CN105518072B - 复合增强原材料及其制作方法 - Google Patents
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- CN105518072B CN105518072B CN201580000440.XA CN201580000440A CN105518072B CN 105518072 B CN105518072 B CN 105518072B CN 201580000440 A CN201580000440 A CN 201580000440A CN 105518072 B CN105518072 B CN 105518072B
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Abstract
本发明提供机械强度优异的复合增强原材料。一种复合增强原材料,其特征在于,其在母材中至少分散有自石墨系碳原材料剥离得到的类石墨烯石墨和增强原材料,前述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),前述菱方晶系石墨层(3R)与前述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上。Rate(3R)=P3/(P3+P4)×100····(式1)式1中,P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度。
Description
技术领域
本发明涉及复合增强原材料及其制作方法。
背景技术
近年来,在各种领域中以小型轻量化等为目的而对各种纳米材料的添加进行了研究。尤其是,在环境、资源的问题中,作为非金属的纳米材料,石墨烯、CNT(碳纳米管)、富勒烯等碳原材料倍受关注,为了提高树脂的物性(拉伸强度、弹性模量等),提出了在树脂中分散有增强原材料(填料)的树脂复合增强原材料。
例如,公开了在聚烯烃等热塑性树脂中添加有薄片化石墨等碳原材料的树脂复合增强原材料(专利文献1)。另外,公开了添加薄片化石墨和无机填料来谋求物性(拉伸模量、刚性、耐冲击性)的改善的复合增强原材料(专利文献2、专利文献3)。
其中,石墨烯在性能方面自不待言,在量产性、处理性等方面也优于其它碳原材料,在各种领域中受到期待,但是为了在将石墨烯等增强原材料和树脂混炼时充分地得到物性改善效果,需要使增强原材料均匀分散。
为了得到石墨的层数少等高品质的石墨烯,研究了如下的方法:对天然石墨在溶剂(NMP)中以长时间(7~10小时)施加弱超声波后,去除底部沉淀的大块,然后,对上清进行离心分离并浓缩,从而得到以0.5g/L左右分散有单层的片(flake)为20%以上、2层或3层的片为40%以上、10层以上的片少于40%的石墨材料的石墨烯分散液的方法(专利文献4)。
现有技术文献
专利文献
专利文献1:日本特开2010-254822号公报([0032]-[0038])
专利文献2:日本特开2014-201676号公报([0048]-[0064])
专利文献3:日本特开2014-210916号公报([0043])
专利文献4:国际公开第2014/064432号(第19页第4行-第9行)
专利文献5:日本特开2013-79348号公报([0083])
专利文献6:日本特开2009-114435号公报([0044])
非专利文献
非专利文献1:石墨研磨所伴随的结构变化;著:稻垣道夫、麦岛久枝、细川健次;1973年2月1日(受理)
非专利文献2:碳加热处理所伴随的概率P1、PABA、PABC的变化;著:野田稻吉、岩附正明、稻垣道夫;1966年9月16日(受理)
非专利文献3:Spectroscopic and X-ray diffraction studies on fluiddeposited rhombohedral graphite from the Eastern Ghats Mobile Belt,India;G.Parthasarathy,Current Science,Vol.90,No.7,10April 2006
非专利文献4:固体碳材料的分类和各自的结构特征;名古屋工业大学川崎晋司
发明内容
发明要解决的问题
然而,专利文献1、2、3中公开的方法中使用了市售的薄片化石墨,薄片化石墨聚集而无法仅依靠混炼来进行分散,无法充分得到由薄片化石墨带来的效果。另外,即使将通过专利文献4中公开的方法得到的石墨材料(单层的片为20%以上、2层或3层的片为40%以上、10层以上的片少于40%)混于溶剂,分散于溶剂的石墨烯的分散量也少,仅能得到稀薄的石墨烯分散液。另外,虽然也可以考虑收集上清并浓缩,但重复进行收集上清并浓缩的工序时,处理耗费时间,存在石墨烯分散液的生产效率差的问题。认为即使如专利文献4中公开那样对天然石墨进行长时间的超声波处理,也只有表面的较弱的部分发生剥离,其它的大部分对剥离没有贡献,存在剥离的石墨烯量少的问题。
另外,为了提高机械强度,通常在聚合物等母材中添加增强原材料,但根据所添加的增强原材料的量,也有时会对聚合物原本的性状(外观)造成影响(专利文献5)。
上述专利文献2、3中,添加增强原材料,提高了弹性模量、耐冲击性等有助于刚性(硬度)的物性。本说明书的实施例5(本申请以前未公开的发明。)中也得到同样的结果。
另外,为了提高拉伸强度(拉伸强度),进行了增强原材料的添加(例如专利文献1)。为了提高拉伸强度,通常作为增强原材料(填料),碳纤维、玻璃纤维、纤维素纤维等带状的原材料是适合的。进而,为了使带状的原材料不易从母材中拉出,也提出了使用相容剂提高拉伸屈服应力的方案(专利文献6)。但是,得到了在仅单纯地添加带状的原材料时无法充分提高拉伸强度等机械强度等这样的见解。认为这是因为,由于母材柔软,因此带状的原材料连带母材一起被拉出。
如上所述,通常,即使对天然石墨直接进行处理,剥离的石墨烯量也少,这成为问题。但是,深入研究的结果,通过对作为材料的石墨实施规定的处理,得到了能容易地剥离成石墨烯、高浓度或高分散的石墨系碳原材料(石墨烯前体)。该石墨烯前体通过超声波、搅拌、混炼而使其一部分或全部剥离,成为自石墨烯前体至石墨烯之间的混合物“类石墨烯石墨”。类石墨烯石墨根据石墨烯前体的添加量、工艺时间等而尺寸、厚度等发生变化,因此没有限定,但优选更薄片化。即换言之,利用现有的搅拌、混炼工艺或装置容易剥离/分散成类石墨烯石墨的石墨为石墨系碳原材料(石墨烯前体)。
通过使该类石墨烯石墨与增强原材料一起少量地分散于母材,从而能够提高机械强度、例如弯曲模量、压缩强度、拉伸强度、杨氏模量等,而且能够制造该复合增强原材料,而不需使制造方法与现有方法大幅不同。
本发明的是着眼于这种问题而做出的,目的在于提供机械强度优异的复合增强原材料及其制作方法。
另外,目的在于提供即使分散/配混于母材的类石墨烯石墨的量少也发挥期望性状的复合增强原材料。
另外,目的在于使用现有的制造工艺提供机械强度优异的复合增强原材料。
用于解决问题的方案
