Colloids and Surfaces A: Physicochem. Eng.

Aspects 477 (2015) 42–48

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Pretreatment and deposition process of electroless Ni plating on

polyimide film for electronic field applications
Libo Li ∗ , Yue Ma, Guanxiong Gao, Heng Wang, Xiuchun Yang, Jingchen Xie, Wentao Wang
Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering,
Harbin University of Science and Technology, Harbin 150040, People’s Republic of China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Continuous electroless Ni coating

was prepared for metallization of
polyimide.
• Alkaline etching and Ni salt activation
was adopted to enhance adhesion.
• Orthogonal experiment method was
used to optimize the experiment.
• Formation process of Ni nucleus in
activated films was characterized and
analyzed.
• Tensile test results showed the higher
adhesion between polyimide and
coatings.

a r t i c l e i n f o a b s t r a c t

Article history: The work is focused on electroless nickel plating on polyimide film. The Ni salt activation, which neglects
Received 10 December 2014 the use of palladium, is adopted in pretreatment. The orthogonal experiment and single factor test are
Received in revised form 13 March 2015 used to optimize the experiment, thus the optimum compositions and conditions of electroless nickel
Accepted 17 March 2015
plating are obtained. The cleaned, activated and deposited polyimide films are also characterized by
Available online 2 April 2015
their structure, morphology, component and chemical state. The activation process of nickel salt is ana-
lyzed on basis of experiment and test. A Ni–P film with fine and dense structure is achieved on the
Keywords:
polyimide film which consists of 92.23 wt.% Ni and 7.77 wt.% P. The result of tensile test indicates that
Coatings
Polymers
the adhesion between the substrate and the coating layer is sufficiently excellent due to dimples by
Etching etching.
Nucleation © 2015 Elsevier B.V. All rights reserved.
Tension test

1. Instruction
The metallization of polymer and non-metal materials has
attracted attention in recent years due to its wide application [1–6].
∗ Corresponding author. Tel.: +86 451 86392713; fax: +86 451 86392708.
E-mail address: llbo2002@126.com (L. Li).
Many polymer films, fibers and plastics are metalized for food
packaging, microelectronics, computer technology and automotive
industry to provide an electromagnetic shielding property [7]. The
wet plating method known as electroless plating, the dry plating
method known as vacuum deposition or metal spraying, and the
coating method such as using a metallic paint are well known as
techniques for metallization of polymer surface [8]. Among them,
electroless metal plating is a preferred way to produce metal-
coated materials [9–11]. Electroless nickel plating can be applied

http://dx.doi.org/10.1016/j.colsurfa.2015.03.036
0927-7757/© 2015 Elsevier B.V. All rights reserved.
 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48 43

Table 3
Results of orthogonal experiment for roughening process.

No. A B C Coverage rate, %

1 1 1 1 70
2 1 2 2 100
3 1 3 3 95
4 2 2 3 90
5 2 3 1 0
6 2 1 2 90
7 3 3 2 0
8 3 1 3 50
9 3 2 1 20

Ij 265 210 90
IIj 180 210 190
IIIj 70 95 235
Rj 195 115 145

Ij , IIj , IIIj – sum of coverage rate of level 1, level 2 and level 3, respectively.
Fig. 1. Photo of polyimide film.
Rj – range: the difference between the largest sum value and the smallest sum value
of each factor.
to most polymer substrates, due to its simplicity in operation,
low equipment cost, and excellent properties in wear, corrosion,
with de-ionized water. The etching process of electroless Ni–P
soldering, electricity, magnetism and metallization of nonmetal-
plating was optimized by orthogonal experiment method. NaOH
materials [12–15].
concentration, temperature and time in etching process, which
Polyimide (PI) is well established material in electronic pack-
were represented by A, B and C, respectively, were taken to be
aging applications due to its low dielectric constant and relatively
three investigation factors. The levels of these factors for orthogonal
high thermal stability [16,17]. However, a low surface energy and
experiment were listed in Table 1.
hence bad intrinsic adhesive properties generally characterize the
In order to get catalytic surface, the polyimide films were
surface of polyimide so that it is difficult for electroless deposition
initially immersed in activation solution for 10 min and then heat-
on the polyimide.
treated for activation at certain temperature. The immersion pH
In this work, we report the electroless deposition of nickel on
polyimide film. A series of special pretreatments, such as alkaline
etching and palladium-free activation were adopted to enhance
the adhesion between coating and polyimide surface and form the
uniform coating.

