CN1326134C - 包含防腐银合金的光学数据存储器和可记录存储媒体 - Google Patents

包含防腐银合金的光学数据存储器和可记录存储媒体 Download PDF

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CN1326134C
CN1326134C CNB038189925A CN03818992A CN1326134C CN 1326134 C CN1326134 C CN 1326134C CN B038189925 A CNB038189925 A CN B038189925A CN 03818992 A CN03818992 A CN 03818992A CN 1326134 C CN1326134 C CN 1326134C
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silver
optical data
storage media
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base alloy
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海纳·利希滕贝格尔
德里克·L·布朗
斯科特·豪卢什卡
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Abstract

一种光学数据记录与储存媒体,包括由银合金形成的一个反射层,除银合金外,包含约0.1到4.0wt%的钐(Sm),钐含量根据合金总重而定。

Description

包含防腐银合金的光学数据存储器和可记录存储媒体
技术领域
本发明涉及光学数据储存,尤其是包含由反应性银合金形成反射层的储存媒体,特别是含稀有金属钐的银合金。
背景技术
反射金属薄膜被用于制造光学储存媒体。这些金属薄层被溅镀在有图案的透明圆盘上以反射激光光源。反射的激光被读取为特定长度的明暗斑块,转换为电子信号,并变换为与音乐、电影,以及数据相关的影像和声音。所有光学媒体形式,包括激光唱片(CD)、影碟(LD),以及数字激光视盘(DVD),使用至少一个单一的反射金属层L1,铝是这层的最佳金属选择。更先进的光学媒体技术利用多重反射层以增加媒体的储存容量。例如,许多DVD如DVD-9、DVD-14,以及DVD-18,包含两个反射层,让两层的信息能从圆盘的一面被读取。第二层,称为L0半反射层,必须足够薄,基本上是少于10nm,让在下面的L1层能被读取,但它必须仍可充分反射(反射性大约18%到30%)以被读取。该圆盘可进一步包括一个或多个从与L1和L0层同一面被读取的附加的半反射层。
包括两个反射层的DVD的结构和读取方式如图1所示。
当数字数据从光学储存媒体被读取时,利用一个内部时钟计时并转换为一个高频电子信号来读取凹坑的长度(基本上有九种不同长度),该电子信号被删截以产生方形波并转化为一个二进制电子数据光束。
因塑造聚碳酸酯或整个凹坑不完整的金属化而导致沟纹长度的变动可能造成在解析激光反射的数据时发生错误。对光学媒体应用而言,解析数据的电子电路特别设计为允许一个特定数量的错误。对光学媒体数据有四个主要的错误指标。这些重要参数被归类为:
1)PI-在一个指定范内围内不能读取的凹坑总数;但工业标准允许280个瑕疵,许多公司将这个参数维持在最大值100。
2)抖动-相比于内部时钟的凹坑或坑间平台长度的定时变化;工业最大值是8%。
3)反射性-从凹坑反射的激光百分比;工业标准为18%到30%。
4)I-14-最长凹坑长度的变动;在一次回转内工业标准少于0.15%且圆盘内少于0.33%。
用于制作聚碳酸酯圆盘的母盘,聚碳酸酯,以及反射材料的初始品质,对制造精确的数据是很重要的。金属化材料不只必须能使沉积与反射性能一致,它也必须能填满储存数据的数据储存凹坑。另外,工业上将圆盘置于一个特定温度与湿度中达一段特定期间以进行环境测试。这项测试的工业标准为温度70℃、50%相对湿度,时间达96小时(70/50/96)。许多公司已采用更严格的内部规格以将温度升高至80℃且湿度升高至85%时间达96小时(80/85/96)。
