CN1226140C - 制造反应性多层金属薄片的方法以及制得的产品 - Google Patents

制造反应性多层金属薄片的方法以及制得的产品 Download PDF

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CN1226140C
CN1226140C CNB018089356A CN01808935A CN1226140C CN 1226140 C CN1226140 C CN 1226140C CN B018089356 A CNB018089356 A CN B018089356A CN 01808935 A CN01808935 A CN 01808935A CN 1226140 C CN1226140 C CN 1226140C
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layer
sheet metal
assembly
alternately arranging
overcoat
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CN1450954A (zh
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蒂莫西·P·魏斯
迈克尔·莱斯
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Johns Hopkins University
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Johns Hopkins University
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    • B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B23K1/00—Soldering, e.g. brazing, or unsoldering
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    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
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    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/06—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of high energy impulses, e.g. magnetic energy
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    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
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    • B23K20/16—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating with interposition of special material to facilitate connection of the parts, e.g. material for absorbing or producing gas
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    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract

根据本发明，通过下述步骤来生产出一种反应性多层金属薄片：提供一个由反应性层构成的组合体(叠层体或者多层)；将该组合体插入到一个外套中；使得带有外套的组合体发生变形，来减少其横剖面积；将带有外套的组合体压扁平成一个薄板；并且然后将外套去除。最好，使所述组合体在插入到所述外套中之前被卷绕成一个圆柱体，并且在变形过程中将带有外套的组合体冷却至一个低于100℃的温度。所制得的多层金属薄片用作在结合、点火或者推进操作中使用的独立式反应金属薄片是有益的。

Description

制造反应性多层金属薄片 的方法以及制得的产品
政府利益
