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 High-melting m e t a l s will be required for rockets with
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 atomic engines. The use of liquid hydrogen or helium is
above l l 0 0 ~ F o r the second and third methods the use of considered; it will be pumped to the regenerative-type
r e f r a c t o r y sheet shields is n e c e s s a r y . Ye. Charnetskiy nozzles and cooled externally after which it will enter the
(Boeing Airplane Company) stated that in employing the r e a c t o r where it will be heated up to 1930 to 3320~ and
second and third methods the weight of the engine d e c r e a s e s subsequently it will be discharged through the nozzle. This
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 type of rocket may exceed the speed of a rocket with chemical
method. This is a factor of major importance since even in fuel f r o m two to three t i m e s .
calculating fuel with a high heating value the ratio of the
launching weight of the rocket to the net load is approxima- Despite the system of regenerative cooling, m e t a l s
tely equal to 150 : 1. 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
High-melting m e t a l s may also be n e c e s s a r y for uniflow medium the oxidizability of the metal will not m a t t e r . The
engines which may be exposed to flight speeds of 2 to 8 f i r s t atomic m i s s i l e which is planned to be launched in the
Maeh.**~' Inasmuch as the length of the flight may amount c o u r s e of 1970 will, apparently, have a gas t e m p e r a t u r e
to s e v e r a l h o u r s the high-melting metals m u s t be protected of 1930~ and a pull to weight ratio of about 12. By 1980 the
by oxidation-resistant coatings. F o r sputniks high-melting 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
tubes m a y be used in which liquid sodium is circulated pull to weight ratio of about 50 may be expected. F o r that
diverting the heat of solar radiation. 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
The specific strength ~ at t e m p e r a t u r e s below 1370~ of that task calls for a t h r e e - s t a g e chemically fueled m i s -
(see Fig. 1) is higher in niobium and molybdenum than in sile with a t h r u s t of 2,700,000 kg.
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- In addition to a "uniflow" atomic missile other types of
tates fabrication. engines including plasma and ionic cesium engines may be
developed. For the plasmic engine a working are tempera-
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
?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 - either etched away or polished off. At t e m p e r a t u r e s of
tive cooling even for high-melting m e t a l s . Regenerative 1300 to 1400~ 63 m m nozzles with a diameter of 100 m m
cooling cannot be introduced to the new engine with a can be produced f r o m 1.8 m m thick tungsten sheet.
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 Even small amounts of additives affect plasticity. Niobium
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 alloy F48, for instance, can be bent into p a r t s even at a
of the heat c a r r i e r f r o m 930 to l l 0 0 ~ 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
The yearly r e q u i r e m e n t of high-melting m e t a l s in the plastic state is 150~ Before submitting a niobium or molyb-
United States is relatively small due to their limited use denum sheet to appreciable deformation the contaminated
(about 500 ton) If n e c e s s a r y the following quantities may 0.075 to 0.125 m m thick surface layer m u s t be removed by
be produced: 10,000 ton tungsten, molybdenum and niobium; sand blasting to avoid the development of cracks d.uring
100 to 1000 ton tantalum and 100 ton r h e n i u m . However, deformation.
cost will r e m a i n high.
R. Frank of the General Electric Company contends
A r e s e a r c h project for high-melting sheet m a t e r i a l s that welding by electronic beam is the basic future method
has been developed. The project includes the development of welding high-melting m e t a l s . In using electronic beam
of alloys, coating methods, quality standards and analyti- welding the searas are endowed with increased plasticity as
cal determinations. At the initial stage of r e s e a r c h the a r e s u l t of degassing the metal under vacuum and grain
conditions and production methods of high-quality sheet will refinement.
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 Seams in tantalum, niobium and niobium alloys were
established. At the third stage, production p r o c e s s e s of 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
sheet p a r t s on an industrial scale and the design of instal- and in molybdenum in molybdenum alloys proved brittle
lations will be investigated. 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
At the p r e s e n t time, the r e s e a r c h project is in its by method of hot deformation applied to the s e a m zone after
initial stage. The Universal--Cyclops Steel Company welding. E. Waisert of the Marquardt Corporation found that
concluded a contract for the production of 3500 kg/high- by using a molbydenum alloy with 0.5% Ti as an additive
quality molybdenum sheet (up to 910 x 2400 ram). The during the welding of wire rod made of a molybdenum alloy
crucible Steel Company of A m e r i c a will manufacture highly with 35 atomic % Re, the s e a m is plastic and r e s i s t s an 80%
plastic niobium sheet with an ultimate tensile strength of bend at r o o m t e m p e r a t u r e along a radius which is equal to
70 k g / m m 2 while Sylvania Electric Products Inc. is working the thickness of the sheet. However, the s e a m becomes s o m e -
on a molybdenum alloy sheet made by powder metallurgical what brittle and is applied to a h e a t - r e s i s t a n t coating which
method. A r m o u r R e s e a r c h Foundation investigates the p o s - may be due to the formation of the alpha-phase. This
sibility of producing molybdenum by KroU p r o c e s s . The undesirable effect may be modified by decreasing the rhenium
Wah Chang company studies the effects of admixtures on the content to 25 atomic %.
quality of molybdenum sheet. Contracts are being prepared
for the production of tungsten sheet. 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
According to R. Dnykin (Ladish Company) forging is does not exceed 0. 007% the quality of the s e a m r e m a i n s high.
used as an intermediate operation in the production of high- With a content of about 0.1% c r a c k s and other imperfections
melting m e t a l s . Molybdenum forgings, for instance, are develop in the s e a m . Insofar as residual gas is usually
as complex as titanium forgings. P a r t s with a surface a r e a located along grain boundaries, c o a r s e - g r a i n e d material is
of about 950 cm 2 have a m i n i m u m thickness of 9 to 12 ram. m o r e susceptible to contamination.

