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org/publications/bulletin

Mo-Si-B Alloys:
blue shading on the lower-left region of
Figure 1 depicts the incremental gain in
service temperatures from such design
refinements. The orange and purple
shaded regions of the figure depict the ad-
vantages to the engine from efficient de-

Developing a sign and the use of advanced materials in

the turbine.
Today’s engines expose superalloys to
temperatures approaching 1150⬚C, while

Revolutionary the turbines themselves are able to operate

at considerably higher temperatures by dis-
tributing cooling air through the advanced
single-crystal airfoils and by using thermal-

Turbine-Engine barrier coatings. However, closer inspec-

tion of the data shown for the PW2037
through PW4084 engines reveals a new

Material
and disturbing trend. While the rotor inlet
temperatures rose with each of these en-
gines in turn, the deviation from ideal per-
formance increased, principally as the
'HQQLV0 'LPLGXNDQG-RKQ+ 3HUHSH]NR result of necessarily increased cooling air
flow. With modern superalloys, the maxi-
mum service temperature of the metal
components has all but stagnated; thus,
$EVWUDFW continued advancement requires new ma-
7KLVDUWLFOHGLVFXVVHVWKUHHPDLQSRLQWV )LUVWXOWUDKLJKWHPSHUDWXUHPDWHULDOVRIIHUD terials for the high-pressure turbine.
ODUJHUHWXUQWRWKHSURSXOVLRQFRPPXQLW\DQGWRWKHHFRQRP\EXWUHSODFLQJ1LEDVHG When looking at new high-temperature
DOOR\VLVDYHU\GLIILFXOWSUREOHPIRUERWKWHFKQLFDODQGILQDQFLDOUHDVRQV 6HFRQGWKH materials systems, many factors must be
R[LGDWLRQUHVLVWDQFHRIVHOHFWHG0R6L%DOOR\VDQGWKHSURVSHFWVIRUFRPELQLQJWKLVZLWK considered, including melting point, den-
XVHIXOVWUXFWXUDOSURSHUWLHVDUHUHPDUNDEOHJLYHQWKHQDWXUHRIFRQYHQWLRQDO0RDOOR\V sity, and cost, to name a few. However, two
KRZHYHUWKHUHDUHQDJJLQJLVVXHVDVVRFLDWHGZLWKWKHLUORZWHPSHUDWXUH⬃⬚& material attributes dominate development
EHKDYLRU 7KLUGIXUWKHUDGYDQFHVLQWKHSURFHVVLQJRIVXFKPDWHULDOVWRJHWKHUZLWK strategies—oxidation resistance and high-
DVVHVVPHQWVRIWKHLUDIIRUGDELOLW\DQGUHOLDELOLW\DUHYLWDOIRUDFKLHYLQJDVXFFHVVIXO temperature creep. While the latter implies
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the need for a high melting point and con-
trol over microstructure, the first suggests
a need to form Al2O3-based or SiO2-based
Keywords: aerospace, high-temperature materials, intermetallic alloys, materials
scales during high-temperature exposure.
development, oxidation, phase equilibria, powder metallurgy, structural materials,
The extreme application environments
turbine engines. above 1000°C render most other oxide
scales either too permeable or too volatile
to offer protection for long periods of time.
,QWURGXFWLRQ Two metal systems that may lead to a good
The invention and discovery of new measure of both material and engine per- compromise of these and other factors are
high-temperature structural metals is one formance is the amount of horsepower Nb- and Mo-based alloys. Both the metals
of the truly hard problems in materials produced as a function of the turbine rotor as pure elements and their previously de-
science and engineering. There is no par- inlet temperature, the T4 temperature of
1
veloped alloys have poor environmental
allel in nature to the remarkable synthetic an engine. This relationship is known for resistance that is intrinsic to their oxida-
achievements in this field, and the potential an ideal gas-turbine engine and is shown tion mechanisms (which are very different
impact of these materials on the economy, in the figure as an analytical expression for the two systems). However, silicide-
our lifestyle, and our future is enormous. and by the green line. Blue bullets in Fig- containing alloys investigated during the
More than 50 years ago, the paradigm for ure 1 represent several Pratt and Whitney last ten years show promise for both Mo
these materials was established within Ni engines that were developed from the 1940s and Nb alloys. The remainder of this ar-
alloys or superalloys,1 and, as the articles through the early 1990s. In each case, the ticle focuses on selected attributes of the
in this issue of MRS Bulletin suggest, there actual engine performance falls short of Mo-Si-B system; see the next article in this
are many reasons for attempting to estab- the ideal line because of inefficiencies in issue, by Bewlay et al., for a discussion of
lish a new paradigm that may not only the engine. Over the years, structural and Nb-based alloys.
sustain many more years of development aerothermal design advances minimized Molybdenum-based alloys such as TZM
and growth of gas turbines, but also spur leakage in the pressurized systems, opti- (Mo-0.5Ti-0.08Zr-0.03C; all compositions
new technologies enabling hypersonic mized aerothermal flows of the engine, expressed in weight percent), and others
flight and ready access to space. and took advantage of highly refined cool- without Si or B additions, are established
A look at the historical data regarding ing and coating schemes to prevent mate- high-temperature materials for inert envi-
the use of Ni alloy technologies in gas- rials from melting in the high-pressure ronments because of their excellent strength
turbine engines reveals the magnitude of turbine (see the fine cooling-hole configu- at elevated temperatures. However, the
this endeavor. As shown in Figure 1, one ration on the airfoil inset in Figure 1). The oxide MoO3 formed over the base metal is

