Pool boiling fouling and corrosion properties on liquid‐phase‐deposition TiO2 coatings with copper substrate

Fouling on the heat transfer surfaces of industrial heat exchangers is an intractable problem, and several techniques have been suggested to inhibit fouling. Surface coatings are of such techniques by which the adhesion force between fouling and heat transfer surface can be reduced with low surface free energy thin films. In this article, liquid phase deposition was applied to coat titanium dioxide thin films on the red copper substrates with film thickness in micro‐ or nano‐meter scale. Coating thickness, contact angle, roughness, surface topography, and components were measured with X‐ray diffraction, contact angle analyzer, stylus roughmeter, scanning electron microscopy, and energy dispersive X‐ray spectroscopy, respectively. Surface free energy of coating layers was calculated based on the contact angle. Heat transfer and fouling characteristics in pool boiling of distilled water and calcium carbonate solution on coated surfaces were investigated. Heat transfer enhancement was observed on coated surfaces compared with untreated or polished surfaces due to the micro‐ and nano‐structured surfaces which may increase the number of nucleation sites. The nonfouling time on the coated surfaces is extended than that on the untreated or polished surfaces due to the reducing of the surface free energy of coated surfaces. Corrosion behavior of coated surfaces soaked in the corrosive media of hydrochloric acid, sodium hydroxide alkali, and sodium chloride salt solutions with high concentration at room temperature a few hours was also explored qualitatively. Anticorrosion results of the coated surfaces were obtained. The coatings resisted alkali corrosion within 7.2 × 10⁵ s, acidic corrosion within 3.6 × 10⁵ s and salt corrosion within 2.16 × 10⁶ s. The present work may open a new coating route to avoid fouling deposition and corrosion on the heat transfer surfaces of industry evaporators, which is very important for energy saving in the related industries. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Fouling Resistance on Chemically Etched Hydrophobic Surfaces in Nucleate Pool Boiling

Chemical etching, liquid phase deposition, and dipping techniques were utilized to fabricate highly hydrophobic micro‐ and nanoscale coating surfaces on stainless‐steel substrates. Heat transfer and fouling characteristics on these surfaces in pool boiling of deionized water and CaSO₄ solution were studied. High roughness and hydrophobicity of coated surfaces were obtained on chemically etched substrates. Compared to the polished stainless‐steel surface, the chemically etched coating surface provided a three times enhanced nucleate boiling coefficient at high heat flux. Obvious decrease of CaSO₄ fouling resistance was obtained on chemically etched surfaces due to the higher roughness and hydrophobicity before the fouling resistance reaches the asymptotic value. Slightly high asymptotic fouling resistance was observed compared with coating surfaces without chemical etching of substrates.     

Mathematical modelling of mixed salt precipitation during convective heat transfer and sub-cooled flow boiling

The main purpose of this investigation was to study the mechanisms of mixed salt crystallisation fouling on heat transfer surfaces during convective heat transfer and sub-cooled flow boiling conditions. In the present investigation, the effects of various operating parameters such as solution composition and hydrodynamics of the system, on crystallisation fouling of mixtures of calcium sulphate and calcium carbonate have been studied experimentally. After clarification of the effects of operating parameters on the deposition process, the results of the experiments were used to develop a mechanistic model for prediction of fouling resistances, caused by crystallisation of mixed salts, under convective heat transfer and sub-cooled flow boiling conditions. Model predictions were compared with the measured experimental data when calcium sulphate and calcium carbonate form deposits on the heat transfer surface simultaneously. Deviations ranging from 6% to 25% were observed which confirm the suitability of the model.     

