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Submitted by
Kamilah Turner
University of Michigan
University Research Alliance
Amarillo, Texas

The storage of nuclear waste has been a problem for years. To reduce the amount and
time of nuclear waste storage, new methods are being developed to mutate spent nuclear
waste into less hazardous materials. One of the processes being developed results in an
equipment failure with the mutation of transuranic (TRU) nitride particles. To avoid this
failure, molybdenum metal as a coating has been evaluated to determine its effectiveness
in preventing the failure with the nitride particles. Two methods of deposition were
investigated; however, chemical vapor deposition was determined to be the method of
choice. Each method was used to coat a surrogate nitride material with molybdenum
metal to determine feasibility of metal coating and deposition conditions. Molybdenum
coated samples were analyzed using x-ray photoelectron spectroscopy (XPS) and
scanning electrode microscopy (SEM). The molybdenum coatings were found to be
highly dispersed, resulting in a very uneven coating at each of the experimental
temperatures. Islands of molybdenum and oxygen of various sizes were found
throughout the sample surface. Molybdenum metal was also found to be extremely air
sensitive; passivation of the material before exposure to air and reduction to the metal
state was required to properly analyze the coating. The design of the deposition
apparatus was found to be ineffective in coating the molybdenum metal to the nitride
substrate. Further experimentation and development of coating apparatus must be
completed to successfully assess the effectiveness of molybdenum coating and deposition


One of the key challenges in the nuclear power industry is the storage of nuclear wastes.
The current United States approach to the disposal of high level nuclear waste is to store
the unreprocessed spent fuel in a geologic repository (1). By some estimates, the storage
areas will be completely filled with spent nuclear fuel by 2015 (1). This indicates that
other waste repositories will need to be identified in the near future, or a process that
could reduce the amount of nuclear waste being stored would have to be developed. In
1999, the U.S. Congress directed the Department of Energy (DOE) to develop a reduction
process under the Accelerator-Driven Transmutation of Waste (ATW) Program (1).

Thus far, Los Alamos National Labs (LANL) has led the development of ATW as an
alternative technological option to the disposition of nuclear waste (1). This technology
allows for spent fuel to be sent to an ATW site where transuranics (TRUs) and particular
long-lived fission products would be destroyed by fission or transmutation within the
facility. There are four key elements in the implementation of the ATW program: system
definition, accelerator, fuel treatment, and target/blanket (2). The focus of research
described in this report is related to the fuel treatment element.

Problem Statement

The ATW fuel treatment portion of the program is focused on the selection of a process
to recover un-transmuted transuranics from irradiated fuel for recycle through the ATW
recycle system. Currently, the ATW program is investigating different processes such as
the volatility process (1). In one process, an irradiated fuel, which consists of solid fuel
particles, is dispersed into a zirconium metal matrix to dilute the high level of fissile
material in the fuel particles. It is in this matrix that the particles will be transmuted to a
non-radioactive or less radioactive species by neutron bombardment.

The TRU fuel particles contain large amounts of fissile material. The heat generated
from the particles is so high, that there is a need to dilute the fuel. To dilute the particles,
they have been dispersed into the metal matrix. Zirconium is an attractive metal for the
matrix material because it has a low neutron absorption cross section, is compatible with
a variety of reactor coolants, has a reasonable thermal conductivity, and melts at high
temperature. The particle recovery process involves removing the TRUs and fission
products from the zirconium (3). In the case of TRU nitride fuel particles, there is a
concern for interactions between the fuel particle and the zirconium matrix at their
interface during normal operation of the fuel at temperatures greater than 1000°C. The
interaction of concern is the formation of a zirconium nitride or oxide. This formation
could lead to a redistribution of the fissile material that could in turn lead to a failure of
the fuel element. To prevent the possible interactions between the nitride fuel
particles and the zirconium metal matrix, it was proposed that a refractory metal be
deposited onto the surface of the fuel particles.

