CN103814080A - 聚对苯二甲酸乙二酯-石墨烯纳米复合物 - Google Patents
聚对苯二甲酸乙二酯-石墨烯纳米复合物 Download PDFInfo
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Abstract
一种纳米复合材料,包含作为基体聚合物的聚对苯二甲酸乙二酯(PET)和提高该基体聚合物强度的纳米颗粒。
Description
相关申请的交叉引用
本申请要求2011年5月3日提交的美国临时申请号61/482,048的权益,通过引用以其全文并入本文,用于所有目的。
发明领域
本公开总体上涉及聚合物,并更具体地涉及通过引入纳米材料来加强聚合物。
发明背景
聚合物已经成为现代生活中常见的成分。曾经利用劳动和/或能量密集型方法由金属和其它重型材料制造的产品现在可以更便宜、更迅速和用更少的能量输入来制造。汽车、医疗、信息技术和保健只是普遍使用聚合物的工业的一小部分。
由聚合物制造装置通常产生比由结构金属或者其它材料制造的等价物品重量更轻的物品。然而重量的减少通常带来强度的降低。强度降低可能是承受扭矩、剪切、压缩、压力或者其它力而不弯曲、破裂或变形至不可接受的程度的能力的降低。
需要的是用于解决上述和相关问题的体系和方法。
发明概述
本公开的发明,在其中一个方面,包含纳米复合材料。该材料包含包括聚对苯二甲酸乙二酯(PET)的基体聚合物,和提高该基体聚合物强度的纳米颗粒。该纳米颗粒可能包含石墨烯纳米片,其可由片层剥离制备。石墨烯纳米片可具有5微米的平均直径。它们可包含约2重量%的纳米复合材料。在其它实施方案中,石墨烯纳米片可包含约5%、10%或15%重量的纳米复合材料。在另一个实施方案中,重量百分比可为约2-约5。
本公开的发明,在其中另一方面,包含生产纳米复合材料的方法。该方法包括提供作为基体聚合物的聚对苯二甲酸乙二酯(PET),和提供纳米颗粒物质。该方法还包括将基体聚合物与纳米颗粒材料混合以形成母料产物,和将该母料产物注塑。该纳米颗粒物质可包含石墨烯。石墨烯可由片层剥离制备。
在一个实施方案中,纳米颗粒物质可包含约2重量%的纳米颗粒物质材料在母料产物中。在其它实施方案中,重量百分比可为约5、10或15。在一些实施方案中,其可为约2%-约15%。
附图简述
图1:xGnP粉末样品的SEM显微图片,(a)1000倍;(b)11000倍。
图2:PET(A)和PET-15% xGnP纳米复合物(B)的经拉伸试验的样品。
图3:(a)PET、(b)PET-2%重量xGnP纳米复合物、(c)PET-5%重量xGnP纳米复合物、(d)具有微孔的PET-10%重量xGnP纳米复合物、(e)5000倍下的PET-10%重量xGnP纳米复合物和(f)PET-15%重量xGnP纳米复合物样品的SEM显微图片。
图4:TEM显微图片显示了PET-15% xGnP纳米复合物中纳米片的分散;(a)10000倍、(b)20000倍的亮场图片和(c)60000倍的暗场图片。
图5:xGnP粉末与PET对照和纳米复合物的XRD图案对比。
图6:PET和PET-xGnP纳米复合物的应力-应变曲线对比。
图7:PET纳米复合物的杨氏模量与对照PET的比较。
图8:预测的PET-石墨烯纳米复合物的模量与实验结果的比较。
优选实施方案详述
基体聚合物可具有许多固有的与它们的外貌、颜色、硬度、强度和许多其它可测量性质相关的特征。在一些情况下,基体聚合物与预定量的材料混合将改变基体聚合物的性质。加入到基体聚合物的材料称为母料,而按照一定方式将母料加入到基体聚合物使得基体聚合物的性质改变的过程可称为母料过程。
