O₄/cobalt phyllosilicate) present in the corresponding calcined PG and DP catalysts were different as a consequence of the preparation methods, and Co OH Co olation and Si O Co oxolation molecular mechanisms were employed to elucidate the chemical phenomena during the different preparation procedures. In addition, the texture (BET), reduction behavior (TPR and in‐situ XRD), surface dispersion and state of cobalt species (XPS), and catalytic performance differ greatly between the samples. Because of small particle size, high dispersion of cobalt species and facile reducibility, the Co/SiO₂ catalyst prepared by precipitation‐gel method presented a much higher activity than the catalyst prepared by deposition‐precipitation method. Metallic cobalt is assumed to be the catalytically active site for the hydrogenolysis reaction according to the catalytic results of both cobalt samples reduced at different temperatures and the structure changes after reaction.     

Stability of the polymerizable surfactant stabilized latex particles during semibatch emulsion polymerization

The effect of the polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (JS-2), on the stability of polybutyl acrylate latex particles during semibatch emulsion polymerization was investigated in this work. Experimental data show that the ionic strength is the most important parameter in determining the latex stability during the reaction. Both the amount of coagulum produced by intensive coagulation and percentage of the particle volume change (ΔV) caused by limited flocculation increase with increasing electrolyte concentration. The parameter Δ V increases significantly when the concentration of JS-2 in the initial reactor charge ([JS-2]_i) increases. The amount of coagulum increases rapidly when the agitation speed is increased from 400 to 800 rpm. Experiments of coagulation kinetics were carried out to study the stability of latex products toward added salts. The experimental data show that the chemical stability of the latex product increases with increasing pH. Furthermore, the critical coagulation concentration and diffuse potential increase with increasing [JS-2]_i. It is postulated that the increasing electrostatic attraction force between two approaching particles due to the increased [JS-2] _i can increase the apparent magnitude of Hamaker constant.     

Phase Transition of Acrylamide‐Based Polyampholyte Gels in Water

The swelling behavior of acrylamide (AAm)–based polyampholyte hydrogels in water and in aqueous salt (NaCl) solutions was investigated. [(Methacrylamido)propyl]trimethyl‐ammonium chloride (MAPTAC) and acrylic acid (AAc) were used as the ionic comonomer in the hydrogel preparation. Three sets of hydrogels containing 70 mol% AAm and 30 mol% ionic comonomers of varying mole ratios were prepared. The variations of the hydrogel volume in response to changes in pH, and salt concentration were measured. As pH increases from 1, the hydrogel volume V _eq in water first increases and reaches a maximum value at a certain pH. Then, it decreases again with a further increase in pH and attains a minimum value around the isoelectric point (IEP). After passing the collapsed plateau region, the gel reswells again up to pH=7.1. The reswelling of the collapsed gels containing 10 and 4% MAPTAC occurs as a first‐order phase transition at pH=5.85 and 4.35, respectively, while the hydrogel with 1% MAPTAC reswells continuously beyond its IEP. Depending on pH of the solution, the hydrogels immersed in salt solutions exhibit typical polyelectrolyte or antipolyelectrolye behavior. The experimental swelling data were compared with the predictions of the Flory‐Rehner theory of swelling equilibrium including the ideal Donnan equilibria. It was shown that the equilibrium swelling theory qualitatively predicts the experimental behavior of polyampholyte hydrogels.     

Comparison of stages in oil agglomeration process of quartz with sodium oleate in the presence of Ca(II) and Mg(II) ions

The oil agglomeration of quartz with sodium oleate in the presence of calcium and magnesium ions comprises three consecutive stages: adsorption of cations onto quartz surfaces, which leads to coagulation of the suspension, shear flocculation with sodium oleate and finally, agglomeration of flocs by kerosene. The effects of pH and cation concentration on these stages were investigated and the results were presented comparatively. It was found that all the stages of oil agglomeration of quartz exhibited sharp dependences on pH and cation concentration. That is, these stages generally took place in the pH and concentration ranges in which hydroxy complexes of the cations existed in the suspension. In the case of magnesium ion, the coagulation, shear flocculation and especially oil agglomeration of quartz improved after precipitation of hydroxide. These species of calcium and magnesium ions formed at high pH were adsorbed on the negatively charged surface of quartz, as a result of which the adsorption of sodium oleate became possible and thus the shear flocculation of the particles was achieved. Thereafter, the hydrophobic quartz flocs could be agglomerated by kerosene as bridging liquid. The increase in the shear flocculation efficiency depending on the increase of surface hydrophobicity enhanced the oil agglomeration of quartz with kerosene. The maximum recoveries for all the stages of the quartz were obtained in the presence of 10(-3) M magnesium and 5x10(-3) M calcium ions at pH 11. However, some differences in the behavior of shear flocculation and oil agglomeration of quartz suspension were observed above 10(-3) M concentration of magnesium ion.     

