JOM, Vol. 73, No.

12, 2021
https://doi.org/10.1007/s11837-021-04850-4
Ó 2021 The Minerals, Metals & Materials Society

CORROSION AND PROTECTION OF MATERIALS AT HIGH TEMPERATURES

Surface Modification and Refinement of Nd–Fe–B Magnetic

Powder Using ITDT and Phosphoric Acid

HAIBO CHEN,1,2 JINGWU ZHENG ,1,4 XIAOTIAN CHENG,1,3

WEI CAI,1 LIANG QIAO,1 and SHENGLEI CHE1,5

1.—Research Center of Magnetic and Electronic Materials, College of Materials Science and
Engineering, Zhejiang University of Technology, Hangzhou 310014, China. 2.—College of
Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310000, China.
3.—Guangxi Iron and Steel Group, Guangxi 530000, China. 4.—e-mail: zhengjw@zjut.edu.cn.
5.—e-mail: cheshenglei@zjut.edu.cn

High-temperature oxidation resistance of Nd–Fe–B magnetic powder is of

great importance for its application in bonded magnet fields. In this work, the
refinement and surface modification of Nd–Fe–B magnetic powders were
integrated and achieved simultaneously. The effects of phosphoric acid, iso-
propyl tris-(dioctyl pyrophosphate acyloxy) titanate (ITDT), and the syner-
gistic addition of them on the oxidation resistance of the powders were
investigated. Also, the formation mechanism of the protective layer on the Nd–
Fe–B powder surface has been proposed. The surface morphology, phase
structure, oxidation resistance, and magnetic properties were studied. The
results show that the synergistic surface modification exhibited optimal oxi-
dation resistance on the refined magnetic powders. Furthermore, the obtained
powders were bonded with polyphenylene sulfide to illustrate the effect of
high-temperature oxidation resistance in practical application. The ITDT
showed excellent protective performance for the magnetic properties at room
temperature, whereas the phosphate showed an excellent oxidation resistance
at high temperatures.

available Nd–Fe–B magnetic powders are com-

INTRODUCTION
Because bonded magnets prepared via injection
molding have many excellent properties, including
high size precision, good chemical stability and
corrosion resistance, stable magnetic properties, low
eddy current loss, and various complex shapes,1–4
they are used for energy conversion and signal
transmission in a wide range of areas, such as
electric motors, household electrical appliances, and
automobiles.5–8 The rare-earth iron-based inter-
metallic compound Nd–Fe–B is a known attractive
magnetic material,9–11 and bonded magnets are
typically produced by mixing the hard magnetic
powder like Nd–Fe–B with a resin binder, followed
via injection molding.12–14 The Nd–Fe–B powder is
the key raw material for developing high-perfor-
mance bonded magnets.15 Currently, commercially
(Received April 8, 2021; accepted August 12, 2021;
published online September 3, 2021)
monly produced via quick quenching,16,17 and
always show a scaly and flaky shape.18 The energy
product of bonded magnets is proportional to the
properties of the magnetic powders and the square
of the magnetic filler’s volume fraction.19 The
reduction in particle size could effectively improve
the melt flow performance and increase the packing
percentage of the magnetic powder filler into the
polymer matrices.20,21 Ball-milling is an effective
way to achieve the refinement of Nd–Fe–B pow-
ders.22 However, the Nd–Fe–B magnetic material
exhibits a high chemical activity.23,24 After refine-
ment, the activity of the magnetic powders
increases further, due to the increase of specific
surface area, and this causes the powders to be
easily oxidized. Moreover, the magnetic powders
must be blended with polymer at a temperature
higher than 200°C when applied in preparing
bonded magnets,19 and this requires excellent
high-temperature oxidation resistance for the Nd–

