Human Factors Engineering in the Metallurgical Industry EAF Protection

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收稿日期：２０２１０６２５ 修稿日期：２０２１０７１８作者简介：屈文涛（１９７０—），男，教授，主要从事人机工效评价与石油天然气机械设备节能减排技术研究工作。Ｅｍａｉｌ：ｗｔｑｕ＠ｘｓｙｕ．ｅｄｕ．ｃｎ

压力分散型锚索锚固段应力分布及影响参数分析屈文涛１，马丽娜１，田　晓２，史婵媛３，习铁宏４（１．西安石油大学机械工程学院，陕西西安７１００６５；２．山东兖矿轻合金有限公司，山东邹城２７３５１５；３．中国石油长庆油田分公司勘探开发研究院，陕西西安７１００１８；４．中地地矿建设有限公司，北京１０００１３）

摘　要：压力分散型锚索在岩土锚固工程中应用较广，具有良好的锚固性能及经济效益，但压力分散型锚索的工程应用超前于其理论研究，对锚固段载荷传递机理的研究并不成熟。为研究压力分散型锚索锚固段应力分布规律，根据压力型锚索锚固段载荷传递函数，利用类比法导出压力分散型锚索锚固段的剪应力和轴向力双曲函数模型，并讨论了相关参数对锚固段应力分布的影响，得出结论：在锚固段应力极限内，增大拉拔载荷可有效增强锚固效果；锚固体轴向刚度要合理取值，避免应力集中现象；在准许抗剪强度内，锚固段长度不宜过长。研究结果为压力分散型锚索的设计及新型锚固技术的开发、应用具有较好的参考价值。关键词：压力分散型锚索；双曲线模型；应力分布中图分类号：ＴＵ４５ 文献标识码：Ａ 文章编号：１６７２—１１４４（２０２１）０５—００２３—０５

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Metallurgical Engineering 冶金工程, 2020, 7(3), 185-194Published Online September 2020 in Hans. /journal/menghttps:///10.12677/meng.2020.73026副枪在转炉自动化控制过程中常见问题及对策张孝兴1，程奎生21铭达科冶金科技(上海)有限公司，上海2达涅利霍高文钢铁技术(上海)有限公司，上海收稿日期：2020年8月28日；录用日期：2020年9月10日；发布日期：2020年9月17日摘要本文阐述了转炉副枪使用过程中影响转炉测温、测样、定碳、取样的主要因素，并逐一提出了对策，通过一系列措施改进，副枪使用成功率在现场稳步提高。

关键词副枪，探头，自动化Common Problems and Countermeasuresin the Operation of Sublancefor the Automatic Controlof ConverterXiaoxing Zhang1, Kuisheng Cheng21MDC Sublance Probe Technology (Shanghai) Co., Ltd., Shanghai2Danieli Hoogovens Steel Technology (Shanghai) Co., Ltd., ShanghaiReceived: Aug. 28th, 2020; accepted: Sep. 10th, 2020; published: Sep. 17th, 2020AbstractThis paper describes the main influence factors of converter temperature measurement, sample measurement, carbon determination and sampling with sublance and puts forward countermea-sures one by one. Through a series of improvements, the success rate of sublance is steadily in-creased on site.张孝兴，程奎生KeywordsSublance, Probe, AutomationCopyright © 2020 by author(s) and Hans Publishers Inc.This work is licensed under the Creative Commons Attribution International License (CC BY 4.0)./licenses/by/4.0/1. 引言近年来随着“中国制造2025”的不断深入，智能制造成为各炼钢企业追求的目标。