烧结型多孔表面管外池沸腾传热特性

实验研究了热通量为0.1~160 kW·m^-2时,去离子水在光管及烧结型多孔表面管管外的池沸腾传热特性,分析了换热管布置方式(垂直与水平)、管径大小(20、25和32 mm)与多孔层颗粒尺寸(30~105 μm)对池沸腾传热特性的影响规律。结果表明:去离子水在多孔管表面的起始沸腾过热度小于光管,比光管低3 K左右;多孔表面管可明显强化核态沸腾传热,其沸腾传热系数可达光管的3~4.5倍;大热通量下,换热管水平布置时的传热效果较垂直布置佳,且布置方式对多孔管换热效果的影响比对光管的影响小;随管径增大,光管与多孔表面管的沸腾传热系数降低;大颗粒尺寸多孔层的强化效果优于小颗粒尺寸多孔层。     

石墨烯/镍复合微结构表面的池沸腾传热特性

采用电刷镀和表面改性技术,在紫铜表面制备了纯镍微结构（TS1）、亲水性石墨烯/镍复合微结构（TS2）以及疏水性石墨烯/镍复合微结构（TS3）。采用扫描电镜和接触角测量仪分别对三类微结构的表面形貌和润湿性进行了表征;以去离子水为工质,对三类微结构表面的池沸腾传热特性进行了实验研究,发现含有石墨烯的TS2和TS3较TS1的沸腾传热性能均显著改善,其中,TS3具有最大的传热系数和最高的临界热流密度,与TS1相比,其最大传热系数和临界热流密度分别提高了135%和97%。分析表明,TS3具有复杂三维堆叠微结构,疏水性微结构减小了气泡成核的活化能,增加了核化密度,是传热系数提高的主要因素,同时,三维堆叠微结构增加了受热表面的毛细吸液再润湿能力,是临界热流密度提高的主要机理。     

The effect of surface properties on CaSO4 scale formation during convective heat transfer and subcooled flow boiling

In this paper the effects of surface energy and surface roughness on the deposition of calcium sulphate during convective and subcooled flow boiling heat transfer to aqueous CaSO₄ solutions are studied. The surfaces of several test heaters have been treated by Ion Beam Implantation, Unbalanced Magnetron Sputtering, Mixed Sputtering and Plasma Arc Deposition to reduce surface energy. One heater was electropolished to reduce surface roughness and one heater was etched by an electrochemical method to increase surface roughness. Fouling runs with these heaters, and with an untreated surface as control, were carried out at different heat fluxes, flow velocities and salt concentrations. The results show that heat transfer surfaces with low surface energy experienced significantly reduced fouling, while electropolishing did not have a notable beneficial effect. The combined effect of reduced surface energy and flow velocity on fouling reduction is considerably stronger than previously reported for pool boiling.     

表面工程技术应用于蒸发器的防垢及沸腾传热强化的研究进展

对传统的表面工程技术和纳米表面工程技术在蒸发器等换热设备的防垢和沸腾传热强化方面的研究进展进行了综述。分析了采用磁控溅射、离子注入、化学复合镀、分子自组装等表面工程技术制得的低能表面,包括纳米涂层传热表面的防垢或强化沸腾传热的功效。认为应用表面工程技术的难点在于如何制备既能防垢又能强化沸腾传热的优良传热表面;高黏物系的污垢形成规律和表面抗垢机理研究,应用纳米表面工程技术进行防垢和强化沸腾传热研究是今后的重要研究方向。     

流动过冷沸腾传热强化及阻垢

在流动沸腾传热实验中,考察了CaCO3污垢溶液的形成过程及各种工艺条件对流动过冷沸腾传热的影响. 研究条件包括流体速度、溶液温度、CaCO3溶液浓度及热通量,实验中发现了一些规律. 同时还考察了不同阻垢剂[聚天冬氨酸(PASP)、2-膦酸丁烷-1,2,4-三羧酸(PBTCA)及氨基三甲叉膦酸(ATMP)]对流动过冷沸腾传热的影响. 结果表明,所选阻垢剂均能抑制污垢的生成并降低了污垢热阻,而且存在最佳浓度范围. 但不同阻垢剂的阻垢效果不尽相同,在本实验条件下,ATMP的阻垢效果最好,PBTCA次之,PASP的阻垢效果较差.     