Periodic precipitation of lanthanum molybdate crystals in silica gel

Formation of Liesegang rings on the growth of La₂(MoO₄)₃·XH₂O in silica gel by single diffusion technique is discussed. The nature of the periodic precipitation is found to depend on the concentration of inner and outer electrolytes, gel medium and its pH. The ‘time law’, ‘spacing law’ and ‘the law relating diffusion depth and width’ are found obeyed in this system. The one-dimensional Liesegang phenomena is thus investigated quantitatively making use of the simple laws of diffusion.     

Coprecipitation Synthesis of a Superconductor via Multi‐Precipitants

A precipitation process has been developed to prepare precursor powders, which can be calcined and sintered to form high‐Tc superconductors such as YBa₂Cu₃O_y. Precursor powders are prepared using a mixed‐precipitants system in which a solution contains precipitating anions such as hydroxide, oxinate and oxalate ions. A theoretical study on the conditions of mixed‐precipitants coprecipitation is performed. The solution pH of complete precipitation of the title system is extended and is maintained between 4.46 and 12.0. A series of experiments were conducted to confirm the as‐derived optimal condition. Finally, characterization of the properties of the YBa₂Cu₃O_y obtained after high temperature treatment is reported.     

双敏性微凝胶的絮凝及聚沉行为

用沉降聚合法制备了聚(N-异丙基丙烯酰胺-co-甲基丙烯酸)微凝胶, 并用NMR, DLS分析测定了微凝胶结构及凝胶颗粒在不同离子强度下粒径和表面电势的变化. 25 ℃时在pH＝7的溶液中Zeta电位为－18 mV, 随离子强度增加, 逐渐减小. 当NaCl浓度达0.2 mol/L时基本不变, 表明微凝胶表面电荷受到屏蔽, 浓度继续增加主要使凝胶颗粒收缩. 加热引起微凝胶收缩, 颗粒表面电荷密度增大, Zeta电位增大. 在0.2 mol/L NaCl溶液中, 41 ℃时微凝胶的Zeta电位可达－12.4 mV, 使微凝胶稳定. 较高离子强度时, Zeta电位随温度升高发生突变, 微凝胶表面几乎为中性, 其突变温度与临界絮凝温度(CFT)相当. CFT随离子强度增加向低温迁移, 微凝胶聚集速率在高温时比低温时快.     

Isolation and purification of an aminoacylase fromAspergillus oryzae

An aminoacylase (EC 3.5.1.14) has been isolated from a surface culture of the fungusAspergillus oryzae (amilorizin P10X) with a 764-fold degree of purification, an activity yield of 32.7%, and a specific activity in relation to the hydrolysis of N-acetyl-D,L-methionine of 99.3 a.u./o.u. The scheme of the purification of the aminoacylase fromAspergillus oryzae includes: extraction at pH 6.7, precipitation with ammonium sulfate (30 and 80% saturation), gel filtration on Acrilex P-150 (pH 7.5), ion-exchange chromatography on amino-Silochrom Cx-1,5 (mean pore radius 790 Å); the sorption of the enzyme takes place at pH 6.2 and elution with 0.05 M borate buffer, pH 8.0; ion-exchange chromatography on AH-Sepharose 4B at pH 8.0, with elution by a stepwise increase in the concentration of sodium chloride to 0.25 M; and, finally, gel filtration on Sephadex G-200 (pH 8.0). According to the results of disk electrophoresis in 7.5% polyacrylamide gel in a Tris-glycine systems of buffers with a separation pH of 8.9 in the presence of Co²⁺ ions (10^–5 M) of theAspergillus oryzae aminoacylase, two components possessing enzymatic activity were detected, with R_f 0.53 (major component) and R_f 0.63 (minor component).All-Union Scientific-Research Institute for the Genetics and Breeding of Industrial Microorganisms, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 619–624, September–October, 1983.     

Polyvinyl pyridines as flocculating agents

Summary High molecular weight poly 2- and 4-vinyl pyridines were synthesized by ionic polymerisation and their flocculation efficiency tested against kaolin and silica dispersions at pH 3. Low additions of the polymers, around 3 parts per 10₃ parts solid, destabilize the dispersions and clarify silica dispersions to a remarkable extent; however, over-addition of polymer leads to partial restabilization. The flocculation efficiency improves with increase of solids content, especially with clay dispersions. Flocculation efficiency increases with polymer molecular weight, especially over the lower part of the range covered, but is relatively independent of pH in the range 2–4. Quaternization of poly(4-vinyl pyridine) with bromobutane produces a good flocculant for aqueous silica dispersions in which the degree of restabilization on over-dosing depends on the KCI content. TheN-oxide derivatives of the vinyl pyridine polymers do not affect the colloidal stability of silica dispersions. The observations are interpreted in terms of bridging flocculation by the cationic polymer molecules between anionic surface sites on the solid particles.     