还可在进一步处理产生成品的母料过程中制备聚合物。例如,如下所述的聚合物或纳米复合聚合物可制备成母料丸粒,其随后经模塑为成品(例如,通过注塑或其它适合方法)。
在本公开的一些实施方案中,纳米尺度的颗粒与聚合物共混或结合成母料丸粒,然后可将母料丸粒注塑为成品。在母料的聚合物中,纳米尺度材料将仅在纳米尺度上相互作用以改变基体聚合物的性质,其相对于较大的增强机制提供了某些益处。基于格里菲斯(Griffith)破裂理论和韦布尔(Weibull)分析,较小颗粒与它们较大的相应部分相比更坚固并且可更有效地增强基质。此外,由于它们提高的表面积和高的宽厚比,较少体积的较小增强体可提供等效的增强作用。
纳米颗粒的选择可基于所需的性质、与基质的相互作用、加工、成本和最终复合物的应用。若干纳米颗粒,例如有机粘土(MMT)、金属纳米颗粒(Al和Ag)、金属氧化物(ZnO、二氧化硅)和碳衍生物(CNT's、富勒烯 、氧化石墨、石墨烯),可用于聚合物纳米复合物的制备。在另一个实施方案中,利用聚对苯二甲酸乙二酯(PET)-石墨烯制造聚合物纳米复合物。该材料适于注塑和吹塑以及其它处理及制造工艺。
石墨烯(其包含单层碳原子)与其它纳米颗粒相比具有优良的机械性质(模量-1060GPa,强度-20GPa)和电性质(50×10-6 I cm)。石墨烯经过表面处理的帮助可在基体聚合物中分散良好。片层剥离石墨烯纳米片(xGnP)为多个石墨烯层堆叠形成片状物。
对于PET与石墨烯的特定组合(例如,像在本公开的某些实施方案中),虽然PET是广泛使用的聚合物,但是迄今为止在实验室研究中被忽视,部分因为其相对较粘并且具有相对高的熔点的事实。此外,PET的组成体单元(constituent mer unit)呈现极性,在产品混合时,其可导致特定极性纳米结构的分解。应注意到石墨烯是极性物质,意味着在PET存在下它可预期溶解或失去它的结构完整性。然而,如本文公开,石墨烯可以并且确实保持足够的完整性以有利地改变PET的物理特征。
在一个实施方案中,PET-片层剥离石墨烯纳米复合物利用注塑经过母料过程制备,其中石墨烯纳米片与PET混合以形成母料丸粒。这些实验结果与利用Halpin-Tsai和Hui-Shia模型的理论结果相比较。
经常基于简化的经验方程估算连续纤维复合物,该经验方程称为“混合物法则”。在纳米增强体的情况下,“混合物法则”会低估或者高估最终性质。这可能是由于它们的低体积部分,以及基质与增强体之间性质的通常较大的差异。
对于纳米复合物,纳米片与基质之间的特殊相互作用在测定它们的弹性性能时是重要的。纳米片的高的宽厚比与基质-增强体界面处的复杂机制相结合,使纳米复合物性质估算变复杂。因此,已修改传统的微观力学模型(micromechanical model)以估算纳米颗粒的机械性质。
实验1
材料
在一个示范中,使用市售可得的被称作oZpetTM的0.80dl/g(I.V.)聚对苯二甲酸乙二酯(GG-3180 FGH,Leading Synthetics,澳大利亚)。如图1所示,平均直径为5 Pm的xGnP?-M-5级别(99.5%碳)片层剥离石墨烯纳米片由XG Sciences , Inc(East Lansing ,MI)以干粉末获得。石墨烯纳米片(xGnP)与所取得的PET树脂通过Ovation Polymers(Medina,OH)利用它们的ExTimaTM技术混合为PET-xGnP母料丸粒。
石墨烯纳米片本质上是憎水的;石墨烯的有效分散产生自氧与羟基官能团(由于在片状物断裂期间原料碳的暴露而形成)在它们表面与PET极性基团的相互作用[19]。从上述过程获得的母料丸粒用作注塑过程的原料。PET对照样品与增加重量分数(2%、5%、10%和15%)的PET-xGnP纳米复合物拉伸条于250℃-260℃温度下,遵循ASTM D 638的型号-I规范(通过引用在此并入)注塑。
