CN112088148B - 用于增材制造技术的陶瓷浆料 - Google Patents

用于增材制造技术的陶瓷浆料 Download PDF

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CN112088148B
CN112088148B CN201980032227.5A CN201980032227A CN112088148B CN 112088148 B CN112088148 B CN 112088148B CN 201980032227 A CN201980032227 A CN 201980032227A CN 112088148 B CN112088148 B CN 112088148B
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ceramic
particles
slurry
ceramic slurry
ceramic particles
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CN112088148A (zh
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C·A·赫尔
杨熙
M·J·奥布里恩
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General Electric Co
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General Electric Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
    • B28B11/243—Setting, e.g. drying, dehydrating or firing ceramic articles
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    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract

用于形成陶瓷制品的陶瓷浆料包括粘结剂、具有第一形态的第一多个陶瓷颗粒、具有不同于所述第一形态的第二形态的第二多个陶瓷颗粒；和光引发剂。还呈现了使用该浆料制造陶瓷制品的方法。

Description

用于增材制造技术的陶瓷浆料
背景
本文公开的主题涉及可光固化的陶瓷浆料，并且更具体地，涉及适用于增材制造(3D打印)技术的可光固化的陶瓷浆料。
陶瓷浆料可用于制造陶瓷部件，例如用于高温应用的耐火组件、固定/支撑结构和热绝缘材料。典型的陶瓷浆料通常包括有机粘结剂，例如可光固化的有机树脂、陶瓷颗粒和添加剂(例如分散剂、光引发剂和稳定剂等)。这些制剂例如在牙科工业中是常见的。一旦已形成并沉积了可光固化的陶瓷浆料，合适的光源就可以提供固化(即聚合)有机粘结剂所需的活化能，使得陶瓷颗粒通过聚合的粘结剂彼此粘合，产生具有所需形状的所谓的生(即未烧制的)陶瓷部件。一旦固化，可以将生陶瓷部件部分烧制，即，加热至低于陶瓷颗粒的烧结温度的温度，以从生陶瓷部件释放有机物(例如脱脂(debind))，产生所谓的棕色陶瓷部件。随后，将棕色陶瓷部件完全烧制(“烧结”)，使得陶瓷颗粒熔合成最终的陶瓷制品。
简要描述
下面概述与最初要求保护的主题的范围相当的某些实施方案。这些实施方案不旨在限制所要求保护的发明的范围，而是这些实施方案仅旨在提供本发明的可能形式的简要概述。实际上，本公开可以涵盖与下面阐述的实施方案可以类似或不同的各种形式。
在一个实施方案中，用于形成陶瓷制品的陶瓷浆料包括粘结剂、具有第一形态的第一多个陶瓷颗粒、具有不同于所述第一形态的第二形态的第二多个陶瓷颗粒和光引发剂。
在第二实施方案中，用于制造制品的方法包括将上述浆料组合物沉积到工作表面上；使至少一部分所述浆料组合物固化以形成生陶瓷材料；将所述生陶瓷材料脱脂以形成棕色陶瓷材料；和烧结所述棕色陶瓷材料以形成最终陶瓷制品。
附图简述
当参照附图阅读以下详细描述时，本发明的这些和其它特征、方面和优点将变得更好理解，其中在整个附图中，相同的字符表示相同的部件，其中：
图1为根据本方法的实施方案，用于制造陶瓷部件的方法的流程图；和
图2为根据本方法的实施方案，用具有含有氧化钇掺杂剂的氧化铝颗粒和丙烯酸酯粘结剂的陶瓷浆料或具有氧化铝颗粒和混杂粘结剂的陶瓷浆料打印的陶瓷部件的平均净收缩(%)的代表性柱状图，其中两种情况的氧化铝颗粒均为圆形和有角颗粒的混合物。
详细描述
下面将描述一个或多个具体实施方案。在试图提供这些实施方案的简明描述中，在说明书中可能没有描述实际实现的所有特征。应当理解，在任何这样的实际实现的开发中，如在任何工程或设计项目中，必须做出许多实现特定的决定以达到开发者的特定目标，例如符合系统相关的和商业相关的约束，其可能从一个实现到另一个实现而变化。此外，应当理解，这样的开发努力可能是复杂且耗时的，但对于受益于本公开的普通技术人员而言，仍然是设计、制作和制造的常规任务。
当介绍本发明的各种实施方案的要素时，冠词“a”、“an”、“the”和“所述”旨在是指存在一个或多个要素。术语“包含”、“包括”和“具有”旨在为包括性的，并且是指可以存在除了所列出的要素之外的另外的要素。此外，以下讨论中的任何数值实例旨在为非限制性的，并且因此另外的数值、范围和百分比在所公开的实施方案的范围内。
如本文所用，“工作表面”旨在表示在增材制造方法期间陶瓷浆料可在其上沉积的表面。工作表面可以包括3D打印机的工作平台或打印的陶瓷层。如本文所用，“粘结剂”表示将未烧制状态的陶瓷颗粒粘结在一起的至少一种材料。如本文所用，术语“形态”当用于颗粒特性的上下文中时是指颗粒的形状。如本文所用，“球度”表示具有与颗粒相同体积的球体的表面积与颗粒的表面积的比率，其中完美球形颗粒的球度为1。具有高球度的颗粒具有与球形颗粒的形态相似的形态，而具有低球度的颗粒具有较少球形且更有角的形态。即，颗粒的球度是指颗粒的形状与完美球体有多接近。如本文所用，“光引发剂”表示在暴露于波长在相应的光活化波长范围内的电磁辐射时对粘结剂的固化反应具有催化作用的化合物。
有许多用于制造制品(例如用于各种应用的金属和陶瓷制品)的技术。例如，模塑技术(例如粉浆浇铸、冷冻浇铸和/或注塑等)可用于制造用于耐火应用的陶瓷部件。为了形成适用于例如耐火支撑物和固定装置、陶瓷模具和芯、传感器组件、高温过滤器和其它应用的多孔陶瓷体，可以由大的粗颗粒(例如中值粒度(d50)在30微米(μm)和60 μm之间的颗粒)制备陶瓷浆料，以减轻陶瓷颗粒在烧制以产生陶瓷制品期间的收缩和致密化。