2. Experimental

2.1. Electroless deposition of the Ni–P alloys

The substrate material used for present investigation is poly-

imide film with a size of 20 mm × 20 mm × 0.2 mm, as shown in
Fig. 1.
The electroless Ni plating on polyimide substrate consisted of
four well defined stages: degreasing, etching, activation, reduction
and metallization. After cleaning the polyimide films in alkaline
degreasing solution, etching them in NaOH solution at certain tem-
perature. Afterwards, polyimide films were thoroughly washed

Table 1
Levels and factors of orthogonal experiment for etching process (L9 (33 )).

Factors Levels

1 2 3

(A) NaOH, g/L 100 150 200

(B) Temperature, ◦ C 80 70 90
(C) Time, min 30 20 10

Table 2
Levels and factors of orthogonal experiment for activation process (L16 (45 )).

Factors Levels

1 2 3 4

(A) NiSO4 ·6H2 O, g/L 30 50 40 60

(B) NaH2 PO2 ·2H2 O, g/L 50 60 30 40
(C) C6 H5 Na3 O7 ·2H2 O, g/L 30 20 40 10
(D) pH 4.5 5 5.5 6
Fig. 2. SEM micrographs of polyimide films before (a) and after (b) etching. There
(E) Heat-treatment time, min 20 30 10 60
are many dimples on the polyimide films surface after alkaline etching.
44 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48

Table 4
Results of orthogonal experiment for activation process.

No. A B C D E Coverage rate, %

1 1 1 1 1 1 20
2 1 2 2 2 2 15
3 1 3 3 3 3 0
4 1 4 4 4 4 60
5 2 1 2 3 4 98
6 2 2 1 4 3 5
7 2 3 4 1 2 2
8 2 4 3 2 1 10
9 3 1 3 4 2 80
10 3 2 4 3 1 25
11 3 3 1 2 4 50
12 3 4 2 1 3 10
13 4 1 4 2 3 10
14 4 2 3 1 4 15
15 4 3 2 4 1 40
16 4 4 1 3 2 2

Ij 95 199 77 47 95
IIj 115 060 163 85 99
Fig. 3. The change in degree of surface coverage of electroless Ni plating as a function IIIj 165 92 105 125 25
of various heat-treatment temperatures in activation process. IVj 67 82 97 184 223
Rj 98 139 86 137 198

Ij , IIj , IIIj ,IVj – sum of coverage rate of level 1, level 2, level 3 and level 4, respectively.
Rj – range: the difference between the largest sum value and the smallest sum value
of each factor.