3941
3942 Chen, Zheng, Cheng, Cai, Qiao and Che

Fe–B powder. Therefore, the refined Nd–Fe–B powders were dried at 50°C in a vacuum oven for
magnetic powder must be surface-modified to 3 h.
increase the oxidation resistance. In recent years,
several works devoted to surface modification Characterizations
research on rare-earth magnetic powders have been
The surface morphology and particle size were
published. For example, soaking and coating using
observed using scanning electron microscopy (SEM;
silicone organics18,25,26 or a phosphorizing agent,27
SU-1510; Hitachi, Japan). The particle size distri-
coating of parylene C by chemical vapor deposition
bution (PSD) of the Nd–Fe–B powders were mea-
polymerization,28 and metal layer coating by elec-
sured via a Sympatec Helos/Rodos laser diffraction
trochemical deposition29 have been reported.
particle size analyzer (Sympatec, Germany), and
Among them, phosphoric acid shows fairly good
the measuring ranges of R1, R3, and R5 in the laser
effects in the aspect of anti-oxidation. However, the
diffraction system were used. Thermogravimetric–
research on the anti-oxidation mechanism and the
differential scanning calorimetry (TG-DSC;
effect of phosphate chemical conversion coatings
Q5000IR; TA Instruments, USA) was conducted to
focuses on sintered magnets, while have been rarely
obtain the curves from room temperature to 300°C
reported on the refined Nd–Fe–B powders used for
with a heating rate of 10 K min1 under air
bonded magnets. Isopropyl tris-(dioctyl pyrophos-
atmosphere. The oxygen content was measured
phate acyloxy) titanate (ITDT) is an effective sur-
using the Oxygen/Nitrogen/Hydrogen Analyzer
face treatment agent. The application of synergistic
(ONH 836; Leco, USA). The elemental analysis
addition of ITDT and phosphoric acid on Nd–Fe–B
was carried out using X-ray fluorescence spectrom-
powders to improve oxidation resistance has not
etry (XRF; ZSX Primus-II; Rigaku, Japan). The X-
been reported in the literature.
ray diffraction (XRD) patterns were measured on an
In this work, the Nd–Fe–B magnetic powders are
X’pert PRO Model powder diffractometer (PANalyt-
simultaneously refined by ball-milling and were
ical, Netherlands) operating at 40 kV and 30 mA
surface-modified using ITDT and phosphoric acid.
using Cu Ka radiation (k = 1.5404 Å). The diffrac-
The morphology, phase, oxidation resistance, and
tograms were recorded in the 2h range from 20° to
magnetic properties were studied. Refined Nd–Fe–B
80°. The magnetic behavior of the Nd–Fe–B pow-
powders with excellent high-temperature oxidation
ders was investigated using a vibrating sample
resistance were obtained, and the mechanism of the
magnetometer (VSM; Lakeshore 7307, USA) with a
