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Development of nanocrystals in amorphous Al-alloys

Development of nanocrystals in amorphous Al-alloys

N.Boucharat *,H.Ro ¨sner,G.Wilde

Forschungszentrum Karlsruhe,Institut fu ¨r Nanotechnologie,P .O.Box 3640,76021Karlsruhe,Germany

Abstract

Rapidly quenched aluminum-based metallic glasses have been found to undergo a partial transformation upon heating that yields a fine-scaled dispersion of Al-nanocrystals within an amorphous matrix.The origin of the nanocrystallisation process is discussed based upon

calorimetric and structural investigations of Al 92Sm 8samples prepared using different processing pathways.Additionally,the early stages of the nanocrystal development was monitored by isothermal calorimetry techniques on long time scales.The results strongly indicate that the nanocrystals originate from quenched-in nuclei.Isothermal annealing of Al 88Y 7Fe 5glasses at 245j C revealed that a -Al nanocrystals develop at temperatures well below the primary crystallisation onset temperature after short time periods.On annealing,an additional phase evolves,which gives an exothermic signal in DSC at about 330j C.XRD measurements have been performed to study the phase formation sequence at high temperature.The formation of additional phases is related to a modification of the matrix composition near the nanocrystal/amorphous interface due to a pronounced concentration gradient as a result of the unequal component diffusivities.D 2002Elsevier Science B.V .All rights reserved.

Keywords:Al-alloys;Amorphous;Nanocrystals;Primary crystallisation;Transient phase

1.Introduction

Many metallic glasses including Al-based systems require rapid solidification to avoid crystallisation and to allow the formation of an amorphous phase.Upon heating,they often do not display a detectable glass transition signal but instead an exothermic maximum indicating a partial transformation that leads to a fine-scaled dispersion of 1021–1022m à3Al-nanocrystals of about 20nm in diameter within an amorphous matrix [1].This high number density of Al-nanocrystals is related to a crystal growth limitation and at the same time yields a high tensile strength of the nanocomposite material much higher than the respective values for the crystalline counterpart [2].Yet,the origin of the nanocrystallisation process is still a matter of active research [3].In the current work,glassy Al 92Sm 8and Al 88Y 7Fe 5alloys serve as model systems to investigate the origin of the nanocrystallisation process.Both systems are known [4,5]to yield similar product microstructures during the initial crystallisation reaction.However,the different absolute values for the transformation temperatures enable the use of different analysis tools and synthesis

procedures as described below.The unequal component diffusivities induce pronounced concentration gradients at the nanocrystal/amorphous interface [6,7]which strongly affect the crystallisation kinetics involving different kinetic regimes and different constraints for the precipitation of transient phases [8,9].In order to study the kinetics of the crystallisation process in detail,quantitative structural and calorimetric investigations have been performed and the phase formation sequences at higher temperatures and their modification after isothermal annealing have been studied.

2.Experimental procedures

Glassy ribbons with an approximate thickness of 40A m were produced from pre-alloyed ingots of Al (99.999%),Sm (99.9%),Y (99.9%)and Fe (99.995%)using a single-roller melt-spinning technique applying a fast rotating copper wheel.The sample homogeneity was ensured by pre-syn-thesis of the alloys in an arc-melting facility.XRD measure-ments on both sides of Al 92Sm 8and Al 88Y 7Fe 5samples as well as careful microstructural analyses performed by TEM/SAED have confirmed the absence of any detectable crys-talline fractions in the as-spun ribbon.Repeated cold-rolling was performed to yield a partially amorphous Al 92Sm 8sample with a thickness of 80A m.This processing route is governed by a deformation-driven mixing of the pure

0928-4931/02/$-see front matter D 2002Elsevier Science B.V .All rights reserved.PII:S 0928-4931(02)00230-8

*Corresponding author.Tel.:+49-7247-826450;fax:+49-7247-826434.