Application of fractal theory for characterisation of crystalline deposits

The objective of this investigation was to study the mechanisms of mixed salt crystallisation fouling on heat transfer surfaces and to characterise the structure of the deposits formed on the heat transfer surfaces. The effects of various operating parameters such as solution composition and hydrodynamics of the system on crystallisation fouling of mixtures of calcium sulphate and calcium carbonate, which are the most common constituents of scales formed on heat transfer surfaces, were studied experimentally. After clarification of the effects of operating parameters on the deposition process, deposits on the heat transfer surfaces were collected for analysis. The crystalline samples were analysed using Scanning Electron Microscopy, X-Ray Diffraction and Ion Chromatography techniques. It was found that crystallisation fouling on heat transfer surfaces exhibits fractal geometry. Therefore, the concept of fractal theory was used to quantify the structure of the deposits by introducing a new quantity called the fractal dimension.     

池式沸腾条件下CaSO_4污垢生成的实验研究

在池沸腾装置中,100℃下CaSO4饱和溶液以及热通量55—300 kW/m2,研究了传热表面性质对硫酸钙污垢沉积的影响。通过现代表面处理技术,例如动态混合离子注入和动态混合磁控溅射技术,对若干加热器表面进行处理,以减小金属表面的表面能。研究表明,表面能低的表面,即经离子注入或磁控溅射的表面具有良好的抗垢性能。     

电场强化乙醚自然对流和池沸腾换热

外加电场强化传热是将电场及其理论引入传热学领域,利用电场力与流场和温度场的相互作用而达到强化传热的一种有效方法．     

固体颗粒对池沸腾换热表面上结垢影响的机理分析

报道了固体颗粒对池沸腾换热表面结垢特性影响的实验研究结果。沸腾工质为ＣａＳＯ４水溶液，换热表面材料为紫铜，固体颗粒是０．５～１ｍｍ的玻璃珠。实验结果表明，在平表面池沸腾条件下引入固体颗粒只能在较短的运行时间内起到强化换热的作用。当运行时间较长时，不仅不能强化换热，反而因结垢而使得换热恶化。     

碳酸钙在流动过冷沸腾条件下的结垢机理研究

Fouling of heat transfer surfaces during subcooled flow boiling is a frequent engineering problem in process industries. It has been generally observed that the deposits in such industrial systems consist mainly of calcium carbonate （CaCO3）, which has inverse solubility characteristics. This investigation focused on the mechanism to control deposition and the morphology of crystalline deposits. A series of experiments were carried out at different surface and bulk temperatures, fluid velocities and salt ion concentrations. It is shown that the deposition rate is controlled by different mechanism in the range of experimental parameters, depending on salt ion concentration. At higher ion concentration, the fouling rate increases linearly with surface temperature and the effect of flow velocity on deposition rate is quite strong, suggesting that mass diffusion controls the fouling process. On the contrary, at lower ion concentration, the fouling rate increases exponentially with surface temperature and is independent of the velocity, illustrating that surface reaction controls the fouling process. By analysis of the morphology of scale, two types of crystal （calcite and aragonite） are formed. The lower the temperature and ion concentration, the longer the induction period and the higher the percentage of calcite nreciDitated.     

亲疏水性对泡沫金属池沸腾换热特性的影响

随着航空飞机和航天器不断向高性能发展,热控制系统的紧凑性和散热效率亟需提高。泡沫金属具有超大的比表面积和高热导率,在航空航天热控制领域具有良好的应用前景。对亲水性和疏水改性泡沫金属内的池沸腾换热特性进行了试验研究,并与未改性泡沫金属进行对比,得出了亲疏水性对不同孔密度和孔隙率泡沫金属池沸腾换热特性的影响规律。测试样件为泡沫铜,孔密度为5、20和40 PPI,孔隙率为85%和95%。结果表明,疏水改性可使泡沫金属内池沸腾的起始过热度降低20%～30%;疏水改性泡沫金属和亲水改性泡沫金属分别在低热通量（q<4×10⁵ W/m²）和高热通量（q≥4×10⁵ W/m²）条件下具有最佳的沸腾换热性能;表面改性对于低孔隙率泡沫金属内池沸腾强化换热效果更加显著,且亲水改性的强化效果优于疏水改性。     