在制造后,数据储存圆盘被监测有无错误,它首先被暴露在环境测试室内,接着再被分析有无错误。如在任何测试阶段根据错误率的工业标准有任何故障,或显著的恶化,即使没有实际的缺点,在环境测试后将导致废弃。为达到反射金属化,环境测试要求抗腐蚀材料。一般而言厚度20nm的铝作为完全反射层是适当的,但在环境暴露后,可能需要提供厚度为40nm的铝作为完全反射层,因为原始铝层的一半厚度在这个环境测试中会被变换为透明的铝氧化物。值得注意的是半反射层更加重要,因为它表面的厚度与反射品质在环境暴露期间不会被变更超过原始相关数值约10%。
除上述提及的测试外,尚有与紫外线或日光曝晒相关的非工业规格。已知以银合金制成的圆盘在日光下可能褪色,尽管此反应的化学原理尚未被完全弄清楚,但大致是由用于半反射层的银合金化合物、以及用于将它贴在完全反射层的黏着剂造成的。只要半反射层或完全反射层的反射性落在18%以下,该圆盘便被视为故障,完全反射层透过黏着剂及半反射层被检视。
铝、金、硅、以及银合金已被成功地用于制造光学储存媒体反射层。由于铝的低成本、杰出的反射性以及在聚合体材质上的溅镀特性,对反射性涂层而言,它是格外适合的金属,当只有一个反射数据层时它几乎是专用的金属,而且也被用于形成两层式DVD上完全反射的L1层。但是,铝容易被氧化,因此它的反射性能可能因环境暴露而减弱。这种氧化作用造成除完全反射层之外的铝完全无法被使用,完全反射层可沉积的较半反射层为多。金与硅是被用于DVD结构的首选材料,但这两种材料均具有重大的缺点。金提供优异的红激光反射性、优异的溅镀特性,以及极佳的抗腐蚀性,但成本极高。硅也具反射性且抗腐蚀,但溅镀不像其它金属一样有效。再者,硅是脆性的,因此在热循环及机械式屈曲时可能爆裂,以至精细的数据无法被读取。美国专利号5,640,382说明了DVD数据储存圆盘的结构,且美国专利号5,171,392说明了用于半反射数据储存层的金与硅;这些专利的公开在此引作参考。
银,和金一样,具有优异的溅镀特性与反射性,但纯银的抗腐蚀性不足以用作半反射层。已耗费相当多的努力以让银有足够的抗腐蚀,以便用于半反射层,如美国专利号6,280,811、6,292,457,以及6,351,446中所述。这些专利的公开在此引作参考。这些专利说明了供光学媒体使用、以银为主的合金,其抗腐蚀性由添加其它贵金属来加以改善,例如钯、铂,以及金。很明显地较只用金便宜很多,但将这些贵金属加到含量最高达30wt%的银上,使它们的成本较纯银显著增加。
对光学数据记录与储存媒体的制造而言,对不需包含更贵的贵金属,具有一致的溅镀特性与改善的抗腐蚀性的银合金,具有不间断的需求。这项需求由本发明的合金符合,其特性让它们特别适合用于光学数据记录与储存媒体,尤其是用于DVD的半反射层内。
发明内容
本发明是指一种光学数据记录与储存媒体,包含一由银合金形成的反射层,根据合金的总重,所述银基合金含有至少约97wt%的银,除银之外,并含有约0.1到约3.0wt%的钐(Sm)。
附图说明
图1是描述两个反射层的光学数据储存圆盘的示意图,其一是薄半反射层,以及它们在圆盘内的位置。
图2是与记录在光学数据储存圆盘上的数字数据相对应的凹坑与坑间平台的示意图,以及由该层产生的反射信号。
图3是显示银、铝以及金在可见光谱上的金属反射性的图表。
图4是电子信号从光学媒体储存圆盘上被读取的示意图。
图5是各种光学媒体格式数据轨道的图解。
具体实施方式
纯银具有优异的反射性,但其抗腐蚀性不足以被用作多层式光学数据储存圆盘内的半反射层。少量特定的易氧化的金属,尤其是稀有金属钐(Sm),被添加至银上可改善它的抗腐蚀性,同时维持它令人满意的反射性,藉此提供一种用于光学记录与储存媒体的反射层的令人满意的材料。虽然本发明的合金特别适合用于薄膜半反射层,但用于单层或多层式媒体的完全反射层时,不论是用在圆盘内或用在其它媒体格式内,它们也可能是有所帮助的,。
图1概要式描述了一包含反射层L1与L0的光学数据储存圆盘。反射层L1是完全反射层且一般而言是由铝形成。半反射层L0是由本发明的银合金形成。从L1层反射的激光光源而来的光被称为RL1;同样的,从L0层反射的光被称为RL0。反射的光RL1和RL0被检测器感应。应注意的是出自雷射光源的光必须穿透半反射层L0两次以读取L1层。
