CN105081306B - 用于3d打印的经稳定的金属纳米粒子 - Google Patents
用于3d打印的经稳定的金属纳米粒子 Download PDFInfo
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- CN105081306B CN105081306B CN201510205172.7A CN201510205172A CN105081306B CN 105081306 B CN105081306 B CN 105081306B CN 201510205172 A CN201510205172 A CN 201510205172A CN 105081306 B CN105081306 B CN 105081306B
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- 239000002082 metal nanoparticle Substances 0.000 title claims description 47
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- 230000000087 stabilizing effect Effects 0.000 claims abstract description 28
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
- H01L21/82—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components
- H01L21/822—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components the substrate being a semiconductor, using silicon technology
- H01L21/8222—Bipolar technology
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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Abstract
本发明公开了一种用于3D打印机中的材料。所述材料可包括多个金属粒子和稳定材料。所述金属粒子可具有小于或等于约100nm的平均横截面长度。所述稳定材料可包括有机胺、羧酸、硫醇及其衍生物、黄原酸、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮或它们的组合。
Description
技术领域
本教导通常涉及三维(“3D”)打印，更特别地涉及在使用激光和/或电子束烧结的3D打印过程中所用的材料。
背景技术
3D打印用于直接由计算机辅助数码设计产生复杂的3D物品。3D打印技术可通常分为三类：(1)立体平版印刷(“SLA”)、(2)熔融沉积造型(“FDM”)和(3)涉及激光束和/或电子束的粉末床技术。SLA通过激光(例如激光烧结)或其他光源而选择性地固化光敏(可UV固化)聚合物，而FDM通过经加热的喷嘴而选择性地沉积热塑性熔融聚合物。然而，SLA和FDM均局限于塑料，并未用于产生金属物品。
粉末床技术可用于通过使用激光烧结，由微米尺寸的粉末产生金属物品。在激光烧结过程中所用的金属粉末可为潜在爆炸性的。为了降低点燃粉末的风险，通常将使用粉末床技术的打印机置于密封有氮气的室中，这使得所述打印机不适用于家庭使用。此外，所产生的物品通常为内部多孔的，当与经由常规方法制得的物品相比时，这使得它们更弱。因此，需要一种改进的3D打印方法和一种在其中使用的改进的金属材料。
发明内容
如下显示了简化概要，以提供对本教导的一个或多个实施例的一些方面的基本理解。所述概要并非广泛的概述，不旨在确定本教导的关键或决定性要素，也不旨在描述本公开的范围。相反，其主要目的仅在于以简化形式显示一个或多个概念以作为之后显示的详细说明的前序。
