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Effect of Cu2+ Doped In Sol on Properties of Sealed Film on Anodized Al Alloy

Effect of Cu2+ Doped In Sol on Properties of Sealed Film on Anodized Al Alloy
Effect of Cu2+ Doped In Sol on Properties of Sealed Film on Anodized Al Alloy

Effect of Cu2+ Doped In Sol on Properties of Sealed Film on Anodized Al

Alloy

Q. Zhou 1, a, X. Wang1, b, L.F. Zhang1, c, X. Ma 2, d, H.B. Li1, C.L. He3

and P. Zhao1

1School of Environment and Chemical Engineering, Shenyang Ligong University , Nanping Middle

Road No.6, Shenyang 110168, PR China

2College of Environmental Science and Engineering, Beijing Forestry University, Tsinghua East

Road No.35, Beijing 100083, PR China

3Research Institute of Surface Engineering, Shenyang University, WangHua South Street No.21,

Shenyang 110044, PR China

a zhouqi2469@https://www.wendangku.net/doc/364590286.html,,

b wangxin558558@https://www.wendangku.net/doc/364590286.html,,

c flz1997@https://www.wendangku.net/doc/364590286.html,,

d maxin19860123@https://www.wendangku.net/doc/364590286.html,,

Keywords: antibacterial; anodize; seal; sol; Cu2+

Abstract. The corrosion resistance of anodic oxide film sealed with alumina sol can improved. Cu2+ was put into the alumina sol so that antibacterial property was endowed to the sealed film. Composition, morphology and corrosion resistance of sealed film doped with Cu2+ were studied by DSC, EIS and SEM etc. The film sealed by doping Cu2+ in sol has less and narrower crack on the surface than the one without Cu2+. The gel without Cu2+ has more chemical reaction and phase transition than that with Cu2+ in the heating process observing from the DSC curve, which results in more cracks on the surface of sealed films without Cu2+. Sol doped with Cu2+ can enhance corrosion resistance inferred from the polarization curve, in a way. The films sealed by sol with Cu2+ have a good antibacterial on Staphylococcus aureus. The antibacterial rate is more than 99%. The results show sol doped Cu2+ not only improve corrosion resistance but also have antibacterial property.

Introduction

A new method has been studied on modified material surface by sol-gel method recently. A series of compact and inert film on the surface of metal matrix can be prepared by sol gel method. Many properties of metal matrix can be enhanced [1]. Such as, yttrium-doped zinc oxide film can be deposited on material surface by sol-gel method, which could improve greatly conduction property [2].The SiO2–P2O5 films have extraordinary optical property by the same method [3].

Yu-Chu Kuo’s [4] research find that high hardness and antibacterial property are provided with Cr–Cu–N nanometer coats.

Pitting potential declines as the Cu content in stainless steel increases. Adding a proper amount of Cu (such as 2 wt.%) gives stainless steel an excellent antibacterial property[5]. Gabrielík [6] etc study the antibacterial property of Cu2+ complexes on the fungus and microbe, they found antibacterial effects are attributed to slow release of Cu2+.

In order to reduce the harmful effects that the bacteria adhered to the surface of the sample will do to people,different ways of making antibacterial coatings are researched.So the coatings will have both corrosion resistance and antibacterial properties by adding Cu2+ to the aluminum oxide sol. The aluminum alloy with this coat has promising applications in medical instruments and food processing equipments.

Experiment

Alumal is used for experimental material. SETARAM DSC131 is used for differential scanning

sealed level of anodized Al substrate were checked by staining solution; Electrochemical Impedance Spectroscopy and Polarization curve were tested with Electrochemical Workstation (PARSTAT 2273). The sealed films were dipped in the 3.5%NaCl solution for two hours before measuring Polarization curve. The surface morphologies photos were taken with scanning electron microscope (JXA-840).Antibacterial test was performed with cultivating Staphylococcus aureus for 24 hours at 37℃.The test adopts tectorial membrane method which refers to Japan JISZ2801-2000 and Chinese light industry QB/T2591-2003 criterion.

