CN103764318A - 镁合金粉末金属压块 - Google Patents
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Abstract
本发明公开了一种粉末金属压块。该粉末金属压块包括包含纳米基质材料的网状纳米基质。该粉末金属压块还包括分散在该网状纳米基质中的多个包含颗粒芯部材料的分散颗粒,所述颗粒芯部材料包含Mg-Zr、Mg-Zn-Zr、Mg-Al-Zn-Mn、Mg-Zn-Cu-Mn或Mg-W合金或其组合。
Description
相关申请的交叉参考
本申请要求2011年8月30日提交的美国申请号13/220824的权益,其通过引用以全文并入本文。
背景技术
石油和天然气井常常使用井孔部件或工具,由于它们的功能,这些部件或工具仅需要具有有限的使用寿命,该使用寿命显著低于井的使用寿命。在部件或工具的使用功能完成后,必须将其去除或处置以恢复用于包括烃生产、CO2封存等等的用途的流体通道的原始尺寸。部件或工具的处置通常通过铣削或钻削该部件或工具出井孔来完成,这通常会耗费时间,并且操作昂贵。
为了消除对铣削或钻削操作的需要,已经提出了使用各种可溶或可腐蚀材料通过溶解或腐蚀从井眼中移除部件或工具。虽然这些材料是有用的,但还希望这些材料轻重量并具有高强度,包括可与用于形成井眼部件或工具的常规工程材料(如各种等级的钢材)的强度相比的强度。因此,非常希望可溶解或可腐蚀材料的进一步改进以提高其强度、可腐蚀性和可制造性。
发明概述
在一个示例性实施方案中,公开了粉末金属压块。该粉末金属压块包括包含纳米基质材料的网状纳米基质。该粉末金属压块还包括分散在网状(cellular)纳米基质中的包含颗粒芯部材料的多个分散颗粒,所述颗粒芯部材料包含Mg-Zr、Mg-Zn-Zr、Mg-Al-Zn-Mn、Mg-Zn-Cu-Mn或Mg-W合金,或其组合。
附图概述
下面参照附图,其中在多张图中以类似数字标记类似元件:
图1是粉末10和粉末颗粒12的示例性实施方案的示意图;
图2是具有本文中所公开的分散颗粒的等轴构型的粉末压块的示例性实施方案的示意图;
图3是具有本文中所公开的分散颗粒的显著伸长构型的粉末压块的示例性实施方案的示意图;
图4是具有网状纳米基质与分散颗粒的显著伸长构型的粉末压块的示例性实施方案的示意图,其中该网状纳米基质与分散颗粒是基本连续的;和
图5是具有网状纳米基质与分散颗粒的显著伸长构型的粉末压块的示例性实施方案的示意图,其中该网状纳米基质与分散颗粒是基本不连续的。
发明详述
公开了轻重量、高强度镁合金纳米基质材料。用于形成这些纳米基质材料的镁合金是高强度镁合金。其强度可以通过向合金中并入纳米结构来提高。这些合金的强度也可以通过并入各种强化亚颗粒与第二颗粒来改进。公开的镁合金纳米基质材料还可以并入各种显微结构特征以控制合金机械性质,如并入显著伸长的颗粒显微结构以提高合金强度,或合金显微结构中的多峰粒度以提高断裂韧度,或其组合以控制强度、断裂韧度与其它合金性质。
本文中公开的镁合金纳米基质材料可用于所有应用方式和应用环境,包括用于各种井眼环境以制造各种轻重量高强度制品,包括井下制品,特别是工具或其它井下部件。除了它们的轻重量、高强度特性之外,这些纳米基质材料还可以描述为受控的电解材料,其可以可选和可控地可处置、可降解、可溶、可腐蚀或以其它方式可以从井眼中去除。用于耐久的和可处置或可降解的制品的许多其它应用也是可能的。在一个实施方案中,这些轻重量、高强度和可选并可控地可降解材料包括由涂覆的粉末材料形成的完全致密的、烧结的粉末压块,所述涂覆的粉末材料包括各种轻重量颗粒芯部和具有各种单层与多层纳米级涂层的芯部材料。在另一个实施方案中,这些材料包括可选并可控地可降解材料,所述可降解材料可以包括由这些涂覆的粉末材料形成的非完全致密的和/或未烧结的粉末压块。
