CN107614245A - 三维成型方法和层压成型材料 - Google Patents

三维成型方法和层压成型材料 Download PDF

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CN107614245A
CN107614245A CN201580077437.8A CN201580077437A CN107614245A CN 107614245 A CN107614245 A CN 107614245A CN 201580077437 A CN201580077437 A CN 201580077437A CN 107614245 A CN107614245 A CN 107614245A
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dimensionally shaped
adhesive
reaction solution
described adhesive
solution
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石原治彦
平林英明
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Toshiba Corp
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Abstract

根据实施方案的三维成型方法制造了三维成型体，并且该方法包括重复进行如下步骤：向各自涂覆有粘合剂的材料颗粒上施加其中溶解有粘合剂或导致与粘合剂的粘合反应的反应溶液，以及沉积材料颗粒的步骤。因此，该三维成型方法可以提高三维成型体的密度和强度，并且提供了均匀的三维成型体。

Description

三维成型方法和层压成型材料
发明领域
本发明的实施方式涉及三维成型方法和添加剂制造材料。
发明背景
提出了通过例如重复如下步骤而制造三维成型体的多种三维成型方法：在制造阶段形成粉末层的粉末层形成步骤；以及将粘合剂由喷墨头排到沉积的粉末层上的预定区域以形成固化层的粘合步骤。
引用列表
专利文件
专利文件1：日本专利申请公开：No.2010-208069
发明概述
本发明要解决的问题
为了粘合粉末，需要使用包含一定量或更多的粘合组分(固含量)的溶液。然而，为了从喷墨头喷射粘合剂，对诸如粘度的液体性质有限制。换句话说，为了提高制造精度，需要降低粘合剂材料的粘度，这使得难以均匀地粘合粉末层。
考虑到上述缺点完成了本发明，并且本发明的目的是提供三维成型方法和用于添加剂制造的材料，其能够提高三维成型体的密度和强度并提供均匀的三维成型体。
解决问题的方法
根据实施方案的三维成型方法制造了三维成型体，并且根据实施方案的三维成型方法包括重复进行如下步骤：向各自涂覆有粘合剂的材料颗粒上施加其中溶解有粘合剂或导致与粘合剂的粘合反应的反应溶液，以及沉积材料颗粒的步骤。
附图简述
图1是说明根据实施方案的三维制造系统的结构和步骤的示意图。
图2是描述该实施方案的三维打印机的截面示意图。
图3是制造槽和供给装置的主体的立体图。
图4是说明用于二次颗粒上表面涂层的粘合剂BD与反应液RL的组合的图(部分1)。
图5是说明用于二次颗粒上表面涂层的粘合剂BD与反应液RL的组合的图(部分2)。
图6是说明官能团之间的键的图。
发明详述
下面参照附图对实施方案进行说明。图1是说明根据实施方案的三维成型系统的结构和步骤的示意图。根据该实施方案的三维成型系统10包括：制备一次颗粒的原料制备装置11；造粒装置12，其将通过原料制备装置11而制备的一次颗粒与粘合剂BD进行混合以生产各自具有涂敷有粘合剂的表面的二次颗粒；作为所谓的“三维打印机”并将所述二次颗粒沉积以制造三维成型体的添加剂制造装置13；以及烧结装置14，其根据预定的升温/降温模式对通过添加剂制造装置13而制造的三维成型物体进行加热并烧结，以提供烧结体。
