溶剂替换法制备氟铃脲水悬浮剂及其分散稳定性

采用溶剂替换法制备了氟铃脲水悬浮剂,通过测定颗粒的平均粒径Dav和颗粒界面的Zeta电位,研究了分散剂种类、添加量以及有机相中乙醇的加入量对水悬浮剂分散稳定性的影响。 结果表明,在相同条件下,以苯乙烯丙烯酸共聚物(MOTAS)作为分散剂制备的水悬浮剂的分散效果较好;当MOTAS添加质量分数为1%时,Dav最小,Zeta电位绝对值最大,体系分散稳定性最好;在有机相中添加乙醇可以显著提高氟铃脲水悬浮剂的分散稳定性,当有机相中乙醇的加入质量分数增加至31.2%时分散稳定性达到最好。     

体系pH值、乳化温度和电解质离子对异丙甲草胺水乳剂稳定性的影响

通过测定药物液滴的平均粒径和Zeta电位研究了体系pH值、 乳化温度和电解质离子对乳化剂三苯乙烯基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐(SCP)稳定的异丙甲草胺水乳剂稳定性的影响. 结果发现, 体系的pH值影响SCP分子在水中的电离能力, 当pH=9时, SCP完全电离, 能为液滴提供较大的静电稳定作用, 水乳剂稳定性最好; 乳化温度低时, SCP分子向液滴界面扩散慢, 且舒展不完全, 液滴所带负电荷较少, 水乳剂稳定性差; 温度升高后, 水相黏度减小, 布朗运动加剧, 液滴碰撞合并几率增大, 且SCP分子热运动增强, 易从界面逃逸, 液滴间静电斥力减弱, 同时SCP亲水性下降, 水乳剂稳定性变差; 电解质离子会压缩界面双电层, 降低Zeta电位, 液滴带电量减少而聚结, 离子浓度越大, 电荷数越大, 水乳剂稳定性越差. 在相同的离子浓度下, 水合半径小的Ca²⁺压缩双电层能力强于Mg²⁺, 添加Ca²⁺后水乳剂稳定性更差.     

苯乙烯-马来酸酐共聚物对20%除虫脲水悬浮剂分散稳定性的影响

以过氧化苯甲酰为引发剂,采用溶液共聚法在不同温度下合成了一系列苯乙烯-马来酸酐共聚物,经磺化制得不同相对分子质量的聚苯乙烯-马来酸酐磺酸钠(SSMA)。 通过测定平均粒径、Zeta电势、黏度等考察了SSMA对20%除虫脲悬浮剂分散稳定性的影响。 结果表明,最佳分散剂为75 ℃聚合得到的SSMA,其质量分数为3%时,水悬浮剂的分散稳定性最好;当pH=9时SSMA分子完全电离,能为颗粒提供较大的空间势垒,水悬浮剂分散稳定性最好;Na+或Ca2+压缩颗粒界面的双电层,降低Zeta电势的绝对值,使颗粒因带电量减少而聚结,导致水悬浮剂分散稳定性变差;当离子浓度相同时,Ca2+的聚沉能力强于Na+,添加Ca2+后的水悬浮剂的分散稳定性更差。     

聚合物分散剂对氟铃脲水悬浮剂流变性质的影响

采用控制应力流变仪研究了聚合物分散剂苯乙烯丙烯酸无规共聚物（MOTAS）用量、分子量及氟铃脲质量分数等对氟铃脲水悬浮剂流变性质的影响。 结果表明,以聚合物MOTAS为分散剂制备的氟铃脲水悬浮剂的流变行为符合Herschel-Bulkley模型。 在固定氟铃脲质量分数为20%时,当分散剂质量分数≤3.0%时,流动行为指数n≤1.0,悬浮体系表现为假塑性流体,当分散剂质量分数≥3.5%时,流动行为指数n≥1.0,悬浮体系具有胀塑性流体特征。 氟铃脲水悬浮剂的流变参数屈服值τH与分散剂MOTAS和氟铃脲的加入量有关。 分散剂MOTAS质量分数≤2.5%时,分散剂在氟铃脲颗粒界面吸附很少,裸露的氟铃脲颗粒界面间相互搭接,具有较大的屈服值τH;当分散剂加入质量分数为3.0%时,分散剂可在氟铃脲颗粒界面形成饱和吸附,若再增加分散剂用量,多余分散剂在悬浮的氟铃脲颗粒间形成搭接,使其屈服值τH增大。 在MOTAS分散剂的分子量在10 000~30 000范围内时,MOTAS分子量愈大,所制得的氟铃脲水悬浮剂的表观粘度和屈服值τH愈小,流变行为指数n虽略有增加,但均小于1,没有改变“剪切变稀”的假塑性特征。     

