CN102712539B - 生产具有封闭的可自由运动的颗粒的空心体的方法 - Google Patents
生产具有封闭的可自由运动的颗粒的空心体的方法 Download PDFInfo
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Abstract
本发明涉及一种生产具有封闭在空心体中的可自由运动的颗粒的空心体的方法，其中a)将其中悬浮有颗粒的凝胶形成液体引入交联浴中，b)分离形成的凝胶芯，c)用包含可烧结材料和粘合剂的组合物涂覆所述芯，并且d)使经涂覆的芯经受热处理，其中凝胶和粘合剂被除去且可烧结材料进行烧结以形成闭合壳。胶凝剂例如为藻酸钠并且交联浴包含钙离子。所述颗粒例如选自ZrO2、AI2O3、TiO2和SiO2或其混合物。所述可烧结材料例如为金属粉如羰基铁粉。
Description
本发明涉及一种生产具有封闭在空心体中的可自由运动的颗粒的空心体的方法。
根据DE 10 2004 003507，具有封闭的可自由运动的颗粒的空心体用作吸音结构体，尤其是用于其中产生结构传递噪音和需要消音的应用中。在DE 10 2004 003507中描述且在实施例中说明的生产方法中，将由至少两个叠加单层组成的涂层施加至由有机材料组成的芯上。这里，直接施加至芯表面的层包含材料的固体颗粒，其通过具有比在另一施加层中所存在材料的颗粒高的烧结温度的材料形成。涂覆操作之后进行热处理，其中首先热解有机成分，释放首先直接在芯上形成的层的粉状颗粒，并且烧结外层的粉状颗粒以形成壳。空心结构部件用作疏松床或在烧结之后借助粘合剂粘合、焊接或烧结而通过粘合相互结合以形成成型体。
DE-A 2342948公开了一种生产空心体的方法，所述空心体包含封闭空心区的陶瓷材料的壳。这里，向由可燃或可热分解的有机材料组成的成型体提供不燃陶瓷材料粉末和粘合剂的涂层，然后将经涂覆的成型体加热到200-2000°C，使得有机材料燃烧或分解，粘合剂燃烧或分解或转化成其本身的陶瓷化合物并且陶瓷材料进行烧结。
EP-A 300 543描述了一种通过将固体层施加至发泡聚合物的基本球状颗粒上且热解经涂覆的聚合物芯而生产空心金属或陶瓷球的方法。在维持运动下用包含溶解或悬浮的粘合剂和金属和/或陶瓷粉末颗粒的含水悬浮液处理发泡聚合物的颗粒，优选膨胀型聚苯乙烯的颗粒。在维持运动下将经涂覆和干燥的颗粒在400-500°C下热解并且在维持运动下在900-1500°C温度下烧结。
在先申请EP 09157551.4描述了一种生产具有封闭在空心体中的可自由运动的颗粒的空心体的方法，其中分散有颗粒的基本闭孔聚合物泡沫颗粒的芯用包含可烧结材料和粘合剂的组合物涂覆，并且经涂覆的芯经受热处理，其中聚合物和粘合剂被除去且可烧结材料进行烧结以形成闭合壳。
本发明目的在于提供一种生产具有封闭的可自由流动的颗粒的空心体的方法，所述方法允许有利地生产具有高填充度的空心体。
该目的通过一种生产具有封闭在空心体中的可自由运动的颗粒的空心体的方法实现，其中
a)将颗粒悬浮于凝胶形成液体中并将凝胶形成液体引入交联浴中，
b)分离形成的凝胶芯，
c)用包含可烧结材料和粘合剂的组合物涂覆所述芯，并且
d)使经涂覆的芯经受热处理，其中凝胶和粘合剂被除去且可烧结材料进行烧结以形成闭合壳。
凝胶形成液体优选为含水凝胶形成液体。其包含在与交联剂接触时进行交联以形成凝胶的胶凝剂。
将其中分散有颗粒的凝胶形成液体通过喷嘴(例如借助泵)滴加至交联浴中。交联浴优选为含水交联浴。其包含在与凝胶形成液体所含胶凝剂接触时进行交联以形成凝胶的交联剂，所述凝胶稳定引入交联浴中的凝胶形成液体液滴的形状并封闭其中分散的颗粒。
