Yi-Ming Sun1, Teng-Fei Ma2, De-Peng Gong3 and Miao Yu4

Study on Organic Modification of Aluminum

Powder Coating
Abstract: In order to prepare coated aluminium pigments, the aluminium powders
were coated with polyacrylic acid through in-situ polymerization. The effects of
dosage of acrylic acid and DAAM-ADH dosage ratio on corrosion inhibiting efficien-
cy of self-crosslinking coated pigment were experimentally investigated. The results
show that, with acrylic acid of 0.5g, mass ratio of DAAM and ADH of 1:2, reaction
temperature of 85°C the rate of corrosion inhibitor of self-crosslinking polyacrylic
acid coated aluminium powder reach to more than 90%. Furthermore, the alumini-
um pigments are analysed by scanning electron microscopy, which reveal that the
aluminium powders are successfully coated with polyacrylic acid. The aluminium
pigments are analysed by Fourier transform infrared spectrum and the experiment
of corrosion inhibitor, which reveal that the polyacrylic acid of coated aluminium
powders generate cross-linking.

Keywords: coated aluminium powder; self-crosslinking; inhibition efficiency; in-situ

polymerization

1 Introduction
Recent years, the government attaches great importance to the environmental issues
so that more and more aluminium flake pigments have been used in waterborne
coatings [1]. However, under the condition of water and oxygen, the lustre of alu-
minium powder was affected because of corrosion. Aluminium flake pigments will
be more serious corrosion in alkaline environments [2].

||
1
School of Materials Science and Engineering, Hubei University of Technology, Key Laboratory of
Green Materials for Light Industry, Hubei University of Technology, Hubei Wuhan, China, E-mail:
[email protected]
2
School of Materials Science and Engineering, Hubei University of Technology, Key Laboratory of
Green Materials for Light Industry, Hubei University of Technology, Hubei Wuhan, China, E-mail:
[email protected]
3
School of Materials Science and Engineering, Hubei University of Technology, Key Laboratory of
Green, Materials for Light Industry, Hubei University of Technology, Hubei Wuhan, China, E-mail:
[email protected]
4
School of Material Science and Engineering, Hubei University of Technology, Key Laboratory of
Green Materials for Light Industry, Hubei University of Technology, Hubei Wuhan, China,
Email:[email protected]

10.1515/9783110516623-005
DOI 10.1515/9783110303568-005
Brought to you by | provisional account
Unauthenticated
Download Date | 12/28/19 2:28 AM
 46 |Yi-Ming Sun, Teng-Fei Ma, De-Peng Gong and Miao Yu

The primary means of aluminium powder protection is coating. In order to protect

the aluminium powder from corrosion Qing-peng li etc [3] use tetraethylorthosilicate
as raw material to coeat aluminium powder with silica, which disadvantage is the
poor compatibility of coated aluminium powder and waterborne coatings. Hongwei
Zhu etc [4] prepar polyacrylic acid / aluminum composite particles using the meth-
od of in-suit polymerization. Aluminium powder was coated with hydrophilic
cacrylic acid, which could inhibit corrosion in some way, however acrylic could
dissolve under aqueous environment for a long time. Liu etc [5] use methods of dou-
ble cladding of organic shell- inorganic core and organic core- inorganic shell, the
corrosion rate of coated aluminium powder up to 96.4%, 97.9%, which disad-
vantages are complex process and high cost.
With the technology of self - crosslinking growing up, many self - crosslinking
systems was used in coatings and adhesives to increase solvent resistance and
hardness [6]. The aluminium pigments become hydrophobic by using self - cross-
linking technology in coated aluminium powder. Xie etc [7] add aziridine cosslinker
in the acrylic resinemulsion to improve the mechanical properties of rubber mem-
brane and water, alkaline resistance, solvent resistance, however, the disadvantage
of aziridine cosslinker are corrosive, high price and toxicity.Chen etc [8] used diace-
tone acrylamide (DAAM) and adipic dihydrazide (ADH) as crosslinker to prepare
room temperature self - crosslinking acrylic resin with core - shell structure by the
method. Of seeded emulsion polymerization.
This article firstly proposed that combination of self - crosslinking technology
and coating keep the hydrophilic and improve its water resistance at the same time.
Acrylic was used to coating raw materials while self - crosslinking system of carbo-
hydrazide was used to crosslink. Self - crosslinking system of carbohydrazide is
characteristic of less pollution, safe and convenient in the process. The preparation
of coating is characteristic of flexibility, mechanical strength, resistance to water [9,
10].

