Journal of Magnetism and Magnetic Materials 416 (2016) 150–154

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Effects of surface modification of Nd-Fe-B powders using parylene C by

CVDP method on the properties of anisotropic bonded Nd–Fe–B
magnets
Bin Ma, Aizhi Sun n, Zhenwen Lu, Chuan Cheng, Chen Xu
Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, PR China

art ic l e i nf o a b s t r a c t

Article history: This paper presents effects of surface modification of Nd–Fe–B powders using parylene C by means of
Received 3 August 2015 chemical vapor deposition polymerization (CVDP) on the properties of anisotropic bonded Nd–Fe–B
Received in revised form magnets. It can be well verified from SEM images and EDS analysis that the surface of Nd–Fe–B powder is
6 April 2016
coated with thin parylene C films. The maximum energy product ((BH)max), degree of alignment (DOA),
Accepted 3 May 2016
Available online 7 May 2016
actual density and corrosion resistance of parylene Nd–Fe–B magnets prepared at room temperature are
much higher than that of non-parylene Nd–Fe–B magnets. (BH)max, DOA and actual density of parylene
Keywords: Nd–Fe–B magnets (70 kJ/m3, 0.342, 5.82 g/cm3) prepared at room temperature under 578 MPa are im-
Parylene Nd–Fe–B magnets proved by 18.6%, 4.6%, 2.1% and 27.3%, 29.1%, 7.8% compared with non-parylene Nd‐Fe‐B magnets pre-
Parylene C thin films
pared at 140 °C (59 kJ/m3, 0327, 5.70 g/cm3) and room temperature (55 kJ/m3, 0.265, 5.40 g/cm3), re-
Actual density
spectively. Additional, the improvement of actual density and the room temperature process also solve
Corrosion resistance
problems such as powders’ sticking wall, non-uniform powder filling, non-uniform magnetic properties,
seriously mould damage, short life cycle of mould and so on, which exists during warm compaction
process. Parylene Nd–Fe–B magnets have better corrosion resistance and worse mechanical properties
than that of non-parylene Nd–Fe–B magnets. The reason for the improvement of magnetic properties and
actual density is the low friction cofficient of parylene C films, which results in lower frictional resistance
and better lubricating property of parylene Nd–Fe–B powders.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction production efficiency by means of surface modification of Nd–Fe–

Bonded Nd–Fe–B magnets, one of the most important func-
tional materials in modern life, have been widely applied in
various fields to convert electrical energy into mechanical energy
or vice versa [1–4]. In recent years, studies on anisotropic bonded
Nd–Fe–B magnets have become increasingly active [5,6], the ap-
plication of warm compaction process has greatly improved the
magnetic properties and actual density of Nd–Fe–B magnets [7–
11]. However, problems of powders’ sticking wall, non-uniform
powder filling, non-uniform magnetic properties, seriously
mould damage and short life cycle of mould still exist and se-
verely limit their further application in many fields. The prime
objective of this work is to prepare anisotropic bonded Nd–Fe–B
magnets with high magnetic properties at room temperature,
solve problems that exists during warm compaction process and
improve the uniformity of product performance and the
n
Corresponding author.
E-mail address: sunaizhi@126.com (A. Sun).
B powders using parylene C
Parylenes, a well-known polymer coating developed by Amer-
ican Union Carbide Company, have excellent properties including
physical and mechanical properties, corrosion resistance and low
friction coefficient [12–15]. Generally available parylene variants
are parylene C (C8H8Cl), parylene D (C8H8Cl2) and parylene N
(C8H8), and parylene C is selected for the work presented here [16].
Parylene has been used as coating materials in various fields be-
cause of its low friction cofficient, good lubricating property and
electrical insulation characteristic [17,18].
The maximum energy product of anisotropic bonded Nd–Fe–B
magnet is sensitive to orientation effect and actual density when
the magnetic powder is incorporated into an organic matrix [6]. In
this work, The DOA and actual density of parylene Nd–Fe–B
magnets prepared at room temperature under 578 MPa are im-
proved by 4.6% and 2.1% compared with non-parylene Nd–Fe–B
magnets prepared at 140 °C, which results in 18.6% increase of
(BH)max. Furthermore, the improvement of actual density and
room temperature process solve problems that still exist during