MRS BULLETIN/SEPTEMBER 2003 639

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Compositions and Alloy Phases
The phase equilibria of refractory-metal
silicides have been well studied for spe-
cific phases such as the disilicides, where
high-temperature stability is vital for oxida-
tion behavior and where low-temperature
characteristics are critical for microelec-
tronic applications (i.e., the Me3Si A15
phases for superconductivity and the
Me5Si3 structures for coatings, where Me is
a refractory metal). There is much less
known about refractory-metal borides.
While the binary refractory-metal boride
and silicide phases have high melting
temperature, elastic modulus, and hard-
ness, they also exhibit no ductility and very
low fracture toughness. Nonetheless, the
need for high-temperature structural al-
loys motivated attempts to include silicide
and borosilicide phases within alloys hav-
ing a refractory metal base. Studies of the
Mo-B-Si and Nb-B-Si systems indicated that
ternary intermetallic phases do form in
Figure 1. Core power versus turbine inlet temperature for selected gas turbine engines. The equilibrium with the refractory metal.
data for specific engines span about 70 years and are compared to the ideal or theoretical Investigations of Mo-Si-B alloys estab-
limit. The data suggest that while horsepower has increased, much of this has come from lished the Mo-rich portion of the phase di-
advanced cooling schemes (blue shaded area) and that overall turbine efficiency has
drifted down from the ideal line. Higher-temperature materials are needed to shift perform-
agram isotherm at 1600°C shown in
ance back toward the ideal limits, but those materials must be manufactured using proc- Figure 2b. Emphasis here is placed on the
esses amenable to the production of complex airfoil components such as the one shown in phase equilibria in the region bounded by
the inset (height: approx. 12 cm.). Specific power is expressed relative to mass of air flow the Mo-MoB-Mo5Si3 phases. The Mo(ss)
(neglecting fuel). 72, 73, and 74 are the fan inlet, compressor exit, and combustor exit phase has a negligible B solubility, but ap-
temperatures, respectively. 5is the ideal gas constant, and ␥ is the ratio of heat capacities, preciable Si solubility to about 3 at.% Si.
&S &Y (usually about 1.4). For a given compressor exit temperature there is a corresponding The Mo3Si phase having the A15 structure
turbine rotor inlet temperature for combustion of the fuel under stoichiometric conditions. has a limited compositional homogeneity
The numbers at the upper right of the ideal curve indicate possible compressor exit region for Si ranging from about 24 at.% to
temperatures, and the lines mark the corresponding turbine inlet temperatures for achieving
stoichiometric conditions.
25 at.% but, similarly, a negligible B solu-
bility. Much the same is true for Mo5Si3 (T1
phase), where the compositional boundary
a solid having a high vapor pressure even composites reinforced with tungsten wires extends only to ⬃37 at.% Si on the Mo-rich
below 760⬚C. Above this temperature, the and observed that while the ends of the W side. The binary boride phases also have
oxide exists in the gaseous state and is wires oxidized away over a short distance, negligible solubility for either B or Si, and
therefore nonprotective. Alternatively, in- the subsequent oxidation of the W was in- the homogeneity range of the ternary
termetallic alloys based on the compound hibited by the formation of a glassy scale Mo5SiB2 T2 phase is likewise modest. The
MoSi2 are long known to provide outstand- that plugged the cavity left by the evapo- compositional variation in the T2 phase
ing oxidation resistance at extremely high rating W. The observation suggested that with respect to the B:Si ratio in the off-
temperatures as a result of SiO2 formation. alloys of Mo prepared with silica formers stoichiometric region is mainly toward
However, extensive study of these alloys (compounds that form silica scales upon B-rich values, which is indicated by B:Si
shows there is no feasible path that can high-temperature exposure in air) and B ratio values greater than 2.0. This is con-
provide both an oxidation-resistant MoSi2 as a fluxing agent could form a protective sistent with an analysis of the stability of
alloy combined with the creep and frac- SiO2-based scale. Berczik found that sili- the T2 phase that points to the relative ease
ture resistance required for structural de- cate scales containing boron, SiO2(B), in B to Si antisite substitution, but not vice
sign.2 Thus, there has been diminishing could be formed on alloys containing versa.5 The variation in the Mo content is
engineering interest in MoSi2 alloys for the Mo-2.2Si-1.0B (wt%). In 1997, Berczik4 was limited. From the standpoints of phase
last several years. But studies of the oxida- granted a patent for a family of alloys equilibria, the ␣-Mo(Si,B) ⫹ Mo3Si ⫹ (T2)
tion behavior of alloys within the Mo-Si-B based on the Mo-Si-B system in the range Mo5SiB2 region of the Mo-Si-B system is
system are encouraging. This system could of 1.6–15.2 at.% Si and 0.0-39.4 at.% B. nearly ideal in that it consists of simple
yield alloys with an SiO2-based oxidation- Under oxidizing conditions, the intermetal- mixtures of nearly line phases or com-
protection mechanism that is distinctly lic phases present—Mo3Si and Mo5SiB2 pounds (only slight solubility range) with
different from that of the traditional Mo- (T2)—provided the necessary Si and B to stability to 1600°C or higher. A representa-
based alloys, in combination with ade- form a coating of SiO2(B) glass. The phase tive microstructure for a three-phase Mo-
quate fracture resistance. stability, processing paths, alloy proper- 14.2Si-9.6B (at.%) as-cast sample is shown
During the early 1990s, Maloney et al.3 ties, and challenges of this family of alloys in Figure 2a. The structures of the relevant
conducted investigations of MoSi2-based are described here. phases are presented in Figure 3, and the