The goal of research described in this report was to investigate the deposition of
molybdenum on nitride fuel particles. The following objectives were established to
achieve the project goal:
1) Determine a refractory metal for deposition
2) Determine the best conditions for deposition
3) Develop an initial schematic for deposition of metal on spherical particles

Refractory Metal Selection

The refractory metals initially chosen for this project were molybdenum, tungsten, and
niobium. These refractory metals were chosen because they were not expected to interact
with the fuel or zirconium, have good oxidation resistance at high temperatures, and
methods for their deposition have already been defined. Due to time constraints,
molybdenum became the refractory metal of choice. Molybdenum was the metal of

choice because the research group supporting the project has substantial expertise
regarding its properties and characteristics.

Deposition Conditions

There are a number of coating processes that can be used to deposit Mo including
chemical vapor deposition (CVD) and physical vapor deposition (PVD). The CVD
process allows for gases containing the deposition material to be introduced into a
reaction chamber and deposited on a substrate to form a coating (4). After evaluating
various methods and equipment availability, CVD was the chosen process for depositing
Mo. In determining a good coating method, it is important to identify the size of the
particles that the material will be deposited on. In the case of the nitride particles, the
optimum particles size is not defined. Work at Argonne National Labs (ANL) is
currently being done to determine the optimum size. The ideal particle size is probably in
the few-hundred micron range. A uniform dispersion needs to be achieved to minimize
the overlap of damage zones.

Determining the deposition conditions was done using flat wafers instead of actual
spherical particles. An important factor in CVD is the geometry of the system during the
coating process. Discovering the best geometry and deposition conditions
simultaneously is a major task; therefore, it has been decided to first determine the
deposition conditions, and then take on the task of determining methods to coat spherical

Deposition on Spherical Particles

After determining the conditions to uniformly coat Mo, an investigation was to be done
to formulate ideas on methods to coat spherical particles in the final system. A literature
search was used to accomplish this objective.

Experimental Design

Material Deposition

Two different methods deposition were involved in experimentation: salt deposition and
chemical vapor deposition (CVD). Salt deposition involves placing the nitride substrate
in a Mo salt solution and heating the water off to leave a Mo salt coating. The substrate
was then reduced in H2 at 800°C leaving the Mo metal. The second deposition involves
chemical vapor deposition (CVD). In the CVD method, MoCl5 was reduced under H2 on
a heated substrate (900 -1300°C) at atmospheric pressure (5). Another more common
method of coating Mo involves the use of a molybdenum hexacarbonyl, Mo(CO)6 (6,12).
Due to safety concerns, this precursor was not used.

The molybdenum precursor, molybdenum (V) chloride (Sigma-Aldrich, 98% purity), is

sensitive to air and moisture. A special reactor was designed to address this issue. This
is discussed in the next section with more detail. Also, for the purposes of
experimentation, instead of a uranium nitride substrate, a radioactive substance, silicon
nitride (Si3N4) wafers were used as a surrogate material. The wafers were made by
University of Michigan Professor, Erdogan Gulari. Silicon nitride was deposited on a
silicon substrate using low pressure CVD (LPCVD); the Si3N4 layer is approximately
2000 angstroms thick. The wafers were broken along its structural lines into 1-cm2
pieces for the reactor. Each wafer, before being placed in the reactor was cleaned with a
trichloroethylene/acetone/methanol/de-ionized (DI) H2 O rinse to remove all
contaminants. The rinse process is detailed in Appendix A.

In the first method, a 10% ammonium heptamolybdate, (NH4)6Mo7O24-4H2O

(Mallinckrodt, crystals), in DI H2O solution was gently stirred and heated moderately
until the salt completely dissolved. The wafer was then placed in the solution and heated
up to100°C until the water completely evaporated. This typically resulted in a very
uneven coating of the salt. The sample was then placed in a reactor rube heated by a PID-
controlled split tube furnace (Applied Test Systems, Inc.) for 3 hours at 800°C. Due to

the large and apparent non-uniformity of the coating, this method was not further

As stated above, the second deposition process is routed in conventional CVD. In a

heated reactor tube, the MoCl5 precursor and silicon nitride substrate were heated
simultaneously while passing H2, the reactant gas, and Ar, the carrier gas, through the
reactor (6).
MoCl5 + H 2 → Mo 0 + HCl

