静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

doi:10.7503/cjcu20180695

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (4): 824.doi: 10.7503/cjcu20180695

静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

赵宇轩¹, 陈艳君^2,³, 潘顾鑫¹, 王畅¹, 彭振博^2,³, 孙宗旭¹, 梁永日¹, 师奇松¹()

1. 北京石油化工学院材料科学与工程学院, 特种弹性体复合材料北京市重点实验室, 北京 102617
2. 宁波职业技术学院化学工程学院, 宁波 315800
3. 宁波职业技术学院乙烯工程副产物高质化利用浙江省应用技术协同创新中心, 宁波 315800

收稿日期:2018-10-16 出版日期:2019-01-15 发布日期:2019-01-15
作者简介:
联系人简介: 师奇松, 女, 博士, 副教授, 主要从事功能材料方面的研究. E-mail: shiqisong@bipt.edu.cn
基金资助:
北京市自然科学基金(批准号: 2172023)、宁波职业技术学院乙烯工程副产物高质化利用浙江省应用技术协同创新中心20182019年度开放课题(批准号: NZXT2018308)和北京市大学生科研训练项目(批准号: 2018J00055)资助.

Preparation and Performance of Novel Tb-PEG+Eu-PEG/PANI/PAN Luminescent-electrical-phase Change Composite Fibers by Electrospinning^†

ZHAO Yuxuan¹, CHEN Yanjun^2,³, PAN Guxin¹, WANG Chang¹, PENG Zhenbo^2,³, SUN Zongxu¹, LIANG Yongri¹, SHI Qisong^1,^*()

1. Beijing Key Lab of Special Elastomer Composite Materials, College of Material Science and Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
2. College of Chemical Engineering, Ningbo Polytechnic College, Ningbo 315800, China
3. Zhejiang Collaborative Innovation Center for High Value Utilization of Byproducts from Ethylene Project, Ningbo Polytechnic College, Ningbo 315800, China

Received:2018-10-16 Online:2019-01-15 Published:2019-01-15
Contact: SHI Qisong E-mail:shiqisong@bipt.edu.cn
Supported by:
† Supported by the Natural Science Foundation of Beijing Municipality, China(No.2172023), the Open Fund of Zhejiang Collaborative Innovation Center for High Value Utilization of Byproducts from Ethylene Project, the Ningbo Polytechnic College, China(No.NZXT2018308) and the College Student Research and Career-creation Program of Beijing City, China(No.2018J00055).

摘要/Abstract

摘要：

以聚丙烯腈(PAN)为载体基质、以铕-聚乙二醇(Eu-PEG)和铽-聚乙二醇(Tb-PEG)为相变荧光材料, 加入掺杂的导电聚苯胺(PANI), 采用静电纺丝技术制得Tb-PEG+Eu-PEG/PANI/PAN复合纤维. 采用扫描电子显微镜(SEM)、荧光光谱(FL) 仪、差示扫描量热(DSC)仪及宽频介电松驰谱(BDS)仪等方法对相变荧光导电复合纤维的性能进行分析. 研究结果表明, 复合纤维具备良好的荧光、相变及导电性能. 在294 nm紫外光激发下, 通过调节Tb-PEG和Eu-PEG的质量比可调节复合纤维的发光强度和颜色, 同时复合纤维的相变温度在5467 ℃之间. 复合纤维的电导率达到10^-6 S/cm, 随着PANI含量的增加, 电导率和介电常数增加. 通过调节Tb-PEG, Eu-PEG和PANI的比例及PEG的分子量, 可以实现复合纤维荧光、导电及相变性能的可控调整.

关键词: 聚乙二醇, 聚苯胺, 相变, 荧光, 导电, 静电纺丝, 复合纤维

Abstract:

Luminescent-electrical-phase change trifunctionalcomposite fibers based on Tb-polyethylene glycol(PEG)+Eu-PEG/polyaniline(PANI)/polyacrylonitrile(PAN) blends in which Tb-PEG and Eu-PEG act as model luminescence-phase change material, PANI acts as electrical material and PAN acts as a supporting material, were fabricated by electrospinning. Scanning electron microscopy, IR spectrum, differential scanning calorimetry, fluorescence spectroscopy and broadband dielectric spectroscopy were used to characterize the morphology structure and properties of the composite fibers. The results indicate that the composite fibers possess excellent photoluminescence, thermal energy storage and electrical conduction. The emitting color of the luminescent composite fibers can be tuned by adjusting the mass ratios of Tb-PEG, Eu-PEG under the excitation of 294 nm single-wavelength ultraviolet light. The melting temperatures of the prepared composite fibers were in the range of 54—67 ℃. The electrical conductivity reaches up to the order of 10^-6 S/cm. The dielectric conductivity and constants are slightly increased with increasing of PANI content. The luminescent intensity and electrical conductivity of the composite fibers can be tuned by adjusting the amounts of Tb-PEG, Eu-PEG, PANI and molecular weight of PEG.