纳米基质材料和制造这些材料的方法总体描述在例如2009年12月8日提交的美国专利申请12/633,682和2011年7月29日提交的美国专利申请13/194,361中,其内容通过引用以全文并入本文。这些轻重量、高强度和可选并可控地可降解材料可以从完全致密的烧结粉末压块至可为烧结或未烧结的前体或生坯状态(不那么完全致密)压块。它们由涂覆的粉末材料形成,所述涂覆的粉末材料包括各种轻重量颗粒芯部和具有各种单层与多层纳米级涂层的芯部材料。这些粉末压块由涂覆的金属粉末制成,所述涂覆的金属粉末包括各种电化学活性(例如具有相对较高的标准氧化电位)的轻重量、高强度颗粒芯部与芯部材料,如分散在由金属涂覆材料的各种纳米级金属涂覆层固结(consolidation)形成的网状纳米基质中的电化学活性金属,并特别可用于井眼应用。该粉末压块可以通过任何合适的粉末压实方法制成,包括冷等静压(CIP)、热等静压(HIP)、动态锻制和挤出,以及其组合。这些粉末压块提供了机械强度性质(如抗压强度和剪切强度)、低密度和可选并可控的腐蚀性质(特别是在各种井眼流体中的快速和受控的溶解)的独特和有利的组合。该流体可以包括任何数量的离子流体或高极性流体,如含有各种氯化物的那些。实例包括包含氯化钾(KC1)、盐酸(HCl)、氯化钙(CaCl2)、溴化钙(CaBr2)或溴化锌(ZnBr2)的流体。关于涂覆粉末的性质与制造和压制该涂覆粉末的方法的'682与'361申请的公开内容通常适用于提供本文中公开的轻重量高强度镁合金纳米基质材料,并且为简要起见在本文中不再重复。
如图1和2中所示,可以选择包含包括颗粒芯部14与芯部材料18与金属涂覆层16和涂覆材料20的粉末颗粒12的粉末10,其配置用于压实和烧结以提供粉末金属压块200,该粉末金属压块200是轻重量(即具有相对低的密度)高强度的,并响应于井眼性质的变化可选与可控地可从井眼中移除,包括可选和可控地可溶于适当的井眼流体,包括本文中公开的各种井眼流体。该粉末金属压块200包括包含纳米基质材料220的网状纳米基质216和分散在该网状纳米基质216中的包含颗粒芯部材料218的多个分散颗粒214,所述颗粒芯部材料218包含Mg-Zr、Mg-Zn-Zr、Mg-Al-Zn-Mn、Mg-Zn-Cu-Mn或Mg-W合金或其组合。
分散颗粒214可以包含用于颗粒芯部14的本文中所述的任何材料,即使分散颗粒214的化学组成由于本文中所述的扩散效应可以不同。在一个示例性实施方案中,分散颗粒214由包含Mg-Zr、Mg-Zn-Zr、Mg-Al-Zn-Mn、Mg-Zn-Cu-Mn或Mg-W合金或其组合的颗粒芯部14形成。在一个示例性实施方案中,分散颗粒214包括颗粒芯部材料218,所述颗粒芯部材料218按重量百分比包含约6.0至约10.0的Al、约0.3至约1.2的Zn、约0.1至约0.6的Mn和余量Mg与不可避免的杂质。在另一个示例性实施方案中,分散颗粒214包括颗粒芯部材料218,所述颗粒芯部材料218按重量百分比包含约0.5至约6.5的Zn、约0.3至约0.75的Zr和余量Mg与不可避免的杂质。分散颗粒214和颗粒芯部材料218还可以包括稀土元素,或稀土元素的组合。如本文中所用,稀土元素包括Sc、Y、La、Ce、Pr、Nd或Er或稀土元素的组合。当存在时,稀土元素或稀土元素的组合可以以按重量计约5%或更少的量存在。
分散颗粒214与颗粒芯部材料218还可以包含纳米结构化材料215。在一个示例性实施方案中,纳米结构化材料215是具有小于约200nm的晶粒尺寸、或亚晶或微晶尺寸、更特别为约10nm至约200nm的晶粒尺寸和甚至更特别小于约100nm的平均晶粒尺寸的材料。该纳米结构可以包括大角度晶界227,其通常用于限定晶粒尺寸,或可以在特定晶粒中作为亚结构出现的小角度晶界229,其有时用于限定微晶尺寸,或其组合。该纳米结构可以通过任何合适的方法在用于形成分散颗粒214的颗粒芯部14中形成,包括形变诱发纳米结构,如可以通过球磨粉末以提供颗粒芯部14、更特别通过低温球磨(例如在低温下的球磨介质中或在低温流体如液氮中球磨)粉末以提供用于形成分散颗粒214的颗粒芯部14来提供。该颗粒芯部14可以通过任何合适的方法形成为纳米结构化材料215,例如通过铣削或低温球磨本文中所述的镁合金的预合金化粉末颗粒。该颗粒芯部14还可以通过各合金成分的所需量的纯金属粉末的机械合金化来形成。