通过常规的模塑技术制造定制设计的陶瓷制品或其它耐火组件通常增加成本。另外，某些设计不能用传统的工具制造。例如，某些陶瓷制品可以使用模具制造，如在注塑和其它模塑方法中。使用模具导致制造时间和成本问题，部分是由于与产生和去除模具相关的制备和处理步骤。另外，模具可能含有残余物，该残余物可能转移到陶瓷制品的表面上，并影响陶瓷制品的整体质量。此外，使用传统模具可能非常难以或甚至不可能形成具有高度复杂性的形状。由于这些原因，使用增材制造技术(在本文中也称为3D打印)来制造陶瓷部件在许多情况下可能是有利的。通过非限制性实例，可用于制造陶瓷制品的增材制造技术包括数字光处理(DLP)、立体光刻(SLA)、粘结剂喷射沉积、喷墨沉积或任何其它合适的增材制造形式。增材制造技术可以提供在不使用模具的情况下制造复杂陶瓷制品的能力，同时还降低制造成本，这部分是由于使用较少的材料(例如，不使用金属冲模和模具，并且使用较少的陶瓷浆料)以及与3D打印相关联的短处理时间。此外，增材制造技术可允许制造具有超出其它制造技术(例如，模塑技术)的限制的复杂几何形状和复杂度的陶瓷制品。
在增材制造技术中，将具有粘结剂(例如可光固化的粘结剂)的陶瓷浆料的层(通常为微米至毫米厚)沉积到工作表面上。一旦已沉积了浆料的层，就可以将其固化，即凝固，例如通过加热、通过与周围环境中的湿气反应、或通过用具有合适波长(例如紫外线、可见光)的电磁辐射照射以引发粘结剂的聚合。该层的全部或仅选定部分可经受固化以形成“生” (未烧制的)陶瓷材料的层。随后，在前一层生陶瓷上沉积另一层浆料，选择性地固化新的层，并重复该逐层过程，直到实现生陶瓷制品的所需结构。可以将生陶瓷制品部分烧制以实现“棕色”陶瓷制品，然后完全烧制(例如烧结)以实现最终陶瓷制品。
耐火组件的增材制造通常沉积约25 μm厚的陶瓷浆料的层。因此，用于增材制造应用的陶瓷浆料通常由d50小于25 μm的细陶瓷颗粒制成。例如，陶瓷浆料可以包括d50在约1 μm和25 μm之间的陶瓷颗粒。然而，相对于使用较大颗粒形成的浆料，使用细陶瓷颗粒通常增加陶瓷浆料的粘度。如果陶瓷浆料的粘度太高，则浆料可能不适合通过典型的增材制造技术来处理。降低浆料粘度的一种方法为增加浆料中陶瓷颗粒的粒度，但是由于上文针对颗粒的尺寸指出的约束，该策略的有效性在增材制造技术中受到限制。因此，认识到设计适用于3D打印的陶瓷浆料制剂是具有挑战性的。
此外，由具有单一/均匀形态和d50小于25 μm (例如，在约1 μm和25 μm之间)的细陶瓷颗粒制成的陶瓷浆料对于增材制造应用也可能是不期望的。例如，由具有单一形态的细陶瓷颗粒(即具有均匀的高球度的陶瓷颗粒)制成的陶瓷浆料制造的陶瓷制品可能导致在烧制后陶瓷制品的不期望的收缩和致密化。因此，陶瓷制品的孔隙率(即孔的体积浓度)可能不适合其中待使用陶瓷制品的所需应用。另外，由过度收缩引起的致密化可增加陶瓷制品的工作强度、热导率、重量或其它性质，使得陶瓷制品可能不适合其预期用途。如上所述，用于使用非增材制造技术制造陶瓷制品的某些陶瓷浆料可以包括d50大于25 μm (例如，在约30 μm和60 μm之间)的粗陶瓷颗粒，以减轻在烧结后陶瓷制品的致密化。因此，需要开发适用于陶瓷制品的3D打印的陶瓷浆料，其在后打印方法期间不导致陶瓷制品的收缩和致密化。
考虑到上述内容，发明人已经认识到，包括具有不同形态的细陶瓷颗粒的混合物而不是具有均匀形态的陶瓷颗粒的某些陶瓷浆料非常适合于陶瓷制品的3D打印。因此，本发明的实施方案涉及陶瓷浆料，其包括具有不同形态的细陶瓷颗粒的混合物，例如，各类颗粒的混合物，其中一类具有相对高的球度(例如，标称球形颗粒)，而第二类颗粒具有相对低的球度(例如，具有更多的小平面或有角形态的颗粒)。如以下讨论的，与常规的陶瓷浆料制剂相比，所公开的陶瓷浆料制剂可以降低打印的陶瓷制品的烧结收缩和致密化。另外，如以下进一步详细讨论的，所公开的陶瓷浆料制剂内的不同颗粒形态提供适合3D打印的浆料粘度。例如，与仅具有基本均匀的低球度形态的细陶瓷颗粒的其它陶瓷浆料相比，在所公开的陶瓷浆料制剂内，圆形、球状的细陶瓷颗粒可更容易地在流动浆料内彼此滑过，降低了浆料粘度。
因此，本文公开的本发明的实施方案包括陶瓷浆料制剂，其包括具有不同形态(例如，圆形和有角)的细陶瓷颗粒(例如，d50小于约25 μm)的混合物，其中浆料制剂适合于多孔陶瓷制品的增材制造，所述多孔陶瓷制品例如耐火支撑物和固定装置、陶瓷模具和芯、传感器组件、高温过滤器等。如以下进一步详细讨论的，所公开的陶瓷浆料制剂的一些实施方案包括至少两类细陶瓷颗粒的混合物，其中各类具有不同的颗粒球度。如本文所用，术语“圆形”是指具有相对高的球度的陶瓷颗粒的类别。如本文所用，术语“有角”是指具有比“圆形”类颗粒更低球度的细陶瓷颗粒。另外，如以下讨论的，使用所公开的陶瓷浆料制剂3D打印的陶瓷制品在烧制(例如，烧结)之后具有期望的密度和孔隙率。
一个实施方案是陶瓷浆料，其包括粘结剂、第一多个陶瓷颗粒、第二多个陶瓷颗粒和光引发剂。根据本公开，浆料可进一步包括溶剂、光敏剂、分散剂、稳定剂、消泡剂、润湿剂、脱模剂等。可以理解，可以以不同的顺序混合各种成分。例如，在某些实施方案中，可首先加入树脂，然后可加入添加剂以形成可光固化的粘结剂。在形成可光固化的粘结剂之后，可以加入细陶瓷颗粒的混合物以形成陶瓷浆料。在某些实施方案中，陶瓷浆料可以机械混合、手动混合、声波混合或其组合，以实现所需的稠度。
第一多个颗粒具有第一形态，而第二多个颗粒具有不同于所述第一形态的第二形态。在某些实施方案中，相应的多个颗粒的颗粒形态之间的该差异的特征在于颗粒接近完美球体形状的程度的差异；如前所述，在本领域中使用数学量球度来量化该特性。出于本公开的目的，多个颗粒的球度是指对颗粒的代表性样品测量的中值球度。因此，在这样的实施方案中，第一多个颗粒具有第一球度，而第二多个颗粒的球度小于第一多个颗粒的球度。在物理术语中，第一多个颗粒比第二多个颗粒更“球状”。这些更球状的颗粒可有助于保持足够低的浆料粘度用于增材制造方法中的有效流动。在一些实施方案中，第一多个颗粒的球度为至少0.9。第二多个颗粒较少球形，并且在一些情况下呈现小平面或有角形态；这样的形状的颗粒倾向于降低浆料的陶瓷材料在烧制期间致密化的倾向，在最终制品中保持所需水平的孔隙率。在一些实施方案中，第二多个颗粒的球度小于0.9，例如小于0.85，并且在一些情况下，小于0.8。
