Applied Mechanics and Materials Submitted: 2014-09-05

ISSN: 1662-7482, Vol. 731, pp 528-534 Revised: 2014-11-17

doi:10.4028/www.scientific.net/AMM.731.528 Accepted: 2014-11-19
© 2015 Trans Tech Publications, Switzerland Online: 2015-01-29

Progress of Surface Modification of Aluminum Pigments

MA Liping1,2,a, ZHOU Shisheng1,2,b, DU Bin1,2,c and LI Min1,2,d

1
Faculty of Printing and Packaging Engineering, Xi’an University of Technology, Xi’an 710048, China
2
Shaanxi Key Laboratory of Printing and Packaging Engineering, Xi’an 710048, China
a
[email protected],[email protected], [email protected],[email protected]

Keywords: Aluminum pigment; Encapsulation; Coloration

Abstract. Improving the printability of silver ink is of great importance to enhance the
anti-counterfeit of bills. As the main ingredient of silver ink, the study of aluminum pigments has
attracted a lot of attention. This paper mainly describes the recent research progress in surface
modification and coloration of aluminum pigments. For the high corrosion resistance, good gloss
reproducibility, strong dispersion of aluminum pigments that required in the application of
water-based ink, this paper first describes different research progresses of enhancing its performance,
including inorganic encapsulation, organic/inorganic hybrid modification, polymer coating,
organic/inorganic/polymer multi-layer encapsulation and so on through a series of modification
methods such as sol-gel method, in-situ polymerization, emulsion polymerization, etc.. In reflection to
the color unity of aluminum pigments, the progress of aluminum pigments coloration was also
introduced in detail, which involves physical adsorption, chemical oxidation, Fe2O3 deposition,
organic/inorganic dye coating, etc..

Introduction
As an important metal pigment, aluminum pigment is mainly used in the field of industrial and
automotive coatings, printing inks and plastics processing[1,2] especially with its metallic effects
and corrosion resistance. Silver ink is a special ink used in anti-counterfeit bill printing, and its main
ingredient is modified aluminum flake with metallic luster and down-flop effect as shown in
Fig.1[3,4]. Silver ink applications achieve anti-counterfeiting, high technology and aesthetics of the
valuable bills initially.

(1-Carrier layer, 2-Flaky aluminum, 3-Substrate)

Fig.1 Sketch map of angle-depended effect of flaky aluminum

Domestic silver ink has poor stability and is prone to gassing, floatability reducing, slurry
decomposition, etc. caused by water erosion in storage. After a period of time, gloss decline,
shedding and other phenomena will occur to aluminum pigments in the coating surface. And these
problems are all related with the surface properties of aluminum pigments. Aluminum can easily
react with oxygen, water, acid and alkali because of its active chemical properties.

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 Applied Mechanics and Materials Vol. 731 529

Aluminum will react with water as follows Eq.1 and Eq.2[5]:

2Al+6H2O→2Al(OH)3+3H2↑. (neutral or slightly alkaline conditions) (1)

2Al+2OH-+6H2O→2Al(OH)-4+3H2↑. (strong alkaline conditions) (2)

In addition, strong hydrophilic properties of aluminum pigment make it hard to combine with resin,
difficult to disperse and easy to picking. Therefore, surface modification in improving the corrosion
resistance and compatibility of aluminum pigments so as to enhance the performance of silver ink and
expand its application field is the key issue to be solved.

