The effects of average grain size on the magnetic properties and corrosion resistance

of NdFeB sintered magnets

D. W. Scott, B. M. Ma, Y. L. Liang, and C. O. Bounds

Citation: Journal of Applied Physics 79, 5501 (1996); doi: 10.1063/1.362291

View online: http://dx.doi.org/10.1063/1.362291
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/79/8?ver=pdfcov
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 Hard Magnets, 2-14-1, Interstitials L. Henderson Lewis, Chairman

The effects of average grain size on the magnetic properties and corrosion
resistance of NdFeB sintered magnets
D. W. Scott, B. M. Ma, Y. L. Liang, and C. O. Bounds
Rhône-Poulenc, Rare Earths and Gallium, CN 7500, Cranbury, New Jersey 08512
Magnets with a nominal composition of Nd14.5Fe79.5B6 have been prepared by the conventional
powder metallurgy technique. Precursor alloy powders with average particle sizes of 2.5, 3.0, 3.5,
and 4.2 mm were included in this study. Average particle size and oxygen content were effectively
manipulated to control the average grain size in the sintered magnets. Typically, for NdFeB sintered
magnets, the corrosion resistance of these magnets was improved with increasing oxygen content.
The corrosion resistance of magnets varied significantly with the average particle size of precursor
alloy powders. For a fixed oxygen content, magnets made from powders of larger sizes exhibited a
higher weight loss ~a poor corrosion resistance! when compared to those made from smaller alloy
powders. However, the H ci of magnets made from 2.5, 3.0, and 3.5 mm precursor alloy powders was
found to decrease drastically with increasing oxygen content while magnets made from the 4.2 mm
powder was found to remain relatively constant with increasing oxygen content. To optimize
magnetic performance, one needs to compromise the corrosion resistance and the H ci obtained by
balancing the average particle size of the precursor alloy powder for magnet fabrication, as well as
the oxygen content and the average grain size in the finished magnet. © 1996 American Institute
of Physics. @S0021-8979~96!31508-9#

INTRODUCTION performance and the corrosion resistance, milled powders

The average grain size of finished magnets has been
found to be a determining factor for the B r , H ci , and BH max
obtained for NdFeB magnets prepared by the powder metal-
lurgy ~P/M! and sintering route.1–3 Using the P/M process,
oxygen pick-up has always been a concern for magnet manu-
facturing. Increasing oxygen content to a certain limit has
been found to improve the bulk corrosion resistance and the
magnetic properties, namely, B r , H ci , and BH max of the
magnets obtained.4,5 This raised an interesting idea for pro-
ducing sintered magnets with both good bulk corrosion re-
sistance and a high H ci and BH max . By balancing the milled
powder particle size ~or the surface area obtained!, powder
handling, oxygen pick-up, and sintering conditions: one can
actually manipulate the average grain size and the oxygen
content in the finished magnets.
In this article, we discuss two different means of control-
ling the average grain size in sintered NdFeB magnets by ~1!
varying the average particle size of precursor alloy powder
and ~2! controlling the oxygen content in finished magnets. It
is our intention to relate the B r , H ci , BH max , and H k of
finished magnets to the average particle size of precursor
alloy powders. The relationship of the bulk corrosion rate of
the finished magnets to the average grain size and oxygen
content will also be discussed.
EXPERIMENT
Magnets included in this study were prepared from a
conventionally cast alloy with a nominal composition of
Nd14.5Fe79.5B6 using classical powder metallurgy techniques.
Four batches of powders with average particle sizes of 2.5,
3.0, 3.5, and 4.2 mm were then prepared by attrition milling.
To study the effects of oxygen content on both the magnetic
were deliberately oxidized in a controlled manner. Other than
the oxidation step, the magnet fabrications and corrosion
testing were identical to regular magnets as reported in pre-
vious work.3
RESULTS AND DISCUSSION
Table I presents the relationships of the bulk corrosion
rate ~the weight loss! and the magnetic properties of finished
magnets to the average particle size of precursor alloy pow-
ders, the average grain size, and the oxygen content in the
finished magnets. Magnets made from powders of 2.5 mm
powders typically exhibit a higher oxygen content than those
made from larger powders exposed to the same amount of
air. When processed under the low oxygen condition ~i.e.,
without introducing any excessive air for controlled oxida-
tion!, the oxygen contents in finished magnets range from
0.12 to 0.14 wt % for all magnets regardless of the average
particle size of powders. When a slight amount of oxygen
~150 ml! was introduced, the oxygen content in finished
magnets increased sharply from a 0.13 wt % to about 0.47,
0.40, 0.37, and 0.41 wt % for magnets made from precursor
alloy powers with the average particle size of 2.5, 3.0, 3.5,
and 4.2 mm, respectively. This rapid increase in oxygen con-
tent suggests that the precursor alloy powders included in
this study exhibit a very high oxygen ~or air! affinity.
Shown in Fig. 1 is the relationship between oxygen con-
tent of finished magnets and the amount of air injected for
controlled oxidation and the average particle size of precur-
sor alloy powders. As mentioned earlier, the oxygen content
in finished magnets increased exponentially at low amounts
of air injection then become relatively flat when the amount
of injected air was increased to more than 300 ml. Because
of the smaller particle size and, presumably, the high surface