Results and Discussion

Corrosion Resistance. Fig.1 shows polarization curves of Cu 2+-doped sol sealed substrate and sol without Cu 2+ sealed substrate. From Fig.1: maintaining passivity current of sol with Cu 2+

-doped sealed anodic oxide film and sol without Cu 2+

-doped sealed anodic oxide film are 1.03×10-3A and 4.62×10-3A. It illustrates that the corrosion resistance of sol with Cu 2+-doped sealed anodic oxide film is better than the latter in netrual NaCl solution. From Fig.1, anodic current density of sol with Cu 2+-doped sealed film is less than the latter. So the impediment of Cu 2+-doped sol sealed film to the anodic process is greater than sol without Cu 2+-doped. And also the prevenient cathodic current density is less than the other. Cu 2+-doped sol sealed film reduce the corrosion mainly by hindering cathodic oxygen diffusion and restraining dissolvement of anodic aluminum.

Acid drip test results: Cu 2+

-doped sol sealed anodic oxide film changed color 101min later, sol without Cu 2+-doped sealed anodic oxide film changed color 34 min later. The acid corrosion resistance of Cu 2+-doped sol sealed anodic oxide film is better than the latter.

Fig.1 Polarization curves of sealed film by sol

Analysis of SEM and EDS. From Fig.2(c,d) shows: in compared with boiling water seal, there are no three-dimensional fishing net micropores on the surface of sol sealed films.There are various small cracks and micropores on the surface. But the rest of the surface is compact and smooth.

Fig.2(a,b)demonstrates that the micropores of Cu 2+-doped sol sealed film are smoother in compared with sol without Cu 2+, the surface of sol without Cu 2+ sealed film has many cracks. The surface craquelure of sol without Cu 2+ sealed film is more obvious than the latter. The craquelure density of the surface of Cu 2+-doped sol sealed film is less than that of none Cu 2+

-doped sol seal. The width of the biggest crack of Cu 2+-doped sol sealed film reached 0.5μm while the latter was 0.7μm. Fig.3 shows: Cu 2+-doped sol sealed anodic oxide film is mainly made up of aluminum, oxygen and

copper.

P

o

t

e n t

i a

l

(

V

)Current (A)

Fig.2 Surface morphologies of film sealed by (a, c) sol with Cu2+; (b) sol without Cu2+; (d) boiling

water

Fig.3 EDS of Cu2+-doped sol sealed film

Differential Scanning Calorimeter Analysis. Fig.4 (a) analysis is as follows: At 40℃, physical adhesive water in the surface of boehmite volatilized which caused decalescence.

(AlOOH)2·(m +n)H2O→nH2O+ (AlOOH)2·mH2O (1) At 80℃ and 127℃ , the following reactions were taken place:

NH4NO3 →NH3+HNO3 (endothermic reaction). (2) 4HNO3 →4NO2+2H2O+O2. (3) In the heating process of gel, when the temperature reached 184℃~191℃,crystalwater in boehmite and physical adhesive water in the cracks would volatilize. Therefore, there’s an endothermic peak. Enthalpy: 5.33 J/g.

As the temperature reached 298℃~310℃, amorphous boehmite gel turned into γ–AlOOH of crystalline state. An extra reaction was taken place:

Fig.4(b) analysis is as follows: At 115℃~160℃, an endothermic peak appeared. The reason was that ammonium nitrate decomposed along with phase transitions.The peak was the biggest at 140℃. As the reactions above, reactions were taken place .

At 160℃~250℃, the peak is formed because of the decomposition of copper nitrate. When copper nitrate was heated up to 170℃, it lost nitric acid and created. As the temperature reached 200℃above, the alkali nitrate copper decomposed to copper oxide. Therefore, two endothermic

As temperature reached 298℃~310℃, amorphous boehmite gel turned into γ–AlOOH of crystalline state [7].