Surface Modification of Aluminum Pigments

Surface Modification Effects. Surface modification of aluminum pigments is equivalent to a
treatment process of ultra-fine inorganic particles. The role of inorganic particle surface treatment
can be summarized as the following three aspects [6]: (1) Increase the inherent characteristics of
aluminum pigments such as tinting strength, hiding power, etc.; (2) Improve its functional
performance and enhance the dispersion and stability of pigments in solvent and resin; (3) Improve
the durability, chemical stability and processing properties of the pigment products. For aluminum
pigment surface modification treatment can improve its corrosion resistance and resin compatibility,
thus enhance the application performance of aluminum pigment and the printability of silver ink.
Surface Modification Methods. Aluminum pigment surface modification methods can be divided
into encapsulation and corrosion inhibition method according to different mechanisms. Corrosion
inhibition method refers to adding some substance that can prevent the aluminum pigments system
from corrosion. The encapsulation method applies organic or inorganic to form one layer or
multilayer on the surface of the aluminum pigments, which prevents the corrosion of contacting
with electrolyte, water, oxygen, etc., to improve their capacity of resistant to acids/alkalis and
maintain their metallic luster. It is a much more promising approach[7].
Sol-gel Method. Sol-gel method uses metal alkoxide as precursor and small amount of acid or
alkali as catalyst, the structural formula of metal alkoxide is R'4-n M(OR)n.
Metal alkoxide hydrolysis will be carried out according to the following formula Eq.3 and produce
metal hydroxyl compound:

R'4-nM(OR)n+nH2O→R'4-nM(OH)n+nROH. (3)

Where, M represents Na, Al, Si, Ti, etc.; R’ represents CH2, CH, CH3, ect.; R represents CH3,
C2H5, C3H7, etc., n ranges from 1 to 4, silicon alkoxide (R'4-nSi(OR)n) has been the most commonly
used. R'4-nM(OR)n is very lively and is prone to self-polycondensation or polycondensation with
R'4-nM (OH) n, forming a three-dimensional network structure[8].
Kiehl[9] prepared inorganic monolayer silica encapsulated aluminum pigments in sol-gel method.
After treatment: their stability, weather resistance, optical properties, adhesion had been greatly
improved. However, silica is inorganic and has strong hydrophilic, it’s difficult to disperse
uniformly in coatings or ink systems as its poor compatibility with organic resin and solvent.
Liu Hui et al.[10] produced inorganic, organic encapsulated aluminum pigments and inorganic-
organic, organic-inorganic double-coated aluminum pigments. Compared with uncoated aluminum
pigments, the corrosion inhibition efficiency of inorganic and organic monolayer-coated products
reached 66.1% and 80.0% respectively, while that of inorganic-organic and organic-inorganic
530 Advanced Printing and Packaging Materials and Technologies

double-coated products reached 96.4% and 97.9% respectively. As a result, double-layer