在圆盘D、第1层及第3层中,一般而言是由塑料如聚碳酸酯或聚酯(甲基丙烯酸甲酯,PMMA)形成的,压印上由凹坑与坑间平台组成的数字信息。第2层为一黏着层,一般而言包含一紫外线硬化的环氧材质,被用于连结第1层和第3层。
图2概要图解储存在光学数据圆盘D上的信息的数字解析。坑间平台离激光器与检测器有一段距离,以让反射的信号同相地返回检测器(明),同时凹坑离激光器及检测器有一第二距离,以让反射的信号不同相地返回检测器(暗)。
图3显示数种重要金属---银、铝,与金---在可见光谱上的反射性。大部份的光学数据圆盘在可见光谱的红色部份内读取大约650nm的光波。但是,最近以来,发出蓝光的激光二极管在市面上已可买到,能储存与读取密集得多的数据。如图3所示,银贯穿整个可见光谱显现出高反射性。
图4图解从光学媒体储存圆盘读取的正弦电子信号,描述它如何被删截并与内部时钟比较以辨认脉冲长度及圆盘上包含的数据。
图5是CD、DVD以及蓝光光学媒体格式上用于数据储存的数据轨道与凹坑的图解。新的蓝色激光器格式,利用一较高频率(较高时钟率)的激光以用两轨间较小的距离来识别较小的数据凹坑,可容纳原来使用红色激光的圆盘上五倍的数据,使它对高清晰度的电视(HDTV)格式特别有用。由本发明的银合金形成的反射层的光学数据记录与储存圆盘可与蓝色激光器并用。
根据本发明形成的以银为主的抗腐蚀性合金,包括约0.1到约4.0wt%的稀有金属钐(Sm);更好一点,钐含量为约0.2到约1.0wt%;再更好一点,钐含量为约0.25到约0.35wt%,钐含量依合金的总重而定。与其它反应性稀有金属相较,钐(Sm)的高溶解度让它能被加在相当大数量的金属内而不会形成第二相,以避免在溅镀期间变成颗粒并在反射性涂层内造成瑕疵。一个多相合金可能溅镀为一个单相层,但如果涂层不像单一相的材料那样稳定,则热暴露可能导致第二相的沉淀,且这也将导致瑕疵,尤其是在恶劣的测试条件下。例如,包含一个半反射层的银合金内稀有金属的相的分离可能造成暗斑并导致光学数据错误。
除了展现良好的银溶解度外,也很令人满意的是这个添加的稀有金属也对空气展现高活泼性。在银合金内加入钐(Sm)具有高反应性,已被发现以在处于严格环境测试中的DVD内产生与纯银相较为高的保护效果。稀有金属的溶解度限度与相关的活泼性见下表1:
表1
  元素     溶解度     活泼性   元素     溶解度     活泼性
  镧(La)     0.06     高   钆(Gd)     1.4     中
  铈(Ce)     0.06     高   钺(Tb)     1.6     中
  镨(Pr)     0.05     高   镝(Dy)     1.9     中
  钕(Nd)     0.25     高   钬(Ho)     2.4     中
  钐(Sm)     0.35*     高   铒(Er)     5.5     中
  铕(Eu)     0.0     高   铥(Tm)     7.0     中
  镏(Lu)     9.0     中
*在我们研究中我们根据显微照相检验判断钐在银中的正确溶解度是约0.35wt%,在参考来源中的引证通常少于1.4wt%。
如表1所示,在具高度活泼性的稀有金属中,钐(Sm)在银中有最高的溶解度。并且,由于它的高活泼性,添加少量的钐(Sm)可提供令人满意的高度抗腐蚀性。美国专利申请公开号2002/0150772描述了稀有金属钕(Nd)被加入在以银为主的合金内,其公开在此引作参考。但,如表1所示,钕(Nd)在银中的溶解度实质上小于钐(Sm)。
铜(Cu)也视需要被包括在本发明的银合金内以促进它们的加工制造特性,并改进它们暴露在严格环境测试条件时的耐储时间与它们的抗腐蚀性。包括在该合金内的铜(Cu)的总数,根据合金总重,以约0.2到约2.0wt%较佳,约0.25到约1.0wt%尤佳。
钛(Ti),在银中有良好的溶解度(2wt%),但它实际上不增加抗腐蚀性,并且因为它在熔化与铸成合金期间的除污效果,它也视需要被包括在本发明的银合金内。它也是用于溅镀的铸造合金在轧制和热处理期间的精粒细化剂。包括在该合金内钛(Ti)的量,根据合金总重,以约0.05到约0.5wt%为佳,约0.1到约0.3wt%更佳。
