化学镀钴液中钴(Ⅲ)的分光光度测定

研究了钴（Ⅲ）－１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）及溴化十六烷基三甲铵（ＣＴＭＡＢ）体系测定钴。钴与ＰＡＮ二元配合物摩尔吸光系数可达９４～１０３Ｌ·ｍｏｌ－１·ｃｍ－１，加入表面活性剂后，钴与ＰＡＮ生成三元配合物，摩尔吸光系数值提高到２１２～１０４Ｌ·ｍｏｌ－１·ｃｍ－１，钴含量在０～２５μｇ／５０ｍｌ范围内符合比耳定律，方法应用于测定化学镀钴液中钴的测定。     

金—钼酸盐—丁基罗丹明B体系显色反应研究

研究了在高氯酸和聚乙烯醇（ＰＶＡ）存在下，金与钼酸盐和丁基罗丹明Ｂ（ＢＲＢ）的显色反应。其适宜条件ＣＨＣｌＯ４＝１．５ｍｏｌ／Ｌ，ＣＭｏＯ２－４＝９．１×１０－４ｍｏｌ／Ｌ，ＣＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ及０．０８％ＰＶＡ。金钼杂多酸—丁基罗丹明Ｂ离子缔合物的最大吸收位于５７０ｎｍ，表观摩尔吸光系数为３．３６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，金量在０～４０μｇ／Ｌ范围内服从比尔定律，测定极限（Ｓ／Ｎ＝３）０．９０μｇ／Ｌ（ｎ＝１０），对于２８μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差２．１％（ｎ＝７）。缔合物至少可稳定５ｈ，摩尔比Ａｕ∶ＢＲＢ＝１∶３。考察了４４种共存离子的影响，大多数常见离子不干扰，用活性炭分离富集金，对砂矿和炭粉中金的测定，结果满意。     

磷锑钼三元杂多酸光度法测定药品中的抗坏血酸

研究了少量抗坏血酸与磷锑钼三元杂多酸体系的显色特性，建立了借磷锑钼三元杂多蓝测定抗坏血酸的分光光度法。最佳显色条件为［ＰＯ３－４］＝３０×１０－４ｍｏｌ·Ｌ－１，［ＳｂⅢ］＝４５×１０－５ｍｏｌ·Ｌ－１，［ＭｏＯ２－４］＝７５×１０－３ｍｏｌ·Ｌ－１，Ｐ∶Ｓｂ∶Ｍｏ＝１∶０１５∶２５，［Ｈ加入］／［Ｍｏ］＝５７。测定波长为λｍａｘ＝７１０ｎｍ，线性范围为１～５０μｇ·ｍＬ－１，回归方程为Ａ＝３６８０Ｃ－００１４，线性相关系数ｒ＝０９９９８，表现摩尔吸光系数ε７１０＝３６８×１０３Ｌ·ｍｏｌ－１·ｃｍ－１，检出限为０２μｇ·ｍＬ－１，标准回收率为９５％～１００％，变异系数ｃｖ≤０３４％（ｎ＝６）。与二元磷钼杂多酸方法相比，省去了水浴加热的繁琐操作，而且由于锑（Ⅲ）的引入，显色在室温下３５ｍｉｎ便可完成，并可稳定５ｈ。     

聚乙烯醇存在下耐尔蓝－铈钼、钪钼杂多酸体系连续光度测定铈和钪

在聚乙烯醇（ＰＶＡ）存在下，耐尔蓝（ＮＢ）与铈钼、钪钼杂多酸络阴离子形成离子缔合物，其最大吸收均位于５８５ｎｍ，表观摩尔吸光度分别为εｃｗ＝３．５２×１０６和εＳｃ＝３．５９×１０＿５Ｌ·ｍｏｌˉ１·ｃｍˉ１，铈和钪服从比耳定律的浓度范围分别为０～０．８μｇ／２５ｍｌ和０～２．０μｇ／２５ｍｌ，测定极限分别为１．３ｎｇＣｅ／ｍｌ（ｎ＝１０）和３．０ｎｇＳｃ／ｍｌ（ｎ＝７），对于０．０２μｇＣｅ／ｍｌ或０．０４μｇＳｃ／ｍｌ测定的相对标准偏差分别为２．７％（ｎ＝９）和２．８％（ｎ＝１０），离子缔合物的摩尔比分别为Ｃｅ：Ｍｏ：ＮＢ＝１：６：４和Ｓｃ：Ｍｏ：ＮＢ＝１：１２：３。本法用于地质标样分析，结果满意。     