SVCStatic Var CompensatorThe key to better arc furnace economyThe key to producing more steel...An electric arc furnace requires a stable and steady voltage supply for optimum performance. An SVC can instantaneously compensate the random variations of reactive power so characteristic of an arc furnace load. The net result is an overallimprovement in arc furnace utilisation.2 The key to producing more steel... | Static Var CompensatorStatic Var Compensator | ...at a lower cost per tonne (3)...at a lower cost per tonne......is a Static Var Compensator (SVC)Reactive power compensation through an SVC helps you to obtain the following benefits:A higher voltage level at the furnace busbar gives: –shorter meltdown times –reduced energy losses–reduced electrode consumption –extended life of furnace liningImproved power factor to:–benefit from lower utility rates–utilise existing electrical plant more effectively –lower plant lossesStabilisation of voltage and reduction of harmonics and phase unbalance to minimise:–disturbances in nearby electrical equipment as well as in the feeding grid–maloperation of protection devices–negative phase sequence currents in motor circuitsBy installing an SVC on the furnace busbar to instantaneously compensate the furnace’s large and continuously varying reactive power demand, troublesome voltage drops andfluctuations can be avoided. The mean power input to the arc furnace is raised, and nearby electrical equipment can oper-ate as usual. The curves above show the furnace busbar’s voltage with and without SVC.4 SVC provides a high and stable bus voltage | Static Var CompensatorSVC provides a high and stable bus voltageFlexible system build-up enables optimum adaptation to customer needsAn electric arc furnace is a complex and heavy load in apower grid. It is a large, unbalanced, and strongly fluctuating consumer of reactive power.These reactive power fluctuations which are very marked, especially at the beginning of the melting operation, lead to voltage drops and fluctuations that reduce the active power to the arc furnace and also to other loads connected to the same feeding busbar. The furnace power varies with the square of the feeding voltage and it is thus very important to keep the voltage high and stable. With a Static Var Compen-sator the reactive power variations are compensated within a few milliseconds and also individually in each phase, providing a balanced and stable voltage.The reactive power needed by the arc furnace is compensat-ed by a thyristor controlled reactor which in combination with harmonic filters on a cycle-by-cycle basis, produces almost a mirror image of the furnace current.ABB can offer many features and options so as to provide the optimum solution for each customer.Examples:–Direct connection to the busbar that is to be compensated. No need for a stepdown transformer. This is valid for all existing EAF bus voltages up to 69 kV.–Most often, the Bi-Directional Control Thyristor (BCT) is used. The BCT brings the advantage of locating two thyristors in one housing, enabling more compact design. – A fully computerized control system. High performance industrial standard buses and fibre optic communication links are utilized.–The thyristor valves are of indoor type, water-cooled for efficiency and compactness.Harmonic filters (FC) in combination with a thyristor-controlled reactor (TCR)Typical layout for an SVC plantThyristor valveTCR reactorsStatic Var Compensator | Unique experience from the steel industry 5Unique experience from the steel industry–Since 1972, ABB has been supplying Static Var Compen-sators to arc furnaces in steel mills all over the world. –We have been involved in design and manufacture of in-dustrial furnaces for almost a century and our metallurgists and engineers are specialists in the metallurgical process and the problems involved in arc furnace applications. –We have our own research, development and manufactu-ring facilities for both components and systems.–We have a world-wide after-sales service organisation and local engineering and manufacturing companies in many countries.ABB holds the key to the best reactive power compensation solutions. Consult us to find out exactly how much you will benefit by installing a Static Var Compensator – it’s usually avery pleasant surprise!6 SVC brings power quality in the grid | Static Var CompensatorSVC brings power quality in the gridElectric arc furnaces are complex loads on the power sup-ply, which is usually the public grid. During operation, unless proper measures are taken, an EAF causes power quality deratings as follows:–Voltage fluctuations and flicker;–Negative-phase sequence components in currents and voltages; –Harmonics.An SVC is an efficient means of maintaining power quality in the plant as well as in the feeding grid. The outcome is a win-ning situation for all:–Compliance with the power quality standards specified by the grid company.–Other consumers connected to the common grid are spa-red the nuisance of disturbances emanating from the steel plant.–The steel manufacturer can operate the steel plant without infringing on operational agreements with the grid company.543210P stTime (hours)09.0010.0011.0012.0013.0014.0015.0016.00Flicker reduction from a steel plant: an example from real life 1). Blue: flicker level, uncompensated; Red/black: flicker level, compensated.A flicker reduction factor up to 2.5 has been reached with the SVC. In cases where this is not sufficient, ABBs SVC Light ® is the answer.1)Recording from a 50 MVA EAF taking its power from a weak 110 kV grid.Static Var Compensator | Cutting of production costs 7Cutting production costsBy increasing the active power available to an arc furnace, a Static Var Compensator can cut the meltdown time (T md ) by up to 20 %.T md can be calculated using this formula:where G = charge weight (tonnes) W = energy consumption (kWh/tonne) F = utilisation factor, approx. 0.75P= furnace power (kW)As a result of increased active power to the furnace, the reduction in meltdown time will be:T md = G x W x F x 60PD T md = G x F x 60 xW 1 W 2()P 1 P 2A typical exampleEAF 75 MVA, 100 T Without SVCWith SVC Improvement (%)SVC (Mvar)0 90 Power factor furnace (p.u.) 0.78 0.78 Power factor supply (p.u.) 0.78 0.99Voltage drop (%) 10 0Melting power (MW) 50 60 20.0Energy (kWh/tonne) 430 420 2.4Melting time (min) 38.7 31.5 22.8Power on time (min) 56.7 49.5 14.5Tap-to-tap time (min) 68.7 61.5 11.7 Electrode consumption 1.61.553.2(kg/tonnes)TimeM W80706050403020100Active power into furnacePowerPotential benefitsBy improving the utilisation of existing plant, not only are operat-ing costs cut, but it will be longer before additional plant needs to be aquired. During periods of low utilisation, over-heads can be trimmed by reducing the number of furnaces online, while still achieving the same level of production.All in all, SVC pay-back times of a year or even less are attainable in many cases.where P 1 = furnace power applied, without SVC (kW) P 2 = furnace power applied, with SVC (kW)W 1 = energy consumption, without SVC (kWh/tonne) W 2 = energy consumption, with SVC(kWh/tonne)Other benefits–Reduced electrode consumption –Reduced energy consumption –Reduced costs of furnace liningContact usA 02-0102 E , 2010-06, E l a n d e r s S v e r i g e A BABB AB FACTSSE-721 64 Västerås, SWEDENPhone: +46 (0)21 32 50 00 Fax: +46 (0)21 32 48 10/FACTS。

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沈阳工业大学硕士学位论文焊接温度场和应力场的数值模拟姓名：王长利申请学位级别：硕士专业：材料加工工程指导教师：董晓强 20050310沈阳工业大学硕士学位论文摘要焊接是一个涉及电弧物理、传热、冶金和力学的复杂过程。

焊接现象包括焊接时的电磁、传热过程、金属的熔化和凝固、冷却时的相变、焊接应力和变形等。

一旦能够实现对各种焊接现象的计算机模拟，我们就可以通过计算机系统来确定焊接各种结构和材料的最佳设计、最佳工艺方法和焊接参数。

本文在总结前人的工作基础上系统地论述了焊接过程的有限元分析理论，并结合数值计算的方法，对焊接过程产生的温度场、应力场进行了实时动态模拟研究，提出了基于ＡＮＳＹＳ软件为平台的焊接温度场和应力场的模拟分析方法，并针对平板堆焊问题进行了实例计算，而且计算结果与传统结果和理论值相吻合。

本文研究的主要内容包括：在计算过程中材料性能随温度变化而变化，属于材料非线性问题；选用高斯函数分布的热源模型，利用函数功能实现热源的移动。

建立了焊接瞬态温度分布数学模型，解决了焊接热源移动的数学模拟问题；通过改变单元属性的方法，解决材料的熔化、凝固问题；对焊缝金属的熔化和凝固进行了有效模拟，解决了进行热应力计算收敛困难或不收敛的问题；对焊接过程产生的应力进行了实时动态模拟，利用本文模拟分析方法，可以对焊接过程的热应力及残余应力进行预测。

