Variables Involved in the Planting of Rice in the Rice Husk Ashs

Characteristics
1

Akasaki JL1*

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Engenharia
Civil, Ilha Solteira, SP, Brazil
2

Silva EJ

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Engenharia
Civil, Ilha Solteira, SP, Brazil
3

Sousa LC

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Engenharia
Civil, Ilha Solteira, SP, Brazil
4

Marinho JHD

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Fsica e
Qumica, Ilha Solteira, SP, Brazil
5

Pay J

UPV Universidad Politcnica de Valencia, Instituto de Ciencia y Tecnologia Del Hormign, Valencia, Spain
6

Tashima MM

UPV Universidad Politcnica de Valencia, Instituto de Ciencia y Tecnologia Del Hormign, Valencia, Spain
7

Melges JL

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Engenharia
Civil, Ilha Solteira, SP, Brazil
8

Manzoli Junior W

Faculdade de Engenharia, UNESP Univ Estadual Paulista, Campus de Ilha Solteira, Departamento de Engenharia
Civil, Ilha Solteira, SP, Brazil

Abstract
Rice production in Brazil in 2008 was approximately 12 million tons, and to achieve that amount several planting techniques
were used with different strains of rice in different rice-growing areas. Since Rice Husk Ash (RHA) is the pozzolan of
vegetable origin that is most studied by researchers working in the field of pozzolanic materials, this paper evaluates the
influence that the form of planting, climate, soil, strain of rice and the origin/amount of nitrogen-based fertilizers used in rice
cultivation have on the chemical composition and crystallographic properties of RHA. The results obtained in this paper
confirm the importance of carrying out routine chemical analysis and X-Ray diffraction to maintain the quality control of the
CCAs produced because in situations of large-scale production, husks of different origins may be used.
Originality
This paper evaluates the influence that the form of planting, climate, soil, strain of rice and the origin/amount of
nitrogen-based fertilizers used in rice cultivation have on the chemical composition and crystallographic properties of
RHA.
Chief contributions
The results obtained in this paper confirm the importance of carrying out routine chemical analysis and X-Ray diffraction to
maintain the quality control of the CCAs produced because in situations of large-scale production, husks of different origins
may be used.
Keywords: Rice Husk, Rice Husk Ash, Chemical Analisys, X-Ray Diffraction

Corresponding author: Email akasaki@dec.feis.unesp.br Tel +55 18 37431213*******, Fax +55 18 37431160

Introduction
By definition, the rice husk is a coating or protective cape formed during grain growth, low density
and high volume. It is a fibrous material whose major components are cellulose (50%), lignin (30%)
and inorganic waste (20%). The inorganic residue contains an average of 95% to 98% by weight of
silica, making up 13% to 29% of the shell (HOUSTON, 1972).
According to Amick (1982), Della (2005) and Gava (1999), the chemical composition of RHA may
vary with the variety of the plant, the system of cultivation, the climate and geographical conditions,
the year of harvest, the tenors and types of fertilizer used in planting, sample preparation and
analytical methods. However, papers by these authors did not have as its main objective the analysis of
these variables in the composition of rice husk ash.
Thenabadu (1977) did a study of the location of the silica contained in rice hulls of four strains of rice
planted in seven different locations, covering three distinct climatic zones of Sri Lanka. The author
showed a significant difference in the quantity of silica in five of the seven sites evaluated.
Thus, this paper aims to contribute to the knowledge of the different variables that make up the
production of rice husk and its consequences in the final characteristics of the RHA, which is an
important agro-industrial residue to be used as pozzolan in mortar/concrete and its improves the waste
re-use.
Materials
Most samples of rice husks for the analysis of the variables soil type, climate, strains of rice and
source/quantity of fertilizer they originated from an agronomic research, aimed to verify the
application of doses taken as high (up to 200 kg of nitrogen per hectare). We evaluated four doses of
nitrogen (50, 100, 150 and 200 kg N ha -1) applied at planting or top dressing. As nitrogen sources
were used to Entec (with nitrification inhibitor and sulfur in its composition), ammonium sulfate and
urea. The experiment was conducted in Selvria, MS, Brazil, in a latossolo vermelho distrofrrico
tpico, previously occupied by cerrado vegetation, sprinkler irrigation on the occurrence of deficits
water. Within this group of samples were taken a few individuals to the development of this paper.
They are: ammonium sulfate 50 kg N ha-1, ammonium sulfate 200 kg N ha -1, urea 50 kg N ha -1,
urea 200 kg N ha-1 and Entec 200 kg N ha- 1. All these samples are strain of rice Curinga because of
its more homogeneous behavior of productivity. Besides these samples, two others were taken from
different regions of the country in order to check the variables of climate, soil and other strains of rice.
One is from the region of Dourados, MS, and the other originated in northeastern Brazil, more
specifically of Maranhao state. Table 1 shows the characteristics of each rice husk used in this phase
of research.
Table 1: Samples of Rice Husks
Farming
System