1,3—二氯丙烯水解反应动力学

本文研究了顺及反—１,３—二氯丙烯混合物水解反应过程的动力学。结果表明,利用１０％ＮａＯＨ水溶液,在６５～８０℃的条件下,顺及反—１,３—二氯丙烯的水解反应均为二级反应,顺、反异构体的表观活化能分别为８７５１ＫＪ·ｍｏｌ－１和１１３６０ＫＪ·ｍｏｌ－１,反应速率常数ｋ顺＝２６２×１０１０ｅｘｐ（－１０５２５６／Ｔ）,ｋ反＝１０９×１０１４ｅｘｐ（－１３６６３１／Ｔ）。     

在聚乙烯醇存在于铂（Ⅳ）—钨酸盐—罗丹明B体系光度法测定铂

研究了在聚乙烯醇（ＰＶＡ）存在下钨酸盐和罗丹明Ｂ（ＲＢ）光度法测定铂,铂（Ⅳ）与钨酸铵和罗丹明Ｂ形成离子缔合物,它的最大吸收波长位于５７０ｎｍ,摩尔吸光系数ε值为３．４１×１０７Ｌ·ｍｏｌ－１·ｃｍ－１,铂量在０～０．１１μｇ／２５ｍｌ范围内服从比耳定律,缔合物至少稳定９６ｈ,缔合物的摩尔比为Ｐｔ（Ⅳ）：ＲＢ＝１：４,考察了５０多种共存离子的影响,大多数元素不干扰。测定铂（Ⅳ）的适宜条件为［Ｈ２ＳＯ４］＝１．３ｍｏｌ／Ｌ,［ＷＯ４２－］＝１．２×１０－４ｍｏｌ／Ｌ,［ＲＢ］＝４．２×１０－５ｍｏｌ／Ｌ,０．０８％ＰＶＡ。本法已用于铂矿中铂的测定,结果满意。     

偏氯乙烯/丙烯腈/苯乙烯悬浮共聚合动力学

本文研究了偏氯乙烯（ＶＤＣ）／丙烯腈（ＡＮ）／苯乙烯（Ｓｔ）三元悬浮共聚合体系的聚合机理、共聚速率、非聚物组成及其特性粘度的影响因素。实验表明随着投料配比的改变,可分成四个不同聚合机理区域。Ｓｔ对ＶＤＣ／ＡＮ／Ｓｔ三元悬浮共聚有缓聚作用。ＶＤＣ三元悬浮共聚速率可用半经验模型,ｄＣ／ｄｔ＝αＣ＾β「Ⅰ」ｏ＾γｅｘｐ（－γｋｄｔ）描述,由实验得到模型参数γ值为２．２４,模型参数α、β是聚合温度与引发剂浓度的函数。ＶＤＣ－ＡＮ－Ｓｔ三元悬浮共聚物存在着较宽的ＶＤＣ组成分布,并受到单体ＡＮ水溶性的影响,经ＡＮ动态相平衡校正后,可预测ＶＤＣ三元共聚物组成。ＶＤＣ－ＡＮ－Ｓｔ共聚物的特性粘度随着转化率的升高而增大。在相同引发剂用量下,高转化率ＶＤＣ－ＡＮ－Ｓｔ共聚物特性粘度的对数与温度的倒数成线性关系。     

新型磷酸酯两性表面活性剂的研究 Ⅰ.化合物的合成及物化性能

以溴代烷与乙醇胺烷基化,再与五氧化二磷酯化,合成了一系列结构为ＲＮ＋Ｈ２ＣＨ２ＣＨ２ＯＰＯＯ－ＯＨ（Ｒ＝ｎ Ｃ１０Ｈ２１、Ｃ１２Ｈ２５、Ｃ１４Ｈ２９、Ｃ１６Ｈ３３）的新型磷酸酯两性表面活性剂,它们在ｐＨ＝４５～８４范围内显示两性特征;在较宽的ｐＨ值范围（６～１０）内表面活性优良,其γＣＭＣ为２５５ｍＮ·ｍ－１,ＣＭＣ为１５１×１０－３ｍｏｌ·Ｌ－１,且具有优良的泡沫和润湿性能。     

2—（2—噻唑偶氮）—5—磺丙氨基苯酚与铁（Ⅱ）的水相显色反应及其应用

研究了２－（２－噻唑偶氮）－５－磺丙氨基苯酚（ＴＡＳＰＡＰ）与Ｆｅ（Ⅱ）的水相配位显色反应,结果表明在ｐＨ５～７．５范围内,ＴＡＳＰＡＰ与Ｆｅ（Ⅱ）形成组成比为３∶１的稳定的水溶性红色配合物。铁量在０～４０μｇ／５０ｍＬ内服从比耳定律,其表观摩尔吸光系数ε７２６＝２．６１×１０４Ｌ·ｍｏｌ－１·ｃｍ－１。所拟方法用于铝合金标样中铁的测定,结果满意     