在颗粒形状表征领域中通常应用其它参数，并因此显而易见的是，除了球度之外，或代替球度，可使用其它参数如圆度(边缘或角的平均曲率半径与最大内切球体的曲率半径的比率)和纵横比(最长凸起与最小凸起的比率)来区分第一多个颗粒与第二多个颗粒。通常，第一多个颗粒具有比第二多个颗粒更高的圆度和更接近1的纵横比。这些特性指示第一多个颗粒比第二多个颗粒更接近球形。本领域中使用的陶瓷粉末常规地合成、研磨、筛分和/或以其它方式处理，以提供所需的形态和尺寸分布。本领域技术人员将理解，工业中的供应商可容易地供应具有由购买者指定的形态特性(如球度)的颗粒。
陶瓷浆料中的颗粒形态的混合物促进对于增材制造可能适宜地低的粘度。例如，圆形细陶瓷颗粒的圆形形态被认为允许圆形细陶瓷颗粒容易地滑过陶瓷浆料中的其它细陶瓷颗粒。然而，当在浆料中单独使用时，圆形细陶瓷颗粒在脱脂和烧结期间可能滑动并重排成更紧密填充的结构，导致过度水平的收缩和致密化。为了减轻该效应，所公开的陶瓷浆料还包括较低球形陶瓷颗粒，所述较低球形陶瓷颗粒在脱脂和烧结期间由于其不同的形态而较不易于滑动和重排。例如，有角颗粒可以在打印的陶瓷制品中的更球形陶瓷颗粒之间产生并保持空隙(例如，间隙、空间)。由此产生的空隙可以减少陶瓷颗粒的颗粒填充，并因此减少3D打印的陶瓷制品在烧结期间的收缩和致密化。因此，通过在陶瓷浆料中使用所公开的高球度陶瓷颗粒和低球度陶瓷颗粒的混合物，与使用缺少所公开的陶瓷颗粒的混合物的陶瓷浆料制成的陶瓷制品相比，可以降低打印的陶瓷制品的收缩和致密化。因此，所公开的3D打印的陶瓷制品通常具有用于其预期应用的期望的密度和孔隙率。
粘结剂(该术语旨在包括在后续处理期间最终形成粘结剂的前体材料)允许陶瓷颗粒在沉积到工作表面上之后彼此粘合，从而形成生陶瓷制品。粘结剂的实例包括有机树脂，其通常包括一种或多种可转化为聚合物的有机化合物。在某些实施方案中，粘结剂包括能够通过自由基机制固化的单官能、二官能和/或多官能的丙烯酸酯和/或甲基丙烯酸酯的混合物。这些丙烯酸酯和甲基丙烯酸酯本质上可以是单体、低聚物或多聚物的。可用于形成粘结剂的材料的实例包括三环癸烷二甲醇二丙烯酸酯、双酚A乙氧基化物二丙烯酸酯、丙烯酸异冰片酯、甲基丙烯酸异冰片酯、二氨基甲酸酯二甲基丙烯酸酯、三羟甲基丙烷乙氧基化物三丙烯酸酯、丙烯酸化聚氨酯和丙烯酸化聚酯。任选地，也可以加入能够通过硫醇-烯反应与丙烯酸酯和甲基丙烯酸酯反应的多官能硫醇。实例包括三羟甲基丙烷三(2-巯基乙酸酯)和三羟甲基丙烷三(3-巯基丙酸酯)。
在另一个实施方案中，粘结剂含有可阳离子固化的单体，例如环氧类、氧杂环丁烷类和/或乙烯基醚。这样的单体的实例包括3,4-环氧环己烷甲酸3,4-环氧环己基甲酯、氢化双酚A二缩水甘油醚低聚物、3-乙基-3-氧杂环丁烷甲醇和1,4-环己烷二甲醇二乙烯基醚。任选地，也可以包括多元醇，例如聚(四氢呋喃)和/或聚己内酯三醇。
在某些实施方案中，本文公开的浆料包括混杂粘结剂。如本文所用，术语“混杂粘结剂”是指包括与反应性硅氧烷混合的有机树脂的粘结剂。例如，在光固化的浆料体系中，当陶瓷浆料的光引发剂暴露于光活化波长范围内的光(例如在所谓的“UV固化的”制剂中的紫外光)时，有机树脂组分和反应性硅氧烷组分聚合。反应性硅氧烷组分可包括能够与有机树脂组分共聚的多官能、短(例如，在约3和约8个硅氧烷(Si-O)单元之间)、环状硅氧烷或多官能、较长、直链硅氧烷聚合物。例如，在某些实施方案中，反应性硅氧烷可包括2、3、4、5、6、7、8个或更多个能够在固化条件下聚合(例如，共聚或均聚)的官能团(例如，乙烯基)。所公开的混杂粘结剂的反应性硅氧烷组分可包括以下中的一种或多种：四乙烯基四甲基环四硅氧烷(D4 Vi)、四(乙烯基二甲基甲硅烷氧基)硅烷(M4 ViQ)、乙烯基甲氧基硅氧烷均聚物(ViOMe，以零件号VMM-010可从Gelest of Morrisville, PA获得)、乙烯基甲基硅氧烷环状化合物(Dx Vi环状化合物，以零件号VMS-005可从Gelest获得)、来自巯基丙基甲基二甲氧基硅烷的水解的混合线性和环状硅氧烷(Dx’)以及甲基丙烯酸酯官能的硅酮树脂。虽然混杂粘结剂的有机树脂部分在部分烧制期间分解并挥发，但是硅氧烷部分转化为二氧化硅，所述二氧化硅被布置在陶瓷颗粒的混合物周围(例如，之间、四周)，以相对于用非混杂粘结剂(例如，仅含有有机树脂)制成的类似部件，增强棕色陶瓷部件的处理强度。混杂粘结剂衍生的二氧化硅与氧化铝颗粒反应以形成铝硅酸盐(例如莫来石)，从而降低氧化铝致密化和烧结收缩。
在其中浆料制剂可通过暴露于电磁辐射而可固化的实施方案中，所公开的浆料通常包括至少一种光引发剂。光引发剂可包括任何合适的结构，该结构能够吸收由活化能源发射的光(例如UV、可见光)，并作为响应，促进粘结剂的固化。例如，在某些实施方案中，光引发剂可以是或包括：2-羟基-2-甲基苯丙酮(HMPP)；苯基二(2,4,6-三甲基苯甲酰基)氧化膦(PBTMBPO) (例如，IRGACURE® 819)；2-羟基-2-甲基-1-苯基-1-丙酮(例如Darocur®1173)；二苯基(2,4,6-三甲基苯甲酰基)氧化膦(例如，Darocur® TPO)；或1-羟基环己基苯基酮(例如IRGACURE® 184)或其它合适的光引发剂。在某些实施方案中，光敏剂和/或光酸产生剂可以与光引发剂结合使用以促进浆料的固化。例如，在某些实施方案中，浆料可以包括4-苯甲酰基-4'-甲基-二苯硫醚、异丙基噻吨酮或9,10-二乙氧基蒽作为光敏剂。在某些实施方案中，浆料可以包括一种或多种二芳基碘鎓和三芳基锍盐，例如四(五氟苯基)硼酸(对甲基苯基)碘鎓，或锍盐UVI-6976或UVI-6990 (可从Dow Chemical, Midland, MI,U.S.A.获得)作为光酸产生剂。在某些实施方案中，可光固化的陶瓷浆料可以包括Omnicat432和550 (可从IGM Resins, Waalwijk, The Netherlands获得)、PAG 290 (可从BASF获得)、SL-6992 (可从Esstech, Inc., Essington, PA, U.S.A.获得)、或碘鎓盐IRGACURE®250 (可从BASF获得)、Omnicat 440 (可从IGM Resins获得)或UV9380C (MomentivePerformance Materials, Waterford, NY, U.S.A.)中的一种或多种作为光酸产生剂。