机械合金化涉及球磨(包括低温球磨)这些粉末成分以机械地包覆和混合该成分并形成颗粒芯部14。除了生成如上所述的纳米结构外,球磨(包括低温球磨)可以有助于颗粒芯部14和芯部材料18的固溶强化,这又有助于分散颗粒214与颗粒芯部材料218的固溶强化。该固溶强化可能是由于能够在固溶体中机械混合比根据特定合金成分相平衡的可能浓度更高浓度的填隙或代位溶质原子,由此阻碍或用于限制颗粒中位错的运动,这进而在颗粒芯部14和分散颗粒214中提供了强化机制。颗粒芯部14还可以通过包括例如惰性气体冷凝、化学气相冷凝、脉冲电子沉积、等离子体合成、非晶固体结晶、电沉积和大塑性变形的方法形成为纳米结构化材料215。该纳米结构还可以包括高位错密度,例如约1017m-2至1018m-2的位错密度,这可能比通过传统技术如冷轧法变形的同类合金材料高两到三个数量级。
分散颗粒214和颗粒芯部材料218还可以包含亚颗粒222,并可以优选包含多个亚颗粒。亚颗粒222在分散颗粒214中提供分散强化机制,并阻碍或用于限制颗粒中位错的运动。亚颗粒222可以具有任何合适的尺寸,在一个示例性实施方案中可以具有约10nm至约1微米的平均粒度,更特别可以具有约50nm至约200nm的平均粒度。亚颗粒222可以包含任何合适形式的亚颗粒,包括嵌入的亚颗粒224、析出物226或分散体228。嵌入颗粒224可以包括任何合适的嵌入亚颗粒,包括各种硬质亚颗粒。嵌入亚颗粒或多个嵌入亚颗粒可以包括各种金属、碳、金属氧化物、金属氮化物、金属碳化物、金属间化合物或金属陶瓷颗粒或其组合。在一个示例性实施方案中,硬质颗粒可以包括Ni、Fe、Cu、Co、W、Al、Zn、Mn或Si,或包含前述的至少一种的氧化物、氮化物、碳化物、金属间化合物或金属陶瓷,或其组合。嵌入亚颗粒224可以通过任何合适的方法嵌入,包括例如通过使硬质颗粒与颗粒芯部材料18一起球磨或低温球磨。析出亚颗粒226可以包括在分散颗粒214中可析出的任何亚颗粒,包括与所感兴趣的镁合金成分的相平衡与其相对量(例如可析出硬化合金)一致的析出亚颗粒226,并包括可以因非平衡条件析出的那些,例如当已经以高于其相平衡极限的量被迫进入合金固溶体(如已知会在机械合金化过程中发生的那样)的合金成分被充分加热至激活允许析出的扩散机制时出现的那些。分散体亚颗粒228可以包括来自于颗粒芯部14的制造的元素的纳米级颗粒或团簇,例如与球磨相关的那些,包括球磨介质(例如球)或球磨流体(例如液氮)或颗粒芯部14自身表面(例如金属氧化物或氮化物)的成分。分散体亚颗粒228可以包括例如Fe、Ni、Cr、Mn、N、O、C和H。该亚颗粒222可以与颗粒芯部14和分散颗粒214一起位于任何位置。在一个示例性实施方案中,如图1中所示,亚颗粒222可以布置在分散颗粒214中或布置在分散颗粒214的表面上,或其组合。在另一个示例性实施方案中,如图1中所示,多个亚颗粒222布置在颗粒芯部14和分散颗粒214的表面上,并还可以包含纳米基质材料216。
粉末压块200包括具有遍及该网状纳米基质216分散的多个分散颗粒214的纳米基质材料220的网状纳米基质216。该分散颗粒214在基本连续的网状纳米基质216中可以是等轴的,或者如本文中所述和如图3中所示是显著伸长的。在其中该分散颗粒214为显著伸长的情况下,分别如图4和5中所示,该分散颗粒214与该网状纳米基质216可以是连续或不连续的。由烧结的金属涂覆层16形成的基本连续的网状纳米基质216与纳米基质材料220通过压实和烧结多个粉末颗粒12的多个金属涂覆层16来形成,例如通过CIP、HIP或动态锻制。由于与烧结相关的扩散效应,纳米基质材料220的化学组成可以不同于涂覆材料20的化学组成。粉末金属压块200还包括多个分散颗粒214,所述分散颗粒214包含颗粒芯部材料218。当金属涂覆层16烧结在一起形成纳米基质216时,分散的颗粒芯部214和芯部材料218对应于多个粉末颗粒12的颗粒芯部14和芯部材料18并由多个粉末颗粒12的颗粒芯部14和芯部材料18形成。由于与烧结相关的扩散效应,芯部材料218的化学组成可以不同于芯部材料18的化学组成。
