Granular urea‐formaldehyde slow‐release fertilizer with superabsorbent and moisture preservation

To improve the utilization of fertilizer and water resource at the same time, a new type of slow‐release fertilizer with superabsorbent and moisture preservation was developed, with the combination of slow‐release technique and superabsorbent polymers. The coatings were formed by the inverse phase polymerization technique. The element analysis results showed that the product contained 22.58% nitrogen element, and the water absorbency of the product was 94 times its own weight if it was allowed to swell in tap water at room temperature for 2 h. The results of the slow‐release behavior of N and the water absorbency and retention properties in soil showed that the product not only had good slow‐release property but also had excellent water absorbency and water retention capacity, which was a significant advantage over the normal slow‐release or controlled‐release fertilizers. The effects of the amount of initiator, crosslinker, reaction time, and the degree of neutralization of acrylic acid on water absorbency were investigated and optimized. At the same, a rather new and simple method was used to make homogeneous urea‐formaldehyde granules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3230–3235, 2006     

Preparation of poly(acrylic acid‐co‐acrylamide)/kaolin and release kinetics of urea from it

A series of poly(acrylic acid‐co‐acrylamide)/kaolin [poly(AA‐co‐Am)/kaolin] composites were prepared by aqueous solution copolymerization of partially neutralized acrylic acid and acrylamide in the presence of kaolin nanopowder, which was synthesized to act as a release carrier of urea fertilizer. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the effect of urea concentration on the swelling was investigated. Furthermore, the effects of the contents of crosslinker, kaolin, and acrylamide, the neutralization degree of acrylic acid, and temperature, pH, and ionic strength of release medium on water absorbency and diffusion coefficient of urea release from poly(AA‐co‐Am)/kaolin were studied systematically. It was found that urea loading percentage could be adjusted by urea concentration of swelling medium, and urea diffusion coefficient could be regulated through the contents of crosslinker, kaolin, and acrylamide, and the neutralization degree of acrylic acid. Additionally, temperature and ionic strength of release medium may also affect the urea release process. The conclusions obtained could provide theoretical basis for urea diffusion behavior in superabsorbent used in agriculture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis,swelling behaviors,and slow‐release characteristics of a guar gum‐g‐poly(sodium acrylate)/sodium humate superabsorbent

Superabsorbents used in agricultural and ecological projects with low‐cost, slow‐release fertilizers and environmentally friendly characteristics have been extensively studied. The use of a natural polymer as the matrix and then further polymerization with some functional material has become the preferred method. In this work, with natural guar gum (GG), partially neutralized acrylic acid, and sodium humate (SH) as the raw materials, ammonium persulfate as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker, GG‐g‐poly(sodium acrylate) (PNaA)/SH superabsorbents were synthesized through a solution polymerization reaction and were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The effects of the SH content and MBA concentration on the water absorbency were investigated. The results showed that the introduction of SH into the GG‐g‐PNaA system could improve the water absorbency, swelling rate, pH‐resistant property, and reswelling capability, and the superabsorbent containing 15 wt % SH had the highest water absorbency of 532 g/g of sample in distilled water and 62 g/g of sample in a 0.9 wt % NaCl solution. The slow release in water and water retention in sandy soil tests revealed that the superabsorbent could act as a fertilizer as well as an effective water‐saving material for agricultural applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multilayer‐coated NPK compound fertilizer hydrogel with controlled nutrient release and water absorbency

A novel trilayered controlled‐release nitrogen, phosphorous, and potassium (NPK) fertilizer hydrogel was prepared by dipping the NPK fertilizer granules sequentially in 7% w v^?1 poly(vinyl alcohol) (PVA) and 2% w v^?1 chitosan (CS) solutions and then cross‐linking the CS layer (cross‐CS) via glutaraldehyde vapor deposition. Different NPK fertilizer hydrogels were then synthesized by inverse suspension polymerization of the dried PVA/cross‐CS bilayer‐coated fertilizer granules in various molar ratios of acrylamide (AM) and acrylic acid (AA) monomers, and polymerization with varying molar ratios of ammonium persulfate, N,N,N′,N′‐tetramethylethylenediamine and N,N′‐methylenebisacrylamide (N‐MBA). The water dissolution time of the obtained PVA/cross‐CS/poly (AA‐co‐AM) trilayer‐coated NPK fertilizer hydrogel granules was prolonged, while the water absorbency increased with increasing AA contents, and decreased with increasing N‐MBA contents in the outer poly(AA‐co‐AM) coating. The optimal trilayer‐coated NPK fertilizer hydrogel obtained released 84 ± 18, 63 ± 12, and 36 ± 15% of the N, P, and K nutrients, respectively, after a 30‐day immersion in water. The release phenomena of the N, P, and K nutrients of the fertilizer hydrogel obeyed both the Korsmeyer‐Peppas and Ritger‐Peppas models with a pseudo‐Fickian diffusion mechanism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41249.     