http://dx.doi.org/10.1016/j.jmmm.2016.05.013
0304-8853/& 2016 Elsevier B.V. All rights reserved.
 B. Ma et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 150–154
warm compaction process. The parylene Nd–Fe–B magnets have
better corrosion resistance and worse mechanical properties than
that of non-parylene Nd–Fe–B magnets. The reason for the im-
provement of magnetic properties and actual density is analyzed
and discussed.
2. Experimental details
2.1. Preparation of Nd–Fe–B powders coated with parylene C by
CVDP
The D-HDDR Nd–Fe–B powders, with powder size of þ400 to
"100 mesh, are used as the original material, where
(BH)max ¼294 kJ/m3, Hcj ¼1084.2 kA/m, Br ¼1.33 T. The original
Nd–Fe–B powders are first cleaned by a organic solution, 5 vol%
silane coupling agent (KH550) and 95 vol% alcohol, for 2 h using a
ultrasonic cleaner (BK-240B, China), and then the surface cleaned
Nd–Fe–B powders are washed three times in ethanol. The dried
Nd–Fe–B powders are placed in deposition region firstly and kept
stirring during the deposition and polymerization process. Par-
ylene C is vaporized to a dimeric gas at 180 °C and then cleaved
into monomer at 680 °C. The monomer vapor is thus deposited
onto the surface of powders and polymerizes into thin films
[17,19]. The glass slide is placed in deposition region together with
Nd–Fe–B powders to characterize the thickness of parylene C thin
films and the thickness of parylene C thin films is 6 um in this
work. The diagram of chemical vapor deposition polymerization of
parylene C is shown in Fig. 1.
2.2. Experimental procedure
The parylene and non-parylene Nd–Fe–B powders are pro-
cessed by 2.5 wt% epoxy resin and 0.5 wt% silane coupling agent
(KH550), which can dissolve in acetone solution [20,21]. the pro-
cessed powders are filled into the mould, preheated at 140 °C for
Fig. 1. Diagram of chemical vapor deposition polymerization of parylene C.
151
1 min and orientated under the magnetic field of 1.8 T, and then
compressed at different pressures. Finally, the compressed Nd–Fe–
B magnets are cured in a drying oven at 140 °C for 60 min.
The magnetic and mechanical properties are measured by a
hysteresis curve measuring instrument (NIM-2000, china) and a
electronic universal testing machine (CMT4305). parylene C thin
films are characterized by scanning electron microscopy (SEM,
QUANTA FEG 450, United States) coupled with energy dispersive
X-ray spectroscopy (EDS). the viscosity cofficient between mag-
netic powders and liquid epoxy resin is measured by rotational
viscometer (NDJ-1, china). polarization curves are used to describe
the corrosion resistance of Nd–Fe–B magnets by electrochemical
analyzer (CHI660E), where dilute solution, working electrode,
auxiliary electrode and reference electrode are 3.5 wt% NaCl so-
lution, Nd–Fe–B magnets, graphite and saturated KCl calomel
electrode. generally, there are three ways to characterize the or-
ientation effect of magnetic powders: Orientation factor ( cos θ )
[22], intensity ratio of X-ray diffraction peak [23] and degree of
orientation (DOA) [24]. in this study, the degree of orientation
(DOA) is selected to describe the orientation effect of anisotropic
bonded Nd–Fe–B magnets, which is expressed by formula (2-1)
DOA = ( Br// − Br⊥ )/Br// (2-1)
where Br// is the remanence parallel to the magnetic field or-
ientation, while Br⊥ is the remanence perpendicular to the mag-
netic field orientation. The density of the anisotropic bonded Nd–
Fe–B magnets is measured by gravimetry on the basis of Archi-
medes method, using distilled water as the medium.
3. Results and discussion
The parylene and non-parylene Nd–Fe–B powders with micro-
graphs of polygon are shown in Fig. 2. It can be seen from Fig. 2
(a) that Nd2O3 is covered on the surface of original Nd–Fe–B pow-
ders and the parylene C films, deposited on the surface of Nd–Fe–B
152 B. Ma et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 150–154

Fig. 2. SEM micrographs of non-parylene Nd–Fe–B powders (a) and parylene Nd–Fe–B powders (b).