640 MRS BULLETIN/SEPTEMBER 2003

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Figure 2. (a) Backscattered electron image of as-cast Mo-14.2Si-9.6B (at%) alloy.
(b) Isothermal section of Mo-Si-B system at 1600°C showing the T2 phase in equilibrium
with Mo (bcc), Mo3Si (A15), and Mo5Si3 (T1) phase.
crystal structure descriptions are summa-
rized in Table I. Naturally, many more
attributes beyond having stable microstruc-
tures and reduced oxidation-rate behavior
are necessary for these materials to be-
come viable structural alloys.
The Mo5SiB2 phase has the D8l structure,
which has a body-centered tetragonal unit
cell (space group I4/mcm), as shown in
Figure 3. Crystal structures of the phases present in typical Mo-Si-B alloys: (a) bcc (Mo);
(b) A15 (Mo3Si); (c) T2 (Mo5SiB2); (d) T1 (Mo5Si3).
MRS BULLETIN/SEPTEMBER 2003
Figure 3c. Recently, Ito et al. successfully
prepared single crystals of this phase
and examined selected high-temperature
properties.6 The unit cell contains 32 atoms,
with 20 Mo, 4 Si, and 8 B atoms situated in
layered arrangements. Three types of
layers were identified: layer A, having only
Mo atoms; layer B, having only Si atoms;
and layer C, having a mixture of Mo and
B atoms. The structure arrangement of
these layers in T2 may be viewed as a means
to achieve efficient atomic packing be-
tween metal atoms such as Mo and metal-
loid constituents (Si and B in this case).7
Limitations exist for enriching the T2 phase
with Si, which may be related to the limited
available volume of the B sublattice, sug-
gesting a strong influence of atomic size
on the phase stability. For example, the
substitution of Mo by Nb expands the cell
volume, which results in the extension of
the T2 phase field to Si-rich compositions.
These basic phase relations identified in
Figure 2b are maintained at 1800°C with
the modification of an enhanced solubility
of Mo in the T2 phase that can be used to
develop a precipitation reaction to yield
fine Mo precipitates in T2.8 The solubility
change with increasing temperature also
indicates that constitutional defects are
present in the T2 phase that can influence
the high-temperature diffusion behavior.
Selected studies explored quaternary and
higher-order alloying additions using
many of the transition-metal elements. A
summary of some of the findings is pre-
sented in Figure 4. The figure indicates
some high-level pathways for developing
engineering alloys based on our knowl-
edge of chemistry and phase stability alone.
One may choose to develop materials
within the two ternary-phase regions
shown, and within each of these, one may
select alloying elements that dissolve
within those ternary base phases, or that
introduce new phases that exist in higher-
order phase spaces. These result in the
combinations of phases or structure types
shown in the last block for the element se-
lections indicated.
Since the Mo neighbors of a Mo site in
the T2 structure are in a bcc arrangement,
it is understandable that the transition
metals exhibit similar solution behavior in
Mo and the T2 phase. However, each of
these alloys requires further exploration of
the processing–structure–property rela-
tionships and will require much greater
time to develop. Still, only a very few of
these multicomponent alloys demon-
strated an improvement in the critical oxi-
dation properties.
Kinetics of Microstructure Evolution
Unlike most structural alloys, the Mo-
Si-B alloys offer very little opportunity for
exploiting naturally occurring solid-state
phase transformations to develop desirable
properties. Figure 4 indicates that with
selected alloying, it is possible to alter the
relative phase stability to induce transfor-
mations between the intermetallic phases
[i.e., T1, T2, and D88 (a Mo5Si3 structure,
hP16, not found in the ternary system but
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with synthesis of prealloyed powders by

