CN113077921A - 生物微流控芯片3d打印电极材料与3d打印电极及其制备方法 - Google Patents
生物微流控芯片3d打印电极材料与3d打印电极及其制备方法 Download PDFInfo
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- CN113077921A CN113077921A CN202110310196.4A CN202110310196A CN113077921A CN 113077921 A CN113077921 A CN 113077921A CN 202110310196 A CN202110310196 A CN 202110310196A CN 113077921 A CN113077921 A CN 113077921A
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Abstract
本发明公开了一种生物微流控芯片3D打印电极材料与3D打印电极及其制备方法。本发明的生物微流控芯片3D打印电极材料制备方法以氧化石墨烯先分散到溶剂中再混合光敏树脂的制备方式,使氧化石墨烯片层充分剥离、分散,使氧化石墨烯更好地分散于光敏树脂中,实现氧化石墨烯的高利用率,从而使制备的生物微流控芯片3D打印电极材料粘度更低,更适合光固化3D打印。且添加了导电颗粒,导电颗粒与氧化石墨烯协同作用提高导电性,使制备的生物微流控芯片3D打印电极材料获得更好的导电性,且不会破坏制备的3D打印电极的表面结构,制备的3D打印电极具有完整的成型形状,无崩塌缺陷,且导电性能优异。
Description
技术领域
本发明涉及生物微流控芯片电极材料技术领域,具体涉及一种生物微流控芯片3D打印电极材料与3D打印电极及其制备方法。
背景技术
微流控芯片是指一项在几微米到几百微米尺度下的流道里对微小剂量的流体(10-9-10-18L)进行各种操纵实验的卓越技术,在分析化学、医学诊断、细胞筛选、基因分析、药物输运等领域领有着广泛的应用。根据检测方法分类,基于微流控芯片的传感器主要有光学检测与电化学检测两类。将电化学分析方法与免疫学技术相结合,可以得到电化学免疫传感器,电化学免疫传感器是生物传感器的一种,它将免疫技术的高特异性和传感技术的高灵敏相结合,具有响应速度快、灵敏度高、操作简单、成本低等优势。
石墨烯是单层碳原子构成的二维纳米材料,具有独特的无间隙锥形能带结构,且其理论比表面积、导电率以及杨氏模量分别高达2630m2·g-1、6000S·cm-1、1.0TPa,故在电学、光学、热学及力学等领域具有广阔的应用前景,是一种优秀的电化学传感材料,目前石墨烯氧化物与还原型石墨烯氧化物已在电化学传感领域取得了广泛的应用。
用三维结构石墨烯作为生物微流控芯片电极是近年来石墨烯功能化的研究热点。传统的三维石墨烯基材料的制备方法,主要包括自组装法(水热还原法、化学还原法及冷冻干燥法)和模板法(胶体模板法、模板辅助化学气相沉积法及模板辅助水热还原法)。但以上三维石墨烯制备方法都无法同时满足形状精确可设计和可规模化制备的要求。
3D打印技术具有打印结构可设计,易实现快速、规模化制造的优点。目前的3D打印技术制备三维石墨烯,多采用喷头挤出式,如《一种基于氧化石墨烯材料的3D打印气凝胶及其制备方法》(申请号201710713401.5),但这种技术缺点在于:受限于挤出喷头产品制备精度不高、挤出头需要沿单层成型面往复运动使得成型效率较低。也有采用光固化方法,如专利《一种石墨烯光固化3D打印方法及其应用》(申请号201710514156.5),将石墨烯或氧化石墨烯微片直接与光敏树脂混合,之后再添加其他添加剂,这种方式的缺点在于石墨烯片之间存在较强的π-π键和范德华力,导致其容易发生团聚或堆叠,而氧化石墨烯具有强亲水性、弱亲油性,因此这种办法其分散效果较差,材料容易产生片层团聚、沉淀。