Preparation and slow‐release property of a poly(acrylic acid)/attapulgite/sodium humate superabsorbent composite

A novel poly(acrylic acid)/attapulgite (APT)/sodium humate (SH) superabsorbent composite was synthesized through the graft copolymerization reaction of acrylic acid on APT micropowder and SH with N,N′‐methylene bisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. Various effects on the water absorbency, including the amounts of the crosslinker, initiator, APT, and SH, were investigated. The superabsorbent composite was characterized with Fourier transform infrared spectroscopy and scanning electron microscopy. The superabsorbent composite synthesized under optimal synthesis conditions with an APT concentration of 20% and an SH concentration of 20% exhibited absorption of 583 g of H₂O/g of sample and 63 g of H₂O/g of sample in distilled water and in a 0.9 wt % NaCl solution, respectively. The slow‐release property of SH from the superabsorbent composite into water was measured, and a test of the water retention of the superabsorbent composite in soil was also carried out experimentally with and without the superabsorbent composite. The results showed that the superabsorbent composite had not only good water retention but also an additional slow‐release property of SH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 37–45, 2007     

Synthesis and characterization of bio‐based PA/EP interpenetrating network polymer as coating material for controlled release fertilizers

A novel controlled release fertilizer was developed using interpenetrating polymer network (IPN) as the coating material. The IPN was successfully sprayed on the surface of the urea particles to form IPN‐coated fertilizers (IPNCU) for controlled nitrogen release. The IPN was synthesized by bio‐based polyamide (PA) from d ‐glucaric acid and epoxy (EP) through network interpenetrating. The chemical structure and microscopic morphology characteristics of IPN were examined by Fourier transform infrared spectroscopy, ¹H‐nuclear magnetic resonance, and scanning electron microscopy. The property of IPN with the different PA/EP mass ratios were investigated and compared with that of EP‐coated fertilizers (EPCU). The nutrient release behaviors of IPNCU in water and soil were detected. The results showed that the IPNCU with 5% PA content increased the nitrogen release longevity by 41 days, raised the water contact angle of surface by 23.9°, and then significantly slowed the nitrogen release rate of the IPNCU. The nutrient release mechanism of IPNCU was discussed in detail. This work indicated that the environment‐friendly IPN with superior controlled release properties could be especially useful in horticultural and agricultural applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46052.     

Preparation and properties of a degradable interpenetrating polymer networks based on starch with water retention,amelioration of soil,and slow release of nitrogen and phosphorus fertilizer

In this study, we aimed to develop a degradable nitrogen and phosphorus (NP) fertilizer with properties of slow release, water retention, and remediation of saline soil; the nitrogen and phosphorus was coated with starch/poly(acrylic acid‐co‐acrylamide) [poly(AA‐co‐AM)] superabsorbent (SAAmF) by reverse suspension radical copolymerization. The variable influences on the water absorbency were investigated and optimized. The results of the structure and morphology characterization of SAAmF show that poly(AA‐co‐AM) was grafted partly from the chain of starch, and the different contents of starch brought about a difference in the size of the three‐dimensional net hole of the coating polymer. The property of water retention, the behaviors of slow release of nutrient, and the degradation of the SAAmF were evaluated, respectively, and the results revealed that the water transpiration ratio of soil with SAAmF was lower by approximately 8 percentage points than that of the blank test, about 60% nutrient was released from SAAmF by the 30th day, and 32 wt % of SAAmF with a content of starch of 20% was degraded after 55 days. Moreover, a considerable decrease in the conductivity was observed, which revealed a sharp reduction in the concentration of residual ions for the soil mixed with SAAmF. It may be inferred from these that the product seems to be a promising vehicle for the management of soils, including saline soils. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Organic silicone‐modified transgenic soybean oil as bio‐based coating material for controlled‐release urea fertilizers

Novel bio‐based polyurethanes (PUs) were synthesized from transgenic soybean oil (TSBO) and then modified with hydroxyl‐terminated dimethyl silicone (HTMS) to coat urea prills for controlling nitrogen (N) release. Different kinds of coated ureas were prepared from these hydrophobic PUs. Physicochemical properties of the coatings were characterized in the laboratory. The N release characteristics of the PU‐coated ureas (PCUs) in water were determined at 25 °C. Experimental results showed that the presence of HTMS in the PUs reduced the coating porosity, increased the water‐contact angle of the coating material, and thus slowed the nutrient release from the PCUs. These results suggested that HTMS improved the structure and properties of coating materials for controlled release. These findings showed that bio‐based PUs derived from TSBOs made excellent coating material, particularly after HTMS modification, and thus may replace petroleum‐based PUs for controlled‐release fertilizers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44097.     

