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Fertilizer Research 22: 63-70, 1990.

1990 KluwerAcademic Publishers. Printed in the Netherlands.


An evaluation of urea-rubber matrices as slow-release fertilizers

Z.A. Hassan, S.D. Young, C. Hepburn* & R. Arizal
School of Agriculture, Nottingham University, Sutton Bonington, Loughborough, Leicestershire,
* Loughborough University of Technology, Loughborough, Leicestershire
Received 30 August; accepted in revised form 7 January 1990

Key words:

Fertilizer, slow-release, rubber matrix, urea, residual

The viability of a 'urea-rubber matrix' (URM) as a slow-release nitrogen fertilizer was assessed by field
trials and incubation studies. Encapsulation of urea in the rubber matrix apparently prevented the
inhibition of seed germination experienced at high temperatures (>20C) following high urea applications. The release of urea from URM increased with temperature and was well described by a diffusion
model which allowed for the temperature-dependence of both the diffusion coefficient in water and the
saturated concentration of urea. Initial results suggest that the effect of varying the size of URM
cuboids on both their release characteristics in moist soil and N-supply to plants is also reasonably well
predicted by the diffusion model. In a ryegrass field trial over 24 weeks, the URM gave higher dry
matter yields than either prilled urea or ( N H 4 ) 2 S O 4 (following a single application at sowing) through
efficient matching of nitrogen supply and crop demand.

Losses of nitrogen following urea application are
relatively high and are associated mainly with the
processes of ammonia volatilization, nitrate
leaching and denitrification. Urea hydrolysis is
quite rapid in soils and proceeds via conversion
to ammonium carbonate [4]. As (NH4)2CO 3 accumulates, soil pH values increase resulting in
volatilization of ammonia gas [3]. Volatilization
losses have been reported as being 50% within
2-3 weeks of application [13]. The remaining
NH4, which is retained in the soil, will be nitrified to NO 3 which is then subject to losses
through leaching and, under anaerobic condition, denitrification.
To reduce such potential losses, it is desirable
to maintain as low a concentration of inorganicN (NH 4 and NO3) in soil-water systems as
possible, without imposing a nutrient stress on
crops. Slow release fertilizers can fulfil this func-

tion and avoid the need for repeated applications

of conventional fertilizers. There are also other
advantages associated with specifically with sustaining a low available nitrogen concentration.
These include a lower chance of over stimulation
due to luxury consumption, reduced disruption
of nutrient balances and minimal injury hazard
to germinating crops from high application rates
One approach to controlling nitrogen availability involves the coating of conventional N
fertilizer granules with slowly permeable materials such as plastic, wax, resin or elemental sulphur. The best known and most widely tested
product is sulphur-coated urea or SCU [2]. However, the cost of producing SCU has limited its
development as a commercial fertilizer [14] and
so limited its use in rice fields because of the
cost/benefit ratio incurred [11]. The coating on
SCU may crack during shipment [10] resulting in
failure following application. Similarly, excessive

impact or abrasion in use may cause breakdown
of the coatings and may alter or destroy the slow
release characteristics of the product [7].
An alternative to a single protective shell may
be the use of a foam matrix to encapsulate
water-soluble fertilizers. A new slow-release
medium for urea fertilizer called 'Urea-Rubber
Matrix (URM)' has recently been developed [7].
A natural rubber (grade SMR 20) was used to
encapsulate prilled urea (46% N) in the form of
a foam matrix, so that the dispersed phase consists of urea crystals. A special mixing technique
in rubber technology known as 'split feeding' was
used to produce the material [6, 7, 8].
The objective of this paper is to appraise the
agronomic significance of URM through the following studies.
a. Germination trials to test URM against prilled urea in terms of the damaging effect to
germinating seedlings caused by NH 3 generation at high temperatures and urea applications.
b. Incubation trials in soil and 0.01 M CaC12 solution to quantify the rate of urea release
from URM at different temperatures and so
develop a predictive model of urea solubilization from the slow release matrix.'
c. A micro-plot ryegrass field trial of URM
against (NH4)2SO4 and urea to examine the
usefulness of the slow release mechanism
under field conditions.

Materials and methods

Urea-rubber matrix was prepared in strips 0.4 cm
thick as described by Arizal [1] and cut into
small cuboids according to sizes required. A
standard size was adopted to 0.5 x0.5
(x0.4) cm.