由此获得的凝胶芯被分离，例如滤出和干燥。它们可根据尺寸通过筛分而分级。凝胶芯用作生产填充空心体的模板。为此，所述芯用包含可烧结材料和粘合剂的组合物涂覆，并且经涂覆的芯经受热处理，其中凝胶和粘合剂被除去且可烧结材料进行烧结以形成闭合壳。这里，凝胶中分散的颗粒也被释放并且以自由运动形式存在于最终空心体中。
胶凝剂例如可为离子交联胶凝剂或共价交联胶凝剂。
合适的共价交联胶凝剂例如为聚丙烯酰胺或聚氨酯，其例如可借助聚醛、聚环氧化物等进行交联。
离子交联胶凝剂是优选的。可能的离子交联胶凝剂为藻酸盐、角叉菜聚糖、脱乙酰壳多糖和果胶酸盐。所用交联剂为金属离子，尤其是多价金属离子如钙离子和/或镁离子。
选择凝胶形成液体中胶凝剂的浓度以致于足够高以在足够速率下进行交联并且所得凝胶芯具有足够稳定性。然而，凝胶形成液体的粘度随着凝胶形成液体中胶凝剂的浓度而增加。凝胶形成液体的粘度越高，越难获得小液滴和由此小凝胶芯。选择交联浴中交联剂的浓度以致于足够高以在足够速率下进行交联。本领域熟练技术人员可容易地在考虑上述因素的情况下确定合适的浓度。
在优选的实施方案中，离子交联胶凝剂为藻酸钠；交联浴包含钙离子，例如呈氯化钙形式。凝胶形成液体中藻酸钠的浓度优选为0.1-5重量%，尤其是0.5-2重量%。交联浴中氯化钙的浓度优选为0.05-20重量%，尤其是0.5-5重量%。
所述芯优选为基本球状的。所述芯通常具有0.1-20mm，尤其是1-3mm的直径(或在非球状芯的情况下沿着最大尺度方向的长度)。
当其中分散有颗粒的凝胶形成液体液滴冲击交联浴表面时，液滴由于交联浴表面张力而可能变形，使得所得凝胶芯的形状或多或少地偏离理想球状。
因此，优选如下的本发明方法实施方案，其中
a1)将与交联浴和凝胶形成液体都不溶混的液相层置于交联浴顶部，
a2)将其中分散有颗粒的凝胶形成液体引入所述液相中，并且
a3)使凝胶形成液体液滴从液相中沉入交联浴中。
在通过液相过程中，在此期间尚未进行交联，其中分散有颗粒的凝胶形成液体液滴可恢复其理想球状。然后，它们从液相中沉入交联浴中，其中由于交联而形成凝胶并且球状被稳定。
合适的液相尤其为与水不溶混且密度低于水的溶剂，例如脂族烃如己烷、环己烷、甲基环己烷；或芳族烃如苯、甲苯、二甲苯等。
凝胶形成液体基于凝胶形成液体和颗粒的总重量通常包含10-90重量%，尤其是30-60重量%的分散颗粒。
本发明所用分散颗粒的密度通常为1000-10000g/l。在热处理期间进行化学和/或形态转变如氢氧化物脱水成氧化物的前体化合物也可分散于所述芯中。
颗粒通常具有比可烧结材料高的烧结温度，例如至少高100K的烧结温度。
在优选的实施方案中，所述颗粒选自无机材料，例如碳化物如碳化硅或碳化硼；氮化物如氮化硅、氮化铝、氮化硼或氮化钛；硅化物和/或铝化物。
特别优选的颗粒为氧化物如Al2O3(呈所有晶型，尤其是α-氧化铝、勃姆石、AIO(OH)或氢氧化铝)、ZrO2、Y2O3、MgO、ZnO、CdO、SiO2、TiO2、CeO2、Fe2O3、Fe3O4、BaTiO3、CuO、NiO、CoO、Co3O4。
所述颗粒例如可以为通常用于生产玻璃(例如硼硅玻璃、钠钙玻璃或熔凝硅石)，玻璃-陶瓷或陶瓷(例如基于氧化物SiO2、BeO、Al2O3、ZrO2或MgO或基于相应混合氧化物的(玻璃-)陶瓷)或非氧化陶瓷如氮化硅、碳化硅、氮化物(例如BN、AlN、Si3N4和Ti3N4)或碳化硼的颗粒。所述颗粒还可以为用作填料或颜料的颗粒。工业上重要的填料例如为基于SiO2的填料，例如石英、方英石、风化硅石(tripolite)、磨石、硅藻土(kieselguhr)、硅藻土(diatomaceous earth)、热解法二氧化硅、沉淀二氧化硅和硅胶，硅酸盐如滑石、叶蜡石、高岭土、云母、白云母、金云母、蛭石、硅灰石和珍珠岩，铝氧化物和二氧化钛。