公开了一种用于3D打印机中的材料。所述材料可包括多个金属粒子和稳定材料。所述金属粒子可具有小于或等于约100nm的平均横截面长度。所述稳定材料可包括有机胺、羧酸、硫醇及其衍生物、黄原酸、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮(polyninylpyrolidone)或它们的组合。
在另一实施例中，所述材料可包括平均横截面长度为约1μm至约250μm的多个金属微粒。所述金属微粒可包括平均横截面长度小于或等于约50nm的多个金属纳米粒子和在所述纳米粒子外表面上的稳定材料。
也公开了一种用于使用3D打印机打印物品的方法。所述方法可包括将多个经稳定的粒子装载至3D打印机的传递床。经稳定的粒子可包括多个金属粒子和稳定材料。所述金属粒子可具有小于或等于约100nm的平均横截面长度。所述稳定材料可包括胺、有机胺、羧酸、硫醇及其衍生物、黄原酸、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮或它们的组合。可将所述经稳定的粒子的一部分由传递床转移至3D打印机的制造床。经稳定的粒子可在小于或等于约200℃的温度下在制造床中烧结，以形成打印物品。
附图说明
引入并构成本说明书的一部分的附图示出了本教导的实施例，并与描述一起用于解释本公开的原理。在图中：
图1显示了根据所公开的一个或多个实施例的用于打印3D金属物品的示例性系统。
具体实施方式
现在将详细参照本教导的示例性实施例，其实例在附图中进行说明。只要有可能，将在整个附图中使用相同的附图标记以表示相同、类似或相似的部分。
如本文所用，除非另外指出，词语“打印机”涵盖为了任意目的进行打印输出功能的任意设备，如数字复印机、造书机、传真机、多功能机、静电照相装置、可制备3D物品的3D打印机等。应了解图中所示的结构可包括为了简化而未显示的另外的特征，尽管所示的结构可被去除或修改。
多个金属粒子可由3D打印机使用，以产生金属物品。金属粒子可为或包括任意金属或金属合金，如银、金、铝、铂、钯、铜、钴、铬、铟、钛、锆、镍、它们的合金或它们的组合。金属粒子可具有小于或等于约100nm、小于或等于约50nm或小于或等于约20nm的平均横截面长度(例如直径)。该尺寸的粒子可称为纳米粒子。金属纳米粒子可为粉末形式。此外，金属纳米粒子可包括银纳米粒子复合材料或金属纳米粒子复合材料，例如Au--Ag、Ag--Cu、Ag--Ni、Au--Cu、Au--Ni、Au--Ag--Cu和Au--Ag--Pd。复合材料的各个组分可以以例如约0.01重量％至约99.9重量％、特别是约10重量％至约90重量％的量存在。
在更高温度下可能难以控制热扩散，这通常引起粉末的不希望的部分的烧结，由此在打印物品中产生不一致。然而，上述尺寸的金属粒子(即“纳米粒子”)可具有小于或等于约200℃、小于或等于约150℃、小于或等于约125℃或小于或等于约100℃的熔化和/或烧结温度。通过将熔化和/或烧结温度降低至上述范围内，也可降低在打印过程中产生的热扩散的量。这可减少不一致，并改进打印精度。
相比于“微米尺寸的粒子”或“微粒”(例如平均横截面长度为约1μm至约999μm的粒子)，金属纳米粒子由于表面等离子体吸光度而在UV和可见区域中具有改进的吸光度。例如，银纳米粒子在大约410-420nm处具有强吸光度。参见例如(J.of Microelectronics andElectronic Packaging，2013，10，49-53)。该吸收可允许使用低功率(和低温)激光(例如蓝色激光)。在一些实施例中，纳米粒子的粒度(即平均横截面长度)可小于烧结光源(激光、氙灯、电子束等)的波长。
另外，相比于更大的微粒，金属纳米粒子散射和/或反射激光束的可能性更小。光散射和/或反射可导致比激光束更大的特征尺寸，因此在产生的物品中导致更低的分辨率。金属纳米粒子可使得在小于或等于约25μm、小于或等于约10μm或小于或等于约5μm的分辨率下的3D打印成为可能。这可有利于产生具有平滑表面(例如，低表面粗糙度)的金属物品。