The sizes of the forgings a r e limited by the ingot sizes. In the welded s e a m s of niobium alloys it is important to
Ring-shaped molybdenum forgings for nozzle a p p a r a t u s e s attain optimal m i c r o s t r u c t u r e by way of subsequent heat
have a 350 to 380 m m diameter. Nozzle p a r t s f r o m tungsten treatment. Heat treatment of the welded p a r t c a r r i e d out at
were produced by closed-die forging and heated by electrical 1065 produces seam b r i t t l e n e s s in Fasteel-82 alloy, for
induction, their diameter not exceeding 215 ram. A 1100 kg instance. In o r d e r to have a plastic seam, annealing m u s t be
forging was produced f r o m a niobium ingot with 1% Zr and applied at 1150 to 1200~ and only then should the part be
a diameter of 380 m m . The cost of the forging is high -- submitted to hardening at 1065~ By analogy, the seam of
a "J7 ~' molybdenum turbine blade came to $280 per kilogram. F-48 alloy can only be bent by 10 ~ after welding whereas a
105 ~ bend is achieved after annealing at 1370~ (the radius
To d e c r e a s e oxidation during forging the use of f u r n a - is equal to the tripled thickness of the sheet).
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 High-melting m e t a l s are also satisfactorily joined by
heating during forging is 1850~ As forging p r o g r e s s e d contact welding.
(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 - F o r continuous hard soldering of molybdenum and its
ties are retained as obtained in the " w a r m " deformation of alloys a Cr - Ni - P d alloy was developed to serve as an
high-melting m e t a l s . 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
In using the above forging techniques oxidation poses no Ni alloys, plastic contact l a y e r s are only produced by using
p r o b l e m s even during heating in air; m o r e o v e r , the oxides a Cu - Pt alloy.
act as effective lubricants. However, in forging niobium and
tantalum special coatings are employed for protection against It is noteworthy that in determining the plasticity of
oxidation. a high-melting metal the rate of load application is v e r y
important. A molybdenum alloy specimen, for instance,
According to the practice of the Aerojet General shows almost no elongation when submitted to tension for
Company the bending of p a r t s manufactured f r o m high- 100 seconds (or l e s s ) . The s a m e alloy tested at a tensile
melting sheet does not involve any difficulties. Plasticity speed of about 0. 005 r a m / r a m x rain (total testing time about
is enhanced in some c a s e s by heating with an oxygen- 600 seconds) is elongated by almost 42%. However, elonga-
acetylene flame. L o s s e s are negligible and the scale is tion does not increase despite slower load application. The
 215