Seedling germination trial

Wick soil series (sandy loam, pH 5.5) was taken
from an experimental plot of the University of
Nottingham, air dried to a moisture content of
around 89mgg -1 and sieved to <0.6cm. The
soil was packed in 8 cm diameter ceramic col-

umns, 70 cm high with perforated polyethylene

at the bottom to allow air penetration. The
columns tops were covered with black polyethylene to maintain the moisture content of the
soil during incubation for one week prior to
fertilization applications. Prilled urea or URM of
standard size (0.5 x 0.5 cm) was applied at rates
of 0, 100, 300 and 500 kg N ha -1, broadcast onto
the soil surface and covered with 2 cm soil. Then
0.3 g of ryegrass seeds (Lolium perenne) was
sown uniformly and covered with a further
0.5cm soil. The columns were irrigated with
50 cm 3 distilled water after sowing and covered
with black polyethylene. Daily temperature was
recorded and the germinated seedlings were
counted 12 days after sowing. All the treatments
were replicated 5 times and a randomized complete block design (RCBD) was adopted for the
layout of columns in an unheated glasshouse.

Incubation of URM in soil and 0.01 M CaCl2

Wick soil series was taken from an arable plot at
the University of Nottingham which receives annual NPK additions. The soil was air dried,
sieved to <0.2 cm and brought to 10.7% (w/w)
moisture content. One kg samples of the soil
were placed in sealed plastic containers and incubated under controlled temperatures of 1.0C,
9.8C, 16.5C, 18.8C or 26.4C for one week to
achieve temperature equilibrium. URM cuboids
of 0.5 x 0.5 (x0.4) cm at a rate of 200 mg N kg -1
dry soil were then distributed throughout the soil
in the containers. Other sizes of URM, including
0 . 2 5 x 0 . 5 c m , 0 . 5 x 1 . 0 c m and 1 . 0 x l . 0 c m
were treated similarly and incubated at a single
temperature of 18.8C. At the end of the incubation period (27 weeks) all the URM cuboids
were removed, cleaned and oven dried at 80C
for 3 days. The dried cubes were digested using
the Kjeldahl method and analysed for total nitrogen using standard automated flow analysis.
For incubation in solution, 0.01 M CaC12 in
CO2-free distilled water was used to simulate the
soil solution phase. Aliquots of the solution
(800 cm 3) were incubated in air-tight containers
covered with aluminium foil, at the same temperatures as for the soil. Sufficient URM cubes
(twenty) of standard size to give 994 mg N per
800 cm 3 solution were pre-washed by shaking

with distilled water for 1.50h to remove free
urea from surface pores so that the slow release
of urea could be studied with greater accuracy.
The urea released after 1.50 h shaking amounted
to 9.0% of total for the standard size of URM.
The cubes were then placed in the pre-incubated
CaCI 2 solution. The resulting suspensions were
regularly shaken and sampled to measure urea
and ammonium concentrations. The urea in the
analytical samples were hydrolysed by incubation
with 0.2% urease for 2 h at 25C and the resulting N H 4 analysed using standard automated flow
analysis. At the end of the incubating period the
U R M cubes were removed, oven dried at 80C
and then digested to determine the residual N.

ume fell below this figure. The concentration of

urea in the external solution was always taken as
zero. The saturated urea concentration was calculated from the equation presented by Jarrel
and Boersma [9]:

Diffusion model of urea release

where Tab S is the absolute temperature.

The diffusion coefficient (D) of a non-adsorbed solute moving through a porous medium is
described as the product of D 1 and a tortuosity
factor (f):

To describe diffusion of urea out of the rubber

foam cuboids a simple numerical solution to
Fick's first law was used. Each cuboid was envisaged as 6 'right pyramids' with bases forming the
outside faces and apexes meeting in the centre of
the cuboid. Each pyramid was then divided into
10 shells or 'finite thickness planes'; the volume
and interracial area of each shell was calculated
from the overall cuboid geometry. The initial
urea content of each shell was calculated from
the total urea content of the cuboid and so the
pore space of each shell was determined from an
assumed solid urea density of 1.32 g cm -3.
Incremental movement of urea between shells
from the apex to the base of each pyramid was
described by:
AU = - D A ( A U J A x ) At


where AU = urea transferred (g) during time increment At

D = t h e diffusion coefficient (cm2s -1)
A = the 'source shell' planar area (cm 2)
AU c = the difference in solution concentration between the source and sink
shells (g cm -3)
Ax = the distance between the centre of
the source and the sink shells (cm)
At = the time increment (seconds).
The solution concentration in each shell was
assumed to be that of a saturated solution until
the urea content divided by the shell pore vol-

Uc(sat) = (6.96 1 0 - 3 ) T + 0.45


where T = the temperature in C.