本发明是受政府支持而做出的，资助号(NSF Grant Nos)：DMR-9702546和DMR-9632526，通过授奖号(Award No.)019620047的军事研究实验室/先进材料特性计划(Army Research Lab/AdvancedMaterial Characterization Program)。
相关申请的交叉引用
本申请要求享受临时申请序列号为No.60/201292的美国在先申请的优先权，该在先申请由T.P.Weihs等于2000年5月2日提交，题目为“反应性多层金属薄片”。本申请还与序列号为＿＿的美国申请和序列号为＿＿的美国申请有关，这两件美国申请均由T.P.Weihs等与本申请同时提交，其中，前一美国申请的题目为“独立式反应性金属薄片”，后一美国申请的题目为“易于加工并且具有较好延展性的反应性多层结构”。通过参考将这三件相关申请结合入本发明中。
本发明的技术领域
本发明涉及反应性多层金属薄片，尤其涉及利用塑性形变制取这种金属薄片的方法。
本发明的背景技术
反应性多层涂层适用于许多需要在一个平面区域内产生剧烈、受控热量的领域中。这种结构通常包括有一系列基层支撑涂层，通过合适的激励作用，这些基层支撑涂层会经历一次放热化学反应，这种化学反应横跨由所述薄层覆盖住的区域发生蔓延，来产生数量精确受控的热量。尽管我们将会将这些反应性涂层主要描述成用于进行焊接、软焊或者硬焊的热量供应源，但是它们也可以用于其它需要产生局部受控放热的操作中，比如推进和点火操作中。
差不多在每一种产业中，由于科技发展使得对结合操作(bonding)进行改进变得日益重要。当即将被发生结合的本体变得更为微小和更为脆弱，这一点尤其现实。此外，新的材料通常难以发生结合并且为了实现产业化已经遇到许多问题。
许多结合方法均需要一个热量源。该热量源可以位于待接合结构的外部或者内部。外部热源通常是一个用于对整个待结合单元，包括待接合本体(the bodies to be joined)(松散材料)和接合材料进行加热的熔炉。由于松散材料将会对于接合操作所需的高温敏感，所以外部的热量源通常会显现出一些问题。它们还会由于热收缩不相匹配而受损。
内部的热量源通常采用反应性粉末。这些反应性粉末通常是某些金属或者化合物的混合物，这些金属或者化合物将会发生放热反应而最终形成一种化合物或者合金。早在20世纪60年代就已经被研究开发，这些粉末能够通过自蔓延高温合成(SHS)而促使发生结合。但是，在SHS反应中通常难以对释放出来的能量和能量的扩散进行控制。从而，利用粉末进行的结合将不可靠或者不充分。
后来研究出来的反应性多层结构减少了与反应性粉末结合相关联的问题。这些结构由能够进行放热反应的薄涂层构成。比如，参见由D.A.Glocker和S.I.Shah编辑的《薄膜处理技术手册》(Handbookof Thin Film Process Technology)(1998年由IOP出版)中B部分、章节F.7由T.P.Weihs发表的文章；于1996年7月23日授权给Barbee和Jr.等的美国专利No.5538795；于1995年1月17日授权给D.M.Makowiecki的美国专利No.5381944。反应性多层结构允许在更为可控并且均匀发热的条件下进行放热反应。这种反应背后的基本驱动力是原子键能的降低。当一系列反应性薄层被点燃时，不同的薄层之间将发生原子混合现象，局部产生热量。这种热量会点燃所述结构中的相邻区域，从而使反应在结构的整个长度上行进，产生热量直至所有的材料均发生反应为止。
但是，即使具有这个进展，仍然存在许多问题。例如，在反应进行时反应性涂层通常会从它们的基层上脱离。这种脱离现象是由于在反应过程中的固有的反应性金属薄片的密实化(inherent reactivefoil densification)和在加热与冷却过程中发生不均匀热膨胀或热收缩而造成的。其明显弱化了接合中的结合力。更值得注意的是，现有的反应性多层金属薄片能够产生脆弱的金属间化合物，这种化合物具有有限的延展性，从而会由于它们在结合组件之间的存在而使得所形成的接头质量下降。因此，内部的或者外部的应力将会导致结合物发生灾难性的机械失效。
除了反应性涂层之外，可以通过冷轧来开发出独立式反应性薄层，参见由L.Battezzatti等在1999年出版的第47卷《材料学报》(actamaterialia)第1901至1914页发表的文章。通过对由镍和铝制成的双层金属薄板进行冷轧操作，随后反复进行人工折叠和冷轧来制取镍-铝多层反应性金属薄片。在第一个双层金属条被滚轧成原始厚度的一半之后，将其折叠一次以重新获得其原始厚度，并且使得层数变成原来的两倍。该步骤多次重复进行。
