Isothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer

doi:10.19894/j.issn.1000-0518.250015

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (9): 1221-1232.DOI: 10.19894/j.issn.1000-0518.250015

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Isothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer

Long ZHOU, Yu-Jing TANG(), Yi-Jing JIA, Xiao-Min LI, Ying-Nan DENG, Si-Jia WEI

Sinopec Beijing Research Institute of Chemical Industry，Beijing 100013，China

Received:2025-01-07 Accepted:2025-07-17 Published:2025-09-01 Online:2025-09-28
Contact: Yu-Jing TANG
About author:tangyj.bjhy@sinopec.com
Supported by:
SINOPEC Project(222101)

Abstract

Abstract:

The isothermal crystallization kinetics and thermodynamics of three ethylene vinyl alcohol copolymers （EVOH） with different ethylene content （molar percent 32%， 38% and 44%） were studied by differential scanning calorimetry （DSC）. The extrapolation curves of the dependence relationship between linear growth rate and crystallization temperature were obtained according to H-L theory. The results showed that with the increase of ethylene content， the equilibrium melting point of EVOHs decreased to 219.6， 218.7 and 216.8 ℃， respectively. The three EVOHs showed mixed growth characteristics of two-dimensional and three-dimensional in the primary crystallization， and one-dimensional growth in the secondary crystallization. The calculation of the fold surface free energy showed that ethylene segment has a blocking effect on the molecular chain folding of EVOHs. The crystallization rate of EVOHs slowed down with the increase of ethylene content under low subcooling condition. It was predicted that the crystallization rate of three different ethylene contents EVOHs reversed at about 135 ℃， and the fastest crystallization rate was found at 112， 104 and 101 ℃， respectively.

Key words: Ethylene vinyl alcohol copolymer, Equilibrium melting point, Isothermal crystallization kinetics

CLC Number:

O631

Long ZHOU, Yu-Jing TANG, Yi-Jing JIA, Xiao-Min LI, Ying-Nan DENG, Si-Jia WEI. Isothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer[J]. Chinese Journal of Applied Chemistry, 2025, 42(9): 1221-1232.

Figures/Tables 14

Fig.1 Time-temperature thermal program for isothermal crystallization experiments

Table 1 Thermodynamic information of F171B， H171B and E105B

Sample	T_m/℃	T_c/℃	T_g/℃	ΔH_m/（J·g^-1）	ΔH_c/（J·g^-1）	X_c/%
F171B	182.31	157.48	60.30	69.80	65.35	44.23
H171B	172.05	150.52	56.10	66.55	62.22	42.17
E105B	168.29	148.50	54.53	63.13	60.29	40.00

Fig.2 Melting DSC curves after cooling at different rates for F171B

Fig.3 DSC curves of EVOH samples （A）F171B，（B）H171B，（C）E105B for secondary heating； D. Equilibrium melting temperatures of F171B （219.6 ℃）， H171B （218.7 ℃） and E105B （216.8 ℃）

Fig.4 Heat flow curve of isothermal crystallization and relative crystallinity of 3 EVOH samples

Table 2 Theoretical values of Avrami index for different nucleation and growth mechanisms［27］

Crystal growth pattern	Heterogeneous nucleation	Homogeneous nucleation
One-dimensional growth （acicular crystal）	1	2
Two-dimensional growth （lamellar crystal）	2	3
Three-dimensional growth （spherocrystal）	3	4

Fig.5 Avrami analysis of the （A） F171B，（B） H171B and （C） E105B for X（t） between 3% and 100%；（D） Super cooling degree dependent of t1/2 for F171B， H171B and E105B

Table 3 Crystallization kinetics parameters of F171B， H171B and E105B

Sample	T_iso/℃	Primary crystallization		Secondary crystallization		t_1/2/min
Sample	T_iso/℃	n₁	K₁/min^-1	n₂	K₂/min^-1	t_1/2/min
F171B	164	2.56	0.046	1.22	0.383	2.88
	165	2.46	0.023	1.18	0.213	4.17
	166	2.63	0.004	1.16	0.098	7.98
	167	2.33	0.003	1.21	0.044	12.20
H171B	158	2.70	0.105	1.10	0.318	2.53
	159	2.54	0.043	1.12	0.186	3.75
	160	2.71	0.011	1.19	0.083	6.90
	161	2.46	0.003	1.05	0.054	12.40
E105B	155	2.58	0.208	1.09	0.431	1.90
	156	2.72	0.064	1.09	0.245	3.05
	157	2.53	0.025	0.98	0.178	4.95
	158	2.34	0.007	1.17	0.047	10.25

Fig 6 （1/n）ln K~1/Tiso curve of F171B， H171B and E105B

Fig.7 3 crystal growth modes： A. Regime Ⅰ， B. Regime Ⅱ， C. Regime Ⅲ， where the shaded part represents the growing surface and the white square represents the folded chain stem cross section

Fig.8 The H-L theoretical fit for F171B， H171B and E105B

Table 4 Calculated value of lateral and fold surface free energy for F171B， H171B and E105B

Sample	K_g/K²	G₀/min^-1	σ/（J·m^-2）	σ_F/（J·m^-2）
F171B	7.29×10⁵	7.19×10¹⁵	0.013	0.313
H171B	9.45×10⁵	9.51×10¹⁸	0.013	0.405
E105B	9.92×10⁵	6.32×10¹⁹	0.012	0.426

Fig.9 Effect of ethylene content on EVOH crystallization. The blue balls represent VA repeating unit of EVOH， and the gray balls represent ET repeating unit. The crystalline of EVOH is represented by light orange areas， and light gray areas are amorphous

Fig.10 Plot of extrapolated half-crystallization time for F171B， H171B and E105B

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Isothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer

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