The previous authors have also developed a
simple algorithm to describe the temperature
dependence of the urea diffusion coefficient in
solution (D 1)
D1 = (5.55 x 10


)Tab Sexp(-2135/T~us)

D =



Combining equations 4 and 7 to measure the

urea movement between shells, and hence the
release to the outside solution, the only unknown paramter is f. The model was therefore
fitted to the experimental data for each temperature by adjusting the tortuosity factor to minimize the error sum of squares. A At value of
8640 seconds was used so that a total of 2000
time increments were employed over the total
diffusion period of 200 days.

Micro-plot field trial

An arable plot of Wick series soil was used to
study the N-nutrition of ryegrass (Lolium perenne) grown in miro-plots. Plastic columns (20 cm
length and 1 cm diameter) were inserted to a
depth of 17 cm from the soil surface at distances
of 75 cm.
( N H 4 ) 2 S O 4 and U R M of standard size were
applied at rates of 0, 50, 200, and 500 kg N ha -~
to a depth of 2 c m from the soil surface. The
othes sizes of U R M used in the soil incubation
trial were also used as a treatment at a single
rate of 200 kg N ha-1. Ryegrass seeds were sown
on 20th May, 1988 at a rate of 0.2 g per column

and covered with 1 cm of soil one week after
fertilizer application. Watering of 0.5cm was
done as necessary up to 1 month after sowing.
All the treatments were replicated 5 times using
an RCBD design. The grass was harvested 3
times with each cut being taken at 8 week intervals. The grass samples were oven dried at 80C
for 3 days, weighed, then ground and digested
for nitrogen analysis. The U R M cubes were
removed from the field after 30 weeks in the
microplots, washed, and analysed for residual N
after Kjeldahl digestion.

reported that urease activity increased linearly

with temperature and reached an optimal level at
37C. However, in the case of URM, urea release from the rubber matrix is not immediate,
so that the urea concentration in the vicinity of
the seeds is low. Damage to seeds from ammonia
following urea hydrolysis is therefore probably
negligible. This suggests that U R M may be safely applied at the time of sowing, and at high N
application rates, without significant risk of
seedling injury or retarded germination.

Urea release in solution

Results and discussion

Effect of URM on seedling germination

The germination of ryegrass was significantly
influenced by the type and rate of fertilizer-N
applied. An increase in prilled urea concentration caused significant (p = 0.01) germination
failure of ryegrass while U R M did not reduce
germination rates significantly (Table 1).
The failure of germination at high application
rates of prilled urea shows the potentially
damaging effect of its use. During the experiment, average daily temperatures (the sum of
the minimum and maximum daily temperature
divided by two) in the glasshouse were high
(20.5 -+ 1. IC); the average daily range was 10.330.6C. High temperatures favour rapid urea
hydrolysis and N H 3 evolution, Gould et al [5]

Table 1. Effect of nitrogen fertilizers on the germination of



kg N ha- 1

% of control





a Average of 5 replication, 12 days after sowing.

b Duncan's multiple range t e s t - any 2 means having a common letter are not significantly different at the 5% level of

A good fit to the data was achieved using the

diffusion model (Fig. 1). Jarell and Boersma [9]
have shown that the temperature dependence of
urea release from SCU can be directly related to
the product of the liquid diffusion coefficient and
the saturated concentration (D I Csat). The U R M
differs from SCU in that instead of a single










Fig. 1. Urea release from rubber cuboids as a function of

temperature and time, Solid lines are generated by the
diffusion model. Data points for different tepmeratures include (N) 1C; (A) 9.8C; ( ~ ) 16.5C; ( 0 ) 18.8C; ()
Y axis: Urea Released (g x 10 -2)
X axis: Time (Weeks)

Table 2. Variation in diffusion model parameters with temperature

Table 3. The effect of cuboid size on residual urea in soilincubated URM (Temperature 18.8C)


D 1 Csat *
(xlO -6)