Effect of the anionic‐group/cationic‐group ratio on the swelling behavior and controlled release of agrochemicals of the amphoteric,superabsorbent polymer poly(acrylic acid‐co‐diallyldimethylammonium chloride)

A series of amphoteric, superabsorbent polymers [poly(acrylic acid‐co‐diallyldimethylammonium chloride)] with different molar ratios of anionic groups to cationic groups were prepared by solution polymerization to investigate their swelling behaviors and the controlled release of agrochemicals. Various factors, including the solution pH, the concentrations of different salt solutions, and the temperature, were studied. The dynamic parameters of hydrogels at different temperatures suggested that diffusion was Fickian at lower temperatures, whereas non‐Fickian diffusion prevailed at higher temperatures. A copolymer hydrogel with a low anionic‐group/cationic‐group ratio showed a higher swelling capacity in water and higher salt tolerance. Also, the anionic‐group/cationic‐group ratio was not the dominant factor in determining the water retention. A poly(acrylic acid‐co‐diallyldimethylammonium chloride) hydrogel could control the release of agrochemicals effectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 986–991, 2006     

Synthesis of a cellulose‐based hydrogel network: Characterization and study of urea fertilizer slow release

In the present study, we synthesized a low‐cost biodegradable hydrogel based on cellulose in order to perform controlled release of fertilizer. For this purpose, the cellulose was modified and crosslinked with urea. Then the prepared hydrogel underwent loading with the fertilizer in order to study the controlled release. Characterization of the samples was carried out by Fourier Transform Infrared (FT‐IR) spectroscopy, elemental analysis, thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM). The hydrogel showed a good swelling behavior in distilled water, tap water, and 0.9% NaCl solution. Besides, water holding and water retention behavior of the hydrogel was investigated. Finally, the release of fertilizer from the loaded hydrogel was studied and showed excellent controlled release. According to the results, this hydrogel can be employed as a suitable moisture‐holding additive in the soil for agricultural purposes. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42935.     

Synthesis and properties of a superabsorbent from an ultraviolet‐irradiated waste nameko mushroom substrate and poly(acrylic acid)

To better use the waste nameko mushroom substrate (WNMS) and prevent its pollution into the environment, a novel superabsorbent polymer was synthesized via the UV irradiation copolymerization of acrylic acid and WNMS in the presence of an initiator (dimethoxy‐2‐phenylacetophenone and ammonium persulfate) and crosslinker N,N′‐methylenebisacrylamide. The factors that had an influence on the water absorbency of the superabsorbent polymer were investigated and optimized. Under the optimized conditions, WNMS–poly(acrylic acid) was obtained. Its swelling behaviors, which followed the pseudo‐second‐order swelling kinetic model, were investigated in distilled water (1701 g/g) and a 0.9 wt % NaCl solution (388 g/g). The water absorbency was 1011 g/g in a 0.1 wt % urea solution and 80% amount of urea diffused into the gels. The urea diffusion followed a Fickian diffusion mechanism. Moreover, the product showed excellent water retention capabilities under the condition of high temperature or high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40471.     

Synthesis and characterization of starch‐g‐Poly(acrylic acid)/Organo‐Zeolite 4A superabsorbent composites with respect to their water‐holding capacities and nutrient‐release behavior

Novel superabsorbent composites were prepared using starch, acrylic acid, and organo‐zeolite 4A micropowder via aqueous solution graft copolymerization. The effects of organo‐zeolite 4A content on water absorbency were tested to determine the optimum conditions that ensure a high swelling ability. Under these conditions, the maximum swelling ability in distilled water was determined to be 511 g/g when the amount of organo‐zeolite 4A in the feed was 10 wt%. The prepared samples were characterized with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscope (SEM). The SEM characterization of the samples indicated that the superabsorbent composites had more pores and water than zeolite‐free superabsorbents. The swelling capacities in distilled water, various salt solutions, and aqueous urea were studied. The on–off switching behavior and the release of urea from the loaded starch‐g‐ poly(acrylic acid)/organo‐zeolite 4A were also determined. The results indicated that the novel composite was responsive to salts and exhibited on–off switching behavior, as evidenced by reversible swelling and de‐swelling. In addition, the slow nutrient release makes this material suitable for many potential applications in the fields of agriculture and horticulture. POLYM. COMPOS., 38:1838–1848, 2017. © 2015 Society of Plastics Engineers     