7DEOH , &U\VWDO6WUXFWXUH,QIRUPDWLRQIRU3KDVHVLQWKH0R6L%6\VWHP rotary gas atomization, but now ingot
processes are being investigated. Quanti-
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ties of less than a few kilograms are rou-
6SDFH Strukturbericht 3HDUVRQ 3DUDPHWHUV tinely prepared by vacuum arc melting.
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0R6L &U6L Pm3n $ F3  and plasma arc melting with reasonable
0R6L% 7 &U% I/mcm 'O W, a ⫽  success. However, the as-solidified (or
c ⫽ 
solidified and heat-treated) ingots prepared
by those methods were prone to solidifi-
0R6L 7 :6L I/mcm
stabilized by additions of Hf, Zr, or Ti)],
but the utility of the transformation is an
unexplored area. While the slight change
in compositional homogeneity range with
temperature is highly desirable for high-
temperature stability, it virtually eliminates
opportunities for varying the microstruc-
ture through heat treatment. Moreover, the
sluggish diffusion rates (D ⬍ 10–16 m2/s at
1600°C),7,8 while attractive for thermal sta-
bility and creep resistance, present a chal-
lenge to microstructure modification. In
this sense, the materials are akin to ceram-
ics and composites in that the initial syn-
thesis methods largely dictate the final
microstructure. These synthesis methods
are not well understood or even widely
explored; however, they do present op-
portunities for the use of thermomechanical
'P W, a ⫽ 
c ⫽  to initial efforts at hot-working.
processing to impart characteristic struc-
ture length scales and to influence the con-
stitutive response of the ␣-Mo(Si, B) phase.
Attempted and Planned Processes
Historically, Mo-based alloys are pre-
pared by synthetic reduction of Mo oxides
in a hydrogen atmosphere followed by cold
pressing and sintering of the resulting pow-
ders. These compacts are subsequently
thermomechanically processed to complete
consolidation and impart a significant
stored dislocation substructure that favor-
ably influences deformation properties.
Recrystallization of the wrought structure
typically leads to a reduced strain to failure.
Unfortunately, such established proc-
esses do not easily transfer to the Mo-Si-B
alloy system. Exploratory research began
cation segregation5 and were not amenable
Slightly greater success has been
achieved by following a variety of powder-
metallurgy methods that include both
prealloyed powder preparation via the
plasma arc rotating-electrode process and
elemental powder routes that parallel the
standard processes for Mo-alloy produc-
tion. These routes require significant fur-
ther advances to achieve pilot-production
quantities in the 50 kg to 500 kg range.
Parallel to any such efforts there should be
more extensive efforts to develop thermo-
mechanical process schedules that en-
hance ductility of the Mo(Si, B) phase and
are consistent with the complete manufac-
turing schedules necessary for aeroengine
airfoil and heat-exchanger components.
Such efforts are in their infancy. Only after
such processes are established can the rep-
resentative defect populations be under-
stood and component design and life
management systems be established.

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Physical Properties
Because of the quite large centrifugal
forces generated in service, material den-
sity is always important for rotating tur-
bine engine structures. The Mo-Si-B alloys
of interest exhibit a density of ⬃9.5 Mg/m3,
which is about 5–7% higher than that for
the single-crystal Ni alloys now commonly
used. However, the first uses of these ma-
terials will likely be limited to static struc-
tures until sufficient experience is gained
for approaching more challenging rotat-
ing components.
The thermal conductivity of Mo-Si-B
alloys is two to four times greater
(49.9–112 W m–1 K–1, between 25°C and
1370°C) than that of many superalloys
within the temperature range of interest.
Further, the mean thermal expansion coef-
ficient is about 2.5 times lower (5.8–6.7 ⫻
10-6 m/m K) throughout the expected range
Figure 4. Schematic of alloy development paths for higher-order Mo-Si-B-X alloys. The of use temperatures. These are significant
figure suggests some high-level pathways for developing engineering alloys based upon
our knowledge of chemistry and phase stability alone. One may chose to develop materials
and favorable attributes for thermal man-
within the two ternary-phase regions shown, and within each of these, one may chose agement in heat engines. The thermal ex-
alloying elements that dissolve within those ternary base phases or that introduce new pansion behavior and high conductivity
phases that exist in higher-order phase spaces. These result in the combinations of phases open new opportunities for controlling
or structure types shown in the last block for the element selections indicated. thermal stresses and reducing cooling air,

