Magnetics 2007 070409

1
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Magnetics 2007
Measurement and Evaluation of
(Neodymium-Iron-Boron)
Magnets
Presented by
Steve Constantinides
Magnetics 2007
Lincolnshire, IL
April 4-5, 2007
Most of the talk today will be focused on Neodymium-Iron-Boron (NdFeB) magnets. But
much of what we discuss is relevant to the other permanent magnets types as well.
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Magnetics 2007
Agenda
Introduction
Motivation for the talk - changes in the marketplace
Precision, Accuracy, and Statistical Relevancy
Magnetic Property Characterization
Gaussmeter
Fluxmeter
Hysteresisgraph (Permeameter)
Other
Evaluating Corrosion Resistance
Autoclave
T&H Chamber
Salt Spray
Magnet market dynamics have dramatically changed in the period 1998 to 2007.
At least four issues have taken place:
1) Magnet manufacturing (and manufacturing of products in which magnets are used) has
largely (though not totally) relocated to Asia
2) Rare Earth magnet pricing declined precipitously from about $90 per pound in 1998 to
less than $25 per pound in 2006 and is now increasing
3) Quality of Chinese manufactured neo improved both in magnetics and corrosion
resistance and are now approaching world-class quality
4) The high temperature capability of neo has been expanded to 200 C+
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Magnetics 2007
Changes in Domestic (USA) PM Manufacturing
Sintered Ferrite
Arnold
Hitachi (Edmore, China Grove)
TDK
Crucible Magnetics
General Magnetic
Sumitok
Kane (Stackpole)
NdFeB (dense)
Ugimag (IG Tech.)
Hitachi
Crucible
Magnequench
Sintered Ferrite
Hitachi (China Grove)
TDK
NdFeB (dense)
(none)
1998 2007
We see here the effect of low import pricing on the domestic manufacturing base for the
first two of the four main material types.
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Magnetics 2007
Changes in Domestic (USA) PM Manufacturing
Alnico
Arnold
Hitachi
Crucible Magnetics
T&S
Permanent Magnet Company
SmCo
Arnold
Crucible (1-5)
EEC
Hitachi
IG Technologies (Ugimag)
Alnico
Arnold
T&S
Permanent Magnet Company
SmCo
EEC
1998 2007
Arnold Manufactures SmCo in Europe
For SmCo there were only a few manufacturers in the US: EEC, Arnold, Crucible (SmCo 1-
5 only), Hitachi (Edmore), IG Technologies.
Erosion of the SmCo manufacturing base started in the early 1990s with the loss of IG
Technologies SmCo manufacture and wound up with the closing of the Hitachi Edmore,
Michigan facility ~2004-5.
Arnold manufactures SmCo at our UK and Swiss facilities. EEC is the remaining domestic
manufacturer.
The situation for bonded magnets is almost as dire the largest domestic manufacturer of
Injection molded magnets as of 2004 was Arnold. It has relocated its molded magnet
business to one of its factories in Shenzhen to meet competitivepricing pressures and to
supply the market developing there. Remaining players are Magnet Applications, Tengam,
ECS and Phoenix Technologies.
The one exception to this exodus is the flexible magnet business which is still dominated
in the US by Arnold, followed by Magnum and Electrodyne.
There is also a very substantial door gasket market in the US primarily served by Ilpea
(Holmes Industries). These are low energy, relatively unsophisticated products.
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Magnetics 2007
Neomax licensees for Mfg and Sale of NdFeB
Source: http://www.neomax.co.jp/english/pdf/200609e.pdf
11 Licensees, in alphabetic order, as of September 2006
Advanced Technology & Materials Co., Ltd. (China): AT&M
Beijing Jingci Magnetism Technology Co. (China): BJMT
Beijing Tsinghua Innovation Technology Development Co., Ltd.(China) changed name to THINOVA Co.,Ltd.
on August 20, 2003
Magnetfabrik Schramberg GmbH (Germany)
Morgan Crucible Company plc (England)
Neorem Magnets Oy (Finland)
Ningbo Yunsheng Co., Ltd. (China)
San Huan New Material High-Tech Inc. (China), sold by Beijing San Huan International Trading Co. (China)
Shin-Etsu Chemical Co., Ltd. (Japan)
TDK Corp. (Japan)
Vacuumschmelze GmbH (Germany)
Hitachi has purchased Sumitomos magnet business.
Magnequench is no longer manufacturing magnets.
Patents are still active (in the USA) and will be for at least afew more years. This requires
licensing from Neomax / Magnequench.
The list on the Neomax website was last updated in 2006 and is presented here. Companies
are listed in alphabetical order with the five Chinese manufacturers highlighted.
Pricing for neodymium-iron-boron (neo) had dropped to a point where it could compete
against sintered ferrite for many applications.
These price reductions have been driven by Chinese companies competing with each other
for the Western market. However, starting in late 2005, raw material supply became
constrained causing neodymium metal price increases of over 100%with no likelihood of
short term relief.
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Magnetics 2007
NdFeB Patent Status
Per Neomax, 2006
Neomax, the jointly formed company by Hitachi and Sumitomo, last updated its patent
status in 2006.
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Magnetics 2007
Agenda
Introduction
Gaussmeter
Fluxmeter
Other
Autoclave
T&H Chamber
Salt Spray
Since most neo and ferrite is now coming out of the Far East, especially China, it is more
important than ever to have a mutual understanding and agreement regarding magnetic and
physical properties.
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Magnetics 2007
Precision and Accuracy
precision (pr-szhn) n.
1. The state or quality of being precise; exactness.
2. The ability of a measurement to be consistently reproduced.
3. The number of significant digits to which a value has been reliably measured.
accuracy (kyr--s) n.
1. Conformity to fact.
2. The ability of a measurement to match the actual value of the quantity being
measured.
To be accurate requires precision measurements.
We would like to think that we all have a common understanding about what magnet
properties have been ordered and are to be supplied. But often, what is received is not what
was desired.
The first issue to address is exactness of measurements. Measurement capability by both
producer and user must be capable of precision adequate to allowcompliance to
specification.
After learning that the measurement equipment has adequate resolution, precision and
repeatability, we then have to determine whose measurements are true that is, whose
measurements conform to national standards. In the USA, traceability goes to NIST.
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Magnetics 2007
Statistical Relevancy
Requires:
Minimum number of parts
Adequate Precision and Repeatability
May Require:
Correlation between fixtures or measurement techniques
(e.g. Customer-Vendor)
Note: requires accuracy when conformance to a standard is
required or when suitable reference magnets for correlative
measurements are unavailable. Otherwise, accuracy may not
be required
Individual measurements are likely to vary around some mean value so we have to ask how
relevant a single or limited number of measurements can be.
Magnetic properties vary between batches, within a batch, or even within a single block of
magnet material. Therefore, how samples are selected is crucial for determining typical
properties of a group of magnets.
Some tests are prohibitively difficult to perform in quantity or are difficult due to the
product shape, thus requiring some alternative test strategy. These alternative tests almost
invariably require correlation testing between supplier and customer.
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Magnetics 2007
Agenda
Introduction
Gaussmeter
Fluxmeter
Other
Autoclave
T&H Chamber
Salt Spray
What I hope to leave with you today is an appreciation for test methods, strengths and
limitations of each and level of repeatability.
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Magnetics 2007
Magnetic Properties & Typical Measurement Tools
Br, Remanent Induction indicates available flux
density of the magnet
Hci (or Hcj), Intrinsic Coercivity indicates the
magnets resistance to de-magnetization
BHmax, Maximum Energy Product a figure of
merit for how much energy is available for motors
and generators
Flux, Measure of magnetic output
Field Strength, Measure of magnetic output
Reversible Temperature
Coefficients, (Br and Hci) these indicate
how the magnetic characteristics (Br and Hcj)
change with temperature
Field Distribution, Measure of the
distribution of the flux
Hysteresisgraph May also
be estimated by Helmholtz Coil
Hysteresisgraph
Hysteresisgraph
Helmholtz Coil &
Fluxmeter
Hysteresisgraph
Gaussmeter positional or as
part of a fixture (e.g. gap probe)
Gauss probe and x-y-z and
rotational stage
These key properties are used to gauge magnetic quality and therefore will require
measurement at some point in the supply chain.
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Magnetics 2007
Review of the Hysteresis Loop
Applied field
I
n
d
u
c
e
d