Fig. 4. SEM images and EDS analysis of polyimide film surface after impregnated in activation solution and heat-treated in activation process: (a) SEM images of polyimide
film surface after impregnated in activation solution; (b) EDS analysis of polyimide film surface after impregnated in activation solution; (c) SEM images of polyimide film
surface after heat-treated in activation process; (d) EDS analysis of polyimide film surface after heat-treated in activation process.
 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48
Fig. 5. XPS results of polyimide film surface after impregnated in activated solution:
(a) Ni; (b) P; (c) O.
value, the heat-treatment time were varied according to the needs
of study. The activation process of electroless Ni–P plating was
carried out by orthogonal experiment. The compositions of three
activation solution and the parameters of conditions mentioned
above were taken to be five investigation factors, which were
represented by A, B, C, D and E, respectively. Table 2 presents
the orthogonal experiment levels of activation process. Simulta-
neously, the influence of heat-treatment temperature from 170 ◦ C
to 220 ◦ C on the coverage rate of electroless Ni coating was inves-
tigated by single factor analysis.
Then, have activated samples reduced in 20 g/L NaH2 PO2 ·2H2 O
solution at 95 ◦ C for 5 min. Finally, the activated polyimide films
45
Fig. 6. XPS results of polyimide film surface after activation heat-treatment: (a) Ni;
(b) P; (c) O.
were introduced into electroless coating bath 30 min for met-
allization. The electroless nickel bath was composed of 25 g/L
NiSO4 ·6H2 O, 30 g/L NaH2 PO2 ·2H2 O, 10 g/L C6 H5 Na3 O7 ·2H2 O and
10 g/L CH3 COONa, and the pH was adjusted to 4.5. The electroless
coating temperature was kept at 95 ± 2 ◦ C. Nickel sulphate was the
source of metal ions, sodium hypophosphite was reducing agent,
sodium citrate used as complexing agent and sodium acetate acted
as a buffering agent to control the pH of bath during plating pro-
cess. All chemicals used in this experiment were analytical reagent
grade. To obtain reliable results, 3 specimens were prepared and
coated for each experimental condition, then average values of 3
measurements was obtained finally.
46 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48
Fig. 7. SEM images (a) and EDS analysis (b) of activated film after reduction in
Na2 H2 PO2 solution.
2.2. Characterizations
A field emission SEM equipped with an EDS (FEI sirion) was
used to characterize the surface morphology and elemental com-
position of etched, activated, reduced and Ni–P coated polyimide
films. Atomic force microscopy (AFM, BIOSCOPE) was also used
to observe the surface morphology of the coated polyimide films.
X-ray photoelectron spectrometer (XPS, PHI-5700, ESCA System)
using monochromes Al K␣ radiation (1486.6 eV) was employed to
characterize the surface composition and the state of activated,
reduced and Ni–P coated polyimide films. All XPS peaks were refer-
enced to the C1s signal at a binding energy of 284.6 eV. X-ray
Diffraction (XRD) measurements of original, reduced and electro-
less plated polyimide films were run with an automatic Japanese
Rigaku RTP 300PC powder diffractometer with monochromatic
CuK␣ radiation. The adhesive strength was determined by tensile
test on EMT2000-B universal tensile test machine.
3. Results and discussion
In order to enhance the adhesion of coating, the surface of sub-
strate has to be etched in an alkaline etching solution. The results of
the orthogonal test (L9 (33 )) which means three factors and three
levels in total nine experiments for etching process of electroless
Ni–P plating on polyimide films surface are listed in Table 3. For
coverage rate, the optimum craft is A1 B1 C3 or A1 B2 C3 ; while more
uniform and compact coating was obtained by A1 B1 C3 , 100 g/L
NaOH at 80 ◦ C for 10 min. Fig. 2 is SEM images of polyimide films
before (a) and after (b) etching. After alkaline etching, the poly-