formation of protective coatings on the Nd–Fe–B
maximum magnetic field of 1350 kA m-1. A B-H
powder surface has been proposed.
analyzer (FE-2100H; Hunan Forever Elegance
Technology, China) was used to test the magnetic
EXPERIMENTAL
properties of the bonded magnets. To fabricate the
Materials bonded magnets for testing, the magnetic compound
was first prepared. The Nd–Fe–B powders (89.7
Nd–Fe–B magnetic powders (Grade: MQP-12-
wt.%) and PPS resin (10.3 wt.%) were pre-mixed
8HD) used in this study were obtained from Mag-
and then fed into a twin-screw extruder using a
nequench. Phosphoric acid (H3PO4, CAS: 7664-38-2)
single-screw conveyor. In the extrusion process, the
was supplied by Shanghai Lingfeng Chemical
temperature was set at 300°C for the feed zone and
Reagent, China. Isopropyl tris-(dioctyl pyrophos-
the die zone, and at 315°C for the melting and melt-
phate acyloxy) titanate (ITDT, CAS: 67691-13-8)
pumping zones. Then, the obtained magnetic com-
was supplied by Hangzhou Jessica Chemical, China.
pound was injected, forming cubic magnets of
Absolute ethanol was purchased from Anhui Ante
10 9 10 9 10 mm, with the barrel temperature of
Food, China. PPS resin (Grade: Ryton XE5501BL)
320°C and the mold temperature of 120°C.
was obtained from Solvay.
RESULTS AND DISCUSSION
Refinement and Surface Modification
Mechanism of Modification and Refinement
Nd–Fe–B magnetic powders were refined using a
planetary ball mill. Typically, 40 g of Nd–Fe–B The morphology of the initial quick-quenched
powders and 400 g of zirconia balls (300g u2 mm magnetic powders and the obtained Nd–Fe–B pow-
and 100g u10 mm) were added into a 0.5-L ball- ders with different milling times and different
milling tank and spun at 250 rpm for the set time. additions are shown in Fig. 1a–f, and the corre-
Phosphoric acid (0.612 g, 85% in H2O), ITDT (0.4 g), sponding PSD curves are illustrated in Fig. 1g.
and the mixture of them were each used as a Dimensionless logarithmic differential (density) dis-
protective agent for surface modification. The tribution, q3lg, was exhibited in PSD curves to
remaining space of the ball-milling tank was filled observe the discrete degree and central tendency of
with ethanol and Ar gas to eliminate air during the the data more intuitively and quickly, and a loga-
ball-milling process. Subsequently, the milled pow- rithmic x-axis was used to show better resolution
ders were separated from the zirconia balls and over the entire distribution width. The magnetic
then rinsed with ethanol several times. Finally, the powder particles were first refined to D50 = 18 lm
Surface Modification and Refinement of Nd–Fe–B Magnetic Powder Using ITDT and 3943
Phosphoric Acid