如本文中所用,使用术语网状纳米基质216不意指粉末压块的主要成分,而是指次要成分,无论按重量计还是按体积计。这有别于其中基质包括按重量或体积计的主要成分的大多数基质复合材料。使用术语基本连续的网状纳米基质意在描述纳米基质材料220在粉末压块200中分布的广泛的、规则的、连续的和互连的性质。本文中所用的“基本连续的”描述了纳米基质材料遍及粉末压块200扩展,以使得其在基本所有分散颗粒214之间扩展并包封基本所有分散颗粒214。基本连续用于表示不需要纳米基质在每个分散颗粒214周围的完全连续性和规则的秩序。例如,在某些粉末颗粒12上在颗粒芯部14上方的涂覆层16的缺陷可导致烧结粉末压块200的过程中颗粒芯部14的桥连,由此导致在网状纳米基质216中获得局部不连续性,即使在该粉末压块的其它部分中该纳米基质是基本连续的,并表现出本文中所述的结构。相反,在显著伸长的分散颗粒214(如通过挤出形成的那些)的情况下,“基本不连续”用于描述在各分散颗粒214周围的纳米基质的不完全的连续性与中断(例如开裂或分离),如可能发生在预定的挤出方向622上或横切该方向的方向上。如本文中所用,“网状”用于表示纳米基质限定了通常重复的、互连的纳米基质材料220的隔室或胞室的网络,该纳米基质材料220包围分散颗粒214并与分散颗粒214相互连接。如本文中所用,“纳米基质”用于描述基质的尺寸或尺度,特别是相邻的分散颗粒214之间该基质的厚度。烧结在一起以形成该纳米基质的金属涂覆层本身是纳米级厚度的涂覆层。由于除了超过两个分散颗粒214相交处之外的大多数位置处的纳米基质通常包含来自具有纳米级厚度的相邻粉末颗粒12的两个涂覆层16的相互扩散与粘结,因此形成的基质同样具有纳米级厚度(例如本文中所述的涂覆层厚度的约两倍)并由此描述为纳米基质。此外,使用术语分散颗粒214并不指粉末压块200的次要成分,而是指主要成分,无论按重量计还是按体积计。使用术语分散颗粒意在表达粉末压块200中颗粒芯部材料218的不连续和离散的分布。
粉末压块200可以具有任何所需的形状或尺寸,包括圆柱形坯、棒、片或可以机加工、成形或以其它方式用于形成可用的制造制品(包括各种井眼工具和部件)的其它形式的形状或尺寸。用于形成前体粉末压块100的压制以及用于形成粉末压块200和使包括颗粒芯部14与涂覆层16的粉末颗粒12变形的烧结与压制过程提供粉末压块200的完全密度和所需宏观形状与尺寸以及其显微结构。分散颗粒214的形貌(例如等轴或显著伸长的形貌)和颗粒层的网状网络216来自于粉末颗粒12的烧结与变形,因为它们被压实并相互扩散和变形以填充颗粒间空隙15(图1)。可以选择烧结温度与压力以确保粉末压块200的密度达到基本完全理论密度。
在一个示例性实施方案中,分散颗粒214由分散在烧结的金属涂覆层16的网状纳米基质216中的颗粒芯部14形成,并且该纳米基质216包括遍及网状纳米基质216在分散颗粒214之间延伸的固态金相结合或结合层,所述网状纳米基质216在烧结温度(Ts)下形成,其中Ts小于该涂层的熔融温度(Tc)和该颗粒的熔融温度(TP)。如所示那样,固态金相粘结通过本文中所述的相邻粉末颗粒12的涂覆层16之间的固态相互扩散以固态形成,所述相邻粉末颗粒在用于形成粉末压块200的压实与烧结过程中被压制至接触。因此,网状纳米基质216的烧结的涂覆层16包括具有由涂覆层16的涂覆材料20的相互扩散程度限定的厚度的固态结合层,所述相互扩散的程度进而由涂覆层16的性质限定,包括它们是单层还是多层涂覆层,选择它们以促进还是限制此类相互扩散、和如本文中所述的其它因素,以及烧结和压实条件,包括用于形成粉末压块200的烧结时间、温度和压力。