f
ie
ld

(
I
n
d
u
c
t
io
n
)
Hc
Br
Normal curve
Intrinsic curve
Hci
Represents the combination of
Applied field and the Induced
field
Represents only the field
contributed by the magnet
H
B
1
st
Quadrant
3
rd
Quadrant 4
th
Quadrant
2
nd
Quadrant
Saturating Field Measurements
Demag Curve Measurements
shown in the 2
nd
quadrant
What each key magnetic characteristic represents can be seen by examining a typical
permanent magnet hysteresis loop.
The loop shape is made by comparing an applied field (usually electromagnetic) to the
induced field (in the magnet). The horizontal axis (H axis) represents the magnitude of
the applied field. The vertical (B) axis represents the measured induced field in the
magnet.
The Normal (green) curve is the plot of H versus B, where B is the sum of the applied field
and the field contributed by the magnet.
The blue Intrinsic curve is obtained by subtracting the magnitude of the applied field (H) at
each point, thus leaving only the field contributed by the magnet.
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Magnetics 2007
Review of the Hysteresis Loop
0
200
400
600
800
1000
1200
-1100 -900 -700 -500 -300 -100
Br
Hc Hci
Bdi (0.9*Br)
Bd
Hd
B axis
(Gauss or
Tesla)
H axis
(Oersteds or
A/m) Hk
Intrinsic Curve
Normal Curve
Demag Curve
2
nd
Quadrant BHmax
Resistance to de-magnetization
depends upon good loop
squareness as well as high Hci
Squareness is measured as the
ratio of Hk to Hci (Hk/Hci)
Product specifications will often
include a minimum Hk value
The value of Br (remanence) is proportional to how strongly a magnet will stick to a
block of steel.
The value of Hci (or Hcj) represents the magnets resistance to demagnetization.
Hk/Hci is useful in determining loop squareness. Poor loop squareness represents a
potential for partial knockdown in the presence of moderate demagnetizing stress, with
elevated temperature, or with both.
Some users specify Hk in addition to Hci to ensure satisfactory magnet performance at
elevated temperature. With the very high Hci values now available, Hxmay be a more
appropriate value.
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Magnetics 2007
Measurement - Hysteresisgraphs
A VSM can substitute for a hysteresisgraph
Computer Control
Fluxmeters
Power Supply
Yoke and Pole Caps
Search Coils
Magnetic Coils
The most common equipment for measuring intrinsic magnetic properties is the
hysteresisgraph (a.k.a. a permeameter or magnetometer).
The measurement is made in closed circuit and only requires a regular geometry where
the magnets poles are flush with the faces of the pole caps in the hysteresisgraph.
Other devices that can measure the intrinsic properties include Vibrating Sample
Magnetometers (VSM) and SQUIDs(SemiconductingQuantum Interference Device) but
sample size and shape are limited to very small, regular cylinders or rectangular prisms.
The use of a Temperature Stage in a hysteresisgraph allows properties to be measured at
temperatures other than room temperature. Arnold, for example, can measure properties
between -40 and 300 C.
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Magnetics 2007
Hysteresisgraph Accuracy and Repeatability
Accuracy and repeatability are a function of at least these items:
Calibration to traceable standards
Proper positioning of the sample and coils
Optimized procedures regarding nulling and zeroing
Calibration and testing at controlled and recorded temperatures
Even with the best care, the measurement
process takes an extended time and is
prone to drift and interference. As a result,
there is always some degree of variability in
output even on the same magnet(s).
Arnold is continuously refining laboratory technique.
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Magnetics 2007
Repeatability of Hysteresisgraph Measurements
Date Run# W# Br Hc Hk Hci BHmax Run# W# Br Hc Hk Hci BHmax
2-Mar-07 1 W7-00839 3,978 3,007 2,892 3,098 3.77 1 W7-00843 11,970 10,640 10,620 11,530 33.88
2-Mar-07 2 W7-00840 4,001 3,017 2,899 3,105 3.82 2 W7-00844 11,980 10,650 10,630 11,520 33.94
2-Mar-07 3 W7-00841 4,002 3,017 2,903 3,105 3.82 3 W7-00845 11,980 10,650 10,630 11,530 33.93
2-Mar-07 4 W7-00842 3,999 3,014 2,900 3,104 3.81 4 W7-00846 11,980 10,660 10,630 11,530 33.92
3-Mar-07 5 W7-00847 3,979 3,025 2,911 3,108 3.77 5 W7-00851 11,960 10,570 10,530 11,450 33.75
3-Mar-07 6 W7-00848 3,978 3,023 2,912 3,111 3.77 6 W7-00852 11,960 10,580 10,560 11,440 33.76
3-Mar-07 7 W7-00849 3,998 3,025 2,909 3,116 3.81 7 W7-00853 11,970 10,600 10,570 11,450 33.79
3-Mar-07 8 W7-00850 3,998 3,023 2,903 3,110 3.81 8 W7-00854 11,980 10,600 10,580 11,450 33.82
5-Mar-07 9 W7-00859 3,970 3,028 2,915 3,116 3.76 9 W7-00855 11,970 10,500 10,460 11,350 33.77
5-Mar-07 10 W7-00860 3,991 3,031 2,914 3,118 3.80 10 W7-00856 11,980 10,490 10,430 11,360 33.78
5-Mar-07 11 W7-00861 3,985 3,030 2,914 3,120 3.78 11 W7-00857 11,980 10,480 10,440 11,340 33.75
5-Mar-07 12 W7-00862 3,998 3,031 2,914 3,117 3.81 12 W7-00858 11,980 10,500 10,460 11,350 33.74
5-Mar-07 13 W7-00867 3,984 3,017 2,905 3,101 3.78 13 W7-00863 11,940 10,570 10,530 11,450 33.57
5-Mar-07 14 W7-00868 3,996 3,020 2,905 3,102 3.81 14 W7-00864 11,970 10,580 10,560 11,450 33.73
5-Mar-07 15 W7-00869 3,987 3,018 2,906 3,106 3.79 15 W7-00865 11,970 10,620 10,570 11,480 33.74
5-Mar-07 16 W7-00870 4,006 3,019 2,899 3,106 3.82 16 W7-00866 11,970 10,600 10,580 11,480 33.74
Max 4,006 3,031 2,915 3,120 3.823 Max 11,980 10,660 10,630 11,530 33.940
Average 3,991 3,022 2,906 3,109 3.795 Average 11,971 10,581 10,549 11,448 33.788
Min 3,970 3,007 2,892 3,098 3.757 Min 11,940 10,480 10,430 11,340 33.570
Std Dev 10.65 6.67 6.70 6.84 0.020 Std Dev 10.42 59.23 67.13 65.32 0.095
3*StdDev% 0.80% 0.66% 0.69% 0.66% 1.60% 3*StdDev% 0.26% 1.68% 1.91% 1.71% 0.84%
+3Sigma 4,023 3,042 2,926 3,129 3.856 +3Sigma 12,003 10,758 10,750 11,643 34.073
-3Sigma 3,959 3,002 2,886 3,088 3.734 -3Sigma 11,940 10,403 10,347 11,252 33.503
NdFeB Ferrite
The data shown on this slide indicates the greater sensitivity of ferrite magnets to
temperature (Br variability). Other test data has shown that the cooling of the
hysteresisgraph coils also chills the pole caps affecting measurements. Handling and
storage of the samples prior to the test is also important.
Dont just walk in with a sample and measure it. Let its temperature stabilize in the
controlled lab environment for 30 minutes or more before testingand record the temperature
at time of the test.
Variability in the Hk and squareness data for the NdFeB sample is affected partly by the
relatively low Hcj values. This shows the importance of proper interpretation of the data.
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Magnetics 2007
Measurement Helmholtz
(Integrating) Fluxmeter Helmholtz Coil Pair
Since the hysteresisgraph requires a regular geometric shape that fits within a search coil (or
on an embedded coil in the pole caps), it is often easier and faster to estimate selected
properties via other test methods.
One such method, Helmholtz flux testing, is a measure of the total flux output of a magnet.
It is quick and easy to perform. The use of production gold standards mutually
established by the supplier and customer provide an excellent quality check and can even be
used as a 100% sort method.
The coil set consists of two identical, spaced coils connected in series. The coils come with
a Coil Factor certified as traceable to a primary certification standard. The Fluxmeter is a
voltage integrating device.
It is necessary to control temperature of the environment where the test is conducted. And
for Ferrite and NdFeB, it is necessary to control handling of the magnets since transfer of
body heat can affect measurements.
Explanations of Helmholtz measurements and calibration include these references:
Lakeshore (type in exactly as follows):
(http://www.lakeshore.com/pdf_files/magnetics/Measuring%20Perm%20Magnets%20App%20Note.PDF)
Magnetic Instrumentation: http://www.maginst.com/specifications/helmholtz_coils.htm
OerstedTechnology: www.oersted.com
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Magnetics 2007
Helmholtz Measurements - Temperature
Flux output changes
commensurate with
change in Br
Values of Alpha at
room temperature can
be used to estimate
change in flux output
as magnet
temperatures change
As shown here, Alnico
is most stable; Ferrite
is least stable
Relative Helmholtz Flux Output
99.60%
99.65%
99.70%
99.75%
99.80%
99.85%
99.90%
99.95%
100.00%
100.05%
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41
Readings Over Approximately 20 Minutes
R
e
l
a
t
i
v
e

