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Physics Procedia 50 (2013) 219 – 224

International Federation for Heat Treatment and Surface Engineering 20th Congress
Beijing,China,23-25 October 2012

Influence of heat treatment for coating of nickel plating on hollow

glass beads
Sijie Wang*, Wei Zhang

National Key Laboratory for Remanufacturing, Academy of Armored Forces Engineering, Beijing 100072, China

Abstract

Ni-plated hollow glass beads (GBs) were firstly prepared by pd-activation and electroless plating, then Ni-plated GBs were heat
treated at 450 for 1h, Ni-plated GBs/PVC composite was fabricated by using polyvinyl chloride (PVC) adhesive. The
microstructure and component of Ni-plated GBs surface were studied by scanning electron microscopy and energy dispersive
spectrometer; heat insulation and reflectivity were detected by heat insulation instrument (home-made) and vector network
analyzer. The results show coatings prepared by electroless plating were uniform, the nickel element in the coating was higher
than 95.71% (mass fraction); with heat treatment, the surface roughness of coating was greater, and the reflectivity descended
apparently, the D-value was 1 dB at the frequency of 15 GHz, but the influence of heat treatment for heat insulation of Ni-plated
GBs was not great.
© 2013 The Authors. Published by Elsevier B.V.
© 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of the Chinese Heat Treatment Society.
Selection and peer-review under responsibility of the Chinese Heat Treatment Society
Key words: Ni-plated hollow glass beads, heat treating, reflectivity, heat insulation;

1. Introduction

Micro hollow glass beads have been of great interest to light-weight and heat insulated material due to their
properties, including small specific weight, large specific area, anti-corrosion, and low cost  Qiuyu Zhang et al.,
2005.
The electromagnetic loss of GBs is enhanced when the metal such as Ni, Fe, or Co is coated onto the surface of
GBs. Ni-plated GBs can be used as electromagnetic shielding and stealth materials (D. Dong et al., 2009). The use of
electroless Ni-P alloy coating is a method in which a metallic film is coated onto the surface of carbon fiber or
activated carbon fiber because of their good corrosion resistance and anti-wear, polishability, magnetic properties

* Corresponding author. Tel.: 15801620756; fax: +86 10 66719325.

E-mail address: wsj665588@126.com

1875-3892 © 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of the Chinese Heat Treatment Society
doi:10.1016/j.phpro.2013.11.035
220 Sijie Wang and Wei Zhang / Physics Procedia 50 (2013) 219 – 224

(Yating Wu et al., 2006). The crystalline structure of the deposited Ni coating could be improved by heat treatment
(Joon Jang and Seung Kon Ryu., 2006), and provide Ni-plated GBs with special performance such as increasing
roughness and layer thickness (Zhao Yan et al., 2010).
In the present study, the GBs are electromagnetic modified by Ni-P alloy coating, and the absorption of the
coating is investigated (Zhenguo An et al., 2008). PVC composite modified by Ni-plated GBs has many advantages
such as improved part densities, heat insulation and microwave absorption properties (Dumont et al., 1997).
In this work, the GBs are electromagnetic modified by electroless nickel plating. In order to see if better
properties, especially the electromagnetic loss and heat insulation, are obtained, the characterization of Ni-plated
GBs and properties of Ni-plated GBs/PVC composite were investigated by SEM, EDS, heat insulation instrument
and Vector Network Analyzer, etc.

2. Experiment

2.1. Preparation of Ni-plated GBs

The electroless nickel plating was used to prepare the Ni-plated GBs. The process is shown as Fig. 1.