imide films substrate appears dimples which are rough enough to
Fig. 8. XPS spectra of Ni (a) and P (b) elements in the activated film after the reduc-
tion.
prevent nickel film from peeling off corresponding to that without
etching.
Before metallization, the polyimide films require an activa-
tion stage in order to get catalytic surfaces. The results of the
orthogonal test (L16 (45 )) which means five factors and four levels
in total sixteen experiments for activation process of electroless
Ni–P plating on polyimide films surface are listed in Table 4. The
optimum activation scheme is A3 B1 C2 D4 E4 , the composition of
the activation solution is 40 g/LNiSO4 ·6H2 O, 50 g/LNaH2 PO2 ·2H2 O,
20 g/L C6 H5 Na3 O7 ·2H2 O, pH value of 6, and the heat-treatment time
of 60 min.
The coverage rate of electroless Ni plating is plotted in Fig. 3
as a function of the heat-treatment temperatures of activation. It
can be seen that the coverage rate strongly increases in monotonic
fashion with the raising of heat-treatment temperatures in activa-
tion process. The highest coverage rate 100% is obtained when the
activation heat-treatment temperature reach up to 200 ◦ C.
The etched polyimide films are put into the activation
solution including 40 g/L NiSO4 ·6H2 O, 50 g/L NaH2 PO2 ·2H2 O,
20 g/L C6 H5 Na3 O7 ·2H2 O for impregnating 10 min, in this case, a
layer of homogeneous activated thin film mainly containing nickel,
phosphorous and oxide elements is observed on the polyimide sur-
faces (Fig. 4a and b). Afterwards, put the samples in oven 60 min for
heat-treating at 200 ◦ C and more compact and continuous thin films
are obtained (Fig. 4c and d). It is worth noting that the oxide element
content in thin film is increased after heat-treatment, which indi-
cates that the activated thin film on polyimide surface is oxidized
at 200 ◦ C.
 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48
Fig. 9. SEM (a), EDS analysis (b) and AFM images (c, d) of electroless Ni plating on
polyimide film surface.
The X-ray photoelectron spectra of the polyimide film surface
after impregnated in activation solution are investigated in order
to analyze the chemical state of thin film, as shown in Fig. 5. The
binding energy of Ni 2p3/2 is 854.4 eV due to Ni2+ in NiSO4 . It also
found that O exists in −2 oxidation state since the peak at 532.2 eV
can be assigned as O2− species in NiSO4 . The peak of P element
at about 132.6 eV indicates that phosphorous exists in oxidation
state of +1 due to Na2 H2 PO2 . After impregnation in activation solu-
tion for 10 min, the polyimide surface has been covered with NiSO4
and Na2 H2 PO2 , which will provide the nucleation reactants includ-
ing Ni2+ and H2 PO− 2 on the non-metal surface in order to produce
the active sites under appropriate conditions. These Ni ions can be
reduced by H2 PO− 2 in the following heat treatment process to form
47
Fig. 10. XRD results of polyimide substrate (a), samples after reduction (b) in acti-
vation process and electroless nickel plating (c).
active nuclei. The chemical reaction taking place during activation
can be written as:
Ni2+ + H2 PO− 0 −
2 + H2 O → Ni + H2 PO3 + 2H
+
(1)
Fig. 6 shows Ni 2p, O1s and P2p spectra of activated film on the
polyimide after heat-treatment at 200 ◦ C for 60 min. The peak of
Ni 2p3/2 at 853.8 eV is mainly assigned to the surface oxide NiO
[18,19] and to be active site after reduction. The narrow peak of P
2p with a binding energy at 133.1 eV corresponds to phosphorous
of +5 oxidation state in P2 O5 . The characteristic O 1s signature with
a binding energy of 531.5 eV can be attributed to the oxygen in
oxide [20]. Therefore, oxygenated species including NiO and P2 O5
are present in greater amount on activated film. Indeed, Reaction
(1) and following oxidation reaction during the heat treatment can
be proposed from the XPS results:
2Ni + O2 → 2NiO(top surface) (2)
Whereas, the nickel oxide can be reduced again into Ni atom
by H2 PO− 2 in the electroless bath as nucleating point. Fig. 7 shows