A complete diagram can be found of the reaction and reactor design in the Appendix B.
Due to extreme reaction temperatures, the reactor tubing was made of quartz. The reactor
tube has a diameter is 1.8 cm (0.71 in.) and a length of 30 cm (11.8 in.). The precursor
was kept in a small quartz boat. A small quartz easel-like stand was used for the
substrate. The reactor tube was assembled in a nitrogen-filled glove box (Vacuum
Atmospheres, MO-20) to avoid entry of air into the system. The reactor tube and system
were purged with argon before introducing hydrogen into the system. The furnace was
ramped to 450°C, then heated to the final reaction temperature which was in the range of
900-1100°C. At the reaction temperature, the H2 gas was introduced into the reactor a
varying flow rates (20-30cc/min). After a 3-hour reaction time, the H2 was shut off and
the reactor cooled. Once reaching temperatures less than 35°C, the coated substrate was
passivated in a mixture of 1%O2/He at 20 cc/min for 3 hours. A scrubber containing DI
water followed the reactor tube to react with the hydrogen chloride gas by-product before
emitting into the hood. Litmus paper (EM-Science, ColorpHast) was used before and
after each reaction to determine how much HCl(g) was converted to its acid form. After
every 4th run, the reactor tube was disassembled and cleaned to remove residual Mo.


X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were
used to characterize the molybdenum samples. XPS was carried out on a Perkin

calibrated using the reference binding energies of Au 4f7/2 at 84.00eV, Cu 3p at 75.13
eV, and Cu 2p3/2 at 932.66 eV. A broad survey spectrum from 600-0eV was initially
taken. The spectra were charge-corrected to carbon 1s at 287 eV. Next, a high-resolution
scan of oxygen and molybdenum was obtained to quantify composition and to determine
the chemical states. Also, a gas phase reactor allowed samples to be heated and reduced
from the passivated state and moved to the XPS analysis chamber without exposure to
air. Curve fitting of the XPS spectra was performed with a nonlinear least squares
method using Gaussian distributions. SEM was carried out on a Phillips XL30 using a
thermally assisted Schottky (5kV) field emission gun for high intensity probe formation.
The system uses a zirconated tungsten filament and has a vacuum of ~10-6 torr.

Results and Discussion

Effect of Passivation

Experiments were done at various temperatures in the range of 900-1100°C and flow rate
ratios of Ar to H2. Some of the initial runs were conducted at 1000° C. The passivation
effects on the Mo coating are shown in Figures 1-3. Table 1 lists binding energies and
characteristics of Mo and some of its oxidation states. These samples, based on substrate
weight change, were coated with approximately 125 microns of Mo metal.

Without passivation, analysis by XPS shown in Figure 4 indicates MoO3 was the only
form of Mo present on the substrate surface.

Compound Binding Energy (eV) Doublet/Singlet: Separation (eV)

Mo 227.7 Doublet: 3.15
MoO2 229.4 Doublet: 3.20
MoO3 232.7 Doublet: 3.20
Table 1. Binding Energies of Mo and MoOx compounds (7)

240 235 230 225 220

Bin d in g En e r g y ( e V )

Figure 1. NON-PASSIVATED 1000°C: MoOx (2<x<3)

In the passivated sample as shown in Figure 2, there were two forms of Mo present:
MoOx and Mo metal. The two forms were found at a Mo0:Mo+x ratio of 0.45. It is
evident that passivation assists in preserving the reduced Mo species on the surface of the


N (E

240 235 230 225 220

Bin d in g En e r g y ( e V )

Figure 2. PASSIVATED 1000°C: Mo metal, MoOx (where 2<x<3)

It is not clear which Mo oxide is present; however, it is definitely an oxide with

composition between MoO2 and MoO3 (see Table 1). As the Mo coating is passivated, a
shallow oxide species of Mo forms on surface. After reducing the passivated sample in-

situ, the Mo multiplex shown in Figure 3 indicated a 66% increase in the Mo metal
content and a 27% decrease in the Mo oxide content.


