CN103890054A - 制造包含纳米粒子的分散体的方法和根据这种方法制造的分散体 - Google Patents
制造包含纳米粒子的分散体的方法和根据这种方法制造的分散体 Download PDFInfo
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Abstract
本发明涉及制造包含微原纤化纤维素和纳米粒子的分散体的方法,其中所述方法包括以下步骤:提供包含预处理的纤维素纤维的浆液,将纳米粒子添加至浆液并通过机械分解处理浆液,使得形成包含微原纤化纤维素的分散体,其中纳米粒子被吸收至微原纤化纤维素的表面和/或吸收至微原纤化纤维素中。本发明还涉及根据所述方法制造的分散体、涂有包含所述分散体的涂层的纸或者板产品和由所述分散体制造的纸或者板产品以及包含所述分散体的复合材料。
Description
技术领域
本发明涉及制造包含微原纤化纤维素和纳米粒子的分散体的方法。本发明还涉及根据所述方法制造的分散体、涂有包含所述分散体的涂层的纸或者板产品和由所述分散体制造的纸或者板产品以及包含所述分散体的复合材料。通过本发明,可制造包含纳米粒子和微原纤化纤维素的非常稳定的分散体。
背景技术
在纸或者板产品的制造期间,经常希望将纳米粒子添加至纸或者板的装饰(furnish)或者形成的纸或者板产品的表面。经常添加纳米粒子以降低制造成本和/或改善完成的纸或者板产品的性质,例如印刷性质。
纳米粒子也在许多其它应用中使用,例如制造复合材料,其中经常添加纳米粒子以降低重量和提高复合材料的弹性模量。
当用包含纳米粒子的分散体或者浆液工作时,问题是,它们不稳定并且纳米粒子容易形成聚集物,这些聚集物的反应性不如游离形式的纳米粒子。而且,包含纳米材料的分散体经常具有与扬尘相关的问题,并且处理包含纳米粒子的分散体也经常是有害的,因为它们例如被皮肤吸附。包含微原纤化纤维素的干燥的分散体也经常具有与扬尘相关的问题。
因此需要制造具有改善的性质的包含纳米粒子的稳定分散体的改善的方法。
发明内容
本发明的一个目的是提供能够以非常有效率和安全的方式制造包含纳米粒子的稳定分散体的方法。
本发明的另一目的是提供涂有包含所述稳定分散体的涂层的纸或者板产品。
这些目的以及其它目的和优势通过权利要求1的方法实现。本发明涉及制造包含微原纤化纤维素和纳米粒子的分散体的方法,其中所述方法包括以下步骤:提供包含预处理的纤维素纤维的浆液,将纳米粒子添加至浆液和通过机械分解处理浆液,使得形成包含微原纤化纤维素的分散体,其中所述纳米粒子被吸收至微原纤化纤维素的表面和/或被吸收至微原纤化纤维素中。通过使用机械分解处理包含预处理的纤维素纤维和纳米粒子的浆液,可制造更加稳定分散体,同时分散体也具有其它改善的性质,例如降低的扬尘问题。
机械分解优选在压力均化器中进行。已经显示,通过使用压力均化器,可制造具有更多敞开区域(open areas)的微原纤化纤维素,并且同时以非常有效率的方式解胶分散体的纳米粒子。
在压力均化器中使用的压力优选为500-4000Bar,更优选为1000-2000Bar。
纳米粒子优选为膨润土、二氧化钛、氧化锌、银、氧化铜、氧化铁、二氧化硅、碳酸钙的纳米粒子,例如纳米沉积的碳酸钙(PCC)和/或碳纳米管。
在分散体的微原纤化纤维素和纳米粒子之间的比率优选为10:90-90:10。取决于最终用途和分散体包含何种微原纤化纤维素和纳米粒子,比率可改变。
优选地,分散体的纳米粒子的大部分,优选至少50%,被吸收在微原纤化纤维素的表面上或者在微原纤化纤维素中。以此方式,在分散体中的游离纳米粒子的量受限并且纳米粒子形成无反应性纳米聚集物的趋势降低。
通过机械分解处理的浆液的干物质含量优选为1-30重量%的纤维。浆液的干物质含量取决于使用的纳米粒子、使用的何种MFC以及用于机械分解的何种设备。
在通过机械分解处理后,分散体的干物质含量优选高于50重量%的纤维。分散体优选在机械分解后脱水,以提高干物质含量。通过提高干物质含量,分散体向其它位置的运输可以以更加有效率的方式进行。而且,已经显示,通过提高分散体的干物质含量,稳定性甚至进一步提高。
所述方法还可包括在机械分解后洗涤分散体。以此方式,可除去分散体的任何游离的纳米粒子。在洗涤中除去的纳米粒子可再循环返回至方法中并因此再次利用。