the surface morphology and the component of activated film after
reduction in Na2 H2 PO2 solution. Many globular particles appear
on the surface of polyimide, Ni and P content is 78.03 wt.% and
14.32 wt.%, respectively. The nickel oxide particles in the active
film have reduced into the spherical granulas like the electroless
Ni coating. But the spherical granulas are smaller, thinner and dis-
continuous.
Fig. 8 presents the XPS spectra of Ni and P elements in the acti-
vated film after reduction. The presentation and narrow peak of
Ni 2p3/2 at 852.9 eV can be attributed to Ni0 [21], and the binding
energy of 129.9 eV is attribute to P0 . The oxygenated species in acti-
vated film are reduced to simple substance in reduction solution.
Ni particles serve to nucleate the metal deposition from electroless
plating bath.
In the following step of Ni electroless plating, nickel ions in plat-
ing solution deposit on the nucleus, and the coating grow laterally
and vertically, finally, form a continuous and dense coating layer
Fig. 9 shows the surface morphology and the component of the
coating. The hemispheric grains of Ni–P alloy with 92.23 wt.% Ni
and 7.77 wt.% P cover on the substrate.
Fig. 10 is XRD results of polyimide substrates (a), samples after
reduction (b) and electroless nickel plating (c), respectively. X-ray
diffraction peak curve bread at about 45◦ is amorphous for reduced
sample in activation process and electroless Ni coating. Some metal
Ni nucleus has formed after reduction in activation process.
48 L. Li et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 477 (2015) 42–48
Fig. 11. Results of tensile test: shear tensile (a) and (b) joint tensile.
The adhesive strength of the coating is also tested by tensile
experiment, as shown in Fig. 11. The examination is performed
three times to obtain the mean shear strength. The shear strength
is 52.21 MPa, 45.41 MPa and 50.88 MPa (Fig. 11a), respectively, and
the mean shear strength is 49.5 MPa. The joint tensile tests for three
times are done and the mean joint strength is achieved. The joint
strength is 7.43 MPa, 7.73 MPa, 8.43 MPa (Fig. 11b), respectively,
and the mean joint strength is 7.86 MPa. The adhesive strength
between the coating and the polyimide substrate is higher.
4. Conclusion
The metallization of polyimide films was elaborated by an elec-
troless plating process using a Ni–P bath. For polymer materials,
the quality of coating not only depend on the deposition pro-
cess but also rely on pretreatment technology and conditions,
including degreasing, etching, activation, reduction and metalliza-
tion. At first, polyimide films were cleaned in alkaline degreasing
solution; secondly, etched in 100 g/L NaOH at 80 ◦ C for 10 min;
thirdly, immersed in the activation solution whose composition
and conditions were 40 g/L NiSO4 ·6H2 O, 50 g/L NaH2 PO2 ·2H2 O,
20 g/L C6 H5 Na3 O7 ·2H2 O, pH value of 6, and heat-treated at 200 ◦ C
for 60 min; fourthly, put into 20 g/L NaH2 PO2 ·2H2 O solution to be
reduced at 95 ◦ C for 5 min. Finally, the activated polyimide films
were introduced into the electroless bath 30 min for metalliza-
tion at 90 ◦ C. The nickel electroless plating bath was composed of
25 g/L NiSO4 ·6H2 O, 30 g/L NaH2 PO2 ·2H2 O, 10 g/L C6 H5 Na3 O7 ·2H2 O
and 10 g/L CH3 COONa, and the pH was adjusted to 4.5.
The pretreatment and plating process model of electroless Ni
deposition on polyimide substrate were analyzed. The polyimide
films appeared surface dimples by etching. And then a layer of
homogeneous activated thin film mainly containing nickel, phos-
phorous and oxygen elements was covered on the polyimide
surfaces. The nickel oxides in activated film were reduced to Ni
particles in 20 g/L NaH2 PO2 ·2H2 O solution which serve to nucleate
the metal deposition from electroless plating bath. After electro-
less Ni plating, the continuous and complete coating obtained and
covered polyimide surfaces with the higher adhesive strength.
