研究与述评

通过化学氧化聚合法合成了掺杂了磷酸盐和硝酸盐的聚吡咯传吕粉复合颜料。一种涂料配方中含有掺杂了磷酸盐的聚吡咯腾吕粉复合颜料、掺杂了硝酸盐的聚吡咯／铝粉复合颜料,其中铝粉的颜料体积溶度为20％。     

不同组成磷酸盐颜料的腐蚀抑制性能

以铬酸锌为参照物,考察了45#钢在不同pH值3.5%NaCl的磷酸盐颜料提取液腐蚀体系下的电化学行为,讨论了传统和新型复合掺杂磷酸盐颜料的腐蚀抑制特性。结果表明,AlZnPO4MoO4.4H2O和AlZn2P3O10-(MoO4)2.2H2O两种新型复合掺杂磷酸盐颜料在不同酸碱度条件下均展现出较为理想的效果,尤其是很好的改善了传统磷酸盐在中性体系中的防腐性能,甚至超过了性能优异的铬酸锌颜料,同时,进一步提升了酸性环境下磷酸盐颜料所具有的优越性。     

钼、钨掺杂磷酸盐防锈颜料的氧化还原性能

以硫酸为支持电解质,在水-1,4-二氧六环混合溶剂中,用循环伏安法研究了掺钼、钨及复合掺杂的磷酸盐颜料的氧化还原特性,分析了掺杂钼和钨的氧化还原能力和可逆性,讨论了单一和复合掺杂对磷酸盐氧化还原性的影响。结果表明,掺钼的磷酸盐氧化性强于掺钨的磷酸盐;不论是正磷酸锌还是三聚磷酸铝,都可以通过掺杂钼和其他的金属离子来改善其氧化还原性,掺杂一种金属离子的性能优于掺杂两种金属离子。     

涂料中“绿色”颜料的抑制剂性能

铬酸锌作为一种防腐颜料常常用于底漆配方中，但由于它对环境的破坏性及毒性较大，所以严重限制了它的使用。为能取代铬酸锌，有人提出了各种环保型替代产品。在过去的十年中，对磷酸锌防腐颜料的防腐性能进行了大量的研究。期间，为使其性能得到改进，对该系列颜料尝试了各种改性，因而产生了“第二代”磷酸盐颜料，即在磷酸盐颜料中引入了钼、铝或铁等元素。本文以铬酸锌为参照物，讨论了磷酸锌和三种第二代磷酸盐的抑制特性。以不同pH值的颜料萃取液作为腐蚀介质，将碳钢样板浸入颜料萃取液中，通过电化学工艺测出它们的腐蚀率。数据表明，铬酸锌在中性和碱性溶液中的抑制力最高，但磷酸盐颜料在酸性溶液中结果较好。由于磷酸盐颜料具有该特点，同时对环境的破坏性较小，所以可作为替代铬酸盐的理想产品，用在酸性条件下使用的防护涂料中。     

酚醛/松香改性酚醛树脂中新型磷酸盐的缓蚀性能

选择酚醛树脂以及酚醛/松香改性酚醛复合树脂,以磷酸锌、三聚磷酸铝APW-I为参照,采用电化学阻抗谱(EIS)考察了含AlZnPO4MoO4·4H2O和AlZn2P3O10(MoO4)2·2H2O两种第二代磷酸盐的涂层在中性3.5%(质量分数)NaCl溶液腐蚀体系中的腐蚀抑制性能,分析了AlZn2P3O10(MoO4)2·2H2O可能的腐蚀失效机制。结合常规的盐水浸泡实验,评价了两种新型磷酸盐颜料在不同涂料中的防腐性能。结果表明:含有改进的聚磷酸盐AlZn2P3O10(MoO4)2·2H2O的酚醛树脂涂层具有一定的自修复作用,中后期阻抗降低较小,展现出更为优异的腐蚀抑制性能;而在酚醛/松香改性酚醛复合树脂中,AlZnPO4MoO4·4H2O的性能更为优异。     

掺杂剂对硫硒化锌基颜料的影响

文中主要研究了在硫硒化锌基颜料中，掺杂剂的种类和掺杂浓度对颜料性质的影响，讨论了理想的掺杂剂的选择原则。利用ＸＲＤ，分光光度计对颜料试样进行分析研究。分析不同掺杂剂及掺杂浓度下颜料的性质，以确定能使硒化锌基颜料生产亮红色的掺杂剂的种类及掺杂深度。     