It came to a conclusion from DSC curves that the reactions of none Cu 2+-doped gel in the heating process were more sophisticated than that of the Cu 2+

-doped gel. So did the phase transitions. The reason is Cu 2+-doped sol had complexation with NH 4+. K a Cu(NH 3)42+ = 4.7×1012; so ammonium

nitrate had a complex decomposition. Gel without Cu 2+-doped created multiple gases which can cause cracks of gel film in the heating process.

Fig.4 differential thermal analysis curves (a) sol without Cu 2+-doped (b) sol with Cu 2+-doped

Antibacterial Property Measurement. Cu2+-doped sol sealed substrate and sol without Cu2+-doped sealed substrate were separately treated with Staphylococcus aureus for antibacterial test. As shown in Fig. 5

Fig. 5 Antibacterial effect of film sealed by sol (a) without Cu 2+; (b) with Cu 2+

Staphylococcus aureus is gram-positive bacterium and typical pathogenic bacterium. From Fig. 5(a), in the antibacterial test of sol without Cu 2+ viable count reached 4.1х104cfu/ml. From Fig. 5(b), in the antibacterial test of sol with Cu 2+ viable count reached 5cfu/ml.

Table 1 antibacterial effect of film sealed by sol with/without Cu 2+

sample viable amount without Cu [cfu/ml] viable count with Cu[cfu/ml] sterilizing rate%

NO.1 4.2х104

4 99.99 NO.2 4.5х104 6 99.98

NO.3 4.4х104

5 99.98 NO.4 4.1х104 3 99.99

As shown in Table 1, sterilizing rate of Cu 2+-doped sol sealed is over 99%. So it reach a conclusion that Cu 2+-doped sol sealed substrate has a good antibacterial effect.

050100150200250300-10-5051015 H e a t

F l

o w /m W sample temperature/℃Peak:40℃Enthalpy:13.2J/g

Peak:80℃

Enthalpy:5.40J/g Peak:127℃Enthalpy:3.99J/g Peak:186℃Enthalpy:5.33J/g Peak:305℃Enthalpy:-44.8J/g (a)050100150200250300350

-30-20

-100

1020

H

e

a

t

F

l o w /

m W sa m p le te m p era tu re /℃P eak :140℃

E nthalp y :78.6J/g

P e ak:1680C

E n th a lp y:3.3J /g

P eak :300℃

E nth alp y :-20.8J/g

(b )a b

Conclusion

The reactions of the none Cu2+-doped gel in the heating process were more sophisticated than that of the Cu2+-doped gel. So did the phase transitions .

It illustrates that the corrosion resistance of Cu2+-doped sol sealed anodic oxide film is better than the latter in netrual NaCl solution.

The micropores of Cu2+-doped sol sealed film are smoother in compared with sol without Cu2+, the surface of sol without Cu2+ sealed film has many cracks.

Antibacterial property of Cu2+-doped sol sealed anodic oxide film is superior to sol without Cu2+-doped sealed anodic oxide film.

Acknowledgments

This work was supported by the experimental projects of Liaoning Province Education Department (No. 2008S202) and Natural Science Foundation (No. 20052003), China.

References

[1]J.H. Ge,Y.J. Wang,Y.D. Zheng,and K.C. Gong:J.Mater.Sci.Eng., Vol.22 (2004), p.442-445

[2]Q.J. Yu, H.B. Yang, W.Y. Fu, L.X. Chang, J. Xu, C.L. Yu, R.H. Wei, K. Du, H.Y. Zhu and M.H.

Li: Thin Solid Films Vol.515 (2007), p.3840-3843

[3]I.Vasiliu, M. Gartner, M. Anastasescu, L. Todan, L. Predoana, M. Elisa, C. Negrila, F.

Ungureanu, C. Logofatu, A. Moldovan and R. Birjega:Thin Solid Films Vol.515 (2007), p.