生产这种经过滚轧的金属薄片既费时又困难。滚轧道次操作(therolling passes)需要使用润滑油，并且在每次滚轧道次操作之后必须对经滚轧材料的表面进行清洁。此外，对薄板叠层体进行人工折叠操作本身就难以进行大批量生产。初始时形成金属薄板的叠层体并且随后进行若干次滚轧和折叠操作将能够简化所述工艺。但是，当同时对许多金属层进行滚轧操作时，这些薄层将发生弹性回复现象，导致所述薄层发生分离并且导致最终的金属薄片质量下降。这种分离现象还会使得层间表面发生所不希望的氧化现象，并且阻止通过冷焊操作使得所述薄层一体化。
因此，在这里需要对生产反应性多层金属薄片的方法进行改进。
本发明的概述
根据本发明，通过以下操作生产出一种反应性多层金属薄片：提供一个反应性层的组合体(叠层体或者多层)，将该组合体插入到一个外套中，使得带有外套的组合体发生变形，来减小其横剖面积，将带有外套的组合体碾压成一个薄板，并且随后将外套去除。最好，在将组合体插入所述外套中之前将所述组合体卷绕成一个圆柱体，并且使得带有外套的组合体在变形过程中被冷却至一个低于100℃的温度，优选的是一个低于25℃的温度。所制得的多层金属薄片有益地用作一个在结合、点火或者推进操作中使用的独立式反应性金属薄片。
对附图的简述
通过研究所图示出的实施例，将可以更为全面地明了本发明的本质、优点及各种不同的技术特征，所述实施例将在下面结合附图进行详细描述。在这些附图中：
附图1是一个示意流程图，示出了一种根据本发明生产多层反应性金属薄片的方法；
附图2图示出了将一个扁平的组合体插入到一外套中的操作；
附图3示出了一个圆柱形组合体的插入操作；
附图4图示出了一个利用附图1中所示工艺制成的独立式多层反应性金属薄片；
附图5示意性示出了一种示例性接合工艺；
附图6示出了一个被穿孔的独立式多层反应性金属薄片；
附图7A和7B示出了将可延展的组件合并入反应性金属薄片中的操作；而
附图8描绘了一种反应性金属薄片示例的微观结构。
应该明白的是，这些附图仅用于图示出本发明的构思，并且除了图解说明之外，均没有按比例绘制。
详细描述
参照附图，附图1是一个示意性流程图，图示出了根据本发明生产一种反应性多层金属薄片的步骤。在附图1中的方框A内示出的第一步骤，是提供一个由交替排布的材料层构成的组合体(叠层体或者多层)，所述材料层由可以进行放热反应的材料制成，所述组合体比如是一个由交替排布的镍箔层与铝箔层构成的组合体。在这里所使用的词语“叠层体”指的是由未结合的层构成的组合体。词语“多层”指的是由比如通过冷焊操作而被接合起来的层构成的组合体。
在方框B中示出的下一步骤是将所述组合体插入到一个外套中。这可以以多种方式进行。例如，如同附图2中所示出的那样，可以将一个扁平的组合体20插入到一个扁平的管状外套21内。扁平的组合体20可以是由交替的层构成的叠层体，或者一个由交替的层构成的扁平圆柱体。或者，正如附图3中所示出的那样，可以将一个扁平的组合体卷绕成一个圆柱体30并且插入到一个管状外套31内。外套31必须易于在不损坏所述组合体中材料的条件下被去除，比如一根铜管，在硝酸中铜可以比镍或者铝更为快速地发生腐蚀。
第三步骤(方框C)是使得带有外套的组合体发生变形，来减小其横剖面积。如果一个圆柱状组合体被插入到一个管状外套中，那么最好通过模锻操作来产生变形。在模锻操作中的尺寸减小现象是由于相匹配的锥形模的冲击作用造成的，所述外套被插入在锥形模中，并且在所有的侧面受到压缩作用。与滚轧操作相比模锻操作具有三个优点。第一个是能够对带有外套的圆柱体进行径向压缩。对成卷的金属薄片对称施加载荷尽可能地减少了在滚轧操作中常见的由于回弹作用造成的层的分离现象。第二个，也是主要的优点在于，变形是三维的从而能够比在滚轧操作中提供更多的延长，在滚轧操作中变形只是二维的。第三个优点与第二个优点相关。在滚轧操作中，组件的厚度以二倍的关系减小一半，导致双层金属厚度以二倍的关系减小并且其长度以二倍的关系增加。但是，使得一根管子的直径以二倍的关系减小，会使得双层金属的有效厚度以大于二倍的关系减少，并且长度以四倍的关系增加，因为横剖面积以四倍的关系减小。在变形过程中，带有外套的组合体必须被保持低于100℃，并且最好低于25℃。
下一步骤(方框D)是使带有外套的组合体变平，比如通过滚轧压平将锻压变形后的材料变成一个平面状几何形状。可以利用附加的冷轧操作来进一步减小双层金属的厚度，以便易于进行点火和具有较好的动力学特性。在压平操作过程中，所述组合体必须被保持低于100℃，并且最好低于25℃。随后，比如利用化学腐蚀、对外套的边缘进行剪切或者裁切操作来将外套材料去除，从而将反应性多层金属薄板显露出来。