2 Experimental
2.1 Materials
Aluminum: CP, Suzhou Alloy Material Co.Ltd; Ethanol: AR, Sinopharm Group chem-
ical reagent Co; Isopropyl alcohol: AR, Sinopharm Group chemical reagent Co;
Acrylic acid ( AA ): AR, Sinopharm Group chemical reagent Co; Ammonium persul-
fate: AR, Sinopharm Group chemical reagent Co; Calcium hydroxide: AR, wind ship
of Tianjin Chemical Reagents Technology Co.Ltd; Ammonia:AR, loading Plant of
Shanghai Chemical Company; Diacetone acrylamide ( DAAM ): AR, Sinopharm

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 Study on Organic Modification of Aluminum Powder Coating | 47

Group chemical reagent Co; Adipic dihydrazide ( ADH ): Analysis of pure, si-
nopharm Chemical Reagent Co. Ltd.

2.2 Apparatus
Infrared Spectrometer: Fourier type FT-IR200, the NICOLET company; Scanning
Electron Microscope: JSM-6390LV, JEOL Japanese Hitachi Company.

2.3 Specimen Preparation

Weighing a certain amount of aluminum powder with anhydrous ethanol washing
three times and then suction filtration.
Taking a certain amount of washed aluminum powder, sodium bicarbonate,
isopropyl alcohol, acid, DAAM and distilled water, then adding the three flasks
fitted with condensing tubes and blenders, and then warming up to the right tem-
perature, constant pressure drop funnel into ammonium persulfate initiator to made
acrylic and DAAM functional monomer polymerization on the surface of aluminum
powder, adjustment of pH to 7-8 using ammonia after cooling, adding ADH solution
and stirring, self - crosslinking coated with aluminium powder was getting after
suction filter.
Repeating the experiment in different reaction conditions.

2.4 Sample Characterization

2.4.1 Corrosion Tests

Weighing 0.5g coated aluminium powder place in the conical flask, Pour 40ml
pH=12 calcium hydroxide solution, and put a catheter inserted in the tank filled with
water in a graduated cylinder, 24h after reading. J corrosion inhibition efficiency is
used to judge the effect of Corrosion Protection of Aluminum pigments:

9  9
- u  (1)
9

Equation (1) is the equation for calculating rates of corrosion inhibitor J,where V0
refers to the volume of release of hydrogen that is not coated with aluminium pow-
der in conditions of solution of calcium hydroxide with pH equals to 12;
V refers to the volume of release of hydrogen of flake aluminium powder Coated
in conditions of solution of calcium hydroxide with pH equals to 12.

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 48 |Yi-Ming Sun, Teng-Fei Ma, De-Peng Gong and Miao Yu

2.4.2 Infrared Spectroscopic Analysis

Infrared analysis of aluminium powder coated: Taking a small amount of drying test
powder pattern and KBR powder, mixing, and mulling, sample scanning ranges
from 4000 to 400cm-1.

2.4.3 Analysis by Scanning Electron Microscope ( SEM )

On self-crosslinking of aluminium powder-coated surface spraying, using Japanese

Neo-Confucianism H-800 test scanning electron microscope, then observing surface.