对于颗粒特别优选的材料为ZrO2、Al2O3、TiO2和SiO2或其混合物。
分散颗粒的平均尺寸通常为5nm-500μm，尤其是0.1-50μm(使用分析超速离心机或动态光散射测量)。
为了实现凝胶形成液体中颗粒的更好分散，可任选伴随使用分散剂。
此外，可将可升华和/或可热解填料悬浮于凝胶形成液体中。所述填料例如选自木粉、软木粉、花生壳、谷粉、纤维素粉和炭黑。伴随使用填料具有的优点在于可改变孔隙率。填料的量基于凝胶形成液体、颗粒和填料的总重量例如为至多30重量%，尤其是0.5-10重量%。
凝胶芯用包含可烧结材料和粘合剂的组合物涂覆。可以各种方式将可烧结材料和粘合剂的涂层施加至所述芯上。例如，将可烧结材料与粘合剂以悬浮液形式混合并用该悬浮液涂覆所述芯，例如在混合器、流化床反应器或造粒盘中。所述芯有利地被引入流化床反应器中。将可烧结材料在溶液中的分散体或粘合剂的分散体引入流化床中。流化气体的温度例如为70-120°C。层施加和干燥通常在5-60分钟内完成。
或者，所述芯可首先用液体粘合剂均匀地喷雾，然后可将可烧结材料涂粉，并且如果通过单次操作尚未达到所需层厚，则重复该操作直到获得所需涂层厚度。
需要的话，随后干燥经涂覆的芯。
可能的可烧结材料为金属粉和陶瓷粉。金属粉或陶瓷粉的混合物也是可以的。可烧结陶瓷例如可包括氮化物、氧化物和硅酸盐陶瓷以及碳化物。
可烧结陶瓷粉的实例为氧化陶瓷粉如Al2O3、ZrO2、Y2O3以及非氧化陶瓷粉如SiC或Si3N4。
可烧结材料优选为金属粉。作为以粉末形式存在的金属，例如可提及铝、铁(尤其是羰基铁粉)、钴、铜、镍、硅、钛和钨。作为粉状金属合金，例如可提及高合金钢或低合金钢，以及基于铝、铁、钛、铜、镍、钴或钨的金属合金，例如青铜。可以使用成品合金粉末或合金各成分的粉末混合物。金属粉、金属合金粉和羰基金属粉也可以混合物使用。
作为金属粉，优选羰基铁粉。羰基铁粉为通过羰基铁化合物热分解产生的铁粉。为了实现流动性和防止附聚，其例如可用SiO2涂覆。作为缓蚀剂，优选伴随使用磷化铁粉。
所述粘合剂通常以溶液或分散体，优选在含水介质中存在。作为粘合剂，可以使用许多聚合物。具体而言，使用来自如下的聚合物或共聚物：乙烯基酯聚合物如聚乙酸乙烯基酯，乙酸乙烯基酯-乙烯，乙酸乙烯基酯-乙烯-氯乙烯，乙酸乙烯基酯-丙烯酸酯，乙酸乙烯基酯-马来酸二正丁酯，乙酸乙烯基酯-月桂酸乙烯基酯，乙酸乙烯基酯-丙烯酸酯的共聚物；部分水解的聚乙酸乙烯基酯，聚乙烯醇；聚乙烯醇缩丁醛(polybutyral)；聚酰胺如聚乙烯基吡咯烷酮；聚丙烯酸酯，苯乙烯-丙烯酸酯的共聚物；纤维素酯；酚醛树脂，氨基树脂，例如尿素树脂或蜜胺树脂；以及环氧树脂。可借助简单试验容易地确定就所选粉末材料和由此规定的热解和烧结条件而言何种粘合剂最适合。聚乙烯醇和纤维素酯是特别合适的。
已由此涂覆的各芯可直接经受热处理或经涂覆的芯可在热处理之前通过粘合而相互结合以获得成型体。所述芯例如可经粘合而相互结合。粘合剂粘合例如可通过用部分地溶解粘合剂的溶剂润湿经涂覆的芯，然后将所述芯一起引入所需排列而进行。可由此提供具有一定程度的机械强度且实现某些限定范围内的载荷特性的自支撑消音结构体。例如可使用根据本发明生产的空心体以该形式获得间壁、门部件或甚至车辆地板。
可通过热处理将凝胶和任选地额外使用的可升华和/或可热解填料以及粘合剂从涂层中除去。将可烧结材料烧结以得到闭合壳。术语“除去”意指包括上游分解和/或热解工艺。热处理可在单级或多级工艺中进行。如果注意粘合剂类型和用量以及足够的层厚，则干燥的固体层对于经涂覆的芯而言具有足够的强度以能够经受高温分解工艺，而壳不变形。在经涂覆的泡沫芯的热解中，粘合剂也从固体层中挥发并留下具有多孔壳结构的自支撑空心球。
