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Cascarilla de Arroz Como Pigmento2016 PDF
Cascarilla de Arroz Como Pigmento2016 PDF
a r t i c l e i n f o a b s t r a c t
Article history: The aim of this study is to introduce rice husk after simple chemical modification as new eco-friendly
Received 15 April 2016 anticorrosive pigments. Uncontrolled burning of rice husk is often considered the most disposal method
Received in revised form 8 August 2016 in Egypt; this seasonal and highly localized massive burning generates excessive air pollution. The usage
Accepted 2 September 2016
of this waste as anticorrosive pigments will decrease the danger of environment pollutions. The new anti-
corrosive pigments based on rice husk as core comprising 80–85% of new pigment covered with thin shell
Keywords:
of ferrites that comprises about 15–20% were prepared using new technique called “core-shell”. The dif-
Core-shell
ferent ferrites/rice husk pigments were characterized using different analytical and spectro-photometric
Rice husk
Anticorrosive pigments
techniques, such as X-ray fluorescence (XRF), Energy dispersive X-ray (EDAX) and transmission electron
Ferrites microscopy (TEM). These core-shell pigments were then incorporated in solvent-based paint formula-
Impedance spectroscopy tions based on epoxy resin. The physico-mechanical properties of dry films were tested. The corrosion
properties using immersion test in 3.5% NaCl and electrochemical impedance spectroscopy (EIS) for
28 days were determined.
© 2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2016.09.004
0300-9440/© 2016 Elsevier B.V. All rights reserved.
310 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
In this work core-shell technique was used as a method for 2.3. Methods of instrumental analysis
utilization of rice husk as pigment, by using it as source of silica
precipitating on its surface a layer of ferrite pigments which is well 2.3.1. X-ray fluorescence
known anticorrosive pigments. The prepared core-shell pigments The different concentrations of each element in the prepared
contain only (10–20%) of ferrite pigments as shell material precip- pigments were determined using an Axios, sequential WDX-ray
itated on (80–90%) rice husk as core. These pigments were tested fluorescence (XRF) spectrometer, PANalytical 2005, USA.
as anticorrosive pigments in paints. The modification of rice husk
was done by precipitating thin layer of (Zn, Mn and Zn·Mn) ferrites 2.3.2. Transmission electron microscopy (TEM) analysis
on its surface. Ferrite pigments (Fe) are known as efficient anticor- Various pigments were examined using JEOL JEM 2100 (Japan)
rosive pigments and they are present in the shell which is in direct technique with micro-analyzer electron probe to determine the
contact with the surrounding materials. The anticorrosive perfor- particle shapes and sizes of the prepared pigments.
mance of the new ferrites/rice husk (Fe/RH) core-shell pigments
was measured to prove their efficiency as anticorrosive pigments in 2.3.3. Scanning electron microscopy (SEM) and energy-dispersive
the different epoxy-based paint formulations. The results showed X-ray (EDAX) analysis
that core-shell pigments based on rice husk are highly efficient in Energy-dispersive X-ray analysis technique and scanning elec-
their anticorrosive performance. tron microscopy (JEOL JX 2840) micro-analyzer electron probe
(Japan) was used in this work to estimate the particle shapes and
elements deposited on silica surface
2. Experimental
2.4. Anti-corrosive paint formulations of ferrite/rice husk
2.1. Materials
core-shell pigments
• Zinc, manganese and ferric nitrates are powders of high purity and
The prepared core-shell ferrites/rice husk pigments were incor-
were obtained from Win-lab, Sigma-Aldrich, ALPHA CHEMIKA,
porated in paint formulations beside paint formulation free of rice
respectively.
husk as blank for comparison. Paint film thicknesses range from
• Rice husk is a by-product obtained from rice plant in Egypt. The
120 to 150 m. All paint formulations were based on epoxy resin,
obtained rice husk was ground to the finest form as preparatory
and the formulations were divided into three groups with different
step to outfit the preparation of the new pigments [12].
pigment loadings from 30 to 50% of the total solids.
Rice husk and prepared core-shell ferrites/rice husk (Fe/RH) 2.5. Mechanical properties of paint films containing the prepared
photos are represented in Fig. 1. pigments
Fig. 2. Schematic diagram for the preparation of ferrite/rice husk (Fe/RH) core-shell pigments.