F
l
u
x
Ferrite
NdFeB
SmCo
Alnico
As with the Hysteresisgraph, accuracy and repeatability are affected by temperature of the
magnet. Ferrite is so sensitive to temperature that a change from 70 to 76 degrees F (such
as from winter to summer thermostat settings) will cause a 0.45%drop in flux output.
Other factors that affect magnet (test) temperature are handlingof the magnet, temperature
heterogeneity in the test area, operator presence and breathing on the test apparatus, etc.
Still other factors affecting test accuracy and repeatability include the presence of
ferromagnetic material within approximately three feet of the coil set. Helmholtz test
stations should be established on wood frame benches and away from steel cabinets. Cell
phone, pens, some eyeglasses, key rings, metal ware carts, all have an affect upon the
readings.
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Magnetics 2007
Measurement Gaussmeter & Probes
Selection of Axial and Transverse Probes
3-Axis Gaussmeter
and probe
Gap Density Measurement
N
N
S
S
S N
Steel
Hall
Probe
Comparative Testing
( C Fixture)
S
N
Steel
Magnet
Under Test
Hall
Probe
Gaussmeters are a combination of a precision volt/current sourceand a Hall chip. The Hall
chip, or Hall effect sensor, redirects current flow as a function of the magnitude of the
applied magnetic field perpendicular to the face of the chip.
A good book on the subject is Ed RamsdensHall Effect Sensors published by Advanstar
Communications Inc. (ISBN: 0-929870-58-1). (The illustration below is from this text).
When a current flows across the Hall chip, the presence of a magnetic field causes the
electron flow to crowd to one side of the chip creating a potential difference from side-to-
side on the chip. This can be measured by sensitive electronicsand is proportional to the
magnitude of the applied magnetic field.
Gauss probes are often used in conjunction with fixtures to measure flux output from
magnets.
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Magnetics 2007
Measurement Field Mapping
Stepper motor drive to lead screws
200 step motors
40 revs per inch lead screws
Smallest step = 0.000125
Gauss probes can also be used alone to scan the field around a magnet or magnetic circuit.
This is an illustration of one of several scanning systems at Arnolds Applications
Laboratory. It is capable of linear, planer and rotational scans with positional accuracy of
+/-0.0005 and step precision of 0.000125.
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Magnetics 2007
Specialized Testing
Torque coupling (e.g. breakaway torque)
Hall probe output versus system position (e.g. rotary
position sensor)
Generated voltage
Waveform (of generated voltage/current)
Fluxgate Magnetometers
Pull-off force gauges
There are many other devices and methods used to measure magnetic fields or the affect of
these fields on systems.
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Magnetics 2007
Determining Maximum Working Temperature
Straight Line performance
to a very low permeance
Coefficient
Function of Hci and
Reversible Temperature
Coefficients
Not specifically a function of
composition or process
that is, a 100 C material can
be used at 150 C if the Pc is
high and the magnet is not
subjected to demag stress
0
1,000
2,000
3,000
4,000
5,000
6,000
7,000
8,000
9,000
10,000
11,000
12,000
13,000
14,000
15,000
0 2,000 4,000 6,000 8,000 10,000 12,000 14,000 16,000 18,000 20,000 22,000 24,000
H, Oersteds
B
, G
a
u
s
s
Typical Magnetic Propoerties for grade indicated
20C
80C
150C 100C
Material : N40M
-40C
Arnold Magnetic Technologies
Pc = 0.5
Pc = 2.2
As the magnet temperature is increased Intrinsic Coercivity (Hci or Hcj) decreases (except
for ferrite). Intrinsic Coercivity is a measure of the magnets resistance to
demagnetization. At some temperature it will decrease to the point that the magnet will
partially or totally demagnetize.
There remains a debate over how to determine a magnets maximum recommended use
temperature.
Options are to say that the Normal curve must remain straight inthe 2
nd
quadrant or remain
straight to an operating point of 1 or some value slightly less than 1.
We see how the demag curves change as temperature changes what is the measurement
for this?
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Magnetics 2007
Reversible Temperature Coefficients
Reversible Temperature Coefficient of Induction (, alpha): Rate
of change in Induction as a function of temperature change.
Reversible Temperature Coefficient of Coercivity (, beta): Rate
of change in Intrinsic Coercivity as a function of temperature
change.
Expressed as % per degree (usually Centigrade)
These are average values over a specified temperature range
In general, for Chinese grades of material, the temperature
range is room temperature to recommended maximum working
temperature
For the sake of simplicity, lets call the ReversableTemperature Coefficients (alpha) and
(beta). These are average changes in output as a function of temperature.
Alpha is approximately linear between 20 and 150 C. However, Beta is not linear. It is
therefore important to specify the range of temperatures over which the average is
calculated. Historically, manufacturers have often been remiss at doing so.
But Hci values vary within and between batches of magnets, so applying an accurate Beta to
a magnet at nominal specification provides only an estimate of what might be expected
over the range of magnetic properties exemplified in a production batch.
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Magnetics 2007
Calculating Temperature Coefficients
y = 0.0981x
2
- 47.759x + 11977
R
2
= 0.9998
y = -0.0115x
2
- 4.4088x + 5267.7
R
2
= 0.9977
0
2000
4000
6000
8000
10000
12000
14000
16000
-100 -50 0 50 100 150 200
MQP-14-12, "N", Br MQP-14-12, "N", Hci
Poly. (MQP-14-12, "N", Hci) Poly. (MQP-14-12, "N", Br)
Br
Hci
Setting the temperature range over
which Beta is calculated is important
as can be demonstrated by this
illustration.
The Reversible Temperature
Coefficient decreases as the range
is expanded from 20 - 100 C to 20 -
150 C as indicated by the slope of
the red dashed line versus the
indigo line.
The actual Betas are:
20 to 100: -0.325% per C
20 to 150: -0.281% per C
Material is injection molded MQP-14-12 in PPS
One method utilized to calculate Alpha and Beta with accuracy isto make numerous
measurements, on multiple magnets where possible, and to plot the data.
A regression analysis of the data provides the ability to calculate change in output between
any two temperatures within the tested range and with minor risk, outside the tested range.
One can see from this illustration how the same magnet can be seen to have two (or more)
reversible temperature coefficients of coercivity by merely adjusting the temperature range
over which they are calculated and specified.
25
Magnetics 2007
Temperature Coefficients
Average Temperature Coefficients
Coefficients Calc
From To Br Hci Br Hci
-40 100 -0.034% -0.187% -0.033% -0.203%
20 100 -0.036% -0.203% -0.035% -0.223%
20 150 -0.037% -0.195% -0.037% -0.215%
20 180 -0.038% -0.190% -0.038% -0.210%
20 200 -0.039% -0.187% -0.038% -0.206%
-40 150 -0.035% -0.180% -0.034% -0.196%
SmCo-2 SmCo-3
The Reversible Temperature Coefficient of Br is also called (the Greek letter alpha)
The Reversible Temperature Coefficient of Hci is also called (the Greek letter beta)
Br and Hci do not change linearly with temperature. Therefore, the range over which the
Coefficients are calculated must be stipulated.
This table, as part of our spreadsheet calculations, provides Alpha and Beta for some
common temperature ranges and the ability to calculate for any desired range (illustrated in
yellow) using the regression formulae.
26
Magnetics 2007
Improvement in
Reversible Temperature Coefficients
The method generally
employed to reduce
Temperature Coefficients in
Neo magnets is addition of
Cobalt
Cobalt raises the Curie
Temperature
As in Dysprosium additions,
special alloying methods are
used to prevent the Cobalt
from significantly reducing Br
300
350
400
450
500
550
0 5 10 15 20 25
Cobalt %
C
u
r
i
e

