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ControlledReleaseFertilizersAndNanotechnologyTracesBiologyEssay
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One of the most significant problems of crop fertilization by ordinary fertilizers is nutrient loss to environment which causes lots
of environmental and human health problems besides decreasing the efficiency of crop nitrification. As a solution, controlled or
slow release fertilizers have been developed to overcome drawbacks of traditional fertilizers. In this review common types of CRFs
and some related concepts. Also, focusing on polymer coated CRFs, different preparation and different coating application
methods will be studied. In addition, some features of nanotechnology and nano-materials in preparation of controlled release
fertilizers in previous works will be reviewed.
Introduction
In general, plants must be supplied with nutrients during the whole vegetation period. In horticulture this is achieved by applying
quickly soluble fertilizer once to twice a week, for example. This kind of fertilizer application is very labour-intensive and requires
considerable specialist knowledge, so as to select the correct rate of application, appropriate time of application and correct
composition for the particular plants to ensure optimum plant production. With the use of slow or controlled release fertilizers
the full amount of nutrients necessary for the whole vegetation period can be applied at the time of planting or at the earliest
stages of plant growth, in the form of a nutrient pool Also, 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 [1].This kind of
environmental concerns of feeding crops with traditional fertilizers has led to developing Slow Release Fertilizers (SRFs) or
Controlled Release Fertilizers (CRFs). SRFs or CRFs are easy and safe to use. They reduce risk of incorrect fertilizer application.
Also, they are labour saving and minimize nutrient losses by leaching or fixation.
The idea of producing SRFs was developed since 1963 by encapsulation of fertilizers by waxes. After that, these products have
been commercialized. There are lots of SRF and CRF brands. Some of these products are Scotts Professional with key brands such
as Osmocote, Sierrablen and Osmoform. Aglukon and SunGro Company are also producing controlled release fertilizers.
Like lots of scientific fields, agriculture industry has been over shadowed by nanotechnology. Applications of nanotechnology in
agriculture includes agriculture crop improvement, nano-biotechnology analysis of gene expression and regulation soil
management, plant disease diagnostics, efficient pesticides and fertilizers, water management, bioprocessing, post harvest
technology, monitoring the identity and quality of agricultural produce and precision agriculture. Efficient pesticides and fertilizers
are recently being developed in terms of nano-composite based slow or controlled release fertilizers.Using nanoparticles as
reinforcing or cementing agent of polymer coatings and also as reservoir of fertilizers are features of nanoparticles which have
been used in preparing slow release fertilizers [2-4].
Fertilizers
Fertilizers are applied to soil to promote plant growth. They contain some beneficial nutrients including macronutrients and
micronutrients. Macronutrients are nitrogen, phosphorus, and potassium which are added to soil in quantities from 0.2% to 4.0%
(on a dry matter weight basis) and are more essential than micronutrients. Micronutrients are elements which are applied to soil
in much smaller amounts, ranging from 5 to 200 ppm, or less than 0.02% dry weigh. These elements could be boron (B), copper
(Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn)[5].
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The main synthetic or mineral fertilizers which are the sources of nitrogen (N), potassium(K), phosphate (P) are urea, ammonium
sulfate, ammonium phosphate, phosphate rock, potassium chloride, super phosphates, calcium ammonium nitrate, potassium
sulfate. Fertilizers could be in compound form (NP, PK, NPK).The most important drawback of synthetic fertilizer is their long term
sustainability. Also, they are more expensive in contrast to organic fertilizers [5].
In addition, fertilizers can be categorized into ordinary and controlled release fertilizers from release properties points of view.
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semi permeable polymer membrane. Water penetrates the coating and dissolves the core. Release rate can be controlled by
varying the composition and thickness of the coating. In addition, pressure builds up can cause cracks to form, from which
fertilizer passes into the soil [8].
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2.6.1. In situ
This method includes formation of fluid dispersion of the soluble fertilizer in a solvent and mixing the prepared solution with
monomers of a polymer coating. Polymerization will happen and depending on the method, granules or particles of fertilizers will
form.