本发明还涉及根据上述方法制造的分散体。已经显示,制造的分散体危害较小并同时具有提高的稳定性,因为它具有降低的扬尘倾向。
分散体的干物质含量优选高于50重量%的纤维。不同的纳米粒子给予分散体不同的流动性质等,因此取决于使用的纳米粒子,分散体的最大干物质含量不同。而且,它也取决于使用的何种MFC以及用于机械分解的何种设备。
分散体的纳米粒子的大部分,优选纳米粒子的至少50%,优选吸附在微原纤化纤维素的表面上或者在微原纤化纤维素中,即,在分散体中的游离纳米粒子的量相当低。以此方式,分散体将更加稳定,以及它在处理时的危害较小。
分散体基本上不含游离纳米粒子也是可能的。通过除去任何游离纳米粒子,优选通过在分散体机械分解后洗涤分散体,可从分散体除去所有或者基本上所有游离纳米粒子,即,分散体不含或者仅基本上不含游离纳米粒子。
本发明还涉及涂有涂层的纸或者板产品,所述涂层包含上述分散体。通过用所述分散体涂覆纸或者纸板,可提供具有改善的涂层的纸或者纸板。如果分散体包含MFC和膨润土纳米粒子,已经显示,用这种分散体涂覆的基底具有非常良好的耐油性,即,产生针对油脂的屏障。如果涂覆至纸或者纸板表面的涂层着色剂(coating color)也包含至少一种聚合物,已经显示,纸或者纸板可具有非常良好的屏障涂层,尤其是针对液体的屏障。
本发明还涉及由上述分散体制造的纸或者板。因此可从所述分散体制造纸或者板产品。因此纸或者板通过以下方法制造:将包含微原纤化纤维素和纳米粒子的分散体添加至造纸网(wire),以形成平幅。然后,将平幅用已知方式处理,以形成纸或者板产品。
本发明还涉及包含上述分散体的复合材料。通过将包含微原纤化纤维素和纳米粒子的分散体添加至复合材料,可以以容易的方式制造具有高纳米粒子量的复合材料。这是由于分散体非常稳定,并因此易于使用分散体作为复合材料的添加剂。
具体实施方式
本发明涉及制造分散体的方法,所述分散体包含纳米粒子和微原纤化纤维素,其中纳米粒子被吸收至微原纤化纤维素的表面上或者微原纤化纤维素中。分散体通过以下方法制造:通过机械分解处理包含预处理的纤维素纤维和纳米粒子的浆液,优选在压力均化器中,其将确保形成具有高敞开表面量的微原纤化纤维素,同时均化纳米粒子并防止形成纳米粒子聚集物。通过提高形成的微原纤化纤维素的敞开表面量和防止纳米粒子形成纳米聚集物,纳米粒子可较大程度地吸收至微原纤化纤维素的敞开表面。还已经显示,通过在压力均化器中处理包含纳米粒子和预处理的纤维素纤维的浆液,纳米粒子将不仅吸收在MFC的表面上,而且吸收至MFC中。以此方式,制造的分散体将非常稳定并形成较少的纳米聚集物。由于提高的稳定性,分散体将更容易处理,并可以以容易的方式将分散体运输至不同地点。
而且,已经显示,根据本发明的分散体具有较少的扬尘问题,甚至在高干物质含量或者甚至当干燥时也是如此。还已经显示,分散体的皮肤吸收减少,这使得处理时危害较小。因此可在较少的安全限制下处理分散体,鉴于改善的工作环境以及它将具有更多经济益处,这使它成为更有吸引力的产品。
机械分解可在许多不同种类的机械处理设备中进行,例如精炼机或者研磨机如masuko研磨机。然而,优选使用压力均化器,其将以非常有效率的方式从预处理的纤维制造微原纤化纤维素纤维,以及均化纳米粒子。压力均化器产生高剪切力,其将分解纤维和纳米粒子。在机械分解期间使用高压力,并且压力优选为500-4000Bar,优选为1000-2000Bar。最佳压力经常为约1500Bar。需要的压力取决于处理的材料。
然而,太高的压力经常不利于使用,因为设备的磨损将太高。具体压力均化器的一个实例是所谓的微流化器。
纳米粒子是指具有任何纳米级外部尺寸或者具有纳米级内部结构或者表面结构的粒子。纳米级是指约1nm-100nm的尺寸范围。可使用的纳米粒子的实例为膨润土、二氧化钛、氧化锌、银、氧化铜、氧化铁、二氧化硅、碳酸钙的纳米粒子,例如纳米沉积的碳酸钙(PCC)和/或碳纳米管。纳米级二氧化钛可给予非常有效的UV屏障,这意味着,具有吸收的或者结合的二氧化钛纳米粒子的MFC将具有UV阻挡性质。也可用氧化铝(Al2O3)涂覆二氧化钛纳米粒子,以降低光活性,这将给予氧化钛作为白色颜料的功能。碳纳米管通常用于复合材料中,并且具有吸收的或者结合的碳纳米管纳米粒子的MFC将具有改善的导电性、抗静电性、提高的韧性和耐火性。对于在用作包装的板产品中使用,提高的韧性是非常有意义的性质。纳米二氧化硅可改善涂有包含MFC和纳米二氧化硅的分散体的纸或者板产品的喷墨印刷性质。