Climate

Strains of rice

Soil Type

SA 50

Terras altas

Humid
Tropical

Curinga

Latossolo vermelho
distrofrrico tpico

SA 200

Terras altas

Humid
Tropical

Curinga

Latossolo vermelho
distrofrrico tpico

UR 50

Terras altas

UR 200

Terras altas

ET 200

Terras altas

MA

Terras altas

Semiarid
with
rainfall

MS

Terras altas

Wet

Humid
Tropical
Humid
Tropical
Humid
Tropical

Curinga
Curinga
Curinga
Possveis:
Aimor, Bonana, Colosso,
Primavera, Talento, Caiap,
Canastra, Carajs e Carisma
Possveis:
Aimor, Primavera, Caiap,
Carajs,
Carisma
e
Maravilha

Latossolo vermelho
distrofrrico tpico
Latossolo vermelho
distrofrrico tpico
Latossolo vermelho
distrofrrico tpico

Fertilizer
phosphorus,
potassium and
ammonium sulfate
phosphorus,
potassium and
ammonium sulfate
phosphorus,
potassium and uria
phosphorus,
potassium and uria
phosphorus,
potassium and Entec

Quantity of
fertilizer
50 kg de N ha-1
200 kg de N ha-1
50 kg de N ha-1
200 kg de N ha-1
200 kg de N ha-1

Latossolo

phosphorus and
potassium

Latossolo

phosphorus and
potassium

It is observed that the wealth of information from samples obtained from the agronomic paper is
higher for samples MS and MA. This happened because of the difficulty of achieving informations on
the origin of husks in the processors where they were collected.
Experimental Programme
The first phase was performed to monitor the harvest of the rice plant on the farm of agronomy at
UNESP and collect the sample from the Maranhaos state and the region of Dourados, Mato Grosso
do Suls state. After harvest, rice was subjected to the processes of threshing and processing, for
subsequent use of the husks.
With the acquisition of samples from rice husks, they have gone through a washing process, in order
to determine possible impurities. To this end, we used deionized water purified by reverse osmosis.
This washing was done manually in a ratio by volume of water 2 to 3 husks. After manual mixing with
a spatula for 5 minutes, the wash water was sieved and filtered on filter paper. Thereafter, the
evaporated water washing up to dry, which then were taken to a furnace and calcined at 650 C for 4
hours. For the calcination of the samples of rice husks, the firing system was used with the furnace
temperature control, heating rate (15 C/min) and temperature plateau (650 C) for the burning
conditions were exactly the same for all samples of rice husk. Importantly, for the tests in the RHAs,
the samples were calcined rice husks without the washing process, because such activity could
compromise the evaluation of the influences studied to achieve the objective of paper.
Results and Discussion
Rinse water from rice husks
According to Della et al. (2006, p. 1175), it is important that the rice husks go through a process of
rinsing with deionized water to remove surface dirt (dust and soil) and possibly other contaminants
present. After the treatments carried out in the wash water, it was observed that the residue from the
washing water of the husk, MA, presented a bluish much more pronounced than the others. Waste was
added HNO3 diluted with water and then they were neutralized with NH4OH diluted to litmus paper.
Neutrality, part of the residue of sample MA flocculate in a much more pronounced than in other
samples, which may indicate the presence of metallic materials. Della et al. (2006, p. 1178) argue that
in cases of bleach and acid washing, metallic substances are separated and subsequently removed.
Without the presence of these substances, carbon is normally released during calcination, as it ceases
to be trapped inside the liquid phase formed on the surface of ash particles by dissociation and
subsequent fusion of the metal oxide fluxes (KRISHNARAO; SUBRAHMANYAM; KUMAR, 2001).
Spectrophotometer
Besides the samples described above, calcined in a furnace, is also presented the results of chemical
absorption of atomic mass of calcined MS sample in an oven with no temperature control (MS-Forno)
and sample of RHA from the company a rice Josapar SA, the region of Pelotas, Brazil, which has
arrived calcined. To complement was also performed chemical analysis of the MA sample calcined in
oven.
The Table 2 presents the results of chemical analysis of all samples of RHA evaluated. Making a
general analysis of the results, it is observed that all samples had the result of SiO2 + Al2O3 + Fe2O3
above the minimum quantity required by the NBR 12653 (ABNT, 1992), which is 70%, with all
samples above 90 % of these constituents, which is consistent with the literature. Regardless of the
variables involved in the process, the quantity of silica present in the RHA is very high.
With regard to item loss on ignition, the samples, the RS, made up the ceiling stipulated by the
standard, which is 6%. This is attributed to the way the husk was burned (flash burns, which traps
carbon due to melting metal oxide prior to oxidation of carbon). The MA sample, which showed a
bluish residue in your washing water after evaporation, showed the second highest, 4.31%.