Fig. 3. Maps of iron, neodymium and chlorine of parylene Nd–Fe–B powders.

powders, can be recognized in Fig. 2(b). Fig. 3 shows the maps of
iron, neodymium and chlorine distributions for the selected sample
areas of parylene Nd–Fe–B powders. It can be confirmed that Nd–
Fe–B powders are coated with parylene C thin films according to
Figs. 1 and 3, parylene C molecules containing chlorine.
Fig. 4 shows (BH)max, DOA and actual density of parylene and
non-parylene Nd–Fe–B magnets under different pressures. It is
clear that values of parylene Nd–Fe–B magnets are higher than
those of non-parylene Nd–Fe–B magnets. (BH)max, DOA and actual
density of parylene Nd–Fe–B magnets (70 kJ/m3, 0.342, 5.82 g/cm3)
prepared at room temperature under 578 MPa are improved by
18.6%, 4.6%, 2.1% and 27.3%, 29.1%, 7.8% compared with non-par-
ylene Nd–Fe–B magnets prepared at 140 °C (59 kJ/m3, 0327,
5.70 g/cm3) and room temperature (55 kJ/m3, 0.265, 5.40 g/cm3),
respectively.
Fig. 5 shows the stress–strain curves of parylene and non-par-
ylene Nd–Fe–B magnets. The maximum compressive strength and
extend value of parylene Nd–Fe–B magnet (144.53 MPa, 0.182 mm)
are lower than those of non-parylene Nd–Fe–B magnet
(167.47 MPa, 0.362 mm), which indicates that parylene Nd–Fe–B
magnet has poorer mechanical properties. The reason for the re-
duction is the lower binding force between parylene C films and
epoxy resin compared with that between Nd–Fe–B powders and
epoxy resin.
Table 1 shows the viscosity cofficient of parylene and non-
parylene Nd–Fe–B powders in liquid epoxy resin, where liquid
epoxy resin is used to characterize the difference of frictional re-
sistance of parylene and non-parylene Nd–Fe–B powders. The
viscosity cofficient between parylene C thin films and liquid epoxy
resin is decreased by 16.1% than that between Nd–Fe–B powders
 B. Ma et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 150–154 153

Fig. 5. Stress–strain curves of parylene and non-parylene Nd–Fe–B magnets.

Table 1
The viscosity cofficient between Nd–Fe–B powders, coated and non-coated par-
ylene C thin films, and liquid epoxy resin.

Samples Viscosity cofficient (Pa s)

Parylene Nd–Fe–B powders 26

Non-parylene Nd–Fe–B powders 31

rearrangement of Nd–Fe–B powders and decreases frictional re-

sistance between Nd–Fe–B powders during orientation process.
Furthermore, the DOA and actual density of parylene Nd–Fe–B
magnet are thus improved [18,25].
It is well known that the corrosion of Nd–Fe–B substrate is an
electrochemical process. And electrochemical polarization is a ef-
ficient and effective method to evaluate the corrosion of Nd–Fe–B
substrate by calculating corrosion current density [26]. The po-
larization curves of parylene and non-parylene Nd–Fe–B magnets
are shown in Fig. 6. Table 2 shows the parameters of polarization
curves of parylene and non-parylene Nd–Fe–B magnets. It can be
seen from Fig. 6 and Table 2 that the corrosion resistance of par-
ylene Nd–Fe–B magnet is much better than that of non-parylene
Nd–Fe–B magnet because of the electrical insulation characteristic
of parylene C films, where the linear polarization resistance in-
creased by 72.03% while the corrosion current decreased by 43%.

Fig. 4. (BH)max, DOA and actual density of parylene and non-parylene Nd–Fe–B
magnets under different pressures.

and liquid epoxy resin. The low friction cofficient of parylene C

films results in lower frictional resistance and better lubricating
property of parylene Nd–Fe–B powders, which promotes the Fig. 6. Polarization curves of parylene and non-parylene Nd–Fe–B magnets.
154 B. Ma et al. / Journal of Magnetism and Magnetic Materials 416 (2016) 150–154