锰(Mn),虽然它可能只添加少量的抗腐蚀性,但它在银中有高度溶解度(33wt%)因此也可视需要包括在本发明的银合金内,以提供溅镀特性反射性控制的改善。包括在合金内锰(Mn)的量,根据合金总重,以约0.1到约1.5wt%为佳,约0.2到约0.8wt%更佳。
铝(Al)也具有良好的银溶解度(6wt%),也视需要被包括在本发明的银合金内以改善反射性能。包括在合金内铝(Al)的量,根据合金总重,约0.1到约0.8wt%为佳,约0.2到约0.4 wt%更佳。
钐(Sm)被包括在本发明以银为主的合金内,根据合金总重,数量不会多于约4.0wt%。当钐(Sm)的添加数量大于约4.0wt%时,可能负面影响银反射性并因而影响半反射层。
基于进一步增加抗腐蚀性的目的,本发明的银合金也可视需要包括少量的贵金属如金、钯、铂或其混合物,根据合金总重,它们相加的量最高可达约2.5wt%为佳。
薄半反射层可藉由本领域内熟知的溅镀技术从本发明的合金被形成。下列有用的银合金范例被描述以说明本发明的范围:
例1:包含约3.0wt%钐的银合金;
例2:包含约1.0wt%钐的银合金;
例3:包含约0.5wt%钐与约0.5wt%钛的银合金;
例4:包含约0.3wt%钐与约1.0wt%铜的银合金;
例5:包含约1.5wt%钐与约0.5wt%锰的银合金;
例6:包含约0.7wt%钐与约0.4wt%铝的银合金;
例7:包含约0.1wt%钐、约1.0wt%铜,与约0.5wt%钛的银合金;
例8:包含约0.9wt%钐、约0.1wt%钛,与约1.0wt%锰的银合金;
例9:包含约0.3wt%钐、约0.7wt%铜,与约0.7wt%铂的银合金;
例10:包含约0.3wt%钐、约0.7wt%铜,与约0.7wt%钯的银合金;
例11:包含约0.3wt%钐、约0.5wt%钛,与约0.5wt%金的银合金;
例12:包含约1.0wt%钐、约0.3wt%锰,与约0.3wt%钯的银合金;
例13:包含约0.5wt%钐、约1.0wt%铜、约0.5wt%钛,与约1.0wt%锰的银合金;
例14:包含约0.3wt%钐、约0.7wt%铜、约0.2wt%钛,与约0.5wt%钛的银合金。
下表2包含测试数据,显示了包含由含钐(Sm)的银合金制成的半反射层的DVD,以及各种对照的DVD的测试数据。每种合金的三种测试条件为:1)在制备DVD后短暂运作的一项初始测试;2)70/50/96-将DVD暴露在室温70℃、50%相对湿度(RH)达96小时后进行的一项测试;3)80/85/96-将DVD暴露在室温80℃、85%相对湿度(RH)达96小时后进行的一项测试。如前所述,PI是特定范围内有瑕疵的凹坑的工业标准术语,抖动由结合因素造成并限制为8%,且I-14是根据内部时钟的长度而定最长凹坑的测量。测试数据依每项条件与标准以通过(P)与不合格(F)的标记方式被呈现。DVD环境测试目前的要求是根据较不严格的测试70/50/96。但是,大部份的主要DVD复制商为内部品质保证使用较严格的80/85/96测试。
如在表2中第一个对照DVD C-1字段内所示,一个纯银的半反射层几乎通过工业规格,只在70/50/96测试后因抖动不合格。但是,在80/85/96暴露条件后,控制C-1不再能被读取。
在对照DVD C-2内包括0.7wt%铜(Cu)的银半反射层中,在标准工业测试下将剧跳改善至一个通过的结果,但较严格的80/85/96暴在所所有测试中均导致不合格。
在对照DVD C-3与C-4内的半反射层由银-铜合金形成,它们各自进一步分别包括0.25wt%铝(Al)与0.75wt%锰(Mn)。这些金属的包含物在80/85/96暴露条件下在PI与抖动测试内均导致通过的结果。但C-3与C-4在最初的I-14中与在两项环境暴露条件下不合格。
在对照DVD C-5与C-6内的半反射层由银-铜合金形成,它们各自进一步分别包括0.75wt%的中度空气反应性稀有金属镝(Dy)与1.0wt%更具空气反应性的稀有金属钕(Nd)。与DVD C-3与C-4相同,对照DVD C-5与C-6在最初的I-14中与在两项环境暴露条件下不合格。另外,DVD C-5在80/85/96 PI测试也不合格。
