Preparation and Characterization of TiO2 Nanorods/SiO2@TiO2 Core Shell Particles and Its Application in PLLA†

doi:10.7503/cjcu20150555

Abstract

Abstract:

Rutile-type titanium dioxide(TiO₂) nanorods were synthesized using titanium trichloride as titanium source, which were further superficially modified by tetraethoxysilane and the nano-TiO₂ coated by SiO₂ were obtained(SiO₂@TiO₂). The average length of TiO₂ nanorods is about 50 nm, the average diameter of TiO₂ nanorods is about 8 nm and the thickness of the SiO₂ coating layer is about 4 nm. The maximum absorption wavelength of SiO₂@TiO₂ has a slight blue shift compared with that of TiO₂. Poly(L-lactic acid)(PLLA)/(SiO₂@TiO₂) nanocomposites were prepared by melt blending. The thermal, crystallization, UV-shielding and stretching properties of PLLA and PLLA/(SiO₂@TiO₂) nanocomposites were characterized by transmission electron microscope(TEM), thermogravimetric analysis(TGA), differential scanning calorimetry analysis(DSC), ultraviolet-visible absorption spectrometry(UV-Vis) and wide angle X-ray scattering(2D-WAXS). The results showed that the SiO₂@TiO₂ nanoparticles were dispersed well in the PLLA matrix. SiO₂@TiO₂ improved the thermal decomposition temperature and crystallization rate of PLLA and had a heterogeneous nucleation role in PLLA. The PLLA/(SiO₂@TiO₂) films had excellent UV shielding property while maintaining high visible transmittance. The orientation and crystallinity of PLLA/(SiO₂@TiO₂) nanocomposites stretched at 90 and 100 ℃ were higher than that of PLLA.

Key words: Poly(L-lactic acid), Nano titanium dioxide, Composite, Stretching property

CLC Number:

O631

TrendMD:

LI Gen, WANG Rui, WANG Feng, LIANG Ningning, ZHU Zhiguo, ZHANG Xiuqin, YANG Mingshu. Preparation and Characterization of TiO₂ Nanorods/SiO₂@TiO₂Core Shell Particles and Its Application in PLLA^†[J]. Chem. J. Chinese Universities, 2015, 36(10): 2024.

Figures/Tables 14

Fig.1 XRD patterns of TiO2(a) and rutile TiO2(b)

Fig.2 TEM images of TiO2(A, B) and SiO2@TiO2(C, D) with different magnifications

Fig.3 FTIR spectra of TiO2(a) and SiO2@TiO2(b)

Fig.4 UV-Vis diffuse reflection spectra of TiO2(a) and SiO2@TiO2(b)

Fig.5 SEM images of PLLA/(SiO2@TiO2) nanocomposites(A) ×3000; (B) ×15000.

Fig.6 TEM images of PLLA/(SiO2@TiO2) nanocomposites(A) ×10000; (B) ×30000.

Fig.7 TG curves(A) and DTG curves(B) of PLLA(a) and PLLA/(SiO2@TiO2) nanocomposites(b)

Fig.8 Nonisothermal crystallization(A) and isothermal crystallization(B) curves of PLLA(a) and PLLA/(SiO2@TiO2) nanocomposites(b)Inset of (A): DSC cooling curves; inset of (B): isothermal crystallization at 130 ℃.

Table 1 Thermal parameters obtained from the DSC curves of PLLA and PLLA/(SiO2@TiO2) nanocomposites*

Sample	T_c/℃	ΔH_c/(J·g^-1)	T_cc/℃	ΔH_cc/(J·g^-1)	T_m/℃	ΔH_m/(J·g^-1)	Χ_c(%)
PLLA	98.6	15.9	112.2	12.9	168.0	39.0	28.0
PLLA/(SiO₂@TiO₂)	100.0	24.3	110.7	3.3	168.0	37.8	37.1

Fig.9 POM images of PLLA(A) and PLLA/(SiO2@TiO2) nanocomposites(B) with isothermally crystallized at 120 ℃ for 20 min

Fig.10 UV-Vis transmittance spectra of PLLA(a) and PLLA/(SiO2@TiO2) nanocomposites(b)

Fig.11 Engineering stress-strain curves of PLLA(solid lines) and PLLA/(SiO2@TiO2) nanocomposites(dashed lines) under different temperatures(A) 30—50 ℃; (B) 60—90 ℃. Inset of (B): 100 ℃ and 110 ℃.

Fig.12 2D-WAXS patterns(A, B) and 1D-WAXS profile(C, D) of PLLA(A, C) and PLLA/(SiO2@TiO2) nanocomposites(B, D) under different stretching temperatures

Fig.13 Variation of orientation(A) and crystallinity(B) of PLLA(a) and PLLA/(SiO2@TiO2) nanocomposites(b) under different stretching temperatures

