213

The author contends that with the given h a r d n e s s value particularly in r e g a r d to strength c h a r a c t e r i s t i c s because
mechanical p r o p e r t i e s determined by tensile t e s t s are not impact toughness is not clearly correlated to h a r d -
affected by the initial s t r u c t u r a l composition (see Fig. 5 ) , hess.

HIGH-MELTING MATERIALS
FOR ROCKETS A N D COSMIC MISSILES*

In manufacturing rocket engines there a r e three p o s - tried for that p u r p o s e .

sibilities of heat protection: cooling, thermoinsulation and
radiation cooling. The application of the last two methods
r e q u i r e s m a t e r i a l s which a r e r e s i s t a n t at t e m p e r a t u r e s
above l l 0 0 ~ F o r the second and third methods the use of
r e f r a c t o r y sheet shields is n e c e s s a r y . Ye. Charnetskiy
(Boeing Airplane Company) stated that in employing the
second and third methods the weight of the engine d e c r e a s e s
by 290 and 390 kg, respectively, in c o m p a r i s o n w i t h t h e f i r s t
method. This is a factor of major importance since even in
calculating fuel with a high heating value the ratio of the
launching weight of the rocket to the net load is approxima-
tely equal to 150 : 1.
High-melting m e t a l s may also be n e c e s s a r y for uniflow
engines which may be exposed to flight speeds of 2 to 8
Maeh.**~' Inasmuch as the length of the flight may amount
to s e v e r a l h o u r s the high-melting metals m u s t be protected
by oxidation-resistant coatings. F o r sputniks high-melting
tubes m a y be used in which liquid sodium is circulated
diverting the heat of solar radiation.
The specific strength ~ at t e m p e r a t u r e s below 1370~
(see Fig. 1) is higher in niobium and molybdenum than in
tungsten and tantalum. Moreover, niobium and tantalum have
a lower critical brittle t e m p e r a t u r e (see Fig. 2) which facili-
tates fabrication.
E. Schnetzer (General Electric Company) calculated
that increasing the t e m p e r a t u r e of gas in a T-58 engine f r o m
925 to 1370~ as it e n t e r s the turbine lowers the weight
to power ratio f r o m 0.113 to 0.045 kg/hp, and fuel c o n s u m p -
tion f r o m 0.32 to 0.227 kg/hp p e r hour. F o r a J-79 engine
an analogons i n c r e a s e in t e m p e r a t u r e with a Mach number
High-melting m e t a l s will be required for rockets with
atomic engines. The use of liquid hydrogen or helium is
considered; it will be pumped to the regenerative-type
nozzles and cooled externally after which it will enter the
r e a c t o r where it will be heated up to 1930 to 3320~ and
subsequently it will be discharged through the nozzle. This
type of rocket may exceed the speed of a rocket with chemical
fuel f r o m two to three t i m e s .
Despite the system of regenerative cooling, m e t a l s
with extremely high fusion points will be required for.. the
nozzles and, particularly, for the r e a c t o r s . In the reducing
medium the oxidizability of the metal will not m a t t e r . The
f i r s t atomic m i s s i l e which is planned to be launched in the
c o u r s e of 1970 will, apparently, have a gas t e m p e r a t u r e
of 1930~ and a pull to weight ratio of about 12. By 1980 the
design of a m i s s i l e with a gas t e m p e r a t u r e of 3220~ and a
pull to weight ratio of about 50 may be expected. F o r that
type of engine a t h r u s t of 450,000 kg is sufficient to get a net
load of 68 ton to a height of 500 km into orbit. The solution
of that task calls for a t h r e e - s t a g e chemically fueled m i s -
sile with a t h r u s t of 2,700,000 kg.
In addition to a "uniflow" atomic missile other types of
engines including plasma and ionic cesium engines may be
developed. For the plasmic engine a working are tempera-
?0 r--'~--- T

of 25 would double t h r u s t and lower the weight to power ratio

I ~ " ~ ' ~ ~ ~1
f r o m 0.15 to 0.045 kg/hp. However, attempts to manufac-
tare molybdenum (and niobium) blades for these turbines
did not produce satisfactory r e s u l t s due to the inadquate
quality of the coatings.