DVD C-7,C-8,与C-9由包含0.7wt%铜(Cu)与0.5wt%锰(Mn)的银合金形成,另外,它们各自还分别包括0.25wt%的稀有金属镝(Dy)、钕(Nd)以及铈(Ce)。类似的结果从C-7、C-8以及C-9取得;各自通过所有测试,PI与80/85/96暴露条件下的抖动除外。依C-5与C-6的对照所示,DVD C-7、C-8与C-9中的内含物锰(Mn)导致在所有测试条件下改善的I-14结果。
本发明的DVD的I-1与I-2,在银半反射层内分别包括1.0与0.25wt%的钐(Sm),在70/50/96暴露条件下全部三种标准工业测试内产生通过的结果,但在80/85/96条件下在同样的测试内不合格。
本发明的数字激光视盘I-3,其中半反射层由包含0.25wt%钐(Sm)与0.7wt%铜(Cu)的银合金形成,在标准的70/50/96暴露条件与更严格的80/85/96条件下,在三项测试中均产生通过的结果。
在70/50/96与80/85/96的条件下,类似的优异测试结果被本项发明的数字激光视盘的I-4与I-5显示,其中银合金包含,除了钐(Sm)与铜(Cu)之外,分别包括0.5wt%锰(Mn)0.2wt%钛(Ti)。
本发明半反射层由含钐(Sm)银合金形成的DVDI-3、I-4,与I-5的结果,与半反射层由包含其它稀有金属,特别是镝(Dy)、钕(Nd)以及铈(Ce),形成的DVD C-5到C-9相较,显示出钐(Sm)即使在严格的暴露条件下较其它稀有金属更能保护数字激光视盘免于损坏的优点。
本发明的DVD I-6与DVDI-3类似,除了它的银合金包含更高浓度的钐(Sm)(0.75wt%对0.25wt%)外;在这种合金中铜的含量是相同的(均为0.7wt%)。DVD I-6也产许非常良好的测试结果,只在严格的80/85/96条件下在PI测试不合格。
同样的,本发明的DVD I-7,与DVD I-1包含同样浓度的钐(Sm),1.0wt%,但也包括0.5wt%的铜(Cu),产生非常良好的结果,只在严格的80/85/96条件下在I-14测试不合格。
本发明的DVD I-8与DVD I-3类似,不同之处在于它的银合金包含相当高浓度的钐(Sm)(4.0wt%对0.25wt%);而在两种合金中铜浓度相同(均为0.7wt%)。DVD I-8在工业标准条件下通过全部三种测试,但在严格的80/85/96条件下在PI和I-14测试不合格。
如表2中呈现的结果所示,包含的钐(Sm)程度最好最高达到约1.0wt%,约0.25到约0.35wt%尤佳,在组成DVD半反射层的银合金中,在严格的环境测试条件下提供有益的结果。进一步包含数量最好最高达约1.0wt%的铜(Cu),可在含钐(Sm)的银合金中提高优点。
本发明已被详细描述,特别是参考某些较佳具体实施例,但可被理解的是在本发明的要意与范围内变动与修正可被影响,该范围由以下权利要求所限定。

Claims (28)

1、一种光学数据记录与储存媒体,其特征在于包括由银基合金形成的一个反射层,基于所述合金的总重,所述银基合金含有至少97wt%的银,并含有0.1到3.0wt%的钐(Sm)。
2、如权利要求1所述的光学数据记录与储存媒体,其特征在于,基于所述合金的总重,所述银基合金含有0.2到1.0wt%的钐(Sm)。
3、如权利要求1所述的光学数据记录与储存媒体,其特征在于,基于所述合金的总重,所述银基合金含有0.25到0.35wt%的钐(Sm)。
4、如权利要求1所述的光学数据记录与储存媒体,其特征在于,基于所述合金的总重,所述银基合金还包含铜(Cu)。
5、如权利要求4所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.2到2.0wt%的铜(Cu)。
6、如权利要求5所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.25到1.0wt%的铜(Cu)。
7、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述银基合金还包含钛(Ti)。
8、如权利要求7所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.05到0.5wt%的钛(Ti)。