Table 2: Chemical Analysis Results

Tests

Chemical Analysis (%)

Absolute Density
(g/cm)
Loss on
ignition

MSForno

MAForno

2,15

n/d

RS
2,16

MS

MA

SA 50

SA 200

UR 50

UR
200

ET 200

Especificacions NBR
12653

n/d

n/d

n/d

n/d

n/d

n/d

n/d

minimum

Mximum

3,79

4,31

6,17

1,69

3,00

3,06

2,28

3,02

2,34

2,46

SiO2

90,37

90,54

88,55

94,88

93,00

93,42

89,58

90,65

93,41

92,21

Fe2O3

0,43

0,24

0,74

0,21

0,16

0,23

0,02

0,13

0,41

0,13

Al2O3

0,12

0,13

1,74

0,31

0,52

0,22

0,58

0,25

0,15

0,37

CaO

1,25

0,04

1,11

0,14

0,04

0,04

0,04

0,04

1,34

0,04

MgO

0,27

0,20

0,32

0,20

0,20

0,33

0,36

0,40

0,33

0,40

Al2O3 + Fe2O3

0,55

0,38

2,45

0,52

0,68

0,45

0,60

0,38

0,56

0,50

SiO2 +Al2O3 +
Fe2O3

91,28

90,92

91,00

95,40

93,68

93,87

90,18

91,03

93,97

92,71

70

Na2O

0,02

0,05

0,13

0,01

0,12

0,01

0,02

0,01

0,02

0,02

K2O

0,48

1,08

0,36

0,24

0,60

0,48

0,68

0,13

0,48

0,48

E. A. (Na2Oeq)

0,16

0,77

0,37

0,17

0,52

0,33

0,50

0,10

0,33

0,34

The figure 1 compares the quantity of silica compounds and the sum of SiO2 + Al2O3 + Fe2O3.The first
analysis to make the graphic is the difference between the quantity of silica samples MS-Forno/MAForno and MS / MA, by virtue of the difference between the procedures used for the roasting. Both the
MS as the MA, calcined in a furnace, have larger quantity of SiO2, Al2O3 and Fe2O3 that calcined in
the oven, which shows the influence on the chemical burning of the same sample under different
conditions.

Figure 1: Quantity of SiO2 and SiO2 + Al2O3+ Fe2O3

Figure 2: Quantity of Na2O + K2O

Analysing the same samples, but setting the variable type of burning, you realize that although they
are regions where soil, climate, strains of rice and fertilizer employees are different, the difference in
silica tenor was low, regardless of the firing.
The RS sample had the lowest percentage of silica among all evaluated. The fact that a higher loss on
ignition just decreasing the quantity of silica percentage in the RHA, which subsequently disrupts their
reactivity on two aspects: a smaller quantity of silica to promote pozzolanic reactions and greater
quantity of carbon, which will require more water and / or superplasticizer in mortars and concretes.
According to the results observed in the samples originated from RHAs of agronomic research, note
that setting the same variables: soil, climate, strains of rice and fertilizer used, there may be difference
in the quantity of silica present in the RHA. There is a difference of 3.83% silica in the samples SA 50
and SA 200. This indicates that the difference of 150 kg / ha of ammonium sulfate was responsible for
this difference. In the case of urea, the difference between samples UR 50 and UR 200 was lower,
2.76%, demonstrating that there is a direct correlation between the quantity of fertilizer and its