3.2. Mechanical properties of paint films containing the prepared freely through the matrix of paint film providing superior tactile
pigments effect, and thus better mechanical properties can be obtained. This
is also supported by the assumption that, the plate structures of
The paint formulations of ferrite/RH pigments were shown in zinc and manganese ferrites around and on the silica surface can
Tables 2–4 . Different mechanical tests (Ductility, Impact resis- enhance adhesion, elasticity and reinforce the polymeric matrix of
tance and hardness) which are represented in Figs. 7–9 , were the paint film [14,15].
carried out to determine the effect of rice husk and the three core-
shell pigments on the mechanical properties of paint films. Paint
films containing prepared core-shell pigments showed (higher duc- 3.3. Corrosion studies
tility and impact resistance) than that containing rice husk. In
case of core-shell pigments some of the carbon-containing mate- 3.3.1. Immersion test in 3.5% NaCl salt solution
rials (organic materials) existing in rice husk were evaporated From the data given in Tables 5–7 and Figs. 10–12 , it is obvious
through the granulated ferrite shell during calcinations of ferrites. that paint formulations containing rice husk and core-shell pig-
Therefore, the core-shell particles have silica now as predominant ments showed high corrosion protection performance. The degree
constituent of rice husk with its spherical shapes, which can move of rusting of paint films containing core-shell pigments was less
than 3% and 10% for paints containing rice husk (untreated). This is
N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 313
Table 1 Table 2
XRF results of the different Ferrites/Rice husk (Fe/RH) pigments. Paint formulations of ferrite/rice husk (Fe/RH) pigments with Epoxy resin (Group I).
(Zn·Mn)Fe/RH MnFe/RH ZnFe/RH RH Concentration Ingredients/paint Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)Fe/RH
(wt,%) numbers (RH)
Fig. 8. Impact resistance of paint films containing the prepared core-shell pigments.
(free of anticorrosive pigments) was the least in its anticorrosive tance, this is indicated by the wide semicircles of capacitive type
performance. and the high Rf values (charge transfer resistance).
Tables 8–10 and Figs. 13–15 showed that, the Rf values for all
samples during the 28 days of immersion. The data revealed that,
Rf values for coatings containing core-shell pigments were higher
3.3.2. Electrochemical impedance spectroscopy (EIS)
than that of rice husk and the blank, also it is noticeable that paint
Data obtained from electrochemical impedance spectroscopy
films containing ZnFe/RH showed the highest Rf values. The corro-
confirmed the immersion test results. There was no noticeable
sion resistance of paint films decreased with time in the first two
difference in the corrosion resistance between the three groups
weeks of immersion (due to the high attack of corrosive materi-
containing different pigment loadings. Also, it was clear that all
als), and then started to be almost steady. This is due to the good
paints containing core-shell pigments showed high corrosion resis-
N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 315
Fig. 10. Corrosion laboratory test results of Group I containing ferrite/rice husk (Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.
building of the compact film and the different corrosion protection ion and contain large number of holes which facilitate the passage
mechanisms offered by the pigments. of corrosive materials to the substrate.
The results obtained from immersion test and confirmed by The good corrosion protection of the paint formulations con-
EIS showed that, paint formulations containing rice husk exhibited taining prepared core-shell anticorrosive pigments reveals the
lower corrosion protection than paint formulations containing the interference between ferrites and rice husk. The presences of fer-
prepared core-shell anticorrosive pigments [16]. This may be due to rites helped in overcoming the disadvantages of rice husk, and their
that, the modified rice husk is arranged in loose honeycombed fash- performance can be related to more than one mechanism as follow;
316 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
Fig. 11. Corrosion laboratory test results of Group II containing ferrite/rice husk (Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.
Table 3 Table 5
Paint formulations of ferrite/RH pigments with Epoxy resin (Group II). Corrosion characteristics of ferrite/RH pigments in Group I.
Ingredients/paint Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn) Test Blank Rice husk ZnFe/RH MnFe/RH (Zn·Mn)
numbers (RH) Fe/RH (RH) Fe/RH
Table 4
Paint formulations of ferrite/RH pigments with Epoxy resin (Group III).