发明内容
为解决现有的制备方法无法精确设计、规模化制备三维石墨烯基的生物微流控芯片电极材料,且现有3D打印方法制备三维石墨烯基的生物微流控芯片电极材料容易发生团聚、分散效果差等缺陷,本发明提供了一种生物微流控芯片3D打印电极材料制备方法。
本发明的目的通过如下技术方案实现。
一种生物微流控芯片3D打印电极材料的制备方法,包括如下步骤:
(1)配制氧化石墨烯凝胶
将氧化石墨烯溶于溶剂中,得到氧化石墨烯凝胶;
(2)制备3D打印电极材料
(2-1)向所述氧化石墨烯凝胶中加入低聚物、活性单体、降解剂、导电颗粒、消泡剂、阻聚剂、分散剂和烧结助剂,球磨混匀;
(2-2)将球磨混匀后的混合物抽真空搅拌,消除气泡;再加入光引发剂,分散均匀,得到所述的生物微流控芯片3D打印电极材料。
优选的,步骤(1)中,采用超声震荡分散或者机械球磨的方式将所述氧化石墨烯溶于溶剂中,得到所述的氧化石墨凝胶。
本发明的制备方法采用氧化石墨烯先分散到溶剂中,再混合光敏树脂。其中,氧化石墨烯在溶剂中经过超声震荡或者机械球磨,片层能充分剥离,溶液具有较高稳定性,不易分层沉淀,避免直接将石墨烯或氧化石墨烯微片与光敏树脂混合造成的分散性问题。
优选的,所述的制备方法中采用的原料组分,按质量百分比计,各组分配比如下:
氧化石墨烯凝胶10~72%,低聚物1~20%,活性单体1~30%,降解剂0.2~10%,导电颗粒0~75%,消泡剂0.01~3%,阻聚剂0.001~1%,分散剂0.01~4%,烧结助剂0.01~2%,光引发剂1~10%。
更优选的,所述的制备方法中采用的原料组分,按质量百分比计,各组分配比如下:
氧化石墨烯凝胶35~65%,低聚物10~20%,活性单体10~30%,降解剂0.2~1%,导电颗粒4~30%,消泡剂0.01~0.8%,阻聚剂0.001~0.1%,分散剂0.05~1%,烧结助剂0.01~1%,光引发剂2~10%。
在生物微流控电极制备时,需要保留具有形态结构并能够导电的部分。本发明的制备方法采用先将氧化石墨烯经超声震荡或机械球磨的方式,进行片层的充分剥离,使氧化石墨烯充分分散在溶剂中,从而充分提高了氧化石墨烯的利用率,且不会出现打印材料粘度过高、石墨烯团聚、材料透射深度低等缺陷,在氧化石墨烯较低含量的情况下赋予生物微流控电极良好的导电性。
另外,材料体系中既有氧化石墨烯又添加了导电颗粒,在生物微流控电极材料经过3D打印成型后,经过高温处理,导电颗粒烧结联通,提高导电性,同时在高温处理过程中,氧化石墨烯发生热还原,成为还原氧化石墨烯,还原氧化石墨烯和导电颗粒互相桥接,弥补了结构中存在的孔隙,进一步提高生物微流控电极材料的导电效果。
优选的,所述氧化石墨烯凝胶中,溶剂为氧化石墨烯的良溶剂,包括水、N,N-二甲基甲酰胺、乙二醇或四氢呋喃。
优选的,氧化石墨烯的质量含量为0.99~3.45%。
优选的,所述氧化石墨烯凝胶中,采用的氧化石墨烯在厚度方向上含层数小于等于10层,在其他方向上的最大尺寸小于等于10微米。
优选的,所述低聚物选自具有不饱和双键基团的树脂、具有环氧基团或者乙烯基醚基团的树脂和水性不饱和树脂中的一种以上。
更优选的,所述具有不饱和双键基团的树脂包括环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚丙甲酸酯和丙烯酸氨基甲酸酯中的一种以上;
和/或,所述具有环氧基团或者乙烯基醚基团的树脂包括环氧树脂和乙烯基醚树脂中一种以上;
和/或,所述水性不饱和树脂包括二官能团水性脂肪族聚氨酯丙烯酸酯、3~4官能团水性脂肪族聚氨酯丙烯酸酯、6官能团水性脂肪族聚氨酯丙烯酸酯以及7~8官能团水性脂肪族聚氨酯丙烯酸酯中的一种以上。
