CN102351543A - 挤出成型组合物和生产挤出成型件的方法 - Google Patents

挤出成型组合物和生产挤出成型件的方法 Download PDF

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CN102351543A
CN102351543A CN2011101757890A CN201110175789A CN102351543A CN 102351543 A CN102351543 A CN 102351543A CN 2011101757890 A CN2011101757890 A CN 2011101757890A CN 201110175789 A CN201110175789 A CN 201110175789A CN 102351543 A CN102351543 A CN 102351543A
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extrusion moulding
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早川和久
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Abstract

挤出成型组合物，其包含纤维素或纤维素衍生物、离子液体和陶瓷材料。可在高成型速度并且没有干燥裂纹下将该组合物挤出成型为陶瓷件。

Description

挤出成型组合物和生产挤出成型件的方法
技术领域
本发明涉及包含离子液体的陶瓷挤出成型组合物和生产陶瓷挤出成型件的方法。
背景技术
一般地，通过将陶瓷原料与成型助剂例如有机粘合剂、表面活性剂、润滑剂和增塑剂组合和捏合以形成捏合的粘土，并通过具有期望形状的模头将粘土挤出形成片、棒、中空管、棱柱、空心棱柱或蜂窝结构体，从而将陶瓷化合物挤出成型。尤其是在汽车和一般工业中使用陶瓷蜂窝结构体的挤出成型作为废气净化催化剂载体、过滤器和换热器。为适应当前严格的排放控制规定，希望提供具有更薄加强筋的陶瓷蜂窝结构体以提高净化性能、降低压力损失和更好的热交换效率。
挤出成型陶瓷组合物的大部分现有技术方法使用纤维素衍生物作为粘合剂，例如，烷基纤维素例如甲基纤维素、羟烷基纤维素例如羟乙基纤维素和羟烷基烷基纤维素例如羟丙基甲基纤维素、羟乙基乙基纤维素。将粘合剂与陶瓷原料及水捏合以形成等于或低于室温下成型的捏合粘土。
纤维素衍生物被用作粘合剂的理由在于它们的可塑性、保水性和热胶凝化。利用纤维素醚或其衍生物有下列好处：在挤出成型期间没有水分离、在从成型步骤转变到干燥步骤过程中成型件不会失去其形状、和因干燥步骤的加热引起纤维素衍生物热胶凝化而对成型件赋予强度，这与加热时粘弹性降低导致成型件可能在其变干之前失去其形状的一般粘合剂的缺点相反。
然而，纤维素醚具有以下的缺点。当使其中加入有足够用于产生经受干燥步骤而所必需强度的热凝胶的量的纤维素醚的陶瓷材料通过模头进行挤出成型时，在材料和模头之间施有较高的摩擦力。挤出温度由于摩擦阻力提高。成型组合物中的纤维素衍生物在加热时经历热胶凝化，由此增塑剂失去流动性，并且使成型压力增加。这阻止成型陶瓷件从模头快速地排出。即当将其中加入了不能热胶凝化的有机粘合剂的陶瓷材料挤出成型时，由有机粘合剂表现的粘度因提高排出温度而降低，由此能够加速成型速度。然而，当将使用这样的能可逆热胶凝化的纤维素衍生物作为粘合剂的陶瓷材料挤出成型时，难以增加成型速度。
为克服这些缺点，JP 3321041和JP-A 2002-293645公开了用于有效改善挤出成型工艺的有机添加剂。这些有机添加剂仍不能令人满意。