6601-6605

[4]Y.C. Kuo, J.W. Lee, C.J. Wang and Y.J. Chang: Surf. Coat. Technol. Vol.202 (2007), p. 854-860

[5]I.T. Hong, C.H. Koo: Mater. Sci. and Eng., A Vol.393 (2005), p.213-222

[6]Gabrielík, Helena Bujdáková, Frantiekere: Chemosphere Vol.44 (2001), p.313-319

[7] F. He and X.D. He: J. Chin. CE. Soc. Vol.35 (2007) , p.638-642

Advances in Functional Manufacturing Technologies

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Effect of Cu2+ Doped in Sol on Properties of Sealed Film on Anodized Al Alloy

doi:10.4028/https://www.wendangku.net/doc/364590286.html,/AMM.33.290

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英语介词用法大全 TTA standardization office【TTA 5AB- TTAK 08- TTA 2C】

介词(The Preposition)又叫做前置词,通常置于名词之前。它是一种虚词,不需要重读,在句中不单独作任何句子成分,只表示其后的名词或相当于名词的词语与其他句子成分的关系。中国学生在使用英语进行书面或口头表达时,往往会出现遗漏介词或误用介词的错误,因此各类考试语法的结构部分均有这方面的测试内容。 1. 介词的种类 英语中最常用的介词,按照不同的分类标准可分为以下几类: (1). 简单介词、复合介词和短语介词 ①.简单介词是指单一介词。如: at , in ,of ,by , about , for, from , except , since, near, with 等。②. 复合介词是指由两个简单介词组成的介词。如: Inside, outside , onto, into , throughout, without , as to as for , unpon, except for 等。 ③. 短语介词是指由短语构成的介词。如: In front of , by means o f, on behalf of, in spite of , by way of , in favor of , in regard to 等。 (2). 按词义分类 {1} 表地点(包括动向)的介词。如: About ,above, across, after, along , among, around , at, before, behind, below, beneath, beside, between , beyond ,by, down, from, in, into , near, off, on, over, through, throught, to, towards,, under, up, unpon, with, within , without 等。 {2} 表时间的介词。如: About, after, around , as , at, before , behind , between , by, during, for, from, in, into, of, on, over, past, since, through, throughout, till(until) , to, towards , within 等。 {3} 表除去的介词。如: beside , but, except等。 {4} 表比较的介词。如: As, like, above, over等。 {5} 表反对的介词。如: againt ,with 等。 {6} 表原因、目的的介词。如: for, with, from 等。 {7} 表结果的介词。如: to, with , without 等。 {8} 表手段、方式的介词。如: by, in ,with 等。 {9} 表所属的介词。如: of , with 等。 {10} 表条件的介词。如:

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用法: 1.原级比较:as + adj./adv. +as(否定为not so/as + adj./adv. +as)当as… as中间有名字时,采用as + adj. + a + n.或as + many / much + n. This is as good an example as the other is . I can carry as much paper as you can. 表示倍数的词或其他程度副词做修饰语时放在as的前面 This room is twice as big as that one. 倍数+as+adj.+as = 倍数+the +n.+of Your room is twice as larger as mine. = Your room is twice the size of mine. 2.比较级+ than 比较级前可加程度状语much, still, even, far, a lot, a little, three years. five times,20%等 He is three years older than I (am). 表示“(两个中)较……的那个”时,比较级前常加the(后面有名字时前面才能加冠词) He is the taller of the two brothers. / He is taller than his two brothers. Which is larger, Canada or Australia? / Which is the larger country, Canada or Australia? 可用比较级形式表示最高级概念,关键是要用或或否定词等把一事物(或人)与其他同类事物(或人)相分离 He is taller than any other boy / anybody else.