湿法脱硫浆液中Hg2+的还原机制研究

针对燃煤电厂湿法脱硫浆液中Hg²⁺易被还原的特性,研究Hg²⁺在模拟湿法脱硫系统中的迁移机制,考察了浆液温度、pH值以及SO₃^2-、Cl^-、Ca²⁺、Mg²⁺浓度等因素对Hg²⁺还原性能的影响。结果表明,Hg²⁺还原率随着浆液中SO₃^2-浓度的增大而降低;pH值对Hg²⁺的还原呈先增加后降低的趋势,在pH值为5.5时还原率最高;温度的升高不利于浆液中稳定的二价汞盐络合物存在,导致Hg²⁺还原率增加;Ca²⁺、Mg²⁺以及Cl^-浓度的增加有利于形成稳定化合物,从而抑制Hg²⁺的还原。     

金属组学在急性心肌梗死早期诊断的应用

为探讨急性心肌梗死(AMI)患者血清中K⁺、Na⁺、Ca²⁺、Fe²⁺、Mg²⁺含量变化,并研究其与心肌梗死患者之间的关系。选取2022年5月至2023年2月收治的AMI患者37例,同时选取健康体检者35例作为对照组。依据入院时或体检时收集的抽血样本进行临床生化分析,比较两组间血清K⁺、Na⁺、Ca²⁺、Fe²⁺、Mg²⁺含量,采用判别方程、主成分分析法(PCA),判断分析哪种金属离子对于心肌梗死的诊断价值大。结果表明,AMI患者的血清中Ca²⁺和Fe²⁺含量低于健康对照组,差异具有统计学意义。基于血钙、铁水平两组具有显著性差异,以它们为基础进行判别分析,获得判别函数式。将血清中K⁺、Na⁺、Ca²⁺、Fe²⁺、Mg²⁺     

磷酸氨中和制备磷铵过程中稀土的选择性回收

以含稀土磷酸为原料,系统研究了Ce³⁺和Fe²⁺/Fe³⁺,Ca²⁺,Mg²⁺,Al³⁺的在氨中和制备磷铵过程中的离子迁移行为差异,并考察了不同条件下稀土沉淀物的过滤性能。结果表明,磷酸氨中和pH约为2时,稀土(Ce³⁺)的沉淀率及其与各杂质的分离系数较优。含稀土磷酸模拟料液氨水中和实验中控制pH=2时,各离子沉淀率分别为Ce³⁺99.58%,Fe³⁺8.66%,Ca²⁺13.80%,Mg²⁺11.90%,Al³⁺4.38%,沉淀物中Ce³⁺的质量分数约为43%。含稀土磷酸氨中和过程中pH=2左右稀土优先沉淀且沉淀物可以实现有效过滤。随温度的升高,沉淀料浆的过滤速率从3.39 mL·min^-1提高至4.17 mL·min^-1。     