influence on the silica tenor of the RHA. The ET 200 sample showed a median value compared with
the others.
By comparing these samples of agronomic research with MS and MA, when all variables are different,
is a variation of up to 5.3% silica, confirming the results found in the literature (IRRI, 1982;
THENABADU, 1977).
With regard to metallic substances Na2O and K2O, Figure 2 shows the result. The quantity in the
sample MA-Forno explains its darker after roasting in the oven so as to furnace. This indicates that the
husk, from the Maranhao, presents a different condition from the others because, although the quantity
of silica was not affected, the high tenor of Na2O + K2O may have contributed to make the RHA
darker (Figure 2).
This fact could derail their use because of cosmetic damage, since the other samples were colored
light, including MS-Forno, burned in the same oven without temperature control. Although the sample
SA 200 also had a high quantity of these substances, their coloration was not affected. Figure 3
illustrates the influence of Na2O and K2O in the loss on ignition of the material.
Disregarding the RS sample, which was burned instantly, the MA-Forno, as expected, had the greatest
loss on ignition. This reflects the high tenor of Na2O + K2O, responsible for the trapping of carbon.
The only case which fell outside this rule was the sample UR 50, whose loss on ignition was not small,
though low in Na2O + K2O.
% 7
6
5
4

3
2
1

0
MS - MA Forno Forno

RS

MS

MA

Perda ao fogo

SA 50

SA
200

UR 50

UR
200

ET
200

Na2O + K2O

Figure 3: Loss on Ignition and quantity of Na2O + K2O

In general, it is noticed that samples of agronomic research had a similar performance as the
percentage of Na2O + K2O and loss on ignition, indicating that the variation of quantity and source of
fertilizer used in the culture did not influence more significantly these properties. This shows that
other variables such as soil type, climate and crops, especially in the sample of Maranhao, favored the
presence of Na2O + K2O RHA, which consequently increased its loss on ignition.
X-Ray diffraction
The experiment of X-ray diffraction, it was found that most of the samples calcined in a furnace
presented an amorphous structure of their silica, which shows that when calcined under appropriate
conditions, even RHAs with high levels of impurities, may have an amorphous structure. There is also
the variable type and source of fertilizer did not affect the tenor of amorphicity RHAs. The following
figures show the test results of samples of the agricultural research. It appears in Figures 4 and 5 that
the UR 50 and 200 samples showed no peak in their results and that the deviation from the baseline
between the angles of 15 and 30 degrees indicates the amorphous samples.
Intensity (Arbitrary Unitis)

Intensity (Arbitrary Unitis)

1000

Amostra UR 50
C- Cristobalita
T - Tridimita

2500

2000

1500

1000

Amostra UR 200
C- Cristobalita
T - Tridimita

800

600

400

200

500

10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 4: X Ray Diffraction UR 50

10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 5: X Ray Diffraction UR 200

Intensity (Arbitrary Unitis)

1000

Amostra SA 200
C- Cristobalita
T - Tridimita

800

600

400

200

0
10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 6: X Ray Diffraction SA 50

Figure 7: X Ray Diffraction SA 200

Figures 6 and 7 also describe trajectories of amorphous material, small peaks of cristobalite and
tridymite were found in the sample ET 200 (Figure 8), however it turns out they are not sufficient to
conclude that such sample to be fertilized with fertilizer Entec with 200 kg/ha, was responsible for the
formation of these peaks . Moreover, it appears that the deviation of the baseline between the angles of
15 and 30 is in agreement with other amorphous samples.
Intensity (Arbitrary Unitis)

2500

Amostra ET - 200
C- Cristobalita
T - Tridimita

2000

1500

C
C
1000

500

10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 8: X Ray Diffraction ET 200

Figure 9: X Ray Diffraction RS

The diffractogram of sample RS (Figure 9) indicates a crystalline behavior, verified through the peaks
of cristobalite and tridymite showing the crystallography of the material. This happened as a function
of how the husk was burned.
800

Intensity (Arbitrary Unitis)

Intensity (Arbitrary Units)