Fig. 1. SEM images of (a) initial coarse Nd–Fe–B powders; (b) powders ball-milled in pure ethanol for 30 min; powders ball-milled for 3 h: (c) in
pure ethanol, (d) in phosphoric ethanol solution, (e) in ITDT ethanol solution, and (f) in ethanol solution with both phosphoric acid and ITDT; (g)
size distribution of Nd–Fe–B powders.

after 30 min of ball milling, as shown in Fig. 1b and
g. Because the quick-quenched Nd–Fe–B powders
were scaly and possessed high diameter-to-thick-
ness ratios, the fracture of the powders occurred
preferentially along the length direction during the
early ball-milling stage. Then, the particle size was
decreased to a size finer than 10 lm after 3 h of ball
milling, as shown in Fig. 1c–g. It can be concluded
from the PSD curves in Fig. 1g that ball milling with
the addition of ITDT caused the magnetic particle
size distribution to be more concentrated and uni-
form by acting as a surfactant.30 The refined Nd–
Fe–B powder with the synergistic addition of phos-
phoric acid and ITDT showed the most uniform and
concentrated size distribution, and the PSD curve
combined the distribution characteristics of the
samples with single phosphoric acid or ITDT
addition.
The schematic of the refinement and surface
treatment effect is shown in Fig. 2. In the process
of ball milling, the flaky powder became granular.
At the same time, ITDT, phosphoric acid, or both of
them reacted to the newly produced surface of fine
powder, and a protective film formed. When only
ITDT existed, as shown in Fig. 2b, the alkoxide
group (—OR) of the ITDT could potentially react
with the hydroxyl groups (—OH) on the magnetic
powder surface to form covalent bonds after the
release of isopropanol.31 This reaction resulted in
the formation of an organic titanium monolayer on
the powder surface to increase the oxidation resis-
tance. However, the amount of hydroxyl groups on
the surface of the magnetic powders was limited,
because the Nd–Fe–B powder was in situ-crushed,
and the surface of the refined powders was newly
created. Therefore, only a very small part of the
powder surface was covered by ITDT through
chemical bonding. To characterize the formation of
the passive film after ball milling and coating, the
phosphorus content was analyzed using the XRF
instrument, and the results are shown in supple-
mentary Table S1. The measured P content in the
3944
Fig. 2. Schematics of refinement and surface treatment effects: (a) refinement of the flaky Nd–Fe–B powder; surface modification with: (b) ITDT,
(c) phosphoric acid, and (d) synergistic addition with phosphoric acid and ITDT; (e) the reaction mechanism of synergistic surface treatment.
sample with only ITDT added was 0.0180 wt.%,
being slightly higher than the value of 0.0056 wt.%
(which might have come from impurities in the raw
materials or the manufacturing equipment) for the
powders without additive agent. This is consistent
with the analysis of Fig. 2b. As shown in Fig. 2c,
when only phosphoric acid was added, the conver-
sion products of ferric phosphate and neodymium
phosphate formed.32–34 The elements of Fe and Nd
in the Nd–Fe–B alloy could react with phosphoric
acid as in Eqs. (1) and (2):
Fe3þ þ PO3
4 ! FePO4
Nd3þ þ PO3
4 ! NdPO4
The insoluble conversion layer covered the sur-
face of the magnetic powders, thereby preventing
the erosion of oxygen. According to supplementary
Table S1, the P element (0.2592 wt.%) was clearly
present in the powders treated with phosphoric
acid, indicating that the phosphate protective film
formed on the surface of the powders. As shown in
Fig. 2d, the addition of a mixture of ITDT and
phosphoric acid led to the formation of a synergistic
protective film. The effects of ITDT and phosphoric
acid were intertwined and complemented each
other. The formation mechanism of the synergistic
film on the Nd–Fe–B powder surface with the
addition of ITDT and phosphoric acid is proposed,
as shown in Fig. 2e. Because there were very few
hydroxyl groups (—OH) existing on the newly
generated surface during the ball-milling process,
Chen, Zheng, Cheng, Cai, Qiao and Che
ITDT was rarely directly and chemically combined
with the surface of the powder. However, when
phosphoric acid (H3PO4) existed simultaneously,
dihydrogen phosphate (H2PO4) and hydrogen
phosphate (HPO42) were formed and bonded on
the surface of the Nd–Fe–B powders. Potentially,
the H atoms of the H2PO4 and HPO42 enabled the
reaction with ITDT after the release of isopropanol