环保型磷酸盐防锈颜料的研究进展

磷酸盐防锈颜料是当前取代红丹和锌铬黄等传统有毒颜料的有效品种,以其突出的耐腐蚀性能和环保特性在涂料工业中引起重视并取得了长足进展。简要论述无毒磷酸盐防锈颜料的种类,以及国内外应用研究情况,并对其组成、应用性能的发展方向提出了建议。     

低红外发射率半导体颜料的制备方法与应用现状

论述了低红外发射率半导体颜料研究的必要性,介绍了低发射率半导体颜料的特性、研究进展与制备方法.建议低发射率半导体颜料的研究按以下方面进行:深入研究半导体的掺杂理论,探索半导体颜料掺杂含量对涂料红外性能的影响,不同半导体颜料的制备方法和工艺条件的选择研究,以及不同颜色体系的半导体颜料的合成等.     

浅色导电颜料的制备

制备了一种在ＺｎＯ表面包覆一层经掺杂Ｓｂ的ＳｎＯ２浅色导电颜料。讨论了ＳｎＯ２的包覆量和Ｓｂ的掺杂量对该颜料体积电阻的影响，该颜料色呈灰白色，具有较好的导除静电能力。     

磷酸盐防锈颜料技术发展态势研究

磷酸盐防锈颜料具有无毒环保、价格低廉、耐腐蚀性好等特点,在涂料工业中得到广泛推广和应用,是红丹和锌铬黄等传统重金属有毒防锈颜料的有效替代品。本文对正磷酸盐、聚磷酸盐及改性磷酸盐防锈颜料的发展现状及发展趋势进行了介绍,并对磷酸盐防锈颜料未来的发展趋势进行了展望。     

磷酸铝包覆氧化铁黄颜料的制备及其耐温性能研究

氧化铁黄颜料受热易脱水变色,限制了其在温度较高环境下的应用。提高氧化铁黄的热稳定性具有很重要的意义。通过液相水解沉积的方法对氧化铁黄表面进行磷酸铝表面包覆,研究了磷酸铝包膜的工艺条件（pH、包膜量、温度）对氧化铁黄包覆的表面形貌和微观结构的影响。结果表明：在pH为7、磷酸铝的包膜量为13%、包覆温度为65 ℃时,在氧化铁黄表面的包覆效果最佳。采用色差法研究了在最佳条件下进行磷酸铝包覆的氧化铁黄颜料,结果表明其耐温性得到显著提高。     

活性超细含钾磷酸锌的制备及其活化机理的研究

合成了一种含磷酸锌钾和四水磷酸锌的新型活性超细磷酸锌颜料。用XRD、FT-IR和纳米激光粒度仪对其进行表征,测定了溶解度、电导率、pH缓冲区间,从理论上探讨了该颜料的活化机理。实验结果表明:与普通正磷酸锌相比,随着局部pH环境的变化,活性含钾磷酸锌能离解出较多的Zn2 和PO43-离子,改善了正磷酸锌的溶解性、水解性和pH缓冲区间,从而提高抑制阴极剥离反应的能力。     

FITC and Ru(phen)32+ co-doped silica particles as visualized ratiometric pH indicator

The performance of fluorescein isothiocyanate (FITC) and tris(1, 10-phenanathroline) ruthenium ion (Ru(phen)32+) co-doped silica particles as pH indicator was evaluated. The emission intensity ratios of the pH sensitive dye (FITC) and the reference dye (Ru(phen)32+) in the particles were dependent on pH of the environment. The changes in emission intensity ratios of the two dyes under different pH could be measured under single excitation wavelength and readily visualized by naked eye under a 365-nm UV lamp. In particular, such FITC and Ru(phen)32+ co-doped silica particles were identified to show high sensitivity to pH around the pKa of FITC (6.4), making them be potential useful as visualized pH indicator for detection of intracellular pH micro-circumstance.     

Inhibitor properties of “green” pigments for paints

Zinc chromate is one of the anticorrosive pigments most frequently used in the formulation of primers. However, its environmental aggressiveness and toxicity severely restrict its use, and different green alternatives have been proposed in order to replace zinc chromate. In the last decade, the behaviour of zinc phosphate as anticorrosive pigment has been intensively researched. During this time, various modifications have been made to this family of pigments to improve its properties, and a “second generation” of phosphate pigments, incorporating elements such as molybdenum, aluminium, or iron, has been produced. In this paper, the inhibitive properties of zinc phosphate and three second-generation phosphates have been investigated, using zinc chromate pigment as a reference. Pigment extract solutions, at different values of pH, have been used as corrosive media. Carbon steel samples were immersed in such solutions and their corrosion rates were measured using electrochemical techniques. The data obtained suggest that zinc chromate provides the highest percentage of inhibition in neutral and basic solutions, but phosphate-based pigments showed better results in acid solutions. Given this performance advantage, together with their less harmful environmental impact, these phosphate-based pigments can be proposed as realistic alternatives to chromates in the formulation of protective paints for use in acidic conditions.     