在形成纳米基质216时,包括金相结合和结合层,金属涂覆层16的化学组成和/或相分布可以改变。纳米基质216还具有熔融温度(TM)。本文中所用的TM包括在纳米基质216中发生初期熔融或液化或其它形式的部分熔融时的最低温度,而不管纳米基质材料220是否包含纯金属、具有各自具有不同熔融温度的多个相的合金或复合材料,包括包含具有不同熔融温度的各种涂覆材料的多个层的复合材料,或其组合,或其它。当分散颗粒214与颗粒芯部材料218与纳米基质216一起形成时,金属涂覆层16的成分也可能扩散到颗粒芯部14中,这会导致颗粒芯部14的化学组成和/或相分布的改变。结果,分散颗粒214和颗粒芯部材料218可以具有不同于TP的熔融温度(TDP)。本文中所用的TDP包括在分散颗粒214中发生初期熔融或液化或其它形式的部分熔融时的最低温度,而不管颗粒芯部材料218是否包含纯金属、具有各自具有不同熔融温度的多个相的合金或复合材料,或其它。在一个实施方案中,粉末压块200在烧结温度(TS)下形成,其中TS小于TC、TP、TM和TDP,并且该烧结完全在固态下进行,获得固态结合层。在另一个示例性实施方案中,粉末压块200在烧结温度(TS)下形成,其中TS大于或等于TC、TP、TM或TDP中的一个或多个,烧结包括如本文所述的粉末压块200中的有限或部分熔融,并进一步可以包括液态或液相烧结,获得至少部分熔融并再凝固的结合层。在这种实施方案中,将选择预定的TS和预定的烧结时间(tS)的组合以保持包括该网状纳米基质216和分散颗粒214的所需显微结构。例如,在所有或一部分纳米基质216中可以例如允许发生局部的液化或熔融,只要保持该网状纳米基质216/分散颗粒214形貌,如通过选择不会导致颗粒芯部完全熔融的颗粒芯部14、TS和tS。类似地,例如,在所有或一部分分散颗粒214中可以允许发生局部的液化,只要保持该网状纳米基质216/分散颗粒214的形貌,如通过选择不会提供涂覆层16完全熔融的金属涂覆层16、TS和tS。例如在烧结过程中沿着金属层16/颗粒芯部14界面,或沿着多层涂覆层16的相邻层之间的界面,可以发生金属涂覆层16的熔融。要认识到,超出预定值的TS和tS的组合会产生其它显微结构,例如,如果纳米基质216(即金属涂覆层16的组合)和分散颗粒214(即颗粒芯部14)熔融,由此允许这些材料的快速相互扩散的话,会产生平衡熔融/再凝固显微结构。
粉末压块200的颗粒芯部14和分散颗粒214可以具有任何合适的粒度。在一个示例性实施方案中,该颗粒芯部14可以具有单峰分布,以及约5微米至约300微米、更特别约80微米至约120微米且甚至更特别约100微米的平均粒径或粒度。在另一个示例性实施方案中,其可以包括多峰粒度分布,该颗粒芯部14可以具有约50纳米至约500微米、更特别约500纳米至约300微米和甚至更特别约5微米至约300微米的平均粒径或粒度。在一个示例性实施方案中,该颗粒芯部14或该分散颗粒可以具有约50纳米至约500微米的平均粒度。
根据对颗粒芯部14和粉末颗粒12所选择的形状,以及用于烧结和压实粉末10的方法,分散颗粒214可以具有任何合适的形状。在一个示例性实施方案中,粉末颗粒12可以是球形或基本球形的,并且分散颗粒214可以包括如本文中所述的等轴颗粒构型。在另一个示例性实施方案中,分散颗粒可以具有非球形形状。在再一个实施方案中,该分散颗粒可以在预定挤压方向622上是显著伸长的,如使用挤压法以形成粉末压块200时发生的那样。如图3-5中所示,显著伸长的网状纳米基质616包含纳米基质材料620的相互连接的伸长晶胞的网络,所述纳米基质材料620具有布置在该晶胞内的多个显著伸长的芯部材料618的分散颗粒芯部614。根据施加以形成伸长颗粒的变形量,伸长的涂覆层与纳米基质616可以如图4中所示在预定方向622上是基本连续的,或如图5中所示是基本不连续的。
可以通过选择用于制造颗粒压块200的粉末10来影响分散颗粒214的分散性质。在一个示例性实施方案中,可以选择具有粉末颗粒12尺寸的单峰分布的粉末10来形成粉末压块200并将在网状纳米基质216中产生分散颗粒214的粒度的基本均匀的单峰分散。在另一个示例性实施方案中,可以选择具有多个粉末颗粒(所述粉末颗粒具有颗粒芯部14,所述颗粒芯部14具有相同的芯部材料18和不同的芯部尺寸和相同的涂覆材料20)的多个粉末10,并如本文中所述均匀混合以提供具有粉末颗粒12尺寸的均匀的多峰分布的粉末10,并可用于形成在网状纳米基质216中具有分散颗粒214的粒度的均匀的多峰分布的粉末压块200。类似地,在再一个示例性实施方案中,可以选择具有多个颗粒芯部14(其可具有相同的芯部材料18和不同的芯部尺寸与相同的涂覆材料20)的多个粉末10,并以不均匀的方式分布以提供粉末颗粒尺寸的不均匀的多峰分布,并可用于形成在网状纳米基质216中具有分散颗粒214的粒度的不均匀的多峰分布的粉末压块200。颗粒芯部尺寸的分布的选择可用于确定例如在由粉末10制成的粉末压块200的网状纳米基质216中分散颗粒214的粒度和颗粒间间距。