为了解决前述问题,本发明的复合增强原材料的制造方法的特征在于,其包括在母材中至少混炼石墨系碳原材料和增强原材料的步骤,
前述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),前述菱方晶系石墨层(3R)与前述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上。
Rate(3R)=P3/(P3+P4)×100····(式1)
式1中,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度。
由此,类石墨烯石墨自石墨系碳原材料被剥离,较薄的类石墨烯石墨大量分散于母材。
此处,
类石墨烯石墨是自前述石墨系碳原材料一部分或全部被剥离而成的、自前述石墨系碳原材料至石墨烯之间的混合物,
石墨烯为属于平均尺寸为100nm以上的晶体、且层数在10层以下的薄片状或片状的石墨烯。
另外,其特征在于,前述增强原材料为带状、线状或薄片状的微粒。
另外,其特征在于,前述微粒的长径比为5以上。
另外,其特征在于,前述石墨系碳原材料相对于前述增强原材料的重量比为1/100以上且低于10。
另外,其特征在于,其是在母材中至少混炼石墨系碳原材料和增强原材料并使前述石墨系碳原材料的一部或全部剥离而得到的复合增强原材料,
前述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),前述菱方晶系石墨层(3R)与前述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上。
Rate(3R)=P3/(P3+P4)×100····(式1)
式1中,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度。
根据该特征,复合原材料的机械强度优异。推测这是因为,类石墨烯石墨在母材中分散而提高母材自身的弹性模量的作用、与增强原材料变得不易拉出的作用协同发挥。另外,作为机械强度,可列举出弯曲模量、压缩强度、拉伸强度、杨氏模量等,例如,拉伸强度优异。
此外,其特征在于,其是在母材中至少分散有自石墨系碳原材料剥离得到的类石墨烯石墨和增强原材料的复合增强原材料,
前述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),前述菱方晶系石墨层(3R)与前述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上。
Rate(3R)=P3/(P3+P4)×100····(式1)
式1中,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度,
类石墨烯石墨是自前述石墨系碳原材料一部分或全部被剥离而成的、自前述石墨系碳原材料至石墨烯之间的混合物,
石墨烯为属于平均尺寸为100nm以上的晶体、且层数在10层以下的薄片状或片状的石墨烯。
根据该特征,复合原材料的机械强度优异。推测这是因为,类石墨烯石墨在母材中分散而提高母材自身的弹性模量的作用、与增强原材料变得不易拉出的作用协同发挥。另外,作为机械强度,可列举出弯曲模量、压缩强度、拉伸强度、杨氏模量等,例如,拉伸强度优异。
其特征在于,前述增强原材料为带状、线状或薄片状的微粒。
根据该特征,在微粒的周围存在类石墨烯石墨,因此能够充分发挥微粒所具有的增强功能。
其特征在于,前述微粒的长径比为5以上。
根据该特征,能够进一步充分发挥微粒所具有的增强功能。
其特征在于,前述石墨系碳原材料和前述类石墨烯石墨的总和相对于前述增强原材料的重量比为1/100以上且低于10。
根据该特征,能够充分发挥增强原材料所具有的增强功能。
其特征在于,前述母材为聚合物。
根据该特征,能够得到机械强度优异的复合增强原材料。
其特征在于,前述母材为无机材料。
根据该特征,能够得到机械强度优异的复合增强原材料。
造型材料的特征在于,其使用了前述复合增强原材料。
根据该特征,能够得到机械强度优异的用于3D打印等的造型材料。
附图说明
图1为示出石墨的晶体结构的图,图1的(a)为六方晶的晶体结构,图1的(b)为菱方晶的晶体结构。
图2为示出通常的天然石墨的X射线衍射图谱的图。
图3为对实施例1的使用了喷磨机(jet mill)和等离子体的制造装置A进行说明的图。
图4为对实施例1的使用了球磨机和磁控管的制造装置B进行说明的图,图4的(a)为对进行粉碎的状态进行说明的图,图4的(b)为对收集石墨系碳原材料(前体)的状态进行说明的图。
图5为示出实施例1的利用制造装置B制造的试样5的石墨系碳原材料的X射线衍射图谱的图。
图6为示出实施例1的利用制造装置A制造的试样6的石墨系碳原材料的X射线衍射图谱的图。
图7为示出表示比较例的试样1的石墨系碳原材料的X射线衍射图谱的图。
图8为示出使用石墨系碳原材料作为前体来制作分散液的分散液制作装置的图。
图9为示出使用表示比较例的试样1和实施例1的利用制造装置B制造的试样5的石墨系碳原材料来制作的分散液的分散状态的图。
图10为分散于分散液的石墨系碳原材料(石墨烯)的TEM拍摄图。
图11为示出分散于使用试样5的石墨系碳原材料(前体)制作的分散液的石墨系碳原材料的分布状态的图,图11的(a)为示出平均尺寸的分布的图,图11的(b)为示出层数的分布的图。
图12为示出分散于使用表示比较例的试样1的石墨系碳原材料制作的分散液的石墨系碳原材料的分布状态的图,图12的(a)为示出平均尺寸的分布的图,图12的(b)为示出层数的分布的图。
图13为示出分散于使用试样1-7作为前体来制作的分散液的石墨系碳原材料的层数的分布的图。
图14为示出相对于分散于分散液的菱方晶的含有率的、10层以下的石墨烯的比例的图。
图15为示出实施例2的改变使用试样5的石墨系碳原材料(前体)制作分散液的条件时的石墨的分布状态的图,图15的(a)为示出组合使用超声波处理和微波处理时的分布的图,图15的(b)为示出进行超声波处理时的层数的分布的图。
图16为示出使实施例3的石墨系碳原材料分散于导电性墨时的电阻值的图。
图17为示出将实施例4的石墨系碳原材料混炼到树脂中时的拉伸强度的图。
图18为示出将实施例5的石墨系碳原材料混炼到树脂中时的弹性模量的图。
图19为用于补充说明实施例5中的分散状态、示出分散于N-甲基吡咯烷酮(NMP)的分散液的石墨系碳原材料的分布状态的图,图19的(a)为示出试样12的分布状态的图,图19的(b)为示出试样2的分布状态的图。
图20为示出实施例6的试验片的拉伸强度及弯曲模量的图表。
图21为石墨烯前体的SEM拍摄图(俯视图)。
图22为石墨烯前体的SEM拍摄图(侧视图)。
图23为分散有类石墨烯石墨的树脂的SEM拍摄图(截面图)。
图24为图23中的类石墨烯石墨的侧SEM拍摄图(侧视图)。
图25为示出实施例7的试验片的拉伸强度及弯曲模量的图表。
图26为示出改变实施例8的增强原材料的形状时的试验片的拉伸强度及弯曲模量的图表。
图27为用于说明实施例8的增强原材料的形状的示意图,(a)用于说明玻璃纤维、碳纤维的形状,(b)用于说明滑石的形状,(c)用于说明二氧化硅的形状。