Liquid fuel rockets use a regenerative cooling s y s t e m

for the walls of the engine which are made of low-melting
alloys although the t e m p e r a t u r e in the zone of burning may -iS Y35 f093 fG~9 220~ ~
go up to 3050~ However, the employment of high-melting
m e t a l s for the edges of the nozzles is planned for these Fig. 1. Specific strength v e r s u s plasticity
engines, too. Regenerative cooling cannot be applied in solid
fuel rockets and the use of high-melting m e t a l s is planned
for nozzle i n s e r t s . Thus, molybdenum is used in the nozzles
of the Polaris m i s s i l e and tungsten and tantalum will also be

o
*~R. Sassner, Metal P r o g r e s s , No. 5, 1960. Review of
p a p e r s submitted to the Conference of Metallurgists in the
United States, 1960 f r o m data of E k s p r e s s - i n f o r m a t s i y a .
~,~Mach number is the speed of sound as it depends on the
b'
medium, t e m p e r a t u r e , etc. -Z40 -f~ 2JJ~ r ,~r 17~ ~
~,~Specific strength is the ratio of ultimate tensile strength
in k g / m m 2 to specific weight in g / c m 2. Fig. 2. Plasticity v e r s u s t e m p e r a t u r e .
214
t u r e would range f r o m 3300 to 6200~ calling for r e g e n e r a -
tive cooling even for high-melting m e t a l s . Regenerative
cooling cannot be introduced to the new engine with a
service t e m p e r a t u r e of 1650 to 220~ Both types of engine
will require great amounts of electric power which can be
obtained f r o m an atomic t u r b o g e n e r a t o r with a t e m p e r a t u r e
of the heat c a r r i e r f r o m 930 to l l 0 0 ~
The yearly r e q u i r e m e n t of high-melting m e t a l s in the
United States is relatively small due to their limited use
(about 500 ton) If n e c e s s a r y the following quantities may
be produced: 10,000 ton tungsten, molybdenum and niobium;
100 to 1000 ton tantalum and 100 ton r h e n i u m . However,
cost will r e m a i n high.
A r e s e a r c h project for high-melting sheet m a t e r i a l s
has been developed. The project includes the development
of alloys, coating methods, quality standards and analyti-
cal determinations. At the initial stage of r e s e a r c h the
conditions and production methods of high-quality sheet will
be determined. At the second stage mechanical c h a r a c t e r -
istics and other p r o p e r t i e s of these m a t e r i a l s will be
established. At the third stage, production p r o c e s s e s of
sheet p a r t s on an industrial scale and the design of instal-
lations will be investigated.
At the p r e s e n t time, the r e s e a r c h project is in its
initial stage. The Universal--Cyclops Steel Company
concluded a contract for the production of 3500 kg/high-
quality molybdenum sheet (up to 910 x 2400 ram). The
crucible Steel Company of A m e r i c a will manufacture highly
plastic niobium sheet with an ultimate tensile strength of
70 k g / m m 2 while Sylvania Electric Products Inc. is working
on a molybdenum alloy sheet made by powder metallurgical
method. A r m o u r R e s e a r c h Foundation investigates the p o s -
sibility of producing molybdenum by KroU p r o c e s s . The
Wah Chang company studies the effects of admixtures on the
quality of molybdenum sheet. Contracts are being prepared
for the production of tungsten sheet.
According to R. Dnykin (Ladish Company) forging is
used as an intermediate operation in the production of high-
melting m e t a l s . Molybdenum forgings, for instance, are
as complex as titanium forgings. P a r t s with a surface a r e a
of about 950 cm 2 have a m i n i m u m thickness of 9 to 12 ram.
The sizes of the forgings a r e limited by the ingot sizes.
Ring-shaped molybdenum forgings for nozzle a p p a r a t u s e s
have a 350 to 380 m m diameter. Nozzle p a r t s f r o m tungsten
were produced by closed-die forging and heated by electrical
induction, their diameter not exceeding 215 ram. A 1100 kg
forging was produced f r o m a niobium ingot with 1% Zr and
a diameter of 380 m m . The cost of the forging is high --
a "J7 ~' molybdenum turbine blade came to $280 per kilogram.
To d e c r e a s e oxidation during forging the use of f u r n a -
ces which allow heating to 1870 in protective a t m o s p h e r e
is recommended. F o r tungsten the t e m p e r a t u r e of initial
heating during forging is 1850~ As forging p r o g r e s s e d
(and the recrystallization t e m p e r a t u r e was lowered) the
heating t e m p e r a t u r e was decreased so that the high p r o p e r -