现有技术文献
专利文件1：JP 3321041(USP 6117377，EP 0897899B1)；
专利文件2：JP-A 2002-293645。
发明内容
本发明的目的是提供能够以高速挤出成型并且没有干燥收缩裂纹的陶瓷挤出成型组合物以及用于制造陶瓷挤出成型件的方法。
本发明人发现，将包含纤维素和/或其衍生物、离子液体和陶瓷粉末的组合物挤出成型时，能够有效地以高成型速度和没有干燥收缩裂纹地来制造陶瓷成型件。
在一方面，本发明提供挤出成型组合物，其包含陶瓷材料、纤维素和/或其衍生物以及纤维素和/或衍生物可溶于其中的离子液体。
一般地，纤维素和/或其衍生物在40-110℃的温度范围溶于该离子液体中。优选的纤维素衍生物是选自烷基纤维素、羟烷基纤维素和羟烷基烷基纤维素的纤维素醚，其均具有至少5000的平均聚合度。
在另一方面，本发明提供用于制造陶瓷挤出成型件的方法，包括步骤：捏合上述定义的组合物组分，将捏合的组合物挤出成型、干燥和烧成。
发明的有益效果
本发明成功地高速挤出成型陶瓷组合物。陶瓷挤出成型件无干燥收缩裂纹。
具体实施方式
可使用任何适当的纤维素，包括从分离于木材的木浆和来源于棉籽的棉绒浆获得的那些纤维素、从像来自竹和麻的纸浆这样的植物产品获得的那些纤维素以及通过从纤维素分离高结晶性级分而获得的结晶纤维素。
可使用任何纤维素衍生物，只要它们在室温或更高的温度下溶于离子液体中。例如包括水溶性的纤维素醚、水不溶性纤维素醚，以及酯化纤维素。水溶性的纤维素醚的优选例子包括烷基纤维素、羟烷基纤维素和羟烷基烷基纤维素，具体地是甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素和羟乙基乙基纤维素。水不溶性纤维素醚的例子包括不溶于水但可溶于碱性水溶液的具有低取状度的乙基纤维素和羟基丙基纤维素。酯化纤维素的例子包括醋酸纤维素、硝化纤维、苄基纤维素、邻苯二甲酸醋酸纤维素、羟丙基甲基纤维素醋酸邻苯二甲酸酯、羟丙基甲基纤维素醋酸琥珀酸酯和羟丙基甲基纤维素邻苯二甲酸酯。
纤维素和纤维素衍生物优选具有至少5000的平均聚合度，因为它们能够溶于离子液体而形成触变性溶液。纤维素的平均聚合度通过测量其在铜-乙二胺溶剂中的粘度来确定。纤维素衍生物的平均聚合度通过通称为GPC-MALLS法的具有多角度光散射检则的凝胶渗透色谱来确定。
从提供期望形状的充分的触变性的观点出发，纤维素和/或纤维素衍生物优选每100重量份陶瓷材料以1至15重量份的量、更优选3至12重量份来添加。
离子液体与纤维素和/或纤维素衍生物组合。这是纤维素和/或纤维素衍生物在40-110℃温度下溶于其中的离子液体，经常选择该温度用于挤出成型。换而言之，在此使用的离子液体具有40-110℃的溶解温度。离子液体优选的例子包括1-丁基-3-甲基氯化及溴化咪唑
Figure BSA00000526711800031
硫代氰酸盐和四氟硼酸盐、和苄基二甲基氯化铵和1-乙基-3-甲基醋酸咪唑
Figure BSA00000526711800032
尤其优选1-乙基-3-甲基醋酸咪唑
Figure BSA00000526711800033
因为挤出成型后离子液体和纤维素和/或纤维素衍生物热解时没有无机离子残留。如果离子液体的溶解温度低于40℃，在挤出成型过程中可能需要冷却。如果离子液体的溶解温度高于110℃，纤维素和/或纤维素衍生物热分解的结果使结合力的损失可能发生。
离子液体的溶解温度，即纤维素和/或纤维素衍生物溶于离子液体中的温度，通过将10mL小瓶装以5g离子液体和0.05克纤维素和/或纤维素衍生物，将小瓶置于磁性搅拌器/热板上，以1℃/min的速率加热小瓶，从而可以测量该温度。
