Effect of Magnesium Ions on the Adsorption of Poly(acrylic acid) onto Alumina

The adsorption isotherms of poly(acrylic acid) (PAA) onto alumina powder have been determined as a function of pH, ionic strength, and magnesium-ion concentration. The adsorption of PAA is strongly enhanced by magnesium ions in alkaline media but less affected under acidic conditions. The adsorption isotherms display a maximum when PAA is fully complexed with magnesium ions in the solution, corresponding to a ratio of 0.25 ± 0.05 [Mg²⁺]/[acrylic acid monomer]. The decrease in adsorbed amount with an increase in PAA concentration at constant magnesium-ion concentration is related to a decrease in the complexation ratio.     

Adsorption equilibrium,kinetics, and dynamic separation of Ca2+ and Mg2+ ions from phosphoric acid-nitric acid aqueous solution by strong acid cation resin

The separation of Ca²⁺ and Mg²⁺ ions from phosphoric acid-nitric acid aqueous solution is very significant for the neutralization process of nitrophosphate fertilizer. This paper studied the adsorption equilibrium, kinetics, and dynamic separation of Ca²⁺ and Mg²⁺ ions by strong acid cation resin, and the effects of phosphoric acid and nitric acid on the adsorption process were investigated. The results reveal that the adsorption process of Ca²⁺ and Mg²⁺ ions in pure water on resin is in good agreement with the Langmuir isotherm model and their maximal adsorption capacities are 1.86 mmol·g^-1 and 1.83 mmol·g^-1, respectively. The adsorption kinetics of Ca²⁺ and Mg²⁺ ions on resin fits better with the pseudo-first-order model, and the adsorption equilibrium in pure water is reached within 10 min contact time, while at the present of phosphoric acid, the adsorption rate of Ca²⁺ and Mg²⁺ ions on resin will go down. The dynamic separation experiments demonstrate that the designed column adsorption is able to undertake the separation of metal ions from the mix acids aqueous solution, but the dynamic operation should control the flow rate of mix acid solution. Besides nitric acid solution was proved to be effective to completely regenerate the spent resin and achieve the recyclable operation of separation process.     

Ionically crosslinked poly(acrylic acid) membranes. I. Wet technique

A study has been made of the ionic crosslinking of poly(acrylic acid) membranes for possible applications in dialysis and reverse osmosis. The technique consists of casting a film of poly(acrylic acid) neutralized with sodium hydroxide, followed by immersion in appropriate metal salts (aluminium, zinc, and chromium salts). A qualitative rate model has been developed to guide this synthesis. Since both metal cations and protons in solution compete for the carboxylic acid sites, acid–base properties of the metal and polycarboxylic acid appear to be important for successful membrane formation. The use of a nonsolvent for the polymer in the crosslinking solution was tested and found to give improved membranes under some conditions. The nonsolvents tested were methanol, acetone, benzene, and dimethylformamide, dimethylformamide being the most successful. Crosslinking agents such as the Zn²⁺ and Cr³⁺ salts were tried but were not as successful as the Al³⁺ salts. A series of membranes was synthesized in aluminium/dimethylformamide crosslinking baths under various conditions in order to determine suitable procedures for preparation of membranes.     

黄腐酸基Cd2+离子印迹聚合物的吸附性能测试

以改性黄腐酸为功能单体,反相悬浮聚合法制备了Cd²⁺离子印迹聚合物,并研究其吸附性能。动力学模型表明,黄腐酸基Cd²⁺离子印迹聚合物对Cd²⁺的吸附符合准二级动力学吸附模型,相关系数达到0.9977;热力学研究发现,黄腐酸基Cd²⁺离子印迹聚合物吸附重金属离子的形式为单分子层表面吸附,与Langmuir等温吸附模型相符;竞争吸附实验显示,竞争离子Pb²⁺、Cr³⁺存在时,Cd²⁺/Pb²⁺、Cd²⁺/Cr³⁺的相对选择性系数分别为4.32、13.47,说明MFA-IIP对模板离子拥有较强的选择识别性能,竞争离子化合价不同,选择识别性更加显著。     

Study of ternary component polymer complexes of poly(methacrylic acid) and poly(acrylic acid) with complementary polymers

Ternary component polymer complexes have been prepared from poly(acrylic acid) and poly(methacrylic acid) with complementary polymers, such as poly(vinylpyrrolidone) and poly(ethylene oxide). The formation of ternary complexes, selective complexation, and mutual compatibility of the complementary polymers attached to the same polycarboxylic acid chain, have been studied by several techniques, such as viscometry, turbidimetry, potentiometry, conductometry, and IR spectra.     