Evaluation of anti-corrosive pigments by pigment extract studies, atmospheric exposure and electrochemical impedance spectroscopy

The inhibition efficiencies of zinc chromate, barium metaborate, calcium silicate, amino carboxylate, calcium barium phosphosilicate, aluminum triphosphate and a modified zinc phosphate on the corrosion of steel and zinc were determined by polarization experiments on pigment extracts. Zinc phosphate and zinc chromate were the best and were studied further to determine the effect of pH and chloride concentration on their inhibition of steel. Zinc chromate is adversely affected by high concentration of chloride ions, which effect seems to be less pronounced on zinc. A low pH, although increasing the solubility of zinc phosphate, does not increase its efficiency. The pigments were also incorporated into an epoxy-poly(amide) binder, applied to cold-rolled steel and galvanized steel, exposed at a marine exposure station and the degradation monitored by electrochemical impedance spectroscopy. There was a general correlation between the results of pigment extract studies and atmospheric exposure except in the case of phosphate pigments on cold rolled steel.     

Methodology for zinc phosphate pigment incorporation into polypyrrole matrix

In this work, the incorporation of a commercial zinc phosphate pigment into polypyrrole (PPy) matrix during its electrochemical synthesis on mild steel was studied in order to produce PPy/zinc phosphate composite films as a protective layer against corrosion. Potassium nitrate, oxalic acid, tosylic acid and sodium salicylate solutions were used as electrolytes in cyclic voltammetry and galvanostatic polarisation studies. The influence of synthesis parameters such as nature, concentration, pH and stirring of the electrolyte on the degree of incorporation of the pigment was investigated, as well as time and current densities of the electropolymerisation process. Their influence on current efficiency was also evaluated. Sodium salicylate was the only electrolyte to show a high current efficiency in the polymerisation reaction and to yield a composite film with a reasonable amount of zinc phosphate. In this electrolyte medium, X-ray photoelectron spectroscopy (XPS) analysis showed that zinc phosphate may be found in the polymeric matrix: (i) as a conductive ionic minority form and (ii) as a non-conductive non-ionic majority one for higher incorporation levels. Scanning electron microscopy (SEM) showed that zinc phosphate is heterogeneously distributed on the surface of the polymer.     

A new pigment for smart anticorrosive coatings

The purpose of this paper was to evaluate the performance of a modified zeolite as an anticorrosive pigment for paints. A procedure to prepare the pigment was outlined and its anticorrosive properties assessed following the electrochemical behavior of a steel electrode in pigment suspension. In a second stage, alkyd paints were formulated employing different anticorrosive pigments: (1) 30% by volume (v/v) of the modified zeolitic rock, (2) 10% (v/v) of zinc phosphate, and (3) a mixture of 10% (v/v) zinc phosphate plus 20% (v/v) of the modified zeolitic rock. In every case, percentages were referred to the total pigment content. Titanium dioxide, zinc oxide, and barium sulfate were incorporated to complete the pigment formula. The pigment volume concentration/critical pigment volume concentration (PVC/CPVC) ratio was 0.8. The performance of the resulting anticorrosive paints was assessed by accelerated (salt spray and humidity chambers) tests and electrochemical (corrosion potential, ionic resistance, and polarization resistance) essays. It was demonstrated that the modified zeolite is effective in protecting steel from corrosion when it is used in combination with zinc phosphate. There exists a synergism between the modified zeolite and zinc phosphate that allows the zinc phosphate content in anticorrosive paints to be reduced.     

N、Mo共掺杂TiO_2光催化剂的制备及对亚甲基蓝降解性能研究

以硫脲、钼酸铵和钛酸四丁酯为原料,利用溶胶-凝胶法制备了未掺杂的和N、Mo共掺杂的TiO2光催化剂。用紫外-可见吸收光谱对制备的催化剂样品进行了表征,考察了不同条件下光催化剂对亚甲基蓝溶液的光催化活性。试验结果表明,N、Mo共掺杂使TiO2催化剂的吸收带边位置发生了红移;在可见光条件下,0.125 gN、Mo共掺杂TiO2(n(N)∶n(Mo)=2∶1)、pH值为6.20、温度为30℃的体系对质量浓度为20 mg/L的亚甲基蓝溶液的脱色效果最好。