T
e
m
p
e
r
a
t
u
r
e
,

C
MQP-C, D
Sintered Neo
MQP-B
The most effective method for changing temperature coefficient properties of NdFeB
magnets is through the addition of Cobalt.
Adding cobalt to the formulation raises the Curie Temperature further away from room
temperature, flattening the output curve nearer to room temperature.
27
Magnetics 2007
Reversible Temperature Coefficients: Comparisons
Listed in order of increasingly negative Beta, except for Ferrite
Alnico suppliers almost never supply the temperature range for the Coef. Measurements
Increases in Curie Temperature are due to the presence of cobalt
Max Use Alpha Beta Tc
Material Grade Min C Max C C C
Alnico, cast 5 20 100+ 520 -0.02 -0.01 900
Alnico, cast 8 20 100+ 520 -0.02 -0.01 860
Sm
2
Co
17
27 MGOe 20 120 350 -0.035 -0.20 810
SmCo
5
20 MGOe 20 120 250 -0.04 -0.40 700
NdFeB, Bonded MQP-A, O 20 100 110, 140 -0.13 -0.40 310
NdFeB, Bonded MQP-B 20 100 110 -0.11 -0.40 360
NdFeB, Bonded MQP-C, D 20 100 125, 110 -0.07 -0.40 470
NdFeB, Sintered L-38UHT 20 180 180 -0.10 -0.50 350
NdFeB, Sintered N38UH 20 180 180 -0.12 -0.65 310
NdFeB, Sintered N48M 20 100 100 -0.12 -0.65 310
Ferrite C-5, 8 20 120 400 -0.20 0.27 450
Temp. Range
A comparison of some Alpha and Beta values for common magnet materials is listed here in
order of increasing Beta with the exception of Ferrite which is shown at the bottom.
Ferrite magnets are ferri-magnetic and exhibit a positive change in Beta with temperature.
This makes them excellent for higher temperature use, but limitstheir low temperature use.
A typical lower temperature limit for Ferrite is -40 C (-40 F).
Unfortunately, Ferrite has a high Alpha resulting in large reduction in flux output as
temperature increases. A practical upper use temperature is 250C. However, in motor
applications, 150 C may be the maximum practical use temperature due to system design
limitations (change in back EMF, torque reduction, etc).
28
Magnetics 2007
Older Hysteresis Loop Shapes
Poor knee shapes Presence of soft phase
Another influence on magnet performance is Loop Shape.
Early imports of NdFeB manufactured in China exhibited problems with uniformity of
properties.
Some of the problems were due to the presence of secondary phases such as neo-oxide or
the presence of soft phases such as from neo rich or alpha-iron phases in the grain
boundaries.
29
Magnetics 2007
Improved Hysteresis Loop Shape
Good loop squareness
High Hci
Excellent BHmax,
especially for the high Hci
Testing at elevated
temperatures provides true
curve shape
Curve shape speaks
nothing about other
characteristics such as
physical strength and
corrosion resistance
Pole Caps saturate at 22,500 Oe
Likely actual curve shape
Note: Pole Cap saturation in hysteresisgraphs prevents accurate curve shape analysis above cap saturation
(at approximately 22,500 Oe)
More recent materials show marked improvement in loop shape and some materials have
extraordinary combinations of high Br and high Hci.
Note that in hysteresisgraph testing materials with Hci over 22,000 oersteds, that the curve
shape will be distorted at values above 22,000 due to saturationof the permendur pole caps.
For example, the material above actually has a curve similar to the dashed line.
Since the curve shape is virtually unchanged with moderately elevated temperature, wecan
compare the shape as measured at higher temperatures, looking for irregularity from a true
square loop and estimate back to room temperature.
30
Magnetics 2007
Magnet Material Evaluation: LTILT
This test is utilized to evaluate long term elevated
temperature degradation of the magnet output as a result of
structural changes from, for example:
Crystallographic changes
Corrosion
Measurements are made at room temperature periodically
during the conduct of the test: magnets are removed from
the test oven(s), cooled to room temperature and tested
Long Term Irreversible Loss Test
It is relatively easy to make a magnet with good magnetic properties and square loop shape.
It is much more difficult to also make that magnet corrosion resistant.
And just because a magnet can survive momentarily at elevated temperature does not
mean it will last for extended periods.
The LTILT test is looking for losses due to structural degradation as a function of time at
temperature.
31
Magnetics 2007
90%
92%
94%
96%
98%
100%
0 168 336 504 672 840 1008 1176 1344 1512 1680 1848 2016 2184 2352 2520 2688
Hours of Exposure to Elevated Temperature
P
e
r
c
e
n
t