ties are retained as obtained in the " w a r m " deformation of
high-melting m e t a l s .
In using the above forging techniques oxidation poses no
p r o b l e m s even during heating in air; m o r e o v e r , the oxides
act as effective lubricants. However, in forging niobium and
tantalum special coatings are employed for protection against
oxidation.
According to the practice of the Aerojet General
Company the bending of p a r t s manufactured f r o m high-
melting sheet does not involve any difficulties. Plasticity
is enhanced in some c a s e s by heating with an oxygen-
acetylene flame. L o s s e s are negligible and the scale is
either etched away or polished off. At t e m p e r a t u r e s of
1300 to 1400~ 63 m m nozzles with a diameter of 100 m m
can be produced f r o m 1.8 m m thick tungsten sheet.
Even small amounts of additives affect plasticity. Niobium
alloy F48, for instance, can be bent into p a r t s even at a
t e m p e r a t u r e of minus 70~ with a content of 0.003% C but
with 0.05 to 0.08% C the t e m p e r a t u r e of transition into the
plastic state is 150~ Before submitting a niobium or molyb-
denum sheet to appreciable deformation the contaminated
0.075 to 0.125 m m thick surface layer m u s t be removed by
sand blasting to avoid the development of cracks d.uring
deformation.
R. Frank of the General Electric Company contends
that welding by electronic beam is the basic future method
of welding high-melting m e t a l s . In using electronic beam
welding the searas are endowed with increased plasticity as
a r e s u l t of degassing the metal under vacuum and grain
refinement.
Seams in tantalum, niobium and niobium alloys were
plastic at r o o m t e m p e r a t u r e w h e r e a s s e a m s in tungsten
and in molybdenum in molybdenum alloys proved brittle
although somewhat m o r e plastic than the base metal.
Attempts are being made to enhance the plasticity of s e a m s
by method of hot deformation applied to the s e a m zone after
welding. E. Waisert of the Marquardt Corporation found that
by using a molbydenum alloy with 0.5% Ti as an additive
during the welding of wire rod made of a molybdenum alloy
with 35 atomic % Re, the s e a m is plastic and r e s i s t s an 80%
bend at r o o m t e m p e r a t u r e along a radius which is equal to
the thickness of the sheet. However, the s e a m becomes s o m e -
what brittle and is applied to a h e a t - r e s i s t a n t coating which
may be due to the formation of the alpha-phase. This
undesirable effect may be modified by decreasing the rhenium
content to 25 atomic %.
In welding molybdenum the contamination of the s e a m
by residual gas is a m a j o r factor. As long as their contents
does not exceed 0. 007% the quality of the s e a m r e m a i n s high.
With a content of about 0.1% c r a c k s and other imperfections
develop in the s e a m . Insofar as residual gas is usually
located along grain boundaries, c o a r s e - g r a i n e d material is
m o r e susceptible to contamination.
In the welded s e a m s of niobium alloys it is important to
attain optimal m i c r o s t r u c t u r e by way of subsequent heat
treatment. Heat treatment of the welded p a r t c a r r i e d out at
1065 produces seam b r i t t l e n e s s in Fasteel-82 alloy, for
instance. In o r d e r to have a plastic seam, annealing m u s t be
applied at 1150 to 1200~ and only then should the part be
submitted to hardening at 1065~ By analogy, the seam of
F-48 alloy can only be bent by 10 ~ after welding whereas a
105 ~ bend is achieved after annealing at 1370~ (the radius
is equal to the tripled thickness of the sheet).
High-melting m e t a l s are also satisfactorily joined by
contact welding.
F o r continuous hard soldering of molybdenum and its
alloys a Cr - Ni - P d alloy was developed to serve as an
additive (instead of a Si = B alloy which f o r m s brittle
l a y e r s in soldering). In soldering high-melting metals with
Ni alloys, plastic contact l a y e r s are only produced by using
a Cu - Pt alloy.
It is noteworthy that in determining the plasticity of
a high-melting metal the rate of load application is v e r y
important. A molybdenum alloy specimen, for instance,
shows almost no elongation when submitted to tension for
100 seconds (or l e s s ) . The s a m e alloy tested at a tensile
speed of about 0. 005 r a m / r a m x rain (total testing time about
600 seconds) is elongated by almost 42%. However, elonga-
tion does not increase despite slower load application. The