下面的示例用于说明附图1中所示方法的优点。该示例用于对一个镍/铝多层金属薄片进行冷轧操作。如果预期的反应性金属薄片总厚度为1毫米并且双层金属的厚度为0.250微米，那么最好利用相对较薄的镍箔和铝箔来开始机械加工工艺，以限制将初始的双层金属厚度减小至0.250微米所需的滚轧程度。但是，比25微米小的初始双层金属厚度需要非常昂贵的镍箔和铝箔，并且还需要一个带有数以千计的单个金属薄片的叠层体。例如，为了获得预期的最终制品，一个双层金属厚度为25微米、带有4000个双层金属并且总厚度为10厘米的初始金属薄片叠层体，其厚度将需要以100倍的关系减小到1毫米的总厚度。对于大量的层来说，对这种叠层体进行处理和机械加工非常困难，尤其是因为材料温度必须保持在室温左右，以防止层之间发生原子混合现象。
用于实现相同目的的一种更为有效的方式是对一个直径为3.5厘米的圆柱状卷绕双层金属叠层体(在一个铜质外套中)进行模锻操作，并且将其直径减小至0.5厘米，从而以一个处于(3.5/0.5)2＝49与7之间的因数关系来减小双层金属的有效厚度。随后，所制得的0.5厘米金属棒将易于以一个处于2至14之间的因数关系滚轧压平，获得所需的1毫米厚反应性金属条。这种模锻操作相对简单并且易于完成。尽管这种技术会在金属条被压平之后在金属条的宽度方向上有些不均匀，但是变化被控制在外边界处，所述外边界可以根据需要被很容易地去除。锻压变形操作的预期量是使得其横剖面积减小30％至99％，并且最好是减少60％至95％。替代锻压操作，也可以通过金属线材滚轧、金属线材拉拔或者挤压操作来减少其横剖面积。以这种方式进行的横剖面积减小操作通常会将所述层冷焊接成一个多层。
附图1中所示工艺具有较好的经济性，并且能够生产出适用于许多领域的高质量反应性金属薄片。与汽相淀积工艺相比，这种工艺更为便宜并且快捷。其使用更为简单的设备、更为便宜的原材料并且适于进行批量生产。其还能够经济地生产出非常厚的金属薄片(厚度超过500微米)，如果利用传统的汽相淀积工艺来生产这种金属薄片其成本将非常昂贵。
正如在附图4中所示出的那样，利用附图1中所示工艺制成的反应性金属薄片44是一个独立式多层反应性金属薄片，该金属薄片尤其适合用作一个发热源。其包括有一系列交替排布的第一材料46和第二材料48，第二材料48可以与第一材料进行放热反应。与薄膜相比，独立式金属薄片易于表现出其特性，这是因为它们可以被如同“松散”试样(”bulk”sample)那样进行处理。使得反应性金属薄片44具有独立性，大大拓宽了它们的应用领域。因为这种反应性金属薄片无需受制于任何特定用途，它们可以批量生产，来用于任何需要一个自蔓延局部热源的用途中。它们的生产并不局限或者受碍于将一个大的或易损坏的物品放到一个即将由一反应性多层金属薄片涂覆的真空腔室内。此外，独立式金属薄片能够使得传导到基层上的不希望的热量最少化。
根据附图1中所示方法制成的独立式金属薄片可以适用于许多应用场合中，包括结合、点火或者推进。例如，独立式金属薄片可以用于将材料本体(在这里被称作“松散材料(bulk material)”)结合起来形成一个整体式制品。独立式金属薄片可以应用于结合、软焊、硬焊、焊接或者其它用于接合松散材料的用途中。在附图5中示出了一种典型的接合应用，其中两个或者多个松散材料50即将被接合起来。松散材料50可以是陶瓷、金属玻璃、金属/合金、聚合物、复合材料、半导体以及其它形式的材料。在附图5中，接合材料52用于将松散材料50接合起来。接合材料52可以是任何即将发生熔融来将松散材料50接合起来的材料层(或者组合层)。接合材料52可以是由金属玻璃、金属/合金、在功能上递变的层、镍-硼薄膜、软焊料、焊铜、自蔓延焊铜、这些材料的组合物或者其它类似接合材料形成的独立式薄板。
根据本发明的一个优选实施例。反应性金属薄片44被置于接合材料52之间，来形成一个多少有些象三明治的结构。由此形成的反应性金属薄片“三明治”最好在某些位置处(比如端部处、接头处、交叉处等等)被置于松散材料50之间，其中，在所述位置处松散材料50即将被接合起来。可选择地，反应性金属薄片44被置于松散材料50之间，这些松散材料50上已经预先涂敷有接合材料52。
所述接合工艺涉及施加力(在附图5中象征性地由台钳示出)来维持松散材料50、接合材料52及反应性金属薄片44的相对位置。最好，所有组件均为压靠在一起的独立构件。在一个可选择的实施例中，接合材料52被表示为一个带有反应性金属薄片44的复合物。
一旦接合工艺的组件得以定位，将一个刺激物(图示为点燃的火柴55)作用于最好是反应性金属薄片44的一个端部处，来启动多层进行反应。在反应性金属薄片44内部进行的原子混合现象会沿着该反应性金属薄片44的整个长度快速产生足以熔化接合材料52的剧烈热量。在这种状态下，由接合材料52将松散材料50接合起来。此后的短时间内，接合起来的松散材料50将恢复到环境温度(比如室温)并且可以去除所施加的力。