表面活性剂对水过冷池沸腾特性影响实验研究

以Tween20、Span20及两者复配物为表面活性剂,实验研究了其对水过冷池沸腾传热特性影响。基于实验结果与表面张力、接触角、临界胶束浓度等基础物性分析发现,单一表面活性剂对沸腾传热的影响由其添加种类、浓度及热通量共同决定。一方面,不同于饱和沸腾情形,过冷状态下Tween20能够有效降低沸腾起始点温度与壁面过热度,但其沸腾强化效果在高热通量下减弱;另一方面,Span20只在低浓度下表现出强化效果,其浓度增大将引起壁面过热度大幅攀升。此外,尽管Tween20与Span20都具有强化沸腾传热的潜力,但两者复配表面活性剂在实验研究浓度范围内均恶化了沸腾传热过程。研究结果可为传热强化复合工质过冷池沸腾传热特性分析提供基础依据,并为其配制提供指导。     

不同压力下HFE-7100在光滑铜基表面的饱和池沸腾传热实验

池沸腾是重要的传热模式之一,广泛应用于诸多工业领域。饱和压力的变化会影响传热工质的热物性,进而引起表面核化及气泡动力学参数的改变,因此饱和压力对池沸腾传热性能具有显著影响。本文在不同饱和压力（0.07MPa、0.10MPa、0.15MPa及0.20MPa）工况下对HFE-7100工质在纳米级粗糙度光滑铜基表面的池沸腾传热及可视化实验进行了研究,针对饱和压力对池沸腾传热的影响机制进行了深入探讨,同时采用相关池沸腾传热及临界热通量预测模型对传热性能曲线进行了对比分析。光滑铜基表面的平均粗糙度为19nm,HFE-7100工质在其上的静态接触角为9.83°。可视化图像展现了沸腾孤立气泡生成、充分发展合并及核化沸腾向膜状沸腾转换的过渡状态。实验数据表明,饱和压力的提升可强化池沸腾传热能力及提升临界热通量。相较于0.07MPa低压池沸腾,0.10MPa、0.15MPa及0.20MPa条件下池沸腾的最大传热系数分别提升29%、59%及75%,传热系数的平均提升率分别为24%、50%和63%,而临界热通量分别增加27%、48%及64%。相对而言,Forster和Zuber（1955）建立的池沸腾传热预测模型及Guan等（2011）建立的临界热通量预测模型较为准确地预测了本研究操控条件下的池沸腾实验数据。     

Investigation of flow boiling in circulating three-phase fluidised bed: Part I: Experiments and results

In flow boiling apparatus, fouling is frequently a problem. Mechanical methods to mitigate fouling include the impact of solids on the deposit to remove it. Solid particles fluidised by the two-phase boiling mixture may accomplish sufficient deposit removal to keep boiling surfaces clean. This results in a self-cleaning fluidised bed boiling heat exchanger. The particles additionally enhance the heat transfer. In this paper, a comprehensive investigation of three-phase fluidised flow boiling in a circulating system is presented. A test apparatus which is a three-phase circulating fluidised bed was built with glass construction to visualise boiling phenomena in a water system. It could also be operated as a two-phase system and this was investigated to provide the basis for comparison and also to verify reproducibility and confirm well-established flow boiling results. For the three-phase system (where steel particles were added), a range of liquid flowrates and heat fluxes was used and three different particle sizes were investigated. Three-phase results were compared with two-phase results. This work is primarily a study of boiling heat transfer enhancement as a result of addition of particles, but the effect of the particles creating a self-cleaning heat exchanger is a significant operational advantage for industrial application.As expected, heat transfer coefficients were higher overall for the three-phase system than for the two-phase system. The onset of nucleate boiling was independent of heat flux and the heat transfer coefficient initially increased with increasing Reynolds number whereafter there was some deterioration of heat transfer. Visualisation of boiling heat transfer phenomena for the three-phase system is also provided which allows mechanistic explanations of the measured phenomena.In Part II of this paper, a correlation is developed, based on boiling heat transfer modelling, to describe heat transfer during boiling in a three-phase circulating fluidised bed. A flow-dependent function is added as is a boiling heat transfer enhancement factor. This correlation is validated against this experimental data and found to show agreement within about 20% and better agreement with the data than an existing correlation.     