N (E
240 235 230 225 220

B i n d in g En e rg y

Figure 3. IN-SITU REDUCED: Mo metal, MoOx

This clearly shows there is definite Mo coverage on the wafer before passivation. It also
verifies that the intermediate MoOx species found before passivation is reducible. Longer
reduction times of approximately 5-6 hours are likely to show complete oxide removal
and Mo metal coating. In addition to the increase in Mo metal between the passivated and
reduced Mo multiplex, there was also a decrease in the oxygen atomic concentration,
indicating reduction was successfully taking place. The time required to complete in-situ
reduction using the XPS facilities on each sample was too intensive for this study.
Consequently, the characterization of other samples was completed using the passivated

Oxygen Content

The initial survey scans showed large percentages of oxygen in the sample. As with Mo,
a multiplex scan was completed to further investigate the O1s peak. Oxygen is found in
the vicinity of 530 eV. The oxygen 1s peak was also found to have shoulder peaks. The
shoulder peak is indicative of the different forms of oxygen present. The separation
between the shoulder and the O1s peak is related to the form of MoOx found in the

material. The number of shoulder peaks with the O1s peak and their location should
correspond with the number and types of molybdenum oxides present in the Mo
multiplex scan, as shown in Figures 4 and 5 and Table 2 below, for the samples prepared
at Ar:H2 ratio of 1:1.


1 (




Figure 4. Oxygen multiplex


N (E )



240 235 230 225 220

B in d in g En e rg y (e V )

Figure 5. Mo multiplex

Temperature(°C) # of Oxygen shoulder Peaks # of MoOx peaks

900 2 2
1000 2 2
1100 2 2
Table 2. Number of O shoulder and MoOx peaks

This observation holds for all samples and further confirms that the same type of Mo
species is present in each sample.

Surface Coverage

Three survey scans were taken of all samples. The Mo and O multiplex scans were taken
based on these initial surveys. As shown in the example in Figure 6, each of these initial
scans also contains Si and N peaks.

N (E
N 1s Si 2p3
BE 401eV BE 102 eV

600 500 400 300 200 100

B i n d i n g En e rg y (e V )

Figure 6. IN-SITU REDUCED: Initial Survey

This indicates that there is not an even film of reduced Mo metal on the Si3N4 substrate.
Scanning electron microscopy (SEM) was used further investigate this observation. The
following micrographs shown in Figures 7 and 8 represent an example of the Mo/MoOx

Figure 7. SEM Scan 1000X (900°C ,1:1)

Figure 8. SEM Scan 5000x (900°C, 1:1)

These micrographs clearly show how sparse the coating actually is. This type of coating
is believed to represent all samples. An elemental analysis, energy dispersive x-ray
spectroscopy (EDX), was done to evaluate the composition of adsorbate islands on the

substrate surface shown in Figure 8. The EDX found larger amounts of O and Mo in
these islands. The amount of O in comparison to Mo was large. This correlates to the
XPS data shown in Figure 6 as Mo has a much higher sensitivity than O, and is found in
much lower percentages than O. (Mo: 2.867, O: 0.711) EDX also showed very small
quantities of oxygen on the surface where there were no islands.

Achieving an even Mo coating has been a difficult task. The reason could be due to
system geometry, and temperature and flow profiles. The diameter of the reactor tube is
1.8 cm with a cross-sectional area of 5.67 cm2. The area of the wafer is 1 cm2. The
distance between the precursor boat and the wafer is ~2 cm. This distance may not be
enough to allow for controlled flow. The Reynolds number was calculated using
viscosity and density of argon, as this is the carrier gas. The Reynolds number was found
to be on the order of 106 indicating turbulent flow. (Viscosity was calculated at 1000°C.)
Turbulent flow consists of large rotational eddies near walls, that degenerate
progressively into smaller eddies. These rotational eddies are likely to be preventing the
Mo from coating the substrate in an even and controlled manner. The Mo appears to be
splattering on the surface. This may be controlled by moving the boat further away from
the substrate, or by possible cooling down the substrate. In the reactor tubing past the
wafer, there was a significant amount of MoOx that condensed in the quartz tubing, as
well as in the Swagelok tubing. This shows that the Mo was definitely moving in the
vapor phase towards the wafer. The condensation in the tubing indicates that a reactor
design which integrates a cooling function could have resulted in a more even coating.

Effect of Temperature and Flow Rate Effects

Two series of runs were completed at temperatures of 900,1000, and 1100°C using Ar:H2
ratios of 2:1, and 1:1. In the runs using a 2:1 ratio, Mo metal was found along with MoOx
in the 900°C and 1000°C runs, as shown in Figure 10. However, in the 1100°C run, there
was no Mo metal observed using XPS. In these runs, data also showed an increase in the
weight change with increasing temperature after each run was completed.