Tortuosity factor (f)

(xlO -4)

Cuboid dimensions









% Urea release after 27 weeks





* From equations of Jarell and Boersma (9).

chamber containing urea there are many, all

interconnected via small pores. Hence the need
for a 'tortuosity factor' in the description of
diffusion. However, because the temperaturedependence of D 1 Csat is allowed for in the
model the tortuosity factor should be constant at
all temperatures for the model to be consistent.
In fact there appears to be a slight increase in the
tortuosity factor at high temperatures (Table 2)
so that changes in D 1 and Csa t may not fully
explain the greater release rate with increasing
temperature. It is possible that the morphology
of the rubber pore walls changes with increasing
temperature, perhaps causing widening of interconnecting channels and hence a higher tortuosity factor. Nevertheless, most of the change in
rate of release can be ascribed to the temperature-dependence of D 1 Csa t.
A further test of the accuracy of the diffusion
model lies in the estimation of residual urea
contained in cuboids equilibrated in soil. We
assumed that at 10.7% soil moisture neither the
rubber-water contact area nor the diffusion of
urea away from the source limited the urea
release from the rubber matrix. The latter assumption should certainly be valid as tortuosity
factors in soil tend to be of the same order of
magnitude as the volumetric water content; thus
f(soil) would be around 1000 times f(URM)- It
should therefore be possible to use the tortuosity
factors derived for the solution experiment to
estimate residual urea in cuboids incubated in
soil. A comparison of model and actual residual
urea in URM is given in tables 3 and 4; in both
cases the figures given by the model are corrected for urea released instantaneously (9.0% of
The effect of soil temperature and cuboid
dimensions are shown to be reasonably well

predicted by the diffusion model given that the

tortuosity factors used were derived from a single experiment using only 1 size of cuboid (0.5 x
0.5 x 0.4 cm) incubated in a completely different
background medium (0.01 M CaC12).

Plant uptake of nitrogen from URM

The nitrogen uptake and ryegrass yield as a
function of nitrogen application are shown for
the 3 consecutive harvests in Figures 2 and 3.
The slow-release properties of URM were apparent in comparison with urea and ammonium
sulphate in Figure 2. Less nitrogen was taken up
by the first cut of ryegrass growing in soil fertilized with URM. There was also a slight reduction from an otherwise linear relationship between uptake and application at the highest urea
application. However second and third cuts
clearly demonstrated the continued supply of
nitrogen by the URM throughout the growing
season. Nitrogen uptake from (NH4)2SO 4 and
prilled urea fell well below that from URM after
the first cut. The total nitrogen uptake over all 3
cuts (Fig. 2d) showed no significant differences
between N sources except in the case of the
highest urea application rate. The lower uptake
in the latter case is thought to be due to a

Table 4. The effect of soil temperature on residual urea in

soil-incubated URM (0.50 x 0.50 0.40 cm)
Soil temperature

% Urea release after 27 weeks








550, a)


300] b)











2z b)











1~0 z~0 3d0 ~0

10. c)

s00 z

, z;0 i;0 ~60



50, ~)



= 8










100 ZOO 360

kbO ~0

" 16o z6o a6o ~bo ~6o



100 2.00 300 ~,00 SO0

1~0 zb0 360 ~60
N, Kg ha-1


Fig. 2. Nitrogen uptake by ryegrass grown in microplots at

Fig. 3. Yields of ryegrass grown in microplots at different

different levels of nitrogen fertilizer: a) First cut, b) Second

cut, c) Third cut, d) Over all uptake. Fertilizers include (11)
Ammonium Sulphate; ([~) Prilled Urea; (0) URM
X axis: Nitrogen Levels (kg ha -~)
Y axis: Nitrogen Uptake (rag microplot ~)

levels of nitrogen fertilizer: a) First cut, b) Second cut, c)