如图1和2中大体所示,如本文中所述,还可以使用涂覆的金属粉末10和附加的或第二粉末30形成粉末金属压块200。使用附加的粉末30提供了还包括如本文中所述的多个分散的第二颗粒234的粉末压块200,所述第二颗粒234分散在纳米基质216中并还相对于该分散颗粒214分散。如本文中所述,分散的第二颗粒234可以由涂覆或未涂覆的第二粉末颗粒32形成。在一个示例性实施方案中,涂覆的第二粉末颗粒32可以涂有与粉末颗粒12的涂覆层16相同的涂覆层36,使得涂覆层36也有助于该纳米基质216。在另一个示例性实施方案中,该第二粉末颗粒232可以是未涂覆的,使得分散的第二颗粒234嵌在纳米基质216中。如本文中公开的那样,粉末10和附加粉末30可以混合以形成分散颗粒214与分散的第二颗粒234的均匀分散,或形成这些颗粒的不均匀分散。分散的第二颗粒234可以由不同于粉末10(这是由于颗粒芯部34和/或涂覆层36中的组成差异)的任何合适的附加粉末30形成,并可以包括本文中公开的用作第二粉末30的任何材料,所述第二粉末30不同于为了形成粉末压块200而选择的粉末10。在一个示例性实施方案中,分散的第二颗粒234可以包括Ni、Fe、Cu、Co、W、Al、Zn、Mn或Si,或包含前述至少一种的氧化物、氮化物、碳化物、金属间化合物或金属陶瓷,或其组合。
纳米基质216是彼此烧结的金属涂覆层16的基本连续的网状网络。纳米基质216的厚度将取决于用于形成粉末压块200的粉末10的性质,以及任何第二粉末30的并入,特别是与这些颗粒相关的涂覆层厚度。在一个示例性实施方案中,纳米基质216的厚度遍及粉末压块200的显微结构是基本均匀的,并包括粉末颗粒12的涂覆层16的厚度的约两倍。在另一个示例性实施方案中,该网状网络216具有约50纳米至约5000纳米的在分散颗粒214之间的基本均匀的平均厚度。如本文中所述,通过挤出形成的粉末压块200具有小得多的厚度,并且可以变成不均匀的和基本不连续的。
如本文中所述,通过相互扩散和产生结合层,通过将相邻颗粒的金属涂覆层16烧结在一起来形成纳米基质216。金属涂覆层16可以是单层或多层结构,并可以选择它们以便促进和/或抑制在该层内、或在金属涂覆层16的层之间、或在金属涂覆层16与颗粒芯部14之间、或在金属涂覆层16与相邻粉末颗粒的金属涂覆层16之间的扩散,取决于涂层厚度、所选择的涂覆材料、烧结条件和其它因素,烧结过程中金属涂覆层16的相互扩散的程度可以是有限的或广泛的。考虑到成分的相互扩散与相互作用的潜在复杂性,纳米基质216和纳米基质材料220的所得化学组成的描述可以简单理解为涂覆层16的成分的组合,取决于发生在分散颗粒214与纳米基质216之间的相互扩散(如果发生的话)的程度,该组合还可以包括分散颗粒214的一种或多种成分。类似地,分散颗粒214与颗粒芯部材料218的化学组成可以简单地理解为颗粒芯部14的成分的组合,取决于发生在分散颗粒214与纳米基质216之间的相互扩散(如果发生的话)的程度,该组合还可以包括纳米基质216和纳米基质材料220的一种或多种成分。
在一个示例性实施方案中,纳米基质材料220具有一种化学组成,颗粒芯部材料218具有与纳米基质材料220的化学组成不同的化学组成,并且可以配置化学组成方面的差异,以便如本文中所述响应于压块200附近的井眼性质或条件的受控变化,包括与粉末压块200接触的井眼流体的性质变化,提供可选和可控的溶解速率,包括可选的从极低溶解速率向非常快的溶解速率的转变。纳米基质216可以由具有单层和多层涂覆层16的粉末颗粒12形成。这种设计灵活性提供了大量材料组合,特别是在多层涂覆层16的情况下,这种设计灵活性可用于通过控制在给定层中、以及在涂覆层16和与之相关的颗粒芯部14或相邻粉末颗粒12的涂覆层16之间的涂覆层成分的相互作用来调节该网状纳米基质216以及纳米基质材料220的组成。