图28为示出改变实施例9的石墨烯前体相对于增强原材料的混合比率时的试验片的拉伸强度及弯曲模量的图表。
具体实施方式
本发明着眼于石墨的晶体结构,首先对其晶体结构的相关内容进行说明。已知天然石墨根据层的重叠方式而分为六方晶、菱方晶和无序这三种晶体结构。如图1所示,六方晶是层按照ABABAB··的顺序层叠而成的晶体结构,菱方晶是层按照ABCABCABC··的顺序层叠而成的晶体结构。
天然石墨在采掘出的阶段几乎不存在菱方晶,但由于在精制阶段会进行破碎等,因此通常的天然石墨系碳原材料中存在14%左右的菱方晶。另外已知,即便长时间进行精制时的破碎,菱方晶的比率也收敛于30%左右(非专利文献1、2)。
另外,除了破碎等物理力之外还已知通过加热使石墨膨胀而薄片化的方法,但是即使对石墨施加1600K(约1300摄氏度)的热来进行处理,菱方晶的比率也为25%左右(非专利文献3)。即使进一步施加超高温的3000摄氏度的热,最多也就达到30%左右为止(非专利文献2)。
如此,通过利用物理力、热对天然石墨进行处理,能够增加菱方晶的比率,但其上限为30%左右。
天然石墨中大量含有的六方晶(2H)非常稳定,其石墨烯彼此的层间的范德华力由(式3)表示(专利文献2)。通过施予超过该力的能量,石墨烯发生剥离。剥离所需的能量与厚度的三次方成反比例,因此在无数层重叠的较厚状态下,在非常微弱的超声波等弱物理力的作用下石墨烯发生剥离,但从薄至一定程度的石墨上剥离时需要非常大的能量。换言之,即使对石墨进行长时间处理,也仅有表面的较弱部分发生剥离,大部分会保持未剥离的状态。
Fvdw=H·A/(6π·t3)····(式3)
Fvdw:范德华力
H:Hamaker常数
A:石墨或石墨烯的表面积
t:石墨或石墨烯的厚度
本申请的发明人等通过对天然石墨实施下述所示那样的规定的处理,成功地使利用粉碎和/或加热至超高温的处理仅能增加至30%左右的菱方晶(3R)的比例增加至更高。作为实验/研究的结果,得到了如下见解:石墨系碳材料的菱方晶(3R)的含有率变得更多时、尤其是31%以上的含有率时,通过将该石墨系碳原材料用作前体,具有易于剥离成石墨烯的倾向,可以简单地得到高浓度、高分散度的石墨烯溶液等。认为这是因为,在对菱方晶(3R)施加剪切等的力时,在层间产生应变,即石墨的结构整体的应变增大,变得容易剥离,而不取决于范德华力。因此,本发明中,将通过对天然石墨实施规定的处理而容易剥离石墨烯、可使石墨烯为高浓度或高分散的石墨系碳原材料称作石墨烯前体,以下,在后述的实施例中,按照示出规定处理的石墨烯前体的制造方法、石墨烯前体的晶体结构、使用了石墨烯前体的石墨烯分散液的顺序进行说明。
此处,本说明书中,石墨烯是指属于平均尺寸为100nm以上的晶体而非平均尺寸为几nm~几十nm的微晶、且层数在10层以下的薄片状或片状的石墨烯。
需要说明的是,石墨烯是平均尺寸为100nm以上的晶体,因此对于作为除天然石墨以外的非晶(微晶)碳原材料的人造石墨、炭黑而言,即便对它们进行处理,也得不到石墨烯(非专利文献4)。
另外,本说明书中,石墨烯复合体是指使用本发明的可用作石墨烯前体的石墨系碳原材料、即Rate(3R)为31%以上的石墨系碳原材料(例如后述的实施例1的试样2-7、实施例5的试样2、21···)制成的复合体。
以下,对于用于实施本发明的复合增强原材料及造型材料的实施例进行说明。
实施例1
<关于可用作石墨烯前体的石墨系碳原材料的制造>
对于利用如图3所示的使用了喷磨机和等离子体的制造装置A来得到可用作石墨烯前体的石墨系碳原材料的方法进行说明。制造装置A中,将施加等离子体作为基于电磁力的处理并且使用喷磨机作为基于物理力的处理的情况作为例子。
图3中,符号1为5mm以下的颗粒的天然石墨材料(日本石墨工业制造的鳞片状石墨ACB-50);2是容纳天然石墨材料1的料斗;3是自料斗2喷射天然石墨材料1的文丘里喷嘴;4是使从压缩机5分八处加压输送来的空气喷射而使天然石墨材料随喷射流在腔室内发生碰撞的喷磨机;7是等离子体产生装置,使来自容器6的氧气、氩气、氮气、氢气等气体9从喷嘴8中喷射,并且由高压电源10对卷绕在喷嘴8外周的线圈11施加电压,在喷磨机4的腔室内产生等离子体,在腔室内的四个位置设置有该等离子体产生装置。13是连接喷磨机4和集尘器14的配管,14是集尘器,15是收集容器,16是石墨系碳原材料(石墨烯前体),17是鼓风机。
接着对制造方法进行说明。喷磨机和等离子体的条件如下所述。
喷磨机的条件如下所述。
压力:0.5MPa
风量:2.8m3/分钟
喷嘴内径:12mm
流速:约410m/秒
等离子体的条件如下所述。
输出功率:15W
电压:8kV
气体种类:Ar(纯度为99.999体积%)
气体流量:5L/分钟
认为,由文丘里喷嘴3投入喷磨机4的腔室内的天然石墨材料1在腔室内被加速至音速以上,通过天然石墨材料1彼此碰撞、与壁碰撞的冲击而被粉碎,与此同时,等离子体12对天然石墨材料1进行放电、激发,从而直接作用于原子(电子),增加晶体的应变而促进粉碎。天然石墨材料1形成微粉至一定程度的粒径(1~10μm左右)时,质量减轻,离心力变弱,由此从与腔室中心连接的配管13被抽出。
从配管13流入集尘器14的腔室的圆筒容器中的混有石墨系碳原材料(石墨烯前体)的气体形成旋流,使与容器内壁碰撞的石墨系碳原材料16落入下方的收集容器15中,同时利用腔室下方的锥形容器部而在腔室的中心产生上升气流,气体从鼓风机17被排出(所谓的旋风分离(cyclone)作用)。利用本实施例中的制造装置A,由作为原料的1kg天然石墨材料1得到约800g可用作石墨烯前体的石墨系碳原材料(石墨烯前体)16(回收效率:8成左右)。
接着,对于利用如图4所示的使用了球磨机和微波的制造装置B得到可用作石墨烯前体的石墨系碳原材料的方法进行说明。制造装置B中,将实施微波作为基于电磁力的处理并且使用球磨机作为基于物理力的处理的情况作为例子。
图4的(a)和图4的(b)中,符号20是球磨机、21是微波产生装置(磁控管)、22是波导管、23是微波流入口、24是介质、25是5mm以下的颗粒的天然石墨材料(日本石墨工业制造的鳞片状石墨ACB-50)、26是收集容器、27是过滤器、28是石墨系碳原材料(石墨烯前体)。
接着对制造方法进行说明。球磨机和微波产生装置的条件如下所述。
球磨机的条件如下所述。
转速:30rpm
介质尺寸:
介质种类:氧化锆球
粉碎时间:3小时
微波产生装置(磁控管)的条件如下所述。
输出功率:300W
频率:2.45GHz
照射方法:间歇
在球磨机20的腔室内投入1kg的天然石墨系碳原料25和800g的介质24,封闭腔室,以30rpm的转速处理3小时。在该处理中对腔室间歇地(每隔10分钟进行20秒)照射微波。认为通过该微波的照射,直接作用于原料的原子(电子),增加晶体的应变。处理后,通过利用过滤器27除去介质24,由此可以将10μm左右的粉体的石墨系碳原材料(前体)28收集在收集容器26中。
<关于石墨系碳原材料(前体)的X射线衍射图谱>