优选的,所述低聚物选自环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚丙甲酸酯、丙烯酸氨基甲酸酯、环氧树脂、乙烯基醚树脂、二官能团水性脂肪族聚氨酯丙烯酸酯、3~4官能团水性脂肪族聚氨酯丙烯酸酯、6官能团水性脂肪族聚氨酯丙烯酸酯、7~8官能团水性脂肪族聚氨酯丙烯酸酯中的一种以上。
优选的,所述低聚物为亲油性有机物时,所述导电颗粒为经过偶联处理的导电颗粒。
更优选的,所述经过偶联处理的导电颗粒采用如下方法制得:
取无水乙醇与水混合,加入冰醋酸调节pH至3~5,再依次加入偶联剂和所述导电颗粒,于80℃恒温水浴搅拌2h,使得导电颗粒进行表面改性,再于60~80℃烘干,研磨粉体,得到所述经过偶联处理的导电颗粒。
更进一步优选的,所述无水乙醇、水、偶联剂以及导电颗粒的质量比为40:4:1:40~80。
使用偶联剂对导电颗粒进行前期处理,使得导电颗粒更好地分散于树脂低聚物和单体之间,并很好地解决了导电颗粒与树脂低聚物之间结合差、容易沉降的问题。
优选的,所述活性单体选自含有乙烯基醚或环氧基基团的单体、单官能团丙烯酸酯、双官能团丙烯酸酯、三官能团丙烯酸酯或多官能团丙烯酸酯。
优选的,所述降解剂为热降解剂,包括过氧化物或过硫酸盐。更优选的,所述过硫酸盐包括过硫酸钾和过硫酸钠中的一种以上。在3D打印生物微流控电极材料进行热处理时,降解剂在高温作用下产生的自由基能够打断树脂的分子链,使得交联的树脂更容易分解成小分子进而去除,提高热处理效率,减少热处理之后电极产品的残碳量。
优选的,所述导电颗粒为各形貌结构的为金属颗粒,包括银颗粒、金颗粒、铜颗粒、铝颗粒或者为其他金属颗粒中的一种或几种。
更优选的,所述导电颗粒为银颗粒,包括球形银粉、纳米银线和纳米银棒中的一种以上。
更优选的,所述导电颗粒的最大尺寸小于等于10微米,使材料具有高的打印精度。
优选的,所述消泡剂选自矿物油类消泡剂、有机硅类消泡剂、聚醚类消泡剂和水性消泡剂中的一种或几种。更优选的,所述消泡剂选自消泡剂BYK-111和消泡剂TEGO Foamex810中的一种以上。
优选的,所述阻聚剂选自酚类阻聚剂和醚类阻聚剂中的一种以上。更优选的,所述阻聚剂选自特丁基邻苯二酚、对叔丁基邻苯二酚、对苯二酚、2—仲丁基—4.6—二硝基苯酚和羟基苯甲醚中的一种以上。
优选的,所述分散剂选自各类型的表面活性剂以及分散剂中的一种以上。更优选的,所述分散剂选自柠檬酸钠、三乙醇胺、乙二胺四乙酸钠、聚乙烯醇、聚氨酯改性丙烯酸分散剂和水性通用分散剂中的一种或几种。
优选的,所述烧结助剂选自HCl、NaCl和KCl中的一种或几种。
优选的,所述光引发剂选自裂解型引发剂、夺氢型引发剂和阳离子引发剂中的一种或几种。更优选的,所述光引发剂选自光引发剂819、光引发剂TPO、光引发剂TPOL、光引发剂LAP、光引发剂2959、光引发剂389、光引发剂651和二芳基碘鎓盐中的一种或几种。
本发明还提供了一种生物微流控芯片3D打印电极材料,该生物微流控芯片3D打印电极材料采用上述任一项所述的方法制备得到。
本发明的另一目的还提供了一种3D打印电极的制备方法,该制备方法采用上述所述的生物微流控芯片3D打印电极材料进行打印制得3D打印电极,包括如下步骤:
将所述生物微流控芯片3D打印电极材料于3D打印设备上光固化成型,得到具有三维结构的坯体;清洗除去未固化部分,再真空冷冻干燥,脱去溶剂;进行热处理,使坯体中的有机成分进一步去除,导电颗粒烧结出现结晶,氧化石墨烯则受热还原并脱去含氧基团变为还原氧化石墨烯,即可得到所述的3D打印电极。
本发明还提供了一种3D打印电极,该3D打印电极采用上述所述的3D打印电极的制备方法制得,具有可设计、且完整的成型形状。
与现有技术相比,本发明具有如下优点和有益效果:
(1)本发明的生物微流控芯片3D打印电极材料制备方法中,以氧化石墨烯先分散到溶剂中再混合光敏树脂的制备方式,使氧化石墨烯片层充分剥离、分散,相比传统直接将石墨烯或氧化石墨烯微片直接与光敏树脂的混合方式,效果更好,使氧化石墨烯更好地分散于光敏树脂中,实现氧化石墨烯的高利用率,从而使制备的生物微流控芯片3D打印电极材料粘度更低,更适合光固化3D打印,使3D打印的微流控芯片电极具有可设计、且完整的成型形状。