Complexation of rhodium on radiation-grafted acrylic acid onto poly(tetrafluoroethylene–perfluorovinyl ether) copolymer films

Radiation-induced graft polymerization of acrylic acid onto poly(tetrafluoroethylene–perfluorovinyl ether) copolymer films has been prepared using γ-irradiation by the mutual method. The grafted copolymer rapidly complexes with rhodium ions through the carboxylic groups. The complexation process was followed by measuring the variation of the pH of aqueous RhCl₃ solution of several concentrations as a function of time. Spectroscopic, electrical, optical, thermal, and diffraction measurements have been investigated. The results revealed the high stability of the ligand–metal complex formed. Thus, a practical application of the grafted copolymer in the field of rare metal waste treatment is implied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1449–1455, 1998     

Adsorption of Pb, Cu and Cd in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)–poly(butilene oxide)–poly(ethylene oxide) triblock copolymer (EO₃₉BO₄₇EO₃₉) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO₂. Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb²⁺, Cu²⁺ and Cd²⁺ in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd²⁺, Cu²⁺ and Pb²⁺ from single ion solutions. Adsorption of Cu²⁺ was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7.     

Effects of calcium cations incorporated into magnesium vanadates on the redox behaviors and the catalytic activities for the oxidative dehydrogenation of propane

The influence of the incorporation of Ca²⁺ into MgV₂O₆, Mg₂V₂O₇ and Mg₃V₂O₈ on the catalytic activities for the oxidative dehydrogenation of propane and the mobility of lattice oxygen in those catalysts has been investigated. On Mg₂V₂O₇ and Mg₃V₂O₈ incorporated with Ca²⁺, the selectivity to propylene evidently increased with increasing the content of Ca²⁺ in those catalysts. A decrease of the conversion of propane was observed on Ca²⁺-added Mg₂V₂O₇ with increasing Ca²⁺-content; while on Ca²⁺-added Mg₃V₂O₈, no dependence on the Ca²⁺-content was observed. The incorporation of Ca²⁺ was rather insensitive to both the selectivity and the conversion on Ca²⁺-added MgV₂O₆. In order to examine the mobility of lattice oxygen in those catalysts, those catalysts were employed for the oxidative dehydrogenation in the absence of oxygen for 2.25 h, followed by the addition of gaseous oxygen into the feedstream. After the addition of gaseous oxygen under the present conditions, oxygen in the effluent was detected at 9, 3.5 and 2 min with Mg₂V₂O₇ incorporated with Ca²⁺ at these Ca/(Mg + Ca) ratios: 0, 0.05 and 0.1. The times were 1.4, 2 and 4 min with Mg₃V₂O₈ incorporated with Ca²⁺ as Mg₂V₂O₇. However, no oxygen was detected with MgV₂O₆ incorporated with Ca²⁺ even 15 min after the addition of the gaseous oxygen. The present results reveal that the mobility of the lattice oxygen in those catalysts is strongly influenced by the amount of Ca²⁺ incorporated, resulting in significant effects on the activities for the oxidative dehydrogenation of propane. ⁵¹V MAS NMR was also employed for the observation of redox behaviors of vanadium species in those catalysts during the reaction.     