参照图5-图7,对于利用制造装置A、B制造的石墨系天然材料(试样6、试样5)和仅使用制造装置B的球磨机得到的10μm左右的粉体的石墨系天然材料(试样1:比较例)的X射线衍射图谱和晶体结构进行说明。
X射线衍射装置的测定条件如下所述。
线源:CuKα射线
扫描速度:20°/分钟
管电压:40kV
管电流:30mA
对于各试样而言,根据X射线衍射法(Rigaku株式会社制造的试样水平型多目的X射线衍射装置Ultima IV),分别在六方晶2H的面(100)、面(002)、面(101)、和菱方晶3R的面(101)显示峰强度P1、P2、P3、P4,由此对各试样进行说明。
此处,X射线衍射图谱的测定中,近年来不论国内外均使用所谓标准化的值。该Rigaku株式会社制造的试样水平型多目的X射线衍射装置Ultima IV是能够以JIS R 7651:2007“碳材料的晶格常数及微晶尺寸测定方法”为基准测定X射线衍射图谱的装置。需要说明的是,Rate(3R)是以Rate(3R)=P3/(P3+P4)×100求得的衍射强度的比,即使衍射强度发生变化,Rate(3R)的值也并不发生变化。换言之,衍射强度的比被标准化,通常用于避免以绝对值进行物质的鉴定,该值不依赖于测定装置。
利用实施基于球磨机的处理和微波处理的制造装置B而制造的试样5如图5和表1所示,峰强度P3、峰强度P1的强度的比例高,用表示P3相对于P3与P4之和的比例的(式1)定义的Rate(3R)为46%。另外,强度比P1/P2为0.012。
Rate(3R)=P3/(P3+P4)×100····(式1)
此处,
P1为六方晶系石墨层(2H)的由X射线衍射法得到的(100)面的峰强度,
P2为六方晶系石墨层(2H)的由X射线衍射法得到的(002)面的峰强度,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度。
表1
同样地,利用实施基于喷磨机的处理和基于等离子体的处理的制造装置A而制造的试样6如图6和表2所示,峰强度P3、峰强度P1的强度的比例高,Rate(3R)为51%。另外,强度比P1/P2为0.014。
表2
另外,仅利用球磨机制造的表示比较例的试样1如图7和表3所示,峰强度P3与试样5、6相比其比例较小,Rate(3R)为23%。另外,强度比P1/P2为0.008。
表3
如此,实施例1的利用制造装置B制造的试样5、实施例1的利用制造装置A制造的试样6显示出:Rate(3R)为46%、51%,与如图2所示的天然石墨、表示比较例的试样1相比,达到40%以上或50%以上。
接着,使用上述制造的石墨烯前体制作石墨烯分散液,对石墨烯的剥离容易度进行比较。
<关于石墨烯分散液>
参照图8对石墨烯分散液的制作方法进行说明。图8中,将在制作石墨烯分散液时在液体中组合使用超声波处理和微波处理的情况作为例子。
(1)在烧杯40中加入可用作石墨烯前体的石墨系碳原材料0.2g和作为分散液的N-甲基吡咯烷酮(NMP)200ml。
(2)将烧杯40放入微波产生装置43的腔室42中,从上方将超声波变幅杆44的超声波的振子44A插入分散液41。
(3)运行超声波变幅杆44,连续地施予3小时的20kHz(100W)的超声波。
(4)在运行上述超声波变幅杆44的期间,运行微波产生装置43,间歇地(每隔5分钟照射10秒)施加微波2.45GHz(300W)。
图9是如上述那样制成的石墨烯分散液经过了24小时的状态。
确认到,使用了利用制造装置B制造的试样5的石墨烯分散液30尽管一部分发生沉淀,但整体呈黑色。认为这是用作石墨烯前体的石墨系碳原材料大多以剥离成石墨烯的状态分散。
确认到,使用了表示比较例的试样1的分散液31中,石墨系碳原材料大部分发生沉淀,一部分以上清液的状态漂浮。由此,认为极少部分剥离成石墨烯而以上清液的形式漂浮。
另外,以能够进行观察的浓度将如上所述制成的石墨烯分散液稀释并涂布在样品台(TEM网)之上,使之干燥,根据透射电子显微镜(TEM)的如图10所示的拍摄图来观察石墨烯的尺寸和层数。需要说明的是,对于试样1,将上清稀释并涂布来使用。例如,图10的情况下,根据图10的(a),尺寸为片(flake)33的最大的长度L,求出约为600nm,根据图10的(b),观察片33的端面,计数石墨烯层的重叠,求出层数为6层(符号34所指的区域)。如此测定各片(片数记为N)的尺寸和层数,求出了图11、图12所示的石墨烯层数和尺寸。
参照图11的(a),实施例1的利用制造装置B制造的试样5(Rate(R3)为46%)的石墨烯分散液中所含有的薄片状的片的粒度分布(尺寸的分布)是以0.5μm作为峰的分布。另外,图11的(b)中,层数是以3层为峰、10层以下的石墨烯为68%的分布。
参照图12,比较例的试样1(Rate(R3)为23%)的分散液中所含有的薄片状的片的粒度分布(尺寸的分布)是以0.9μm为峰的分布。另外,层数是30层以上占大部分、10层以下的石墨烯为10%的分布。
由该结果可知,利用制造装置B制造的试样5用作石墨烯前体的情况下,可以得到10层以下的石墨烯多、石墨烯的分散性优异且高浓度的石墨烯分散液。
接着,参照图13,对石墨烯前体的比例Rate(3R)与石墨烯分散液中的层数之间的关系进行说明。图13中的试样1、5、6是上述试样。试样2、3、4是利用实施基于球磨机的处理和微波处理的制造装置B而制造出的,使用使微波的照射时间短于试样5而制造出的石墨烯前体制作石墨烯分散液。另外,试样7是利用实施基于喷磨机的处理和等离子体处理的制造装置A而制造出的,使用施予输出功率高于试样6的等离子体而制造的石墨烯前体制作石墨烯分散液。
根据图13,Rate(3R)为31%和38%的试样2和3的层数分布形状为在13层左右具有峰的接近正态分布的形状(使用试样2、3的分散液)。Rate(3R)为40%以上的试样4-7的层数分布形状为在几层(较薄的石墨烯)的部分具有峰的所谓的对数正态分布的形状。另一方面,Rate(3R)为23%的试样1的层数为在30层以上的部分具有峰的形状(使用试样1的分散液)。即,可知如下倾向:Rate(3R)达到31%以上时,层数分布形状与小于31%不同,进而Rate(3R)达到40%以上时,层数分布形状与小于40%明显不同。另外,对于10层以下的石墨烯的比例而言,使用试样3的分散液的Rate(3R)为38%,另一方面,使用试样4的分散液的Rate(3R)为42%,可知Rate(3R)达到40%以上时,10层以下的石墨烯的比例骤增。
由此可认为,Rate(3R)为31%以上的情况下容易剥离成10层以下的石墨烯,并且随着Rate(3R)增多至40%、50%、60%,变得更容易剥离成10层以下的石墨烯。另外,着眼于强度比P1/P2时,对于试样2-试样7,强度比P1/P2为较窄的0.012~0.016的范围内的值,由于超过被认为可在晶体结构中产生应变而易于剥离成石墨烯的0.01,因而均优选。