可将稳定材料(或稳定剂)添加至金属纳米粒子中，以形成经稳定的纳米粒子基体(例如粉末形式)。稳定材料可为或包括胺(例如有机胺)、羧酸、硫醇及其衍生物、-OC(S)SH(黄原酸)、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮和其他有机表面活性剂或它们的组合。具有至少部分围绕其的稳定材料的金属纳米粒子可为平均横截面长度(例如直径)小于或等于约100nm、小于或等于约50nm或小于或等于约20nm的多个粒子的形式。在一些实施例中，稳定材料的至少一部分可附接至金属纳米粒子的表面。换言之，金属纳米粒子可通过稳定材料而彼此分离，从而形成不连续相。在实施例中，稳定材料可为有机稳定剂。“有机稳定剂”中的术语“有机”指，例如，一个或多个碳原子的存在，但有机稳定剂可包含一个或多个非金属杂原子，如氮、氧、硫、硅、卤素等。有机稳定剂可为有机胺稳定剂，如美国专利No.7,270,694中描述的那些。有机胺的例子可包括烷基胺，例如丁基胺、戊基胺、己基胺、庚基胺、辛基胺、壬基胺、癸基胺、十六烷基胺、十一烷基胺、十二烷基胺、十三烷基胺、十四烷基胺、二氨基戊烷、二氨基己烷、二氨基庚烷、二氨基辛烷、二氨基壬烷、二氨基癸烷、二氨基辛烷、二丙基胺、二丁基胺、二戊基胺、二己基胺、二庚基胺、二辛基胺、二壬基胺、二癸基胺、甲基丙基胺、乙基丙基胺、丙基丁基胺、乙基丁基胺、乙基戊基胺、丙基戊基胺、丁基戊基胺、三丁基胺、三己基胺等或它们的混合物。其他有机稳定剂的例子可包括例如硫醇及其衍生物、-OC(S)SH(黄原酸)、聚乙二醇、聚乙烯基吡啶、聚乙烯吡咯烷酮和其他有机表面活性剂。有机稳定剂可选自硫醇(例如丁硫醇、戊硫醇、己硫醇、庚硫醇、辛硫醇、癸硫醇和十二硫醇)、二硫醇(例如1,2-乙二硫醇、1,3-丙二硫醇和1,4-丁二硫醇)或硫醇与二硫醇的混合物。有机稳定剂可选自黄原酸，例如O-甲基黄原酸酯、O-乙基黄原酸酯、O-丙基黄原酸、O-丁基黄原酸、O-戊基黄原酸、O-己基黄原酸、O-庚基黄原酸、O-辛基黄原酸、O-壬基黄原酸、O-癸基黄原酸、O-十一烷基黄原酸、O-十二烷基黄原酸。含有吡啶衍生物(例如十二烷基吡啶)的有机稳定剂和/或可稳定金属纳米粒子的有机膦(organophosphine)也可用作稳定剂。
经稳定的银纳米粒子的另外的例子可包括：描述于美国专利申请公布No.2009/0148600中的羧酸-有机胺络合物稳定的银纳米粒子；描述于美国专利申请公布No.2007/0099357A1中的羧酸稳定剂银纳米粒子；和描述于美国专利申请公布No.2009/0181183中的可热去除的稳定剂和可UV分解的稳定剂。
稳定材料可涂布金属纳米粒子，以降低或消除纳米粒子在通过激光加热时点燃或爆炸的可能性。例如，稳定材料可形成充当缓冲的至少部分围绕金属纳米粒子的非导电有机壳。金属纳米粒子的爆炸可使用Kst爆炸值评价。在一些实施例中，Kst值可小于100bar*m/sec，小于50bar*m/sec，或小于25bar*m/sec。Kst表示定容爆炸的尺寸归一化的最大压力上升速率，如使用标准化测试工序在标准化设备中所测定。其为爆炸性参数。
金属纳米粒子可以以约65wt％至约75wt％、约75wt％至约85wt％、约85wt％至约95wt％或更多的量存在于经稳定的纳米粒子基体中，且稳定材料可以以约5wt％至约15wt％、约15wt％至约25wt％、约25wt％至约35wt％或更多的量存在于经稳定的纳米粒子基体中。金属纳米粒子可以以约20vol％至约30vol％、约30vol％至约40vol％、约40vol％至约50vol％、约50vol％至约60vol％或更多的量存在于经稳定的纳米粒子基体中，且稳定材料可以以约40vol％至约50vol％、约50vol％至约60vol％、约60vol％至约70vol％或更多的量存在于经稳定的纳米粒子基体中。在一个实施例中，金属纳米粒子可以以约20vol％至约49vol％的量存在于经稳定的纳米粒子基体中，且稳定材料可以以约51vol％至约80vol％的量存在于经稳定的纳米粒子基体中。