Ni et al [42] have developed a double-coated urea fertilizer. For preparation of poly (N-vinyl-pyrrolidone) hydrogels containing
urea (PCU), the monomer and a solution of urea in N-vinyl-pyrrolidone were mixed together. The polymerization was carried out
at 65-C for 3 h. The resulting samples were vacuum-dried, milled, screened and stored. After that first coating was dried, sample
and some amounts of urea were mixed with sodium alginate (SA) solution. Mixed solution was then added drop wise into 5%
(w/w) CaCl2 aqueous solution and stirred constantly. The drops immediately turned into granules (about 4mm in diameter)
because the SA in the drop was crosslinked by Ca2+ at once. The granules were filtered and dried in oven at 70- C. Then the
granules were added to ethylcellulose - ethanol solution. Multiple ethylcellulose (EC) coatings were prepared by immersion of the
previously coated granules into the ethylcellulose solution repeatedly. Thus, EC-coated urea granules with different coating
thickness were obtained (Figure 1)
Fig 1. SEM images of the surface (a) and cross section (b) of prepared
CRF
Hanafi et al [43], have coated a compound fertilizer by polyvinyl chloride (PVC), polyacrylamide (PA), natural rubber (NR), and
polylactic acid (PLA) using in situ method. For encapsulation of compound fertilizer with polyacrylamide the granules were added
to the solution mixture of monomers. Then the polymerization reaction will start in existence of fertilizers. The thickness of the
coating layer on the compound fertilizer granules, determined by SEM(Fig.2), gave PVC compound coated fertilizer the highest
value of 3.04 lm, and the lowest was obtained by PA (2.04 m). Variation in the characteristics of the polymers would be utilized in
producing CR compound fertilizer that fit the requirements of growing plants.
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was stuck on the granules by means of epoxy dissolved in acetone. The adhesive was applied by spraying at regular time intervals.
The process was finished until compact and homogeneous coating formed on fertilizer granule. The coated granules were dried to
a constant mass at room temperature for 6 h. Then the CTS-coated NPK compound fertilizer granules were obtained. CTS-coated
fertilizer granules were dipped in water and then were immediately placed on PAADU powder and shaken. In this manner, PAADU
could adhere to the surface of CTS-coated NPK compound fertilizer and form the outer coating. The surface of the product was
crosslinked by spraying methanol solution of epoxy chloropropane and then dried in a 70 °C oven to obtain the final product
which is a double-coated slow-release fertilizer with superabsorbent and water-retention properties.
Hansen et al [26], encapsulate the granular fertilizer with the epoxy resin using spray method. In this research not coated fertilizer
was placed in a rotating drum and pre heated to 250° F. A rapid drying solution of copolymers dicyclopentadiene and a
modified vegetable oil were applied over fertilizer using spray in a thin stream of resin. Simultaneously hot air was passed
through drum. Next monomers of second resin including a mixture of epoxidized soybean oil and polyester curing agent were
applied over prepared granules. The solvent was a mixture of xylene and Cellosolve acetate.
Hansen et al [29] also have used the above mentioned method for encapsulation of fertilizer with polyurethane. First of all the
preheated fertilizer was coated by a synthetic drying oil. After drying the coating for a few minutes fertilizer were dusted by clay.
Then urethane solution in xylene and Cellosolve acetate was applied using spray.
2.6.3. Mixing
In this method granules are simply mixed with the coating at its melting point or with a solution of polymer in a suitable solvent.
Tomaszewska et al [48] used this method for coating the granular NPK fertilizer with polysulfone (PSF), cellulose acetate (CA) and
polyacrylonitrile (PAN). The coating solutions were prepared by the dissolution of the solid polymer in adequate solvent. The NPK
fertilizer was successively added to adequate polymer solution, and was covered by a thin layer of the solution. Subsequently,
granules were dropped into water, where the gelation process takes place. The coated granules were removed from the
precipitation bath and then dried to a constant mass. The multiple coatings were prepared by immersion of the single coated
fertilizer into adequate polymer solution, then into water and drying.
Hon [37] has prepared the coated granules by mixing method. After melting the thermoplastic polymer by heating, the cellulosic
additive has been added to melt resin. Then after allowing the temperature to drop, for avoiding the fertilizer damage, the
granules or powder fertilizer has been mixed with the prepared mixture using a Brabender Mixer.
Markusch et al [49] just has mixed the fertilizer pellets with at first, a diluted polyol and then with a diluted isocyantae to make a
polyurethane coating. Then the feretilizer were placed in oven for drying.
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destroying by soil microbe's activity. In polymer coatings or combination of different coatings release will happen by diffusion of
water through wall's porosities. In this case release rate can be controlled by the particle size of coated granules, thickness of
coating and permeability of coating surface.
Also, changing the chemical composition of fertilizer core and also the coating will change permeability of coating. This means that
even basic or acidic environment will change the permeability. In some researches when the coating has been starch-vinyl,
increasing size of encapsulated granules has led to slowing down the nutrient release [61,62].
There are some standard test methods for measurement of controlled release properties. According To European standard the
standard release time of N during 24 h should be 15%
of total core nutrient. Also, release rate for 15 day should be 75% of total nutrients. Also American and Japanese standards say
that the initial release shouldn't be more than 40% of total nutrient.
