Inertial Heavy Alloys 391

The newer friction products include combinations such as aluminum with boron
carbide, silicon-silicon carbide-graphite, and carbon-carbon. The Al-B4C composite
is formed from mixed powders using hot pressing, while the Si-SiC-C composites rely
on infiltration of molten silicon into a graphite preform followed by a bake to partially
react the two phases. In carbon-carbon composites, graphite fibers are bonded using
resin infiltration. That mixture is baked to convert the resin into graphite. Although
expensive, graphite composites are widely adopted for aircraft brakes.

Inertial Heavy Alloys

Following the discovery of radioactivity in the late 1890s, needs arose for safe
means to ship and handle radioactive materials [34]. The solution came from high
tungsten content composites. Usually, the composite is consolidated using a liquid
phase at temperatures near 1500 C (1773 K). Normally, tungsten is brittle at room
temperature, but when alloyed with the transition metals such as Ni, Cu, Co, or Fe,
there is surprising ductility imparted by the matrix phase [34–38]. These tungsten
heavy alloys are abbreviated WHA, W being the chemical symbol for tungsten.
Most tungsten heavy alloys range from 15 to 19 g/cm3, density levels consider-
ably higher than lead. Due to the high density, the tungsten composites provide
excellent containment for radioactive materials. Although lead is soft and easily
fabricated, tungsten composites require less volume and avoid toxicity associated
with lead, mercury, or uranium. Tungsten heavy alloys are significantly lower cost
when compared to high atomic number options, such as platinum, rhenium,
osmium, iridium, or gold. Tungsten is the safest and lowest cost option among
the high density metals.
The tungsten heavy alloys consist of tungsten grains in an alloy matrix. Fig-
ure 11.23 is a microstructure showing single crystal tungsten grains surrounded by
the alloy matrix. In this case the composition is W-3.5Ni-1.5Fe, corresponding to
about 88 vol% tungsten. Note the tungsten grains bond to form a three-dimensional
skeleton. The matrix alloy occupies the spaces between the tungsten grains to form
a second interpenetrating network. The matrix alloy is designed to avoid interme-
tallic formation during cooling from the sintering temperature, ensuring a high
ductility. For this reason the alloys favor specific ratios such as Ni:Cu ¼ 6:4 or Ni:
Fe ¼ 7:3. An example is W-7Ni-3Fe. When sintered at 1500 C (1773 K) this
composite exceeds a density of 17.4 g/cm3 with a yield strength of 675 MPa and
29 % fracture elongation. Further property adjustments are possible through post-
sintering heat treatments.
Inertial materials have high densities for used in applications such as in radiation
absorption, medical X-ray shielding, sporting equipment weights, projectiles,
vibration dampening weights, watch winding weights, gyroscope balances, and
aircraft wing counterbalances. They are also used in armor piercing projectiles.
Long rod shapes are produced by deformation and heat treated to reach high
strength levels. Several applications are summarized in Table 11.11.
392 11 Applications

Fig. 11.23 Microstructure

of a tungsten heavy alloy
composite consisting of
W-3.5Ni-1.5Fe. The
tungsten grains form a
bonded skeletal structure
with matrix alloy
(Ni-Fe-W) filling the
intergranular spaces. This
composition corresponds to
88 vol% tungsten with
12 vol% of the structure
consisting of solidified
53Ni-24W-23Fe

Table 11.11 Heavy alloy composites and uses

Typical
Application Key property composition
Armor piercing projectiles Density, strength, toughness, hardness W-Ni-Co-Fe
Boring bars Elastic modulus, vibration dampening W-Ni-Fe
Casing for oil well logging High density, corrosion resistance W-Ni-Fe
Cell phone, pager, vibrator Low cost, high density W-Ni-Cu
Collimator for radiation tumor High tungsten content, radiation W-Ni-Fe
treatment absorption
Counterbalance and golf club Density, inertial response, machinability W-Ni-Cu
weights
Die cast tooling Resistance to molten metal, high tempera- W-Mo-Ni-Fe
ture strength
Inertial gyroscope guidance Density, inertia, low thermal expansion W-Ni-Cu
devices
Isotope storage container Tungsten content, easy machining, radia- W-Ni-Cu
tion opacity
Lead replacement birdshot Low cost, easy forming, density W-Cu-Sn-Fe
Race car crankshaft adjustment Density, vibration dampening W-Ni-Cu,
W-Ni-Fe
Radiation containment High tungsten content W-Ni-Fe
Throwing dart bodies Density, low cost, aesthetics W-Ni-Cu
Vibration damping devices High stiffness, inertia W-Ni-Fe
Watch self-winding weight Low cost, density W-Ni-Cu
Inertial Heavy Alloys 393