Characterization of p(AA‐co‐AM)/bent/urea and its swelling and slow release behavior in a simulative soil environment

In this work, a novel slow release fertilizer contained 14.98% nitrogen was prepared via free radical polymerization of acrylic acid, acrylamide, and bentonite in the presence of cross‐linker (N,N′‐methylenebis acrylamide), initiator (potassium persulfate), and nutrient source (urea). The samples were analyzed using a Fourier transform infrared spectrometer, X‐ray diffraction, Scanning electron microscopy, Thermogravimetric analysis, and Brunauer, Emmett and Teller analysis. Results showed that the swelling and release behaviors were strongly dependent on the type and concentration of salt solution added to the medium, pH levels of the solutions, and temperature. Moreover, the experimental data indicated that the addition of Bent not only improved water absorbency and water retention capacities but also controlled the release of nutrients. The release kinetic simulation analysis findings showed that the release of urea was predominated by a Case II release mechanism with skeleton erosion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43082.     

Synthesis and characterization of slow‐release nitrogen fertilizer with water absorbency: Based on poly(acrylic acid‐acrylic amide)/Na‐bentonite

A novel slow‐release nitrogen fertilizer with high‐water absorbency (SRNFWA) was prepared by cross‐linking poly (acrylic acid‐acrylic amide)/bentonite and urea. The synthesis conditions were studied systematically and optimized by using the response surface methodology (RSM). Meanwhile, the effects of the concentration of cross‐linker, initiator, bentonite, and degree of neutralization of acrylic acid on WA were investigated. The SRNFWA was characterized by Fourier transform infrared (FTIR) spectroscopy, elemental analysis, and scanning electron microscopy (SEM). The results of SEM showed the undulant and coarse surface, facilitated the permeation of nutrition into the polymeric network. We also investigated the slow release property and release mechanism of the nitrogen from the network structure, and the WA in different external solutions. The released characteristic of nitrogen was less than 15% by the third day and reached up to almost 75% after 30 days in distilled water. The WA was 700 g g^?1 and 150 g g^?1 in distilled water and 0.9 wt % NaCl solutions, respectively. These studies exhibited the excellent slow‐release property and WA capacity of this polymer in 0.9 wt % NaCl solution and could be quite effective in improving the utilization of fertilizer and its water retention capacity simultaneously. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Utilization of plant ash for the fabrication of novel superabsorbent composites with potassium‐release characteristics

Design and synthesis of the agricultural and ecological superabsorbent materials with cost‐efficient and fertilizer‐release characteristics has recently attracted considerable interests. In this work, the novel poly(sodium‐potassium acrylate‐co‐acrylamide)/plant ash (PNa‐KA‐co‐AM/PA) superabsorbent composites with potassium‐release characteristics were prepared using partially neutralized acrylic acid (Na‐KA), acrylamide (AM), and plant ash (PA) as raw materials, ammonium persulfate (APS) as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker. The structure, morphologies, and thermal stability of the composites were characterized by Fourier transform infrared spectrophotometer, scanning electron microscopy, and TGA techniques, respectively. The effects of MBA concentration and PA content on water absorbency were studied, and the swelling properties of the composites in saline solutions and various pHs solution as well as their potassium‐release capabilities were also evaluated. Results indicate that the composites exhibit better thermal stability, salt‐resistant performance, pH‐stability, and potassium‐release properties, and can act as a fertilizer and an effective water‐saving material for agricultural and ecological application. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Controlled release of nitrogen‐source fertilizers by natural‐oil‐based poly(urethane) coatings: The kinetic aspects of urea release

Urea is the most common source of nitrogen fertilizer, but it has serious disadvantages with respect to volatilization and leaching; these can be controlled by polymeric coatings on the granules. However, the effectiveness of this strategy depends on the formed polymer presenting good adhesion, reactivity with the urea surface, uniformity, and efficient release kinetics control. Therefore, in this study, we evaluated the release kinetics of urea coated by polyurethane produced from two oils (soybean and castor) by analyzing the influence of the thickness, coating stability, deposition interface, and total release time. The results demonstrate that castor oil produced superior materials, which achieved a total release time in water immersion of over 40 days with a total coating mass of less than 4% of the total mass. The good interface suggested that this material may produce coatings of good quality and long release times with minimum thickness, and this will maximize the total nitrogen present in the granule. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43790.     