用作原料制备装置11的是将助剂适当地加入通过固相法、液相法或气相法而制备的粉末状陶瓷原料(主料)中，并进行粉碎、分散、混合及其他处理的装置，其中所述助剂包括粘合剂BD。例如，用作原料制备装置11的是例如球磨机、珠磨机和喷射磨的粉碎混合装置。根据需要还进一步使用喷雾干燥器等。
然后对造粒装置12进行说明。所述造粒装置12对接收的以预定比例由第一原料制备装置11-1和第二原料制备装置11-2制备的一次颗粒的注入物以及作为辅助剂的预定粘合剂的注入物进行造粒，以生产二次颗粒。作为造粒装置而使用的是粉碎混合装置，例如球磨机、珠磨机和喷射磨。
下面对用作添加剂制造装置13的三维打印机进行描述。图2是描述根据该实施方式的三维打印机的截面示意图。三维打印机13为采用粉末固定沉积方法(powder fixingdepositing method)的三维成型装置。如图2所示，三维打印机13包括加工室21；容纳用于制造三维成型体的原料(二次颗粒)的材料槽22；实际进行三维成型的制造槽23；将容纳于材料槽22中的原料供给到制造槽23的擦具装置24；喷墨成型装置25，其将反应溶液RL喷射到以层为单位的原料(二次颗粒)上，所述二次颗粒是由擦具装置24供应到制造槽23，反应溶液RL喷射在根据切片数据(slice data)每个层上对应于三维成型体的位置(图案)；以及控制材料槽22、制造槽23、擦具装置24和喷墨成型装置25的控制单元26。
在上述结构中，所述加工室21内部具有密封空间。材料槽22、制造槽23、擦具(wiper)装置24以及喷墨成型装置25在加工室21中以预定位置布置。加工室21的内部供有惰性气体，例如来自气体供应装置(并没有示出)而通过供入口21A的氮气和氩气，以保持加工室内部的清洁。在三维成型中产生的不必要的气体组分等通过排出口21B而排出到加工室21的外部。
在材料槽22内部具有放置台22A，其通过液压提升装置22B而能够垂直移动。用作原料的二次颗粒P20置于放置台22A上。在三维成型时，在每个预定的成型步骤，所述放置台向上移动，因而将对应于预定层厚的原料量向材料槽22的上部进行移动。
所述制造槽23包括放置台23A、液压提升装置23B和外围壁23D。将用作材料的二次颗粒P20基于切片数据(slice data)而依次供应到放置台23A的上表面。
所述擦具装置24包括挤压叶片。在图2中该擦具装置24被水平驱动，由此把向材料槽22的上部移动的对应于预定层厚的量的原料提供给制造槽23，同时使它们水平以使其具有均匀的厚度。
所述喷墨成型装置25将溶解有粘合层或者引起粘合反应等的反应溶液RL喷射到供给到制造槽23的二次颗粒P20的表面上，从而使二次颗粒P2彼此结合。因此，该喷墨成型装置25使二次颗粒P20沉积并固定。所述喷墨成型装置25包括将反应溶液RL喷射到供给到制造槽23的二次颗粒P20上的喷射装置61；使喷射装置61移动的移动装置62；容纳原料的容纳装置63和收集未用于成型的原料(二次颗粒)的收集装置64。
图3是制造槽和供给装置的主体的立体图。如图3所示，所述喷墨成型装置25的喷射装置61包括支座71；与支座71完整地结合在一起的多个喷嘴72A至72E；以及分别对应于喷嘴72A至72E的多个槽73A至73E。
支座71支撑槽73A至73E，并且在对应于槽73A至73E的下表面分别配有喷嘴72A至72E。
在上述结构中，槽73A至73E可以在其中存储相同反应溶液RL，或者在其中存储多种不同类型的未稀释的反应溶液RL0，混合的例如用作反应溶液RL。
为了简化下面的说明，下面描述其中例如槽73A至73E在其中存储相同反应溶液RL的情况。
所述移动装置72包括轨道81和一对输送器82。所述移动装置72使喷射装置61在沿着X轴和Y轴方向上进行移动，从而使与喷射装置61的支座71结合的槽73A至73E相对于制作槽23而移动。
所述轨道81置于制造槽23的上方，并且比沿着Y轴方向的制造槽的尺寸更长。所述喷射装置61的支座71可以沿轨道81移动。通过驱动包括诸如发动机、齿轮和带的各种部件的机构，使得喷射装置61沿着轨道81移动。喷射装置61的喷嘴72A至72E也沿着轨道81移动并喷射反应溶液RL，从而在制造槽23中沉积二次颗粒P20。