Table 11.12 Nominal W-Cu-Sn-Fe

compositions for tungsten
W-Ni-Fe
heavy alloy composites
W-Ni-Co
W-Ni-Cr
W-Ni-Cu
W-Ni-Fe-Co
W-Ni-Mn-Cu
W-Mo-Ni-Fe

Tungsten contents are from 88 to 98 wt%, but compositions with as little as

50 wt% tungsten are possible. These combinations suppress formation of brittle
phases during cooling from the sintering temperature. Alloying enables property
adjustments over a wide range, as summarized in Table 11.12 [1, 34, 38, 39]. For
example, the addition of molybdenum increases strength retention to high temper-
atures as useful for hot tooling. The W-Cu-Sn-Fe composition is used for lead-free
birdshot; with 50 wt% tungsten the density is 12 g/cm 3. The twofold difference in
elastic modulus between tungsten and the matrix provides excellent vibration
attenuation for tool holders in precision machining.
The WHA composites are formed from mixed elemental powders nominally
from 1 to 5 μm in size. After mixing, the powders are compacted at 200–600 MPa.
If the shape is a small and flat, such as for self-winding watch weights, then uniaxial
die compaction is employed. Injection molding is applied to complicated three-
dimensional shapes, such as fishing sinkers. Long rods are formed using cold isostatic
pressing. The pressed compact can be machined prior to sintering. Near full density is
attained by sintering at temperatures near 1500 C (1773 K), usually with a
30–60 min hold. Hydrogen is the typical sintering atmosphere, but vacuum is also
used. Prolonged sintering causes microstructure coarsening and reduced strength;
pores coalesce and grow over time, resulting in swelling and ductility. After 120 min
at temperature, bubbles are evident inside the component as the pores coarsen.
After sintering, the tungsten grain size is 20–50 μm. This represents thousands of
particles fusing into one grain during sintering. Dopants are used to reduce the grain
size, such as molybdenum, tantalum, or rhenium. Each grain is a single crystal
bonded to neighboring grains. Usually as the degree of tungsten-tungsten bonding
or contiguity increases the ductility decreases. For W-Ni-Fe compositions, the
matrix is approximately 53Ni–23Fe–24W.
The mechanical properties of representative alloys are summarized in Table 11.13
[1, 38, 39]. The elastic modulus ranges from 320 GPa for the low tungsten con-
tents (82 wt% W) to 380 GPa for the high tungsten contents (97 wt% W). Thermal
and electrical characteristics change little with composition. Thermal conductivity is
about 120 W/(m C) and the electrical conductivity is about 13 % of the International
Annealed Copper Standard (IACS). The thermal expansion coefficient is low due to
the high tungsten content, averaging near 5 10 6 1/ C (or 5 ppm/ C, where ppm
implies parts per million). The heat capacity is near 1.5 J/(g C). These attributes are
desirable in measurement gauges where stability is desired independent of ambient
temperature.
394 11 Applications

Table 11.13 Representative properties of heavy alloy composites [1, 38, 39]
Density, Hardness, Yield strength, Tensile Elongation,
Composition g/cm3 HV MPa strength, MPa %
74W-16Mo- 15.3 365 850 1150 10
8Ni-2Fe
82W-8Mo-8Ni- 16.2 315 690 980 24
2Fe
85W-5Ta-7Ni- 16.6 354 740 1025 3
3Fe
86W-4Mo-7Ni- 16.6 280 625 980 24
3Fe
90W-8Ni-2Fe 17.2 290 550 920 36
90W-5Mo-3Ni- 17.4 280 620 1000 17
2Fe
90W-7Ni-3Fe 17.1 270 530 920 29
93W-5Ni-2Fe 17.7 280 590 930 30
94W-3Ni-1.5Fe- 18.3 325 645 940 25
0.5Co
95W-3.5Ni- 18.1 280 600 920 18
1.5Fe
97W-2Ni-1Cu 18.6 280 600 660 3
97W-2Ni-1Fe 18.6 300 610 900 19