642 MRS BULLETIN/SEPTEMBER 2003

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as well as offering a potentially better ther-
momechanical compatibility with ceramic
materials that will require attachments to
metal components. Clearly, there is a need
for new design practices suggested by
these physical properties alone.
Environmental Properties
To evaluate the suitability of alloys for
high-temperature exposure in oxidizing
environments, two quantitative metrics of
oxidation damage are used: weight change
per unit area and time; and recession rate,
or rate of thickness loss from a flat specimen
per unit time. The ␣-Mo(Si, B) ⫹ Mo3Si ⫹
(T2)Mo5SiB2 alloys exhibit an interesting
oxidation response as determined by these
two measures. Beyond an initial transient
time period, they exhibit parabolic-rate
kinetics for selected temperatures (in the
weight-change experiment). The kinetic
rate attained at temperatures above
⬃1000°C is sufficiently slow that the mate-
rials are attractive for engineering design.
However, unlike most high-temperature
materials, this alloy class exhibits chal-
lenges with oxidation control at lower tem-
peratures where the oxidation rates can be
linear.
The early engineering evaluations of
oxidation properties gave mixed results
for these alloys. Berczik4 measured reces-
sion rates of ⬃3048 ␮m/100 h for a
Mo-10.8Si-24.9B (at.%) alloy, which is near
the stoichiometric Mo5SiB2 composition
at 1093°C. Examining three-phase ␣-
Mo(Si, B) ⫹ Mo3Si ⫹ (T2)Mo5SiB2 alloys,
Schneibel et al.9 reported poor oxidation
behavior for alloys for which the material
was completely consumed after 24 h
exposure in air at 1200⬚C or 1300⬚C. How-
ever, three alloys [Mo-10Si-18B, Mo-14Si-
10B, and Mo-17Si-4B (at.%)] survived and
exhibited only modest weight losses.
Microstructural evaluation of these alloys
showed that the oxidation resistance might
be sensitively tied to the exact phases
present (the details remain unresolved).
Fortunately, Berczik10 also examined
higher-order and multiphase alloys and
found that the best oxidation resistance at
1093⬚C and 1370⬚C occurred for the Mo-
10Ti-6.3Si-8.1B (at.%) composition. He
later found11 that the alloy Mo-0.14Hf-
6.1Si-7.9B (at.%) showed a recession rate
of 450 ␮m/100 h at 1093⬚C, and that alloys
containing 3 wt% Si and 3 wt% Hf exhibit
recession rates of only 75 mm/100 h, which
stimulated much of the current interest in
this alloy system. Several other studies12–14
examined Mo-Si-B alloys having composi-
tions that reside outside of the three-phase
␣-Mo(Si, B) ⫹ Mo5SiB2 ⫹ Mo3Si region,
but these are of lesser interest as structural
materials since they exist within either a
MRS BULLETIN/SEPTEMBER 2003
narrow two-phase ␣-Mo(Si, B) ⫹ Mo5SiB2 At progressively higher temperatures, the
region or contain no ␣-Mo(Si, B) phase scale forms more quickly but also loses B
and therefore have less opportunity for through evaporation more quickly, thus
developing both fracture and oxidation protecting the base metal after a shorter
resistance. transient. The lower oxygen permeability
Since these exploratory studies, there that results from a lower B content within
have been at least three mechanistic studies the scale further enhances the protection.
of the oxidation behavior of alloys in the Most interestingly, Berczik et al.18 recently
␣-Mo(Si, B) ⫹ Mo3Si ⫹ Mo5SiB2 region.15–17 determined that selected higher-order al-
Results show that the oxidation resistance loying additions have an important favor-
for these alloys derives from a delicate bal- able effect on the rapid transient during
ance established during transient oxidation which SiO2(B) forms at high temperatures.
behavior. The alloys form a B-containing These additions can result in a metal-loss
SiO2(B) scale over a range of temperatures rate of approximately 1 ␮m/h at 1370°C—
and Mo:B:Si ratios. However, the rate of an interesting finding to explore.
scale formation, its permeability to oxygen Below temperatures of ⬃500°C, the oxida-
and oxidized species, and the loss of B from tion rates for these alloys are so slow that
the scale over time are all critical factors that they are of little consequence to engineering
establish the metal loss during early tran- structures. However, between ⬃500°C and
sients and the protective nature of the scales 650°C, a MoO3(Si, B) scale forms that is
formed. These findings are summarized in non-protective. Between 650°C and 750°C,
Figure 5. At temperatures above ⬃650°C, there is a transient wherein MoO3(Si, B)
the oxidation rates of alloys having low Si begins to evaporate, and SiO2(B) does not
and B contents are controlled by evapora- yet form. This is the regime of rapid oxi-
tion of MoO3, and SiO2(B) does not form dation that is most critical for engineering
as a continuous scale. However, for the Si use of these alloys. The future utility of