橡胶硫化曲线变化的数学模型似合—Ⅱ.转矩上升的硫化曲线

用孟山都流变仪测定了１种ＮＢＲ－１８硫化体系和２种ＮＢＲ－２６硫化体系在１７０℃下的硫化曲线，三者的转矩Ｐ均随硫化时间ｔ的增加而增大。用数学模型ｙ（Ｐ）＝ｆ１（ｔ）＋ｆ２（ｔ）来描述Ｐ的变化，各试样ｆ１（ｔ）的函数形式相同，即ｆ１（ｔ）＝Ａｅｘｐ〔－Ｋ（ｔ－ｔ０）〕；ｆ２（ｔ）的函数形式因试样不同而异，试样１为ｆ２（ｔ）Ｂ－Ｋ２（ｔ－ｔ０），试样２为ｆ２（ｔ）＝Ｂｅｘｐ〔－Ｋ２（ｔ－ｔ０）〕，试样     

炭黑填充型粉末天然橡胶的密炼机塑炼特性研究

采用实验室微型密炼机（Brabender转矩流变仪）研究了炭黑填充型粉末天然橡胶[P（NR/HAF）]的密炼机塑炼/混炼性能,即塑炼时间、塑炼温度和转速等基本工艺参数对胶料门尼粘度的影响。与传统的块状天然橡胶/炭黑（NR/HAF）的密炼机混炼相比,P（NR/HAF）在密炼机混炼时具有较高的混炼温升和较快的升温速率,使得胶料在较高的温度下被塑炼,从而表现出与传统的NR/HAF不同的密炼机混炼特性,其最佳塑炼温度有所降低。通过逐步回归分析建立的“门尼粘度-塑炼条件”模型可以较好地拟合和预测不同塑炼条件下P（NR/HAF）密炼机塑炼后胶料的门尼粘度。     

基于多因素的混炼胶质量预测模型

根据密炼机胶料混炼流变理论和瞬时功率控制法等理论,基于填充因数、转子功率、转子转速、排胶温度和压砣压力5个因素建立混炼胶粘度预测模型.检验结果表明,门尼粘度预测值与实际值很接近,两者差的平均值为0.827,预测效果良好。     

密炼机混炼胶分散度预测数学模型的建立

从单台机的角度运用回归分析方法,建立了预测混炼胶分散度的数学模型,在此模型中,填充因数γ和整个混炼过程的平均功率E／T为自变量,此模型的预测值与实测值之差的平均值为0．567,与一般实测值的误差相近,具有一定的实用价值。     

提高混炼胶分散性及预测精度的研究

使用自制的ＭＧＫＪ型密炼机混炼微机监控系统,采用日常生产混炼工艺过程的有关参数,剔除数据中的奇异点,根据泰勒开原理进行变量变换后,数学模型仍欠理想,只有进一步根据橡胶混炼机理,减去压砣提起时的能量和时间后,数学模型的复相关因数Ｒ才等于０．９５。有关检验均已通过,预测相对标准误差达到１０％以内,这一结果同时也证明,密炼机混炼的高功率条件下对炭黑附聚体的分散才最有效。     

Effect of blend ratio on bulk properties and matrix-fibril morphology of polypropylene/nylon 6 polyblend fibers

Ternary blends of polypropylene (PP), nylon 6 (N6) and polypropylene grafted with maleic anhydride (PP/N6/PP-g-MAH) as compatibilizer with up to 50 wt% of N6 were investigated. PP-g-MAH content was varied from 2.5 to 10%. Blends of the two polymers PP/N6 (80/20) without the compatibilizer were also prepared using an internal batch mixer and studied. The ternary blends showed different rheological properties at low and high shear rates. The difference depended on the amount of N6 dispersed phase. Co-continuous morphology was observed for the blend containing 50% N6. This blend also exhibited higher viscosity at low shear rate and lower viscosity at high shear rates than the value calculated by the simple rule of mixture. At higher shear rates, viscosity was lower than that given by the rule of mixture for all blend ratios. An increase in viscosity was observed in the 80/20 PP/N6 blend after the concentration of the interfacial agent (PP-g-MAH) was increased. Polyblends containing up to 30% N6 could be successfully melt spun into fibers. DSC results showed that dispersed and matrix phases in the fiber maintained crystallinity comparable to or better than the corresponding values found in the neat fibers. The dispersed phase was found to contain fibrils. By using SEM and LSCM analyses we were able to show that the N6 droplets coalesced during melt spinning which led to the development of fibrillar morphology.     