表征技术
产生的纳米复合物拉伸条(如图2所示)利用通用材料试验机(Instron 5582型)测试。测试遵循ASTM D 638标准,十字头速度为5mm/分钟。使用非接触式激光伸长计(Electronic Instrument Research,Model LE-05)记录无仪器柔度的位移。激光伸长计记录来自放置在测量长度上的自反射粘着物的反射的位移。
三个每一种复合物与纯PET样品一起测试用于对比。以100ms时间间隔同时记录十字头的激光位移和负荷。
利用电子显微镜(SEM,TEM)和X射线衍射观察石墨烯纳米片的分散。xGnP粉末以及PET和PET-片层剥离石墨烯纳米复合物断面的SEM显微图片利用Hitachi S-4800获得。
PET对照和具有较低石墨烯含量的纳米复合物利用Balzers Union MED 010涂布机涂布Au/Pt。用于透射成像的薄片(厚度为70nm)利用Reichert-Jung Ultracut E薄片切片机切片。透射显微图片利用JEOL JEM-2100显微镜在200kV操作电压下采集。X射线衍射图案在Bruker D8 Discovery衍射计上以反射采集,利用Cu Kα(λ=1.54054?)辐射。XGnP粉末连同PET样品的XRD扫描在40kV和40mA下采集,曝露时间为120秒。
结果
扫描电子显微镜法
XGnP干粉末的SEM显微图片显示在图1(b),其显示了聚集的片状物,每一个片状物由大量石墨烯层共同堆叠组成。这些片状物平均直径为5-10 Pm和厚度为数纳米(5-20nm)。
PET-石墨烯纳米复合物失效表面的显微图片(图3(b)、(c)、(d) 、(e)和(f))显示,石墨烯纳米片保持完整并且分散到PET基质内,没有聚集迹象。显微图片说明纳米复合物在拉伸负荷下的失效是通过易碎的微观破裂的联合。可从具有5%和10%石墨烯纳米片重量分数的纳米复合物样品的SEM显微图片注意到微孔的存在和从这些空隙引发的破裂。SEM显微图片显示纳米片突出断面以外。它们看起来已变形并与基质混合。
透射电子显微镜法
纳米复合物的性能取决于纳米颗粒的分散。TEM显微图片采集自70nm的薄部以得到对纳米片分散的更好了解。图4显示的透射显微图片揭示了石墨烯纳米片保持完整为片状物并且分散到聚合物基质中,没有发现石墨烯片(完全的片层剥离物)的单独分散。显微图片以亮场和暗场两种模式采集。由于纳米片由若干单独的石墨烯片组成,使用的70nm厚部可能含有聚合物和石墨烯片的层,因此暗场模式是有利的。石墨烯比聚合物基质更导电,因此在透射成像中,这个区别提供了对比度。
X射线衍射
从干的xGnP粉末、PET对照和PET-xGnP纳米复合物采集的XRD图案显示在图5中。石墨烯纳米片的衍射图案显示石墨烯-2H特征峰在26.6°(d=3.35?)和54.7°(d=1.68?)2θ处。在26.6°2θ处峰的轻微宽化说明存在不同尺寸的片状物。在大约19.2°2θ处观察到PET对照样品的宽的无定形峰。这证实对照样品具有无定形的微观结构。如图5所示,在26.6°2θ处的石墨烯峰的强度随纳米片的重量分数提高。未观察到峰移动。这与TEM显微图片一起证实纳米片并非基本上为片层[20]。此外,衍射图案证实PET基质如预期至少在0.2mm的表面内为无定形的。
机械性能
绘制PET对照和纳米复合物的应力-应变曲线,如图6所示,其基于拉伸试验收集的数据。添加石墨烯纳米片使性能(模量)提高,与纯PET相比高至300%,并且遵循指数趋势,如图7所示。虽然观察到主要为线性的行为,但15%纳米复合物的应力-应变曲线中的峰表明此复合物与另一较低体积部分相比有附加的韧化机制。这可能是由于增强体-增强体的相互作用。