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(一)介词概述 介词是一种虚词,在句子中不单独作任何句子成分。它是一种表示名词和句中其他词之间关系的词。它常和名词、动词、形容词等搭配,构成固定短语,表示不同意思。介词还可以与名词构成介词短语,表示方位、方向、时间、地点、方式、原因等。这些介词短语在句中可充当定语、状语、补语等。2000—2005年的中考中主要考了形容词与介词的搭配:如:be famous for;表示时间的介词,如:at night;动词与介词的搭配,如:arrive in/have dinner with sb.;表示方式、手段的介词,如:by phone/in English. (二)基础知识梳理 1.名词与介词的搭配 a bit of有一点儿 a couple of两个、几个 a kind of一种、一类cover an area of占地面积 have pity on sb.怜悯某人huge amounts of大量的 make friends with与……交朋友make fun of拿……开玩笑 meet the needs of迎合……的需要one after another一个接一个;连续地 play a trick on捉弄the week after next下下周 2.动词与介词的搭配 agree with sb.同意某人的意见apologize to sb. for sth.为某事向某人道歉arrive at/in a place到达某地ask for请求、寻求 be covered with被……所覆盖be made of由……制成 be made up of由……组成belong to属于 break into破门而人、闯入 call on拜访 care for照顾、喜欢carry out执行 check in办理登机come across被理解;遇见 come from出生于、来自come on跟我来、走吧

at,in与on的用法区别

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The meeting was held at [in] the hotel. 会议在宾馆举行。 ③at与in的另一个区别是:at多用于指较小的地方,而in多用于指较大的地方:in Shanghai 在上海at the station 在车站 ④介词on 用于地点,主要指在某物的表面: What’s on the table? 桌上有什么? There’s a wallet lying on the ground. 地上有个钱包。 【注】在少数搭配中,也用介词on: He works on a farm. 他在农场工作。 3. 在某些搭配中,三者的区别与英国英语和美国英语有关: in the street (英) / on the street (美) 在街上 in the road (英) / on the road (美) 在路上 in the team (英) / on the team (美) 在这个队 at the weekend (英) / on the weekend (美) 在周末 at weekends (英) / on weekends (美) 在周末 4. 有时三者的差别与搭配习惯和用法有关: in bed / on the bed 在床上 in the tree (多指树外之物) / on the tree (多指树本身之物) 在树上

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3.谓语的替代 在as和than 引导的比较状语从句中,由于句式同前面 主句相同,为避免重复,常把主句中出现而从句中又出现的动词用do的适当形式来代替。 John speaks German as fluently as Mary does. 4.前后的比较对象应一致 不管后面连词是than 还是as,前后的比较对象应一致。The weather of Beijing is colder than Guangzhou. x than前面比较对象是“天气”,than 后面比较对象是“广州”,不能相比较。应改为: The weather of Bejing is colder than that of Guangzhou. 再如: His handwriting is as good as me. 应改为: His handwriting is as good as mine. 5.可以修饰比较级的词 常用来修饰比较级的词或短语有: Much,even,far,a little,a lot,a bit,by far,rather,any,still,a great deal等。 by far的用法: 用于强调,意为“...得多”“最最...”“显然”等,可修饰形容词或副词的比较级和最高级,通常置于其后,但是若比较级或最高级前有冠词,则可置于其前或其后。

介词in,on,to表示方位的用法

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英语方位词知识分享

英语方位词的用法 (一)in the east 与 on the east的区别 1.in the east表示我们生活中和地理位置上的绝对方向。如: The sun rises in the east and sets in the west. 太阳从东边升起,从西边落下。 The Great Wall begins in the east from the Shanghaiguan Pass and ends at the Jiayu guan Pass in the west. 长城东起山海关,西至嘉峪关。 2.on the east表示某事物位于另一事物所朝的方向。这里的方向是相对而言的。如: China faces the Pacific on the east. 中国东临太平洋。 The United States faces the Atlantic on the east and the Pacific on the west. 美国东临大西洋,西濒太平洋。 (二) in (to,on,at) the east of 1.要表示A在B的东部,即:A在B的范围之内时就用"A is in the east of B",如: Japan is in the east of Asia.日本在亚洲东部。 Italy is in the south of Europe.意大利在欧洲南部。 2.如果A在B的东方,即:A在B的范围之外,且相隔有一定的距离,就用"A lies to the east of B".口语中有时可将to the省去。如: Japan lies (to the) east of China.日本位于中国东方。 France lies (to the) east of England.法国位于英国东方。 3.如果A在B的东边(侧),即:A与B相邻接。就用"A is on the east of B". 如: Guangdong is on the south of Hunan.广东在湖南南边。

英语地点介词的正确使用方法

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