此外,对Rate(3R)和10层以下的石墨烯含有的比例进行对比,将结果示于图14。参照图14可以判明,Rate(3R)达到25%以上时,10层以下的石墨烯从31%附近开始增加(形成向右上升的斜率),并且在40%左右处10层以下的石墨烯骤增(对于10层以下的石墨烯的比例,使用试样3的分散液的Rate(3R)为38%,另一方面,使用试样4的分散液的Rate(3R)为42%,由于Rate(3R)增加4%,10层以下的石墨烯的比例以增加24%的方式骤增)且在总体中10层以下的石墨烯占50%以上。需要说明的是,图14中的黑方块的点为各不相同的试样,也包括上述试样1-7和这些以外的其它试样。
由此,使用Rate(3R)为31%以上的试样作为石墨烯前体制作石墨烯分散液时,10层以下的石墨烯的分散比例开始增加,进而,使用Rate(3R)为40%以上的试样作为石墨烯前体制作石墨烯分散液时,生成50%以上的10层以下的石墨烯。即,可以得到石墨烯为高浓度且高分散的石墨烯分散液。另外,如上所述,该分散液所含有的石墨系碳原材料(前体)基本上未沉淀,因此可以简单地得到较浓的石墨烯分散液。通过该方法,还可以在不进行浓缩的条件下制成石墨烯浓度超过10%的石墨烯分散液。尤其,从10层以下的石墨烯的分散比例骤增至50%以上的观点出发,Rate(3R)更优选为40%以上。
据此可知,Rate(3R)为31%以上、优选为40%以上、进一步优选为50%以上时,分离成10层以下的石墨烯和10层左右的薄层的石墨系碳原材料的比例高,使用这些石墨系碳原材料作为石墨烯前体时,可以得到石墨烯的分散性优异且高浓度的石墨烯分散液。另外,由后述的实施例5明显可知,Rate(3R)为31%以上时,作为石墨系碳原材料石墨烯前体是有用的。
另外,认为没有必要对Rate(3R)的上限进行特别规定,但从在制作分散液等时容易分离成石墨烯出发,优选使强度比R1/R2同时满足0.01以上。需要说明的是,在使用制造装置A、B的制造方法的情况下,从易于制造石墨烯前体的观点出发,上限为70%左右。另外,制造装置A的组合使用基于喷磨机的处理和等离子体处理的方法容易得到Rate(3R)高的材料,因而是更优选的。需要说明的是,组合使用基于物理力的处理和基于电磁力的处理而使Rate(3R)达到31%以上即可。
实施例2
实施例1中,对得到石墨烯分散液时组合使用超声波处理和微波处理的情况进行了说明,而实施例2中,仅进行了超声波处理而没有进行微波处理,其它条件与实施例1同样。
图15的(b)示出使用利用制造装置B制造的试样5(Rate(3R)=46%)的石墨烯前体实施超声波处理而得到的石墨烯分散液的层数的分布。需要说明的是,图15的(a)与实施例1的利用制造装置B制造的试样5的图11的(b)所示的分布同样。
其结果,层数的分布的倾向大致相同,但10层以下的石墨烯的比例为64%,与实施例1的68%相比稍有降低。由此可以判明,在制作石墨烯分散液时,同时进行物理力和电磁力的处理这两者会更有效果。
实施例3
实施例3中,对用于导电墨的例子进行说明。
将实施例1的试样1(Rate(3R)=23%)、试样3(Rate(3R)=38%)、试样5(Rate(3R)=46%)、试样6(Rate(3R)=51%)作为石墨烯前体,制作在水和作为导电性赋予剂的碳原子数为3以下的醇的混合溶液中设为导电性墨所使用的浓度的墨1、墨3、墨5、墨6,比较各自的电阻值。根据该结果,得到电阻值随着Rate(3R)升高而降低的结果。
实施例4
实施例4中,对混炼到树脂中的例子进行说明。
在制作分散有石墨烯的树脂片时,添加有玻璃纤维的树脂片的拉伸强度非常良好,因而对其原因进行了研究,结果得到如下见解:与玻璃纤维同时添加的相容剂有助于前体进行石墨烯化。因此,对将分散剂和相容剂混入到树脂的情况进行了研究。
将1重量%的实施例1的试样5(Rate(3R)=46%)作为前体直接添加于LLDPE(聚乙烯),利用捏合机、双螺杆混炼机(挤出机)等一边施加剪切(剪切力)一边进行混炼。
树脂中石墨系碳原材料发生石墨烯化、发生高分散时拉伸强度会增加,这是公知的,因而通过测定树脂的拉伸强度,可以相对地推测石墨烯化和分散的程度。拉伸强度利用岛津制作所株式会社制造的台式精密万能试验机(AUTOGRAPH AGS-J)以试验速度500mm/分钟的条件进行测定。
另外,为了比较由添加剂的有无带来的石墨烯化和分散性,进行了下述(a)、(b)、(c)三种比较。
(a)无添加剂
(b)常规分散剂(硬脂酸锌)
(c)相容剂(接枝改性聚合物)
参照示出测定结果的图17,对结果进行说明。需要说明的是,图17中,圆形标记是使用了比较例的试样1的树脂材料、四方标记是使用了实施例1的试样5的树脂材料。
在(a)不加入添加剂的情况下,拉伸强度的差异小。
在(b)添加有分散剂的情况下,可知试样5的石墨烯前体的石墨烯化得到一定程度的促进。
在(c)添加有相容剂的情况下,可知试样5的石墨烯前体的石墨烯化得到大幅促进。认为这是因为,相容剂除了使石墨烯分散的效果之外,还发挥如下的作用:使石墨烯层结合体与树脂结合,在该状态下施加剪切时,会撕扯石墨烯层结合体。
作为分散剂,以硬脂酸锌为例进行了说明,但可以选择性质与化合物匹配的分散剂。例如,作为分散剂,可以举出阴离子(anion)表面活性剂、阳离子(cation)表面活性剂、两性离子表面活性剂、非离子(nonion)表面活性剂。尤其,对于石墨烯,优选阴离子表面活性剂和非离子表面活性剂。更优选为非离子表面活性剂。非离子表面活性剂是氧亚乙基、羟基、糖苷等的糖链等利用与水的氢键呈现亲水性而不会解离成离子的表面活性剂,因此没有离子性表面活性剂般的强亲水性,但具有能够在非极性溶剂中使用的优点。并且还因为:通过改变其亲水基团链长,能够使其性质在从亲油性至亲水性之间自由变化。作为阴离子表面活性剂,优选为X酸盐(X酸例如为胆酸、脱氧胆酸)、例如优选为SDC:脱氧胆酸钠、磷酸酯等。另外,作为非离子表面活性剂,优选为脂肪酸甘油酯、山梨醇酐脂肪酸酯、脂肪醇乙氧基化物、聚氧乙烯烷基苯基醚、烷基糖苷等。
实施例5
为了进一步验证在实施例1也说明了的使Rate(3R)为31%以上时作为石墨烯前体是有用的,在实施例5中使用混炼到树脂中的例子进一步进行说明。对将包括实施例1中的试样1~7在内的在图14中标绘出的Rate(3R)的石墨系碳原材料用作前体的树脂成形品的弹性模量进行说明。
(1)将作为前体的上述石墨系碳原材料、LLDPE(聚乙烯:Prime Polymer Co.,Ltd.制造的20201J)5重量%与分散剂(非离子系表面活性剂)1重量%一起混入到离子交换水中,以同样的条件运行上述图8的装置,得到石墨烯和/或石墨系碳原材料达到5重量%的石墨烯分散液。
(2)立即使用捏合机(Moriyama Company Ltd.制造的加压型捏合机WDS7-30)将(1)中得到的石墨烯分散液0.6kg混炼到树脂5.4kg中,制作粒料。关于混炼条件,在下文中叙述。需要说明的是,选择树脂与分散液的配混比例,使得最终的石墨烯和/或石墨系碳原材料的添加量为0.5重量%。
(3)使用(2)中制成的粒料用注射成型机制作试验片JIS K71611A型(总长165mm、宽度20mm、厚度4mm)。
(4)基于JIS K7161,利用株式会社岛津制作所制造的台式精密万能试验机(AUTOGRAPH AGS-J)以试验速度:500mm/分钟的条件测定通过(3)制成的试验片的弹性模量(Mpa)。