常/微重力下微结构表面强化沸腾换热研究进展

表面改性是提高沸腾换热性能的重要手段。本文以自主开发的微结构表面为基础，简述了近三年来常重力条件下的微/纳结构表面强化池沸腾换热、临界热流密度预测模型及经验关联、微重力条件下（重力水平为10^-2～10^-3 g ₀，g ₀=9.8m/s²）加热面尺寸对沸腾换热的影响和气泡动力学等方面的研究进展。对柱状微结构参数和排布方式进行优化后的多尺度复合微结构表面相比柱状微结构表面和光滑表面，其壁面温度可分别降低8K和30K以上，而临界热流密度（CHF）则分别提高了28%和119%以上。体积分数为0.02%的乙醇/银纳米流体相对于单纯的乙醇工质，相同条件下换热壁面温度可降低8～15K，而机械作用对CHF约有25%的提高。通过对柱状微结构的几何参数以及临界发生时的供液机理研究，建立了考虑柱状微结构参数的CHF关联式、微/纳结构表面考虑液体毛细芯吸作用的CHF预测模型以及考虑液体铺展速度的CHF预测关联式。根据微重力下加热面尺寸对沸腾的影响的研究，提出了基于恒定热流密度的换热预测关联式。考虑微重力条件下主气泡和小气泡的表面张力，对传统的气泡脱离直径预测的力平衡模型进行了改进，进一步提高了微重力下气泡的脱离半径的预测精度。此外，对近年来以FC-72为工质的其他强化池沸腾换热微结构表面的研究成果进行了总结，并与自主研发的微结构表面换热性能进行了对比与分析，为今后的研究方向和应用指出了方向。     

复合粉末多孔表面管的沸腾传热

采用管内去离子水加热管外丙酮沸腾的方法对复合粉末多孔表面管的沸腾传热特性进行了实验研究,获得了沸腾传热系数和K值随温度和几何参数的变化情况,并与国内几种多孔表面管的实验结果进行了比较,同时对多孔管的抗垢性能进行了分析.实验结果表明,多孔层孔隙率对沸腾传热系数的影响最大,多孔管的沸腾传热系数是同类型的光滑管的14倍,多孔管具有一定的抗垢性能.所得结果为该种类型多孔管的工业化应用提供了科学依据.     

Effect of titania particles preparation on the properties of Ni–TiO2 electrodeposited composite coatings

In this paper, the effect of titania particles preparation on the properties of Ni–TiO₂ electrocomposite coatings has been addressed. Titania particles were prepared by precipitation method using titanium tetrachloride as the precursor. The titanyl hydroxide precipitate was subjected to two different calcinations temperatures (400 and 900 °C) to obtain anatase and rutile titania particles. These particles along with commercial anatase titania particles were separately dispersed in nickel sulfamate bath and electrodeposited under identical electroplating conditions to obtain composite coatings. The electrodeposited coatings were evaluated for their microhardness, wettability, corrosion resistance, and tribological behavior. The variation of microhardness with current density exhibited a similar trend for all the three composite coatings. The composite coating containing anatase titania particles exhibited higher microhardness and improved wear resistance. However, the corrosion resistance of the composite coating containing commercial titania powder was superior to that of plain nickel, Ni–TiO₂ composite coatings containing anatase and rutile titania particles. The poor corrosion resistance of these composite coatings was attributed to the higher surface roughness of the coatings. This problem was alleviated by incorporating ball-milled titania powders. The composite coatings with higher surface roughness were modified with a low surface energy material like fluoroalkyl silane to impart hydrophobic and superhydrophobic properties to the coatings. Among these coatings, Ni–TiO₂–9C coating exhibited the highest water contact angle of 157°.