金属纳米粒子和/或经稳定的纳米粒子基体(即金属纳米粒子加上稳定材料)可以以至少三种不同的形式装载至3D打印机中。在第一形式中，金属纳米粒子和/或经稳定的纳米粒子基体可附聚而形成平均横截面长度(例如直径)为约1μm至约500μm、约5μm至约250μm或约100μm至约250μm的粒子。换言之，3D打印机中所用的金属纳米粒子可为微米粒子。每个微粒可包括多个纳米粒子。
在第二形式中，金属纳米粒子和/或经稳定的纳米粒子基体可在一种或多种液体溶剂中分散，以形成糊剂。溶剂可为或包括烃、醇、酯、酮、醚或它们的组合。示例性的烃包括脂族烃(如萘烷、联环己烷(bicyclohexyl)、十二烷、十四烷、Isopar等)、芳族烃(如二甲苯、三甲苯、乙苯、丙苯、丁苯、戊苯、甲基乙基苯、四氢化萘等)。示例性的醇可包括萜品醇、乙二醇、乙醇、丁醇、卡必醇等。示例性的酯可包括丙二醇乙酸单乙酯(PGMEA)或DPGMEA。糊剂可防止金属纳米粒子在制造过程中形成尘雾。另外，使用溶剂稀释基体还可降低纳米粒子被激光加热时点燃或爆炸的风险。此外，糊剂可在制造床(如下所述)中更均匀地以层施用，这可提供打印物品中更大的均匀度。
在第三形式中，金属纳米粒子可分散于聚合物基质中，以形成微米尺寸的粒子(例如粉末)。聚合物基质可为或包括聚酯、聚碳酸酯、聚苯乙烯、丙烯酸酯聚合物、聚乙烯基吡啶、聚乙烯基吡咯烷酮或它们的组合。微米尺寸的粒子可通过如下方式形成：将金属纳米粒子分散于溶剂(例如如上公开的溶剂中的一种或多种)中、干燥金属纳米粒子以及分解所得固体以形成微米粉末。
图1显示了根据所公开的一个或多个实施例的用于打印3D金属物品的示例性3D打印机100。打印机100可包括传递床110和传递活塞116，所述传递床110由一个或多个侧壁112限定。经稳定的金属纳米粒子(例如基体)102可以以粉末和/或糊剂的形式装载至传递床110中。一旦装载，则经稳定的金属纳米粒子102的上表面104可与侧壁112的上表面114齐平或在侧壁112的上表面114以下。传递活塞116可随后在箭头118的方向上向上移动，直至经稳定的纳米粒子102的上表面104与侧壁112的上表面114齐平或在侧壁112的上表面114以上。
转移构件(例如辊)120可随后将在侧壁112的上表面114以上的经稳定的金属纳米粒子102的一部分106从传递床110转移至制造床130中(例如在箭头122的方向上)。制造床130可由一个或多个侧壁132和制造活塞136限定。经稳定的纳米粒子102的被转移的部分106可在制造床130中形成厚度为约10μm至约50μm、约50μm至约100μm、约100μm至约250μm或更大的第一层。
扫描系统140可扫描第一层中的经稳定的金属纳米粒子102，激光142可随后响应扫描结果而烧结第一层。激光142可为连续波激光或脉冲激光。当激光142为脉冲激光时，可调节脉冲长度和间隔以获得适当的烧结。例如，当在打印过程中使用金属纳米粒子糊剂时，脉冲可具有相对较长的间隔(例如约100ms至约5s)，以提供使溶剂至少部分蒸发的时间。烧结可在小于或等于约200℃的温度下，在小于或等于约150℃、小于或等于约125℃、或小于或等于约100℃的温度下发生。
一旦第一层已在制造床130中烧结，传递活塞116可随后在箭头118的方向上再次向上移动，直至经稳定的纳米粒子102的上表面104再次与传递床110的侧壁112的上表面114齐平或在传递床110的侧壁112的上表面114以上。制造活塞136可向下移动。转移构件120可随后将侧壁112的上表面114以上的经稳定的纳米粒子102的另一部分从传递床110转移至制造床130中，以在第一层上和/或第一层上方形成第二层。激光142可随后烧结第二层。可重复该过程直至产生所需的3D物品。
实例
如下实例为了说明的目的而提供，且不旨在为限制性的。在包含30ml萘烷和6ml甲醇的溶剂中混合88.91g十二烷基胺。混合物在氩气氛下在反应烧瓶中加热至40℃，直至十二烷基胺溶解。混合物随后降低至30℃，当混合物搅拌时将6.54g还原剂(苯肼)添加至混合物中。随后在30℃至35℃之间的温度下在2小时时间内将20g乙酸银逐渐添加至混合物中。这导致混合物的颜色由澄清改变为深棕色，这表明银纳米粒子的形成。