o
f

I
n
i
t
i
a
l

F
l
u
x
Ferrite
SmCo
NdFeB
Molded
Comp
LTILT Comparison of
Various Permanent Magnet Materials
Sintered Ferrite
Initial loss is a function of Permeance Coefficient, Magnet Hci and Reversible
Temperature Coefficients of Hci
Continuing loss, as indicated by the slope of the curve to 2000 hours
or more, is a function of structural degradation of the magnet
Some curves show significant structural loss due to
chemical reaction during the first 1-3 weeks of testing
Sintered SmCo
Sintered NdFeB
Inj. Molded NdFeB
Comp. Bonded NdFeB
When plotted, the LTILT data curve shows an initial drop that isa function of: material
intrinsic coercivity, permeance coefficient of the magnet, Reversible Temperature
Coefficient, and temperature of the test. This drop occurs in the first few hours of the test.
From test durations of 1 week to many weeks, the slope of the decay line provides a
forecast for flux loss over extremely extended periods. In our experience, the shape of the
extended decay curve can be almost perfectly linear (sintered SmCo and sintered NdFeB)
or a decay curve, close to linear but with a 2
nd
order polynomial fit (bonded NdFeB).
We see here a comparison of typical curve shapes for several common magnet materials.
This is representative and shown for comparison only. In evaluating your application,
please have tests performed to verify actual performance.
32
Magnetics 2007
Example: Sintered SmCo with Nickel Plating
Sm2Co17 exposed to 165 C
y = -0.0000001279x + 0.9961282080
y = -0.0000000019x + 0.9943275233
98.5%
99.0%
99.5%
100.0%
500 668 836 1004 1172 1340 1508 1676 1844 2012 2180 2348 2516 2684 2852 3020 3188 3356 3524 3692 3860 4028 4196 4364 4532 4700 4868 5036
Hours on Test
P
e
r
c
e
n
t

o
f

I
n
i
t
i
a
l

F
l
u
x
Square Magnets
Round Magnets
12 Weeks 6 Weeks 18 Weeks 24 Weeks 30 Weeks
In this real-world example, the cylindrical SmCo magnet on test at 165 C is showing a rate
of decay that will result in a loss of 1% of flux after 602 years of exposure to this
temperature (after the initial drop).
Flux loss (after the initial drop) is calculated by multiplying the slope of the line times the
number of hours exposure. Refer to the regression formula in the chart.
The Y-axis intercept is a good approximation of the short term loss.
33
Magnetics 2007
Agenda
Introduction
Gaussmeter
Fluxmeter
Other
Autoclave
T&H Chamber
Salt Spray
Of the four commonly available and widely used permanent magnet materials, Ferrite is the
most corrosion resistant.
Alnico also shows considerable resistance to corrosion. One example of this resistance is
the use of Alnico cow magnets where cigar-shaped magnets are fed to cows. The magnet
remains in the cows stomach (in mild hydrochloric acid) holding magnetic debris (e.g.
barbed wire and nails) from moving on to the second and more delicate stomach.
Incidentally a Google of cow magnet returns 21,400 hits!
But the rare earth magnets (SmCo and NdFeB) are more reactive, often requiring coating to
protect them from the environment. It is important, therefore, to understand a magnets
limitations and also how to evaluate it for successful performance capability.
34
Magnetics 2007
Corrosion Resistance: Introduction
Good performance requires both a good coating and a good
alloy base onto which to apply the coating
Even an excellent quality coating will eventually fail when the
mechanical join between the coating and magnet fails
Improvements in coating technology have masked some alloy
problems
Improvements in the base alloy are now providing a great
combination of excellent alloy and coating
SmCo is more corrosion resistant than NdFeB, so most of these comments relate to Neo
magnets.
Perhaps a remarkable state of understanding is the recognition that coating alone will not
solve NdFeB magnet performance issues: a sound base alloy must also be present.
However, such strides in coating technologies have been made as to allow use of marginal
materials in some demanding applications.
35
Magnetics 2007
What has been the problem?
NdFeB magnets consist of particles of
2-14-1 phase glued together with a grain
boundary phase that was historically
neodymium rich and prone to oxidation and
(galvanic) corrosion
This phase was necessary to achieve good
magnetic properties
Reducing the thickness of the boundary
improved corrosion, but made achieving good
magnetic properties difficult
Most of us consider neo magnets to be a metal, an alloy, like steel.
Actually, it is more like a ceramic, full of fine particles glued together by a grain
boundary phase.
This makes the material behave with considerable brittleness.
The grain boundary is also the source of good magnetic loop squareness, high Hcj, and the
source of (galvanic) corrosion and hydrogen decrepitation.
36
Magnetics 2007
Alloy Improvements
At least these three improvements have been made:
The RE (rare earth) content of the alloy has been reduced to
~31% by weight (down from 33.5%) thus reducing the presence
of unstable oxides
Grain boundary modifiers have been added (Cu and Ga) to
reduce the RE requirement and reduce the galvanic couple with
the 2-14-1 phase
The grain boundary composition has changed from a RE rich
material to alloys containing Co, Dy, Ga, Cu and other elements
Improving corrosion resistance has required the reduction of theRE-rich grain boundary
phase by reducing the rare earth content from 34% in the mid 1980s to between 30 and
31.5% (by weight) today (depending upon manufacturer and formulation).
The excess rare earth (neodymium) was required for liquid phase sintering and coating of
the grains to develop coercivity. Older alloy casting techniques also allowed the separation
of alpha-iron.
Some formulations have been modified to include Co, Dy, Ga, Cu, Al, and more, in an
effort to reduce or eliminate the galvanic couple between the grain boundary and the 2-14-1
particles. Reduction of neodymium in the grain boundary also reduces hydrogen absorption
which would lead to volume expansion and cracking.
Putting Co and Dy in the grain boundary, rather than the base alloy, has secondary benefits
regarding magnetic properties, but is beyond the scope of todays talk.
37
Magnetics 2007
Evaluating Performance
Base Alloy
Bulk Corrosion Test (PCT): Autoclave for 96 hours at 8 psi
pressure; magnets are un-coated and un-magnetized;
measurement is weight loss per unit surface area (mg/cm
2
)
Coated Magnet
Autoclave Test (HAST) for either 4 or 11 days depending
upon pressure
T&H Chamber: typically 85 %RH / 85 C; with or w/o Tape
Peel (Cross-Hatch Adhesion) Testing
Salt Spray (ASTM B117)
Thermal Cycling and/or Thermal Shock
Both the base magnet and the coating affect performance.
The base magnet should be tested as part of a system of process control. A rather kludgy
but very effective method is the Bulk Corrosion test (BCT) started by Dr. SimNarasimhan
at Crucible in 1985. the un-magnetized and un-coated magnet is placed in an autoclave for
96 hours. Weight loss during the test is calculated as a function of unit surface area. The
lower the weight loss, the better the expected performance in-use.
Coated magnets have received numerous tests over the years. More recently, the HAST test
is increasingly specified. It is a more rigorous alternative tothe BCT as well see on the
next slide.
38
Magnetics 2007
Autoclave Test Alternatives
HAST per EIA/JEDEC Test Method A110-B
100
150
200
250
300
350
400
100 105 110 115 120 125 130 135 140
Degrees C
P
r
e
s
s
u
r
e
,