and B levels of interest, several different these materials is critically tied to either
limiting behaviors may occur depending creative engineering design practices that
upon the temperature. At temperatures minimize exposure times and the effects of
above ⬃750°C, the mechanistic process is rapid oxidation in this narrow tempera-
tied to B, Mo, and MoO3 loss through the ture regime, or future inventions and dis-
SiO2(B) scale that forms continuously over coveries that may permit control of this
the surface. Rates of metal loss are faster behavior through alloying or surface engi-
at low temperatures because the rate of neering. Clearly, further developments are
SiO2(B) formation is low, and its perme- warranted, and a variety of other environ-
ability is high because of a high B content. mental properties, such as sulfidation,
Figure 5. Oxidation mechanism map in temperature–composition space for selected Mo
and Mo-Si-B alloys. For Mo-Si-B alloys, solid MoO3 scales form at low temperatures. At
slightly higher temperatures, MoO3 is a gaseous phase and evaporates, but temperatures
are too low for SiO2(B) scale formation. Thus, oxidation rates are high. At temperatures
above 750°C, a SiO2(B) glass scale forms that offers varying levels of oxidation protection
as boron increasingly evaporates from the scale at progressively higher temperatures.
643
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behavior in moist-air environments, and
the effects of high-velocity gas streams, still
require evaluation and understanding.
Mechanical Behavior
It is premature to comment on the me-
chanical properties of Mo-Si-B alloys in
any depth. While it is commonly expressed
within the materials science community
that material structure controls properties,
structural materials metallurgists know
well that this is only true when defects
are treated integrally as a constituent of
structure, and Mo-Si-B alloys are no ex-
ception. As already mentioned, these are
low-ductility alloys for which the known
mechanical properties are heavily influ-
enced by the underdeveloped processes
used for alloy exploration. Current alloys
usually possess microstructures consist-
ing of 10–50 ␮m diameter grains of bcc
␣-Mo(Si, B) surrounded by, or co-
continuous with, a nearly continuous
necklace of the Mo5SiB2 and Mo3Si phases
3–10 ␮m in size. Thus, yield strengths
cannot be measured in tension below tem-
peratures of ⬃1100°C, since processing
flaws lead to early onset of fracture for
most alloys. Compression tests indicate
that the yield strength varies approximately
linearly from ⬃1500 MPa at room tempera-
ture to ⬃400 MPa at 1370°C, which gives a
density-normalized strength of 43–158 MPa/
Mg/m3 over the temperature range. Low-
temperature fracture strengths are com-
monly measured at ⬃600 MPa; however,
these are likely to vary considerably as
processes mature. Further processing de-
velopments are required to determine
what strength and tensile-ductility values
can be achieved for selected alloy and
component configurations.
There have been several studies of frac-
ture toughness, impact resistance, and
most recently, fatigue strength for simple
ternary Mo-Si-B alloys. Perhaps most no-
table among these is the study by Choe
et al.,19 which indicates fracture-toughness
values in the range of 4–7 MPa m1/2 at
room temperature and of 7–12 MPa m1/2
at 1300°C. In the past, comparably low
fracture-toughness values for other mate-
rials proved to be an obstacle to the suc-
cessful design of turbine-rotor hardware.
This study also reports rather high values
of fatigue-crack-growth thresholds, rang-
ing from 4 MPa m1/2 to ⬃8 MPa m1/2
at room and elevated temperature, respec-
tively, for an R 苷 0.1, 25 Hz testing condi-
tion. (R is the ratio of maximum to
minimum cyclic stress in a fatigue test).
Crack-growth-rate slopes in the Paris law
regime are in the 40–60 range between
room temperature and 1300°C. One unpub-
lished study by Kumar et al.20 determined
644
values for alternating stress versus cycles
to failure (SN curves) for a Mo-6Si-8B
alloy and found the fatigue strength to be
about 45% greater than that for the TMZ
Mo-based alloy.
Mendiratta et al.21 studied Mo-12Si-12B
and Mo-11Si-11B compositions, making
simple estimates of creep rates for mate-
rials prepared by arc melting and heat
treatment. At 1200⬚C/100 MPa, the com-
pressive creep rate was 1 ⫻ 10⫺9/s; at
1300°C/100 MPa, it was about 1 ⫻ 10⫺8/s.
These are outstanding results that illus-
trate the potential advantage of these al-
loys over superalloys and niobium-based
systems.
While published data are sparse, perhaps
a few conclusions can be drawn about the
mechanical behavior of these materials.
First, irrespective of the process path, the
brittle-to-ductile transition temperature is
likely to be high (above ⬃800°C), simply as