本文建立了可行的三维焊接温度场、应力场的动态模拟分析方法，为优化焊接结构工艺和焊接规范参数，提供了理论依据和指导。

关键词：焊接，数值模拟，有限元，温度场，应力场沈阳工业大学硕士学位论文ＳｉｍｕｌａｔｉｏｎｏｆｗｅｌｄｉｎｇｔｅｍｐｅｒａｔｕｒｅｆｉｅｌｄａｎｄｓｔｒｅｓｓｆｉｅｌｄＡｂｓｔｒａｃｔＷｅｌｄｉｎｇｉｓａｃｏｍｐｌｉｃａｔｅｄｐｈｙｓｉｃｏｃｈｅｍｉｃａ／ｐｒｏｃｅｓｓｗｌｆｉｅｈｉｎｖｏｌｖｅｓｉｎｅｌｅｃｔｒｏｍａｇｎｅｔｉｓｍ，Ｍａｔｔｒａｎｓｆｅｒｒｉｎｇ，ｍｅｔａｌｍｅｌｔｉｎｇａｎｄｆｒｅｅｚｉｎｇ，ｐｈａｓｅ?ｃｈａｎｇｅｗｅｌｄｉｎｇＳＯｓｔｒｅｓｓａｎｄｄｅｆｏｒｍａｔｉｏｎａｎｄｏｎ，Ｉｎｏｒｄｅｒｔｏｇｅｔｈｉｇｈｑｕａｆｉｔｙｗｅｌｄｉｎｇｓｔｍｃｔｔｌｒｅ，ｔｈｅｓｅｆａｃｔｏｒｓｈａｖｅｔｏｂｅｃｏｎｔｒｏｌｌｅｄ．Ｉｆｃａｎｗｅｌｄｉｎｇｐｒｏｃｅｓｓｂｅｓｉｍｕｌａｔｅｄｗｉｔｈｃｏｍｐｕｔｅｒ，ｔｈｅｂｅｓｔｄｅｓｉｇｎ，ｐｍｃｅｄｕｒｅｍｅｔｈｏｄａｎｄｏｐｔｉｍｕｍｗｅｌｄｉｎｇｐａｒａｍｅｔｅｒｃａｎｂｅｏｂｔａｉｎｅｄ．ＢａｓｅｄＯｉｌｓｕｍｍｉｎｇｕｐｏｔｈｅｒ’Ｓｅｘｐｅｒｉｅｎｃｅ，ｅｍｐｌｏｙｉｎｇｎｕｍｅｒｉｃａｌｃａｌｃｕｌａｔｉｏｎｍｅｔｈｏｄ，ｔｈｉｓｐａｐｅｒｒｅｓｅａｒｃｈｅｒｓｙｓｔｅｍｉｃａｌｌｙｄｉｓｃｕｓｓｅｓｔｈｅｆｉｎｉｔｅｅｌｅｍｅｎｔａｎａｌ删ｓｙｓｔｅｍｏｆｔｈｅｗｅｌｄｉｎｇｐｒｏｃｅｓｓｂｙｒｅａｌｉｚｉｎｇｔｈｅ３Ｄｄｙｎａｍｉｃｓｉｍｕｌａｔｉｏｎｏｆｗｅｌｄｉｎｇｔｅｍｐｅｒａｔｕｒｅｆｉｅｌｄａｎｄｓｔｒｅｓｓｆｉｅｌｄ，ｔｈｅｎｕｓｅｓｔｈｅｒｅｓｅａｒｃｈｒｅｓｕｌｔｔｏｓｉｍｕｌａｔｅｔｈｅｗｅｌｄｉｎｇｐｒｏｃｅｓｓｏｆｂｏａｒｄｓｕｒｆａｃｉｎｇｂｙＦＥＭｓｏｆｔＡＮＳＹＳ．Ａｔｔｈｅｔｈｅｏｒｙｒｅｓｕｌｔ．ｓａｍｅｔｉｍｅ．ｔｈｅｃａｌｃｕｌａｔｉｏｎｒｅｓｕｌｔａｃｃｏｒｄｓｗｉｔｈｔｒａｄｉｔｉｏｎａｌａｎａｌｙｓｉｓｒｅｓｕｌｔａｎｄＴｈｅｍａｉｎｃｏｎｔｅｎｔｓｏｆｔｈｅｐａｐｅｒａｒｅａｓｆｏｌｌｏｗｉｎｇ：ｔｈｅｃａｌｃｕｌａｔｉｏｎｉｎｗｅｌｄｉｎｇｐｒｏｃｅｓｓｉｓａｍａｔｅｒｉａｌｎｏｎｌｉｎｅａｒｐｒｏｃｅｄｕｒｅｔｈａｔｔｈｅｍａｔｅｒｉａｌｐｒｏｐｅｒｔｉｅｓｃｈａｎｇｅｔｈｅｆｕｎｃｔｉｏｎｏｆＧａｕｓｓａｓｗｉｔｈｔｈｅｔｅｍｐｅｒａｔｕｒｅ；ｃｈｏｏｓｅｈｅａｔｓｏｕｒｃｅｍｏｄｅｌ．ｕｓｅｔｈｅｆｕｎｃｔｉｏｎｃｏｍｍａｎｄｔｏａｐｐｌｙｌｏａｄｏｆｍｏｖｉｎｇｈｅａｔＳ０１２Ｉｅ－２．ＡｍａｔｈｅｍａｔｉｃｍｏｄｅｌｏｆｔｒａｎｓｉｅｎｔｔｈｅｒｍａｌｐｒｏｃｅｓｓｉｎｗｅｌｄｉｎｇｉｓｅｓｔａｂｌｉｓｈｅｄｔｏｓｉｍｕｌａｔｅｔｈｅｍｏｖｉｎｇｏｆｔｈｅｈｅａｔｓｏＢｒｃｅ．Ｔｈｅｅｆｆｅｃｔｓｏｆｍｅｓｈｓｉｚｅ，ｗｅｌｄｉｎｇｓｐｅｅｄ，ｗｅｌｄｉｎｇｃｕｒｒｅｎｔａｎｄｅｆｆｅｃｔｉｖｅｒａｄｉｕｓｅｌｅｃｔｒｉｃａｒｃｏｎｔｅｍｐｅｒａｔｕｒｅｆｉｅｌｄａ比ｄｉｓｃｕｓｓｅｄ．Ｔｈｅｐｒｏｂｌｅｍｏｆｔｈｅｆｕｓｉｏｎａｎｄｓｏｌｉｄｉｆｉｃａｔｉｏｎｏｆｍａｔｅｒｉａｌｈａｓｂｅｅｎｓｏｌｖｅｄｂｙｔｈｅｍｅｔｈｏｄｏｆｃｈａｎｇｉｎｇｔｈｅｅｌｅｍｅｎｔｍａｔｅｒｉａｌ．Ｔｈｅｐｒｏｂｌｅｍｏｆｔｈｅｃｏｎｖｅｒｇｅｎｃｅｄｉｆｆｉｃｕｌｔｙｏｒｔｈｅｕｎ—ｃｏｎｖｅｒｇｅｎｃｅｄｕｒｉｎｇｔｈｅｃａｌｃｕｌａｔｉｎｇｏｆｔｈｅｔｈｅｒｍａｌｓｌＴｅｓｓｉｓｓｏｌｖｅｄ；ｔｈｒｏｕｇｈｒｅａｌ－ｔｉｍｅｄｙｎａｍｉｃｓｉｍｕｌａｔｉｏｎｏｆｔｈｅｓｔｒｅｓｓｐｒｏｄｕｃｅｄｉｎｗｅｌｄｉｎｇｐｒｏｃｅｓｓ，ｔｈｅｔｈｅｒｍａｌｓｔｒｅｓｓａｎｄｒｅｓｉｄｕａｌＳｌｌ℃ＳＳｉｎｗｅｌｄｉｎｇｃａｎｂｅｐｒｅｄｉｃｔｅｄｂｙｕｓｉｎｇｔｈｅｓｉｍｕｌａｔｉｖｅａｎａｌｙｓｉｓｍｅｔｈｏｄｉｎｔｈｉｓｐａｐｅｒ．Ｉｎｔｈｉｓｐａｐｅｒ，ａｆｅａｓｉｂｌｅｓｌＩｅｓｓｄｙｎ黜ｆｉｅｓｉｍｕｌａｔｉｏｎｍｅｔｈｏｄｏｎ３Ｄｗｅｌｄｉｎｇｔｅｍｐｅｒａｔｕｒｅｆｉｅｌｄ，ｏｎｆｉｅｌｄｈａｄｂｅｅｎｅｓｔａｂｌｉｓｈｅｄ，ｗｈｉｃｈｐｒｏｖｉｄｅｓｔｈｅｏｒｙｆｏｕｎｄａｔｉｏｎａｎｄｉｎｓｔｒｕｃｔｉｏｎｏｐｔｉｍｉｚｉｎｇｔｈｅｗｅｌｄｉｎｇｔｅｃｈｎｏｌｏｇｙａｎｄｐａｒａｍｅｔｅｒｓ．ＫＥＹＷＯＲＤ：Ｗｅｌｄｉｎｇ，ＮｕｍｅｒｉｃａｌＳｉｍｕｌａｔｉｏｎ，Ｆｉｎｉｔｅｅｌｅｍｅｎｔ，Ｔｅｍｐｅｒａｔｕｒｅｆｉｅｌｄ，Ｓｔｒｅｓｓｆｉｅｌｄ．２．独创性说明本人郑重声明：所呈交的论文是我个人在导师指导下进行的研究工作及取得的研究成果。

