Scientia Agricultura Sinica ›› 2022, Vol. 55 ›› Issue (20): 3970-3982.doi: 10.3864/j.issn.0578-1752.2022.20.009

• SOIL & FERTILIZER·WATER-SAVING IRRIGATION·AGROECOLOGY & ENVIRONMENT • Previous Articles     Next Articles

Preparation and Properties of Bionic Modified Water-Based Polymer Coated Urea

CHEN ChunYu(),CHEN SongLing,HAN YanYu,REN LiJun,ZOU HongTao(),ZHANG YunLong   

  1. College of Land and Environment, Shenyang Agricultural University/Key Laboratory of Arable Land Conservation (Northeast China), Ministry of Agriculture and Rural Affairs/National Engineering Laboratory for Efficient Utilization of Soil and Fertilizer Resources, Shenyang 110866
  • Received:2021-08-24 Accepted:2021-11-09 Online:2022-10-16 Published:2022-10-24
  • Contact: HongTao ZOU E-mail:13504929762@163.com;zouhongtao2001@163.com

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Abstract:

【Objective】The water-based polymer material is widely used in slow-release fertilizers due to its degradability, non-toxicity and good film-forming properties, but due to its poor water resistance, resulting in poor slow-release effect of the prepared coated fertilizer. In order to improve its water resistance ability, according to the principle of bionics, the nano silica and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane were used for hydrophobic modification, the optimal modification ratio and mechanism were determined, and then the environmentally friendly coated urea with better slow-release effect was prepared. 【Method】 This experiment used a three-factor three-level L9 (33) orthogonal design to explore the content of chitosan (0.5%, 1.0%, and 1.5%), starch content (0.5%, 1.0%, and 1.5%) and polyvinyl alcohol (PVA) content ( 2%, 3%, and 4%) on the performance of water-based polymer films, the optimal ratio with better hydrophobic effect was screened through water absorption and range analysis. Furthermore, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, and 3.0% of nano silica was add to the preferred coating materials for hydrophobic modification, respectively. The optimal amount of nano silica was confirmed by measuring the water absorption and permeability of the nano-modified water-based polymer films. Subsequently, the preferred nano-modified water-based polymer film was placed in the nhexane solution containing 0.5%, 1.0%, 1.5%, and 2.0% 1H,1H,2H,2H-perfluorodecyltrimethoxysilane for self-assembly modification, and then the effect of assembly concentration on the properties of films was explored. The modification effect was clarified by the changes of the film's hydrophobicity and permeability, and the hydrophobic modification mechanism was explored through the infrared spectrum characteristics and surface microstructure changes of the films before and after modification. The nutrient release experiments in soil were conducted to explore the nutrient release characters of the biomimetic modified water-based copolymer coated urea. The results of the nutrient release experiments in soil were used to investigate the sustained nutrient release period of nano-modified and biomimetic modified water-based copolymer-coated urea.【Result】 When the content of chitosan was 0.5%, the content of starch was 1.5%, and the content of PVA was 4.0%, the water absorption of the prepared water-based polymer film was the lowest, which was 42.50%. Compared with water-based polymers, the water absorption rates of nano-silica modified water-based copolymer, nano-silica and FAS dual-modified water-based copolymer membrane materials were reduced by 38.54% and 55.98%, respectively, the water permeability were reduced by 36.14% and 60.98%, respectively, and the NH4+ permeability were reduced by 24.14% and 44.58%, respectively. Infrared spectroscopy results showed that the amount of -OH in the nano-silica modified water-based copolymer membrane material was reduced, and Si-O-Si swing vibration and anti-symmetric stretching vibration were observed. The water after the double modification of nano-silica and FAS C-F bonds were observed on the surface of the base copolymer material. The scanning electron microscopy and energy spectrum analysis results showed that Si element appeared on the surface of nano-silica modified water-based copolymer membrane material, and F element appeared on the surface of nano-silica and FAS dual-modified water-based copolymer membrane material and observed a rough surface structure, the water contact angles were increased from 62.5º to 118.6º, and then the coating material could slow down the release effect. In addition, the results of soil culture experiments showed that the control release period of nutrients for nano-silica modified water-based copolymer-coated urea (NWCU), nano-silica and FAS dual-modified water-based copolymer-coated urea (SNWCU) was significantly prolonged. The control release period of nano-silica and FAS dual-modified water-based copolymer-coated urea was increased to about 28 days compared with those of WCU about 10 days. 【Conclusion】 According to the principle of biomimetics, the combined modification with nano-silica and FAS could significantly improve the water resistance and permeability of water-based polymer films, which the prepared biomimetic modified water-based copolymer coated nitrogen fertilizer had a good slow-release effect.