a result of the refractory-metal base and the
brittle intermetallic phases present. Further,
the only conclusion that can yet be drawn
about processing–structure–property re-
lationships is that no systematically sup-
ported conclusions can be drawn and
much more work is needed. Finally, the
very few studies of crack-growth resis-
tance for Mo-based alloys indicate high
values of Paris law slopes, thus indicating
challenges for today’s damage-tolerance-
based design practices. Alternative ap-
proaches that design for crack initiation
and propagation in the near-threshold
regime are needed. Developing this design
system may pose the greatest challenge
to the introduction of these materials,
irrespective of creep behavior and other
properties.
&KDOOHQJHVIRU0DWHULDOV
'HYHORSPHQW
In this centennial year of flight, it is ap-
propriate to ask: What technological ad-
vances are seen for the future of aviation?
While complete answers are beyond the
scope of this focused view of Mo-Si-B al-
loys, one answer alluded to here is “too
few,” if design is constrained by today’s
materials and processes. Development en-
gineering of high-temperature structural
materials has somehow lost the fashion-
able position in the scientific community
that it held a decade or more ago. Thus,
the prospects for further advance will in
large part be determined by how the gov-
ernment and aerospace companies ad-
dress the financial and technological
challenges facing the aerospace sector.
There should be no doubt that a sustained
advance in aeropropulsion capability will
not occur without a materials-centric tech-
nology readiness effort. Any such effort
must focus upon three pervasive aspects
of structural materials technologies: per-
formance, affordability, and reliability.
For Mo-Si-B alloys, the challenges to
materials performance are tied foremost
to the processing of the alloys into compo-
nents. These alloys appear most likely to
succeed by achieving dispersed intermetal-
lic phases of a controlled maximum size
with low interconnectivity, and by doing
so for complex engineered structures such
as the airfoil shown in Figure 1. There may
also be a requirement for particular defor-
mation processes to impart greater ductil-
ity to the ␣-Mo(Si, B) phase. The challenge
is similar to that faced by the discontinu-
ously reinforced metal composites commu-
nity, but with more severe restrictions on
viable process routes for extreme proc-
essing temperatures. Clearly, inventions
are needed; thus, the time to readiness is
unbounded.
Provided that processes favorably evolve,
the mechanical properties are likely to be
useful in structural design only with a
modified design practice that moves be-
yond the damage-tolerance approaches
that dominate the present-day aerospace
community. These approaches, which try
to forecast the useful life of the component
based on the growth of a minimal flaw in
the most severely loaded volume of the
component, are relatively stagnant and in-
capable of treating materials that do not
have useful crack-growth lives in the Paris
law regime. Unfortunately, virtually all
new high-temperature structural alloys,
including composites, intermetallics, re-
fractory alloys, and ceramic composites,
fail to meet that criterion. Further, many of
these (including the Mo-Si-B alloys) may
require methods that place primary re-
liance on coating systems and surface
treatments, not simply for life extension as
in current practice, but also for meeting
basic mission requirements. There could
be ample opportunities to test such revo-
lutionary technologies within uninhabited
air vehicles; however, such opportunities
have yet to emerge. Nonetheless, these ad-
vancements will take time, since the
development of new design systems for
components that risk human life in service
is necessarily and justifiably a protracted
process.
Materials affordability is determined by
too many issues to treat here, but a few
may be mentioned. For Mo-Si-B alloys,
first-order affordability will be dictated by
how closely the required processes match
current production processes and equip-
ment for refractory alloys. Further, the
volume of production and its expected
change with time must also match the
infrastructure evolution in the metals sup-
MRS BULLETIN/SEPTEMBER 2003
 0R6L%$OOR\V 'HYHORSLQJD5HYROXWLRQDU\7XUELQH(QJLQH0DWHULDO
ply industry. Next, the alloys will un-
doubtedly require a high level of quality
control to succeed, since they are funda-
mentally rate-sensitive, low-ductility ma-
terials. However, maintaining the desired
quality must not add significant cost to the
product. Finally, there will be some inertia
resisting the introduction of Mo-Si-B alloys,
which is associated with the experience
with and confidence in established Ni
alloys. Ni alloy airfoils are approximately
a $3 billion per year (or more) industry