第一章习题答案一、解释下列名词1、弹性比功：又称为弹性比能、应变比能，表示金属材料吸收弹性变形功的能力。

2、滞弹性：在弹性范围内快速加载或卸载后，随时间延长产生附加弹性应变的现象。

3、循环韧性：金属材料在交变载荷下吸收不可逆变形功的能力，称为金属的循环韧性。

4、包申格效应：先加载致少量塑变，卸载，然后在再次加载时，出现σe升高或降低的现象。

5、解理刻面：大致以晶粒大小为单位的解理面称为解理刻面。

6、塑性、脆性和韧性：塑性是指材料在断裂前发生不可逆永久（塑性）变形的能力。

韧性：指材料断裂前吸收塑性变形功和断裂功的能力，或指材料抵抗裂纹扩展的能力7、解理台阶：高度不同的相互平行的解理平面之间出现的台阶叫解理台阶；8、河流花样：当一些小的台阶汇聚为在的台阶时，其表现为河流状花样。

9、解理面：晶体在外力作用下严格沿着一定晶体学平面破裂，这些平面称为解理面。

10、穿晶断裂和沿晶断裂：沿晶断裂：裂纹沿晶界扩展，一定是脆断，且较为严重，为最低级。

穿晶断裂裂纹穿过晶内，可以是韧性断裂，也可能是脆性断裂。

11、韧脆转变：指金属材料的脆性和韧性是金属材料在不同条件下表现的力学行为或力学状态，在一定条件下，它们是可以互相转化的，这样的转化称为韧脆转变。

二、说明下列力学指标的意义１、Ｅ（Ｇ）：Ｅ（Ｇ）分别为拉伸杨氏模量和切变模量，统称为弹性模量，表示产生100%弹性变形所需的应力。

２、σr、σ0.2、σs: σr :表示规定残余伸长应力，试样卸除拉伸力后，其标距部分的残余伸长达到规定的原始标距百分比时的应力。

σ0.2：表示规定残余伸长率为0.2%时的应力。

σs：表征材料的屈服点。

３、σb：韧性金属试样在拉断过程中最大试验力所对应的应力称为抗拉强度。

４、n:应变硬化指数，它反映了金属材料抵抗继续塑性变形的能力，是表征金属材料应变硬化行为的性能指标。

５、δ、δgt、ψ：δ是断后伸长率，它表征试样拉断后标距的伸长与原始标距的百分比。

第 4 期第 138-145 页材料工程Vol.52Apr. 2024Journal of Materials EngineeringNo.4pp.138-145第 52 卷2024 年 4 月镁合金表面不同MOF 超疏水涂层的耐蚀行为Corrosion resistance behavior of different MOF superhydrophobic coatings on magnesium alloy surface刘金玉，张志远，王东，蒋世权，温玉清，尚伟*（桂林理工大学 化学与生物工程学院 广西电磁化学功能物质重点实验室，广西 桂林 541004）LIU Jinyu ，ZHANG Zhiyuan ，WANG Dong ，JIANG Shiquan ，WEN Yuqing ，SHANG Wei *（Guangxi Key Laboratory of Electrochemical and Magnetochemical Function Materials ，School of Chemical and Biological Engineering ，Guilin University of Technology ，Guilin 541004，Guangxi ，China ）摘要：对AZ91D 镁合金表面三种不同超疏水涂层（MZS -1，MZS -2和ZnO@ZIF -8）在5%（质量分数）NaCl 溶液中的耐蚀性能进行研究。