离子液体优选每100重量份陶瓷材料以10-50重量份、更优选20-40重量份的量来添加。在该范围外，包含更少量的离子液体的成型组合物可能发硬和难以成型至期望的形状，而包含过量的离子液体的成型组合物可能变得难以保持期望的形状。
陶瓷材料的例子包括介电陶瓷，典型地是氧化铝、氧化钛和钛酸钡，压电陶瓷例如锆钛酸铅(PZT)，氧化物陶瓷例如包含高岭土和滑石的堇青石陶瓷、氮化硅、碳化硅和氮化铝。
如果是期望的，可对成型组合物添加增塑剂，只要本发明的益处不被削弱。合适的增塑剂包括甘油和其衍生物、山梨糖醇酐脂肪酸酯、聚丙烯、聚乙烯、乙烯-丁二烯共聚物、以及它们的衍生物。还可以加入有机造孔剂以使陶瓷更轻或多孔。这样的添加剂可优选每100重量份陶瓷材料以0.1-20重量份、更优选1-10重量份的量来添加。
只要本发明的益处不被削弱，还可以添加通常和水溶性纤维素醚组合的合成的水溶性聚合物例如聚乙烯醇、聚乙二醇和聚丙烯酰胺，天然水溶性聚合物例如瓜耳胶和微生物发酵的多糖例如文莱胶(welan gum)，以及其它添加剂。
现在描述制造陶瓷挤出成型件的方法。这种方法首先将二者都是粉末形式的陶瓷材料与纤维素或纤维素衍生物混合。对混合物添加离子液体，随后进行湿法混合。将混合物在预定的溶解温度下在捏合机上粉碎，得到陶瓷捏合混合物。
将螺杆或活塞式挤出机调节至内部温度高于离子液体的溶解温度。随后将陶瓷捏合混合物在高于该溶解温度的温度下通过挤出机挤出，得到成型件。在挤出机螺杆或活塞内，纤维素或纤维素衍生物保持溶于离子液体以使具有均匀分散并混合的陶瓷颗粒的捏合混合物可以保持流动化。流动化的捏合混合物当是热的时显示出高触变性的流动性。在此使用的术语“触变性”性质意指将变形力施加于成型件时，捏合的混合物以完全屈服的方式变形，但没有变形力时，捏合的混合物迅速地恢复非变形的刚性状态。捏合的混合物在流动和变形过程中呈现粘度极低的状态，但将其以期望的形状从挤出机排出而停止流动时显示出很高的粘度。将捏合混合物在排出后冷却至低于溶解温度时，捏合混合物形成足够保持其形状的粘度。然后，将非流动态的捏合混合物干燥。将有机物质通过干燥步骤的加热而分解时，保持触变性。将挤出成型件逐渐地烧结而不损失其形状。
应指出，挤出温度的上限是130℃。在更高温度时，纤维素和/或纤维素衍生物可能在挤出成型过程中分解，从而失去所期望的触变性。
将具有期望形状的挤出成型件保持在3-30℃的环境温度下，然后并进行干燥。在干燥步骤过程中，在离子液体中的纤维素和/或纤维素衍生物的溶液增加其粘度以使挤出成型件保持其成型时的形状。将挤出成型件在环境温度下保持至少3小时。此时，将制件倒置并且目测检查裂纹和形状保持性。
下一步骤是烧成。烧成步骤导致包括离子液体和纤维素和/或纤维素衍生物的有机组分在至少500℃的高温下热解以使粘合剂实现烧尽。在至少500℃的高温下，在将陶瓷颗粒结合于边界并因此而烧结时，使有机组分分解成在气氛中变成气态的有机部分(fraction)并烧尽。燃烧温度的上限尽管不是关键性的，但通常最高为2500℃。
实施例
以下通过示例而非限制性的方式给出实施例
实施例和比较例
按照表1中所示的配方(重量份)使用陶瓷材料和能够可逆地热胶凝化的水溶性纤维素醚来制备陶瓷挤出成型组合物。在表1所示的条件下将它们挤出成型。
陶瓷
(1)氧化铝陶瓷：AL-160，Showa Denko K.K.制
(2)堇青石陶瓷：AF-2，Marusu Glaze Co.Ltd.制
(3)锆钛酸铅(PZT)：PE-60A，Fuji Titanium Industry Co.Ltd.制
(4)钛酸钡：YT-51，KCM Corp.制
水溶性纤维素醚
