18Material Science and Technology of Japan, 54㸦2017㸧100㹼105Jun. 2017

Regular Paper
Quaternary Ammonium Salt Additives for High TiO2 Particle Contentin Electrodeposited Zn-TiO2 Composites
Tomiyuki ARAKAWA1, Yuya YAMAMOTO2, Mitsuru NOZAWA3,
Nobuaki WATANABE3 and Ichiro KOIWA2,3*
1

Institute of Science and Technology, Kanto Gakuin University, 1-50-1 Mutsuura-Higashi, Kanazawa-ku,
Yokohama, Kanagawa 236-8501, Japan
2

Graduate School of Engineering, Kanto Gakuin University, 1-50-1 Mutsuura-Higashi, Kanazawa-Ku,
Yokohama, Kanagawa 236-8501, Japan

3

College of Science and Engineering, Kanto Gakuin University, 1-50-1 Mutsuura-Higashi, Kanazawa-Ku,
Yokohama, Kanagawa 236-8501, Japan

Received Feb. 11, 2017; accepted for publication Apr. 21, 2017
Abstract
Quaternary ammonium salts of four different chemical structures, used as additives in electrodeposition baths, werecompared in order to obtain a higher TiO2 particle content in electrodeposited Zn-TiO2 composites. Electrodeposition
baths containing 0.1 mol/dm3 ZnSO4·7H2O, 0.2 mol/dm3 MgSO4, 0.15 mol/dm3 H3BO3, and 10g/dm3 TiO2 powder
were prepared. In addition, benzylcetyldimethylammonium chloride (BCDAC), benzyldimethyltetradecylammonium
chloride dehydrate, hexadecylpyridinium chloride monohydrate, and benzethonium chloride were introduced to thebaths as additives. The titanium content ratio in the Zn-TiO2 electrodeposited from a bath with 2.0 g/ dm3 BCDAC
additives reached 59.9 atomic% at an electrodeposition current density of 500 A/m2. Furthermore, a higher TiO2
content in the Zn-TiO2 composites caused a greater dendritic aggregation of TiO2 particles on the surface. Thesefindings suggest that BCDAC containing a benzene ring and a longer group provides a higher TiO2 particle content inthe Zn-TiO2 composites, and more dendritic structure.
Keywords: Electrodeposition, Zn-TiO2, Quaternary ammonium salts, BCDAC

1.

Introduction

increase in TiO2 content gives the increase in a reaction field andZn-TiO2 composites are expected to improve corrosion

an adsorption activity site. Furthermore, a ZnCl2-based

resistance[1],

furthermore

anattractivecoatingasaelectrodeposition bath led to a higher TiO2 particle content in thephotocatalytic material [2]. Several researchers have investigatedZn-TiO2 composites [5]. In any case, the TiO2 content needs tocontrolling the co-deposited TiO2 particle content using various

be controlled and optimized for the application.

methods [3-6]. Camargo et al. reported the influence of

The behavior of particles in the composites is affected byultrasound on the electrodeposition of Zn-TiO2 composites indifferent parameters of the electrodeposition conditions [7]. The

which the TiO2 particle content was 0.53–0.78 wt% [5].

introduction of surfactants as additives prevents particles fromAchieving a TiO2 particle content of 2.26 to 5.58 wt% depended

aggregatingon the bath temperature [4]. Also, the hardness of Zn-TiO2

generation on cathodes during electrodeposition, and change thecoatings increased with increasing TiO2 particles wt% in thesurface potential of particles [6]. Surfactants have been used forcoatings in the region of 2.26–5.58 wt% [4]. The photocatalysis

electrodeposited Ni-Al2O3 [8,9], Ni-WC [10], and Ni-SiC [6,11]

is likely to be improved by increasing TiO2 content, because thecomposites. Cationic surfactants influence the amount of*Corresponding author: koiwa@kanto-gakuin.ac.jp(100)

inelectrolyte

solutions,suppresshydrogen