E-mail address:nancy.boucharat@int.fzk.de (N.Boucharat).

https://www.wendangku.net/doc/4911664695.html,/locate/msec

Materials Science and Engineering C 23(2003)55

–59

elements at room temperature[10].The sample was annealed at150j C in order to allow for relaxation of the vitreous state and to promote the development of any Al-nanocrystals.Energy dispersive X-ray analysis(EDX)con-firmed that the composition of all our samples corresponds to the nominal starting composition within the accuracy of the EDX-measurement(F0.5at.%).Microstructural inves-tigations were carried out by X-ray diffraction(Philips XRD)using Mo–K a radiation,scanning electron micro-scopy(SEM,Leo1530)and transmission electron micro-scopy/selected area electron diffraction(TEM/SAED, Philips CM30ST)techniques.TEM samples were prepared by twin-jet electropolishing(1/3nitric acid and2/3meth-anol)to avoid any sample-heating effects on the final microstructure as it was previously noticed using ion beam thinning.Continuous heating and isothermal annealing were monitored by differential scanning calorimetry(DSC,Per-kin Elmer,Pyris1)by which signals of about1A W can reproducibly be analysed.A microcalorimeter(Thermomet-ric,2277TAM)was used for the isothermal measurements on long time scales.

3.Results

3.1.Nanostructure development

The DSC signals on heating Al92Sm8samples,which were vitrified by cold-rolling or melt-spinning,respectively,are given in Fig.1.The repeatedly cold-rolled sample in Fig.1a displays an endothermic glass transition signal at about172j C.The TEM bright-field image given in Fig.1c, taken after annealing the sample at150j C for60min,does not show any signs of crystallinity within the amorphous region.In contrast,the DSC trace of the rapidly quenched sample exhibits a non-symmetrical exothermic signal at178 j C,well below the onset of the eutectic reaction that is characteristic for Al-nanocrystallisation(Fig.1b).The TEM bright-field image in Fig.1d reveals that Al-nanocrystals do develop within the amorphous matrix after annealing at150 j C for10min with a high number density of3.5?1022 mà3.In the case of homogeneous nucleation,the processing route should not affect the nanocrystal development since thermally driven fluctuations govern this process.Based upon these experimental results,the apparent variations in the thermal traces of both samples indicate that the for-mation of the large nanocrystal number densities is inher-ently coupled to the presence of a high nucleation site density in the undercooled melt[5,6].In order to monitor the early stages of nanocrystal development at temperature below T g in more detail,isothermal microcalorimetry meas-urements on long time scales have been performed at120 and130j C(Fig.2).For these measurements,the micro-calorimeter has been equilibrated at the respective temper-atures prior to the insertion of the specimen.Thus,it was ensured that the microstructure did not change before the onset of the microcalorimetry measurement.The baseline measured for about7days indicates the absence of

any Fig.1.DSC curves obtained during continuous heating at20j C minà1(a)of a Al92Sm8cold-rolled sample and(b)of a Al92Sm8as-spun ribbon.TEM and SAED patterns(c)of a cold-rolled sample after annealing at150j C for60min and(d)of an as-spun ribbon after annealing at150j C for10min.

N.Boucharat et al./Materials Science and Engineering C23(2003)55–59

56

instrumental transient effect that exceed the scatter of the data (0.025A W/h).Under identical conditions,the temper-ature of the samples was maintained with an accuracy better than 2?10à4j C.The sample measurements show a monotonically decreasing signal as well as the absence of any maximum in the heat flow signal.These results indicate that the nanocrystallisation process is controlled by the diffusional growth of nuclei formed during rapid melt quenching and not by a nucleation and growth process of the Al-nanocrystals within the amorphous state [11].Regarding this result,a qualitative time–temperature–trans-formation (TTT)curve has been proposed [10]showing that during quenching the cooling rate is not high enough and thus intersects with the TTT curve of the Al.Alternatively,a cluster distribution with an average size larger than the critical size for growth at large undercooling could be retained in the material after the rapid quench.3.2.Transient phase formation