J. Appl. Phys. 79 (8), 15 April 1996 0021-8979/96/79(8)/5501/3/$10.00 © 1996 American Institute of Physics 5501
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 TABLE I. Magnetic properties for Nd14.5Fe80.5B6 sintered magnets for different particle sizes.

Air added Oxygen content Weight loss Grain size Br Hc H ci BH max Hk Density
~ml! ~wt %! ~mg/cm2! ~mm! ~kG! ~kOe! ~kOe! ~MGOe! ~kOe! ~g/cc!

2.5 micron powder

0 0.14 21.2 7.1 13.2 11.2 12.8 41.3 10.9 7.54
150 0.47 0.2 ••• 12.6 6.9 8.8 29.8 4.1 7.47
300 1.55 220.1a ••• 3.4 0.3 0.3 0.3 0.1 5.63
450 1.77 •••b ••• 3.0 0.2 0.2 0.2 0.1 5.56
600 1.75 •••b ••• 3.1 0.2 0.3 0.3 0.1 5.67

3.0 micron powder

0 0.12 30.6 7.5 12.9 11.6 13.4 39.4 11.6 7.55
150 0.40 0.7 7.1 13.2 10.6 12.0 40.6 10.1 7.58
300 0.53 0.1 6.9 12.9 9.2 10.1 38.1 7.2 7.56
450 0.65 0.0 6.2 12.9 8.1 9.0 37.6 6.2 7.56
600 0.52 0.1 7.5 13.0 8.4 9.2 39.2 7.2 7.56

3.5 micron powder

0 0.13 54.2 8.8 13.2 11.0 13.4 40.8 10.6 7.56
150 0.37 8.0 ••• 13.1 11.1 13.1 40.5 10.7 7.57
300 0.47 3.2 ••• 13.2 10.5 11.7 41.6 10.2 7.54
450 0.49 2.3 ••• 13.0 10.4 11.6 40.5 10.1 7.54
600 0.49 1.1 ••• 13.0 10.4 11.5 39.9 10.0 7.54

4.2 micron powder

0 0.13 107.8 9.0 13.0 10.3 11.1 39.6 10.1 7.55
150 0.41 52.3 ••• 13.0 11.3 12.7 40.2 11.2 7.51
300 0.41 43.0 ••• 12.8 11.1 12.8 38.6 10.9 7.50
450 0.43 38.7 ••• 12.9 11.3 12.7 39.6 11.2 7.50
600 0.43 32.2 ••• 13.0 10.9 12.4 40.1 10.7 7.50
a
Indicates a weight gain.
b
Sample was destroyed during testing.

area and chemical potential, magnets made from precursor
alloy powder of 2.5 mm in size yielded an oxygen content of
more than 1.5 wt % when 300 ml of air was injected for
controlled oxidation. This value is much higher than magnets
made from 3.0, 3.5, and 4.2 mm powders when exposed to
the same amount of air. These trends suggest that the average
particle size of the precursor alloy powder is a very impor-
tant factor for magnet processing. Thus, the desired average
particle size of precursor alloy powder must be balanced
with the oxygen pick-up occurring during processing in or-
der to optimize desired properties.
For a fixed precursor alloy powder, the weight loss of
magnets obtained decreased with increasing oxygen content
in finished magnets. However, there is an important phenom-
enon which should be addressed concerning the relationship
of the bulk weight loss to the oxygen content of finished
magnets. Shown in Fig. 2 is the relationship of weight loss of
finished magnets with a 0.1 and 0.4 wt % oxygen content to
the average particle size of precursor alloy powders. For a
fixed oxygen content, the weight loss increased with increas-
ing size of precursor alloy powder. When the oxygen content
of finished magnets was increased from 0.1 to 0.4 wt %, a
lower weight loss ~i.e., a better corrosion resistance! was
obtained as anticipated. This phenomenon may be explained

FIG. 1. Relationship of oxygen content in finished magnets to the average

particle size of precursor alloy powder and the amount of air injection used FIG. 2. Relationship of weight loss to the average particle size of precursor
for conduction control oxidation. alloy powder and the oxygen content in finished magnets.