混炼条件如下所示。
混炼温度:135℃
转子转速:30rpm
混炼时间:15分钟
炉内加压:开始后的10分钟为0.3MPa、经过10分钟后卸压至大气压
此处,关于上述(2)的石墨烯分散液向树脂中的分散,通常树脂的熔点为100℃以上,所以在大气中水会蒸发,但加压捏合机可以对炉内加压。在炉内,提高水的沸点,使分散液停留在液体的状态,由此可以得到分散液与树脂的乳液。进行规定时间的加压后,逐渐卸除压力,水的沸点下降,水逐渐蒸发。此时,被限制在水中的石墨烯残留于树脂中。认为由此石墨烯石墨系碳原材料高分散在树脂中。
另外,对于石墨烯分散液而言,随着时间的经过,石墨烯石墨系碳原材料具有沉降的倾向,因此优选在得到石墨烯分散液后立即混炼到树脂中。
需要说明的是,得到分散液与树脂的乳液的手段除了加压捏合机之外还可以是化学推进器、旋涡混合器、均质混合器、高压均化器、水压剪切(hydroshear)、喷射混合器、湿式喷磨机、超声波产生器等。
另外,作为分散液的溶剂,除了水以外还可以使用2-丙醇(IPA)、丙酮、甲苯、N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)等。
表4中示出Rate(3R)在30%附近的Rate(3R)与树脂成形品的弹性模量之间的关系。需要说明的是,表4中的试样00是未混炼有前体的空白试样,试样11、12是Rate(3R)在试样1与试样2之间的试样,试样21是Rate(3R)在试样2与试样3之间的试样。
表4
由图18和表4可以判明,相对于试样00(空白)的弹性模量之差(弹性模量的增加比例)在Rate(3R)达到31%为止约在10%左右,大致恒定,以Rate(3R)31%为界,该差骤增至32%,在Rate(3R)为31%至42%之间,该差单调增加至50%,在Rate(3R)为42%以及之后,该差微增并收敛于60%左右。如此,若Rate(3R)为31%以上,则可以得到弹性模量优异的树脂成形品。另外,由于树脂成形品中含有的石墨烯和/或石墨系碳原材料为0.5重量%这样的少量,因此对树脂原本具有的性状造成的影响小。
认为该倾向是因为:以Rate(3R)31%为界,与树脂接触的包含10层以下的石墨烯的薄层的石墨系碳原材料骤增。此处,实施例5中,由于用于使之分散在水中的分散剂的影响,即便利用TEM进行观察,也无法确认石墨烯的层数。因此,作为参考,基于表4中示出的分散在NMP中时的石墨系碳原材料的层数分布,对上述骤增的理由进行研讨。将试样12与试样2进行对比,石墨烯(层数为10层以下)均为25%。另一方面,如图19所示,试样2中少于15层的薄层的比例多于试样12,即认为这是因为:作为前体而分散的石墨系碳原材料的表面积大,与树脂接触的面积急剧增大。
如此,根据实施例5,Rate(3R)为31%以上时,可用作石墨烯前体的石墨系碳原材料明确显示出分离成10层以下的石墨烯和/或薄层的石墨系碳原材料的倾向。
实施例6
实施例5中仅分散有类石墨烯石墨,仅观察到弹性模量的上升,没有观察到那么多的拉伸强度的上升。
于是,进行了将利用上述方法制造的石墨烯前体和玻璃纤维添加于树脂的实验。
<各条件>
树脂:PP(聚丙烯)Prime Polymer Co.,Ltd.制造J707G、
相容剂:KAYABRID(KAYAKU AKZO CO.,LTD.制造006PP马来酸酐改性PP)
玻璃纤维(GF):CENTRAL GLASS CO.,LTD.制造ECS03-631K(直径13μm、长度3mm)、
石墨系碳原材料:石墨烯前体(通过上述方法制造)、
混合机:转鼓混合机(SEIWA GIKEN Co.,Ltd.制造)、
<混合条件1:转速25rpm×1分钟>、
混炼机:双螺杆挤出机(神户制钢株式会社制造HYPERKTX 30)、
<混炼条件1:料筒温度180℃、转子转速100rpm、喷出量8kg/h>
试验片:JIS K7139(170mm×20mm×t4mm)、
测定装置:岛津制作所制造台式精密万能试验机AUTOGRAPH AGS-J
<实验步骤>
步骤1.将玻璃纤维(GF)40重量%、相容剂4重量%、树脂56重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件1下混炼,得到母料1。
步骤2.将表5中示出的Rate(3R)不同的石墨烯前体12重量%和树脂88重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件1下混炼,得到母料2。
步骤3.将母料1 25重量%、母料2 25重量%、树脂50重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件1下混炼。
步骤4.将步骤3中混炼得到的物质用注射成型机成型为试验片,根据JIS K7139以试验速度500mm/分钟观察机械强度的变化。
为了确认类石墨烯石墨的影响,按照表5中示出的混合比率,以Rate(3R)为23%(试样1)、31%(试样2)、35%(试样21)、42%(试样4)进行实验。
表5
根据表5及图20,关于拉伸强度,观察到实施例6-2、6-3、6-4高于实施例6-1、比较例6-1、6-2、6-3。特别是观察到如下倾向:石墨烯前体的比例Rate(3R)成为31%以上时,与0%(比较例6-2)(严格地说并非Rate(3R)=0%,由于未添加石墨烯前体,因此无法在同一图表中标绘,因此为了方便标绘于0%的位置。后文中0%为相同含义。)、23%(实施例6-1)相比,拉伸强度提高30%以上这样的值得注意的倾向。需要说明的是,图20中未标绘出不含GF的比较例6-1、6-3。
另外,关于弯曲模量,与拉伸强度同样地观察到实施例6-2、6-3、6-4高于实施例6-1、比较例6-1、6-2、6-3。特别是观察到如下倾向:石墨烯前体的比例Rate(3R)成为31%以上时,与0%(比较例6-2)、23%(实施例6-1)相比,弯曲模量提高40%以上这样的值得注意的倾向。
将Rate(3R)为31%以上(实施例6-2、6-3、6-4)的石墨烯前体与GF组合使用时,拉伸强度及弯曲模量变高。对此推测,在PP间分散有厚度0.3~几十nm、尺寸几nm~1μm的类石墨烯石墨,使PP自身的弹性模量上升,而且与利用相容剂使GF密合于PP而变得不易拉出的GF接触的类石墨烯石墨发生所谓楔作用,利用PP自身的弹性模量的上升的作用与楔作用的协同作用而使拉伸强度及弯曲模量各自上升。打个比方,是与带倒钩的桩即使刺入疏松地面也容易拉出,但在夯实的地面中则难以拉出的状态相同的状态。另外,推测也是因为,通过相容剂的添加而促进类石墨烯石墨等自石墨系碳原材料剥离,较薄的类石墨烯石墨大量存在。
需要说明的是,Rate(3R)低于31%(实施例6-1)时,分散的类石墨烯石墨的量少,认为没有充分发挥由添加石墨烯前体而带来的效果。
另外,Rate(3R)为35%以上(实施例6-3、6-4)时,与在这些值以下的情况相比,弯曲模量及拉伸强度良好。认为是因为,与Rate(3R)为31%(实施例6-2)相比,使PP的弹性模量上升的类石墨烯石墨的数量增加。