As outlined in Fig. 11.24, composition impacts mechanical properties. Tungsten

provides strength while the matrix provides toughness. As sketched in Fig. 11.25,
four possible fracture paths exist within the microstructure. The actual behavior
depends on the relative interface properties; failure occurs by a mixture of matrix
rupture, tungsten grain cleavage, tungsten-tungsten grain boundary failure, and
tungsten-matrix interface failure. Figure 11.26 is a scanning electron micrograph
fracture surface showing mixed fracture paths. Weak interfaces trace to impurity
segregation to interfaces, a problem that is cured by rapid cooling. Properties such
as density, elastic modulus, and yield strength, are relatively immune to interface
characteristics, but elongation, fracture toughness, ultimate tensile strength, and
impact toughness vary with interface quality.
The yield strength for annealed tungsten is about 550 MPa with an elastic
modulus of 400 GPa. For the 7:3 Ni:Fe alloy, the matrix yield strength is
205 MPa and elastic modulus is 225 GPa. A composite of 85 W-10.5Ni-4.5Fe
corresponds to 67 vol% tungsten grains and delivers a yield strength of 411 MPa
and elastic modulus of 330 GPa. These properties are as expected based on the
constituents. On the other hand, properties related to plastic deformation are less
predictable. Tungsten is brittle at room temperature, but the heavy alloy composite
exhibits ductility with excellent work hardening. Although tungsten strain softens at
high strain rates, meaning that strength declines during deformation, the composite
exhibits the opposite behavior with strain hardening. Accordingly, the composite
hardens when used as an armor piercing projectile.
Inertial Heavy Alloys 395

Fig. 11.24 Six factors determine the mechanical properties of tungsten heavy alloys, especially
elongation and toughness. These include the (1) composition in terms of W content, matrix type,
and ratio of ingredients in the matrix; (2) powders in terms of the particle size and purity;
(3) processing cycle including the forming pressure, heating rate, peak temperature, and hold
time; (4) post-sintering deformation and heat treatment cycles; (5) defects including residual
porosity; and (6) microstructure grain size

Fig. 11.25 A schematic of the four possible fracture paths in a composite consisting of (1) brittle
grain cleavage, (2) ductile matrix failure, (3) grain boundary separation, and (4) interface separa-
tion. The latter two paths are sensitive to impurity segregation and are manipulated by heat
treatments and cooling rates
396 11 Applications

Fig. 11.26 Fracture surface imaged by backscatter scanning electron microscopy, where the
tungsten is white and the lower atomic number matrix is dark. The fracture paths noted in
Fig. 11.25 are evident here. The predominance of grain-matrix interface failure indicates this
material was not optimized for fracture resistance, since impurity segregation on cooling is a
typical cause of interface separation

Fig. 11.27 Correlation

between yield strength and
fracture elongation for
tungsten heavy alloy
composites. Although the
results are scattered, the
general trade-off between
strength and ductility is
evident

Property trade-offs are possible via composition, deformation, and heat treat-
ment. Figure 11.27 is a plot of yield strength versus fracture elongation. Although
scattered, the behavior illustrates how the composite provides either a high strength
or high ductility, but not both. For low ductility compositions the ultimate tensile
Iron Neodymium Boron Magnets 397

Fig. 11.28 Fracture

elongation as a function of
the tungsten grain volume
for W-Ni-Fe compositions
fabricated with the same
processing conditions. The
trend line passes through
zero ductility at 100 %
tungsten

strength is also low. Figure 11.28 plots fracture elongation versus composition for
the same materials shown in Fig. 11.27. Underlying these plots are changes in the
tungsten grain boundary area, a typical weakness in the microstructure. A few
applications are pictured in Fig. 11.29, including weighted throwing darts, vibration
weights, birdshot, fragmentation projectiles, and fishing weights.

Iron Neodymium Boron Magnets

Exceptional hard magnetic properties for the Fe14Nd2B intermetallic compound

were identified in the 1980s. The compound provides the largest energy product
attainable in a magnet; about 20-fold better than magnetic steel and eightfold better
than earlier magnets [40, 41]. The contour plot in Fig. 11.30 indicates the magnetic
field strength versus composition. The sweet spot is slightly off the Fe14Nd2B
compound, since a two phase composite microstructure is optimal. The excess
rare earth, usually about 5 wt% Nd, Dy, Pr, or Tb, is intentionally oxidized and
segregated to grain boundaries to decrease electrical conduction between the
Fe14Nd2B grains. The oxide constitutes about 5–8 vol% of the structure. Residual
pores also act to disrupt conduction. These magnets are widely employed in
cameras, generators, automotive systems, pumps, motors, business machines,
loud speakers, headsets, telephones, power tools, and home appliances.
If the powder has anisotropic magnetic behavior, then a magnetic field is applied
during powder pressing. Isotropic powders are magnetized after consolidation.