(2)本发明的生物微流控芯片3D打印电极材料制备方法中,添加了导电颗粒。其中,石墨烯的导电方式为片层搭接导电,而导电颗粒是烧结后颗粒联通导电,两者混合后可相互填补孔隙,通过石墨烯片层和导电颗粒的搭接,导电颗粒与氧化石墨烯协同作用提高导电性,使制备的生物微流控芯片3D打印电极材料获得更好的导电性;且该提高导电性的协同作用方式不会破坏石墨烯材料作为微流控芯片电极的表面效果,利于生物粒子捕捉固定。
(3)本发明的生物微流控芯片3D打印电极材料中,氧化石墨烯片径小,同时导电颗粒的粒径为微纳米级别,使该生物微流控芯片3D打印电极材料具有高的光固化成型精度。
(4)本发明的3D打印电极具有完整的成型形状,无崩塌缺陷,且导电性能优异,能很好地应用于生物微流控芯片中。
附图说明
图1为具体实施例中本发明的生物微流控芯片3D打印电极材料的制备流程示意图;
图2为导电颗粒与石墨烯片层协同增强导电性能的效果图;
图3为具体实施例中本发明的3D打印电极的制备流程示意图;
图4为实施例1中制备3D打印电极的热处理曲线图;
图5a和图5b为实施例1制备的3D打印电极在不同倍率下的电镜扫描图;
图6为实施例1中制备的3D打印电极的微观组织结构图;
图7为实施例2中制备的3D打印电极的微观组织结构图。
具体实施方式
以下结合具体实施例对本发明的技术方案作进一步详细的描述,但本发明的保护范围及实施方式不限于此。本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例。相反地,提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
并且,除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本发明的生物微流控芯片3D打印电极材料的制备方法,具体流程如图1所示,包括如下步骤:
(1)配制氧化石墨烯凝胶
将氧化石墨烯溶于溶剂中,得到氧化石墨烯凝胶;
(2)制备3D打印电极材料
(2-1)向所述氧化石墨烯凝胶中加入低聚物、活性单体、降解剂、导电颗粒、消泡剂、阻聚剂、分散剂和烧结助剂,球磨混匀,收集得到浆料;
(2-2)将球磨混匀后收集的浆料抽真空搅拌,消除气泡;再加入光引发剂,电动搅拌分散均匀,得到所述的生物微流控芯片3D打印电极材料。
在本发明的生物微流控芯片3D打印电极材料制备中,添加了导电颗粒。其中,石墨烯的导电方式为片层搭接导电,而导电颗粒是烧结后颗粒联通导电;参见图2所示,两者混合后可相互填补孔隙,通过石墨烯片层和导电颗粒的搭接,导电颗粒与氧化石墨烯协同作用提高导电性,使制备的生物微流控芯片3D打印电极材料获得更好的导电性;且该提高导电性的协同作用方式不会破坏石墨烯材料作为微流控芯片电极的表面效果,利于生物粒子捕捉固定。
本发明的3D打印电极的制备方法,采用上述制备的所述生物微流控芯片3D打印电极材料进行打印制得3D打印电极,具体流程如图3所示,包括如下步骤:
将所述生物微流控芯片3D打印电极材料于3D打印设备上光固化成型,得到具有三维结构的坯体;清洗除去未固化部分,再于真空冻干机真空冷冻干燥,脱去溶剂;于真空、惰性气氛或还原性气氛中进行热处理,得到所述的3D打印电极。
实施例1
本实施例的生物微流控芯片3D打印电极材料的制备,具体步骤如下:
(1)配制氧化石墨烯凝胶:
取8.7g分析纯单层氧化石墨烯粉末(片径2-5μm)置于烧杯中,再加入650ml N,N-二甲基甲酰胺,将烧杯置于超声震荡设备中以180W功率超声分散30min,得到充分剥离片层的氧化石墨烯凝胶。
(2)制备3D打印电极材料