聚(丙烯酸-共聚-苯并-18-冠醚-6-丙烯酰胺)的铯离子响应特性及其铯离子检测性能

制备了一种聚(丙烯酸-共聚-苯并-18-冠醚-6-丙烯酰胺)（PAB）线形共聚物,并系统研究了不同丙烯酸含量的PAB线形共聚物对铯离子的响应特性及其用于铯离子浓度检测的性能。结果表明,在不同浓度的铯离子溶液中,PAB线形共聚物的低临界溶解温度（LCST）会随着铯离子浓度增加向低温迁移;在实验范围内,当PAB线形共聚物中的丙烯酸质量分数为30%时,其铯离子响应特性最有利于水溶液中铯离子浓度的检测。通过系统实验研究,确立了PAB共聚物的LCST与水溶液中铯离子浓度的关系函数;利用该关系函数,可简单地通过测定未知铯离子浓度的PAB溶液LCST,即可推断出该溶液中的铯离子浓度。该研究为铯离子的便捷检测提供了新手段。     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

固相法制备掺杂型高色度CoxM1-xAl2O4/高岭土复合颜料

为了制备低成本、高色度的钴蓝颜料,本文以高岭土为载体,以Al₂O₃和Co₃O₄为主要原料,通过引入ZnO、CaO及MgO不同金属氧化物,采用固相法制备了高色度(Co_xM_1-xAl₂O₄)/高岭土复合颜料(M为Ca²⁺、Mg²⁺或Zn²⁺)。系统考察了研磨时间、煅烧温度、煅烧时间和不同金属氧化物掺量对复合颜料呈色性能的影响规律。研究表明,在煅烧温度1 200 ℃、研磨时间12 h和n(Co²⁺)/n(M²⁺)为3:2时,制得的复合颜料具有最好的呈色性能(L^*=53.68,a^*=7.58,b^*=-62.89)。同时,引入不同的金属元素,可实现对复合颜料颜色的调控,引入Ca²⁺后,所制备的Co_xCa_1-xAl₂O₄复合颜料偏红相,而引入Zn²⁺后,所制备的Co_xZn_1-xAl₂O₄复合颜料偏绿相。通过相关表征,提出了复合颜料的呈色机理,在颜料制备过程中,引入与Co²⁺离子半径接近的Mg²⁺或Zn²⁺,Mg²⁺或Zn²⁺可进入CoAl₂O₄的四面体配位中,部分替代Co²⁺,形成MgAl₂O₄-CoAl₂O₄或ZnAl₂O₄-CoAl₂O₄的固溶体,而引入离子半径较大的Ca²⁺,形成CaAl₂O₄和CoAl₂O₄的均相混合物。最后,将制得复合颜料应用到有机硅耐热涂料中,可以明显提高有机硅涂料的热稳定性。     

Ultrafiltration recovery of alginate: Membrane fouling mitigation by multivalent metal ions and properties of recycled materials

Recovery of alginate extracted from aerobic granular sludge (AGS) has given rise to a novel research direction. However, these extracted alginate solutions have a water content of nearly 100%. Alternately, ultrafiltration (UF) is generally used for concentration of polymers. Furthermore, the introduction of multivalent metal ions into alginate may provide a promising method for the development of novel nanomaterials. In this study, membrane fouling mitigation by multivalent metal ions, both individually and in combination, and properties of recycled materials were investigated for UF recovery of sodium alginate (SA). The filtration resistance showed a significantly negative correlation with the concentration of metal ions, arranged in the order of Mg²⁺ < Ca²⁺ < Fe³⁺ < Al³⁺ (filtration resistance mitigation), and the moisture content of recycled filter cake showed a marked decrease. For Ca²⁺, Mg²⁺, Fe³⁺, and Ca²⁺+Fe³⁺, the filtration resistances were almost the same when the total charge concentration was less than 5 mmol·L^-1. However, when the total charge concentration was greater than 5 mmol·L^-1, membrane fouling mitigation increased significantly in the presence of Ca²⁺ or Fe³⁺ and remained constant for Mg²⁺ with the increase of total charge concentration. The filtration resistance mitigation was arranged in the order of Fe³⁺ > Fe³⁺ + Ca²⁺ > Ca²⁺ > Mg²⁺. Three mechanisms were proposed in the presence of Fe³⁺, such as the decrease of SA concentration, change in pH, and production of hydroxide iron colloids from hydrolysis. The properties of recycled materials (filter cake) were investigated via optical microscope observation, dynamic light scattering, Fourier transform infrared, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The results provide further insight into UF recoveries of alginate extracted from AGS.     