浆料可以含有任选的添加剂，例如分散剂、染料和稳定剂。用于这些功能的典型材料及其相应的浓度将是本领域从业者容易知道或可辨别的。在一些实施方案中，分散剂可用于改变陶瓷浆料的粘度。分散剂是当以小比例(通常小于整个浆料的5重量%)加入时，可改变浆料的流变性质的任何化学品或化学品的混合物。分散剂的选择将取决于陶瓷颗粒表面和粘结剂的性质以及在一定剪切速率下所需的粘度和流变行为。分散剂的实例包括但不限于Triton™ X-100 (Dow Chemical Company)、Variquat®产品(Evonik Industries)、Jeffamine® (Huntsman)、油胺、油酸、硬脂酸、Hypermer™ KD产品(Croda)和Silwet™(Momentive Performance Materials Inc.)。
通常将陶瓷颗粒与粘结剂混合以形成浆料，例如可光固化的陶瓷浆料。在某些实施方案中，浆料中的陶瓷颗粒(即包括第一多个颗粒和第二多个颗粒)的总颗粒负载在浆料的约45体积%至约75体积%的范围内。第一多个陶瓷颗粒和第二多个陶瓷颗粒可以各自以任何合适的相对比例负载。例如，在某些实施方案中，浆料包含约20%至约99%的第一多个陶瓷颗粒和约1%至约80%的第二多个陶瓷颗粒，其中这些相对比例表示为存在于浆料中的总陶瓷加入的体积百分比。第一多个颗粒与第二多个颗粒的相对体积比的实例包括但不限于90:10、85:15、75:25、60:40、50:50、40:60和30:70；相对比率的选择将取决于许多因素，尤其包括浆料的所需粘度、固化的制品的生强度和成品制品的孔隙率。在某些实施方案中，第一多个颗粒与第二多个颗粒的体积比为至少1.5 (即，至少3体积份的第一多个颗粒:2体积份的第二多个颗粒)；具有相对高水平的更球形的颗粒可有助于将浆料粘度保持在可用于某些增材制造技术的范围内。用于第一多个和第二多个的陶瓷颗粒可以独立地包括任何合适的陶瓷材料中的一种或多种，通常但不是必须地，氧化物材料，实例包括但不限于二氧化硅、氧化铝、锆石、氧化锆、氧化钛、碳酸钠、氧化钙、三氧化二硼、氧化钇、铝酸钇、氧化镁、铝酸镁、碳酸钙、氧化铁、磨砂玻璃、氧化钴、氧化钠、氧化铒和包括这些中的一种或多种的任何组合。
如上所述，用于陶瓷部件的增材制造的陶瓷浆料通常由中值粒度分布(d50)小于25μm的陶瓷颗粒制成。例如，陶瓷颗粒的d50可以是约1 μm-25 μm，例如在约1 μm和25 μm、约2μm和25 μm、约5 μm和15 μm、或约10 μm和15 μm之间。
在一些情况下，浆料性质不仅受第一多个颗粒和第二多个颗粒的相对浓度水平的影响，而且受它们的尺寸影响。特别地，可以操纵两类颗粒形态之间的尺寸差异以达到所需的浆料特性。因此，在某些实施方案中，第一多个陶瓷颗粒可具有与第二多个陶瓷颗粒不同的d50值；在特定实施方案中，第一多个颗粒的d50大于第二多个颗粒的d50。例如，在某些实施方案中，第一多个陶瓷颗粒的d50在约8 μm至约15 μm的范围内，而第二多个陶瓷颗粒的d50在约2 μm至约8 μm的范围内。在一些情况下，通过使第二多个颗粒比第一多个颗粒相对更小，可以增强这些颗粒抑制过度收缩和/或致密化的效力，这是因为例如，具有较低球形形态的颗粒可以更容易地位于较大的、更球形颗粒之间，以在固结期间保持尺寸稳定性。在备选实施方案中，较低球形颗粒的d50大于更球形颗粒的d50；实验已经证明，该组合物也可以在处理的制品中导致期望水平的孔隙率。例如，在某些实施方案中，第一多个陶瓷颗粒的d50在约4 μm至约10 μm的范围内，而第二多个陶瓷颗粒的d50在约8 μm至约15 μm的范围内，其中第二多个颗粒的d50大于第一多个颗粒的d50。
下面阐述的实施例1描述可用于使用3D打印技术制造多孔陶瓷部件的陶瓷浆料。
实施例1
通过混合下列物质制备可光固化的树脂共混物：46份乙氧基化三羟甲基丙烷三丙烯酸酯和20份三环癸烷二甲醇二丙烯酸酯。可光固化的树脂共混物还包括34份二氨基甲酸酯二甲基丙烯酸酯和0.1份叔丁基儿茶酚(稳定剂)和2份双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(光引发剂)。可光固化的树脂粘结剂负载有约53体积%的具有以下氧化铝粉末组成的陶瓷颗粒：(1)约75%的具有相对高球度且d50为约12 μm的氧化铝颗粒和(2)约25%的相对于(1)的颗粒具有较低球度且d50为约6 μm的氧化铝颗粒。还将氧化钇(Y2O3)加入到粘结剂中，使得加入到浆料中的陶瓷粉末的总量由94重量%的氧化铝和6重量%的氧化钇组成；包括氧化钇以部分地降低在高温(例如，高于1200摄氏度(℃)的温度)下烧结的陶瓷部件中的蠕变倾向。
本发明的另一个实施方案包括使用本文所述的浆料组合物用于形成陶瓷制品的方法。说明的方法50包括将陶瓷浆料的层沉积(方框56)到工作表面上。如上所述，在某些实施方案中，陶瓷浆料的层可以沉积到3D打印机的工作平台上或沉积到正在形成的部件的先前固化的层的顶部上。沉积的浆料层的厚度范围可以从几微米到几毫米。在某些实施方案中，沉积的浆料层的厚度可以小于用于固化可光固化的陶瓷浆料的光源的穿透深度，以确保在照射(例如通过与3D打印机相关联的固化单元)时整个层完全固化。
说明的方法50继续用适于固化可光固化的陶瓷浆料的光源固化(方框58)可光固化的陶瓷浆料的沉积层的部分，以产生生陶瓷制品11的一部分。例如，固化单元可以包括光源(例如，激光、灯、LED)，其能够选择性地提供电磁活化能，该电磁活化能引发陶瓷浆料中的粘结剂的聚合，导致粘结剂的固化和生陶瓷制品11的固化层的形成。如箭头60所示，可重复进行方框56和58表示的步骤，以逐层方式构建整个生陶瓷制品11。在某些实施方案中，可将溶剂施加到生陶瓷制品11 (例如，在层沉积之间，在生陶瓷制品11的打印完成之后)，以从生陶瓷制品11的固化部分去除任何未固化的浆料。
说明的方法50继续在低于圆形和有角细陶瓷颗粒的烧结温度的温度下部分烧制(脱脂) (方框64)生陶瓷制品11，以去除粘结剂，产生处理强度，并产生棕色陶瓷制品68。可以理解，方框64的部分烧制步骤的温度应当足够高(例如，大于约500℃，在约500℃和约1000℃之间，在约500℃和约1200℃之间)，以确保粘结剂分解并从生陶瓷制品11中释放。通常选择在该部分烧制步骤期间温度升高的速率以确保粘结剂的分解和分解产物的释放不会快速发生以破坏制品。选择的具体速率和该步骤的持续时间将部分取决于粘结剂的组成和被烧制的浆料的体积(即，部件的尺寸)；这样的考虑对于本领域的从业者是熟悉的。对于一些部件，该部分烧制步骤的持续时间可以是约数天。通过具体实例，在某些实施方案中，可以首先将生陶瓷制品11在2天的过程中以缓慢的升温加热至最高温度(例如1200℃)，然后在最高温度下保持约30分钟。