Key words: water-based copolymer, hydrophobic modification, microstructure characteristics, infrared spectroscopy characteristics, nutrient release characteristics

Table 1

The ratio of water based polymer coatings"

编号
Number		 壳聚糖
Chitosan (g)		 淀粉
Starch (g)		 聚乙烯醇
PVA (g)		 醋酸
Acetic acid (g)		 水
Water (g)		 戊二醛
Glutaral (g)
W1 0.5 0.5 2.0 1.0 95.9 0.1
W2 0.5 1.0 3.0 1.0 94.4 0.1
W3 0.5 1.5 4.0 1.0 92.9 0.1
W4 1.0 0.5 3.0 1.0 94.4 0.1
W5 1.0 10 4.0 1.0 92.9 0.1
W6 1.0 1.5 2.0 1.0 94.4 0.1
W7 1.5 0.5 4.0 1.0 92.9 0.1
W8 1.5 1.0 2.0 1.0 94.4 0.1
W9 1.5 1.5 3.0 1.0 92.9 0.1

Table 2

The water adsorption capacity of water-based copolymer films"

编号
Number		 壳聚糖Chitosan
(%)		 淀粉
Starch
(%)		 PVA
(%)		 吸水率
Water absorbency
(%)
W1 0.5 0.5 2.0 70.47c
W2 0.5 1.0 3.0 56.80c
W3 0.5 1.5 4.0 42.50d
W4 1.0 0.5 3.0 92.70ab
W5 1.0 1.0 4.0 68.06c
W6 1.0 1.5 2.0 60.25c
W7 1.5 0.5 4.0 93.92ab
W8 1.5 1.0 2.0 86.58b
W9 1.5 1.5 3.0 105.72a

Table 3

The range analysis for the water absorbency of water- based polymer films"

项目Item A B C
k1 56.59 85.70 72.43
k2 73.67 70.48 85.07
k3 95.40 69.49 68.16
R 38.81 15.21 12.64

Fig. 1

Water absorption rate of nano-modified water-based polymer films Different small letters above the bars indicate significant difference among treatments at 0.05 level. The same as below"

Fig. 2

The water permeability of nano-modified water-based polymer films"

Fig. 3

Water absorption rate of biomimetic modified water- based polymer films"

Fig. 4

Permeability and water absorption of biomimetic modified water- based polymer films"

Fig. 5

FTIR spectra of biomimetic modified water-based polymer films"

Fig. 6

Microstructure features and water contact angles of biomimetic modified water-based polymer films A1, A2 and A3 showed the surface of W3, NW6 and SNW3 (1 000×), respectively;B1, B2 and B3 showed the surface of W3, NW6 and SNW3 (50 000×)"

Fig. 7

EDX spectra and scanning site distribution of biomimetic modified water-based polymer surface A, B, C showed the EDX spectra of W3, NW6 and SNW3"

Fig. 8

Nutrient release characteristics of different types of modified water-based polymer coated urea in soil"

Fig. 9

Nutrient release characteristics of biomimetic modified water-based polymer coated urea under different soil water content (soil field water holding capacity 40%, 60%, and 80%)"

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[1] SONG Yuan-Yuan, CAO Ming, FAN Xiao-Lin. Nutrient Release Characteristics of Controlled Release Urea Coated by Vegetable Oil in the Soil at Four Stages of Banana Growing [J]. Scientia Agricultura Sinica, 2013, 46(1): 80-88.
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