References 32

[1]	Lakshmi S. N., Cato T. L., Prog. Polym. Sci., 2007, 32(11), 762—798
[2]	Pang X. A., Zhuang X. L., Tang Z. H., Chen X. S., Biotech. J., 2010, 5(11), 1125—1136
[3]	Li J., Zhen W. J., Acta Polymerica Sinica, 2013, 4, 534—541
	(李进, 甄卫军. 高分子学报, 2013, 4, 534—541)
[4]	Raquez J. M., Habibi Y., Murariu M., Dubois P., Prog. Polym. Sci., 2013, 38(10), 1504—1542
[5]	Xu X. J., Hu L. F., Gao N., Liu S. X., Wageh S., Al-Ghamdi A. A., Alshahrie A., Fang X. S., Adv. Funct. Mater., 2015, 25, 445—454
[6]	Han S. S., Hu L. F., Liang Z. Q., Wageh S., Al-Ghamdi A. A., Chen Y. S., Fang X. S., Adv. Funct. Mater., 2014, 24, 5719—5727
[7]	Lee J. H., Youn J. I., Kim Y. J., Oh H. J., J. Mater. Sci. Technol., 2015, 31, 664—669
[8]	Xu L. X, Cui F., Wang H., Yao T. J., Cui T. Y., Chem. J. Chinese Universities, 2014, 35(12), 2694—2697
	(徐林煦, 崔放, 汪浩, 姚同杰, 崔铁钰. 高等学校化学学报,2014, 35(12), 2694—2697)
[9]	Li Y. H., Chen C. H., Li J., Su X. Z., Sun S., J. Appl. Polym. Sci., 2012, 124(4), 2968—2977
[10]	Luo Y. B., Wang X. L., Wang Y. Z., Xu D. Y., Acta Mater., 2009, 57(11), 3182—3191
[11]	Luo Y. B., Wang X. L., Wang Y. Z., Polym. Degrad. Stabil., 2012, 97(5), 721—728
[12]	Zhang H. C., Huang J. T., Yang L., Chen R.Y., Zou W., Lin X. K., Qu J. P., RSC Adv., 2015, 5, 4639—4647
[13]	Zhu Y. F., Filomena P., Giovanna G. B., Marino L., Eugenio A., Luigi A., ACS Appl. Mater. Interfaces, 2012, 4(1), 150—157
[14]	Qi L., Ding Y. F., Dong Q. X., Wen B., Wang F., Zhang S. M., Yang M. S., J. Appl. Polym. Sci., 2014, 131(16), 40601—40609
[15]	Yang M. S., Chen J., Zhang S. M., Preparation Methods for Nano Titanium Dioxide/Silica Core Shell Structures by Fe Doping, CN 102205418A, 2011-10-05
	(阳明书, 陈景,张世民. 铁掺杂的纳米二氧化钛/二氧化硅核壳结构的纳米粒子的制备方法,CN 102205418A, 2011-10-05)
[16]	Qi L., Ding Y. F., Dong Q. X., Wen B., Liu P., Wang F., Zhang S. M., Yang M. S., Chinese J. Polym. Sci., 2014, 32(7), 834—843
[17]	Chen J., Yang M. S., J. Am. Ceram. Soc., 2011, 94(10), 3547—3551
[18]	Zhang X. Q., Schneider K., Liu G. M., Chen J. H., Bruning K., Wang D. J., Stamm M Polymer, 2011, 52(18), 4141—4149
[19]	Xiong Z. J., Zhang X. Q., Liu G. M., Zhao Y., Wang R., Wang D. J., Chem. J. Chinese Universities, 2013, 34(5), 1288—1294
	(熊祖江, 张秀芹, 刘国明, 赵莹, 王锐, 王笃金. 高等学校化学学报,2013, 34(5), 1288—1294)
[20]	Chen X. B., Mao S. S., Chem. Rev., 2007, 107(7), 2891—2959
[21]	Dai C. A., Gao C. R., Feng L., Chem. J. Chinese Universities, 2013, 34(9), 2057—2062
	(戴春爱, 高常锐, 冯琳. 高等学校化学学报,2013, 34(9), 2057—2062)
[22]	Li G., Wang F., Wang R., Zhang X. Q., Yang M. S., Polymer Bulletin, 2015, 7, 7—16
	(李根, 王峰, 王锐, 张秀芹, 阳明书. 高分子通报, 2015, 7, 7—16 )
[23]	Fei P., Fei B. H., Yu Y., Xiong H. G., Tan J., J. Appl. Polym. Sci., 2014, 131(3), 39846—39856
[24]	Xi X., Zhen W. J., Bian S. Z., Chem. J. Chinese Universities, 2015, 36(3), 559—567
	(席习, 甄卫军, 卞生珍. 高等学校化学学报,2015, 36(3), 559—567)
[25]	Zhang X. Q., Xiong Z. J., Liu G. M., Yin Y. A., Wang R., Wang D. J., Acta Polymerica Sinica, 2014, 8, 1048—1055
	(张秀芹, 熊祖江, 刘国明, 尹永爱, 王锐, 王笃金. 高分子学报, 2014, 8, 1048—1055)
[26]	Stoclet G., Seguela R., Lefebvre J. M., Elkoun S., Vanmansart C., Macromolecules, 2010, 43(3), 1488—1498
[27]	Stoclet G., Seguela R., Lefebvre J. M., Rochas C., Macromolecules, 2010, 43(17), 7228—7237
[28]	Sun Z. Q., Zhang H., Pang X., Bian X. C., Chen W. Q., Chem. Res. Chinese Universities, 2014, 30(2), 333—338)
[29]	Yin Y. A., Zhang X. Q., Song Y., Vos S. D., Wang R. Y., Joziasse P., Liu G. M., Wang D. J., Polymer, 2015, 65(10), 223—232
[30]	Zhang X. Q., Schneider K., Liu G. M., Chen J. H., Bruning K., Wang D. J., Stamm M., Polymer, 2012, 53(2), 648—656
[31]	Zhang X. Q., Xing Q., Li R. B., Wang R., Wang D. J., Chinese J. Polym. Sci., 2013, 31(2), 275—284
[32]	Pan P., Kai W., Zhu B., Dong T., Inoue Y., Macromolecules, 2007, 40(19), 6898—6905

Preparation and Characterization of TiO₂ Nanorods/SiO₂@TiO₂Core Shell Particles and Its Application in PLLA^†

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