Study on preparation and crystalline properties of PET/ZnO nanocomposites

doi:10.19491/j.issn.1001-9278.2025.04.005

Abstract

Abstract:

PET/ZnO nanocomposites were prepared through melt blending using polyethylene terephthalate （PET） and sodium oleate⁃modified nano⁃ZnO （4.73 nm） as raw materials for at nano⁃ZnO contents of 0， 0.02， 0.5， and 1.0 wt%. Differential scanning calorimetry was carried out to investigate the effect of cooling rate on the crystallization behavior of the nanocomposites. The results indicated that the crystallization temperature of PET/ZnO nanocomposites shifted to a low temperature， followed by a gradual increase in the width of crystallization peak， and their half crystallization time also tended to decrease with an increase in the cooling rate. In contrast pure PET， the crystallization ability and crystallization rate of the nanocomposites were improved at the same cooling rate with an increase in the nano⁃ZnO content. The non⁃isothermal crystallization kinetics was studied by the Jeziorny's method. The results indicated that the range of n value varied， indicating that the addition of nano⁃ZnO generated a certain effect on the original growing mode of PET. The crystallization rate constant （Z_c） increased with an increase in the nano⁃ZnO content. However， the Z_c value of the nanocomposites almost did not change at a nano⁃ZnO content of 1.0 wt%. The thermal stability and crystalline morphology of the nanocomposites were further analyzed by thermogravimetric analysis and hot⁃plate polarizing microscope. The results demonstrated that the incorporated nano⁃ZnO could act as a nucleating agent for the crystallization of PET， but it had little effect on the thermal stability of PET.

Key words: polyethylene terephthalate, nano-ZnO, nanocomposite, crystallization rate, non?isothermal crystallization kinetics

CLC Number:

TQ323.4

GUO Yousheng, CHEN Yanming, WANG Haiyue, ZHANG Wenshuai. Study on preparation and crystalline properties of PET/ZnO nanocomposites[J]. China Plastics, 2025, 39(4): 25-30.

Figures/Tables 11

Fig.1. DSC heating and cooling curves of PET and PET/ZnO nanocomposites

样品名称	T_m/^oC	T_c/^oC
PET	251.68	171.29
PET/ZnO-0.02%	250.33	183.17
PET/ZnO-0.5%	251.21	206.22
PET/ZnO-1%	250.13	206.47

Tab. 1. Thermal performance data for composite samples

Fig.2. DSC curves of PET and PET/ZnO nanocomposites at different cooling rates

Fig.3. The relationship curves between relative crystallinity and crystallization time of PET and PET/ZnO nanocomposites

样品名称	Φ/℃·min^-1	T₀/℃	$T ∞$ /℃	T_c/℃	ΔT/℃	t_1/2/s
PET	5	204.55	170.07	179.94	34.48	279.31
	10	195.08	158.07	171.29	37.01	131.05
	15	188.17	144.15	164.25	44.02	97.38
	20	186.29	132.14	158.67	54.15	82.04
PET⁃0.02%	5	213.07	183.55	194.70	29.52	212.01
	10	205.17	169.12	183.24	36.05	126.98
	15	197.34	155.27	175.08	42.07	86.68
	20	195.31	142.55	175.08	52.76	75.05
PET⁃0.5%	5	216.88	206.15	212.28	10.73	51.05
	10	211.42	196.03	206.22	15.39	33.11
	15	208.58	192.56	202.89	16.02	21.95
	20	206.23	188.78	200.95	17.45	17.59
PET⁃1%	5	217.57	209.04	213.71	8.53	43.11
	10	212.10	195.94	206.47	16.16	28.85
	15	209.19	191.56	202.63	17.63	22.37
	20	206.83	186.39	199.36	20.44	17.20

样品名称	Φ/℃·min^-1	T₀/℃	$T ∞$ /℃	T_c/℃	ΔT/℃	t_1/2/s
PET	5	204.55	170.07	179.94	34.48	279.31
	10	195.08	158.07	171.29	37.01	131.05
	15	188.17	144.15	164.25	44.02	97.38
	20	186.29	132.14	158.67	54.15	82.04
PET⁃0.02%	5	213.07	183.55	194.70	29.52	212.01
	10	205.17	169.12	183.24	36.05	126.98
	15	197.34	155.27	175.08	42.07	86.68
	20	195.31	142.55	175.08	52.76	75.05
PET⁃0.5%	5	216.88	206.15	212.28	10.73	51.05
	10	211.42	196.03	206.22	15.39	33.11
	15	208.58	192.56	202.89	16.02	21.95
	20	206.23	188.78	200.95	17.45	17.59
PET⁃1%	5	217.57	209.04	213.71	8.53	43.11
	10	212.10	195.94	206.47	16.16	28.85
	15	209.19	191.56	202.63	17.63	22.37
	20	206.83	186.39	199.36	20.44	17.20