Acknowledgement
This work is supported financially by Educational Commission
of Heilongjiang Province of China (12521z008).
References
[1] J.B. Fei, J.B. Li, Controlled preparation of porous TiO2 –Ag nanostructures
through supramolecular assembly for plasmon-enhanced photocatalysis, Adv.
Mater. 27 (2015) 314–319.
[2] J.B. Fei, L. Gao, J. Zhao, C. Du, J.B. Li, Responsive helical self-assembly of AgNO3
and melamine through asymmetric coordination for Ag nanochain synthesis,
Small 9 (2013) 1021–1024.
[3] Y. Su, Q. He, X. Yan, J. Fei, Y. Cui, J.B. Li, Peptide mesocrystals as templates
to create an Au surface with stronger surface-enhanced Raman spectroscopic
properties, Chem. Eur. J. 17 (2011) 3370–3375.
[4] H. Kinoshita, S. Yonezawa, J. Kim, M. Kawai, M. Takashima, T. Tsukatani, Elec-
troless Ni-plating on PTFE fine particles, J. Fluor. Chem. 129 (2008) 416–423.
[5] L.M. Abrantes, J.P. Correia, Polypyrrole incorporating electroless nickel, Elec-
trochim. Acta 45 (2000) 4179–4185.
[6] M. Charbonnier, M. Romand, Polymer pretreatments for enhanced adhesion
of metals deposited by the electroless process, Int. J. Adhes. Adhes. 23 (2003)
277–285.
[7] S.C. Domenech, V. E.L.J. Drago, J.C.D. Lima, N.G.B. Jr., A.O.V. Avila, V. Soldi,
Electroless plating of nickel–phosphorous on surface-modified poly(ethylene
terephthalate) films, Appl. Surf. Sci. 220 (2003) 238–250.
[8] M. Shibata, T. Ito, Metallization of cross-linked polyurethane resins by reduc-
tion of polymer-incorporated metal ion, Polymer 44 (2003) 5617–5623.
[9] E. Correa, A.A. Zuleta, L. Guerra, M.A. Gómez, J.G. Castaño, F. Echeverría, H. Liu,
P. Skeldon, G.E. Thompson, Tribological behavior of electroless Ni–B coatings
on magnesium and AZ91D alloy, Wear 305 (2013) 115–123.
[10] S. Ranganatha, T.V. Venkatesha, K. Vathsala, Development of high performance
electroless Ni–P–HNT composite coatings, Appl. Surf. Sci. 263 (2012) 149–156.
[11] H.B. Hassan, Z.A. Hamid, Electroless Ni–B supported on carbon for direct alcohol
fuel cell applications, Int. J. Hydrog. Energy 36 (2011) 849–856.
[12] W. Wang, S. Ji, I. Lee, A facile method of nickel electroless deposition on various
neutral hydrophobic polymer surfaces, Appl. Surf. Sci. 283 (2013) 309–320.
[13] B. Karagoz, O. Sirkecioglu, N. Bicak, Surface rejuvenation for multilayer metal
deposition on polymer microspheres via self-seeded electroless plating, Appl.
Surf. Sci. 285 (2013) 395–402.
[14] K. Lin, H. Wu, Y. Yu, C. Ho, M. Wei, F. Lu, W.J. Tseng, Preparation of PMMA–Ni
core-shell composite particles by electroless plating on polyelectrolyte-
modified PMMA beads, Appl. Surf. Sci. 282 (2013) 741–745.
[15] S.C. Domenech, E.L. Jr., V. Drago, J.C. De Lima, N.G.B. Jr., A.O.V. Avila, V. Soldi,
Electroless plating of nickel–phosphorous on surface-modified poly(ethylene
terephthalate) films, Appl. Surf. Sci. 220 (2003) 238–250.
[16] Y. Jung, Y. Yang, S. Kim, H. Kim, T. Park, B.W. Yoo, Structural and composi-
tional effects on thermal expansion behavior in polyimide substrates of varying
thicknesses, Eur. Polym. J. 49 (2013) 3642–3650.
[17] C. Demian, H. Liao, R. Lachat, S. Costil, Investigation of surface properties and
mechanical and tribological behaviors of polyimide based composite coatings,
Surf. Coat. Technol. 235 (2013) 603–610.
[18] N. Kitakatst, V. Maurice, C. Hinnen, P. Marcus, Surface hydroxylation and local
structure of NiO thin films formed on Ni(1 1 1), Surf. Sci. 407 (1998) 36–58.
[19] X. Yu, H. Wang, Z. Yang, P.X. Xin, XPS and AES investigation of two electroless
composite coatings, Appl. Surf. Sci. 158 (2000) 335–339.
[20] H. Li, H. Li, W. Dai, W. Wang, Z. Fang, XPS studies on surface electronic charac-
teristics of Ni–B and Ni–P amorphous alloy and its correlation to their catalytic
properties, Appl. Surf. Sci. 152 (1999) 25–34.
[21] H. Li, W. Wang, H. Li, J. Deng, Crystallization deactivation of Ni–P/SiO2 amor-
phous catalyst and the stabilizing effect of silica support on the Ni–P amorphous
structure, J. Catal. 194 (2000) 211–221.