((CH3)2CHOH). This reaction resulted in the forma-
tion of a dense synergistic protective layer that was
connected by chemical bonds on the surface of
powders to increase the anti-oxidant capacity. The
ð1Þ XRF results in supplementary Table S1 show the
highest phosphorus content (0.3839 wt.%) in this
sample, which was caused by the phosphorus in the
ð2Þ combined ITDT and phosphate, and this is consis-
tent with the scheme proposed above.
XRD Analysis
The phase compositions of the magnetic powders
that were treated using different passivation
reagents were analyzed via XRD, and the results
are shown in Fig. 3. As seen from the diffraction
peaks, the curve (Fig. 3e) of the sample synergisti-
cally treated with the synergistic addition of phos-
phoric acid and ITDT contained the least impurity
peaks and matched best with the diffraction peaks
(Fig. 3a) of the raw Nd–Fe–B powders. Meanwhile,
it can be seen in the enlarged view (20–46°) in Fig. 3
that the diffraction peaks (Fig. 3b) of the sample
milled without protective addition shifted to higher
angles compared to the peaks in Fig. 3a, for
instance, the patterns of the crystalline planes
Surface Modification and Refinement of Nd–Fe–B Magnetic Powder Using ITDT and
Phosphoric Acid
Fig. 3. XRD patterns of (a) the raw Nd–Fe–B powders; and Nd–Fe–
B powders ball-milled for 3 h: (b) in pure ethanol, (c) in ITDT ethanol
solution, (d) in phosphoric ethanol solution, and (e) with synergistic
addition of phosphoric acid and ITDT in ethanol solution
(214), (105), (313), (224), and (314); in contrast,
there were no diffraction peak shifts observed in the
other samples. These observations indicate that the
interplanar spacing increased for the sample with-
out an added protective agent, which was a result of
the doping of the H and O atoms into the lattice
space. In summary, both ITDT and phosphoric acid
showed effective protective effects on the crystalline
structure of the Nd–Fe–B sample during the ball-
milling process, and the synergistic addition of the
two agents showed the best protective effect.
Oxidation Resistance Properties
The refined Nd–Fe–B powders, which were ball-
milled for 3 h with different passivation agents,
were placed at 250°C under air atmosphere and the
reactions were observed. As seen in Fig. 4a, the
powders without a passivation agent partially
became red-hot, like burning charcoal, in about 30
s, and the red rapidly spread to the surrounding
powders; while the color of the powders after cooling
turned black. The sample that was treated with
ITDT also became red-hot and combusted, as shown
in Fig. 4b, but the start time was prolonged to
around 1 min 28 s. For the powders that were
treated with phosphoric acid and with the syner-
gistic treatment of ITDT and phosphoric acid, no
red-hot combustion phenomenon was observed, as
shown in Fig. 4c and d. This indicates that both the
naked powders without a protective film and the
powders which were coated with a single ITDT
organic film showed poor oxidation resistance at
high temperature, whereas the phosphate film
significantly improved the oxidation resistance.
For comparison, the original coarse powders before
refinement (D50 = 138 lm) were heat-treated under
the same conditions, and the results were as shown
in supplementary Fig. S1. The apparent color of the
raw powders turned form bright silver-gray before
3945
Fig. 4. Phenomenon of the refined Nd–Fe–B powders before and
after heating in the air at 250°C: (a) not added, (b) ITDT added, (c)
phosphoric acid added, and (d) synergistic addition with phosphoric
acid and ITDT.
heating to burnt yellow after heating, due to the
oxidation of the powder surface, but no burning was
observed. It can be concluded that the refined Nd–
Fe–B powders, which were under the synergistic
coating protection of ITDT and phosphoric acid,
possess the anti-combustion and anti-oxidation per-
formance just like the original coarse powders.
TG-DSC measurements were conducted on the
Nd–Fe–B magnetic powders with different passiva-
tion agents after 3 h of ball milling, and the results
are shown in Fig. 5. The original coarse powder
before refinement was also tested for comparison.
As seen from the TG curves in Fig. 5a, the naked
powders and ITDT-treated powders started to gain
weight at around 100°C. The naked powders had
rapid oxidative weight gain around 200°C, and this
indicates that the powders began to combust. For
the ITDT-treated powders, the weight rapidly