Void content of a viscoelastic composite melt: Reduction during mixing

Mica and polystyrene in four ratios were sheared for three different times, each at three speeds, and at two temperatures in the viscoelastic region, in a screw mixer. From precise density measurements on the resulting composites, void volume fractions were calculated and found to be proportional to mica concentration and independent of total screw rotations. Experimental void/mica ratios were represented by a kinetic model; they decreased from a single value common to all conditions to a steady-state value proportional to the square root of the screw speed. Void formation and elimination occur simultaneously. The goodness of the fit to the data is insensitive to the details of the kinetic model. The characteristic rate constant depends only on temperature, increasing at the same rate as the reciprocal of the low-frequency dynamic viscosity. Cavitation in regions of diverging flow of the mixer may inhibit void elimination.     

Haake混合器中双组分聚合物熔体共混过程的数值模拟研究

采用有限元分析软件POLYFLOW对发生在Haake密闭式混合器中的双组分聚合物熔体共混过程进行了二维等温数值模拟，并进行了实验验证。首先采用仅和流场有关的黏度模型对共混过程进行了数值模拟，模拟结果与实验结果符合较好。进而又考虑了共混体系中组分含量对共混体系黏度的影响，对原来的黏度模型进行了修正，修正后的数值模拟结果和实验结果更接近。通过利用数值模拟的方法进一步获悉了双组分聚合物体系对流混合的规律。     

幂律流体在Kenics型静态混合器中流动特性分析

为了探究Kenics型静态混合器内扭旋叶片剪切作用对幂律流体流动的影响,利用旋转流变仪测量了浓度为0.5wt%, 0.7wt%, 0.9wt%的羧甲基纤维素(CMC)水溶液的流变参数,采用数值模拟与实验研究了扭旋叶片作用下幂律流体流动阻力和剪切稀化特性。对流场研究表明,扭旋叶片诱导产生了内流涡旋、绕流涡旋和近壁面涡旋,有效强化了静态混合器内流体流动的剪切作用。受多个纵向涡旋分布的影响,扭旋叶片局域流场中周向45°位置速度最高,周向30°位置涡量与剪切应力最高而黏度最低。径向0.4倍半径位置速度最高,0.7倍半径位置黏度最高。静态混合器有效提高了流体的二次流流动速度和剪切应力,降低了幂律流体的黏度和流动阻力系数。     

Size adjustment of spherical temperature-sensitive hydrogel beads by liquid–liquid dispersion using a Kenics static mixer

Temperature-sensitive hydrogel beads were prepared by Kenics static mixer technology. The temperature-sensitive monomer N,N-diethylacrylamide and photo-crosslinkable pre-polymer ENT were used as model hydrogel materials. Drop dispersion of high viscosity polymer material in low viscosity hexadecane was made using the static mixer. Drops of a solution of the mixed materials were rapidly photo-crosslinked by UV irradiation after mixing in the static mixer, and spherical hydrogel beads with narrow, normal size distribution were thus prepared. The Kenics static mixer is a useful device for the preparation of spherical beads of temperature-sensitive hydrogels. The Sauter Mean Diameter of the hydrogel beads swollen in deionized water at 293 K was measured. The experimentally determined dimensionless swollen hydrogel bead diameter was well correlated with the Weber number, degree of swelling and viscosity ratio. The effects of gelation and ENT addition on the bead size were evaluated from the degree of swelling. The correlation equation can be used for size adjustment of temperature-sensitive spherical hydrogel beads.     

Factors influencing encapsulation behavior in composite droplet-type polymer blends

In this study the influence of the molecular weight of the dispersed phase components on encapsulation effects in the composite droplet phase was examined for high density polyethylene (HDPE)/PS/PMMA ternary blends. Three different blends composed of various PS and PMMA materials dispersed in an HDPE matrix were prepared using an internal mixer. The morphology was studied by light and electron microscopy. Current models used for predicting encapsulation effects and composite droplet formation in ternary systems (based on static interfacial tension) predict in all cases that PS will encapsulate the PMMA. However, in one case, an unexpected encapsulation of PS by PMMA was observed. It was found that arguments based on the effect of viscosity ratio or the absolute viscosity of the different dispersed phases do not explain that discrepancy. In addition, the reversal of that latter composite droplet morphology from PMMA encapsulating PS to PS encapsulating PMMA was observed upon annealing treatment. Considering all the above, a conceptual model was developed to predict encapsulation effects in composite droplet type systems based on the use of a dynamic interfacial tension (i.e. taking into account the elasticity of the polymer components). Calculations based on the dynamic interfacial tension model, using elasticities based on constant shear stress, were able to account for all of the observed encapsulation effects in this study.