Desalination 240 (2009) 21 Á26

Controlled-release fertilizer encapsulated by starch/polyvinyl alcohol coating
Xiaozhao Hana,b, Sensen Chena, Xianguo Hub*

School of Chemical Engineering, Hefei University of Technology, 230009 Hefei, People's Republic of China School of Mechanical Engineering, Hefei University of Technology, 230009 Hefei, People's Republic of China Tel. +86 551 290 1359; Fax +86 551 290 2956; email:
Received 22 June 2007; revised 11 January 2008; accepted 18 January 2008


Abstract Encapsulation through polymeric membranes to control the release rate of fertilizers can reduce fertilizer’s losses and minimize environmental pollution. A biodegradable starch/polyvinyl alcohol (PVA) blend film for coating the soluble granular fertilizer has been prepared. The influence of the blending ratio of starch/PVA and the content of formaldehyde on the properties of the film has been investigated. The membrane (starch:PVA 0/7:3, crosslinked by formaldehyde content:10 wt%) structure was observed by X-ray diffraction (XRD), Fourier transform infrared absorption spectra (FTIR), and atomic force microscopy (AFM). The XRD results shows that the crystal structure of PVA was changed after being crosslinked with starch, whose vice-bond was broken and crystal was destroyed. The FTIR explores the starch was linked with PVA by chemical binding the crosslinking reaction results in an improvement of compatibility of the starch/PVA blend films. The AFM results show that the films’ surface became level and smooth due to the crosslinking reaction with the application of formaldehyde. The starch/PVA blend films could biodegrade in the soil environment. Keywords: Starch; Polyvinyl alcohol; Film; Crosslinking; Controlled-release fertilizers

1. Introduction Fertilizers are one of the most important products of the agrochemical industry. They are added to the soil to release nutrients necessary for
*Corresponding author.

plant growth [1]. However, the potential hazards of fertilizers to the environment have results in stringent limitation to their use. About half of the applied fertilizers, depending on the method of application and soil condition, is lost to the environment, which results in the contamination of water [2,3]. Use of conventional fertilizers

Presented at the Third Membrane Science and Technology Conference of Visegrad Countries (PERMEA), Siofok, Hungary, 2–6 September 2007.
0011-9164/09/$– See front matter # 2009 Elsevier B.V. All rights reserved. doi: 10.1016/j.desal.0000.00.000

The type of coating is responsible for the mechanism of release elements from encapsulated fertilizers [6]. the mixture was removed from the heat. Experimentals 2. The volume was maintained by adding water. lower frequency of application in accordance with normal crop requirement.22 X.2. 2. the contents of formaldehyde in the membrane-forming solution on the membrane properties. Preparation of starch/polyvinyl alcohol blend films Starch/PVA blend films were produced as follows.1. Water absorbency Exactly weighed blend films were immersed in distilled water for 3 h until sufficiently swollen. The coating materials used should be inexpensive and exhibit a good coating property.5]. These fertilizers can be physically prepared from the granules of the soluble fertilizers by coating them with materials. increased efficiency of the fertilizer. and the solution was distributed into a leveled glass-plate mold. PVA. Then remove excess water and weigh the swollen films to calculate the absorbency. butanol was used to avoid frothing. which blended with the synthetic polymer polyvinyl alcohol (PVA) has been studied as a potential biodegradable polymer. we prepared the biodegradable starch/PVA blend films for CRF through crosslinking and we investigated the films’ structure and the influences of the blending ratio of starch and PVA. or in the surrounding environment [4]. The mechanical properties and biodegradability of starch/PVA blend films have been reported by researchers [7. minimized potential negative effects associated with over dosage. the foam was skimmed off. When completely suspended the temperature of the mixture was slowly raised to 808C maintaining stirring. Starch is one of the most abundant polysaccharides polymer. and a little glycerin were mixed at various ratios (PVA content is from 10Á50 wt%) and the mixture was slowly added to distilled water at room temperature under continuous stirring. formaldehyde of 0Á20 wt% was then added to the mixture and stirring was maintained for 3 h to completely gelatinize the starch. Soluble starch (Shantou Xilong Chemical Factory. such as decreased rate of removal of the fertilizers from the soil by rain or irrigation water. and reduced toxicity [4. After raising the temperature to 958C. In this study. China) was pre-dried in the vacuum oven at 608C for 10 h. In addition. Ltd. Materials All the reagents used were of analytical purity. which reduce their dissolution rate. 2. China) had a degree of hydrolysis between 99. And then. which could lead to crop damage.0 and 99.8%. / Desalination 240 (2009) 21 Á26 may lead to concentration levels that are too high for effective action. Films were cast and stored in polyethylene bags before use in further studies. PVA (Sinopharm Chemical Reagent Co. sustained supply or minerals for a prolonged time. Han et al. CRF demonstrate many advantages over the conventional type. One method of reducing nutrient losses involves the use of controlled-release fertilizers (CRF). they should undergo testing for degradation in soil which might form any toxic substance that could affect the crop. the films were allowed to dry in a hot-air oven at 608C for 8 h and dried starch/PVA films were removed from the mold.8]. The calculated amounts of starch.3. A high concentration may produce undesirable side effects either in the target area. 2. After drying the solution at room temperature. .