以了解石墨烯纳米片作为增强体的有效性为目的,微观力学模型(例如Halpin-Tsai和Hui-Shia模型)用于测定该PET-石墨烯纳米复合物的理论弹性机械性能。微观力学模型基于假设而估算性质,例如完美增强体、均质分散或增强体的一致取向。石墨烯纳米复合物优异性能的理想情况是具有所需长度的无缺陷石墨烯片(单层),其良好分散在基质内并沿着最大负荷方向取向。
Gong等人[16]已经测定石墨烯片作为增强体有效的所需长度(>30μm)。Georgantzinos等人[22]用分子模拟观察到,石墨烯片的机械性能,例如硬度和泊松比率,随包含的层数的增加而减少。他们估计包含五层的片状物的硬度与单层石墨烯相比减少了15%,并且它们还注意到石墨烯的性质基于它们的取向而有所区别。已经报道的石墨烯片状物(薄片)的模量为0.795 TPa [23]。
表1:用于理论预测的石墨烯和PET的性质
本研究中,从TEM显微图片观察具有宽范围的长度(或存在于平面方向之外的片状物直径)和厚度的石墨烯片。颗粒尺寸由较大(5μm)石墨烯干粉末到较小(300nm)石墨烯干粉末(如TEM图像(图4)中观察到的尺寸)的变化,可归因于在混合和模塑过程期间的剪切。表1显示了片状物的平均尺寸,以及最小值和最大值。然后将这些片状物性质用于测定纳米复合物的性能范围,基于微观力学模型(误差条显示在图8中)。相对于实验结果,绘制得自微观力学模型的预测的纳米复合物模量,显示于图8。经过Halpin-Tsai模型估算的模量与实验值对比较高。Halpin-Tsai模型估算复合物的模量,其中片状物沿着负荷方向排列。然而,片状物通常不按负荷方向排列。另外,与基质相比较,增强体的非常高的硬度(>250倍)使得通过Halpin-Tsai模型准确预测变得困难[22]。Hui-Shia模型显示最好的一致性。Hui-Shia模型估算在平行(轴1和2)和垂直方向(沿着轴3)两者上均负载有片状物的纳米复合物的弹性模量,如图8所示。这个模型与Halpin-Tsai模型相比,对于宽范围的硬度比率是有效的[22]。
此外,在复合物中基质到增强体之间的应力传递对控制它们的机械行为是关键的。例如,PMMA基质中的石墨烯纳米复合物,基质与石墨烯片和石墨烯片-石墨烯片之间的应力传递显示为由弱范德华力主导,降低了潜在的机械性能。然而,微观力学模型没有考虑在应力传递行为中的这些变化。这导致了与实验值的偏差。
当前的实验模量显示了与理论预测合理的一致性。这并未考虑片状物几何形状的宽范围(参见表格)。最佳情况是模量与片状物平行(方向-3)的Hui-Shia模型。这表明增强体的合理的有效性。当增强体随机分布时,可预期平行的和垂直的两种Hui-Shia预测之间的性能。对片状物分布的随机性的进一步研究需要另外的估算。如果片状物具有更高的宽厚比,则甚至可预期更硬的模量增强体,因为预测的模量对宽厚比敏感。由于在添加剂的生产以及它们与基质的加工方面有持续的提高,所以这是合理的目标。显然,纳米尺度的增强体有利于机械性质的提高。
此外,由X射线衍射,石墨烯片的加入未显示出对PET最终结晶的影响。规模经济可改善任何这些添加剂的成本。更了解纳米片对注塑过程的影响,可帮助进一步改善复合物性质。例如,许多不同的螺杆类型可用于注塑,并且需要探索它们在添加剂的混合和分散中的优点。
测试结论
本公开表明石墨烯纳米片对聚对苯二甲酸乙二酯或者PET实现提高的强度特性(例如弹性模量)是有效的。母料丸粒的注塑是一种成功的用于制备PET-石墨烯(xGnP)纳米复合物(重量分数2-15%)的方法。与简单机械模型的对比说明了它们的优异性能。硬度可能不仅取决于增强体硬度,还取决于宽厚比以及基质与增强体之间界面应力传递的主要机制。还有一些迹象表明增强体-增强体的相互作用在体积分数超过10%时起重要作用。