随后将混合物加热至40℃，并搅拌1小时。随后通过在搅拌的同时添加100ml甲醇而使混合物沉淀，然后通过过滤收集混合物。将收集的固体转移至玻璃烧杯，并在50ml甲醇中搅拌。该产物通过过滤收集，并在室温(例如20℃)下在真空烘箱中干燥24小时，生成13.11g深蓝色银纳米粒子。银含量为87.6wt％，如通过灰(Ash)技术所测得。假设银纳米粒子的密度为10g/ml，十二烷基胺的密度为1.0g/ml，则在经稳定的银纳米粒子中的银估计为约41vol％。
使银纳米粒子粉末进行Kst测量。据发现Kst值为约20bar*m/sec，表明粉末为非爆炸性的。这可能是由于在银纳米粒子粉末中高体积百分比的稳定剂。在其他实施例中，Kst值可小于50bar*m/sec。
将银纳米粒子配制为在聚对苯二甲酸乙二醇酯(“PET”)基材上的作为薄线条的喷墨油墨。打印线条的一部分在130℃下在烘箱中热烧结10分钟，而使线条的剩余部分经受在100μs至50ms的不同脉冲长度下的脉冲光熔融。据发现，打印线条可使用脉冲光烧结，以获得与通过热烧结而烧结的那些相同的电导率。脉冲光可包括激光、氙灯、汞灯或它们的组合。
也将银纳米粒子的一部分分散于萜品醇中作为糊剂。将糊剂装载至传递床中。使用刮片将银糊剂的均匀层(约200μm)施用至制造床。使用氩激光(488nm)在所需位置处将银纳米粒子烧结成纯的导电银。银纳米粒子具有约420nm至约440nm的表面等离子体吸收。在烧结银纳米粒子的第一层之后，将传递活塞提升约200μm，使用刮片将银糊剂的第二层转移至制造床。第二层为约200μm厚。使用激光烧结糊剂的第二层，以继续构建3D物品。
尽管列出了本教导的广范围的数值范围和参数为近似值，在具体实例中列出的数值尽可能精确地进行报道。然而，任何数值固有地含有必然源于在它们各自的测试测量中所出现的标准偏差的某些误差。此外，本文公开的所有范围应理解为涵盖其中包括的任何和所有子范围。例如，“小于10”的范围可包括在最小值零和最大值10之间的任何和所有子范围(包括最小值零和最大值10)，即，具有等于或大于零的最小值和等于或小于10的最大值的任何和所有子范围，例如1至5。
Claims (17)
1.一种用于3D打印机中的材料，所述材料包含：
平均横截面长度为1μm至250μm的多个金属微粒，其中所述金属微粒包含：
平均横截面长度小于或等于50nm的多个金属纳米粒子，所述金属纳米粒子在不连续相中；和
布置在所述纳米粒子外表面上的稳定材料，其中所述稳定材料包括有机胺、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮或它们的组合。
2.根据权利要求1所述的材料，其中所述金属纳米粒子的平均横截面长度小于或等于20nm。
3.根据权利要求2所述的材料，其中所述金属纳米粒子包括金、银、铝、铂、钯、铜、钴、铬、铟、钛、锆、镍、它们的合金或它们的组合。
4.根据权利要求2所述的材料，其中所述金属纳米粒子配置为在小于或等于200℃的温度下熔化。
5.根据权利要求4所述的材料，其中所述稳定材料至少部分覆盖所述金属纳米粒子，且其中具有所述稳定材料的所述金属纳米粒子具有小于或等于100nm的平均横截面长度。
6.根据权利要求4所述的材料，其中所述金属纳米粒子以65wt％至95wt％的量存在于所述材料中，且所述稳定材料以5wt％至35wt％的量存在于所述材料中。
7.根据权利要求6所述的材料，其中所述金属纳米粒子以20vol％至49vol％的量存在于所述材料中，且所述稳定材料以51vol％至80vol％的量存在于所述材料中。
8.根据权利要求1所述的材料，其还包含溶剂，所述溶剂包括烃、醇、酮、酯、醚或它们的组合。
9.根据权利要求1所述的材料，其中所述金属纳米粒子和所述稳定材料附聚而形成所述微粒。
10.根据权利要求1所述的材料，其中所述金属微粒具有小于50
bar*m/sec的爆炸Kst值。
11.一种使用3D打印机打印物品的方法，所述方法包括：