k
P
a
0
5
10
15
20
25
30
35
40
P
r
e
s
s
u
r
e
,

R
e
l
a
t
i
v
e
,

p
s
i
HAST 96 hour test
85% RH, 130 C
230 kPa (18.8 psi relative
HAST 264 hour test
85% RH, 110 C
122 kPa, 2.9 psi (relative)
BCT 96 hour test
97-100% RH, 113 C
156 kPa, 8 psi (relative)
Autoclave Testing
70%
100%
95%
90%
85%
80%
75%
RH %
BCT 96 hour test
97-100% RH, 120 C
205 kPa, 15 psi (relative)
At least these four test conditions have been used for Autoclavetesting.
Note that the BCT, whether at 1.6 or at 2 atmospheres, is conducted near 100% RH. In
contrast, the HAST test is conducted at 85% RH.
Control of RH below 100% above 100 C is difficult to achieve and requires very expensive
equipment.
Autoclaves for use to 2 atmospheres maximum are readily available. However, the
recommended operating range is typically lower than 2 atmospheres except for more
expensive units. This cost differential, in the US, is due to laws governing pressure vessels
with the break-over point at 2 atmospheres.
39
Magnetics 2007
Correlation (Approximate) of Coated Magnet Testing: NdFeB
From TDK presentation of June 1990 and their Catalog of June 15, 2005
Many companies have tried to correlate test performance in order to utilize the shortest,
most cost effective test. For the most part, these correlationshave not been successful.
TDK has done extensive testing and presents this comparison of results.
40
Magnetics 2007
Correlation (Approximate) of Coated Magnet Testing: NdFeB
Correlation is approximate and affected by magnet type, underlying magnet material stability, grade, coating and shape
Thermal Cycling is per MIL-STD-202G, 2003-JUL-18, Test Method Standard Electronic and Electrical Component Parts. See also ASTM D6944.
10
100
1,000
10,000
100,000
1,000,000
24 48 72 96 120
Autoclave, 8 psi, 113 C, hours
H
o
u
r
s