Zeta电位法选择农药悬浮剂所需润湿分散剂

采用Zeta电位法对质量分数为20%的吡氟草胺悬浮剂所需润湿分散剂进行筛选,以激光粒度分布仪对实验体系的平均粒径(Dav)进行了验证。研究结果表明,除木质素磺酸钠以外,阴离子型润湿分散剂均可使体系的Zeta电位绝对值(│ζ│)达到40mV以上,体系较为稳定;阴离子型润湿分散剂NNO和MorwetD425复配后,相同使用量下体系的│ζ│较单一使用NNO和MorwetD425的大;当m(NNO):m(MorwetD425)=1:4,复配润湿分散剂的总质量分数为1%时,│ζ│达到最大值,颗粒平均粒径最小,热贮前后变化很小,体系达到最佳分散效果。因此,Zeta电位表征润湿分散剂在农药悬浮剂中的润湿分散性能与体系颗粒平均粒径的变化规律有良好的对应关系,故Zeta电位可作为表征润湿分散剂分散性能优劣的指标。     

聚羧酸盐分散剂在农药水悬浮剂中的应用及作用机理分析

聚羧酸盐分散剂具有独特的分散性能,可显著提高农药水悬浮剂等剂型的稳定性.本文应用3种聚羧酸盐分散剂分别制备了3种农药水悬浮剂,研究了聚羧酸盐分散剂在原药颗粒表面的吸附特征和吸附热力学,研究了聚羧酸盐分散剂对农药水悬浮体系Zeta电势和流变性质的影响,并分析了体系在热贮前后各稳定性参数的变化,最终得到了具有长期储存稳定性的农药水悬浮剂产品.研究结果显示,聚羧酸盐分散剂在原药颗粒表面的吸附符合Langmuir单分子层吸附模型,其中吸附热力学参数?G_(ad)0、?S_(ad)0、?H_(ad)0且|?H_(ad)|40 kJ mol~(-1),表明该吸附为自发进行的、放热、熵增的物理吸附过程.聚羧酸盐分散剂通过提高悬浮体系的Zeta电势,使得分散粒子间相互排斥,改善了体系的流动性能,从而提高农药水悬浮剂产品的长期储存稳定性.     

金属阳离子对聚丙烯酰胺溶液黏度的影响及其降黏机理研究

聚丙烯酰胺(HPAM)是油田常用的驱油聚合物,用油田污水配制HPAM溶液易导致其黏度明显降低,影响驱油效果。依据埕东油田污水实测的各种金属阳离子含量来配制HPAM溶液,测得各金属阳离子对其黏度影响由大到小的顺序为:Na⁺>Fe²⁺>Ca²⁺>K⁺>Mg²⁺;通过红外光谱和扫描电镜分析金属阳离子导致HPAM溶液降黏的机理,Na⁺、K⁺、Ca²⁺、Mg²⁺主要是通过与HPAM链上的羧酸根阴离子静电引力相互作用,降低HPAM分子表面原有的电荷密度,造成分子链卷曲,同时减弱了极性基团的溶剂化能力,释放大量的"束缚水",从而使黏度显著降低;Fe²⁺离子主要是与水中溶解氧共同作用,引发自由基反应,导致HPAM骨架水解断裂,致使黏度显著降低。     

酯化淀粉乳化剂制备的高效氯氟氰菊酯O/W乳液的稳定机制

通过测定辛烯基琥珀酸淀粉钠的用量、盐离子、pH值和温度等因素对油滴Zeta电位及表面吸附量的影响,分析了以酯化淀粉辛烯基琥珀酸淀粉钠为乳化剂制备的5％高效氯氟氰菊酯水乳剂的稳定机制.结果表明,辛烯基琥珀酸淀粉钠质量分数为7％时,Zeta电位达到最大值,油滴表面吸附量接近饱和;Na+、Mg2+和Al3+压缩油滴表面的双电层,降低Zeta电位,削弱静电排斥作用,增加辛烯基琥珀酸淀粉钠分子柔性,提高辛烯基琥珀酸淀粉钠表面吸附量,且随着Na+、Mg2、Al3+离子强度依次增大,压缩双电层能力依次增强,Zeta 电位降低和表面吸附量增加程度依次增大;pH值影响辛烯基琥珀酸淀粉钠在水中的解离,在碱性范围内解离出较多羧酸根,静电排斥力较大,Zeta电位较高,但表面吸附量有所降低;温度升高,辛烯基琥珀酸淀粉钠在水溶液中溶解度增大,呈舒展状态,且辛烯基琥珀酸淀粉钠从油滴表面逃逸的趋势增加,油滴表面Zeta电位和表面吸附量均随着温度升高而降低,在低温区差别不大,温度越高二者变化越明显.辛烯基琥珀酸淀粉钠通过吸附于油滴表面为其提供较强的静电斥力和空间位阻作用而维持O/W乳液稳定.     