可以理解，尽管方框64的部分烧制(脱脂)的温度通常低于用于制造生陶瓷制品11的特定陶瓷颗粒的烧结温度，但在某些实施方案中，在该部分烧制步骤期间可能发生有限量的烧结，这可能进一步提高棕色陶瓷制品68的强度。然而，可以理解，在部分烧制温度范围内发生的有限烧结仅代表在陶瓷颗粒表面之间的少量熔合。因此，在某些实施方案中，在部分烧制步骤期间发生的有限量的烧结可以有助于观察到的棕色陶瓷制品68的处理强度的改进。生陶瓷制品11通常在方框64的部分烧制步骤期间经历收缩(即脱脂收缩)，并且一般而言，较少的脱脂收缩通常有益于最终陶瓷部件的质量和产量。
说明的方法50继续在等于或高于陶瓷颗粒的烧结温度的温度下完全烧制(烧结)(方框70)棕色陶瓷制品68，以产生最终陶瓷制品。在该烧结步骤期间，将棕色陶瓷制品68加热至其中陶瓷颗粒熔合成基本连续的多孔陶瓷制品的温度。例如，通常将棕色陶瓷制品68暴露于能量源，该能量源加热棕色陶瓷制品68并固结棕色陶瓷制品68的打印层的混合形态陶瓷颗粒，以形成孔隙率小于或等于棕色陶瓷制品68的孔隙率的最终固结的陶瓷制品72。烧结赋予棕色陶瓷制品68强度和完整性，使得固结的陶瓷制品72适用于其预期应用。在某些实施方案中，方框70的完全烧制可以包括加热到至少约1500℃(例如，在约1500℃和1900℃之间)的温度合适的时间长度，例如，在约2和24小时之间。本领域技术人员将理解，根据例如材料的具体类型和制品最终使用所需的条件来调节温度和在该温度下的时间可能是可取的。
在方框70的完全烧制步骤期间，棕色陶瓷制品68通常经历收缩，并且对于多孔制品，较小的收缩通常有益于固结的陶瓷制品72的质量和产量。如前所述，通过使用本文公开的陶瓷浆料，其包括具有不同形态和/或尺寸的陶瓷颗粒的混合物，可以减轻陶瓷制品的收缩，以提供具有适用于多孔耐火制品的密度、强度和孔隙率的陶瓷制品。例如，在某些实施方案中，使用目前描述的陶瓷浆料可以在烧结棕色陶瓷制品68之后实现减小的收缩(例如小于3%)。通过非限制性实例，在烧结后棕色陶瓷制品68的平均净收缩可以在约0.25%和3%之间，使得最终陶瓷制品的孔隙率在约25%和45%之间。这种水平的孔隙率与由大的粗陶瓷颗粒(例如，d50在约25 μm和50 μm之间)制成的陶瓷浆料产生的陶瓷制品相当。
将上述实施例1的可光固化的陶瓷浆料的固化样品切成多个棒，以测量脱脂和烧结收缩。通过用刮刀将可光固化的浆料流延成5厘米(cm)×5 cm的正方形，并用紫外(UV)灯固化10秒，制备实施例1的可光固化的浆料的固化样品。随后流延五(5)至十(10)层可光固化的浆料，并固化以形成厚度在约1.0和1.5 cm之间的陶瓷板。将固化的陶瓷板切割成宽度为约18毫米(mm)且厚度为约2 mm的棒。将棒在1200℃下部分烧制三十(30)分钟。测量脱脂收缩，然后在1600℃下烧结三(3)小时，之后测量烧结收缩。
实施例2
通过混合下列物质制备可光固化的树脂共混物：35份乙氧基化三羟甲基丙烷三丙烯酸酯、30份丙烯酸异冰片酯、35份二氨基甲酸酯二甲基丙烯酸酯、0.05份叔丁基儿茶酚、0.25份双(2,4,6-三甲基苯甲酰基)-苯基氧化膦和0.25份1-羟基环己基-1-苯基甲酮。可光固化的树脂负载有约53体积%的具有以下氧化铝粉末制剂的浆料：约25%的d50为约57 μm的熔合氧化铝粉末、约27%的d50为约26 μm的熔合氧化铝粉末、约2%的d50为约14 μm的熔合氧化铝粉末、约36%的d50为约7 μm的熔合氧化铝粉末和约10%的d50为约6 μm的熔合氧化铝粉末。陶瓷粉末由89.9重量(wt)%的氧化铝粉末制剂、约1.8重量(wt)%的用作晶粒生长抑制剂的氧化镁(MgO)和约9.3 wt%的降低在高温(例如高于1200℃的温度)下的蠕变的氧化钇(Y2O3)组成。特别地，用于该制剂的氧化铝颗粒在所有尺寸类别中具有通常相同的形态，并且d50大于25微米。以与上述使用实施例1的浆料组合物制备的棒类似的方式使用该浆料形成测试棒。
实施例3
比较由两种浆料制剂形成的棒的脱脂收缩和烧结收缩。如下表1所示，由实施例1的可光固化的陶瓷浆料(其包括颗粒形态的混合物，并且粒度比实施例2的制剂更细)制造的陶瓷棒的平均净收缩(例如脱脂和烧结收缩)与由实施例2的常规的可光固化的浆料(其包括d50大于25 μm的粗陶瓷颗粒)制造的陶瓷棒的平均净收缩相似。因此，具有d50小于约25μm的陶瓷颗粒和混合颗粒形态的可光固化的陶瓷浆料减轻在成品处理期间的收缩和致密化。
表1. 由实施例1和2中的可光固化的陶瓷浆料制造的陶瓷棒的平均脱脂、烧结和平均净收缩。
在其它实验中，评价使用陶瓷浆料3D打印的样本的平均收缩，所述陶瓷浆料包括具有相对更球形形态的陶瓷颗粒，或具有相对更有角形态的陶瓷颗粒，或其不同的混合物。用具有100%的更球形陶瓷颗粒且不含有角陶瓷颗粒的陶瓷浆料制造的陶瓷样本在部分烧制后的脱脂收缩是其它提供的陶瓷浆料的约3倍。另外，用具有100%的更有角陶瓷颗粒且不含更球形陶瓷颗粒的陶瓷浆料打印的陶瓷制品在部分烧制和烧结之后具有比其它提供的陶瓷浆料更高的平均收缩；此外，具有该组成的浆料具有高粘度，并因此不太适于3D打印。相反，具有较低球度陶瓷颗粒和较高球度陶瓷颗粒的混合物的陶瓷浆料(包括例如更球形颗粒与较低球形颗粒的相应体积比为1:1和3:1的混合物)证明用于3D打印的合适粘度，并且产生具有期望的低脱脂收缩和烧结收缩的样本。由含有混合形态陶瓷颗粒的浆料制造的样本在部分烧制和烧结后证明平均收缩比由仅具有一种颗粒形态类型的浆料制造的样本低约20%至约50%。作为非限制性实例，当根据本文所述的一些实施方案处理时，陶瓷部件在烧结之后的平均烧结收缩可在约0.1%和1.5%之间。
在某些实施方案中，浆料进一步包含掺杂剂，即，浆料的添加剂，其改变构成成品的陶瓷材料的性质。例如，掺杂剂可以以小于陶瓷浆料的约10体积% (vol%)的水平加入到陶瓷浆料中，以在陶瓷制品中实现期望的机械性质，例如抗蠕变性。在一些实施方案中，掺杂剂包括加入到陶瓷浆料中的惰性化合物。通过非限制性实例，掺杂剂可包括氧化锆、氧化钛、氧化钇或另一合适的氧化物。在某些实施方案中，可使用氧化锆掺杂，其中浆料的主要陶瓷成分是氧化铝陶瓷颗粒；在其它实施方案中，可以使用氧化钛掺杂，其中浆料的主要陶瓷成分是二氧化硅陶瓷颗粒。或者，掺杂剂可与陶瓷浆料中的第一多个陶瓷颗粒和/或第二多个陶瓷颗粒反应以形成固溶体或新的相。例如，氧化铝浆料基质中的氧化钇掺杂可在处理期间形成铝酸钇，并且氧化铝的氧化镁掺杂可在处理期间形成铝酸镁。掺杂剂可以作为氧化物或当加热至脱脂或烧结温度时形成氧化物的前体加入。可适用于陶瓷浆料或存在于固结的陶瓷部件中的掺杂剂的实例包括但不限于氧化钇、铝酸钇、二氧化硅、铝酸硅、硅酸镁、铝酸镁、硅酸钠、铝酸钠、硅酸钙、铝酸钙、氧化钙、氧化镁、氧化钠、氧化铝、氧化锆、钇稳定的氧化锆和氧化钛。