increased at around 260°C, which was higher than
for the naked powder, indicating that ITDT reduced
and delayed the oxidation of powder. The powder
treated with phosphoric acid showed nearly no
oxidation weight gain at a temperature˛ lower than
125°C, and the TG curve was relatively smooth,
indicating that the phosphate film which wrapped
around the Nd–Fe–B powder had a good effect on
oxidation resistance. The weight increase of the
3946
Fig. 5. TG-DSC curves of Nd–Fe–B powders ball-milled for 3 h: (a) TG, and (b) DSC.
synergistically treated powder was very gentle,
showing nearly no oxidation weight gain at a
temperature lower than 200°C. Even exposed in
air atmosphere at a temperature higher than 200°C,
for the synergistically coated powders, the oxidation
weight increase was small, showing remarkably
better oxidation resistance than the other samples
and being closest to the coarse powders. In the DSC
curves shown in Fig. 5b, the naked and ITDT-coated
powders showed exothermic peaks around 100°C,
indicating that the powders underwent a rapid
oxidative exothermic process. For the phosphoric
acid-treated powders and the synergistically coated
powders, no rapid exothermic phenomenon was
observed; in particular, the curve of the synergisti-
cally coated powders was quite smooth, being closest
to the coarse powders. This indicates that the
synergistic coating is the optimal method for
improving the oxidation resistance of the refined
powders at a high temperature, being consistent
with previous TG results.
Two groups of Nd–Fe–B magnetic powders were
passivation-ball-milled (one group for 30 min and
the other for 3 h) and then heat-treated at different
temperatures for 1 h in air atmosphere. Then, the
oxygen contents were measured. To exclude the
factor of the oxygen contained in phosphoric acid
and ITDT, the increase in the value of oxygen
content (D oxygen content) was considered, as seen
in Fig. 6. Usually, when the environmental temper-
ature was higher, the powder oxidation was more
severe and the value of D oxygen content was
higher. As shown in Fig. 6a, for the sample which
was ball-milled for 30 min without protective
agents, the powders showed an obvious increase in
oxygen content when the temperature was higher
than 100°C, and it burned when the temperature
was higher than 175°C with the oxygen content
rapidly increasing. For the powders milled for 30
min with ITDT addition, the oxygen content rapidly
Chen, Zheng, Cheng, Cai, Qiao and Che
increased at a temperature higher than 200°C. By
contrast, the powder samples treated with phospho-
ric acid and synergistic addition showed the notice-
ably lower value of D oxygen content even at a
temperature as high as 300°C, exhibiting good
oxidation-resistant performance. When the particle
size was finer, the activity was higher. The situa-
tions for the samples ball-milled for 3 h are shown in
Fig. 6b. The powder samples without protective
agents and with ITDT addition both showed obvious
increases in oxygen contents after 50–100°C and
burned at 150–300°C with rapid increases in oxygen
content. In sharp contrast, the oxygen increases
were relatively low for the two powders that were
treated with phosphoric acid and with synergistic
addition. Specifically, in an environment higher
than 200°C, the synergistically modified sample
exhibited the lowest value of D oxygen content,
indicating an excellent oxidation resistance
performance.
Magnetic Properties
In order to characterize the anti-oxidation effect
of the refined magnetic powder after surface mod-
ification and the influence on the magnetic proper-
ties, the Nd–Fe–B powders passivation-ball-milled
for 3 h were heat-treated in air atmosphere for 1 h
at different temperatures. The magnetic properties
were characterized using demagnetization curves,
and the results are shown in Fig. 7. The sample of
the raw coarse powder before refinement was also
tested for comparison. As seen in Fig. 7a, the
optimal magnetic properties of the refined powders
were obtained from sample coated with synergistic
addition of both ITDT and phosphoric acid (Br =
0.75 T, Hcj = 633 kA/m), and the ITDT-coated
powders also exhibited good magnetic properties (Br
= 0.75 T, Hcj = 624 kA/m), indicating that adding
ITDT during the milling process can effectively
protect the magnetic properties of the powders.
Surface Modification and Refinement of Nd–Fe–B Magnetic Powder Using ITDT and 3947
Phosphoric Acid

