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寻找无序世界中的有序

已有 7356 次阅读 2011-6-30 15:55 |个人分类:分享|系统分类:论文交流

金属玻璃(Metallic Glass)是现代材料科学领域中的“新贵”。1960年,美国加州理工学院的Pol Duwez教授第一次在实验室制备出这种新型材料,研究结果发表在当年9月3日出版的Science杂志上。除了Pol Duwez教授及其合作者外,David Turnbull也是值得一提的金属玻璃国际研究先驱,因为他在1948年就提出,金属可以在其结晶温度以下呈现相当程度的过冷(undercooled)。
经过50多年的研究,如今金属玻璃已有广泛的用途,包括运动器材、包覆材料、变压材料等等。它比普通金属强度更高,可以说是目前世界上强度最高的金属材料;具有耐腐蚀、耐磨的优良性能,还有很高的弹性极限。金属玻璃制成的手机外壳可以恒久光亮如新,制作的高尔夫球杆能把球送到更远的地方,它还可以用于制造一些造型精巧的微小器件。 
金属玻璃——由金属元素构成,但内部的原子又像玻璃一样无序排列。金属玻璃内部杂乱无章的原子阵列阻碍了科学家对于材料性能认识和研发新型材料。1995年,凝聚态物理奠基人、诺贝尔奖获得者P.W. Anderson就曾在《Science》杂志上说:“有关对无序玻璃态认识的问题是目前凝聚态物理最重要也是最困难的问题之一。”
最近,这一难题终于被科学家破解。浙江大学材料科学与工程学系新结构材料国际研究中心的蒋建中教授领衔的课题组发现:在高压状态下,看似无序的金属玻璃呈现出有序结构。研究论文《Long-range topological order in metallic glass》发表在今年6月17日出版的Science杂志上,第一作者是浙大材料系新结构材料国际研究中心曾桥石博士后。
传统观念认为,金属玻璃的微观原子结构不存在长程有序,实验上从未有过相关报道。浙大这一课题组采用天然材料中最硬的金刚石,在实验室里对头发丝大小的一块金属玻璃样品进行“挤压”,因为受力面积小,压强可以达到25万个大气压,然后在电子显微镜下观察其原子排列。他们惊喜地发现,在一定条件下,长程拓扑序的确存在。
浙大的这个课题组之前还成功地合成出世界上尺寸最大的稀土基大块金属玻璃材料。这次他们又第一次揭示了金属玻璃中可以存在长程拓扑有序,改变了人们对玻璃结构的传统理解和认识,为玻璃结构的研究提供了一个全新的思路。该研究工作得到了Science杂志审稿人的高度评价。
这项重要的研究工作可以说还颇具一番哲学意味:有序中包含无序,无序中包含有序。
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  • Why are metallic glasses so special?

All metals prefer to form crystals, as  the metal atoms easily form structured bonds with other atoms. So easy in fact that even when the metal is melted some of that arrangement carries over into the liquid. This makes the formation of a crystal the preferred pathway once the melt is cooled down again. Glass on the other hand is amorphous, which means that the atoms are disordered and there is no long-range periodicity. This is not something metals prefer. Unlike the window glass made of silicon oxide. In comparison, metallic glasses are a very different animal. 

So how to create a metallic glass? The answer is to give the metal atoms not the slightest chance to form a crystal. This means to cool the material superfast. Typical cooling speeds for the first metallic glasses made were on the order of a Million Kelvin per second: from about 1,300 degrees Celsius to room temperature in about a millisecond. This fast cooling can be done only for small samples, and the first metallic glass sample was a tiny flake: 0.2 mm2 area, and only 2o micrometers thick.

Then, about 15 to 20 years ago, William Johnson, Akihisa Inoue and others then discovered metallic glasses that are much easier to make, and with lower cooling rates. This meant that metallic glasses could now be produced in larger volumes, hence the name of these glasses: ‘bulk metallic glasses’. They have enabled the commercialization of metallic glasses.

  • The uses of metallic glasses

The absence of any long-range order in these metallic glasses comes as a benefit, not a curse. Metallic glasses might be disordered on the atomic scale, but this disorder looks very homogeneous when looking on a larger scale. The properties of crystals are easily messed up and degraded by imperfections in their structure. In contrast, in a metallic glass the imperfection is what makes the glass. There is no need to be concerned about degraded properties through disruptions.

Close-up of a metallic glass after failure. The so-called shear bands are typical indicators of irreversible damage and eventually cause fracture. Image reprinted by permission from Macmillan Publishers Ltd: Nature Materials 2, 661 - 663 (2003).

An example of how useful this is are iron-based metallic glasses. They are excellent soft magnetic materials, which are magnetic compounds whose magnetisation follows that of an external magnetic field. In a crystal, imperfections can make it difficult for a soft magnetic material to change its magnetisation in response to an external field. This requires additional energy, and results in energy losses during the switching process. Not so in magnetic glasses, which are far more homogeneous and therefore show lower losses. Consequently, magnetic metallic glasses are used in transformer cores, where they are very economical in converting high voltages down to household levels. They are also great sensors for magnetic fields, for example as tiny compasses. In terms of looks, they look like regular metal.

Metallic glasses are also very tough, even though they can be very brittle once they fail. Still, their toughness means that they are very useful in a number of areas, ranging from medical instruments to possibly metal casings for electronic devices. Sports equipment is another, perhaps a more unusual one. But it highlights another intriguing property: as well as being tough, metallic glasses are also lightweight and elastic. Hence they bounce a ball better than steel. For this reason metallic glasses are used in ski equipment, baseball bats, golf clubs, and others.

Another very promising use are medical implants. Because they metallic glasses are so lightweight, tough and cheaper than high-quality steels or titanium alloys, they make very good implants. For example as prosthetic hip joints. Another application are degradable implants. MgZnCa metallic glasses are not only biocompatible, but also biodegradable. Mg, Zn, and Ca all occur naturally in the body and they can be absorbed by the body without harm. In the case of MgZnCa glasses, they are absorbed at a rate of about a microgram a day. This allows their use as nails to hold fractured bones together and that slowly dissolve as the bone grows. However, while successfully tested on animals, none of these bioimplants has been approved yet for human use.

Metallic glasses have not always been an easy system to study. It took more than 30 years after the original demonstration to come up with ways to fabricate them in sufficient quantities. Once that problem was solved, metallic glasses have slowly but surely made it into applications. Still, even after all that time a systematic and thorough understanding of the properties of metallic glasses is lacking. We are still far away from a situation where a metallic glass can be ‘designed’ according to specifications. But one thing is sure: metallic glasses will continue the successful path of the past 50 years. Cheers to that!

Reference:

KLEMENT, W., WILLENS, R., & DUWEZ, P. (1960). Non-crystalline Structure in Solidified Gold–Silicon Alloys Nature, 187 (4740), 869-870 DOI: 10.1038/187869b0



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