Preparation and properties of a slow release NP compound fertilizer with superabsorbent and moisture preservation

A slow‐release NP compound fertilizer with superabsorbent and moisture preservation was prepared by carboxyl methyl starch, acrylic acid, ammonia, urea, diammonium phosphate, and so on. The effects of the amount of initiator, crosslinker, and the degree of neutralization of acrylic acid on water absorbency were investigated and optimized. The product was characterized by FTIR, ICP, and element analysis, and the results showed that the product contained 22.6% nitrogen element and 7.2% phosphor (shown by P₂O₅) element. Its water absorbency was about 85 (g · g^?1) times its own weight in tap water. We also investigated the water retention property of the product and the slow release behavior of N and P in the product. The results showed that the product had a good water retention capacity and slow release property. The mechanism of the release of N and P in water was also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2132–2138, 2005     

Poly(acrylamide‐co‐vinyl alcohol)—Superabsorbent materials reinforced by modified clay

A series of copolymeric superabsorbent materials comprising polyacrylamide (PAM), polyvinyl alcohol (PVA) reinforced with variable wt% of modified clay were prepared. The copolymer/clay composite was characterized by Fourier transformed infrared, transmission electron microscopy, and scanning electron microscopy. The water absorbencies of poly(acrylamide‐co‐vinyl alcohol)/clay composites were measured by calculating their percentage swelling ratio. The effects of copolymerization, type of clay, and clay content on the water absorbencies were studied. The swelling was measured in acidic, alkaline, and saline condition to ensure its versatility. The results indicated a remarkable increase in swelling ratio by incorporation of modified clay having higher hydrophilicity and optimum clay loading. The poly(acrylamide‐co‐vinyl alcohol)/clay composite hydrogel was found to have better re‐swelling ability and water retention capacity compared to the virgin copolymer. The substantial enhancement of swelling properties enables the superabsorbent poly(acrylamide‐co‐vinyl alcohol)/clay suitable for agricultural and horticultural application. POLYM. COMPOS., 34:1794–1800, 2013. © 2013 Society of Plastics Engineers     

Synthesis and properties of a novel superabsorbent polymer composite from microwave irradiated waste material cultured Auricularia auricula and poly (acrylic acid‐co‐acrylamide)

A novel superabsorbent polymer composite was successfully synthesized from waste material cultured Auricularia auricula (WMCAA) and poly (acrylic acid‐co‐acrylamide) (P(AA‐co‐AM)) using microwave irradiation. Optimal synthesis conditions were determined by investigating the water absorbency of the superabsorbent composite. The effects associated with weight ratios of WMCAA, acrylamide (AM) monomers, initiators, and acrylic acid (AA) crosslinkers, as well as the degree of neutralization of AA were examined. The maximum water absorbencies were found to be 1548 g/g (distilled water) and 72 g/g (0.9% NaCl solution). Fourier transform infrared spectroscopy (FTIR) was applied to determine the molecular structure of the superabsorbent composite, and scanning electron microscopy (SEM) was used to demonstrate the characteristic compact and porous structure of the material. Further studies conducted via transmission electron microscopy (TEM) revealed the formation of a novel interpenetrating polymer network structure. Thermogravimetry/differential thermal (TG/DTG) analysis demonstrated improved thermal stability in the composite material compared with WMCAA. Additionally, high water absorption rates observed in the polymer during the swelling process indicated first‐order kinetics. The water absorption and adsorption of the superabsorbent composite were studied in a variety of fertilizer solutions, revealing an indirect relationship between water absorbing ability and fertilizer concentration. Conversely, a direct relationship was observed between absorbed fertilizer and fertilizer concentration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3674–3681, 2013     

Preparation of starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite

A novel starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of starch, acrylamide (AM), and attapulgite micropowder using N.N‐methylene‐bisacrylamide (MBA) as a crosslinker and ammonium persulphate (APS) as an initiator in aqueous solution, followed by hydrolysis with sodium hydroxide. The effects on water absorbency, such as amount of crosslinker, initiator, attapulgite, weight ratio of acrylamide to starch in the feed, gelatinization conditions of starch and molar ratio of NaOH to acrylamide, and so forth, were investigated. These superabsorbent composites were characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The water absorbencies for these superabsorbent composites in water and saline solution were investigated, and water retention tests were carried out. Results obtained from this study showed that the water absorbency of superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibit absorption of 1317 g H₂O/g sample and 68 g H₂O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1351–1357, 2005