Third cut, d) Overall yield. Fertilizers include: (ram) Ammonium Sulphate; (D) Prilled Urea; (a) URM.
X axis: Nitrogen Levels (kg ha -~)
Y axis: Dry weight Yields (grams microplot -~)

combination of ammonia volatilization and the

effect of seedling damage as shown by the lower
uptake for the first harvest.
The yield at first harvest achieved from the
three N sources (Fig. 3a) further demonstrates
the potentially damaging effect of prilled urea at
high concentration There was a significant reduction in plant growth at the highest urea level.
It is also noticeable that although N uptake for
U R M fell well below that for (NH4)2SO 4 (Fig.
2a), the respective yields are much closer (Fig.
3a). This is inconsistent with the poorer efficiency of nitrogen use in dry matter production
expected for large applications of 'soluble' N
fertilizers. The relatively higher yields of rye-

grass on U R M plots achieved for the second and

third cuts (Fig. 3b and 3c) is expected given that
the plant growth is probably limited by available
nitrogen at that stage. Finally, the value of the
more even spread of nitrogen availability across
the growing season is reflected in the higher
overall yield achieved with U R M for the two
high N application rates (Fig. 3d). For 200 and
5 0 0 k g N h a -1, the U R M gave a 17.3 and 29.1%
higher yield than (NH4)~SO 4 respectively; these
figures are clearly higher if the U R M is compared with urea at applications large enough to
damage the crop.
The discussion of the field trial so far has
concerned a 'standard size' of U R M (0.5 x 0.5 x

Table 5. A comparison of theoretical urea release and measured N uptake by ryegrass, under field conditions, over 24

Cuboid dimension
0.25 x 0.50 x 0.40 (SV)*
0.50 x 0.50 x 0.40
0.50 x 1.00 x 0.40
1.00 x 1.00 x 0.40

Urea release
as % SV*

N uptake
as % SV*

* Smallest volume
0.4cm) cuboid. The same 4 different cuboid
volumes described previously were also tested
and showed an ability to supply N over the 24
weeks growth period which was fairly consistent
with the extent of urea release predicted by the
diffusion model. In table 5 we present both the
urea release (24 weeks, t e m p e r a t u r e 13.4C) and
the total nitrogen uptake by ryegrass as a percentage of that for the smallest cuboid volume
(0.25 x 0.5 x 0.4 cm). The average soil t e m p e r a ture ( 1 0 c m depth) over the growing season
(13.4C) was taken from the Sutton Bonington
meteorological station. Again, the model values
are corrected for the small amount of urea which
is released instantaneously. Clearly the theoretical urea release given in Table 5 must be regarded as approximate as this will depend on
specific soil t e m p e r a t u r e fluctuations; taking an
average t e m p e r a t u r e is not strictly valid. The soil
moisture content will also affect the diffusion of
urea from the cuboid; in another series of incubation trials it was found that the rate of urea
release fell dramatically when the volumetric soil
water content fell below 0.074 for Wick series
It is possible that the availability of urea from
U R M is affected by processes other than simple

Table 6. Changes in mass of standard size of rubber cuboids

with temperature for URM incubated in soil over 27 weeks

* Corrected for residual urea

Mass of rubber*

Plate 1. Clustering of ryegrass roots around URM cuboid.

diffusion when in a rhizosphere environment.

Two possibilities include biological decay of the
rubber matrix and root penetration of the
cuboid. The soil incubation experiment showed
that the final mass of rubber of each cuboid was
not t e m p e r a t u r e - d e p e n d e n t (Table 6). Some degree of biological decay m a y occur under field
conditions but this may be peripheral to urea
solubilization. H o w e v e r , root-penetration of
U R M was considerable, (Plates 1 and 2). The
cuboids were firmly held within root mats recovered from the field experiment; most of the
storage pores within the r u b b e r matrix a p p e a r e d
to be filled with fine root material. In addition,
larger roots penetrated the U R M structure
(Plate 2). It is likely however, that root penetration occured after swelling of the U R M caused
by influx of water and following release of urea
by diffusion. The supply of urea would therefore
still be limited by diffusion across the interconnecting rubber walls separating urea storage
pores within the U R M .

a cheap alternative to natural rubber a worthwhile goal.


Plate 2. Penetration of U R M cuboid by individual ryegrass



The release of urea from U R M in moist soil is

affected by temperature and matrix volume in a
manner which is quite well predicted by a diffusion model. It should therefore be possible to
utilize matrix volume (size of cuboid) as the
determining variable for required urea-release
rates under different temperatures. Future research could profitably be directed towards investigating the relationship between matrix 'tortuosity' and the chemistry of different matrix
formulations. Certainly the advantages of single,
large fertilizer applications giving a controlled
supply and minimal loss of nitrogen make finding

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a natural rubber matrix. PhD thesis. Loughborough University of Technology UK
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