Table 2 References
The parameters of polarization curves of parylene and non-parylene Nd–Fe–B
magnets.
[1] B.M. Ma, J.W. Herchenroeder, B. Smith, M. Suda, D.N. Brown, Z. Chen, J. Magn.
Magn. Mater. 239 (2002) 418–423.
Equilibrium po- Linear polarization Corrosion cur-
[2] J.M.D. Coey, J. Alloy. Compd. 326 (2001) 2–6.
tential (V) resistance (ohm) rent (A) [3] J. Li, Y. Liu, S.J. Gao, M. Li, Y.Q. Wang, M.J. Tu, J. Magn. Magn. Mater. 299 (2006)
195–204.
Parylene Nd–Fe–B " 0.863 535 7.901 $ 10 " 5 [4] M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto, Y. Matsuura, IEEE Trans.
magnet Magn. 55 (1984) 1584–1589.
Non-parylene " 0.925 311 1.388 $ 10 " 4 [5] M.T. Clavaguera-Mora, N. Clavaguera, J. Magn. Magn. Mate R 203 (1999) 66–68.
Nd–Fe–B [6] J. Xiao, J.U. Otaigbe, J. Alloy. Compd. 309 (2000) 10 0–10 6.
magnet [7] H. Matsunaga, M. Okita, S. Mino, et al., J. Magn. Soc. Japan 20 (1996) 217–220.
[8] C. Mishima, N. Hamada, H. Mitarai, Y. Honkura, IEEE Trans. Magn. 37 (2001)
2467–2470.
4. Conclusions [9] J.W. Kim, S.H. Kim, S.Y. Song, Y.D. Kim, J. Alloys. Compd. 551 (2013) 180–184.
[10] O.G. Eisch, M.A. Willard, E. Bruck, C.H. Chen, S.G. Sankar, J.P. Liu, Adv. Mater. 23
(2011) 821–842.
The parylene Nd–Fe–B magnets prepared at room temperature, [11] L. Lv, S.X. Bai, H. Zhang, J. Funct. Mater. Dev. 9 (2003) 337–339.
where Nd–Fe–B powders are coated with parylene C thin films by [12] I. Garcíaa, A.R. Luzuriagaa, H. Grande, L. Jeandupeux, J. Charmet, E. Laux,
H. Keppner, D. Mecerreye, G. Cabanero, Mater. Chem. Phys. 124 (2010)
chemical vapor deposition polymerization (CVDP), show higher
780–784.
(BH)max, DOA, actual density and better corrosion resistance [13] W.F. Gorham, J. Polym. Sci. Part A: Polym. Chem. 4 (1966) 3027–3030.
compared with non-parylene Nd–Fe–B magnets prepared at room [14] H.T. Pu, X.R. Sun, Acta Polym. Sin. 4 (2006) 603–608.
temperature and 140 °C. The (BH)max, DOA and actual density of [15] J.D. Han, A.D. Xu, Mater. Dev. 1003 (353) (2011) 430–433.
[16] A. Khabaria, F.K. Urban, J. Non-Cryst. Solids 351 (2005) 3536–3541.
parylene Nd–Fe–B magnets (70 kJ/m3, 0.342, 5.82 g/cm3) prepared [17] H.T. Pu, F.J. Jiang, Y.X. Wang, B. Yan, Colloids Surf. A: Physicochem. Eng. Aspects
at room temperature under 578 MPa are improved by 18.6%, 4.6%, 361 (2010) 62–65.
2.1% and 27.3%, 29.1%, 7.8% compared with non-parylene Nd–Fe–B [18] S. Wu, A.Z. Sun, Z.W. Lu, C. Cheng, Mater. Chem. Phys. 153 (2015) 359–364.
[19] H.T. Pu, Y.X. Wang, Z.L. Yang, Mater. Lett. 61 (13) (2007) 2718–2722.
magnets prepared at 140 °C (59 kJ/m3, 0327, 5.70 g/cm3) and room [20] M. Yue, Y.P. Wu, Y.F. Xiao, J.X. Zhang, Mater. Sci. Technol. 15 (2007) 541–544.
temperature (55 kJ/m3, 0.265, 5.40 g/cm3), respectively. The new [21] D.B. Chen, W.S. Zha, J.Y. Liu, Y. Yan, J. Ran, G.M. Liu, Chin. Rare Earths 29 (2009)
process by coating parylene C on the surface of Nd–Fe–B powders 72–74.
solves problems such as powders’ sticking wall, non-uniform [22] C.W. Searle, V. Davis, R.D. Hutchens, J. Appl. Phys. 53 (1982) 2395.
[23] T.S. Chin, M.P. Hung, D.S. Tsai, J. Appl. Phys. 64 (1988) 5531.
powder filling, non-uniform magnetic properties, seriously mould [24] S.Z. Zhou, Q.F. Dong, Rare-earth Iron-based Permanent Magnet Materials,
damage, short life cycle of mould and so on, which exist during second ed., Metallurgical Industry Press, Beijing, 2004.
warm compaction process. The reason for the improvement of [25] C.N. Degoix, A. Griffo, R.M. German, Int. J. Powder Metall. 34 (2) (1998) 29–33.
[26] I. Costa, M.C.L. Oliveira, H.G. de Melo, R.N. Faria, J. Magn. Magn. Mater. 278
magnetic properties and actual density is the low friction coffi- (2004) 348–358.
cient of parylene C films, which results in lower frictional re-
sistance and better lubricating property of parylene Nd–Fe–B
powders.