Dispersion of Silica Fines in Water-Ethanol Suspensions

The dispersion of silica fines in water-ethanol suspensions has been studied through the measurement of settling efficiency, wetting rate, zeta potential, and viscosity. The measurements were performed on two silica samples with mean volumetric diameters of 5.02 and 0.272 &mgr;m at different fractions of ethanol in water-ethanol suspensions. The results have demonstrated that the dispersion stability of the silica suspensions increased as the fraction of ethanol increased and reached to maximum at the fraction of 50%, followed by a decline. The stability was stronger in a pure ethanol suspension than in a pure water suspension. It was observed that the stability closely correlated with the lyophilicity of the particles, but was not predominated by the surface charge of the particles as predicted by the DLVO theory. Viscosity measurements have been used to estimate the solvation film thickness on silica particles immersed in water-ethanol suspensions, on the basis of Einstein's theory of the viscosity of dispersions. It was found that the solvation film thickness on silica fines in a water-ethanol (1 : 1) suspension is about double that in a pure water suspension and about 1.4-fold that in a pure ethanol suspension, respectively, which well explains the dispersion behaviors of the silica fines in the water-ethanol suspensions because a thicker solvation film will cause a stronger disjoining pressure to prevent the proximity of the particles. Copyright 2001 Academic Press.     

Preparation of agglomeration-free hematite particles coated with silica and their reduction behavior in hydrogen

To prepare silica-coated hematite particles without agglomeration, the effects of solid fraction, ion content in solution, and designed layer thickness on agglomeration and dispersion behavior after silica coating were examined. Since the ion concentration remained high in suspension after the hematite particles were prepared, these particles formed aggregates by the compression of an electric double layer on the hematite and silica layer produced a solid bridge between primary hematite particles. Silica bridge formation and agglomeration were almost completely prevented by decreasing the ion concentration and solid fraction of the hematite particles. Furthermore, the effects of the silica-layer thickness and structure on the reduction of hematite to iron under hydrogen gas flow and the iron core stability under air were discussed. When the solid fraction was low in suspension to prevent agglomeration during coating, a densely packed structure of nanoparticles formed by heterogeneous nucleation was observed on the silica-layer surface. Since this structure could not completely prevent oxide diffusion, the layer thickness was increased to 40 nm to obtain a stable iron core under air. Although a dense uniform layer was produced at a high solid fraction during coating, its thickness was reduced to 20 nm to completely reduce hematite to iron.     

Effect of Dispersant on the Colloidal Stability of Nano‐sized CuO Suspension

The stabilization of nano‐sized CuO suspensions was examined to look for the primary mechanism of dispersion. The dispersion stability of suspension was characterized by sedimentation tests, Zeta potential, granularity tests, and infrared spectroscopy (IR). Influence factors such as pH and the concentration of the dispersant on the colloidal stability of the suspension were investigated. The results showed that sodium polyacrylate was fit to stabilize the suspension of CuO nanoparticles through electrosteric repulsion. Also, smaller viscosity and better dispersion effects were achieved when sodium polyacrylate mass fraction was 0.4%～0.8% (based on the powder), pH was 10.     