Tab.2. Non⁃isothermal crystallization parameters for PET and PET/ZnO nanocomposites

Fig.4. Relationship curves of temperature and relative crystallinity for PET and PET/ZnO nanocomposites

Fig.5. ln［-ln（1-Xt ）］⁃lnt relationship curves for PET and PET/ZnO nanocomposites at different φ

样品名称	φ/^oC·min^-1	n	lnZ_t	Z_c
PET	5	2.59	-14.96	0.05
	10	2.71	-13.51	0.26
	15	2.54	-11.81	0.46
	20	2.48	-11.21	0.57
PET/ZnO⁃0.02%	5	1.82	-9.89	0.14
	10	1.81	-8.83	0.41
	15	1.86	-8.36	0.57
	20	1.77	-7.80	0.68
PET/ZnO⁃0.5%	5	1.89	-7.60	0.22
	10	1.59	-5.78	0.56
	15	1.63	-5.16	0.71
	20	1.75	-5.14	0.77
PET/ZnO⁃1%	5	1.99	-7.71	0.21
	10	1.76	-6.11	0.54
	15	1.64	-5.32	0.70
	20	1.88	-5.60	0.75

Tab.3. Non⁃isothermal crystallization behavior parameters of PET and PET/ZnO nanocomposites

Fig.6. TG and DTG curves for PET/ZnO nanocomposites

样品	T_{10 %}/℃	T_{50 %}/℃	残炭率/%
PET	404.34	436.84	7.16
PET⁃0.5%	410.34	440.16	9.31
PET⁃1%	411.38	441.46	11.08

Tab.4. TG data of PET/ZnO nanocomposites

Fig.7. PLM of PET and PET/ZnO nanocomposites

References 16

1	Qu D， Cai J， Huang F， et al. High⁃performance optical PET analysis via non⁃isothermal crystallization kinetics［J］. Polymers， 2022， 14（15）： 3 044.
2	Wu Y H， Wang C C， Chen C Y. Nucleation effect of aliphatic polycarbonate in its blends with poly （ethylene terephthalate）［J］. Materials Chemistry and Physics， 2020， 12（2）： 248⁃256.
3	Zhao Z， Wu Y， Wang K， et al. Effect of the trifunctional chain extender on intrinsic viscosity， crystallization behavior， and mechanical properties of poly （ethylene terephthalate）［J］. ACS Omega， 2020， 5（30）： 19 247⁃19 254.
4	Dong S， Jia Y， Xu X， et al. Crystallization and properties of poly （ethylene terephthalate）/layered double hydroxide nanocomposites［J］. Journal of Colloid and Interface Science， 2019， 539： 54⁃64.
5	Onyishi H O， Oluah C K. Effect of stretch ratio on the induced crystallinity and mechanical properties of biaxially stretched PET［J］. Phase Transitions， 2020， 93（9）： 924⁃934.
6	Xia J， Luo X， Huang J， et al. Preparation of core/shell organic⁃inorganic hybrid polymer nanoparticles and their application to toughening poly （methyl methacrylate）［J］. RSC Advances， 2021， 11（54）： 34 036⁃34 047.
7	Beyou E， Bourgeat⁃Lami E. Organic⁃inorganic hybrid functional materials by nitroxide⁃mediated polymerization［J］. Progress in Polymer Science， 2021， 121： 434⁃465.
8	Saxena D， Jana K K， Soundararajan N， et al. Potency of nanolay on structural， mechanical and gas barrier properties of poly （ethylene terephthalate） Nanohybrid［J］. Journal of Polymer Research， 2020， 27： 1⁃9.
9	Hao T， Wang Y， Zhang M， et al. The addition of GO⁃SiO₂ to synthesis polyethylene terephthalate composite with enhanced crystalline and mechanical properties［J］. Journal of Materials Research and Technology， 2022， 18： 1 746⁃1 753.
10	Zhang X， Zhao S， Mohamed M G， et al. Crystallization behaviors of poly （ethylene terephthalate）（PET） with monosilane isobutyl⁃polyhedral oligomeric silsesquioxanes （POSS）［J］. Journal of Materials Science， 2020， 55：14 642⁃14 655.
11	郭又晟，陈延明，王立岩，等. 不同尺寸纳米氧化锌的制备及其抗菌性能研究［J］. 化学研究与应用， 2024， 36（1）：118⁃127.
	GUO Y S， CHEN Y M， WANG L Y，et al. Preparation of nano ZnO with different sizes and study of its antibacterial properties［J］. Chemical Research and Application， 2024， 36（1）：118⁃127.
12	苏成晓，王道波，张传辉，等.PA10T和PA10T/1012的非等温结晶动力学［J］.工程塑料应用， 2019， 47（11）：105⁃110+116.
	SU C X， WANG D B， ZHANG C H，et al. Non⁃isothermal crystallization kinetics of PA10T and PA10T/1012［J］.Engineering Plastics Application， 2019， 47（11）：105⁃110+116.
13	Chen S， Fu X， Jing Z， et al. Non⁃isothermal crystallization kinetics and rheological behaviors of PBT/PET blends： effects of PET property and nano⁃silica content［J］. Designed Monomers and Polymers， 2022， 25（1）：32⁃46.
14	Wang Z， Meng H， Shao R， et al. Non⁃isothermal crystallization kinetics of TPEE［J］. China Elastomerics， 2020， 30（1）：17⁃21.
15	Yin Y， Wang Y， Meng L. UIO-66 as nucleating agent on the crystallization behavior and properties of poly （ethylene terephthalate）［J］. Polymers， 2021， 13（14）： 2 266.
16	Hao T， Wang Y， Liu Z， et al. Emerging applications of silica nanoparticles as multifunctional modifiers for high performance polyester composites［J］. Nanomaterials， 2021， 11（11）： 2 810.

