海洋钢铁件锌铝喷涂技术典型工程实例回顾

我国的热喷涂防腐蚀技术起步晚,在腐蚀严重的海洋环境中钢铁设施的热喷涂长效防护应用目前仍是空白.研究热喷涂锌、铝及其合金涂层在腐蚀严重的海洋环境中钢铁设施的热喷涂长效防护性能,对于人类开发和利用海洋具有重大的战略意义.介绍了喷涂锌铝涂层技术在国内外海洋平台、海上大桥和海上舰船等海洋钢铁构件的应用实例,结果表明,热喷涂锌铝及其合金涂层已成为一种成熟的近海和海洋钢铁设施的防护技术,经过适当封闭的热喷铝涂层在常温和高温下对处于飞溅区的钢结构均表现出优良的防腐蚀性能.     

金属喷涂长效复合防护涂层在海洋大气环境中的应用

通过对钢铁基底热喷涂锌、铝及锌铝合金复合有机涂层封闭防护体系在厦门海域进行的实海试验腐蚀状况分析 ,发现Zn Al合金涂层在海洋环境条件下的耐蚀性优于Al涂层及Zn涂层 ,在此基础上 ,提出了某大型工程项目适用的热喷涂长效复合防护涂层方案。     

金属热喷涂在海洋采油平台防腐中的应用

热喷涂技术经过近100年的发展,已在国民经济各部门获得了广泛的应用。目前在海洋采油平台防腐中应用的热喷涂技术主要是由喷涂锌、铝金属涂层加有机封闭层组成的长效防护复合涂层。与一般有机涂层相比,其主要优点有：①防护期长：喷锌、喷铝复合涂层,防护有效期一般可达30—50年②不存在老化变质问题③耐磨、耐冲刷、抗擦伤性能好。本文以电弧喷涂为例,介绍了金属热喷涂工艺流程和施工要点。     

金属涂层与有机涂层在5%NaCl溶液中的腐蚀特征

为了解金属锌涂层与有机涂层性能的变化规律,测试了电弧喷涂锌涂层和有机涂层在5%NaCl溶液中的电化学阻抗谱(EIS),并结合扫描电镜(SEM)观察,分析了金属涂层及有机涂层腐蚀特征的变化过程.结果表明:锌涂层表现出自封闭作用,其防护性能主要体现在腐蚀后期,而有机涂层在腐蚀初期有较好的防护性能;锌涂层的电化学行为可以用等效电路Rs(RpoCc)(RpCdl)来描述;随着浸泡的进行,锌涂层极化电阻增大,有机涂层极化电阻减小.     

热喷涂锌铝合金超疏水涂层的制备及性能

用电弧喷涂技术在Q235钢板上喷涂锌铝合金涂层,用硬脂酸/乙醇的表面修饰技术在锌铝合金涂层表面构筑了一层超疏水膜。用接触角测量仪(OCA-20),扫描电子显微镜(SEM)和智能型傅立叶红外光谱仪(ATR)等手段表征了涂层修饰前后的润湿性、表面形貌以及化学结构,并用三电极体系电化学工作站(Solartron analytical)对硬脂酸表面修饰前后锌铝涂层进行了阻抗谱和极化测试。结果表明:热喷涂锌铝涂层具有微/纳复合结构,修饰前涂层表现为亲水性,因为金属涂层具有高表面能;经过硬脂酸表面修饰后涂层的静态接触角达到153.2°,滚动角小于10°;红外分析结果表明,锌铝涂层表面由大量的疏水性烃基长链组成,有超疏水作用;腐蚀测试结果表明,修饰处理能明显提高锌铝涂层的防腐蚀性。涂层表面形成的超疏水膜阻碍了界面电化学反应腐蚀产物的脱落与溶解,提高了电荷转移电阻,降低了电流腐蚀密度,从而提高了涂层的防腐蚀性。     