respectively. respectively [10]. CNH4 0 7500 mg/L) sealed by the selected films. Cups were stored in a conditional room (258C and 100% RH) for 24 h and variation of water weight was recorded. and S 02.1. Water absorbency. Variations in film morphology and disintegration time were recorded. Water permeability Water permeability was measured using 6-cm diameter permeability cups containing silica gel sealed by the selected films. Water absorbency. 1 shows that the water absorbency.0. 1. Dm is the increasing weight of silica gel (g). Results and discussion 3.X. h–1) + NH4 permeability (mg/cm2 . Atomic force microscopy (AFM) images were obtained using a Digital Instruments Dimension 3100 AFM with a nanoscope a controller.4. tS 550 ' where NP is the NH4 permeability (mg/L m2 ' À1 h ). Fourier transform infrared absorption spectra (FTIR) was used to determine the bonding introduced by crosslinking between starch and PVA polymer chains.6. 2. ' water permeability. / / / 2. the ratio of the weight of the swollen film to the dried film [9].2. and NH4 permeability of blend films as a function of PVA content. NH4 permeability ' NH4 permeability was measured using 6-cm diameter permeability cups containing NH4SO4 ' solution (50 mL. / /  2. and  NH4 permeability Fig. Biodegradability Films were cut into small squares (3)3 cm). Chemical structure X-ray diffraction (XRD) (Bruker D8 Advanced diffractometer) was used to detect the crystallinity Absorbency (%) NP ¼ C water permeability + NH4 permeability absorbency 600 .5. 2.826)10(3 m2. Han et al. t02 h. / Desalination 240 (2009) 21 Á26 23 i. / where WP is the water permeability (g/m2 hÀ1 ).e. DC is the NH4 concentration in distilled water.7. the films were recorded on a Nexus470 FTIR spectrophotometer. The NH4 permeability is calculated by the formula / 3. The two dimensional images were converted to three dimensional images and a roughness analysis was done using WSxM Image Browser software v. Cups were put upwards toward beakers containing 200 ml distilled water ' for 2 h (258C and 100% RH). h–1) 20 16 12 500 8 450 4 400 0 10 20 30 40 50 PVA content (%) ' Fig. and NH4 permeability of Water permeability (g/m2 . NH4 concentration in distilled water was measured by Kjeldahl ' method. water permeability.826)10(3 m2. t is 24 h and S02. water permeability. The water permeability is calculated by the formula WP ¼ Dm tS of starch/PVA blend films. Each specimen was weighed and placed in agricultural soil in a pot. The pots were exposed to ambient conditions for 50 days.