3 Results and Discussions

3.1 Corrosion Tests Results in Different Reaction Conditions
Studing on the effects of the amount of acrylic acid on the aluminum powder coat-
ing corrosion efficiency when aluminum powder of 2g, ammonium persulfate of
0.2g, mass ratio of DAAM and ADH of 2:1, reaction time of 2 hour and reaction tem-
perature of 85°C. In Figure 1it can be seen that with the increase of amount of acrylic
acid, inhibition efficiency increased gradually. With the increase the amount of
acrylic acid on the one hand increases the chance of contact with aluminium pow-
der, more polies - acrylic acid coating on aluminum flake powder. Besides, the more
amount of acrylic acid the more chance of reaction with functional monomer of
DAAM, polyacrylic acid on the surface of the aluminum powder crosslinking more
fully.

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 Study on Organic Modification of Aluminum Powder Coating | 49

100 Self cross-linking polyacrylic acid - coated aluminum powder

90

80

70

60
J/%

50

40

30

20
0.1 0.2 0.3 0.4 0.5
AA/g

Fig.1: A plot of (J) corrosion inhibition efficiency versus the mass of AA

Studying on the effects of the mass ratio of DAAM and ADH on the aluminum pow-
der coating effects of corrosion efficiency when aluminum powder of 2g, acrylic acid
of 0.3, ammonium persulfate of 0.2, reaction time of 2 hour and reaction tempera-
ture of 85°C. In Figure 2 it can be seen that increase the quality of ADH, inhibition
corrosion efficiency of coated aluminium powder is also on the rise when the mass
ratio of ADH and DAAM small than 0.5, because the increased quality of ADH in-
crease the chances of reacting to the DAAM, which increases the degree of crosslink-
ing systems, and makes polypropylene acid on the surface of coated aluminium
powder more resistant to water and corrosion; Inhibition corrosion efficiency of
coated aluminium powder is little change when the mass ratio of ADH and DAAM
more than 0.5, because the quality of ADH increases, but the quality of DAAM not
increase, there is no functional groups of cross-linking react with ADH, so the de-
gree of crosslinking will not increase, the water resistance and corrosion resistance
of aluminum powder will not improve, so the inhibition efficiency was also little
changed.

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 50 |Yi-Ming Sun, Teng-Fei Ma, De-Peng Gong and Miao Yu

86
Self cross-linking polyacrylic acid - coated aluminum powder
84
82
80
78
76
J/%

74
72
70
68
66
0.0 0.5 1.0 1.5 2.0 2.5 3.0
ADH/DAAM

Fig. 2: A plot of corrosion inhibition efficiency versus mass ratio of DAAM and ADH

3.2 Infrared Spectroscopy

Comparing with figure3 (a) and 3(b), the wave number in the field of 1500-1675 only
one peak which is the characteristics absorption of carbon - carbon double bond
stretching vibration can be found in fig.a, while in figure b in the field of 1500-1675
has two peaks, which is carbon - carbon double bond extension vibration and car-
bon - nitrogen double bond extension vibration. The Carbon - Nitrogen double bond
is formed by hydrazide crosslinking reaction.

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 Study on Organic Modification of Aluminum Powder Coating | 51

polyacrylic acid coated aluminum particles

1092.55
1587.91
2925.87 1458.94
3411.42

3500 3000 2500 2000 1500 1000 500 0


Wave numberFP

Self cross-linking polyacrylic acid - coated aluminum powder

2933.99
3415.72 1367.13
1713.18 1457.68
1632.12
1170.23
1537

3500 3000 2500 2000 1500 1000 500 0

-1
Wave number/cm

Fig. 3: The FTIR spectrum: a is polyacrylic acid coated aluminium powder; b is self - crosslinking
polyacrylic acid coated aluminium powder

3.3 Scanning Electron Microscopy ( SEM ) Analysis

Aluminum powder particle surface can be seen angular from figure4 (a), according
to which, the grooves can be show clearly, figure4 (c) can't shows a clear edge and

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 52 |Yi-Ming Sun, Teng-Fei Ma, De-Peng Gong and Miao Yu

notch, however, a fuzzy layer of material on it, because aluminum powder coating
cross linked polyacrylic acid.
a b

c d

Fig. 4: SEM of aluminum powder and coated aluminium powder (a) the local morphology of alumi-
num powder; (b) the overall morphology of aluminum powder; (c) the local topography of coated
aluminum particles; (d) the overall top ography of coated aluminum particles.