that will not easily be displaced or even
complemented, regardless of the potential
performance benefits offered by the new
alloys.
The reality of the aerospace sector, de-
fense included, is that the structural alloy
technologies employed often place high
levels of financial capital and human life
at risk. Thus, all structural alloy technolo-
gies evolve within regimented processes
that restrict risk and quantify component
reliability. The methods for doing this are
intimately tied to the material choices, but
all of the ultrahigh-temperature materials
treated in this issue bring the need for a
new set of lifetime and reliability assess-
ment technologies. What may be less ob-
vious is that they also bring a common
need for growth in the design and reliabil-
ity practices, away from the historically
proven low-risk methods for ductile mate-
rials. Ductile materials sustain useful lives
within a crack-growth regime that is de-
termined by inspection. However, the
new materials require unproven (perhaps
even currently unknown) practices for es-
sentially brittle materials and demand
that components be designed within the
probabilities of crack initiation and crack-
growth-rate thresholds. These, in turn, are
dictated by the statistical aspects of the mi-
crostructure and by processing nuances.
Considerable time may be necessary to es-
tablish and prove the required new meth-
ods. Interestingly, perhaps one of the best
measures of the community’s success in
this regard is the evolutionary advance of
␥ -titanium aluminide alloys and the chal-
lenges they have faced in a similar vein.
6XPPDU\
Ultrahigh-temperature materials offer
pervasive enabling capabilities to the aero-
space and power-generation sectors of the
economy. Pursuit of them is worthwhile,
but replacing Ni-based alloys is a difficult
problem for both technical and financial
reasons. The oxidation resistance of se-
lected Mo-Si-B alloys is truly remarkable,
given the nature of conventional Mo alloys
in general, but there are still challenging
issues associated with their processing,
low-temperature (⬃700⬚C) oxidation be-
havior, and the need to obtain a useful
MRS BULLETIN/SEPTEMBER 2003
balance of properties. While developing termetallics 7 (1999) p. 153.
appropriate processes for these alloys 13. M. Akinc, M.K. Meyer, M.J. Kramer, A.J.
dominates current activity in the area, a Thom, J.J. Huebsch, and B. Cook, Mater. Sci.
complete demonstration of not only mate- Eng., A A261 (1999) p. 16.
14.V. Supatarawanich, D.R. Johnson, and C.T.
rials performance (properties) but also af- Liu, Mater. Sci. Eng., A A344 (2003) p. 328.
fordability and reliability is required for 15. M.G. Mendiratta, T.A. Parthasarathy, and
their further advance. These alloys are D.M. Dimiduk, Intermetallics 10 (2002) p. 225.
among the broad spectrum of advanced 16. T.A. Parthasarathy, M.G. Mendiratta, and
materials that appear to require a new D.M. Dimiduk, Acta Mater. 50 (2002) p. 1857.
foundation for design that focuses on 17. J.S. Park, R. Sakidja, and J.H. Perepezko,
the specialized requirements for crack- Scripta Mater. 46 (2002) p. 765.
intolerant materials. 18. D.M. Berczik (unpublished).
19. H. Choe, J.H. Schneibel, and R.O. Ritchie,
$FNQRZOHGJPHQWV Metall. Mater. Trans. A 34A (2003) p. 225.
20. K.S. Kumar, Brown University (private
We gratefully acknowledge several
communication).
useful and insightful discussions with 21. M.G. Mendiratta, P.R. Subramanian, T.A.
Drs. M.G. Mendiratta, P.L. Martin, T.A. Parthasarathy, and D.M. Dimiduk (unpub-
Parthasarathy, R. Dutton, and R. Sakidja lished).
regarding progress and prospects for 22. P. Villars and L.D. Calvert, Pearson’s Hand-
these new high-temperature materials. book of Crystallographic Data for Intermetallic
Special thanks are due to D.M. Berczik for Phases (ASM International, Materials Park, OH,
sharing his extensive experience and un- 1985). ■
published results. This work is sponsored
by the Air Force Office of Scientific Research
(AFOSR Task #2306-AL and contract
F33615-01-C-521 for D.M. Dimiduk and
grant F49620-03-1-0033 for J.H. Perepezko),
which is gratefully acknowledged.
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For more information, see http://advertisers.mrs.org
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MRS Materials Connections
w w w. m r s . o r g / g a t e w a y /
10. D.M. Berczik, U.S. Patent No. 5,693,156
(December 2, 1997). Your source for Materials Research-Related Information!
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Research news, materials data sources,
Workshop on Very High Temperature Structural materials Web site database,
Materials, Turtle Bay, HI, December 9–11, 1998 meetings calendar, and more.
(private communication).
Check it out today!
12. M.K. Meyer, A.J. Thom, and M. Akinc, In-
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