如上所述，在某些实施方案中，陶瓷浆料可以包括混杂粘结剂。如所提及的，在脱脂期间，混杂粘结剂可以至少部分分解成二氧化硅，其能够增强脱脂后的棕色陶瓷制品68的处理强度(图1的方框64)，促进反应粘合以减轻某些类型的陶瓷颗粒(例如，通过形成铝硅酸盐的氧化铝)在烧结期间的收缩，并改进最终陶瓷制品的抗蠕变性。
图2是使用本文公开的陶瓷浆料的实施方案3D打印的陶瓷部件的以任意单位(AU)的平均净收缩(即脱脂收缩86和烧结收缩90)的代表性柱状图114，所述陶瓷浆料包括更球形和较低球形陶瓷颗粒的混合物。更具体地说，柱118表示用具有相对圆形和相对有角掺杂的氧化铝颗粒(例如，氧化钇掺杂)的混合物和非混杂粘结剂(例如，丙烯酸酯粘结剂)的陶瓷浆料打印的陶瓷部件。柱120和124表示用具有相对圆形和相对有角非掺杂的氧化铝颗粒的混合物和混杂粘结剂的陶瓷浆料打印的陶瓷部件。通常应当注意，图2中表示的陶瓷浆料的平均净收缩显著低于(例如，低约1-4 AU)以上讨论的不包括混杂粘结剂或掺杂的陶瓷浆料的平均净收缩值，证明通过混合形态陶瓷颗粒与混杂粘结剂或掺杂剂的组合能够显著降低平均净收缩。
本发明的技术效果尤其包括具有不同形态和粒度的陶瓷颗粒的混合物的陶瓷浆料，其可用于3D打印应用。例如，本文公开的陶瓷浆料包括陶瓷颗粒形态的混合物，在各种实施方案中，所述陶瓷颗粒形态使得浆料粘度能够适于3D打印，使得在脱脂和烧结期间3D打印的部件内的收缩和蠕变能够显著降低，并且使得陶瓷部件能够具有用于耐火应用的合适的密度和孔隙率。在某些实施方案中，陶瓷颗粒可以被掺杂(例如，掺杂氧化钇)以进一步减少打印的陶瓷部件的脱脂和烧结收缩。在某些实施方案中，陶瓷浆料包括混杂粘结剂，其在脱脂期间形成硅酸盐以赋予棕色体陶瓷部件处理强度。此外，在包括混杂粘结剂和氧化铝陶瓷颗粒的实施方案中，形成的硅酸盐进一步降低陶瓷部件在烧结期间的收缩。
本书面描述使用实例来公开本发明，包括最佳模式，并且还使本领域技术人员能够实践本发明，包括制造和使用任何装置或系统以及执行任何结合的方法。本发明的可专利范围由权利要求限定，并且可以包括本领域技术人员想到的其它实例。如果这样的其它实例具有与权利要求的字面语言没有不同的结构要素，或者如果它们包括与权利要求的字面语言无实质差异的等同结构要素，则这样的其它实例旨在处于权利要求范围内。

Claims (13)

1.用于形成陶瓷制品的陶瓷浆料，所述陶瓷浆料包含：
粘结剂，光引发剂和陶瓷颗粒；
其中所述陶瓷颗粒由具有第一形态的第一多个陶瓷颗粒和具有不同于所述第一形态的第二形态的第二多个陶瓷颗粒组成；
其中所述第一多个陶瓷颗粒的中值球度大于所述第二多个陶瓷颗粒的中值球度，其中所述第一多个陶瓷颗粒的中值球度为至少0.9，所述第二多个陶瓷颗粒的中值球度小于0.9；
其中所述第一多个陶瓷颗粒的中值粒度在8微米至15微米的范围内，所述第二多个陶瓷颗粒的中值粒度在2微米至8微米的范围内；以及
其中所述陶瓷浆料的总颗粒负载在陶瓷浆料的45体积％至75体积％的范围内，所述陶瓷浆料包含20体积％至99体积％的第一多个陶瓷颗粒和1体积％至80体积％的第二多个陶瓷颗粒，并且第一多个陶瓷颗粒和第二多个陶瓷颗粒的体积比为至少1.5。
2.权利要求1所述的陶瓷浆料，其中所述陶瓷浆料进一步包含掺杂剂。
3.权利要求2所述的陶瓷浆料，其中所述掺杂剂包含氧化物。
4.权利要求3所述的陶瓷浆料，其中所述氧化物包含氧化钇、二氧化硅、氧化锆、氧化钛、氧化镁、氧化钴、氧化铝、锆石、氧化钙、氧化钠和氧化铒中的一种或多种。
5.权利要求2所述的陶瓷浆料，其中所述掺杂剂的量小于所述陶瓷浆料的固体部分的10体积％。
6.权利要求1所述的陶瓷浆料，其中所述粘结剂包含有机树脂组分。
7.权利要求6所述的陶瓷浆料，其中所述粘结剂进一步包含硅氧烷。
8.权利要求1所述的陶瓷浆料，其中所述第一多个陶瓷颗粒包含二氧化硅、锆石、氧化铝和氧化锆中的一种或多种。
9.权利要求1所述的陶瓷浆料，其中所述第二多个陶瓷颗粒包含二氧化硅、锆石、氧化铝、氧化锆中的一种或多种。
10.用于制造制品的方法，所述方法包括：
将权利要求1-9中任一项所述的陶瓷浆料沉积到工作表面上；
使至少一部分所述陶瓷浆料固化以形成生陶瓷材料；
将所述生陶瓷材料脱脂以形成棕色陶瓷材料；和
烧结所述棕色陶瓷材料以形成最终陶瓷制品。
11.权利要求10所述的方法，其中所述最终陶瓷制品的孔隙率在25％至45％的范围内。
12.权利要求10所述的方法，其中固化包括用具有合适波长的电磁辐射照射沉积的陶瓷浆料以引发粘结剂的聚合。
13.权利要求10所述的方法，其中所述陶瓷浆料进一步包含掺杂剂，所述掺杂剂包含氧化物或其前体，并且以小于所述陶瓷浆料的固体部分的10体积％的量存在于所述陶瓷浆料中。
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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11217415B2 (en) * 2019-09-25 2022-01-04 Littelfuse, Inc. High breaking capacity chip fuse
US11578002B2 (en) * 2020-02-27 2023-02-14 General Electric Company Ceramic slurries with photoreactive-photostable hybrid binders
CN112537948A (zh) * 2020-12-19 2021-03-23 西北工业大学 一种氧化铝基陶瓷型芯的光固化3d打印制造方法
CN113461427B (zh) * 2021-07-21 2023-02-03 广东工业大学 一种光固化4d打印陶瓷基前驱体浆料、陶瓷件及制备方法
CN114709691A (zh) * 2022-03-16 2022-07-05 深圳市泛海统联智能制造有限公司 一种承烧治具及基于承烧治具制备微型连接器的方法