encapsulation on the aluminum pigments surface can improve the corrosion resistance effectively.
According to Li Lijun et al.[11], aluminum pigments were first coated with a smooth sol-gel film
contain an unsaturated double bond by using TEOS and VTES as precursors under alkaline catalyst,
followed by free radical copolymerization of styrene(St), divinylbenzene(DVB) and maleic acid
anhydride(MAA), forming an inorganic-organic hybrid coating and the corrosion inhibition
efficiency was up to 99.8%. Chen Kun, Pi Pihui et al.[12] used MTES and TEOS as precursors,
ammonia as catalyst, forming an organic-inorganic hybrid coating on the surface of aluminum
pigments by sol-gel method. The corrosion resistance of aluminum pigments significantly
improved.
Gao Aihuan[13] prepared PMBV/SiO2 encapsulated aluminum pigments by hydrolysis and
condensation of PMBV and TEOS on the surface of pigments via sol-gel method using ammonia as
catalyst and ethanol/H2O as dispersion media. Its gloss fell only 0.24, corrosion resistance, adhesion,
compatibility were significantly improved. Liu Y et al.[14]used 3-methacryloxypropyl trimethoxy-
silane and TEOS, vinyl trimethoxy silane and TEOS, γ-glycidoxypropyl trimethoxysilane ether and
TEOS to prepared organic-inorganic hybrid coated aluminum pigments respectively. Huang Shuli[15]
used tetrabutyl titanate as precursor to form a dense TiO2 layer on SiO2/A1 particles by sol-gel method.
The best encapsulation can be acquired when the volume ratio between TEOS and TBT was 3:5.
In-situ Copolymerization. In this method, nanoscale inorganic powder is dispersed uniformly in
the monomer first, then polymerization reaction which is similar to bulk polymerization method
occurs to obtain nanocomposites. Liu et al.[16]studied aluminum pigments encapsulated by in-situ
copolymerization of St and MA. When the mass ratio of monomer St-MA and aluminum pigments
is 20%, the corrosion inhibition efficiency of St-MA coated aluminum pigments is 83% and its
gloss decreases about 10%. By adsorption of initiator and polymerization of monomer, Liu et al.[17]
grafted methyl methacrylate (MMA) on the surface of aluminum pigments.
Liu Hui et al.[18] first coated aluminum pigments with MPS, followed by in situ polymerization
of acrylic and styrene on the surface of aluminum pigments. MPS acts as "molecular bridge"
between aluminum pigments and polymers, which makes the copolymer adhere firmly so as to
improve its corrosion resistance. Based on the in-situ polymerization of TMPTA on the aluminum
pigments surface, Liu Hui[19] prepared composite particles PTMPTA/Al with core-shell structure.
Compared with the original aluminum pigments, the dispersion, corrosion resistance, thermal
stability and activity retention of the modified particles have been significantly improved and
enhanced. Zhu et al.[20] coated aluminum pigments with polyacrylic acid by in situ polymerization.
Under the optimum conditions, the corrosion inhibition efficiency reached 99.7% and the gloss
reduced 1.8, which implies that the acquired aluminum pigment is an excellent water-based
pigment.
Emulsion Polymerization. Emulsion polymerization is often used in the encapsulation of
inorganic fine particles, Batzilla [21] discussed an emulsion polymerization-like process for the
encapsulation of aluminum pigments with polymer, the key point of this method is to use a
protective agent compound and keep low polymerization temperature. The advantage of emulsion
polymerization reflects in the dispersion medium of water, organic monomer is hydrophobic and is
easily to adsorb on the surface of aluminum pigments; while the drawback is the necessity of
pre-treatment before coating.
Liu et al.[22] prepared PMMA/Al composite particles in the presence of coupling agent MPS
and initiator by means of in situ emulsion polymerization of MMA. The corrosion resistance of the
aluminum pigments has been significantly increased. A Japanese Patent[23] elaborates the process
 Applied Mechanics and Materials Vol. 731 531

of polymer coated aluminum pigments as: reacting aluminum fine particles having ≤1 µm average
particle diameter with a coupling agent in an aprotic organic solvent to cover the surface of the
aluminum fine particles with the coupling agent and successively carrying out microemulsion
polymerization of the aluminum fine particles with a polymerizable compound having a
hydrophobic group and a hydrophilic group and having a carbon-carbon double bond in an aprotic
organic solvent. The obtained polymer-coated aluminum pigment shows good water dispersible
property. Chen Yuqiong[24] studied butyl acrylate-styrene copolymers/flaky aluminum composite
particles by emulsion polymerization in aqueous dispersion medium using SDS as emulsifier and
APS as initiator. The anticorrosion efficiency of the composite particles reaches 76.86%.

Aluminum Pigment Surface Coloring Methods

Coloring Pigment Adsorption. The color of aluminum pigment can be changed by adding color
pigments to its surface through physical or chemical adsorption. Before the adsorption of color
pigments, pretreatment is generally required to form a porous layer on the surface of aluminum
pigment so that the color pigments can easily adsorb on it.
Zhou Yi et al.[25] placed aluminum pigments into the weak alkaline solution for 60 min reacting
of boiling heat, an oxidized-layer formed on the surface of aluminum pigments as shown in Fig.2.
Then disperse the pre-treated aluminum pigments in the Light Turquoise GL(1.5 g/L) water solution,
keeping pH ranges from 8 to 10, temperature from 60 to 70℃. After 40min, they got light blue
aluminum powder. Eckart[26] implanted coloring pigments into SiO2 film while depositing SiO2 on
the surface of flaky aluminum powder by sol-gel method and obtained colored aluminum pigments.
Yin Guo Xiang et al.[27] prepared blue alumina powders by co-depositing PBP and SiO2 on the
powder in a sol-gel made of TEOS, the obtained colored aluminum powder reflect with a smooth，
dense and corrosion-resistant surface, good hydrophilic and dispersive characteristics.