2 shows those of starch/PVA blend films crosslinked by formaldehyde which shows that the water absorbency of films decreased as the increase of formaldehyde due to the crosslinking reaction. 2. / 3. So it could be confirmed that the water absorbency of the blend films decreased with the application of formaldehyde. the application of formaldehyde led intermolecular and intramolecular linkage of ÁOH between starch and PVA molecules and therefore the hydrophilic groups were reduced. When forming the film. from which we can see that the water absorbency. 3. Fig. Fourier transform infrared absorption spectra The FTIR spectra of starch and PVA were studied and compared with the spectra of the . and NH4 permeability of blend films as a function of formaldehyde content (starch:PVA0/ 7:3). Fig. PVA has a diffraction peak at 2u = 208. meanwhile the decrease of starch may affect the compatibility of the films. crystallinity. ' NH4 permeability rate [11]. respectively. which increased the water.3. Han et al. h–1) X. thus lessened PVA crystallinity indicates strong action present between starch and PVA polymer chains after crosslinking [13]. However. PVA has more ÁOH than starch which can increase the polarity. and (c) blend film (starch:PVA0/ 7:3) crosslinked with formaldehyde content (10 wt%). 3 shows XRD patterns of starch. Generally. (b) PVA. the interface bonding formed between starch and PVA may result in a decrease in the number of hydrogen bonds. ' and NH4 permeability of starch/PVA blend films increased along with PVA content. whose vice-bond was broken and the crystal was destroyed. PVA. Fig. XRD patterns of (a) starch. water permeability. and is characteristic for an orthorhombic lattice [12]. the gap between molecules exist introduced by crosslinking reaction. water permeability. And the ' water. and blend film (starch:PVA0 7:3) crosslinked with formaldehyde content 10 wt%. when the formaldehyde content is lower (below 10 wt%).24 Water permeability (g /m2 .2. h–1) + NH4 permeability (mg /cm2 . due to hydrogen bondings between the hydroxyl groups exist. indicating that the crystal structure was changed after being crosslinked with starch. 3. PVA is a semicrystalline polymer in which high physical interactions present between the polymer chains. starch/PVA blend films. Starch has a number of well resolved peaks overlapping an amorphous hump. X-ray diffraction Fig. 3(c) shows that the crystallinity changed after mixing. respectively. / Desalination 240 (2009) 21 Á26 + NH4 permeability 480 water permeability absorbency 16 12 (a) Absorbency (%) Relative intensity 450 420 8 390 4 360 0 5 10 15 Formaldehyde content (%) 20 (b) (c) 10 20 30 2 Theta (deg) 40 50 ' Fig. NH4 permeability also decreased with formaldehyde content (when it is above 10 wt%) because of the decreasing affinity between film and water molecules resulting from the crosslinking reaction between starch and PVA by formaldehyde. Water absorbency. The crystallinity of PVA decreased. and hydrophilicity of starch/PVA blend films.

the intramolecular hydrogel (1646. (b) the crystallinity-dependent 1147 cmÀ1 peak of PVA weakened.62 cmÀ1 represent CÁC stretching. and (c) blend films (starch:PVA 0/ 7:3) crosslinked with formaldehyde content (10 wt%). For PVA. which have been shown to be sensitive to the degree of crystallinity in PVA.5. So it may be deduced from these results that the starch was linked with PVA by chemical binding introduced .26 cmÀ1 ) in the granular starch [14]. and (c) the absorption peak of 922. These results suggest that the surface of starch/PVA blend films became level and smooth due to the crosslinking reaction with the application of formaldehyde. Fig. The FTIR spectra shows the following three sets of changes in the film: (a) the peak at 3300Á 3400 cmÀ1 of absorption bands weakened. 4. This kind of linkage has great effect on the improvement of compatibility. In Fig. a broad band at 3400Á3100 cmÀ1 due to OÁH stretching vibration and another band at 2936. 5 shows the three-dimensional images of starch/PVA blend films. IR spectra of (a) PVA. 5.87 cmÀ1 ). The weight losses were probably underestimated due to soil and debris adhered to the film surface.96 cmÀ1 assigned as CÁH stretching vibration were observed. 6. when these kind of films were applied [16. Biodegradability After 50 days of exposure in soil. by formaldehyde. Conclusion A biodegradable starch/PVA blend film for coating the soluble granular fertilizer has been prepared. (b) starch. The absorption peaks of 922. 4b shows the presence of ÁOH stretching vibration (3426. The weakness. Atomic force microscopy Fig. Fig. and NH4 permeability of the films starch/PVA blend film.17]. The water absorbency. 3.34 nm. specimens appeared brittle and fragile and diminished in size indicating the natural biodegradation of these films in the soil environment.62 cmÀ1 of PVA disappeared and the peak of 854 cmÀ1 shifted. AFM images of starch/PVA blend films (starch: PVA 0/ 7:3) crosslinked with formaldehyde content (10 wt%).8 cmÀ1 . water perme' ability. The controlled-release fertilizers with a better controlled diffusion performance could be prepared.4. The 1200Á1100 cmÀ1 region contains a number of modes. it could be observed that the ultimate weight loss exceeded 50%. Han et al.X.25 cmÀ1 ) and ÁCH2OH stretching vibration (1260 cmÀ1 ) as well as CÁOÁC ring vibration (928. and shift of the characteristic absorption bands may result from the interaction of different ÁOH groups in the starch and PVA molecular chains. / Desalination 240 (2009) 21 Á26 25 (a) Transmittance (%) (b) (c) 500 1000 1500 2000 2500 (cm–1) 3000 3500 Wavenumber Fig. disappearance. The peak at 1147 cmÀ1 is crystallinity-dependent [15]. The amplitude parameters analysis shows that the roughness average is only 1. 858. 3. 4.

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