电弧喷涂锌铝伪合金涂层的耐中性盐雾腐蚀性能

Al含量超过15％的锌铝合金涂层脆性大,限制了其在钢铁防护中的应用。采用电弧喷涂技术在Q235钢表面制备出了纯锌涂层和含铝20％（质量分数）的锌铝伪合金涂层,通过中性盐雾试验及电化学极化测试研究了2种涂层在中性盐雾环境中的耐蚀性,并结合扫描电镜（SEbl）和x射线衍射仪（XRD）对涂层表面形貌及腐蚀产物的相结构进行了观测分析。结果表明：2种涂层均匀致密,孔隙率小,与基体结合良好;随盐雾试验时间增长,锌铝伪合金涂层表面形成了致密的腐蚀产物层,其屏蔽作用有效阻碍了腐蚀介质的渗入,使Q235钢的腐蚀速率快速降低。锌铝伪合金涂层的自腐蚀电流密度小于纯锌涂层,表现出更为优越的防腐蚀性能。     

热喷涂高铝含量锌铝涂层的耐腐蚀性能研究

为了探究高铝含量的锌铝涂层的耐腐蚀性能,通过热喷涂技术制备了3种高铝含量的锌铝涂层,采用超景深显微镜、电化学极化曲线、电化学阻抗谱(EIS)、X射线衍射仪(XRD)等手段,分析了不同铝含量的锌铝涂层的耐腐蚀性能.结果 表明:含Zn涂层在腐蚀过程中首先发生锌的活化溶解,涂层表面附着的腐蚀产物使得涂层表现出微弱的自封闭效果;Zn-Al60涂层兼有锌的阴极保护作用和铝的钝化屏蔽作用,在3种涂层中表现出最优的耐腐蚀性能.     

电弧喷涂耐海水腐蚀金属涂层的研究进展

电弧喷涂金属涂层作为钢结构表面防护的一种重要措施,经过几十年的发展,已成为成熟的表面工程技术和产业。同时,随着新的喷涂工艺、设备和材料的不断研发,电弧喷涂金属涂层应用领域日益广泛。与此同时,使用电弧喷涂技术进行防腐的缺点也日益突出,尤其是喷涂过程中存在有害物质排放等问题,严重制约了其发展。电弧喷涂制备的涂层孔隙率低、微观组织致密、结合强度高且经济性好。相比于其他传统防腐技术,电弧喷涂金属涂层应用于钢结构的表面防护具有如下优势:(1)电弧喷涂沉积效率高、操作容易,便于现场施工;(2)涂层在海洋苛刻腐蚀环境中服役时间长。然而,电弧喷涂耐海水腐蚀金属涂层的服役环境介质不同,对涂层的耐蚀性能提出了更高的要求。因此,近几十年来除研究电弧喷涂工艺参数外,科研工作者们着力研发多功能、高性能的喷涂材料,并取得了丰硕成果,同时充分利用电弧喷涂技术的优势可显著提高涂层的性能。目前电弧喷涂金属涂层材料正朝着复合化、新型化方向发展。目前,用于钢结构表面防护且已取得广泛应用的喷涂材料有锌/铝及其合金、镍基合金、铁基合金和铜基合金等。其中锌、铝及其合金是使用最早且最广泛的喷涂材料;镍基合金可通过加入铬、钼等抗点蚀、缝隙腐蚀的合金元素,提高材料的耐蚀性能;铁基合金中添加少量Mo等元素,能有效抑制晶界腐蚀发生;铜基合金中加入1%的锡,能抑制合金脱锌过程并提高其力学性能。近几年的研究重点为多种合金材料复合及新型合金材料的使用,以电弧喷涂技术为手段制备耐腐蚀涂层,可实现涂层功能和性能的双提升。本文以分析钢结构在近海岸海洋环境各区域带的腐蚀规律为基础,比较了目前用于钢结构表面腐蚀防护的方法及其优缺点,阐述了电弧喷涂涂层的研究现状和防腐机理。从电弧喷涂耐海水腐蚀涂层的微观组织结构、涂层性能及防腐机理等方面,分析了电弧喷涂金属涂层防腐面临的问题并展望了其前景,以期为工业领域钢结构表面的长效防护提供参考。     