取决于所用粉末类型，经涂覆的泡沫颗粒的热解可在空气、惰性气体中或在还原条件下进行。达到约500°C的温度的加热时间至多为3小时且取决于所用凝胶的类型和组成。为了提高原始强度，在金属粉末情况下可有利地在略微氧化条件下进行热解。由此实现残余碳的更好去除和在金属粉末颗粒表面上强度提高的氧化物表层。
在用于除去经涂覆的凝胶芯以及进行有机粘合剂的至少部分去除的热解处理之后进行烧结工艺。在900-1500°C温度下的该烧结工艺在炉如旋转管式炉、搅拌炉或带式炉中进行。炉设备中的气氛可与每种情况下用于涂覆的粉末材料相匹配。由此，其可以在减压下、在氧化或还原条件下或在保护气体下进行。
可通过维持空心体运动或借助用惰性粉末进行外部涂覆来防止各空心体烧结在一起，只要该惰性粉末在所用温度下不与空心体材料进行任何化学或物理反应。该类惰性粉末可容易地在烧结工艺之后机械或化学地从空心体中除去。它们也可在热解和烧结工艺期间用作实际空心球的支撑壳，尤其是当空心体的壁厚非常薄或实际空心体粉末层在热解之后尚不具有足够的原始强度时。取决于空心体材料，合适的惰性粉末例如为碳、氢氧化铝或白垩。
如果例如需要结构部件和吸音轻质组件之间的强结合，则各空心体可在热处理之后进行成型。如上所述，空心体可形成呈疏松床形式的吸音结构体。然而，还可以将空心体在热处理之后通过粘合而相互结合，这可通过粘合剂粘合、焊接或烧结实现。根据本发明生产的空心体也可埋入基质内，这例如可借助合适的可固化聚合物如环氧树脂或较低熔点的金属进行。
本发明借助所附附图和以下实施例说明。
图1显示出适用于生产本发明所用芯的设备。
根据图1，交联浴(B)覆盖有与交联浴和凝胶形成液体(C)都不溶混的液相(A)层。液相(A)借助发动机驱动搅拌器(发动机)搅拌。借助泵(泵)将凝胶形成液体(C)逐滴引入液相(A)中，并且凝胶形成液体液滴从液相(A)中沉入交联浴(B)中。
实施例1：
将1%浓度的CaCl2水溶液引入立式圆筒中至填充高度为20cm并覆盖有15cm的甲苯层。通过1.8mm喷嘴以约1滴/秒的速率将100g氧化铝粉末在1g藻酸钠于100ml水中的溶液中的分散体引入制成的交联浴中。在加料完成之后，取出所形成的球。湿润球具有3.5-4.0mm的直径。将所述球在炉中在减压下在60°C下干燥。干燥球具有2.8-3.4mm的直径。
由此生产的球例如可在流化床中用羰基铁粉在聚乙烯醇水溶液中的悬浮液涂覆。所生产的原始球可随后在保护气体气氛下在1120°C的最大烧结温度下经受热处理。这里，除去有机组分并且通过烧结使球壳固结。在所得球中，氧化铝颗粒以自由运动形式存在于密实的球壳中。
实施例2：
重复实施例1，额外将10g木粉分散于凝胶形成液体中。湿润球具有3.2-3.6mm的直径。干燥球具有2.9-3.1mm的直径。
Claims (23)
1.一种生产具有封闭在空心体中的可自由运动的颗粒的空心体的方法，其中
a)将颗粒悬浮于凝胶形成液体中并将凝胶形成液体引入交联浴中，
b)分离形成的凝胶芯，
c)用包含可烧结材料和粘合剂的组合物涂覆所述芯，并且
d)使经涂覆的芯经受热处理，其中凝胶和粘合剂被除去且可烧结材料进行烧结以形成闭合壳，
其中所述颗粒选自无机材料。
2.根据权利要求1的方法，其中所述凝胶形成液体包含离子交联胶凝剂。
3.根据权利要求2的方法，其中所述离子交联胶凝剂选自藻酸盐、角叉菜聚糖、脱乙酰壳多糖和果胶酸盐。
4.根据权利要求3的方法，其中所述离子交联胶凝剂为藻酸钠且所述交联浴包含钙离子。