向步骤(1)的氧化石墨烯凝胶中加入180g二官能团脂肪族聚氨酯丙烯酸酯,将烧杯放置在电动搅拌设备上对混合物进行搅拌,转速150r/min,时间20min,得到均匀混合的液体。
将液体倒入球磨罐中,再添加120g活性单体TMPTA、5g聚氨酯润湿分散剂、0.5g烧结助剂NaCl、2.5g降解剂过硫酸钠、0.03g阻聚剂对叔丁基邻苯二酚以及5g消泡剂BYK-111,加入2kg的研磨锆球,以转速200r/min球磨1h,球磨完成之后,收集得到的浆料。
将收集的浆料置于真空搅拌设备中消去气泡,消泡完毕后加入50g光引发剂TPOL,再次置于电动搅拌设备上进行搅拌,转速100r/min,时间20min,即可得到3D打印电极材料。
3D打印电极的制备,采用本实施例制备的3D打印电极材料进行制得,具体步骤如下:
将所述3D打印电极材料置于光固化的3D设备,且设计成型的结构为蜂窝状结构,进行坯体成型,得到三维结构的坯体,用乙醇清洗去掉未反应部分;之后使用冷冻干燥机在-50℃进行真空冷冻干燥,脱去溶剂;
再于真空环境下进行热处理,热处理工艺控制操作如图4所示(具体的热处理工艺为:以2℃/min的升温速率升温至300℃,保温12min;再以0.75℃/min的升温速率升温至480℃,保温30min;再以1℃/min的升温速率升温至500℃,保温30min;再以10℃/min的升温速率升温至900℃,保温30min;最后,以30℃/min的降温速率降温至常温;);取出,得到3D打印电极。
制备的3D打印电极的电镜扫描图如图5a和图5b所示,为蜂窝状结构,具有完整的成型形状。对制备的3D打印电极进行导电性测试,电阻率为1.10Ω·cm。
对比例1
本实施例的生物微流控芯片3D打印电极材料的制备,具体步骤如下:
(1)向球磨罐中加入8.7g分析纯单层氧化石墨烯粉末(片径2-5μm)、380g二官能团脂肪族聚氨酯丙烯酸酯、570g活性单体TMPTA、5g有机硅分散剂、0.5g烧结助剂NaCl、2.5g降解剂过硫酸钠、0.03g阻聚剂对叔丁基邻苯二酚以及5g消泡剂BYK-111,加入2kg的研磨锆球,以转速200r/min球磨1h,球磨完成之后,收集得到的浆料。
(2)将收集的浆料置于真空搅拌设备中消去气泡,消泡完毕后加入50g光引发剂819,再次置于电动搅拌设备上进行搅拌,转速100r/min,时间20min,即可得到对照组的3D打印材料。
3D打印电极的制备,采用本对比例制备的3D打印电极材料进行制得,具体制备步骤与实施例1相同。制备的3D打印电极在热处理过程中崩塌,不具有完整的成型形状,且不导电。
实施例2
本实施例的生物微流控芯片3D打印电极材料的制备,与实施例1相同。进一步的,在球磨过程中,添加50g球形银粉(0.5微米粒径)。
3D打印电极的制备,采用本实施例制备的3D打印电极材料进行制得,具体制备步骤与实施例1相同。制备的3D打印电极为蜂窝状结构,具有完整的成型形状。对制备的3D打印电极进行导电性测试,电阻率为214mΩ·cm,相比实施例1制备的3D打印电极具有更优异的导电性能。
对实施例1和实施例2制备的3D打印电极进行微观组织观察,实施例1和实施例2制备的3D打印电极的微观组织结构图分别如图6和图7所示。其中,图6显示的是未掺加银粉的石墨烯电极,由于缺少石墨烯片层的搭接作用,材料表面可见孔隙等缺陷,并由此导致了该3D打印电极的导电性降低;图7显示出电极表面材料孔隙等缺陷有所减少,这是因为实施例2增加的银颗粒在烧结过程中熔为液体,与石墨烯片层充分连接,并由此该3D打印电极的导电性得到极大提高。
实施例3
本实施例的生物微流控芯片3D打印电极材料的制备,具体步骤如下:
(1)配制氧化石墨烯凝胶:
取0.5g分析纯单层氧化石墨烯粉末(片径2-5μm)置于球磨罐中,再加入50ml去离子水,加入200g的研磨锆球,以转速200r/min球磨1h,球磨完成之后,得到充分剥离片层的氧化石墨烯凝胶。