由接合材料52和反应性金属薄片44构成的复合结构可以通过淀积工艺(比如汽相淀积工艺)或者利用接合材料52的机械力(比如冷轧操作)成形到反应性金属薄片44的一个侧面上。随后，另外一个接合材料层通过汽相淀积工艺或者利用机械力在反应性金属薄片44的第二侧面上而与反应性金属薄片44组合起来。
有益的是，可以加入一个浸润/粘附层，以利于润湿用于反应性金属薄片44、松散材料50或者二者兼有的表面。浸润/粘附层能够使得接合材料均匀散布，以确保对松散材料进行均匀接合。浸润/粘附层可以是一个由接合材料(比如焊铜)、钛、锡、金属玻璃等形成的薄层。也可以使用商业供应的合金，比如银-锡、银-铜-钛、铜-钛、铜-锡以及镍-硼。
本发明的优选实施例可以用作具有较大总厚度的独立式反应性金属薄片44。这种反应性金属薄片的总厚度取决于用于形成所述金属薄片的元件层的厚度和数目。小于10微米的金属薄片非常难以进行处理，因为它们趋于自身发生卷绕。100微米级的金属薄片不易弯曲，因此易于进行处理。较厚的金属薄片还能够减少自蔓延反应在金属薄片中熄灭的可能性。在利用反应性金属薄片的接合操作中，必须使得金属薄片的发热速率与热量传导到周围焊铜层和即将形成的接头中的速率保持均衡。如果热量的传导速率大于发热速率，那么所述反应将熄灭，并且无法形成接头。金属薄片越厚越难以熄灭所述反应，这是因为对于相同的热量散失表面来说产生了更多的热量。
更厚的金属薄片可以在更低的反应温度下加以利用，通常能够获得更为稳定的金属薄片。具有较高生成反应温度的金属薄片通常是不稳定和脆的，因此是危险的并且难以使用。例如，脆的金属薄片将易于发生破裂，导致局部过热点(通过释放弹性应变能和摩擦作用)，局部过热点点燃所述金属薄片。由于这种易碎金属薄片在裁切过程中很有可能破裂成无法使用的碎片或者发生点燃现象，所以难以对这种易碎金属薄片进行裁切(比如为了获得特定的接头尺寸)。厚的独立式金属薄片能够克服先前描述过的热急变和密实化问题，热急变和密实化会对传统工艺产生负面影响。两种现象均涉及金属薄片的尺寸快速变化。在反应过程中，传统的金属薄片快速发热并且力图延展到对它们产生约束的基层之外。这将导致产生热急变现象，并且沉积于基层上的金属薄片将会发生脱离，从而导致不均匀并且低效的结合。随着反应的进行，由于化学键的变化会使得金属薄片更为致密。这种密实化现象也会导致从基层上发生脱离现象以及不一致和无效的结合。通过使得反应性金属薄片独立化，可以防止发生脱离现象，并且易于对金属薄片进行操控和处理。从而，这种金属薄片适合于更多的用途。根据一个优选实施例，更厚的反应性金属薄片的厚度为50微米至1厘米。
如同附图6中所示出的那样，金属薄片44可以带有一个或者多个贯穿金属薄片结构的开口或者穿孔62。最好，所述开口62被制成一个横跨金属薄片区域的周期性图案，比如一个矩形阵列。可以采用任何公知方法来形成所述开口。例如，可以通过在金属薄片44上淀积光致抗蚀剂，使光致抗蚀剂形成图案，并且随后穿过形成图案的孔对底部金属薄片进行蚀刻来利用光刻法形成开口62。另外一种示例性技术是在金属薄片44上以物理方式冲压出孔62。最好，所述开口具有10至10000微米的有效直径。(非圆形开口的有效直径是相等面积的圆形开口的直径。)
正如在附图6中所示出的那样，当接合材料52通过金属薄片44发生放热反应而被加热并熔融时，金属薄片44上的开口允许接合材料52，或在某些情况下是松散材料50，挤压穿过这些穿孔62(如同箭头66所示出的那样)。在进行挤压时，一层接合材料52或松散材料50可以与位于独立式金属薄片44另一侧面上的另一层接合材料52或松散材料50发生接触和结合。形成图案的穿孔62增强了松散材料50之间的相互结合以及与反应性金属薄片44的结合，形成更为坚固或者更为均匀一致的结合物。
利用本发明中的一个或者多个实施例，可以更为有实效和有效率地满足多种不同用途。例如，当最终制品，包括所述结合物和起反应的金属薄片层是一种仅由金属玻璃制成的结构时，金属玻璃松散材料能被接合。也可以加入具有不同化学组分、热性能以及其它物理性能的松散材料，这些松散材料历来难以进行结合操作。半导体或者微电子装置可以被结合到线路板或者其它结构上，并且与此同时可以形成多根与所述装置错综复杂地联结的引线。半导体或者微电子装置还可以被气密性封接起来。
这些接合操作通过本发明得到强化，其中，避免或者至少减少了热损坏的可能性，这种可能性通常与诸如锡焊这样的软焊、铜焊这样的硬焊以及焊接操作相关联。
此外，利用由附图1中所示工艺制成的反应性金属薄片，被接合起来的松散材料可以是独立式的。这就意味着在对松散材料进行实际接合操作之前无需直接在独立的松散基层上方淀积任何焊铜层。另外，松散的基层无需预结合反应性金属薄片或者其它预处理操作。所涉及的松散材料可以在进行结合来形成一个牢固并且永久性接头的同时，被简便地牢固固定在一个独立式焊铜层或者独立式反应性金属薄片上。