预处理的纤维素纤维可为任何种类的木纤维的纤维,例如硬木纤维、软木纤维和/或农业纤维。可能的预处理可为机械处理如分解、酶处理、羧甲基化、TEMPO氧化、CMC接枝、化学溶胀、酸水解或者促进微原纤化纤维素形成的其它方法。优选地,预处理为酶处理。预处理可在超过一个步骤中进行。预处理的纤维素纤维也可包含纤维素原纤维。而且,也可在机械分解之前将微原纤化纤维素添加至预处理的纤维。
所述微原纤化纤维素(MFC)也被称为纳米纤维素。它是一种通常由木质纤维素纤维(硬木或者软木纤维)制造的材料。它也可由微生物来源、农业纤维如小麦麦秆纸浆、竹子或者其它非木质纤维来源制造。在微原纤化纤维素中,各个微原纤维已经部分或者全部地彼此分开。微原纤化纤维素纤维正常情况下非常细(约20nm)并且长度经常为100nm-10μm。然而,微原纤维也可较长,例如为10-200μm,但是由于宽的长度分布,甚至可发现2000μm的长度。已经原纤化和在表面上具有微原纤维的纤维和被分开和位于浆液水相中的微原纤维包含在定义MFC中。而且,晶须(whiskers)也包含在定义MFC中。
通过用机械分解如在压力均化器中处理浆液,已经显示,在分散体中纳米粒子的量可提高。因此可制造包含大量纳米粒子的分散体。这是由于在预处理的纤维素纤维的机械分解期间新的敞开区域的形成,其给予纳米粒子新的附着位点。而且,机械分解将防止纳米粒子聚集物的形成,该聚集物对MFC的敞开位点无反应性。添加的纳米粒子的大部分被吸收,即,它们不存在于分散体的液相中。优选地,添加的纳米粒子的至少50%被吸收在MFC上或者吸收至MFC中,更优选地,添加的纳米粒子的至少70%并且甚至更优选至少80%被吸收。
也可从分散体除去任何未吸收的纳米粒子。这可通过以下方法进行:在通过机械分解处理后洗涤分散体。这可例如通过以下方法进行:用例如水洗涤,离心分散体并然后除去一部分包含游离纳米粒子的分散体,或者使用电渗。优选地,使从浆液除去的纳米粒子返回至工艺中以再次使用纳米粒子。游离纳米粒子能够以许多不同的方式搞破坏,例如,它们使得分散体的处理更加困难,因为游离纳米粒子具有以下危险:吸附至处理它的人员的皮肤或者肺中。通过除去任何游离纳米粒子,由此可制造甚至更安全的产品。
在分散体中在纳米粒子和MFC之间的比率优选为10:90-90:10。经常优选尝试尽可能地提高分散体的纳米粒子的量,并因此降低微原纤化纤维素的量。然而,取决于何种MFC以及纳米粒子,相应的量不同,以产生尽可能稳定的分散体。
在通过机械分解处理之前,浆液的干物质含量优选为1-30重量%纤维。取决于使用的纤维素纤维、使用的纳米粒子以及用于机械分解的设备,浆液的干物质含量不得不改变。已经显示,通过在机械分解之前或者之中增加浆液的固含量,纳米粒子向微原纤化纤维素中的吸附/吸收可增加。通过干燥浆液或者通过施用其它液体介质减少方法,固含量可增加。
在通过机械分解处理后,分散体的干物质含量优选高于50重量%纤维。优选的是在机械分解后脱水分散体以提高分散体的干物质含量。已经显示,较高干物质含量将提高分散体稳定性,以及运输具有高干物质含量的分散体在经济上更加有利,因为运输的水量减少。
本发明还涉及根据所述方法制造的分散体。分散体的提高的稳定性使得更加容易处理。例如,更容易在运输期间在不改变分散体性质的情况下将分散体运输至消费者。以此方式,促进消费者对于分散体的处理,因为原位制造分散体可能不是必须的。相反,消费者可根据他们的愿望购买最终的分散体来使用。
分散体可在许多不同的产品中使用。例如,作为防晒水中的组分,作为清洁和卫生产品中的组分,在包含纳米材料增强的复合材料的产品如塑料、运动物品和移动电话中,在阻燃应用中,为了给予摩擦降低,作为抗微生物复合材料例如清洁表面、滤纸、用于敏感产品的包装,在导电或者不导电表面例如电池和一次性电子设备中,在自清洁表面中,用于太阳能电池板(sunpanels)和/或作为导电印刷油墨中的组分。