Epoxy Resin 32
Epoxy: Hardner 5:3
Fe2 O3 20 15 15 15 15
TiO2 7 5 5 5 5
Kaolin 30 9 9 9 9
ZnO 11 5 5 5 5
Rice husk (RH) – 34 – – –
ZnFe/RH – – 34 – –
MnFe/RH – – – 34 –
(Zn·Mn)Fe/RH – – – – 34
Total pigment 68
Total 100
P/B 2.21
Fig. 12. Corrosion laboratory test results of Group III containing ferrite/rice husk
• Passivating the steel substrate through the formation of an oxide
(Fe/RH) core-shell pigments after 28 days immersion in 3.5% NaCl.
layer on the substrate with a stoichiometry approximately the
same as Fe3 O4 [10].
• Buffering the medium and the corrosive reactions on the cathode, layer can be hydrated and exists as Fe2 O3 + H2 O or oxy-hydroxide
thereby stimulating its hydrolysis. The Fe3+ oxide in the external FeOOH [17].
N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321 317
Fig. 13. EIS measurement of Group I containing rice husk and the core-shell pigments in 3.5% NaCl.
Table 6
Corrosion characteristics of ferrite/RH pigments in Group II.
Table 7
Corrosion characteristics of ferrite/RH pigments in Group III.
Fig. 15. EIS measurement of Group III containing rice husk and the core-shell pigments in 3.5% NaCl.
• Reducing the concentration of corrosive compounds penetrating • The anticorrosive and physico-mechanical properties of the
through the film. Thus, they can bind Cl− , O2 , H2 O, and NOx which prepared pigments were studied in anticorrosive epoxy paint
could otherwise cause the substrate corrosion [18]. formulations.
• The results revealed excellent physico-mechanical and corrosion
protection properties of paint films containing the new core-
It is clear that, ZnFe/RH pigment showed the best corrosion pro-
shell Ferrites/RH. These pigments are considered economically
tection in the whole groups. This may be due to, Zn2+ ions that can
feasible, besides possessing high efficiency in protecting metal
reach the anodic regions on the metal surface causing a significant
substrates. These results were confirmed via electrochemical
decrease in the metal oxidation reaction rate, which leads to an
impedance spectroscopy measurements.
increase in the protection efficiency. • The performance of ZnFe/RH pigment was the best among the
prepared pigments.
• Using RH as core in the new pigments created extra routs for
4. Conclusions
saving the environment and protecting it from air pollution by
avoiding their burning.
• New class of core-shell ferrite/rice husk pigments containing dif-
ferent cations was prepared in this work.
320 N.M. Ahmed et al. / Progress in Organic Coatings 101 (2016) 309–321
Coating containing RH
Time Rp (Ohm cm2 )
1 day 695
7 days 1338 Table 10
14 days 904 EIS results for different paint formulations containing ferrite/rice husk core-shell
21 days 752 pigments of group III.
28 days 522
Blank
Coating containing ZnFe/RH
Time Rp (Ohm cm2 )
Time Rp (Ohm cm2 )
1 day 8452 1 day 588
7 days 6199 7 days 452
14 days 4264 14 days 320
21 days 3068 21 days 752
28 days 1733 28 days 475
Coating containing MnFe/RH Coating containing RH
Time Rp (Ohm cm2 ) Time Rp (Ohm cm2 )
1 day 1221 1 day 524
7 days 4206 7 days 1280
14 days 3230 14 days 1227
21 days 2513 21 days 1026
28 days 1733 28 days 842
Coating containing (Zn·Mn)Fe/RH Coating containing ZnFe/RH
Time Rp (Ohm cm2 ) Time Rp (Ohm cm2 )
1 day 1150 1 day 6740
7 days 3514 7 days 4426
14 days 1044 14 days 6251
21 days 1416 21 days 2933
28 days 1677 28 days 2114
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703–713. Technol. 99 (2008) 703–713.
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[12] M. Nehdi, J. Duquette, A. El Damatty, Cem. Concr. Res. 33 (2003) 1203–1210. [17] N.M. Ahmed, W.M. Abd El-Gawad, E.R. Souaya, Anti-Corros. Methods Mater.
[13] W. Xu, T.Y. Lo, S.A. Memon, Const. Build. Mater. 29 (2012) 541–547. 63 (2016) 1–11.
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