用于参考,对于石墨烯前体的扫描电子显微镜(SEM)拍摄图进行说明。由实施例1得到的石墨烯前体例如如图21、图22所示为长度7μm、厚度0.1μm的薄层石墨的层叠体。
另外,关于分散于树脂的类石墨烯石墨,可以将成形的试验片用精密高速切断机(ALLIED公司制造TechCut5)等切断,利用扫描电子显微镜(SEM)等进行观察。例如图23中示出了分散有碳纳米管和类石墨烯石墨的树脂的截面,线状的部分为碳纳米管、白斑状的部分为类石墨烯石墨。该类石墨烯石墨例如如图24所示为厚度3.97nm的薄层石墨的层叠体。
实施例7
进行使用通过上述方法制造的石墨烯前体而得到树脂成形品的实验。
<各条件>
树脂:PA66(66尼龙)旭化成制造1300S、
相容剂:KAYABRID(KAYAKU AKZO CO.,LTD.制造006PP马来酸酐改性PP)
玻璃纤维(GF):CENTRAL GLASS CO.,LTD.制造ECS03-631K(直径13μm、长度3mm)、
石墨系碳原材料:石墨烯前体(通过上述方法制造)、
混合机:转鼓混合机(SEIWA GIKEN Co.,Ltd.制造)、
<混合条件1:转速25rpm×1分钟>、
混炼机:双螺杆挤出机(神户制钢株式会社制造HYPERKTX 30)、
<混炼条件2:料筒温度280℃、转子转速200rpm、喷出量12kg/h>
试验片:JIS K7139(170mm×20mm×t4mm)、
测定装置:岛津制作所制造台式精密万能试验机AUTOGRAPH AGS-J
<实验步骤>
步骤1.将玻璃纤维(GF)40重量%、相容剂4重量%、树脂56重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件2下进行混炼,得到母料1。
步骤2.将表6中示出的Rate(3R)不同的石墨烯前体12重量%和树脂88重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件2下进行混炼,得到母料2。
步骤3.将母料1 37.5重量%、母料2 25重量%、树脂37.5重量%用转鼓混合机预先在混合条件1下混合,然后,用双螺杆挤出机(挤出机)在混炼条件2下进行混炼。
步骤4.将步骤3中混炼得到的物质用注射成型机成型为试验片,根据JIS K7139以试验速度500mm/分钟观察机械强度的变化。
为了确认类石墨烯石墨的影响,按照表6中示出的混合比率,以Rate(3R)为23%(试样1)、31%(试样2)、35%(试样21)、42%(试样4)进行实验。
表6
根据表6及图25,关于拉伸强度,观察到实施例7-2、7-3、7-4高于实施例7-1、比较例7-1、7-2、7-3。特别是观察到如下的倾向:石墨烯前体的比例Rate(3R)成为31%以上时,与0%(比较例7-2)、23%(实施例7-1)相比,拉伸强度提高20%以上这样的值得注意的倾向。需要说明的是,图25中未标绘出不含GF的比较例7-1、7-3。
另外,关于弯曲模量,与拉伸强度同样地观察到实施例7-2、7-3、7-4高于实施例7-1、比较例7-1、7-2、7-3。特别是观察到如下的倾向:石墨烯前体的比例Rate(3R)成为31%以上时,与0%(比较例7-2)、23%(实施例7-1)相比,弯曲模量提高20%以上这样的值得注意的倾向。
认为拉伸强度及弯曲模量提高的理由与实施例6中的说明同样。
由实施例6、7观察到,添加GF时,无论作为母材的树脂如何,拉伸强度及弯曲模量都会提高。关于与GF一起添加石墨烯前体的情况进行说明。观察到,作为石墨烯前体,Rate(3R)为23%的情况(实施例6-1,7-1)下,无论作为母材的树脂如何,与未添加石墨烯前体的情况(比较例6-2,比较例7-2)相比拉伸强度及弯曲模量的提高轻微,但作为石墨烯前体使用Rate(3R)为31%以上的石墨烯前体时,拉伸强度及弯曲模量急剧提高(提高10%以上)。
实施例8
进行将通过上述方法制造的石墨烯前体和增强原材料添加于树脂的实验。
实施例8中,作为增强原材料,使用玻璃纤维(GF)、碳纤维(CF)、滑石、二氧化硅,确认由增强原材料的形状造成的影响。增强原材料以外的实验条件等与实施例6同样。
如图27所示,作为增强原材料,GF、CF是其直径为几十μm、其长度为几百μm的带状和/或线状。滑石代表性地为长度几~几十μm、厚度几百nm的薄片状,二氧化硅是其直径为几十nm~几μm的粒状。
表7
如表7、图26所示,添加有增强原材料的例子与未添加增强原材料的比较例6-1相比拉伸强度、弯曲模量均提高。将添加有增强原材料和石墨烯前体的例子(实施例6-2、8-1、8-2、8-3)与仅添加有增强原材料的例子(比较例6-2、8-1、8-2、8-3)进行比较,与石墨烯前体一起添加的增强原材料为GF时,拉伸强度和弯曲模量分别为1.4倍、1.4倍(实施例6-2相对于比较例6-2的增减率。)。同样地,CF的情况下,为1.3倍、1.3倍,滑石的情况下,为1.3倍、1.1倍,二氧化硅的情况下,为1.0倍、2.0倍。由此可知,石墨烯前体与带状、线状或薄片状的增强原材料组合使用时,拉伸强度和弯曲模量提高10%以上,是优选的。推测带状、线状或薄片状的纳米增强原材料由于其形状而每单位质量的表面积大,因此提高拉伸强度的效果高且能够使弯曲模量上升,与类石墨烯石墨的亲和性良好。进而,关于增强原材料判明了,作为带状、线状或薄片状的形状,特别优选长径比为5以上。反之,如二氧化硅那样长径比为5以下的增强原材料成为仅使弯曲模量上升的结果。需要说明的是,对于薄片状的原材料的长径比,求出平均厚度相对于最长部分的比即可。此处所说的长径比是指,可以由增强原材料的产品目录等中记载的直径或厚度的平均值和长度的平均值求出。特别是没有产品目录等时,利用SEM等电子显微镜观察任意个数,由其长度和厚度的平均值求出。
实施例9
接着,进行使用通过上述方法制造的石墨烯前体而得到树脂成形品的实验。
在使Rate(3R)为31%的石墨烯前体相对于增强原材料的混合比率为表8所示的条件下进行实验。实验条件等与实施例6同样。
表8
如表8、图28所示,石墨烯前体相对于增强原材料的混合比率大于1(实施例9-4)时,拉伸强度及弯曲模量成为大致同样的值,观察到特性已饱和。另外,石墨烯前体的混合比率成为10以上时,对母材的性状的影响变大。另一方面,观察到,混合比率为1/100(实施例9-8)时,与未添加石墨烯前体的比较例6-2相比,拉伸强度增加4%以上,弯曲模量增加10%以上。另外观察到,拉伸强度以该混合比率1/10(实施例6-2)骤增,弯曲模量以该混合比率1/3(实施例9-1)以上骤增。
由此,混合比率的下限为1/100以上、优选为1/10以上,上限为10以下、优选为1以下是优选的。
需要说明的是,图28中未标绘出不含GF的比较例6-1。
此处,实施例6-9中,通过如上所述利用基于电磁力的处理和/或基于物理力的处理制造石墨烯前体,因此不需要氧化、还原处理。进而,制造试验片时,不需要还原处理,因此不需要设为高温,试验片的制造容易。