金属阳极涂层在化工大气环境中的腐蚀行为

为了解化工大气环境对碳钢表面金属阳极涂层的腐蚀性,开展了热喷涂锌、铝、锌铝合金涂层以及热镀锌、渗锌钢在化工大气环境中的曝露腐蚀试验。通过试样的腐蚀形貌、腐蚀速率变化及电化学测试,考察了金属阳极涂层在石油炼化大气环境中的腐蚀行为。结果表明:化工大气环境腐蚀等级为C4级;喷铝层的腐蚀速率最低;渗锌层的耐蚀性优于热镀锌层。10μm厚热镀锌板耐腐蚀寿命约为4 a,40μm厚热镀锌和渗锌层寿命大于10 a,150μm的喷涂层耐蚀寿命大于30 a。     

Mo-B耐熔锌侵蚀合金涂层在锌及其合金水平连铸中的应用

水平连铸工艺制取锌及其合金线坯的过程中,对熔体温度测控精度有较高要求,但是浸入熔体中的测温热电偶金属保护管,容易被熔锌及其合金侵蚀,造成熔体温度测控失效。本文采用在热电偶金属保护管表面热喷涂一层Mo-B合金层,同时涂衬一层非有机密封材料,试验表明,在热电偶金属保护管热喷涂一层0.1-0.2mm、且硼含量在10％左右的Mo-B合金喷涂层,能起到最佳的耐侵蚀性能,寿命最长可达1000h。     

海洋环境下钢材表面镀铝工艺的研究进展

钢材作为基础性结构材料被广泛应用于海洋工程领域,随着国家对海洋开发的支持力度不断加大,对应用于此环境下的钢材的需求也不断增加。但是,暴露于苛刻海洋环境下的钢材极易与周围的含氯、硫等介质发生反应而受到严重腐蚀,同时,潮汐、日照、溶解氧、微生物以及深海压力和热液带来的高温等环境条件也会加速钢材的腐蚀,严重影响海洋工程设施的服役安全、寿命以及可靠性。 因此,对钢材进行表面处理提高其耐腐蚀性能成为研究热点,其中涂层制备技术是最常用的腐蚀控制方法。铝及铝合金在腐蚀环境及高温氧化环境下表面可以形成一层致密的氧化膜,是一种常用的耐腐蚀涂层材料,通过不同工艺在钢材表面制备的铝涂层已达到了长效的防腐蚀效果。 目前,制备铝涂层的工艺主要有热浸镀法、电镀法、包埋渗铝法及热喷涂法等。热浸镀铝工艺因操作简单、成本低廉而被广泛应用于海洋平台、海洋码头、桥梁等海洋基础设施。电镀铝工艺制备的涂层厚度、组织、形貌可控,可以实现在微小零件上的精准沉积。新型绿色环保的离子液体体系的开发,在提高电镀效率和涂层质量的同时降低了对环境的污染。粉末包埋渗铝制备的涂层具有极高的抗高温氧化性能,被广泛应用于海洋油气开采工程。低温包埋渗铝工艺可避免传统渗铝工艺高温导致的钢材力学性能下降。此外,浆料渗铝以及气相渗铝等工艺的开发拓宽了渗铝工艺的应用领域。热喷涂工艺在海洋环境下应用最为广泛,所制备的铝涂层具有极高的耐腐蚀性能,其中火焰喷涂、电弧喷涂、冷喷涂等工艺能够实现新型防腐蚀铝涂层的设计与制备。 本文针对海洋环境下应用的钢材,详细介绍了在其表面镀铝工艺的研究进展,包括热浸镀、电镀、包埋渗铝和热喷涂等,并对不同镀铝工艺在海洋环境下的应用及发展方向做了展望。     

Development of dense corrosion resistant coatings by an improved HVOF spraying process