1200

Amostra MS
C- Cristobalita
T - Tridimita
600

400

Amostra MA
C- Cristobalita
T - Tridimita

800

C
400

200

0
10

15

20

25

30

35

40

45

50

2 Theta (Degrees)

Figure 10: X Ray Diffraction MS

10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 11: X Ray Diffraction MA

The figures 10 and 11 show the MS and MA samples burned in a furnace. It appears that the MS
sample is amorphous, and the MA, however, there is a peak of cristobalite higher, around 23 of the
MA sample.
Analyzing the behavior of these samples of RHA, one sees little influence of the variables soil type,
climate, strains of rice and type/quantity of fertilizer used. This is attributed to the form of burning,
which is ideal for the disposal of the impurities, and low temperature firing, which prevented the
crystallization of the RHA.
For samples MS-Forno and MA-Forno, different behaviors were observed in Figures 12 and 13.
As the sample MS-Forno presents amorphous, with only a small peak of cristobalite, MA- Forno has
many peaks of tridymite and cristobalite. As the furnace temperature reaches 850 C and stays there
over 16 h, possibly in excess metallic substances present in the sample MA-Forno accelerated the
crystallization process of silica (KRISHNARAO; SUBRAHMANYAM; KUMAR, 2001). Moreover,

it is believed the lower stability of MS-Forno due to higher CaO compared to MA-Forno, as shown in
Table 6. The CaO is a powerful agent of glazing used in the manufacture of glass.
Figure 11 has presented evidence (cristobalite peak around 23) that the silica contained in the MA
sample could crystallize more easily than the other samples, where the calcination temperature
increased.
Amostra MS-Forno
C- Cristobalita
T - Tridimita

2000

1500

C
1000

6000

Intensity (Arbitrary Unitis)

Intensity (Arbitrary Unitis)

2500

Amostra MA-Forno
C- Cristobalita
T - Tridimita

4000

2000

500

C
C

C C C C
0
10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 12: X Ray Diffraction MS-Forno

10

15

20

25

30

35

40

45

50

55

60

2Theta (degress)

Figure 13: X Ray Diffraction MA-Forno

Conclusions
Through this paper, we conclude that all variables are addressed (way of planting, climate, soil, satrain
and source/quantity of nitrogen-based fertilizers) influence on the quantity of silica, the presence of
metallic materials and the loss on ignition RHA. With respect to the crystallographic property, we can
conclude that the variable source and quantity of fertilizer used did not exert significant influence.
However, it was found in a sample of RHA (MA) assessed a strong tendency to crystallization of
silica, while the MS sample, subjected to the same calcination process without temperature control,
appeared amorphous. Thereafter, there is the importance of making testing routine chemical analysis
and X-ray diffraction to maintain quality control of RHAs produced because, in a situation of
production of RHA in a large scale, can be used husks different origins. Moreover, it is concluded that
the approach of the variables involved in the planting of rice can enrich the discussion and
understanding of research results that address the use of RHA in the civil building.

References
- Amick, J. A. Purificacion of Rice Hulls as a Source of Solar Grade Silicon for Solar Cells. Journal of the
Electronchemical Society, Nova Jersey, v. 129, n. 1, p. 864-866, 1982.
- Associao brasileira de normas tcnicas. NBR 12653: materiais pozolnicos: especificao. Rio de Janeiro,
1992. 3 p.
- Della, V. P. Sntese e Caracterizao do Pigmento Cermico de Hematita, Obtida a partir de Carepa de Ao,
Encapsulada em Slica Amorfa Obtida a partir da Casca de Arroz. 2005. 9 f. Tese (Doutorado em Engenharia de
Materiais) Faculdade de Cincia e Engenharia dos Materiais, Universidade Federal de Santa Catarina,
Florianpolis, 2005.
- Della, V. P. et al. Estudo Comparativo entre Slica Obtida por Lixvia cida da Casca de Arroz e Slica Obtida
por Tratamento Trmico da Cinza de Casca de Arroz. Qumica Nova, So Paulo, v. 29, n. 6, p. 1175-1179, 2006.
- Gava, G. P. Estudo Comparativo de Diferentes Metodologias para a Avaliao da Atividade Pozolnica. 1999.
118 f. Dissertao (Mestrado em Engenharia Civil) Curso de ps-graduao em Engenharia Civil,
Universidade Federal de Santa Catarina, Florianpolis, 1999.
- Houston, D. F. Rice hulls, Rice Chemistry and Technology. Minnessota: American Association of Cereal
Chemistry, 1972. p. 301-352.
Krishnarao, r. V.; Subrahmanyam, j.; Kumar, T. J. Studies on the Formation of Black Particles in Rice Husk Ash. Journal of the European Ceramic Society, Gr Bretanha, v. 21, n. 1, p. 99-104, 2001.
- Thenabadu, M. W. Silica content of rice rusk as determined by soil properties and varietal differences. Trop.
Agric. 133: 71-80, 1977.