Oil cleaning Surface coarsening Sensitization/activation

Heat treating Electro less nickel plating Reduction

Fig.1 Process of electroless Ni plating

The GBs with the diameters mainly in the range of 8~100 Km, the density of 0.1~0.25 g/cm3 and the purity above
99% were firstly put into alkaline solution (30 g/L NaOH and 40 g/L Na2CO3) at room temperature, and treated by
ultrasonic cleaning for 1.5h. The purpose is to clear the oil of the GBs surface.
GBs were then added into coarsening solution (1 mol/L HF acid and 0.05 mol/L NaF), magnetic stirred for 5
minutes. Then GBs were filtered, washed and dried. The purpose is to increase the oxygen groups and coarseness,
enhance the deposition of Pd element onto GBs surface, improve the compatibility between coating and GBs surface.
Hydrochloric acid0.2 mol/Lwas dropped into PdCl2 0.5 g/Lsolution, and heated to 70  slowly, then
SnCl2•2H2O  20g/L  and de-ionized water were added to form activated solution. Subsequently the coarsened
GBs were added in, magnetic stirred for 30 minutes, and then filtered, washed and dried.
The nickel-plated solution was fabricated according to Table 1.
Table1. Composition of Nickel ion

Reagent Concentration(g/L)
NiSO4·6H2O 30
NaC2H3O2·3H2O 20
NaH2PO2 40
C6H15NO3 25
NH4C1 30
Na3C6H5O7 ·2H2O 6

The activated GBs were added into the solution with load of 5 g/L, and magnetic stirred for 3 hours at 60  ,
ammonium chloride (NH4Cl, 99%) was used as a complexion agent to control the rate of release of the free nickel
metal. The pH value of the electroless solution was approximately 4.5~6.0, which was controlled by the addition of
3.6% ammonium hydroxide solution (mass fraction) in the solution, the process was optimized at 80  and Ni-
deposited GBs were washed with distilled water and dried at 110.
 Sijie Wang and Wei Zhang / Physics Procedia 50 (2013) 219 – 224 221

2.2 Ni-plated GBs heat treatment

In order to improve the surface roughness of Ni-plated GBs, the Ni-plated GB was put into muffle furnace and
heat treated in nitrogen protection at 450 (temperature rise by 50/h) for 3h, and cooled naturally.

2.3 Preparation of test sheets

PVC, plasticizing (DOP) and antioxidant (Sb2O3) were mixed to form emulsion (mass ratio: 100:30:2). Then the
GBs and Ni-plated GBs were added to form the required emulsion according to a certain mass fraction (15%).
The emulsion was sprayed layer by layer onto the preformed glossy aluminum plate. The reflectivity samples
with a square of 180mm×180mm×1.5mm, and heat insulate samples with a square of 180mm×180mm×2mm
were prepared at 170 for 30 minutes, and cooled naturally.

2.4 Characterization methods

The surface morphology of GBs and Ni-plated GBs with and without heat treating were observed using a
scanning electron microscopy (SEM), the surface component changes were equipped with an energy dispersive
spectrometer (EDS).
The heat insulation of Ni-plated GBs/PVC composite was detected using heat insulation instrument (home-made).
The electromagnetic parameters of Ni-plated GBs with and without heat treating were illustrated by vector
network analyzer (HP8722ES).

3. Result and discussion

3.1Surface morphology and composition

Fig.2 shows the morphology and component of unmodified and modified GBs surface. The GBs surface was
glossy and intact but with a few convexities (Fig. 2a), the main composition of GBs was SiO2 (Table2).

Fig. 2 SEM images and EDS of GBs/Ni-plated GBs/ Ni-plated GBs with heat treatmen (a) Before plating; (b) After plating (c) The coating with
heat treatment
222 Sijie Wang and Wei Zhang / Physics Procedia 50 (2013) 219 – 224

Table2 Elements analysis of Fig. 2

heat treated Ni-

GBs(a) Ni-plated GBs(b)
Element plated GBs(c)
Wt% Wt% Wt% At% Wt% At%
OK 40.68 54.68 6.14 8.46 1.46 1.87
SiK 47.47 36.34 3.58 4.64 - -
AlK 6.57 6.15 1.21 0.53 - -
CaK 5.27 2.83 - - - -
PK - - 3.21 7.08 2.83 4.03
NiK - - 85.86 81.29 95.71 94.1
Totals 100.00 100.00 100.00

Fig. 2(b) shows typical surface morphology of Ni-plated GBs, after electroless Ni-plating, a compact and uniform
Ni-p alloy layer was prepared. From the analysis of EDS (Table2), it can be concluded that the main composition of
the coating was Ni-P alloy, and the nickel element in the coating was higher than 85.86% (mass fraction) but it
appeared the peaks of the Si and O, which was due to some local of the coating was thin, the electron beam touched
the depth of 1m below the surface of coating.
According to the reports, coat size and morphology appearance changes dramatically by heat treating (C.Y.
Huang et al., 2004). Fig 2c shows surface morphology and composition of Ni-plated GBs after heat treating (at 450
 ), from these figures, heat treatment modified the structure, compared to the coating without heat treatment,
coating roughness increased greatly, and the Si and O peaks disappeared, the results implied that thickness of the
coating increased.