所述收集装置64通过收集管66而与收纳装置63连接。收集装置64吸收未被固定的粉末状二次颗粒P20，并将其传输并收集在收纳装置63中。
在上述结构中，控制单元26控制制造槽23、擦具装置24和喷墨成型装置25，以使每个涂覆有固定剂的二次颗粒彼此固定，从而还制造出三维成型体MD。此外，控制单元26控制收集装置64，以吸收未用于制造的粉末状二次颗粒P20并将其传输并收集在收纳装置63中。
上述制造的三维成型体MD根据预定的升温模式和预定的降温模式通过烧结装置14而进行加热。因此，所述三维成型体MD得以烧结并形成为用作烧结体的三维成型体MD2。更具体而言，用作烧结体的三维成型体的长度降低至大约70％。所述三维成型体的以体积计的尺寸为三维成型体MD的尺寸的50％至60％。
下面详细描述具有粘合剂BD的二次颗粒上的表面涂层和反应溶液RL的优选组合。首先描述要点。给出如下五种组合作为用于二次颗粒上的表面涂层的粘合剂BD与反应溶液RL的组合的实例。
(1)粘合剂BD：有机涂料(例如丙烯酸类)
反应溶液RL：溶剂
(2)粘合剂BD：无机涂料(例如SiO2、Al2O3和TiO2)
反应溶液RL：无机纳米颗粒溶液(例如，与粘合剂BD相同的材料或胶体二氧化硅)
(3)粘合剂BD：无机涂料(例如SiO2、Al2O3和TiO2)
反应溶液RL：有机硅烷溶液等
(4)粘合剂BD：金属涂料
反应溶液RL：硅烷偶联剂(例如硫醇基)
(5)粘合剂BD：硅烷偶联剂(例如氨基)
反应溶液RL：硅烷偶联剂(例如羧基)
下面更详细描述粘合剂BD和反应溶液RL的组合。图4是说明用于二次颗粒表面涂层的粘合剂BD与反应液RL的组合的图(部分1)。
[1]有机涂料+溶剂
下面描述将有机涂料用作粘合剂BD并将溶剂用作反应溶液RL的情况。如图4的第一部分所述，由有机涂料制成的粘合剂BD的实例包括但不限于PVDF(聚偏二氟乙烯)、PVB(聚乙烯醇缩丁醛)、聚酯、PVC(聚氯乙烯)、丙烯酸类、聚氨酯、聚丙烯、聚乙烯、环氧树脂、EVA(乙烯-乙酸乙烯酯共聚物)、聚酰胺、PVA(聚乙烯醇)、松香、氟、FEVE(氟乙烯乙烯基醚共聚物)、(苯)酚、SBR(丁苯橡胶)、HPMC(羟丙基甲基纤维素)、蜡等。有机涂料可适当地选自上述材料。作为反应溶液RL，使用溶解有机涂料的流体(例如有机溶剂和水)。在此情况下，使二次颗粒P20相互结合的方法是二次颗粒P20通过溶解后涂料的再次固化而彼此结合的机理。结合原理被认为是由树脂固化而引起的物理干扰。由喷墨成型装置25施加到反应溶液RL(图4中称为IJ液体)的添加剂的实例包括但不限于提供最佳粘度的粘度调节剂、改善润湿性的表面活性剂等。
[2]无机涂料+无机纳米颗粒溶液
下面描述将无机涂料用作粘合剂BD并且将无机纳米颗粒溶液用作反应溶液RL的情况。
如图4的第二部分所述，由无机涂料制成的粘合剂BD的实例包括但不限于SiO2(二氧化硅)、Al2O3(三氧化二铝)、TiO2(二氧化钛)、Au(金)、Cu(铜)、Ag(银)等。无机涂料适当地选自上述材料。
将由与无机涂料相同的材料制成的纳米颗粒溶液或胶状二氧化硅溶液用作反应溶液RL。在此情况下，使二次颗粒P20彼此结合的方法是二次颗粒P20通过分子间力和静电力而彼此结合的机理。该结合原理被认为是静电吸引(库仑力)。
由喷墨成型装置25施加到反应溶液RL(图4中称为IJ液体)的添加剂的实例包括但不限于提供最佳粘度的粘度调节剂、改善润湿性的表面活性剂、使纳米颗粒在溶液中均匀分散的分散剂等。
图5是说明用于二次颗粒上表面涂层的粘合剂BD与反应溶液RL的组合的图(部分2)。
[3]无机涂料+有机硅烷溶液
下面描述将无机涂料用作粘合剂BD并将有机硅烷溶液用作反应溶液RL的情况。
如图5中的第三部分所述，由无机涂料制成的粘合剂BD的实例包括但不限于SiO2(二氧化硅)、Al2O3(三氧化二铝)、TiO2(二氧化钛)等。无机涂料适当地选自上述材料。将硅烷偶联剂用作反应溶液RL。