本发明的实施例允许至少对一种由金属玻璃制成的松散材料进行结合操作。在接合过程中不需要焊铜与所述玻璃协同使用。这是因为反应性金属薄片可以被设计成在反应时直接与金属玻璃结合起来。为了完成这种接合过程，反应性金属薄片可以自身发生反应来形成一种金属玻璃。至于更进一步的细节，请参照下文中的示例3。
本发明的实施例还允许当松散材料包括有微电子或者半导体装置时进行高级结合操作。在将这样一个装置粘结到一个诸如线路板这样的基底层上的过程中，可能会损坏所述装置是一个必须考虑的因素。通过利用独立式反应性金属薄片来将所述装置接合到所述基底层上，所产生的能够损坏所述装置或者相邻组件的热量较少。半导体装置可以以更自由和方便的方式被置于所述基底层上。可以利用特定的金属薄片组成，比如镍/铝或者蒙乃尔高强合金/铝。这种组合的金属薄片不仅远比过去的金属薄片易于进行处理，而且由镍、铜和铝形成的组合物能够使得独立式金属薄片具有更高的热导率和电导率。
在另一实施例中反应性多层焊铜(比如由交替排布的镍-铜合金层、铝层及钛-锆-铪合金层形成的各层)可以用作接合材料，该接合材料与用于接合操作中的反应性金属薄片协同使用。当所述反应性多层发生混合形成接合材料时，反应性多层焊铜将提供一个额外的能量供应源。反应性多层金属薄片与反应性多层焊铜的组合使得可以使用在无金属薄片条件下无法自蔓延的反应性焊铜。
附图7A是一个示意图，描述了在用于形成反应性金属薄片的叠层体中加入能延展的金属的工艺。能延展的金属网格70或者金属粉末被包括于某些或者所有的组成层46、48之间。随后，如同附图1中所描述的那样对所述叠层体进行处理。附图7B示出了在将反应性金属薄片置于即将发生结合并且随后进行反应的两个组件之间之后，所制得的能延展的金属筋71或者支柱的构造。这种能延展的能延展的支柱或者筋71的存在，用于阻止在通常易碎的金属间反应制品中发生龟裂，并且提高接头的总体机械稳定性和可靠性。
附图1中所示出的工艺还可以用于生产包括有氧化物层和某些将以放热方式对氧化物层的氧进行分离去除的材料层的多层金属薄片。除了产生热量之外，金属薄片还可以生产出一种能延展的反应制品，该能延展的反应制品可以用作一种如同焊铜和焊锡那样的接合材料。例如，利通过将图1中所示操作应用于铝/铜氧化物层的组合体而制得的金属薄片会发生反应，来生产出用作接合材料的铜。参见下面所述的示例2。
在利用附图1中所示工艺制取一个较厚的多层金属薄片之后，人们可以通过在该较厚的多层上汽相淀积一系列相对较薄的反应性层而有利于对该较厚的薄层进行点火操作。在使用过程中，较薄的层能够较为快速地燃烧并且横向蔓延的燃烧沿纵向点燃较厚的层。可选择地，人们可以利用附图1中所示工艺制取出厚的和薄的多层金属薄片，并且通过冷轧操作将它们层压在一起。
示例
通过研究下面的特定示例将可以更好地理解本发明。
            示例1--机械成形镍/铝多层体
通过叠置交替排布的镍箔层和铝箔层来制备出一种样品。随后，将该叠层体轧制和插入到一个铜质外套内并且封闭起来，其中所述铜质外套随后反复经受初步抽气操作，并且回填入氩气。带有外套的组合体随后被锻压成一个较小直径的金属棒，并且滚轧成扁平状。某些样品(在滚轧成扁平之前)通过利用50％硝酸对铜进行腐蚀而从它们的外套内释放出来，进行再裹包、再锻压然后进行扁压操作，以便用更大的变形(较小的双层金属厚度)，获得相同厚度的金属条。铜质外套随后通过腐蚀工艺而被去除，并且对可利用的混合热量(利用示差的扫描量热法)、反应速率、力学性能(拉伸测试)和微观结构进行分析研究。首先利用12微米厚的镍箔和18微米厚的铝箔制取五根金属条(100厘米×10厘米)，各层以交替方式叠置起来形成一个100厘米长、10厘米宽的5个双层的金属叠层体。这种细长的金属条被卷绕成一个圆周为6厘米的金属棒，将端部去除并且随后进行压扁操作形成一个10厘米×3厘米具有200个双层金属的叠层体。随后，对该叠层体进行短向滚轧，形成一个10厘米长的卷状物，该卷状物被装配到一个具有合适尺寸的铜质管子内。将管子的外尺寸从0.875”逐渐锻压至0.187”。随后对这种较小的金属棒进行冷轧操作，来达到40至250微米的不同厚度。
附图8是一个显微照片，描绘了反应性金属薄片的微观结构。在该附图所示出的微观结构内显现出了交替排布的铝层(80)和镍层(81)。由此制备出的反应性金属薄片在点燃时能够产生出大量的热量，这也可以通过示差扫描量热分析得以确认。还发现所述金属薄片能延展并且能够弯曲，允许进行裁切、冲压或者进一步的加工成形操作。