Temperature(°C) Weight Increase (mg) % Weight Increase
900 0.4 0.20
1000 0.6 0.29
1100 0.8 0.38
Table 3. Mo Deposition Uptake w.r.t. CVD Temperature

Table 3 shows that as reaction temperature increased there was more Mo and MoOx on
the substrate. As mentioned above, no reduced Mo metal was seen in the 1100°C run. A
possible reason as to why Mo is not seen yet there is a weight change increase is related
to the passivation of the Mo coating before removing from the reactor. The passivation
reaction is believed to occur as follows:
Mo 0 + O2 → MoO x

With the increase in weight change of the substrate, it is clear more Mo is being coated.
Because there is more Mo metal on the surface, there is a concentration increase in
reactant, and the reaction will move much more rapidly to form a thicker oxide product
layer. Also, the strength of interaction between the substrate and adsorbate is often lower
at higher loadings as shown in Figure 11. This could allow more reduced Mo metal to be
oxidized (8).

Adsorbate-Adsorbate Interactions

Surface-Adsorbate Interactions Surface-Adsorbate Interactions

Figure 11. Surface and Adsorbate Interactions

At 1100°C, it is proposed that MoOx forms completely over the Mo metal in a uniform
subsurface layer of approximately 10-20 angstroms, such that no Mo metal is within sight
of the XPS scans. In the 900°C and 1000°C runs at the 2:1 reactant gas ratio, there is less
Mo metal on the substrate, meaning lower local Mo concentration. As a results, the
substrate has a much stronger interaction with the adsorbate and oxidation occurs at a
slower rate over a smaller volume.


1 (
0R2 0R2 0R

Figure 10. Mo multiplex.

While in 900°C there appears to be more Mo metal than molybdenum oxide, it is also
shown that the amount of oxide increases between 900°C to 1000°C. The ratio of Mo0 to
Mo+x was calculated based on peak intensities for both runs. As shown in Table 4, the
ratio does not change much, even though there is an increase in weight change. Both of
these observations give more support to the idea that the amount of Mo on the surface
affects how well the passivation reaction will occur.

Temperature (°C) Mo0:Mo+x*
900 0.45
1000 0.42
1100 ---
*Note: 2<x<3
Table 4. Temperature vs. Metal:Oxide ratio

For the runs completed using a Ar:H2 ratio of 1:1, XPS showed no signs of Mo metal in
the material without reduction in the Mo multiplex. These runs showed only MoOx.


N (E )


240 235 230 225 220

B in d in g En e rg y (e V )

Figure 11. 1:1 Mo Multiplex Peaks

It is proposed that the reason Mo metal is seen at Ar: H2 2:1 ratio and not 1:1, is due to
the Mo vapors ability to get a better trajectory to the substrate. With less argon in the
flow, the Mo atoms have more mobility. The increased mobility possibly results in a
trajectory that yields a Mo film that is more uniform. This allows for a thicker
passivation layer; therefore, only MoOx is shown in XPS scan, as shown in Figure 11.

In the section discussing oxygen content, it was observed that as the type of MoOx varied
in the Mo multiplex, the number and locations of shoulder peaks found in the oxygen
multiplex varied. In the 1:1 runs, as the temperature increases the MoOx found in the
sample moves closer to that of MoO3. (See Figure 11 above.) This further supports the

theory of passivation occurring on materials that have more Mo. The initial passivation at
1100°C occurs faster, and more oxygen is able to diffuse into the passivation layer.

Deposition on Spherical Particles

The focus of this project was to determine how Mo metal coated to silicon nitride to give
an idea of how the metal would coat with uranium nitride. All experimentation was done
on flat wafer. The actual application occurs with spherical particles. The reactor design
used here is not applicable. The conventional method of coating spheres is through open
bounce pan configuration (9). In this method, the bounce is induced by piezoelectric
transducers that control lateral and transverse motions to the pan. Issues arise when the
capsule mass and diameter change due to the addition of the coating. This requires
constant calibration of the bounce pan and its motion. Another important issue with this
conventional method and other methods is the geometry of deposition source and
aperture (opening to chamber with substrate) size. Both of these vary with the deposition
that is being achieved.

A better method to coat Mo on nitride spheres uses pulsed-gas levitation (9).