For 6 years, we have developed corrosion resistant coatings to protect steel structures in the marine environment by using a thermal spray technique. This paper summarizes the major developments and results obtained. Such a coating requires primarily impermeability and secondarily homogenous and clean microstructure. In order to make denser and highly corrosion resistant coatings, we selected spray materials and improved fabrication processes. HastelloyC was a suitable material for High Velocity Oxy-Fuel (HVOF) spraying to form corrosion resistant coatings because of its high resistance against thermal oxidation as well as seawater corrosion, especially crevice and pitting corrosion. An inert gas shroud system was attached with a commercial HVOF apparatus and this attachment increased the in-flight velocity of spray particles over 750 m s^?1 and simultaneously suppressed oxidation significantly. In addition, some new methods were designed to evaluate the sprayed particle’s state and the coating properties with high accuracy and sensitivity. Thermal energy of in-flight spray particles was revealed by molten fraction of spray particles, determined by quantitative analysis of melted and unmelted particles captured in an agar gel. Through-porosity of the coatings with open porosity below 0.1% was determined by using Inductively Coupled Plasma analysis of dissolved substance from substrate through the penetrating path of the coatings. The coating of HastelloyC nickel base alloy by the HVOF spraying with the gas shroud attachment had zero through-porosity and 0.2 mass% of oxygen content. The laboratory corrosion tests showed that the on-shroud HastelloyC coating was comparable to the bulk material of HastelloyC in terms of corrosion resistance. This coating, formed on steel, demonstrated an excellent protective performance over 10 months in the marine exposure test.     

冷喷涂铝/银纳米线复合涂层的海洋耐蚀防污性能研究

腐蚀和生物污损是海工装备长效服役面临的主要问题,也是海工装备防护的重点和难点.为此,提出了采用低成本水热法制备铝/银纳米线复合颗粒、利用冷喷涂的低温特性制备铝/银纳米线复合涂层的新思路,通过复合涂层成分和结构设计,构筑了致密的复合涂层;分别采用人造海水溶液和革兰氏阳性枯草芽孢杆菌评估了复合涂层的耐蚀和防污性能.结果表明...     

冷喷涂Al基复合涂层的制备及耐蚀性能研究

铝合金以其轻量化特性及优异的耐腐蚀性能得到广泛应用.冷喷涂技术具有低温高速沉积的特点,是制备铝防腐涂层的有效方法.采用机械混合的方式制备了铝基-陶瓷相混合粉末,并通过冷喷涂在Al1060表面制备了Al5056,Al5056-Al2O3,Al5056-SiC,Al5056-WC 4种涂层.通过 Image-Pro Plu...     

Monodisperse Ag@SiO2 core-shell nanoparticles as active inhibitors for marine anticorrosion applications

Monodisperse Ag@SiO2 core-shell structured nanoparticles were firstly utilized as a novel corrosion inhibitor for marine anticorrosion applications. The related marine anticorrosion properties were evaluated with an electrochemical noise (ECN) analysis during 2 weeks of accelerated immersion tests in natural seawater with the addition of various inorganic salts and nutriments. The experimental results indicate that the corrosion activity is markedly reduced by nearly 1-3 orders of magnitude owing to the introduction of Ag@SiO2 core-shell nanoparticles into coating. The inhibition efficiency of corrosion can reach as high as about 99%. More importantly, such a coating exhibits an excellent long-term sustained marine anticorrosion effect. So it could be reasonably inferred that silver cores as active inhibitors effectively prevent the corrosion damage from microorganisms, while silica shells act as a good protection for silver nanoparticles, delay the release of silver ions, and also function as the corrosion inhibiting action for inorganic salts. Therefore, this would make monodisperse Ag@SiO2 core-shell nanoparticles a potential and promising corrosion inhibitor for developing future advanced multifunctional coatings.     

水性环氧聚氨酯富锌涂料的防腐蚀性能研究

为制得环保且防腐蚀性能优异的富锌涂料,引入环氧树脂来改性水性聚氨酯,以水性环氧聚氨酯为基料制备富锌涂料,通过对其腐蚀电位和电化学阻抗谱(EIS)的测试分析,研究了添加不同含量锌粉的富锌涂层在3%NaCl溶液中的腐蚀电化学行为,并与添加少量铝粉的富锌涂料及传统富锌涂料进行了对比.结果表明,水性环氧聚氨酯富锌涂料的防腐蚀能力比传统环氧富锌底漆强;锌粉的添加量对涂层的防腐蚀效果有一定的影响,添加少量铝粉能提高涂层的防腐蚀性能.     