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因此,本发明良好适应于实施所述目的并获得上述结果和优点以及其中固有的那些。虽然为了本公开的目的描述了现有优选实施方案,但许多变化与修改对本领域的普通技术人员将显而易见。这些变化与修改包括在如权利要求限定的本发明的精神之内。
Claims (17)
1. 一种纳米复合材料,其包含:
包括聚对苯二甲酸乙二酯(PET)的基体聚合物;和
提高所述基体聚合物强度的纳米颗粒。
2. 权利要求1的材料,其中所述纳米颗粒包含石墨烯纳米片。
3. 权利要求2的材料,其中所述石墨烯包含片层剥离纳米片。
4. 权利要求2的材料,其中所述石墨烯纳米片的平均直径为5微米。
5. 权利要求2的材料,其中所述纳米片包含约2重量%的所述纳米复合材料。
6. 权利要求2的材料,其中所述纳米片包含约5重量%的所述纳米复合材料。
7. 权利要求2的材料,其中所述纳米片包含约10重量%的所述纳米复合材料。
8. 权利要求2的材料,其中所述纳米片包含约15重量%的所述纳米复合材料。
9. 权利要求2的材料,其中所述纳米片包含约2重量%-约15重量%的所述纳米复合材料。
10. 一种生产纳米复合材料的方法,其包含:
提供聚对苯二甲酸乙二酯(PET)作为基体聚合物;
提供纳米颗粒物质;
将所述基体聚合物与所述纳米颗粒材料混合以形成母料产物;和
将所述母料产物注塑。
11. 权利要求10的方法,其中提供纳米颗粒物质进一步包含提供石墨烯。
12. 权利要求11的方法,其还包含通过片层剥离制备所述石墨烯。
13. 权利要求10的方法,其中提供纳米颗粒物质还包含在所述母料产物中提供约2重量%的所述纳米颗粒物质材料。
14. 权利要求10的方法,其中提供纳米颗粒物质还包含在所述母料产物中提供约5重量%的所述纳米颗粒物质材料。
15. 权利要求10的方法,其中提供纳米颗粒物质还包含在所述母料产物中提供约10重量%的所述纳米颗粒物质材料。
16. 权利要求10的方法,其中提供纳米颗粒物质还包含在所述母料产物中提供约15重量%的所述纳米颗粒物质材料。
17. 权利要求10的方法,其中提供纳米颗粒物质还包含在所述母料产物中提供约2重量%-约15重量%的所述纳米颗粒物质材料。
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CN107849292A (zh) * | 2015-03-17 | 2018-03-27 | 尼亚加拉装瓶有限责任公司 | 石墨烯增强的聚对苯二甲酸乙二醇酯 |
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CN105525381A (zh) * | 2015-10-27 | 2016-04-27 | 济南圣泉集团股份有限公司 | 一种含有石墨烯的复合聚酯纤维、其制备方法和用途 |
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CN105603568A (zh) * | 2016-01-21 | 2016-05-25 | 济南圣泉集团股份有限公司 | 一种改性中空棉及其制备方法 |
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CN105525384B (zh) * | 2016-01-22 | 2019-05-10 | 济南圣泉集团股份有限公司 | 一种改性中空棉的用途 |
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