Fig. 6. Relative oxygen contents of the Nd–Fe–B powders heated in air atmosphere at different temperatures of the samples ball-milled for (a) 30
min, and (b) 3 h.

Fig. 7. Demagnetization curves of the refined Nd–Fe–B powders after heat treatment in air atmosphere at (a) room temperature, (b) 100°C, and
(c) 200°C; (d) demagnetization curves of the Nd–Fe–B/PPS bonded magnets

Figure 7b and c shows that the magnetic properties
of the synergistically coated powders were effec-
tively protected in the environments of 100°C and
200°C. However, the magnetic properties of the
ITDT-coated powders were well-protected at 100°C,
but the powders combusted at 200°C, causing a
rapid drop in remanence Br and coercivity Hcj.
Although the initial magnetic properties of
phosphoric acid-treated samples were not high,
their properties were well maintained even after
being heated at 200°C in air atmosphere, indicating
that the added phosphoric acid played a good role in
improving the high-temperature oxidation resis-
tance of the magnetic powders. This suggests that
the organic protective film formed by ITDT alone on
the powder surface had an excellent protective
3948
performance at room temperature. However, its
effect of high-temperature oxidation resistance was
poor, and oxidation and combustion occurred with
an increase in the temperature when exposed to air
atmosphere. The high-temperature oxidation resis-
tance of the single phosphate film was obvious;
however, the protective effect on the magnetic
properties during ball milling at room temperature
was relatively weak. Under the synergistic effect of
phosphoric acid and ITDT, the refined powders
with the combined protective film showed the best
initial performance, closest to that of the raw
coarse powders, and exhibited excellent oxidation
resistance performance in high-temperature
environments.
Typical and extensively used binders in bonded
magnets are thermoplastic binders, such as poly-
amides (PA, with a melting point of about 180°C)
and polyphenylene sulfide (PPS, with a high melt-
ing point up to 280°C).35,36 To judge the oxidation
resistance at a higher temperature in practical
application, the magnetic compounds with Nd–Fe–
B powders and PPS resin were prepared and
injected into a mold forming 10.0 9 10.0 9
10.0 mm magnetic cubes for testing. The cube with
the original coarse powder was not obtained because
of the low melt flow performance. In addition, both
of the samples using the naked powders and the
ITDT-coated powders burned during the injection-
molding process. That was because these two types
of powders oxidized and combusted at high temper-
ature, and then the mixed PPS resin was ignited.
So, the bonded magnetic cubes of them were not
obtained. In contrast, for the phosphoric acid-
treated and the synergistically treated samples,
the injection-molding process was very smooth. The
demagnetization curves of the obtained bonded Nd–
Fe–B magnetic cubes were measured using a B-H
analyzer, as shown in Fig. 7d. The synergistically
treated samples exhibited both a higher coercivity
and a higher remanence than the sample treated
with phosphoric acid alone, indicating that the
additions of phosphoric acid and ITDT showed
synergistic effects on high-temperature oxidation
resistance, and that the refined Nd–Fe–B magnetic
powders possess excellent high-temperature oxida-
tion resistance. Thus, synergistic modification with
phosphoric acid and ITDT is of great significance for
the maintenance of the magnetic properties of the
Nd–Fe–B powder and the final energy product of
magnets.
CONCLUSION
During the refinement process of the Nd–Fe–B
powders, the synergistic treatment using ITDT and
phosphoric acid significantly improved the high-
temperature oxidation resistance of the magnetic
powders. Both ITDT and phosphoric acid had
protective effects on the crystalline structure of
Chen, Zheng, Cheng, Cai, Qiao and Che
Nd–Fe–B during the ball-milling process, and the
synergistic protection was optimum. The ITDT
protective film showed excellent protective perfor-
mance for the magnetic properties at room temper-
ature, but showed poor high-temperature oxidation
resistance. The phosphate film showed an excellent
oxidation resistance at high temperatures, but its
protective effect on the magnetic properties is
relatively weak during the ball-milling process.
The H atom from phosphoric acid enabled the
reaction with ITDT after the release of isopropanol,
and a dense synergistic protective layer formed on
the powder surface with the phosphate–ITDT film
intertwining and complementing each other. The
insoluble protective layer covers the surface of the
magnetic powders, thereby preventing the erosion
of oxygen. Thus, the combined film formed by the
synergistic addition of phosphoric acid and ITDT
enables the refined powders to achieve a good initial
magnetic performance and excellent oxidation resis-
tance at high temperatures.
ACKNOWLEDGEMENTS
The authors acknowledge the researchers (Li-
qiang Jiang, Senqi Shen, and Junjie Zhou) of
Hangzhou Haisheng Technology Company for the
assistant in the experimental of preparing bonded
magnets.
DATA AVAILABILITY
Raw data generated and analyzed in this research
are available from the corresponding author on
reasonable request.
CONFLICT OF INTEREST
The authors declare that they have no conflict of
interest.
SUPPLEMENTARY INFORMATION
The online version contains supplementary
material available at https://doi.org/10.1007/s11837-
021-04850-4.
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