羟丙基甲基纤维素和甲基纤维素可以从Shin-Etsu Chemical Co.Ltd.获得，以及羟乙基纤维素可以从SE Tylose GmbH获得，它们具有通过GPC-MALLS法测得的聚合度(如表1所示)。
纤维素醚A：羟丙基甲基纤维素，具有25wt％的甲氧基取代度和8wt％的羟丙基取代度。
纤维素醚B：羟丙基甲基纤维素，具有28wt％的甲氧基取代度和5wt％的羟丙基取代度。
纤维素醚C：羟丙基甲基纤维素，具有29wt％的甲氧基取代度和9wt％的羟丙基取代度。
纤维素醚D：甲基纤维素，具有30wt％的甲氧基取代度。
纤维素醚E：羟乙基纤维素，具有56wt％的羟乙基取代度。
离子液体
1-乙基-3-甲基醋酸咪唑
Figure BSA00000526711800061
(溶解温度65℃)，
1-丁基-3-甲基氯化咪唑
Figure BSA00000526711800062
(溶解温度110℃)，
两种试剂可以从Aldrich Co.获得。
将表1中所示的陶瓷和纤维素醚成分在亨舍尔混合器上混合3分钟，和预定量的离子液体组合，然后，在已调节到使捏合混合物可能达到选定温度的温度下，在4×3/4英寸(Inoue Mfg.Co.Ltd.)小型三辊磨机上磨5转。使用具有20mm直径螺杆的实验室真空挤出成型机，将捏合混合物在6.5至8MPa的挤出压力下挤出成型为具有20.5mm外径、加强筋间距2.5mm和加强筋厚度0.5mm的蜂窝结构体坯体。测定挤出成型温度。将成型件切割成50mm长度的片，将其在室温下老化3小时，倒置6次并且目测检查是否有裂纹形成和保持形状。结果示于表1。
将老化的片置于烧结炉中，在炉中在500℃下将其加热3小时以使粘合剂实现烧尽。然后，在氧化铝陶瓷的情况下将干燥的片在1650℃下保持3小时来烧结，或在其它陶瓷的情况下通过封包在氧化镁套壳中和在1300℃下保持3小时来烧结。对烧结的片进行裂纹和形状保持性的评价，结果示于表1。每个试验包括100片成型件。在没有发现裂纹时将样品评为“A”，裂纹片占小于1％时评为“B”，以及裂纹片时占多于1％时评为“C”。对于形状保持性，没有发现变形时将样品评为“A”，变形片占小于1％时评为“B”，和变形片占多于1％时评为“C”。
在另一流程中，将具有通过铜-乙二胺溶剂中的粘度测量确定的聚合度的纤维素和陶瓷材料在亨舍尔混合器上混合3分钟，与预定量的离子液体组合，然后在调节到使捏合混合物可能达到选定温度的温度下，在4×3/4英寸(InoueMfg.Co.Ltd.)的小型三辊磨上磨5转。使用具有20mm直径螺杆的实验室真空挤出成型机，将捏合混合物在6.5至8MPa的挤出压力下挤出成型为具有20.5mm外径、加强筋间距2.5mm和加强筋厚度0.5mm的蜂窝结构体坯体。测定挤出成型温度。将成型件切割成50mm长度的片，将其室温下老化3小时，倒置6次并且目测检查是否有裂纹形成。结果示于表2和3。然后在进行相似的评价之前将挤出成型件在1500℃下烧结8小时。
表1
Figure BSA00000526711800081
表2
Figure BSA00000526711800091
表3
*比较例1不能挤出。

Claims (4)

1.挤出成型组合物，包含陶瓷材料、纤维素和/或其衍生物以及纤维素和/或衍生物可溶解于其中的离子液体。
2.如权利要求1所述的组合物，其中纤维素和/或其衍生物在40-110℃的温度范围内溶解于离子液体中。
3.如权利要求1所述的组合物，其中纤维素衍生物是选自具有至少5000的平均聚合度的烷基纤维素、羟烷基纤维素和羟烷基烷基纤维素的纤维素醚。
4.陶瓷挤出成型件的制造方法，包括步骤：捏合权利要求1的组合物组分，将捏合的组合物挤出成型、干燥和烧成。
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