利用附图1中所示工艺制成的经滚轧反应性多层金属薄片在表面形貌(surface topography)、层次(layering)、晶粒尺寸和纹理组织方面不同于汽相淀积而成的金属薄片。在表面形貌方面，与汽相淀积而成的金属薄片相比，经过滚轧的金属薄片趋于具有一个更粗糙表面(均方根粗糙度大于0.1微米)。在层次方面，经过滚轧的金属薄片中的薄层沿着该金属片的长度方向和宽度方向厚度发生明显变化。实际上，具有较小塑性顺从性的薄板(比如镍)将趋于断裂成碎片，这些碎片的横剖面如同细长颗粒那样。所述碎片将在长度、宽度和厚度上从百分之十至百分之几百进行变化。经过滚轧的金属薄片具有沿着滚轧方向细长的颗粒(“薄饼结构(pancake structure)”的颗粒)。相反，汽相淀积而成的金属薄片趋于具有其宽度和长度类似于或者小于它们厚度的颗粒，所述厚度取决于层的厚度。
纹理组织指的是在晶体中平面与方向的晶体学排布。在冷锻压和冷轧而成的金属薄片中，面心立方体(FCC)通常大部分与它们的{110}平面和平行于变形方向的<112>方向相平齐。体心立方体(BCC)通常大部分与{100}平面和平行于形变方向的<110>方向相对齐，密排六方体(HCP)与它们的{0001}平面和平行于变形方向的<2 1 10>方向相平齐。
               示例2--铝/氧化铜多层的机械成形
铝/氧化铜反应所产生的热量大约是铝/镍混合反应所释放热量的3倍。对于许多用途来说这些热量太多，在反应过程中所达到的温度如此高以致于大部分制品会在熔融金属的“雨滴(shower)”中发生汽化和爆炸。尽管这有助于燃烧和推进，但是用于结合操作的理想制品比如是恰好能够使得反应性制品仅仅发生液化的制品。因此，减小了制品发生成团或者汽化的趋势，但是仍旧能够促使匹配表面发生湿润。此外，金属与陶瓷的力学固结作用通常极其困难。通过包括一种稀释剂(质量比高达90％)，能够实现前述的两个目的。通过利用这种步骤，最终的反应温度得以降低，并且即将固结起来的材料的力学兼容性得以增强。
为了制取这种多层，我们需要利用由氧化反应物(在这种情况下是铝)制成的薄层和由还原制品(在这种情况下是铜)制成的薄层。接着，铜箔在一个燃烧炉中的流动空气环境内得以氧化(为了生产不同化合物可以对环境进行改变)。目前，铜箔是一个三明治结构，该三明治结构由带有氧化铜表面涂层的铜质内层构成。氧化铜涂层的厚度和质量可以通过对燃烧炉温度和加热与冷却的时间-温度曲线进行修正而加以控制。氧化铜的冷加工性能(尤其是当涂层较薄并且在生长过程中温度不会快速变化时)明显增强并且与铜质稀释剂一致地发生变形。在一个载体(铜)上生长所述反应物(CuO)还能够使得更易于对前体材料进行处理(CuO是易碎的并且在进行折叠或者加工时将变成粉末)。从而，铝和CuO/Cu/CuO金属薄片可以被叠置起来，并且利用结合附图1所描述的工艺制成-个反应性多层。
示例3--非晶体形反应性金属薄片(Amorphous-Forming Reactive
                     Foils)的机械制造工艺
通过叠置包括有铝、镍、铜、钛、锆、铪薄板或者镍-铜或钛-锆-铪的合金薄板的金属薄板，并且如前所述那样通过对这些叠层体进行裹包、锻压和冷轧操作，可以制得将在室温处或者室温附近处(＜200℃)发生自蔓延的反应性金属薄片。这些金属薄片将发生反应而形成非晶体材料。必须注意的是，要在锻压和冷轧步骤中将叠层体保持在室温处或者低于室温，以减少在生产过程中的能量损失。最终的反应性金属薄片具有若干有益用途：
1) 形成松散的金属玻璃：前述经过锻压和滚轧而成的金属薄片可以被用于以自蔓延方式形成松散的金属玻璃。
2) 接合操作：尽管独立式反应性金属薄片(具有成形反应的金属薄片、具有氧化还原反应的金属薄片或者通过反应变成非晶体的金属薄片)总体上可以在无需焊铜的条件下将松散的金属玻璃粘结到另一组成部分上，但是前述的反应性金属薄片(利用铝、镍、铜、钛、锆、铪薄板或者镍-铜或钛-锆-铪合金薄板机械形成的金属薄片)可以将金属玻璃松散材料接合成一个仅由金属玻璃制成的单一整体式结构，其中包括有结合物和起反应的金属薄片层。
3) 反应性接合材料：前述的反应性多层金属薄片还可以用作一种接合材料，该接合材料与一种用于接合操作中的反应性金属薄片协同使用。除了由所述反应性金属薄片提供的能量之外，由于所述层发生混合，反应性多层焊铜将提供一个能量供应源并且形成所述接合材料。反应性多层金属薄片与反应性多层焊铜的组合体允许使用在无金属薄片的条件下无法进行自蔓延的反应性焊铜，并且使得能够利用较少的总热量来应用所述反应性多层金属薄片。
应该明白的是，前述实施例仅仅是许多可能存在的特定实施例中的一部分，这些实施例均能够体现本发明中的基本原理。在不脱落本发明的技术构思和保护范围的条件下，本技术领域中的技术人员可以做出多种不同的其它方案。

Claims (31)

1.一种用于生产反应性多层金属薄片的方法，包括下述步骤：
提供一个由交替排布的材料层构成的组合体，所述交替排布的材料层的材料能进行放热反应；
将所述组合体插入到一个外套中；