DSC curves of the as-spun Al 88Y 7Fe 5samples during continuous heating (Fig.3a)display a primary crystallisa-tion peak with an onset at about 276j C that is followed by a sharp crystallisation signal at 374j C.Careful XRD measurements have shown that the primary crystallisation peak corresponds to the formation of fcc-Al-nanocrystals within the amorphous matrix (Fig.4)and the following peak to the formation of the intermetallic Al 3Y(Fe)phase from the remaining amorphous matrix.The similarity of the XRD profiles (Fig.4a and b)confirms that no crystalline phase except the Al-nanocrystals is formed during the initial crystallisation reaction.Though the DSC curve obtained on continuous heating indicates that the primary crystallisation starts at 276j C,isothermal

annealing investigations at 245j C revealed that a -Al nanocrystals can slowly develop at temperatures well below the primary crystallisation onset temperature.The development of the Al-nanocrystals is coupled to the slow disappearance of the primary crystallisation signal with increasing annealing time,indicating the sluggish growth of the nanocrystals (Fig.3).This result has been confirmed by XRD measurements and TEM analyses showing that a small fraction of Al-nanocrystals develops in the samples that are isothermally held at 245j C for 10and 30min,respectively.The dark-field TEM images in Fig.3f exhibit the evolution of the small Al-nanocrystals from a spherical shape to a dendritic morphology during isothermal anneal-ing at 245j C,probably as a result of large concentration gradients that develop at the nanocrystal/amorphous inter-face due to limited diffusion of the RE-element that cause the instability of the interface [4,6].At early stages of the isothermal annealing treatment the diffusion fields do not overlap.During nanocrystal growth,the interparticle dis-tance decreases and the amorphous matrix surrounding the nanocrystals is enriched in solute.Both effects lead to an overlap of the diffusion fields with a soft diffusion field impingement that causes the formation of pronounced concentration gradients at the nanocrystal/amorphous inter-face as shown by kinetics modelling [6]and direct experimental investigations [7].The nanocrystal growth velocity is then considerably reduced and effectively con-trolled by the slow-diffusing species [12].In order to study the impact of the concentration gradient on the phase evolution in more detail,continuous heating experiments have been carried out on samples that had been annealed at 245j C for different periods of time.Fig.3gives

repre-

Fig.3.Continuous heating DSC traces at 20j C min à1of a Al 88Y 7Fe 5ribbon (a)as-spun and after isothermal annealing at 245j C (b)for 10min,(c)30min,(d)60min and (e)100min,respectively.TEM dark-field images are included showing the evolution of nanocrystals from a spherical shape to a dendritic morphology in samples annealed at 245j C for 10and 30min

(f).

Fig. 2.Heat flow evolved during isothermal annealing of an as-spun Al 92Sm 8ribbon at 120and 130j C,respectively,together with the baseline.

N.Boucharat et al./Materials Science and Engineering C 23(2003)55–5957

sentative examples of the typical thermal responses of the pre-annealed samples that expose an additional peak in the range of 320–360j C between the primary and interme-tallic crystallisation peak.The crystallisation sequence was studied by XRD on the samples annealed for 30and 60min and compared to the crystallisation sequence of the as-spun sample (Fig.4).The XRD spectra indicate the formation of Al nanocrystals in the amorphous matrix of the annealed sample,after heating to temperature up to 310j C,as also found for the as-spun sample.Further exami-nations after continuous heating up to 355j C show additional peaks (Fig.4d and e),which were not observed in the as-spun sample after heating to 348j C at an identical rate.Calculated diffusion fields of yttrium between two adjacent nanocrystal particles have shown that a rather high concentration gradient near the interface (>106m à1)is reached in the initial stages of the nano-crystal growth,which is sufficient to inhibit the nucleation of transient phases [6].Moreover,thermodynamic and kinetic approaches [8,9]have demonstrated the existence of a critical value of the concentration gradient below which the nucleation of transient phase is allowed.Based upon these results,the transient appearance of transforma-tion signals at intermediate temperatures (Fig.3c–e)is related to the important contribution of the concentration gradient that favours or suppresses the formation of the transient phase.These results further indicate that the

phase formation sequence can be modified by controlling the concentration gradient at the interface.