Fig.2 Scheme of oxide layer on the surface of aluminum

Chemical Oxidation. In a weak alkaline aqueous solution, oxidation will occur on the surface of
aluminum pigments and create amorphous hydrated alumina, and gradually transform into Al2O3 •
H2O and anhydrous Al2O3, forming an effectively coloring layer. Put the pre-treated aluminum
pigments in the Light Turquoise GL(1.5 g/L) water solution to be colored, the obtained blue
aluminum pigments must be processed by increasing mechanical strength and pro-oil treatment[28].
The storage period of stained aluminum pigments can be extended by successive dehydration with
ethanol, butanol, and then cover stearate on the surface[29].
Interference Layer Deposition. Encapsulating interference layer on the surface of aluminum
pigments will realize down-flop effect, optical effects and color variations can be observed by
controlling the type and thickness of the surface envelope. BASF Corporation studied gas envelope
method in the 1980s[30]. Put aluminum pigments into a heatable fluid bed reactor to make it
fluidization in the mixture gas of and air (O2<3%). Heat the system to 200℃, add iron pentacarbonyl
532 Advanced Printing and Packaging Materials and Technologies

steam, control oxidation to obtain iron oxide coated with different colors of aluminum pigments.
BASF Corporation also studied other metal oxide interference layer (including TiO2, SiO2 or PMMA)
coated aluminum pigments.
Li Xiaoyuan et al.[31] obtained Al/TiO2/Fe2O3, Al/TiO2/Cr2O3, Al/TiO2/Bi2O3 etc. used in the
stealth materials by liquid phase deposition. Wu Yin et al.[32] coated flash chip aluminum pigments
with PMMA to obtain gold aluminum pigments. Fu Yiping[33], Chen Jana[34] first coated a low
refractive index layer of SiO2 with TEOS on the surface of aluminum powder by sol-gel method;
then encapsulated another layer Fe(OH)3 with FeCl3 by hydrolysis of liquid precipitation. Iron oxide
generated by the thermal decomposition of Fe(OH)3, and then formed a layer Fe2O3 with high
refractive index on the surface of aluminum powder. Thus the reaction created a interference layer
and obtained aluminum powder with bright colors and metallic luster as shown in Fig.3.

Fig.3 Schematic representation of encapsulating aluminum pigments with SiO2andFe2O3

Organic Dye Coating. Organic dye coating refers to forming thin colored layer of specific
structure on the surface of aluminum pigments through the role of cross-linking agent. BASF
Corporation [26] adopted a kind of molecule with optical groups and multi-helical structure to
realize aluminum pigments pre-treatment. Under the function of optical space groups and
multi-helix structure, the refractive index of aluminum pigments changes and produces various
interference colors.

Conclusion
Compared with in-situ polymerization and emulsion polymerization, it can be observed that
sol-gel method is relatively much more effective to aluminum pigments surface modification. A
wide variety of substrates especially polymer can be applied in sol-gel method and the modification
process is relatively simple. The modified aluminum pigments reflect the best corrosion resistance,
the minimum gloss deterioration, good adhesion and compatibility. While the in-situ polymerization
and emulsion polymerization can’t improve the corrosion resistance notably and the pre-treatment
process is very cumbersome. Through analysis for existing coloring methods of aluminum pigment
surface, the coloring effect of coloring pigment adsorption and interference layer deposition is
relatively good, the obtained products show good metallic luster and bright color, the process is
simple and easy to be implemented.
Silver ink formulated with modified aluminum pigments is water-soluble, non-toxic,
non-polluting and is convenient to prepare which makes it in line with the needs of today's
water-based, environmental friendly, green developed printing inks. Therefore, further study on
polymers much more suitable for aluminum pigments modification and resins applied in silver ink
and improve their overall performance will be the new research direction.
 Applied Mechanics and Materials Vol. 731 533

Acknowledgements
This work is supported by the “13115” science and technology innovation project in shaanxi
province. (No. 2009ZDGC-06)

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10.4028/www.scientific.net/AMM.731

Progress of Surface Modification of Aluminum Pigments

10.4028/www.scientific.net/AMM.731.528

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