采用场发射扫描电子显微镜、静态接触角测试仪、电化学工作站和盐水喷雾试验机分别对超疏水复合涂层进行微观形貌、润湿性、耐蚀性能等进行测试与表征。

结果表明：经过盐雾处理后，三种超疏水涂层均在192 h 后出现腐蚀，其中MZS -1超疏水涂层的腐蚀最为严重，MZS -2超疏水涂层240 h 后表面出现点蚀，同时经过盐雾处理后仍能维持较高的接触角，故MZS -2复合涂层耐蚀性能最好。

I.J. Engineering and Manufacturing, 2019, 6, 53-64Published Online November 2019 in MECS ()DOI: 10.5815/ijem.2019.06.05Available online at /ijemThermodyamic and Kietic Study on the Corrosion of Aluminium in Hydrochloric Acid using Benzaldehyde as Corrosion Inhibitor*Musa Husaini, Muhammad Bashir Ibrahima Department of Pure and Industrial Chemistry ,Faculty of Physical Sciences, Bayero University, P.M.B. 3011BUK, Kano. NigeriaReceived: 07 September 2019; Accepted: 15 October 2019; Published: 08 November 2019AbstractThe inhibition of the corrosion of aluminium by benzaldehyde in 1.4 M HCl was investigated using weight loss method and characterized by FT-IR analysis. The results showed that the corrosion rate of aluminium in 1.4 M HCl decreases with increase in concentration of the inhibitor. The inhibition efficiency increases progressively as the concentration of the inhibitor increases. Effects of temperature on the inhibition efficiency of the inhibitor showed that inhibition efficiency decreases with increase in temperature. The value of activation energy (Ea) was found to be 20.55 Kjmol-1 for aluminium corrosion in 1.4 M HCl which was increased to 34.49 Kjmol-1 in the presence of 0.1 M inhibitor concentration. The calculated values for enthalpy of activation (ΔHa) were all positive indicating the endothermic nature of the aluminium dissolution process. The obtained values of Gibbs free energy (ΔGads) was in the range of -17.94 to -18.27 kJ mol-1. Kinetics of the reaction in the presence of the inhibitor revealed that it follows a first order reaction. The value of rate constant (k) was reduced from uninhibited acid to the inhibited acid solution, while the half-life values in the presence of the inhibitor were higher compared to the value in uninhibited acid solution suggesting that inhibition efficiency increases with increase in the concentration of the inhibitor.Index Terms: Aluminum, benzaldehyde, FT-IR analysis, kinetic parameters, thermodynamic parameters and weight loss.© 2019 Published by MECS Publisher. Selection and/or peer review under responsibility of the Research Association of Mode rn Education and Computer Science* Corresponding author.E-mail address: musahusaini36@54 Thermodyamic and Kietic Study on The Corrosion of Aluminium in Hydrochloric Acid UsingBenzaldehyde as Corrosion Inhibitor1.IntroductionAluminium is the most widely used non-ferrous metal in all the fields of domestic and industrial applications like construction, transportation, packaging, a wide range of household items, electrical transmission and outer shell of consumer electronics etc. Aluminium is remarkable for its low density and ability to resist corrosion due to the passivation phenomenon [1]. The protective coating of aluminium destroyed when exposed to acid or alkaline environment and corrosion of aluminium occurs, yielding Al+3 ion in acid solution and AlO2 in the alkaline solution [2]. Acid pickling is usually used for aluminium surface treatment. Aluminium can react with hydrochloric acid to produce hydrogen gas. The chloride ions of the HCl cause a substantial loss of the metal by corrosion and Cl- ions of the acid create extensive localized attack over the surface of aluminium. Hence to avoid such kind of attack on the base metal during pickling and cleaning aluminium surfaces with acidic solutions, the use of inhibitors become necessary. The use of inhibitors is among the most practical methods for protection against corrosion in acidic media. Various organic compounds are reported as good corrosion inhibitors for aluminium in hydrochloric acid media [3, 4].A great number of research have being devoted to the subject of corrosion inhibitors in both the laboratory and fields. Corrosion inhibition is of great practical importance, as it’s extensively employed in shortening wastage of engineering materials and reducing corrosion control costs. Inhibitor applications is quite varied usually playing an important role to minimize localized corrosions and unexpected sudden failures in water treatment facility, oil extraction and processing industries, ferrous metal cleaners, heavy industrial manufacturing, water treatment chemicals, water-containing hydraulic fluids, automatic transmission fluids, automotive component manufacture, cutting fluids, engine coolants etc. Most of the well-known acid inhibitors are organic compounds containing nitrogen, oxygen, phosphorus, sulfur and π bonds, as well as aromatic rings in their structure which are the major adsorption centers [5]. Generally, a strong interaction causes higher inhibition efficiency, the inhibition effect increases in the sequence O < N < S [6, 7]. Compounds with π-bonds also exhibit good inhibitive properties due to interaction of π orbital with metal surface. The objectives of the present research is to study the kinetic parameters, thermodynamic parameters, adsorption isotherm and the inhibition effect of benzaldehyde as inhibitor on the corrosion of aluminium in hydrochloric acid at different inhibitor concentration and temperature. The weight loss method was used in this study as its quantitative and possibly most accurate method in monitoring and measuring corrosion of metallic structures.1.1 Significance of the ResearchThe investigation of the corrosion inhibition of benzaldehyde on aluminium provided a useful information on surface coverage, inhibition efficiency, thermodynamic and kinetic data, and the type of adsorption of benzaldehyde inhibitor on the surface of aluminium. The use of benzaldehyde inhibitor will reduce the rates of usage of inorganic inhibitors which are toxic to environment. This submission is in advancement of contribution toward the sustained world-wide in looking for friendly, non-toxic and commercially available corrosion inhibitors.1.2 Literature ReviewSeveral report have been made to the organic compounds that contain nitrogen, sulfur and nitrogen as polar groups and conjugated double bonds in their structures to be good corrosion inhibitors for many metals and alloys in corrosive environment [8]. The inhibiting effect of these organic compounds is usually attributedto their interactions with the metallic surfaces through their adsorption. Polar functional groups serves as the reaction center that stabilitizes