NMF effect on photosensitized charge separation using partially quaternized poly(1-vinylimidazole)-bound ruthenium(II) complexes

The solvent effects on the photosensitized charge separation using partially quaternized poly(1-vinylimidazole)-bound ruthenium(II) complexes (RuQPIm), in which bis(2,2′-bipyridine)ruthenium(II) complexes are coordinated to the imidazolyl residues on the poly(1-vinylimidazole) partially quaternized by 1-bromohexadecane and the degree of quaternization is 19 (RuQPIm-19) and 44 (RuQPIm-44) molar percentage, have been investigated in methanol and methanol–NMF (NMF: N-methylformamide). These systems consist of RuQPIm-19 and RuQPIm-44 as photosensitizers, 1,1′-dimethyl-4,4′-bipyridinium dication (MV²⁺) and 1,1′-didodecyl-4,4′-bipyridinium dication (C₁₂V²⁺) as electron acceptors, and triethanolamine (TEOA) as a sacrificial donor. The addition of NMF mainly affect the forward and back reactions in the charge separation reactions. In RuQPIm-19 systems, the reaction proceeds through an interactive process, which is through the viologen having π–π interaction for MV²⁺ and van der Waals interaction for C₁₂V²⁺. In contrast, the reaction proceeds through a direct process by MV²⁺ having no interaction and through an interactive process by C₁₂V²⁺ undergoing van der Waals interaction with the polymer for RuQPIm-44 systems. For MV²⁺, the rates of MV^·+ formation increased, although the quenching efficiency decreased with increasing NMF content for RuQPIm-19 and RuQPIm-44. These results are attributed to stabilization of MV^·+ species by π–π interaction for RuQPIm-19 and steric repulsion between MV^·+ species and RuQPIm-44; namely, the restriction of the back reactions by these effects. In contrast, for C₁₂V²⁺, the rates of C₁₂V^·+ formation decreased and the quenching efficiency increased with the addition of NMF. These are attributed to that the addition of NMF increases the van der Waals interaction of the C₁₂V²⁺ with these polymers and the diffusion of the C₁₂V^·+ species into the bulk solution; namely, the back reaction is accelerated. Furthermore, it is suggested that the conformational changes in these polymers contribute to the charge separation reaction.     

草酸强化三价铁离子的反萃性能

二(2-乙基己基)磷酸(P204)常作为溶液净化除铁的萃取剂，P204-磺化煤油体系中Fe³⁺与有机相形成络合能力较强的萃合物，使得Fe³⁺反萃比较困难，需采用较高浓度的酸作为反萃剂，但高浓度的酸会破坏有机分子的结构，影响萃取剂循环利用。针对P204-磺化煤油负铁有机相反萃困难的问题，提出利用草酸为反萃剂对负载1g/L铁的P204-磺化煤油有机相的反萃行为进行研究，考察了反萃转速、草酸浓度、反萃温度、反萃时间和相比对Fe³⁺反萃率的影响。结果表明：以反萃转速200r/min，草酸0.4mol/L，反萃时间10min，反萃温度40℃，反萃相比1∶1，采用二级逆流萃取方式，铁的反萃率可以达到99%以上；Fe³⁺反萃过程是吸热反应，其反应的焓变为81.58kJ/mol，反萃过程符合准一级反应动力学方程，对应活化能为49.5kJ/mol。进一步研究了反萃后P204-磺化煤油有机相对Fe³⁺的萃取性能。结果表明：经5次草酸反萃后的P204-磺化煤油有机相萃铁性能几乎不变，对比于高浓度的酸反萃，草酸反萃简化了反萃流程，降低了萃取剂的消耗。     

Selective removal of iron(III) from highly salted chloride acidic solutions by solvent extraction using di(2-ethylhexyl) phosphate

Metal ions including Fe³⁺, Ca²⁺, Mg²⁺, Ni²⁺, Co²⁺ and Cu²⁺ are commonly found in the leaching solution of laterite-nickel ores, and the pre-removal of Fe³⁺ is extremely important for the recovery of nickel and cobalt. Di(2-ethylhexyl)phosphate acid (D2EHPA) showed high extraction rate and selectivity of Fe³⁺ over other metal ions. The acidity of the aqueous solution is crucial to the extraction of Fe³⁺, and the stoichiometry ratio between Fe³⁺ and the extractant is 0.86:1.54. The enthalpy for the extraction of Fe³⁺ using D2EHPA was 19.50 kJ/mol. The extraction of Fe³⁺ was ≥99% under the optimized conditions after a three-stage solvent extraction process. The iron stripping effects of different reagents showed an order of H₂C₂O₄>NH₄HCO₃>HCl>NaCl>NaHCO₃>Na₂SO₃. The stripping of Fe was ≥99% under the optimized conditions using H₂C₂O₄ as a stripping reagent.     