(2)制备3D打印电极材料
向步骤(1)的盛有氧化石墨烯凝胶的球磨罐中加入1g 6官能团水性聚氨酯丙烯酸酯、30g活性单体丙烯酰吗啉、加入分散剂BYK-333 0.73g、消泡剂TEGO Airex 900 0.75g、0.5g烧结助剂KCl、0.5g降解剂过硫酸钾、0.02g阻聚剂叔丁基对苯二酚,13g铝粉(2微米颗粒)以转速200r/min球磨2h,球磨完成之后,收集得到的浆料。
将收集的浆料置于真空搅拌设备中消去气泡,消泡完毕后加入3g光引发剂819DW,再次置于电动搅拌设备上进行搅拌,转速100r/min,时间20min,即可得到3D打印电极材料。
3D打印电极的制备,采用本实施例制备的3D打印电极材料进行制得,具体步骤如下:
将所述3D打印电极材料置于光固化的3D设备,进行坯体成型,得到三维结构的坯体,用乙醇清洗去掉未反应部分;之后使用冷冻干燥机在-50℃进行真空冷冻干燥,脱去溶剂;再于真空环境下进行热处理,热处理工艺控制操作如图4所示;取出,得到3D打印电极。
制备的3D打印电极具有完整的成型形状,且制备的3D打印电极的微观组织结构图参见图7所示,其表面材料孔隙等缺陷少,并具有高的导电性,电阻率为99mΩ·cm。
实施例4
本实施例的生物微流控芯片3D打印电极材料的制备,具体步骤如下:
(1)配制氧化石墨烯凝胶:
取1.2g分析纯单层氧化石墨烯粉末(片径2-5μm)置于球磨罐中,再加入35g乙二醇,加入200g的研磨锆球,以转速200r/min球磨2h,球磨完成之后,得到充分剥离片层的氧化石墨烯凝胶。
(2)偶联处理的导电颗粒:
称取400mL无水乙醇放置于烧杯中,加入40g去离子水,加入冰醋酸调节PH至5,加入10gKH570水解1小时。称取400g的铜粉(0.5微米颗粒)加入此烧杯,于80℃恒温水浴搅拌2h,使得铜粉颗粒进行表面改性,再于60~80℃烘干,研磨粉体,得到所述经过偶联处理的铜粉。
(3)制备3D打印电极材料
向步骤(1)的盛有氧化石墨烯凝胶的球磨罐中加入20g环氧丙烯酸酯、10g活性单体1,6-己二醇二丙烯酸酯、加入0.3g分散剂三乙醇胺、0.7g消泡剂Defoamex 820N、0.14g烧结助剂KCl、0.65g降解剂过硫酸钾、0.01g阻聚剂对苯二酚,30g经过偶联处理的铜粉,以转速200r/min球磨2h,球磨完成之后,收集得到的浆料。
将收集的浆料置于真空搅拌设备中消去气泡,消泡完毕后加入2g光引发剂TPO,再次置于电动搅拌设备上进行搅拌,转速100r/min,时间20min,即可得到3D打印电极材料。
3D打印电极的制备,采用本实施例制备的3D打印电极材料进行制得,具体步骤如下:
将所述3D打印电极材料置于光固化的3D设备,进行坯体成型,得到三维结构的坯体,用乙醇清洗去掉未反应部分;之后使用冷冻干燥机在-50℃进行真空冷冻干燥,脱去溶剂;再于真空环境下进行热处理,热处理工艺控制操作如图4所示;取出,得到3D打印电极。
制备的3D打印电极具有完整的成型形状,且制备的3D打印电极的微观组织结构图参见图7所示,其表面材料孔隙等缺陷少,并具有高的导电性,电阻率为82mΩ·cm。
以上所述实施例的各技术特征可以进行任意的组合,本说明书为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述。然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。而且,以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
1.一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,包括如下步骤:
(1)配制氧化石墨烯凝胶
将氧化石墨烯溶于溶剂中,得到氧化石墨烯凝胶;
(2)制备3D打印电极材料