[1]	HU Lingxiao, JIANG Huihui. The relationship between the defoaming process after PET film bonding and pressure based on visual experiments [J]. China Plastics, 2024, 38(9): 82-87.
[2]	ZHANG Xinpeng, XU Jun, DU Xiyan, GUO Baohua. Study on modification and properties of starch esterified composite nano montmorillonite [J]. China Plastics, 2024, 38(8): 8-12.
[3]	LUO Guanqun, ZHAO Le, PAN Yaqi. Study on co⁃pyrolysis characteristics and kinetics of waste PE and PET plastics [J]. China Plastics, 2024, 38(3): 86-93.
[4]	MEI Yuan, LI Zhen, XU Lubo, MA Yiming. Study on properties of transparent toughened rPET/rPCTG alloys [J]. China Plastics, 2023, 37(9): 39-43.
[5]	CHEN Congbo, FAN Shuo, ZHANG Rui, LI Hui, LUO Siqi, REN Yijin. Non⁃isothermal crystallization kinetics and crystal structure of PVDF/PMMA blends [J]. China Plastics, 2022, 36(11): 59-66.
[6]	ZHOU Yang, ZHAO Shikun, ZHAO Biao, LIU Huipeng, LI Jie, CAO Zhiwen, PAN Kai. Synthesis and nonisothermal crystallization kinetic study of semi⁃aromatic polyamide 6T/6I/6 [J]. China Plastics, 2022, 36(10): 15-22.
[7]	LI Shuai, LONG Chunguang, MIN Jianxin, ZHOU Zhuo. Comparative Study on Limiting Pressure⁃velocity Test and Tribological Properties of Modified PET [J]. China Plastics, 2021, 35(9): 87-94.
[8]	ZHU Daofeng. Development and Application of PET/PE Alloy Sheet by Recycling Polyester [J]. China Plastics, 2021, 35(8): 100-104.
[9]	ZHOU Yingxin, WENG Yunxuan, ZHANG Caili, DIAO Xiaoqian, SONG Xinyu. Review of Recovery Technology and Standard Status of Poly（ethylene terephthalate） [J]. China Plastics, 2021, 35(8): 162-171.
[10]	LIU Shaoshuai, RAN Qidi, HUANG Jianwen, LI Jinlong, ZHANG Shiqi, ZHU Kai, GONG Xinchao, CAO Kun. Progress in modification of polyethylene terephthalate and its foaming materials [J]. China Plastics, 2021, 35(12): 137-144.
[11]	YIN Nianwei, CHEN Feng, FU Xuejun, CAO Shaoqiang. Effect of mass ratio of PET to PBT on surface of flame retardant reinforced PET/PBT alloy [J]. China Plastics, 2021, 35(12): 32-36.
[12]	KANG Wei, LIU Xijun, CAO Weiyan, WANG Yuwei, YAN Jie. Preparation and Performance of PMMA/DEAM⁃RGO Nanocomposites [J]. China Plastics, 2021, 35(1): 47-53.
[13]	Can JIANG, Peng CHEN, Shuo HAN, Shihong CHEN, Zhiyin YE, Xiangdong WANG. Effects of Surlyn on the Rheological and Crystallization Behaviors of PET and Its Composites [J]. China Plastics, 2020, 34(7): 44-48.
[14]	QIAO Wenyu, WANG Chenglei, HU Hao. Research on Modification of PETG Series Filament for FDM [J]. China Plastics, 2020, 34(10): 24-31.
[15]	KANG Wei, LIU Xijun, WANG Yuwei, SHEN Luyan, HAN Xianxin. Preparation of PMMA/Graphene Nanocomposites by Emulsion Polymerization [J]. China Plastics, 2019, 33(10): 11-16.