5.根据上述权利要求中任一项的方法，其中额外将可升华和/或可热解填料悬浮于所述凝胶形成液体中。
6.根据权利要求1-4中任一项的方法，其中
a1)将与交联浴和凝胶形成液体都不溶混的液相层置于交联浴顶部，
a2)将其中分散有颗粒的凝胶形成液体引入所述液相中，并且
a3)使凝胶形成液体液滴从液相中沉入交联浴中。
7.根据权利要求5的方法，其中
a1)将与交联浴和凝胶形成液体都不溶混的液相层置于交联浴顶部，
a2)将其中分散有颗粒的凝胶形成液体引入所述液相中，并且
a3)使凝胶形成液体液滴从液相中沉入交联浴中。
8.根据权利要求1-4中任一项的方法，其中所述凝胶形成液体基于凝胶形成液体和颗粒的总重量包含10-90重量%的分散颗粒。
9.根据权利要求7的方法，其中所述凝胶形成液体基于凝胶形成液体和颗粒的总重量包含10-90重量%的分散颗粒。
10.根据权利要求6的方法，其中所述颗粒包括碳化物、氮化物、氧化物、硅化物和/或铝化物。
11.根据权利要求7的方法，其中所述颗粒包括碳化物、氮化物、氧化物、硅化物和/或铝化物。
12.根据权利要求8的方法，其中所述颗粒选自ZrO2、Al2O3、TiO2和SiO2及其混合物。
13.根据权利要求9的方法，其中所述颗粒选自ZrO2、Al2O3、TiO2和SiO2及其混合物。
14.根据权利要求1-4中任一项的方法，其中所述颗粒的平均尺寸为5nm-500μm。
15.根据权利要求9-13中任一项的方法，其中所述颗粒的平均尺寸为5nm-500μm。
16.根据权利要求1-4中任一项的方法，其中所述可烧结材料为金属粉。
17.根据权利要求15的方法，其中所述可烧结材料为金属粉。
18.根据权利要求16的方法，其中所述金属粉为羰基铁粉。
19.根据权利要求17的方法，其中所述金属粉为羰基铁粉。
20.根据权利要求1-4中任一项的方法，其中所述芯基本上为球状。
21.根据权利要求17-19中任一项的方法，其中所述芯基本上为球状。
22.根据权利要求1-4中任一项的方法，其中所述芯具有0.1-20mm的直径。
23.根据权利要求21的方法，其中所述芯具有0.1-20mm的直径。
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| DE102015221853B4 (de) * | 2015-11-06 | 2019-05-16 | Technische Universität Bergakademie Freiberg | Verfahren zur Herstellung von kohlenstoffhaltigen keramischen Bauteilen |
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| CN108883031B (zh) * | 2016-03-24 | 2022-01-25 | 生物辐射实验室股份有限公司 | 使用凝胶珠来控制液滴分散 |
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| CN114524617B (zh) * | 2022-03-31 | 2023-11-28 | 郑州圣莱特空心微珠新材料有限公司 | 一种碳化硅改性的高导热、低介电中空玻璃微珠及其制备方法 |
| CN115228470A (zh) * | 2022-07-01 | 2022-10-25 | 重庆工商大学 | 一种超疏水超亲油羰基铁负载纳米二氧化钛光催化剂的制备方法 |
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