3.2Heat insulation

Micro-GBs have advantage of heat insulation, GBs/ PVC composite is a kind of excellent temperature control
material. Fig.3 shows the effect of Ni-plating for heat insulation.

13 PVC sheet
12 GB PVCsheet
11
Ni-plated GB PVCsheet
Ni-plated/heat treated GB PVCsheet
10
Cooling amplitude ()

9
8
7
6
5
4
3
2
1
20 40 60 80 100 120 140
Ambient temperature ()

Packing radio (20%), PVC composite

Fig.3 The influence of Ni-plating for heat insulation

PVC has excellent heat insulation property, and the heat insulation was improved by addition of GBs significantly.
Nickel plating and heat treating occurred, resulting in reduction of the heat insulation, but comparing with GBs PVC,
 Sijie Wang and Wei Zhang / Physics Procedia 50 (2013) 219 – 224 223

there was little difference in the low temperature range, in the high temperature range, the difference was relatively
larger, but maximum D-value was only 2 at 140  ; This indicates the influence of GBs nickel plated and heat
treated for heat insulation was not obvious.

3.3 The reflectivity

The absorbing property can be affirmed by calculating the reflectivity (Zhao Yan et al., 2010). Fig.4 shows the
reflectivity of GBs, Ni-plated GBs with and without heat treatment.

PVC sheet
1.5
GB PVCsheet
1.0 Ni-plated GB PVCsheet
Ni-plated/heat treated GB PVCsheet
0.5

0.0

-0.5
Reflectivity
dB

-1.0

-1.5

-2.0

-2.5

-3.0

-3.5

-4.0
0 2 4 6 8 10 12 14 16 18 20
Frequency(GHz)

Fig.4 The reflectivity before and after heat treating

Observed from Fig.4 (a), in the frequency range of 2-18 GHz, the reflectivity of GBs with nickel layer reduces
obviously compared with that without electroless plating. When the frequency is 12-17GHz and the band is as broad
as 5 GHz, the reflectivity of GBs with electroless plating is below-2.0 dB, while that without plating is-0.5dB under
the same condition. The variable tendency of reflectivity before and after heat treating is identical, but the
reflectivity after heat treating is less than that of the one before heat treating, and the reflectivity is less in high-
frequency wave, the D-value is 1 dB at the frequency of 15 GHz. This is because GBs obtain great dielectric
properties due to its structural characteristics, the reflected energy is reduced by the increasing of roughness (Fig.5),
and the reflection loss of Ni-plated GBs/PVC composite is enhanced.

Fig.5 Propagation of detection wave in glossy and rough surface (Zhenguo An et al., 2008)

4. Conclusions
224 Sijie Wang and Wei Zhang / Physics Procedia 50 (2013) 219 – 224

(1) A pure nickel composite membrane has been successfully prepared on hollow glass beads by electroless
plating, compared with that without electroless plating, the reflectivity of GBs with nickel layer reduces obviously.
(2) The influence of nickel plating on GBs for heat insulation was not obvious, after heat treating at 450, coat
size and morphology appearance changes dramatically, the surface roughness and thickness of coating was increased,
the reflection loss was enhanced.
(3) The influence of GBs nickel plated and heat treated for heat insulation was not obvious, and it is possible to
utilize modified GBs as absorbent in electromagnetic shielding materials.

Acknowledgements

This work was partially financed by the National Science Foundation of China (Nos. 50775222 and 50735006)
and the National Key Technology Research and Development Program of the Ministry of Science and Technology
of China2011BAC10B05.

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