以上,利用附图说明了本发明的实施例,但具体的技术方案不限定于这些实施例,即使存在不超出本发明的要旨的范围内的变更、追加,也包括在本发明之内。
例如,作为分散增强原材料和石墨系碳原材料的母材,可列举出以下物质。但是,母材的比例也可以小于增强原材料、石墨系碳原材料。另外,也有时在使用时因燃烧、氧化、气化、蒸发等而消失。例如,涂布剂等母材为挥发性的溶剂的情况下,可列举出如C/C混合物那样使母材燃烧、碳化等。
作为树脂,可列举出聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚氯乙烯(PVC)、ABS树脂(ABS)、聚乳酸(PLA)、丙烯酸类树脂(PMMA)、聚酰胺/尼龙(PA)、聚缩醛(POM)、聚碳酸酯(PC)、聚对苯二甲酸乙二醇酯(PET)、环状聚烯烃(COP)、聚苯硫醚(PPS)、聚四氟乙烯(PTFE)、聚砜(PSF)、聚酰胺酰亚胺(PAI)、热塑性聚酰亚胺(PI)、聚醚醚酮(PEEK)、液晶聚合物(LCP)等热塑性树脂。另外,合成树脂当中,作为热固化性树脂或紫外线固化树脂,可列举出环氧树脂(EP)、酚醛树脂(PF)、三聚氰胺树脂(MF)、聚氨酯(PUR)、不饱和聚酯树脂(UP)等,作为导电性高分子,可列举出PEDOT、聚噻吩、聚乙炔、聚苯胺、聚吡咯等、纤维状的尼龙、聚酯、丙烯酸类树脂、维尼纶、聚烯烃、聚氨酯、人造丝等的纤维,作为弹性体,可列举出异戊二烯橡胶(IR)、丁二烯橡胶(BR)、苯乙烯丁二烯橡胶(SBR)、氯丁二烯橡胶(CR)、腈橡胶(NBR)、聚异丁烯橡胶/丁基橡胶(IIR)、乙烯丙烯橡胶(EPM/EPDM)、氯磺化聚乙烯(CSM)、丙烯酸类橡胶(ACM)、环氧氯丙烷橡胶(CO/ECO)等,作为热固化性树脂系弹性体,可列举出一部分的聚氨酯橡胶(U)、硅橡胶(Q)、氟橡胶(FKM)等,作为热塑性弹性体,可列举出苯乙烯系、烯烃系、聚氯乙烯系、聚氨酯系、酰胺系的弹性体。
作为无机材料,可列举出混凝土、陶瓷、石膏、金属粉末等。
作为增强原材料,可列举出以下物质。
作为金属材料,有银纳米颗粒、铜纳米颗粒、银纳米线、铜纳米线、鳞片状银、鳞片状铜、铁粉、氧化锌、纤维状金属(硼、钨、氧化铝、碳化硅)等。
作为碳原材料,有炭黑、碳纤维、CNT、石墨、活性炭等。
作为碳以外的非金属材料,有玻璃纤维、纳米纤维素、纳米粘土(蒙脱石等粘土矿物)、芳纶纤维、聚乙烯纤维等。
另外,作为用于制造用作石墨烯前体的石墨系碳原材料的天然石墨,以5mm以下的颗粒的天然石墨材料(日本石墨工业制造鳞片状石墨ACB-50)为例进行了说明,但从容易取得的观点出发优选天然石墨为鳞片状石墨、且粉碎至5mm以下,Rate(3R)低于25%且强度比P1/P2低于0.01的天然石墨。通过近年的技术开发,变得能够合成人造的天然石墨状的石墨(晶体重叠成层状的石墨),因此石墨烯及类石墨烯石墨的原料不限于天然石墨(矿物)。对于需要控制金属含量的用途,优选使用纯度高的人造石墨。另外,Rate(3R)为31%以上时,也可以为通过除上述基于物理力的处理、基于电磁力的处理以外的方法而得到的人造石墨。
需要说明的是,用作石墨烯前体的石墨系碳原材料通常被称为石墨烯、石墨烯前体、石墨烯纳米薄片(GNP)、少层石墨烯(FLG)、纳米石墨烯等,但没有特别限定。
产业上的可利用性
本发明以具有强度的复合增强原材料作为对象,其应用领域不限。需要说明的是,本发明中,例如,有下述那样的领域。
(1)母材为有机材料(树脂、塑料)的例子
(1-1)交通工具
飞行器、汽车(客车、卡车、公交车等)、船舶、游乐场设备等的壳体、部件等结构构件。(结构构件为复合树脂、改性树脂、纤维增强树脂等)
(1-2)通用品
家具、家电、家庭用品、玩具等的壳体、部件等结构构件。
(1-3)3D打印机
用于热熔层叠造型法(FDM)、光造型法(SLA)、粉末固着、粉末烧结造型法(SLS)、多射流造型法(MLM、喷墨造型法)的、树脂长丝、UV固化树脂等各种造型材料。
(1-4)涂布剂
在有机溶剂中与树脂一起分散,通过喷雾或涂装等来涂布,对表面进行涂布。除了提高强度之外,还有拒水、防锈、耐紫外线等的效果。用途有建筑物(桥墩、大楼、墙壁、道路等)、汽车、飞行器等的表面/内部涂装、头盔、保护装置等树脂成型物等。
(2)母材为无机材料的例子
水泥(混凝土、砂浆)、石膏板、陶瓷、C/C混合物(碳纤维增强碳复合材料)等纤维增强结构构件。将这些无机材料作为母材使类石墨烯石墨及增强原材料分散。
(3)母材为金属材料
铝、不锈钢、钛、黄铜、青铜、软钢、镍合金、碳化钨等的结构构件。(结构构件为纤维增强金属等)。将这些金属材料作为母材使类石墨烯石墨及增强原材料分散。
Claims (8)
1.一种复合增强原材料的制造方法,其特征在于,其包括在母材中至少混炼石墨系碳原材料和增强原材料的步骤,
所述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),所述菱方晶系石墨层(3R)与所述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上,
Rate(3R)=P3/(P3+P4)×100····(式1)
式1中,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度,
所述复合增强原材料至少分散有石墨烯,
所述石墨烯是平均尺寸为100nm以上的晶体,且层数在10层以下。
2.根据权利要求1所述的复合增强原材料的制造方法,其特征在于,所述增强原材料为带状、线状或薄片状的微粒。
3.根据权利要求2所述的复合增强原材料的制造方法,其特征在于,所述微粒的长径比为5以上。
4.根据权利要求1或2所述的复合增强原材料的制造方法,其特征在于,所述石墨系碳原材料相对于所述增强原材料的重量比为1/100以上且低于10。
5.根据权利要求1所述的复合增强原材料的制造方法,其特征在于,所述母材为聚合物。
6.根据权利要求5所述的复合增强原材料的制造方法,其特征在于,在所述步骤中使用相容剂。
7.根据权利要求1所述的复合增强原材料的制造方法,其特征在于,所述母材为无机材料。
8.一种复合增强原材料,其特征在于,其是在母材中至少混炼石墨系碳原材料和增强原材料并使所述石墨系碳原材料的一部分或全部剥离而得到的,
所述石墨系碳原材料具有菱方晶系石墨层(3R)和六方晶系石墨层(2H),所述菱方晶系石墨层(3R)与所述六方晶系石墨层(2H)的由X射线衍射法得到的由以下(式1)定义的比例Rate(3R)为31%以上,
Rate(3R)=P3/(P3+P4)×100····(式1)
式1中,
P3为菱方晶系石墨层(3R)的由X射线衍射法得到的(101)面的峰强度,
P4为六方晶系石墨层(2H)的由X射线衍射法得到的(101)面的峰强度,
所述复合增强原材料至少分散有石墨烯,
所述石墨烯是平均尺寸为100nm以上的晶体,且层数在10层以下。
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