4 Conclusions
(1)Through analyzing the study on preparing self - crosslinking coated aluminum
particles by using in - situ polymerization of acrylic acid and then introducing
hydrazine crosslinking system,it’s found that the more amount of acrylic acid
corrosion rate the better of self - crosslinking coated aluminum particles, mass
ratio of ADH and DAAM affect the degree of crosslinking of coated aluminum
particles.

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
 Study on Organic Modification of Aluminum Powder Coating | 53

(2)The corrosion rate of preparatied self - crosslinking polyacrylic acid coated alu-
minum is higher than 90% under the conditions acrylic acid of 0.3g, mass ratio
of DAAM and ADH of 2:1, reaction time of 2 hour and reaction temperature of
95 °C.
(3)A layer of film on aluminum powder can be observed by scanning electron mi-
croscopy, which proved polyacrylate coat on aluminium powder successly. It’s
found the characteristics absorption peak of the Carbon - Nitrogen double bond
by IR spectra, which is due to the formation of cross – linking.

References
[1] Gao Aihuan, Pi Pihui, Wen Xiufang, Cheng Jiang, “Research Progress of modification of alu-
minum pigments for corrosion protection,” Chemical Industry and Engineering Progress, Vol.
28, pp. 485-490 2009
[2] Liang Wei,Ye Hongqi, Chen Yuqiong, Liu Xiuyun, “Corrosion Resistance of the Flaky Alumi-
num Powder Coated by Emulsion Polymerization,” Journal of Chinese Society for Corrosion
and Protection, vol. 31, pp. 68-71 2011
[3] Li Qingpeng,Ding Guoqiang,Liu Jianguo, He Xiujuan,Yan Chuanwei, “Inhibition of Hydrogen
Evolution for Powder Mixture of Zn and Al by SiO2 Coated Al,” Paint Industry, vol. 42, pp. 75-
79 2012
[4] Hongwei Zhu, Zhenxing Chen, Yong Sheng, Thu Thuy Luong Thi, “ Flaky polyacrylic ac-
id/aluminium composite particles prepared using in-suit polymerization,” Dyes and Pigments,
vol. 86, pp. 155-160 2010
[5] Liu hui,Ye Hongquan, “Influence of Double-Layer Coating on the Anticorrosion Behavior of
Aluninium Powders,” Materials Protection, vol. 41, pp. 38-40 2008
[6] Peng Jun,Ren Biye,Ou Yang, “Propress in Ambient Self-Crosslinking Technology of One Com-
ponent Waterborne Coatings,” Paint and Coatings Industry, vol. 42, pp. 73-79 2012
[7] Xie Fei,Liu Zonghui,Wei Deqing, “ Properties and Curing Kinetic of Acrylic Resin Cured with
Aziridine Crosslinker,” synthetic chemistry, vol. 10, pp. 120-125 2002
[8] Chen Jia,Qiang Xihuai, “Synthesis and Characterization Research of Keto-hydrazine Cross-
linking Core-shell Structure Acrylate Emulsion,” Fine Chemical Industry, vol. 29, pp. 1212-1216
2012
[9] Yan Xu,Tang Yifeng,Tang Liming, “Synthesis,structure and properties of water-based ambi-
ent self-crosslinkable polyacrylate emulsion,” Electroplating and Finishing, vol. 32, pp. 57-61
2013
[10] Fu Xiaokun,Qu Linchuan, “Consideration on the Fire Protection Technology of Construction
Steel Structure,” Shang hai coating, vol. 52, p.44-46 2014

Brought to you by | provisional account

Unauthenticated
Download Date | 12/28/19 2:28 AM
Brought to you by | provisional account
Unauthenticated
Download Date | 12/28/19 2:28 AM