ultimate strength of an N-155 alloy at 1150~ is 1.4; 4.2
and 7.7 k g / m m 2 , respectively, at a rate of load application
of 10 -5 x 10 -3 and 10 -2 r a m / r a m x s e c .
As shown by R. Jaffe of the Batelle Memorial Institute
the employment of high-melting nonmetallic compounds is
complicated as a r e s u l t of the difficulty of consolidating and
refining the grain during hot deformation. Evidently, the
reduction of porosity only by diffusion during sintering does
not give theoretical density. Since with a porosity of 10~
density is lowered by about 50% that problem is of major
importance.
In using oxides, the high volatility of certain oxides
(MgO, for instance) should be taken into account as well as
the possibility of hydrolysis as a r e s u l t of reaction with the
air m o i s t u r e at low t e m p e r a t u r e s .
Changes in the elastic moduli of different m a t e r i a l s with
t e m p e r a t u r e changes a r e shown in Fig. 3. A certain s i m i -
larity between m e t a l s and nonmetals is apparent. A It was found that h e a t - r e s i s t a n t coatings on high-melting
d r a s t i c drop in strength f r o m 0.35 to 0.60 at the equicobosive
t e m p e r a t u r e is a r e s u l t of the transition f r o m the grain
deformation to the boundary deformation.
Most nonmetallic m a t e r i a l s r e m a i n brittle up to m e l t -
ing point t e m p e r a t u r e s . Intermetallie compounds become
plastic at t e m p e r a t u r e s which lie n e a r the transition t e m -
p o r a t u r e s for m o r e brittle m e t a l s . The strength of metals
at subcritical t e m p e r a t u r e s exceeds the strength of non-
metallic m a t e r i a l s which is, evidently, due to the notch
sensitivity of nonmetallic m a t e r i a l s . Only at t e m p e r a t u r e s
above 2400~ is graphite s t r o n g e r than high-melting
metals.
The strength of high-melting m e t a l s may be increased
by alloying. It is noteworthy that none of the high-melting
metals are not subject to polymorphic t r a n s f o r m a t i o n . This
fact m a k e s it m o r e difficult to change the p r o p e r t i e s of the
alloys by heat t r e a t m e n t but accounts for their structural
stability. Strength can be enhanced by aging at high t e m -
p e r a t u r e s (higher than the s e r v i c e t e m p e r a t u r e ) . D.
Levinson of the A r m o r R e s e a r c h Foundation investigated the
Ti - W d i a g r a m . He found that up to 21 atomic % W and in
tungsten up to 25 atomic % Ti are soluble in beta-titanium.
By small carbon additions an alloy can be developed which
would be strengthened (by the dispersion of carbides) up to
high t e m p e r a t u r e s .
PAPERS SUBMITTED TO THE
SYMPOSIUM ON STAINLESS STEELS*
DISPERSION HARDENING OF
STEEL
The author of the paper classified the dispersion
hardening of stainless steels and characterized their basic
p r o p e r t i e s and the strengthening cycles.
The author pointed out that strengthening by hardening
~See MiTOM, No. 2, p. 56, 1960.
215
kg/mm ,
3 5 150 ~-
)'~ 060
7o~o ~.
Zt~ '~ ,
0 200 400 600 800 1000 1209 ~
Fig. 3. Effect of t e m p e r a t u r e on the
modulus of elasticity of some high-
melting m a t e r i a l s .
metals m u s t meet a number of r e q u i r e m e n t s ; one o~ them
being the ability to overcome defects and cracking. Satisfac-
tory r e s u l t s were obtained by coating niobium with a protective
layer of aluminum oxide, with a vitreous bond and by p r o -
tecting molybdenum with aluminum oxide with chromium
serving as a bond.
A protective coating can be applied by plating. Thus,
niobium and molybedenum may be coated with an Inconel
alloy w h e r e a s niobium alloy with considerable amounts of
titanium or zirconium is suitable as a deposit on a high-
strength niobium alloy.
The investigations c a r r i e d out by the Naval R e s e a r c h
Laboratory as reported by J . Zandotz showed that zinc
coating effectively protects niobium f r o m oxidation at 870 to
1090~ Zinc oxide apparently r e s i s t s oxygen diffusion.
The cohesion of the layer enriched by zinc is implemented
by the formation of an intermetallic compound on the surface
(niobium-zinc). Holding at high t e m p e r a t u r e s r e s u l t s in
a partial evaporation of the zinc oxide. However, the dif-
fusion of zinc f r o m the coating to the surface compensates
for the loss and enhances the s e l f - i m p r o v e m e n t of the
protective oxide layer. The layer is easily applied and
has a long service life. Its shortcomings are a loss in
stability of t e m p e r a t u r e s above 1090~ (zinc evaporation)
and its limited application to niobium and its alloys only.
L. COLO~4BIER,
France
of "17-7 Ti martensitic steel from I050~ (~s = 55 kg/mm2;
(~b = I00 kg/mm2) andagingat 500~ ((3s = 145 kg/mm2;
crb = 155 k g / m m 2) takes place as a r e s u l t of the formation
of an iutermetallic compound Ni3Ti. The effect of aging is all the
m o r e pronounced the higher the temperature of hardening. How-
ever, as r e s u l t of that type of treatment the impact tough-
n e s s of steel is lowered. Therefore, the optimal combination