本发明还涉及涂有涂层的纸或者板产品,所述涂层包含本发明的分散体。在涂饰着色剂中分散体的使用可向纸或者板提供非常良好的屏障性质。已经显示,如果将包含膨润土纳米粒子和MFC的分散体涂覆至纸或者板的表面,可形成非常良好的针对油脂的屏障。涂饰着色剂也可包含一些种类的聚合物,并且这种涂层经常将给予纸或者板产品优异的液体阻挡性质。本发明的分散体给予纸或者板产品良好阻挡性质的原因可能是由于在产品的表面上形成更致密的结构。如果使用具有特殊形式如刀状结构的纳米粒子,那么也可发生物理阻碍。这种物理阻碍意味着,例如,氧气或者液体为了穿透进入基底中被迫走过较长的路,并以此方式,形成改善的产品屏障。而且,存在的MFC将防止聚合物和纳米粒子太远地渗入产品中,以及提高屏障层的强度,从而使它对于机械缺陷更有耐性。涂覆本发明的分散体的另一优点是,涂饰着色剂的流变性将改善,其改善涂布工艺的流动性以及降低在涂层中针孔或者其它缺陷的量。而且,由于本发明的分散体包含大量纳米粒子(其为在干燥之后或者之中不收缩或者改变的粒子),产品将显示较少的与翘曲或者在干燥后收缩导致的其它缺陷相关的问题。
本发明还涉及由上述分散体制造的纸或者板。因此可由分散体制造纸或者板产品。因此纸或者板通过以下方法制造:将包含微原纤化纤维素和纳米粒子的分散体添加至造纸网,以形成平幅。然后,将平幅用已知方式处理,以形成纸或者板产品。已经显示,可由本发明分散体制造非常良好的纸产品。由于分散体的稳定性,可制造具有大量纳米粒子的纸产品。
本发明还涉及包含上述分散体的复合材料。通过将包含微原纤化纤维素和纳米粒子的分散体添加至复合材料,可以以非常容易的方式制造具有高纳米粒子量的复合材料。这是由于分散体非常稳定,并因此容易使用分散体作为复合材料的添加剂。复合材料因此将包含大量纳米粒子和一些MFC,这将给予复合材料改善的性质。
实施例:
浆液包含比率为50:50的预处理的纤维(酶预处理)和膨润土纳米粒子的混合物。酶为纤维素酶,更具体为内切葡聚糖酶(EGII)。浆液的干物质含量为6重量%。将浆液在微流化器中以1500Bar的压力压力均化。
然后,目测检查制造的分散体的稳定性。在四周后,分散体仍然稳定。
可将其与仅含膨润土纳米粒子的分散体进行比较,仅含膨润土纳米粒子的分散体倾向于在贮存期间沉积,和与包含微原纤化纤维素的分散体进行比较,包含微原纤化纤维素的分散体倾向于在贮存时"析出"水。
结果,本发明的分散体稳定得多。
鉴于本发明上面的详细描述,其它修饰和改变对于本领域技术人员而言将变得显而易见。
然而,显然这种其它修饰和改变可被得出,而不脱离本发明的主旨和范围。
Claims (18)
1.制造包含微原纤化纤维素和纳米粒子的分散体的方法,其中所述方法包括以下步骤:
-提供包含预处理的纤维素纤维的浆液,
-将纳米粒子添加至所述浆液,和
-通过机械分解处理所述浆液,使得形成包含微原纤化纤维素的分散
体,其中所述纳米粒子被吸收至所述微原纤化纤维素的表面和/或被吸
收至所述微原纤化纤维素中。
2.权利要求1的方法,其中所述机械分解在压力均化器中进行。
3.权利要求2的方法,其中在所述压力均化器中使用的压力为500-4000Bar。
4.前述权利要求中的任一项的方法,其中所述纳米粒子为膨润土、二氧化钛、氧化锌、银、氧化铜、氧化铁、二氧化硅、碳酸钙的粒子,例如纳米沉积的碳酸钙(PCC)和/或碳纳米管。
5.前述权利要求中的任一项的方法,其中在所述微原纤化纤维素和纳米粒子之间的比率为10:90-90:10。
6.前述权利要求中的任一项的方法,其中所述纳米粒子的大部分,优选至少50%,被吸收在所述微原纤化纤维素和/或所述纤维素原纤维的表面上或者被吸收在所述微原纤化纤维素和/或所述纤维素原纤维中。
7.前述权利要求中的任一项的方法,其中所述待通过机械分解处理的浆液的干物质含量为1-30重量%的纤维。
8.前述权利要求中的任一项的方法,其中在通过机械分解处理后所述分散体的干物质含量为高于50重量%的纤维。
9.前述权利要求中的任一项的方法,其中所述方法还包括在所述机械分解后洗涤所述分散体。
10.分散体,其根据权利要求1-9中的任一项的方法制造。
11.权利要求10的分散体,其中所述分散体的干物质含量为高于50重量%的纤维。
12.权利要求10-11中的任一项的分散体,其中所述纳米粒子的大部分,优选纳米粒子的至少50%,被吸附在所述微原纤化纤维素的表面上或者被吸附在所述微原纤化纤维素中。