煤基聚苯胺防腐蚀性能及其机理的研究

为了进一步弄清煤基聚苯胺与环氧树脂共混防腐蚀涂料的性能及其相关机理,采用干/湿态附着力、加速浸泡后涂层的鼓泡和腐蚀性能测试、SEM分析、电化学测试等方法,对相关性能进行了分析,并与几种常规防腐蚀涂料(如环氧富锌底漆、聚氨酯防腐蚀漆、银粉漆和氧化铁红防锈漆)进行了对比.结果证明,该涂料在屏蔽性能、阳极保护作用效果和缓蚀性能等方面都具有良好的效果.建立了相关的模型,并解释了煤基聚苯胺具有这些作用的相关防腐蚀机理.     

Corrosion behaviour of hot dip zinc and zinc-aluminium coatings on steel in seawater

A comparative investigation of hot dip Zn-25Al alloy, Zn-55Al-Si and Zn coatings on steel was performed with attention to their corrosion performance in seawater. The results of 2-year exposure testing of these at Zhoushan test site are reported here. In tidal and immersion environments, Zn-25Al alloy coating is several times more durable than zinc coating of double thickness. At long exposure times, corrosion rate for the Zn-25Al alloy coating remains indistinguishable from that for the Zn-55Al-Si coating of similar thickness in tidal zone, and is two to three times lower than the latter in immersion zone. The decrease in tensile strength suggested that galvanized and Zn-55Al-Si coated steel suffer intense pitting corrosion in immersion zone. The electrochemical tests showed that all these coatings provide cathodic protection to the substrate metal; the galvanic potentials are equal to −1,050, −1,025 and −880 mV (SCE) for zinc, Zn-25Al alloy and Zn-55Al-Si coating, respectively, which are adequate to keep the steel inside the immunity region. It is believed that the superior performance of the Zn-25Al alloy coating is due to its optimal combination of the uniform corrosion resistance and pitting corrosion resistance. The inferior corrosion performance by comparison of the Zn coating mainly results from its larger dissolution rate, while the failure of the Zn-55Al-Si coating is probably related to its higher susceptibility to pitting corrosion in seawater.     

Sol-gel法制备耐蚀涂层的技术及应用

Sol-gel法制备耐蚀涂层对提高基材的化学耐久性、防止氧化、控制腐蚀有显著的效果,有望完全替代传统材料表面腐蚀控制处理使用的毒性物质铬酸盐处理工艺,可以减轻对环境的污染,是一项可持续发展的表面处理技术.为了阐述该项技术的工艺方法及特点,综述了Sol-gel法制备技术在不同的金属基体--不锈钢、铝合金和铜合金表面中的应用现状和最新研究进展.分析了采用Sol-gel法制备耐蚀涂层可以有效地阻止腐蚀介质对基体金属材料的破坏,延长材料在实际应用环境中的使用寿命等方面的作用原理,从理论上对Sol-gel耐蚀涂层的形成机制和耐蚀机理进行了初步讨论,并对Sol-gel技术的应用前景作一简要展望.     

Cavitation behavior of active thermal-sprayed coatings

As a first stage in the development of active coatings to improve both localized corrosion resistance and cavitation resistance in sea water, we studied flame-sprayed coatings of aluminum, zinc and Zn-15 wt.% Al applied to steel substrates. Cavitation was carried out in distilled water and in 3.5 wt.% NaCl solution, and was characterized by weight loss and by scanning electron microscopy. Open-circuit potentials in 3.5 wt.% NaCl solution were measured in an attempt to monitor internal fracture, which would allow seepage of solution through the coating to the more noble steel substrate.Cavitation damage rates were found to be significantly higher in the saline solution for the alloy and the aluminum coatings, whereas little sustained change in damage rate was found for the zinc coatings. The data indicate that the strength of the particle matrix essentially governs the overall strenght of the coating. However, in saline solution the effects of alloy strengthening are slightly reduced by the tendency of localized corrosion attack to initiate coating flaws and eventual failure.