According to European standards for measuring the release rate encapsulated fertilizer should be immersed in pure water at 25
°C (room temperature) in incubated state [63, 64]. For example Detrick et all [33] have investigated the release behavior of
their product by immersion of 20 g of encapsulated granules for 8 h in water. After filtration of solid they dried the solid.
Evaporation of water was done at 100 °C for 8 hours. Also, Ma et all [21] placed 14 g of granules in wire mesh holder and
then placed it into a jar with 300 ml water at 23 °C and agitated it by an orbital shaker. Then, adequate water was taken for
elemental analysis. Locquenghien et al [30] for investigation the slow release effect of fertilizer extracted some amounts of
fertilizer continuously with water. For this purpose the granules were arranged in layer in a cylindrical vessel field with water.
Water was passed through this layer and its nitrogen content was analyzed.
Table 1
Interactions between clay minerals and organic compounds [66]
Mechanism
Mineral examples
Organic functional groups involved
Hydrophobic interactions (van der Waals)
Any clay with neutral sites (e.g., kaolinite, smectites)
Uncharged, non polar (e.g., aromatic, alkyl C)
Hydrogen bonding
Any clay with oxygen surfaces (e.g., kaolinite)
Amines, carbonyl, carboxyl, phenylhydroxyl, heterocycle N
Protonation
Alumino silicate edge sites, Fe and Al oxides, allophane, imogolite
Amines, heterocycle N, carbonyl, carboxylate,
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Ligand exchange
Aluminosilicate edge sites, Fe and Al oxides, allophane, imogolite
Carboxylate, Phenolate
Cation exchange (permanent charge sites)
Smectite, vermiculite, illite
Amines, ring NH, heterocyclic N
pH-dependent charge sites (anion exchange usually, cation exchange rarely)
Aluminosilicate edge sites, Fe and Al oxides, allophane, imogolite
Carboxylate for anion exchange, amines, ring NH, heterocyclic N for cation exchange
Cation bridging
Smectite, vermiculite, illite
Carboxylate, amines, carbonyl, alcoholic OH
Water bridging
Reviewing the literatures shows that intercalation of urea into clay d-spacing has been done by three methods including solution
method, mechano-chemical mixing and melt mixing method. The only published work about intercalation of urea into clay dspacing to provide controlled release fertilizer has used melt mixing method. In this research, intercalation of metal-urea
complexes has been done providing controlled release N containing fertilizer. The main reasons for using Mg (Urea) x instead of
pure urea are two barriers. One is decomposing urea at its melting temperature (132.7) and another is neutral structure of urea
which is not accommodated easily by anionic Na+ montmorillonite. Fig.4 is a schematic illustration of intercalated montmorillonite
and release process in this work.
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Liu et al [70] also prepared two kinds of nano-coating for providing controlled release fertilizer including kaolinite-polystyrene
nano-composite and a nano-structured polystyrene-starch coating. To prepare kaolinite nano-composite, polystyrene monomer
was mixed with kaolinite using ultrasonic technique. Nano- structured coating was prepared by semi-emulsification technique.
Barati [71] has used in situ method to prepare nano-composite based CRFs. In this work monomers including acrylonitrile and
carbohydrate in presence of initiator are mixed. Then inorganic nano powder will be dispersed in mixture and fertilizer nutrient
will be added. Nano powder could be bentonite,kaolinite, natural zeolite, talc, titanium dioxide. After adding crosslinking agent
(methylene bis-acrylamide) polymerization will occur and granules will form.
3. Conclusion
Among preparation methods used by scientist for developing polymer coated CRFs, spray method and mechanical mixing
methods seem more convenient especially because of instruments which could be accessible. Also, the review of researches
about the polymers, water absorbent coatings seems good choices for drought-prone areas because of water retention; not very
suitable for rainy areas like Malaysia. On the other hand, biodegradable coatings like ethylcellulose or starch containing polymers
are suitable choices because of environmental concerns and automatic degrading.
From current literature review, we can find out that published articles and patents using nano-technology features in preparing
controlled release fertilizers are very rare. Although there are lots of ideas and potential suggestion about using nano-particles
characteristics in CRF industry and you can find only a few published articles in this field. But using nanoparticles in other fields
like drug delivery [86-88], smart inhibitor release [89] would be a good idea to develop in CRF industry. High surface area of
nanoparticles is one of the useful properties of nanoparticles which can be used for carrying and reserving the fertilizers. Using
Urea as an intercalating agent for Clay particles is one of the more interesting areas have been carried out by researchers,
although, there are rare published any application of these modified nano-clays in CRFs.
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