o
r

C
y
c
l
e
s
Ambient, 75, 75
T&H 70/95
T&H 85/85
Thermal Cycling
Hour s
Cycles
Hour s
Hour s
Please note
This graphically shows the relationship.
However, I believe that test results are greatly affected by both the magnet structure and the
coating type and integrity. Therefore, this chart should only be used as a general guide and
any correlation developed for the specific magnet and application.
41
Magnetics 2007
Coatings: Characteristics
Organic Coatings (epoxy, urethanes) are not hermetic (do not seal
against moisture or oxygen) but do slow the reaction with the magnet
Nickel: electrolytic nickel provides a hermetic seal but is prone to
corrosion in salt and acidic conditions; electroless (chemical) nickel
offers improved coating into crevices, internal threads, ID holes but is
less protective of the magnet
Zinc plating is sacrificial releasing particulates. By itself, performance
is marginal, so conversion coatings are often used in conjunction with
zinc.
Aluminum IVD is a malleable coating that requires bead blasting and
conversion coatings to provide good seal against the elements
Conversion Coatings provide short-term protection only, but are used
in conjunction with other coatings to enhance performance
Combination Coatings, typically nickel plating plus an organic
overcoat, offer improved resistance to salt spray plus protection from
moisture and oxygen
There are very many coatings to select from today! Some manufacturers offer only a few of
the more effective and popular coatings such as spray epoxy, e-coat and nickel plating.
Each coating has its advantage(s) and disadvantage(s).
For neo magnets, electrolytic nickel plating has become a standard. The nickel forms a
hermetic shield around the magnet, protecting even suspect material. For most sizes and
shapes, nickel is applied via barrel plating which is very economical.
E-coat (electrophoretic epoxy, a plated type of epoxy coating) and spray epoxy are both
widely used for less critical applications and some special formulations have been
developed which contain PTFE to enhance protection of the magnet. (See Everlubes
website: www.everlubeproducts.com).
Salt Spray requirements pose a special problem in that nickel does not stand up well to it.
Aluminum (plus conversion coating), which does, is quite expensive. One compromise
coating is nickel plating to protect the magnet and epoxy overcoat to protect the nickel.
42
Magnetics 2007
Coating Performance Summary: NdFeB
Rack plating has lower performance due to rack marks
Other coatings include Ti-Nitride, tin plating, nickel+tin, conversion coatings, conversion coatings plus epoxy, parylene
Aluminum seal-coating is with tri-valent chromate
Characteristic
or Test Detail Uni ts
Nickel
Electrolytic
Nickel
Electroless
(Chemical)
Epoxy
(no conv. coating) E-Coat
Aluminum
(with conv. coating) Zinc
Hybri d
(Nickel & Epoxy)
Thickness microns 10 - 25 15 - 20 15 - 50 15 - 25 8 - 25 30 - 40
Application
Method
Electro-deposit,
Barrel or Rack
Chemical bath,
Barrel or Rack
Dry Spray Chemical bath,
Rack
IVD, Barrel or Rack Electro-deposit Electro-deposit
+ Dry spray
70C / 90% RH Days >2,500 >500 >1000 >1000 >2,500
85C / 85% RH Days >500 >100 >500 >400 >500
HAST 110C Hours >72
PCT 113C Hours >500 >500
Hast 130C Hours
Salt Spray 5%, ASTM B117 Hours ~24 <48 >100 >500 >250
-40 to 150 C Cycles >500
MIL-202, -10 to
65C, 90%RH
Cycles >500
Advantages Hard, durable,
hermetic, generally
corrosion resistant
Flat, even coating;
fills ID's and cracks
and crevices
Good adhesion to
substrate; resistant
to wide range of
chemical attack
Combination of
advantages: epoxy
adds corrosion
protection to salt
spray and acids
Dis-advantages Poor performance
in salt spray, dog-
boning at edges,
won't fill ID's cracks
and crevices
More difficult to
obtain hermetic
microstructure
Not hermetic:
moisture and air can
penetrate to react
with substrate;
thicker than nickel;
dogboning at edges
Not hermetic; won't
fill ID's cracks and
crevices; requires
rack mounting
Expensive process
requires high volume
to be cost effective;
requires bead
blasting and
conversion coating to
realize full benefit
Anodic to NdFeB,
offering little actual
corrosion protection;
requires conversion
coating to perform
effectively
Combined process
provides a thick
coating and is more
expensive;
improvements in salt
spray are limited