在一个示例性实施方案中,纳米基质216可以包含纳米基质材料220,所述纳米基质材料220包含Ni、Fe、Cu、Co、W、Al、Zn、Mn、Mg或Si,或其合金,或包含前述至少一种的氧化物、氮化物、碳化物、金属间化合物或金属陶瓷,或其组合。
可以配置本文中公开的粉末金属压块200以提供使用预定井眼流体(包括本文中所述那些)可选和可控地可处置、可降解、可溶、可腐蚀的或以其它方式可以从井眼中去除。这些材料可以配置为提供至多约500mg/cm2/hr的腐蚀速率、更特别为约0.5至约50mg/cm2/hr的腐蚀速率。这些粉末压块200还可以配置为提供高强度,包括至多约85ksi、更特别为约40ksi至约70ksi的极限抗压强度。
本文中术语“一个”和“一种”不意味着量的限制,而是意味着存在至少一种所述项目。修饰词“约”与量结合使用时包括所述值,并具有上下文所指定的含义(例如包括与特定量的测量方法相关的误差程度)。此外,本文中公开的所有范围是包容性的并可组合(例如,“至多约25重量%(wt.%)、更特别为约5wt.%至约20wt.%和甚至更特别为约10wt.%至约15wt.%”的范围包括端点和该范围的所有中间值,例如“约5wt.%至约25wt.%、约5wt.%至约15wt.%”等等),除非另行限定。与合金组合物的成分列表一起使用“约”应用于所有列举的成分,并与一范围结合至该范围的两个端点。最后,本文中所用的技术与科学术语具有本发明所述领域的技术人员通常理解的相同含义,除非另行定义。本文中所用后缀“(s)”意在包括其修饰的术语的单数和复数形式,由此包括该术语的一个或多个(例如,金属(s)包括一种或多种金属)。在整篇说明书中提到“一个实施方案”、“另一个实施方案”、“一实施方案”等等意味着与该实施方案一起描述的特定元素(例如特征、结构和/或特性)包括在本文中所述的至少一个实施方案中,并可以存在或不存在于其它实施方案中。
要理解的是,与本文中描述的合金组合物一起使用“包含”具体公开并包括了其中该合金组合物“基本上由指定组分组成(即含有指定组分,并且不含明显不利地影响所公开的基本和新颖特征的其它组分)”的实施方案和其中该合金组合物“由指定成分组成(即除了天然和不可避免地存在于各指定组分中的污染物之外仅含有指定组分)”的实施方案。
虽然已经显示并描述了一个或多个实施方案,但可以对其进行修改和替换,而不偏离本发明的精神与范围。因此,要理解的是,以阐述而非限制的方式描述本发明。
Claims (30)
1.粉末金属压块,包含:
包含纳米基质材料的网状纳米基质;
分散在所述网状纳米基质中的包含颗粒芯部材料的多个分散颗粒,所述颗粒芯部材料包含Mg-Zr、Mg-Zn-Zr、Mg-Al-Zn-Mn、Mg-Zn-Cu-Mn或Mg-W合金或其组合。
2.权利要求1的粉末金属压块,其中所述颗粒芯部材料按重量百分比包含约0.5至约6.5的Zn、约0.3至约0.75的Zr和余量Mg与不可避免的杂质。
3.权利要求1的粉末金属压块,其中所述颗粒芯部材料按重量百分比包含约6.0至约10.0的Al、约0.3至约1.2的Zn、约0.1至约0.6的Mn和余量Mg与不可避免的杂质。
4.权利要求1的粉末金属压块,其中所述颗粒芯部材料或所述纳米基质材料或其组合包含纳米结构化材料。
5.权利要求4的粉末金属压块,其中所述纳米结构化材料具有小于约200nm的晶粒尺寸。
6.权利要求5的粉末金属压块,其中所述纳米结构化材料具有约10nm至约200nm的晶粒尺寸。
7.权利要求4的粉末金属压块,其中所述纳米结构化材料具有小于约100nm的平均晶粒尺寸。
8.权利要求1的粉末金属压块,其中所述分散颗粒进一步包含亚颗粒。
9.权利要求8的粉末金属压块,其中所述亚颗粒具有约10nm至约1微米的平均粒度。
10.权利要求8的粉末金属压块,其中所述亚颗粒包含预成型的亚颗粒、析出物或分散体。