CN116003136B (zh) * 2023-01-04 2023-10-27 厦门理工学院 一种Si-Zr-O-C陶瓷材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103779A (en) * 1995-04-26 2000-08-15 Reinforced Polmers, Inc. Method of preparing molding compositions with fiber reinforcement and products obtained therefrom
WO2017050983A1 (de) * 2015-09-25 2017-03-30 Ivoclar Vivadent Ag Keramik- und glaskeramikschlicker für die stereolithography
CN106673646A (zh) * 2017-01-20 2017-05-17 广东工业大学 一种基于光固化成型的3d打印制备氧化锆陶瓷的方法
CN106810215A (zh) * 2017-01-18 2017-06-09 深圳摩方新材科技有限公司 一种陶瓷浆料的制备及3d打印光固化成型方法
WO2017124065A1 (en) * 2016-01-15 2017-07-20 Hrl Laboratories, Llc Resin formulations for polymer-derived ceramic materials
CN107586136A (zh) * 2017-10-17 2018-01-16 广东工业大学 一种3d打印氮化硅陶瓷的方法
CN107635945A (zh) * 2015-05-28 2018-01-26 3M创新有限公司 使用包含纳米级颗粒的溶胶制作陶瓷制品的增材制造方法
CN107635531A (zh) * 2015-05-28 2018-01-26 3M创新有限公司 包含纳米氧化锆颗粒的溶胶在用于制备三维制品的增材制造方法中的用途

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179548A (en) 1975-10-28 1979-12-18 General Electric Company UV curable resin compositions containing urethanes of hydroxybenzotriazoles or urethanes of hydroxy benzophenones
US4061652A (en) 1975-10-28 1977-12-06 General Electric Company Urethanes of hydroxybenzotriazoles
US5488017A (en) 1989-04-14 1996-01-30 General Electric Company Fibert reinforced ceramic matrix composite member
US5496682A (en) 1993-10-15 1996-03-05 W. R. Grace & Co.-Conn. Three dimensional sintered inorganic structures using photopolymerization
US6117612A (en) 1995-04-24 2000-09-12 Regents Of The University Of Michigan Stereolithography resin for rapid prototyping of ceramics and metals
US7343960B1 (en) 1998-11-20 2008-03-18 Rolls-Royce Corporation Method and apparatus for production of a cast component
US20030207959A1 (en) 2000-03-13 2003-11-06 Eduardo Napadensky Compositions and methods for use in three dimensional model printing
US7265161B2 (en) 2002-10-02 2007-09-04 3M Innovative Properties Company Multi-photon reactive compositions with inorganic particles and method for fabricating structures
US6814926B2 (en) 2003-03-19 2004-11-09 3D Systems Inc. Metal powder composition for laser sintering
US7282274B2 (en) 2003-11-07 2007-10-16 General Electric Company Integral composite structural material
EP2402127B1 (en) 2004-10-19 2018-07-18 Rolls-Royce Corporation Method associated with anisotropic shrink in sintered ceramic items
US20080135721A1 (en) 2006-12-06 2008-06-12 General Electric Company Casting compositions for manufacturing metal casting and methods of manufacturing thereof
US8475946B1 (en) 2007-03-20 2013-07-02 Bowling Green State University Ceramic article and method of manufacture
US9561622B2 (en) 2008-05-05 2017-02-07 Georgia Tech Research Corporation Systems and methods for fabricating three-dimensional objects
EP2151214B1 (de) 2008-07-30 2013-01-23 Ivoclar Vivadent AG Lichthärtende Schlicker für die stereolithographische Herstellung von Dentalkeramiken