9、如权利要求8所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.1到0.3wt%的钛(Ti)。
10、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述银基合金还包含锰(Mn)。
11、如权利要求10所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.1到1.5wt%的锰(Mn)。
12、如权利要求11所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.2到0.8wt%的锰(Mn)。
13、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述银基合金还包含铝(Al)。
14、如权利要求13所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.1到0.8wt%的铝(Al)。
15、如权利要求14所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.2到0.4wt%的铝(Al)。
16、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述银基合金还包含由金(Au)、钯(Pd)、铂(Pt)及其混合物组成的群组中选取的一种贵金属,总量为合金的2.5wt%。
17、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述银基合金还包含铜(Cu)、钛(Ti)以及锰(Mn)。
18、如权利要求17所述的光学数据记录与储存媒体,其特征在于,所述银基合金含有0.25到0.35wt%的钐(Sm)、0.25到1.0wt%的铜(Cu)、0.1到0.3wt%的钛(Ti),以及0.2到0.8wt%的锰(Mn),其余为银(Ag)。
19、如权利要求18所述的光学数据记录与储存媒体,其特征在于,所述银基合金基本上含有0.3wt%的钐(Sm)、0.7wt%的铜(Cu)、0.2wt%的钛(Ti),以及0.5wt%的锰(Mn),其余为银(Ag)。
20、如权利要求1所述的光学数据记录与储存媒体,其特征在于,所述反射层是一个薄膜半反射层。
21、如权利要求1所述的光学数据记录与储存媒体,其特征在于,还包括一个与所述反射层相邻接的第二反射层。
22、如权利要求1所述的光学数据记录与储存媒体,其特征在于,该媒体为一个DVD。
23、如权利要求1所述的光学数据记录与储存媒体,其特征在于,该媒体为一个可由高频蓝光激光读取的高密度磁盘。
24、一种银基合金,其特征在于,包含银以及基于合金总重的0.1到3.0wt%的钐(Sm)。
25、如权利要求24所述的银基合金,其特征在于,基于合金总重,含有0.25到0.35wt%的钐(Sm)。
26、如权利要求24所述的银基合金,其特征在于,还包含一种金属,该金属选自由铜(Cu)、钛(Ti)、锰(Mn)、铝(Al)、金(Au)、钯(Pd)、铂(Pt)以及其混合物组成的群组。
27、如权利要求26所述的银基合金,其特征在于,还包含0.2到2.0wt%的铜(Cu)。
28、如权利要求26所述的银基合金,其特征在于,含有0.25到0.35wt%的钐(Sm)、0.25到1.0wt%的铜(Cu)、0.1到0.3wt%的钛(Ti)以及0.2到0.8wt%的锰(Mn),其余为银(Ag)。
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US20040058222A1 (en) 2004-03-25
US7033730B2 (en) 2006-04-25
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CN1675700A (zh) 2005-09-28
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CA2490901A1 (en) 2004-01-08

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