二价金属离子对含铜水滑石结构稳定性的影响

通过构建不同的二价金属离子(M²⁺=Mg²⁺, Ca²⁺, Zn²⁺, Cd²⁺, Ni²⁺, Co²⁺)部分取代铜离子形成CuM₂Al 水滑石(CuM₂Al-LDHs)的周期性模型, 基于密度泛函理论(DFT), 用CASTEP程序模块对周期性模型进行几何全优化和性质计算, 通过分析各体系的结构参数、电子排布、Mulliken 电荷布居、氢键、结合能, 总结出含铜水滑石体系结构的稳定性规律. 计算结果表明: 在CuM₂Al-LDHs 体系中, 主客体间作用力对层板厚度的影响占主要因素; M离子对中心三价铝离子的影响较小, 对二价铜离子的影响较大, 其中价电子均匀排布的M离子对铜的畸变影响小于价电子不均匀排布的M离子. 另外在价电子均匀排布的CuM₂Al-LDHs 体系中, 主客体间的静电作用力和氢键强度逐渐增强. 总体上, 随着M离子周期数的增加, 体系的畸变角增大, 结合能绝对值逐渐减小, 体系的稳定性下降. 价电子不均匀排布的CuCo₂Al-LDHs 体系的稳定性最差. 这有助于从理论上更好地认识含铜水滑石的合成规律.     

Decationization and dealumination of clinoptilolite tuff and ammonium exchange on acid-modified tuff

The paper presents results of investigation of exchange of the clinoptilolite tuff cations with hydrogen ions from HCl solution of concentration 0.1 mmol cm(-3) and ammonium ions solutions of concentrations 0.0071 to 2.6 mmol cm(-3). Molal concentrations, x (mmol g(-1)) of cations exchanged in acid solution and in ammonium ions solutions were compared with molal concentrations of cations obtained by determination of the cation-exchange capacity of clinoptilolite tuff. The obtained results show that at ammonium ion concentrations lower than 0.1 mmol cm(-3), with regard to exchange capacity for particular ions, best exchanged are Na+ ions, followed by Mg2+ and Ca2+ ions, while exchange of K+ ions is the poorest (Na+ > Mg2+ > Ca2+ > K+). At ammonium concentrations from 0.2 to 1 mmol cm(-3) the order is Na+ > Ca2+ > Mg2+ > K+. At concentrations higher than 1 mmol cm(-3) the order is Na+ > Ca2+ > K+ > Mg2+. The results are a consequence of the uptake of hydrogen ions by zeolite samples in ammonium ions solutions at concentrations lower than 1 mmol cm(-3) and indicate the importance of Mg2+ (besides Na+ ions) for the exchange between clinoptilolite cations and H+ ions, in contrast to K+ ions, whose participation in the reaction with H+ ions is the lowest. During decationization of the clinoptilolite in acid solution, best exchanged are Na+, Mg2+, and Ca2+ ions, while exchange of K+ ions is the poorest. Due to poor exchange of K+ and H+ ions and good exchange of Na+, Mg2+, and Ca2+ ions, it is to be assumed that preservation of stability of the clinoptilolite structure is caused by K+ ions present in the channel C. Clinoptilolite is dissolved in the clinoptilolite A and B channels where Na+, Mg2+, and Ca2+ ions are present. On the acid-modified clinoptilolite samples, exchange of ammonium ions is poorer than on natural zeolite. The longer the contact time of the zeolite and acid solution, the worse ammonium ions exchange. It can be assumed that H+ ions exchanged with zeolite cations are consumed for solution of aluminum in the clinoptilolite structure; therefore the concentration of H+ ions as exchangeable cations decreases. In the ammonium ion solution at a concentration of 0.0065 mmol cm(-3), from the acid-modified zeolite samples, Al3+ ions are exchanged best, followed by Na+, Mg2+, Ca2+, and K+ ions. Further to the results, it is to be assumed that exchangeable Al3+ ions available from clinoptilolite dissolution are best exchanged with H+ ions in acid solution.     