kg/mm ,
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 3 5 150 ~-
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 )'~ 060
importance.
7o~o ~.
Zt~ '~ ,
In using oxides, the high volatility of certain oxides
(MgO, for instance) should be taken into account as well as 0 200 400 600 800 1000 1209 ~
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 . Fig. 3. Effect of t e m p e r a t u r e on the
modulus of elasticity of some high-
Changes in the elastic moduli of different m a t e r i a l s with melting m a t e r i a l s .
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 metals m u s t meet a number of r e q u i r e m e n t s ; one o~ them
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 being the ability to overcome defects and cracking. Satisfac-
deformation to the boundary deformation. 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 -
Most nonmetallic m a t e r i a l s r e m a i n brittle up to m e l t - tecting molybdenum with aluminum oxide with chromium
ing point t e m p e r a t u r e s . Intermetallie compounds become serving as a bond.
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 A protective coating can be applied by plating. Thus,
at subcritical t e m p e r a t u r e s exceeds the strength of non- niobium and molybedenum may be coated with an Inconel
metallic m a t e r i a l s which is, evidently, due to the notch alloy w h e r e a s niobium alloy with considerable amounts of
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 titanium or zirconium is suitable as a deposit on a high-
above 2400~ is graphite s t r o n g e r than high-melting strength niobium alloy.
metals.
The investigations c a r r i e d out by the Naval R e s e a r c h
The strength of high-melting m e t a l s may be increased Laboratory as reported by J . Zandotz showed that zinc
by alloying. It is noteworthy that none of the high-melting coating effectively protects niobium f r o m oxidation at 870 to
metals are not subject to polymorphic t r a n s f o r m a t i o n . This 1090~ Zinc oxide apparently r e s i s t s oxygen diffusion.
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 The cohesion of the layer enriched by zinc is implemented
alloys by heat t r e a t m e n t but accounts for their structural by the formation of an intermetallic compound on the surface
stability. Strength can be enhanced by aging at high t e m - (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
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. a partial evaporation of the zinc oxide. However, the dif-
Levinson of the A r m o r R e s e a r c h Foundation investigated the fusion of zinc f r o m the coating to the surface compensates
Ti - W d i a g r a m . He found that up to 21 atomic % W and in for the loss and enhances the s e l f - i m p r o v e m e n t of the
tungsten up to 25 atomic % Ti are soluble in beta-titanium. protective oxide layer. The layer is easily applied and
By small carbon additions an alloy can be developed which has a long service life. Its shortcomings are a loss in
would be strengthened (by the dispersion of carbides) up to stability of t e m p e r a t u r e s above 1090~ (zinc evaporation)
high t e m p e r a t u r e s . and its limited application to niobium and its alloys only.

PAPERS SUBMITTED TO THE

SYMPOSIUM ON STAINLESS STEELS*

DISPERSION HARDENING OF L. COLO~4BIER,

STEEL France
The author of the paper classified the dispersion of "17-7 Ti martensitic steel from I050~ (~s = 55 kg/mm2;
hardening of stainless steels and characterized their basic (~b = I00 kg/mm2) andagingat 500~ ((3s = 145 kg/mm2;
p r o p e r t i e s and the strengthening cycles.
crb = 155 k g / m m 2) takes place as a r e s u l t of the formation
The author pointed out that strengthening by hardening 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-
~See MiTOM, No. 2, p. 56, 1960. n e s s of steel is lowered. Therefore, the optimal combination