5502 J. Appl. Phys., Vol. 79, No. 8, 15 April 1996 Scott et al.
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 FIG. 3. Optical micrograph of magnets produced from precursor alloy pow-
ders with average particle size of ~a! 2.5, ~b! 3.0, ~c! 3.5, and ~d! 4.2 mm
~FSSS! under low oxygen process. The oxygen content of these magnets
were all maintained at about 0.13–0.14 wt %. The average grain size of
these magnets are 7.1, 7.5, 8.8, and 9.0 mm, respectively.
by the fact that the Nd-rich phase is more evenly distributed
in magnets made from precursor alloy powders of smaller
sizes; this issue requires further investigation.
Shown in Figs. 3~a!–3~d! are optical micrographs of
magnets made from precursor alloy powders with average
particle sizes of 2.5, 3.0, 3.5, and 4.2 mm, respectively, at the
lowest oxygen content ~0.13–0.14 wt %!. As with any P/M
process, grain growth occurs during sintering resulting in
average grain sizes in the sintered magnets of 7.1, 7.5, 8.8,
and 9.0 mm, respectively. Although the average particle size
of powder measured by the FSSS cannot be directly trans-
lated to the average grain size of finished magnets measured
by an image analyzer, it is known that grain growth is more
rapid in magnets made from powder of 2.5 mm when com-
pared to those made from 3.5 or 4.2 mm. Besides the differ-
ence in average grain sizes of finished magnets, the size of
the Nd-rich phase6 in a magnet made from the 4.2 mm pow-
der appeared to be larger than that made from 2.5 mm. The
large size of Nd-rich grain boundary phase may be one cause
of the high weight loss of magnets made from powders of
large average particle size.
Shown in Figs. 4~a!– 4~d! are optical micrographs of
magnets made from precursor alloy powder with an average
particle size of 3.0 mm with oxygen contents of 0.12, 0.40,
0.53, and 0.65 wt %, respectively. The average grain sizes of
these magnets ~7.5, 7.1, 6.9, and 6.2, respectively! decreased
slightly with increasing oxygen content in finished magnets
suggesting that the oxygen ~or oxides formed! may act as a
grain growth inhibitor during sintering. The size of the Nd-
rich grain boundary phase also appeared to be larger and
more agglomerated in magnets of low oxygen content ~0.12
wt %! than those of higher oxygen contents ~0.40, 0.53, and
0.65 wt %!. This change in the size and the distribution of
the Nd-rich grain boundary phase may contribute to the im-
provement in weight loss of magnets with oxygen content of
more than 0.4 wt %.
J. Appl. Phys., Vol. 79, No. 8, 15 April 1996
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FIG. 4. Optical micrographs of magnets made from precursor alloy powder
with average particle size of 3.0 mm with oxygen content of ~a! 0.12, ~b!
0.40, ~c! 0.53, and ~d! 0.65 wt % in finished magnets.
Despite the improvement in corrosion resistance ~lower
weight loss!, the H ci of magnets made from 3.0 mm powder
decreased from 13.4 to 9.0 kOe ~listed in Table I! when the
oxygen content was increased from 0.12 to 0.65 wt %. The
opposing trends of corrosion resistance and H ci with increas-
ing oxygen content raises an interesting issue: one may need
to compromise low weight loss ~good corrosion resistance!
with high H ci by adjusting the oxygen content in magnets.
The decrease of H ci with increasing oxygen content suggests
that the Nd-grain boundary phase may have been over oxi-
dized and transforms into nucleation centers during magne-
tization reversal. The decrease in H ci with increased oxygen
content becomes more pronounced when magnets were pre-
pared from the 2.5 mm precursor alloy powder. A similar
trend ~but less severe! can also be observed on magnets made
from 3.5 mm precursor alloy powder. For magnets made
from the 4.2 mm precursor alloy powder, this situation is
reversed: a slight increase in H ci can be observed when the
oxygen content was increased from 0.13 to 0.40 wt %. This
opposite trend may be attributed to the fact that the large size
of the Nd-rich grain boundary phase is only partially oxi-
dized and still serves as grain insulators for enhancing the
H ci .2 Unlike H ci , both B r and BH max seem to be less sensi-
tive to the increasing oxygen content. The variation of H k
with the size of precursor alloy powder or the oxygen con-
tent appeared to be very similar to that of H ci .
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