在这种情况中，使二次颗粒P20彼此结合的方法是二次颗粒P20通过可水解基团(例如烷氧基)的键合力而彼此结合的机理，其中所述可水解基团与无机物相容(对其具有亲和力)。该结合原理被认为是可水解基团与玻璃、金属等反应并结合。
由喷墨成型装置25施加到反应溶液RL(图5中称为IJ液体)的添加剂的实例包括但不限于提供最佳粘度的粘度调节剂、改善润湿性的表面活性剂等。
[4]金属涂料+硅烷偶联剂
下面描述将金属涂料作为粘合剂BD并且将硅烷偶联剂用作反应溶液RL的情况。如图5的第四部分所述，由金属涂料制成的粘合剂BD的实例包括但不限于Au(金)、Cu(铜)、Ag(银)等。金属涂料适当地选自上述材料。
硅烷偶联剂用作反应溶液RL。在此情况中，使二次颗粒P20彼此结合的方法是二次颗粒P20通过分子间力和静电力而彼此结合的机理。
该结合原理是二次颗粒P20通过官能团(例如硫醇基[＝氢巯基、巯基或巯基])的键合力而彼此结合的机理，其中所述官能团与金属相容。
由喷墨成型装置25施加到反应溶液RL(图4中称为IJ液体)的添加剂的实例包括但不限于提供最佳粘度的粘度调节剂、改善润湿性的表面活性剂等。
[5]硅烷偶联剂+硅烷偶联剂
下面描述将硅烷偶联剂用作粘合剂BD和反应溶液RL二者的情况。如图5的第五部分所述，将硅烷偶联剂用作粘合剂BD，将硅烷偶联剂用作反应溶液RL。
在此情况中，使二次颗粒P20彼此结合的方法是二次颗粒P20通过官能团(例如氨基+羧基)之间可能反应(具有高反应性)而导致的键(例如肽键、酯键、酰胺键和二硫键)的键合力而彼此结合的机理。
图6是用于说明官能团之间的键的图。如图6所示，若将具有羧基(-COOH)的硅烷偶联剂用作粘合BD，并且将具有氨基(-NH2)的硅烷偶联剂用作反应溶液RL，则通过脱水反应而形成肽键(OH+H→H2O)，由此提供了强键。
该结合原理是二次颗粒P20通过官能团之间的静电结合力而彼此结合的机理。由喷墨成型装置25施加到反应溶液RL(图4中称为IJ液体)的添加剂的实例包括但不限于提供最佳粘度的粘度调节剂、改善润湿性的表面活性剂等。
如上所述，根据该实施方案，使二次颗粒P20彼此结合而使粘合剂BD成为可粘合状态的反应溶液RL不包括固含量。该结构利于调节液体粘度。因而，所述喷墨成型装置25可以将反应溶液RL可靠且均匀地施加到二次颗粒P20的涂层，从而均匀结合了粉末层作为二次颗粒P20的聚合体的。因此，该实施方案可以减少制造失误，并提供了具有高强度和精确度的均匀三维形状的物体。
虽然已经对本发明的某些实施方案进行了描述，但是这些实施方案仅是示例性的，而并不意图限制本发明的范围。本新颖的实施方案可以以各种其他形式而实现，并且可以在不脱离本发明精神的情况下进行各种省略、替换和变化。本实施方案及其修改包括在本发明的范围和精神以及本发明的权利要求书及其等同物中。
虽然上述实施方案使用一种二次颗粒进行三维制造，但是它们可以使用例如多种类型的二次颗粒类似地进行三维制造。

Claims (18)

1.一种用于制造三维成型体的三维成型方法，该方法包括重复进行如下步骤：
向各自涂覆有粘合剂的材料颗粒施加其中溶解有粘合剂或导致与粘合剂的粘合反应的反应溶液的步骤，和
沉积材料颗粒的步骤。
2.根据权利要求1的三维成型方法，其还包括将所述粘合剂加入用作所述三维成型体的材料的一次颗粒以提供用作二次颗粒的材料颗粒的步骤，所述二次颗粒各自具有用所述粘合剂涂覆的表面。
3.根据权利要求1或2的三维成型方法，其中
将有机涂料用作所述粘合剂，并且
将溶解所述有机涂料的溶剂用作所述反应溶液。
4.根据权利要求3的三维成型方法，其中
所述有机涂料选自PVDF(聚偏二氟乙烯)、PVB(聚乙烯醇缩丁醛)、聚酯、PVC(聚氯乙烯)、丙烯酸类、聚氨酯、聚丙烯、聚乙烯、环氧树脂、EVA(乙烯-乙酸乙烯酯共聚物)、聚酰胺、PVA(聚乙烯醇)、松香、氟、FEVE(氟乙烯乙烯基醚共聚物)、苯酚、SBR(丁苯橡胶)、HPMC(羟丙基甲基纤维素)和蜡，并且
所述溶剂选自能够溶解所述有机涂料的有机溶剂和水。