the adsorption process. Nevertheless the adsorption of an inhibitor on a metal surface depends on certain factors which include; the inhibitor’s chemical structure, nature and surface charge of the metal, the type of the electrolyte solution and the adsorption mode [9].The Inhibition of Aluminum corrosion in 3.5% NaCl solution using diisopropyl thiourea (DISOTU) has been reported by Karthikeyan et al [10] using weight loss, electrochemical polarization technique, impedance method and quantum mechanical measurement. It was found that the aluminium corrosion in the sea water medium was minimize effectively by the compound. Adsorption of the compound on metal was noticed to follow Langmuir adsorption isotherm. The inhibition efficiency (IE) increases with increase in inhibitor concentration. The adsorption of protective layer of inhibitor on aluminium surface was confirmed by using Quantum mechanical studies.The effect of formazan of benzaldehyde (FB) on the corrosion of mild steel in acidic media (1.0 M HCl and 2 M HCl) has been investigated by Anand [11] using weight loss measurements, electrochemical studies and surface analysis. These studies have also shown that formazan of benzaldehyde is a good inhibitor for mild steel in 1.0 M HCl and 2 M HCl acid solutions at room temperature in 2h. In 1.0 M HCl the inhibition efficiency was high when compared to 2 M HCl acid solutions. The surface analysis also confirms the corrosion inhibition of the mild steel by the inhibitor (FB).Aluminium and its alloys are vitally preferred materials of construction in many chemical and engineering fields due to their light weight corrosion resistant properties. Nitrogen-containing organic compounds, like amines and diamine derivatives offer good protection of metallic materials on the corrosion for many metals in acidic solutions. Arvnabh et al [12] analyzed the corrosion inhibition of aluminium alloys of grade 1060, 1100 and 3003 in trichloroacetic by using conductivity and potentiostatic polarization in different inhibitors of diamine such as ethyl amino ethylamine, di-methyl amino ethylamine, 1:3 di-amino propane, tetra methyl ethylene diamine. Diamines are act as mixed inhibitors as revealed by polarization curves in the case of alloy of 3003 grade.In the recent investigation effect of Triethylenetetramine [TETA] and 2-(2-aminoethylamino) ethanol [AEAE] as corrosion inhibitors for N80 steel in 15% HCl solution was studied by Yadav et al [13] using polarization, AC impedance (EIS) and weight loss measurements. Both inhibitors were found to be effective inhibitors. Inhibition efficiency was found to increase significantly with increasing inhibitor concentration. Mixed-type inhibitors were revealed from polarization studies. Charge transfer resistance increases and double layer capacitance decreases in presence of inhibitors as revealed by AC impedance studies. Inhibitors adsorption on the surface of N80 steel follows Langmuir adsorption isotherm.2.Material and Methods2.1 Specimen PreparationRectangular specimen of aluminium (99.5 %) obtained from Metal Focus Fabrication Technology Incubation Centre Kano State, Nigeria was used in this study [14]. The specimen of size 3 x 2 x 0.1 cm with a small hole near the upper edge was used for the determination of corrosion rate. The specimen was polished using different grade of emery paper, degreased in absolute ethanol, dried in acetone and stored in a moisture-free desiccators prior to use.2.2 Preparation of SolutionsDouble distilled water was used to prepare a stock solution of analytical grade hydrochloric acid (36.5%, 1.18g/ cm3). The required concentration of the acid solution was prepared by appropriate dilutions. The used inhibitor was benzaldehyde (95% 1.04 g/cm3), and concentrations of the inhibitor used for the study was 0.02, 0.04, 0.06, 0.08 and 0.1 M. Each of these concentrations was diluted in the prepared desired concentrations of acids for use as test solutions in weight loss.2.3 Weight loss MeasurementThe prepared weighted specimens were immersed in 100 ml beaker containing the acid solution in the absence and presence of various concentrations of the inhibitor (0.02, 0.04, 0.06, 0.08 & 0.1 M) at 308 K and 3hrs immersion time, after which they were retrieved, washed, dried, re-weighted and recorded. The experiment were performed in replicate. The effect of temperature was studied at a temperature range of 308, 313 and 318 K. The weight loss of aluminium was calculated in grams as the difference between the initial weight and the weight after the removal of the corrosion product. The weight loss (Δw) corrosion rate (C.R), inhibition efficiency (I.E) and degree of surface coverage (Ө) were calculated using the Equations 1, 2, 3 and 4 respectively.Δw = (1)C.R = (2)Ө = (3)I.E = × 100 (4)Where wi and wf are the initial and final weight of Aluminium samples, w1 and w0 are the weight loss values in presence and absence of inhibitor, respectively. A is the total area of the aluminium specimen and t is the immersion time.2.4 Fourier Transform Infrared Spectroscopic AnalysisFT-IR analysis was carried out for the fresh inhibitor and that of the corrosion product obtained from the reaction of aluminium immersed in 1.4 M HCl solution for 3 hrs immersion time in the presence of 0.1 M benzaldehyde at 308 K using Agilent Technology, FTIR (Cary 630) Fourier Transform Infrared Spectrophotometer. 650 – 4000 cm-1 wave number was used to scan the sample during the analysis.3.Results and DiscussionThe data of all figures presented in this section are obtained from the result presented in Table 1.3.1 Effect of inhibitor on corrosion rate and inhibition efficiencyFigure 1 shows the plot of corrosion rate against inhibitor concentration for aluminium corrosion in 1.4 M HCl at different temperatures. The figure reveals that the rate of corrosion of aluminium in 1.4 M hydrochloric acid decreases with increase in inhibitor concentration at all the temperatures studied. The values of the corrosion rate of inhibited system was found to be lower compared to the uninhibited system due to the inhibitive effect of the inhibitor. Increase in inhibitor concentration causes the increase in the rate at which the inhibitor molecules adsorbed on the surface of the aluminium thereby forming a barrier for charge and mass transfer which results into a decrease in the interaction between the metal surface and the corrosive media and also, reduces the rate of corrosion.Table 