EFFECT OF GAMMA RAYS IN THE PREPARATION OF POLYMER AND HYDROGEL FROM ACRYLAMIDE MONOMER

The formation of polymer and hydrogel from aqueous solutions having 20, 30 and 40% concentrations ofacrylamide monomer by γ-ray irradiation processing in the dose range 0.06-30 kGy using a Co-60 source and theircharacterization have been observed. Polymer conversion and gel fraction are found to depend on radiation doses. Polymerconversion increases with the increase of dose, depending on the solution concentration, where maximum conversion isachieved at 0.18, 0.16 and 0.10 kGy for 20%, 30% and 40% concentrations, respectively. On the other hand, gel fractionincreases with dose from the gel point (0.12 kGy) for all concentrations, where 100% conversion of gel occurs at doses≥5 kGy. Tensile strength, viscosity and molecular weight (M_w) of polymer samples increase with both the dose and theconcentration, showing a high value of M_w up to≈10~8. Swelling of hydrogels under water with respect to time varies due tothe variation of cross-linking density formed in the gels and the maximum swelling mainly occurs within 24 h. A remarkable change of surface morphology reveals characteristic features of monomer, polymer and hydrogel films.     

Radiochemical studies on the separation of cobalt with sodium alginate

⁶⁰Co was used as indicator for studies on the separation of cobalt with sodium alginate. Effect of eight experimental parameters (digestion time, digestion temperature, mode of separation, concentration of reagents, pH, order of heating, ammonia, mixing of reagents) on the precipitation and separation of cobalt alginate have been investigated.     

Synthesis,Characterization, and Silver Nanoparticles Fabrication in N-isopropylacrylamide-Based Polymer Microgels for Rapid Degradation of p-Nitrophenol

Multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels were synthesized by precipitation polymerization in aqueous medium. Then silver-poly(N-isopropylacrylamide-co-methacrylic acid) hybrid microgels were prepared by in-situ reduction of silver ions. Formation of microgels was confirmed by Fourier transform infrared spectroscopic analysis. pH and temperature sensitivity of microgel was studied by dynamic light scattering. Hydrodynamic radius of microgels decreases with increase in temperature at pH 8.20 and show volume phase transition temperature around 45°C. At pH 2.65, hydrodynamic radius decreases with increase in temperatures upto 35°C but further increase in temperature causes aggregation and microgel becomes unstable due to increase of hydrophobicity. With increase in pH of medium, the hydrodynamic radius of microgels increases sigmoidally. Formation of silver nanoparticles inside microgel and pH dependence of surface plasmon resonance wavelength of the hybrid microgels were investigated by ultraviolet-visible spectroscopy. The value of surface plasmon resonance band and absorbance associated with surface plasmon resonance band increases with increases in pH of the medium. The apparent rate constant of reduction of p-nitrophenol was found to be linearly dependent on volume of hybrid microgels used as catalyst. The system has a potential to be used as effective catalyst for rapid degradation of industrial pollutant.     

Latex Thermostimulated Flocculation in Poly(N-Vinylcaprolactam) Solutions

The effect of temperature on the flocculation of dilute polystyrene latex in the presence of poly(N-vinylcaprolactam) (PVC), a thermosensitive polymer interacting with water to form systems characterized by a lower critical mixing temperature, is studied by the nephelometry. It is shown that PVC induces latex flocculation only in the presence of a small amount of an inorganic electrolyte. Dependence of the initial flocculation rate on PVC concentration has an extremal pattern, which is typical of polymer flocculants. At concentrations close to those of optimal flocculation, heating in the range below the phase separation temperature (T _ps) increases the flocculation rate and the sizes of forming aggregates. It is found that, at PVC concentrations that do not induce the flocculation at room temperature, heating in the range above T _ps (in the presence of a sensitizing electrolyte) results in an irreversible latex flocculation. The disclosed thermostimulated flocculation is assumed to be due to the deterioration of the solvent thermodynamic quality.     

Flocculation of cellulose fibres: new comparison of crowding factor with percolation and effective-medium theories

New comparisons of percolation and effective-medium theories on one hand, and predictions from the crowding factor on the other hand, are described for calculating critical concentrations in suspensions of cellulose fibres. The connectivity threshold from percolation theory appears to correspond to the “gel crowding factor”, which occurs at crowding factor (N) of N = 16 rather the criterion for fibre collisions, N = 1, postulated in earlier work. The rigidity threshold from percolation theory corresponds to the onset of coherent fibre flocs having mechanical network strength, which occurs at about N = 60. The latter value exceeds the gel crowding factor value by a factor of 3.75. In comparison, percolation theory predicts that flocculation occurs at a rigidity concentration four times higher than the connectivity threshold. These ratios are in good agreement.     

Factors affecting electrical conductivity of carbon black-loaded rubber. II. Effect of concentration and type of carbon black on electrical conductivity of SBR

Effect of the concentration of four types of carbon black, namely, HAF, FEF, ISAF and GPF, on the electrical conductivity of SBR (1502) was studied. The anomalous behavior of conductivity [σ_min in σ(T) curves] becomes more pronounced as we approach a characteristic value of carbon concentration, F₀, at which maximum anomaly occurs; F₀ was found to depend on the type of carbon black. Moreover, the depth of the valley shape of the σ(T) curve increases with the particle size of carbon black used.