Coating of carbon fibers with adhesion-promoting thin poly(acrylic acid) and poly(hydroxyethylmethacrylate) layers using electrospray ionization

Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiber–epoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (‘electrophoretic effect’). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions.     

不同金属盐破乳对丁基橡胶硫化行为的影响

为考察金属盐凝固剂对丁基橡胶(isobutylene isoprene rubber,IIR)硫化行为的影响,采用流变仪研究了搅拌破乳及11种金属盐破乳后IIR的硫化历程,并分析了其硫化动力学。研究发现金属盐的阳离子及阴离子种类对硫化过程均有显著影响。与传统Ca²⁺凝固剂相比,过渡金属离子Cu²⁺、Zn²⁺破乳会延长焦烧期及正硫化时间,降低硫化表观活化能,硫化膜储能模量较高。与搅拌破乳相比,主族金属离子Ca²、Mg²⁺、Al³⁺破乳对硫化过程影响较小。阴离子Cl^-及NO₃^-有显著的硫化抑制作用,降低硫化表观速率常数,延长正硫化时间;阴离子SO₄^2-和OAc^-对IIR的硫化历程影响较小,相应的IIR硫化胶具有更高的模量。     

Complex formation of methylcellulose with poly(acrylic acid)

Complex formation between poly(acrylic acid) and methylcellulose in aqueous solutions has been studied by viscometric and turbidimetric methods. The critical pH values in their dependence of polymer concentration were determined. The influence of the nature of a nonionic polymer on the composition and stability of interpolymer complexes is shown. The phase behaviour of acrylic acid‐graft‐methylcellulose copolymer in aqueous solutions is analysed from their complexation point of view. © 2000 Society of Chemical Industry     

Preparation and characterization of MgO powders having Ca or Ba as surface dopants

The tendency of large dopant cations towards surface segregation has here been utilised to prepare high surface area MgO powders carrying Ca²⁺ or Ba²⁺ as surface impurities in amounts equivalent to 0.2 to 5 monolayers of CaO or BaO. Computational approaches had pointed to possibilities for reconstruction of such impurity monolayers into “rumpled” arrangements as a means of minimizing their energies: the rumpled arrangement favoured for Ca²⁺/MgO would have alternate oxygen anions displaced outward from the original (100) plane, whereas that favoured for Ba²⁺/MgO would involve large outward displacement of alternate Ba²⁺ ions. Ions displaced in that way would necessarily feature lower coordination to counter-ions than species on non-rumpled surfaces, and hence could be expected to exhibit higher surface reactivity and/or catalytic activity. This paper presents results of experiments aimed at: (i) preparation of powdered MgO materials having monolayer amounts of CaO or BaO segregated upon their surfaces; and (ii) testing whether such monolayer-doped Ca²⁺/MgO and Ba²⁺/MgO materials exhibit physical and/or chemical properties indicative of the “rumpling” favoured by computations. Chemical comparisons made between surface reactivities of Ca²⁺/MgO and Ba²⁺/MgO versus the pure MgO support include: lability of surface oxide ions, as manifested in ease of heterophase oxygen isotope exchange at 623–873 K, and relative activities for oxidative coupling of methane at 923–958 K. Physical comparisons include: extent and spectral distribution of surface-sensitive luminescence; BET surface areas; X-ray diffraction and scanning electron microscopy.     

The effect of transition metal ions (M2+=Mn2+, Ni2+, Co2+, Cu2+) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I~-/I_3~-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn~(2+),Ni~(2+),Co~(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu~(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu~(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni~(2+), PANI-Co~(2+),PANI-Mn~(2+) and PANI-Cu~(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M~(2+)=Mn~(2+),Ni~(2+),Co~(2+),Cu~(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.