Gas inlet
Figure 12. Pulsed-gas levitation (9)

The capsule moves by oscillating a partial flow of the reactant gas beneath it. The
diameter of the pulsed-gas inlet tube is 70-80% of the capsule diameter. The flow of the

pulsed-gas is varied throughout to account for weight changes and to have an even
coating. This flow variation can be determined by energy balances of forces and changes
in capsule lateral or transverse movements. Hydrogen and argon would travel through
the gas inlet, and argon would travel through the tubing to levitate the capsule. The
system must be air-tight and heated for the deposition to occur.


Molybdenum metal coating on Si3N4 was prepared using a basic CVD method.
Passivation of the coating is needed to prevent exposure to air from converting Mo
completely to MoO3. This method results in an non-uniform film. The Mo metal will
deposit on the nitride substrate, however it the results is a severely uneven coating in the
experimental reactor design. Further development of a more efficient reactor design may
results in a more uniform coating.


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Driven Systems, The Uranium Institute 24th Annual Symposium, 1999, London.

2. A Roadmap for Developing Accelerator Transmutation of Waste, A Report to

Congress, October, 1999.

3. Laidler, J. Bresee, J. Pyrochemical Processing of Irradiated Transmuter Fuel.

4. Holmberg K, Matthews A. Coatings Tribology: Properties, Techniques and

Applications in Surface Engineering, Tribology Series 28, Dowson D. (ed.)
Elsevier: Amsterdam, 1994; 3,7-29.

5. Galasso F., Chemical Vapor Deposited Materials, CRC Press, Inc. 1991

6. Endler et. al, Chemical Vapour deposition of MoS2 coatings using the precursors
MoCl5 and H2S, Surface and Coatings Technology 120-121 (1999) 482-488.

7. Handbook of X-Ray Photoelectron Spectroscopy, Physical Electronics Division,

Perkin Elmer Corporation, Minnesota, 1979.

8. Somorajai, Gabor, “ Introduction to Surface Chemistry and Catalysis:, John Wiley

and Sons, Inc. 1994.

9. Jankowski et al., Chambered capsule coatings, Thin Solid Films, 398-399 (2001

10. Briggs D., Seah M.P. Practical Surface Analysis b Auger and X-ray
Photoelectron Spectroscopy, John Wiley & Sons, 1983.

11. Chemical Vapor Deposition, Surface Engineering Series Vol.2, ASM

International, The Materials Information Society, 2001.

12. Chemical Vapor Deposition- Principles and Applications, Academic Press, 1993.

13. Ivanova et al., Investigation of CVD molybdenum oxide films, Materials Letters,
53 (2002) 250-257).

14. Mikhailov et al., The behaviour of the molybdenum-CVD diamond interface at

high temperature, Diamond and Related Materials 4 (1995) 1137-1141.

15. Perry’s Chemical Engineers Handbook, 6th edition, McGraw Hill, 1984.

16. Petigny et al., Molybdenum deposition on TiO2 (110) surfaces with different
stoichiometries, Applied Surface Science 142 (1999) 114-119.

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Zambonin, VCH Verlagsgesesllschaft mbH, D-6940 Weinheim, 1993.

Appendix A

TCE Rinse: Initial Wafer Clean

1) If fingerprints or other residue appears on the wafer surface, swab it clean with a
Q-tip dipped in trichloroethylene.
2) Immerse in warm TCE for 5 minutes. (Room temperature for new wafers.) Pour
used TCE slowly into a designated TCE waste bottle.
3) Immerse in acetone for 3 minutes. This immersion removes the TCE residue and
acts as a further cleaning solvent. Pour used acetone into waste solvent container.
4) Immerse in methanol for 3 minutes. This rinse removes the acetone residue. Pour
used methanol slowly into the waste solvent bottle.
5) Rinse in running DI water for 3 minutes.


Appendix B



Metal caps
Ar M
3-way (vent)
O2/H2O traps Valves 2-way
H2 M
Three way


Vent to
30 cm

Dimensions of furnace: dia: 3.0 cm, length =15 cm Scrubber

Dimensions or rxtr. tube: dia: 1.8 cm, length = 30 cm
Not drawn to scale


MoCl5 vapor Reacts with H2