11.权利要求8的粉末金属压块,其中所述亚颗粒布置在分散颗粒中或布置在分散颗粒表面上,或其组合。
12.权利要求11的粉末金属压块,其中所述亚颗粒布置在分散颗粒表面上并还包含所述纳米基质材料。
13.权利要求1的粉末金属压块,其中所述分散颗粒具有约50纳米至约500微米的平均粒度。
14.权利要求1的粉末金属压块,其中所述分散颗粒的分散包括在网状纳米基质中粒度的多峰分布。
15.权利要求1的粉末金属压块,其中所述颗粒芯部材料进一步包含稀土元素。
16.权利要求1的粉末金属压块,其中所述分散颗粒具有等轴颗粒形状,并且所述纳米基质是基本连续的。
17.权利要求1的粉末金属压块,其中所述纳米基质和所述分散颗粒是在预定方向上显著伸长的。
18.权利要求17的粉末金属压块,其中所述纳米基质与所述分散颗粒是基本连续的。
19.权利要求17的粉末金属压块,其中所述纳米基质与所述分散颗粒是基本不连续的。
20.权利要求1的粉末金属压块,进一步包含多个分散的第二颗粒,其中所述分散的第二颗粒也分散在所述网状纳米基质中并相对于所述分散颗粒分散。
21.权利要求1的粉末金属压块,其中所述分散的第二颗粒包含金属、碳、金属氧化物、金属氮化物、金属碳化物、金属间化合物或金属陶瓷,或其组合。
22.权利要求21的粉末金属压块,其中所述分散的第二颗粒包含Ni、Fe、Cu、Co、Mg、W、Al、Zn、Mn或Si,或包含前述至少一种的氧化物、氮化物、碳化物、金属间化合物或金属陶瓷,或其组合。
23.权利要求1的粉末金属压块,其中所述纳米基质材料包含金属、碳、金属氧化物、金属氮化物、金属碳化物、金属间化合物或金属陶瓷,或其组合。
24.权利要求1的粉末金属压块,其中所述纳米基质材料包含球磨介质或球磨流体的成分。
25.权利要求23的粉末金属压块,其中所述纳米基质材料包含Ni、Fe、Cu、Co、W、Al、Zn、Mn、Mg或Si,或包含前述至少一种的氧化物、氮化物、碳化物、金属间化合物或金属陶瓷,或其组合。
26.权利要求1的粉末金属压块,其中所述纳米基质材料包含多层材料。
27.权利要求1的粉末金属压块,其中所述纳米基质材料具有一种化学组成,所述颗粒芯部材料具有不同于所述纳米基质材料的化学组成的化学组成。
28.权利要求1的粉末金属压块,其中所述网状纳米基质具有约50nm至约5000nm的平均厚度。
29.权利要求1的粉末金属压块,进一步包含在分散颗粒之间遍及所述网状纳米基质延伸的结合层。
30.权利要求29的粉末金属压块,其中所述结合层包括基本固态的结合层。
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CN103764318B (zh) | 2018-12-04 |
CA2843011C (en) | 2017-07-25 |
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EP2750818A4 (en) | 2016-01-20 |
US20130047785A1 (en) | 2013-02-28 |
AP2014007454A0 (en) | 2014-02-28 |
BR112014004456A2 (pt) | 2017-03-28 |
AU2012302060B2 (en) | 2017-02-09 |
WO2013033185A1 (en) | 2013-03-07 |
MY173154A (en) | 2019-12-31 |
US9109269B2 (en) | 2015-08-18 |
EP2750818A1 (en) | 2014-07-09 |
CA2843011A1 (en) | 2013-03-07 |
US9802250B2 (en) | 2017-10-31 |
US10737321B2 (en) | 2020-08-11 |
AU2012302060A1 (en) | 2014-01-30 |
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