Key words: Polyethylene glycol, Polyaniline, Phase change, Luminescence, Electrical, Electrospinning, Composite fiber

中图分类号:

TrendMD:

赵宇轩, 陈艳君, 潘顾鑫, 王畅, 彭振博, 孙宗旭, 梁永日, 师奇松. 静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维. 高等学校化学学报, 2019, 40(4): 824.

ZHAO Yuxuan,CHEN Yanjun,PAN Guxin,WANG Chang,PENG Zhenbo,SUN Zongxu,LIANG Yongri,SHI Qisong. Preparation and Performance of Novel Tb-PEG+Eu-PEG/PANI/PAN Luminescent-electrical-phase Change Composite Fibers by Electrospinning^†. Chem. J. Chinese Universities, 2019, 40(4): 824.

图/表 15

Scheme 1 Synthesis of Tb-PEG with different molecular weights

Table 1 Compositions and contents of spinning solutions

Sample	Component	M_w of PEG	m(Tb-PEG): m(Eu-PEG)	m(Tb-PEG)/g	m(Eu-PEG)/g	m(PANI· DBSA)/g
S1	Tb-PEG6000/PANI/PAN	6000	10:0	0.18	0	0.18
S2	Tb-PEG8000/PANI/PAN	8000	10:0	0.18	0	0.18
S3	Tb-PEG10000/PANI/PAN	10000	10:0	0.18	0	0.18
S4	Tb-PEG+Eu-PEG(7/3)/PANI/PAN	10000	7:3	0.126	0.054	0.18
S5	Tb-PEG+Eu-PEG(6/4)/PANI/PAN	10000	6:4	0.108	0.072	0.18
S6	Tb-PEG+Eu-PEG(5/5)/PANI/PAN	10000	5:5	0.09	0.09	0.18
S7	Tb-PEG+Eu-PEG(4/6)/PANI/PAN	10000	4:6	0.072	0.108	0.18
S8	Eu-PEG10000/PANI/PAN	10000	0:10	0	0.18	0.18
S9	Tb-PEG10000/PANI35/PAN	10000	10:0	0.18	0	0.21
S10	Tb-PEG10000/PANI45/PAN	10000	10:0	0.18	0	0.27
S11	Tb-PEG10000/PANI55/PAN	10000	10:0	0.18	0	0.33

Fig.1 IR spectrum of the PEG6000 functional compound

Fig.2 SEM images of Tb-PEG6000/PANI/PAN(A), Tb-PEG8000/PANI/PAN(B) and Tb-PEG10000/PANI/PAN(C)

Fig.3 Corresponding diameter distributions of Tb-PEG6000/PANI/PAN(A), Tb-PEG8000/PANI/PAN(B) and Tb-PEG10000/PANI/PAN(C)

Fig.4 EDS spectrum of Tb-PEG10000/PANI/PAN

Fig.5 SEM images of Tb-PEG+Eu-PEG/PANI/PAN composite fibers(S4—S7)m(Tb-PEG):m(Eu-PEG): (A) 7:3; (B) 6:4; (C) 5:5; (D) 4:6.

Fig.6 Excitation(A) and emission(B) spectra of Tb-PEG10000/PANI/PAN composite fibers

Fig.7 Emission spectra of Tb-PEG6000/PANI/PAN(a), Tb-PEG8000/PANI/PAN(b) and Tb-PEG10000/PANI/PAN(c) composite fibers

Fig.8 Excitation(A) and emission(B) spectra of Eu-PEG10000/PANI/PAN composite fibers

Fig.9 Emission spectra of Tb-PEG+Eu-PEG10000/PANI/PAN composite fibers m(Tb-PEG):m(Eu-PEG): a. 10:0; b. 7:3; c. 6:4; d. 5:5; e. 4:6; f. 0:10.

Fig.10 DSC curves of Tb-PEG+Eu-PEG/PANI/PAN composite fibers(A) a. S1; b. S2; c. S3. (B) a. S4; b. S5; c. S6; d. S7.

Table 2 Melting temperatures(Tm) of electrospun composite fibers

Sample	Content	T_m/℃	Sample	m(Tb-PEG):m(Eu-PEG)	T_m/℃
PEG6000	PEG6000	48.40	S4	7:3	56.91
PEG8000	PEG8000	61.82	S5	6:45:5	58.49
PEG10000	PEG10000	64.22	S6	5:5	58.80
S1	Tb-PEG6000/PANI/PAN	54.87	S7	4:6	60.38
S2	Tb-PEG8000/PANI/PAN	64.93
S3	Tb-PEG10000/PANI/PAN	66.02

Fig.11 Frequency dependent electric conductivity(A), dielectric constant(B) and dielectric loss(C) of the fibers S9(a), S10(b) and S11(c)

Table 3 Electrical conductivity and dielectric constant of the samples doped with various amount of PANI

Sample	Mass ratio of PANI·DBSA to PAN(%)	10⁶Conductivity/(S·cm^-1)	Dielectric constant at 1 kHz
S9	35	0.98	145
S10	45	1.42	227
S11	55	1.50	263

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静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维

Preparation and Performance of Novel Tb-PEG+Eu-PEG/PANI/PAN Luminescent-electrical-phase Change Composite Fibers by Electrospinning^†

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