EP2233449B1 (de) 2009-03-27 2014-12-17 Ivoclar Vivadent AG Verwendung eines Schlickers für die Herstellung von Dentalkeramiken mittels Hot-Melt-Inkjet-Druckverfahren
US8240383B2 (en) * 2009-05-08 2012-08-14 Momentive Specialty Chemicals Inc. Methods for making and using UV/EB cured precured particles for use as proppants
CN102958466B (zh) * 2010-06-25 2015-07-01 松下健康医疗控股株式会社 牙科磨削用成型制品及其制造方法
EP2404590B1 (de) 2010-07-08 2019-06-12 Ivoclar Vivadent AG Lichthärtende Keramikschlicker für die stereolithographische Herstellung von hochfesten Keramiken
KR102275337B1 (ko) * 2011-07-07 2021-07-12 쓰리엠 이노베이티브 프로퍼티즈 컴파니 다성분 섬유 및 중공 세라믹 미소구체를 포함하는 물품 및 그의 제조 및 사용 방법
JP6586553B2 (ja) 2013-11-11 2019-10-09 ダウ・東レ株式会社 誘電体セラミック形成材料用剥離フィルム用高エネルギー線硬化性アクリロキシ官能シリコーン組成物、及びそれを用いた誘電体セラミック形成材料用剥離フィルム
CA2885074A1 (en) 2014-04-24 2015-10-24 Howmet Corporation Ceramic casting core made by additive manufacturing
US20150328678A1 (en) * 2014-05-19 2015-11-19 General Electric Company Methods and compositions for formation of ceramic articles
KR101601107B1 (ko) 2014-07-09 2016-03-08 현대자동차주식회사 차량용 자동변속기의 유성기어트레인
US10300624B2 (en) 2014-10-17 2019-05-28 United Technologies Corporation Functional inorganics and ceramic additive manufacturing
GB2533161C (en) * 2014-12-12 2019-07-24 Nexeon Ltd Electrodes for metal-ion batteries
WO2017029673A1 (en) 2015-08-19 2017-02-23 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd 3d polymerizable ceramic inks
US10023500B2 (en) * 2016-08-30 2018-07-17 General Electric Company Light-curable ceramic slurries with hybrid binders
JP7395514B2 (ja) * 2018-06-15 2023-12-11 ビーエーエスエフ ソシエタス・ヨーロピア セラミック光樹脂配合物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103779A (en) * 1995-04-26 2000-08-15 Reinforced Polmers, Inc. Method of preparing molding compositions with fiber reinforcement and products obtained therefrom
CN107635945A (zh) * 2015-05-28 2018-01-26 3M创新有限公司 使用包含纳米级颗粒的溶胶制作陶瓷制品的增材制造方法
CN107635531A (zh) * 2015-05-28 2018-01-26 3M创新有限公司 包含纳米氧化锆颗粒的溶胶在用于制备三维制品的增材制造方法中的用途
WO2017050983A1 (de) * 2015-09-25 2017-03-30 Ivoclar Vivadent Ag Keramik- und glaskeramikschlicker für die stereolithography
WO2017124065A1 (en) * 2016-01-15 2017-07-20 Hrl Laboratories, Llc Resin formulations for polymer-derived ceramic materials
CN106810215A (zh) * 2017-01-18 2017-06-09 深圳摩方新材科技有限公司 一种陶瓷浆料的制备及3d打印光固化成型方法
CN106673646A (zh) * 2017-01-20 2017-05-17 广东工业大学 一种基于光固化成型的3d打印制备氧化锆陶瓷的方法
CN107586136A (zh) * 2017-10-17 2018-01-16 广东工业大学 一种3d打印氮化硅陶瓷的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Effect of the particle size and the debinding process on the density of alumina ceramics fabricated by 3D printing based on stereolithography;Haidong Wu等;《Ceramics International》;20160805;第42卷;第2.1, 2.2, 2.3, 2.4小节，样品2，表1，图1-5 *

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