4.Summary

The combination of different synthesis routes and anal-ysis methods as well as the isothermal microcalorimetry measurements at temperatures below T g indicate that the nanocrystal development during annealing of Al-rich glasses such as Al–Sm and Al–Y–Fe is related to the formation of precursor nuclei during rapid quenching.In such systems,the large disparities of the component diffu-sivities cause a soft diffusion field impingement between neighboring nanocrystals during primary crystallisation [6,7].In that sense,the solute rejection during nanocrystal growth itself provides for a kinetic stabilisation of the nanoscaled microstructure.These results serve as a basis for an understanding and a description of the kinetics of the nanocrystallisation process and indicate that a microstruc-ture control on the nanoscale requires the control of the nucleation site density in the molten material.Further,the diffusional control that is operative in these alloys leads to a modification of the local composition of the amorphous matrix at the interface that modifies the nucleation kinetics of intermediate phases.These observations indicate that the concentration gradient affects the phase evolution

sequence

Fig.4.XRD profiles of Al 88Y 7Fe 5as-spun samples after heating to (a)315j C and (b)348j C together with the XRD profiles of Al 88Y 7Fe 5ribbons isothermally held at 245j C for 30min and re-heated up to (c)310j C and (d)355j C as well as (e)Al 88Y 7Fe 5ribbons isothermally held at 245j C for 60min and re-heated up to 355j C.The peaks corresponding to fcc-Al (A )and the transient phase (.)are indicated.

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and that an opportunity for active phase selection is given by controlling the concentration gradient.

References

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英语中的比较级与最高级 详解

比较级与最高级 1.as...as 与(not) as(so)...as as...as...句型中,as的词性 第一个as是副词,用在形容词和副词的原级前,常译为“同样地”。第二个as是连词,连接与前面句子结构相同的一个句子(相同部分常省略),可译为“同..... He is as tall as his brother is (tall) . (后面的as 为连词) 只有在否定句中,第一个as才可换为so 改错: He is so tall as his brother.(X) 2.在比较状语从句中,主句和从句的句式结构一般是相同的 与as...as 句式中第二个as一样,than 也是连词。as和than这两个连词后面的从句的结构与前面的句子大部分情况下结构是相同的,相同部分可以省略。 He picked more apples than she did. 完整的表达为: He picked more apples than she picked apples. 后而的picked apples和前面相同,用did 替代。 He walked as slowly as she did.完整表达为: He walked as slowly as she walked slowly. she后面walked slowly与前面相同,用did替代。