1. Variation of Corrosion Parameters for Corrosion of Aluminium in 1.4 M HCl in the Absence and Presence of Different Concentrations of Inhibitor. InhibitorConc. (M) Corrosion rate (mgcm -2h -1) 308 K 313 K 318 K Surface Coverage (Ө) 308 K 313 K 318 K Inhibition efficiency (%) 308 K 313 K 318 K Blank0.020.040.060.080.10 19.527 21.290 25.138 13.366 16.566 19.761 12.450 15.483 18.577 11.888 14.633 17.916 11.266 13.483 17.072 10.733 12.527 16.405 - - - 0.3155 0.2451 0.2131 0.3624 0.2945 0.2602 0.3911 0.3332 0.2866 0.4230 0.3855 0.3202 0.4503 0.4292 0.3468 - - - 31.55 24.51 21.31 36.24 29.45 26.02 39.11 33.32 28.66 42.30 38.55 32.02 45.03 42.92 34.68Fig.1. Variation of Corrosion Rate with Inhibitor Concentration for Al Corrosion in 1.4 M HClFig.1 shows the variation of inhibition efficiency against the different concentration of the inhibitor at 308, 313 and 318 K. The figure reveal that the inhibition efficiency increases with increase in the concentration of the inhibitor. This is due to the formation of more protective barrier film of the inhibitor molecules on the metal surface, which further supporting the inhibitive action of the inhibitor against the corrosion of the metal. Similar result was reported by Karthikaiselvi and Subhashini [15].3.2 Effect of Temperature on Corrosion Rate and Inhibition EfficiencyThe corrosion rates of aluminium in the absence and presence of various concentrations of the inhibitor at different temperatures was shown in Fig.3. The result obtained showed that the rate of corrosion of aluminium58 Thermodyamic and Kietic Study on The Corrosion of Aluminium in Hydrochloric Acid UsingBenzaldehyde as Corrosion Inhibitorincreased with increase in temperature. This phenomenon is due to the fact that chemical reaction rates normally increases when the temperature increase. Increase in temperature leads to increase in the average kinetic energy possessed by the reacting molecules thereby making the molecules to overcome the energy barrier and react faster [16].Fig.2. Variation of Inhibition Efficiency with Inhibitor Concentration for Al Corrosion in 1.4M HClFig.3. Variation of Corrosion Rate with Temperature for Al Corrosion in 1.4 M HClVariation of inhibition efficiency with temperature at different concentration of the inhibitors is shown in Figure 4. The result obtained showed that the inhibition efficiency decreases with increase in temperature, this is due to the desorption of adsorbed inhibitor molecules from aluminium surface. The significant difference between values of inhibition efficiency of the given inhibitor obtained at the studied temperature suggested that the mechanism of adsorption of inhibitor on aluminum surface is consistent with physical adsorption mechanism. For a physical adsorption mechanism, inhibition efficiency of the inhibitor increases with decrease in temperature which mean physical adsorption mechanism occurred on the aluminium surface. Similar result was reported by reported by Eddy et al [17] and Abdallah [18].3.3Adsorption behaviourTo understand the mechanism of corrosion inhibition process, the adsorption behaviour of the adsorbate on the aluminium surface must be known. The information on the interaction between the metal surface andBenzaldehyde as Corrosion Inhibitorthe inhibitor molecules can be provided by adsorption isotherm. The degree of surface coverage (Ө) for different concentrations of inhibitor was evaluated from weight loss measurements. The data was applied to various isotherms. Attempts were made to fit the experimental data into different isotherms. The result indicates that Langmuir adsorption isotherm model best described the adsorption characteristics of the inhibitor on the aluminium surface. Langmuir adsorption isotherm is the ideal adsorption isotherm for physical and chemical adsorption on a smooth surface, and it is valid for monolayer adsorption onto a surface containing a finite number of identical sites. According to this isotherm, the surface coverage (Ө) is related to the inhibitor concentration Cinh by the equation given below;Fig.4. Variation of Inhibition Efficiency with Temperature for Al Corrosion in 1.4 M HClinh C 1= C inhads K θ+ (5)Where K ads is the adsorption equilibrium constant, C inh is the inhibitor concentration in the solution, and Ө is the surface coverage. The plot of C inh /Ө against C inh gave a straight line with slope equal to unity and R 2 close to 1 indicating that the adsorption of the inhibitor on the surface of aluminium is consistent with Langmuir adsorption isotherm. The correlation coefficient (R 2) and adsorption equilibrium constant (K ads ) are presented in Table 3.3.4 Kinetic Study3.4.1 Rate Constant (k) and Half Life (t 1/2)Kinetic analysis of the data is considered necessary since corrosion reaction is a heterogeneous process that composed of anodic and cathodic reactions with the same or different rate. In this current study, the initial weight of aluminum specimen at given time, t is designated as W i , the weight loss is W L and the weight change at time t is (W i - W L ), while k 1 is the first order rate constant.ln (Wi - W L ) = -k 1t + lnW L (6) The plots of ln (Wi - W L ) against time (hr) at 308 K showed a linear variation which confirms a first order reaction kinetics with respect to the corrosion of aluminium in 1.4 M HCl solutions in the presence of the inhibitor. The first order reaction rate constants (k 1) calculated from the slope of the plot are presented in Table 2. The result shows that the values of rate constant (k 1) for the corrosion of aluminium was found to be higher in the case of uninhibited acid solution than inhibited acid solution. This confirmed the inhibition ofBenzaldehyde as Corrosion Inhibitoraluminium corrosion in acids solution by the presence of inhibitors.The half-life (t1/2) was calculated from equation 7t1/2 = 0.693 / k(7) From Table 2, the values of the half-lives (t1/2) increased from uninhibited solution to inhibited solution. The increase in half-lives (t1/2) in the presence of the inhibitor compared to the uninhibited solution support the earlier results that corrosion rate decreases in the presence of the inhibitor compared to the uninhibited solution. It can also be seen that as the concentration of the inhibitor increases,the half-life also increases which results into a decrease in the corrosion rate suggesting that more protection of the aluminium by the inhibitor has been established.3.4.2 Activation Energy (Ea)The rate of most chemical reactions increases with temperature following Arrhenius equation [17]. In the case of the electrochemical reactions, temperature favors the kinetics of corrosion reactions and more specifically, the anodic dissolution of the metal. The activation energy of the corrosion process was calculated using the Arrhenius law equationln(C.R) =EB alnRT(8)Where B is a constant which depends on the metal type, R is the universal gas constant, and T is the absolute temperature. The plot of ln (C.R) Vs reciprocal of absolute temperature (1/T) gave a straight line with slope = −Ea/R, from which the activation energy values for the corrosion process was calculated. The calculated activation energy values were tabulated in Table 2. The activation energy value in uninhibited hydrochloric acid solution is low com¬pared to inhibited hydrochloric acid solution. The higher activa¬tion energy values in the presence of inhibitor molecules strongly support the results of corrosion rate studies and confirms the physisorption mechanism (inhibition efficiency decreases with an increase in solution temperature).Table 2. Kinetic Parameters for Aluminium Corrosion with and without various inhibitor concentrationsInhibitor Concentration(M) Activation Energy(kj mol-1)Rate Const. (k ×10-3) (hour-1) Half-life (hours)Blank 20.55 144.39 4.790.02 31.84 91.75 7.550.04 32.60 84.59 8.190.06 33.39 80.28 8.630.08 33.81 75.56 9.170.10 34.49 71.57 9.683.5 Thermodynamic StudyThe Thermodynamic parameters like enthalpy of activation (ΔHa) and entropy of activation (ΔSa) were calculated using the transition state equation. The linear form of transition state equation is given by the equation belowBenzaldehyde as Corrosion Inhibitora a RS H C R T Nh ln R RT ln ∆∆⎛⎫⎛⎫⎛⎫⎛⎫- ⎪ ⎪ ⎪ ⎪⎝⎭⎝⎭⎝⎭⎝=⎭+ (9)Where h is Plank’s constant and N is Avagadro’s number. A plot of ln (C.R /T) vs 1/T gave a straight line with slope = −ΔHa/T and intercept = ln(R/Nh) +ΔSa /R. The calculated values of enthalpy of activation (ΔHa) and entropy of activation (ΔSa) are tabulated in Table 3. The positive signs of the enthalpies reflect the endothermic nature of the aluminium dissolution process. Large negative values of entropies show that the activated complex in the rate determining step is an association rather than dissociation step meaning that a decrease in disordering takes place on going from reactants to the activated complex.Table 3. Enthalpy and Entropy change of the reaction process with various concentrations of the inhibitorInhibitor Concentration(M)ΔH (kJ mol -1) - ΔS (kJ mol -1k -1) blank17.95 219.63 0.0229.24 186.05 0.0430.00 184.19 0.0630.79 182.04 0.0831.21 181.21 0.10 31.89 179.483.5.1 Free Energy of Adsorption (ΔGads,)The free energy of adsorption (ΔGads) is related to adsorption equilibrium constant (Kads) by the equation given belowΔG ads = - RT ln (55.5 K ads ) (10) The negative values of free energy of adsorption (Gads) presented in Table 4 suggests that the inhibitor molecules are strongly adsorbed on the metal surface, the values also shows a spontaneous adsorption of the inhibitor molecules mainly characterized by the strong interactions with the metal surface. The values of ΔGads around -20 kJmol-1 are consistent with electrostatic interaction between charged molecules and a charged metal indicating physical adsorption (physisorption) mechanism, while those around -40 kJmol-1 involve charge sharing or transfer of electrons to form a co-ordinate type of bond otherwise known as chemical adsorption (chemisorption) mechanism. In the present study, the values of ΔGads are less than -20 kJ mol-1 which indicate that the adsorption of the inhibitor on the aluminium surface confirms a physical adsorption mechanism. Similar result was reported by Vimala et al [19].Table 4. Adsorption Parameters Deduced from Langmuir Adsorption Isotherm for Corrosion Inhibition of Aluminium.Temperature (K)R 2 K ads ΔG (kJ mol -1) 308313318 0.9943 0.9918 0.9986 19.90 18.69 18.08 -17.94 -18.07 -18.273.6 Infrared Spectroscopy Analysis ResultsBenzaldehyde as Corrosion InhibitorThe FTIR spectra of the inhibitor (benzaldehyde) and that of the corrosion product are presented in Figures 5 and 6. The analysis of the inhibitor presented in Figure 5 revealed the presence of carbonyl group C=O stretch, aromatic C-H stretch and aldehyde C-H stretch. The analysis of the corrosion product presented in Figure 6 shows the appearance of carbonyl group C=O stretch, aromatic C-H stretch and aldehyde C-H stretch and this confirmed that the adsorption of the inhibitor on the metal surface took place.Fig.5. FT-IR Spectra of BenzaldehydeFig.6. FT-IR Spectra of Aluminium in 1.4 M HCl with 0.1 M Benzaldehyde4.ConclusionFrom the result of this study it can be concluded that benzaldehyde served as good inhibitor in reducing the rate of hydrochloric acid attack on the surface of aluminium, by electrostatic interaction between the charged inhibitor molecules and the charged surface of aluminium. This make the adsorption process occurred through physical adsorption mechanism (physisorption). The calculated values of Gibbs free energy of adsorption, enthalpy and activation energy also support the physisorption mechanism of the process. The presence ofBenzaldehyde as Corrosion Inhibitorfunctional group of the inhibitor molecule in the FT-IR of the corrosion product confirmed that the adsorption of the inhibitor on the metal surface took place. The adsorption of different concentrations of the inhibitor on the surface of the aluminium in hydrochloric acid followed Langmuir adsorption isotherm.This work is only limited to the thermodyamic and kietic study on the corrosion of aluminium in hydrochloric acid using benzaldehyde as corrosion inhibitor using only weight loss method. It’s recommended that the feature work on the corrosion inhibition effect of benzaldehyde to include other methods of corrosion inhibition analysis such as gravimetric, thermometric, electrochemical impedance spectroscopy e.t.c. References[1] Abdel-Gaber, A. M., Abd-El-Nabey, B. A., Sidahmed, I. M. El-Zayady, A. M. and Saadawy, M. (2006). Kinetics and Thermodynamics of Aluminium Dissolution in 1.0 M Sulphuric Acid Containing Chloride Ions. Mater., Chem. Phys., 98: 291-297.[2] Stansbury, E. E. and Buchanan, R. A. (2000). Fundamentals of Electrochemical Corrosion, ASM International Materials Park, USA.[3] Li, X., Deng, S. and Fu, H. (2011). 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