T&H Chamber
Thermal Shock
Autoclave
Charts like this are offered by most manufacturers.
We have observed that the test results are dependent upon numerous factors including shape
complexity of the magnet and magnetic assembly. They are most especially affected by
base alloy corrosion resistance. There are pronounced improvements taking place which
make earlier generated data superseded.
However, the retained data do provide some insight and customersare encouraged to
inquire regarding their specific applications.
43
Magnetics 2007
Imports of Metal Magnets
Rare Earth, Alnico
1998 1999 2000 2001 2002 2003 2004 2005 2006
2006
Percent
of
Total
Totals 95,353,320 105,350,341 116,680,389 94,318,178 182,607,474 133,635,064 125,957,466 141,581,511 150,257,500
China 25,713,246 31,732,447 28,002,414 31,228,775 30,753,420 39,456,683 53,225,517 63,643,976 83,704,100 55.7%
Japan 25,413,101 30,499,364 44,130,144 30,288,617 30,929,697 36,431,420 31,193,059 33,597,527 28,812,500 19.2%
Germany 8,086,545 10,014,090 11,216,542 6,459,038 10,483,749 7,554,336 9,250,506 8,468,790 9,005,300 6.0%
United Kingdom 13,951,894 14,983,789 16,160,897 10,433,397 10,655,518 7,662,211 5,580,081 5,499,716 5,306,800 3.5%
Mexico 1,692,759 1,074,595 1,701,478 951,574 86,840,552 28,362,925 9,256,327 11,947,434 3,809,900 2.5%
Taiwan 3,023,565 3,919,033 3,776,890 3,070,409 3,005,438 4,646,615 2,931,960 3,813,380 3,569,700 2.4%
Philippines 132,137 82,059 95,223 745,303 691,740 506,962 630,758 1,272,799 2,640,100 1.8%
Switzerland 3,508,828 3,528,842 3,040,812 2,179,500 1,878,664 1,578,135 2,174,743 2,276,674 2,322,900 1.5%
Korea 658,627 778,721 2,069,484 1,814,324 2,000,659 1,716,384 4,205,649 2,437,947 2,101,900 1.4%
New Zealand 441,251 27,000 60,480 0 0 0 706,803 1,258,569 1,264,500 0.8%
Malaysia 2,469,833 2,075,550 874,566 682,728 671,145 549,475 179,498 243,277 1,143,500 0.8%
Hong Kong 703,626 906,137 700,867 2,247,951 654,940 658,469 679,031 707,226 699,000 0.5%
Brazil 43,777 12,061 49,388 47,195 0 66,286 45,246 21,920 669,000 0.4%
Denmark 135,852 53,385 11,307 11,544 344,729 11,708 40,639 50,091 591,800 0.4%
Canada 628,979 917,178 719,380 499,356 280,028 418,418 1,637,448 499,138 590,000 0.4%
Netherlands 310,439 128,894 84,931 384,586 251,838 437,716 1,055,769 1,119,095 527,700 0.4%
India 267,397 143,300 169,099 123,517 495,776 719,401 430,226 812,085 484,000 0.3%
Italy 626,327 717,610 242,229 128,697 182,482 357,137 293,532 279,714 381,500 0.3%
Finland 2,022 5,338 46,875 44,839 197,947 43,298 222,566 490,306 337,100 0.2%
France 1,278,087 631,845 390,684 352,982 529,297 313,185 288,151 657,168 281,100 0.2%
Australia 253,063 264,058 340,676 273,595 383,635 521,564 341,079 573,210 251,700 0.2%
Sweden 80,535 66,444 516,677 462,336 95,002 132,002 141,646 234,780 228,800 0.2%
Israel 14,308 2,400 30,479 64,665 252,738 253,071 169,782 145,101 218,800 0.1%
Lithuania 19,538 0 0 0 0 343,427 470,101 460,441 218,300 0.1%
Russia 1,771,529 73,108 109,341 341,732 169,760 359,452 73,811 446,020 202,100 0.1%
Country In Actual Dollars
HTS - 85051100: Permanent magnets, Metal
Including articles intended to become permanent magnets after magnetization
I usually include some comments in my talks about import of magnets.
Rare earth metal prices have more than doubled in the last 12 months. Since RE is
approximately 30% by weight of the neo magnet, prices might alsobe expected to increase
by 30%. And in large part they have.
Imports of Metal Magnets from China represent 56% of all metal magnet imports.
However, many imports from China have funneled through other non-manufacturing
countries such as Mexico.
Increasingly, many metal magnets also enter the US as part of assemblies or in finished
products.
44
Magnetics 2007
Major Exporters to the US
Major Sources of Metal Magnets
0
20
40
60
80
100
120
140
160
180
200
1998 1999 2000 2001 2002 2003 2004 2005 2006
Year of Import
T
a
r
r
i
f

V
a
l
u
e
,

$
m
i
l
l
i
o
n

U
S
D
Taiwan
Mexico
United Kingdom
Germany
Japan
China
Total
Imports of metal magnets from China (directly or indirectly) have grown quickly on a dollar
basis. Simultaneously, the cost per pound for magnets decreasedfrom 1998 through 2005
(but are now rising). Thus the number of imported magnets has grown even more quickly
than the $ increase shown here.
45
Magnetics 2007
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