5.根据权利要求1或2的三维成型方法，其中
将无机涂料用作所述粘合剂，并且
将对应所述无机涂料的无机纳米颗粒溶液用作所述反应溶液。
6.根据权利要求5的三维成型方法，其中
所述无机涂料选自SiO2(二氧化硅)、Al2O3(三氧化二铝)、TiO2(二氧化钛)、Au(金)、Cu(铜)、Ag(银)，并且
所述反应溶液选自以与所述无机涂料的材料相同的材料制成的纳米颗粒溶液和胶体二氧化硅溶液。
7.根据权利要求1或2的三维成型方法，其中
将无机涂料用作所述粘合剂，并且
将有机硅烷溶液用作所述反应溶液。
8.根据权利要求7的三维成型方法，其中
所述无机涂料选自SiO2(二氧化硅)、Al2O3(三氧化二铝)和TiO2(二氧化钛)。
9.根据权利要求1或2的三维成型方法，其中
将金属涂料用作所述粘合剂，并且
将有机硅烷溶液用作所述反应溶液。
10.根据权利要求9的三维成型方法，其中所述金属涂料选自Au(金)、Cu(铜)和Ag(银)。
11.根据权利要求1或2的三维成型方法，其中：
将具有第一种官能团的第一种硅烷偶联剂用作所述粘合剂，并且
将具有与第一种官能团反应的第二种官能团的第二种硅烷偶联剂用作所述反应溶液。
12.根据权利要求11的三维成型方法，其中能够形成肽键、酯键、酰胺键或二硫键的硅烷偶联剂用作第一种硅烷偶联剂和第二种硅烷偶联剂。
13.根据权利要求1的三维成型方法，其还包括将三维成型体加热以形成烧结体的步骤。
14.一种添加剂制造材料，其用于通过向各自涂覆有粘合剂的材料颗粒施加反应溶液并且沉积所述材料颗粒而制造三维成型体，其中所述反应溶液其中溶解有所述粘合剂或者导致与所述粘合剂的粘合反应，其中
所述反应溶液为选自能够溶解所述有机涂料的有机溶剂和水中的溶剂，
所述添加剂制造材料包含：
所述材料颗粒；和
用作所述粘合剂的有机涂料，其选自PVDF(聚偏二氟乙烯)、PVB(聚乙烯醇缩丁醛)、聚酯、PVC(聚氯乙烯)、丙烯酸类、聚氨酯、聚丙烯、聚乙烯、环氧树脂、EVA(乙烯-乙酸乙烯酯共聚物)、聚酰胺、PVA(聚乙烯醇)、松香、氟、FEVE(氟乙烯乙烯基醚共聚物)、苯酚、SBR(丁苯橡胶)、HPMC(羟丙基甲基纤维素)和蜡。
15.一种添加剂制造材料，其用于通过向各自涂覆有粘合剂的材料颗粒施加反应溶液并且沉积所述材料颗粒而制造三维成型体，其中所述反应溶液其中溶解有粘合剂或者导致与所述粘合剂的粘合反应，其中
所述反应溶液选自由与所述粘合剂的无机材料相同的材料而制成的纳米颗粒溶液和胶体二氧化硅溶液，
所述添加剂制造材料包含：
所述材料颗粒；和
用作所述粘合剂的选自SiO2(二氧化硅)、Al2O3(三氧化二铝)、TiO2(二氧化钛)、Au(金)、Cu(铜)和Ag(银)的无机涂料。
16.一种添加剂制造材料，其用于通过向各自涂覆有粘合剂的材料颗粒施加反应溶液并且沉积所述材料颗粒而制造三维成型体，其中所述反应溶液其中溶解有所述粘合剂或者导致与粘合剂的粘合反应，其中
所述反应溶液为有机硅烷溶液，
所述添加剂制造材料包含：
所述材料颗粒；和
用作所述粘合剂的选自Au(金)、Cu(铜)和Ag(银)的金属涂料。
17.一种添加剂制造材料，其用于通过向各自涂覆有粘合剂的材料颗粒上施加反应溶液并且沉积所述材料颗粒而制造三维成型体，其中所述反应溶液其中溶解有所述粘合剂或者导致与粘合剂的粘合反应，其中
所述反应溶液为有机硅烷溶液，
所述添加剂制造材料包含：
所述材料颗粒；和
用作所述粘合剂的选自Au(金)、Cu(铜)和Ag(银)的金属涂料。
18.一种添加剂制造材料，其用于通过向各自涂覆有粘合剂的材料颗粒上施加反应溶液并且层压所述材料颗粒而制造三维成型体，其中所述反应溶液其中溶解有所述粘合剂或者导致与所述粘合剂的粘合反应，其中
所述反应溶液为具有第一种官能团的第一种硅烷偶联剂，
所述添加剂制造材料包含：
所述材料颗粒；和
用作所述粘合剂的第二种硅烷偶联剂，其具有与第一种官能团反应且能够形成肽键、酯键、酰胺键和二硫键之一的第二种官能团。
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