The liquidlike ordering of lipid A-diphosphate colloidal crystals: the influence of Ca2+, Mg2+, Na+, and K+ on the ordering of colloidal suspensions of lipid A-diphosphate in aqueous solutions

A comprehensive study was performed on electrostatically stabilized aqueous dispersion of lipid A-diphosphate in the presence of bound Ca2+, Mg2+, K+, and Na+ ions at low ionic strength (0.10-10.0-mM NaCl, 25 degrees C) over a range of volume fraction of 1.0 x 10(-4)< or =phi< or =4.95 x 10(-4). These suspensions were characterized by light scattering (LS), quasielastic light scattering, small-angle x-ray scattering, transmission electron microscopy, scanning electron microscopy, conductivity measurements, and acid-base titrations. LS and electron microscopy yielded similar values for particle sizes, particle size distributions, and polydispersity. The measured static structure factor, S(Q), of lipid A-diphosphate was seen to be heavily dependent on the nature and concentration of the counterions, e.g., Ca2+ at 5.0 nM, Mg2+ at 15.0 microM, and K+ at 100.0 microM (25 degrees C). The magnitude and position of the S(Q) peaks depend not only on the divalent ion concentration (Ca2+ and Mg2+) but also on the order of addition of the counterions to the lipid A-diphosphate suspension in the presence of 0.1-microM NaCl. Significant changes in the rms radii of gyration (R2G) 1/2 of the lipid A-diphosphate particles were observed in the presence of Ca2+ (24.8+/-0.8 nm), Mg2+ (28.5+/-0.7 nm), and K+ (25.2+/-0.6 nm), whereas the Na+ salt (29.1+/-0.8 nm) has a value similar to the one found for the de-ionized lipid A-diphosphate suspensions (29.2+/-0.8 nm). Effective particle charges were determined by fits of the integral equation calculations of the polydisperse static structure factor, S(Q), to the light-scattering data and they were found to be in the range of Z*=700-750 for the lipid A-diphosphate salts under investigation. The light-scattering data indicated that only a small fraction of the ionizable surface sites (phosphate) of the lipid A-diphosphate was partly dissociated (approximately 30%). It was also discovered that a given amount of Ca2+ (1.0-5.0 nM) or K+ (100 microM) influenced the structure much more than Na+ (0.1-10.0-mM NaCl) or Mg2+ (50 microM). By comparing the heights and positions of the structure factor peaks S(Q) for lipid A-diphosphate-Na+ and lipid A-diphosphate-Ca2+, it was concluded that the structure factor does not depend simply on ionic strength but more importantly on the internal structural arrangements of the lipid A-diphosphate assembly in the presence of the bound cations. The liquidlike interactions revealed a considerable degree of ordering in solution accounting for the primary S(Q) peak and also the secondary minimum at large particle separation. The ordering of lipid A-diphosphate-Ca2+ colloidal crystals in suspension showed six to seven discrete diffraction peaks and revealed a face-centered-cubic (fcc) lattice type (a=56.3 nm) at a volume fraction of 3.2 x 10(-4)< or =phi< or =3.9 x 10(-4). The K+ salt also exhibited a fcc lattice (a=55.92 nm) at the same volume fractions, but reveals a different peak intensity distribution, as seen for the lipid A-diphosphate-Ca2+ salt. However, the Mg2+ and the Na+ salts of lipid A-diphosphate showed body-centered-cubic (bcc) lattices with a=45.50 nm and a=41.50 nm, respectively (3.2 x 10(-4)< or =phi< or =3.9 x 10(-4)), displaying the same intensity distribution with the exception of the (220) diffraction peaks, which differ in intensity for both salts of lipid A-diphosphate.     

苯乙烯丙烯酸共聚物分散剂在氟铃脲颗粒界面的吸附性能

利用残余质量浓度法、ζ电位测定、红外光谱和XPS法系统地研究了苯乙烯丙烯酸共聚物(MOTAS)分散剂在氟铃脲颗粒界面的吸附量、吸附状态、ζ电位、吸附作用力和吸附层厚度等性能. 实验结果表明, MOTAS分散剂在氟铃脲界面的吸附符合Langmuir吸附等温式, 其饱和吸附量和吸附平衡常数k、ζ电位和吸附层厚度均随MOTAS分散剂相对分子量增加而增大, MOTAS分散剂在氟铃脲界面呈多点吸附, 氢键是分散剂分子与氟铃脲界面结合的重要作用力. 分析实验结果发现, MOTAS分散剂在氟铃脲颗粒界面吸附后具有静电排斥和空间位阻双重作用.