将多个经稳定的金属微粒装载至所述3D打印机的传递床中，其中所述经稳定的金属微粒具有1μm至250μm的平均横截面长度，并且其中所述经稳定的金属微粒包括：
多个金属纳米粒子，所述多个金属纳米粒子具有小于或等于50nm的平均横截面长度，并且所述金属纳米粒子在不连续相中；和
在所述纳米粒子外表面上的稳定材料，所述稳定材料包括有机胺、聚乙二醇、聚乙烯基吡啶、聚乙烯基吡咯烷酮或它们的组合；
将所述经稳定的金属微粒的一部分由所述传递床转移至所述3D打印机的制造床；和
在小于或等于200℃的温度下在所述制造床中烧结所述经稳定的金属微粒，以形成打印物品。
12.根据权利要求11所述的方法，其中将所述经稳定的金属微粒的所述部分转移至所述制造床包括形成具有10μm至250μm厚度的所述经稳定的金属微粒层。
13.根据权利要求11所述的方法，其中所述烧结通过多次脉冲光进行。
14.根据权利要求11所述的方法，其中所述经稳定的金属微粒是糊剂的形式并且还包含溶剂，且其中所述溶剂包括烃、醇、酮、酯、醚或它们的组合。
15.根据权利要求11所述的方法，其中所述金属纳米粒子以65wt％至95wt％的量存在于所述经稳定的金属微粒中，并且其中所述稳定材料以5wt％至35wt％的量存在于所述经稳定的金属微粒中。
16.根据权利要求11所述的方法，其中所述金属纳米粒子以20vol％至60vol％的量存在于所述经稳定的金属微粒中，并且其中所述稳定材料以40vol％至80vol％的量存在于所述经稳定的金属微粒中。
17.根据权利要求11所述的方法，其中所述打印物品配置为烧结后具有小于或等于25μm的分辨率。
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| US20130344232A1 (en) * | 2012-06-22 | 2013-12-26 | Xerox Corporation | Methods of forming conductive features on three-dimensional objects |
| CN103785860B (zh) * | 2014-01-22 | 2016-06-15 | 宁波广博纳米新材料股份有限公司 | 3d打印机用的金属粉末及其制备方法 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001152204A (ja) * | 1999-11-25 | 2001-06-05 | Matsushita Electric Works Ltd | 三次元形状造形物製造用の粉末材料、三次元形状造形物の製造方法、および、三次元形状造形物 |
| JP2013041683A (ja) * | 2011-08-11 | 2013-02-28 | Tamura Seisakusho Co Ltd | 導電性材料 |
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| RU2015116659A (ru) | 2016-11-20 |
| JP2015218395A (ja) | 2015-12-07 |
| CA2891304A1 (en) | 2015-11-16 |
| DE102015208141A1 (de) | 2015-11-19 |
| RU2015116659A3 (zh) | 2018-05-18 |
| US9505058B2 (en) | 2016-11-29 |
| JP6518121B2 (ja) | 2019-05-22 |
| RU2662044C2 (ru) | 2018-07-23 |
| CA2891304C (en) | 2019-01-15 |
| CN105081306A (zh) | 2015-11-25 |
| US20150328835A1 (en) | 2015-11-19 |
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