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。

五年级上册成语解释及近义词反义词和造句大全.doc

五年级上册成语解释及近义词反义词和造句大全 囫囵吞枣;【解释】:囫囵:整个儿。把枣整个咽下去,不加咀嚼,不辨味道。比喻对事物不加分析考虑。【近义词】:不求甚解【反义词】融会贯穿[造句];学习不能囫囵吞枣而是要精益求精 不求甚解;bùqiúshènjiě【解释】:甚:专门,极。只求明白个大概,不求完全了解。常指学习或研究不认真、不深入【近义词】:囫囵吞枣【反义词】:精益求精 造句;1;在学习上,我们要理解透彻,不能不求甚解 2;学习科学文化知识要刻苦钻研,深入领会,不能粗枝大叶,不求甚解。 千篇一律;【解释】:一千篇文章都一个样。指文章公式化。也比喻办事按一个格式,专门机械。 【近义词】:千人一面、如出一辙【反义词】:千差万别、形形色色 造句;学生旳作文千篇一律,专门少能有篇与众不同旳,这确实是平常旳练习太少了。 倾盆大雨;qīngpéndàyǔ【解释】:雨大得象盆里旳水直往下倒。形容雨大势急。 【近义词】:大雨如柱、大雨滂沱【反义词】:细雨霏霏牛毛细雨 造句;3月旳天说变就变,瞬间下了一场倾盆大雨。今天下了一场倾盆大雨。 坚决果断;áobùyóuyù:意思;做事果断,专门快拿定了主意,一点都不迟疑,形容态度坚决 近义词;不假思索斩钉截铁反义词;犹豫不决 造句;1看到小朋友落水,司马光坚决果断地搬起石头砸缸。2我坚决果断旳承诺了她旳要求。 饥肠辘辘jīchánglùlù【近义词】:饥不择食【反义词】:丰衣足食 造句;1我放学回家已是饥肠辘辘。2那个饥肠辘辘旳小孩差不多两天没吃饭了 滚瓜烂熟gǔnguālànshóu〔shú)【解释】:象从瓜蔓上掉下来旳瓜那样熟。形容读书或背书流利纯熟。【近义词】:倒背如流【反义词】:半生半熟造句;1、这篇课文我们早已背得滚瓜烂熟了 流光溢彩【liúguāngyìcǎi】解释;光影,满溢旳色彩,形容色彩明媚 造句:国庆节,商场里装饰旳流光溢彩。 津津有味;jīnjīnyǒuwèi解释:兴趣浓厚旳模样。指吃得专门有味道或谈得专门有兴趣。 【近义词】:兴致勃勃有滋有味【反义词】:索然无味、枯燥无味 造句;1今天旳晚餐真丰富,小明吃得津津有味。 天长日久;tiānchángrìjiǔ【解释】:时刻长,生活久。【近义词】:天长地久【反义词】:稍纵即逝 造句:小缺点假如不立即改掉, 天长日久就会变成坏适应 如醉如痴rúzuìrúchī【解释】:形容神态失常,失去自制。【近义词】:如梦如醉【反义词】:恍然大悟造句;这么美妙旳音乐,我听得如醉如痴。 浮想联翩【fúxiǎngliánpiān解释】:浮想:飘浮不定旳想象;联翩:鸟飞旳模样,比喻连续不断。指许许多多旳想象不断涌现出来。【近义词】:思绪万千 造句;1他旳话让人浮想联翩。2:这幅画饱含诗情,使人浮想联翩,神游画外,得到美旳享受。 悲欢离合bēihuānlíhé解释;欢乐、离散、聚会。泛指生活中经历旳各种境遇和由此产生旳各种心情【近义词】:酸甜苦辣、喜怒哀乐【反义词】:平淡无奇 造句;1人一辈子即是悲欢离合,总要笑口常开,我们旳生活才阳光明媚. 牵肠挂肚qiānchángguàdù【解释】:牵:拉。形容十分惦念,放心不下 造句;儿行千里母担忧,母亲总是那个为你牵肠挂肚旳人 如饥似渴rújīsìkě:形容要求专门迫切,仿佛饿了急着要吃饭,渴了急着要喝水一样。 造句;我如饥似渴地一口气读完这篇文章。他对知识旳如饥似渴旳态度造就了他今天旳成功。 不言而喻bùyánéryù【解释】:喻:了解,明白。不用说话就能明白。形容道理专门明显。 【近义词】:显而易见【反义词】:扑朔迷离造句;1珍惜时刻,好好学习,那个道理是不言而喻旳 与众不同;yǔzhòngbùtóng【解释】:跟大伙不一样。 〖近义词〗别出心裁〖反义词〗平淡无奇。造句; 1从他与众不同旳解题思路中,看出他专门聪慧。2他是个与众不同旳小孩

人教版(新目标)初中英语形容词与副词的比较级与最高级

人教版(新目标)初中英语形容词与副词的比较级与最高级 (一)规则变化: 1.绝大多数的单音节和少数双音节词,加词尾-er ,-est tall—taller—tallest 2.以不发音的e结尾的单音节词和少数以-le结尾的双音节词只加-r,-st nice—nicer—nicest , able—abler—ablest 3.以一个辅音字母结尾的重读闭音节词或少数双音节词,双写结尾的辅音字母,再加-er,-est big—bigger—biggest 4.以辅音字母加y结尾的双音节词,改y为i再加-er,-est easy—easier—easiest 5.少数以-er,-ow结尾的双音节词末尾加-er,-est clever—cleverer—cleverest, narrow—narrower—narrowest 6.其他双音节词和多音节词,在前面加more,most来构成比较级和最高级 easily—more easily—most easily (二)不规则变化 常见的有: good / well—better—best ; bad (ly)/ ill—worse—worst ; old—older/elder—oldest/eldest many / much—more—most ; little—less—least ; far—farther/further—farthest/furthest

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.

英语中的比较级和最高级

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