(2-1)向所述氧化石墨烯凝胶中加入低聚物、活性单体、降解剂、导电颗粒、消泡剂、阻聚剂、分散剂和烧结助剂,球磨混匀;
(2-2)将球磨混匀后的混合物抽真空搅拌,消除气泡;再加入光引发剂,分散均匀,得到所述的生物微流控芯片3D打印电极材料。
2.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,按质量百分比计,各组分配比如下:
氧化石墨烯凝胶10~72%,低聚物1~20%,活性单体1~30%,降解剂0.2~10%,导电颗粒0~75%,消泡剂0.01~3%,阻聚剂0.001~1%,分散剂0.01~4%,烧结助剂0.01~2%,光引发剂1~10%。
3.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,
按质量百分比计,各组分配比如下:
氧化石墨烯凝胶35~65%,低聚物10~20%,活性单体10~30%,降解剂0.2~1%,导电颗粒4~30%,消泡剂0.01~0.8%,阻聚剂0.001~0.1%,分散剂0.05~1%,烧结助剂0.01~1%,光引发剂2~10%。
4.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,所述氧化石墨烯凝胶中,氧化石墨烯的质量含量为0.99~3.45%;
和/或,所述氧化石墨烯凝胶中,采用的氧化石墨烯在厚度方向上含层数小于等于10层,在其他方向上的最大尺寸小于等于10微米。
5.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,所述低聚物选自具有不饱和双键基团的树脂、具有环氧基团或者乙烯基醚基团的树脂和水性不饱和树脂中的一种以上;
所述具有不饱和双键基团的树脂包括环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂、聚丙甲酸酯和丙烯酸氨基甲酸酯中的一种以上;和/或,所述具有环氧基团或者乙烯基醚基团的树脂包括环氧树脂和乙烯基醚树脂中一种以上;和/或,所述水性不饱和树脂包括二官能团水性脂肪族聚氨酯丙烯酸酯、3~4官能团水性脂肪族聚氨酯丙烯酸酯、6官能团水性脂肪族聚氨酯丙烯酸酯以及7~8官能团水性脂肪族聚氨酯丙烯酸酯中的一种以上。
6.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,所述低聚物为亲油性有机物时,所述导电颗粒为经过偶联处理的导电颗粒;
所述经过偶联处理的导电颗粒采用如下方法制得:
取无水乙醇与水混合,加入冰醋酸调节pH至3~5,再依次加入偶联剂和所述导电颗粒,于80℃恒温水浴搅拌2h,烘干,研磨,得到所述经过偶联处理的导电颗粒;
所述无水乙醇、水、偶联剂以及导电颗粒的质量比为40:4:1:40~80。
7.根据权利要求1所述的一种生物微流控芯片3D打印电极材料的制备方法,其特征在于,所述活性单体选自含有乙烯基醚或环氧基基团的单体、单官能团丙烯酸酯、双官能团丙烯酸酯、三官能团丙烯酸酯或多官能团丙烯酸酯;
和/或,所述导电颗粒为银颗粒、金颗粒、铜颗粒、铝颗粒或者为其他金属颗粒中的一种或几种。
8.一种生物微流控芯片3D打印电极材料,其特征在于,采用权利要求1~7任一项所述的方法制备得到。
9.一种3D打印电极的制备方法,其特征在于,采用权利要求8所述的生物微流控芯片3D打印电极材料进行打印制得3D打印电极,包括如下步骤:
将所述生物微流控芯片3D打印电极材料于3D打印设备上光固化成型,得到具有三维结构的坯体;清洗除去未固化部分,再真空冷冻干燥,脱去溶剂;进行热处理,得到所述的3D打印电极。
10.一种3D打印电极,其特征在于,采用权利要求9所述的方法制备得到。
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