使得带有外套的组合体发生变形，来减小其横剖面积；
使经过形变处理后的带有外套的组合体变成扁平；以及
将所述外套去除。
2.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的所述组合体是一个金属薄片的叠层体。
3.如权利要求1中所述的方法，还包括在将所述组合体插入到所述外套中之前，将该组合体卷绕成一个圆柱体。
4.如权利要求3中所述的方法，还包括在将所述圆柱体插入到所述外套中之前，将该圆柱体压成扁平。
5.如权利要求1中所述的方法，其特征在于：使得带有外套的组合体发生变形的操作包括使得该带有外套的组合体发生径向变形。
6.如权利要求5中所述的方法，其特征在于：所述径向形变操作是通过模锻、拉拔或者挤压操作完成的。
7.如权利要求1中所述的方法，其特征在于：使经过变形处理的带有外套的组合体变平的操作包括有滚轧操作。
8.如权利要求1中所述的方法，其特征在于：在变形过程中带有外套的组合体被保持处在一个低于100℃的温度。
9.如权利要求1中所述的方法，其特征在于：在使变扁平的过程中带有外套的组合体被保持在一个低于100℃的温度。
10.如权利要求1中所述的方法，其特征在于：所述外套是通过化学腐蚀工艺被去除。
11.如权利要求1中所述的方法，其特征在于：去除所述外套的操作包括对外套进行剪切操作。
12.如权利要求1中所述的方法，其特征在于：由交替排布的材料层构成的组合体中包括有交替排布的由金属或者合金制成的层。
13.如权利要求1中所述的方法，其特征在于：所述外套由金属或者合金构成。
14.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的叠层体中包括有与含还原材料的层交替排布的含氧化制品的层。
15.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的组合体还包括有一个或者多个接合材料层。
16.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的叠层体中包括有与含还原材料的层交替排布的含成形制品的层。
17.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的叠层体中包括有反应物的颗粒。
18.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的叠层体中包括有稀释剂。
19.如权利要求1中所述的方法，其特征在于：由交替排布的层构成的叠层体在该叠层体内的层之间包括有能延展的金属网或者粉末。
20.如权利要求1中所述的方法，其特征在于：一个或者多个交替排布的层由沉积于一稀释材料层的上反应物材料层构成。
21.一种反应性多层金属薄片，包括有一个经过变形和层压处理后的叠层体，该叠层体由交替排布的材料层构成，其中，交替排布的材料层能够进行放热反应，并且所述叠层体在压力作用下变形为一个薄板，该薄板带有利用冷焊操作层压在一起的层。
22.如权利要求21中所述的反应性多层金属薄片，还包括有一个或者多个粘附于所述薄板上的接合材料层。
23.如权利要求21中所述的反应性多层金属薄片，还包括有粘附于所述薄板顶部和底部上的接合材料层。
24.如权利要求21中所述的反应性多层金属薄片，还包括有多个贯穿所述薄板的开口，这些开口的有效直径为10至10000微米。
25.如权利要求24中所述的反应性多层金属薄片，其特征在于：所述开口中填充有能延展的金属。
26.如权利要求21中所述的反应性多层金属薄片，其特征在于：所述交替排布的层包括有与镍或者镍合金层交替排布的铝或者铝合金层。
27.如权利要求21中所述的反应性多层金属薄片，其特征在于：所述交替排布的薄层通过氧化还原作用发生反应。
28.如权利要求21中所述的反应性多层金属薄片，其特征在于：所述交替排布的层通过去氧生成作用(reduction-formation)发生反应。
29.如权利要求21中所述的反应性多层金属薄片，其特征在于：所述交替排布的层包括有与氧化铜层交替排布的铝或者铝合金层。
30.如权利要求21中所述的反应性多层金属薄片，其特征在于：由交替排布的层构成的叠层体中包括有用于吸收能量的稀释材料，从而降低反应温度。
31.一种用于将第一本体结合到第二本体上的方法，包括下述步骤：
在第一本体与第二本体之间设置一个独立式反应性多层金属薄片，该金属薄片包括有一个经过变形处理后的组合体，该组合体由可以进行放热反应的材料制成，这些材料通过变形操作被层压在一起；
将所述本体压贴到所述反应性金属薄片上；以及
点燃所述金属薄片。
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