13.权利要求10-12中的任一项的分散体,其中所述分散体基本上不含游离纳米粒子。
14.包含涂层的纸或者板产品,所述涂层包含权利要求10-13中的任一项的分散体。
15.权利要求14的纸或者板产品,其中所述涂层包含膨润土纳米粒子和MFC,并且所述涂层在所述纸或者纸板的表面上形成针对油脂的屏障。
16.权利要求14或者15的纸或者纸板产品,其中所述涂层还包含聚合物,所述聚合物在所述纸或者纸板的表面上形成屏障。
17.纸或者板,其由权利要求10-13中的任一项的分散体制造。
18.复合材料,其包含权利要求10-13中的任一项的分散体。
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE1150997A SE536780C2 (sv) | 2011-10-26 | 2011-10-26 | Förfarande för framställning av en dispersion som innefattarnanopartiklar samt en dispersion framställd enligt förfarandet |
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PCT/IB2012/055866 WO2013061266A1 (en) | 2011-10-26 | 2012-10-25 | Process for producing a dispersion comprising nanoparticles and a dispersion produced according to the process |
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CN115196910B (zh) * | 2016-04-04 | 2023-11-10 | 菲博林科技有限公司 | 用于在天花板、地板和建筑产品中提供增加的强度的组合物和方法 |
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CN112921687A (zh) * | 2021-04-01 | 2021-06-08 | 安徽新立滤清器有限公司 | 一种通过微生物酶降解改性木质纤维束制备方法 |
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Also Published As
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KR20140095469A (ko) | 2014-08-01 |
SE536780C2 (sv) | 2014-08-05 |
EP2771387B1 (en) | 2017-03-08 |
EP2771387A1 (en) | 2014-09-03 |
CN103890054B (zh) | 2016-09-07 |
SE1150997A1 (sv) | 2013-04-27 |
JP2014530946A (ja) | 2014-11-20 |
RU2014120753A (ru) | 2015-12-10 |
PL2771387T3 (pl) | 2017-08-31 |
WO2013061266A1 (en) | 2013-05-02 |
JP6267645B2 (ja) | 2018-01-24 |
BR112014009901A2 (pt) | 2017-04-25 |
US9365978B2 (en) | 2016-06-14 |
BR112014009901B1 (pt) | 2021-09-14 |
US20140302336A1 (en) | 2014-10-09 |
RU2585017C2 (ru) | 2016-05-27 |
EP2771387A4 (en) | 2015-04-15 |
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